HETEROCYCLIC STEROID COMPOUNDS

Abstract: The present invention relates to novel substituted 15-oxa-, 15-thia-, and 15-aza-dihydrolanosterols, to pharmaceutical compositions containing such compounds, and to methods of using these compounds to suppress the activity of 3-hydroxy-3-methylglutaryl coenzyme A reductase (HMGR), an enzyme which is important in cholesterol biosynthesis. The overall effect of these heterocyclic lanosterol analogs is to decrease cholesterol formation, thereby resulting in lower serum cholesterol levels in mammals, and impaired ergosterol synthesis in fungi.

Description: HETEROCYCLIC STEROID COMPOUNDS FIELD OF THE INVENTION The present invention relates to novel substituted 15-oxa-, 15-thia-, and 15-aza- dihydrolanosterols, to pharmaceutical compositions containing such compounds, and to methods of using these compounds to suppress the activity of 3-hydroxy-3- methylglutaryl coenzyme A reductase (HMGR) , an enzyme which is important in sterol biosynthesis. The overall effect of these heterocvclic lanosterol analogs is to decrease sterol formation, thereby resulting in lower serum cholesterol levels in mammals, and impaired ergosterol synthesis in fungi. STATE OF THE ART Clinical studies have demonstrated that elevated concentrations of serum cholesterol are a major - 4 - INFORMATION DISCLOSURE Heterocyclic steroid compounds have been prepared in the past. For example, U.S. Patent Nos. 3,845,203 (Williams et al.) ; 3,887,433 (Williams et al.) ; 3,887,564 (Williams et al.) ; 3,947,453 (Jones); 3,987,055 (Berlin et al.) ; 3,972,884 (Jones); 4,001,246 (Jones); 4,008,238 (Jones); and 4,039,547 (Chamberlin) are directed to various aza steroid compounds. Oxa steroid derivatives are disclosed in U.S. Patent Nos. 3,872,076 and 4,053,487 (Rosen), and in Ferland and Lefebfre, Can. J. Chem. , 62: 315-319 (1984). Thia steroids are disclosed in Tolsti ov et al. , Zhurnal Orσanicheskoi Khimi, 22: 121-132 (1986). None of the aforementioned heterocyclic steroid compounds are described as having utility against cholesterol biosynthesis. Thus, additional compounds which affect HMGR and/or other enzymes critical to serum cholesterol biosynthesis are needed. The present invention is directed to this end. SUMMARY OF THE INVENTION The present invention provides novel substituted 15-oxa-, 15-thia-, and 15-aza-dihydrolanosterol compounds of the formula: Formula 1 - 5 - wherein the broken lines represent optional double bonds and: R is a side chain having either 8 or 9 carbon atoms and from 15 to 20 hydrogen atoms, optionally with one site of unsaturation; R 2 is H, C^-Cg alkyl, C 2 -C 8 alkenyl, C 2 -C 6 alkynyl, arylalkyl; R 3 is H, C-L-Cg alkyl, C -C 8 alkenyl, C 2 -Cg alkynyl, arylalkyl, C(R 4 ) 2 R 5 , C0R 4 , CSR 4 , C(=NR 4 )R 4 , C0R 5 , CSR5, C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 C0R 4 , C(R 4 ) 2 CSR 4 , C(R 4 ) 2 C(=NR 4 )R 4 , C(R 4 ) 4 C0R 5 , C(R 4 ) 2 CSR 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 N0R 4 , CR 4 NOR 6 , CR 4 NN(R 4 ) 2 , CR 4 NNR 4 Rg, CHR 4 NHOR 4 , CHR 4 NH0R g , CHR 4 NHN(R 4 ) 2 , CHR 4 NHNR 4 Ng, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 N0Rg CHR 4 CR 4 NN(R 4 ) 2 , CHR 4 CR 4 NNR 4 Rg CHR 4 CHR 4 NH0R 4 , CHR 4 CHR 4 NHORg-, CHR 4 CHR 4 NHN(R 4 ) 2 , C(0)NR 4 0R 4 , C(0)NR 4 OR 6 , C(S)NR 4 OR 4 , C(S)NR 4 ORg, CR 4 =CR 4 Rg, C ≡ CRg, CR 4 =CR 4 C(R 4 ) 2 Z, C=CC(R 4 ) 2 Z, CR 4 =CR 4 C(R 4 ) 2 ORg, C≡CC(R 4 ) 2 OR 6 , poly-(0R 4 , OR g , epoxy)-C- j^ -Cg alkyl; R 4 is H, C- j^ -Cg alkyl, C 2 -C 8 alkenyl, C 2 -Cg alkynyl, aryl, arylalkyl; R 5 is 0R 4 , SR 4 , N(R 4 ) 2 , NR 4 R g ; R 6 is COR 4 , CSR 4 , C(=NR 4 )R 4 ; R 7 is H, alkyl, C 2 -C 20 alkenyl, c 2" c 20 a l k y n yl aryl, arylalkyl ; - 6 - X is O, S, SO, S0 2 , N, NR 4 , NR g , N(0)R 4 ; Z is halogen; and n is 1 or 2; and their physiologically acceptable salts. The compounds of Formula I are effective suppressants of 3-hydroxy-3- methylglutaryl coenzyme A reductase (HMGR) activity. By interfering with this enzyme, which is essential in the cholesterol biosynthetic pathway, cholesterol formation is decreased and serum cholesterol levels lowered. Thus, the present invention also includes therapeutic pharmaceutical compositions for suppressing HMGR activity, decreasing cholesterol formation and lowering serum cholesterol levels. The pharmaceutical compositions comprises (i) an effective amount of a compound of the formula: Formula 1 wherein the broken lines represent optional double bonds and: is a side chain having either 8 or 9 carbon wherein the broken lines represent optional double bonds and: R is a side chain having either 8 or 9 carbon atoms and from 15 to 20 hydrogen atoms, optionally with one site of unsaturation; R 2 is H, C-^-Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, arylalkyl; R 3 is H, ^-Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, arylalkyl, C(R 4 )- > R 5 , COR 4 , CSR 4 , C(=NR 4 )R 4 , C0R 5 , CSR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 CSR 4 , C(R 4 ) 2 C(=NR 4 )R 4 , C(R 4 ) 4 C0R 5 , C(R 4 ) 2 CSR 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 N0R 4 , CR 4 NOR 6 , CR 4 NN(R 4 ) 2 , CR 4 NNR 4 Rg, CHR 4 NHOR 4 , CHR 4 NHOR g , CHR 4 NHN(R 4 ) 2 , CHR 4 NHNR 4 Ng, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NORg CHR 4 CR 4 NN(R 4 ) 2 , CHR 4 CR 4 NNR 4 Rg CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg, CHR 4 CHR 4 NHN(R 4 ) 2 , C(0)NR 4 0R 4 , C(0)NR 4 OR 6 , C(S)NR 4 0R 4 , C(S)NR 4 ORg, CR 4 =CR 4 Rg, C≡CRg, CR 4 =CR 4 C(R 4 ) 2 Z, C ≡ CC(R 4 ) 2 Z, CR 4 =CR 4 C(R 4 ) 2 ORg, C≡CC(R 4 ) 2 OR 6 , poly-(OR 4 , ORg, epoxyJ-C^Cg alkyl; R 4 is H, C-^-Cg alkyl, C 2 -C 8 alkenyl, C 2 -Cg alkynyl, aryl, arylalkyl; R 5 is 0R 4 , SR 4 , N(R 4 ) 2 , NR 4 R 6 ; R 6 is COR 4 , CSR 4 , C(=NR 4 )R 4 ; R 7 is H, ^-C^ alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, arylalkyl; - 8 - and (ii) a pharmaceutically acceptable carrier or diluent. In addition, the present invention encompasses methods for suppressing HMGR activity, decreasing cholesterol formation and lowering serum cholesterol levels comprising administering to a host an effective amount of a compound of the formula: Formula 1 wherein the broken lines represent optional double bonds and: R is a side chain having either 8 or 9 carbon atoms and from 15 to 20 hydrogen atoms, optionally with one site of unsaturation; R 2 is H, C 1 -C 6 alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, arylalkyl; R 3 is H, C 1 -Cg alkyl, C 2 -C 8 alkenyl, C 2 -C 6 alkynyl, arylalkyl, C(R 4 ) 2 R 5 , C0R 4 , CSR 4 , C(=NR 4 )R 4 , C0R 5 , CSR5, - 9 - C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 CSR 4 , C(R 4 ) 2 C(=NR 4 )R 4 , C(R 4 ) 4 C0R 5 , C(R 4 ) 2 CRS 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NOR 6 , CR 4 NN(R 4 ) 2 , CR 4 NNR 4 Rg, CHR 4 NHOR 4 , CHR 4 NHORg, CHR 4 NHN(R 4 ) 2 , CHR 4 NHNR 4 Ng, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NOR 6 CHR 4 CR 4 NN(R 4 ) 2 , CHR 4 C 4 NNR 4 Rg CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg, CHR 4 CHR 4 NHN(R 4 ) 2 , C(0)NR 4 OR 4 , C(0)NR 4 OR 6 , C(S)NR 4 OR 4 , C(S)NR 4 OR 6 , CR 4 =CR 4 R 6 , C=CR 6 , CR 4 =CR 4 C(R 4 ) 2 Z, C≡CC(R 4 ) 2 Z, CR 4 =CR 4 C(R 4 ) 2 OR 6 , CΞCC(R 4 ) 2 ORg, poly-(OR 4 , ORg, epoxyJ-C^-Cg alkyl; R 4 is H, C^ ^ -C alkyl, C 2 -C alkenyl, C 2 -C 8 alkynyl, aryl, arylalkyl; R 5 is OR 4 , SR 4 , N(R 4 ) 2 , NR 4 R 6 ; R 6 is COR 4 , CSR 4 , C(=NR 4 )R 4 ; R 7 is H, 1 -C 2Q alkyl, C 2 -C 20 alkenyl, c 2~ c 20 a kynyl, aryl, arylalkyl; X is 0, S, SO, S0 2 , N, NR 4 , NRg, N(0)R 4 ; Z is halogen; and n is 1 or 2. In the above formulae, the R side chain is preferably selected from the cholesterol side chain ( C 8 H 17) and the ergosterol side chain ( g H 17 ^ These are generically represented by the foπnul≤.: - 10 - where the dashed line represents an optional double bond and the circled alpha-methyl group is likewise optional. However, when the D ring is piperidine or the N-oxide thereof, the R side chain is not an ergosterol side chain. Likewise, in the above formulae, the ring structure may be unsaturated between carbons 7 and 8 or 8 and 9. When X is N the structure has an additional double bond between C-14 and N and C-14 does not have 3 substitution. As used herein, the substituent designated as "poly-(0R 4 , OR 5 , epoxy) ^-Cg alkyl" shall be taken to mean a C^ to Cg alkyl chain substituted with one or more of any combination of OR , OR 5 and epoxy. As used herein, the term "alkyl" employed either alone or in combination with other terms such as "poly-(OR 4 , OR 5 , epoxy) ^-Cg alkyl" or "arylalkyl", denotes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl, and the different butyl, pentyl or hexyl isomers. As used herein, the term "alkynyl", employed either alone or in combination with other terms, denotes straight chain or branched mono- or poly- unsaturated alkyl, e.g., ethynyl, propynyl (propargyl) , 2-butynyl isomers, and the different pentynyl, hexadiynyl and hexynyl isomers. As used herein, the term "acyl", employed either alone or in combination with other terms, denotes a carbonyl group attached to an alkyl, alkenyl, alkynyl, arylalkyl or aryl group e.g. acetate, butyrate, benzoate, and different alkyl, alkenyl, alkynyl, or aryl isomers. C(R 4 ) 2 C(R 4 ) 2 R 5/ C(R 4 ) 2 COR 4 , C(R 4 ) 2 CSR 4 , C(R 4 ) 2 C(=NR 4 )R 4 , C(R 4 ) 4 COR 5 , C(R 4 ) 2 CRS 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NOR 6 , CR 4 NN(R 4 ) 2 , CR 4 NNR 4 Rg, CHR 4 NHOR 4 , CHR 4 NHORg, CHR 4 NHN(R 4 ) 2 , CHR 4 NHNR 4 N g , CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NORg CHR 4 CR 4 N (R 4 ) 2 , CHR 4 CR 4 NNR 4 R g CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg, CHR 4 CHR 4 NHN(R 4 ) 2 , C(0)NR 4 OR 4 , C(0)NR 4 OR 6 , C(S)NR 4 OR 4 , C(S)NR 4 OR 6 , CR 4 =CR 4 R 6 , C ≡ CR 6 , CR 4 =CR 4 C(R 4 ) 2 Z, C Ξ CC(R 4 ) 2 Z, CR 4 =CR 4 C(R 4 ) 2 OR 6/ C≡CC(R 4 ) 2 OR 6 , poly-(OR 4 , ORg, epoxy)-C^-C alkyl; R 4 is H, C j^ -C alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, aryl, arylalkyl; R 5 is OR 4 , SR 4 , N(R 4 ) 2 , NR 4 R 6 ; R 6 is COR 4 , CSR 4 , C(=NR 4 )R 4 ; R 7 is H, alkyl, C 2 -C 2Q alkenyl, c 2" c 2 0 alkynyl, aryl, arylalkyl; X is 0, S, SO, S0 2 , N, NR 4 , NRg, N(0)R 4 ; Z is halogen; and n is 1 or 2. In the above formulae, the R side chain is preferably selected from the cholesterol side chain ( 8 H 17) and the ergosterol side chain These are generically represented by the for ula: - 12 - General Procedures for the Preparation of Heterocyclic Lanosterol Derivatives The compounds of the present invention accommodate the necessary requirements for suppression of HMGR activity. To allow the introduction of various functional groups at 14-position, a strategy, which involves an opening and a reclosing of the D ring of the steroidal structure, was developed. In the schemes and tables which follow, for simplicity, only the cholesterol side chain (C g H 17 ) is shown. It is to be understood that the ergosterol side chain (C 9 H 17 ) or modifications of either side chain may be present instead of the illustrated cholesterol side chain. 15-Oxa-Lanosterols The common intermediate for 15-oxa-, thia- and aza- dihydrolanosterols, the enone-aldehyde 4, has been obtained by an osmium tetroxide hydroxylation on the 8,14-diene (Compound 2) followed by an oxidative cleavage of the resulting diol. Compound 3 (See, Scheme I). - 13 - SCHEME I 1, 2 a R,-H 3a R, -H 2 b R, » p-CH 3 OC 8 H <i CH 2 ( pMBn ) 3 b R^ Bπ 6a R 1 -H, Rg-CH j 7a *ι : H, R j a R^ a CHg 6 b R 1 a pMBn, R. * CH j 7b *1 pMBn, Rg-CH^ R j -H 12a R^.Rg.H 7c « ■ pMSn, τ R 7 a CH 3 12b R^.p Bn, R j -H 13a Ri i Rg H, R » CHg 18a RT-H, Rg-CH-C^ 13b «ι .pMBn, Rg-F^-H 18b RT- BΠ, R3»CH»CH 2 13c Ri .pMBn, Ra-H, RJ.CRJ 19a Ri ' H, Rg a CHaCH j , R7 a CH 19b Rι .pMBn, Rg-CH-CH j , R 7 «H 19c i -pMBn, Ra-CH-CH j . R 7 -CH 3 - 14 - The starting species, Compound 2a, 4-dimethyl- 5a-cholesta-8,14-dien-3b-ol, was prepared from 7-dehydrocholesterol (Sigma Chemical Co., P.O. Box 14508, St. Louis, MO 63178) by the method described by Bloch and Gautschi in J. Chem. Soc. , 223 (6) , 1343 (1958). Treatment of the 8,14-dien-3b-ol (2a) with sodium hydride (Alfa Products, P.O. Box 299, Danvers, MA 01923) and 4-methoxybenzyl chloride [prepared by the method described by R. L. Schriner and C. J. Hull in J. Orσ. Chem. , 10, 228 (1945)] in 4 parts of tetrahydrofuran and 1 part of N,N-dimethylformamide at 70°C afforded the corresponding p-methoxybenzyl ether 2b in near quantitative yield. Hydroxylation of the diene 2b with stoichiometric amount of osmium tetroxide (Alfa) in the presence of 10 equivalents of anhydrous pyridine (Aldrich Chemical Co., Inc., 940 West St., Paul Ave., Milwaukee, WI 53233) in benzene provided the 14,15-diol in 82% yield. Opening of the steroid D-ring was achieved by reacting the diol 3b with lead tetraacetate (Aldrich, recrystallized from acetic acid) in benzene to give the corresponding tricyclic enone-aldehyde 4b in quantitative yield. Selective conversion of the enone-aldehyde 4b to a dimethyl acetal 5b by with trimethyl orthoformate (Aldrich) and camphorsulfonic acid (Aldrich) in methanol (>95% yield) ensured the functionalization at C-14 without complication at C-15. The necessary functional groups at 14-position were introduced at this stage by adding various nucleophiles to the carbonyl. Diisobutyl aluminum hydride (Aldrich, 1 molar solution in hexane) reduction of the enone 5b in methyl chloride afforded the alcohol 12b in 85% yield. A methyl group was introduced by a Grignard reaction with methyl magnesium bromide (Aldrich, 3 - 13 - SCHEME I 4a R, -H 5a R^-H 4b R 1 a pMBn 5b R pMBn 6a R,-H, Rg-CHg 7a | a H, Rg a Rγ a CHg 6 b R 1 a pMSπ, Rg CH, 7b R^pMBn. Rg-CHg, R^H 12a R^.Rg.H 7c R, pM8n, Rg R 7 CH 3 12b R^pMSn, R 3 «H 13a r » Mg β ri t H^ a* ^*^3 18a RT-H, RJ-CH-CI^ 13b R, pMBn, Rg a Ry a H 18b RT -PMBΠ, Rg«CH«CH 2 13c R,-pMBπ, Rg-H, 7 aCH j 19a R^ a H, Rg a CH CH j , 7 CHg 19b R - pMBn, Rg « CH-CH^ R 7 - H 19C F -p Bn, R--CH-CH-, R τ - - 16 - This unstable mixture of diols 9b was reacted with sodium periodate (Aldrich) in 4 parts of diethyl ether, 4 parts of methanol and l part of water in the presence of camphorsulfonic acid to give a mixture of p-methoxy- benzyl ether of 16-methoxy-15-oxa-dihydrolanosterol 10b and p-methoxybenzyl ether of 16-hydroxy-15- oxa-dihydrolanosterol 10c in about 7:1 ratio. The mixture was then treated with excess triethylsilane (Aldrich) and then redistilled boron trifluoride etherate (Aldrich) in methylene chloride to give the desired 15-oxa-dihydrolanosterol (11a) in 40% overall yield from the compound 7b. The p-methoxy benzyl protecting group at C-3 was conveniently cleaved during this process to afford the free hydroxy compound. In the same manner the C-14 hydride compound 12b and the C-14 vinyl compound 18b have also been transformed successfully into the corresponding 4,4-dimethyl-15-oxa-5a-cholest-8-en-3b-ol (17a) and 4,4-dimethyl-15-oxa-14a-vinyl-5a-cholest-8-en-3b-ol (23a) in 36% and 50% overall yields respectively. The compounds 17a, 11a, and 23a constitute three examples of 15-oxa-lanosterols within the scope of the present invention. Exposing the 14a-vinyl-oxa-sterol (23a) to acetic anhydride (Fischer Scientific, Fair Lawn, NJ 07440) in anhydrous pyridine gave 3b-acetoxy-4,4-dimethyl-15-oxa- vinyl-lanost-8-ene (23c) , a compound within the scope of the present invention, in 81% yield. Esters of other lanosterol derivatives within the scope of the invention may be prepared in this or a similar manner. - 17 - SCHEME II pMBnO 7b R 3 »CH 3 8b Rg CHg 13b R g -H 14b Rg-H 19b R-,»CHaCH, 20b RgaCHaCH 2 9b R,-CK, 10b Rg-CK j 15b :H 16b gaH 21b R, « CHaCH, 22b Rg a CHaCH 2 11 R, - H, Rg . CHg 17 R,»H, R g »H 23c R^CHgCO. Rg-CH-CH 2 - 18 - Further elaboration at the 14-position was achieved by treating the vinyl compound 23c with osmium tetroxide in pyridine to afford a diastereomeric mixture of diols 24c and 25c (2.84:1) in 45% yield (Scheme III) . The mixture of diols 24c and 25c was reacted with sodium metaperiodate in 4 parts of ethanol and 1 part of water to give 3b-acetoxy-15-oxa-lanost-8-en-32-al (26c) in near quantitative yield. Hydrolysis of the acetate-aldehyde 26c by 3 molar potassium hydroxide afforded the corresponding free hydroxy-aldehyde 26a in near quantitative yield. Reduction of the aldehyde 26a with sodium borohydride (Fischer Scientific) in ethanol afforded 15-oxa-lanost-8-ene-3b, 32-diol (27) in near quantitative yield. The same chemistry is also applicable to the free hydroxy-vinyl compound 23a to provide 24a, 25a, and 26a directly. Compounds 24a, 24c, 25a, 25c, 26a, 26c and 27 are seven additional examples of 15-oxa-lanosterols within the scope of the present invention. SCHEME II 9b Rg-C} ■ «3 10b Rg a CHg 15b RgaH 16b Rg-H 21b R 3 »Cl =CH 2 22b Rg . CH=CH 2 11 R, - H, Rg . CH g H-C^ 23c R^CHgCO. Rg-CH-CH 2 - 20 - The aldehyde functional group of the Compound 26 allows further functionalization at the 32-position of lanosterol. A Grignard addition to the aldehyde 26c with vinyl magnesium bromide (Alfa, 1.6 molar solution in tetrahydrofuran) in refluxing tetrahydrofuran provided a diasteromeric mixture of allylic alcohols 28 and 29 (1.4:1) in >95% combined yield. Upon exposing the aldehyde 26a to hydroxylamine hydrochloride (Aldrich) in pyridine at 80°, the corresponding oxime 30 was obtained in quantitative yield. Compounds 28, 29, and 30 constitute three additional examples of 15-oxa- lanosterols within the scope of the present invention. - 21 - Table 1 sets forth various oxasterols of the present invention. - 22 - Table 1 Ex. No. R-, R- j No . M. P , 1 OH CH 3 CH 3 8 11 amorphous* 2 OH CH 3 H 8 17 amorphous* 3 OH CH 3 CH=CH 2 8 23a amorphous* 3a CH 3 CH 3 CH=CH 2 8 23c 4 OH CH 3 CHOHCH 2 ; OH- (R) 8 24c 5 OH CH 3 CHOHCH 3 OH- (S) 8 25c 6 CH 3 CO CH 3 CHO 8 26c amorphous* 7 OH CH 3 CHO 8 2a amorphous* 8 OH CH 3 CH 2 OH 8 27 9 OH CH 3 C0 2 CH 3 8 10 OH CH 3 CH=NOH 8 30 amorphous* 11 OH CH 3 CHOHCH= =CH 2 -(R) 8 28 amorphous* 12 OH CH 3 8 29 amorphous* 13 OH H CH 3 8 47 14 OH H H 8 15 OH H CH=CH 2 8 16 OH H CHOHCH- ,OH- (R) 8 17 OH H CHOHCH 2 ,OH- (S) 8 Table 1 sets forth various oxasterols of the present invention. - 24 - Table 1 (Continued) Ex. No R l No. M.P, 43 OH CH- CH 2 SH 8 44 OH CH 3 CH SCH-3 8 45 OH CH 3 CH 2 SC 2 H 5 8 46 OH CH 3 CH 2 SPr 8 47 OH CH 3 CH 2 SCH 2 CH=CH 8 48 OH CH 3 CH 2 SPh 8 49 OH CH 3 CH 2 SCOH 3 8 50 OH CH : CH 2 NH 2 8 51 OH CH, CH 2 NHCH 3 8 52 OH CH : CH 2 NHC 2 H 5 8 53 OH CH, CH 2 NHC 3 H ? 8 54 OH CH, CH 2 NHi-Pr 8 55 OH CH, CH 2 NHC 6 H 13 8 56 OH CH, CH 2 NHPh 8 57 OH CH, CH 2 NMe 2 8 58 OH CH, CH 2 NEt 2 8 59 OH CH, CH 2 NHCHO 8 60 OH CH, CH 2 NHCOCH 3 8 61 OH CH, CH 2 NHCSCH 3 8 62 OH CH 3 CH 2 NH(C=NH)CH 3 8 63 OH CH- COCH- 8 64 OH CH 3 COC 2 H 5 8 65 OH CH 3 COC 3 H 7 8 66 OH CH 3 COi-C 3 H 7 8 67 OH CH 3 COC 6 H 13 8 - 25 - Table 1 (Continued) Ex. No • R l R 2 R 3 D No . M . P . 68 OH CH 3 COCH=CH 2 8 69 OH CH 3 COCH 2 CH=CH 2 8 70 OH CH 3 COCH=CHCH 3 8 71 OH CH 3 COC≡CH 8 72 OH CH 3 COCH 2 C=CH 8 73 OH CH 3 coc=cc: 3 8 74 OH CH 3 COPh 8 75 OH CH 3 CSCH 3 8 76 OH CH 3 CSC 2 H 5 8 78 OH CH 3 CSC 3 H 7 (i) 8 79 OH CH 3 CSC 6 H 13 8 80 OH CH 3 CSCH=CH 2 8 81 OH CH 3 CSCH CH = CHo 8 82 OH CH 3 CSCH=CHCH 3 8 83 OH CH 3 CSC≡CH 8 84 OH CH 3 CSCH 2 CH 8 85 OH CH 3 CSC=CCH 3 8 86 OH CH 3 CSPh 8 87 OH CH 3 C(=NH)CH 3 8 88 OH CH 3 C(=NH)C 3 H 7 8 89 OH CH 3 C(=NH)C 3 H 7 8 90 OH CH 3 C(=NH)Ph 8 91 OH CH 3 C(=NH)CH 3 8 92 OH CH 3 C(=NCH 3 )C 2 H 5 8 O O O O O O O O O 0 O w O 0 O O O O O 0 O O O 0 W w W W W w w W W w X w w W X X w W W W X W o 0 Jw Uw) wJ OJw OJw 0 0 0 O OJw ωw OJw Jw oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo ∞ oo oo oo oo oo oo Table 1 (Continued) Ex. No R 2 R 3 D No. M.P. 68 OH CH 3 COCH=CH 2 8 69 OH CH 3 COCH 2 CH=CH 2 8 70 OH CH 3 COCH=CHCH 3 8 71 OH CH 3 COC^CH 8 72 OH CH 3 COCH 2 C=CH 8 73 OH CH 3 COC=CC" 3 8 74 OH CH 3 COPh 8 75 OH CH 3 CSCH 3 8 76 OH CH 3 CSC 2 H 5 8 77 OH CH 3 CSCoH'7 8 78 OH CH 3 CSC 3 H 7 (i) 8 79 OH CH 3 CSCgH 13 8 80 OH CH 3 CSCH=CH 2 8 81 OH CH 3 CSCH 2 CH=CH 2 8 82 OH CH 3 CSCH=CHCH 3 8 83 OH CH 3 CSC^CH 8 84 OH CH 3 CSCH 2 CH 8 85 OH CH 3 CSC=CCH 3 8 86 OH CH 3 CSPh 8 87 OH CH 3 C(=NH)CH 3 8 88 OH CH 3 C(=NH)C 3 H 7 8 89 OH CH 3 C(=NH)C 3 H 7 8 90 OH CH 3 C(=NH)Ph 8 91 OH CH 3 C(=NH)CH 3 8 92 OH CH 3 C(=NCH 3 )C 2 H 5 8 -28- Table 1 (Continued) Ex. No. R l- R- R- No. M.P. 143 OH CH, CH 2 CH 2 NH 2 8 144 OH CH, CH 2 CH(CH 3 )NH 2 8 145 OH CH, CH 2 CH 2 NHCH 3 8 146 OH CH- CH 2 CH 2 NHC 2 H 5 8 147 OH CH, CH 2 CH 2 NHPh 8 148 OH CH 3 CH 2 CH(CH 3 )NHCH 3 8 149 OH CH 3 CH 2 CH 2 NMe 2 8 150 OH CH 3 CH 2 CH 2 NHCOCH 3 8 151 OH CH 3 CH 2 CH(CH 3 )NHCOCH 3 8 152 OH CH 3 CH 2 CH 2 NHCSCH 3 8 153 OH CH 3 CH 2 CH(CH 3 )NHCSCH 3 8 154 OH CH 3 CH 2 CH 2 NHC(=NH)CH 3 8 155 OH CH 3 CH 2 CH(CH 3 )NHC(=NH)CH 3 8 156 OH CH 3 CH 2 CHO 8 157 OH CH 3 CH 2 COCH 3 8 158 OH CH 3 CH 2 COC 2 H 5 8 159 OH CH„ CH 2 COCH=CH 2 8 160 OH CH 3 CH 2 COCH 2 CH=CH 2 8 161 OH CH 3 CH 2 COCH=CHCH 3 8 162 OH CH 3 CH 2 COC≡CH 8 163 OH CH 3 CH 2 COPh 8 164 OH Cri 'ϊ CH SCH* 5 8 166 OH CH 3 CH 2 CSCH=CH 2 8 167 OH CH- Cfio SCH^ CH — CHΛ 8 -29- Table 1 (Continued) Ex. No. R l R 2 R 2 D No. M.P. 168 OH CH 3 CH 2 CSCH=CHCH 3 8 169 OH CH 3 CH 2 CSCΞCH 8 170 OH CH 3 CH 2 CSPh 8 171 OH CH 3 CH 2 C(=NH)CH 3 8 172 OH CH 3 CH 2 C(=NH)C 2 H 5 8 173 OH CH 3 CH 2 C(=NCH 3 )CH 3 8 174 OH CH 3 CH 2 C(=NCH 3 )C 2 H 5 8 175 OH CH 3 CH 2 C(=NH)Ph 8 176 OH CH 3 CH O COOCHT 8 177 OH CH 3 CH 2 C0 2 C 2 H 5 8 178 OH CH 3 CH 2 C0 2 CH 2 CH=CH 2 8 179 OH CH 3 CH 2 C0 2 Ph 8 180 OH CH 3 CH 2 COSCH 3 8 181 OH CH 3 CH 2 COSCH 3 8 181 OH CH 3 CH 2 COSC 2 H5 8 182 OH CH 3 CH 2 COSPh 8 183 OH CH 3 CH 2 CONH 2 8 184 OH CH 3 CH 2 CONHCH 3 8 185 OH CH 3 CH 2 CONHC 2 H 5 8 186 OH CH 3 CH 2 CONHPh 8 187 OH CH 3 CH 2 CONMe 2 8 188 OH CH 3 CH 2 CONHCOCH 3 8 189 OH CH 3 CH 2 CSNH 2 8 190 OH CH 3 CH 2 C(=NH)NH 2 8 191 OH CH 3 CH 2 C1 8 -30- Tab e 1 (Continued) Ex. No. R l- -H-. NO , M . P . 192 OH CH- CH 2 Br 8 193 OH CH- CH 2 CH 2 C1 8 194 OH CH, CHo CHn Br 8 195 OH CH, CN 8 196 OH CH, C (CH 3 ) =NOH 8 197 OH CH, CH=NOCH 3 8 198 OH CH, CH=NOC 2 H 5 8 199 OH CH, CH=NOCOCH 3 8 200 OH CH, CH=NNH-, 8 201 OH CH 3 CH=NNHCH 3 8 202 OH CH 3 CH=NNHCOCH 3 8 203 OH CH 3 CH=NNHCSCH 3 8 204 OH CH 3 CH 2 NHOH 8 205 OH CH 3 CH 2 NHOCH 3 8 206 OH CH 3 CH 2 NHOCOCH 3 8 207 OH CH 3 CH 2 NHNH 2 8 208 OH CH 3 CH 2 NHNHCH 3 8 209 OH CH 3 CH 2 NHNHCOCH 3 8 210 OH CH 3 CH 2 NHNHCSCH 3 8 211 OH CH 3 CH 2 CN 8 212 OH CH 3 CH 2 CH=NOH 8 213 OH CH 3 CH 2 C ( CH 3 ) =NOH 8 214 OH CH 3 CH 2 CH=NOCH 3 8 215 OH CH 3 CH 2 CH=NOC 2 H 5 8 216 OH CH 3 CH 2 CH=NOCOCH 3 8 Table 1 (Continued) Ex. No. R l R 2 R 3 D Nlo. M.P. 168 OH CH 3 CH 2 CSCH=CHCH 3 8 169 OH CH 3 CH 2 CSC^CH 8 170 OH CH 3 CH 2 CSPh 8 171 OH CH 3 CH 2 C(=NH)CH 3 8 172 OH CH 3 CH 2 C(=NH)C 2 H 5 8 173 OH CH 3 CH 2 C(=NCH 3 )CH 3 8 174 OH CH 3 CH 2 C(=NCH 3 )C 2 H 5 8 175 OH CH 3 CH 2 C(=NH)Ph 8 176 OH CH 3 CH 2 C0 2 CH 3 8 177 OH CH 3 CH 2 C0 2 C 2 H 5 8 178 OH CH 3 CH 2 C0 2 CH 2 CH=CH 2 8 179 OH CH 3 CH 2 C0 2 Ph 8 180 OH CH 3 CH 2 COSCH 3 8 181 OH CH 3 CH 2 COSCH 3 8 181 OH CH 3 CH 2 COSC 2 H5 8 182 OH CH 3 CH 2 COSPh 8 183 OH CH 3 CH 2 CONH 2 8 184 OH CH 3 CH 2 CONHCH 3 8 185 OH CH 3 CH 2 CONHC 2 H 5 8 186 OH CH 3 CH 2 CONHPh 8 187 OH CH 3 CH 2 CONMe 2 8 188 OH CH 3 CH 2 CONHCOCH 3 8 189 OH CH 3 CH 2 CSNH 2 8 190 OH CH 3 CH 2 C(=NH)NH 2 8 191 OH CH 3 CH 2 C1 8 -32- Table 1 (Continued) Ex. No. R l- R- No . M . P . 242 OH CH 3 CH=CHC (=NH) CH 3 8 243 OH CH 3 C≡CCHO 8 244 OH CH 3 CΞCCOCH 3 8 245 OH CH 3 CΞCCOC 2 H 5 8 246 OH CH 3 C=CCSCH 3 8 247 OH CH 3 C≡CCSC 2 H 5 8 248 OH CH 3 C≡CCH=NH 8 249 OH CH 3 C=CC(=NH)CH 3 8 250 OH CH 3 CH=CHCH 2 C1 8 251 OH CH 3 CH=CHCH 2 Br 8 252 OH CH 3 C≡CCH 2 C1 8 253 OH CH 3 C≡CCH 2 Br 8 254 OH CH 3 CH=CHCH 2 OCOCH 3 8 255 OH CH 3 CH=CHCH 2 OCOC 2 H 5 8 256 OH CH 3 C≡CCH 2 OCOCH 3 8 257 OH CH 3 C≡CCH 2 OCOC 2 H 5 8 258 OH CH 3 CH 2 CHOHCH 2 OH 8 259 OH CH 3 CHOHCHOHCH 2 OH 8 261 OH CH-3 CHoCH—CH 0 262 OH CH,3, CHOHCH-/CH-2, 0 263 OH H C 2 H 5 -34- Table 1 (Continued) Ex. No. R l R 2 R-, D No . M . P . 289 OH H CONHCOCH 3 8 290 OH H CSNH 2 8 291 OH H CSNHCH 3 8 292 OH H CSNMe 2 8 293 OH H CSNHCOCH 3 8 294 OH H CH 2 CH 2 OH 8 295 OH H CH 2 CH 2 OCH 3 8 296 OH H CH 2 CH 2 OCOCH 3 8 297 OH H CH CH^SH 8 298 OH H Cxi CH SCH-j 8 299 OH H CH 2 CH 2 SCOCH 3 8 300 OH H CH 2 CH 2 NH 2 8 301 OH H CH 2 CH 2 NHCH 3 8 302 OH H CH 3 CH 2 NMe2 8 303 OH H CH 2 CH 2 NHCOCH 3 8 304 OH H CH 2 CH 2 NHCSCH 3 8 305 OH H CH 2 CH 2 NHC(=NH) CH 3 8 306 OH H CH 2 CHO 8 307 OH H CH 2 COCH 3 8 308 OH H CH 2 COCH=CH 2 8 309 OH H CH 2 CSCH 3 8 310 OH H CH 2 CSCH=CH 2 8 311 OH H CH 2 C(=NH)CH 3 8 312 OH H CH 2 C(=NCH 3 )CH 3 8 313 OH H CH T CO T CH-> 8 t to to to to t to to to to to to to to to to to to to to to to to to σ j oo oo oo oo oo ω oo oo -J -^J ^J ^J -o - j ^ j ^ j - j -o σv Λ σv v n oo -o ui ^ oJ to H o vo oo ^4 cn ui i. oJ t ι-' o o o3 ~J cn ui 00 00 00 00 00 00 03 00 03 00 00 00 03 00 00 00 00 00 00 00 00 03 00 00 -36- Table 1 (Continued) 338 OH H CH 2 NHNHCSCH 3 8 339 OH H CH 2 CN 8 340 OH H CH 2 CH=NOH 8 341 OH H CH 2 CH=NOCH 3 8 342 OH H CH 2 CH=NOCOCH 3 8 343 OH H CH 2 CH=NNH 2 8 344 OH H CH 2 CH=NNHCH 3 8 345 OH H CH 2 CH=NNHCOCH 3 8 346 OH H CH 2 CH=NNHCSCH 3 8 347 OH H CH 2 CH 2 NHOH 8 348 OH H CH 2 CH 2 NHOCH 3 8 349 OH H CH 2 CH 2 NHOCOCH 3 8 350 OH H CH 2 CH 2 NHNH 2 8 351 OH H CH 2 CH 2 NHNHCH 3 8 352 OH H CH 2 CH 2 NHNHCOCH 3 8 353 OH H CH 2 CH 2 NHNHCSCH 3 8 354 OH H CONHOH 8 355 OH H CONHOCH 3 8 356 OH H CONHOCOCH 3 8 357 OH H CSNHOH 8 358 OH H CSNHOCH 3 8 359 OH H CSNHOCOCH 3 8 360 OH H CH=CHCHO 8 361 OH H CH=CHCOCH-, 8 OJ OJ OJ OJ OJ 0J 0J OJ OJ 0J 0J 0J OJ 0J J OJ OJ 0J OJ 0J OJ OJ 00 00 00 00 ω ^1 ^j ^J ^1 ^1 -O -4 -0 -J ^J CΛ (Λ CΛ CΛ CΛ CΛ (Λ OJ to H o vo ω -0 CΛ Ul * OJ to H O o 03 -O CΛ Ul 0J II II II II O O O O o o o O o O o o o O o o o o o o O O W w W w w w w w W w w w w w w w w w O o O o w w w w w w X w W w w w w w w w w w w w w w OJ OJ J OJ 00 00 CO 00 00 00 03 0O 0O 00 O3 0O 00 0O 0O 0O 00 00 00 00 0O 00 -40- Table 1 (Continued) Ex. No. R- D No, M.P. 434 OCH- CH- CH=CH 2 8 435 OCH- CH- CHOHCH 2 OH-(R) 8 436 OCH- CH- CHOHCH 2 OH-(S) 8 437 OCH- CH- CHO 8 438 OCH- CH- CH 2 OH 8 439 OCH- CH- C0 3 H 8 440 OCH- CH- C0 2 CH 3 8 441 OCH- CH- CH=NOH 8 442 OCH, CH, CHOHCH=CH 2 -(R) 8 443 OCH, CH- CHOHCH=CH 2 -(S) 8 444 OCH, CH- CH 2 SH 8 445 OCH, CH, CH 2 NH 2 8 446 OCH, CH, COCH 3 8 447 OCH, CH, CONH 2 8 448 OCH, CH- CSNH 8 449 OCH, CH, CH 2 CH 2 OH 8 450 OCH, CH, CH 2 CHO 8 451 OCH, CH, CH 2 COCH 3 8 452 OCH, CH, CH 2 C0 2 CH 3 8 453 OCH, CH, CH 2 CONH 2 8 454 OCH, CH, CH 2 C1 8 455 OCH, CH, CH 2 CH 2 C1 8 456 OCH- CH, CN 8 457 OCH, CH, CH=NNH 2 8 458 OCH, CH, CH 2 NHOH 8 Ul Ul Ul Ul Ul Ul Ul Ul J 4» 4* . * 4*. 4a. 4k 4^ 4 * 4>. 4*- 4a. *» 4 O O O O O O O o vo O O O VO o VO VO O O 00 00 00 00 00 03 ω -O CΛ Ul 4 OJ to H o vo 00 -0 CΛ Ul 4a. OJ to X H o vo 00 -0 CΛ Ul a. OJ 0O O0 O3 00 0O 00 0O 00 O3 0O O3 0O 0O 0 0O 00 00 O3 0O O3 3 0O 00 3 00 ID Ul Ul Ul Ul Ul Ul ui Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul 4a. a, 4a. 4a. 4a. 4a. 4a. 4a. 4 . OJ CΛ Ul 4 J to H o VO 00 si Λ Ul 4a. OJ to H O vo 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 03 00 00 00 00 00 00 00 00 UI UI UI UI UI UI UI UI UI UI UI UI UI UI UI UI UI UI UI UI UI UI UI UI UI OO OO l J J l l J l l l sl CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ Ul Ul Ul H O V0 03 l CΛ U1 4a. 0J tO I-' O V0 00 J CΛ U1 4a. 0J tO H O V0 00 --J O O O O O O O O O O o o o o o o o o o o o o o o o w w w w w oo oo oo oo oooo oo oo oo oo oo oo oo o o o o o o w IW rt o o o o o o o H- O O H- tr wtr wtr ol-» oo o H o o H o H o I I 4a. 4a. o * I OJ o «o -o j i Ul Ul Ul Ui O O W W w w w W W W W 4^ 4a. VO VO VOwOoJ wJ OJ tO OJ OJ OJ tO OJ OJ OJ W W W H VO H OJ UI VO H H vo vo i O 33 o w o i 00 00 03 00 00 00 00 00 03 00 03 00 00 03 03 00 00 03 00 o II o II o II o II o II o II o II o II w o w o w o w o w o w o w o w o w o w o w o w o ow w o w o w o w o w o o o o rx o o o W w w w w w w w w w w w o o o o O o W w w w w X w w w w w OJw OJw OwJ w |to OJ OJ OJ OJ OJ OJ OJ OJ OJ J J | l l J J J l | l J J -O I l ] J l | l l | l | J J -0 iσ Table 1 (Continued) Ex. No. R l 2 R 3 D No. M . P . 557 OCOC 3 H 7 CH 3 CH 2 OH 8 558 OCOi-C 3 H 7 CH 3 CH 3 8 559 OCOC 4 H 9 CH 3 CH 3 8 560 OCOC 4 H 9 CH 3 CHO 8 561 OCOC 4 H 9 CH 3 CH 2 OH 8 562 ocoi-c 4 H 9 CH 3 CH 3 8 563 0C0t-C 4 H 9 CH 3 CH 3 8 564 OCOC15H 31 CH 3 CH 3 8 565 OCOC15H 31 CH 3 CHO 8 566 OCOC15H 31 CH 3 CH 2 OH 8 567 OCOC15H 2g CH 3 CH 3 8 568 OCOC17H 35 CH 3 CH 3 8 569 OCOC17H 33 CH 3 CH 3 8 570 OCOC17H31 CH 3 CH 3 8 571 OCOC17H 29 CH 3 CH 3 8 572 OCOC19H 31 CH 3 CH 3 8 573 OCOPh CH 3 CH 3 8 574 OCOPh CH 3 CHO 8 575 OCOPh CH 3 CH 2 OH 8 576 OH CH 3 CH 3 7 577 OH CH 3 H 7 578 OH CH 3 CH=CH 2 7 579 OH CH 3 CHOHCH 2 OH-(R) 7 580 OH CH 3 CHOHCH 2 OH-(S) 7 581 OH CH, CHO 7 -48- Table 1 (Continued) Ex. No. R l R 3 D No. M. 633 OCH 3 CH 3 CH=NOH 7 634 OCH 3 CH 3 CHOHCH= CH 2 -(R) 7 635 OCH 3 CH 3 CHOHCH= CH 2 -(s) 7 636 OCH 3 H CH 3 7 637 OCH 3 H H 7 638 OCH 3 H CH=CH 2 7 639 OCH 3 H CHOHCH 2 OH- (R) 7 640 OCH 3 H CHOHCH 2 OH- (S) 7 641 OCH 3 H CHO 7 642 OCH 3 H CH 2 OH 7 643 OCH 3 H C0 2 H 7 644 OCH 3 H C0 2 CH 3 7 645 OCH 3 H CH=NOH 7 646 OCH 3 H CHOHCH= CH 2 "( ) 7 647 OCH 3 H CHOHCH= CH 2 -(S) 7 648 OCOCH 3 CH 3 CH 3 7 649 OCOCH 3 CH 3 H 7 650 OCOCH 3 CH 3 CH=CH 2 7 651 OCOCH 3 CH 3 CHOHCH 2 OH- (R) 7 652 OCOCH 3 CH 3 CHOHCH 2 OH- (S) 7 653 OCOCH 3 CH 3 CHO 7 654 OCOCH 3 CH 3 CH 2 OH 7 655 OCOCH 3 CH 3 C0 2 H 7 656 OCOCH 3 CH 3 C0 2 CH 3 7 657 OCOCH CH, CH=NOH 7 -49- Table 1 (Continued) Ex. No. R l E 2 R 3 D No . M . P . 