bluuebunny/crossref_metadata_2025 huggingface dataset:
The stereochemistry of 1,6,7,12b‐Tetrahydro‐2H,4H‐[1,2] oxazino[3′,4′:1,2]‐pyrido[3,4‐b]indole and of 1,2,3,6,7,12b‐Hexahydro‐3‐methyl‐4H‐pyrimido[3′,4′:1,2]pyrido[3,4‐6] indole
Authors: Crabb T. A. , Mitchell J.
Published: March 2009

From an analysis of nmr spectral data, 1,6,7,12b‐tetrahydro‐2H,4H‐[1,3 ]oxazino[3′, 4′ :1,2]‐pyrido[ 3,4‐b ]indole is shown to exist in solution at room temperature almost entirely in the cis‐fused ring conformation with the nitrogen lone pair bisecting the C4 methylene group whereas under the same conditions 1,2,3,6,7,12b‐hexahydro‐3‐methyl‐4H‐pyrimido[3′,4′:1,2] pyrido‐[3,4‐b ]indole exists as an approximately 50:50 equilibrium mixture of the cis and trans‐fused ring conformations.
Halogenated ketenes. XXIII. 2‐Oxetanones
Authors: Brady William T. , Patel Arvind D.
Published: March 2009

The cycloaddition of dichloroketene with several simple ketones to produce 2‐oxetanones is described. The ketene is generated in situ by the zine dehalogenation method and the zinc/zinc chloride activates the carbonyl group of the ketone. The cycloaddition of methylchloro‐ and methylbromoketenes with some activated carbonyl compounds is also deseribed.
Reactions of 4,5‐diaminouracils
Authors: Youssefyeh R. D. , Kalmus A.
Published: March 2009

Reactions of 4,5‐diaminopyrimidines with various phthalic derivatives, depending on the conditions employed, led to pyrimidines with a 5‐N‐substituted phthalamic acid (III), 5‐N‐substituted phthalimide (II) and 4,5‐bis‐N‐substituted phthalimide (VI).
Spirans XVIII . gem‐Dialkyl and spirotetrahydrocarbazoles
Authors: Rice Leonard M. , Sheth Bhagvandas S. , Wheeler James W.
Published: March 2009

The reactions of 4,4‐dialkylcyclohexanones, spiro[4.5]decan‐8‐one and various spiro[5.5]‐undecanones with phenylhydrazines to produce corresponding 3,3‐dialkyltetrahydro and spiro (cycloalkyl 1,n′)‐1′,2′,3′,4′‐tetrahydrocarbazoles (n = 1, 2 or 3) by the Fischer indole synthesis were examined. Structural assignment of the one isomeric product derived from spiro[5.5]‐undecan‐2‐one was obtained on the basis of pmr spectra.
Benzo[b] thiophene derivatives XVII. Electrophilic substitution of 4‐hydroxybenzo[b] thiophene derivatives
Authors: Campaigne E. , Dinner A. , Haseman M.
Published: March 2009

A variety of eleclrophilic substitution reactions have been carried out on 4‐methoxybenzo[b]‐thiophene (IIIa) and 4‐benzoyloxybenzo[b ] thiophene (IVa). Substitution occurs in the 7‐position of IIIa and, with the exception of bromination, in the 7‐position of IVa. Bromination of IVa occurs in the 3‐position. Bromination of 4‐hydroxybenzo[b] thiophene (IIa) occurs in the 5‐position. The nmr spectra of eleven disubstituted benzo[b] thiophenes have been tabulated.
Geometrical isomerism of ethyl N‐(2‐pyridinyl)aminomethylenecyanoacetates
Authors: Nishigaki Sadao , Ichiba Misuzu , Shinomura Kazuko , Yoneda Fumio
Published: March 2009

The pure cis‐ and trans‐isomers of ethyl N‐(2‐pyridinyl)aminomethylenecyanoacetates were obtained and their structure and their interconvertibility is diseussed. 4H‐Pyrido[1,2‐a]pyrimidin‐4‐one‐3‐carboxylic acids were synthesized by treatment of both cis‐ and trans‐isomers with hydrochloric acid.
Synthesis of 5,12‐diazadibenz[a,h]anthracene
Authors: Klemm L. H. , Johnson W. O. , Weisert Annekäte
Published: March 2009

5, 12‐Diazadibenz[a,h]anthracene (20) was synthesized in 21% overall yield for seven steps. Salient features of the synthesis include the initial, one‐step conversion of trans, trans‐1,4‐bis‐(β‐nitrovinyl)benzene into 2,2″‐dinitro‐p‐terphenyl by Diels‐Alder condensation plus elimination, monocyclization of the derived 2,2″‐diformylamino‐p‐terphenyl to give 8‐(2‐amino‐1‐phenyl)‐phenanthridine (10) in the presence of fortified polyphosphoric acid, and accomplishment of a second cyclization step only after reduction of the heteroring in 10 (by means of diisobutyl‐aluminum hydride) plus formylation. The 6‐methyl and 6,13‐dimethyl derivatives of 20 were prepared similarly.
Heterocycles. LXXXII. Some investigations on 1,2,3‐benzotriazines
Authors: Stanovnik B. , Tišler M.
Published: March 2009

