STEROIDAL 17 alpha -SILYL ETHERS AND PROCESS TO CORTICOIDS AND PROGGESTERONES

Abstract: 17 beta -Cyano-17 alpha -hydroxy steroids (I) are transformed to 17 alpha -halo silyl ethers (II) which are intermediates useful in the production of progesterones (V), 17-hydroxyprogesterones (VI), corticoids (VII) and 21-halo corticoids (III) which can readily be transformed to corticoids (VII).

Description: - 1- STEROIDAL 17α-SILYL ETHERS AND PROCESS TO CORTICOIDS AM) PROGESTERONES BACKGROUND OF THE INVENTION 1. Field of the Invention This invention includes 17 -halo silyl ether steroidal 17/3- 5 cyanohydrins useful as intermediates in the production of progester- ones, 17-hydroxyprogesterones and corticoid pharmaceuticals as well as processes to produce and use the intermediates. 2. Description of the Related Art Steroidal 17 / 3-cyano-17o:-hydroxy-17-ethers are known, see for 10 example, US Patents 4,500,461, 4,548,748 and 4,585,590 which disclose a variety of ethers including the silyl ethers, t-butyldimethyl silyl and TMS (trimethylsilyl) . However, those ethers are not operable in the present invention, -halo (halo) silyl ethers are known and have been used as precursors to silicon-stabilized nucleophilic car- 15 banions. See particularly, Silicon in Organic Synthesis, E. Colvin, Butterworth, 1981, pp 21-29, Synthesis 717 (1985), Tetrahedron Letters 25, 4245 (1984) and Journal of Organic Chemistry 48, 2110 (1983). Many examples of intermolecular addition of carbon nucleophiles, 20 such as methyl Grignard, to protected or unprotected cyanohydrins are known. For the unprotected cyanohydrin see Organic Reactions, S. M. McElvain, Vol IV, p 264. For examples of addition to TMS protected cyanohydrins see Synthesis 270 (1981) , Tetrahedron Letters 24, 4075 (1983) and Tetrahedron Letters 27, 1933 (1986). 25 This intermolecular reaction has been used to convert protected steroidal Ylβ-cyanohydrins to pregnanes and corticoid derivatives, see US Patents 4,500,461, 4,548,748 and 4,585,590. Similar chemistry is also described in Bull. Chem. Soc. Japan 58, 978 (1985), Japan Kokai 57-062296, 57-062298, 57-062299 and 57-0622300 (Derwent 30 Abstracts 82-42275E/21, 82-42277E/21, 82-42278E/21 and 82-42279E/21 respectively) , Tetrahedron Letters 2005 (1971) and US Patent 3,697,510. Deprotonation of α-halo silanes to afford nucleophiles is also known, see J. Am. Chem. Soc. 99, 4536 (1977), J. Chem. Soc. Chem. 35 Comm. 513 (1977) and 297 (1978) and Tetrahedron 39, 867 (1983). Silicon-stabilized carbanions are well known in the art, see E. Colvin, Silicon in Organic Synthesis, Butterworths, 1981. p 21-29 and Synthesis 717 (1985). With regard to the formation of silicon-- stabilized carbanion silyl ethers see J. Org. Chem., 48, 2110 (1983) and Tetrahedron Letters 25, 4245 (1984) where chloromethyl silyl ethers are reduced with magnesium to form the carbanion, which is added to a variety of electrophiles, but not nitriles. α-Lithio silyl carbanions are similarly prepared by reduction with lithium, J. Am. Chem. Soc, 76, 1619 (1954), and the corresponding sodium and potassium derivatives are known, J. Org. Chem., 26, 2604 (1961). With regard to the deprotonation of the halomethyl silanes see J. Am. Chem. Soc, 99, 4536 (1977), J. Chem. Soc. Chem. Comm. , 513 (1977), J. Chem. Soc Chem. Con___. , 297 (1978) and Tetrahedron 39, 867 (1983) where trimethylchloromethylsilane is deprotonated with sec-butyl- lithium. Although these latter silicon-stabilized carbanions have been added to a variety of electrophiles they have not been added to a nitrile carbon and have not been used in steroid chemistry. Intramolecular cyclizations incorporating a silyl ether in the ring are known, but are limited to radical cyclizations onto carbon- carbon double and triple bonds and not to nitriles, see, J. Org. Chem., 49, 2298 (1984), J. Am. Chem. Soc, 107, 500 (1985), Tetrahed¬ ron Letters 27, 2255 (1986), M. Koreeda presentation given at the 190th ACS National Meeting in Chicago on September 11, 1985. The difficulty of promoting intramolecular free-radical cyclizations onto a nitrile is described in J. Org. Chem., 50, 5409 (1985). A process for cyclizing ω-halogenated nitriles using magnesium or lithium metal is discussed in J. Organometallic Chem. 87, 25 (1975). While that process uses t_>-haloger_ated nitriles it is far different than the process of the present invention. The present invention requires an ether linkage, a silicon atom in the cyclizing sidechain and a steroid parent nucleus. Most importantly the ω-halogenated nitriles of the prior art (lacking the ether linkage and the silicon atom) once cyclized can not be opened to form the C j _ side chain necessary for the production of corticoids, progesterones or 17-hydro__yproges- terones as can the α-halo silyl ether (II) . Oxidative cleavage reactions are known to those skilled in the art, see J. Org. Chem., 48, 2120 (1983), Tetrahedron Letters 25, 4245 (1984), J. Organometallic Chem., 269 (1984), Tetrahedron 39, 983 (1983) and Tetrahedron Letters 27, 75 (1986). STXMARY OF THE INVENTION Disclosed is an α-halo silyl ether of formula (IIA) and the C^ epimer thereof where: (A-I) R 6 is -CH 2 or α-Rg_ι: -Rg_ 2 > R 10 is α - R 10-l : ^" R 10-2 and R 7 is a-K'.β-R, where one of Rg_ι and g_2 ^ s "*> and trιe other is -H, -F, -Cl or C^-C alkyl, Rio-2 is m(~ ~Z> R 10-l and R 5 taken together are -(CH2)2" c (" R 3-3)- CH ~ or -CH-CH-C(-R3_3)-CH-, where R3.3 is =N-R3_g where 3.8 -- c l" c 5 alkyl, -φ or -C ~ 2-φ, -X21-CH2CH2- 22" where X2 and X22 are the same or different and are -0- or -S-, α "^21"^23 ' <^"^22"^24 wrιere ^23 ~ < - ^24 tιe same or different and are C -C5 alkyl or ~φ and where X2 and X22 are as defined above, or -H: j S-0R3_4 or a-0R2_^:β-R, vhere R3.4 is -H, -CO-X25 where X 2 5 is -H, C 1 -C 7 alkyl or -φ, -C-Φ , - R2-Φ, -CO-CF3, -CO-CCI3, -CO-0-R 3 . 8 where R 3 . 8 is as defined above, -Si 26X27^28 where X26> -^27 -~- " 2& are ~" & same or different and are C -C5 alkyl or -ό, or -Si(Xι)(X2)-C(X 3 )(X 4 )(X 5 ) where X ] _ is -F, -Cl, -Br, -CH3, -φ or -0Xι_- j _ where is C -C5 alkyl or -φ, X 2 is -F, -Cl, -Br, -CH3, -φ or -0X 2 _ι where X2.1 is C -C5 alkyl or -φ, X3 is -H, -Cl, -Br or -I, Σ is -H and X5 is -Cl, -Br or -I; (A-II) R 5 is R5_3.R 5 .4. Rg is R 6 . 3 :R 6 . 4 , R χo is _-R 10 . 3 :/3-Rι 0 . 4 and R is α-H: 3-H, where one of g_3 and Rg_4 is -H, -F, -Cl, C1-C3 alkyl, and the other taken together with one of R5.3 and R5.4 forms a second bond between C5 and Cg, o-4 - s -CH3, ιo-3 - n - tne other of R5.3 and R5.4 taken together is where R3.3 is as defined above; (A-III) Rio and R5 taken together are »CH-CH=C(0R3_g)-CH- where R3_g is R3.4, -H, C1-C5 alkyl, lithium, sodium, potassium, magnesium; Rg is α-Rg_ 5 : -Rg_g where one of Rg.5 and Rζ.ζ is -H, and the other is -H, -F, -Cl or C1-C3 alkyl and R 7 is a-E:β- ~ ; (A-IV) R 5 is α-R 5 . 7 :^-R 5 . 8 , Rg is α-Rg_ 7 : -R _ 8 , R y is a-R:β-K . and R o is α-Rιo-7 : $" l0-8> wners one °f R 5-7 and R 5-8 ^ s "*» 10-7 and the other of R5_ 7 and R5.3 taken together are - - CH2, where R3.3 is as defined above, R10-8 - s "^3> where one of Rg_ 7 and Rg_ 8 is -H and the other is -H, -F, -Cl or C7-C3 alkyl; (A-V) Rg is R6-9 :R 6-10> R 7 is R 7-9 :R 7-10> R 10 is a " R 10-9 : ^- R 10-10' where one of Rg.9 and Rg_ιo -H, -F, -Cl, C^-C3 alkyl and the other taken together with one of R7.9 and 7 _ιo forms a second bond between Cg and C 7 , and the other of R7.9 and R7-10 is -H, Rio-10 is -CH3, ιo-9 and R- taken together are -(CH2 2-G(-R3_3) -CH=- or -CH=CH-C(HR.3_3)-CH-, where R3.3 is as defined above; (A-VI) Rg is -CH 2 or α-R 6 . 11 ;3-Rg. 1 2, Rio s ^-Rl0-ll : ^- R 10-12 and R 7 is α-H:^-H where one of Rg_n and R _i2 is -H, and the other is -H, -F, -Cl or C -C5 alkyl, Rιo-12 is - CH 3» RlO-11 and R 5 taken together are -C^-CH-C^.g -CH-, where R3.9 is -N 29 30 where 29 and X30 are the same or different and are C -C5 alkyl, -φ , -CE.2'Φ and where 29 and Q are taken together with the attached nitrogen atom to form a heterocyclic ring selected from the group consisting of pyrrolidine, piperidine and morpholine or ~<0 3-6 where R^. ξ is as defined above, and where R3_ is as defined above; (A- II) R 5 is R5-13.R5-14. Rδ R6-13 :R 6-14> R 7 is <--≡:β-≡, 0 is α-Rιθ-13 : -Rιθ-14 where one of Rg.13 and Rg.1 is -H, -F, -Cl or C -C3 alkyl and the other taken together with one of R5.13 and R5_i forms a second bond between C5 and Cg, Rio-14 -CH3, R 10-13 take together with the other of R5.13 and R5.14 are -CH=CH- ~ (~-3-3,) ~ ~" 2- where R3.3 is as defined above; (A-VIII) R 5 is R 5 -15- R 5-16' R 6 is ~£ -15 R 6 -16 > R 10 is <-' lO-i5:/3-CH3 and R is α-H:3-H, where one of R _i5 and Rg_ g is -H, -F, -Cl and C1-C3 alkyl and the other taken together with one of R5_15 and R5_ιg forms a second bond between C5 and C , R o-15 and the other of R5.15 and R5_ taken together are -CE=CH-C(R3_g)=CH- where R 3-9 is as defined above; (A-IX) R 5 is R5-17 :R 5-18> R 6 is R 6-17 :R 6-18» R 10 is α - R 10-17 : ^- 10-18 anα - R 7 ~- xβ- , where one of Rg_ι 7 and Rg_ι 8 is -H, -F, -Cl, and C1-C3 alkyl, and the other taken together with one of R5..17 and 5_ι 8 forms a second bond between C5 and Cg, Rio-17 and the other of R5.17 and R5.13 taken together are -CH2-CH2-C R3_9 =CH-, where R3. 9 is as defined above and where Rio-18 i -CH3; (A-X) R 5 is -R5_ιg:,9-R5_20> R 7 is α-H./S-H and R is α-Rι 0 . where R5.20 and R 10-19 taken together are -CH2-CH2-CHZ-CH2- , where Z and R5-19 taken together are a carbon-carbon single bond, Rg is α-H:/9-OR _20 where Rg-20 s G l' c 5 --^ ~ Y- ' < (C-I) En is Rn-i'-Rii-2' wnere one °f ll-1 and R ll-2 ^ s taken together with R9 to form a second bond between Cg and C^ and the other of Rn-i and Rn_2 s -H; (C-II) R11 is α-H:/3-0-, where β-0- is taken together with Rg to form an epoxide between Cg and C^ in the β-configuration; (C-III) α-Rg is -H, -Br, -Cl or -F and ] _ ] _ is -0 or α-R^.5: ." R ll-6 > where one of R11.5 and Rn_ is -H, and the other of n.5 and R^.g is -H, or -OR3-4 where is as defined above; (C-IV) α-Rg is -0Rg.]_ where Rg_ι is -H, -SiX2gX27X28 where 26 > X2 7 and X 8 are as defined above, -CO-φ , -CO-Rg.2 where R _2 i s ' " • C ] _-C5 alkyl, -ORg.3 where Rg.3 is C1-C5 alkyl or -CH2-< , and R lχ is α-H:3-H; R i6 is -CH 2 or α- l6-l : < 5 - R 16-2- where Rι _ι is -H, -F, -CH3 or -OR3.4 where R3.4 is as defined above, i .2 s -H, -F and -CH3 with the proviso that one of R g.i and Ri .2 i s '**> l is -F, -Cl, -Br, -CH 3 , -φ or -0Xι_ 1 where ∑ι_ is C 1 -C 5 alkyl or -φ ; X is -F, -Cl, -Br, -CH3, -φ or -0X 2 _ι where X 2 _ι is C- j _-C5 alkyl or -φ ; X 3 is -H, -Cl, -Br or -I, X4 is -H and X 5 is -Cl, -Br or -I. Disclosed is a process for the production of an α-halo silyl ether of formula (II) and the Cι 7 epimer thereof where: Xl, ~ 2 , X3 > X4, 5 and Ri are as defined for the α-silyl ether (IIA) which comprises (1) contacting a 17-cyano-17-hydroxy steroid of formula (I) and the Cι 7 epimer thereof where Rig is as defined above with an α- halo silyl ether adduct, Xg-SiXιX -CX3X4X5 (IV) where Xg is -Cl, -Br, imidazolyl, CF 3 -C(-0-) (-N-) , CH 3 -C(-0-) (=N-) , -0-S0 2 -CF 3 and -C10 4 and where X j _, X2, X3, X4 and X5 are as defined above. It is preferred that the α-halo silyl ether (II) be the α-halo silyl ether (IIA) . Also disclosed is a process for the production of a α-halo silyl ether of formula (II) and the Cι 7 epimer thereof where , ∑2 > 3 > X4, X5 and R^ are as defined for the α-silyl ether (IIA) which comprises (1) contacting a halogenated silated ether of formula (IIB) and the C 7 epimer thereof where X 3 . B is -H, -Cl, -Br or -I, 5-B - s ~ c -' ~^ r or "^ and w ^ ere 16> ' ^2 an ^ are as defined above with iodide, bromide or chloride. It is preferred that the α-halo silyl ether (II) be the α-halo silyl ether (IIA). Disclosed is a process for producing a 21-halo corticoid of formula (III) and the C χ epimer thereof where: X 3 is -H, -Cl, -Br or -I; X 5 is -Cl, -Br or -I; R g is -CH2 or <*- ιg-i: - ιg-2< where i .i is -H, -F, -CH3 or -0R3_4 where R3_4 is -H, -CO-X25 where X25 Is -H, C-^-G j alkyl or -φ, -~-φ-, -CR2~Φ, -C0-O-R 3 . 8 where R3_ 8 is C ] _-C 5 alkyl, -φ or -CH2-0, -SiX26^27^28 where 2 . ∑27 and 2 8 are the same or different and are C -C5 alkyl or -φ, or -Si(X 1 )(X 2 )-C(X 3 )(X 4 )(X 5 ) where X is -F, -CH3 or -φ, X2 is -F, -CH3 or -φ, X is -H and X3 and X5 are as defined above, Riβ-2 is ~^ > " ~ anα ^ -CH3 with the proviso that one of Rig. and Rι _2 is -H; which comprises (1) contacting an. α-halo silyl ether of formula (II) and the Gy j epimer thereof where: X , ~ -2, " -, X4, X5 and R are as defined above for the α-halo silyl ether (IIA) ; with at least one equivalent of a non-nucleophilic base and (2) contacting the reaction mixture of step (1) with a protio- desllation reagent and a nitrogen, to oxygen exchange reagent. It Is preferred that the 21-halo corticoid (III) be the 21-halo corticoid (IIIA) where (A-I) Rg is =CH 2 or -Rg_ :/3-Rg_2, R Q is α-Rιo-i: - τ . g_ 2 and R 7 is α-H: -H, where one of Rg_ι and _2 is -H, and the other is -H, -F, -Cl or C1-C3 alkyl, RiO-2 i s ~ G 3» 10-l and 5 taken together are -(CH 2 )2-C(-R3-3)-CH- or -CH-CH-C(-R3_3) -CH-, where R3.3 is -0, " X 21" CH 2 CH 2" X 22" w h ere x 21 and x 22 are ^ e same or different and are -0- or -S-, α-X2i"X23-y3-X22" 24 w h ere 23 and x 24 ~" e same or different and are C -C5 alkyl or -φ and where X21 and X22 are as defined above, or -H: / 9-OR3_4 or - R^ .^ .' β-R , where R3.4 is -H, -CO-X25 where X25 is -H, ~ \- ~~ alkyl or -φ , -C-φ 3 , -C " 2- , -CO-0-R3_ 8 where 3_ 8 is C1-C5 alkyl, -φ or -C^-^, -SiX2 X27 x 28 where X26> x 27 an X 28 are the same or different and are C -C5 alkyl or -φ , or -Si(Xι)(X 2 )-C(X 3 )(X4)(X 5 ) where X χ is -F, -CH 3 or -φ , X 2 is -F, -CH 3 or -φ , X 3 is -H, -Cl, -Br or -I, X is -H and X5 is -Cl, -Br or -I; (A-II) R 5 is 5-3:R5-4, Rg is Rg_ 3 :Rg_4, R 10 is a-R 10 . 3 : J S-R 10 . 4 and R7 is α-H:3-H, where one of Rg.3 and Rg.4 is -H, -F, -Cl, C -C3 alkyl, and the other taken together with one of R5.3 and R5.4 forms a second bond between C5 and Cg, RiQ-4 is -CH3, io-3 and the other of R5.3 and R5.4 taken together is -(CH 2 ) 2 -C(=R3.3) -CH2- where R3.3 is as defined above; (A-III) Rio and R5 taken together are -CH-CH=C(OR3_g)-CH- where R3_ is R3.4, -H, C1-C5 alkyl; Rg is α-Rg.5: 3-Rg_g where one of Rg.5 and Rg.g is -H, and the other is -H, -F, -Cl or C1-C3 alkyl and R7 is α-H: -H; (A-IV) R 5 is α-R 5 . 7 :^-R 5 . 8 , Rg is α-Rg.7: -Rg_ 8 , R7 is - " :β- " and Rio is α-RiQ.7:/S-Rιθ-8 > where one of R5.7 and 5_ 8 is -H, R10-7 and the other of R5.7 and R5_ 8 taken together are -(CH2)2"C(=R3_3)- CH2 1 where R3.3 is as defined above, 10-8 i -CH3, where one of Rg.7 and Rg_ 8 is -H and the other is -H, -F, -Cl or ' \- ~ -i, alkyl; (A-V) Rg is R6-9 :R 6-10> R 7 is R 7-9 :R 7-10> R 10 is α - R 10-9- ' β- 10-10 > where one of Rg.g and Rg_ιo is -H, -F, -Cl, C1-C3 alkyl and the other taken together with one of 7_g and 7-10 forms a second bond between Cg and C7, and the other of R7_g and R7_ιo -H, iO-10 is -CH3, Rio.g and R5 taken together are -(CH 2 ) -0(^3.3)-CH- or -CH=CH-C(-R 3 .3)-CH-, where R3.3 is as defined above; (A-VI) Rg is -CH 2 or a-Rg_ii; 3-R 6 _i 2 , Rio is «-RlO-ll : -RlO-12 " ' and R7 is α-H:3-H where one of Rδ-H and Rg.χ2 is -H, and the other is -H, -F, -Cl or C 1 -G 5 alkyl, iO-12 is " CH 3> R 10-ll and R 5 taken together are -CH 2 -CH-C(R3.g)-CH-, where R3.9 is -0 3_ where R3_ is as defined above, and -CH(α-ORι)-CH-C(OR3_g)-CH- where 3_ is as defined above; (A-VII) R 5 is R 5 -13:R5-1 . R 6 is R 6-13 :R 6-14' R 7 is «-H:.3-H, R 10 is α-Rι 0 .i3:/3-Rιθ-1 where one of Rg.13 and Rg. 4 is -H, -F, -Cl or C -C3 alkyl and the other taken together with one of R5.13 and 5_i forms a second bond between C5 and Cg, Ri Q -14 is -CH3, RlO-13 taken together with the other of R5-13 and R5.14 are -CH-CH- C(R3_3 -CH2- where R3.3 is as defined above; (A- III) R 5 is 5 -i5: 5-l6> R 6 is R 6-15 :R 6-16> R 10 is α " R 10-15 : <^" CH 3 and R 7 is a -H- : β-R' where one of Rg.15 and Rg_ιg is -H, -F, -Cl and C1-C3 alkyl and the other taken together with one of R5-I5 and Rs_ιg forms a second bond between C5 and C , Rio-15 and the other of R5.15 and s_ι taken together are -CH-CH-C(R3_g)=CH- where 3_ is as defined above; (A-IX) R 5 is R5-17: 5-18> R 6 ls R 6-17 :R 6-18> R 10 is <-- ~ -.0~17 'β~ R 10-18 n R 7 -- s -- " •' β-l-, where one of Rg.17 and Rg_ι 8 is -H, -F, -Cl, and C -C3 alkyl, and the other taken together with one of R5.17 and R5..18 forms a second bond between C5 and Cg, Rio-17 and the other of R5..17 and R5_i8 taken together are -CH2-CH2-C(R3_9)-CH-, where R 3 _ 9 is as defined above and where io-18 - s ~ ~" 3 > (A-X) R 5 is - 5 _i9: - 5_20' R 7 is ~- ~ 'β-R and R Q IS α-Rι 0 . ι_g: -CH3 where R5.20 and R 10-19 taken together are -CH2-CH2-CHZ-CH2-, where Z and R5.19 taken together are a carbon-carbon single bond, Rg is α-H: J _?-ORg_20 where Rg_20 s c l" c 5 alkyl; (C-I) ^i is _i:Rn. 2 f where one of n_ι and Rn_2 i taken together with Rg to form a second bond between Cg and Cn and the other of Rn_ι and n_2 -H. (C-II) R is α-H:^-0-, where β-0- is taken together with Rg to form an epoxide between Cg and Cn in the -configuration; (C-III) α-Rg is -H, -Br, -Cl or -F and R^ is =0 or 0^.5: β- ll-6 , where one of Rn_5 and n_ is -H, and the other of Rn_5 and n_ Is -H, or -OR3-4 where is as defined above; (C-IV) α-Rg Is -0Rg_ι where Rg_ι is -H, -Si 2 X 2 7X28 where X 2 g, 27 and ∑2 8 are as defined above, -CO-φ , -C0-Rg_2 where Rg_2 is -H, c l" c 5 alkyl, -ORg.3 where Rg_3 is C1-C5 alkyl or -CH 2 -< , and ^ is " a-Riβ-R. Further disclosed is a process for the production of a proges¬ terone of formula (V) where Rig is -CH 2 or α- i6-l : - R 16-2< where Ri .i is -H, -F, -CH3 or -OR3.4 where R3.4 is -H, -CO-X25 where 2 5 is -H, C -C7 alkyl or -φ, -C-Φ2, -CΑ2~Φι -CO-O-R3.8 where R3.8 is C1-C5 alkyl, -φ or -C -Φ, -SiX2gX27 28 where X26. 27 and x 28 are ~- e same or different and are C-L-C5 alkyl or -φ, or -Si(X 1 )(X 2 )-C(X 3 )(X )(X 5 ) where X is -F, -CH3 or -φ, X 2 is -F, -CH3 or -φ, X3 is -H, -Cl or -Br, X 4 is -H and X 5 is -Cl or -Br, R .2 is -H, -F and -CH3 with the proviso that one of Rι _ι and Ri .2 -H, which comprises: (1) contacting an α-halo silyl ether of formula (II) and the C- | _ 7 epimer thereof where Xl, 2, X3, X4, X5 and Rig are as defined above for the α-halo silyl ether (IIA) ; with an effective amount of a Type B reducing agent in the presence of at least one equivalent of a proton source and (2) contacting the mixture of step (1) with a protiodesilation reagent and a nitrogen to oxygen exchange reagent. It is preferred that the progesterone (V) be the progesterone (VA) where (A-I) Rg is -CH 2 or α-Rg_ 1 : -Rg_ 2 , RIQ is and R y is α-H: 3-H, where one of Rg.i and Rg. 2 is -H, and the other is -H, -F, -Cl or C]_-C3 alkyl, ιo-2 i " G ^3> R 10-l an R 5 taken together are -(CH 2 ) 2 -C(=R 3 .3)-CH- or -CH=CH-C(-R 3 _ 3 )-CH=, where R3.3 is =0, -X2i-CH 2 CH 2 -X22" where X ι is -0- and X 2 2 is -0- or -S-, α- 2 ι-X 2 3:S-X 2 -X 2 4 where 2 3 and X 2 4 the same or different and are C^-C5 alkyl or -φ and where X21 and X 22 are as defined above, or or -0R 3 _4: -H, where R3.4 is -H, -C0-X 25 where X 2 5 is -H, C1-C7 alkyl or -φ, - ~ -Φ ' , -C~ -Φ' -C0-0-R3_8 where R3.8 is ~ - ~ - alkyl, -φ or -C 2-Φ , -SiX26 x 27 28 where X26' x 27 and - X 28 are the same or different and are ~ \- ~ - alkyl or -φ , or -Si(Xι)(X 2 -C(X3)(X4)(X5) where i is -F, -CH 3 or -φ , X 2 is -F, -CH3 or - , X 3 is -H, -Cl or -Br, X 4 is -H and X5 is -Cl or -Br; (A-II) R 5 is R 5 .3:R5-4, ~ -s R _3:Rg-4, Rio i α-R 10 _3: -R 10 _ 4 and R 7 is a-R:β-R, where one of Rg.3 and Rg.4 is -H, -F, -Cl, C1-C3 alkyl, and the other taken together with one of R5.3 and R5.4 forms a second bond between C5 and C , Rχo-4 i -CH3, R10-3 and the other of R5_3 and R5.4 taken together is -(CH2')2~ c ( =R 3-3 -CH2- where R3.3 Is as defined above; (A-III) R o and R5 taken together are =CH-CH=C(OR 3 _g)-CH= where 3_g is R3.4, -H, C1-C5 alkyl; Rg is α-Rg_ 5 : -Rg_g where one of Rg.5 and Rg.g is -H, and the other is -H, -F, -Cl or C1-C3 alkyl and R7 is a-R:β-R; (A-IV) R 5 is α-R 5 _7:jS- 5_8, Rg is α-Rg_ 7 : -Rg_ 8 , R ? is α-H:/S-H and Rio is c_-R o-7 : <3- io-8' where one of R5.7 and R5_ 8 is -H, R10.7 and the other of R ~ .j and R5_ 8 taken together are -(CH2) 2 -C( = R3-3)- CH2, where'R3_3 is as defined above, io-8 - s ~ ~" - > where one of Rg.7 and Rg_ 8 is -H and the other is -H, -F, -Cl or C1-C3 alkyl; (A-V) Rg is R6-9 :R 6-10> R 7 is R 7-9 :R 7-10' R 10 is α-R 10 _. 