658 OCOCH 3 CH 3 CHOHCH=CH 2 -(R) 7 659 OCOCH 3 CH 3 CHOHCH=CH 2 -(S) 7 660 OCOCH 3 H CH 3 7 661 OCOCH 3 H H 7 662 OCOCH 3 H CH=CH 2 7 663 OCOCH 3 H CHOHCH 2 OH-(R) 7 664 OCOCH 3 H CHOHCH 2 OH-(S) 7 665 OC0CH 3 H CHO 7 666 OCOCH 3 H CH 2 OH 7 667 OCOCH 3 H C0 2 H 7 668 OCOCH 3 H C0 2 CH 3 7 669 OCOCH 3 H CH=N0H 7 670 OCOCH 3 H CHOHCH=CH 2 -(R) 7 671 OCOCH 3 H CHOHCH=CH 2 -(S) 7 * Further analytical data are available in the examples section -50- The six-membered 15-oxa-D-homo-lanosterol derivatives are synthesized by reducing the six-membered cyclic acetals and hemiacetals under conditions similar as those used for the five-me bered 15-oxa-lanosterols. However, the entire sequence was carried out more conveniently in higher overall yield without the protecting group at the 3-position. Thus the unprotected 8,14-diene 2a was converted to a mixture of six-membered cyclic acetal 7a in the same manner as described earlier for p-methoxybenzyl protected intermediates (Scheme I) . The cyclic hemiacetal 7a was treated with triethylsilane and redistilled boron trifluoride etherate in methylene chloride to afford 15-oxa-D-homo-dihydrolanosterol (31) in 92% yield (See, Scheme IV) . The corresponding cyclic acetal 7d is also converted to the compound 31 in slightly lower yield than the acetal 7a. 4,4-Dimethyl-15-oxa-D-homo-5a-cholest-8-en-3b-ol (32) and 4,4-dimethyl-15-oxa- 14a-vinyl-5a-cholest-8-en- 3b-ol (33) have also been prepared in the same manner through the secondary alcohol 6a and the doubly allylic alcohol 8a respectively in comparable yields. Compounds 31, 32, and 33 are all within the scope of the present invention. Table 1 (Continued) Ex . No . *1— R 3 D No. M. P. 658 0C0CH 3 CH 3 CHOHCH=CH 2 -(R) 7 659 OCOCH 3 CH 3 CHOHCH=CH 2 -(S) 7 660 OCOCH 3 H CH 3 7 661 0C0CH 3 H H 7 662 OCOCH 3 H CH=CH 2 7 663 OCOCH 3 H CHOHCH 2 OH-(R) 7 664 0C0CH 3 H CH0HCH 2 0H-(S) 7 665 0C0CH 3 H CHO 7 666 OCOCH 3 H CH 2 0H 7 667 OCOCH 3 H C0 2 H 7 668 0C0CH 3 H C0 2 CH 3 7 669 0C0CH 3 H CH=NOH 7 670 OCOCH 3 H CHOHCH=CH 2 -(R) 7 671 OCOCH H CHOHCH=CH 2 -(S) 7 * Further analytical data are available in the examples section -52- For further functionalization at the 14-position, the vinyl compound 33 was converted to a 1:1 mixture of diasteromeric diols 34 and 35 in 84% combined yield by reacting with osmium tetroxide as described earlier for five-membered 15-oxa-lanosterols. The mixture of diols 34 and 35 was treated with sodium etaperiodate in 4 parts of ethanol and 1 part of water to give 15-oxa-32- oxo-D-homo-dihydrolanosterol (36) in near quantitative yield. Reduction of the aldehyde 36 with sodium borohydride in ethanol provided 15-oxa-D-homo-lanost- 8-ene-3b-32-diol (37) in near quantitative yield. Compounds 34, 35, 36 and 37 also constitute four additional examples of 15-oxa-lanosterols within the scope of the present invention. Elaborations of the aldehyde 36 may yield the corresponding oxime, allylic alcohol, etc., which are within the scope of the present invention, as described in the synthesis of five-membered 15-oxa-lanosterols. - 53 - Table 2 sets forth additional oxasterols of the present invention. - 54 - Table 2 672 OH CH 3 CH 3 8 31 amorphous* 673 OH CH 3 H 8 32 amorphous* 674 OH CH 3 CH=CH 2 8 32 amorphous* 675 OH CH 3 CHOHCH 2 OH- (R) 8 34 amorphous* 676 OH CH 3 CHOHCH 2 OH- (S) 8 35 amorphous* 677 OH CH 3 CHO 8 36 amorphous* 678 OH CH 3 CH 2 OH 8 37 amorphous* 679 OH CH 3 C0 2 H 8 680 OH CH 3 C0 2 CH 3 8 681 OH CH 3 CH=NOH 8 682 OH CH 3 CHOHCH= CH 2 -(R) 8 683 OH CH 3 CHOHCH= CH 2 -(S) 8 684 OH H CH 3 8 685 OH H H 8 686 OH H CH=CH 2 8 687 OH H CHOHCH 2 OH- (R) 8 Table 2 sets forth additional oxasterols of the present invention. si si si si i si si si si si si si si si s| si si si si si si si si J OJ OJ J J OJ OJ to t to to to to to to to to H H (_. |_J (_J (_1 CΛ Ul J> OJ t H O O 00 si l a. J to H o o oo j CΛ Ul a II II II II II II II II II II II II II O O O O O O O O O O O O O O O w O Ow Ow w w w O O w wO Ow Ow w O O o o O o o o o o o o O o w o O o o o O o O W Jw OJw OJw OJw OJw OJw wJ OwJ OJw OJw wJ OJw OJ OwJ OwJ OJw Jw Jw OwJ Ow |to O J OwJ OwJ 00 00 00 00 00 00 00 00 00 00 00 00 00 oo oo oo oo oo oo ∞ ∞ oo oo lα 1 * sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl CΛ CΛ Ul Ul Ul Ul UI Ul UI Ul Ul U1 4a. 4a 4a. ,tk ιf>. 4a> 4a 4a. 4a 4a OJ J OJ H O VO OO sl cΛ Ul 4a. OJ t H O VO OO sl CΛ U1 4a. OJ tO H O VO OO sl o o o o o o o o o o O O O O II II II II II II II II II II II O O O O O O O O O O O O O O O O O O O O O O O O O 33 PC 33 33 PC PC 33 33 PC PC PC 33 PC PC w w wo o o wo o o o o o o o w w w w w w w w w w w OJ OJ OJ Ow o J OJ OJ OwJ OJwOJwOw w IW |to OJ J Ow w w w w J o o ^3 1 o o o o o o o o o o o w o o o o o o o o o o w 3 0> w w w w o o w w w w w w w O O W w w w w rt tr Ul OJ o o II t to to o o o II OJ o 5 o5 II to to to o o o II H- H si w w 2! o w o w w o w w 2! rx X o w w o 3 Φ o o o w w o o w o o O X w o o w P 1 w w w OJ w w to w w W OJ w w to W Φ t II II t to II II to to |0J Pi o o o o o o o o w w w w w w w to t 1 1 t to 1 w 1 II 1 ^ cn W n w CΛ W cn w — ' " — 00 00 00 00 00 00 03 03 00 00 00 03 00 00 00 00 00 00 00 00 00 00 00 00 00 ID si si si si si si i si si si si si si s] i si si s| i si si si si j 03 00 00 00 00 00 00 si s| si s] si si si s| si |w si CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ en Ul a. OJ t H O O 00 si CΛ ui 4a. OJ to H O VO 00 si CΛ Ul 4a. 0J to X O O O O O O O O O O O O O O O O O O O O O O O O O O O O » ti w w o O O O O O O O O O O O O O O O O O O w X X tr tr r 4a 4a. 4a. J U J tO tO t W W W W W W W W W W t to to W W W W W W W W W OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ vo VO VO sl sl sl Ul Ul Ul 1*7* W ► ti W tr tr tr w w w w w w w w IW w |to OJ OJwOJwOJw OJwOwJ OJwOJw wJ J w O wJ OJ w OJ w OJ w O wJ Ul 00 03 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 03 00 00 iσ B * * • o O o O Oo Oo Oo Oo Oo Oo Oo o O o O Oo Oo O II II II II II II II II II II w w w w w w w w w w w w w o o o o o o o o o o o OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJw w w o o o o o o o o o o o o PC PC PC 33 PC PC 33 33 33 33 33 , PC 33 PC 33 33 33 33 33 PC 33 33 33 |tιow ) ) ) ) tJ CO > > CO J i C w o OJw 00 00 00 00 00 03 00 00 CO 00 00 00 03 00 00 00 00 03 03 03 00 00 CO 00 00 iσ - 60 - Table 2 (Continued) 812 OCOC 2 H 5 CH 3 CHO 8 813 OCOC 2 H 5 CH 3 CH 2 OH 8 814 OCOC 3 H 7 CH 3 CH 3 8 815 OCOC 3 H 7 CH 3 CHO 8 816 OCOC 3 H 7 CH 3 CH 2 OH 8 817 OCOC 4 H 7 CH 3 CH 3 8 818 OCOC 4 H 9 CH 3 CHO 8 819 OCOC 4 H 9 CH 3 CH 2 OH 8 820 OCOC 15 H 31 CH 3 CH 3 8 822 OCOC 15 H 31 CH 3 CH 2 OH 8 823 OCOC 15 H 29 CH 3 CH 3 8 825 OCOC 17 H 33 CH 3 CH 3 8 826 OCOC 17 H 31 CH 3 CH 3 8 827 OCOC 17 H 29 CH 3 CH 3 8 828 OCOC ιg H 31 CH 3 CH 3 8 829 OCOPh CH 3 CH 3 8 830 OCOCPh CH 3 CH 3 8 831 OCOCPh CH 3 CH 3 8 832 OH CH 3 CH 3 7 833 OH CH 3 CHO 7 834 OH CH 3 CH 2 OH 7 835 OH CH 3 C0 2 H 7 836 OH H CH,, 7 * * rt tr ID φ - 62 - A 4,4-bis-normethyl 15-oxasterol (R 2 of the general structure 1 is H) , 14 -methyl-15-oxa-5 - cholest-8-en- 3b-ol (47) , has also been synthesized from 5 -cholesta- 8,14-diene-3b-ol by following the sequence of the reaction steps depicted in the synthesis of 15-oxa-dihydrolansterol (11a) . Conversion of the normethyl 8,14-diene 38a to the corresponding p-methoxybenzyl ether 38b followed by an osmium tetroxide hydroxylation, an acetalization, a Grignard reaction with methyl magnesium bromide and hydrolysis in 80% aqueous acetic acid provided the six-membered cyclic hemiacetal 43a in 50% overall yield (See, Scheme V). The compound 43a was subsequently transformed into the desired 14 -methyl-15-oxa-5 -cholest-8-en-3b-ol (47) by glycal formation, osmium tetroxide hydroxylation, oxidative cleavage by sodium metaperiodate, and reduction with triethylsilane and boron trifluoride etherate in 34.5% overall yield from the cyclic hemiacetal 43a. Compound 47 is another example within the scope of the present invention and its synthesis is an example, which demonstrates that preparative methods for compounds with dimethyl at C-4 in the scope (Formula I, with R 2 = CH 3 ) are applicable to di-bis-normethyl compounds in the scope (Formula I, with R 2 = H) . Table 2 * 1 [Continued) Ex. No. R l R 3 No. M, 837 OH H CHO 7 838 OH H CH 2 0H 7 839 =0 CH 3 CH 3 7 840 =0 CH 3 CHO 7 841 =0 CH 3 CH 2 0H 7 842 =0 H CH 3 7 843 =0 H CHO 7 844 =0 H CH 2 OH 7 845 0CH 3 CH 3 CH 3 7 846 0CH 3 CH 3 CHO 7 847 0CH 3 CH 3 CH 2 OH 7 848 0CH 3 H CH 3 7 849 0CH 3 H CHO 7 850 0CH 3 H CH 2 OH 7 851 OCOCH 3 CH 3 CH 3 7 852 OCOCH 3 CH 3 CHO 7 853 OCOCH 3 CH 3 CH 2 OH 7 854 OCOCH 3 H CH 3 7 855 0C0CH 3 H CHO 7 856 OCOCH 3 H CH 2 OH 7 * *, * Further analytical data are available in the examples section - 64 - 15-Thia-lanosterols For the synthesis of 15-thia-lanosterols, a novel class of compounds, a convenient and novel process has been developed. Traditionally cyclic sulfides are prepared by displacing a halide, a sulfonate or an equivalent leaving group by an internal thiol. Taking advantage of the ability to form a stable carbonium ion at the 14-position, a mixture of the cyclic hemiacetal 10b, and cyclic hemiacetal 10c, the intermediates for 15-oxa-dihydrolanosterol, was treated with gaseous hydrogen sulfide (Union Carbide Corp., Linde Division, Danbury, CT 06817) and boron trifluoride etherate in methylene chloride followed by triethylsilane to obtain the desired 15-thia-dihydro- lanosterol (50) in 60% yield (43% overall yield from the six-membered cyclic hemiacetal 7b) (See, Scheme VI). The one pot cyclic sulfide formation reaction presumably occurs via cyclic thioacetal 48 and the intermediate 48 is reduced by triethylsilane in the presence of boron trifluoride etherate. The p-methoxybenzyl protecting group at the 3-position was conveniently cleaved during the hydrogen sulfide and boron trifluoride treatment to carry out three operations in a single reaction vessel. This novel cyclic sulfide preparation method may also be operable when a stable carbonium ion formation is possible at the latent alcoholic center by other functional groups ' such as alkynyl, aryl and other alkenyl. 4,4-Dimethyl- 15-thia-5a-cholest-8-en-3b-ol (49) and 4,4-dimethyl-15- thia-14a-vinyl-5a-cholest-8-en-3b-ol (51) have also - 65 - been synthesized from the compounds 16b and 22b in 26% and 27% overall yields from the compounds 13b and 19b respectively. Compounds 49, 50, and 52 constitute three examples of 15-thia-lanosterols within the scope of the present invention. - 66 - SCHEME VI 10b Rg-CH, 48 16b R,«H 22b Rg . CHBCHJ been synthesized from the compounds 16b and 22b in 26% and 27% overall yields from the compounds 13b and 19b respectively. Compounds 49, 50, and 52 constitute three examples of 15-thia-lanosterols within the scope of the present invention. - 68 - Tables 3, 4, and 5 set forth various thiasterols of the present invention. - 69 - Table 3 Ex. No. - — S 2 R 3 D No. M. P. 857 OH CH 3 CH 3 8 49 amorphous 858 OH CH 3 H 8 50 amorphous 859 OH CH 3 CH=CH 2 8 51 amorphous 860 OH CH 3 CHOHCH 2 OH- (R) 8 861 OH CH 3 CHOHCH 2 OH- (S) 8 862 OH CH 3 CHO 8 863 OH CH 3 CH 2 OH 8 864 OH CH 3 C0 2 H 8 865 OH CH 3 C0 2 CH 3 8 866 OH CH 3 CH=NOH 8 867 OH CH 3 CHOHCH= CH 2 -(R) 8 868 OH CH 3 CHOHCH= ■ CH 2 -(S) 8 869 OH H CH 3 8 870 OH H H 8 871 OH H CH=CH 2 8 872 OH H CHOHCH 2 OH- ( ) 8 873 OH H CHOHCH 2 OH- (S) 8 874 OH H CHO 8 875 OH H CH 2 OH 8 876 OH H C0 2 H 8 877 OH H C0 2 CH 3 8 - 70 - Table 3 (Continued) Ex. No. R D No^ M. P. 1— *2 R 3 878 OH H CH=NOH 8 879 OH H CHOHCH-CH 2 -(R) 8 880 OH H CHOHCH=CH 2 -(S) 8 881 OH CH 3 C 2 H 5 8 882 OH CH 3 CH CH = CH 8 883 OH CH 3 C=CH 8 884 OH CH 3 CH 2 Ph 8 885 OH CH 3 CH 2 OCH 3 8 886 OH CH 3 CH 2 OCOCH 3 8 887 OH CH 3 CH 2 SH 8 888 OH CH 3 Cri SCHo 8 889 OH CH 3 CH 2 SCOCH 3 8 890 OH CH 3 CH 2 NH 2 8 891 OH CH 3 CH 2 NHCH 3 8 892 OH CH 3 CH 2 NHCOCH 3 8 893 OH CH : CH 2 NHCSCH 3 8 894 OH CH ; CH 2 NHC(=NH)CH 3 8 895 OH CH- COCH 3 8 896 OH CH ; COCH=CH 2 8 897 OH CH : CSCH 3 8 898 OH CH : CSCH=CH 2 8 899 OH CH : C(=NH)CH 3 8 900 OH CH- C0 2 C 2 H 5 8 901 OH CH : COSCH 3 8 902 OH CH- CONH 2 8 903 OH CH- CONHCH 3 8 904 OH CH- CONHCOCH 3 8 905 OH CH- CSNH 8 Table 3 Ex. No. -*1— E 2 R 3 D No. M. P. 857 OH CH 3 CH 3 8 49 amorphous 858 OH CH 3 H 8 50 amorphous 859 OH CH 3 CH=CH 2 8 51 amorphous 860 OH CH 3 CHOHCH 2 OH- ( ) 8 861 OH CH 3 CHOHCH 2 OH- (S) 8 862 OH CH 3 CHO 8 863 OH CH 3 CH 2 OH 8 864 OH CH 3 C0 2 H 8 865 OH CH 3 C0 2 CH 3 8 866 OH CH 3 CH=NOH 8 867 OH CH 3 CHOHCH= CH 2 -(R) 8 868 OH CH 3 CHOHCH= CH 2 -(S) 8 869 OH H CH 3 8 870 OH H H 8 871 OH H CH=CH 2 8 872 OH H CHOHCH 2 OH- (R) 8 873 OH H CHOHCH 2 OH- (S) 8 874 OH H CHO 8 875 OH H CH 2 OH 8 876 OH H C0 2 H 8 877 OH H C0-,CH, 8 - 72 - Table 3 (Continued) Ex. No. — *ι— R 3 D No. M. P. 934 OH CH 3 CH=NOCOCH 3 8 935 OH CH 3 CH=NNH 2 8 936 OH CH 3 CH=NNHCH 3 8 937 OH CH 3 CH=NNHCOCH 3 8 938 OH CH 3 CH=NNHCSCH 3 8 939 OH CH 3 CH 2 NHOH 8 940 OH CH 3 CH 2 NHOCH 3 8 941 OH CH 3 CH 2 NHOCOCH 3 8 942 OH CH 3 CH 2 NHNH 2 8 943 OH CH 3 CH 2 NHNHCH 3 8 944 OH CH 3 CH 2 NHNHCOCH 3 8 945 OH CH 3 CH 2 NHNHCSCH 3 8 946 OH CH 3 CH 2 CN 8 947 OH CH 3 CH 2 CH=NOH 8 948 OH CH 3 CH 2 CH=NOCH 3 8 949 OH CH 3 CH 2 CH=NOCOCH 3 8 950 OH CH 3 CH 2 CH=NNH 2 8 951 OH CH 3 CH 2 CH=NNHCH 3 8 952 OH CH 3 CH 2 CH=NNHCOCH 3 8 953 OH CH 3 CH 2 CH=NNHCSCH 3 8 954 OH CH 3 CH 2 CH 2 NHOH 8 955 OH CH 3 CH 2 CH 2 NHOCH 3 8 956 OH CH 3 CH 2 CH 2 NHOCOCH 3 8 957 OH CH 3 CH 2 CH 2 NHNH 2 8 958 OH CH 3 CH 2 CH 2 NHNHCH 3 8 959 OH CH 3 CH 2 CH 2 NHNHCOCH 3 8 960 OH CH 3 CH 2 CH 2 NHNHCSCH 3 8 961 OH CH, CONHOH 8 - 73 Table 3 (Continued) 962 OH CH 3 CONHOCH 3 8 963 OH CH 3 CONHOCOCH 3 8 964 OH CH 3 CSNHOH 8 965 OH CH 3 CSNHOCH 3 8 966 OH CH 3 CSNHOCOCH 3 8 967 OH CH 3 CH=CHCHO 8 968 OH CH 3 CH=CHCOCH 3 8 969 OH CH 3 CH=CHCSCH 3 8 970 OH CH 3 CH=CHCH-NH 8 971 OH CH 3 CH=CHC(=NH)CH 3 8 972 OH CHn C=CCHO 8 973 OH CH, C=CCOCH 3 8 974 OH CH, C=CCSCH 3 8 975 OH CH 3 C=CCH=NH 8 976 OH CH ; C=CC(=NH)CH 3 8 977 OH CH ; CH=CHCH 2 C1 8 978 OH CH : C=CCH 2 C1 8 979 OH CH, CH=CHCH 2 OCOCH 3 8 980 OH CH : C=CCH 2 OCOCH 3 8 981 OH CH- CH 2 CHOHCH 2 OH 8 982 OH CH- CHOHCHOHCH 2 OH 8 983 OH CH- CH-CH-, 8 V 984 OH CH- CH,CH-CH, 8 2 \ / l 985 OH CH- CHOHCH-CH-, \ / 2 0 986 OH H CH 2 SH H VO VO VO VO VO VO VO vO VO VO VO VO VO O O O O O O O O O O O O O O O VO VO VO VO VO VO VO VO VO VO OO OO OO l _ι H H H O O O O O O O O O O VO OO sl 0J tO H O VO OO sl OJ tO H O VO OO sl CΛ U1 4* OJ IO H o rx rx IW X X w w w w w w w w w w w w w w w w w w w w w w w w w w |to OJ OJ 00 oo 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 ID » • vo vo vo VO VO VO O O VO vo O O VO VO VO VO VO O VO O vo V0 VO VO vo IW 00 00 00 00 03 00 00 i si si si si si i i si i CΛ CΛ σ> σv CΛ CΛ cn CΛ X cn Ul 4 OJ to H O VO 00 si CΛ Ul £> 0J t H O O 00 si (Λ Ul 4*. J to Wo w O ow wo ow ow ow ow ow wo ow ow wo ow wo ow wo ow wo wo ow ow wo ow ow w o o o o o o o rx o o o o o o rx o o o o o o o o w w w w w w • w w w X w w w w w w X w w w w w w w w |to 0J OJ J 00 OJ 0J OJ OJ 0J OJ OJ OJ OJ OJ OJ OJ OJ J OJ OJ J 0J OJ OJ o o 1 3 Ol rt tr si o o o w / ,n o O O o o o o o o o o o o o o o o o o o H- h- 1 J w w x w w II W II w II II II II II w w w w w to to to o o 3 tt> to o to °s ' o to o II o II o o o o o II II II II II a 25 a ≥5 a P 1 to w sO ^o w O o o o o o o o o o o o o o o o w w w 3 w (D 0J w ^ o /x w o w w w w w * - w t o w w w w w w o o o o o CL /w O 1 t w o t o to o II II o o o o o o o o o o w o o w •— * c> l ^o o w O w o w 2! a w w w CO o w o w o w |OJ ^o w w o o to r-' to w w 0J OJ II 1 o o o o OJ o J w to o to w o o o a a w w w w t w o o o X w 0J OJ J OJ to O w o w o w OJ o OJ rx w w X OJ J 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 03 00 00 00 00 00 00 00 H H H H H H H I-' I-' H I-' H H H > t-> -> i-> i-* t-> r J r J > }-> IW O O O O O O O O O O O O O O O O O O O O O O O O O \X CΛ eΛ CΛ CΛ CΛ CΛ Ul Ul Ul Ul Ul Ul Ul Ul Ul l £>- 4^. £>. ^. >. * > £k U1 4*. OJ tO H O VO CO sl CΛ U1 4» OJ tO H O VD 00 sl CΛ Ul *>. 0J tO H II II II II II II II II II II II II II II II II II II II II II II II O O O O O O O O O O O O O O O O O O O O O O O o o w w w w w w w w w w w w O O O O O O O O O O O IW W W W W W W W W W W W |t OJ w O wJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ oo oo oo oo oo oo oo oo oo oo oo oo oo oo 00 00 03 00 00 03 00 00 03 00 00 - 77 - Table 3 (Continued) Ex. No. _Bι R 3 D No. M. P. 1066 OCH 3 CH 3 CH=CH 2 8 1067 OCH 3 CH 3 CHOHCH 2 OH- (R) 8 1068 0CH 3 CH 3 CHOHCH 2 OH- (S) 8 1069 OCH 3 CH 3 CHO 8 1070 OCH 3 CH 3 CH 2 OH 8 1071 OCH 3 CH 3 C0 2 H 8 1072 OCH 3 CH 3 C0 2 CH 3 8 1073 OCH 3 CH 3 CH=NOH 8 1074 OCH 3 CH 3 CHOHCH=CH 2 -(R) 8 1076 OCH 3 CH 3 CH 2 SH 8 1077 OCH 3 CH 3 CH 2 NH 2 8 1078 0CH 3 CH 3 COCH 3 8 1079 OCH 3 CH-, CONH 2 8 1080 OCH 3 CH, CSNH 2 8 1081 OCH 3 CH, CH 2 CH 2 OH 8 1082 OCH 3 CH, CH 2 CHO 8 1083 OCH-, CH, CH 2 COCH 3 8 1084 OCH- CH, CH 2 C0 2 CH 3 8 1085 OCH, CH- CH 2 CONH 2 8 1086 OCH, CH- CH 2 C1 8 1087 OCH : CH- CH 2 CH 2 C1 8 1088 OCH, CH- CN 8 1089 OCH, CH- CH=NNH 2 8 1090 OCH, CH- CH 2 NHOH 8 1091 OCH- CH- CH 2 NHNH 2 0 1092 OCH- CH- CH 2 CN 8 -> r J i-* \-> > t-> 1 > l-> t-> > > r^ t- 1 ^ IW i-' \-> i-> i-> ' r J r J ' i- i > \-> \-* -> r J > \-* \-> O O O O O O O IX H H H H H H H H H O O O O O O O O O O VO VO VO vo vo o vo V0 00 s! CΛ U1 4* t0 H O V0 00 sl <Λ Ul *»- 0J tO H O VO 03 s] CΛ Ul ^ OJ B o o o o o o o o o o o O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O W W W W W W W W W W W W W W W W W W W W W w OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ tO OJ OJ OJ OJ tO OJ OJ OJ OJ |H O O O O O W W W W W W W W W W W O O O O O O O O O O IW w w OJ w OJ w OJ w W W W W W W W W W W |t OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ 0O 00 00 00 00 00 00 00 00 00 00 00 00 O3 CO 00 00 00 00 00 03 00 00 00 00 00 ID Table 3 (Continued) Ex. No, B 2 No. M. 1066 OCH 3 CH 3 CH=CH 2 8 1067 OCH 3 CH 3 CHOHCH 2 OH-(R) 8 1068 OCH 3 CH 3 CHOHCH 2 OH-(S) 8 1069 0CH 3 CH 3 CHO 8 1070 OCH 3 CH 3 CH 2 OH 8 1071 OCH 3 CH 3 C0 2 H 8 1072 OCH 3 CH 3 C0 2 CH 3 8 1073 OCH 3 CH 3 CH=NOH 8 1074 OCH 3 CH 3 CHOHCH=CH 2 -(R) 8 1075 OCH 3 CH 3 CHOHCH=CH 2 -(S) 8 1076 OCH 3 CH 3 CH 2 SH 8 1077 0CH 3 CH 3 CH 2 NH 2 8 1078 OCH 3 CH 3 COCH 3 8 1079 OCH 3 CH 3 CONH 2 8 1080 OCH 3 CH 3 CSNH-, 8 1081 OCH 3 CH 3 CH 2 CH 2 OH 8 1082 OCH, CH 3 CH 2 CHO 8 1083 OCH, CH 3 CH 2 COCH 3 8 1084 OCH, CH 2 CH 2 C0 2 CH 3 8 1085 OCH, CH, CH 2 CONH 2 8 1086 OCH, CH, CH 2 C1 8 1087 OCH, CH, CH 2 CH 2 C1 8 1088 OCH- CH, CN 8 1089 OCH- CH, CH=NNH 2 8 1090 OCH- CH, CH 2 NHOH 1091 OCH- CH- CH 2 NHNH 2 1092 OCH- CH- CH 2 CN - 80 - Table 3 < [Continued) Ex . No . *1— R 3 D No. M. P. 1148 0C0CH 3 CH 3 CONH 2 8 1149 OCOCH 3 CH 3 CSNH 2 8 1150 OCOCH 3 CH 3 CH 2 CH 2 OH 8 1151 OCOCH 3 CH 3 CH 2 CHO 8 1152 OCOCH 3 CH 3 CH 2 COCH 3 8 1153 OCOCH 3 CH 3 CH CO CHT 8 1154 OCOCH 3 CH 3 CH 2 CONH 2 8 1155 OCOCH 3 CH 3 CH 2 C1 8 1156 OCOCH 3 CH 3 CH 2 CH 2 C1 8 1157 OCOCH 3 CH 3 CN 8 1158 OCOCH 3 CH 3 CH-NNH 2 8 1159 OCOCH 3 CH 3 CH 2 NHOH 8 1160 OCOCH 3 CH 3 CH 2 NHNH 2 8 1161 OCOCH 3 CH 3 CH 2 CN 8 1162 OCOCH 3 CH 3 CH 2 CH=NOH 8 1163 OCOCH 3 CH 3 CH 2 CH=NNH 2 8 1164 OCOCH 3 CH 3 CH 2 CH 2 NHOH 8 1165 OCOCH- j CH 3 CH 2 CH 2 NHNH 2 8 1166 OCOCH 3 CH 3 CONHOH 8 1167 OCOCH 3 CH 3 CH=CHCHO 8 1168 OCOCH 3 CH 3 CH=CHCOCH 3 8 1169 OCOCH 3 CH 3 CH=CHCH 2 C1 8 1170 OCOCH 3 CH 3 CH 2 CHOHCH 2 OH 8 1171 OCOCH-, CH 3 CHOHCH-CH-, 8 V 1172 OCOCH, H CH 3 8 1173 OCOCH, H H .8 1174 OCOCH, H CH=CH-, 8 - 81 - Table 3 (Continued) Ex. No. R l 2 D No . M . P . 1175 OCOCH 3 H CHOHCH 2 OH- (R) 8 1176 OCOCH 3 H CHOHCH 2 OH- (S ) 8 1177 OCOCH 3 H CHO 8 1178 OCOCH 3 H CH 2 OH 8 1179 0C0CH 3 H C0 2 H 8 1180 OCOCH 3 H C0 2 CH 3 8 1181 OCOCH 3 H CH=NOH 8 1182 OCOCH 3 H CHOHCH=CH 2 - (R) 8 1183 OCOCH 3 H CHOHCH=CH 2 - (S ) 8 1184 OCOC 2 H 5 CH, CH 3 8 1185 OCOC 2 H 5 CH 3 CHO 8 1186 OCOC 2 H 5 CH 3 CH 2 OH 8 1187 OCOC 3 H 7 CH, CH 3 8 1188 OCOC 3 H 7 CH, CHO 8 1189 OCOC 3 H 7 CH, CH 2 OH 8 1190 OCOi-C 4 H ? CH, CH 3 8 1191 OCOC 4 H 9 CH, CH 3 8 1192 OCOC 4 H 9 CH, CHO 8 1193 OCOC 4 H 9 CH, CH 2 OH 8 1194 OCOi-C 4 H 9 CH, CH 3 8 1195 OCOt-C 4 H 9 CH, CH 3 8 1195 OCOC 15 H 31 CH, CH 3 8 1197 OCOC 15 H 31 CH- CHO 8 1198 OCOC 15 H 31 CH- CH 2 OH 8 1199 OCOC 15 H 29 CH- CH 3 8 1200 OCOC 1? H 35 CH- CH 3 8 1201 OCOC 17 H 33 CH- CH 3 8 1202 0C0C 17 H 31 CH- CH, 8 - 82 - Table 3 (Continued) Ex. No. — — B 2 R 3 D D No . M . P . 1203 OCOC 17 H 29 CH 3 CH 3 8 1204 OCOC ιg H 31 CH 3 CH 3 8 1205 OCOPh CH 3 CH 3 8 1206 OCOPh CH 3 CHO 8 1207 OCOPh CH 3 CH 2 OH 8 1208 OH CH 3 CH 3 7 1209 OH CH 3 H 7 1210 OH CH 3 CH=CH 2 7 1211 OH CH 3 CHOHCH 2 OH-(R) 7 1212 OH CH 3 CHOHCH 2 OH-(S) 7 1213 OH CH 3 CHO 7 1214 OH CH 3 CH 2 OH 7 1215 OH CH 3 C0 2 H 7 1216 OH CH 3 C0 2 CH 3 7 1217 OH CH 3 CH=NOH 7 1218 OH CH 3 CHOHCH=CH 2 -(R) 7 1219 OH H CH 3 7 1220 OH H H 7 1221 OH H CH=CH 2 7 1222 OH H CHOHCH 2 OH-(R) 7 1223 OH H CHOHCH 2 OH-(S) 7 1224 OH H CHO 7 1225 OH H CH 2 OH 7 1226 OH H C0 2 H 7 1227 OH H C0 2 CH 3 7 1228 OH H CH=NOH 7 1229 OH H CHOHCH-CH 2 -(R) 7 1230 OH H CHOHCH-CH 2 -(S) 7 Table 3 (Continued) Ex. No. —*1— R- No . M . P . 1175 OCOCH 3 H CHOHCH 2 OH- (R) 8 1176 OCOCH 3 H CHOHCH 2 OH- (S ) 8 1177 OCOCH 3 H CHO 8 1178 OCOCH 3 H CH 2 OH 8 1179 OCOCH 3 H C0 2 H 8 1180 OCOCH 3 H C0 2 CH 3 8 1181 OCOCH 3 H CH=N0H 8 1182 OCOCH 3 H CHOHCH=CH 2 - (R) 8 1183 OCOCH 3 H CHOHCH=CH 2 - (S ) 8 1185 OCOC 2 H 5 CH 3 CHO 8 1186 OCOC 2 H 5 CH 3 CH 2 OH 8 1188 OCOC 3 H 7 CH 3 CHO 8 1189 OCOC 3 H 7 CH 3 CH 2 0H 8 1190 OCOi-C 4 H 7 Crio Cri 8 1191 0C0C 4 H 9 CH-> ^" 3 ° 1192 OCOC 4 H g CH 3 CHO 8 1193 OCOC 4 H 9 CH 3 CH 2 0H 8 1194 OCOi-C 4 H 9 CH-5 CH 3 8 1195 OCOt-C 4 H 9 CH-i CH-, 8 1195 OCOC 15 H 31 CH 3 CH 3 8 1197 OCOC 15 H 31 CH 3 CHO 8 1198 OCOC 15 H 31 CH 3 CH 2 0H 8 1199 OCOC 15 H 2g CH-3 CH-3 8 1200 OCOC 17 H 35 CH CH-3 O 1201 OCOC 17 H 33 Cri'ϊ Cri 8 1202 OCOC •yH-j -t CHo CHT 8 - 84 - Table 3 (Continued) Ex. No. R l S 2 R 3 D No. M . P . 1259 OCH 3 CH 3 CH0HCH 2 OH- (S) 7 1260 OCH 3 CH 3 CHO 7 1261 OCH 3 CH 3 CH 2 OH 7 1262 OCH 3 CH 3 C0 2 H 7 1263 OCH 3 CH 3 C0 2 CH 3 7 1264 OCH 3 CH 3 CH=NOH 7 1265 OCH 3 CH 3 CHOHCH= CH 2 -(R) 7 1266 OCH 3 CH 3 CHOHCH= CH 2 -(S) 7 1267 0CH 3 H CH 3 7 1268 0CH 3 H H 7 1269 OCH 3 H CH=CH 2 7 1270 OCH 3 H CHOHCH 2 OH- (R) 7 1271 OCH 3 H CHOHCH 2 OH- (S) 7 1272 OCH 3 H CHO 7 1273 OCH 3 H CH 2 OH 7 1274 OCH 3 H C0 2 H 7 1275 OCH 3 H C0 2 CH 3 7 1276 OCH 3 H CH=NOH 7 1277 OCH 3 H CHOHCH= ; CH 2 -(R) 7 1278 OCH 3 H CHOHCH= ; CH 2 -(S) 7 1279 0C0CH 3 CH 3 CH 3 7 1280 OC0CH 3 CH 3 H 7 1281 OCOCH 3 CH 3 CH=CH 2 7 1282 OCOCH 3 CH 3 CHOHCH 2 OH- (R) 7 1283 OCOCH 3 CH 3 CHOHCH 2 OH- (S) 7 1284 OCOCH 3 CH 3 CHO 7 1285 OCOCH 3 CH 3 CH 2 OH 7 1286 OCOCH 3 CH 3 C0 2 H 7 - 85 - Table 3 (Continued) Ex. No. R l E 2 R 3 D No. M . P . 1287 0C0CH 3 CH 3 C0 2 CH 3 7 1288 OCOCH 3 CH 3 CH=N0H 7 1289 0C0CH 3 CH 3 CH0HCH= : CH 2 ' "(R) 7 1290 0C0CH 3 CH 3 CH0HCH= =CH 2 -(S) 7 1291 0C0CH 3 H CH 3 7 1292 OCOCH 3 H H 7 1293 0C0CH 3 H CH=CH 2 7 1294 0C0CH 3 H CHOHCH 2 OH- (R) 7 1295 OCOCH 3 H CH0HCH 2 OH- (S) 7 1296 0C0CH 3 H CHO 7 1297 OCOCH 3 H CH 2 OH 7 1298 0C0CH 3 H C0 2 H 7 1299 0C0CH 3 H C0 2 CH 3 7 1300 OCOCH 3 H CH=NOH 7 1301 0C0CH 3 H CH0HCH= =CH 2 -(R) 7 1302 OCOCH 3 H CHOHCH= =CH 2 -(S) 7 * Further analytical data are available in the examples section. - 86 - Table 4 E . No. ] No . M . P . s l— E 2 R 3 1303 OH CH 3 CH 3 8 52 amorphous* 1304 OH CH 3 H 8 53 amorphous* 1305 OH CH 3 CH=CH 2 8 54 amorphous* 1306 OH CH 3 CHOHCH 2 OH-(R) 8 1307 OH CH 3 CHOHCH 2 OH-(S) 8 1308 OH CH 3 CHO 8 1309 OH CH 3 CH 2 OH 8 1310 OH CH 3 C0 2 H 8 1311 OH CH 3 C0 2 CH 3 8 1312 OH CH 3 CH=NOH 8 1313 OH CH 3 CHOHCH=CH 2 - ( R ) 8 1314 OH CH 3 CHOHCH=CH 2 - ( S ) 8 1315 OH H CH 3 8 1316 OH H H 8 1317 OH H CH=CH 2 8 1318 OH H CHOHCH 2 OH- (R) 8 1319 OH H CHOHCH 2 OH- (S ) 8 1320 OH H CHO 8 1321 OH H CH 2 OH 8 1322 OH H C0 2 CH 3 8 1323 OH H CH=NOH 8 Table 3 (Continued) Ex. No. R l E 2 R 3 D No. M . 1287 OCOCH 3 CH 3 C0 2 CH 3 7 1288 0C0CH 3 CH 3 CH=NOH 7 1289 OCOCH 3 CH 3 CH0HCH= :CH 2 ' -(R) 7 1290 OCOCH 3 CH 3 CHOHCH= ; CH 2 ' -(S) 7 1291 OCOCH 3 H CH 3 7 1292 0C0CH 3 H H 7 1293 OCOCH 3 H CH=CH 2 7 1294 OCOCH 3 H CH0HCH 2 ,OH- (R) 7 1295 OCOCH 3 H CHOHCH 2 ,OH- (S) 7 1296 OCOCH 3 H CHO 7 1297 0C0CH 3 H CH 2 0H 7 1298 OCOCH 3 H C0 2 H 7 1299 OCOCH 3 H C0 2 CH 3 7 1300 OCOCH 3 H CH=N0H 7 1301 0C0CH 3 H CHOHCH= =CH 2 -(R) 7 1302 OCOCH 3 H CHOHCH= =CH 2 -(S) 7 * Further analytical data are available in the examples section. - 88 - Table 4 (Continued) Ex. No. R l S 2 R 3 D No. M. 1349 OH CH 3 CH=CHC0CH 3 8 1350 OH CH 3 CH=CHCH 2 C1 8 1351 OH CH 3 CH 2 CHOHCH 2 OH 8 1352 OH CH 3 CHOHCH-CH, 8 \ / 2 0 1353 =o CH 3 CH 3 8 1354 =0 CH 3 CHO 8 1355 =0 CH 3 CH 2 0H 8 1356 =0 H CH 3 8 1357 =0 H CHO 8 1358 =0 H CH 2 0H 8 1359 OCH 3 CH 3 CH 3 8 1360 0CH 3 CH 3 CHO 8 1361 OCH 3 CH 3 CH 2 0H 8 1362 0CH 3 H CH 3 8 1363 0CH 3 H CHO 8 1364 OCH 3 H CH 2 0H 8 1365 OPh CH 3 CH 3 8 1366 OPh CH 3 CHO 8 1367 OPh CH 3 CH 2 0H 8 1368 0CH 2 Ph CH 3 CH 3 8 1369 OCH 2 Ph CH 3 •CHO 8 1370 0CH 2 Ph CH 3 CH 2 0H 8 1371 0C0CH 3 CH 3 CH 3 8 1372 0C0CH 3 CH 3 CHO 8 1373 0C0CH 3 CH 3 CH 2 0H 8 1374 OCOCH 3 H CH 3 8 1375 0C0CH 3 H CHO 8 1376 0C0CH-, H CH^OH 8 H H H H H H H H H H H H H H H H H H H H H H H H H 4 4» OJ OJ J OJ OJ OJ OJ OJ J J OJ J OJ OJ 0J OJ OJ OJ OJ O OJJ 0OJJ JJ O OJJ w X O O VO O VO VO VO VO VO VO VO VO 00 00 00 00 00 00 00 00 00 00 si si si a H O VO 03 si CΛ Ul 4*. OJ to H O VO 00 si CΛ Ul 4* OJ t H o VO 03 si a 0 • o o o w w w o o o w w w o o o w w o o tO OwJ OwJ Jw OwJ OwJ OwJ OwJ OwJ Ow W J Ow o o J w o o w J OwJ OwJ wJ OwJ Ow | J - 90 - Table 4 (Continued) Ex. No. R l H R 3 D No. M . P . 1402 0C0CH 3 H CH 3 7 1403 0C0CH 3 H CHO 7 1404 0C0CH 3 H CH 2 OH 7 * Further analytical data are available in the examples section. H H H H H H H H H H H H H H H H H H H H H H H H H 4 * OJ OJ J OJ OJ J OJ J J J OJ J OJ OJ J OJ OJ OJ OJ OJ J J OJ O O VO VO O VO o o vo VO O VO 00 00 00 00 00 00 00 00 00 CO si si s H O VO 00 si CΛ Ul *. OJ t H O vo 03 si CΛ Ul *» OJ to H o vo 00 si H H H H H H H 4 4 * *. *. 4 Ul Ul 4 *> 4 * 4* H o VO 00 si CΛ Ul O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O W W IW W W W W W W W W W W W W W W W W W W W W W W W |to O OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ 00 00 00 00 03 03 00 03 03 00 00 00 03 00 00 00 00 00 00 00 00 03 00 00 03 ID la o - 93 - Table 5 s * (Continued) I Ex. No. R l S 2 R 3 D No. M . 1452 OH CH 3 CH=CHCOCH 3 8 1453 OH CH 3 CH 2 CHOHCH 2 OH 8 1455 OH CH 3 CHOHCH-CH-, 8 V 1456 =0 CH 3 CH 3 8 1457 =0 CH 3 CHO 8 1458 =0 CH 3 CH 2 0H 8 1459 =0 H CH 3 8 1460 =0 H CHO 8 1461 =0 H CH 2 0H 8 1462 0CH 3 CH 3 CH 3 8 1463 OCH 3 CH 3 CHO 8 1464 OCH 3 CH 3 CH 2 0H 8 1465 0CH 3 H CH 3 8 1466 0CH 3 H CHO 8 1467 0CH 3 H CH 2 0H 8 1468 OPh CH 3 CH 3 8 1469 OPh CH 3 CHO 8 1470 OPh CH 3 CH 2 OH 8 1471 OCH 2 Ph CH 3 CH 3 8 1472 OCH 2 Ph CH 3 CHO 8 1473 OCH 2 Ph CH 3 CH 2 OH 8 1474 OCOCH 3 CH 3 CH 3 8 * 1475 OCOCH 3 CH 3 CHO 8 % 1476 OCOCH 3 CH 3 CH 2 0H 8 - 94 - Table 5 (Continued) EX. No. R 3 D No. M. P 1477 OCOCH 3 H CH 3 8 1478 OCOCH 3 H CHO 8 1479 OCOCH 3 H CH 2 OH 8 1480 OCOPh CH 3 CH 3 8 1481 OCOPh CH 3 CHO 8 1482 OCOPh CH 3 CH 2 OH 8 1483 OH CH 3 CH 3 7 1484 OH CH 3 CHO 7 1485 OH CH 3 CH 2 OH 7 1486 OH CH 3 CH 2 H 7 1487 OH H CH 3 7 1488 OH H CHO 7 1489 OH H CH 2 OH 7 1490 =0 CH 3 CH 3 7 1491 =0 CH 3 CHO 7 1492 =0 CH 3 CH 2 OH 7 1493 =0 H CH 3 7 1494 =0 H CHO 7 1495 =0 H CH 2 OH 7 1496 0CH 3 CH 3 CH 3 7 1497 OCH 3 CH 3 CHO 7 1498 OCH 3 CH 3 CH 2 OH 7 1499 OCH 3 H CH 3 7 1500 OCH 3 H CHO 7 1501 OCH 3 H CH 2 0H 7 H H H H H H H H H H H H H H H H H H H H H H H H W J * * 4 4 * 4*- *> *»• 4* 4 4> 4 4 » 4* 4* 1. 4> 4* 4> X s s] s] si si si si CΛ CΛ CΛ CΛ CΛ <Λ (Λ CΛ CΛ CΛ Ul Ul Ul Ul Ul Ul Ul • CΛ ui 4. OJ to H O VO 00 si CΛ Ul 4^. OJ t H O O 03 si CΛ Ul OJ to a o o o o o o o o o o o o w w w w 33 33 PC 33 33 33 w w W |to OJ OJ O wJ OJ OJ w O w J w OJ w OJ w w w w o o o w w w o o o J O Lo co ) ω u OJ OJ OJ 00 00 00 03 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 03 00 00 ID - 96 - The six-membered 15-thia-D-homo-lanosterol derivatives have also been synthesized from the six-membered 15-thia-lanosterols synthesis. Treatment of the mixture of the cyclic acetal 7d with hydrogen sulfide and boron trifluoride etherate in methylene chloride followed by triethylsilane afforded the desired 15-thia-D-homo-dihydrolanosterl (57) in 44% yield (See, Scheme VII) . 4,4-Dimethyl-15-thia-D-homo-5a-cholest-8-en-3b-ol (56) has also been prepared in the same manner from the compound 13d in 59.2% yield. 