Various 4‐substituted 1,2,3‐benzotriazines (2, 6, 7) have been prepared and of particular interest was the 4‐azido derivative (11) as a potential azidotetrazolo tautomerism exhibiting compound. However, no such interconversion could be established and this compound exists exclusively in the azido form. 2,5‐bis‐(Arylamino)‐1,3,4‐thiadiazoles (9) have been found to result from the reaction between 4‐hydrazino‐1,2,3‐benzotriazine and aryl isothiocyanates. In addition, a ring opening reaction between 4‐hydrazino‐1,2,3‐benzotriazine gave 2‐(tetrazol‐5″‐yl)‐2′,4′‐dihy‐droxyazobenzene (10) and photochemical conversion of the 4‐azido derivative gave s‐tetrazino‐[2,3‐b:5,6‐b′]diindazole(12).
Application of a thermal rearrangement reaction to questions of structure of condensed dihydrodiazepinones: Synthesis and characterization of isomeric dihydropyrido[3,4‐b] [1,4]diazepinones from 3,4‐diaminopyridine and ethyl acetoacetate
Authors: Israel Mervyn , Jones Lynne C.
Published: March 2009

Reaction of ethyl acetoacetate with 3,4‐diaminopyridine can theoretically give rise to the iso‐meric dihydrodiazepinones 1 and 3. However, only one of these (compound 1) was formed on direct condensation of the reactants in boiling toluene. The preparation of 3 required the synthesis of the pyridylaminocrotonate 2, which cyclized under conditions of base catalysis. When subjected to dry fusion, both diazepine derivatives rearranged to give isomeric isopropenylpyridoimidazol‐ones. The structures of these rearranged products were used to characterize the diazepines from which they were derived, according to a technique previously described (20,21). Our results contradict a recent report (17) ascribing structure 3 to the product from 3,4‐diaminopyridine and ethyl acetoacetate in boiling xylene.
7‐Benz[c] acridinemethanols as tetracyclic analogs of the 2‐phenyl‐4‐quinolinemethanol antimalarials
Authors: Rosowsky Andre , Chaykovsky Michael , Yeager Sandra A. , St. Amand Richard A. , Lin May , Modest Edward J.
Published: March 2009

A series of new 7‐benz[c]acridinemethanols and 5,6‐dihydro‐7‐benz[c]acridinemethanols was prepared as rigid, tetracyclic analogs of the antimalarial 2‐phenyl‐4‐quinolinemethanols. Condensation of 5,7‐dichloroisatin with 6‐chloro‐, 7‐chloro‐, and 6,7‐dichloro‐1‐tetralone furnished halogenated 5,6‐dihydro‐7‐benz[c]acridinecarboxylic acids, which were transformed into the corresponding acid chlorides, acyl malonates, α‐bromomethyl ketones, and epoxides. Fully aromatic members of the series obtained via dehydrogenation of the 5,6‐dihydro acids were likewise converted into epoxides via the acylmalonate route. Although all the epoxides studied proved to be exceptionally resistant to ring‐opening by di‐n‐butylamine, probably on account of steric effects, they could be cleaved readily with piperidine or morpholine. Nmr spectra of the resulting amino alcohols suggest that these compounds exist in a single preferred conformation stabilized by internal O‐H····N hydrogen bonding, and that free rotation about the side chain C‐C bond does not occur at room temperature.
Studies on the syntheses of azole derivatives. Part IX. Formation of 2,4‐disubstituted δ2 ‐1,3,4‐oxadiazolin‐5‐one and 4‐substituted 1,2,4‐triazolidin‐3,5‐dione derivatives by thermal reaetion of N‐aryl‐N‐benzylearbamoyl azides
Authors: Kametani T. , Shibuya S. , Shio M.
Published: March 2009

The structure of the novel produets, 2,4‐ltis‐(N‐benzy1‐4‐nitroanilino)‐Δ2‐1,3,4‐oxadiazolin‐5‐one (VII), 2‐benzy1‐1‐(N‐benzy1‐4‐chloroanilino)‐4‐(4‐chlorophenyl)‐1,2,4‐triazolidin‐3,5‐dione (XIVa), and 2‐benzy1‐1‐(N‐benzylanilino)‐4‐pheny1‐1,2,4‐triazolidin‐3,5‐dione (XIVb), obtained upon thermal reaction of N‐bcnzyl‐N‐(4‐nitrophenyl)carbamoyl azide (la), N‐benzyl‐N‐(4‐chloro‐phenyl)carbamoyl azide (Ib) and N‐benzyl‐N‐phcnylcarbamoyl azide (le), respectively, were determined.
Preparation and thermal degradation of α,ω‐alkylene bis[5‐(1,2,3,4‐thiatriazolyl)] sulfides
Authors: Pilgram Kurt , Görgen Franz
Published: March 2009