9 :0- R 10-10 > where one of Rg.g and Rg_ιo is -H, -F, -Cl, C^-C3 alkyl and the other taken together with one of R7_g and R7_ιo forms a second bond between Cg and C7, and the other of R .g and R7_ o - " > RlO-10 is -CH3. R o-9 and R5 taken together are -(CH2)2 _ G(-R3_3)-CH— or -CH-CH-C(=R3_3 -CH-, where R3.3 is as defined above; (A-VI) Rg is -CH 2 or α-Rg_u; -Rg_ι 2 , R i0 is «"RlO-ll : ^- R 10-12 and R7 is a-R:β-R where one of Rg_n and Rg_i2 i -H, and the other is -H, -F, -Cl or G\- ~ - alkyl, R O-12 is -CH3, Rio-H and R- taken together are -CH2-CH=C(R3_g -CH=, where R3_ is -OR3_ where R3_g Is as defined above, and where R 3 .g is as defined above; (A- II) R 5 Is R5-13--R5-1 , Rg is R6-13* R 6-14> R 7 is α-H:/3-H, R 10 Is where one of Rg.13 and Rg_i is -H, -F, -Cl or C^-C3 alkyl and the other taken together with one of R5.13 and R5.14 forms a second bond between C5 and Cg, RiO-1 is -CH3, R 10-13 taken together with the other of 5-13 and R5_ 4 are -CH-CH- C(R3-3 -CH 2 - where R3.3 is as defined above; (A-VIII) R 5 is 5 .ι 5 :R5.i6. Rδ is R 6-15 :R 6-16- R 10 is α " R ] _0_3_5:/3-CH3 and R 7 is a-R:β-R, where one of .15 and Rg_ιg is -H, -F, -Cl and C1-C3 alkyl and the other taken together with one of 5-15 and Rs.ig forms a second bond between C5 and Cg, io-15 and the other of R5.15 and Rs. g taken together are -CH=CH-C(R3_9)-CH- where R3_ is as defined above; (A-IX) R 5 is R5-17.R5-I8. Rδ is R 6-17 :R 6-18> R 10 is «- iθ-17^ R 10-18 and R 7 ^ s α "H:^-H, where one of Rg_ι 7 and Rg.13 is -H, -F, -Cl, and C1-C3 alkyl, and the other taken together with one of R5_ι 7 and R5.I8 forms a second bond between C5 and C , iO-17 - — the other of 5.ι 7 and R5-I8 taken together are -CH 2 -CH 2 -C(R3.g)-CH- , where R3_ g is as defined above and where R 0-I8 i s -CH3; (A-X) R5 is α-R5. 1 g:3-R 5 .2o. 7 is α-H^-H and R 10 is α-R 10 . 1 g:_?-CH3 where R5.20 and R 10-19 taken together are -CH -CH 2 -CHZ-CH 2 - , where Z and 5-i taken together are a carbon-carbon single bond, Rg is α-H:S-ORg_2o where Rg. 2 o is G l" c 5 alkyl; (C-I) R11 is Rli-i: ll- . where one of Rn-i and Rn. 2 is taken together with R9 to form a second bond between Cg and Cn and the other of Rn-i and Rn_ is -H; (C-II) R11 is α-H:^-0-, where β-0- is taken together with Rg to form an epoxide between Cg and C ] _ι in the ^-configuration; (C-III) α-Rg is -H, -Br, -Cl or -F and n is =0 or α-Rn.5: β-R\χ. β , where one of n_5 and n. is -H, and the other of n.5 and Rn_ is -H, or -OR3-4 where is as defined above; (C-IV) α-Rg is -OR9.1 where Rg_ι is -H, -SL gX 2 7X 2 8 where X 2 g, X 2 7 and X 28 are as defined above, -CO-φ , -C0-Rg_ where Rg_ 2 is -H, C1-C5 alkyl, -ORg.3 where Rg.3 is C1-C5 alkyl or -CH 2 - , and Rχ j _ is α-H:^-H. Additionally disclosed is a process for the production of a 17- hydroxyprogesterone of formula (VI) and the C17 epimer thereof where Y is -H, -Cl, -Br and -I; R is =CH2 or <*-R _ι:j9-Rι _2, where Rig.i is -H, -F, -CH3 or -0R3_ where R3.4 is -H, -CO-X25 where 2 5 is -H, C1-C7 alkyl or -φ , - ~ -φ ~ , -CH2-<?, -C0-0-R3_ 8 where R 3 . 8 is C1-C5 alkyl, -φ or -CR2 -Φ , -SiX2gX27X28 where X26> 27 an 28 are the same or different and are C1-C5 alkyl or -φ , or -Si(Xι)(X 2 )-G(X 3 )(X4)(X5) where X is -F, -CH 3 or -φ , X 2 Is -F, -CH3 or -φ , X 3 is -H, -Cl or -Br, X is -H and X5 Is -Cl or -Br, R g_2 Is -H, -F and -CH 3 with the proviso that one of R .i and Rιg_ 2 is -H, which comprises: (1) contacting an α-halo silyl ether of formula (II) and the C17 epimer thereof where X- j _, X 2 , X3, X4, X5 and R- j _g are as defined above for the α-halo silyl ether (IIA) , with an effective amount of a Type A reducing agent, (2) hydrolyzing the mixture of step (1) with a protiodesilation reagent and a nitrogen to oxygen exchange reagent. It is preferred that the 17-hydroxyprogesterone (VI) be the 17- hydroxyprogesterone (VIA) where (A-I) Rg is =CH 2 or α-Rg_ : -Rg_ 2 , Rio is and R 7 is α-H:yS-H, where one of Rg_ι and Rg_2 is -H, and the other is -H, -F, -Cl or C1-C3 alkyl, iO-2 - s - CH 3» R 10-l and R 5 taken together are -(CH2 2 -C(=R3_3)-CH- or -CH=CH-C(=R3_ .3 )-CH-, where R3.3 is =0, - 21-CH2CH2- 22" where 2 ι and X 22 are the same or different and are -0- or -S-, α ~ 21~ 23 : " 22~ 24 where X23 and X2 the same or different and are C -C5 alkyl or -φ and where X21 and X22 are as defined above, or -H:S-0R3_4 or -0 3 _4: -H, where R3.4 is -H, -CO-X25 where X 2 5 is -R, G^-G alkyl or -φ , -C-^3, - 2- , -CO-0-R3_ 8 where R3_ 8 is G j _-C 5 alkyl, -φ or -CH 2 -.5, -SIX2gX27X28 where 26' X27 an 28 are he same or different and are C ] _-G$ alkyl or -φ , or -S1(X 1 )(X 2 )-C(X 3 )(X 4 )(X 5 ) where χ is -F, -CH 3 or -φ , X 2 is -F, -CH3 or -φ , X3 is -H, -Cl or -Br, X is -H and 5 is -Cl or -Br; (A-II) R 5 is R5-3:R 5 -4, Rg Is Rg_ 3 .Rg_ 4 , R 10 is α-R 10 _ 3 :3-R 10 _4 and R7 is α-H: ?-H, where one of R5.3 and Rg.4 is -H, -F, -Cl, G^-C^ ' alkyl, and the other taken together with one of R5_3 and R5.4 forms a second bond between C5 and Cg, Rio-4 Is -CH3, RIQ-3 and the other of R5.3 and R5.4 taken together is -(CH 2 ) 2 " , -(~R3-3)-CH 2 - where R3.3 is as defined above; (A-III) Rχo and R5 taken together are -CH-CH-C(0R 3 .g) -CH- where R 3 .g is R3.4, -H, C1-C5 alkyl; Rg is α-R .5:/9-Rg_g where one of Rg_ 5 and Rg.g is -H, and the other is -H, -F, -Cl or C1-C3 alkyl and R7 is α-H: / 3-H; (A-IV) R 5 is α-R 5 _ 7 : / _.-R5_8, δ s α-Rg_ 7 : -Rg. 8 , 7 is α-H:,S-H and R ] _ Q s α- R l0-7 ' β-~±Q. - , where one of R5.7 and R5.3 is -H, R o-7 and the other of R5.7 and R5.8 taken together are - (CH 2 ) 2 -C(=R3_3)- CH 2 , where R3.3 is as defined above, I Q .5 is -CH3, where one of Rg_7 and Rg_8 is -H and the other- is -H, -F, -ϋl or C -C3 alkyl; (A-V) Rg is Rδ-9 :R 6-10> R 7 is R 7-9 :Z 7-10' R 10 is α " 10-9 : ^- R 10-10 > where one of Rg.9 and Rg_ιo is -H, -F, -Cl, C1-C3 alkyl and the other taken together with one of R7.9 and R7.10 forms a second bond between Cg and C7, and the other of 2.7.9 and R 7-10 - s ~ H < R 10-10 is -CH3, Rio-9 and R 5 taken together are -(CH 2 ) 2 -C(=R3_ 3 ) -CH- or -CH=CH-C(-R3_3) -CH-, where R3.3 is as defined above; (A-VI) Rg is =CH 2 or α-Rδ-11, -Rδ-12' Rio is <*-Riθ-li:j8-&10-12 and R7 is α-H: ?-H where one of Rg.n nd _ 2 i -H, and the other is -H, -F, -Cl or C 1 -C 5 alkyl, Rιo-12 ∑ -CH 3< R 10-ll and R 5 taken together are -CH2-CH=C(R3_g)-CH-, where 3_g is -0R3_g where R 3 .g Is as defined above, and -CH(α-ORι)-CH-C(OR 3 .g)-CH- where R3_£ is as defined above; (A-VII) R 5 is R5_13.R5.x4, Rδ is Rδ-13 :R 6-14' R 7 is «-H:,9-H, R 10 is <*-Rιo_i3:/S-Rιo-14 where one of Rg.13 nd R .14 is -H, -F, -Cl or C -C3 alkyl and the other take- together with one of R5.13 and R5.14 forms a second bond between C5 and Cg, Rχo-14 i -CH3, Rχθ_i3 taken together with the other of 25.13 an 5-14 are -CH-CH- C(R3_3 -CH 2 - where R3.3 is as defined above; (A-VIII) R 5 is R5-i5.R5.i6> Rδ is *-5-15 :R 6-16. R 10 is ~ - R 10-15- ' β- ~ T~- and R7 is α-H: .-H, where one of Rδ-15 and Rg_ιg is -H, -F, -Cl and C1-C3 alkyl and the other taken together with one of R5-I5 and - .iς, forms a second bond between C5 and Cg, RiO-15 and the other of R5.15 and Rs_ι taken together are -CH-CH-C(R3_g)=CH- where R3.9 is as defined above; (A-IX) R 5 is 5 -17: 5-18> R 6 is ^-17^6-18' R 10 is α - R 10-17 - ' ' 10-18 an 7 s ct- : β-R, where one of R-5-17 and R -i 8 s -H, -F, -Cl, and G-^-C^ alkyl, and the other taken together with one of R5.17 - and R5_χ8 forms a second bond between C5 and Cg, χ -17 and the other of R5.17 and 5.I8 taken together are -CH -CH 2 -C(P_3_g)-CH-, where R3. g is as defined above and where Rio-18 is - ~ »- t' (A-X) R5 is α- 5 .ιg:)3-R5„ 2 o, R7 Is α-H:/3-H nd R i0 is α-R 10 . ιg: -CH3 where Rs_20 and R 10-19 taken together are -CH2-CH2-CHZ-CH2-, where Z and R5.19 taken together are a carbon-carbon single bond, Rg is α-H:j9-ORg_2o where Rg_20 is G l" c 5 a ^kyl; (C-I) 11 is χ -i:Rii-2' where one of Rn-i d Rn-2 is taken together with Rg to form a second bond between Cc and Cχι and the other of Rχχ.χ and Rn- 2 is -H; (C-II) RT1 Is α-H: -0-, where β-0- is taken together with Rg to form an epoxide between Cg and 0 χ in the -configuration; (C-III) α-Rg is -H, -Br, -Cl or -F and Rχι is -O or α-R^.5: β-Rl . ζ , where one of Rn.5 and Rχχ.g Is -H, and the other of Rχχ_5 and Rχι_g is -H, or -OR3- where is as defined above; (C-IV) α-Rg is -0Rg_ι where Rg_ι is -H, -SiX 2 ~X27 x 28 where X 2 g, X27 and X28 are as defined above, -CO-φ , -C0-Rg_ 2 "where Rg_2 is -H, c l" c 5 alkyl. -ORg.3 where Rg_3 is G ] _-C 5 alkyl or -C ~ 2-φ , and R^ is Disclosed is a process for the production c a corticoid of formula (VII) and the C-^ epimer thereof where R is as defined for the 17-hydroxyprogesterone (VI) above, which comprises: (1) contacting an α-halo silyl ether of formula (II) and the C17 epimer thereof where , X 2 , X3, X4, X5 and g are as defined above for the α-halo silyl ether (IIA) ; with an effective amount of a Type A reducing agent and (2) contacting the mixture of step (1) with an oxidizing agent and (3) contacting the mixture of step (2) with a protiodesilation reagent and a. nitrogen to oxygen exchange reagent. It is preferred that the corticoid (VII) be the corticoid (VIIA) where R5, Rg, R7, Rg, IQ, Rχι and Rig are as defined for the 17- hydroxyprogesterone (VIA) . DETAILED DESCRIPTION OF THE INVENTION The α-halo silyl ether (II) is prepared froir the correspondin ' 17-cyano-17-hydroxy steroid (I) by reacting it wi-__h the appropriate α-halo silyl ether adduct (IV) . It is preferred that the α-halo silyl ether (II) be the α-halo silyl ether (IIA) . The 17-cyano-17- hydroxy steroids (I) are known to those skilled in the art or can be readily prepared from known 17-keto androstanes (0) by methods known to those skilled in the art, see for example US Patent 4,500,461, for ^-cyanohydrins, and Tetrahedron Letters 24, 4559 (1983) for α- cyanohydrins. With the 17-cyano-17-hydroxy steroids (I) and the α- sutstituted silyl ethers (II), the cyano group at Cχ7 can be in either the α- or ^-configuration; it is preferred that the cyano group at C- | _7 be in the £-configuration giving 17 / 3-cyano-17α-hydroxy steroids (I) and 173-cyano-17α-silyl ethers (II). Therefore, when the term "17-cyano-17-hydroxy" is used in the present patent applica¬ tion it means and includes both C^7 epimers, except when referring to particular steroidal compounds. The 17α-cyano-17?-hydroxy steroids (II) and the 17 / 9-cyano-17α-hydroxy steroids (II) are both operable in all aspects of the present invention, and can be prepared by methods known to those skilled in the art. For example, PREPARATIONS 7 and 9 are applications of the method described in Tetrahedron Letters 24, 4559 (1983). The 17-cyano-17-hydroxy steroid (I) is first slurried with a dry organic solvent. Suitable organic solvents include methylene chlori¬ de, THF, toluene, dichloroethane, DMF, dimethox ethane, acetonitrile and mixtures thereof. It is preferred that the organic solvent be methylene chloride or DMF. The reaction mixture is then preferably cooled to about -10 to 0°. The 17-cyano-17-hydroxy steroid (I) is then contacted with the α-halo silyl ether adduct (IV) . The α-halo silyl ether adducts (IV) are either known to those skilled in the art or can be readily prepared from known compounds by means known those skilled in the art. The α-halo silyl halides (IV), for example, can be easily prepared by halogenation of the corresponding alkyl silyl halides. Thus, chloromethyldimethylchlorosilane (IV) is prepared by chlorination of trimethylchlorosilane. Likewise dichloromethyl- dimethylchlorosilane is prepared by dichlorination of trimethyl¬ chlorosilane and chloromethyltrichlorosilane by chlorination of methyltrichlorosilane, etc. See Tetrahedron 26, 279 (1970) and J. Am. Chem. Soc, 73, 824 (1951). It is preferred that the contacting be in the presence of an acid scavenger selected from the group consisting of alkyl lithium, calcium and sodium hydride, mesityl lithium, tert-butyllithium, sec-butyllithium, n-butyllithium, lithium- t-butoxide, potassium t-butoxide, sodium tertiary amylate, di- sodiocyanamide, dilithio N,N' -diphenylhydrazine, and metal-N(X7) (X 8 ) where metal is lithium, sodium, potassium or magnesium, X7 is C -C7 alkyl, trimethylsilyl and cyclohexyl, X 8 is X 7 and l-(l-phenyl- pentyl) , and the metal salts of piperidine, 2,2,6,6-tetramethyl- piperidine, 2,6-di-t-butylpiperIdine, 2,6-dimethylρiperidine, ethylenediamine, trlmethylethylenediamlne, morpholine, imidazole, 2- amlnopyridine and amines. Acid scavengers are compounds which scavenge or trap free protons in solution and thereby prevent undesirable side reactions. Amine acid scavengers are of the formula NXl2 13 14 where i2 > Xl3 and χ4 the same or different and are -H, - , -GH2-#, -CH 2 CH 2 -< , methylphenyl, Cχ-Cg alkyl optionally sub¬ stituted with 1 or more oxygen or nitrogen atoms, the alkyl groups can be cyclized with the attached nitrogen atom and 1 or more oxygen or nitrogen atoms to form 1 through' 3 rings selected from the group consisting of pyridlne optionally substituted with 1 through 3 C1-C alkyl, pollyallylamine, polyethylenlmine, benzylated polyethylen- i ine, polyvlnylpyridine, biazabicyclo[2.2.2]octane, imidazole, X- methyI orpholine, N-methylpiperidine, N-methylimidazole, 2-methyli__.- Idazole, 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-dIazabicyclo- [4.3.0]non-5-ene with the proviso that not more than 2 of 12. 3 and Xχ can be -H. Preferred acid scavengers include triethylamine, tributylamlne r diisopropylethylamine, trimeth lamine, pyridine, imidazole, N-methylmorpholine, N-methylpiperidlne, N-methylimidazole, 2-methylimidazole, most preferred are TEA and imidazole. The acid scavenger should be added in an amount from about 1 to about 5 e- quivalents; preferably about 1.3 equivalents If TEA is used. It Is preferred that the contacting take place in the presence of a silylation catalyst. Suitable silylation catalysts Include pyridine substituted in the 4- position with with -NXι Xχ7 where Xig and χ7 are the same or different and are C -C5 alkyl and where the alkyl groups can optionally be taken together with the attached nitrogen atom and 1 or more nitrogen or oxygen atoms to form a heterocyclic ring, pyridine-N-oxide, benzimidazole, substituted imidazoles where the substituent is C1-C alkyl or -φ , preferred is 4-dlmethylamino- pyridine or imidazole. The silylation catalyst should be added in an amount of about 0.5 to 10 mole %; preferably about 2 mole %. With regard to the α-halo silyl ether adduct (IV) at least 1 equivalent, preferably about 1.1 to about 1.5 equivalents, more preferably about 1.2 equivalents should be used. The reaction is monitored by TLC, HPLC, etc and is usually complete within 2 hr (if a catalyst is used) depending on the temperature. For example, with chloromethyldi- cethylchlorosilane (IV) using TEA as the acid scavenger and 4- dimethylaminopyridine as the silylation catalyst the reaction is complete in less than 1 hr at -5°. The reaction can be quenched by adding the reaction mixture to a quenching agent which permits easy isolation of the α-halo silyl ether (II). In some cases one can simply filter off the acid scavenger-acid complex. One can often carry on the reaction of the α-halo silyl ether (II) directly without its isolation, in this case quenching of the reaction mixture is not necessary, see EXAMPLE 74. Examples of quenching agents include, for example, phosphate buffer, ammonium chloride buffer and dilute acetic acid. The pH of the quench mixture is controlled to avoid hydrolyz- ing acid or base sensitive functions or the silyl ether itself. Generally, phosphate buffer (pH 4.5) is preferred, a potassium or sodium dihydrogen phosphate solution. The α-halo silyl ether (II) is obtained by extraction in the usual manner. In situtations where either or both of X ] _ and X 2 is an ether, -0-Xχ_ι and -0X 2 _ι respectively, or -F, the starting α-halo silyl ether adduct (IV) preferably has X ] _ and/or X as -Cl or -Br which can be selectively replaced to give the desired product; see EXAMPLES 48-53. The α-halo silyl ether adduct (IV) is reacted first with a 17-cyano-17-hydroxy steroid (I), then with an alcohol. This is the preferred order of displacement, although any order will be operable and deemed equivalent. For X^ or X 2 to be -F, the α-halo substituted adduct (IV) must be treated with a suitable fluoride source which includes potassium, sodium or tetrabutylammonium fluoride. Although these α-halo silyl ethers (IV) are operable in all aspects of the present invention, they are particularly suited for the direct preparation of the corticoids (VII) using a Type A reducing agent followed by an oxidizing agent. The α-halo silyl ethers (II) are useful in the production of progesterones (V) , hydroxyprogesterones (VI) , corticoids (VII) and 2i-halo corticoids (III) which are intermediates in the production of corticoids (VII) as is explained below. Each of the α-halo silyl ethers (II) disclosed here can be transformed to the corresponding progesterone (V) , hydroxyprogesterone (VI) , corticoid (VII) and 21- halo corticoid (III) as disclosed and exemplified below. It is preferred that the α-halo silyl ether (II) be the α-halo silyl ether (IIA) . It Is preferred that the cyano group at C17 be in the .-configuration. It Is preferred that the α-halo silyl ether (II) be a Δ^-3-keto steroid or a Δ^ 1 -3-keto steroid or protected forms (A-VI, A-VIII and A-IX) thereof. It is preferred that the C- ring contain (1) Δ '^-' functionality, (2) have α-Rg be -H or -F when Rχi is -0 or c_-Rιι_ :£-Rn_g, where one of Rιχ_5 and Rχχ.g is -H, and the other of Rχι_5 and Rχi-g is -H or -OH, and (3) α-Rg is -H, -F, -Cl or -Br when R x is Q--Rχχ.5:3-Rχχ.g, where one of Rχχ.5 and Rχχ.g Is -H, and the other of Rχχ.5 and Rχχ.g is -H, -OH, -Si 2 X27 28 or -Si(Xχ)(X 2 )-C(X 3 )(X4)(X5) . It is preferred that one of Rχg.χ and Rχg_2 is -H and the other Is -H or -CH3. It is preferred that Xx is -CH 3 or -0Xχ.χ and X 2 is -CH3 or -0X 2 .