4,4-dimethyl-15-thia-14a-vinyl-D-homo-5a-cholest-8- en-3b-ol (58) may also be synthesized in the same manner from the corresponding cyclic acetal 19a or cyclic acetal 19d. Compounds 56, 57 and 58 constitute three additional examples within the scope of the present invention. The 15-thia-D-homo-lanosterol 56 was reacted with sodium metaperiodate in 5 parts of ethanol and 1 part of water to provide the corresponding sulfoxide 59, also within the scope of the present invention. The 14-methyl and 14-vinyl derivatives 60 and 61, which are likewise within the scope of the present invention, may also be synthesized in the same manner. As mentioned earlier in the 5-membered case, sulfones with the general structure 62, which are within the scope of the present invention may be synthesized from the corresponding sulfides or sulfoxides. Further functionalization at C-14 to prepare the compounds within the scope may also be achieved by converting the vinyl group of 58 to an aldehyde and carrying out other necessary chemistry as discussed in 15-oxa-lanosterol section, supra. - 97 - SCHEME VII a Ra-CHa 56 ** • .CHa 62 59 j »CH 3 60 R,«H 61 R 3 .CH.CH2 - 98 - Tables 6, 7, and 8 set forth various thiasterols of the present invention. SCHEME VII a R3-CH3 56 R g . CH g 62 59 R 3 .CH 3 60 Rg.H 61 Rg-CH«CH 2 - 100 - Table 6 (Continued) Ex. No. R R 3 No. M. 1530 OH H CHOHCH=CH 2 -(R) 8 1531 OH H CHOHCH=CH 2 -(S) 8 1532 OH CH 3 CH 2 SH 8 1533 OH CH, CH 2 NH 2 8 1534 OH CH, COCH„ 8 1535 OH CH, CONH 2 8 1536 OH CH, CSNH 2 8 1537 OH CH, CH 2 CH 2 OH 8 1538 OH CH, CH 2 CHO 8 1539 OH CH, CH 2 COCH 3 8 1540 OH CH, CH 2 C0 2 CH 3 8 1541 OH CH, CH 2 CONH 2 8 1542 OH CH, CH 2 C1 8 1543 OH CH, CH 2 CH 2 C1 8 1544 OH CH, CN 8 1545 OH CH, CH=NNH 2 8 1546 OH CH, CH 2 NHOH 8 1547 OH CH, CH 2 NHNH 2 8 1548 OH CH, CH 2 CN 8 1549 OH CH, CH 2 CH=NOH 8 1550 OH CH- CH 2 CH=NNH 2 8 1551 OH CH, CH 2 CH 2 NHOH 8 1552 OH CH, CH 2 CH 2 NHNH 2 8 1553 OH CH- CONHOH 8 1554 OH CH- CH=CHCHO 8 ** -> -> t- 1 ' > \-' i- l -' t- > i-' - i t-' ' r^ t-' H H H H Ul Ul Ul Ul Ul Ul Ul l si si si si si si UI UI UI UI UI UI UI UI UI UI Ul Ul Ul Ul w UI UI X sj si sl sl CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ Cn Ul Ul Ul ui • VO 00 si (Λ Ul * OJ tO H O VO OO sl cΛ Ul ^ OJ tO H O 00 si CΛ Ul a o • IH w o o o o o o o o o W W W O O O W W W O O O O O IW w w w w w w w w w W W W w w W W W W |to OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ J OJ OJ OJ 00 00 00 00 00 00 00 00 00 03 00 03 00 00 00 00 00 00 00 CO 00 00 00 03 ID pi - 102 - Table 6 ( [Continued) Ex. No. R l H R 3 D No. M . P 1580 OCOCH 3 H CH 3 8 1581 OCOCH 3 H CHO 8 1582 OC0CH 3 H CH 2 OH 8 1583 OCOPh CH 3 CH 3 8 1584 OCOPh CH 3 CHO 8 1585 OCOPh CH 3 CH 2 OH 8 1586 OH CH 3 CH 3 7 1587 OH CH 3 CHO 7 1588 OH CH 3 CH 2 OH 7 1589 OH CH 3 C0 2 H 7 1590 OH H CH 3 7 1591 OH H CHO 7 1592 OH H CH 2 0H 7 1593 =0 CH 3 CH 3 7 1594 =0 CH 3 CHO 7 1595 =0 CH 3 CH 2 0H 7 1596 =0 H CH 3 7 1597 =0 H CHO 7 1598 =0 H CH 2 OH 7 1599 OCH 3 CH 3 CH 3 7 1600 OCH 3 CH 3 CHO 7 1601 OCH 3 CH 3 CH 2 0H 7 1602 OCH 3 H CH 3 7 1603 0CH 3 H CHO 7 1604 OCH 3 H CH 2 OH 7 Table 6 (Continued) Ex. No. E R 3 D No , M . 1555 OH CH 3 CH=CHCOCH 3 8 1556 OH CH 3 CH=CHCH 2 C1 8 1557 OH CH 3 CH 2 CHOHCH 2 OH 8 1558 OH CH 3 CHOHCH-CH, 8 \ / 2 0 1560 =0 CH 3 CHO 8 1561 =0 CH 3 CH 2 OH 8 1562 =0 H CH 3 8 1563 =0 H CHO 8 1564 =0 H CH 2 OH 8 1565 0CH 3 CH 3 CH 3 8 1566 0CH 3 CH 3 CHO 8 1567 0CH 3 CH 3 CH 2 OH 8 1568 OCH 3 H CH 3 8 1569 OCH 3 H CHO 8 1570 OCH 3 H CH 2 OH 8 1571 OPh CH 3 CH 3 8 1572 OPh CH 3 CHO 8 1573 OPh CH 3 CH 2 0H 8 1574 OCH 2 Ph CH 3 CH 3 8 1575 OCH 2 Ph CH 3 CHO 8 1576 OCH 2 Ph CH 3 CH 2 OH 8 1577 OCOCH 3 CH 3 CH 3 8 1578 OCOCH 3 CH 3 CHO 8 1579 OCOCH 3 CH 3 CH 2 0H 8 - 104 - Table 7 NO. R l R 3 D No. M. P. 1611 OH CH 3 CH 3 8 59 amorphous* 1612 OH CH 3 H 8 60 amorphous* 1613 OH CH 3 CH=CH 2 8 61 amorphous* 1614 OH CH 3 CHOHCH 2 OH- (R) 8 1615 OH CH 3 CHOHCH 2 OH- (S) 8 1616 OH CH 3 CHO 8 1617 OH CH 3 CH 2 OH 8 1618 OH CH 3 C0 2 H 8 1619 OH CH 3 C0 2 CH 3 8 1620 OH CH 3 CH=NOH 8 1621 OH CH 3 CHOHCH= CH 2 -(R) 8 1622 OH CH 3 CHOHCH= CH 2 -(S) 8 1623 OH H CH 3 8 1624 OH H H 8 1625 OH H CH=CH 2 8 1626 OH H CHOHCH 2 OH- (R) 8 1627 OH H CHOHCH 2 OH- (S) 8 1628 OH H CHO 8 1629 OH H CH 2 OH 8 1630 OH H C0 2 H 8 1631 OH H C0 2 CH 3 8 1632 OH H CH=NOH 8 - 105 - Table 7 « # (Continued) 1633 OH H CHOHCH=CH 2 -(R) 8 1634 OH H CHOHCH-CH 2 -(S) 8 1635 OH CH 3 CH 2 SH 8 1636 OH CH 3 CH 2 NH 2 8 1637 OH CH 3 COCH 3 8 1638 OH CH 3 CONH 2 8 1639 OH CH 3 CSNH 2 8 1640 OH CH 3 CH 2 CH 2 OH 8 1641 OH CH 3 CH 2 CHO 8 1642 OH CH 3 CH 2 COCH 3 8 1643 OH CH 3 CH 2 C0 2 CH 3 8 1644 OH CH 3 CH 2 C0NH 2 8 1645 OH CH 3 CH 2 C1 8 1646 OH CH 3 CH 2 CH 2 C1 8 1647 OH CH 3 CN 8 1648 OH CH 3 CH=NNH 2 8 1649 OH CH 2 CH 2 NH0H 8 1650 OH CH 3 CH 2 NHNH 2 8 1651 OH CH, CH 2 CN 8 1652 OH CH, CH 2 CH=NOH 8 1653 OH CH, CH 2 CH=NNH 2 8 1654 OH CH, CH 2 CH 2 NHOH 8 1655 OH CH, CH 2 CH 2 NHNH 2 8 1656 OH CH, CONHOH 8 1657 OH CH- CH=CHCHO 8 1658 OH CH- CH=CHCOCH 3 8 1659 OH CH, CH=CHCH 2 C1 8 1660 OH CH, CH 2 CHOHCH 2 OH 8 1661 OH CH- CHOHCH-CH-, 8 1662 CH- CH, H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H CΛ CΛ CΛ CΛ CΛ cn CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ cn CΛ CΛ CΛ σv CΛ CΛ (Λ (Λ O O VO vo 00 00 00 00 00 00 00 00 00 00 si si si si si si si si si si CΛ CΛ CΛ CΛ CΛ σv cn OJ t H o VO 03 si σv Ul OJ t H O o 00 s| cn Ul * 0J to H O VO 00 si CΛ Ul * 0J W O O O O O O O W W W O O O O O O O O O W W W O O O W W W O O IW W W W W W W W W W W W W W W W W W W W W W |to OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ J J j si si oo oo oo oo oo oo oo co oo oo oo oo oo ω oo oo oo oo oo oo oo oo oo oo oo oo ID - \ H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ σv CΛ CΛ CΛ CΛ a CΛ CΛ CΛ U1 U1 U1 U1 U1 Ul Ul Ul Ul U1 4^ 4^ 4^ 4^ 4^ ^ ^ ^ ^ 4^ OJ OJ J OJ OJ OJ OJ o • to H O VO OO sl CΛ Ul *» J to H O VO OO sl CΛ U1 4* OJ tO H O VO 00 i CΛ Ul 4 OJ o o o o o o o o o o o o o n o o o o o o o o o o o o o o w w IW wo OJ 00 ∞ oo oo oo oo oo oo oo oo oo oo ∞ oo oo oo oo oo oo oo oo ω oo oo oo oo oo oo oo oo ID - 108 - Table 8 No . 2 - No . M . P . 1714 OH CH, CH 3 8 1715 OH CH, H 8 1716 OH CH, CH=CH 2 8 1717 OH CH, CHOHCH 2 OH-(R) 8 1718 OH CH, CHOHCH 2 OH-(S) 8 1719 OH CH, CHO 8 1720 OH CH, CH 2 OH 8 1721 OH CH, C0 2 H 8 1722 OH CH, C0 2 CH 3 8 1723 OH CH, CH=NOH 8 1724 OH CH, CHOHCH=CH 2 -(R) 8 1725 OH CH, CHOHCH=CH 2 -(S) 8 1726 OH H CH 3 8 1727 OH H H 8 1728 OH H CH=CH 2 8 1729 OH H CHOHCH 2 OH-(R) 8 1730 OH H CHOHCH 2 OH-(S) 8 1731 OH H CHO 8 1732 OH H CH 2 OH 8 1733 OH H C0 2 H 8 1734 OH H C0 2 CH 3 8 1735 OH H CH=NOH 8 - 109 - Table 8 (Continued) No. 1— s 2 - D No. M. 1736 OH H CHOHCH=CH 2 -(R) 8 1737 OH H CHOHCH=CH 2 -(S) 8 1738 OH CH 3 CH 2 SH 8 1739 OH CH 3 CH 2 NH 2 8 1740 OH CH 3 COCH 3 8 1741 OH CH 3 CONH 2 8 1742 OH CH 3 CSNH 2 8 1743 OH CH 3 CH 2 CH 2 OH 8 1744 OH CH 3 CH 2 CHO 8 1745 OH CH 3 CH 2 COCH 3 8 1746 OH CH 3 CH 2 C0 2 CH 3 8 1747 OH CH 3 CH 2 CONH 2 8 1748 OH CH 3 CH 2 C1 8 1749 OH CH 3 CH 2 CH 2 C1 8 1750 OH CH 3 CN 8 1751 OH CH 3 CH=NNH 2 8 1752 OH CH 3 CH 2 NHOH 8 1753 OH CH 3 CH 2 NHNH 2 8 1754 OH CH-, CH 2 CN 8 1755 OH CH, CH 2 CH=NOH 8 1756 OH CH, CH 2 CH=NNH 2 8 1757 OH CH, CH 2 CH 2 NHOH 8 1758 OH CH, CH 2 CH 2 NHNH 2 8 1759 OH CH, CONHOH 8 1760 OH CH, CH=CHCHO 8 1761 OH CH, CH=CHCOCH 3 8 1762 OH CH, CH=CHCH 2 C1 8 1763 OH CH, CH 2 CHOHCH 2 OH 8 1764 OH CH- CHOHCH-CH-, 8 1765 =0 CH- CH- (_. (-1 H H H H H H H H H H H H H H H H H H H H i-' t-* * i- 1 s| si si si si s si si si si si si si si sl sl sl sl sl sl sl sl sl sl sl si s| si si si si o o o o vo O O 00 00 00 00 00 00 00 OO OO OO sl sl sl sl sl sl sl s] si si CΛ cn Λ CΛ CΛ Ul 4 OJ tO H O vo 00 si cn Ul 4*. J IO H O Vθ ω sl cΛ U1 45» OJ tO H O VO 03 si CΛ O Ow Ow Ow Ow W O O O O O O O W W W O O O O O O O O O W W W O O O W W W O O IW W W W W W W W W W W W W W W W W W W W W W |to OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ J J I cn si si si si oo ω oo ω ω oo oo oo oo oo ω ω oo oo ω oo oo oo oo oo oo oo oo oo oo ω |o Table 8 ( Continued) 1736 OH H CHOHCH=CH 2 -(R) 8 1737 OH H CHOHCH=CH 2 -(S) 8 1738 OH CH 3 CH 2 SH 8 1739 OH CH 3 CH 2 NH 2 8 1740 OH CH 3 COCH 3 8 1741 OH CH 3 CONH 2 8 1742 OH CH 3 CSNH 2 8 1743 OH CH 3 CH 2 CH 2 OH 8 1744 OH CH 3 CH 2 CHO 8 1745 OH CH 3 CH 2 COCH 3 8 1746 OH CH 3 CH 2 C0 2 CH 3 8 1747 OH CH 3 CH 2 CONH 2 8 1748 OH CH 3 CH 2 C1 8 1749 OH CH 3 CH 2 CH 2 C1 8 1750 OH CH 3 CN 8 1751 OH CH 3 CH=NNH 2 8 1752 OH CH 3 CH 2 NHOH 8 1753 OH CH 3 CH 2 NHNH 2 8 1754 OH CH 3 CH 2 CN 8 1755 OH CH 3 CH 2 CH=NOH 8 1756 OH CH 3 CH 2 CH=NNH 2 8 1757 OH CH 3 CH 2 CH 2 NHOH 8 1758 OH CH 3 CH 2 CH 2 NHNH 2 ' 8 1759 OH CH 3 CONHOH 8 1760 OH CH 3 CH=CHCHO 8 1761 OH CH 3 CH=CHCOCH 3 8 1762 OH CH 3 CH=CHCH 2 C1 8 1763 OH CH 3 CH 2 CHOHCH 2 OH 8 1764 OH CH, CHOHCH-CH 8 0 1765 =0 CH- CH, - 112 - 15-Azasterols Because the same chemistry could not be utilized for 15-azasterols as was used for 15-oxasterols and 15-thiasterols, a new synthetic route, which involves a Curtis rearrangement as the key step, has been developed for 15-aza-lanosterols. Thus the enone-aldehyde 4b was oxidized with sodium chlorite (Aldrich) in the presence of sulfamic acid (Fisher) in 4 parts of tertiary butanol and 1 part of water to afford the corresponding carboxylic acid 63 in near quantitative yield (See, Scheme VIII) . The acid 63 was converted to an acyl azide under phase transfer catalysis conditions. It was first treated with isobutyl chloroformate (Aldrich) and N-methyl-morpholine (Aldrich) in dry methylene chloride and then the intermediate mixed anhydride was reacted with sodium azide (Fisher) and tetrabutylammonium bromide (Aldrich) in methylene chloride and water to give acyl azide 64 in quantitative yield. A Curtis rearrangement of the acyl azide 64 in a refluxing mixture of ethyl acetate and methanol (1:5) provided the corresponding carbamate 65 which was pure enough to be carried onto the next reaction. The carbamate 65 was hydrolyzed with potassium silanoate (Petrach Systems, Bristol, PA 19007) in refluxing tetrahydrofuran to give a five-membered cyclic imine 66b in 73% overall yield for six steps starting from the 8,14-diene 2b. Finally the p-methoxybenzyl protecting group at C-3 was cleaved by treating with allyltri ethylsilane and boron trifluoride etherate in methylene chloride to afford the unprotected 15-azasterol 66a, a compourid within the scope of this invention, in 93% yield. - 113 - SCHEME VIII 66« R,»H, R^-CH, 71 66b R^pMBπ, R j -CH 3 701 R^-H, R^-H 70b R^pMBn, R j -H - 114 - A bis-4,4-normethyl 15-azasterol (R 2 of the general structure 1 is H) has also been synthesized from the enone-aldehyde 40 by following the sequence of the reaction steps described in the synthesis of 15-azasterol 66a. Oxidation of the aldehyde 40 followed by acyl azide formation, Curtis rearrangement and hydrolysis of carbamate provided the protected 15-azasterol 70b in 61% overall yield for six steps starting from the 8,14-diene 38b. Deprotection of 70b at C-3 gave compound 70a in 96% yield based on the recovered starting material 70b. Compound 70a is another example of a 15-aza-lanosterol within the scope of the present invention. Further functionalizations at the 14 and 15 positions of 15-azasterol may be achieved by a reduction or an addition to the imine followed by appropriate transformations to synthesize additional compounds within the scope, which have general structure 71 in the scheme. Tables 9-13 set forth various azasterols of the present invention. SCHEME VIII pMBnO 66t R,-H, R j -CH, 71 70b R^pMBn, R j -H - 116 - Table 9 (Continued) NO. n No. M. P. — 1839 oi-c 4 H 9 H 8 1 1840 Oi-C 4 H 9 C 2 H 5 8 1 1841 Ot-C 4 H g CH 3 8 1 1842 Ot-C 4 H 9 H 8 1 1843 Ot-C 4 H g C 2 H 5 8 1 1844 OPh CH 3 8 1 1845 OPh H 8 1 1846 OPh C 2 H 5 8 1 1847 OCH 2 Ph CH 3 8 1 1848 OCH 2 Ph H 8 1 1849 OCH 2 Ph C 2 H 5 8 1 1850 OCOH CH 3 8 1 1851 OCOH H 8 1 1852 OCOH C 2 H 5 8 1 1853 OCOCH 3 CH 3 8 1 1854 OCOCH3 H 8 1 1855 OCOCH3 C 2 H 5 8 1 1856 OCOC 2 H 5 CH 3 8 1 1857 OCOC 2 H 5 H 8 1 1858 OCOC 2 H 5 C 2 H 5 8 1 1859 OCOC 3 H 7 CH 3 8 1 1860 OCOC 3 H 7 H 8 1 1861 OCOC 3 H 7 C 2 H 5 8 1 1862 OCOi-C 3 H 7 CH 3 8 1 1863 OCOi-C 3 H 7 H 8 1 1864 OCOi-C 3 H ? C 2 H 5 8 1 1865 OCOC 4 H 9 CH 3 8 1 1866 OCOC 4 H 9 H 8 1 1867 OCOC 4 H 9 C 2 H 5 8 1 1868 OCOi-C 4 H 9 CH 3 8 1 1869 OCOi-C 4 H 9 H 8 1 H | _ι t r- > r-' -' i 1 - > r J H H VO 00 00 00 ∞ OO OO OO OO OO OO OO 00 00 O VO O VO VO VO VO VO VO VO VO OO 00 00 O VO 00 si CΛ U1 4 OJ tO H O VD 00 si o o o o o o o o w w oo o o o o W Wo oW oO oO tr tr tr r r Λ VO VO W W OJ OJ H H o w Wotoo w Wo too w Wotoo w Wotoo w Wotoo w Wotoo w Wotoo w Wotoo w Wotoo w W OJ W OJ W OJ W OJ W OJ W OJ W O W OJ W O W I UI UI UI UI UI UI UI UI UI 00 00 00 00 00 00 00 00 00 00 CO 00 00 00 00 00 O3 00 00 00 00 00 00 O3 O3 00 00 t-> r^ i- 1 -> H H H ,_ι H H H R * - 1 i- 1 H H H H H H H H H H H H H H H H H H H o vo vo vo vo vo vo vo vo ø vo vo vø vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo OJ OJ tO tO tO tO tO IO tO tO tO W H H H H H H H H H H O O O O O O H O VO OO sl CΛ Ul 4^ 0J tO H O V0 00 sl CΛ U1 4^ 0J t H O V0 ω sl cΛ Ul 4^ O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O W W W rt rt rt H- P- H- O O H- H- H- o o o o o o o o o o W W W tr tr tr i i I I i I ^ ^ I I i OJ OJ OJ to to to W W W W to to r O O O O O O W W W O O O W W W W W W OJ OJ OJ W W W 4 4. 4>. 4>. ** V0 VO VO U> J OJ s] s] sl Ul Ul Ul tr tr tr W W W W W o o o o o o si si si O O W O O W O O W O O W O O W O O W O O W O O W O O W O W to W to W tJ W to W to w to W to W to W to W t O OJ W OJ W OJ OJ W OJ W OJ W J W OJ W OJ U1 U1 U1 Ul Ul Ul UI UI Ul sl sl sl sl sl sl sl sl sl sl sj sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl H H H H (_. H H H H H H H |_l (-1 t-t i-> > H H H H H H H H H H H H H H H H H H H H H H H H H H H H H VO 00 0O 00 00 00 0O O3 00 00 00 00 00 00 O3 00 00 00 00 O3 00 00 O3 03 00 00 03 00 00 O VO VO VO VO VO VO VO VO VO VO CO ω OO OO OO OO CO OO OO OO sl sl sl sl sl sl sl sl O VO OO sl U1 4*. OJ t H O VD OO sl CΛ Ul W J tO H O VO CO sl cΛ Ul 4 : >- OJ tO to o w o W too w o W too w o W too w o W too w o W too w o W too w o W too w o W too w o W too w W OJ W OJ W OJ W OJ W OJ W OJ W OJ W OJ W OJ W Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul 00 00 00 00 O0 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 CO 00 O3 00 00 00 00 i- 1 r^ t-> y-> \-^ \-> i- 1 h-' > t- 1 r^ H H H H ' - 120 - Table 9 (Continued) No. R l -*a D n * No. M. P. 1963 OCOC 17 H 35 C 2 H 5 7 1 1964 OCOC 17 H 33 CH 3 7 1 1965 OCOC 17 H 33 H 7 1 1966 OCOC 17 H 33 C 2 H 5 7 1 1967 OCOC 17 H 31 CH 3 7 1 1968 OCOC 17 H 31 H 7 1 1969 OCOC 17 H 31 C 2 H 5 7 1 1970 OCOC 17 H 29 CH 3 7 1 1971 OCOC 17 H 29 H 7 1 1972 OCOC 17 H 29 C 2 H 5 7 1 1973 OCOC 19 H 31 CH 3 7 1 1974 OCOC 19 H 31 H 7 1 1975 OCOC 19 H 31 C 2 H 5 7 1 1976 OCOPh CH 3 7 1 1977 OCOPh H 7 1 1978 OCOPh C 2 H 5 7 1 1979 OH CH 3 8 2 1980 OH H 8 2 1981 OH C 2 H 5 8 2 1982 =0 CH 3 8 2 1983 =0 H 8 2 1984 =0 C 2 H 5 8 2 1985 OCH 3 CH 3 8 2 1986 OCH 3 H 8 2 1987 OCH 3 C 2 H 5 8 2 1988 OC 2 H 5 CH 3 8 2 1989 OC 2 H 5 H 8 2 1990 OC 2 H 5 C 2 H 5 8 2 1991 OC 3 H 7 CH 3 8 2 1992 OC 3 H 7 H 8 2 1993 0C 3 H 7 C 2 H 5 8 2 - 121 - Table 9 (Continued) No. R- n No. M. — Δ_ 1994 Oi-C 3 H ? CH 3 8 2 1995 Oi-C 3 H 7 H 8 2 1996 Oi-C 3 H 7 C 2 H 5 8 2 1997 0C 4 H 9 CH 3 8 2 1998 OC 4 H 9 H 8 2 1999 OC 4 H g C 2 H 5 8 2 2000 Oi-C 4 H g CH 3 8 2 2001 Oi-C 4 H 9 H 8 2 2002 oi-C 4 H 9 C 2 H 5 8 2 2003 Ot-C 4 H 9 CH 3 8 2 2004 Ot-C 4 H 9 H 8 2 2005 Ot-C 4 H g C 2 H 5 8 2 2006 OPh CH 3 8 2 2007 OPh H 8 2 2008 OPh C 2 H 5 8 2 2009 OCH 2 Ph CH 3 8 2 2010 OCH 2 Ph H 8 2 2011 OCH 2 Ph C 2 H 5 8 2 2012 OCOH CH 3 8 2 2013 OCOH H 8 2 2014 OCOH C 2 H 5 8 2 2015 OCOCH 3 CH 3 8 2 2016 OCOCH 3 H 8 2 2017 OCOCH 3 C 2 H 5 8 2 2018 OCOC 2 H 5 CH 3 8 2 2019 OCOC 2 H 5 H 8 2 2020 OCOC 2 H 5 C 2 H 5 8 2 2021 OCOC 3 H 7 CH 3 8 2 2022 OCOC 3 H 7 H 8 2 2023 OCOC 3 H 7 C 2 H 5 8 2 2024 OCOi-C 3 H 7 CH 3 8 2 - 122 - Table 9 (Continued) * No. R ^ n - - 2., D D n No. M. 2025 OCOi-C 3 H 7 H 8 2 2026 OCOi-C 3 H 7 C 2 H 5 8 2 2027 OCOC 4 H 9 CH 3 8 2 2028 OCOC 4 H 9 H 8 2 2029 OCOC 4 H 9 C 2 H 5 8 2 2030 OCOi-C 4 H g CH 3 8 2 2031 OCOi-C 4 H 9 H 8 2 2032 0C0i-C 4 H g C 2 H 5 8 2 2033 OCOt-C 4 H 9 CH 3 8 2 2034 OCOt-C 4 H 9 H 8 2 2035 0C0t-C 4 H g C 2 H 5 8 2 2036 0C0C 15 H 31 CH 3 8 2 2037 OCOC 15 H 31 H 8 2 2038 0C0C 15 H 31 C 2 H 5 8 2 2039 0C0C 15 H 29 CH 3 8 2 2040 OCOC 15 H 29 H 8 2 2041 OCOC^ 5 H 29 C 2 H 5 8 2 2042 OCOC 17 H 35 CH 3 8 2 2043 OCOC 17 H 35 H 8 2 2044 OCOC 17 H 35 C 2 H 5 8 2 2046 OCOC 17 H 33 H 8 2 2048 OCOC 17 H 31 CH 3 8 2 2049 OCOC 17 H 31 H 8 2 2050 OCOC 17 H 31 C 2 H 5 8 2 2051 OCOC 17 H 29 CH 3 8 2 2052 OCOCη " 29 H 8 2 2053 OCOC 17 H 29 C 2 H 5 8 2 2054 OCOC 19 H 31 CH 3 8 2 2055 OCOC 19 H 31 H 8 2 Table 9 (Continued) NO. -*ι— - D n * No. M . 1994 oi-C 3 H 7 CH 3 8 2 1995 Oi-C 3 H 7 H 8 2 1996 Oi-C 3 H ? C 2 H 5 8 2 1997 0C 4 H 9 CH 3 8 2 1998 OC 4 H 9 H 8 2 1999 OC 4 H 9 C 2 H 5 8 2 2000 Oi-C 4 H 9 CH 3 8 2 2001 Oi-C 4 H 9 H 8 2 2002 Oi-C 4 H 9 C 2 H 5 8 2 2003 Ot-C 4 H 9 CH 3 8 2 2004 Ot-C 4 H 9 H 8 2 2005 Ot-C 4 H g C 2 H 5 8 2 2006 OPh CH 3 8 2 2007 OPh H 8 2 2008 OPh C 2 H 5 8 2 2009 OCH 2 Ph CH 3 8 2 2010 OCH 2 Ph H 8 2 2011 OCH 2 Ph C 2 H 5 8 2 2012 OCOH CH 3 8 2 2013 OCOH H 8 2 2014 OCOH C 2 H 5 8 2 2015 OCOCH 3 CH 3 8 2 2016 OCOCH3 H 8 2 2017 OCOCH3 C 2 H 5 8 2 2018 OCOC 2 H 5 CH 3 8 2 2019 OCOC 2 H 5 H 8 2 2020 OCOC 2 H 5 C 2 H 5 8 2 2021 OCOC 3 H 7 CH 3 8 2 2022 OCOC 3 H 7 H 8 2 2023 OCOC 3 H 7 C 2 H 5 8 2 2024 OCOi-C 3 H ? CH 3 8 2 - 124 - Table 9 (Continued) No . —=-&. No. . P . — 2087 OPh CH 3 7 2 2088 OPh H 7 2 2089 OPh C 2 H 5 7 2 2090 OCH 2 Ph CH 3 7 2 2091 OCH 2 Ph H 7 2 2092 OCH 2 Ph C 2 H 5 7 2 2093 OCOH CH 3 7 2 2094 OCOH H 7 2 2095 OCOH C 2 H 5 7 2 2096 OCOCH3 CH 3 7 2 2097 OCOCH3 H 7 2 2098 OCOCH3 C 2 H 5 7 2 2099 OCOC 2 H 5 CH 3 7 2 2100 OCOC 2 H 5 H 7 2 2101 OCOC 2 H 5 C 2 H 5 7 2 2102 OCOC 3 H 7 CH 3 7 2 2103 OCOC 3 H 7 H 7 2 2104 OCOC 3 H 7 C 2 H 5 7 2 2105 ocoi-c 3 H 7 CH 3 7 2 2106 0C0i-C 3 H 7 H 7 2 2107 0C0i-C 3 H 7 C 2 H 5 7 2 2108 0C0C 4 H g CH 3 7 2 2109 OCOC 4 H 9 H 7 2 2110 OCOC 4 H 9 C 2 H 5 7 2 2111 0C0i-C 4 H g CH 3 7 2 2112 OCOi-C 4 H 9 H 7 2 2113 OCOi-C 4 H 9 C 2 H 5 7 2 2114 OCOt-C 4 H 9 CH 3 7 2 2115 OCOt-C 4 H 9 H 7 2 2116 OCOt-C 4 H g C 2 H 5 7 2 2117 OCOC 15 H 31 CH 3 7 2 * to NJ to to to to to to to t to to t to to t t to to W KJ to to H H H H H H H H H H H H H H H H H H 1 1 1 > I 4k OJ OJ J OJ J OJ J OJ J J to to to to to to to o tO tO tO -> t-* VO 00 si CΛ Ul 4k OJ to H o vo 00 si en Ul 4k OJ tO H O VO 00 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O HoHoHoHoHoHoHoHoHoHoHoHoHoHoHoHoHoHoHoHo VO VO VO sl sl sl sl sl sl sl sl sl sl sl sl Ul Ul Ui Ul Ul W W W W W W W W W W W W W W W W W W W W OJ OJ OJ tO tO tO OJ OJ OJ OJ OJ OJ OJ OJ OJ tO tO tO OJ OJ H H H VO VO VO H H H OJ OJ OJ UI UI UI VO VO VO H H - 126 - Table 10 No , 1- £ 2 R 3 D No. M . P , 2141 OH CH 3 CH 3 H 8 66a 2142 OH CH 3 H H 8 2143 OH CH 3 CH=CH 2 H 8 2144 OH CH 3 CHOHCH 2 OH- (R) H 8 2145 OH CH 3 CHOHCH 2 OH- (S) H 8 2146 OH CH 3 CHO H 8 2147 OH CH 3 CH 2 OH H 8 2148 OH CH 3 C0 2 H H 8 2149 OH CH 3 C0 2 CH 3 H 8 2150 OH CH 3 CH=NOH H 8 2151 OH CH 3 CHOHCH= CH 2 -(R) H 8 2152 OH CH 3 CHOHCH= CH 2 -(S) H 8 2153 OH H CH 3 H 8 2154 OH H H H 8 70a 2155 OH H CH=CH 2 H 8 2156 OH H CHOHCH 2 OH- (R) H 8 2157 OH H CHOHCH 2 OH- (S) H 8 2158 OH H CHO H 8 2159 OH H CH 2 OH H 8 2160 OH H C0 2 H H 8 2161 OH H C0 2 CH 3 H 8 2162 OH H CH=NOH H 8 Table 9 * (Continued) t No. R l ^2 D n * No. M. P. 2118 0C0C 15 H 31 H 7 2 2119 OCOC 15 H 31 C 2 H 5 7 2 2120 OCOC 15 H 29 CH 3 7 2 2121 OCOC 15 H 29 H 7 2 2122 OCOC 15 H 29 C 2 H 5 7 2 2123 0C0C 17 H 35 CH 3 7 2 2124 0C0C 17 H 35 H 7 2 2125 0C0C 17 H 35 C 2 H 5 7 2 2126 OCOC 1? H 33 CH 3 7 2 2127 OCOC 17 H 33 H 7 2 2129 OCOC 17 H 31 CH 3 7 2 2130 OCOC 17 H 31 H 7 2 2131 OCOC 17 H 31 C 2 H 5 7 2 2132 OCOC 17 H 29 CH 3 7 2 2133 OCOC 17 H 29 H 7 2 2134 OCOC 17 H 29 C 2 H 5 7 2 2135 OCOC 19 H 31 CH 3 7 2 2136 OCOC ιg H3 1 H 7 2 2137 OCOC 19 H 31 C 2 H 5 7 2 2138 OCOPh CH 3 7 2 2139 OCOPh H 7 2 2140 OCOPh C 2 H 5 7 2 * - provided that when n=2, the upper side chain (R) is no ergosterol. - 128 - Table 10 (Continued) No. R 1- S 2 R 3 D No. M. 2193 OH CH 3 CH 2 CH 2 OCH 3 H 8 2194 OH CH 3 CH 2 CH 2 OCOCH 3 H 8 2195 OH CH 3 CH*^CH SH H 8 2196 OH CH 3 CM Cli SCfl-5 H 8 2197 OH CH 3 CH 2 CH 2 SCOCH 3 H 8 2198 OH CH 3 CH 2 CH 2 NH 2 H 8 2199 OH CH 3 CH 2 CH 2 NHCH 3 H 8 2200 OH CH 3 CH 2 CH 2 NHCOCH 3 H 8 2201 OH CH 3 CH 2 CHO H 8 2202 OH CH 3 CH 2 COCH 3 H 8 2203 OH CH 3 CH 2 COCH=CH 2 H 8 2204 OH CH 3 CH- j CSCHo H 8 2205 OH CH 3 CH 2 CSCH=CH 2 H 8 2206 OH CH 3 CH 2 C(=NH)CH 3 H 8 2207 OH CH 3 CH 2 C0 2 CH 3 H 8 2208 OH CH 3 CH 2 COSCH 3 H 8 2209 OH CH 3 CH 2 CONH 2 H 8 2210 OH CH 3 CH 2 CONHCH 3 H 8 2211 OH CH 3 CH 2 CONHCOCH 3 H 8 2212 OH CH 3 CH 2 CSNH 2 H 8 2213 OH CH 3 CH 2 C(=NH)CH 3 H 8 2214 OH CH 3 CH CHoCl H 8 2215 OH CH 3 CN H 8 2216 OH CH 3 CH=N0CH 3 H 8 2217 OH CH 3 CH=NOCOCH 3 H 8 2218 OH CH 3 CH=NNH 2 H 8 2219 OH CH 3 CH=NNHCH 3 H 8 2220 OH CH 3 CH=NNHCOCH 3 H S 2221 OH CH 3 CH=NNHCSCH 3 H 8 2222 OH CH 3 CH 2 NHOH H 8 2223 OH CH- CH 2 NHOCH 3 H 8 ** to t to to to to to to to to to t to to to I to to to t to to to to to to t to to to t t t to to to to to to to to to to to to to to to to to to to to to to to Ul Ul k 4k 4k k 4k 4k 4 4k 4k OJ J OJ J OJ OJ OJ OJ OJ OJ to to to to to to H o O 00 si CΛ Ul 4 J to H O VO 03 si CΛ Ul 4k OJ to H o VO 00 si CΛ Ul 4*. o o o o o o o o o o o o o o o o o o o o o o o o o o o o IW 1*7* O O O O O O O O O O O O O O O O O O O O O O O O O O O O IW ^ ^ ^ ^ ^ tM tM tM tM tM tM tM tM tM rM tM tM tM tM tM tM tM tM r tM ^ \VO w w w w w w w w w w w w w w w w w w w w w w w w w w w 00 00 00 03 00 03 00 00 00 00 00 00 00 03 03 00 03 03 03 00 03 03 00 00 00 00 00 00 pi P to to to to to to t to to t to to to to to to to to to N) t to to t to to to to to to to t t to to to to t to to to t to to to to t to to to to to si si si si si si si si cn b CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ Ul Ul Ul Ul ui ui Ul Ul CΛ Ul 4k OJ to H o vo 00 si CΛ Ul * OJ to H O VO 00 i CΛ Ul 4k OJ to S IΪ H K W W HM W HI o O O O O O O O O O O O O O O O O IW w W W W W W W W W W W W W W |to OJ OJ w W W OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ w w w w w w w w w W W IW |4k 00 00 03 03 00 00 00 00 00 00 00 00 00 00 00 00 00 03 03 00 00 03 00 00 00 00 ID B 3 ** to to to to to to t to to to to t to to to to to to to to t to t t to t to to t to to to to to to to to to W to to t to to to to t t to to to t to to to to Ul Ul 4 4k k 4 4k k k 4k OJ J OJ l OJ OJ OJ OJ J OJ to to to to to IO H O O 00 si (Λ Ul k OJ to H O VO 03 si CΛ Ul 4 OJ to H o o 00 si CΛ Ul 4 o o o o o o o o o o o o o o o o o o o o o o o o o o o o tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM Jw O O O O O O O O O O O O O O O O O O O O O O O O O O O O IW t vo w w w w w w w w w w w w w w w w w w w w w w w w w w w CXJ O3 ∞ 0O O3 ω 0O 0O O3 00 00 OO 0O 00 O3 00 0O 00 O0 O0 00 0O 0O O0 O3 00 00 O3 pi P II II II II II II II II II II II II II O O O O O O O O O O O O o oII W O O O O O O O O O O O O O O O O O O O O O O O O O O O IW w w w w w w w w w w w w w w w w w w w w w w w w w w w oo Oi OO OO OO OO CO OO OO OO OO OO OO OO OO OO OO OO OO OO OO OO OO OO OO OO OO OO p 3 ** to to to to to to to to to to to to to to to to to t to to to to to to to to to to t OJ OJ J J J OJ OJ OJ OJ OJ J J OJ OJ OJ OJ J J OJ OJ OJ J OJ OJ OJ 0J OJ J OJ CΛ CΛ CΛ Ul Ul Ul Ul Ul Ul Ul ui Ul Ul 4> 4k 4k 4> 4k 4k 4 4k 4>. J OJ OJ OJ OJ OJ t H o VO 00 si CΛ Ul 4k J to H o VO 00 si CΛ Ul 4 OJ to H o VO 00 si CΛ Ul J Oo Oo Oo Oo oO oO Oo Oo Oo Oo oO Oo Oo Oo Oo Oo oO oO oII oII oII II II II II II II II II I o o o o o o o o lw CJ ) ^ > ) CJ CJ t OJ U> ) J I ) OJ CJ Cv> CJ V ow ow wo ow wo wo ow ow wo ow wo ow ow ow ow owo owo wo w w w w w w w w w w W ,IW |to OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ w w w w w w w w w w w w w w w w w w w w w w w w w w w w w oo oo <Xι C 00 00 00 03 00 O3 00 00 00 00 00 O3 00 O3 00 00 CO 03 00 00 00 00 00 00 pi \o 3 to to to to w to to to OJ J OJ J OJ 0J OJ 0J o 00 00 00 00 00 00 00 o vo 00 si CΛ Ul 4k OJ O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O JW OJ OJ OJ OJ OJ OJ OJ OJ W W W W W W W W W W W W W W W W W W W W OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ V w w w w w w w w W W W W W W W W W W W W W W W W W W W W , |4ιkw 00 00 00 00 03 00 00 00 03 00 00 00 00 00 00 00 00 00 00 03 00 03 00 00 00 00 00 00 ID B t to to to to to t to to to to to to to t to to to NJ to to to to to to to to to to OJ OJ OJ OJ J OJ OJ OJ OJ OJ OJ OJ J OJ J J OJ OJ J J J J J OJ OJ OJ OJ 0J J CΛ CΛ CΛ Ul Ul Ul Ul Ul Ul Ul Ul ui Ul 4 4k k 4k 4 4k 4 k *• 4 OJ OJ J OJ OJ OJ to H o VO 00 si CΛ Ul 4k OJ to H o vo 00 si CΛ Ul * OJ to H o VO 00 si CΛ ui 4> O O O O O O O O O O O O O O O O O O II II II II II II O O O O O O O O O O O O O O O O O O O O I W ffi W W ffi W W W W W κH hπ H p3 tM tM tM tM o o o II II II II o o o o o lw V O O O O O O O O O O O O O O O O O O W W W W W W W W W W W IW tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM |t w w w w w w w w w w w w w w w w w w w w w w w w w w w w w oo oo oo co oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo 3 t to to to to to to to to to to to to to to to to to to to to to to to to to to 12) 4 4k 4k 4 4 4k 4 4k k 4k k ι^ 4k k k 4k 4k. 4k k 4k 4 |θ l tk 4k 4k 4k 4k 4k 4k J U OJ OJ J J OJ OJ OJ J tO tO tO t tO t tO tO tO tO |> OO U1 4k OJ tO H O VO OO sl CΛ U1 4 k OJ tO H O VO OO sl CΛ Ul 4k. ω W H O w w w w w w w w w w w w w w w w w w w w w w w w w w w w oo cxj ∞ oo oo oo ro rø cn ω ω oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo B 3 W t to to to to to to to to to to to to to to to to to to to t to to to to to to 4k k 4k 4k 4k k 4k k 4k 4 4k 4k 4k 4k 4k 4k 4 4k 4k 4 4k 4k 4k 4k 4k 4k si si si si si i si CΛ CΛ CΛ CΛ cn CΛ cn cn CΛ CΛ Ul Ul Ul Ul Ul Ul Ul l Ul ui CΛ Ul 4 OJ to H O O 00 si CΛ Ul 4k OJ to H O O 00 si CΛ Ul 4k OJ to H O ow ow wo o o o o o o ow o o o o w w w w w w w w w w w w o o ,IW o o H3 w w |to OJ OJ OJ OwJ OJw OJwOJw OwJ OwJ OJ OwJ OwJ OwJ OwJ OJ OJ 3 OJ rt tr H p- H OJ 3 Φ j P O O Φ w w w w Pi O OJ OJ OJ w w w w w w w w w w w w w w w w w w w w w w w w w 00 00 C.ι oo oo oo 00 00 03 00 00 03 W W 00 O3 00 O3 O3 00 0O 0O 0O 00 03 W ID 00 03 03 3 - 138 - Table 10 (Continued) o. D No. M. P -*!