Syntheses of some extremely shock sensitive α,ω‐alkylene bis[ 5‐(1,2,3,4‐thiatriazolyl)] sulfides via reaction of sodium 1,2,3,4‐thiatriazoline thionate (1) and α,ω‐dihaloalkanes are described. Dichloromaleic imide reacted analogously with 1 to give 3,4‐bis(5‐(1,2,3,4‐thiatriazolyl)thio)maleic imide. The compounds decompose thermally in solution with formation of α,ω‐alkylene bis(thio‐cyanates), nitrogen and sulfur. The infrared spectra are discussed.
Reaction of 2,6‐dibutylaminohepta‐2,5‐dien‐4‐one with malononitrile
Authors: Van Allan J. A. , Reynolds G. A.
Published: March 2009

Malononitrile reacted with the title compound to give 6‐amino‐5‐cyano‐2‐(3,3‐dicyano‐2‐methylallylidene‐4‐methyl‐2H‐pyran (3). Treatment of 3 with hot 80% sulfuric acid yielded 4,7‐dimethyl‐56‐hydroxy‐2(1H)quinolone. With concentrated aqueous sodium hydroxide, 3 gave 5‐amino‐3,6‐dicyano‐4,7‐dimethyl‐2(1H)quinolone and 5‐amino‐6‐carbamoyl‐3‐cyano‐4,7‐dimethyl‐2(1H)quinolone. The reaction of 3 with hydrochloric in acetic acid gave a mixture of 6‐amino‐3,7‐dicyano‐2,8‐dimethyl‐4‐quinolizone and 3‐cyano‐4‐methyl‐6‐(3,3‐dicyano‐2‐methylallyl)‐2‐pyrone. Compound 3 also reacted with methylamine, butylamine and piperidine to give 8‐amino‐5‐cyano‐4‐methyl‐2‐pyridone, 6‐bulylamino‐5‐cyano‐4‐methyl‐2‐pyridone and 5‐eyano‐4‐methyl‐6‐piperidino‐2‐pyridone respectively.
Synthetic quinine, analogs. V. Quinolinemethanols related to desvinylquinine
Authors: Bender D. R. , Coffen D. L.
Published: March 2009

Aldol condensation of quinolinecarboxaldehydes with 3‐quinuelidinone followed by acid‐catalyzed hydration of the resulting α,β‐unsalurated ketones provides a short and versatile synthesis of desvinylquinine derivatives. A novel rearrangement of 2‐(9‐phenanthrylmethylene)‐3‐quinuclidinyl earbinols leading to dibenzoindole derivatives is described.
Synthesis of some N‐substituted 6,7‐dimethoxy‐1,2‐benzothiazin(4H)‐3‐one 1,1‐dioxides
Authors: Catsoulacos P.
Published: March 2009

Substituted 1,2‐benzothiazin‐3‐ones have been prepared by cyclization of 4,5‐dimethoxy‐2‐carboethoxymethybenzenesulfonamides. The latter were obtained by the action of ammonia and primary and secondary amines on 4,5‐dimethoxy‐2‐carboethoxymethylbenzenesulfonyl chloride which in turn was obtained from ethyl 3,4‐dimethoxyphenylacetate and chlorosulfonic acid.
Photochemical preparation and rearrangement of some symmetrical methoxypyridyl phenyl glycols (pinacols)
Authors: Brown Ellis V. , Shambhu M. B.
Published: March 2009

Solutions of 6‐methoxy‐3‐pyridyl phenyl ketone and 3‐, 4‐, 5‐ and 6‐methoxy‐2‐pyridyl phenyl ketones in isopropyl alcohol were subjected to ultraviolet radiation. All the ketones except 3‐methoxy‐2‐pyridyl phenyl ketone were observed to undergo bimolecular reduction to give the corresponding pinacols in 30‐100 percent yields. In cold concentrated sulfuric acid the pinacols were found to rearrange with the exclusive migration of the phenyl group. The pinacols hearing the 3‐pyridyl groups rearranged at a much faster rate than the 2‐pyridyl isomers.
N‐p‐toluenesulfonyl‐2‐oxazolidones Via the cycloaddition reaction of p‐tolucnesulfonyl isocyanate and epoxides
Authors: Herweh J. K. , Kauffman W. J.
Published: March 2009

The reaction of styrene oxide and phenyl glycidyl ether with p‐toluenesulfonyl isocyanate, employing a hydrocarbon‐soluble adduct of tributylphosphine oxide and lithium bromide as catalyst, results in excellent yields of the N‐p‐toluenesulfonyl‐2‐oxazoIidones. The 5‐isomeric‐2‐oxazolidone is obtained from phenyl glycidyl ether, but in contrast to conventional isocyanates, the p‐toluenesulfonyl isocyanate, upon reaction with styrene oxide, produces the 4‐isomeric 2‐oxazolidone as the major product. The effect of the N‐sulfonyl group on the nmr spectra of 2‐oxazolidones is discussed.
Reaction of β‐aeylarylhydrazines with dimethylformamide in the presence of calcium hydride. A novel route to 3‐pyrazolin‐5‐ones
Authors: Kornet Milton J. , Ong Tjoan Ho , Thio Poo An
Published: March 2009