ι, X3 is -H, -Cl, -Br and X5 is -Cl or -Br. It is more preferred that Xi and 2 are -CH3, X3 is -H and X5 is -Cl. Preferred α-halo silyl ethers (II) the compounds of EXAMPLES 1-3, 7-13, 16, 19-21, 25, 28-39, 40A, 41-48, 54, 57-59, 67, 70-72 and 82. More preferred are the α-halo silyl ethers (II) of EXAMPLES 1, 3, 7, 33, 36, 43 and 45. The α-halo silyl ethers (II) can be prepared from other α-halo silyl ethers (II) by a displacement reaction using iodide, bromide or chloride. The halo group α- to silicon (X3 or X5) is easy to exchange for a different halide by a displacement reaction. For example, with the α-halo silyl ether (II) when and X2 are -CH3, X3 and X are -H and X5 Is -Br, it is possible to convert X5 into -Cl or -I by contacting the α-halo silyl ether (II) with chloride or iodide ion. This is the preferred method of preparing the α-halo silyl ether (II) where X 5 Is -I, see EXAMPLES 58 and 67. This also means it is Important in the operation of this invention that the α-halo silyl ether (II) not be allowed to contact undesired halide ions for longer than is necessary. For example, if in the execution of EXAMPLE 2, 13 or 57, the reaction mixture is left in contact longer than necessary to complete silylation, significant amounts of the chloromεthjldimethyl silyl ether (II) will form, by exchange of rhe -Br with chloride ions in the reaction from the TEA hydrochloride formed. The α-halo silyl ether (II) is transformed to the 21-halo corticoid (III) by contacting the α-halo silyl ether (II) with at least one equivalent of a non-nucleophilic base followed by contact¬ ing (quenching) with a protiodesilation reagent and a nitrogen to oxygen exchange reagent. A non-nucleophilic base, is a base which is sufficiently strong to deprotinate X4. Examples of non-nucleophilic bases include mesityl lithium, tert-butyllithium, sec-butyllithium, n-butyllithium, lithium t-butoxide, potassium t-butoxide, sodium tertiary amylate, disodiocyanamide, dilithio N,N' -diphenylhydrazine, and met l-N(X7 (X 8 ) where metal is lithium, sodium, potassium or magnesium, X7 is G^-G alkyl, trimethylsilyl and cyclohexyl, X8 is X7 and 1-(1-ρhenylpentyl) , and the metal salts of piperidine, 2,2,6,6- tetramethylpiperidine, 2,6-di- -butylpiperidine, 2,6-dimeth lpiperi- dine, ethylenediamine, trimethylethylenediamine, morpholine, im¬ idazole and 2-aminopyridine. Preferred non-nucleophilic bases are mesityl lithium, tert-butyllithium, sec-butyllithium, n-butyllithium, disodiocyanamide, dilithio N,N' -diphenylhydrazine, and metal-N- (X7) (X 8 ) where metal is lithium, sodium, potassium or magnesium, X7 is -^- - alkyl, trimethylsilyl and cyclohexyl, Xg is X7 and 1-(1- phenylpentyl) , and the metal salts of piperidine, 2,2,6,6-tetra- methylpiperidine, 2,6-di-t-butylpiperidine, 2,δ-dimethylpiperidine " , ethylenediamine, trimethylethylenediamine, morpholine, imidazole and 2-aminopyridine, more preferred is IDA. When X3 and X5 are -Cl or -Br it is preferred the non-mucleophilic base is one where X7 and X 8 are trimethylsilyl. About 1 to about 4 equivalents of the non- nucleophilic base are used. At least 1 equivalent is required, preferably about 1.5 equivalents (in the absence of reactive func¬ tional groups in the molecule) should be used. If the α-halo silyl ether (II) has a hydroxyl group at -_ and/or an unprotected A-ring (3-ketone) an additional equivalent for each reactive functionality is necessary as is known to those skilled in the art. For example, with a ll3-hydroxy-Δ 4 -3-keto α-halo silyl ether (II) (EXAMPLE 26), at least 3 equivalents are needed, one for the llS-hydroxyl functionali¬ ty, one for the A-ring and one for the reaction. When the reaction is complete as monitored by TLC or HPLC it is quenched a protio- desilation reagent and a nitrogen to oxygen exchange reagent. A protiodesilylation reagent is selected from the group consisting of 1) water or an alcohol and an acid where the alcohol is of the formula R5 Q -OH where R50 is selected from the group consisting of C^-C7 alkyl, -φ , -CR 2 -Φ , -CH 2 CH 2 -OCH3, HO-R51-OH where R 5 χ is C 2 -C 7 alkyl, propylene glycol, ethylene glycol, glycerol; where the acid is selected from the group consisting of HF, HCl, HBr, HI, H3PO4, H 2 S0 4 , perchloric, fluoroboric, NaHS0 , aH 2 Pθ4, polymeric sulfonic acid cation exchange resins, H00C-(CH 2 ) n - COOH where n is 0 through 12, tartaric acid, citric acid, B( ^g)3, Al(X g) 4 , Sn(Xιg) 4 , Sn(Xχg) 2 and Ti(Xχg) 4 where X 9 Is -F, -Cl, -Br and -I, R 52 -C00H and R 52 -S0 3 -H where R 52 is -H, Cχ-Cχ2 alkyl, -φ , methylphenyl, -CF3, -CCI3, hydrochloride and hydrobromide salts of amines of the formula NXχ 2 χ3X 4 where Xχ 2 » 13 and X14 the same or different and are -H, -φ , -CR2-Φ , -G 2GR2-Φ , methylphenyl, C ] _-Cg alkyl optionally substituted with 1 or more oxygen or nitrogen atoms, the alkyl groups can be cyclized with the attached nitrogen atom and 1 or more oxygen or nitrogen atoms to form 1 through 3 rings with the proviso that at least 1 of 12, χ3 and Xχ4 is -H; or 2) a fluoride salt where the fluoride salt is selected from the group ' consisting of BF3, CsF, F, NaF, L1F, LLBF4 and n-(butyl) 4 _vF. The nitrogen to oxygen exchange reagent is selected from the group consisting of 1) water and an acid as is defined above or 2) a ketone of the formula R53-CO-R5 where R53 and R54 are the same or different and are Cχ-C7 alkyl, the alkyl groups can be taken together with the attached carbonyl group to form a saturated ring of from 5 to 7 members, an aldehyde of the formula R55-CHO where R 5 is C -C5 alkyl or -φ , or pyruvic acid. The simplist, easiest, cheapest and the preferred procedure is to use just one reagent which falls into both catagories. It is preferred that that reagent is water and an acid. It is preferred to use at least one equivalent of water and almost any acid is operable. It is preferred that the acid be selected from the group consisting of HF, HCl, HBr, HI, H3PO4, E 2 S04 r perchloric, fluoroboric, formic, acetic, proplonlc and oxalic. It is more preferred that the acid be HF, HCl, HBr, H2SO4. methanesulfonlc and acetic. When X5 is -Br it is preferred that the acid be HBr. In the case of a 3-keto steroid it is preferred to conduct the first step using besides the additional non-nucleophilic base 0.5 to 1.0 equivalents of a compound selected from the group consisting of Cl- Si- (0.3)3, (F 3 C-C0) 2 -0- , X 20 -Si-X Xιo n where X , Xχ 0 and X^ are C j _-C5 alkyl, -φ , -Cl, -OX15 where X15 is C1-5 alkyl or -φ and where X 20 is -Cl or -Br, (Xι 8 -C0) 2 -0- where Xig is -φ or t-butyl, Xι 8 -CO- Cl. Preferred is chlorotrimethylsilane. The chlorotrimethylsilane can be added at any time during the addition of the non-nucleophilic base, but preferreably before the non-nucleophilic base is added. The non-nucleophilic base can be added to the α-halo silyl ether (II) , or the α-halo silyl ether (II) can be added to the non-nucleop- hilic base. It is preferred to conduct the second step in the presence of an alcohol. The alcohol is not necessary but often increases the rate of hydrolysis. Examples of alcohols include R50" OH where R50 i selected from the group consisting of C1-C7 alkyl, - φ , -CR 2 -Φ > -CH 2 CH 2 -0CH3, HO-R51-OH where R 51 is C 2 -C 7 alkyl, propylene glycol, ethylene glycol and glycerol. It is preferred that the alcohol be ethylene glycol, ethanol or isopropanol. hen the α- halo silyl ether (II) has a Δ 1, -3-keto A-ring, it is preferred that reaction sequence be as follows (1) contacting the α-halo silyl ether (II) with at least 1 equivalent of LiHMDS, (2) contacting the reaction mixture with at least 2 equivalents of a non-nucleophilic base and (3) contacting the reaction mixture of step (2) with at least one equivalent of water and an acid. It is more preferred that the reaction sequence be as follows (1) contacting the α-halo silyl ether (II) with at least 1 equivalent of LiHMDS, (2) trapping the C3- enolate as an ether, (3) contacting the reaction mixture with at least 2 equivalents of a non-nucleophilic base and (4) contacting the reaction mixture of step (3) with at least 1 equivalent of water and an acid. The contacting of the first step should be performed at < 80°, preferably from about 25 to about -80°. When the base is IDA the contacting should generraly be at < -15° dependint on the α-halo silyl ether (II) . Suitable solvents for the reaction include THF, dimethox ethane, toluene, methyl t-butyl ether, cyclohexane and mixtures thereof. The solvent is preferably THF but in the situtaion where the LDA is in hexane, the preferred solvent is a THF/hexane mixture. Preferred 21-halo corticoids (III) are the compounds of EXAMPLES 5, 6, 17, 22, 26, 40B, 55, 60, 63, 75-77, 79, 80 and 83. More preferred are the 21-halo corticoids (III) of EXAMPLES 5, 17, 22, 75-77 and 83. The 21-halo corticoids (III) are well known to those skilled in the art and are readily transformed to pharmaceutically useful corticoids by methods known to those skilled in the art and are themselves pharmaceutically useful see US Patent 4,619,921. For example, 21-chloro-17α-hydroxypregna-4,9(11)-diene-3,20-dione is known, see US Patent 4,357,279 (Example 5) and US Patent 4,342,702 (Example 5). 21-Bromo-17α-hydroxypregna-4,9(11)-diene-3,20-dione is known, see US Patent 4,041,055 (Example 59). Thus displacement with acylate gives 21-acyl corticoids, for example displacement with acetate gives 21-acetyl-17α-hydroxypregna-4,9(ll) -diene-3,20-dione, useful in the preparation of hydrocortisone 21-acetate. Reduction of the 21-substituent with, for example, zinc and acetic acid gives 17- hydroxyprogesterones. When Rgx is -CH3 the 17-hydroxyprogesterone is useful in the preparation of medroxyprogesterone acetate. The α-halo silyl ether (II) can also be transformed to the cor¬ responding 17-hydroxyprogesterone (VI) by contacting it with (1) an effective amount of a Type A reducing agent, (2) contacting the mixture of step (1) with a protiodesilation reagent and a nitrogen to oxygen exchange reagent. It is more preferred that the reaction sequence be contacting the α-halo silyl ether (II) with (1) two or more equivalents of a Type A reducing agent, (2) contacting the mixture of step (1) with an aprotic quenching agent and (3) contact¬ ing with a protiodesilation reagent and a nitrogen to oxygen exchange reagent. A type A reducing agent is a reagent which when reacted with an α-halo silyl ether (II) in an effective amount followed by reaction with an aprotic quenching agent, and a protiodesilation reagent and a nitrogen to oxygen exchange reagent produces a 17- hydroxyprogesterone (VI) . Examples of Type A reducing agents include lithium and sodium complex with the following: anthracene, naph- thacene, benzanthracene, 20-meth lcholanthrene, nitrobenzene, meta- dinitrobenzene, 1,3,5-trintrobenzene, 2,3,7-trInitrofluorenone, benzophenone, naphthalene; lithium complex with the following: biphenyl, di-tert-butylbiphenyl, dimethylaminonaphthalene, trimesityl borane, di-tertbutylnaphthalene; lithium, sodium, potassium or calcium dissolved with ammonia, hexamethyl phosphoric triamide, 18- crown-6 or tris(3,6-dioxaheptyl)amine; magnesium, lithium; or n- butyllithlum when X5 is -I. It is preferred that the Type A reducing agent be lithium or sodium naphthalenide, lithium and sodium anthrac-- ene, lithium biphenyl, lithium di-tert-butylbiphenyl, lithium di¬ methylaminonaphthaiene, lithium trimesityl borane, lithium di-tert- butylnaphthalene, lithium, sodium, potassium or calcium dissolved with ammonia, hexamethyl phosphoric triamide, 18-crown-6 or tris(3,6- dioxaheptyl)amine; magnesium; n-butyllithium when X5 is -I. It is more preferred the Type A reducing agent be lithium biphenyl, sodium or lithium naphthalide or lithium 4,4' -di- ert-butylbiphenyl. It is preferred that about 2.2 to about 5 equivalents, more preferably about 2.5 to about 3 equivalents of the Type A reducing agent be used. Equivalents refers to the number of equivalents of electrons donated by the reducing agent. Any remaining Type A reducing agent is then destroyed with an aprotic quenching agent such as X38 where X37 and X3 8 are the same or different and are G-^-C^ alkyl or -φ ; 3 3 2 X33C-CX 3 4X35X3g where X 3 χ, X 32 , X33, X34, X35 and X 36 are the same or different and are -H, -F, -Cl, -Br, -I, C^-C7 alkyl, C -C4 halo alkyl where the halo atoms are -F, -Cl, -Br and -I; X 31 X 32 X 33 C " CH " CH " CX 34 X 35 X 36; x 31 x 32 c " cx 34" cx 35~ cx 35 x 36 and benzoate. Preferred is dichloroethane, dibromoethane, and benzoate, . more preferred is 1,2-dichloroethane. The purpose of the aprotic quench- ing agent is to remove excess Type A reducing agent from the reaction mixture before protons are added in the course of further processing. If protons are added prior to removal of the reducing agent, most of the reducing agents will produce significant (those included as Type B reducing agents) amounts of the corresponding progesterone (V) as a byproduct. Ideally, to produce only the 17-hydroxyprogesterone (VI), either a Type A-non-Type B reducing agent (such as magnesium) can be used, or the amount of Type A reducing agent can be limited to be just sufficient to consume the starting α-halo silyl ether (II) . In practice, it is often easier and preferred to use an excess of the Type A reducing agent, then destroy the excess Type A reducing agent with the aprotic quenching agent. Suitable solvents Include THF, dimethoxyethane alone or mixed with non-reactive solvents such as hexanes, heptanes, octanes, toluene, methyl-tert-butylether and mixtures thereof. Preferred is THF. The contacting is performed at about -80 to about 20°, preferably about -20 to about 0°, more prεferrably about -10° depending on the particular reducing agent and ' particular α-substituted silyl ether (II). As is known to those skilled in the art for a particular situation the reducing agent and - silyl ether (II) are contacted at a low temperature and the mixture is warmed until reaction occurs as measured by TLC. In that way one obtains the desired reaction using the minimum amount of heat. The reaction is complete (contacting time) in less than one minute or over twenty hours depending on the particular silyl ether (II) , the solvent, the temperature, etc as Is known to those skilled in the art. Usually the reaction is complete in a short time, for example in about 1 to about 5 minutes. The aprotic quenching agent Is added until the reducing agent disappears. The reaction mixture is then quenched and hydrolyzed in the same manner and same way using the same reagents as described above for the 21-halo corticoids (III) . The α-halo silyl ether (II) can also be transformed to the 21- halo corticoid (III) by a similar procedure if both X3 and X5 are not H, see EXAMPLE 78. The α-halo silyl ether (II) can be transformed to the cor¬ responding progesterone (V) by contacting It with with ____. effective amount of a Type B reducing agent in the presence of one or more equivalents of protons followed by reaction with a protiodesilation reagent and a nitrogen to oxygen exchange reagent. .____, effective amount of a Type B reducing agent requires at least 4 equivalents, preferrably about 4.5 to about 6 equivalents are used. Examples of Type B reducing agents include lithium and sodium com lex of the following anthracene, naphthacene, benzanthracene, 20-methylchol- anthrene, nitrobenzene, meta-dinitrobenzene, l,3,5-tri_-trobenzene, 2,3,7- rinitrofluorenone, benzophenone, naphthalene; lit___lu__. complex of the following biphenyl, di-tert-but lbiphenyl, dim thylamino- naphthalene, trimesltyl borane, di-tertbutylnaphthalen ; lithium, sodium, potassium or calcium dissolved with ammonia, hexamethyl phosphoric triamide, 18-crown-6 or tris(3,6-dioxaheptyl)a__±ne. Preferred are lithium or sodium naphthalenide, lithium and sodium anthracene, lithium biphenyl, lithium di-tert-but lblphe__yl- lithium dimethylaminonaphthalene, lithium trimesltyl borane, lithium di-tert- butylnaphthalene, lithium, sodium, potassium or calci-E__r dissolved with ammonia, hexamethyl phosphoric triamide, 18-crown-6 cr tris(3,6- dioxaheptyl)amine, more preferred are lithium biphenyl. sodium or lithium naphthallde or lithium 4,4' -di-tert-butylbiphenv . Alterna¬ tively, treatment of the silyl ether (II) with a Type A reducing agent followed by sufficient amount of Type B reducing agent is operable. It Is preferred that the reducing agent used be all of of the Type B. In order to accomplish the reduction to progesterones (V) the contacting must take place in the presence of one or more equivalents of protons. Suitable proton sources include water, 50" OH where R50 is selected from the group consisting of Cχ-C7 alkyl, -φ , -CR 2 -Φ , -CH 2 CH 2 -OCH3, HO-R 5 χ-OH where R 5 χ is C 2 -C 7 alkyl, propylene glycol, ethylene glycol, glycerol, acids selected from the group consisting of HF, HCl, HBr, HI, H3PO4, H 2 Sθ4, perchloric, fluoroboric, aHS04, NaH 2 Pθ , polymeric sulfonic acid cation exchange resins, H00C-(CH ) n -COOH where n is 0 through 12, tartaric acid, citric acid, B(X ) 3 , Al( ιg) , Sn(Xιg)4, Sn(Xιg) 2 and Ti(X g) 4 where X g is -F, -Cl, -Br and -I, R 52 -C00H and R 52 -S0 3 -H where R 52 is -H, C j _-C ] _2 alkyl, -φ , methylphenyl, -CF3, -CCI3; hydrochloride and hydrobromide salts of amines of the formula NXi2 x 13 x 14 where Xι 2 , 13 and X14 the same or different and are -H, -φ , -CH 2 -<^, -CH 2 CH 2 -ό, methylphenyl, C1-C9 alkyl optionally substituted with 1 or more oxygen or nitrogen atoms, the alkyl groups can be cyclized with the attached nitrogen atom and 1 or more oxygen or nitrogen atoms to form 1 through 3 rings with the proviso that at least 1 of Xι , X13 and X ] _4 is -H and the steroid portion of the α-halo silyl ether (II) when it contains a free -OH group. Preferred proton sources are water and an acid. The α-halo silyl ether (II) itself can serve as the proton source, if it contains unprotected hydroxyl groups. The proton source may be added either with the α-halo silyl ether (II) , or following the contacting between the α-halo silyl ether (II) and the reducing agent. It is preferred to add the proton source following the contacting between the α-halo silyl ether (II) and the reducing agent. Suitable solvents include THF, dime hoxyethane and non- reactive solvents such as hexanes, heptanes, octanes, toluene, methyl-tert-butyl ether and mixtures thereof. Preferred is THF. The contacting Is performed at about -80 to about 20", preferably about -30 to about -10°, more preferably about -20°. The reaction is complete in less than one minute or over twenty hours depending on the particular silyl ether (II), the solvent, the temperature, etc as is known to those skilled in the art. Usuallv the reaction is complete In a short time about 1 to about 5 minutes. The reaction ■ mixture is quenched and hydrolyzed in the same manner and the same way using the same reagents as described above for the 21-halo corticoids (III) . For convenience, It is preferred that the proton source and the a protiodesilation reagent and a nitrogen to oxygen exchange reagent be the same, for example a mixture of aqueous hydrochloric or sulfuric acid in me hanol or ethylene glycol. Oxidative cleavage reactions of silicon-carbon bonds are known to those skilled in the art, see J. Org. Chem., 48, 2120 (1983), Tetrahedron Letters 25, 4245 (1984), J. Organometallic Chem., 269 (1984), Tetrahedron 39, 983 (1983) and Tetrahedron Letters 27, 75 (1986). _ The α-halo silyl ether of formula II can be transformed directly to a corticoid (VII) by (1) contacting it with an effective amount of a Type A reducing agent, (2) contacting the mixture of step (1) with an oxidizing agent and (3) contacting the mixture of step (2) with a protiodesilation reagent and a nitrogen to oxygen exchange reagent. As exemplified in EXAMPLE 62, oxidative cleavage of a silicon-carbon bond following reaction of the α-halo silyl ether (II) with two or more equivalents of a Type A reducing agent and (optionally) an aprotic quenching agent gives corticoids (VII) directly. Suitable Type A reducing agents and aprotic quenching agents are set forth supra. Suitable oxidative agents include hydrogen peroxide, t-butyl hydroperoxide, peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, perphthalic acid, trifluoroperacetic acid, cumyl hydroperoxide, trimethylamine-N-oxide, acetone hydroperoxide; hexafluroacetone hydroperoxide, N-phenylsulfonyl-3-phenyloxazirldlne and m-chloroper- benzole acid, preferred are hydrogen peroxide, m-chloroperbenzoic acid and trimethylamine-N-oxide. Salts of the oxidizing agents are equivalent to the free oxidizing agents. The reaction mixture is quenched and hydrolyzed In the same manner and the same way using the same reagents as described above for the 21-halo corticoids (III) . The difference between the process to the progesterones (V) and 17-hydroxyprogesterones (VI) from the α-halo silyl ether (II) Is, with regard to the progesterones (V) , at least 4 equivalents of the reducing agent are required and at least 1 equivalent of a proton source must be present during the contacting of step (1) . With the process to the 17-hydroxyprogesterones (VI) only 2 equivalents of the Type A reducing agent are required and an aprotic quenching agent may be used. For Instance, with the process to the 17-hydroxyproges¬ terones (VI) , 4 equivalents of the Type A reducing agent can be used - (preferably not) , if no proton source is present and the quenching agent is an aprotic quenching agent. It is important that the α-halo silyl ether (II) have any reducible functional groups present protected, if it is desired that they not be reduced. Reducible functional groups include enones, ketones and halides, depending on the reducing agent. Enones are protected as the ketal or dienol ether or dienolate, as is known to those skilled in the art, if it is desired not to have such function¬ al groups reduced by the reducing agent. For the production of the 21-halo corticoids (III) , proges¬ terones (V) and 17-hydroxyprogesterones (VI) it is important that the reactions and quenches be conducted in an Inert atmosphere, preferab¬ ly of nitrogen or argon, most preferably of argon. The compounds of the present invention (I-III, V and VI) have an asymmetric center at C17. Because of the planar nature of the steroid ring system the two substituents at Cu have a relationship to each other of above and below the plane of the steroid ring system which is denoted as α (below) and β (above) configuration by those skilled In the art. hile the chemical formulas set forth in CHARTS A thru D (and the claims) show the normal configuration for the formulas set forth, these formulas are meant to disclose and include the epi configuration as well. For example, with the cyanohydrin (I), the normal configuration is that set forth in formula (I), 173- cyano-17α-hydroxy. However, this formula by definition is meant to, and does, include the epi configuration for the cyanohydrin (I) which is 17α-cyano-17β-hydroxy. Likewise for the steroids (II, III and VI). Although the 173-hydroxy