- R 3 2477 OCOC 15 H 31 CH 3 CH 2 OH H 8 2478 OCOC 15 H 29 CH 3 CH 3 H 8 2479 OCOC 17 H 35 CH 3 CH 3 H 8 2480 OCOC 17 H 33 CH 3 CH 3 H 8 2481 OCOC 17 H 31 CH 3 CH 3 H 8 2482 OCOC 17 H 29 CH 3 CH 3 H 8 2483 OCOC ιg H 31 CH 3 CH 3 H 8 2484 OCOPh CH 3 CH 3 H 8 2485 OCOPh CH 3 CHO H 8 2486 OCOPh CH 3 CH 2 OH H 8 2487 OH CH 3 CH 3 H 7 2488 OH CH 3 H H 7 2489 OH CH 3 CH=CH 2 H 7 2490 OH CH 3 CHOHCH 2 OH- (R) H 7 2491 OH CH 3 CHOHCH 2 OH- (S) H 7 2492 OH CH 3 CHO H 7 2493 OH CH 3 CH 2 OH H 7 2494 OH CH 3 C0 2 H H 7 2495 OH CH 3 C0 2 CH 3 H 7 2496 OH CH 3 CH=NOH H 7 2497 OH CH 3 CHOHCH= =CH 2 -(R) H 7 2498 OH CH 3 CHOHCH= =CH 2 ; -(S) H 7 2499 OH H CH 3 H 7 2500 OH H H H 7 2501 OH H CH=CH 2 H 7 2502 OH H CHOHCH 2 OH- -(R) H 7 2503 OH H CHOHCH 2 OH- "(S) H 7 2504 OH H CHO H 7 2505 OH H CH 2 OH H 7 to to to to to to to to to to t to to to t to to to to to t to to t to to to to 2! k k k 4 4k k 4 4k 4k 4k 4k 4k 4k 4k 4k 4k 4k k 4k 4k 4k k 4k k 4k 4k 4k 0 si si si si si si si CΛ CΛ CΛ CΛ <Λ CΛ CΛ σ\ cn CΛ Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul 4k • CΛ Ul 4k OJ to H O O 00 si CΛ Ul 4k OJ to H O O 00 si CΛ Ul 4k J to H o VO oo oo oo oo oo oo oo oo oo W W oo oo oo oo oo oo oo oo oo oo 03 W ID 3 - 140 - Table 10 (Continued) No. - - R 3 D No. M. P 2535 OCH 3 CH 3 CH 3 H 7 2538 OCH 3 CH 3 CHOHCH 2 OH- (R) H 7 2539 OCH3 CH 3 CHOHCH 2 OH- (S) H 7 2540 OCH 3 CH 3 CHO H 7 2541 OCH 3 CH 3 CH 2 OH H 7 2542 OCH 3 CH 3 C0 2 H H 7 2543 OCH 3 CH 3 C0 2 CH 3 H 7 2545 OCH3 CH 3 CHOHCH= =CH 2 -(R) H 7 2546 OCH3 CH 3 CHOHCH= =CH 2 -(S) H 7 2550 OCH3 H CHOHCH 2 OH- (R) H 7 2551 OCH3 H CHOHCH 2 OH- (S) H 7 2557 OCH3 H CHOHCH= =CH 2 -(R) H 7 2558 OCH3 H CHOHCH= =CH 2 -(S) H 7 2559 OCOCH3 CH 3 CH 3 H 7 2560 OCOCH3 CH 3 H H 7 2561 OCOCH3 CH 3 CH=CH 2 H 7 2562 OCOCH3 CH 3 CHOHCH 2 ; OH- (R) H 7 2563 OCOCH3 CH 3 CHOHCH 2 ,0H- (S) H 7 to to to to to to to to to to to to to to to to to to to to to to to to to to Ul Ul Ul l Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul VO VD VO OO Oo ω OO OO OO OO OO OO OO sl sl sl sl sl sl sl sl sl sl cΛ CΛ CΛ tθ P' O V ω sl CΛ U1 4k OJ tO H O VD OO sl CΛ U1 4k J tO H O VO OO sl O O O O O O O O O O W W W W W W W W W W W W W W W O O O O O W W W W W W W W W W W W O O O O 33 33 33 33 33 P3 33 33 33 u ω i) u u L to w o o o w o o w o o o o o o o o o rx o w o o o o o o w w w o w w w w w w o o w w w X w w w w w o to to o OJ to to o OJ o o II to to to o o o II J o o II to w o w o w w 25 O w o w X o w w 25 O w w o o o w w o rx w o o o w w w W OJ w X to w w W OJ II II to to II II o o o o o o w w w w w w to to 1 1 t t 1 1 *-> 1 1 cn W cn w cn w tM tM tM tM tM tM tM tM tM tM tM tM tM Wo Wo oW oW Wo Wo Wo Wo Wo Wo w w w OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ oo oo oo oo oo oo oo oo oo oo to to t to to to to to to t to to to t to to to to to to to to to to t to to to to CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ cn cn CΛ CΛ CΛ Ul ui Ul Ul ui Ul Ul t to H H H H H H H H H H O O O O O o o o o o VO VO VO vo vo o vo H O VO 00 s] CΛ Ul 4k OJ to H O VO 00 s| CΛ Ul 4k OJ t H o vo 03 si (Λ Ul 4k 0J oo oo oo oo o oo oo oo O II II II II II II II II II II o o o o O O O O O O O O O O o o o o o o O O O O O O O O O O O O O O O O O O O O O O O O O O O O O OwJ OJwOwJ OJwOJwOwJ OJwOJwOwJ wJ 1 I • "rt *τ 111 i 11 *ττ^ ^T^ I 11 I 11 V OJ OJ OJ OJ OJ OJ OJ OJ OJ w w w w o o o o o w w w w w o o o o O W W W W W O O O O O IW w W W W W W Ito O wJ OJw OJw OJw OJw OJ OJw OJw OJw OJ J OJ OJ OJ OJ O O O O O O O O O O O O O O O O O O O O O O O O O O O O IW W W W W W W W W W W W |k OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ 00 03 00 00 00 03 00 03 00 03 00 00 00 00 03 00 00 00 03 03 00 00 00 03 00 00 00 00 00 ID B »« • *«> ** to t t t to t to to to to to to to tO N) to to to t to to to to to to to to to to 25 Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul Ul vo vo vo 00 00 00 00 00 00 00 00 00 00 si si si i si si si si si si CΛ CΛ cn CΛ o CΛ CΛ t H O o 00 si cn Ul 4k J t H o VO 00 si CΛ Ul 4k OJ t o VO 00 si CΛ Ul 4k o o o o o o o o o o w w w w w w w w w w IW w w w w w o o o o o w w w w w w w w w w w w o o o o o o o w OJw 00w OwJ OJw OJw W |to OwJ OJw OJw OwJ OwJ OJw 0J oo oo oo oo θ3 θ3 θo θ3 θo ID pi 3 to to to to t to to t t to to t t t to t to to to to to to to t to to CΛ cn cn CΛ CΛ CΛ CΛ CΛ CΛ CΛ en CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ <Λ i si s) i s| si si si CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ Ul Ul Ul Ul Ul Ul Ul Ul Ul |. CΛ Ul k OJ to H O VO 00 si CΛ Ul 4k OJ to H O VO 00 si CΛ Ul 4k OJ to H II II II II o o o o o o o o o o o o o o o o o o o o o o o o o o w w w w w w w w w w o o o o o o o o o o o o ,JW o O oO oO oO oO oO oO oO oO oO OwJ OwJ 33 33 33 33 33 33 33 33 33 33 V CJ CJ OJ > ( CJ J ) Cv ) » O O O O W W W W W O O O O O W W W W W O O O O O W W IW OJW OWJ OWJ OJW OJW OWJ OWJ OJW OWJ OWJ OWJ OJW OWJ OWJ |to O O O O O O O O O O O O O O O O O O O O O O O O O O IW W W W W W W W W W W W W W W W W W W W W W W W W W W |4 k O O O O O O O O O O O O O O OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ oo oo oo oo oo oo oo oo oo oo oo oo oo oo ID ** to to to to to to t to t to t to to t to to to to to t to to to to to to to 55 si si si si CΛ CΛ CΛ CΛ cn CΛ CΛ CΛ CΛ cn CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ 0 o O O O vo VO VO VO vo o vo O VO vo 03 OO 00 00 00 00 03 OJ 00 03 si si si • OJ to H O vo 00 si CΛ Ul 4 OJ to H O VO 00 si σv Ul 4 OJ to H O VO 00 si o w w w w w o o o o o w w w w w o o o o o w w w w w o w IW w |to OJw OJw OJwOJwOJw OJ OwJ OwJ OwJ OwJ OJ wo Ul O O O O O O O O O O O O O O O O O O O O O O O O O O O IW ^ tM tM tM tM tM t tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM tM ^ I**-* O O O O O O O O O O O O O O O O O O O O O O O O O O O CO 00 CD 00 CD 00 CX3 00 00 0O 00 00 CO 00 03 O3 00 03 O3 00 O3 C0 00 C0 00 00 ID p P to to to to to to to to to to to to to to to to to to to to to to to to to to sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl sl tO tO tO tO tO tO tO tO W tO H H H H H H H H H H O O O O O O VO OO s) CΛ Ul 4k OJ NJ H O VO OO sJ CΛ U1 4k U tO H O V0 03 sl σv Ul 4k O oO oO oO oO oO Oo oII oII oII oII oII oII oII oII oII o II wO wO wO wO wO wO wO wO wO ,JW OJ OJ OJ OJ OJ OJ OJ V W W O O O O O W W W W W O O O O O W W W W W O O O O IW W W W W W W W W W W W W W W |to OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ W O OJw O O O O O O O O O O O O O O O O O O O O O O O O O O w O wO wO wO wO wO wO wO wO wO wO wO wO wO wO wO wO wO wO wO wO wO wO wO wO wO I. »* *• to to to to to to to to to to to t to to to to to to to to to to to to to to to 2; sl sl sl sl CΛ Cn tΛ CΛ CΛ CΛ CΛ CΛ Cn cΛ CΛ CΛ CΛ Cn CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ 0 O O O O VO VO VO VO VO VD VO VO VD VO ω OO OO OO OO OO OO OO OO OO sl sl sl OJ tO |-' O VO OO sl CΛ Ul 4k OJ tO H O VO OO sl CΛ U1 4k OJ tO H O VO OO s] O O O O O O O O O O O O O O O O O O O O Oo Oo O O O O O O O O O _ O_ O. O. O_ O_ O._ O.. O.. oo 0 0 0 0 0 0 0 0 0 0 0 0 0 JW o o o w w w w w w w w w w O O O O O O O O OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ W W W W W W W W W OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ w w w o w w w o o o o o w w w w w o ιw W w w o oW W o Wo w W W W W W |to OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ 0 4k w OJ Ul O O O O O O O O O O O O O O O O O O O O O O O O O O O IW ^ ^ tM t M tM t M t M t M t M tM tM t M tM tM tM tM tM tM tM tM tM tM tM rM tM tM ^ |»-* O O O O O O O O O O O O O O O O O O O O O O O O O O O OO OO OO OO CD OO OO OS OO OO OO OO OO OO OO OO OO OO OO OO OO OO CXJ OS OO OO to to to to to to to to to to to to to to to to to to to to to to to to to to to to to 2! sl sl sl sl sl s) sl sl sl sl sl sl sl sl sl s) sj sl sl sl s) s) s] sl sl sl s| s| s) O 0O OO 0O 0O 00 OO 0O 00 s| sl sl s} sl sl s| s] sl s] CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ CΛ Ul • sl cΛ Ul 4k OJ tO H O VD OO sl CΛ U1 4 k OJ tO H O VO OO sl CΛ υi ^. OJ tO H O VO o o o o o W w w w w ow o o o o w w w w w o o o o o W w w w w w w w w w w W w W w w w w w |to OJ J OJ OJ OJ J OJ J OJ OJ OJ OJ OJ OJ OJ O O O O O O O O O O O O O O O O O O O O O O O O O O O O O Oo Oo oO Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo Oo oO oO Oo Oo O O w o o Oo Oo Oo Oo Oo Oo O Oo Oo OJ OJwOJ OwJ OJwOJwOJwOJwOJwOJwOJwOJwOwJ Ow o J OwJ OwJ OJwOJwOJwOwJ OwJ OJwOwJ OJwOJwOJwUwOwJ OwJ 00 00 03 O3 00 00 00 00 00 00 00 O3 00 00 03 03 00 CO 00 00 00 00 00 03 ID ** t t to to to to to to to to to to to to t to to t to to to t to t t t t to to 00 00 00 00 00 00 00 03 00 03 00 00 00 00 00 00 03 si si s si si si si sj s) si i si Pi o H H H H H H H O O O O O O o o o O VO VO vo O VO O VO VO VO O 00 00 CΛ Ul 4k OJ to H O VO 03 si CΛ Ul k J to H O VO 00 si CΛ Ul k OJ t H O o 03 o o o o w w w w w o o o o o W W W W W O O O O O W W W W W IW W W W W W |to OJ w OJ w OJ w O wJ OJ w OJ w OJ w OJ w O wJ OJ OJ OJ OJ OJ O O O O O O O O O O O O O O O O O O O O ,IW O O O O O O O O O O O O O Ow O wo ow ow ow o Oo o o oO Oo Oo oO oO oO oO |4k O OJwOJwOJ OJwOJwO OJ OJ OJ OJ OwJ OwJ OwJ OJwOJwOJwOJwOJwOJwOwJ OJw - 150 - Table 10 (Continued) No. -1- Λ' E 4 No. M. 2817 OC0CH : CH : C0 2 H COCH-, 7 2818 OCOCH : H CH 3 COCH-; 7 2819 0C0CH : H CHO C0CH : 7 2821 OCOCHr H CH 2 OH COCH : 7 2822 OCOCH- H C0 2 H COCH, 7 ** to to to to to to to to to to to to to to to t to to t to to to to to to to to to to 25 00 00 00 03 00 00 00 00 ∞ 03 00 00 00 00 CO 00 00 si si si si si si s] si si si si s] o o P H H H H H H H O o O o O o o o vo vo vo o vo vo VO vo vo vo 00 00 cn Ul 4k OJ t H O O 00 si CΛ Ul 0J to H o vo 00 si CΛ Ul 4k 0J to H o vo 00 O O O O O O O O O O O O O O H II II II II II II II o o o o o o o O O O O O O O O O O O O O o o o o o o o o o o o w w w w w IW IH O O oO oO OwJ OJw OJw OwJ OJw OJw OJw OJw OJw w W W W W OJ OJ OJ OJ o o o o w w w w w o o o o o w |to OJ w OJ w O wJ OJ w OJ w OJ w OJ w OJ OJ w w w w w w o o o o w w w OJw OJw OJw Ow w w J w IW Oo Oo Oo oo oo oo oo oo oo oo oo oo o M o M o i oI-H oI-H o.HH oHM oi-H oμLi o l io-H o OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ to to to to t to to to to to to to to to to to to to t to to to to to to to to to 55 03 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 CO 00 00 00 00 00 03 00 00 00 00 00 0 si si si cn CΛ CΛ σv σv CΛ CΛ cn σv CΛ Ul Ul Ul Ul l Ul Ul Ul ui Ul » *> 4k 4 • to H O o 00 si CΛ Ul 4 OJ to H o o 00 si σv Ul 4k OJ t H o o 00 si σv Ul oo oo oo o o o o o o o o o o o o o II II II II II II II II II II o o I o o o o o o o o o o o o o o o O O O O O o o o o o w w lw O O oO oO oO oO oO OJwOJwOJwOwJ OwJ OJwOwJ OwJ OwJ w w w w w w OJ OJ OJ OJ OJ J OJ w w o o o o o w w w w w o o o o W W W W W O O O O O W W IW W W W W W Ito OJ OJ OJ OJ OJ J J J J OJ OJ OJ OJ OJ cn w O O O O O O O O O O O O O O O O O O O O O O O O O O O O IW OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ O3 0O O3 00 00 00 00 O3 00 03 0O O3 00 00 0O 00 00 O3 00 0O 00 00 00 0O 00 O3 00 00 3 #• to to to to t to t to to to t to to to t to to to to t t to to to to t to to 25 vo 00 00 00 00 03 00 00 00 00 00 00 00 03 00 00 00 00 00 00 00 00 00 00 00 00 00 03 o VO vo VO o vo vo o vo vo vo 03 CD 00 00 00 00 00 00 CO 00 si si si si si si i o o vo 00 si CΛ Ul 4k OJ t H o vo 00 si cn Ul 4k J to H o vo 00 si CΛ Ul 4k J o o o o o w w w w w o o o o o w w w w w o o o o o w w w IW W W W W W |to OJ w O wJ OJ w OJ w wJ OJ w O wJ O wJ OJ w OJ w OJ OJ OJ OJ OJ o o o o o o o o o o o o o o o o o o o o o o o o o o o o ιw OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ 00 00 00 ID B to to ivj to to to to to to to to to to to to P vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo oi H H H H H H O O O O O O O O O U1 4 k OJ tO H O VO OO sl cΛ U1 4 k OJ tO H o o o o o o o o o o o o o o o - o - o - Q o o Q o - o o o o o o o o o o o o o o - o - o ,JW O 33 33 33 33 33 |H O O O O O O O O O O OJ OJ OJ OJ OJ tM *M tM tM W W W OJ OJ J OJ OJ OJ OJ OJ OJ OJ W W W W W O O O O O W W W W W IW W W W W |to OJ OJ OJ OJ OJ O O O O O O O O O O O O O O O IW W W W W W W W W W W W W W W W I* OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ 155 P to to to to to to to to to t to to to to to to to to to to to to to to to to to to VO OO OO ∞ ∞ ∞ ∞ ∞ OO OO OO OO OO OO OO OO OO OO GO OO OO OO GO OO OO OO OO OO O VO VO VO VO VO VO VO VO VO VO OO OO OO OO OO OO OO OO OO OO sJ sl sl sl sl sl sl O VO OO sl CΛ U1 4 k OJ N ) |-> O VO OO sl CΛ U1 4k OJ tO H O VO OO si σv U1 4k OJ O O O O o II II II II II II II II II II O O O O O O O O O O O O O o o O O o o o o o o o O O O O W W W W W W W W W W O O O w w w w w OJ OJ J OJ J o o o o o o OJ w O w w V J OJ o o o o w w w w w rx rx rx rx rx x W W W W O O O O O W W W IW w W W W W |to OJ w wJ J OJ w OJ w O wJ wJ OJ w J w O wJ J OJ OJ OJ OJ O O O O O O O O O O O O O O O O O O O O O O O O O O O O IW W W W W W W W W W W W W W W W W W W W W W W W W W W W W |4k OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ j 00 03 00 ID to t to to to to to t to to to to to io to to to to to to to to to to to to to to 2 vo vo vo o vo vo VO VO VO VO vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo o CΛ CΛ CΛ Ul Ul Ul Ul Ul Ul Ul Ul UI U1 4k 4k 4k 4k 4k 4k 4k 4k 4k 4k J OJ OJ J J • tO H O VO 00 si CΛ Ul 4k OJ t H O V0 03 sl CΛ Ul 4 k J tO H O VO OO sl CΛ Ul Ow Ow Ow Ow Ow Ow wO Ow Ow Ow Ow Ow Ow Ow Ow Ow wO Ow Ow wO Ow wO Ow Ow wO Ow Ow Ow ,JW O O O O O O O O O O O O O O O O O O O O O O O W W W W W IW 33 PH 33 33 33 33 P3 3J 33 33 33 33 33 33 33 W 33 33 33 33 33 33 33 \^ cn w W W W W W W W W W W W W W W W W W W W W W W W W W W W W IW |4k 00 rø ∞ ∞ 00 0O 00 00 O3 O0 0O 00 00 O3 00 O3 00 00 00 00 00 O3 00 O3 00 00 00 00 ID B β* *> to t to to to t t to t to to to to to to t to to t to to to t to to to to VO vo vo vo VO vo o vo VO vo vo vo vo VO VO o o vo vo o vo VO vo vo vo vo pi vo 00 00 00 00 00 00 00 00 00 00 si si si si s| si si si si sj cn CΛ σ> CΛ CΛ CΛ CΛ 1 |°« vo 00 si CΛ Ul k OJ to H o vo 00 si CΛ Ul 4k 0J t H o vo 00 si CΛ Ul k 0J oo oo o o oo oo oo oo wo oo oo o o o II II II II II II o o o o o o o II O o o o o o o II o o o o o o o w w w l» O O Oo O OoOwJ OJwOwJ OJoOwJ OJwOJwOJwOJw W W W V OJ OJ OJ OJ OJ tM tM tM tM tM tM )M tM tM tM tM tM tM tM * tM tM tM tM tM tM t t w w IW |4k 0O 00 O3 O3 00 0O 0O 00 CO 00 00 0O 0O 00 00 0O 03 00 0O 00 00 O3 00 00 oo oo oo ID OJ OJ OJ J OJ 00 OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ tO tO M tO tO tO tO tO tO o o O O o o o o o o O O O O O O O O VD VO VO VO VO VD VO VO VO VO H H H H H H H H o o O O O O O O O O VO VO VO VO VO VO VO VO VO VO si CΛ Ul 4k J to H O vo CO s J σv U1 4 k J tO H O VO OO sl cΛ U1 4k OJ M H O O O O W W W W W O O O O O W W W W W O O O O O W W W W W IW W W W W W W W W W W W W W |to OJ OJ OJ OJ 00 OJ OJ OJ OJ OJ OJ OJ OJ si si si si i 00 00 00 00 00 to to to to to t to to to NJ to to to to to to to to to to to to to to to to to 25 VO o o vo vo vo vo vo vo vo vo o vo vo o VO VO o V0 VO vo vo V0 O vo VO o O 00 00 00 00 00 00 00 00 00 00 si si i si si si si si i si CΛ CΛ CΛ σv CΛ CΛ CΛ vo 00 si CΛ Ul 4k 0J NJ H o o 00 si CΛ Ul 4k OJ to H o vo 00 si CΛ Ul *» 00 o o o o o w w w w w o o o o w w w w w o o o o o o o o W w OJw OJw OJw OJw OJw wJ 0Jw OJw OwJ 00w 00w 00w oow OJw OwJ OJw Ito 0J w w w w w w w w w w w w w w w w w w w w w w w w W W W OO OO 0O 00 OO 0O O3 OO 0O OO 0O 0O O0 OO 0O 0O O3 0O O3 0O O0 OO 0O O0 oo 00 03 ID OJ OJ OJ OJ OJ OJ OJ J 00 OJ J OJ 00 OJ J 0J OJ OJ 0J OJ OJ ω J 00 OJ J ω OJ 00 o O o o o o o o O O O o o o o o o o o o o o o si si o o o o o si si si o CΛ CΛ CΛ CΛ CΛ σv CΛ CΛ cn CΛ Ul Ul Ul Ul ui Ul Ul Ul Ul ui 4k 4k 4k 4k OJ to H o vo 00 si CΛ Ul 4 00 to H o VO 00 si CΛ Ul 4 00 to H o vo 03 si CΛ oo oo oo oo o o oo oo oo oo oo Oo Oo o O Oo o O Oo Oo O O O II II II II II II II II II o o o o o o o o o o w w w w w w w wo ow o o o o o o o o o o ,JW O O O O O O O O O O OJ OJ Oo oo J OJ OJ OJ OJw tM tM tM tM tM tM tM tM tM tM OJ OO OJ OJ OJ OJ OJ OJ OJ OJ V w w w w oW oW oW oW oW w w w w w oo ow ow ow ow w w w w w ow ow ow ow , |toιw OJ OJ OJ OJ OJ OJ OJ OO OJ OJ J oo J oo w o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM o tM , l*ι*w OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OO OJ OJ OJ OJ OO OJ OO OJ OJ OO OO OO OJ OJ OO OJ OJ OJ C» 00 00 CO CD 00 CO 00 CO CO C» Cn CO CO 00 CX) C» 00 00 00 ∞ 0O CX) 00 00 00 00 00 00 ID OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OO OJ o o o o o o o o o o o o o o o o o o o o o o o o o o o o p oa 4k 4k 4k 4k. 4k 4k OJ OO OJ O OJ J J OO OJ J I t tO tO tO M tO tO tO tO H H U1 4k OJ tO H O VO O sl cΛ Ul 4k O tO |- J O VO OO sl CΛ Ul 4k OJ t H O VO O II O O O O O O O O O O O O O O O O O O O O O O O O O O O O W W W W W W W W W W O O O O O O O O O O O O O O O O O ,.w O O O O O O O O O O W W W W W W W O O O O O O O Ω O O OJ OJ Oo oo oj OJ OJ 33 33 33 33 33 33 *M 33 33 P3 V o w w w w w o o o o o w w w w w o o o o o w w w w w o o iw W W W W W W W W W W W W W |to 00 OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ O O O O O O O O O O O 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 P3 , tM tM tM tM t M tM t M tM tM tM |ιkw 00 00 00 03 00 00 00 00 00 00 00 ID I? 3 FOR THE PURPOSES OF INFORMATION ONLY Codes used to identify States party to the PCT on the front pages of pamphlets publishing international applications under the PCT. AT Austria ES Spain MG Madagascar AU Australia Fl Finland ML Mali BB Barbados FR France MN Mongolia BE Belgium GA Gabon MR Mauritania BF Burkina Faso GB United Kingdom MW Malawi BG Bulgaria GN Guinea NL Netherlands BJ Benin GR Greece NO Norway BR Brazil HU Hungary PL Poland CA (Canada IT Italy RO Romania CF Central African Republic JP Japan SD Sudan CG Congo KP Democratic People's Republic SE Sweden CH Switzerland of Korea SN Senegal Cl Cόtc d'lvoire R Republic of Korea su Soviet Union CM Cameroon LI Liechtenstein TD Chad CS Chechoslovakia LK Sri Lanka TG Togo DE Germany LU Luxembourg US United Slates of America DK Denmark MC Monaco OJ J OJ OJ OJ OJ J OJ OJ J OJ OJ OJ OJ 0J 0J 00 00 00 OJ 00 00 00 OJ 0J OJ 0J 0J H H H O O o o o o o o o o o o o o o o o o o o o o o o o O O O VO VO vo vo vo o vo vo vo VO 00 00 00 00 00 00 00 00 00 00 si si si si si to H O VO 00 si σv Ul 4k OJ to H o vo 00 si cn Ul 4k J to H o vo 00 si cn Ul o oo oo oo o o o o II II II II II II II II O O O O O w w w o o o o o o o oII o II ow wo wo ow wo ow ow wo wo ow IW OO OJ OJ OJ OJ OJwOJ OJw 1^ w w w o o o o o W w w w w o o o o o W w w w w o o o o o w w w w w w w w w w w w w w w W Ito 00 oo 00 OJ 00 OJ 0J 00 oo 00 OJ J OJ OJ OJ O O O O O O O O O O O O O O O O O O O O O O O O O O O O IW W W W W W W W W W W W W W W W W W W W W W W W W W W W W |k OO OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ 00 OJ OJ 00 00 00 OJ OJ J OJ J 0J OJ OJ 0J OJ J 00 00 OJ OJ 00 OJ 0J 0J 00 J 2! H H H H H H H H H H H H H H H H H H H H H H O OJ to to to to to to to to to to H H H H H H H H H O O O O O O O o VO 00 s] CΛ Ul 4k 0J to H o VO 00 si cn Ul 00 to H O VO 03 s] CΛ Ul 4k 00 II II II II II ιι o o o o o o o o o O_ o o o o o o w w w w w w w w w w Ow Ow Ow Ow Ow Ow Ow O w O O O O O O O O O O O O O O O O O O Ow O O Ow Ow O O O O O Ow wO wO O Ow wO O O OwJ OJwOJwOJwOJwOwJ OJwOJwOJwOJwOJwOJw 0O O3 OO 0O 0O 0O 0O O3 0O 0O 0θ 0O O3 00 00 O3 sl 15 OJ OJ OJ 00 00 OJ 00 00 oo 00 00 OJ OJ OJ 00 OJ OJ OJ OJ OJ OJ OJ OJ OJ J OJ OJ H H H H H H H H H H H H H H H H H H H H H H H H H H H Ul Ul Ul Ul Ul Ul on Ul Ul k- 4k 4k 4 4 k 4 4k k OJ OJ OJ OJ OJ ω OJ J 00 00 si CΛ Ul J to o VO 00 s] <Λ Ul 4k 00 to H O VO 00 s] CΛ Ul J OJ to H o o o o o o o o o o o o o o o o o o o o o o o o II w w w w o o o o o o o o o o o o o o o o o o o o o o o o o o JW O O O oO oO oO oO oO oO oO OwJ OJw OwJ OJw OJw OwJ OwJ OJw OJw OwJ w 00 OJ OJ OJ OJ J J CΛ 00 O O O O O O O O O O O O O O O O O O O O O O O O O O O O IW w O W W O wO wO wO wO wO wO wO wO wO wO wO wO wO wO w w w k O W O W |4 O O'WO wO wO wO wO w O O O 00 00 00 00 00 00 03 03 00 00 00 03 03 00 00 00 00 00 03 03 00 00 00 00 ID o w w w w w o o o o o w w w w w o o o o o w w w w w o IW 33 33 33 33 33 33 33 33 3* 33 33 33 H |t w o O wJ O O O O O O O O O O O O O O O O O O O O O O O O O O O O IW W W W W W W W W W W W W W W W W W W W W W W W W W W W W |4k O O O O O O O O O O O O O O O O O O O O O O O O O O O O si ID I? *w *# OJ OJ OJ OJ 00 oo OJ 0J 0J J 0J 0J 0J OJ 0J OJ OJ 0J 0J 0J OJ J OJ 0J 0J 0J OJ OJ 25 to to to to to to to to to to to to t to to H H H H H H H H H H H H H O H H H H H O o o o o o o o o o vo vo VO VO O VO O VO O O 00 00 00 * 4k OJ to H O vo 00 j CΛ Ul 4 OJ to H o vo 00 si CΛ Ul 4k OJ to H o VO 00 si II II II II II II II II II II o o o o o o o o o o o o o o o o o o o o o o o o o o o o w W W W W W W W W W o o o o o o o o w o o o o o o o o o o o o o o o o > tM tM tM tM tM tM tM C CJ 0 > LJ C0 CJ » CΛ Ul o o o o o o o o o o o o o o o o o o o o o o o o„ o oo o o IW o oO oO oO oO Oo oO oO oO Oo Oo oO oO oO oO oO Oo Oo oO oO wO wo " ow ~ ow - ow w w w l* » ' o o o W W W W W W W W W W W W W W W W W W W W OO OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OO OJ OJ OJ 00 03 00 CO 00 03 00 O3 00 O3 O3 CO 00 00 00 CO 00 00 00 03 sl ID pa b 3 OJ OJ OJ OJ OJ J 00 OJ OJ OJ OJ J 00 OJ 00 0J 00 00 00 00 00 0J ω 0J 00 OJ OJ OJ to t to to to to to to t to t t to to to to to to to to to to to to t to to to p 4k 4k *>. J J OJ OJ OJ OJ OJ OJ 00 OJ to t to to to to to to to t H H H H H oa to H O O 00 si cn ui 4k OJ to H O vo 00 si cn ui 4k J to H O vo 00 si cn Ul ow ow ow wo ow ow ow ow w w w o o o o o w w w w w o o o o o w w w w w o o o o o W W W W W W W W W W w w w IW |to OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJw s] sl sl O3 03 O3 0O O3 00 00 O3 00 O3 O3 00 00 03 O3 00 0O 00 0O 0O ID ** 00 00 oo OJ 00 00 00 OJ 0J 00 J 00 OJ OJ 0J 00 OJ t t to to t t to to to to to to to to to to to si si cn σv cn CΛ CΛ CΛ CΛ CΛ CΛ CΛ Ul Ul Ul Ul Ul H O vo 00 si CΛ Ul 4k OJ to H O VO 00 si cn Ul w w w w w w w Wo Wo Wo Wo Wo w w w w w Wo Wo oW Wo Wo w w |toIW OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ W O O O O O O O O O O O O O O O O O O O O O O O O O O O O O IW O O O O O O O O O O O O O O O O O O O O O O O O O O O O O |4k O O O O O O O O O O O O O O O O O O O O O O O O O O O O W W W W w w w w w w w w w w w w w w w w w w w w w w w w OJ OJ OJ OO OO OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OJ OO OJ OJ OJ OJ OJ OO OJ OJ OJ OO OJ OJ Table 12 (Continued) No. R l E 2 R 3 No. M. P. 3272 OCOCH 3 H CHO COCH-. 7 3273 OCOCH 3 H CH 2 OH COCH- 7 3274 OCOCH3 H C0 2 H COCH- 7 No . 1- E 2 D No. M. 3275 OH CH 2 CH, CH 3 8 3276 OH H 2 H CH 3 8 3277 OH CH, CH=CH 2 CH 3 8 3278 OH CH 2 CHOHCH 2 OH- (R) CH 3 8 3279 OH CH, CHOHCH 2 OH- (S) CH 3 8 3280 OH CH, CHO CH 3 8 3281 OH CH, CH 2 OH CH 3 8 3282 OH CH, CH 2 H CH 3 8 3283 OH CH, C0 2 H 3 CH 3 8 3284 OH CH, CH=NOH CH 3 8 3285 OH CH : CHOHCH= =CH 2 -(R) CH 3 8 3286 OH CH : CHOHCH= =CH 2 -(S) CH 3 8 3287 OH H CH 3 CH 3 8 3288 OH H H CH 3 8 3289 OH H CH=CH 2 CH 3 8 3290 OH H CHOHCH 2 ,OH- (R) CH 3 8 3291 OH H CHOHCH 2 ,OH- (S) CH 3 8 3292 OH H CHO CH 3 8 3293 OH H CH 2 OH CH 3 8 • 3294 OH H C0 2 H CH 3 8 * 3295 OH H C0 2 CH 3 CH 3 8 3297 OH H CHOHCH= =CH 2 -(R) CH, 8 J 00 OJ OJ OJ 00 00 0J 0J OJ J 0J OJ J J J OJ OJ 00 0J OJ 00 OJ 00 OJ OJ OJ OJ OJ 00 OJ J OJ 00 0J 00 OJ J 0J 0J OJ OJ 00 OJ OJ OJ OJ OJ OJ J OJ J OJ OJ t to p oi to tO M to to to to H H H H H o o 4k J o o o o o o o o o vo CΛ Ul to H o VO 00 si Ul k J to H O 00 si tΛ Ul 4». OJ to H o vo 00 oO oO oO oO oO oO oO oO OII W W W W W W W W o II oII oII oi o II oII oII oII oII ow Iw OJ OJ OJ OJ OJ OJ OJ OJ * w w w w o W oW oW oW oW w w w w oW oW Wo oW w w w w w oW oW oW oW oW w |tIoW OJ OJ J OJ J OJ OJ J OJ to J J J OJ cn w Ow Ow Ow Ow Ow Ow O OJw O O O O O O O O O O O O O O O O O O O O IW OO OJ OJ OJ OJ OJ OJ OwJ OwJ OwJ OwJ OwJ OwJ OwJ OwJ OwJ OwJ OwJ OOwOwJ OwJ OwJ OwJ OwJ OJwOJwOwJ \*> 00 00 00 00 03 00 00 00 00 03 00 00 00 00 00 00 00 00 00 00 00 03 00 03 00 00 00 00 ID Table 13 (Continued) o. -*!- R 3 *4 No. M. 3327 0C0CH 3 H C0 2 H CH 3 8 3328 OH CH 3 CH 3 CH 3 7 3329 OH CH 3 H CH 3 7 3330 OH CH 3 CHO CH 3 7 3331 OH CH 3 CH 2 OH CH 3 7 3332 OH CH 3 C0 2 H CH 3 7 3333 OH H CH 3 CH 3 7 3334 OH H H CH 3 7 3335 OH H CHO CH 3 7 3336 OH H CH 2 OH CH 3 7 3337 OH H C0 2 H CH 3 7 3338 =0 CH 3 CH 3 CH 3 7 3339 =0 CH 3 H CH 3 7 3340 =0 CH 3 CHO CH 3 7 3341 =0 CH 3 CH 2 0H CH 3 7 3342 =0 CH 3 . C0 2 H CH 3 7 3343 =0 H CH 3 CH 3 7 3344 =0 H H CH 3 7 3345 =0 H CHO CH 3 7 3346 =0 H CH 2 OH CH 3 7 3347 =0 H C0 2 H CH 3 7 3348 OCH 3 CH 3 CH 3 CH 3 7 3349 OCH 3 CH 3 H CH 3 7 3350 OCH 3 CH 3 CHO CH 3 7 3351 OCH 3 CH 3 CH 2 OH CH 3 7 3352 OCH 3 CH 3 C0 2 H CH, 7 3353 OCH 3 H CH 3 CH, 7 3354 OCH-, H H CH, 7 Table 13 (Continued) NO . '-1- E 2 R 3 D No. M. 3355 OCH 3 H CHO CH 3 7 3356 0CH 3 H CH 2 OH CH 3 7 3357 OCH 3 H C0 2 H CH 3 7 3358 OCOCH, CH 3 CH 3 CH 3 7 3359 OCOCH, CH 3 H CH 3 7 3360 OCOCH, CH 3 CHO CH 3 8 3361 OCOCH, CH 3 CH 2 OH CH 3 7 3362 OCOCH, CH 3 C0 2 H CH 3 7 3363 OCOCH, H CH 3 CH 3 7 3364 OCOCH, H H CH 3 7 3365 OCOCH, H CHO CH 3 7 3366 OCOCH, H CH 2 OH CH 3 7 3367 OCOCH, H C0 2 H CH 3 7 NOTE: When the D-ring is piperidine or the N-oxide thereof, upper side chain (R) is not the ergosterol side chain. SYNTHETIC EXAMPLES The following examples describe synthetic procedures employed in production of specific compounds within the scope of the present invention. Unless otherwise indicated, all percentages in the following Examples and in the General Procedures set forth above are by weight and all temperatures are reported in degrees Celsius (°C) . All parts for reaction and chromatography solvents were determined by volume. All proton NMR spectra are referenced to tetramethylsilane (TMS) at 0.00 ppm. The following abbreviations are employed in the Examples: NMR: nuclear magnetic resonance spectroscopy IR: infrared spectroscopy MS: mass spectroscopy HRMS: high resolution mass spectroscopy El: electron impact Cl: chemical ionization EA: elemental analysis .p. : melting point MPLC: medium pressure liquid chromatography Rf: retention factor on silica gel thin layer chromatography Particular intermediates or products are identified by reference to the numbered compounds in the general synthetic procedures summarized above. Physical data for various compounds produced by procedures substantially corresponding to the description contained in each Example are provided following the individual Examples. EXAMPLE 1 Preparation of 15-Oxadihydrolanosterol (Compound 11a) A. Preparation of 4,4-dimethyl-3b-r C4- methoxybenzyl)oxyl-5a-cholesta-8,14-diene (Compound 2b) To a stirred solution of sodium hydride (50% in oil, 23.2 g, washed with 3 portions of 50 ml of dry tetrahydrofuran) in dry tetrahydrofuran (800 ml) and anhydrous N,N-dimethylformamide (200 ml) at 0° was added 4,4-dimethyl-5a-cholesta-8,14-dien-3b-ol (Compound 2a) (40 g, 96.8 m ole) and the mixture was stirred for 10 min. 4-Methoxybenzyl chloride [16.8 ml, 193.6 mmole, prepared by the method described by Schriner, et al. J. Orσ. Chem. , 10: 228 (1945)] was added and the mixture was stirred for 24 hr. at 70° under nitrogen atmosphere. After cooling to 5° water (80 ml) was added dropwise to the mixture and it was stirred for 5 min. It was poured into ether (1 L) and the layers were separated and the organic phase was washed with water (3 X 300 ml) . The combined aqueous layers were extracted with additional diethyl ether (300 ml) . The combined organic solutions were washed with brine, and dried over anhydrous magnesium sulfate and evaporated under reduced pressure to afford a crystalline solid residue. Recrystallization from diethyl ether and methanol provided 42.5 g of purified Compound 2b. The mother liquor residue was column chromatographed on silica gel with elution by 1:9 ethyl acetate - hexane to give additional 8.2 g of Compound 2b (50.7 g total, 98% yield) . Physical Data (Compound 2b) : NMR (300 MHz, CDC1 3 ) ; delta 7.28 (d, J=8.7 Hz, 2H) , 6.87 (d, J=8.7 Hz, 2H) , 5.35 (br s, 1H) , 4.60 (d, J=11.4 Hz, 1H) , 4.37 (d, J=11.4 Hz, 1H) , 3.80 (s, 3H) , 2.92 (dd, J=3.6 Hz, 11.7 Hz, 1H) , 2.40-1.00 (m, 24H) , 1.04 (s, 3H) , 0.99 (s, 3H) , 0.93 (d, J=6.3 Hz, 3H) , 0.87 (d, J=6.3 Hz, 6H) , 0.86 (s, 3H) , 0.80 (s, 3H) ; IR (KBr) : 2939, 2888, 2870, 1513, 1470, 1249, 1101, 1095 cm "1 . B. Preparation of 4,4-dimethyl-3b-r (4- methoxybenzvHoxyl-5a-cholest-8-ene-14a, 15a-diol (Compound 3b) To a solution of the 8,14-diene (Compound 2b) (16 g, 30 mmole) and dry pyridine (24.4 ml, 300 mmole) in benzene (640 ml) at 0° was added a solution of osmium tetroxide (8 g, 31.4 mmole) in methylene chloride (160 ml) dropwise over a period of 1 hr. The dark brown mixture was stirred for 2 hr. at room temperature. At the end of this period hydrogen sulfide (Union Carbide Corp., Linde Division, Danbury, CT 06817) was bubbled through the solution for about 20 min. and the black precipitates that formed were filtered off through Celite (Manville Products Corp. Denver, CO) . The filtrate was evaporated under reduced pressure to afford a brown solid residue (17.5 g) of the diol (Compound 3b) . This material was routinely used for further transformations without purification. An analytical sample of Compound 3b was obtained in the following manner: A solution of the compound in benzene was filtered through a plug of silica gel (Kieselgel 60, EM Science, 111 Woodcrest Rd. , Cherry Hill, NJ 08034-0395) with elution by 2:8 ethyl acetate - hexane and the solvents were evaporated under reduced pressure to give a white crystalline solid. This was recrystallized from ethyl acetate and hexane to give a chromatographically homogeneous sample of Compound 3b. Physical Data (Compound 3b) : m.p. = 124-126.5° (decomposed); NMR (300 MHz, CDC1 3 ): delta 7.28 (d, J=8.7 Hz, 2H) , 6.87 (d, J=8.7 Hz, 1H) , 4.66 (d, J=11.4 Hz, 1H) , 4.37 (d, J=11.4 Hz, 1H) , 2.45 (d, J=9.9 Hz, 1H) , 2.35-0.80 (m, 26H) , 1.02 (s, 3H) , 0.97 (s, 3H) , 0.86 (d, J=6.3 Hz, 6H) , 0.86 (d, J=6.6 Hz, 3H) , 0.85 (s, 3H) , 0.69 (s, 3H) ; IR (KBr) : 3406, 2949, 2869, 2841, 1615, 1514, 1465, 1376, 1360, 1346, 1245, 1117, 1031 cm "1 ; HRMS for C 37 H 56 0 3 (M-H 2 0) : Calcd. 548.4229; found 548.4252. C. Preparation of 4 , 4-Dimethyl-3b-r (4- methoxybenzyl) ozv1-15-oxo-5a-14 , 15- secocholest-8-en-14-one (Compound 4b) To a stirred solution of the diol (Compound 3b) (30 mmole in dry benzene (880 ml, distilled from calcium hydride) in the dark was added lead tetraacetate (14 g, 31.5 mmole Aldrich, recrystallized from acetic acid) in small portions over a period of 1 hr. and the mixture was stirred at room temperature for 1 hr. under nitrogen atmosphere and in the dark. The mixture was filtered through Celite and the filter cake rinsed with benzene several times. Evaporation of the solvent under reduced pressure provided an oily residue (17.1 g) of crude keto-aldehyde (Compound 4b) . The crude product was routinely used for further transformations without purification. An analytical sample of Compound 4b was obtained by column chromatography on silica gel with elution by 1:9 ethyl acetate - hexane then 2:8 ethyl acetate - hexane. Physical Data (Compound 4b) : NMR (300 MHz, CDCl 3 ) : delta 9.57 (s, 1H) , 7.28 (d, J=8.4 HZ, 2H) , 6.87 (d, J=8.4 Hz, 2H) , 4.60 (d, J=11.4 HZ, 1H) , 4.40 (d, J=11.4 Hz, 1H) , 3.80 (s, 3H) , 3.01 (dd, J=4 Hz, 11.7 HZ, 1H) , 2.58-1.00 (m, 24H) , 1.07 (S, 3H) , 1.02 (S, 3H) , 0.97 (s, 3H) , 0.92 (d, J=6.9 Hz, 3H) , 0.87 (s, 3H) , 0.86 (d, J=6.6 Hz, 6H) ; IR (film) : 2951, 2868, 2719, 1725, 1654, 1623, 1617, 1514, 1465, 1458, 1247, 1098, 1037, cm "1 ; HRMS for C 36 H 56°4 ( M+ ) : Calcd. 564.4179; found 564.4209. D. Preparation of 15.15-Dimethoxy-4 ,4-dimethyl- 3b-f f4-methoxybenzyl ' ) oxy!5a-14 ,15- secocoholest-8-en-14-one (Compound 5b) To a solution of the keto-aldehyde (Compound 4b) (30 mmole) in methanol (600 ml) were added trimethyl orthoformate (Aldrich) (48 ml, 439 mmole) and camphorsulfonic acid (Aldrich) 3.2 g, 13.8 mmole) and the mixture was stirred at room temperature for 2 hr. under nitrogen atmosphere. At the end of the stirring saturated sodium bicarbonate solution (120 ml) was added and most of the methanol was evaporated under reduced pressure. The residue was extracted with diethyl ether (3 x 500 ml) and the combined extracts were washed with brine, dried over anhydrous magnesium sulfate, and evaporated to give an oil residue (18.12 g) of the crude keto-acetal (Compound 5b) . The crude material was normally used for the next reaction. For analytical purposes, Compound 5b was column chromatographed on silica gel with elution by 2:8 ethyl acetate - hexane affording a purified sample of the Compound 5b. Physical Data (Compound 5b) : NMR (300 MHz, CDCI3) : delta 7.27 (d, J=8.4 Hz, 2H) , 6.86 (d, J=8.4 Hz, 2H) , 4.60 (d, J=11.4 Hz, IH) , 4.37 (d, J=11.4 Hz, IH) , 4.05 (t, J=6 Hz, IH) , 3.26 (s, 3H) , 3.21 (s, 3H) , 2.90 (dd, J=4 Hz, 12 Hz, IH) , 2.60 (dd, J=5 HZ, 17 Hz) , 2.40-0.90 ( , 26H) , 1.08 (s, 3H) , 1.10 (s, 3H) , 0.99 (d, J=6.5 Hz, 6H) ; IR (film): 2952, 2869, 1661, 1615, 1514, 1464, 1458, 1248, 1123, 1099, 1 1007777 ccmm ""11 ;; HHRRMMΣS for C 37 H 54 0 3 : Calcd. 546.4073; found 546.4126, E. Preparation of 15,15-Dimethoxy-3b-r (4- * methoxybenzyl)oxyl-14 ,15-secolanost-8-en-l4-ol (Compound 6b) To a solution of the keto-acetal (Compound 5b) (30 mmole) in dry diethyl ether (600 ml) was added a solution of methyl magnesium bromide in diethyl ether (3 ml, Aldrich) 50 ml, 150 mmole) dropwise at 0° and the mixture was stirred at 30-40° for 2 hr. After cooling it to 0°, hydrochloric acid (0.5 ml, 400 mmole) was added slowly and it was stirred for about 1 min. The product was extracted with diethyl ether (3 x 500 ml) , and the combined extracts washed with water and brine and dried over anhydrous magnesium sulfate) . Evaporation of the solvent afforded an oily residue of the tricyclic alcohol (Compound 6b) . The crude product was routinely used for next reaction without purification. An analytical sample of the Compound 6b was obtained by column chromatography on silica gel with elution by 2:8 ethyl acetate - hexane. Physical Data (Compound 6b) : NMR (300 MHz, CDCI3): delta 7.29 (d, J=8.4 Hz, 2H) , 6.88 (d, J=8.4 Hz, 2H) , 4.61 (d, J=11.4 Hz, IH) , 4.38 (d, J=11.4 Hz, IH) , 4.21 (dd, J=2.7 Hz, 9 Hz, IH) , 3.81 (s, 3H) , 3.49 (s, 3H) , 3.48 (s, 3H) , 2.95 (dd, J=3.9 Hz, 11.7 Hz, IH) , 2.35 (dd, J=5.4 Hz, 18 Hz, IH) , 2.20-0.90 (m, 24H) , 1.19 (s, 3H) , 1.01 (S, 3H) , 0.98 «* (s, 3H) , 0.93 (d, J=6.9 Hz, 3H) , 0.90 (s, 3H) , 0.86 (d, J=6.3 Hz, 6H) , 0.86 (s, 3H) ; HRMS for 3 gH 56 0 2 » • (M-2CH 3 OH-H 2 0) : Calcd. 