Reaction of β‐acylarylhydrazines with calcium hydride in refluxing dimethylformamide (DMF) was found to lead to the formation of 2‐aryl‐3‐pyrazolin‐5‐ones (V). Application of this novel synthetic method resulted in fair to good yields of a series of 2,4‐diaryl‐3‐pyra7,olin‐5‐ones. The infrared spectra (potassium bromide) of the products (V) showed that these compounds exist as the laetim tautomer (VI). An oxindole (IIc) was obtained when dimethylbenzamide was substituted for DMF under similar reaction conditions.
The synthesis of malonimide derivatives as potential penicillin analogs
Authors: Golik Uri
Published: March 2009

Malonimidoacetic acid derivatives (VIII, XIII) were synthesized as a potential penicillin analogs, hut they failed to inhibit the growth of bacteria when tested in vitro against a range of Gram‐positive and Gram‐negative microorganisms.
Synthesis of some heterocyclic derivatives of 3,5‐dinitro‐o‐toluic acid
Authors: Wu M. T.
Published: March 2009

The synthesis of a series of heterocyclic derivatives of 3,5‐dinitro‐o‐toluic acid is described.
The crystal and molecular structure of 1,1,4,4‐tetraphenyl‐1,4‐diphosphoniacyclohexane dibromide
Authors: Brown J. N. , Trefonas L. M.
Published: March 2009

The crystal and molecular structure of 1,1,4,4‐tetraphenyl‐1,4‐diphosphoniacyclohexane dibromide has been determined by a single‐crystal, x‐ray diffraction study using diffractometer data. The compound crystallizes in the monoclinic space group P21/c with unit cell constants of a = 12.777(1), b = 26.180 (2), c = 16.283 (1) Å, and β = 91.18(1)°. The structure was solved by the heavy atom method with the 4176 independent and statistically significant structure factors refining to a value of R = 0.07. The diphosphonium ring is in the chair conformation with each phosphorus ion having an axial and equatorial phenyl ring attached. P‐C and C‐C bond lengths of 1.78 ± .03 Å and 1.53 ± .03 Å respectively agree well with the literature value for these distances.
The effect of 4‐substituents on the stability of pyridinium dicarbethoxymethylides
Authors: Douglass James K. , Tabor M. Wilson , Spradling Julius E.
Published: March 2009

The effect of 4‐substituents on the stability of pyridinium dicarbethoxymethylides, as determined by pKa measurements, is found to correlate well with their effect on the stability of similarly substituted pyridine 1‐oxides. Displacements in chemical shift in the ylides, particularly of the α‐protons, are also found to correlate well with substituent effects. Intramolecular charge‐transfer transitions in the electronic spectra, characteristic of pyridinium ylides, are reported.
A mass spectrometric study of substituted furfuryl compounds
Authors: Loughran E. D. , Wewerka E. M. , Hammons G. J.
Published: March 2009

The mass spectra of six furfuryl compounds — namely, furfuryl alcohol, 5‐furfuryl‐furfuryl alcohol, difurfuryl ether, difurylmethane, 2,5‐difurfurylfuran, and 4‐furfuryl‐2‐pentenoic acid‐γ‐lactone — have been studied. Their fragmentation mechanisms are discussed in detail with particular emphasis on the modes that lead to the formation of aromatic fragments. The majority of the fragment ions are formed by elimination of CO and C2H2 from even‐electron precursor ions and HCO from odd‐electron precursor ions. Molecules containing two furan rings linked by a methylene group give mass spectra that exhibit large abundances of aromatic fragment ions.
Photo‐ and thermal elimination of nitrogen from 4‐phenyl‐ and 4,5‐diphenyl‐1,2,3‐triazole
Authors: Selvarajan R. , Boyer J. H.
Published: March 2009

Phenylacetonitrile (2) (32%) and small amounts of benzyl methyl ether (3), benzonitrile (5) and methyl benzoate (6) were produced by irradiation of either 4‐phenyl‐1,2,3‐triazole (1) or 4‐phenyl‐5‐deutero‐1,2,3‐triazole (7) in methanol at 254 nm. In methylene chloride, irradiation of 1 produced 2 (15%) and small amounts of 3,6‐diphenyl‐1,2,4,5‐tetrazine (8). Irradiation of 4,5‐diphenyl‐1,2,3‐triazole (9) in methanol gave 2,4,5‐triphenylimidazole (11) (4%) and trace amounts of diphenylacetonitrile (10), benzamide (12), and compounds 3, 5, and 6. Irradiation of 2,3‐diphenyl‐2H‐azirine (13) in methanol gave small amounts of 3, benzaldehyde (4), and compounds 5, 6, 12 as well as 2,3,5,6‐tetraphenylpyrazine (14) and in methylene chloride it gave 11 (16%) and small amounts of 4, 5, 14, and acetophenone (15).