steroids are not generally utilized as pharmaceutical agents and thus fewer of them are known and described than the 17α-hydroxy steroids, they can be useful intermediates in the production of pharmaceuticals. EXAMPLE 40 describes the prepara¬ tion of a 21-chloro-173-hydroxypregnane and its conversion to a useful melengestrol acetate precursor (US Patent 4,567,001). EXAMPLES 54-56 describe the prepartion of a precursor for 17-epi hydrocortisone, useful as an analytical standard for determining the level of this impurity in hydrocortisone. DEFINITIONS AND CONVENTIONS The definitions and explanations below are for the terms as used- throughout this entire document including both the specification and the claims. I. CONVENTIONS FOR FORMULAS AND DEFINITIONS OF VARIABLES The chemical formulas representing various compounds or molecu- lar fragments in the specification and claims may contain variable substituents in addition to expressly defined structural features. These variable substituents are identified by a letter or a letter followed by a numerical subscript, for example, "Z" or "R^ where "i" Is an integer. These variable substituents are either monovalent or bivalent, that is represent a group attached to the formula by one or two chemical bonds. For example, a group Z would represent a bivalent variable if attached to the formula CH3-C(-Z)H. Groups ^ and RA would represent monovalent variable substituents if attached to the formula CH -CH 2 -C(R j _)(R )H 2 . When chemical formulas are drawn in a linear fashion, such as those above, variable substituents contained in parentheses are bonded to the atom immediately to the left of the variable substituent enclosed in parenthesis. When two or more consecutive variable substituents are enclosed in paren¬ theses, each of the consecutive variable substituents is bonded to the immediately preceding atom to the left which is not enclosed in parentheses. Thus, in the formula above, both R j _ and Rs axe. bonded to the preceding carbon atom. Also, for any molecule with an established system of carbon atom numbering, such as steroids, these carbon atoms are designated as C^, where "I" is the integer cor- responding to the carbon atom number. For example, Cg represents the 6 position or carbon atom number in the steroid nucleus as tradition¬ ally designated by those skilled in the art of steroid chemistry. Likewise the term "Rg" represents a variable substituent (either monovalent or bivalent) at the Cg position. Chemical formulas or portions thereof drawn in a linear fashion represent atoms in a linear chain. The symbol "-" in general represents a bond between two atoms in the chain. Thus CH3-O-CH2- C(R^)H-CH3 represents a 2-substituted-l-methoxypropane compound. In a similar fashion, the symbol "—" represents a double bond, e.g., and the symbol " ~ " represents a triple bond, e.g., Carbonyl groups are represented in either one of two ways: -CO- or -C(=0)-, with the former being preferred for simplicity. Chemical formulas of cyclic (ring) compounds or molecular fragments can be represented in a linear fashion. Thus, the compound 4-chloro-2-methylpyridine can be represented in linear fashion by N*-C(CH3)-CH-CC1-CH-C*H with the convention that the atoms marked with an asterisk (*) are bonded to each other resulting in the formation of a ring. Likewise, the cyclic molecular fragment, 4- (ethyl)-1-piperazinyl can be represented by -N -(CH 2 ) - (C 2 H5)-CH 2 - C*H 2 . A rigid cyclic (ring) structure for any compounds herein defines an orientation with respect to the plane of the ring for substituents attached to each carbon atom of the rigid cyclic compound. For saturated compounds which have two substituents attached to a carbon atom which is part of a cyclic system, -C(Xχ)(X )- the two sub¬ stituents may be in either an axial or equatorial position relative to the ring and may change between axial/equatorial. However, the position of the two substituents realative to the ring and each other remains fixed. While either substituent at times may lie in the plane of the ring (equatorial) rather than above or below the plane (axial) , one substituent is always above the other. In formulas depicting such compounds, a substituent (X ) which is "below" another substituent (X 2 ) will be identified as being in the alpha (α) configuration and is identified by a broken, dashed or dotted line attachment to the carbon atom, i.e., by the symbol "- - -" or "...". The corresponding substituent attached "above" (X 2 ) the other ( i) is identified as being in the beta (3) configuration and is indicated by an unbroken line attach¬ ment to the carbon atom. When a variable substituent is bivalent, the valences may be taken together or separately or both in the definition of the variable. For example, a variable R^ attached to a carbon atom as- C(-R^)- might be bivalent and be defined as oxo or keto (thus forming a carbonyl group (-CO-) or as two separately attached monovalent variable substituents c_-Rχ.-! and β-R±- ]f hen a bivalent variable, R^, is defined to consist of two monovalent variable substituents, the convention used to define the bivalent variable is of the form "α-Rχ.4 or some variant thereof. In such a case ' both α-R and β- . ^ are attached to the carbon atom to yield -C(α- R i-i) ( < ^- R i-k)~ • ^ or example, when the bivalent variable Rg, -C(-Rg)- ■ , (at Cg) is defined to consist of two monovalent variable substi¬ tuents, two monovalent variable substituents are α-Rg_ ] _:$-Rg_ 2 , .... etc, yielding -C(α-Rg. ) 0_.-Rg_ 2 )-, -C(α-Rg. ) (β- R 6-10-."' etc. Likewise, for the bivalent variable R^, -C(-R χ)-, (at Cχι) two monovalent variable substituents are c_-Rιi-i:<#-Rn_2- For a ring substituent for which separate α and β orientations do not exist (e.g. due to the presence of a carbon carbon double bond in the ring) , and for a substituent bonded to a carbon atom which is not part of a ring the above convention is still used, but the α and β designations are omitted. Just as a bivalent variable may be defined as two separate monovalent variable substituents, two separate monovalent variable substituents may be defined to be taken together to form a bivalent variable. For example, in the formula -C ] _(R^)H-C2(Rj)H- (Ci and C 2 define arbitrarily a first and second carbon atom, respectively) R^ and R,- may be defined to be taken together to form (1) a second bond between Ci and C 2 or (2) a bivalent group such as oxa (-0-) and the formula thereby describes an epoxide. When R^ and Rs are taken together to form a more complex entity, such as the group -X-Y- , then the orientation of the entity is such that Ci in the above formula Is bonded to X and C2 is bonded to Y. Thus, by convention the designa¬ tion "... x and R are taken together to form -CH2-CH2-O-CO- ..." means a lactone in which the carbonyl is bonded to C2. However, when designated "... R and R^ are taken together to form -CH2-CH2-O-CO- the convention means a lactone in which the carbonyl is bonded to 0χ. The carbon atom content of variable substituents is indicated in one of two ways. The first method uses a prefix to the entire name of the variable such as "C1-C ", where both "1" and "4" are integers representing the minimum and maximum number of carbon atoms in the variable. The prefix is separated from the variable by a space. For example, π Cχ-C alkyl" represents alkyl of 1 through 4 carbon atoms, (including isomeric forms thereof unless an express•Indication to the contrary is given) . Whenever this single prefix is given, the prefix indicates the entire carbon atom content of the variable being defined. Thus C2-C alkoxycarbonyl describes a group CH3-(CH<.) n -0- C0- where n is zero, one or 2. By the second method the carbon atom content of only each portion of the definition is indicated separate¬ ly by enclosing the "Ci-Cj" designation in parentheses and placing it immediately (no intervening space) before the portion of the defini¬ tion being defined. By this optional convention (Cχ-C3)alkoxy- carbonyl has the same meaning as C 2 -C4 alkoxycarbonyl because the "C1-C " refers only to the carbon atom content of the alkoxy group. Similarly while both C 2 -Cg alkoxyalkyl and (C^-C3)alkoxy(C1-C3)alkyl define alkoxyalkyl groups containing from 2 to 6 carbon atoms, the two definitions differ since the former definition allows either the alkoxy or alkyl portion alone to contain 4 or 5 carbon atoms while the latter definition limits either of these groups to 3 carbon atoms. When the claims contain a fairly complex (cyclic) substituent, at the end of the phrase naming/designating that particular sub¬ stituent will be a notation in (parentheses) which will correspond to the same name/designation in one of the CHARTS which will also set forth the chemical structural formula of that particular substituent. II. DEFINITIONS All temperatures are in degrees Centigrade. TLC refers to thin-layer chromatography. HPLC refers to high pressure liquid chromatography; which was performed on a C-18 250 cm column, at 20-25° with Iml/min, 30 min, eluting with water/acetonitrile/methanol (40/40/20) using a gradient to acetonitrile/methanol (70/30) . LDA refers to lithium diisopropylamide; [for metal-N(X7) (X 8 ) metal is lithium, X7 and X 8 are isopropyl] . LiHMDS refers to lithium bis(trimethylsilyl)amide THF refers to tetrahydrofuran. DMF refers to dimethylformamide. TEA refers to triethylamine. NMR refers to nuclear (proton) magnetic resonance spectroscopy, chemical shifts are reported in ppm (5) downfield from tetramethyl- silane. TMS refers to trimethylsilyl. φ refers to phenyl (CgH j ) . When solvent pairs are used, the ratios of solvents used are volume/volume (v/v) . Medroxyprogesterone acetate refers to 17α-hydroxy-6α-methyl- • preg__ι-4-ene-3,20-dione 17-acetate. THF refers to tetrahydrofuran. p-TSA refers to p-toluenesulfonic acid monohydrate . Saline refers to an aqueous saturated sodium chloride solution. Ether refers to diethyl ether. EXAMPLES Without further elaboration, it is believed that one skilled In the art can, using the preceding description, practice the present invention to its fullest extent. The following detailed examples describe how to prepare the various compounds and/or perform the various processes of the invention and are to be construed as merely illustrative, and not limitations of the preceding disclosure in any way whatsoever. Those skilled in the art will promptly recognize appropriate variations from the procedures both as to reactants and as to reaction " conditions and techniques . PREPARATION 1 17^-Cyano-3 ,17α-dlhydroxyandrosta-3,5,9(ll) -triene 3- methyl ether (I) Following the general procedure of US Patent 4.548,748, Example 214, and making non-critical variations but starting with 17 -cyano - 17α-hydroxyandrosta-4,9(ll)-dlen-3-one (US Patent 4,548,748, Example 2) , the title compound is obtained. PREPARATION 2 17jS-Cyano-3 ,ll ,17α-trihydroxyandrosta-3,5-diene 3- ethyl ether (I) 17£-Cyano-ll ,17α-dihydroxyandrost-4-en-3-one (1.5793 g) , toluene (4.7 ml), ethanol (1.6 ml), triethylorthoformate (0.44 eq) , pyridine hydrochloride (0.6 eq) and formic acid (0.11 eq) are combined and heated to 55° and stirred. Additional triethylortho¬ formate is added. Additional ethanol is added to solubilize every¬ thing. When the reaction is complete as determined by TLC (ethyl acetate/hexane , 1/1) the mixture is distilled under reduced pressure adding TEA and hexane. After sitting solids precipitate. The mixtue Is filtered and the solids are washed. The filtrate is concentrated to an oil (after more solids are filtered off) to give the title compound. PREPARATION 3 17 -Cyano-110,17α-dlhydroxy-6α-methylandrost-4-en-3- one (I) Following the general procedure of PREPARATION 1 and making non- critical variations but starting with ll,β-hydroxy-6α-methylandrost-4- " ene-3,17-dlone (0), "the title compound is obtained, m.p. 215.3- 217.5°; NMR (CD 2 C1 2 /CD 3 0D) 1.0, 1.2, 1.5, 4.5 and 5.7 S. PREPARATION 4 17 -Cyano-ll , 17α-dihydroxy-6α-nathylandrosta-l,4- dien-3-one (I) Glacial acetic acid (0.050 ml) is added to llJ-hydroxy-6α- methylandrosta-l,4-dien-3,17-dione (0, 236.4 ng) , potassium cyanide (97.47 mg) in methanol (0.396 ml) and water (0.264 ml) and the mixture stirred at 20-25°. Initially, a single product forms by TLC which is gradually replaced by a second product over the course of the reaction. When this conversion is complete as measured by TLC, glacial acetic acid (0.0605 ml) is added. The reaction mixture is dissolved in a minimal amount of methanol, water and methylene chloride. The mixture is concentrated under reduced pressure until crystallization of the product appears complete. The slurry is filtered, and the crystals washed with several portions (1 ml) of methanol/water (1/1) . The crystals are triturated with ethyl acetate acidified with acetic acid, filtered and dried under reduced pressure at 45° overnight to give the title compound, a.p. 257.7-258.9°; NMR (DMS0-d 6 ) 1.0, 1.1, 1.4, 4.3, 4.8, 5.8, 6.1, 6\2 and 7.3 5 . PREPARATION 5 11 β-Cyano-6α-fluoro-3,17α-dihydroxyandrosta-3,5,9(11)- triene 3-methyl ether (I) Glacial acetic acid (0.61 ml) is added to 6α-fluoro-3-hydroxy- androsta-3,5,9(11) -trien-17-one 3-methyl ether (0, 1.647 g) , potas¬ sium cyanide (1.126 g) slurried in THF (1.4 ml) and methanol (4.1 ml) under nitrogen at 42° . After 15 min water (1.4 ml) is added dropwise over 1 minute maintaining the temperature between 29° and 35° . After 45 min, seed crystals of the title compound are added. Initially, a single product forms by TLC which is gradually replaced by a second product over the course of the reaction. When this conversion is complete, glacial acetic acid (0.38 ml) is added and the mixture is cooled to 20-25°. The resultant crystals are collected by vacuum filtration, washed with methanol/water (1/1, 2 x 10 ml), and dried at 50° under vacuum for 6 hrs to give the title compound, m.p. 167-172°; NMR (CDC1 3 ) 0.9, 1.1, 3.6, 5.5 and 5.6 8. ' PREPARATION 6 17^-Cyano-6α-fluoro-17α-hydroxyandrosta-4,9(11)-dien- 3-one (I) To 173-cyano-6-fluoro-3,17α-dihydroxyandrosta-3,5,9(11)-triene 3-methyl ether (PREPARATION 5, 196.8 mg) , glacial acetic acid (1.00 ' ml), water (0.10 ml), then p-TSA monohydrate (23.3 mg) is added. The mixture is stirred at 20-25° for 17 min then poured into a mixture of - aqueous potassium phosphate monobasic (20 ml) and methylene chloride (20 ml) . The phases are separated and the aqueous layer washed with methylene chloride (5 ml) . The combined organic layers are washed with water (10 ml) and dried on anhydrous sodium sulphate. The mixture is concentrated under reduced pressure to an oil. Column chromatography eluting with ethyl acetate/hexane (30/70) gives the title compound, m.p. 222° (dec); NMR (CDCI3/CD3OD) 0.8, 1.3, 5.7 and 6.0 5 . PREPARATION 7 17α-Cyano-17^-hydroxy-16-methyleneandrost-4-en-3-one (I) Trlmethylsilylcyanide (4.7 ml) and 18-crown-6/potassium cyanide complex (0.211 g) are added to a solution of 3-hydroxy-16-methylene- androsta-3,5-dien-17-one 3-methyl ether (0, US Patent 4,416,821 Example 8, 10 g) in methylene chloride (50 ml) . The mixture is stirred for 1 hr. Methanol (50 ml) and hydrofluoric acid (48%, 10 ■ ml) are added and the mixture is stirred for 2.5 hr then partitioned between methylene chloride and saline. The aqueous layer is ex¬ tracted with methylene chloride. The organic extracts are washed with saline, dried over sodium sulfate and concentrated to a crystal- line product which is recrystallized from isopropanol to give the title compound, NMR (CD 2 C1 2 > 5.30, 5.51 and 5.69 δ . PREPARATION 8 17 -Cyano-11/9,17α-dihydroxy-6-methyleneandrost-4-en-3- one (I) Following the general procedure of PREPARATION 3 and making non- critical variations but starting with ll3-hydroxy-6-methyle__androst- 4-ene-3,17-dione (0) the title compound is obtained, m.p. 245-255°; NMR (CDCl 3 /DMS0-dg> 1.1, 1.2, 4.3, 4.5, 5.0, 5.7, and 6.3 δ . PREPARATION 9 17α-Cyano-17^-hydroxyandrosta-4,9(11)-dien-3-one (I) Following the general procedure of PREPARATION 7 and making non- critical variations but starting with 3-hydroxyandrosta-3,5,9(11)- trien-17-one 3-methyl ether (0, US Patent 3,516,991), the title compound is obtained. PREPARATION 10 17jS-Cyano-17α-hydroxyandrosta-5,9(ll)-diene 3-ethylene ketal (I) Following the general procedure of EXAMPLE 59 and making non- critical variations but starting with androsta-5,9(ll)-dien-17-one 3- ' ethylene ketal (0) , the title compound Is obtained. EXAMPLE 1 17 / S-Cyano-17α-hydroxyandrosta-4,9(ll)-dien-3-one 17- (chloromethyl)dimethylsilyl ether (II) 173-Cyano-17α-hydroxyandrosta-4,9(11)-dien-3-one (I, US Patent 4,500,461 Example 2, 75.03 g) is mixed with methylene chloride (150 ml) . Atmospherically, 75 ml of the methylene chloride is distilled off and the procedure is repeated. The mixture is then cooled to -4°. A mixture of 4-dimethylaminopyridine (0.6358 g) In methylene chloride (10 ml) is added to the steroid mixture. This is followed by addition of triethylamine (44 ml) over 3 min maintaining the temperature < 5°. Chloromethyldimethylchlorosilane (38.8 ml) is added from an addition funnel maintaining the temperature < 0° . The mixture is stirred until the reaction is complete .as measured by TLC. The reaction mixture is then added via a cannula to a mixture of aqueous potassium phosphate monobasic (243 ml) and methylene chloride (75 ml) which had been previously cooled to 2° with vigorous stirr- Ing. The reaction mixture flask is rinsed with methylene chloride, stirring is stopped and the layers separated. The aqueous layer is washed with methylene chloride (3 x 50 ml) and the organic phases are combined. The organic phase is backwashed with water (300 ml) . Each aqueous backwash is in turn backwashed in order with a mixture of iso-octanes (75 ml) . • The iso-octane layer is combined with the previous organic layers. The mixture is concentrated under reduced pressure while adding iso-octane. Distillatio -is stopped when the vapor temperature is about 38° . The slurry is cooled and filtered. The solids are dried under reduced pressure at about 50° to give the title compound, m.p. 138-141°; NMR (CDC1 3 ) 0.9, 1.0, 1.2, 3.9 and 5.7 5. EXAMPLE 2 17£-Cyano-17α-hydroxyandrosta-4,9(11)-dien-3-one 17- (bromomethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 1 and making non- critical variations but using bromomethyldimethylchlorosilane, the title compound is obtained. EXAMPLE 3 17£-Cyano-3,17α-dihydroxyandrosta-3,5,9(11)-triene 3- ethyl ether 17-(chloromethyl)dimethylsilyl ether (II) Triethylamine (70.82 g) is added dropwise over a period of 5 minutes to a suspension of 17/3-cyano-3,17α-dihydroxyandrosta- 3,5,9(11)-triene 3-methyl ether (PREPARATION 1, 168.38 g) , 4-di- methyla inopyridine (3.1562 g) and methylene chloride (860 ml) at 1° under nitrogen maintaining the temperature at about 1° . Chloro-. methyldimethylsllyl chloride (91.78 g) is added dropwise over 11 min with the temperature rising to 10° . Methylene chloride (10 ml) is used as a rinse. The reaction mixture is poured into phosphate buffer (1.5 M potassium dihydrogen phosphate/sodium hydroxide to pH 7, 860 ml) containing ice (about 700 g) . The mixture is stirred vigorously for about 10 min with the pH remaining at 7.5. The mixture is extracted with methylene chloride (3 x 500 ml) . An intermediate layer is formed. It is filtered. The resulting solid is washed with water, then with methylene chloride. The combined methylene chloride layers are dried over magnesium sulfate, filtered, and the filtrate concentrated to about 800 ml. This filtrate Is warmed under reduced pressure to remove the methylene chloride. As methylene chloride Is removed, heptane (650 ml) is added to maintain a reasonably constant volume. Crystals begin to form after about 500 ml of heptane has been added. After all the heptane is added the mixture is warmed to 30° for 10 min to remove the remaining methylene - chloride. The mixture is cooled to 0° and held for 15 min. The resulting solid is filtered and washed with heptane (3 x 100 ml) , dried at 20-25* to constant weight to give the title compound. The filtrate is concentrated to a ' mushy solid residue using heat (40°) and reduced pressure overnight. The mixture is triturated with heptane and filtered, the solid is washed with heptane (2 x 20 ml) to obtain additional title compound, m.p. 145-153°; NMR (CDCI3) 0.4, 0.9, 1.2, 2.9, 3.6, 5.2 and 5.3 δ . EXAMPLE 4 21-Chloro-17α-hydroxypregna-4,9(ll)-dlene-3,20-dione (HI) 17^-Cyano-3,17α-dihydroxyandrosta-3,5,9(11)-triene 3-methyl ether 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 3, 10.8 g) and dry THF (34.8 ml), are cooled to - 40°. IDA [1.94 molar bis- (tetrahydrofuran complex) in a mixture of iso-octanes, 19.3 ml] is added dropwise with stirring over 6 minutes maintaining the tempera¬ ture at < -18° . After 1/2 hr the reaction is quenched by adding the reaction mixture to a mixture of concentrated hydrochloric acid (25 ml) and ethylene glycol (4.2 ml) at -30°. The reaction mixture is stirred at about -30 to about 25° for about 3.5 hr, iso-octane (70 ml) Is added over 5 minutes followed by the addition of water (225 ' ml) over about 10 minutes. The reaction mixture is filtered, washed with water followed by iso-octane and the dried overnight at about . 