544.4280; found 544.4258. F. Preparation of 3b-f f4-Methoxybenzyl')oxyl-14a- oxa-D-homo-lanost-8-en-15-ol (Compound 7b) A solution of the tricyclic alcohol (Compound 6b) (30 mmole) in methylene chloride (160 ml) and 80% aqueous acetic acid (600 ml) was stirred at room temperature for 2 days and the solvents were evaporated under reduced pressure to give an oily residue of the cyclic hemiacetal (Compound 7b) and the cyclic acetal (Compound 7c) . Compound 7b was separated from Compound 7c by column chromatography on silica gel with elution by 15:85 ethyl acetate - hexane followed by 3:7 ethyl acetate - hexane to afford 3.5 g of the Compound 7c (Rf = 0.48, 2:8 ethyl acetate - hexane) and 11.6 g of the Compound 7b (Rf = 0.23, 2:8 ethyl acetate - hexane) as oils. The compound 7c was dissolved in methylene chloride (55 ml) 80% aqueous acetic acid (160 ml) and 1M hydrochloric acid (1 ml) and the solution was stirred at room temperature for 1 day. It was worked up and purified as described above to provide an additional 1.9 g of Compound 7b (total 13.5 g, 77.5% overall yield from Compound 3b) and 1.2 g of Compound 7c (6.7% overall yield from Compound 3b) . Physical Data (Compound 7b) : NMR (300 MHz, CDC1 3 ): delta 7.28 (d, J=8.7 Hz, 2H) , 6.87 (d, J=8.7 Hz, 2H) , 4.60 (d, J=11.5 Hz, IH) , 4.52 (t, J=7.5 HZ, IH) , 4.37 (d, J=11.5 Hz, IH) , 3.80 (Ξ, 3H) , 2.93 (dd, J=4.2 Hz, 11.7 Hz, IH) 2.32 (dd, J=4 Hz, 11 Hz, IH) , 1.95-0.90 (m, 24H) , 1.17 (s, 3H) , 0.99 (s, 3H) , 087 (d, J=6.6 Hz, 6H) , 0.85 (s, 3H) ; HRMS for C 38 H 5 6 °2 : Calcd - 544.4280; found 544.4197. G. Preparation of 3b- \ 4-Methoxybenzyl)oxyl- 14a-oxa-D-homo-lanosta-8,15-diene (Compound 8b) To a stirred solution of the cyclic hemiacetal (Compound 7b) (13.5 g, 23.2 mmole) and anhydrous triethylamine (Aldrich) (33 ml, 232 mmole, distilled from calcium hydride) in dry methylene chloride (310 ml, distilled from phosphorous pentoxide) at 0° was added methanesulfonyl chloride (Aldrich) (5.43 ml, 69.6 mmole, filtered freshly through basic alumina) dropwise over a period of 5 min. and the mixture was stirred at 0° to 20° for 1 hr. under nitrogen atmosphere. The reaction mixture was poured into diethyl ether (1 L) and the solution was washed with water, saturated sodium bicarbonate solution, water and brine. After drying over anhydrous magnesium sulfate the solvents were evaporated under the reduced pressure to give an oily residue of the glycal (Compound 8b) . This crude material was normally used for next reaction without purification. The analytical sample was prepared by column chromatography on silica gel with elution by 1:9 ethyl acetate - hexane to afford a purified sample of Compound 8b. Physical Data (Compound 8b) : NMR (300 MHz, CDCI 3 ): delta 7.28 (d, J=8 Hz, 2H) , 6.88 (d, J=8 Hz, 2H) , 6.21 (dd, J=2.5 Hz, 6 Hz, IH) , 4.61 (d, J=11.5 Hz, IH) , 4.52 (dd, J=1.2 Hz, 6.3 Hz, IH) , 4.38 (d, J=11.5 Hz, IH) , 3.81 (s, 3H) , 2.94 (dd, J=4 Hz, 11 Hz, IH) , 2.30-0.90 (m, 22H) , 1.23 (s, 3H) , 1.01 (s, 3H) , 0.98 (s, 3H) , 0.87 (d, J=7 Hz, 6H) , 0.87 (s, 3H) , 0.85 (s, 3H) ; HRMS for C 38 H 56 0 2 (M-H 2 0) : Calcd. 544.4280; found 544.4281. H. Preparation of 3b-r4-Methoxybenzyl)oxyl- 14a-oxa-D-homo-lanost-8-ene-15,16-diol (Compound 9b) To a stirred solution of the glycal (Compound 8b) (23.2 mmole) and pyridine (18.8 ml, 232 mmole) in benzene (600 ml) at 0° was added a solution of osmium tetroxide (6 g, 23.6 mmole) in methylene chloride (120 ml) over a period of 10 min. and the dark brown solution was stirred at room temperature for 1 hr. At the end of the stirring hydrogen sulfide gas was bubbled through the solution for about 15 min. and the resulting black precipitates were removed by filtration through Celite. The filter cake was rinsed with ethyl acetate several times and the filtrate was evaporated under reduced pressure to give a dark brown oily residue of the diol (Compound 9b) as a mixture of diastereomers. Due to the complexity and instability of the product, analysis was carried out after the next transformation. Physical Data (Compound 9b) : NMR (300 MHZ, CDC1 ): delta 7.29 (d, J=8 Hz, 2H) , 6.88 (d, J=8 Hz, 2H) , 4.60 (d, J=12 Hz, IH) , 4.39 (d, J=12 Hz, IH) , 4.34 (d, J=7 Hz, IH) , 3.81 (s, 3H) , 3.56 (dd, J=8.5 Hz, 11.5 Hz, IH) , 3.45 (brs, IH) , 2.95 (dd, J=4 Hz, 11 Hz, IH) , 2.35-0.90 (m, 23H) , 1.18 (s, 3H) , 1.12 (d, J=6 HZ, 3H) , 0.97 (s, 3H) , 0.89 (s, 3H) , 0.88 (d, J=6 Hz, 6H) , 0.83 (s, 3H) . I. Preparation of 16-Methoxy-3b-r (4- methoxybenzyl)oxyl-15-oxa-lanost-8-ene (Compound 10b) To a solution of the diol (Compound 9b) (23.2 mmole) in diethyl ether (550 ml) , methanol (550 ml) and water (140 ml) were added sodium metaperiodate (Aldrich) (33 g, 154 mmole) and camphorsulfonic acid (7 g, 30 mmole) and the mixture was stirred at room temperature for 20 hrs. After addition of saturated sodium bicarbonate (350 ml) the mixture was extracted with diethyl ether (3 x 500 ml) and the combined organic layers were washed with brine. The aqueous layers were re-extracted with diethyl ether (300 ml) and the extract was washed with brine. The combined extracts were dried over anhydrous magnesium sulfate and evaporated under reduced pressure to give a dark brown oily residue (13 g) of crude five-membered cyclic acetal (Compound 10b) . Product of this purity was routinely used for next transformation without further purification. The analytical sample of purified Compound 10b was obtained by a preparative thin layer chromatography on silica gel with elution by 1:9 ethyl acetate - hexane. Physical Data (Compound 10b) : NMR (300 MHz, CDC1 3 ): delta 7.29 (d, J=8.7 Hz, 2H) , 6.88 (d, J=8.7 Hz, 2H) , 4.59 (d, J=11.6 Hz, IH) , 4.53 (d, J=5.7 Hz, IH) , 4.38 (d, J=11.6 Hz, IH) , 3.81 (s, 3H) , 3.36 (s, 3H) , 2.98 (dd, J=4.2 Hz, 11.5 Hz, IH) , 2.20-0.80 (m, 22H) , 1.13 (s, 3H) , 0.98 (s, 3H) , 0.95 (d, J=5.4 HZ, 3H) , 0.95 (s, 3H) , 0.88 (s, 3H) , 0.87 (d, J=6.3 HZ, 6H) , 0.83 (s, 3H) ; IR (film): 2945, 2869, 1514, 1459, 1375, 1347, 1171, 1108, 1094, 1038, 1011 cm "1 ; HRMS for 37 H 56 0 3 : Calcd. 548.4230; found 548.4203. J. Preparation of 15-Oxa-dihydrolanosterol (Compound 11a) To a solution of Compound 10b (23.2 mmole) and triethylsilane (Aldrich) (16 ml, 0.1 mmole) in dry methylene chloride (420 ml) was added boron trifluoride etherate (Aldrich) (2.7 ml, 22 mmole) dropwise and the mixture was stirred at room temperature for 3 hr. under nitrogen atmosphere. The reaction was quenched by addition of saturated sodium bicarbonate and the products were extracted with methylene chloride ( 3 x 400 ml) . The combined extracts were washed with water, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to give a dark brown oily residue. The oil was purified by column chromatography on silica gel with elution by 1:9 ethyl acetate - hexane followed by 2:8 ethyl acetate - hexane to provide 15-oxa-dihydrolanosterol (Compound 11a) (4.0 g, 40% overall yield from Compound 7b. Physical Data (Compound 11a) : NMR (300 MHz, CDC1 3 ): delta 3.76 (t, J=9 Hz, IH) , 3.44 (dd, J=8.4 Hz, 9 Hz, IH) , 3.25 (dd, J=4.8 Hz, 11.4 HZ, IH) , 2.25-0.80 (m, 23H) , 1.11 (s, 3H) , 1.02 (s, 3H) , 0.95 (d, J=6.3 Hz, 3H) , 0.95 (s, 3H) , 0.86 (d, J=6.6 Hz, 6H) , 0.86 (s, 3H) , 0.81 (s, 3H) ; IR (film): 3566, 2934, 1466, 1375, 1097, 1079, 1039, 1030 cm "1 ; HRMS for C 29 H 50 O 2 (M+) : Calcd. 430.3811; found 430.3772; for C 28 H 47 0 2 (M-CH 3 ): Calcd. 415.3576; found 415.3583. EXAMPLE 2 Preparation of 4,4-Dimethyl-15-oxa-5a- cholest-8-en-3b-ol (Compound 17a) K. Preparation of 15,15-Dimethoxy-4,4-dimethyl- 3b-r 4-methoxybenzyl)oxyl-5a-14,15- Secoholest-8-en-14-ol (Compound 12b) To a-stirred solution of the keto-aldehyde (Compound 5b) (2.7 g, 4.42 mmole) in a dry methylene chloride (60 ml) was added a solution of diisobutyl aluminum hydride in hexane (Aldrich) 1 M/L, 8.84 ml, 8.84 mmole) dropwise at 0° and the mixture was stirred at 0° for 1 hr. at room temperature for 1 hr. The excess reagent was destroyed by dropwise «l » addition of methanol (0.64 ml) at 0° and stirring for 10 min. Then water (1.1 ml) was added dropwise to the *, mixture and it was stirred at room temperature for 1 hr. The resulting precipitates were filtered off over Celite and the filtrate was evaporated under reduced pressure to give a white foamy residue of the secondary allylic alcohol (Compound 12b) as a mixture of diastereomers. The crude material was used in the next reaction without purification. L. Preparation of 4,4-Dimethyl-3b-r f4- methoxybenzyl)oxy]-14a-oxa-D-homo-5a- cholest-8-en-15-ol (Compound 13b) Following the method described for Compound 7b (Example 1-F) the secondary allylic alcohol (Compound 12b) (4.42 mmole) was transformed to the six-membered cyclic hemiacetal (Compound 13b) (0.81 g) and the corresponding cyclic acetal (Compound 13c) (1.34 g) as oils. The Compound 13c was resubjected to the reaction to afford an additional 0.69 g of Compound 13b (total 1.5, 60% overall yield from Compound 12b) after purification by column chromatography on silica gel with elution by 15:85 ethyl acetate - hexane. Physical Data (Compound 13b) : NMR (300 MHz, CDC1 3 ) delta 7.28 (d, J=8.5 Hz, 2H) , 6.86 (d, J=8.5 Hz, 2H) , 4.69 (t, J=6 Hz, IH) , 4.59 (d, J=12 Hz, IH) , 4.37 (d, J=12 Hz, IH) , 3.80 (s, 3H) , 2.92 (dd, J=4 Hz, 12 Hz, IH) , 2.20-0.90 (m, 26H) , 0.99 (s, 6H) , 0.97 (s, 3H) , 0.93 (d, J=6.5 Hz, 3H) , 0.88 (d, J=6.5 HZ, 6H) , 0.86 (s, 3H) ; IR (film): 3413, 2952, 2930, 2870, 1654, 1636, 1465, 1457, 1376, 1365, 1087, 1065, 1036, 1013 cm "1 . M. Preparation of 4,4-Dimethyl-3b-r (4- methoxylbenzyl)oxyl-14a-oxa-D-homo-5a- cholest-8,15-diene (Compound 14b) Following the method described for Compound 8b (Example 1-G) the cyclic hemiacetal (Compound 13b) (0.15 g, 0.26 mmole) was transformed to the glycal (Compound 14b) in 87% yield. The crude product from the reaction was routinely used for next conversion without purification. The analytical sample was obtained by filtering a concentrated solution of the crude Compound 14b in diethyl ether through a Florisil (Fischer Scientific) column with elution by diethyl ether. N. Preparation of 4,4-Dimethyl-3b-r (4- methoxybenzyl)oxyl-14a-oxa-D-homo-5a-cholest- 8-ene-15,16-diol (Compound 15b) Following the method described for Compound 9b (Example 1-H) the glycal (Compound 14b) (0.126 g, 0.23 mmole) was transformed to the diol (Compound 15b) . The crude product was used for next reaction without purification. 0. Preparation of 4,4-Dimethyl-16-methoxy-3b- f (4-methoxybenzyl)oxyl-15-oxa-5a-cholest- 8-ene (Compound 16b) Following the method described for Compound 10b (Example l-I) the diol (Compound 15b) (0.23 mmole) was transformed to the five-membered cyclic acetal (Compound 16b). The crude product (0.139 mg) was used for the next reaction without purification. P. Preparation of 4.4-Dimethyl-15-oxa-5a-cholest- 8-en-3b-ol (Compound 17a) Following the method described for Compound 11a (Example 1-J) the cyclic acetal (Compound 16b) (0.23 mmole) was converted to the 15-oxa steroid (Compound 17a) (0.04 g, 35.7% overall yield from Compound 13b). Physical Data (Compound 17a) : NMR (300 MHz, CDCl 3 ); delta 3.96 (t, J=8.1 Hz, IH) , 3.72 (s, IH) , 3.65 (br s, IH) , 3.51 (dd, J=9.9 Hz), 8.1 Hz, IH) , 3.25 (dd, J=4.5 Hz, 11.1 Hz, IH) , 2.27 (m, IH) , 2.02-0.70 (m, 21H) , 1.01 (s, 3H) , 1.00 (s, 3H) , 0.97 (s, 3H) , 0.95 (d, J=6.6 Hz, 3H) , 0.86 (d, J=6.6 Hz, 6H) , 0.81 (s, 3H) ; IR (film): 3448, 2951, 2932, 2869, 1465, 1458, 1376, 1365, 1091, 1032 cm "1 . EXAMPLE 3 Preparation of 4,4-Dimethyl-15-oxa-l4a- vinyl-5a-cholest-8-en-3b-ol (Compound 23a) Q. Preparation of 15,15-Dimethoxy-4-4-dimethyl- 3b-r f4-methoxybenzyl)oxy1-14-vinyl-5a-14,15- secocholest-8-en-14-ol (Compound 18b) To a stirred solution of the keto-acetal (Compound 5b) (8.2 g, 13.4 mmole) in dry tetrahydrofuran (270 ml) was added dropwise a solution of vinyl magnesium bromide in THF (1.6 M/L, Aldrich) (82 ml, 131.2 mmole) at 0° and the mixture was stirred at 70° for 2 hr. under nitrogen atmosphere. After cooling to 0° about 300 ml of 0.5 M - hydrochloric acid was added to the solution and it was stirred for 0.5 min. The product was extracted with diethyl ether (3 x 300 ml) and the combined extracts were washed with water and brine. The ethereal solution was dried over anhydrous magnesium sulfate and evaporated under reduced pressure to give the tricyclic alcohol (Compound 18b) as an oil. The crude product was routinely used for the next reaction without purification. Physical Data (Compound 18b) : IR (film): 3450, 2952, 2870, 1514, 1466, 1247, 1121, 1099, 1078, 1053, 1043 cm "1 . R. Preparation of 4,4-Dimethyl-3b-r (4- methoxybenzyl)oxyl-14a-oxa-14a-vinyl-D-homo- 5a-cholest-8-en-15-ol (Compound 19b) A solution of the tricyclic alcohol (Compound 18b) (13.4 mmole) in methylene chloride (80 ml) and 80% aqueous acetic acid (300 ml) containing 1 M hydrochloric acid (0.5 ml) was stirred at room temperature for 20 hrs. The acid and water were evaporated off under reduced pressure to give an oily residue of the cyclic hemiacetal (Compound 19b) and the cyclic acetal (Compound 19c) . The two products were separated by column chromatography on silica gel with elution by 1:9 ethyl acetate - hexane followed by 2:8 ethyl acetate - hexane to afford 3.2 g of the compound 19c (Rf = 0.32, 2:8 ethyl acetate-hexane) as oils. The Compound 19c was dissolved in methylene chloride (40 ml) and 80% aqueous acetic acid (150 ml) and the solution was stirred at room temperature for 7 days. It was worked up and purified as described above to provide additional 2.31 g of Compound 19b (Total 5.81 g, 73% overall yield from Compound 18b) . Physical Data: NMR (300 MHZ, CDC1 3 ) : delta 7.28 (d, J=8.5 Hz, 2H) , 6.87 (d, J=8.5 Hz, 2H) , 5.74 (dd, J=10.8 Hz, 174. Hz, IH) , 5.05 (dd, J=1.8 Hz, 10.8 Hz, 17.4 Hz, IH) , 4.65 (d, J=2.1 HZ, IH) , 4.61 (d, J=11.4 Hz, IH) , 4.38 (d, J=11.4 Hz, IH) , 3.80 (s, 3H) , 2.95 (dd, J=4.5 Hz,10.5 Hz, IH) , 1.95-1.00 (m, 26H) , 1.03 (s, 3H) , 0.99 (S, 3H) , 0.94 (d, J=6.9 Hz, 3H) , 0.86 (d, J=6.6 Hz, 6H) , 0.84 (s, 3H) , 0.82 (s, 3H) ; HRMS for C 39 H 58°3 (M-H 2 0) : Calcd. 574.4386; found 574.4316. S. Preparation of 4,4-Dimethyl-3b-f (4- methoxybenzyl)oxy1-14a-oxa-14a-vinyl-D- homo-5a-cholesta-8,15-diene (Compound 20b) By the method described for Compound 8b (Example 1-G) the cyclic hemiacetal (Compound 19b) (2.65 g, 4.46 mmole) was transformed to the glycal (Compound 20b) (2.412 g, 94% yield) as a foamy solid. The crude product was normally used for next reaction without purification. Analytical sample was obtained by filtering a concentrated solution of the crude product in diethyl ether through a short Florisil column with elution by diethyl ether. T. Preparation of 4.4-Dimethyl-3b-f (4- methoxybenzyl)oxy1-14a-oxa-14a-vinyl-D- homo-5a-cholest-8-ene-15,16-diol (Compound 21b) By the method described for Compound 9b (Example 1-H) the glycal (Compound 20b) (2.412 g, 4.19 mmole) was converted to the diol (Compound 21b) (2.31 g, 90.5% yield) as an oil. The crude product was routinely used for next reaction without purification. U. Preparation of 4,4-Dimethyl-16-methoxy-3b- T (4-methoxybenzyl)oxy1-15-oxa-14a-vinyl- 5a-cholest-8-ene (Compound 22b) By the method described for Compound 10b (Example « » l-I) the diol (Compound 21b) (2.31 g, 3.79 mmole) was transformed to five-membered cyclic acetal (Compound 22b) (2.125 g, 94.6% yield) as a foamy solid.. The crude product was used for the next reaction without purification. V. Preparation of 4,4-Dimethyl-15-oxa-14a-vinyl- 5a-cholest-8-en-3b-ol (Compound 23a) To a stirred solution of the five-membered cyclic acetal (Compound 22b) (1.17 g, 2.64 mmole) and triethylsilane (1.6 ml, 10 mmole) in dry methylene chloride (50 ml) at -30° was added boron trifluoride etherate (0.2 ml, 1.63 mmole) dropwise and the mixture was stirred at -30° to 20° for 2 hr. The reaction was quenched by addition of saturated sodium bicarbonate (20 ml) and the products were extracted with diethyl ether (2 X 100 ml) . The ether extracts were washed with water and brine, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to give an oily residue. It was purified by column chromatography on silica gel with elution by 15:85 ethyl acetate-hexane to give the 15-oxa-sterol (Compound 23a) (0.71 g, 81% yield) as a foamy solid. Physical Data: NMR (300 MHz, CDC1 3 ): delta 5.73 (dd, J=10.8 Hz, 17.4 Hz, IH) , 5.12 (dd, J=l.8 Hz, 10.8 Hz, IH) , 5.00 (dd, J=1.8 Hz, 17.4 Hz, IH) , 3.88 (t, J=8.7 Hz , IH) , 3.55 (t, J=9 HZ, IH) , 3.26 (dd, J=4.8 Hz, 11.7 Hz, IH) , 2.07-0.80 (m, 23H) , 1.01 (s, 6H) , 0.95 (d, J=6 Hz, 3H) , 0.86 (d, J=6.3 Hz, 6H) , 0.81 (s, 3H) , 0.78 (s, 3H) ; IR (film): 2933, 2868, 1512, 1467, 1375, 1095, 1040, 1029, 1033 cm "1 ; HRMS for C 30 H 50 O 2 (M+) : Calcd. 442.3811; found 442.3806. EXAMPLE 4 Preparation of 3b-Acetoxy-4 ,4-dimethyl-15- oxa-14a-vinyl-5a-cholest-8-ene (Compound 23c) A solution of the 15-oxa-sterol (Compound 23a) (2g, 4.52 mmole) acetic anhydride (Fischer Scientific) (2 ml, 21.2 mmole) and dimethylaminopyridine (Aldrich) (0.1 g, 0.82 mmole) in anhydrous pyridine (Aldrich) (20 ml) was stirred at room temperature for 18 hr. under nitrogen atmosphere. After addition of methanol (5 ml) the mixture was evaporated under reduced pressure, and the residue was partitioned between water and diethyl ether. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to give an oily residue. It was column chromatographed on silica gel with elution by 5:95 ethyl acetate - hexane followed by 1:9 ethyl acetate - hexane to afford the 14-vinyl-15-oxa-sterol acetate (Compound 23c) (1.78 g, 81% yield) . Physical Data: NMR (300 MHz, CDC1 3 ) : delta 5.72 (dd, J=10.8 Hz, 15.9 Hz, IH) , 5.12 (dd, J=1.8 Hz, IH) , 5.00 (dd, J=1.8 HZ, 15.9 Hz, IH) 4.52 (dd, J=4.8 Hz, IH) , 3.87 (t, J=8.7 Hz, IH) , 3.55 (t, J=8.7 Hz, IH) , 2.06 (s, 3H) , 2.06-0.80 (m, 22H) , 1.03 (s, 3H) , 0.94 (d, J=6.3 Hz, 3H) , 0.89 (s, 3H) , 0.88 (s, 3H) , 0.87 (d, J=6 Hz, 6H) , 0.78 (s, 3H) . EXAMPLE 5 Preparation of both Diasteroemers of 3b-Acetoxy-32-hvdroxymethyl-15-oxa-lanost- 8-en-32-ol (Compounds 24c and 25c) To a solution of the 14-vinyl-15-oxa-sterol acetate (Compound 23c) (1.78 g, 3.67 mmole) was added osmium tetroxide (1 g, 3.94 mmole) and the resulting dark brown solution was stirred at room temperature for 2 days. At the end of the stirring hydrogen sulfide gas was bubbled through the solution and the black precipitates were removed by filtration over Celite. After washing the filter cake with ethyl acetate several times the filtrate and the washings were evaporated to give a black oily residue. It was purified by column chromatography on silica gel with elution by 3:7 ethyl acetate - hexane to afford 0.25 g of unreacted starting Compound 23c, 0.54 g of Compound 24c (Rf = 0.20, 3:7 ethyl acetate - hexane) and 0.19 g of Compound 25c (Rf = 0.16, 3:7 ethyl acetate - hexane) in 44.6% combined corrected yield. Physical Data (Compound 24c) : IR (Film): 3451, 2951, 2870, 1733, 1650, 1642, 1632, 1467, 1366, 1246, 1100, 1028 cm "1 ; HRMS for C 30 H 49°3 (M-CHOHCH 2 OH) : Calcd. 457.3681;; found 457.3640. Physical Data (Compound 25c) : HRMS for C 30 H 49 O 3 (M-CH0HCH 2 0H) : Calcd. 457.3681; found 457.3659. EXAMPLE 6 Preparation of 3b-Acetoxy-15-oxa-32-oxo- lanost-8-ene (Compound 26c) To a solution of the diol (Compound 24c) (492 mg, 0.95 mmole) in ethanol (34 ml) at 0° was added a solution of sodium periodate (664 mg, 2.85 mmole) in 8.5 ml of water dropwise and the mixture was stirred at 0° for 30 min. It was extracted with diethyl ether (150 ml) and the organic layer was washed with brine. After drying over anhydrous magnesium sulfate the solvents were evaporated under reduced pressure to give an oily residue of the aldehyde (Compound 26c) (460 mg, ca. 100% yield) . Physical Data: NMR (300MHz, CDC1 3 ): delta 9.56 (s, IH) , 4.47 (dd, J=4.5 Hz, 11.4 Hz, IH) , 3.98 (t, J=8.4 Hz, IH) , 3.66 (t, J=8.7 HZ, IH) , 2.15-0.90 (m, 22H) , 2.02 (s, 3H) , 1.02 (s, 3H) , 1.02 (s, 3H) , 0.91 (d, J=6.3 Hz, 3H) , 0.88 (s, 3H) , 0.84 (brs, 9H) , 0.82 (s, 3H) ; IR (film): 2949, 2871, 2798, 2689, 1733, 1471, 1466, 1457, 1374, 1366, 1246, 1027 cm "1 . EXAMPLE 7 Preparation of 15-Oxa 32-oxo- dihvdrolanosterol (Compound 26a) * V To a solution of the aldehyde-acetate (Compound 26c) (30 mg, 0.062 mmole) ethanol (0.7 ml) was added 3M potassium hydroxide (41 1, 0.124 mmole) and the mixture was stirred at room temperature for 20 hr. After addition of diethyl ether (15 ml) the organic solution was washed with water and brine and dried over anhydrous magnesium sulfate. Evaporation of the solvent under reduced pressure afforded a foamy solid residue of chromatographically purified free hydroxy compound (Compound 26a) (27.5 mg, 100% yield) . Physical Data: NMR (300 MHz, CDCl 3 ) : delta 9.59 (s, IH) , 4.03 (t, J=8.4 Hz, IH) , 3.70 (dd, J=8.1 Hz, 9.6 Hz, IH) , 3.26 (dd, J=4.5 Hz, 11.4 Hz, IH) , 2.20-0.90 (m, 24H) , 1.04 (s, 3H) , 1.01 (s, 3H) , 0.95 (d, J=6.6 Hz, 3H) , 0.92 (s, 3H) , 0.86 (d, J=6.3 Hz, 6H) , 0.81 (s, 3H) ; IR (film): 3446, 2946, 2933, 2870, 2691, 1731, 1468, 1383, 1378, 1365, 1064, 1042, 1027 cm "1 ; HRMS for C 28 H 47°2 (M-CHO) : Calcd. 415.3576; found 415.3600. EXAMPLE 8 Preparation of 15-Oxa-lanost-8-ene- 3b,32-diol (Compound 27) To a stirred solution of the aldehyde (Compound 26a) (15 mg, 0.034 mmole) in ethanol (1 ml) at 0° was added sodium borohydride (Fischer Scientific) (10 mg, 0.26 mmole) and the mixture was stirred at the same temperature for 1 hr. The excess sodium borohydride was destroyed by adding several drops of saturated ammonium chloride solution and the product was extracted with diethyl ether. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and evaporated to give the diol (Compound 27) (ca. 100% yield) as a white crystalline solid. Physical Data: HRMS for C 28 H 47 0 2 (M-CH 2 OH) : Calcd. 415.3576; found 415.3562. EXAMPLE 9 Preparation of both Diastereomers of 15-Oxa-32-vinyl-lanost-8-ene-3b,32-diol (Compounds 28 and 29) To a stirred solution of the aldehyde (Compound 26c) (23 mg, 0.052 mmole) in dry tetrahydrofuran (1 ml) was added 1 M vinyl magnesium bromide in tetrahydrofuran (0.52 ml, 0.52 mmole) dropwise and the mixture was stirred at 70° for 0.5 hr. under nitrogen atmosphere. After cooling to 0° about 2 ml of 0.5 M hydrochloric acid was added slowly and the mixture was extracted with diethyl ether. The ether layer was washed with saturated sodium bicarbonate, water and brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to give an oily residue of Compounds 28 and 29 (1.4:1 ratio, determined by GC, ca. 100% yield) . EXAMPLE 10 Preparation of 3b-Hydroxy-15-oxa-lanost- 8-en-32-aldoxime (Compound 30) A solution of the aldehyde (Compound 26a) (17 mg, 0.038 mmole) and hydroxylamme hydrochloride (Aldrich) (20 mg, 0.29 mmole) in pyridine (0.5 ml) was stirred at 80° for 7 hr. After addition of diethyl ether the solution was washed with water and brine, dried over anhydrous magnesium sulfate and evaporated to give an oily residue. The crude product was purified by preparative thin layer chromatography to obtain purified oxime (Compound 30) as a foamy solid (ca. 100% yield) . Physical Data: NMR (300 MHz, CDCl 3 ) : delta 3.93 (t, J=8.1 Hz, IH) , 3.62 (t, J=8.1 HZ, IH) , 3.26 (dd, J=4.8 Hz, 11.4 HZ, IH) , 2.10-0.70 (m, 25H) , 1.01 (s, 2\3H) , 0.98 (s, 3H) , 0.95 (d, J=6.3 HZ, 3H) , 0.89 (S, 3H) , 0.86 (d, J=6.6 HZ, 6H) , 0.81 (s, 3H) ; IR (film): 3336, 2932, 2870, 1467, 1458, 1383, 1377, 1266, 1040, 1028, 924, 737 cm "1 . EXAMPLE 11 Preparation of 14a-Oxa-D-homo- dihydrolanosterol (Compound 31) . Preparation of 4,4-Dimethyl-5a-cholest-8- ene-3b-,14a.15a-triol (Compound 3a) By the method described for Compound 3b (Example 1-B) the 8,14-diene (Compound 2a) (4.64 g, 11.21 mm I^) was transformed to triol (Compound 3a) . The crude product was filtered through a plug of silica gel with elution by 4:6 ethyl acetate-hexane followed by 7:3 ethyl acetate-hexane and crystallized from diethyl ether and hexane to afford purified Compound 3a as white short needles (4.18 g, 83.3% yield), .p. = 133-134° (dec.) Physical Data: NMR NMR (300 MHz, CDC1 3 -D 20 (5%)): delta 4.11 (dd, J=5 Hz, 9 Hz, 1 Hz), 3.22 (dd, J=5 Hz, 11 Hz, IH) , 2.33 (m, IH) , 2.26 (brm, IH) , 2.09 (brm, 2H) , 2.00-1.05 (m, 20H) , 1.01 (d, J=3 Hz, 6H) , 0.87 (s, 3H) , 0.86 (d, J=8 Hz, 3H) , 0.85 (s, 3H) , 0.82 (s, 3H) , 0.69 (s, 3H) ; IR (film): 3422 (bs, OH), 2950 (s) , 1652 (s) , 1465 (m) , 1036 (m) cm "1 ; EA for C 29 H 50 O 3 : Calcd. C 77.97%, H 11.28%; found C 78.05%, H 11.19%. X. Preparation of 4,4-Dimethyl-3b-hvdroxy-15- oxo-5a-14,15-Secocholest-8-en-14-on (Compound 4a) By the method described for Compound 4b (Example 1-C) the triol (Compound 3a) (1 g, 2.24 mmole) was transformed to keto-aldehyde (Compound 4a) (0.97 g, 97.4% yield) the crude material was normally used for next reaction without purification. Physical Data: NMR (300 MHz, CDCI3): delta 3.93 (t, J=8.1 Hz, IH) , 3.63 (t, J=8.1 Hz, IH) , 3.26 (dd, J=4.8 Hz, 11.4 Hz, IH) , 2.10-0.70 (m, 25H) , 1.01 (s, 3H) , 0.98 (s, 3H) , 0.95 (d, J=6.3 Hz, 3H) , 0.89 (s, 3H) , 0.88 (d, J=6.6 Hz, 6H) , 0.81 (s, 3H) ; IR (film): 3336, 2932, 2870, 1467, 1458, 1383, 1377, 1266, 1040, 1028, 924, 737 cm "1 . Y. Preparation of 15,15-Dimethoxy-4 ,4-dimethyl- 3b-hvdroxy-15-oxo-5a-14,15-secocholest-8-en- -14-one (Compound 5a) By the method described for Compound 5b (Example Id) the keto-aldehyde (Compound 4a) (0.97 g, 2.18 mmole) was transformed to keto-acetal (Compound 5a) (1.09 g, ca. 100% yield) as a foamy solid. The crude product was normally used for the next reaction without purification. An analytical sample of Compound 5a was obtained by column chromatography on silica gel by elution with 3:7 ethyl acetate - hexane. Physical Data: NMR (300 MHZ, CDC1 3 ) : delta 4.06 (t, J=5.8 Hz, IH) , 3.26 (S, 3H) , 3.26-3.27 (m, IH) , 3.22 (s, 3H) , 2.62 (dd, J=6 HZ, 17 Hz, IH) , 2.35-0.90 (m, 25H) , 1.07 (s, 3H) , 1.02 (s, 3H) , 0.98 (d, J=7.2 Hz, 3H) , 0.95 (s, 3H) , 0.86 (d, J=6.6 HZ, 6H) , 0.84.(s, 3H) ; IR (film): 3490, 2952, 2870, 1659, 1622, 1642, 1434, 1373, 1123, 1076, 1061 cm "1 ; HRMS for C 29 H 46 0 2 (M-2CH 3 OH) : Calcd. 426.2498; found 426.3415. Z. Preparation of 15,15-Dimethoxy-14.15- Secolanost-8-ene-3b.14-diol (Compound 6a) By the method described for Compound 6b (Example 1-E) the keto-acetal (Compound 5a) (200 mg, 0.41 mmole) was transformed to tricyclic alcohol (Compound 6a) (210 mg, ca. 100% yield) as an oil. The crude material was routinely used for next reaction without purification. Physical Data: NMR (300 MHz, CDC1 3 ): delta 4.05 (t, J=6 Hz, IH) , 3.27-3.20 (m, IH) , 3.26 (s, 3H) , 3.22 (s, 3H) , 2.61 (dd, J=5.1 Hz, 17.7 Hz, IH) , 2.50-0.80 (m, 25H) , 1.07 (s, 3H) , 1.02 (s, 3H) , 1.02 (s, 3H) , 0.98 (d, * J=6.9 Hz, 3H) , 0.95 (s, 3H) , 0.86 (d, J=6.6 Hz, 6H) , 0.85 (s, 3H) , 0.84 (s, 3H) . % AA. Preparation of 14a-Oxa-D-homo-lanost-8- ene-3b,15-diol (Compound 7a) A solution of the tricyclic alcohol (Compound 6a) (0.41 mmole) in methylene chloride (2 ml) and 80% aqueous acetic acid (10 ml) was stirred at room temperature for 1.5 hr. and the solvents were evaporated off under reduced pressure to give an oily residue. The residue was dissolved in diethyl ether (20 ml) and washed with saturated sodium bicarbonate and brine. After drying over anhydrous sodium sulfate the ether solution was evaporated under reduced pressure to give an oily residue that was column chromatographed on silica gel. Elution with 25:75 ethyl acetate-hexane afforded 117 mg of cyclic hemiacetal (Compound 7a) (28% overall yield from Compound 6a) as an oil. AB. Preparation of 14a-0xa-D-homo dihvdrolanosterol (Compound 31) To a stirred solution of the cyclic hemiacetal (Compound 7a) (34 mg. 0.073 mmole) in dry methylene chloride (1.5 ml) at -30° were added triethylsilane j (35 L, 0.22 mmole) and 2 drops of boron trifluoride etherate and the mixture was stirred at -30° to 8° » t for 45 min. under nitrogen atmosphere. After addition of saturated sodium bicarbonate (3 ml) the reaction mixture was extracted with diethyl ether (2 x 15 ml) . The combined extracts were washed with brine, dried over anhydrous sodium sulfate and evaporated under reduced pressure to give an oily residue of Compound 312 (30 mg, 92.4%) yield). It was purified by MPLC on silica gel with elution by IL (ethyl acetate - hexane to give a purified sample as a white foamy solid. Physical Data: NMR (300 MHz, CDC1 3 ): delta 3.67 (dd, J=2.7 Hz, IH) , 3.31-3.25 (m, 2H) , 2.37 (dd, J=5.5 Hz, 18 Hz, IH) , 2.20-0.909 (m, 24H) , 1.12 (s, 3H) , 1.04 (s, 3H) , 0.98 (s, 3H) , 0.94 (d, J=7.2 Hz, 3H) , 0.92 (s, 3H) , 0.88 (d, J=6.6 HZ, 6H) , 0.83 (s, 3H) ; HRMS for C 30 H 52 O 2 (M+) , Calcd. 444.3967, found 444.3942; for C 29 H 49 ° 2 (M-CH 3 ), Calcd. 