On heating 4‐phenyl‐1,2,3‐triazole (1) in n‐hexadecane, elimination of nitrogen at 290° left phenylacetonitrile (2) as the only identified product. Similar pyrolysis of 4,5‐diphenyl‐1,2,3‐triazole (9) produced 2,3,5,6‐tetraphenylpyrazine (14) along with an intractable material. An efficient thermal isomerization of 2,3‐diphenyl‐2H‐azirine (13) gave 2‐phenylindole (17).
Pyrimido[5,4‐b]quinolines. I. Synthesis of substituted tricyclic systems related to riboflavin
Authors: Levine Edward M. , Bardos Thomas J.
Published: March 2009

Two alternative synthetic routes were investigated for the synthesis of 2,4,10‐substituted‐7,8‐dimethylpyrimido[5,4‐b]quinolines: (1) cyclization of 5‐(3,4‐xylidino)‐2,4‐disubstituted‐pyrimidine‐6‐carboxylic acids, and (2) cyclization of N‐5‐(2,4‐disuhstituted‐pyrimidinyl)‐4,5‐dimethylanthranilic acids. Route (1) invariably led to isomeric mixtures of the corresponding 7,8‐ and 8,9‐dimethylpyrimido[5,4‐b]quinolines which were difficult to separate, while route (2) yielded only the desired 7,8‐dimelhyl derivatives. The required intermediates were synthesized by Ullman‐type condensation of the appropriate pyrimidine and benzene derivatives. Cyclization with polyphosphoric acid, or phosphorus oxychloride (under various conditions) led to a number of new pyrimido[5,4‐b]quinoline derivatives, with oxo, methoxy and/or chloro substituents in the 2,4 and 10 positions. A mild, but effective chlorination procedure was developed for the chlorination of the 10‐(oxo) position without the cleavage of methoxyl groups at positions 2 and 4.
Reactions of dilithiooximes, dilithiophenylhydrazones and trilithiohydrazones with nitriles. Acid‐cyclization to isoxazoles or pyrazoles
Authors: Beam Charles F. , Foote Robert S. , Hauser Charles R.
Published: March 2009

Certain C(α)O‐dilithiooximes, C(α)N‐dilithiophenylhydrazones, and C(α)N,N‐trilithiohydrazones were treated with a variety of nitriles. The intermediates were not isolated, but cyclized with acid to give isoxazoles or pyrazoles.
The conversion of isotopically labeled glycine to 1‐methyl‐2‐amino‐2‐imidazolin‐4‐one (creatinine)
Authors: Rowley G. L. , Kenyon G. L.
Published: March 2009

A procedure is presented which allows the conversion of glycine to creatinine (1‐methyl‐2‐amino‐2‐imidazolin‐4‐one). The scheme was devised to optimize the yield based on the amount of glycine used so that the relatively readily available isotopically labeled glycines could be efficiently converted to the correspondingly labeled creatinines. In this case 1‐(13C)‐glycine was converted to 4‐(13C)‐1‐methyl‐2‐amino‐2‐imidazolin‐4‐one.
The crystal and molecular structure of phenothiazine‐10‐propionic acid
Authors: Malmstrom Sister Mary Carl , Cordes A. W.
Published: March 2009

The crystal structure of phenothiazine‐10‐propionic acid, C12H8SNC2H4COOH, was determined from three‐dimensional X‐ray diffraction data collected with a manual diffractomer using MoKα (λ 0.71069 Å) radiation. The space group is P21/c with a = 7.888 (2)Å, b = 8.703 (2)Å, c = 19.700 (8)Å, β = 101.42 (1)°, Z = 4, Dmeas = 1.35(2) g. cm−3 and Dcalc = 1.36 g. cm−3 at 23°. The structure was determined by the direct method and refined with 500 observed reflections by full‐matrix least squares to an R of 0.072. The molecule is folded along the S‐N axis and the dihedral angle is 136.5°. The C‐S‐C angle is 98.5(7)° and the average C‐S bond is 1.77(2)Å. The shortening of the C‐S bond, the small value of the C‐S‐C angle and the folding of the molecule are typical of the phenothiazine class of compounds and are assumed to be due to sulfur d orbital participation in ring bonding.
Reinvestigation of the rearrangement of 2‐acetylbenzofuran oxime tosylate
Authors: Vargha L. , Kuszmann J. , Sohár P. , Horváth Gy.
Published: March 2009

The acetal, resulting from the rearrangement of anti‐2‐acetylbenzofuran oxime tosylate (I) was proved to be a mixture of trans‐ (IX) and cis‐ (X) 2,3‐dihydro‐2‐acetyl‐2,3‐dimethoxybenzofuran. The structure of these isomers as well as that of their oximes XI and XII was elucidated by ir, nmr, and mass spectral investigation and by the ir and nmr spectra of the benzoyl (XIII and XIV) and acetyl (XV and XVI) derivatives of the oximes. A new reaction mechanism concerning the rearrangement process is discussed.
Synthesis of some phenanthridone derivatives
Authors: Cookson R. F. , James J. W. , Rodway R. E. , Simmonds R. G.
Published: March 2009