45° to give the title compound. EXAMPLE 5 21-Chloro-17α-hydroxypregna-4, 9(11) -diene-3,20-dione (III) 11 β-Cyano-17α-hydroxyandrosta-4,9(11)-dien-3-one 17-(chloro- methyl)dimethylsilyl ether (II, EXAMPLE 1, 10.4541 g) and dry THF (35 ml) are cooled to -39°. Chlorotrimethylsilane (2.7 ml) is added followed by a nitrogen flush. LDA [1.94 molar bis(tetrahydrofuran complex) in a mixture of iso-octanes, 32.2 ml] is added dropwise with stirring maintaining the temperature < - 30° . The reaction mixture is then cooled to -57° and stirred for an additional hour. LDA (1.8 ml) is then added permitting the temperature to rise to -26°. The reaction mixture is then added to concentrated hydrochloric acid (30 ml) and ethylene glycol (4.2 ml). THF/iso-octanes (1/1, 20 ml) is washed into the mixture and the temperature is permitted to rise to 8°. When the reaction is complete, as monitored by HPLC, iso-octanes (70 ml) is added dropwise over about 10 mi followed by addition of water (225 ml) . The reaction mixture is filtered, washed with water/iso-octanes dried under reduced pressure with heat to give the title compound, NMR (CDCI3-CD3OD) 0.5, 1.2, 4.4, 5.4 and 5.6 δ . EXAMPLE 6 21-Bromo-17α-hydroxypregna-4,9(11) -diene-3,20-dione (III) Following the general procedures of EXAMPLES 4 and 5, and making non-critical variations but starting with 17 / 9-cyano-17α-hydroxy- androsta-4,9(11)-dien-3-one 17-(bromo ethyl)dimethylsilyl ether (II, EXAMPLE 2) , the title compound is obtained. EXAMPLE 7 17 / 3-Cyano-17α-hydroxyandrosta-l,4,9(11)-trien-3-one 17-(chloromethy1)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 173-cyano-17α-hydroxyandr- osta-l,4,9(ll)-trien-3-one, the title compound is obtained, m.p. 170.5-172°; NMR (CDCI3) 0.5, 1.3, 4.4, 5.5, 6.0, 6.2 and 7.1 5. EXAMPLE 8 17 / S-Cyano-17α-hydroxyandrost-4-en-3-one 17-(bromo¬ methyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 2 and making non- critical variations but starting with 17?-cyano-17α-hydroxyandrost-4- en-3-one (US Patent 4,500,461, Example 1) and bromomethyldimethyl- ' chlorosilane, the title compound is obtained, m.p. 133-136°; NMR (CDCI3) 0.4, 0.9, 1.2, 2.5, and 5.7 5. EXAMPLE 9 17J-Cyano-17α-hydroxyandrost-5-en-3-one 3-ethylene ketal 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 170-cyano-17α-hydroxyandr- ost-5-en-3-one 3-ethylene ketal (US Patent 4,500,461, Example 3), the title compound is obtained, m.p. 135-136°. EXAMPLE 10 17 -Cyano-3-ethoxy-17α-hydroxyandrosta-3,5,9(11)- triene 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 17/3-cyano-3-ethoxy-17α- hydroxyandrosta-3,5,9(11)-triene, the title compound is obtained, m.p. 111-118°. EXAMPLE 11 17 -Cyano-17α-hydroxyandrost-4-en-3-one 17-(chloro¬ methyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with llβ-cyano-17α-hydroxyandr- ost-4-en-3-one (US Patent 4,500,461, Example 1), the title compound is obtained, m.p. 143-146°. EXAMPLE 12 17 -Cyano-3,17α-dihydroxyandrosta-3,5-diene 3-methyl ether 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 173-cyano-17α-hyάroxy-3- hydroxyandrosta-3,5-diene 3-methyl ether, the title compound Is obtained, m.p. 117-120°_ EXAMPLE 13 17 -Cyano-3,17α-dihydroxyandrosta-3,5-diene 3- ethyl ether 17-(bromomethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 17^-cyano-17α-hydroxy-3- hydroxyandrosta-3,5-diene 3-methyl ether and bromomethyldimethyl- chlorosilane, the title compound is obtained, m.p. 122-130°; NMR (CDC1 3 > 0.4, 0.5, 1.0, 2.1, 3.5, 5.1 and 5.2 δ . EXAMPLE 14 21-Chloro and 21-Bromo Corticoids (III) Following the general procedure of EXAMPLES 4, 5 and 6 and making non-critical variations but starting with the α-halo silyl ethers (II) of EXAMPLES 7 through 13, the corresponding 21-chloro and 21-bromo corticoids (III) are obtained. EXAMPLE 15 17i9-Cyano-17α-hydroxy-16jS-methylandrosta-l,4,9(11)- trien-3-one (I) 16,3-Methylandrosta-1,4,9(11 . -triene-3,17-dione (US Patent 3,010,958, 12.0 g) and potassium, cyanide (7.909 g) are suspended in methanol (24 ml) . The resulting slurry is then treated with glacial acetic acid (3.5 ml) and allowed to stir in a tightly stoppered flask at 20-25° for 72 hr. TLC (acetone/methylene chloride, 4/96). The reaction mixture is then cooled to 0° and quenched with glacial acetic acid (4.2 ml). The solids are then collected by filtration, triturated with methanol/water '1/1, 3 x 10 ml) and dried by heating (60°) under reduced pressure (60 mm) to obtain the title compound, m.p. 241-247.5°; NMR (CD 2 Cl 2 ) 1.32, 1.42, 5.58, 6.08, 6.30 and 7.25 5. EXAMPLE 16 17 / 3-Cyano-17α-hydroxy-16^-methylandrosta-l ) 4,9(11)- trien-3-one 17- (chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 173-cyano-17α-hydroxy-163- methylandrosta-l,4,9(ll)-trien-3-one (I, EXAMPLE 15) the title compound is obtained, NMR (CDC1 3 ) 0.30, 0.30, 0.91, 1.27, 1.38, 2.81, 5.55, 6.02, 6.24 and 7.17 8 . EXAMPLE 17 21-Chloro-17α--rrdroxy-16/3-methylpregna-l,4,9(11) - trieήe-3,20-dio__= (III) * 17 / 9-Cyano-17α-hydroxy-16 / 9-_ιethylandrosta-l,4,9(ll) -trien-3-one 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 16, 0.213 g) is dissolved in THF (3.0 ml). The resulting mixture is coolded to -30°, then treated with a mixture of lithium hexamethyldisilazide (.71 mmoles) in THF (2.0 ml). The resulting mixture is stirred at -30° for 5 min, then treated with a mixture of trimethylchlorosilane (45 mg) in THF (1.0 ml). The resulting mixture is stirred at -30° for 10 min, then treated with a mixture of LDA bis(tetrahydrofuran)complex in a mixture of iso-octanes (2.22 M, 0.95 ml). The resulting mixture is stirred at -20° for 50 mir.. at which time all of the starting material had been consumed according to TLC (ethyl acetate/cyclohex- ane, 30/70). The reaction mixture is added to a polyethylene bottle containing aqueous hydrofluoric acid (48%, 1.6 ml). The mixture is stirred under argon at 20-25° for 23 hr, then poured into water (100 ml) , extracted with methylene chloride (6 x 20 ml) . The combined extracts are dried over anhydrcu≤ magnesium sulfate and concentrated to give the title compound, NME (CDCI3) 0.85, 1.11, 1.42, 4.42, 4.69, 5.55, 6.07, 6.27, and 7.25 5. EXAMPLΞ 18 17α,21-Dlhydroxy-16 / S-methylpregna-l,4,9(11)-triene- 3,20-dione 21-acetate (VII) 21-Chloro-17α-hydroxy-16 / 3-methylpregna-l,4,9(11)-triene-3,20- dione (III, EXAMPLE 17, 0.151 g) , potassium acetate (0.099 g) , trlbutylmethylammonium chloride (0.014 g) , acetic acid (0.010 g) and water are dissolved in methylene chloride (1.0 ml) and acetone (2.5 ml). The mixture is stirred at 55° for 17 hr at which time the conversion of starting material into product is complete (TLC- sllica gel, acetone/methylene chloride, 10/90) . The reaction mixture is poured in aqueous hydrochloric acid (5%, 50 ml) and extracted with methylene chloride (3 x 15 ml) . The combined extracts are dried over anhydrous magnesium sulfate and concentrated to give the title compound, NMR (CD 2 C1 2 ) 0.74, 1.09, 1.38, 2.11, 4.88, 4.97, 5.54, 5.98, 6.20 and 7.23 5. EXAMPLE 19 17 -Cyano-17α-hydroxyandrosta-l,5,9(11)-trien-3-one 17-(chloromethyl)dimethylsilyl ether (II) A mixture of lithium bis(trimethylsilyl)amide Is added to 173- cyano-17α-hydroxyandrosta-1,4,9(11)-trien-3-one 17-(chloromethyl)- dimethylsilyl ether (II, EXAMPLE 7, 2.987 g) * in dry THF (15 ml) stirring at -50° over a period of 4 minutes. The mixture is warmed to 15° and stirred for 36 min. The mixture Is quenched by adding to ammonium chloride buffer and pentane. Extraction from the buffer mixture gives the title compound, NMR (CDCI3) 0.4,0.9, 1.4, 2.8, 5.5, 5.8, 5.9 and 7.3 δ . EXAMPLE 20 17 -Cyano-3,17α-dlhydroxyandrosta-l,4,9(11)-triene 3- trimethylsilyloxy ether 17-(chloromethyl)dimethylsilyl ether (II) Chlorotrimethylsilane (0.73 ml) Is added to 17 / 9-cyano-17α- hydroxyandrosta-4,9(ll)-dIen-3-one 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 1, 3.0061 g) in dry THF (7.0 ml) stirred at -20°. This is followed by dropwise addition of bis(trimethylsilyl)amine (0.3 ml), then LDA (1.99 M bis(tetrahydrofuran) in a mixture of iso- octane, 3.6 ml). The mixture is quenched by adding to ammonium chloride buffer (2 M) and pentane. Extraction from the buffer mixture gives the title compound, NMR (CDCI3) °- 4 > °- 9 > 1 - 1 » 2 - 9 > 4.8, 5.3 and 5.4 5. EXAMPLE 21 17/9-Cyano-3-ethoxy-17α-hydroxyandrosta-3,5-dlene 17 - (chloromethy1)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 17/ -cyano-3-hydroxy-17α- hydroxyandrosta-3,5-diene 3-ethyl ether (I) and chloroethyldimethyl- chlorosilane, the title compound is obtained, NMR (CDCI3) 0.4, 0.9, 1.0, 1.3, 2.9, 3.8 and 5.2 5. EXAMPLE 22 21-Chloro-17α-hydroxypregna-l,4,9(11)-triene-3,20- dione (III) Following the general procedure of EXAMPLE 17 and making non- critical variations but starting with 17/3-cyano-17α-hydroxyandrosta- l,4,9(ll)-trien-3-one 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 7), the title compound is obtained, m.p. 205-206°. EXAMPLE 23 Progesterone (V) 17 j 9-Cyano-3-ethoxy-17α-hydroxyandrosta-3,5-diene 17-(chloro¬ methyl)dimethylsilyl ether (II, EXAMPLE 21, 7.21 g) is dissolved in dry THF (17.5 ml). This mixture is added to a solution of lithium biphenyl (0.097 moles) in THF (0.2 M) over 9 minutes at -20°. The funnel is rinces with THF (5 ml) . Once the addition is complete a solution of sulfuric acid (6 M, 72 ml) in methanol (36 ml) is added over a period of "one minute. The -20° bath is replaces with an ice bath and the reaction is allowed to warm to 20-25° and stirred until the reaction is complete as measured by TLC. Additional methanol is added to dissolve the solids and water (25 ml) is added. The reaction is concentrated to a low volume, ■ filtered, washed with water until the filtrate is no longer acidic The solids are dissolved in methylene chloride and chromatographed on a column. The column is eluted with ethyl acetate (10→30%) in methylene chloride. The appropriate fractions are pooled and concentrated to give the title compound, which is consistent with a known sample, TLC (acetone/- ethylene chloride, 5/95) R f - 0.75. EXAMPLE 24 17α-hydroxyprogesterone (VI) 17J-Cyano-3,17α-dihydroxyandrosta-3,5-diene 3-methyl ether 17- (chloromethyl)dimethylsilyl ether (II, EXAMPLE 12, 2.98 g) in dry THF (5 ml) . This solution is then added to a solution of lithium naphthalenide (21.1 mmol, 0.5 M in THF) that has been cooled to -78°. The steroid solution is added dropwise but very fast. The syringe is rinsed with THF (2.4 ml). Sufficient dichloromethane (0.25 ml) is added quickly dropwise. The total time from the begining of the addition of the silyl ether (II) to the quenching with methylene. chloride Is 9 min. The reaction mixture is stirred 4 min. Hydro¬ chloric acid (21.0 ml) is added over 5 minutes; the first half is added more slowly than the last half. When the acid quench is complete, the reaction mixture Is removed fron the dry ice acetone bath, methanol (21 ml) is added and the reaction mixture is permitted to warm to 20-25°. Once the reaction is complete as measured by TLC (acetone/me hylene chloride: 5/95), the mixture is concentrated or a rotory evaporatory to remove the solvents, cooled, filtered, the c___ca is washed with water until the filtrate is no longer acidic. The solid is dried under reduced pressure for 2 hr. The solid is then slurrled in a mixture of iso-octaήes (20ml) at 54-60° for 35 mϊ__.. The hot slurry is filterd, the solids are washed with hot iso-octar_=s (3 x 4 ml) and dried to give the title compound, which Is consistent with a known sample, TLC (acetone/methylene chloride, 5/95) Rf - 0.25; HPLC retention time = 10.63 min. EXAMPLE 25 17^-Cyano-ll/3,17α-dihydroxyandrost-4-en-3-one 17- (chloromethyl)dimethylsilyl ether (II) 17 β-Cyano-113,17α-dihydroxyandrost-4-en-3-one (US Patent 4,585,590, Example 25, 6.28 g) and imidazole (1.82 g) are suspended in methylene chloride (20 ml) and cooled to 0° . Chloro(chloro¬ methyl)dimethylsilane Is added dropwise and the resulting mixture is stirred for 15 min at 0° . The reaction is quenched by adding saturated sodium bicarbonate (1 ml), resulting in two liquid phases. The phases are separated. The aqueous phases is extracted with methylene chloride (7 ml) , the organic phases are combined a d distilled atmospherically. After most of the solvent is removed, additional methanol is added (10 ml) and the distillation is ccn- tinued. Again, after most of the solvent is removed methanol (10 ml) and water (10 ml) are added. The mixture is cooled to 20-25° and filtered. The solids are washed with cold (0°) aqueous methanol (33% aqueous) , dried at 45° under reduced pressure (27" Hg) for several hours to give the title compound, m.p. 258-262° (dec); NMR (CDCI3) 0.3, 1.2, 1.4, 2.8, 4.4 and 5.6 δ. EXAMPLE 26 21-Chloro-ll ,17α-dihydroxypregn-4-ene-3,20-dione (III) 17/3-Cyano-ll ,17α-dihydroxyandrost-4-en-3-one 17-(chloro- " methyl)dimethylsilyl ether (II, EXAMPLE 25, 1.032 g) is suspended in THF (6 ml) . The slurry is cooled to -45° and trimethylsilyl chloride - (0.24 ml) is added. The flask is flushed with nitrogen and LDA (1.5 M in chclohexane, 6 ml, 3.8 equivalents) is added dropwise to the slurry over a period of 5 min maintaining the temperature below- 35°. The reaction is then permitted to warm up to -20°. After one hour at -20° , the mixture is cooled to -78"and transferred to a flask containing ethylene glycol (0.5 ml) and hydrochloric acid (12 M, 6 ml) cooled to -45° . The mixture is stirred for 1 hr while warming to 20-25°. The mixture is then distilled under reduced pressure at 20°, until 5 ml of distillate is collected. Water (5 ml) is then slowly added. The slurry is stirred at 20-25° for 10 min, then cooled to 5° and filtered. The precipitate is washed with water (2 x 5 ml) and hexane (2 x ml) . The solids are dried overnight at 60° under reduced pressure to give the title compound, m.p. .217-221 (dec); NMR (CDCI3) 0.95, 1.5, 4.4, 4.5 and 5.7 δ . EXAMPLE 28 17/3-Cyano-9 / 9,ll / 9-epoxy-17α-hydroxyandrost-4-en-3-one 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 17/9-cyano-9/9,ll / 9-epoxy-17α- hydroxyandrost-4-en-3-one (I), the title compound is obtained. EXAMPLE 29 17 / 3-Cyano-3,llS,17α-trihydroxyandrosta-3,5-diene 3- ethyl ether 17-(chloromethyl)dimethylsilyl ether (II) 173-Cyano-3,113,17α-trihydroxyandrosta-3,5-diene 3-ethyl ether • (I, PREPARATION 2) is cooled in a wet ice/acetone bath. Methylene chloride (3 ml) is added followed by a solution of 4-dimethylamino- pyridine (0.03 eq) in methylene chloride (0.5 ml). This is followed by the dropwise addition of chloromethyldimethylchlorosilane (1.3 eq) . The mixture is stirred at 0° . The reaction mixture is then transferred by cannula into a solution of 1.0 M dipotassium phosphate in methylene chloride (50 ml/50ml) cooled in an ice water bath. The two phases are permitted to separate. The aqueous layer is washed three times with methylene chloride. All the organic phases are combined and backwashed with water, dried over sodium sulfate, concentrated and filtered. The filtrate is column chromatographed on silica gel eluting with ethyl acetate/hexane (10/90) . The appropriate fractions are pooled and concentrated to give the title compound. EXAMPLE 30 17/ -Cyano-9/9,ll / 9-epoxy-17α-hydroxyandrosta-l,4-dien-3- one 17-(chloromethyl)dimethylsilyl ether (II) Glacial acetic acid (0.071 ml) is added to a mixture of 9/9,113- eρoxyandrosta-l,4-dlene-3,17-dione (0, 340.5 mg) , potassium cyanide (137.6 mg) in methanol (0.43 ml), water (0.43 ml), and THF (0.14 ml). After 3 hrs at 20-25°, glacial acetic acid (200 μl) , methylene chloride (10 ml) and water (5 ml) are added. The layers are separa¬ ted and the organic phase Is concentrated under reduced pressure. Methylene chloride (1 ml) is added, then distilled off under reduced pressure. DMAP (8.8 mg) , methylene chloride (2 ml) and TEA (0.207 ml) are added and the mixture stirred at 20-25° for 2 hours. The mixture is cooled to < -5°C, and chloromethyldimethylchlorosilane (0.180 ml) is added. After 30 min, aqueous potassium phosphate monobasic (5 ml) is added and the phases separated. The aqueous layer is washed with methylene- chloride (5 ml). The organic layers are combined, washed with water (10 ml) and then concentrated under reduced pressure to an oil. The oil is purified by column chromato¬ graphy eluting with ethyl acetate/hexane (30/70) to give the title compound, m.p. 182-185°; NMR (CD 2 C1 2 ) 0.4, 1.1, 1.4, 2.9, 3.3, 6.1 and 6.6 . EXAMPLE 31 17/9-Cyano-11^,17α-dihydroxyandrosta-l,4-dien-3-one 17- (chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 173-cyano-ll ,17α-di- hydroxyandrosta-l,4-dien-3-one (I), the title compound is obtained, NMR (CDCI3/CD3OD) 0.3, 1.2, 1.4, 2.8, 4.4, 6.0, 6.1, 6.3 and 7.3 δ . EXAMPLE 32 17 -Cyano-17α-hydroxyandrosta-l,4-diene-3,11-dione 17- (chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 173-cyano-17α-hydroxya- ndrosta-l,4-diene-3,ll-dlone (I), the title compound is obtained. EXAMPLE 33 17 / 9-Cyano-17α-hydroxy-6α-methylandrosta-4,9(11)-dien- 3-one 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 30 and making non- critical variations but starting with 17 -cyano-17α-hydroxy-6α- methylandrosta-4,9(ll)-dien-3-one (I), the title compound is ob- tained, NMR (CDCI3) 0.3, 0.9, 1.1, 1.3, 2.8, 5.5 and 5.8 5. EXAMPLE 34 17 / 9-Cyano-9/9,ll/9-epoxy-17α-hydroxy-6α-methylandrost-4- en-3-one 17-(chloromethyl)dimethylsilyl ether (II) Following the-general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 17 / 9-cyano-9 / 9,11 / 9-epoxy-17α- hydroxy-6α-methylandrost-4-en-3-one (I), the title compound is obtained. EXAMPLE 35 17 -Cyano-ll / 9,17α-dihydroxy-6α-methylandrost-4-en-3- one 17-(chloromethyl)dime hylsilyl ether (II) Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 11 β-cyano-11/3,17α-dihydro- xy-6α-methylandrost-4-en-3-one (I, PREPARATION 3), the title compound is obtained, m.p. 238.3-239.1°; NMR (CD 2 C1 2 /CD 3 0D) 0.3, 1.0, 1.1, 1.4, 2.8, 4.4 and 5.7 δ . EXAMPLE 36 17 / 9-Cyano-17α-hydroxy-6α-methylandrosta-l,4,9(11)- trien-3-one 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 30 and making non- critical variations but starting with 173-cyano-17α-hydroxy-6α- methylandrosta-l,4,9(ll)-trien-3-one (I), the title compound is ob¬ tained, m.p. 143-154°; NMR (CDCI3) 0.3, 0.9, 1.1, 1.4, 2.8, 5.6, 6.1, 6.3 and 7.2 δ . EXAMPLE 37 17,3-Cyano-9/ ,ll/9-epoxy-17α-hydroxy-6α-methylandrosta- - l,4-dien-3-one 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 30 and making non- critical variations but starting with 17 / 9-cyano-9,9,ll,_3-epoxy-17α- hydroxy-6α-methylandrosta-l,4-dien-3-one (I), the title compound is obtained, m.p. 161-163; NMR (CDCI3) 0.3, 1.1, 1.2, 1.4, 2.8, 3.3, 6.1, 6.2 and 6.6 δ . EXAMPLE 38 17^-Cyano-11/3,17α-dihydroxy-6α-methylandrosta-l,4- dien-3-one 17-(chloromethyl)dimethylsilyl ether (II) Chloromethyldimethylchlorosilane (0.092 ml) is added over a period of 1 minute to 173-cyano-11 / 8,17α-dihydroxy-6α-methylandrosta- l,4-dien-3-one (I, PREPARATION 4, 192.8 mg) and DMAP (8.8 mg) in methylene chloride (0.87 ml) and TEA (0.11 ml) and the mixture cooled to -12°. The mixture is stirred for 52 min at <-8°, then aqueous potassium phosphate monobasic (3 ml) is added, followed by methylene chloride (5 ml) . The layers are separated and the aqueous layer is washed twice with methylene chloride (2 ml) . The organic extracts are combined and backwashed with water (5 ml) , then concentrated- under reduced pressure to give a solid. This solid is dissolved in a minimal amount of hot ethyl acetate then cooled to <0°. The resul- tant crystals are filtered, washed with hexane, and then dried in vacuo at 45° overnight to give the title compound, m.p. 250.5- 251.4°; NMR (CD 2 C1 2 /CD 3 0D) 0.3, 1.1, 1.2, 1.5, 2.9, 4.5, 6.0, 6.3, and 7.45 δ . EXAMPLE 39 17 / 