429.3733, found 429.3717. EXAMPLE 12 Preparation of 4,4-dimethyl-14a-Oxa-D-homo- 5a-cholest-8-en-3b-ol (Compound 32) AC. Preparation of 15.15-Dimethyl-4,4-dimethyl -5a-14.15-Secocholest-8-ene-3b,14-diol (Compound 12) By the method described for Compound 12b (Example 2-K) the keto-acetal (Compound 5a) (121 mg, 0.25 mmole) was transformed to tricyclic secondary alcohol (Compound 12a) as an oil. The crude product was used for next reaction without purification. Physical Data: NMR (300MHz, CDC1 3 ): delta 5.30 (s, IH) , 4.41 (dd, J=3 HZ, 9 Hz, IH) , 3.91 (d, J=4.2 Hz, IH) , 3.45 (s, 3H) , 3.36 (s, 3H) , 3.36 (s, 3H) , 3.21 (m, IH) , * 2.15-0.95 (m, 25H) , 0.99 (s, 6H) , 0.92 (d, J=6.6 Hz, 3H) , 0.87 (d, J=6.6 HZ, 6H) , 0.81 (S, 3H) , 0.61 (s, * 3H) ; HRMS for C 30 H 52 O 3 (M-CH 3 OH) : Calcd. 460.3916; found 460.3891. AD. Preparation of 4.4-Dimethyl-14a-oxa-D-homo- 5a-cholest-8-ene-3b,15-diol (Compound 13a) By the method described for Compound 7a (Example 11-AA) with exception of reaction time (4 hr.) the secondary alcohol (Compound 12a) (0.25 mmole) was transformed to the six-membered cyclic hemiacetal (Compound 13a) (70 mg, 62.7% overall yield from Compound 5a) as an oil. Physical Data: NMR (300MHz, CDCl 3 ): delta 5.30 (s, IH) , 4.72 (dd, J=3.3 Hz, 8.7 Hz, IH) , 3.79 (brs, IH) , 3.25 (dd, J=4.5 HZ, 11.1 HZ, IH) , 2.20-.080 (m, 25H) , 1.01 (s, 3H) , 0.98 (s, 3H) , 0.96 (s, 3H) , 0.93 (d, J-6.9 Hz, 3H) , 0.86 (d, J=6.6 Hz, 6H) , 0.81 (s, 3H) ; AE. Preparation of 4,4-Dimethyl-14a-Oxa-D-homo- 5a-cholest-8-en-3b-ol (Compound 32) To a stirred solution of the cyclic hemiacetal (Compound 13a) (31.8 mg, 0.071 mmole) and triethylsilane (34 1, 0.21 mmole) in dry acetonitrile f (1.5 ml) and dry methylene chloride (0.5 ml) at -15° was added a drop of boron trifluoride etherate and the mixture was stirred at -15° to -10° for 15 min. After addition of saturated sodium bicarbonate it was extracted with diethyl ether. The ether extract was washed with brine, dried over anhydrous sodium sulfate and evaporated to give an oily residue of Compound 32. It was purified by preparative thin layer chromatography on silica gel plate with elution by 3:7 ethyl acetate - hexane to afford 12 mg of purified sample (39.2% yield) as a white foamy solid. EXAMPLE 13 Preparation of 4,4-Dimethyl-14a-oxa-14-a oxa-14a-vinyl-D-homo-5a-cholest-8-en-3b-ol (Compound 33) AF. Preparation of 15,15-Dimethoxy-4,4-dimethyl- 14-vinyl-5a-14,15-secocholest-8-ene-3b,14- diol (Compound 18a) By the method described for Compound 18b the keto-acetal (Compound 5a) (230 mg, 0.47 mmole) was transformed to a tricyclic allylic alcohol (Compound 18a) as an oil. The crude material was normally used for next reaction without purification. Physical Data: NMR (300 MHz, CDC1 3 ) : delta 5.80 (dd, J=9.9 Hz, 17.7 Hz, IH) , 5.08 (d, J=9.9 Hz, IH) , 5.05 (d, J=17.1 Hz, IH) , 4.50 (dd, J=2.7 Hz, 9 Hz, IH) , 4.20 (s, IH) , 3.42 (s, 3H) , 3.28 (s, 3H) , 3.24 (dd, J=4.8 Hz, 12 Hz, IH) , 2.47 (dd, J-10.8 Hz, 14.4 Hz, IH) , 2.15-0.90 (m, 24H) , 1.03 (s, 3H) , 1.01 (s, 3H) , 0.94 (s, 3H) , 0.93 (d, J=4.5 Hz, 3H) , 0.87 (d, J=6.3 Hz, 6H) , 0.82 (s, 3H) ; IR (film): 3455, 2954, 2871, 1466, 1375, 1122, 1067, 1045 cm "1 . AG. Preparation of 4,4-Dimethyl-14a-oxa-14a- * vinyl-d-homo-5a-cholest-8-ene-3b,15-diol (Compound 19a) J « By the method described for Compound 7a (Example 11-AA) the allylic alcohol (Compound 18a) (0.47 mmole) was transformed to six-membered cyclic hemiacetal (Compound 19a) (140 mg, 63% overall yield from Compound 5a) . AH. Preparation of 4,4-Dimethyl-14a-oxa-14a- vinyl-D-homo-5a-cholest-8-en-3b-ol (Compound 33) By the method described for Compound 31 (Example 11-AB) the cyclic hemiacetal (Compound 19a) (73.8 mg. 0.16 mmole) was transformed to compound 33 (70 mg, 95.8% yield). Purified sample of Compound 33 as a white foamy solid was obtained by column chromatography on silica gel with elution by 1:9 ethyl acetate - hexane. Physical Data: NMR (300MHz, CDC1 3 ): delta 5.71 (dd, J=10.8 Hz, 17.4 Hz, IH) , 5.07 (dd, J=1.5 Hz, 10.8 Hz, IH) , 4.96 (dd, J=1.5 HZ, 17.4 HZ, IH) , 3.74 (dd, J=3.3 Hz, 10.5 Hz, IH) , 3.34 (t, J=ll.l Hz, IH) , 3.28 (dd, J=3.9 Hz, 11.1 Hz, IH) , 2.10-0.80 (m, 25H) , 1.04 (s, 3H) , 1.03 (s, 3H) , 0.94 (d, J=6.6 Hz, 3H) , 0.86 (d, J=6.6 Hz, 6H) , 0.83 (s, 3H) , 0.82 (s, 3H) ; IR (film): 3438, 2947, 2933, 2868, 1635, 1466, 1399, 1377, 1265, 1096, * f 1040, 1027, 1003, 922, 736 cm "1 ; HRMS for C 31 H 5 2° 2 ( M+ ) : Calcd. 456.3968; found 456.3955. EXAMPLE 14 Preparation of both Diastereomers of 32- hydroxy-14a-oxa-lanost-8-ene-3b.32- diol (Compounds 34 and 35) To a solution of the 14-vinyl-D-homo-oxasterol (Compound 33) (250 mg, 0.55 mmole) in anhydrous pyridine (10 ml) was added a 5% solution of osmium tetroxide in methylene chloride (3.4 ml, 0.66 mmole) and the mixture was stirred at room temperature for 7 days. At the end of that period, hydrogen sulfide gas was bubbled through the solution for about 5 min. and the resulting black precipitates were removed by filtration over Celite. The filter cake was rinsed with ethyl acetate several times and the filtrate and washings were evaporated to give a black oily residue. It was column chromatographed on silica gel with elution by 6:4 ethyl acetate - hexane to afford 150 mg of the unreacted starting material (compound 33) and 90 mg (foamy solid) of the triols 34 and 35 as a mixture (83.8% corrected yield) . EXAMPLE 15 Preparation of 14a-Oxa-32-oxo-D-homo-dihvdro- lanosterol (Compound 36) To a stirred solution of the diasteromeric mixture of triols (Compounds 34 and 35) (90 mg, 0.184 mmole) in ethanol (4 ml) was added a solution of sodium periodate (118 mg, 0.55 mmole) in water (1 ml) dropwise over a period of 3 min. The mixture was stirred at room temperature of 0.5 hr. and diethyl ether (30 ml) was added to the mixture. The ether solution was washed with water and brine, dried over anhydrous magnesium sulfate and evaporated to give an oily residue. It was purified by MPLC on silica gel with elution by 2:8 ethyl acetate-hexane to provide purified aldehyde (Compound 36) as a white foamy solid (80-90% yield) . Physical Data: NMR (300 MHz, CDCl 3 ) : delta 9.51 (s, IH) , 3.91 (dd, J=4.5H, 11.1 HZ, IH) , 3.35 (t, J-11.4 Hz, IH) , 3.27 (dd, J=4.5 Hz, 11.4 Hz, IH) , 2.04-0.80 (m, 25H) , 1.05 (S, 3H) , 1.02 (s, 3H) , 0.94 (d, J=6.9 Hz, 3H) , 0.92 (s, 3H) , 0.86 (d, J=6.6 Hz , 6H) , 0.81 (s, 3H) ; IR (film): 3481, 2951, 2868, 2725, 1734, 1466, 1459, 1378, 1365, 1098, 1043, 1027, 1004, 733 cm "1 . EXAMPLE 16 Preparation of 14a-Methyl-15-oxa-5a-cholest -8-en-3b-ol (Compound 47) Al. Preparation of 3b-f (4-Methoxybenzyl)oxy15a- cholesta-8,14-diene (Compound 38b) By the method described for the diene p-methoxybenzyl ether (Compound 2b) (Example l-A) 5a-cholesta-8,14-dien-3b-ol (18.6 g, 48.4 mmole) was transformed to p-methoxybenzyl ether (Compound 38b) as white crystals (17.4 g, 71.2% yield), .p. = 109 - 110°C. Physical Data: NMR (300 MHz, CDC1 3 ): delta 7.28 (d, 8.7 Hz, 2H) , 6.82 (d, J=8.7 Hz, 2H) , 5.36 (m, IH) , 4.52 (d, J=ll Hz, IH) , 4.47 (d, J=ll Hz, IH) , 3.80 (s, 3H) , 3.35 (m, IH) , 2.40-0.80 ( , 26H) , 0.99 (s, 3H) , 0.94 (d, J=6.3 HZ, 3H) , 0.87 (d, J=6.5 Hz, 6H) , 0.81 (s, 3H) ; IR (KBr) : 3932, 2868, 2835, 1613, 1513, 1465, 1457, 1243, 1086, 1071, 1041 cm "1 . AJ. Preparation of 3b-r (4-Methoxybenzyl)oxyll- 5a-cholest-8-ene-14a, 15a-diol (Compound 39) By the method described for the diol (Compound 3b) (Example 1-b) the diene (Compound 38b) (3.8 g, 7.5 mmole) was transformed to the corresponding diol (Compound 39) . The crude white solid product was normally used for next reaction without purification. Physical Data: NMR (300 MHz, CgDg) ; delta 7.34 (d, J=8.2 Hz, 2H) , 6.86 (d, J=8.2 Hz, 2H) , 4.51 (d, J=12 Hz, IH) , 4.46 (d, J=12 HZ, 12H) , 4.05 (dd, J=7.5 Hz, 17 Hz, IH) , 3.30 (s, 3H) , 3.30 (m, IH) , 2.45-0.80 (m, 28H) , 0.95 (d, J=6.5 Hz, 3H) , 0.90 (d, J=6.6 Hz, 6H) , 0.84 (s, 3H) , 0.62 (s, 3H) ; IR (film): 3500, 2933, 2889, 1615, 1587, 1514, 1457, 1374, 1302, 1247, 1171, 1109, 1083, 1035 cm "1 ; HRMS (El) for C 35 H 52 0 3 (M-H 2 0) , Calcd. 520.3917; found 520.3895. A . Preparation of 3b-r (4-Methoxybenzyl) oxyl-15- oxo-5a-14.15-secocholest-8-en-14-one (Compound 40) By the method described for the keto-aldehyde (Compound 4b) (Example 1-C) the diol (Compound 39) (7.5 mmole) was transformed to the corresponding keto-aldehyde (Compound 40) . * The crude oily product was used for next reaction without purification. • Physical Data: NMR (300 MHz, CDC1 3 ) : delta 9.56 (s, IH) , 7.27 (d, J=8.4 Hz, 2H) , 6.87 (d, J=8.4 Hz, 2H) , 4.52 (d, J=11.7 Hz, IH) , 4.47 (d, J=11.7 Hz, IH) , 3.80 (s, 3H) , 3.41 (m, IH) , 2.57-0.90 (m, 26H) , 1.02 (s, 3H) , 0.97 (s, 3H) , 0.91 (d, J=6.6 Hz, 3H) , 0.87 (d, J=6.6 Hz, 6H) ; IR (film) : 2950, 2934, 2869, 1725, 1655, 1615, 1513, 1442, 1375, 1301, 1248, 1103, 1077, 1037 cm -1 ; HRMS for C 34 H 50 0 3 (M-CH 2 0) : Calcd. 506.3760; found 506.3763. AL. Preparation of 15, 15-Dimethoxy-3b-r (4- methoxybenzyl) oxy15a-14.15-secocholest-8- en-14-one (Compound 41) By the method described for the keto-acetal (Compound 5b) (Example 1-D) the keto-aldehyde (Compound 40) (7.5 mmole) was transformed to the corresponding keto-acetal (Compound 41) . The crude oily product was used for next reaction without purification. Physical Data: NMR (300 MHz, CDCl 3 ) : delta 7.26 (d, J-8.4 Hz, 2H) , 6.87 (d, J=-8.4 Hz, 2H) , 4.51 (d, J=11.4 Hz, IH) , 4.47 (d, J=11.4 Hz, IH) , 4.07 (t, J=6 Hz, IH) , 3.80 (s, 3H) , 3.30 (m, IH) , 3.26 (s,- 3H) , 3.21 (s, 3H) , 2.53 (brd, J=16.5 Hz, IH) , 2.40-1.00 (m, 25H) , 1.02 (s, 3H) , 0.98 (d, J=7.2 HZ, 3H) , 0.96 (s, 3H) , 0.86 (d, J=6.6 % Hz, 6H) ; IR (film): 2934, 2867, 1661, 1654, 1617, 1513, 1465, 1438, 1248, 1078, 1058, 1039 cm "1 ; HRMS (El) for C 36 H 54 0 4 (M+-CH30H) , Calcd. 550.4022, found 550.4021. AM. Preparation of 15,15-Dimethoxy-3b-r (4- methoxybenzyl)oxyl-14-methyl-14,15- secocholest-8-en-14-ol (Compound 42) By the method described for the tricyclic alcohol (Compound 6b) (Example 1-E) the keto-acetal (Compound 41) (7.5 mmole) was transformed to the corresponding tricyclic alcohol (Compound 42) . The crude oily product was used for next reaction without purification. Physical Data: NMR (300 MHz, CDCl 3 ) : delta 7.27 (d, J=8.7 Hz, 2H) , 6.87 (d, J=8.7 Hz, 2H) , 4.50 (brs, IH) , 4.52 (d, J=14.1 HZ, IH) , 4.49 (t, J=3 Hz, IH) , 4.46 (d, J=14.1 HZ, IH) , 3.80 (s, 3H) , 3.49 (s, 6H) , 3.35 (m, IH) , 2.30-0.90 (m, 26H) , 1.19 (s, 3H) , 0.92 (d, J=5.7 Hz, 3H) , 0.90 (s, 3H) , 0.86 (s, 3H) , 0.86 (d, J=6.6 Hz, 6H) ; IR (film): 3464, 2933, 2869, 1514, 1465, 1457, 1120, 1063, 1052, 1040 cm "1 ; HRMS (El) for C 36 H 54°3 (M+2CH30H) , Calcd. 534.4073, found 534.4071. AN. Preparation of 3b-r (4-Methoxybenzyl)oxy1- 14a-methyl-14a-oxa-D-homo-5a-cholest-8-en- 15-QI (Compound) By the method described for the six-membered cyclic hemiacetal (Compound 7b) (Example 1-F) the tricyclic alcohol (Compound 42) (Example 1-F) the tricyclic alcohol (Compound 42) (7.5 mmole) was transformed to the corresponding cyclic hemiacetal (Compound 43a) and cyclic acetal (Compound 43b) . The oily residue of the mixture was column chromatographed on silica gel with elution by 15:85 ethyl acetate - hexane followed by 3:7 ethyl acetate - hexane to afford 1.6 g of the cyclic * hemiacetal (Compound 43a) and 1.19 g of the cyclic acetal (Compound 43b) . The compound 43b was subjected i to the reaction condition and stirred at room temperature for 4 days. It was worked up and purified as described above to provide additional 0.47 g of the compound 43a (Total 2.07 g, 50% overall yield from Compound 38b) and 0.6 g of the Compound 43b (14.1% overall yield from Compound 38b) . Physical Data: NMR (300 MHz, CDC1 3 ): delta 7.27 (d, J=8.1 Hz, 2H) , 6.87 (d, J=8.1 Hz, 2H) , 4.53 (brs, IH) , 4.49 (brs, IH) , 3.80 (s, 3H) , 3.34 (m, IH) , 2.23 (brd, J-17.1 Hz, IH) , 2.10-1.00 (m, 26H) , 1.18 (s, 3H) , 0.86 (d, J=6.3 Hz, 6H) ; HRMS for C 36 H 54 0 3 (M-H 2 0) : Calcd. 534.4073; found 534.4114. AO. Preparation of 3b-r f4-Methoxybenzyl)oxy]- 14a-methyl-14a-oxa-D-homo-5a-cholesta-8,15- diene (Compound 44) By the method described for the glycal (Compound 8b) (Example 1-G) the cyclic hemiacetal (43a) (2.07 g, 3.74 mmole) was transformed to the corresponding glycal (Compound 44) . The crude oily product was used for the next reaction without purification. Physical Data: IR (film): 2950, 2931, 2866, 1660, 1514, 1467, * 1248, 1171, 1093, 1072, 1039 cm "1 . AP. Preparation of 3b-F (4-Methoxybenzyl) oxyl-l4a- methyl-14a-oxa-D-homo-5a-cholest-8-ene-15,16- diol (Compound 45) By the method described for the diol (Compound 9b) (Example 1-H) the glycal (Compound 44) (3.74 mmole) was transformed to the corresponding diol (Compound 45) . The crude black oily product was used for next reaction without purification. AQ. Preparation of 16-Methoxy-3b-r (4-methoxy- benzyl)oxyl-14a-methyl-15-oxa-5a-cholest-8-ene (Compound 46) By the method described for the 5-membered cyclic acetal (Compound 10b) the diol (Compound 45) (3.784 mmole) was transformed to the corresponding 5-membered cyclic acetal (Compound 46) . The crude oily product was used for next reaction without purification. Analytical sample of purified Compound 46 was obtained by a preparative thin layer chromatography on silica gel with elution by 1:9 ethyl acetate - hexane. Physical Data: NMR (300 MHz, CDC1 3 ): delta 7.27 (d, J=8.5 Hz, 2H) , 6.87 (d, J=8.5 Hz, 2H) , 4.52 (d, J=5.4 Hz, IH) , 4.51 (d, J=12 Hz, IH) , 4.51 (d, J=12 Hz, IH) , 4.46 (d, J=12 HZ, IH) , 3.81 (s, 3H) , 3.37 (m, IH) , 3.35 (s, 3H) , 2.35 (S, 3H) , 2.35-1.00 (m, 24H) , 1.13 (s, 3H) , 0.94 (d, J=6.6 HZ, 3H) , 0.90 (s, 3H) , 0.88 (s, 3H) , 0.86 (d, J=6.6 Hz, 6H) ; IR (film) : 3923, 3865, 1613, 1514, 1466, 1374, 1248, 1171, 1093, 1071, 1038, 1011 cm "1 ; HRMS (El) for 35 H 52 0 3 (M-CH 3 OH) : Calcd. 520.3916; found 520.3880. AR. Preparation of 14a-Methyl-15-oxa-5a-cholest- 8-en-3b-ol (Compound 47) By the method described for 15-oxa-dihydro- lanosterol (Compound 11a) (Example 1-J) the cyclic acetal (Compound 46) (3.74 mmole) was transformed to 15-oxasterol (Compound 47) . The crude product was purified by MPLC on silica gel with elution by 2:8 ethyl acetate-hexane to provide 0.52 g of the purified compound as foamy solid (34.5% of overall yield from Compound 43a) . Physical Data: NMR (300 MHz, CDC1 3 ): delta 3.75 (t, J=8.4 Hz, IH) , 3.62 (m, IH) , 3.44 (t, J=8.7 Hz, IH) , 2.30 (s, IH) , 2.10-1.00 (m, 24H) , 1.12 (s, 3H) , 0.95 (d, J=6.3 Hz, 3H) , 0.91 (s, 3H) , 0.87 (s, 3H) , 0.86 (d, J=6 Hz, 6H) ; IR (KBr) : 3389, 2929, 2861, 1467, 1457, 1375, 1 1003377 ccmm ""11 ;; HHRRMMSS ((EEll)) ffoorr C 26 H 46 0 2 (M+) , Calcd. 402.3498, found 4092.3524 EXAMPLE 18 Preparation of 4,4-Dimethyl-15-thia-5a- cholest-8-en-3b-ol fCompound 49) Hydrogen sulfide gas was bubbled through a solution of 4,4-dimethyl-16-methoxy-3b-[ (4-methoxybenzyl)oxy]- 15-oxa-5a-cholest-8-ene (Compound 16b) (1.426 mmole, crude material, prepared by procedures M, N, and 0 from Compound 13b (0.81 g, 1.426 mmole) in 40 ml of dry methylene chloride at 0° for 120 min. Boron trifluoride etherate (2.5 ml) was added to the mixture and it was stirred at 0° for 0.5 hr. and at room temperature for 1.5 hr. under nitrogen atmosphere. At the end of the stirring it was cooled to -30° and triethylsilane (2.2 ml, 13.8 mmole) was added dropwise to the solution. The mixture was stirred at room temperature for 1.5 hr. under nitrogen atmosphere and saturated aqueous sodium bicarbonate solution (50 ml) was added to quench the reaction. It was extracted with diethyl ether twice and the combined extracts were washed with brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to give a dark brown oily residue. It was purified by column chromatography on silica gel with elution by 15:85 ethyl acetate-hexane to afford purified Compound 49 (158 mg, 26% overall yield from Compound 13b) . Rf: 0.24, 2:8 ethyl acetate - hexane. Physical Data: NMR (300 MHZ, CDC1 3 ) : delta 3.24 (dd, J=4.5 Hz, 11.1 Hz, IH) , 2.75 (t, J=8.4 Hz, IH) , 2.66 (dd, J=9.6 Hz, 11.7 HZ, IH) , 2.57 (m, IH) , 2.11-2.03 (m, 2H) , 1.90-0.80 (m, 20H) , 1.30 (s, 3H) , 1.01 (s, 3H) , 1.01 (d, J=6.6 HZ, 3H) , 0.94 (s, 3H) , 0.88 (s, 3H) , 0.87 (d, J-6.3 Hz, 6H) , 0.80 (s, 3H) ; IR (film): 3415, 2950, 2869, 1465, 1439, 1376, 1367, 1082, 1026, 1001, 736 cm "1 . EXAMPLE 19 Preparation of 15-thia-dihvdrolanosterol " (Compound 50) By the method described for 15-thiasterol (Compound 49) (Example 18) five-membered cyclic acetal (Compound 10b) (198 mg, 0.34 mmole) was transformed to 15-thia-dihydrolanosterol (Compound 50) (65.4 mg, 43% overall yield from Compound 7b) . Physical Data: NMR (300 MHz, CDCl 3 ): delta 3.24 (dd, J=4.8 Hz, 11 HZ, 3H) , 3.23 (S, IH) , 2.85 (t, J=10.2 Hz, IH) , 2.77 (dd, J=7.2 Hz, 10.2 Hz, IH) , 2.20-0.80 (a, 23H) , 0.99 (s, 3H) , 0.95 (s, 3H) , 0.88 (d, J=8.7 Hz, 3H) , 0.87 (d, J=6.6 Hz, 6H) , 0.81 (s, 3H) ; IR (film): 3443, 2953, 2932, 2869, 1465, 1457, 1382, 1375, 1366, 1089, 1034, 1016, 1004, 736 cm "1 . EXAMPLE 20 Preparation of 4 ,4-Dimethyl-15-thia-14a-vinyl- 5a-cholest-8-en-3b-ol (Compound 51) By the method described for 15-thiasteroid (Compound 49) (Example 18) five-membered cyclic acetal (Compound 22b) (274 mg, 0.46 mmole) was transformed to 15-thia-14-vinyl-sterol (Compound 51) (57.3 mg, 27.2% overall yield from Compound 19b) . Physical Data: NMR (300 MHz, CDC1 3 ): delta 5.84 (dd, J=109.5 Hz, IH) , 5.12 (dd, J=1.5 Hz, 10.5 Hz, IH) , 4.94 (dd, J=1.5 Hz, 17.1 Hz, IH) , 3.26 (dd, J=4.8 Hz, IH) , 2.85 (dd, J=7.2 Hz, 9.6 Hz, IH) , 2.74 (dd, J=10.8 Hz, 11.7 Hz, IH) , 2.46 (m, IH) , 2.06 (dd, , J=3.9 Hz, 7.2 Hz, 114 Hz, IH) , 1.96-0.75 (m, 21H) , 1.02 (S, 3H) , 1.01 (s, 3H) , 1.01 (d, J=6 Hz, 3H) , 0.87 (d, J=6.6 Hz, 6H) , 0.81 A * (s, 3H) , 0.80 (s, 3H) ; IR (film): 3394, 2949, 2867, 1473, 1465, 1457, 1376, 1365, 1093, 1030, 1004, 918 cm " . EXAMPLE 21 Preparation of sulfoxide (Compound 53) To a stirred solution of 15-thia-dihydrolano- sterol (Compound 50) (20 mg, 0.045 mmole) in ethanol (3 ml) was added a solution of sodium periodate (38 mg, 0.18 mmole) in water (1 ml) and the mixture was stirred at room temperature for 30 mins. After addition of diethyl ether (ca. 10 ml) it was filtered to remove the precipitates and the filtrate was evaporated under reduced pressure to give an oily residue. It was purified by preparative thin layer chromatography on silica gel with elution by 5:95 methanol - methylene chloride to give 14 mg of purified sulfoxide (Compound 53) (67% yield) . Physical Data: NMR (300 MHz, CDC1 3 ): delta 3.74 (dd, J=7.2 Hz, 13.2 Hz, IH) , 3.22 (dd, J=4.8 Hz, 11.4 Hz, IH) , 2.49 (t, J=13.2 HZ, IH) , 2.36-0.80 (m, 23H) , 1.34 (s, 3H) , 1.01 (d, J=6 Hz, 3H) , 1.01 (s, 3H) , 0.98 (s, 3H) , 0.87 (d, J=6.6 Hz, 6H) , 0.81 (s, 3H) ; IR (film): 3394, 2950, 2932, 2868, 1457, 1437, 1384, 1376, 1364, 1015, 731 cm "1 . EXAMPLE 22 Preparation of 4 ,4-Dimethyl-14a-thia-D-homo- 5a-cholest-8-en-eb-ol (Compound 56) To a stirred solution of the cyclic acetal (Compound 13d) (300 mg, 0.65 mmole) in dry methylene chloride (10 ml) at 0° was bubbled hydrogen sulfide to saturate the solution and boron trifluoride etherate (0.9 ml, 7.3 mmole) was added dropwise. , After stirring at room temperature for 1.5 hr. it was cooled to 0° and triethylsilane (1.4 ml, 8.76 mmole) was added. It was stirred at the same temperature for 2.5 hr. and saturated sodium carbonate (ca. 20 ml) was added to quench the reaction. The mixture was extracted with diethyl ether (2 x 30 ml) and the combined extracts were washed with water and brine, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to give a foamy solid residue. It was purified by column chromatography on silica gel with elution by 15:85 ethyl acetate-hexane to afford purified Compound 56 (172 mg, 59.2% yield) as a white foamy solid. Physical Data: NMR (300 MHz, CDC1 3 ): delta 3.27 (dd, J=4.8 Hz, 11.4 Hz, IH) , 2.33-2.23 (m, 4H) , 1.90-0.80 (m, 21H) , 1.12 (S, 3H) , 1.09 (S, 3H) , 1.03 (s, 3H) , 0.99 (S, 3H) , 0.90 (d, J=6.9 Hz, 3H) , 0.87 (d, J=6.6 Hz, 6H) , 0.82 (s, 3H) ; IR (film): 3427, 2951, 2869, 2853, 1467, 1457, 1376, 1025, 1002, 734 cm "1 . EXAMPLE 23 Preparation of 14a-thia-D-homo-dihydro- lanosterol (Compound 57) By the method described for Compound 56 (Example Λ * 22) the cyclic acetal (Compound 7d) (300 mg, 0.63 mmole) was transformed to six-membered cyclic sulfide (Compound 57) (129 mg, 44.3% yield) as a white foamy solid. Physical Data: NMR (300 MHz, CDC1 3 ): delta 3.26 (dd, J=4.8 Hz, 11.1 Hz, IH) , 2.75 (s, IH) , 2.50-2.25 (m, 3H) , 2.05-0.90 (a, 24H) , 1.13 (s, 3H) , 1.01 (s, 3H) , 0.99 (S, 3H) , 0.89 (d, J=6.9 Hz, 3H) , 0.86 (d, J=6.6 Hz, 6H) , 0.81 (s, 3H) . EXAMPLE 24 Preparation of 14-Aza-4.4-dimethyl-5a- cholesta-8,14-dien-3b-ol (Compound 66a) AS. Preparation of 4.4-dimethyl-3b-r(4- methoxybenzyl)oxy1-14-oxo-5a-14.15- secocholest-8-ene-15-carboxylic acid (Compound 63) To a stirred solution of the enone aldehyde (Compound 4b) [15 mmole, crude material, prepared from Compound 2b (8 g, 15 mmole)] in tert-butanol (340 ml) and water (85 ml) were added sodium chlorite (Aldrich) (2.91 g, 30 mmole) and the mixture was stirred at room temperature for 1 hr. At the end of the stirring was added methylene chloride (500 ml) to the mixture and it was washed with water (2 x 150 ml) . The combined aqueous layers were re-extracted with methylene chloride (200 ml) and washed with water once. The methylene chloride extracts were dried over anhydrous magnesium sulfate and evaporated under reduced pressure to give a solid residue of crude acid (Compound 63) in near quantitative yield. The crude material was routinely used for next transformation without purification. The analytical sample was obtained by recrystallization from ethyl acetate and * hexane, m.p. = 126-126.5°C. Physical Data: * NMR (300 MHz, CDC1 3 ): delta 7.29 (d, J=8.4 Hz, 2H) , 6.87 (d, J=8.4 Hz, 2H) , 4.60 (d, J-11.4 Hz, IH) , 4.40 (d, J=11.4 HZ, IH) , 3.80 (s, 3H) , 3.00 (dd, J=3.6 Hz, 11.4 Hz, IH) , 2.47 (dd, J=7 Hz, 17.5 Hz, IH) , 2.38-0.80 (m, 22H) , 1.06 (s, 3H) , 1.05 (s, 3H) , 0.97 (s, 3H) , 0.96 (d, J=6.6 HZ, 3H) , 0.87 (s, 3H) , 0.86 (d, J=6.9 Hz, 6H) ; IR (film): 3435, 2951, 2937, 2869, 1707, 1654, 1624, 1616, 1513, 1465, 1301, 1247, 1098 cm "1 ; HRMS for C 37 H 54 0 4 (M-H 2 0) ; Calcd. 562.4022, found 562.4054. AT. Preparation of 4,4-dimethyl-3b-r (4- methoxybenzyl)oxyl-14-oxo-5a-14,15- secocholest-8-ene-15carboxylic acid azide (Compound 64) To a solution of the carboxylic acid (Compound 63) (15 mmole) and N-methylmorpholine (4.96 ml, 45 mmole) in dry methylene chloride (270 ml) at 0° was added isobutyl chlorofor ate (2.92 ml, 22.5 mmole) dropwise over a period of 5 min. and the mixture was stirred at 0° for 1 hr. Then a solution of sodium azide (9.78 g, 75 mmole) and tetrabutylammonium bromide (1.1 g, 3.4 mmole) in water (90 ml) was added and the two phase mixture was stirred at 0° for 1.5 hrs. The methylene chloride layer was separated and the aqueous layer was extracted with methylene chloride (2 x 50 ml) . The % combined extracts were washed with water and brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to give an oily residue of the crude acyl azide (Compound 64) (9.1 g, quantitative mass recovery) . The crude product was normally used for next reaction without purification. Physical Data: IR (film): 3522, 2952, 2938, 2869, 2315, 1720, 1657, 1623, 1615, 1514, 1464, 1248, 1172, 1096 cm "1 . AU. Preparation of 15-Aza-4,4-dimethyl-3b-r (4- methoxybenzyl)oxyl-15-methoxycarbonyl-5a- 14.15-secocholest-8-en-14-one (Compound 65) A solution of the acyl azide (Compound 64) (7 g, 11.6 mmole, crude material) in ethyl acetate (20 ml) and methanol (100 ml) was refluxed under nitrogen atmosphere for 5 hr. and the solvents were evaporated off. The oily residue of the crude carbamate (Compound 65) was normally used for next reaction without purification. Analytical sample of purified Compound 65 was obtained by crystallization from diethyl ether and hexane, m.p. = 144-144.5°. Physical Data: NMR (300 MHz, CDC1 3 ) : delta 7.27 (d, J=8.4 Hz, 2H) , 6.86 (d, J=8.4 Hz, 2H) , 4.60 (dm J=11.4 Hz, IH) , 4.52 (t, J=6 HZ, IH) , 4.35 (d, J=11.4 Hz, IH) , 3.80 (s, 3H) , 3.53 (s, 3H) , 3.33 (dd, J=7.5 Hz, 13.5 Hz, IH) , 2.90 (dd, J=3.9 Hz, 11.4 Hz, IH) , 2.84 (m, IH) , 2.56 (dd, J=6 Hz, 18 Hz, IH) , 2.25-0.80 (m, 21H) , 1.13 (d, J=6.6 Hz, 3H) , 1.06 (s, 3H) , 1.00 (s, 3H) , 0.97 (s, 3H) , 0.86 (d, J=6.6 HZ, 6H) , 0.86 (s, 3H) ; IR (film): 3464, 3366, 2952, 2869, 1727, 1654, 1623, 1617, 1514, 14654, 1458, 1380, 1247, 1099, 1037 cm "1 ; HRMS for C 38 H 59 N0 5 (M+) : Calcd. 609.4393; found 609.4404. AV. Preparation of 15-Aza-4,4-dimethyl-3b-r C4- ethoxybenzyl)oxy1-5a-cholest-8-, 14-diene (Compound 66b) To a solution of the carbamate (Compound 65) (11.6 mmole) in dry tetrahydrofuran (150 ml) was added potassium trimethylsilanolate (12.8 g, 100 mmole) and the mixture was refluxed under nitrogen atmosphere for 2 hrs. After cooling to room temperature diethyl ether (200 ml) was added and the organic layer was washed with water and brine. The combined aqueous layers were re-extracted with diethyl ether and the extracts were washed with brine. The ether extracts were dried over anhydrous sodium sulfate and evaporated under reduced pressure to give a solid residue. It was purified by column chromatography on silica gel with elution by 2:8 ethyl acetate - hexane to give 4.5 g of purified cyclic imine (Compound 66b) as white solid (72.7% overall yield from Compound 2b) . It was crystallized from methylene chloride and hexane to afford 3.6 g of crystalline product, m.p. = 159-160°. Physical Data: NMR (300 MHz, CDCl 3 ): delta 7.28 (d, J=8.4 Hz, 2H) , 6.87 (d, J=8.4 Hz, 2H) , 4.61 (d, J=11.7 Hz, IH) , 4.39 (d, J=11.7 Hz, IH) , 3.93 (dd, J=6 Hz, 14.5 Hz, IH) , 3.81 (S, 3H) , 3.34 (dd, J=9.3 Hz, 14.5 Hz, IH) , 2.93 (dd, J=3.9 Hz, 11.7 Hz, IH) , 2.40-0.78 (m, 22H) , 1.09 (s, 3H) , 1.01 (s, 3H) , 0.91 (d, J=5.1 Hz, 3H) , 0.88 (s, 3H) , 0.87 (d, J=5.7 Hz, 6H) , 0.86 (s, 3H) ; IR (KBr) : 2942, 2871, 2848, 1625, 1614, 1600, 1513, 1470, ■* * 1456, 1249, 1114, 1100, m 1037, 819 cm "1 ; HRMS for C 36 H 55 N0 2 (M+) : Calcd. 533.4232; found 533.4218. AW. Preparation of 14-Aza-4,4-dimethyl-5a- cholesta-8,14-dien-3b-ol (Compound 66a) To a stirred solution of Compound 66b (300 mg, 0.56 mmole) and allyltrimethylsilane (0.18 ml, 1.12 mmole) in dry methylene chloride (6 ml) was added boron trifluoride etherate (0.39 ml, 2.53 mmole) portionwise and the mixture was stirred at room temperature for 16 hr. under nitrogen atmosphere. Saturated sodium bicarbonate solution was added slowly to make the solution basic and the product was extracted with ethyl acetate. The extract was washed with water and brine, dried over anhydrous sodium sulfate and evaporated to give a solid residue. It was purified by column chromatography on silica gel with elution by 3:7 ethyl acetate-hexane followed by 7:3 ethyl acetate - hexane, to afford 217 mg of purified Compound 66a (93.3% yield) . Physical Data: NMR (300 MHZ, CDC1 3 ) : delta 3.94 (dd, J=6.6 Hz, 15.6 HZ, IH) , 3.35 (dd, J=9.6 Hz, 15.3 Hz, IH) , 3.25 (dd, J=4.5 Hz, 11.4 Hz, IH) , 2.42 (d, J=6 Hz, IH) , 2.30 (dm J=7.5 Hz, IH) , 2.10-0.90 ( , 21H) , 1.08 (s, 3H) , 1.03 (s, 3H) , 0.91 (d, J=5.7 Hz, 3H) , 0.87 (d, J=6.6 HZ, 6H) , 0.87 (S, 3H) , 0.85 (s, 3H) ; IR (KBr) : 3442, 3432, 2945, 2932, 2870, 1618, 1465, 1457, 1388, 1092, 1 1004433,, 11002266,, 11000099 ccmm ""11 ;; HHRRMMSS ffoorr C 28 H 47 N0 (M+) : Calcd. 413.3658; found 413.3646. EXAMPLE 25 Preparation of 14-Aza-5a-cholesta-8.14-dien- 3b-ol (Compound 70a) AX. Preparation of 3b-f (4-Methoxybenzyl)oxyl-14- oxo-5a-14,15-secocholest-8-ene-15-carbσxylic acid (Compound 67) By the method described for carboxylic acid (Compound 63) (Example 24-AS) 3b-[ (4-Methoxyl-benzyl) oxy]-15-oxo-5a-14, 15-secocholest-8-ene-14-one (Compound 40) (7.5 mmole, crude material, prepared from Compound 38b) (3.8 g, 7.5 mmole)) was transformed to carboxylic acid (Compound 67) (4.08 g, foamy solid residue) The crude material was used for next transformation without purification. Physical Data: NMR (300 MHz, CDC1 3 ): delta 7.27 (d, J=8.1 Hz, 2H) , 6.87 (d, J=8.1 Hz, 2H) , 4.53 (d, J=ll Hz, IH) , 4.47 (d, J=ll HZ, IH) , 3.80 (s, 3H) , 3.39 (m, IH) , 2.43-0.90 (m, 27H) , 1.01 (s, 3H) , 0.98 (s, 3H) , 0.95 (d, J=6.9 HZ, 3H) , 0.86 (d, J=6.6 Hz, 6H) ) ; IR (film): 3150, 2935, 2867, 1706, 1657, 1614, 1514, 1466, 1459, 1377, 1302, 1249, 1172, 1036 cm "1 ; HRMS for C 27 H 43 °4 (M-CH 3 OC 6 H 4 CH 2 ) : Calcd. 431.3161; found 431.3224. AY. Preparation of 3b-F (4-Methoxybenzyl)oxyl-14- oxo-5a-14,15-secocholest-8-ene-15-carbσxylic acid azide (Compound 68) By the method described for acyl azide (Compound 64) (Example 24-AT) carboxylic acid (Compound 67) (7.5 mmole) was transformed to acyl azide (Compound 68) as an oil. The crude material was used for next transformation without purification. Physical Data: NMR (300 MHz, CDCl 3 ) : delta 7.27 (d, J=8.4 Hz, 2H) , 6.87 (d, J=8.4 Hz, 2H) , 4.52 (d, J=11.7 Hz, IH) , 4.47 (d, J-11.7 Hz, IH) , 3.80 (s, 3H) , 3.39 (m, IH) , 2.42-0.90 (m, 26H) , 1.02 (S, 3H) , 0.96 (s, 3H) , 0.93 (d, J=6.3 Hz, 3H) , 0.86 (d, J=6.6 Hz, 6H) ; IR (film): 2953, 2935, 2868, 2135, 1720, 1658, 1620, 1614, 1513, 1467, 1377, 1248, 1180, 1172, 1087 cm "1 . AZ. Preparation of 15-Aza-3b-r (4-methoxybenzyl)- oxy1-15-methoxycarbonyl-5a-14.15-secocholest- 8-en-14-one (Compound 69) By the method described for carbamate (Compound 65) (Example 24-AU) acyl azide (Compound 68) (7.5 mmole) was transformed to carbamate (Compound 69) as an oil. The crude product was used for next reaction without purification. The analytical sample of purified Compound 69 was obtained by crystallization from diethyl ether and hexane. Physical Data: NMR (300 MHz, CDC1 3 ): delta 7.25 (d, J=8.2 Hz, 2H) , 6.86 (d, J=8.4 Hz, 2H) , 4.48 (s, 2H) , 3.79 (s, 3H) , 3.51 (s, 3H) , 3.30 (m, IH) , 2.85 ( , IH) , 2.50-0.90 (m, 26H) , 1.11 (d, J=6.6 Hz, 3H) , 1.01 (s, 6H) , 0.86 (dm J=6.6 Hz, 6H) ; IR (KBr) : 3463, 3363, 2952, 2934, 2867, 1726, 1654, 1617, 1513, 1466, 1457, 1376, 1247, 1109, 1104, 1075, 1034 cm "1 ; HRMS for C 3 4 H 5 0 ° 3 (M-NH 2 C0 2 CH 3 ) : Calcd. 