The alkylation of phenanthridone and some nuclear‐substituted phenanthridones using sodium hydride in DMF/benzene is reported. Various 5‐cyanoalkylphenanthridones were converted to further derivatives by either hydrolysis or reduction.
An improved synthesis of homopteroic and homofolic acids
Authors: Kim Young‐Ho , Grubliauskas Vytautas , Friedman Orrie M.
Published: March 2009

A more practical synthesis of homopteroic and homofolic acids involving condensation of 2,4,5‐triamino‐6(1H)pyrimidinone (3) with 1‐acetoxy‐4‐[N‐acetyl‐(p‐carbethoxyphenyl)amino]‐2‐butanone (7) is described. The biological activities of homofolic (1‐b) and homopteroic (2‐b) acids were compared and found to be identical with the activities of these products prepared by the unambiguous route.
Mass spectra of thiazoloquinolines
Authors: Barni Ermanno
Published: March 2009

The behaviour under electron impact of sixteen thiazoloquinolines, unsubstituted and containing methyl substituents in both the pyridine and the thiazole rings, was investigated. Some decomposition schemes related to the main fragmentations in these fused heteroaromatic systems are proposed on the basis of available results on simpler related structures like thiazoles, benzo‐thiazoles and quinolines.
Novel 6‐(trifiuoromethyl)cytosines and 6‐(trifluoromethyl)uracils
Authors: Lutz Albert W. , Trotto Susan H.
Published: March 2009

Ethyl 3‐amino‐4,4,4‐trifluorocrotonate (3) has been converted by a one step reaction with alkyl and aryl isocyanates to novel 3‐substituted‐6‐(trifluoromethyI)uracils. Also several 3‐amino‐4,4,4‐trifluorocrotonitriles (11a‐c) have been cyclized to novel 6‐(trifluoromethyI)cytosines (13a‐c) and then hydrolyzed to the corresponding uracils (4, 14b‐c). Alkylation studies with isopropyl bromide of three 6‐(trifluoromethyl)uracils (1, 4, 5) are described.
The hydrolysis of α,α'‐dimethoxydihydrofurans
Authors: Hirsch Jerry A. , Szur Alex J.
Published: March 2009

A series of α,α ‐dimethoxydihydrofurans have been prepared and subjected to various acidic and neutral hydrolysis conditions in attempts to prepare conjugated enediones in a stereospecific manner. Isomerization of the 3‐hexene‐2,5‐diones and rearrangements of other enediones to β,γ‐unsaturated‐γ‐lactones have been uncovered. Methods of assignment of stereochemical configuration to the enediones are evaluated; reaction with hydrazine hydrate in the absence of acid is proposed as a useful criterion.
1,4‐Benzodiazepines III . Cyclization paths of hexaminium salts of 2‐chioroacetamido‐5‐ehlorobenzophenone and its N‐methyl derivative
Authors: Blažević N. , Šunjić V. , Crvelin I. , Kolbah D. , Kajfež F.
Published: March 2009

This study reports the isolation and characterization of hexaminium salts of 2‐chloroacetamido‐5‐chlorobenzophenone (I) and of 2‐(N‐methyl)chloroacetamido‐5‐chlorobenzophenone (II). The 7‐chloro‐1,3‐dihydro‐5‐phenyl‐2H‐1,4‐benzodiazepin‐2‐one (VI) and 7‐chloro‐1,3‐dihydro‐1‐meth‐yI‐5‐phenyl‐2H‐1,4‐benzodiazepin‐2‐one (VII), respectively are of pharmacodynamic importance. Based on chromatographic separation of some intermediates, and on spectrophotometric monitoring of cyclizations I → VI and II → VII, respectively, two different pathways for these reactions have been proposed. Since the slowest step in the reaction sequence II → VII follows the quasi first order rate law, intramolecular nucleophilic attack of the benzophenone carbonyl group on the hexamine moiety proved to be decisive for the cyclization (scheme II). However, cyclization I → VI seems to incorporate quite different solvolytic pathways in addition to one corresponding to the sequence II → VII. Isolated 4‐imidazolidinone intermediates N,N' ‐methylene‐bis[3‐{2 ‐benzoyl‐4‐chIoro)phenyI]‐4‐imidazolidinone(III), and 3‐(2 ‐benzoyl‐4′‐chlorophenyI)‐4‐imidazolidinone hydrochloride (IV) recyclize into the 1,4‐benzodiazepine VI. The optimal reaction conditions have been found to be between pH 6‐7.
Derivatives of 7‐Oxabicyclo[2.2.1 ]hept‐5‐ene and 7‐Oxabicyclo[2.2.1 ] heptane. Synthesis, transformations, and stereochemistry using nmr methods
Authors: Nelson Wendel L. , Allen David R.
Published: March 2009