9-Cyano-6α-fluoro-17α-hydroxyandrosta-4,9(11)-dien- 3-one 17-(chloromethyl)dimethylsilyl ether (II) To 173-cyano-6α-fluoro-17α-hydroxyandrosta-4,9(11)-dien-3-one (I, PREPARATION 6, 73.8 mg) Is added methylene chloride (2.0 ml) and DMAP (4.6 mg) . The mixture cooled to -10°. TEA (0.049 ml) followed by chloromethyldimethylchlorosilane (0.033 ml) is added. After 5 min, TEA (0.060 ml) is added. After 40 min, aqueous potassium phosphate monobasic (5 ml) followed by methylene chloride (5 ml) Is added and the phases separated. The aqueous layer is washed with methylene chloride (5 ml. and the combined organic layers washed with water (10 ml) . The organic layer is dried over anhydrous sodium sulphate and filtered through silica gel (1 g) . Concentrated hydrochloric acid (15 ml) is then added and the mixture vigorously shaken for 5 min. The layers are separated and the organic layer washed with several portions of water to pH = 6.0. The organic layer is dried over anhydrous sodium sulphate and concentrated to an oil under reduced pressure. Ethyl acetate (1 ml) followed by hexane (1 ml) is added and the mixture cooled to -10° for 5 hrs. The resultant crystals are collected by filtration, washed with hexane, and dried in vacuo at 20-25° to give the title compound, m.p. 131-132°C; NMR (CDC1 3 ) 0.4, 0.9, 1.4, 2.9, 5.8, and 6.2 δ. EXAMPLE 40A 17α-Cyano-17 / 9-hydroxy-16-methyleneandrost-4-en-3-one 17-(chloromethyl)dimethylsilyl ether (II) A slurry of 17α-cyε-_o-17j9-hydroxy-16-methyleneandrost-4-en-3-one (I, PREPARATION 7, 2.50 g) and DMAP (0.038 g) in methylene chloride (12.5 ml) is cooled to -10 to -15° while stirring under a nitrogen atmosphere. TEA (1.40 ml) and chloromethyldlmethylchlorosilane (1.20 ml) are added to the steroid mixture and the resulting mixture is stirred for 1 hr and then poured in to a mixture of potassium dihydrogen phosphate (1.0 M, 15 ml) and methylene chloride (20 ml). The mixture is stirred vigorously at -10 to -5° for 10 in. The layers are then separated and the aqueous layer is extracted with methylene chloride. The organic extracts are washed with water, dried over sodium sulfate and concentrated to the crude product. The product is purified by chromatography on silica gel (230-400 mesh, 400 g) eluting with ethyl acetate/cyclohexane (20/80) . The ap¬ propriate fractions are pooled and concentrated to give the title compound, NMR (CD 2 C1 2 ) 0.42, 0.43, 0.79, 1.19, 2.93, 5.24, 5.40 and 5.67 5. EXAMPLE 40B 21-Chloro-17/9-hydroxy-16-methylenepregn-4-ene-3,20- dione (III) Trimethylsilyl chloride (0.32 ml) and LDA (4.99 M, 4.4 ml) in a mixture of iso-octanes are added to a solution of 17α-cyano-17 / 9- hydroxy-16-methyleneandrost-'4-en-3-one 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 40A, 1.0 g) in THF (10 ml). The mixture is stirred for 5 min at -71° then warmed to -20°, then cooled to -71° and stirred for 15 min more. The reaction mixture is added to a solution of concentrated hydrochloric acid (4.8 ml) and methanol (8.0 ml) stirring rapidly under a nitrogen atmosphere at -71°. After 15 min the resulting mixture is warmed to 20-25° and partitioned between methylene chloride and water. The organic phase is washed with water and dried over sodium sulfate and concentrated. The concentrate is purified by chromatography on silica gel (230-400 mesh, 150 g) eluting with ethyl acetate/cyclohexane (25/75) . The appropriate fractions are pooled and concentrated to give the title compound, NMR (CD 2 C1 2 ) 0.88, 1.17, 3.0, 4.60, 5.16 and 5.69 5. EXAMPLE 40C 17/9-Hydroxy-16-methylenepregn-4-ene-3 ,20-dione (V) Zinc dust (0.030 mg) and glacial acetic acid (0.13 ml) is added to a solution of 21-chloro-17j9-hydroxy-16-methylenepregn-4-ene-3,20- dione (III, EXAMPLE 40B, 0.050 g) in ethyl acetate (1.5 ml). The reaction system is purged with nitrogen and warmed to 45° . After stirring for 16.5 hr, THF (5 ml) is added and the mixture is filtered thru celite to remove the remaining zinc. The filtrate is then partitioned between water (5 ml) and ether (5 ml) . . The organic extract is washed with sodium bicarbonate (5%) and water, dried over sodium sulfate and concentrated to give the title compound, NMR (CD 2 C1 2 ) 0.87, 1.17, 2.20, 3.40, 5.10 and 5.65 δ . EXAMPLE 41 17^-Cyano-11/9,17α-dihydroxyandrost-4-en-3-one 11- dimethylsilyloxy ether 17-(chloromethyl)dimethylsilyl ether (II) 17 / 9-Cyano-113,17α-dihydroxyandrosta-4-en-3-one (I, 2.68 gm) is suspended in methylene chloride (10 ml) and imidazole (1.66 gm) is added. After cooling to 0°, chloro(chloromethyl)dimethylsllane (1.29 ml) Is added. After 30 min at 0°, methanol (0.07 ml) Is addedd, and the mixture is warmed to 20-25°. Chlorotrimethylsilane (1.55 ml) is added, and after 5 hrs water (2 ml) is added. The organic phase is washed with water (2 ml), dried over anhydrous potassium carbonate, and the solvent Is evaporated under vacuum to give the title com¬ pound, NMR (CDC1 3 ) 0.1, 0.3, 1.1, 1.3, 2.8, 4.4 and 5.6 8. EXAMPLE 42 17 -Cyano-17α-hydroxy-6-methylenandrosta-4,9(ll) -dien- -3-one 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 30 and making non- critical variations but using 6-methylenandrosta-4,9(ll)-diene 3,17- dione (0, 18792-JPP-l-A) the title compound is obtained, m.p. 123- 136°; NMR (CDCI3) 0.4, 0.9, 1.3, 2.8, 5.0, 5.1, 5.6, and 5.9 δ . EXAMPLE 43 17 -Cyano-17α-hydroxy-6-methylandrosta-4,6,9(11)- trien-3-one 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedures of EXAMPLE 30 and making non- critical variations but starting with 6-methylandrosta-4,6,9(ll)- triene-3,17-dione (0), the title compound is ' obtained, m.p. 149-159°; NMR (CDCI3) 0.3, 0.9, 1.2, 1.8, 2.8, 5.5, 5.8, and 5.9 δ . EXAMPLE 44 17 -Cyano-ll/9,17α-dihydroxy-6-methylenandrost-4-en-3- one 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 38 and making non- critical variations but using 17/3-cyano-ll / 9,17α-dihydroxy-6-methylen- androst-4-en-3-one (I, PREPARATION 8) the title compound is obtained, m.p. 204-206°; NMR (CDCI3) 0.3, 1.2, 1.3, 2.8, 4.5, 5.0, and 5.8 δ . EXAMPLE 45 17 -Cyano-6-fluoro-3,17α-dlhydroxyandrosta-3,5,9(11)- triene 3-methyl ether 17-(chloromethyl)dimethylsilyl ether (II) TEA (0.080 ml) is added to 17/S-cyano-6-fluoro-3,17α-dihydroxy- androsta-3,5,9(ll)-triene 3-methyl ether (I, PREPARATION 5, 78.5 mg) and DMAP (2.9 mg) in methylene chloride (0.50 ml) , and the mixture is cooled to -12°. Chloromethyldimethylchlorosilane (0.033 ml) is added and the mixture stirred at <-10° for 25 min. Chloromethyldimethyl- chlorosilane (0.033 ml) then TEA (0.035 ml) is added. After 18 min, aqueous potassium phosphate monobasic (4 ml) is added followed by methylene chloride (5 ml) . The layers are separated and the aqueous layer washed with methylene chloride (2 ml) . The combined organic layers are dried over anhydrous sodium sulphate and filtered. The. filtrate is concentrated under reduced pressure to an oil. Column chromatography eluting with ethyl acetate/hexane (5/95) gives the title compound; NMR (CDCI3) 0.4, 0.9, 1.2, 2.9, 3.6, 5.5, and 5.6 5 . EXAMPLE 46 17/9-Cyano-11 / 3,17α-dihydroxyandrosta-l,4-dien-3-one 11- trimethylsilyloxy ether 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 41 and making non- critical variations but starting with 173-cyano-113,17α-dihydroxy- androsta-l,4-dien-3-one (I), the title compound is obtained. EXAMPLE 47 17 / 9-Cyano-17α-hydroxyandrosta-l,4,9(11)-trien-3-one 17-(dichloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 70 and making non- critical variations but starting with 173-cyano-17α-hydroxyandrosta- 1,4, 9(11)-trien-3-one (I), the title compound is obtained, m.p. 199- 201.5°; NMR (CDCI3) 0.4, 0.5, 1.0, 1.4, 5.3, 5.6, 6.0, 6.2, 6.3 and 7.2 δ . EXAMPLE 48 17?-Cyano-17α-hydroxyandrost-4-en-3-or_e 17-(chloro- methyl)methoxymethylsilyl ether [mixture of dia- stereomers at the silicon center] (II) DMAP (11.3 mg) , methylene chloride (1.4 ml) ar_d TEA (0.152 ml) are added to 17 / 9-cyano-17α-hydroxyandrosta-4-en-3-one (I, 284.6 mg) and the mixture cooled to < -5°. Chloromethylmethyldichlorosilane (0.128 ml) is added and the mixture allowed to want to 20-25° for 15 min then cooled -10°. TEA (0.16 ml) followed by methanol (0.044 ml) is added and the mixture allowed to warm to 20-25*. After 50 min, methanol (0.10 ml), methylene chloride (10 ml) and aqueous potassium phosphate monobasic (5 ml) is added and the layers separated. The organic layer is washed with water (5 ml), then concentrated under reduced pressure. The resultant oil is dissolved in 2 ml ethyl acetate, dried over sodium sulphate, filtered and concentrated to an oil under reduced pressure. Crystallization at -10° from a mixture of ethyl acetate and hexane gives crystals which were filtered, then dried under high vacuum to give the title compound, NMR (CDCI3) 0.4, 0.9, 1.2, 2.8, 3.6, and 5.7 5. EXAMPLE 49 17/3-Cyano-3,17α-dihydroxyandrosta-3,5, (11)-triene 3- methyl ether 17-(chloromethyl)methoxy__iethylsilyl ether, [mixture of diastereomers at the silicon center] (II) Following the general procedures of EXAMPLE 4S and making non- critical variations but starting with 173-cyano-3,17α-dihydroxy- androsta-3,5,9(11)-triene 3-methyl ether (I), the title compound is obtained; NMR (CDCI3) 0.4, 0.9, 1.1, 2.8, 3.6, 5.1, 5.2, and 5.5 δ . EXAMPLE 50 17/9-Cyano-3,17α-dlhydroxyandrosta-3,5,9(ll)trlene 3- methyl ether 17-(chloromethyl)isopropoxymethylsilyl ether [mixture of diastereomers at the silicon center] ID DMAP (0.3716 g) , methylene chloride (25 ml) and TEA (2.70 ml) are added to 17/3-cyano-3,17α-dihydroxyandrosta-3,5,9(11)-triene 3- methyl ether (I) and the mixture cooled to < -5° . Chloromethylmethy- ldichlorosilane (2.20 ml) is added and the mixture allowed to warm to 20-25°. After 25 min, the mixture is cooled to -5° and TEA (2.70 ml) then 2-propanol (3.60 ml) is added. After 15 min, aqueous potassium phosphate monobasic (10 ml) is added and the layers separated. The aqueous layer is washed with methylene chloride (5 ml). The combined organic layers are washed with water (5 ml) , dried over sodium sulphate, filtered and concentrated to an oil. Column chromatography eluting with ethyl acetate/hexane (2/98) gives the title compound; NMR (CDCI3) 0.4, 0.9, 1.1, 1.2, 2.8, 3.6, 4.2, 5.1, 5.2, and 5.5 δ . EXAMPLE 51 173-Cyano-17α-hydroxyandrost-4-en-3-one 17-(chlorome¬ thyl)diisopropoxysilyl ether (II) DMAP (12.3 mg) and methylene chloride (1.0 ml) is added to 17 / 9- cyano-17α-hydroxyandrost-4-en-3-one (I, 266.2 mg) and the mixture is cooled to < -5°. TEA (0.150 ml) followed by chloromethyltrichloro- silane (0.114 ml) is added and the mixture stirred for 25 min. TEA (0.290 ml) is added followed by 2-propanol (0.149 ml). After 5 min, the mixture is warmed to 20-25°. After 45 min, the reaction mixture Is poured Into pentane (30 ml) and aqueous potassium phosphate monobasic (7 ml) . The reaction flask is rinsed with pentane (10 ml) . The layers are separated and the aqueous layer washed with pentane (5 ml) . The organic layers are combined, dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure. Column chromatography of the concentrate and eluting with ethyl acetate/- hexane (10/90) gives the title compound; NMR (CDCI3) 1.0, 1.2, 1.3, 2.8, 4.3, and 5.7 5. EXAMPLE 52 173-Cyano-17α-hydroxyandrosta- ,9(11)-dlen-3-one 17- " (chloromethyl)diisopropoxysilyl ether (II) Pentane (3 ml) , water (1 ml) and glacial acetic acid (35 ml) is . added to 173-cyano-3 ,17α-dihydroxyandrosta-3, 5,9(11) -triene 3-methyl ether 17-(chloromethyl)diisopropoxysilyl ether (I, EXAMPLE 53, 244 mg) . After stirring vigorously for 2 min, the reaction mixture is poured into ethyl acetate (30 ml) and aqueous potassium phosphate monobasic (10 ml) . The layers are separated and the organic layer dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to give the title compound; NMR (CDCI3) 0.9, 1.2, 1.3, 2.7, 4.3, 5.5, and 5.7 8 . EXAMPLE 53 173-Cyano-3,17α-dihydroxyandrosta-3,5,9(11)-triene 3- methyl ether 17-(chloromethyl)diisopropoxysilyl ether (ID 4-Dimethylaminopyridine (0.7013 g) and methylene chloride (50 ml) followed by TEA (32.0 ml) are added to 173-cyano-3,17α-dihydroxy- androsta-3,5, (11)-triene 3-methyl ether (I, 18.58 g) . When the mixture becomes homogeneous, the mixture is cooled to -10° and chloromethyltrichlorosilane (7.9 ml) is added. The mixture is stirred for 3 hr maintaining the temperature below -5°. The mixture is cooled to -78° and isopropanol (23 ml) is added at such a rate as to maintain the temperature below -10°. The mixture is then stirred at 20-25° for 2 hr, then poured into pentane (400 ml) over aqueous potassium phosphate monobasic (150 ml) . The phases are separated and the aqueous phase is washed with pentane (200 ml) . The combined organic phases are washed with water (100 ml) and concentrated to ap¬ proximately 400 ml under reduced pressure, then cooled to -20° for 3 days. The resultant crystals are removed by vacuum filtration and washed with pentane (100 ml) . The mother liquour is dried over anhydrous sodium sulphate, filtered, and concentrated to a oil. This is placed on a silica gel (50 g) column and eluted with ethyl acetate/hexane (2/98, 100 ml). The first 240 ml are discarded and the remaining eluent is concentrated to a clear oil, under reduced pressure. This oil is placed under high vacuum at 20-25° for 2 days, then allowed to crystallize at -20° for 5 days. The crystals are washed with pentane (2 x 20 ml) at -20° and dried at 20-25° under high vacuum for 1 day to give the title compound, m.p. 79-81°; NMR (CDCI3) 0.9, 1.1, 1.2, 2.7, 3.6, 4.3, 5.1, 5.3, and 5.5 δ . EXAMPLE 54 17α-Cyano-17 / 3-hydroxyandrosta-4,9(11)-dien-3-one 17- (chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 40A and making non- critical variations but starting with 17α-cyano-173-hydroxyandrόsta- 4,9(ll)-dien-3-one (I, PREPARATION 9), the title compound is ob¬ tained, m.p. 135.8-138.8°; NMR (CDCI3) 0.4, 0.8, 1.4, 2.9, 5.6 and 5.7 δ . EXAMPLE-55 21-Chloro-173-hydroxypregna-4,9(11)-dlene-3,20-dIone (III) Following the general procedure of EXAMPLE 40B and making non- critical variations but starting with 17α-cyano-173-hydroxyandrosta- 4,9(ll)-dien-3-one 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 54), the title compound is obtained, m.p. 227-228.5°; NMR (CDCI3) 0.2, 0.7, 2.7, 5.5 and 5.6 5. EXAMPLE 56 17/9,21-Dihydroxyρregna-4,9(11) -diene-3,20-dione 21- acetate (VII) Following the general procedure of EXAMPLE 18 and making non- critical variations but starting with 21-chloro-173-hydroxypregna- 4,9(ll)-dlene-3,20-dione (III, EXAMPLE 55) the title compound is obtained, m.p. 175-176.8°. EXAMPLE 57 173-Cyano-17α-hydroxyandrost-5-en-3-one 3-ethylene ketal 17-(bromomethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 2 and making non- critical variations but starting with 173-cyano-17α-hydroxyandrost-5- en-3-one 3-ethylene ketal (I, US Patent 4,500,461 Example 3), the title compound Is obtained, NMR (CDCI3) 0.4, 0.9, 1.0, 1.5, 2.6, 3.9 and 5.5 δ. EXAMPLE 58 173-Cyano-17α-hydroxyandrost-5-en-3-one 3-ethylene ketal 17-(iodo ethyl)dimethylsilyl ether (II) 173-Cyano-17α-hydroxyandrost-5-en.-3-one 3-ethylene ketal 17- (bromomethy1)dimethylsilyl ether (II, EXAMPLE 57, 0.857 gm) and sodium iodide (0.52 gm) are taken up in acetone (.5 ml) and heated at reflux for 3 hrs. The solvent is removed under vacuum and the residue partitioned between ethyl acetate and hexane. The organic phase is separated, dried over anhydrous sodium sulfate, and the solvent removed under vacuum while being replaced with hexane. The product separates to give the title compound, NMR (CDCI3) 0.4, 0.9, 1.0, 2.1, 3.9, and 5.3 δ . EXAMPLE 59 17/9-Cyano-17α-hydroxyandrosta-4, 9(11) -dien-3 -one 17-. (dichloromethyl) dimethylsilyl ether (II) Following the general procedure of EXAMPLE 1 and making non- critical variations but starting with dichloromethyldimethylchloro- silane, the title compound is obtained, m.p. 165-174°. EXAMPLE 60 21, 21-Dichloro-17α-hydroxypregna-4,9(11)-diene-3,20- dione (III) A solution of lithium hexamethyldisilazide (LiHMDS) in THF (1.0 molar, 0.7 ml) is added dropwise to a solution of 173-cyano-17α- hydroxyandrosta-4,9(ll)-dien-3-one 17-(dichloromethyl)dimethylsilyl ether (II, EXAMPLE 59, 0.1095 gm) in THF (1.0 ml) at -65° under nitrogen maintaining the temperature at about -65° to 45°. The temperature is then allowed to warm to 0° . The reaction is cooled again to -45° . The reaction is quenched with a solution of methanol (3 ml) and concentrated hydrochloric acid (3 ml) . The reaction is allowed to warm to 20-25° . The mixture is extracted with methylene chloride. The combined layers are dried over sodium sulfate, filtered and concentrated. The concentrate is chromatographed on silica gel using ethyl acetate hexane (20/80) followed by ethyl acetate/hexane (50/50) to obtain the title compound, NMR (CDCI3) 0.7, 1.3, 5.5, 5.7 and 6.5 δ . EXAMPLE 61 17α-Hydroxypregna-4,9(11)-diene-3,20-dione (VI) Dry THF (20 ml) is added to lithium wire (64.1 mg) and 4,4' -di- t-butylbiphenyl (3.047 g) under argon. The mixture is cooled to -10°, then sonicated until it has a persistent blue-green color. The mixture is stirred for 3 hr at -5°, then cooled to -70°. 173-Cyano- 3,17α-dihydroxyandrosta-3,5,9(ll) -triene 3-methyl ether 17-(chloro- methyl)diisopropoxysilyl ether (II, EXAMPLE 53, 928.0 mg) in THF (20 ml) is added dropwise over 5 min. Immediately, 1,2-dichloroethane (10 ml) followed by methanol (5 ml) and sulphuric acid (6 M, 10 ml) are added. The mixture is warmed to 20-25° and stirred for 20 hrs. The phases are separated and the aqueous phase washed with methylene chloride (30 ml) . The combined organic phases are washed with water (2 x 20 ml). Methanol (30 ml) is added to the organic phase which is then dried over sodium sulfate. The mixture is filtered and con¬ centrated to crystals under reduced pressure. The crystals are triturated with hot pentane (100 ml) , collected by vacuum filtration and washed with pentane (3 x 50 ml) . The crystals are dried at 50° for 20 hr to give the title compound; NMR (CDCI3/CD3OD) 0.4, 1.2, ■ 2.0, 5.4, and 5.5 δ . EXAMPLE 62 17α,21-Dihydroxypregna-4,9(11)-diene-3,20-dione (VII) -54- To lithium wire (77.9 mg) and 4,4' -di-t-butylbiphenyl (3.780 g) under argon is added THF (30 ml) . The mixture is cooled to -10° , then sonicated until it has a persistent blue-green color. The mixture is stirred at -18° for 17 hrs, then cooled to -52°, 173- cyano-3,17α-dihydroxyandrosta-3,5,9(ll)-triene 3-methyl ether 17- (chloromethyl)diisopropoxysilyl ether (II, EXAMPLE 53, 912.3 g) in THF (7 ml) is added dropwise over 2 min. Immediately, 1,2-dichloro- ethane (0.30 ml) followed by aqueous hydrogen peroxide (30%, 8 ml) is added. The temperature is maintained at less than -10° for 1 hr, then methanol (5 ml) and sulfuric acid (6 M, 10 ml) is added. The mixture is then stirred at 20-25° for 1 hr. Methylene chloride (30 ml) Is added and the phases separated. The aqueous layer is washed with methylene chloride (2 x 10 ml) . The organic layers are combined and washed with water (2 x 20 ml) , aqueous sodium thiosulphate (1 M, 50 ml) and water (2 x 50 ml) . Methanol (25 ml) is added to the organic phase which is then dried over anhydrous sodium sulphate. The mixture is filtered and concentrated to crystals under reduced pressure. Column chromatography on silica gel eluting with acetone/- ethylene chloride (5/95) gives the' title compound, m.p. 243-249°; NMR (CDCI3/CD3OD) 0.4, 1.2, 5.4, and 5.5 δ. EXAMPLE 63 21-Bromo-17α-hydroxypregn-4-ene-3,20-dlone (III) 173-Cyano-3,17α-dihydroxyandrosta-3,5-diene" 3-methyl ether 17- (bromomethyl)dimethylsilyl ether (II, EXAMPLE 13, 0.5005 gm) and dry THF (0.7 is) are cooled to -31°. A solution of LDA in a mixture of Iso-octanes (2.07 M, 1.0 ml) is added dropwise with stirring over 2 min maintaining the temperature at -31°. After 8 min the reaction is cooled to -70° and quenched by adding a solution of concentrated hydrochloric acid (0.9 ml) and ethylene glycol (0.17 ml). The reaction mixture is warmed to 20-25° and stirred 18 hr. Cyclohexane (0.6 ml) is added followed by water (2.6 ml). The reaction mixture is filtered and washed with water followed by cyclohexane and dried overnight at 60° to give the title compound, (mixed with the 21- chloro steroid), NMR (CD3OD/CDCI3) 0.6, 1.1, 3.2, 4.3, 4.4, and 5.6 δ . EXAMPLE 64 21-Bromo-17α-hydroxypregn-4-ene-3,20-dione (III) Following the general procedure of EXAMPLE 63 and making non- critical variations but using hydrobromic acid in place of hydro¬ chloric acid, the title compound Is obtained free of the correspond- ing 21-chloro steroid, 21-chloro-17α-hydroxypregn-4-ene-3,20-dione. EXAMPLE 65 21-Bromo-17α-hydroxypregn-4-ene-3,20-dione (III) Following the general procedure of EXAMPLE 63 and making non- critiacl variations but allowing the reaction mixture to stir for 10 min at 20-25° followed by quenching give the title compound, substan¬ tially free of the corresponding 21-chloro steroid, 21-chloro-17α- hydroxypregn-4-ene-3,20-dione. EXAMPLE 66 21-Chloro-17α-hydroxypregna-4,9(11)-diene-3,20-dione (III) 3-Hydroxyandrosta-3,5,9(ll) -trien-17-one 3-methyl ether (0, U„S Patent 3,516,991 Example 1, 22.5 g) , potassium cyanide (9.1 g) , methanol (30.3 ml) and THF (18 ml) are combined and heated to 32°. Acetic acid (6.3 ml) is added over 30 min and the mixture stirred at 32° for 1.5 hr followed by acetic acid (6.3 ml) added over 30 min and stirring for 1 hr. Methanol (3.6 ml) is added over 1 hr and then the mixture is stirred for 30 min. Water (30 ml, 15 ml and 7.5 ml) is added over periods of 1.5 hr, 1.5 hr and 30 min with stirring inbetween additions of water of 4 hr and 0.5 hr respectivly. The mixture is cooled to 0°, acetic acid (2.5 ml) is added and the mixture stirred for 30 min at 0°. Methanol (4.7 ml), water (50 ml) and acetic acid (0.3 ml) are added, the mixture filtered and dried to obtain 17/9-cyano-3,17α-dihydroxyandrosta-3,5,9(11)-triene 3-methyl ether (I). 