506.3760; found 506.3769. BA. Preparation of 14-Aza-3b-r (4-Methoxybenzyl)- * oxyl-5a-cholest-8,14-diene (Compound 50b) * By the method described for cyclic imine (Compound 66b) (Example 24-AV) carbamate (Compound 69) (7.5 mmole) was transformed to cyclic imine (Compound 70b) . The solid residue was purified by column chromatography on silica gel with elution by 3:7 ethyl acetate-hexane to afford 2.33 g of purified Compound 70b as solid (61.4% overall yield from Compound 38b) . It was crystallized from methylene chloride and hexane to give analytically purified sample. Physical Data: NMR (300 MHZ, CDC1 3 ): delta 7.27 (d, J=8.7 Hz, 2H) , 6.87 (d, J=8.7 Hz, 2H) , 4.52 (d, J=11.4 Hz, IH) , 4.47 (d, J=11.4 Hz, IH) , 3.94 (dd, J=6.9 Hz, 15.3 Hz, IH) , 3.80 (S, 3H) , 3.35 (s, 3H) , 3.35 (m, 2H) , 2.40-0.80 (m, 24H) , 1.04 (s, 3H) , 1.04 (s, 3H) , 0.91 (d, J=6 Hz, 3H) , 0.87 (s, 3H) , 0.87 (d, J=6.3 Hz, 6H) ; IR (film): 3921, 2869, 2852, 1620, 1614, 1598, 1515, 1466, 1454, 1369, 1301, 1249, 1104, 1092, 1078, 1032, 8 82200 ccmm "11 ;; HHRRMMSS ffoorr CC 3344 HH 5 , 1 NOI 2 (M+) : Calcd. 505.3920; found 505.3961, BB. Preparation of 14-Aza-5a-cholesta-8,14-dien- 3b-ol (Compound 70a) By the method described for azasterol (Compound 66a) (Example 24-AW) cyclic imine (Compound 70b) (1 g, 1.98 mmole) was transformed to azasterol (Compound 70a) * as a solid. It was purified by column chromatography on silica gel with elution by 3:& ethyl acetate - hexane followed by 8:2 ethyl acetate - hexane to obtain 207 mg of unreacted starting material (Compound 70b) and 673 mg of azasterol (Compound 70a) (96.3% yield based on the recovered starting material) . The product was crystallized from diethyl ether and hexane, m.p. = 178-179°. Physical Data: NMR (300 MHz, CDCl 3 ) : delta 3.94 (dd, J=6.9 Hz, 15.3 Hz, IH) , 3.60 (m, IH, 3.34 (dd, J=9.6 Hz, 15 Hz, IH) , 2.45-0.80 (m, 25H) , 1.04 (s, 3H) , 0.92 (d, J=6 Hz, 3H) , 0.87 (s, 3H) , 0.87 (d, J=6.6 Hz, 6H) ; IR (film) : 3304, 2931, 2867, 2858, 1620, 1597, 1467, 1453, 1371, 1 1005566,, 11002255 ccmm ""11 ;; HHRRMMSS ffoo:r C 26 H 43 BI (M+) : Calcd. 385.3344; found 385.3344. BIOACTIVITY EXAMPLE 26 3-Hvdroxy-3-Methylglutaryl Coenzyme A Reductase (HMGR) Suppression Assay The ability of the compounds of Formula I to suppress the activity of HMGR, the rate limiting enzyme of cholesterol biosynthesis, was tested as follows. Chinese Hamster Ovary (CHO) cells were divided twice weekly and were maintained in McCoy's 5A medium supplemented with 1% carbosil delipidated Fetal Bovine System (FBS) (obtained from Gibco Laboratories, Chagrin Falls, OH) . Cells were harvested during the logarithmic phase of growth and cell cultures were prepared by adding 0.5 x 10 cells to each well in a 24 well cluster dish (obtained from Costar, Data Packaging Corp., Cambridge, MA) employing 1 ml of the above medium per each well. The cell cultures were incubated for 48 hr. at 37° in a 5% C0 2 , 95% air environment. The test compounds in a 2.5% suspension of bovine serum albumin (BSA) (Fatty acid free) in ethanol were then added to the cultures such that the final ethanol and BSA concentrations in the incubation medium were 0.5% and 0.25% respectively. Treated cells were incubated with the indicated compounds for 6 hr. at 37° in a 5% C0 2 , 95% air environment. Control cells were treated in an identical fashion to those which received test compound, except they were * * incubated with the BSA and ethanol suspension only. HMGR activity was then measured in digitonin-permeabilized cells by the method developed by Leonard et al. , J. Biol. Chem. , 262: 7914-1719 (1987) . Specifically, the medium in each well was aspirated and the cells rinsed with a 50 mM solution of phosphate buffered saline (PBS) . One ml of 30 mg/ml of digitonin in CSK buffer (prepared using 10 mM Pipes [piperazine-N,N / -bis (2-ethansulfonic) acid], 100 mM KCl, 2.5 mM MgCl 2 , 300 mM sucrose, 1 mM EGTA, pH 6.8) was added to each well and incubated for 10 min. at 22° to permeabilize the cells. The buffer was carefully aspirated and the wells were rinsed twice each time with 1 ml of PBS. HMGR activity was measured directly by adding 75 ml of PIB buffer (50 mM potassium phosphate, 1 mM Na 2 EDTA, 10 mM dithiothreitol, pH 7.4) to each well and incubating the cells for 30 minutes at 37° as described above. The enzyme assay was initiated by the addition of 83 μl of substrate/cofactor mixture such that the final assay contained the following: 0.1 M potassium phosphate, 5 mM dithiothreitol, 20 mM glucose-6-phosphate, 2.5 mM NADP, 0.175 units of glucose-6-phosphate dehydrogenase, 150 mM [ 14 C] HMG-Coenzyme A (15 DPM/pmol) , pH 7.4. The assay mixture was incubated for 30 min. at 37° and terminated by the addition of 70 ml of [ 3 H]-mevalonic acid (35,000 DPM/assay) , 0.15 mg/ml in 3 N HCI. The reaction was left to lactonize for an additional 30 min. at 37° or overnight at room temperature. Reaction products were separated by thin layer chromatography on silica gel G (obtained from Analtech, Newark, DE) developed in an unsaturated environment with acetone:benzene (3:2, v:v) . The band corresponding to mevalonolactone was identified by exposure to iodine vapor and was scraped into counting vials. The extent of conversion of starting substrate, HMG-CoA, to mevalonic acid was determined by liquid scintillation counting in Biofluor (obtained from New England Nuclear, Boston, MA) . Corrections for recovery and blank values were made for each sample. Protein determinations were made by Bio-Rad (Bio-Rad, Richmond, CA) dye binding assay according to the manufacturer's instruction using bovine serum albumin as standard. Cellular protein was solubilized from culture dishes by the addition of 20 μl of 16 N KOH and assayed directly for protein amount. Suppression values are expressed as the amount of compound required to suppress HMGR activity by 50% relative to that of the controls. The results of HMGR suppression assays are reported in Table 1. TABLE I -Hvdroxy-3-Methylglutaryl Coenzyme A Reductase (HMGR) Suppression Assay Ex. No. IC 5Q fuM) 1 0.18- 2 0.3 3 0.17 6 0.075 7 0.04 8 2.5 10 0.2 13 2.5 16 2.5 17 1.95 18 0.3 19 2.08 386 0.08 672 673 1.46 677 2.5 678 857 0.06 858 0.55 859 0.06 1303 0.3 1508 1.25 1509 5. 1817 0.5 1818 0.16 The ability of compounds of this invention to effectively suppress HMGR activity is demonstrated by the data in Table I. As a comparison, it should be * noted that cholesterol, lanosta-8,24-diene-3b-ol and lanost-8-en-3b-ol, when tested under these same conditions, were without effect on measured HMGR activity. Thus, the potent HMGR suppression activities of these compounds make them very attractive as hypocholesterolemic agents. EXAMPLE 27 Lowering Blood Cholesterol Levels in Hamsters The ability of the compounds of Formula I to lower blood cholesterol levels has been demonstrated in hamsters utilizing the following protocol. Male Golden Syrian hamsters (50-60 grams) were obtained from Charles River, Inc. (Wilmington, MA) . Animals were housed in individual suspension cages and were maintained on a light cycle consisting of 12 hours of light followed by 12 hours of dark. Animals were allowed free access to water and feed (Agway ground chow, RMH 3200, Agway, Syracuse, N.Y.) containing 1% (w/w) corn oil) for a minimum of 4 weeks. Following this stabilization period a sample of blood was collected by orbital sinus bleeding under light ether anesthesia into heparinized capillary tubes. Plasma was separated by centrifugation (600 x g _ for 10 minutes) and plasma cholesterols were determined by an autoanalyzer (Centrifichem 600, Baker Instruments, Allentown, PA) . Based upon measured plasma cholesterol values, the animals were randomized into two groups such that the mean plasma cholesterol values were identical for both groups. Animals in the two groups were then placed on one of two diets: (1) Diet A, consisting of ground chow plus 1% (w/w) corn oil, as described above; or (2) Diet B, consisting of Diet A plus 0.2% (w/w) of a test compound. Animals on Diet B, the treated animals, were allowed free access to feed and water, while animals on Diet A were pair-matched with Diet B animals and served as pair-fed controls. The animals were kept on their respective diets for 7-days at which time they were bled by cardiac puncture under C0 2 anesthesia. Total plasma cholesterol levels were determined as described above. The results are presented in Table II. The data is reported as means + SEM (standard error of the mean) , in units of mg/dl. The value "N" represents the number of animals in each group. TABLE II Effect of Various Test Compounds Upon Plasma Cholesterol Levels in Hamsters Plasma Cholesterol Example No. Control Treated (mg/dl) λ 133.0 + 4.0 120. + 2.0 (N=20) (N=10) 1 Values represent means +SEM for the number of animals given in parenthesis 2 Dosed at 0.2% (w/w) in feed As the data in Table II indicate, blood cholesterol levels can be significantly lowered by administration of compounds of Formula 1. EXAMPLES 28-31 Scheme IX generally depicts the synthetic sequence for the preparation of the compounds of Examples 28-30. In the initial reaction. Compound 72 is preferably converted to Compound 73 using catalytic osmium tetroxide. Preferred methods for the other synthetic conversions are provided in the examples which follow this scheme. SCHEME IX 74 R 2 = CH 3 75 R 2 = CH 3 EXAMPLE 28 Preparation of (22E)-4,4-Dimethyl-15-oxa-14α-vinyl- ergosta-8,22-dien-3β-ol (Compound 78) BC. Preparation of (22E)-4, -Dimethyl-ergosta-8,22- diene-3β,14CC, 15α-triol (Compound 73) To a stirred solution of (22E)-4, -dimethyl- ergosta-8, 14,22-trien-3β-ol (Compound 72, 10 g, 23.5 mmole) prepared by the emthod described by Dolle, et al. J. Qrσ. Chem.. 51: 4027 (1986), in 1,4-dioxane (400 ml) were added pyridine (10 ml), 1,8-diazabicyclo- [4.4.0.]undec-7-ene (DBU, Aldrich Chemical Co.) (4 ml) , an aqueous solution of trimethylamine N-oxide dihydrate (Aldrich Chemcial Co.) (5.4 g, 47 mmole in 50 ml of water) and a 20% solution of osmium tetraoxide in methylene chloride (1.5 ml, 1.18 mmole) and the mixture was heated under reflux for 24 hr. After cooling to room temperature was added 20% solution of sodium bisulfite (50 ml) and the mixture was stirred for 0.5 hr. It was extracted with ethyl acetate (3 x 200 ml) and the combined extracts were washed with water and brine. The organic extracxt was dried over magnesium sulfate and evaporated to give a solid residue. The crude product was dissolved in a minimum amount of ether and passed through a short silica gel column with elution by ether to remove the colored impurities. The solvent was evaporated off to afford a white crystalline solid (7.47 g) of the triol (Compound 73). Physical data: NMR (300 MHZ, CDCL3) : delta 5.23 (dd, J=7.3 Hz, 15.4 Hz, IH) , 5.13 (dd, J=7.3 Hz, 15.4 Hz, IH) , 4.10 (m, IH) , 3.24 (m, IH) , 2.41 (d, J=9.5 Hz, IH) , 2.38-0.08 (m, 21H), 1.02(s,3H), 1.00(s,3H), 0.97 (d, J=5.8 Hz, 3H) , 0.91 (d, J=6.6Hz, 3H) , 0.84-0.81 (m, 9H) , 0.71 (s, 3H) . BD. Preparation of (22E)-4,4-Dimethyl-3β-hydroxy-15- oxo-14,15-secoergosta-8,22-dien-14-one (Compound 74) To a stirred solution of the triol (Compound 73, 13.2 g, 28.9 mmole) in dry benzene (360 ml) in the dark was added lead tetraacetate (12.8 g, 28,9 mmole) in small portions over a period of 1 hr. and the mixture was stirred at room temperature for 1 hr. under nitrogen atomosphere and in the dar . The mixture was filtered through Celite and the filtercake was rinsed several times. Evaporation of the solvent provide a foamy solid of the enone aldehyde (Compound 74) in near quantitative yield. Physical date: NMR (300 MHz, CDCI3) : delta 9.55 (brs, IH) , 5.24- 5.22 (m, 2H) , 3.30 (dd, J=4.7 Hz, 11.3 Hz, IH) , 2.56- 0.08 ( , 20H) , 1.03 (s, 3H) , 1.01 (s, 3H) , 0.93 (d, J=6.9 Hz, 3H) , 0.93 (s, 3H) , 0.89 (d, J=6.9 Hz, 3H) , 0.82-0.77 (m, 9H) . BE. Preparation of (22E)-4,4-Dimethyl-3β-hydroxy-15- (1'-piperdino)-14,15-secoergosta-8,15,22- trien-14-one (Compound 75) To a solution of the enone-aldehyde (Compound 74, 11.9 g, 26 mmole) in benzene (240 ml) was added piperidine (12 ml) and the mixture was refluxed under a Dean-Stark trap until the removal of water is completed (ca. 1 hr.) . The excess piperidine and the solvent were evaporated off under reduced pressure after cooling to give a foamy solid residue of the enamine (Compound 75) in quantitative yield. Physical data: NMR (300 MHz, CDCI3) : delta 5.56 (d, J=13.5 Hz, IH) , 5.28 (dd, J=8.4 Hz, 15.4 Hz, IH) , 5.14 (dd, J=7.7 Hz, 15.4 Hz, IH) , 4.20 (br, IH) , 4.17 (dd, J=10.6 Hz, 13.5 Hz, IH) , 3.28 (dd, J=4.7 Hz, 11.3 Hz, IH) , 2.88 (m, 4H) , 2.80-0.80 (m, 19H) , 1.60 (m, 4H) , 1.04 (s, 3H) , 1.03 (s, 3H) , 0.95 (s, 3H) , 0.93 (d, J=6.6 Hz, 3H) , 0.91 (d, J=6.6 Hz, 3H) , 0.84-0.79 (m, 9H) . BG. Preparation of (22E) -4, 4-Dimethyl-3β-hydroxy-16- oxo-14, 16-seco-D-nor-ergosta-8,22-dien-14-one (Compound 76) A solution of the enamine (Compound 75, 26 mmole) in dry methylene chloride (200 ml), containing ca. 10 mg of Sudan Red 7B as an indicator, was bubbled with ozone at -78° until the color become light pink. After stirring for 5 min. dimethyl sulfide (5 ml) was added and the mixture was stirred for 30 min. at -78°. The residue after evaporation of the solvent was dissolved in a small amount of ether and passed through a plug of silica gel to remove polar impurities . Evaporation of the solvent afforded a foamy solid of the enone aldehyde (Compound 76) . Physical data: NMR (300 MHz, CDC13) : delta 9.73 (d, J=4.7 Hz, IH) , 5.33 (m, 2H) , 3.28 (dd, J=4.6 Hz, 11.5 Hz, IH) , 2.32 (br, 2H) , 2.18 (dd, J=6.2 Hz, 13.5 Hz, IH) , 2.60-0.8 (m, 15H) , 1 . 21 ( s , 3H) , 1 . 07 (s , 3H) , 1 . 04 (d, J=6 . 6 Hz , 3H) , 1 . 04 ( s , 3H) , 0 . 91 (d, J=6 . 9 Hz , 3H) , 0 . 84-0 . 81 (m, 9H) . BH. Preparation of (22E) 3βl6-Dihydroxy-4, 4-dimethyl- 14, 16-seco-D-nor-ergosta-8,22-dien-14-one (Compound 77) To a solution of the enone-aldehyde (Compound 76, 26 mmole) in methanol (115 ml) at -40° was added sodium borohydride (0.59 g, 15.6 mmole) and the mixture was stirred for 1 hr. at from about -40°, with warming to about 10°. The excess sodium borohydride was destroyed by stirring for 5 min. with acetic acid (1 ml) . It was then neutralized with saturated solution of sodium bicarbonate and concentrated under reduced pressure. The residue was extracted with ethyl acetate (3 x 100 ml) and the combined extracts were washed with water and brine, dried over magnesium sulfate, and evaporated to give an oily residue. The crude product was column chromatographed on silica gel with elution by ethyl acetate - hexane (2 : 8) to give 6 g of pure enone- alcohol (Compound 77) . Physical data: NMR (300 MHz, CDCI3) : delta 5.32-5.28 (m, 2H) , 3.69 (dd, J=5.3 Hz, 6.8 Hz, IH) , 3.61 (dd, J=4.4 Hz, 6.8 Hz, IH) , 2.64-.8 ( , 19H) , 1.14 (d, J=7.0 Hz, 3H) , 1.07 (s, 6H) , 1.03 (s, 3H) , 0.92 (d, J=7.0 Hz, 3H) , 0.85-0.80 (na, 9H) . BI. Preparation of (22E)-4,4-Dimethyl-15-oxa-14α-vinyl- ergosta-8, 22-dien-3fi-ol (Compound 78) To a solution of the enone-alcohol (Compound 77, 1.98 g, 4.45 mmole), 2,6-lutidine (1.71 ml, 14.7 mmole) * and 4-dimethylamino-pyridine (0.1 g) in dry methylene chloride (22 ml) at 0° was added chlorotrimethysilane I (1.7 ml, 13.4 mmole) dropwise and the mixture was stirred for 40 min. at 0° and for 10 min. at 25°. The reaction was quenched by methanol (1 ml) and the mixture was poured into ether. The ether solution was washed with water and brine, dried over magnesium sulfate and evaporated to give a foamy solid residue. The residue was then dissolved in dry tetrahydrofuran (25 ml) and was added lM-vinyl magnesium bromide in dry tetrahydrofuran (8.9 ml, 8.9 mmole) . The mixture was heat under reflux for 1 hr. and cooled to 0°. It was treated with IN HCI (18 ml) and extracted with ethyl acetate (3 x 30 ml) . The combined extracts were washed with water and brine, dried over magnesium sulfate, and evaporated to give an oily residue. It was dissolved in methanol (25 ml) containing p-toluenesulfonic acid (0.5 g) and the mixture was stirred for 16 hr. at room temperature. Then the reaction mixture was made basic with saturated solution of sodium bicarbonate and extracted with ethyl acetate (3 x 30 ml) . The combined organic solutions were washed with brine, dried over magnesium sulfate and evaporated to afford to foamy solid residue. The crude product was purified by column chromatographed on silica gel with elution by ethyl acetate - hexane (1 : 9) to provide 1.12 g of pure vinyl-oxasterol (Compound 78) . Physical data: NMR (300 MHZ, CDCl 3 ) : delta 5.71 (dd, J=11.0 Hz, 17.6 Hz, IH) , 5.26 (dd, J=7.9 Hz, 15.2 Hz, IH) , 5.11 (d, J=11.0 Hz, IH) , 5.10 ( , IH) , 5.00 (d, J=17.4 Hz, IH) , 3.67 (t, J=8.4 Hz, IH) , 3.49 (t, J=8.6 Hz, IH) , 3.29 (brt, J=5.3 Hz, IH) , 2.12-0.8 ( , 18H) , 1.02 (s, 3H) , 1.01 (s, 3H) , 0.90 (d, 6.5 Hz, 3H) , 0.84-0.8 (m, 15H) . EXAMPLE 29 BJ. Preparation of (22E)-15-0xa-14α-vinyl-ergosta-8,22- dien-3β-ol (Compound 80) By the method described for 4, 4-dimethyl-vinyl- oxasterol (Compound 79) (Example 28-BC through BI) (22E) -ergosta-8, 14,22-trien-3β-ol [prepared by the method described by Dolle, et al. J. Orσ. Chem. f 51: 4027 (1986) ] was transformed to the corresponding normethyl-vinyl-oxasterol (Compound 80) . Physical Data: NMR (300 MHz, CDCI3) : delta 5.71 (dd, J=10.8 Hz, 17.2 Hz, IH) , 5.27 (dd, J=7.7 Hz, 15.1 Hz, IH) , 5.11 (dd, J=2.2 Hz, 10.8 Hz, IH) , 5.10 (m, IH) , 5.01 (dd, J=2.2 Hz, 17.2 Hz, IH) , 3.67 (t, J-8.10 Hz, IH) , 3.49 (t, J=8.8 Hz, IH), 2.08-0.89 (m,21H), 1.04 (d, J=5.9 Hz, 3H) , 0.97 (s, 3H) , 0.90 (d, J=7.0 Hz, 3H) , 0.84-0.80 (m, 9H) . EXAMPLE 30 BK. Preparation of 14α-Ethyl-15-oxa-ergost-8-en-3β-oi (Compound 81) A solution of the vinyl-oxasterol (Compound 80, 5C mg, 0.12 mmole) and 10% palladium on carbon (10 mg) in 3 ml of ethyl acetate - acetic acid (95 : 5) was stirred under hydrogen atmosphere (1 atm.) for 30 min. After removal of the catalyst by filtration through Celite the solvents were evaporated to give a foamy <*r solid of the ethyl-oxasterol (Compound 81) in quantitative yield. Physical data: NMR (300 MHz, CDC1 3 ) : delta 3.76 (t, J=8.5 Hz, IH) , 3.66 (m, IH) , 3.43 (t, J=8.6 Hz, IH) , 2.17-0.75 (m, 26H) , 0.97 (s, 3H) , 0.94 (s, 3H) , 0.84 (d, J=6.9 Hz, 3H) , 0.81-0.73 ( , 12H) . EXAMPLE 31 Assay of 14 C-Acetate Incorporation into the Biosynthesis of Cholesterol The HepG2 cells (a human hepatoma cell line) used in this example were obtained from the American Type Culture Collection (ATCC, Rockville, MD) . They were maintained in Dulbecco's Modified Eagles Medium and Ham's F12 Medium (1:1) supplemented with 10% heat inactivated Fetal Bovine serum, 10 μM Herpes, 1 mM sodium pyruvate, 1 x Non-essential Amino Acids (Gibco) and 2 mM L-glutamine. The cells were harvested by washing cultures with 10 ml Hank's Balanced Salt Solution (2X) and incubating with 0.125% Trypsin in Versene (0.02% EDTA) for approximately one minute. After the cells are visibly * * rounded and loosened from the flask, 9 ml of the above medium is added. The cells are transferred to a 100 mM culture dish and syringed up and down through a 20 gauge needle to break up aggregated clumps of cells. Cell cultures are plated at 0.1 x 10 6 /ml and 0.075 x 10 6 /ml in two 24 well plates, respectively, aliquoting 1 ml cells/well. The cells are allowed to attach for 24 hours (48 hours for the lower density plate) before washing 2X with HBSS and refed with 1 ml of the above medium with 1% Cabosil delipidated serum instead of Fetal Bovine Serum. The cells are treated with the test compounds after 24 hours of exposure to the delipidated serum media. Chemicals are routinely prepared as a 10 ΦH solution in 100% ethanol or dimethyl sulfoxide (DMSO) . All test compounds are added at 50 μM, 25 μM, 10 μM, 1 μM at a final concentration of 0.45% solvent, 0.25% Bovine Serum Albumin (BSA) suspension per well. The solvent BSA is sonicated for 10 seconds to ensure maximum solubilization before addition to the cells. Control wells receive solvent/BSA at the same concentrations as the drug treated cultures. After incubation for one hour at 37°C, 5% CO 2 , 20 μCi/ml 3 H-MVAL is added per well in ethanol/medium so the final concentration of solvent is 1.2%. After 22 hours of incubation with the test compounds 2.5 μCi of 14 C-acetate is added per well for an additional 2 hours so that the final concentration of ethanol is 1.6%. Two known cholesterol biosynthesis inhibitors are included with each assay, namely 25-hydroxycholesterol and Lovastatin, to determine the reliability and validity of each assay. The cultures are harvested by aspirating the media and washing twice with ice cold 0.5 M Tris, 0.15 M NaCl, pH 7.4 to remove excess radiolabel not incorporated into the cells. Stop Reagent (1 ml of 15% potassium hydroxide, 85% methanol, 100 μg/ml butylated hydroxytoluene (BHT) is added to each well and the plate is sonicated in a mild water sonicating bath to release the cells from the bottom of the well. The digested cell extracts are transferred to 15 ml extraction tubes . Each well is rinsed with an additional 1 ml of the Tris/NaCl buffer which is added to the appropriate extraction tube. An aliquot (100 μl) is removed for protein determination at this point if desired. The cell extracts are saponified at 80°C for 30 minutes. After cooling 8 ml petroleum ether is added and the tubes are twirled on a rotary extractor for 5-10 minutes to extract the sterols into the organic solvent phase. The top organic phase is removed and passed through a Silica Seppak (Waters) which binds all sterols and free fatty acids. Sterols are eluted with a 5 ml diethyl ether:hexane (1:1) rinse. This sterols extraction is automated using the Millilab (Waters) to ensure reproducibility and accuracy from sample to sample. The eluted sterols are dried under nitrogen gas and resuspended in 150 μL ethanol. A 15 μL aliquot is removed from each sample and added to a scintillation vial filled with Formula 989 (NEN) . The samples are counted on the dual label 3R : 14Q program on the Beckman scintillation counter Model LS 7800. The incorporation of both radiolabeled precursors into sterols is compared between the treated and non- treated (control) cultures and expressed as "% control" for each precursor. Test compounds are classified as being "active" or "inactive" from these results and IC50 values were determined for active compounds. Analysis of sterol profiles is performed on the remainder of the sample by reversed phase HPLC. Analyses are done using an Ultrasphere octyl column (Altex) (0.46 x 25 cm), with a mobile phase consisting of acetonitrile:methanol:H2θ (44.5:44.5:10) . Chromatography is performed at a flow rate of 1.5 ml per minute at 45°C. RESULTS The following IC50 values represent the level of inhibition of the incorporation of 14 C-acetate into the cholesterol biosynthesis pathway, as determined above: Compound Example 28 (Compound 78) 0.05 Example 29 (Compound 80) >50.0 Example 30 (Compound 81) 0.60 AGRICULTURAL UTILITY Some compounds of this invention have also shown utility as plant disease control agents. They are effective in controlling a wide range of plant diseases, including economically important diseases caused by fungi of the Ascomycetes. Basidiomvcetes. and Oomycetes classes. Plant disease control is ordinarily accomplished by applying an effective amount of the compound either pre- or post-infection to the portion of the plant to be protected, such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compound may also be applied to the seed from which the plants to be protected are to be grown. Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5000 g/ha of active ingredient. Plants growing in soil treated at a rate of from less than 1 g/ha to 5000 g/ha of active ingredient. Plants growing in soil treated at a concentration from 0.1 to about 20 kg/ha can be protected from disease. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.06 to about 3 grams per kilogram of seed. EXAMPLE A The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on apple seedlings. The following day plants were inoculated with a spore suspension of Venturia inaegualis. the casual agent of apple scab, and incubated in a saturated humidity chamber at 20°C for 24 hours and then in a growth chamber at 22°C for 11 days, when disease ratings were made. EXAMPLE B The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant TREM 0124 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on peanut seedlings. The following day plants were incubated in a saturated humidity chamber at 22°C for 24 hours, then in a high humidity chamber at 27°C for 7 days, and then in a growth chamber at 29°C for 7 days, when disease ratings were made. EXAMPLE C The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant TREM 0914 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on broad bean seedlings. The following day plants were inoculated with a spore suspension of Botyrtis cinerea. the causal agent of bean grey mold, and incubated in a saturated humidity chamber at 20°C for 24 hours when disease ratings were made. EXAMPLE D The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on wheat seedlings. The following day plants were inoculated with a spore dust of Ersiphe qraminis f. sp. tritici, the causal agent of wheat powdery mildew, and incubated in a growth chamber at 20°C for 6 days, when disease ratings were made. EXAMPLE E The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on rice seedlings. The following day plants were inoculated with a spore suspension of Pyricularia oryzae, the causal agent of rice blast, and incubated in a saturated humidity chamber at 27°C for 24 hours and then in a growth chamber at 29°C for 4 days, when disease ratings were made. EXAMPLE F The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 220 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on rice seedlings. The following day plants were inoculated with a mycelial suspension of Rhizoctonia solani. the causal agent of rice sheath blight, and incubated in a saturated humidity chamber at 27°C for 48 hours and then in a growth chamber at 29°C for 4 days, when disease ratings were made. EXAMPLE G The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 220 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on wheat seedlings. The following day plants were inoculated with a spore suspension of Puccinia recondita. the causal agent of wheat leaf rust, and incubated in a saturated humidity chamber at 20°C for 48 hours and then in a growth chamber at 20°C for 8 days, when disease ratings were made. EXAMPLE H The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on tomato seedlings. The following day plants were inoculated with a spore suspension of Phvtophthora mfestans, the causal agent of tomato late blight, and incubated in a saturated humidity chamber at 20°C for 48 hours and then in a growth chamber at 20°C for 5 days, when disease ratings were made. EXAMPLE I The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on grape seedlings. The following day plants were inoculated with a spore suspension of Plasmopara victicola. the causal agent of grape downy mildew, and incubated in a saturated humidity chamber at 20°C for 24 hours and then in a growth chamber at 20°C for 7 days, and then held in a saturated humidity chamber, at 20°C for 24 hours, when disease ratings were made. EXAMPLE J The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 200 ppm in purifϊ^n. water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on grape seedlings. The following day plants were inoculated with a spore suspension of Botrvtis cinerea. the causal agent of grape grey mold, and incubated in a saturated humidity chamber at 20°C for 96 hours when disease ratings were made. EXAMPLE K The test compounds were dissolved in acetone in an amount equal to 6% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant TREM 014 (polyhydric alcohol esters) . This suspension was sprayed to the point of run-off on cucumber seedlings. The following day plants were inoculated with a spore suspension of Botrvtis cinerea, the causal agent of cucumber grey mold, and incubated in a saturated humidity chamber at 20°C for 4 days when disease ratings were made. Results of Examples A-K for two compounds of the invention are presented in Table III. In this table, « rating of 100 indicated 100% disease control, and a rating of 0 indicates no disease control relative to untreated plants that were inoculated and incubated as described in each Example. A dashed entry indicates the specified test was not performed. TABLE III Example A B C D E F G H I J K 1817 90 25 97 92 1 0 62 - - 97 99 1818 99 95 95 98 6 0 100 94 100 78 100 The present invention has been described in detail, including the preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/or improvements on this invention and still be within the scope and spirit of this invention as set forth in the following claims.