Synthesis and stereochemistry of various endo‐2‐ and exo‐2‐substituted‐7‐oxabicyclo[2.2.1]‐hept‐5‐enes and ‐heptanes are described. The nmr spectra of several derivatives are reported and discussed. Use is made of this data to allow determination of the stereochemical integrity of the system. Facile chromatographic separation methods were found for endo‐ and exo‐2‐sub‐stituted‐7‐oxabicyclo[2.2.1 ]hept‐5‐enes and ‐heptanes.
A novel synthesis of aromatic methoxy and methylenedioxy substituted 2,3,4,5‐tetrahydro‐1H‐3‐benzazepines
Authors: Pecherer B. , Sunbury R. C. , Brossi A.
Published: March 2009

A new synthesis of aromatic methoxy and methylenedioxy substituted 2,3,4,5‐tetrahydro‐1H‐3‐benzazepines is described. Suitably substituted phenethylamines and their α‐methyl homologs in the form of their N‐acetyl derivatives are chloromethylated, the resulting benzyl chlorides are reacted with cyanide and hydrolysis of the latter yields 2‐(2‐aminoethyl)phenylacetic acid derivatives. Thermal cyclization yields the corresponding lactams. Hydride reduction of these lactams furnishes the substituted 2,3,4,5‐tetrahydro‐1H‐3‐benzazepines which may be methylated on nitrogen by formaldehyde and hydrogen. By this sequence a number of previously unde‐scribed compounds have been prepared.
Aromatie‐substituted derivatives of 2,3,4,5‐tetrahydro‐7,8‐methylenedioxy‐1H‐3‐benzazepine. Syntheses via chloromethylation
Authors: Pecherer B. , Sunbury R. C. , Brossi A.
Published: March 2009

Chloromethylation of N‐acetyl‐2,3,4,5‐tetrahydro‐7,8‐methylenedioxy‐1H‐3‐benzazepine (4) proceeded, depending on reaction conditions, at the 6‐ or 6,9‐ positions. Subsequent transformation of these intermediates provided a series of mono and bis aromatic‐substituted derivatives of the parent benzazepine 3.
5‐ and 7‐substituted 2‐methyl‐8‐quinolinols
Authors: Gershon Herman , Mcneil Maynard W.
Published: March 2009

The synthesis and characterization of the 5‐ and 7‐monosubstituted 2‐methyl‐8‐quinolinols where the substituents are fluorine, chlorine, bromine, iodine, nitro, amino, and sulfonic acid groups were carried out. The bischelates with copper(II) of those ligands containing hydrogen, fluorine, chlorine, bromine, iodine, and nitro are also reported.
Folate antagonists. 6. Synthesis and antimalarial effects of fused 2,4‐diaminothieno[2,3‐d]pyrimidines
Authors: Elslager Edward F. , Jacob Patricia , Werbel Leslie M.
Published: March 2009

2,4‐Diamino‐5,7‐dihydro‐6H‐thiopyrano[4′,3′:4,5]thieno[2,3‐d]pyrirnidine, 2,4‐diamino‐9H‐mdeno[1′,2′:4,5]thieno[2,3‐d]pyrimidine, 2,4‐diamino‐5H‐indeno[2′,1′:4,5]thieno[2,3‐d]pyrimidine, 9,11‐diamino‐5,6‐dihydronaphtho[1′,2′:4,5]thieno[2,3‐d]pyrimidine, 7,9‐diamino‐5,6‐dihydronaphtho[2′,1′:4,5]thieno[2,3‐d]pyrimidine, 2,4‐diamino‐7‐benzy]‐5,6,7,8‐tetrahydropyrido[4′,3′:4,5]thieno[2,3‐d]pyrimidine, and various 2,4‐diamino‐5,6,7,8‐tetrahydro‐[1]benzothieno[2,3‐d]pyrimidines were synthesized by cyclization of the requisite fused 2‐aminothio‐phenene‐3‐carbonitriles utilizing chloroformamidine hydrochloride in diglyme. Several compounds exhibited strong inhibitory effects againstStreptococcus faecalis(MGH‐2),Staphylococcus aureus(UC‐76),Streptococcus faecium(ATCC 8043),Lactobacillus casei(ATCC 7469), andPediococcus cerevisiae(ATCC 8081)in vitro, and three compounds displayed antimalarial activity againstPlasmodium bergheiin mice andP. falciparum(Uganda I)in vitro.
Reactions of 4‐methoxypyrylium salts with secondary amines
Authors: Van Allan J. A. , Reynolds G. A. , Petropoulos C. C.
Published: March 2009

4‐Aminopyrylium derivatives were prepared from secondary amines and 4‐methoxy‐2,6‐dimethylpyrylium perchlorate (1a) and the corresponding 2,6‐diphenyl derivative. Excess amine or elevated temperature resulted in the addition of two equivalents of amine to 1a. The reactions of the aminopyrylium salts with hydroxide, ammonia, primary amines, hydrazines, cyanoacetamides, ethyl cyanoacetate, malononitrile, nitromethane, sodium sulfide, and a Grignard reagent are described.
Kinetics of styrylquinolinc formation
Authors: Lynch Steven M. , Gordon Marshall
Published: March 2009