173-Cyano-3.17α-dihydroxyandrosta-3,5,9(11)-triene 3-methyl ether (I, 20 g) , methylene chloride (140 ml), pyridine in methylene chloride (2 ml in 10 ml) are mixed. Sodium chloride (3.5 g) in water (10 ml) is added and the mixture stirred for 5 min. The phases are separated, the aqueous phase is extracted with methylene chloride (2 x 10 ml) and the organic phases are combined. The mixture is concentrated by distillating off 85 ml and cooled to 0° . Inidazole (2.5 g) in TEA (8.2 ml) is added followed by slow addition of chloromethyldimethylchlorosilane (10.8 ml) and methylene chloride rinse (1 x 1 ml, 1 x 5 ml) maintaining the temperature at 0 +2°. The mixture is degassed, water (110 ml) added and stirred vigorously for 10 min. The phases are separated, the aqueous phase is extracted with methylene chloride (2 x 10 ml) and combined with the original organic phase. The organic phase is concentrated replacing the methylene chloride with heptane (123 ml) until GC assay shows meth lene chloride < 1% by volume. The mixture is stirred, cooled to 0° and filtered to give 173-cyano-3,17α-dihydroxyandrosta-3,5,9(11)- triene 3-methyl ether 17-(chloromethyl)dimethylsilyl ether (II). The silyl ether (II, 24 g) in THF (62.5 ml) is cooled to -40° and LDA (42 ml) is added slowly keeping the temperature at about -35 t about -40° . Concentrated hydrochloric acid (72 ml) and ethylene glycol (8.75 ml) precooled to < -40° are added maintaining the temperature at 0° . The mixture Is hydrolyzed for 1 hr at 20° +2° . Heptane (16 ml) and water (10 ml) are added the the mixture heated to 50° while stirring for 1 hr. The mixture is cooled to -5° and stirred for 30 min while adding water (2 x 30 ml) . The mixture is filtered and the solid dryed at 60° under nitrogen to give the title compound. Before disposing of the non-used phases, filtrates, washes etc, a check should be made for cyanide and if necessary treatment with sodium hypochlorite and quenching with sodium sulflte along with proper disposal. EXAMPLE 67 173-Cyano-3,17α-dihydroxyandrosta-3,5-diene 3-methyl ether 17-(iodomethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 58-and making non- critical variations but starting with 173-cyano-3,17α-dlhydroxy- androsta-3,5-diene 3-methyl ether 17-(bromomethyl)dimethylsilyl ether (II, EXAMPLE 13), the title compound is obtained, NMR (CDC1 3 ) 0.4, 0.9, 1.0, 2.0, 3.5, 5.1 and 5.2 δ . EXAMPLE 68 17α-hydroxyprogesterone (VI) Sodium metal (0.1507 gm) and anhydrous ammonia (approximately 13 ml) are combined in a dried nitrogen purge flask. The mixture is refluxed to insure all the sodium metal dissolved. 173-Cyano-17α- hydroxyandrost-5-en-3-one 3-ethylene ketal 17-(chloromethyl)dimethyl- silyl ether (II, EXAMPLE 9, 0.4419 gm) Is dissolved in THF (2.0 ml) and is added dropwise over 3 min at -78° . The reaction is quenched with isoprene by adding it dropwise until the color of the reaction changes. Ammonium chloride (0.7537 gm) is added and the reaction is allowed to warm to 20-25° . The ammonia is removed by reduced pressure and the mixture is cooled and concentrated hydrochloric acid/methanol (2/1, 30 ml) is added. The reaction mixture is stirred overnight. Water is added and an extractive workup using methylene chloride is done. The combined organic layer is back-washed, dried with sodium sulfate and concentrated under reduced pressure to to obtain the title compound. The identity of the title compound is confirmed by comparison with an authentic sample using LC. EXAMPLE 69 17α-hydroxyprogesterone (VI) 173-Cyano-17α-hydroxyandrost-5-en-3-one 3-ethylene ketal 17- (iodomethyl)dimethylsilyl ether (II, EXAMPLE 58, 0.4935 gm) is mixed with THF (2.0 ml) and cooled to -78°. A solution of butyllithium in hexanes (1.6 molar, 0.89 ml) is added over 2 min. The reaction is stirred until complete as measured by TLC. A solution of methanol (10 ml) and concentrated hydrochloric acid (10 ml) is added to quench the reaction allowing the temperature to reach 5° . The reaction is stirred at 20-25° until complete by TLC and LC. Heptane is added to the reaction (2.5 to 5 ml). The mixture is concentrated under reduced pressure while adding water. The resulting slurry is cooled, filtered, washed with water and hexane. The solids are dried under reduced pressure to give the title compound. The identity of the title compound is confirmed by comparison with an authentic sample using TLC (silica gel and acetone/methylene chloride, 10/90) Rf = 0.5. EXAMPLE 70 173-Cyano-17α-hydroxyandrosta-5,9(11)-dien-3-one 3- ethylene ketal 17-(dichloromethyl)dimethylsilyl ether (ID TEA (1.00 ml) is added to 173-cyano-17α-hydroxyandrosta-5,9(11)- dien-3-one 3-ethylene ketal (I, PREPARATION 10, 1.586 g) and 4- dimethylaminopyridine (49.5 mg) in methylene chloride (5.0 ml) and the mixture cooled to -10°. Dichloromethyldimethylchlorosilane (0.875 ml) is then added over 20 seconds. The mixture is stirred for 2 hr below -5° then aqueous monobasic potassium phosphate (15 ml) is added to adjust the pH to 7 followed by ethyl acetate (10 ml) . The phases are separated and the aqueous layer is washed with ethyl acetate (10 ml) . The combined organic phases are washed with water (10 ml), dried usin anhydrous sodium sulphate, filtered and conc¬ entrated to a oil. Hexane (5 ml) is added and the mixture allowed to crystallize at 20-25° . The crystals are collected by vacuum filtra- tion, washed with hexane (2 x 20 ml) and dried under vacuum at 45° for 18 hr to give the title compound, m.p. 131-134°; NMR (CDCI3) 0.5, - 0.9, 1.3, 4.0, 5.3, 5.4, and 5.5 δ . EXAMPLE 71 173-Cyano-17α-hydroxyandrosta-5,9(11)-dien-3-one 3- ethylene ketal 17-(chloromethyl)dimethylsilyl ether ID Following the general procedure of EXAMPLES 1 and 3 and making non-critical variations but starting with 173-cyano-17α-hydroxy- androsta-5,9(ll)-dlen-3-one 3-ethylene ketal (I), the title compound is obtained. EXAMPLE 72 173-Cyano-17α-hydroxyandrosta-5,9(11)-dlen-3-one 3- ethylene ketal 17-(bromomethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLES 2 and making non- critical variations but starting with 17 -cyano-17α-hydroxyandrosta- 5,9(ll)-dien-3-one 3-ethylene ketal (I), the title compound is obtained. EXAMPLE 73 17α-hydroxyprogesterone (VI) A mixture of 173-cyano-17α-hydroxyandrost-5-en-3-one 3-ethylene ketal 17-(bromomethyl)dimethylsilyl ether (II, EXAMPLE 57, 360.7 mg) and magnesium powder (180 mg) in dry THF (3 ml) is treated with methyl iodide (0.020 ml) and dibromoethane (0.030 ml). The mixture is sonicated briefly. Dibromoethane (0.25 ml) Is added dropwise with stirring and slight heating to maintain a reflux. The resulting slurry Is taken up in THF, and the mixture quenched with aqueous hydrochloric acid (6 molar)/methanol (1/1, 5 ml). The solvent is replaced with water by distillation, the mixture filtered to give the title compound, which Is identical to an authentic sample by TLC (silica gel, acetone/methylene chloride, 5/95), Rf = 0.44. EXAMPLE 74 21-Chloro-17α-hydroxypregna-4,9(ll)-diene-3,20-dione (III) 173-Cyano-17α-hydroxyandrosta-4,9(ll)-dien-3-one (I, 3.316 gm) and 4-dimethylaminopyridine (63 mg) are slurried in dry THF (5 ml) , treated with TEA (1.9 ml) and immediately cooled in an ice-acetone bath. With rapid stirring chloromethyldimethylchlorosilane (1.54 ml) Is added dropwise. After 1 hr, the mixture is allowed to warm to 20- 25° over the course of 2 hrs, giving a mixture containing 173-cyano- 17α-hydroxyandrosta-4,9(11)-dien-3-one 17-(chloromethyl)dimethylsilyl ether (II) . This mixture is transferred dropwise (10 min) to a solution of LDA (which is prepared from dlisopropyl amine [7.0 ml] and 7-butyllithium-hexanes [1.6 molar, 26.6 ml, 42.6 mmol]) in dry. THF (75 ml) , stirring rapidly in a dry ice-acetone bath, After stirring 1 hr, the mixture is quenched with aqueous hydrochloric acid (6 M, 25 ml) , allowing the exotherm to carry the temperature to about 0° . Water (-50 ml) and methanol (-50 ml) are added, and the mixture is allowed to stir vigorously for 20 hrs at 20-25°. The product is recovered by filtration and washed successively with water and methanol to give the title compound. A second crop is obtained on concentrating the mother liquors. EXAMPLE 75 21-Chloro-6α-fluoro-17α-hydroxypregna-4,9(11)-diene- 3,20-dione (III) Following the general procedure of EXAMPLE 5 and making non- critical variations but starting with 173-cyano-6α-fluoro-17α- hydroxyandrosta-4,9(ll) -dien-3-one 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 39), the title compound is obtained. EXAMPLE 76 21-Chloro-17α-hydroxy-6α-methylpregna-4,9(11) -diene- 3,20-dione (III) Following the general procedure of EXAMPLE 5 and making non- critical variations but starting with 173-cyano-17α-hydroxy-6α- methylandrosta-4,9(ll)-dien-3-one 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 33), the title compound is obtained. EXAMPLE 77 21-Chloro-17α-hydroxy-6α-methylpregna-l,4,9(11) - triene-3,20-dione (III) " Following the general procedure of EXAMPLE 17 and making non- critical variations but starting with 173-cyano-17α-hydroxy-6 - methylandrosta-l,4,9(ll)-trien-3-one 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 36), the title compound is obtained. EXAMPLE 78 21-Chloro-17α-hydroxypregna-4,9(11)-diene-3,20-dione (III) and 17α-hydroxypregna-4,9(11)-diene-3,20-dione (VI). THF (15 ml) is added to lithium wire (49.6 mg) and 4,4' -di-tert- butylbiphenyl (2.337 g) under argon. The mixture is cooled to -10°, then sonicated until it has a persistent blue-green color and stirred at -20° for 18 hr, then cooled to -78°. A solution of 173-cyano-17α- hydroxyandrosta-5,9(11)-dien-3-one 3-ethylene ketal 17-(dichloro- methyl)dimethylsilyl ether (II, EXAMPLE 70, 338.1 mg) in THF (10 ml) at -78° is added rapidly. Immediately, 1,2-dichloroethane (1.2 ml) followed by methanol (3.3 ml) in sulfuric acid (6 M, 7.7 ml) is added. The mixture is stirred at 20-25° for 2 days, then methylene • chloride (50 ml) and water (50 ml) is added. The phases are separa¬ ted and the aqueous layer washed with methylene chloride (10 ml) . The combined organic layers are washed with water (2 x 20 ml) , then concentrated to an oil under reduced pressure to and chromatographed by reversed phase gradient HPLC to obtain the title compound (III) , retention time — 13.48 min (consistent with an authentic sample), other appropriate fractions are pooled and concentrated to give the title compound (VI) . EXAMPLE 79 21-Chloro-11/9,17α-dlhydroxypregn-4-ene-3,20-dione (III) Following the general procedure of EXAMPLE 5 and making non- critical variations but starting with 173-cyano-113,17a-dihydrox- yandrost-4-en-3-one 17-(chloromethyl) imethylsilyl ether (II, EXAMPLE 25) and using 3.8 equivalents of LDA and trimethylsilylchlorlde, the title compound is obtained, m.p. 247-249°. EXAMPLE 80 21-Chloro-113,17α-dihydroxypregna-l,4-dlene-3,20-dlone (III) Following the general procedure of EXAMPLE 17 and making non- critical variations but starting with 173-cyano-113,17α-dihydrox- yandrosta-l,4-dien-3-one 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 31) and using 2 eqivalents of LiHMDS and -3.8 equivalents of LDA, the title compound is obtained, m.p. 238-240°. EXAMPLE 81 21-Chloro-113,17α-dihydroxypregn-4-ene-3,20-dione (III) Following the general procedure of EXAMPLE 5 and making non- critical variations but starting with 173-cyano-113,17α-dihydroxy- androst-4-en-3-one 11-dimethylsilyloxy ether 17-(chloromethyl)di¬ methylsilyl ether (II, EXAMPLE 41) and using 2.8 equivalents of LDA and 1 equivalent of trimethylsilylchloride, the title compound is obtained, m.p. 247-249°. EXAMPLE 82 173-Cyano-9α-fluoro-113,17α-dlhydroxyandrosta-l,4- dIen-3-one 17-(chloromethyl)dimethylsilyl ether (II) Following the general procedure of EXAMPLE 17 and making non- critical variations but starting with 173-cyano-6α-fluoro-113,17α- dihydroxyandrosta-l,4-dien-3-one (I), the title compound is obtained, m.p. -267-274°. EXAMPLE 83 21-Chloro-113,17α-dihydroxy-6α-methylpregna-l,4-diene- 3,20-dione (III) Following the general procedure of EXAMPLE 17 and making non- critical variations but starting with 173-cyano-113,17α-dihydroxy-6α- methylandrosta-l,4-dien-3-one 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 38), the title compound is obtained. EXAMPLE 84 Pregna-4,9(11)-diene-3,20-dione (V) Following the general procedure of EXAMPLE 23 and making non- critical variations but starting with 173-cyano-3-ethoxy-17α-hydroxy- androsta-3,5,9(ll)-triene 17-(chloromethyl)dimethylsilyl ether (II, EXAMPLE 10) , the title compound is obtained. CHART A (I) 10 CHART B GHART C 25 CHART D (IIB)

Claims: -66- CLAIMS 1. An α-halo silyl ether of formula IIA and the G^ j epimer thereof where: (A-I) R 5 is -CH 2 or α-R 6 _χ:3-R 6 _2, Rχo is α - χθ-l : ^- R 10-2 and R 7 Is α-H:3-H, where one of Rg_χ and Rβ_2 -- _H » and the other is -H, -F, -Cl or C -C3 alkyl, Rχo-2 - s "CH3, Rχo-X and 5 taken together are -(CH 2 )2-C(=-R3-3 - c H- or -CH-CH-C(=R3_ 3 )-CH-, where R3.3 is -0, -N-R3.8 where R3_g Is C1-C5 alkyl, -φ or -CH2-<?5, -X2X-CH2CH2- 22" where X2 and X22 are the same or different and are -0- or -S-, α-X2 -X23: -X22"X24 h ere X23 ano - ^24 t ^ ιe same or different and are Cχ-Cg alkyl or -<^ and where X21 and X22 are as defined above, or α-H: -0R3_ or α-0R3_ :3-H, where R3.4 is -H, -CO-X25 where X25 is -H, Cχ-C j alkyl or -φ , -C-Φ2 , -C 2-Φ , -CO-CF3, -CO-CCI3, -C0-0-R 3 . s where R 3 _g is as defined above, -SiX25X27X28 where X2δ> X27 ano - ^28 are c ^ e same or different and are C1-C5 alkyl or -φ , or -Si(Xχ)(X 2 )-C(X3)(X 4 )(X 5 ) where X χ is -F, -Cl, -Br, -CH 3 , -φ or -0Xχ.χ where-X^.i is C 1 -C 5 alkyl or " -φ , " 2 is -F, -Cl, -Br, -CH 3> -φ or -OX2-I where X 2 .χ is Cι-C 5 alkyl or -φ , X 3 is -H, -Cl, -Br or -I, X is -H and X 5 is -Cl, -Br or -1; . (A-II) R 5 is R 5 .3:R 5 .4, R 6 is R 6 . 3 :R 6 .__<- Rχo i- s tt -RlO- : ^" R 10- and Ry is α-H:/9-H, where one of Rg_3 and Rg_4 is -H, -F, -Cl, C -C3 alkyl, and the other taken together with one of R5.3 and R5.4 forms a second bond between C5 and Cg, Rχo-4 - s -GH3, Rχo-3 and the other of R5.3 and R5.4 taken together is -(CH2)2- c ( =R 3-3)" CH 2~ where R3.3 is as defined above; (A-III) Rχ 0 and R5 taken together are =CH-CH=C(0R 3 .g) -CH- where R 3 .g is R3.4, -H, C -C5 alkyl, lithium, sodium, potassium, magnesium; Rg is α-Rg_5.- 3-Rg_g where one of Rg.5 and Rg.g is -H, and the other is -H, -F, -Cl or C 1 -C 3 alkyl and R 7 is α-H:3-H; (A-IV) R 5 is α-R 5 . 7 :3-R 5 .8, R 6 is α " R 6-7 : ^" R 6-8- R 7 is ~ - - β-R and Rχo is α-Rχ .7:3- χo-8> wnere one ° ~ R5.7 and R5.8 is -H, Rχo-7 and the other of R5.7 and R5.8 taken together are -(CH2)2-C( =R 3-3) - CH2, where R3.3.is as defined above, Rχo-8 - s ~ ~ H-3 > where one of Rg.7 and Rg_s i -H and the other is -H, -F, -Cl or C -C3 alkyl; (A-V) Rg is Rg.g.Rg.xo- R7 is R 7-9 :R 7-10< R 10 is α-Rl0-9 : ^- Rχθ_χo > where one of Rg.9 and Rg.χo -- -H, -F, -Cl, Cχ-C3 alkyl and the other taken together with one of R7.9 and 7.10 forms a second bond between Cg and 07, and the other of R7.9 and R7.10 is -H, Rχo-10 is -CH3, Rχo-9 and 5 taken together are - (CH2)2- c (=R3-3)" CH= or -CH=CH-C(-R3_3)-CH-, where R3.3 is as defined above; (A-VI) Rg is -CH 2 or a.-Rg-li;3-Rg_ 12 , Rχ 0 is and R7 is α-H:3-H where one of Rg.χχ and Rg.χ2 -H, and the other is -H, -F, -Cl or Cχ-C 5 alkyl, Rχθ-12 is _CH 3' R 10-ll and R 5 ta k n together are -C^-CH-C^.g)-CH-, where R3.9 is -NX29 30 w h ere 29 - ( - ^30 are -^- e same or different and are C1-C5 alkyl, -φ , -C 2-Φ and where X29 and X3 Q are taken together with the attached nitrogen atom to form a heterocyclic ring selected from the group consisting of pyrrolidine, piperidine and morpholine or -0R3_ where R3.g is as defined above, and -CH(α-0Rχ)-CH-C(0R3_g)-CH- where R3_ is as defined above; (A-VII) R 5 is R5-I3.R5-14, Rg is Rg-I3 :R 6-14' R 7 is <-- " - β- " , R 10 is α-Rχo.χ3:3-Rχo.χ where one of Rg.χ3 and Rg.χ4 is -H, -F, -Cl or Cχ-C3 alkyl and the other taken together with one of 5.13 and R5-14 forms a second bond between C5 and C , Rχo-14 -CH3, Rχθ.χ3 taken together with the other of R5.X3 and R5.14 are -CH-CH- C(R3_3)-CH2- where R3.3 is as defined above; (A-VIII) R 5 is R5_15.R5.xg, Rg is Rg.χ5: 6-16. R 10 is α " R ] _ Q _τ_g:3-CH3 and -7 is α-H:3-H, where one of Rg_χ5 and Rg.χg is -H, -F, -Cl and C -C3 alkyl and the other taken together with one of g. g and R5_χ forms a second bond between C5 and Cg, χo-15 and the other of R5_χs and Rg_ taken together are -CH-CH-C(R3_g)-CH- where 3-9 Is as defined above; (A-IX) R 5 is R5-17 :R 5-18> R 6 is R 6-17 :R 6-18> R 10 is <----10-ll ' - β- R 10-18 I10* • R 7 ~ s a ~R'-β-R> where one of Rg.χ7 and Rg.χs -H, -F, -Cl, and C -C3 alkyl, and the other taken together with one of R5.X7 and 5.X8 forms a second bond between C5 and Cg, Rχθ-17 and t ^ ιe other of R5.X7 and R5.X8 taken together are , where R3. 9 Is as defined above and where Rχo-18 - s - ~" -3 > (A-X) R 5 is -R 5 _ιg:3-R5_20> R 7 is αs-H./S-H and Rχ 0 is α-Rχ 0 . χg:3-CH3 where 5_20 and R 10-19 ta ken together are -CH2-CH2-CHZ-CH2- , where Z and s_χg taken together are a carbon-carbon single bond, Rg is α-H:3-ORg_20 where Rg_20 is c l" c 5 alkyl; (C-I) R]_ is ii-i:Rn-2' here one of Rχχ.χ and Rχχ_2 is taken together with Rg to form a second bond between Cg and G _ and the other of Rχχ_χ and Rχχ_2 s -H; (C-II) R- Is α-H:3-0-, where 3-0- is taken together with Rg to form an epoxide between Cg and 0χχ in the 3-configuratioτι; (C-III) α-Rg is -H, -Br, -Cl or -F and Rιχ is =0 or ct-Rχχ.5: /9-Rχχ.g, where one of Rχχ.5 and Rχχ_g Is -H, and the other of Rχχ.5 and Rχχ.g is -H, or -OR3-4 where Is as defined above; (C-IV) α-Rg is -0Rg.χ where Rg.χ is -H, -SiX 2 gX27X28 where X 2 g, X27 and X 8 are as defined above, -CO-φ , -C0-Rg_2 where Rg_2 ^ s "**» C 1" G 5 alkyl, -0Rg_3 where Rg_3 is Cχ-C 5 alkyl or -CH2-^, and Rχι is α-H:S-H; ig is -CH2 or α- χδ-χ:3-Rχ6-2> where Rχg.χ is -H, -F. -CH3 or -OR3.4 where R3.4 is as defined above, Rχg_2 is -H, -F and -CH3 with the proviso that one of Rχg.χ and Rχg_2 is _H ; XX is -F, -Cl, -Br, -CH 3 , -φ or -0X 1 . l where Xχ.χ is Cχ-C 5 alkyl or -φ ; X2 is -F, -Cl, -Br, -CH3, -φ or -0X 2 .χ where X2-X is Gχ-C 5 alkyl or -φ ; 3 is -H, -Cl, -Br or -I, X4 is -H and X 5 is -Cl, -Br or -I. 2. An α-halo silyl ether (II) according to claim 1 where Rg is -CH2 or α-Rg.χ:3-Rg.2 and R^Q is α_ Rχθ-l : ^" 10-2 where one ° ~ Rg.χ and Rg_2 i -H, and the other is -H, -F, -Cl or C1-C3 alkyl, Rχθ-2 is -CH3, Rχo-X and R5 taken together are -(CH 2 )2- c ( = 3-3) - CH= " where R3.3 is -0. 3. An α-halo silyl ether (II) according to claim 1 where Rg is -CH2 or α-Rg_χ:3-Rg-2 and 10 ^ s α - 10-l : ^" 10-2 where one of δ-1 and R 6-2 is " H > and che other is -H, -F, -Cl or C1-C3 alkyl, R 10-2 is " GH 3> R 10-l and R 5 taken together are -CH-CH-CO-CH-. 4. An α-halo silyl ether (II) according to claim 1 where Rg is -CH 2 or α.-Rg.χχ;3-Rg_χ 2 , Rχo is β -Rlθ-ll : ^" R 10-12 and R 7 is <-' H:3-H. 5. An α-halo silyl ether (II) according to claim 1 where R 5 is 5-i5<R5-ig< Rg is R6-15 :R 6-16» Rχo i α-R 10 . 15 :3-CH 3 and R 7 is α-H./S-H. 6. An α-halo silyl ether (II) according to claim 1 where R 5 is R5-17 :R 5-18> R 6 is R 6-17 :R 6-18> R 10 is α - R 10-17 : 0- R 10-18 and R 7 is α-H:3-H. 7. An α-halo silyl ether (II) according to claim 1 where χ is Rχχ.