Claims: WHAT IS CLAIMED IS: 1. Compounds having the formula: wherein R is a side chain having either 8 or 9 carbon atoms and from 15 to 20 hydrogen atoms, optionally with one site of unsaturation; and the substituents R- independently each of R 2 , and R 3 , are selected from the groups defined as follows: is =0, OR 7 , or OCOR 7 ; is H, ^-Cg alkyl, C 2 ~C alkenyl, C 2 -C 8 alkynyl, or benzyl; R- is H, ^-Cg alkyl, C 2 ~Cg alkenyl, C 2 -C 6 alkynyl, benzyl, C(R 4 ) 2 R 5 , C0R 4 , CSR 4 , C(=NR 4 )R 4 , C0R 5 , CSR 5i C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 CSR 4 , C(R 4 ) 2 C(=NR 4 )R 4 , C(R 4 ) 2 COR 5 , C(R 4 ) 2 CRS 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NOR 6 , CR 4 NN(R 4 ) 2 , CR 4 NNR 4 R 6 , CHR 4 NHOR 4 , CHR 4 NHORg, CHR 4 NHN(R 4 ) 2 , CHR 4 NHNR 4 R 6 , CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NOR 6 , CHR 4 CR 4 NN(R 4 ) 2 , CHR 4 CR 4 NNR 4 Rg, CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg, CHR 4 CHR 4 NHN(R 4 ) 2 , C(0)NR 4 OR 4 , C(0)NR 4 OR 6 , C(S)NR 4 OR 4 , C(S)NR 4 ORg, CR 4 =CR 4 R 6 , C Ξ CRg, CR 4 =CR 4 C(R 4 ) 2 Z, C ≡ CC(R 4 ) 2 Z, CR 4 =CR 4 C(R 4 ) 2 ORg, C=CC(R 4 ) 2 ORg, or poly-(OR 4 , ORg, epoxy)-C^-Cg alkyl; 4 is H, C^ ^ -Cg alkyl, C 2 ~Cg alkenyl, C 2 -Cg alkynyl, phenyl or phenyl substituted with C^-C- j alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; R 5 is OR 4 , SR 4 , N(R 4 ) 2 , or NR 4 R 6 ; Rg is COR 4 , CSR 4 , or C(=NR 4 )R 4 ; R 7 is H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, c 2~ c 2 0 a l^Y n yl» phenyl or phenyl substituted with C^-C- j alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; X is 0, S, SO, S0 2 , N, NR 4 , NRg, or N(0)R 4 ; Z is halogen; and n is 1 or 2; and their physiologically acceptable salts. 2. The compounds of Claim 1, wherein: R 3 is H, ^-Cg alkyl, C 2 -C 8 alkenyl, C 2 -Cg alkynyl, benzyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NOR 6 , CHR 4 NHOR 4 , CHR 4 NHORg, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NORg, CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg, C(0)N 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 Rg, C≡CRg, CR 4 =CR 4 C(R 4 ) 2 ORg, C^CC(R 4 ) 2 OR 6 , or poly-(OR 4 , ORg, epoxy)-C^Cg alkyl. 3. The compounds of Claim 1, wherein: R 3 is H, C- j^ -C alkyl, C 2 -Cg alkenyl, C 2 -C 6 alkynyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NORg, C(0)NR 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 OR 6 , or poly-(OR 4 , ORg, epoxy)-C^-Cg alkyl. 4. The compounds of Claim 1, wherein X is 0, S, SO, N, NR 4 , or NRg. * 5. The compounds of Claim 1, wherein n is 1. * 6. The compounds of Claim 1, wherein: R 3 is H, C 1 -Cg alkyl, C 2 -Cg alkenyl, C 2 -C 6 alkynyl, benzyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NORg, CHR 4 NHOR 4 , CHR 4 NHORg, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NOR 6 , CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHOR 6 , C(0)NR 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 R 6 , C=CRg, CR 4 =CR 4 C(R 4 ) 2 ORg, C≡CC(R 4 ) 2 ORg, or poly-(OR 4 , ORg, epoxy)-C-^-Cg alkyl; X is 0, S, SO, N, NR 4 , or NR g ; and n is 1 7. The compounds of Claim 1, wherein: R 3 is H, ^-Cg alkyl, C 2 -Cg alkenyl, C 2 -C 6 alkynyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 N0R 4 , CR 4 N0R 6 , C(0)N 4 0R 4 , C(0)NR 4 OR 6 , CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 ORg, or poly-(0R 4 , ORg, epoxy)-C 1 -C 4 alkyl; X is 0, S, SO, N, NR 4 , or NR 6 ; and n is 1. 8. The compounds of Claim 1, wherein: R 2 is H, C^C- j alkyl, C 2 -C 3 alkenyl; 2~ c 3 alk y n Y!, or benzyl; R 3 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C(R 4 ) 2 R 5 , C0R 4 , C0R 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NOR g , C(0)NR 4 OR 4 , C(0)NR 4 OR 6 , CR 4 =CR 4 Rg, V CR 4 =CR 4 C(R 4 ) 2 ORg, or poly-(OR 4 , 0R 6' e P oχ y)~ c ι~ c 4 alkyl; R 4 is H, ^-^ alkyl, C 2 -C 4 alkenyl, C -C 4 alkynyl, phenyl or phenyl substituted with C-^-C^ j alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; and Rg is COR 4 . 9. The compounds of Claim 1, wherein: R is H, C^C- j alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, or benzyl; R 3 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NORg, C(0)NR 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 0R 6 , or poly-(OR 4 , ORg, epoxy)-C 1 -C 4 alkyl; R 4 is H, alkyl, C -C alkenyl, C 2 -C 4 alkynyl, phenyl or phenyl substituted with ^-C- j alkyl, OR 2 , Z, N(R 2 ) , or CF 3 ; or benzyl; R 6 is C0R 4 ; X is 0, S, SO, N, NR 4 , or NR 6 ; and n is 1. * 10. The compounds of Claim 1, wherein: R 2 is H, C-^-^ alkyl, or C 2 -C 3 alkenyl; R 3 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C(R 4 ) 2 R 5 , C0R 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NORg, C(0)NR 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 ORg, or poly-(OR 4 , ORg, epoxy)~ 1 -C 4 alkyl; R 4 is H, ^-^ alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl,. phenyl or phenyl substituted with C^C- j alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; Rg is COR 4 ; X is 0, S, SO, N, NR 4 , or NR 6 ; and n is 1. 11. The compounds of Claim 1, wherein: R 2 is H, ^-0 3 alkyl, C 2 -C 3 alkenyl; R 3 is H, C1-C4 alkyl, C 2 -C 4 alkenyl, CH 2 R 5 , CH0HCH=CH 2 , COR 4 , C0R 5 , CH 2 CH 2 R 5 , CH 2 COR 4 , CN, CH=NORg, CH=NOR 5 , CONHOR 4 , CONHORg, CH=CHRg, CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH 2 , CHOHCH-CH 2 ; O O R 4 is H, C- - ^ alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl or phenyl substituted with C 1 -C 3 alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; R g is COR 4 ; and X is 0, S, SO, N, NR 4 , or NRg. 12. The compounds of Claim 1, wherein: R 2 is H, C^C- j alkyl, C 2 -C 3 alkenyl; R 3 is H, C χ -C 4 alkyl, C 2 -C 4 alkenyl. CH 2 R 5 , CHOHCH=CH 2 , COR 4 , CORg, CH 2 CH 2 R 5 , CH 2 COR 4 , CN, CH=NOR 4 , CH=NORg, CONHOR 4 , CONHORg, CH=CHRg, CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH 2 , CHOHCH-CH,; 0 R 4 is H, C-L-C ή alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl or phenyl substituted with C 1 -C 3 alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; Rg is COR 4 ; X is 0, S, SO, N, NR 4 , or NR 6 ; and n is 1. 13. The compounds of Claim 1, wherein: R 2 is H or CH 3 , R 3 is H, CH 3 , CH=CH 2 , CH 2 OH, CHOHCH=CH 2 , CH 2 OCOCH 3 , CHO, C0CH 3 , C0 2 H, CONH 2 , C0 2 CH 3 , CH 2 CH 2 OH, CH 2 CHO, CH 2 C0 2 H, CH 2 C0 2 CH 3 , CN, CH=N0H, CH=NOCOCH 3 , CONHOH, CONHOCOCH 3 , CH=CHC0 2 CH 3 , CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH,, CHOHCH-CH,; and 0 0 X is 0, S, SO, N, NH, NCH 3 , NCHO, or NC0CH 3 . 14. The compounds of Claim 1, wherein: R 2 is H or CH 3 , R 3 is H, CH 3 , CH=CH 2 , CH 2 0H, CH0HCH=CH 2 , CH 2 OCOCH 3 , CHO, C0CH 3 , C0 2 H, CONH 2 , C0 2 CH 3 , CH 2 CH 2 OH, CH 2 CH0, CH 2 C0 2 H, CH 2 C0 2 CH 3 , CN, CH=N0C0CH 3 , CONHOH, C0NH0C0CH 3 / CH=CHC0 2 CH 3 , CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH,, CHOHCH-CH,; \ / 2 \/ 2 O O X is 0, S, SO, N, NH, NCH 3 , NCHO; or NCOCH 3 ; and n is 1. 15. The compounds of Claim 1, wherein: R is H, CH-}; R 3 is H, CH 3 , CH=CH 2 , CH 2 0H, CHOHCH=CH 2 , CHO, C0 2 H, CONH 2 , COCH 3 , CH=NOH, CHOHCH 2 OH, CHOHCHOHCH 2 OH; and X is 0, S, SO, N, NH, or NCHO. 16. The compounds of Claim 1, wherein: R 3 is H, CH 3 , CH=CH 2 , CH 2 OH, CHOHCH=CH 2 , CHO, C0 2 H, C0NH 2 , C0CH 3 , CH=NOH, CH0HCH 2 OH, CHOHCHOHCH 2 OH; X is 0, S, SO, N, NH, or NCHO; and n - 1. 17. A compound of Claim 1 which is selected from the group consisting of: 15-Oxa-dihydrolanosterol, 4 , 4-Dimethyl-15-oxa-5α-cholest-8-en-3β-ol , 4 , 4-Dimethyl-15-oxa-14α -vinyl-5α-cholest- 8-en-3B-ol, 3β-Acetoxy-4,4-dimethyl-15-oxa-l4α-vinyl-5 - cholest-8-ene, 3β-Acetoxy-32-hydroxymethyl-15-oxa-lanost-8-en- 32-ol, 3β-Acetoxy-15-oxa-32-oxo-lanost-8-ene, 15-Oxa-32-oxo-dihydrolanosterol, 15-Oxa-lanost-8-ene-3β,32-diol, 15-Oxa-32-vinyl-lanost-8-ene-3β,32-diol, 3B-Hydroxy-15-oxa-lanost-8-en-32-aldoxime, 3B-Hydroxy-15-oxa-lanost-8-en-32-carboxylic acid, 14α-Oxa-D-homo-dihydrolanosterol, 4,4-Dimethyl-14α-oxa-D-homo-5α-cholest-8-en-3β-ol, 4,4-Dimethyl-14 -oxa-14α-vinyl-D-homo-5α-cholest-8- en-3B-ol, 32-Hydroxymethyl-14α-oxa-D-homo-lanost-8-ene-3β 32-diol, 14α-θxa-32-oxo-D-homo-dihydrolanosterol, 14α-Methyl-15-oxa-5α-cholest-8-en-3β-ol, 15-Oxa-14α-vinyl-5α-cholest-8-en-3B-ol, 14α-(l' ,2'-Dihydroxy-ethyl)-15-oxa-5α-cholest-8- 14α-Formyl-15-oxa-5α-cholest-8-en-3β-ol, 14o-Hydroxymethyl-15-oxa-5α-cholest-8-en-3β-ol, 4,4-Dimethyl-15-thia-5 α -cholest-8-en-3B-ol, 15-Thia-dihydrolanosterol, 4,4-Dimethyl-15-thia-14α-vinyl-5α-cholest-8-en- 3B-ol, 3B-Hydroxy-15-thia-lanost-8-en-15-oxide, 4,4-Dimethyl-14α-thia-D-homo-5α-cholest-8-en- 3B-ol, 14α-Thia-D-homo-dihydrolanosterol, 15-Aza-4, -dimethyl-5α-cholesta-8,14-dien-3fi-ol, and 15-Aza-5α-cholesta-8,14-dien-3β-ol. 18. A compound of claim 1, which is selected from the group consisting of: 15-Oxa-dihydrolanosterol, 4,4-Dimethyl-15-oxa-5α-cholest-8-en-3β-ol, 4,4-Dimethyl-15-oxa-14 -vinyl-5α-cholest- 3B-Acetoxy-4,4-dimethyl-15-oxa-14t-vinyl-5α- cholest-8-ene, 3β-Acetoxy-32-hydroxymethyl-15-oxa-lanost-8-en- 32-ol, 3B-Acetoxy-15-oxa-32-oxo-lanost-8-ene, 15-Oxa-32-oxo-dihydrolanosterol, 15-Oxa-lanost-8-ene-3B,32-diol, 15-Oxa-32-vinyl-lanost-8-ene-3B,32-diol, 3B-Hydroxy-15-oxa-lanost-8-en-32-aldoxime, 3β-Hydroxy-15-oxa-lanost-8-en-32-carboxylic acid, 14 -Methyl-15-oxa-5α-cholest-8-en-3B-ol, 15-Oxa-14α-vinyl-5α-cholest-8-en-3β-ol, 14 α -(1 ' ,2'-Dihydroxy-ethyl)-15-oxa-5α- cholest-8-en-3β-ol, 14α-Formyl-15-oxa-5α-choelst-8-en-3B-ol, 14α-Hydroxymethyl-15-oxa-5α-cholest-8-en-3β-ol-; 4,4-Dimethyl-15-thia-5α-cholest-8-en-3 ' β-ol, 15-Thia-dihydrolanosterol, 4,4-Dimethyl-15-thia-14α-vinyl-5α- cholest-8-en-3B-ol, 3B-Hydroxy-15-thia-lanost-8-en-15-oxide, 15-Aza-4,4-dimethyl-5α-cholesta-8,14-dien-3β-ol, and 15-Aza-5α-cholesta-8,14-dien-3β-ol. 19. A composition suitable for decreasing cholesterol formation in mammals, said composition comprising (i) an effective amount of an active compound of the formula: Formula 1 wherein R is a side chain having either 8 or 9 carbon atoms and from 15 to 20 hydrogen atoms, optionally with one site of unsaturation; and wherein the substituents R^ independently each of R 2 , and R 3 , are selected from the groups defined as follows: is =0, 0R 7 , or 0C0R 7 ; is H, ^-Cg alkyl, C 2 -C 8 alkenyl, C 2 -Cg alkynyl, or benzyl; is H, C j^ -Cg alkyl, C 2 -C 8 alkenyl, C 2 -C 6 alkynyl, benzyl, C(R 4 ) 2 R 5 , C0R 4 , CSR 4 , C(=NR 4 )R 4 , C0R 5 , CSR 5' C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 C0R 4 , C(R 4 ) 2 CSR 4 , C(R 4 ) 2 C(=NR 4 )R 4 , C(R 4 ) 2 C0R 5 , C(R 4 ) 2 CRS 5 , C R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 N0R 4 , CR 4 N0Rg, CR 4 NN(R 4 ) 2 , CR 4 NNR 4 R 6 , CHR 4 NH0R 4 , CHR 4 NH0Rg CHR 4 NHN(R 4 ) 2 , CHR 4 NHNR 4 R 6 , CHR 4 CR 4 N0R 4 , CHR 4 CR 4 NOR g , CHR 4 CR 4 NN(R 4 ) 2 , CHR 4 CR 4 NNR 4 Rg, CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg, CHR 4 CHR 4 NHN(R 4 ) 2 , C(0)NR 4 OR 4 , C(0)NR 4 ORg, C(S)NR 4 OR 4 , C(S)NR 4 ORg, CR 4 =CR 4 R 6 , C ≡ CRg, CR 4 =CR 4 C(R 4 ) 2 Z, C≡CC(R 4 ) 2 Z, CR 4 =CR 4 C(R 4 ) 2 ORg, C^CC(R 4 ) 2 OR g , or poly-(OR 4 , ORg, epoxy)-C^Cg alkyl; R 4 is H, C j^ -Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, phenyl or phenyl substituted with C^C- j alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; R 5 is OR 4 , SR 4 , N(R 4 ) 2 , or NR 4 R 6 ; Rg is COR 4 , CSR 4 , or C(=NR 4 )R 4 ; R 7 is H, c l "" c 2 0 al kγ!/ C 2~ C 2 0 a lk en Yl C 2 -C 20 alkynyl, phenyl or phenyl substituted with C 1 -C 3 alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; X is 0, S, SO, S0 2 , N, NR 4 , NRg, or N(0)R 4 ; Z is halogen; and n is 1 or 2; and their physiologically acceptable salts; and (ii) an acceptable pharmaceutical or veterinary carrier or diluent. 20. The composition of claim 19, wherein: R 3 is H, C- j^ -Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, benzyl, C(R 4 ) 2 R 5 , COR 4 , C0R 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NOR 6 , CHR 4 NHOR 4 , CHR 4 NHORg, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NORg, CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg, C(O)N 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 R g , C≡CRg, CR 4 =CR 4 C(R 4 ) 2 OR 6 ,C≡CC(R 4 ) 2 ORg, or poly-(OR 4 , ORg, epoxy)-C 1 ~Cg alkyl. 21. The composition of claim 19, wherein: R 3 is H, ^-Cg alkyl, C 2 -C 8 alkenyl, C 2 -C 6 alkynyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NOR 6 , C(0)NR 4 OR 4 , C(0)NR 4 OR 6 , CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 ORg, or poly-(OR 4 , ORg, epoxy)-C-^-Cg alkyl. 22. The composition of claim 19, wherein X is O, S, SO, N, NR 4 , or NRg. 23. The composition of claim 19, wherein n is l. 24. The composition of claim 19, wherein: R 3 is H, C 1 -Cg alkyl, C 2 -C 8 alkenyl, C 2 -Cg alkynyl, benzyl, C(R 4 ) R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NORg, CHR 4 NHOR 4 , CHR 4 NHORg, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NORg, CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHOR g , C(O)NR 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 Rg, C≡CR g , CR 4 =CR 4 C(R 4 ) 2 ORg, C=CC(R 4 ) 2 OR 6 , or poly-(OR 4 , ORg, epoxy)-C j^ -Cg alkyl; X is O, S, SO, N, NR 4 , or NR 6 ; and n is 1 25. The composition of claim 19, wherein: R 3 is H, C^Cg alkyl, C 2 -Cg alkenyl, C 2 -C 6 alkynyl, C(R 4 ) 2 R 5 , COR 4 , C0R 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NOR 6 , C(0)NR 4 OR 4 , C(0)NR 4 OR 6 , CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 OR 6 , or poly-(OR 4 , ORg, epoxy) -C-^-C^ alkyl; X is 0, S, SO, N, NR 4 , or NR 6 ; and n is 1. 26. The composition of claim 19, wherein: R 2 is H, C-^-C- j alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, or benzyl; R • 3 is H, C -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C(R 4 ) 2 R 5 , COR 4 , C0R 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 N0R 4 , CR 4 NOR 6 , C(0)NR 4 0R 4 , C(0)NR 4 ORg, CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 OR 6 , or poly-(0R 4 , ORg, epoxy) -C^-C^ alkyl; R 4 is H, C^- ^ alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl or phenyl substituted with C^C- j alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; and R 6 is C0R 4 . 27. The composition of claim 19, wherein: R 2 is H, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, or benzyl; R 3 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NORg, C(0)NR 4 OR 4 , C(0)NR 4 OR 6 , CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 OR 6 , or poly-(OR 4 , ORg, epoxy)-C 1 -C alkyl; R 4 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl or phenyl substituted with ^-0 3 alkyl, OR 2 , Z, N(R ) , or CF 3 ; or benzyl; Rg is COR 4 X is 0, S, SO, N, NR , or NR 6 ; and n is 1. 28. The composition of claim 19, wherein: R 2 is H, alkyl, or C 2 -C 3 alkenyl; R 3 is H, C- | _-C 4 alkyl, C 2 -C 4 alkenyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NORg, C(0)NR 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 OR g , or poly-(OR 4 , ORg, epoxy)-C- | _-C 4 alkyl; R 4 is H, C - ^ alkyl, C 2 ~C 4 alkenyl, or phenyl or phenyl substituted by C-L-C 3 alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; Rg is COR 4 ; X is O, S, SO, N, NR 4 , or NR 6 ; and n is 1. 29. The composition of claim 19, wherein: R 2 is H, ^-0 3 alkyl, C 2 -C 3 alkenyl; R 3 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, CH 2 R 5 , CHOHCH=CH 2 , COR 4 , COR 5 , CH 2 CH 2 R 5 , CH 2 COR 4 , CN, CH=NOR 4 , CH=NOR g , CONHOR 4 , CONHORg, CH=CHRg, CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH 2 , CHOHCH-CH,; O V R 4 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl or phenyl substituted by C^C j alkyl, OR 2 , Z, N( ^2^2' or CF 3' or benzyl ; Rg is COR 4 ; and X is 0, S, SO, N, NR 4 , or NRg. 30. The composition of claim 19, wherein: R 2 is H, alkyl, C 2 -C 3 alkenyl; R 3 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, CH 2 R 5 , CHOHCH=CH 2 , COR 4 , COR 5 , CH 2 CH 2 R 5 , CH 2 COR 4 , CN, CH=N0R 4 , CH=NORg, CONHOR 4 , CONHORg, CH=CHRg, CHOHCH,OH, CHOHCHOHCH,OH, CH-CH,, Δ ^ \ / ^ CH0HCH-CH 2 ; 0 R 4 is H, C -C alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkenyl, phenyl or phenyl substituted by C 1 -C 3 alkyl, OR 2 , z, N(R ) , or CF 3 ; or benzyl; Rg is COR 4 ; X is 0, S, SO, N, NR 4 , or NR 6 ; and n is 1. 31. The composition of claim 19, wherein: R 2 is H or CH 3 , R 3 is H, CH 3 , CH=CH 2 , CH 2 OH, CH0HCH=CH 2 , CH 2 OCOCH 3 , CHO, COCH 3 , C0 2 H, CONH 2 , C0 2 CH 3 , CH 2 CH 2 0H, CH 2 CH0, CH 2 C0 2 H, CH 2 C0 2 CH 3 , CN, CH=NOH, CH=NOCOCH 3 , CONHOH, CONHOCOCH 3 , CH=CHC0 2 CH 3 , CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH,, CHOHCH-CH-,; and V V 2 X is O, S, SO, N, NH, NCH 3 , NCHO, OR NCOCH 3 32. The composition of claim 19, wherein: R 2 is H or CH 3 , R 3 is H, CH 3 , CH=CH 2 , CH 2 0H, CH0HCH=CH 2 , CH 2 OCOCH 3 , CHO, COCH 3 , C0 2 H, CONH 2 , C0 2 CH 3 , CH 2 CH 2 OH, CH 2 CHO, CH 2 C0 2 H, CH 2 C0 2 CH 3 , CN, CH=NOH, CH=N0C0CH 3 , CONHOH, C0NH0C0CH 3 , CH=CHC0 2 CH 3 , CHOHCH 2 OH, CHOHCHOHCH 2 OH, X is O, S, SO, N, NH, NCH 3 , NCHO, or NC0CH 3 ; and n is 1. 33. The composition of claim 19, wherein: R 3 is H, CH 3 , CH=CH 2 , CH 2 OH, CHOHCH=CH 2 , CHO, C0 2 H, CONH 2 , COCH 3 , CH=NOH, CHOHCH 2 OH, CHOHCHOHCH 2 OH; and X is 0, S, SO, N, NH, or NCHO. 34. The composition of claim 19, wherein: R 2 is H, CH 3 , R 3 is H, CH 3 , CH=CH 2 , CH 2 OH, CHOHCH=CH 2 , CHO, C0 2 H, C0NH 2 , COCH 3 , CH=NOH, CHOHCH 2 OH, CHOHCHOHCH 2 OH; X is O, S, SO, N, NH, or NCHO; and n is 1. 35. The composition of claim 19, wherein the preferred compound is selected from the group consisting of: 15-0xa-dihydrolanosterol, ,4-Dimethyl-15-oxa-5α-cholest-8-en-3β-ol, 4, -Dimethyl-15-oxa-14α-vinyl-5α-cholest- 3β-Acetoxy-4,4-dimethyl-15-oxa-14α-vinyl-5α- cholest-8-ene, 3B-Acetoxy-32-hydroxymethyl-15-oxa-lanost-8-en- 32-ol, 3β-Acetoxy-15-oxa-32-oxo-lanost-8-ene, 15-Oxa-32-oxo-dihydrolanosterol, 15-Oxa-lanost-8-ene-3B,32-diol, 15-Oxa-32-vinyl-lanost-8-ene-3B,32-diol, 3B-Hydroxy-15-oxa-lanost-8-en-32-aldoxime, 3B-Hydroxy-15-oxa-lanost-8-en-32-carboxylic acid. 14α-Oxa-D-homo-dihydrolanosterol, 4 , 4-Dimethyl-14α-oxa-D-homo-5α-cholest-8-en-3β-ol , 4 , 4-Dimethyl-14 -oxa-14 -vinyl-D-homo-5α-cholest-8- en-3B-ol, 32-Hydroxymethyl-14α-oxa-D-homo-lanost-8-ene-3β 32-diol, 14ατOxa-32-oxo-D-homo-dihydrolanosterol, 14α-Methyl-15-oxa-5α-cholest-8-en-3β-ol, 15-Oxa-14α-vinyl-5α-cholest-8-en-3β-ol, 14α-(l',2'-Dihydroxy-ethyl)-15-oxa-5α-cholest-8- 14α-Formyl-15-oxa-5α-cholest-8-en-3β-ol, 14 α -Hydroxymethyl-15-oxa-5α-cholest-8-en-3β-ol, 4,4-Dimethyl-15-thia-5α-cholest-8-en-3β-ol, 15-Thia-dihydrolanosterol , 4,4-Dimethyl-15-thia-14 α -vinyl-5 α -cholest-8-en- 3B-ol, 3B-Hydroxy-15-thia-lanost-8-en-15-oxide, 4,4-Dimethyl-14α-thia-D-homo-5α-cholest-8-en- 3B-ol, 14α-Thia-D-homo-dihydrolanosterol, 15-Aza-4,4-dimethyl-5 α -cholesta-8,14-dien-3β-ol, and 15-Aza-5α-cholesta-8,14-dien-3β-ol. 36. The composition of claim 19, wherein the preferred compound is selected from the group consisting of: 15-Oxa-dihydrolanosterol, 4,4-Dimethyl-15-oxa-5cι-cholest-8-en-3β-ol, 4,4-Dimethyl-15-oxa-14 -vinyl-5α-cholest- 3β-Acetoxy-4,4-dimethyl-15-oxa-14α-vinyl-5α- cholest-8-ene, 3B-Acetoxy-32-hydroxymethyl-15-oxa-lanost-8-en- 32-ol, 3β-Acetoxy-15-oxa-32-oxo-lanost-8-ene, 15-Oxa-32-oxo-dihydrolanosterol, 15-Oxa-lanost-8-ene-3β,32-diol, 15-Oxa-32-vinyl-lanost-8-ene-3B,32-diol, 3B-Hydroxy-15-oxa-lanost-8-en-32-aldoxime, 3B-Hydroxy-15-oxa-lanost-8-en-32-carboxylic acid, 14α-Oxa-D-homo-dihydrolanosterol, 4,4-Dimethyl-14α-oxa-D-homo-5α-cholest-8-en-3β-ol, 4,4-Dimethyl-14α-oxa-14α-vinyl-D-homo-5α-cholest-8- 32-Hydroxymethyl-14 -oxa-D-homo-lanost-8-ene-3β, 32-diol, 14 α -Oxa-32-oxo-D-homo-dihydrolanosterol, 14 α -Methyl-15-oxa-5α-cholest-8-en-3B-ol, 15-Oxa-14o-vinyl-5α-cholest-8-en-3B-ol, 14α-(l',2'-Dihydroxy-ethyl)-15-oxa-5α-cholest-8-, en-3B-ol, 14α-Formyl-15-oxa-5α-cholest-8-en-3β-ol, 14α-Hydroxymethyl-15-oxa-5α-cholest-8-en-3β-ol, 4,4-Dimethyl-15-thia-5α-cholest-8-en-3β-ol, 15-Thia-dihydrolanosterol, 4,4-Dimethyl-15-thia-14α-vinyl-5α-cholest-8-en-, 3B-ol, 3B-Hydroxy-15-thia-lanost-8-en-15-oxide, 4,4-Dimethyl-14α-thia-D-homo-5α-cholest-8-en-, 3B-ol, 14α-Thia-D-homo-dihydrolanosterol, 15-Aza-4,4-dimethyl-5α-cholesta-8,14-dien-3β-ol, and 15-Aza-5α-cholesta-8,14-dien-3B-ol. 37. A method of decreasing cholesterol formation in mammals in need of such therapy, said method comprising administering an effective amount of an active compound of the formula: wherein R is a side chain having either 8 or 9 carbon atoms and from 15 to 20 hydrogen atoms, optionally with one site of unsaturation; and wherein the substituents 1# independently each of R 2 , and R 3 , are selected from the groups defined as follows: is =0, OR 7 , or OCOR 7 ; is H, C 1 -C 6 alkyl, 2 -C 8 alkenyl, C 2 -Cg alkynyl, or benzyl; is H, ^-Cg alkyl, C 2 ~Cg alkenyl, C 2 -Cg alkynyl, benzyl, C(R 4 ) 2 R 5 , C0R 4 , CSR 4 , C(=NR 4 )R 4 , C0R 5 , CSR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 CSR 4 , C(R 4 ) 2 C(=NR 4 )R 4 , C(R 4 ) 2 COR 5 , C(R 4 ) 2 CRS 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 N0Rg, CR 4 NN(R 4 ) 2 , CR 4 NNR 4 R 6 , CHR 4 NHOR 4 CHR 4 NH0Rg, CHR 4 NHN(R 4 ) 2 , CHR 4 NHNR 4 Rg, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 N0Rg, CHR 4 CR 4 NN(R 4 ) 2 , CHR 4 CR 4 NNR 4 Rg, CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg, CHR 4 CHR 4 NHN(R 4 ) 2 , C(0)NR 4 OR 4 , C(0)NR 4 ORg, C(S)NR 4 OR 4 , C(S)NR 4 ORg, CR 4 =CR 4 R 6 , C≡CRg, CR 4 =CR 4 C(R 4 ) 2 Z, C ≡ CC(R 4 ) 2 Z, CR 4 =CR 4 C(R 4 ) 2 ORg, C≡CC(R 4 ) 2 OR 6 , or poly-(OR 4 , ORg, epoxy)-^-C alkyl; R is H, C j^ -Cg alkyl, C 2 -C 8 alkenyl, C 2 -Cg alkynyl, phenyl or phenyl substituted with 0 -05 alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; R 5 is OR 4 , SR 4 , N(R 4 ) 2 , or NR 4 R g ; Rg is COR 4 , CSR , or C(=NR )R 4 ; R 7 is H, C 1 -C 2Q alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, phenyl or phenyl substituted with alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; X is 0, S, SO, S0 2 , N, NR 4 , NRg, or N(0)R 4 ; Z is halogen; and n is 1 or 2; and their physiologically acceptable salts in an acceptable pharmaceutical or veterinary carrier or diluent to said mammal. 38. The method of claim 37, wherein: R 3 is H, ^-Cg alkyl, C 2 -C 8 alkenyl, C 2 -C 6 alkynyl, benzyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , ■ C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NORg, CHR 4 NHOR 4 , CHR 4 NHORg, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NORg, CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg, C(0)NR 4 OR 4 , C(0)NR 4 0R 6 , CR 4 =CR 4 R 6 , C≡CRg, CR 4 =CR 4 C(R 4 ) 2 ORg,C≡CC(R 4 ) 2 OR g , or poly-(OR 4 , ORg, epoxy)-C 1 -C 8 alkyl. 39. The method of claim 37, wherein: R 3 is H, C- j^ -Cg alkyl, C 2 -Cg alkenyl, C 2 -C 6 alkynyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NORg, C(0)NR 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 ORg, or poly-(OR 4 , ORg, epoxy)-C^Cg alkyl. 40. The method of claim 37, wherein X is 0, S, SO, N, NR 4 , or NRg. 41. The method of claim 37, wherein n is 1. 42. The method of claim 37, wherein: R 3 is H, alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, benzyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NORg, CHR 4 NHOR 4 , CHR 4 NHORg, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 N0Rg, CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHOR g , C(O)NR 4 OR 4 , C(0)NR 4 OR 6 , CR 4 =CR 4 Rg, C≡CR g , CR 4 =CR 4 C(R 4 ) 2 OR 6 , C=CC(R 4 ) 2 ORg, or poly-(OR 4 , ORg, epoxy)-C^Cg alkyl; X is 0, S, SO, N, NR 4 , or NR 6 ; and n is 1 44. The method of claim 37, wherein: R 3 is H, C- j^ -Cg alkyl, C 2 -Cg alkenyl, C 2 -C 6 alkynyl, C(R 4 ) 2 R 5 , C0R 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NOR 6 , C(0)NR 4 OR 4 , C(0)NR 4 0R 6 , CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 0R 6 , or poly-(OR 4 , ORg, epoxy)-C -C 4 alkyl; X is 0, S, SO, N, NR 4 , or NR g ; and n is 1. 45. The method of claim 37, wherein: R 2 is H, c ι~ c 3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, or benzyl; R 3 is H, C-^-^ alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C(R 4 ) 2 R 5 , C0R 4 , C0R 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 N0Rg, C(0)NR 4 OR 4 , C(0)NR 4 0Rg, CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 ORg, or poly-(0R 4 , ORg, epoxy)-C^^ alkyl; R 4 is H, C2-C4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl or phenyl substituted with C-^-^ alkyl, OR 2 , z, N(R 2 ) 2 , or CF 3 ; or benzyl; and 46. The method of claim 37, wherein: R 2 is H, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, c 2~ c 3 a l k Y n yl, or benzyl; R 3 is H, C- -C^ alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NORg, C(0)NR 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 ORg, or poly-(OR 4 , ORg, epoxy)-C- ] _-C 4 alkyl; R is H, C 1 -C alkyl, C -C alkenyl, c 2~ c 4 a l J Y n yl, phenyl or phenyl substituted with ^-^ alkyl, OR 2 , Z, N(R 2 ) 2 / or CF 3 ; or benzyl; Rg is COR 4 ; X is 0, S, SO, N, NR 4 , or NRg,* and n is 1. 47. The method of claim 37, wherein: R 2 is H, C^C- j alkyl, or C 2 -C 3 alkenyl; R 3 is H, C^- ^ alkyl, C 2 -C 4 alkenyl, C(R 4 ) 2 R 5 , COR 4 , C0R 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NOR 6 , C(0)NR 4 OR 4 , C(0)NR 4 0Rg, CR 4 =CR 4 R 6 , CR 4 =CR 4 C(R 4 ) 2 ORg, or poly-(0R 4 , 0R 6 , epoxy)-C χ -C 4 alkyl; R 4 is H, C 1 -C 4 alkyl, C 2 ~C 4 alkenyl, C 2 -C alkynyl, phenyl or phenyl substituted by C χ - C 3 alkyl, OR 2 , Z, N(R 2 ) , or CF 3 , or benzyl; Rg is COR 4 ; X is 0, S, SO, N, NR 4 , or NR 6 ; and n is 1. 48. The method of claim 37, wherein: R 2 is H, C 1 -C 3 alkyl, C 2 -C 3 alkenyl; R 3 is H, C 1 -C 4 alkyl, C 2 ~C 4 alkenyl, CH 2 R 5 , CHOHCH=CH 2 , COR 4 , COR 5 , CH 2 CH 2 R 5 , CH 2 COR 4 , CN, CH=NORg, CH=NOR 5 , CONHOR 4 , CONHORg, CH=CHRg, CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH 2 , CHOHCH-CH,; O V R is H, C 1 -C alkyl, C -C 4 alkenyl, phenyl or phenyl substituted by ^- - C 3 alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 , or benzyl; Rg is C0R 4 ; and X is 0, S, SO, N, NR 4 , or NRg. 49. The method of claim 37, wherein: R 2 is H, C-L-C-J alkyl, C 2 -C 3 alkenyl; R 3 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, CH 2 R 5 , CH0HCH=CH 2 , C0R 4 , CORg, CH 2 COR 4 , CN, CH=N0R 4 , CH=NORg, CONHOR 4 , CONHOR g , CH=CHRg, CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH 2 , CHOHCH-CH 2 R 4 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl or phenyl substituted by C 1 - C 3 alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 , or benzyl; R 6 is COR 4 ; X is 0, S, SO, N, NR 4 , or NR 6 ; and n is 1. 50. The method of claim 37, wherein: R 2 is H or CH 3 , R 3 is H, CH 3 , CH=CH 2 , CH 2 OH, CHOHCH=CH 2 , CH 2 OCOCH 3 , CHO, COCH 3 , C0 2 H, CONH 2 , C0 2 CH 3 , CH 2 CH 2 OH, CH 2 CHO, CH 2 C0 2 H, CH 2 C0 2 CH 3 , CN, CH=N0H, CH=NOCOCH 3 , CONHOH, CONHOCOCH 3 , CH=CHC0 2 CH 3 , CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH,, CHOHCH-CH, ; and V V X is 0, S, SO, N, NH, NCH 3 , NCHO, or NCOCH 3 51. The method of claim 37, wherein: R 2 is H or CH 3 , R 3 is H, CH 3 , CH=CH 2 , CH 2 OH, CHOHCH=CH 2 , CH 2 OCOCH 3 , CHO, C0CH 3 , C0 2 H, C0NH 2 , C0 2 CH 3 , CH 2 CH 2 OH, CH 2 CH0, CH 2 C0 2 H, CH 2 C0 2 CH 3 , CN, CH=NOH, CH=NOCOCH 3 , CONHOH, C0NH0C0CH 3 , CH=CHC0 2 CH 3 , CH0HCH 2 0H, CHOHCHOHCH j OH, ; is 0, S, SO, N, NH, NCH 3 , NCHO; or NC0CH 3 ; and n is 1. 52. The method of claim 37, wherein: R 2 is H, CH 3 ; R 3 is H, CH 3 , CH=CH 2 , CH 2 0H, CHOHCH=CH 2 , CHO, C0 2 H, C0NH 2 , C0CH 3 , CH=NOH, CHOHCH 2 OH, CHOHCHOHCH 2 OH; and X is 0, S, SO, N, NH, or NCHO. 53. The method of claim 37, wherein: R 2 is H, CH 3 ; R 3 is H, CH 3 , CH=CH 2 , CH 2 0H, CH0HCH=CH 2 , CHO, C0 2 H, C0NH 2 , COCH 3 , CH=N0H, CHOHCH 2 OH, CHOHCHOHCH 2 OH; X is 0, S, SO, N, NH, or NCHO; and n is 1. 54. The method of claim 37, wherein the preferred compound is selected from the group consisting of: 15-0xa-dihydrolanosterol, 4,4-Dimethyl-15-oxa-5a-cholest-8-en-3B-ol, 4,4-Dimethyl-15-oxa-14 α -vinyl-5α-cholest- 8-en-3fi-ol, 3B-Acetoxy-4,4-dimethyl-15-oxa-14o-vinyl-5α- cholest-8-ene, 3β-Acetoxy-32-hydroxymethyl-15-oxa-lanost-8-en- 32-ol, 3β-Acetoxy-15-oxa-32-oxo-lanost-8-ene, 15-Oxa-32-oxo-dihydrolanosterol, 15-Oxa-lanost-8-ene-3β,32-diol, 15-Oxa-32-vinyl-lanost-8-ene-3fi,32-diol, 3β-Hydroxy-15-oxa-lanost-8-en-32-aldoxime, 3β-Hydroxy-15-oxa-lanost-8-en-32-carboxylic acid, 14α-Oxa-D-homo-dihydrolanosterol, 4 , 4-Dimethyl-14α-oxa-D-homo-5α-cholest-8-en-3β-ol , 4 , 4-Dimethyl-14 α -oxa-14 α -vinyl-D-homo-5α-cholest-8- 32-Hydroxymethyl-14α -oxa-D-homo-lanost-8-ene-3β 32-diol , 14 α-θxa-32-oxo-D-homo-dihydrolanosterol , 14 α-Methyl-15-oxa-5α -cholest-8-en-3β-ol , 15-Oxa-14α -vinyl-5α-cholest-8-en-3β-ol , 14 α- ( ι ' , 2 ' -Dihydroxy-ethyl ) -15-oxa-5 α-cholest-8 - 14α -Formyl-15-oxa-5α-cholest-8-en-3β-ol , 14 .-Hydroxymethyl-15-oxa-5 α -cholest-8-en-3β-ol , 4 , 4-Dimethyl-15-thia-5 α -cholest-8-en-3β-ol , 15-Thia-dihydrolanosterol , 4 , 4-Dimethyl-15-thia-14α-vinyl-5α-cholest-8-en- 3β-Hydroxy-15-thia-lanost-8-en-15-oxide, 4 , 4-Dimethyl-14α-thia-D-homo-5α-cholest-8-en- 14α-Thia-D-homo-dihydrolanosterol, 15-Aza-4,4-dimethyl-5α-cholesta-8,14-dien-3β-ol, and 15-Aza-5α-cholesta-8,14-dien-3β-ol. 55. The method of claim 37, wherein the preferred compound is selected from the group consisting of: 15-Oxa-dihydrolanosterol, 4,4-Dimethyl-15-oxa-5α-cholest-8-en-3β-ol, 4,4-Dimethyl-15-oxa-14α-vinyl-5α-cholest- 3β-Acetoxy-4,4-dimethyl-15-oxa-14α-vinyl-5α- cholest-8-ene, 3β-Acetoxy-32-hydroxymethyl-15-oxa-lanost-8-en- 32-ol, 3β-Acetoxy-15-oxa-32-oxo-lanost-8-ene, 15-Oxa-32-oxo-dihydrolanosterol, 15-Oxa-lanost-8-ene-3β,32-diol, 15-Oxa-32-vinyl-lanost-8-ene-3β,32-diol, 3β-Hydroxy-15-oxa-lanost-8-en-32-aldoxime, 3β-Hydroxy-15-oxa-lanost-8-en-32-carboxylic acid, 14α-Oxa-D-homo-dihydrolanosterol, 4,4-Dimethyl-14 α -oxa-D-homo-5α-cholest-8-en-3β-ol, 4 , 4-Dimethyl-14α-oxa-14α -vinyl-D-homo-5α-cholest-8- 32-Hydroxymethy1-14α-oxa-D-homo-lanost-8-ene-3β, 32-diol, 14 -Oxa-32-oxo-D-homo-dihydrolanosterol, 14α-Methyl-15-oxa-5α-cholest-8-en-3β-ol, 15-Oxa-14α-vinyl-5o-cholest-8-en-3β-ol, 14α-(l',2'-Dihydroxy-ethyl)-15-oxa-5α-cholest-8-, 14α-Formyl-15-oxa-5α-cholest-8-en-3β-ol, 14α-Hydroxymethyl-15-oxa-5 α -cholest-8-en-3β-ol, 4,4-Dimethyl-15-thia-5 α -cholest-8-en-3β-ol, 15-Thia-dihydrolanosterol, 4,4-Dimethyl-15-thia-14α-vinyl-5α-cholest-8-en-, 3B-ol, 3β-Hydroxy-15-thia-lanost-8-en-15-oxide, 4,4-Dimethyl-14α-thia-D-homo-5α-cholest-8-en-, 3β-ol, 14α-Thia-D-homo-dihydrolanosterol, 15-Aza-4,4-dimethyl-5α-cholesta-8,14-dien-3β-ol, and 15-Aza-5o-cholesta-8,14-dien-3β-ol. 56. A process for the formation of 15-thia-lanosterols having the formula: wherein R is a side chain having either 8 or 9 carbon atoms and from 15 to 20 hydrogen atoms, optionally with one site of unsaturation; and wherein the substituents R lf independently each of R 2 , and R 3 , are selected from the groups defined as follows: is OR 7 or OCOR 7 ; is H, C 1 -Cg alkyl, C 2 -C 8 alkenyl, C 2 -Cg alkynyl, or benzyl; is H, C^-Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, benzyl, C(R 4 ) 2 R 5 , (R4) 2 C(R 4 ) 2 R g , CR 4 =CR 4 Rg, C≡CRg; is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -Cg alkynyl, phenyl or phenyl substituted with C 1 -C 3 alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; is OR 4 , SR 4 , N(R 4 ) 2 , or NR 4 R g ; is COR 4 , CSR 4 , or C(=NR 4 )R 4 ; R- is H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, c 2 ~ c 2 0 phenyl or phenyl substituted with C 1 -C 3 alkyl, OR 2 , z, N(R 2 ) 2/ or CF 3 ; or benzyl; X is S; Z is halogen; and n is 1 or 2. which process comprises treating a cyclic hemiacetal of the corresponding 15-oxa-dihydrolanosterol (X=0) with hydrogen sulfide and boron trifluoride etherate in a suitable reaction medium, under suitable reaction conditions, followed by reaction of the unisolated cyclic thioacetal intermediate with a trialkylsilane to yield the desired 15-thia-dihydrolanosterol. 57. The process of claim 56, wherein 15-thia-dihydrolanesterol (R 3 = CH 3 ) is formed. 58. The process of claim 56, wherein 4,4-Dimethyl-15-thia-5 -cholest-8-en-3β-ol (R 3 = H) is formed. 59. The process of claim 56, wherein 4,4-dimethyl-15-thia-14 -vinyl-5 -cholest-8-en-3β-ol (R 3 = CH=CH 2 ) is formed. 60. A method of controlling plant fungal diseases caused by fungi of the Ascometes. Basidiomvcetes. and Oomycetes classes, which method comprises treating plants in need of such treatment with an effective antifungal amount of one or more compounds having the formula: Formula 1 wherein R is a side chain having either 8 or 9 carbon atoms and from 15 to 20 hydrogen atoms, optionally with one site of unsaturation; and wherein the substituents R l7 independently each of R 2 , and R 3 , are selected from the groups defined as follows: is =0, 0R 7 , or OCOR 7 ; is H, C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -Cg alkynyl, or benzyl; is H, ^-C alkyl, C 2 -C 8 alkenyl, C 2 -Cg alkynyl, benzyl, C(R 4 ) 2 R 5 , C0R 4 , CSR 4 , C(=NR 4 )R 4 , C0R 5 , CSR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 CSR 4 , C(R 4 ) 2 C(=NR 4 )R 4 , C(R 4 ) 2 COR 5 , C(R 4 ) 2 CRS 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NORg, CR 4 NN(R 4 ) 2 , CR 4 NNR 4 Rg, CHR 4 NHOR 4 , CHR 4 NHORg, CHR 4 NHN(R 4 ) 2 , CHR 4 NHNR 4 Rg, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NORg, CHR 4 CR 4 NN(R 4 ) 2 , CHR 4 CR 4 NNR 4 Rg, CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg, CHR 4 CHR 4 NHN(R 4 ) 2 , C(0)NR 4 OR 4 , C(0)NR 4 ORg, C(S)NR 4 OR 4 , C(S)NR 4 OR g , CR 4 =CR 4 R 6 , C≡CR g , CR 4 =CR 4 C(R 4 ) 2 Z, C ≡ CC(R 4 ) 2 Z, CR 4 =CR 4 C(R 4 ) 2 ORg, C≡CC(R 4 ) 2 OR 6 , or poly-(OR 4 , ORg, epoxy)-C^Cg alkyl; R 4 is H, C^ ^ -Cg alkyl, C 2 -Cg alkenyl, C 2 -C 6 alkynyl, phenyl or phenyl substituted with C^C- j alkyl, OR 2 , Z, N(R ) 2 , or CF 3 ; or benzyl; R 5 is OR 4 , SR 4 , N(R 4 ) 2 , or NR 4 R g ; R 6 is C0R 4 , CSR 4 , or C(=NR 4 )R 4 ; R 7 is H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, phenyl or phenyl substituted with C 1 -C 3 alkyl, 0R 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; X is N, NR 4 , NRg, or N(0)R 4 ; Z is halogen; and n is 1 or 2; and salts thereof. 61. The method of Claim 60, wherein: R 3 is H, ^-Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, benzyl, C(R ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NOR 6 , CHR 4 NHOR 4 , CHR 4 NHOR 6 , CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NORg, CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg, C(0)NR 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 Rg, C≡CRg, CR 4 =CR 4 C(R 4 ) 2 ORg, C≡CC(R 4 ) 2 OR 6 , or poly-(OR 4 , ORg, epoxy)-^-Cg alkyl. 62. The method of Claim 60, wherein: R 3 is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 COR 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NOR 6 , C(0)NR 4 OR 4 , C(0)NR 4 0R 6 , CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 ORg, or poly-(OR 4 , ORg, epoxy)-C -Cg alkyl. 63. The method of Claim 60, wherein X is N, NR 4 . 64. The method of Claim 61, wherein n is 1. 65. The method of Claim 1, wherein: R 3 is H, C-^-C alkyl, C 2 -C alkenyl, C 2 -C 6 alkynyl, benzyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 C0R 4 , C(R 2 ) 4 C0R 5 , C(R 4 ) 2 Z, C(R 4 ) 2 C(R 4 ) 2 Z, CN, CR 4 NOR 4 , CR 4 NOR 6 , CHR 4 NHOR 4 , CHR 4 NHORg, CHR 4 CR 4 NOR 4 , CHR 4 CR 4 NORg, CHR 4 CHR 4 NHOR 4 , CHR 4 CHR 4 NHORg , C(0)NR 4 OR 4 , C(0)NR 4 0R 6 , CR 4 =CR 4 R 6 , C≡CR g , CR 4 =CR 4 C(R 4 ) 2 ORg, C≡CC(R 4 ) 2 OR 6 , or poly-(0R 4 , ORg, epoxy)-C 1 -Cg alkyl; X is N, NR 4 , or NR 6 ; and n is 1. 66. The method of Claim 60, wherein: R 2 is H, C 1 -C 3 alkyl, or C 2 -C 3 alkenyl; R 3 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C(R 4 ) 2 R 5 , COR 4 , COR 5 , C(R 4 ) 2 C(R 4 ) 2 R 5 , C(R 4 ) 2 C0R 4 , C(R 4 ) 2 COR 5 , CN, CR 4 NOR 4 , CR 4 NORg, C(0)NR 4 OR 4 , C(0)NR 4 ORg, CR 4 =CR 4 Rg, CR 4 =CR 4 C(R 4 ) 2 ORg, or poly-(OR 4 , ORg, epoxy)-C^-^ alkyl; R 4 is H, C 1 -C alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl or phenyl substituted with C-^-C j alkyl, OR 2 , Z, N(R ) 2 1 o CF 3 ; or benzyl; R fi is COR X is 0, S, SO, N, NR 4 , or NRg; and n is 1. 67. The method of Claim 60, wherein: R 2 is H, C^C j alkyl, C 2 -C 3 alkenyl; R 3 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, CH 2 R 5 , CHOHCH=CH 2 , C0R 4 , COR 5 , CH 2 CH 2 R 5 , CH 2 COR 4 , CN, CH=NOR 4 , CH=N0Rg, CONHOR 4 , CONHORg, CH=CHRg, CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH 2 , CHOHCH-CH,; O V R 4 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl or phenyl substituted with C 1 -C 3 alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; Rg is COR 4 ; and X is N, NR 4 , or NRg. 68. The method of Claim 60, wherein: R 2 is H, C 1 -C 3 alkyl, C 2 -C 3 alkenyl; R 3 is H, ^-^ alkyl, C 2 -C 4 alkenyl, CH 2 R 5 , CHOHCH=CH 2 , COR 4 , COR 5 , CH 2 COR 5 , CN, CH=NOR 4 , CH=NORg, CONHOR 4 , CONHOR g , CH=CHR g , CHOHCH 2 OH, CHOHCHOHCH 2 OH, ςH-CH 2 , CHOHCH-CH 2 R 4 is H, C 1 -C 4 alkyl, C 2 -C alkenyl, C 2 -C 4 alkynyl, phenyl or phenyl substituted with alkyl, OR 2 , Z, N(R 2 ) 2 , or CF 3 ; or benzyl; R 6 is COR 4 ; X is N, NR 4 , or NR 6 ; and n is 1. 69. The method of Claim 60, wherein: R 2 is H or CH 3 , R 3 is H, CH 3 , CH=CH 2 , CH 2 OH, CHOHCH=CH 2 , CH 2 OCOCH 3 , CHO, C0CH 3 , C0 2 H, C0NH 2 , C0 2 CH 3 , CH 2 CH 2 OH, CH 2 CHO, CH 2 C0 2 H, CH 2 C0 2 CH 3 , CN, CH=NOH, CH=NOCOCH 3 , CONHOH, CONHOCOCH3, CH=CHC0 2 CH 3 , CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH,, CHOHCH-CH,; and X is N, NH, NCH 3 , NCHO, or NCOCH 3 . 70. The method of Claim 60, wherein: R 2 is H or CH 3 , R 3 is H, CH 3 , CH=CH 2 , CH 2 0H, CHOHCH=CH 2 , CH 2 OCOCH 3 , CHO, COCH 3 , C0 2 H, CONH 2 , C0 2 CH 3 , CH 2 CH 2 OH, CH 2 CHO, CH 2 C0 2 H, CH 2 C0 2 CH 3 , CN, CH=NOH, CH=NOCOCH 3 , CONHOH, CONHOCOCH 3 , CH=CHC0 2 CH 3 , CHOHCH 2 OH, CHOHCHOHCH 2 OH, CH-CH,, CHOHCH-CH- > ; V X is N, NH, NCH 3 , NCHO, or NCOCH 3 ; and n is 1. 71. The method of claim 60, wherein: R 3 is H, CH 3 , CH=CH 2 , CH 2 OH, CHOHCH=CH 2 , CHO, C0 2 H, CONH 2 , COCH3, CH=NOH, CHO- HCH 2 OH, CHOHCHOHCH 2 OH; and X is N, NH, or NCHO. 72. The method of claim 60, wherein: R 3 is H, CH 3 , CH=CH 2 , CH 2 OH, CHOHCH=CH 2 , CHO, C0 2 H, CONH 2 , COCH3, CH=NOH, CHOHCH 2 OH, CHOHCHOHCH 2 OH; X is N, NH, or NCHO; and n is 1. 73. The method of claim 60, wherein the preferred compound is selected from the group consisting of: 15-Aza-4,4-dimethyl-5 α -cholesta-8,14-dien-3β-ol, 15-Aza-5 -cholesta-8,14-dien-3β-ol, 15-Aza-4,4-dimethyl-5α-cholest-8-en-3β-ol, 15-Aza-5α cholest-8-en-3β-ol, 15-Aza-4,4-dimethyl-15-formyl-5 -cholest-8-en-3β-ol, 15-Aza-15-formyl-5α-cholest-8-en-3β-ol, 15-Aza-4,4-dimethyl-15-acetyl-5 -cholest-8-en-3β-ol, 15-Aza-15-acetyl-5 α -cholest-8-en-3β-ol, 15-Aza-14α-cyano-4,4-dimethyl-5 -cholest-8-en-3β-ol, and 15-Aza-14 α -cyano-5α-cholest-8-en-3β-ol. 74. The method of claim 60, wherein the preferred compound is selected from the group consisting of: 15-Aza-4,4-dimethyl-5α-cholesta-8,14-dien-3β-ol and 15-Aza-5α-cholesta-8,14-dien-3β-ol.

Inventors: KO SOO S, TRZASKOS JAMES M, KO, SOO, S., TRZASKOS, JAMES, M.
Applicants: DU PONT MERCK PHARMA, THE DU PONT MERCK PHARMACEUTICAL COMPANY
Application year: 1991
Main classification: A61K31
IPC codes: C07J73