χ:Rχχ-2 > where one of Rχχ.χ and Rχχ_2 i taken together with Rg to form a second bond between C9 and C j _ ] _ and the other of Rχχ.χ and χχ-2 i - ■ 8. An α-halo silyl ether (II) according to claim 1 where α-Rg is -H, or -F and R^ is -0 or α-Rχχ-5:/3-Rχχ.g where one of Rχι. 5 and Rχχ.g is -H, and the other of Rχχ.5 and Rχχ.g is -H or -OH. 9. An α-halo silyl ether (II) according to claim 1 where α-Rg is -H, -F, -Cl or -Br, Rχι is α-Rχχ.5-'3-Rχχ.g, where one of Rχχ_ 5 and Rχχ.g is -H, and the other of Rχχ-5 and Rχχ.g is -H, -OH, -SiX 2 gX 27 X28 °- -Si(X 1 )(X 2 )-C(X 3 )(X4)(X5). 10. An α-halo silyl ether (II) according to claim 1 where ] _ is -CH 3 or -0Xχ.χ. 11. An α-halo silyl ether (II) according to claim 1 where X 2 is -CH3 12. An α-halo silyl ether (II) according to claim 1 where X3 is -H, -Cl and -Br. 13. An α-halo silyl ether (II) according to claim 1 where 5 is -Cl or -Br. 14. An α-halo silyl ether (II) according to claim 1 where one of Rχg.χ and Rχg. 2 i -H and the other is -H or -CH3. 15. An α-halo silyl ether (II) according to claim 1 where the cyano group at C 7 Is in the 3-configuration. 16. An α-halo silyl ether (II) according to claim 1 where the α-halo silyl ether (II) is selected from the group consisting of 17 -cyano- 17α-hydroxyandrosta-4,9(11)-dien-3-one 17-(chloro-methyl)dimethyl¬ silyl ether, 173-cyano-17α-hydroxyandrosta-4,9(11)-dien-3-one 17-(bromo¬ methyl)dimethylsilyl ether, 173-cyano-3,17α-dihydroxyandrosta-3,5,9(11)-triene 3-methyl ether 17-(chloromethyl)dimethylsilyl ether, 17/9-cyano-17α-hydroxyandrosta-l,4,9(ll)-trien-3-one 17-(chloro¬ methyl)dimethylsilyl ether, 173-cyano-17α-hydroxyandrost-4-en-3-one 17-(bromomethyl)di- methylsilyl ether, 17/9-cyano-17α-hydroxyandrost-5-en-3-one 3-ethylene ketal 17- (chloromethyl)dimethylsilyl ether, 17/9-cyano-3-ethoxy-17α-hydroxyandrosta-3,5,9(11)-triene 17- (chloromethyl)dimeth lsily1 ether, 173-cyano-17α-hydroxyandrost-4-en-3-one 17-(chloromethyl)di¬ methylsilyl ether, 173-cyano-3,17α-dihydroxyandrosta-3,5-diene 3-methyl ether 17- (chloromethyl)dimethylsilyl ether, 173-cyano-3,17α-dihydroxyandrosta-3,5-diene 3-methyl ether 17- (bromomethyl)dimethylsilyl ether, 173- yano-17α-hydroxy-163-methylandrosta-1,4,9(11)-trien-3-one 17-(chloromethyl)dimethylsilyl ether, 173-cyano-17α-hydroxyandrosta-l,5,9(ll)-trien-3-one 17-(chloro¬ methyl)dimethylsilyl ether, 173-cyano-3,17α-dihydroxyandrosta-2,4,9(ll)-triene 3-trimethyl- silyloxy ether 17-(chloromethyl)dimethylsilyl ether, 173-cyano-3-ethoxy-17α-hydroxyandrosta-3,5-diene 17-(chloro- methyl)dimethylsilyl ether, 17 -cyano-113,17α-dihydroxyandrost-4-en-3-one 17-(chloro¬ methyl)dimethylsilyl ether, 173-cyano-93,113-epoxy-17α-hydroxyandrost-4-en-3-one 17-(chloro¬ methyl)dimethylsilyl ether, 173-cyano-3,113,17α-trihydroxyandrosta-3,5-diene 3-methyl ether 17-(chloromethyl)dimethylsilyl ether, 173-cyano-93,113- po χ y-I7α-hydroxyandrosta-l,4-dien-3-one 17- (chloromethyl)dimethylsilyl ether, 173-cyano-113,17α-dihydroxyandrosta-l,4-dien-3-one 17-(chloro- methyl)dimethylsilyl ether, 173-cyano-17α-hydroxyandrosta-l,4-diene-3,11-dione 17-(chloro¬ methyl)dimethylsilyl ether, 173-cyano-17α-hydroxy-6α-methylandrosta-4,9(11)-dien-3-one 17- (chloromethyl)dimethylsilyl ether, 173-cyano-93,113-epoxy-17α-hydroxy-6α-methylandrost-4-en-3-one 17-(chloromethyl)dimethylsilyl ether, 173-cyano-113,17α-dihydroxy-6α-methylandrost-4-en-3-one 17- (chloromethyl)dimethylsilyl ether, 173-cyano-17α-hydroxy-6α-methylandrosta-1,4,9(11)-trien-3-one 17-(chloromethyl)dimethylsilyl ether, 173-cyano-93,113-epoxy-17α-hydroxy-6α-methylandrosta-l,4-dien-3- one 17-(chloromethyl)dimethylsilyl ether, 173-cyano-113,17α-dihydroxy-6α-methylandrosta-l,4-dien-3-one 17-(chloromethyl)dime hylsilyl ether, 173-cyano-6α-fluoro-17α-hydroxyandrosta-4,9(11)-dien-3-one 17- ■ (chloromethyl)dimethylsilyl ether, 17α-cyano-173-hydroxy-16-methyleneandrost-4-en-3-one 17- (chloro¬ methyl)dimeth lsilyl ether, 17 -cyano-113,17α-dihydroxyandrost-4-en-3-one 11-dimethylsilyl¬ oxy ether 17-(chloromethyl)dimethylsilyl ether, 173-cyano-17α-hydroxy-6-methylenandrosta-4,9(11)-dien-3-one 17- (chloromethyl)dimethylsilyl ether, 173-cyano-17α-hydroxy-6-methylandrosta-4,6,9(11)-trien-3-one 17- (chloromethyl)dimethylsilyl ether, 173-cyano-113,17α-dlhydroxy-6-methylenandrost-4-en-3-one 17- (chlorome hyl)dimethylsilyl ether, 173-cyano-6-fluoro-3,17α-dihydroxyandrosta-3,5,9(11)-triene 3- methyl ether 17-(chloromethyl)dimethylsilyl ether, 173-cyano-113,17α-dihydroxyandrosta-1,4-dien-3-one 11-trimethyl- silyloxy ether 17-(chloromethyl)dimethylsilyl ether, 173-cyano-17α-hydroxyandrosta-1,4,9(11)-trien-3-one 17-(di- chloromethyl)dimethylsilyl ether, 173-cyano-17α-hydroxyandrost-4-en-3-one 17-(chloromethyl) - methoxymethylsilyl ether, 17α-cyano-17/9-hydroxyandrosta-4,9(11)-dien-3-one ^-(chloro¬ methyl)dimethylsilyl ether, 173-Cyano-17α-hydroxyandrost-5-en-3-one 3-ethylene ketal 17- (bromomethyl)dimethylsilyl ether, 173-cyano-17α-hydroxyandrost-5-en-3-one 3-ethylene ketal 17- (iodomethyl)dimethylsilyl ether, 173-cyano-17α-hydroxyandrosta-4,9(11)-dien-3-one 17-(dichloro- methyl)dimethylsilyl ether, 173-cyano-3,17α-dihydroxyandrosta-3,5-diene 3-methyl ether 17- (iodomethyl)dimethylsilyl ether, 173-cyano-17α-hydroxyandrosta-5,9(11)-dien-3-one 3-ethylene ketal 17-(dichloromethyl)dimethylsilyl ether, 173-cyano-17α-hydroxyandrosta-5,9(11)-dien-3-one 3-ethylene ketal 17-(chloromethyl)dimethylsilyl ether, 17/9-cyano-17α-hydroxyandrosta-5,9(11)-dien-3-one 3-ethylene ketal 17-(bromomethyl)dimethylsilyl ether, I7 -cyano-9α-fluoro-113,17α-dihydroxyandrosta-1,4-dien-3-one 17- (chloromethyl)dimethylsilyl ether. 17. An α-halo silyl ether (II) according to claim 16 where the α- halo silyl ether (II) is selected from the group consisting of 173-cyano-17α-hydroxyandrosta-4, (11)-dien-3-one 17-(chloro- -73- methyl)dimethylsilyl ether, 17 / 3-cyano-3,17α-dihydroxyandrosta-3,5,9(11)-triene 3-methy ether 17-(chloromethyl)dimethylsilyl ether, 17 / 3-cyano-17α-hydroxyandrosta-l,4,9(ll)-trien-3-one 17-(chloro methyl)dimethylsilyl ether, 17 -cyano-17α-hydroxy-6α-methylandrosta-4,9(ll) -dien-3-one 17- (chloromethyl)dimethylsilyl ether, 17/3-cyano-17α-hydroxy-6α-methylandrosta-l,4,9(ll)-trien-3-one 17-(chloromethyl)dimethylsilyl ether, 17 / 9-cy__no-17α-hydroxy-6-methylandrosta-4,6,9(11) -trien-3-one 17- (chloromethyl)dimethylsilyl ether, 173-cyano-6-fluoro-3,17α-dihydroxyandrosta-3,5,9(11)-triene 3- methyl ether 17-(chloromethyl)dimethylsilyl ether. 18. A process for producing a 21-halo corticoid of formula III and the C 7 epimer thereof where: X 3 is -H, -Cl, -Br or -I; X 5 is -Cl, -Br or -I; R 16 is -CH 2 or α-Rχg. :3-Rχδ-2 > where Rχg.χ is -H, -F, -CH 3 or • -OR3.4 where R3.4 is -H, -CO-X 2 5 where X 2 5 is -H, C -C7 alkyl or -φ , - ~-φ- , -CH 2 -ψ, -CO-O-R3.8 where R _g is Cχ-C 5 alkyl, -φ or -CH 2 -^, -Si X 2 X 2 8 where X g, X 2 7 and X g are the same or different and are C -C5 alkyl or -φ , or -Si(Xχ)(X 2 )-C(X 3 )(X )(X 5 ) where is -F, -CH 3 or -φ , X 2 is -F, -CH 3 or -φ , X 4 is -H and X 3 and X 5 are as defined above , Rχg_2 i -H, -F and -CH3 with the proviso that one of Rχg_χ and Rχg _ 2 Is -H; which comprises (1) contacting an α-halo silyl ether of formula II and the C 7 epimer thereof where: χ_ is -F, -Cl, -Br, -CH3, -φ or -0Xχ_χ where Xχ.χ is Cχ-C 5 alkyl or *φ X 2 Is -F, -Cl, -Br, -CH3, -φ or -0X 2 .χ where X 2 .χ is Cχ-C 5 alkyl or -φ X 3 is -H, -Cl, -Br or -I; X4 Is -H; X 5 is -Cl, -Br or -I; j_g is -CH or α:-Rχδ-i:3-Rχg_ 2 , where Rχg.χ is -H, -F, -CH3 or -0 3_ 4 where 3_ is -CO-X 25 where X 25 is -H, Cχ-Cy alkyl or -φ , - ~-φ ~ , -CH 2 -^, -CO-O-R3.8 where 3.8 is Cχ-C 5 alkyl, -φ or -CH 2 -<£, -SiX 2 X yX 2 8 where X 2 g, X 2 7 and X 2 8 are the same or different and are C -C5 alkyl or -φ, or -SiC -i)(X 2 )-C(X 3 )(X 4 )(X 5 ) where X Is -F, -Cl, -Br, -CH3, -φ or -0Xχ.χ where Xτ__ is Cχ-C 5 alkyl or -φ , X 2 is -F, -Cl, -Br, -CH3, - or -0X 2 . where X 2 .χ is C L -C 5 alkyl or -φ , X 3 is -H, -Cl, -Br or -I, X 4 is -H and X 5 is -Cl, -Br or -I, Rχg_ 2 is -H. -F and -CH3 with the proviso that one of Rχg.χ and Rχg. 2 is -H with at least one equivalent of a non-nucleophilic base -75- sufficiently strong enough to deprotonate the -CX3X4X5 portion of th α-halo silyl ether (II) and (2) contacting the reaction mixture of step (1) with a protio¬ desilation reagent and a nitrogen to oxygen exchange reagent. 5 19. A process according to claim 18 for producing a 21-halo cor¬ ticoid of formula (III) where the non-nucleophilic base is LDA; which in step (1) uses Cl-Si- (^3)3; 10 the protiodesilation reagent and a nitrogen to oxygen exchange reagent is at least 1 equivalent of water and an acid where the acid is selected from the group consisting of HF, HCl, HBr, HI, H 3 P0 4 , H 2 S0 4 , perchloric, fluoroboric, formic, acetic, propionic and oxalic; the contacting of step (2) is performed in the presence of an 15 alcohol where the alcohol is ethylene glycol, methanol or isopropan- ol; the cyano group at C- j _ in the α-halo silyl ether (II) is in the 3-configuration. 20 20. A process for the production of an α-halo silyl ether of formula II 30 and the Gy j epimer thereof where: X is -F, -Cl, -Br, -CH3, -φ or -OXχ.χ where Xχ.χ is C -C 5 alkyl 35 or -φ ; X 2 is -F, -Cl, -Br, -CH3, -φ or -0X 2 .χ where X 2 .χ is Cχ-C 5 alkyl or -φ ; X 3 is -H, -Cl, -Br or -I; - 76- X 4 is -H; X 5 is -Cl, -Br or -I; 5 Is -CH or α- l6-l.3- i5- 2 , where Rχg.χ is -H, -F, -CH3 or ~ 0R 3-4 where R3.4 is 5 -H, -C0-X 2 5 where X 25 is -H, C -C alkyl or -φ , -C-^3, -CH 2 -< , -CO-CF3, -C0-CC1 3J -CO-0- 3_8 where 3.8 is C -C 5 alkyl, -φ or -CH 2 -.&. 10 -SiX2gX27 28 where X 2 g, X 2 7 and 2 8 are the same or different and are C -C5 alkyl or -φ , or -Si(X 1 )(X 2 )-C(X 3 )(X4)(X 5 ) where Xχ > X 2 , X3, X4 and X5 are as defined above, R g. 2 is -H, -F and -CH3 with the proviso that one of Rχg_χ and Rχg_ is -H, which comprises 15 contacting a 17-cyano-17-hydroxy steroid of formula I 25 and the C epimer thereof where R Is as defined above with an α- halo silyl ether adduct, X -S-_X X2-CX 3 X 5 (IV) where Xg is -Cl, -Br, imidazolyl, CF 3 -C(-0-)(-N-) , CH 3 -C(-0-)(-N-) , -0-S0 2 -CF 3 and -C10 4 30 and where X^, X 2 , X3, X 4 and X5 are as defined above. 21. A process according to claim 20 for the production of an α- substituted silyl ether (II) , where the contacting is performed in the presence of an acid scavenger 35 which is selected from the group consisting of triethylamine, trlbutylamine, diisopropylethylamine, trimethylamine, pyridine, imidazole, N-methylmorpholine, N-methylpiperidine, N-methylimidazole, 2-me hylimidazole; -77- the contacting is performed in the presence of a silylation catalyst selected from the group consisting of 4-dimethylamino- pyridine, 4-pyrrolidinopyridine, imidazole, N-methylimidazole and 2- methylimidazole; - j _ is -CH 3 or -OX 1 . , X 2 is -CH 3 or -0X 2 .χ, X 3 is -H, -Cl, -Br and 5 is -Cl or -Br and the cyano group at C^7 is in the -configuration. 22. A process for the production of a progesterone of formula V where R]_g is -CH 2 or c_-Rχg.χ:/3-Rχg.2 > where Rχg_χ is -H, -F, -CH3 or -OR3.4 , where R3.4. is -H, -CO-X 2 5 where X 5 is -H, C -C alkyl or -φ , - ~ -Φ~ > - ~~ -2 ' ' -CO-0-R3_8 where R3.8 is C -C5 alkyl, -φ or -CH 2 -^, -SiX X 2 7X 2 8 where X 2 6> ^27 an ^28 are ~" s same or different and are C -C5 alkyl or -φ , or -Si(Xι)(X 2 )-C(X 3 )(X 4 )(X 5 ) where X is -F, -CH3 or -φ , X 2 is -F, -CH 3 or -φ , X 3 is -H, -Cl or -Br, X 4 is -H and X 5 is -Cl or -Br, Rχg_ 2 is -H, -F and -CH3 with the proviso that one of Rχg.χ and Rχg. 2 is -H, which comprises: (1) contacting an α-halo silyl ether of formula II and the C 7 epimer thereof where X is -F, -Cl, -Br, -CH 3 , -φ or -0Xχ_χ where X 1 _ 1 is Cχ-C 5 alkyl or -φ \ X 2 is -F, -Cl, -Br, -CH 3 , -φ or -0X 2 .χ where X 2 .χ is Cχ-C 5 alkyl or -φ ; X 3 is -H, -Cl, -Br or -I; X is -H; X 5 is -Cl, -Br or -I; R 5 is -CH 2 or o:-Rχg_χ:3-Rχ6_. 2 , where Rχg.χ is -H, -F, -CH3 or -OR3.4 where R3.4 is -H, -C0-X 25 where X 2 5 Is -H, Cχ-C j alkyl or -φ , - ~ -φ- , -CR 2 -φ , -CO-CF3, -CO-CCI3, -CO-O-R3.8 where R 3 . 8 is Cχ-C 5 alkyl, -φ or -C 2-Φ , -SiX X 2 X 8 where X 2 g, X 7 and X 2 8 are the same or different and are C -C5 alkyl or -φ , or -Si(X 1 )(X 2 )-C(X 3 )(X4)(X 5 ) where X χ is -F, -Cl, -Br, -CH 3 , -φ or -0Xχ.χ where Xχ.χ is Cχ-C 5 alkyl or -φ ; X 2 is -F, -Cl, -Br, -CH3, -φ or -0X 2 .χ where X 2 .χ is ~ - ^ alkyl or -φ ; X3 is -H, -Cl, -Br or -I, X 4 is -H and X5 is -Cl, -Br or -I, Rχg_ 2 Is -H, -F and -CH3 with the proviso that one of Rχg_χ and Rχg. is -H; with an effective amount of a Type B reducing agent in the presence of at least one equivalent of a proton source and (2) contacting the mixture of step (1) with a protiodesilation reagent and a nitrogen to oxygen exchange reagent. -79- 23. A process according to claim 22 for the production of a proges terone (V) where 4 or more equivalents of the Type B reducing agent are used; the Type B reducing agent is lithium biphenyl, sodium or lithiu naphthalide or lithium 4,4' -di-tert-butylbiphenyl; the proton source is water and an acid; the protiodesilation reagent and a nitrogen to oxygen exchang reagent is at least 1 equivalent of water and an acid where the acid is selected from the group consisting of HF, HCl, HBr, HI, H3PO4., H 2 S0 4 , perchloric, fluoroboric, formic, acetic, propionic and oxalic; the cyano group at Cχ is in the 3-configuration. 24. A process for the production of a 17-hydroxyprogesterone o formula VI and the C^- j epimer thereof where Y is -H, -Cl, -Br and -I; R is -CH 2 or α-Rχ6-I :3 - R 16-2' where Rχg.χ is -H, -F, -CH3 or -OR3_ 4 where 3. 4 is -H, -CO-X 2 5 where X 25 is -H, C -C alkyl or -φ , -C-<^3, -CH -^, -CO-O-R3.8 where 3.8 is Cχ-C 5 alkyl, -φ or -CH 2 -^, -Si 2 gX 2 X 2 8 where X 2 g, X 2 7 and X 2 8 are the same or different and are C -C5 alkyl or -φ , or -Si(Xχ)(X 2 )-C(X3)(X 4 )(X 5 ) where is -F, -CH3 or -φ , X 2 is -F, -CH3 or -φ , X 3 is -H, -Cl or ■ 80- -Br, X 4 is -H and X 5 is -Cl or -Br, Rχg. 2 is -H, -F and -CH 3 with the proviso that one of Rχg.χ and Rχg_ is -H, which comprises: (1) contacting an α-halo silyl ether of formula II and the Gy j epimer thereof where X L is -F, -Cl, -Br, -CH 3 , -φ or -0Xχ.χ where Xχ_χ is Cχ-C 5 alkyl or -φ; X 2 is -F, -Cl, -Br, -CH3, -φ or -0X 2 .χ where X 2 _χ is Cχ-C 5 alkyl or -φ; X 3 is -H, -Cl, -Br or -I; X is -H; X 5 is -Cl, -Br or -I; Is —CH 2 or α- χ6-i:3-R g-2' where Rχg.χ is -H, -F, -CH3 or -03_ 4 where 3_ 4 is -H, -CO-X25 where X 2 5 is -H, Cχ-C 7 alkyl or -φ, -~-Φ ~ , - 2-Φ, -CO-CF3, -CO-CCI3, -CO-0-R 3 _ 8 where R3.8 is Cχ-C 5 alkyl, -φ or -CR 2 -φ, -SiX 2 6 x 27 x 28 whe re X 2 6> x 27 and x 28 are ttιe same or different and are C -C5 alkyl or -φ, or -Si(X 1 )(X 2 )-C(X 3 )(X )(X 5 ) where X-χ is -F, -Cl, -Br, -CH 3 , -φ or -0Xτ_.χ where Xχ.χ is Cχ-C 5 alkyl or -φ; X 2 is -F, -Cl, -Br, -CH3, -φ or -0X 2 .χ where X .χ is Cχ-C 5 alkyl or -φ; X3 is -H, -Cl, -Br or -I, X 4 is -H and X 5 is -Cl, -Br or -I, Rχg. is -H, -F and -CH3 with the proviso that one of Rχg.χ and Rχg. is -H, with an effective amount of a Type A reducing agent, (2) hydrolyzing the mixture of step (1) with a protiodesilation -81- reagent and a nitrogen to oxygen exchange reagent. 25. A process according to claim 24 for the production of a 17 hydroxyprogesterone (VI) where the Type A reducing agent is lithium biphenyl, sodium or lithiu πaphthalide or lithium 4,4' -di-tert-butylbiphenyl; about 2.2 to about 5 equivalents of the Type A reducing agent are used; the protiodesilation reagent and a nitrogen to oxygen exchang reagent is at least 1 equivalent of water and an acid where the acid is selected from the group consisting of HF, HCl, HBr, HI, H3PO4 H2SO4, perchloric, fluoroboric, formic, acetic, propionic and oxalic the aprotic quenching agent is selected from the group consist ing of dichloroethane, dibromoethane, and benzoate; the cyano group at C of the α-halo silyl ether (II) is in th 3-configuratio . 26. A process for the production of a α-halo silyl ether of formul II and the C 7 epimer thereof where Xx is -F, -Cl, -Br, -CH3, -φ or -0Xχ.χ where Xχ.χ is Cχ-C 5 alkyl or -φ ; X 2 is -F, -Cl, -Br, -CH3, -φ or -0X 2 .χ where X 2 .χ is C -C^ alkyl or -φ ; X 3 is -H, -Cl, -Br or -I; X4 is -H; X5 is -Cl, -Br or -I; •82- Rχ 6 is -CH 2 or α-Rχg-i:3-Rχg-2 > where Rχg.χ is -H, -F, -CH 3 or -OR3.4 where _ -H, -CO-X25 where X 25 is -H, Cχ-C 7 alkyl or -φ , - ~-φ-. , -CΑ-'Φ, -CO-CF3, -CO-CCI3, -CO-O-R3.8 where R3.8 is ^-C 5 alkyl, -φ or -CH -<^, -S__X 2 X 2 7X 2 8 where X g, X 2 7 and X 2 g are the same or different and are C -C5 alkyl or -φ , or -Si(Xχ)(X 2 )-C(X 3 )(X 4 )(X 5 ) where is -F, -Cl, -Br, -CH 3J -φ or -0Xχ_χ where Xχ.χ is Cχ-C 5 alkyl or -φ, X 2 is -F, -Cl, -Br, -CH3, -φ or -0X 2 .χ where X 2 .χ is C 1 -C 5 alkyl or -φ, X 3 is -H, -Cl, -Br or -I, X 4 Is -H and X5 is -Cl, -Br or -I, Rχg_ 2 is -H, -F and -CH3 with the proviso that one of Rχg.χ and Rχg_ 2 is -H, which comprises (1) contacting a halogenated silated ether of formula IIB and the C 7 epimer thereof where X 3 . B is -H, -Cl, -Br or -I, X5..B is -Cl, -Br or -I and where Rχg» Xχ» X 2 and X 4 are as defined above with iodide, bromide or chloride. 27. A process according to claim 26 for the production of an α-silyl ether (II) where X3 and X3.B are -H and which uses iodide. 28. A process for the production of a corticoid of formula VII -83- and the C epimer thereof where Rx is -CH 2 or c_-Rχg.χ: / 3-Rχg. , where Rχg.χ is -H, -F, -CH3 or -OR3_ 4 where R3_ is -H, -CO-X 2 5 where X 2 5 is -H, Cχ-C 7 alkyl or -φ , -C-Φ2 , -CR2-Φ , -CO-O-R3.8 where R3.8 is Cχ-C 5 alkyl, -φ or -CH 2 - , -SiX 2 gX 2 7X 2 8 where X 2 6> x 27 an( - X 28 are c ^ e same or different and are C -C5 alkyl or -φ , or -Si(X 1 )(X 2 )-C(X 3 )(X 4 )(X 5 ) where XX is -F, -CH 3 or -φ , X 2 is -F, -CH3 or -φ , X 3 is -H, -Cl or -Br, X 4 is -H and X5 is -Cl or -Br, Rχg_ 2 s -H, -F and -CH3 with the proviso that one of Rχg.χ and Rχg_ 2 is -H, which comprises: (1) contacting an α-halo silyl ether of formula II and the C 7 epimer thereof where is -F, -Cl, -Br, -CH3, -φ or -0Xχ.χ where X i . 1 is Cχ-C 5 alkyl or -φ ; X 2 is -F, -Cl, -Br, -CH 3 , -φ or -0X 2 .χ where X 2 .χ Is Cχ-C 5 alkyl or -φ ; X3 is -H, -Cl, -Br or -I; X 4 is -H; X 5 Is -Cl, -Br or -I; Rχ 6 is =CH 2 or α:-R 1 g.χ:3-Rχg_ 2 , where Rχg.χ Is -H, -F, -CH3 or -OR3_ 4 where R3.4 Is -H, -C0-X 2 5 where X 25 is -H, Cχ-C 7 alkyl or -φ , - --Φ3 , -CH 2 -<^, -CO-CF3, -CO-CCI3, -CO-O-R3.8 where R 3 . 8 is Cχ-C 5 alkyl, -φ or -CH 2 -< , -SIX 2 gX 27 X 2 8 where X 2 g, 2 7 and X 2 8 are the same or different and are Cχ-C5 alkyl or -φ , or -Si(Xχ)(X 2 )-C(X 3 )(X 4 )(X 5 ) where X χ is -F, -Cl, -Br, -CH3, -φ or -0Xχ_χ where Xχ.χ is Cχ-G 5 alkyl or -φ ; X 2 is -F, -Cl, -Br, -CH3, -φ or -0X 2 .χ where X .χ is C -C5 alkyl or -φ ; X3 Is -H, -Cl, -Br or -I, X 4 Is -H and 5 is -Cl, -Br or -I, Rχg_ 2 is -H, -F and -CH^ with the proviso that one of Rχg_χ and Rχg_ 2 is -H, with an effective amount of a Type A reducing agent and (2) contacting the mixture of step (1) with an oxidizing agent and (3) contacting the mixture of step (2) with a protiodesilation reagent and a nitrogen to oxygen exchange reagent. 29. A process according to claim 28 for the production of a cor¬ ticoid (VII) where the cyano group at C 7 of the α-halo silyl ether (II) is in the β-configuration; the Type A reducing agent Is selected from the group consisting of lithium biphenyl, sodium or lithium naphthalide or lithium 4,4'- di-ter -butylbipheny1; the oxidizing agent Is hydrogen peroxide, m-chloroperbenzoic- acid and trimethylamine-_f-oxide; the protiodesilation reagent and a nitrogen to oxygen exchange reagent Is at least 1 equivalent of water and an acid where the acid -85- is selected from the group consisting of HF, HCl, HBr, HI, H3PO4., H 2 S0 4 , perchloric, fluoroboric, formic, acetic, propionic and oxalic; the aprotic quenching agent is dichloroethane, dibromoethane, and benzoate. 30. A process according to any of claims 18 to 29, where the α-halo silyl ether (II) is the compound according to any of claims 1 to 17 , and the respective product/starting material of formula (III) , (I) , (V), (VI), (IIB) or (VII) has the corresponding structure.

Inventors: DENMARK SCOTT, LIVINGSTON DOUGLAS A, PEARLMAN BRUCE A, DENMARK, SCOTT, LIVINGSTON, DOUGLAS, A., PEARLMAN, BRUCE, A.
Applicants: UPJOHN CO, THE UPJOHN COMPANY
Application year: 1987
Main classification: C07J51
IPC codes: C07F7, C07J1, C07J5, C07J7, C07J41, C07J51, C07J71, C07J75