A comprehensive kinetic investigation of reactions occurring in the formation of styryl‐quinolines has been conducted. Specific rate data such as rate equations, rate constants, and thermodynamic activation values have been determined and utilized in a study of which factors are of greatest importance in the reactions forming 2‐styrylquinolines. A mechanism has been proposed for the condensation reaction which agrees with rate relationships found. Gas‐liquid partition chromatography was used to follow the kinetics of the condensation reactions. A rate constant of 5.41 × 10−2M−1min−1 was found for the reaction of benzaldehyde with 2‐methyl‐quinoline using zinc chloride as a catalyst at 104.0°. Rate constants of 1.28 × 10−2 MT−1 min−1 and 1.05 × 10−2 M−1 min−1 were found for the reactions of p‐methylbenzaldehyde and p‐methoxybenzaldehyde with quinaldine to form 2‐(p‐methylstyryl)quinoline and 2‐(p‐methoxystyryl)‐quinoline, respectively at 92.4°. A linear relationship was found using the Hammett equation. An Arrhenius plot was constructed from rate constants determined at five different temperatures for the reaction of benzaldehyde and quinaldine to form 2‐styrylquinoline, using zinc chloride as a catalyst. The energy of activation, Ea, was found to be 22.2 kcal/mole for this reaction. The enthalpy of activation, ΔH‡, free energy of activation, ΔF‡, and entropy of activation, ΔS‡, were found to be 21.4 kcal/mole, 27.7 kcal/mole and ‐16.7 eu/mole, respectively, at 104.0°. The mechanism proposed in the formation of 2‐styrylquinoline involves the fast formation of a carbanion‐zinc chloride complex, which then attacks, in the rate determining step, the aldehyde utilized in the reaction. The lack of reaction of certain methylquinolines is attributed to the inadequacy of the carbanion formed and not to the difficulty involved in the initial formation of the carbanion.
Synthesis of 2,3,10,11 ‐tetraalkoxy‐substituted tetrahydrobenzo [a] naphtho [1,2‐g] quinolizines
Authors: Zee‐Cheng Kwang Y. , Nyberg Wayne H. , Cheng C. C.
Published: March 2009

2 Four3,10,11‐tetraalkoxy‐substituted 5,6,15,15a‐tetrahydro‐8H‐benzo[a]naphtho[1,2‐g]‐quinolizines were prepared by the Pictet‐Spengler cyclization of the respective 1‐(6,7‐dialkoxy‐2‐naphthylmethyl)‐6,7‐dialkoxy‐1,2,3,4‐tetrahydroisoquinolines. The latter compounds were obtained by a chemical reduction of the corresponding dihydro compounds, which, in turn, were formed by a Bischler‐Napieralski cyclization of the appropriate amides.
Rearrangement of ketone hydrazones derived from 4‐hydrazino‐1H‐2,3‐benzoxazines
Authors: Pifferi Giorgio , Vigevani Aristide , Consonni Pietro , Gallo Gian Gualberto
Published: March 2009

The ketone hydrazones IV, derived from 4‐(1‐methylhydrazino)‐1H‐2,3‐benzoxazines and various ketones, rearrange by the action of anhydrous acids and/or heating to the phthalanylidene compounds V, which are the first reported examples of α‐aminoazoaliphatic derivatives. The structure assignment was based on spectroscopic (ir, pmr, and uv) data and on the study of the hydrolysis products. A mechanism for the rearrangement is proposed and briefly discussed.
Stereochemical studies with methyl substituted piperidyl‐2‐carbinols
Authors: Cahill R. , Crabb T. A.
Published: March 2009

Configurations have been assigned to some methyl substituted 3‐p‐nitrophenylhexahydro‐3H‐oxazolo[3,4‐a]pyridines (1) and to the methyl piperidyl‐2‐carbinols (2) derived from these on the basis of nmr and ir spectral data.
The preparation of 3‐chlorothieno[3,2‐b] thiophene derivatives from thiophene‐2‐acrylic acids
Authors: Wright W. B.
Published: March 2009

Thiophene‐2‐acrylic acids react with thionyl chloride in the presence of pyridine to form derivatives of 3‐chlorothieno[3,2‐b]thiophene‐2‐carbonyl chloride. These compounds are easily converted to the corresponding acids and esters.
The synthesis and reactions of β‐substituted ethyl sulfates
Authors: Tomalia Donald A. , Falk John Carl
Published: March 2009

The synthesis of β‐substituted ethyl sulfates and their reactions with nucleophilic reagents has been studied. Amines, phenolates, carboxylates, amine oxides, carbanions, and thiophenolates reacted with ethylene sulfate in high yield, with short reaction times, and at low temperatures, to form β‐substituted ethyl sulfates. The β‐substituted ethyl sulfates were easily hydrolyzed and in some cases were converted into polymeric material.
Novel polycyclic heterocycles. VIII. 6,11‐dihydro‐12H‐dibenzo[b,f] [1,4]thiazocines and their derivatives
Authors: Yale Harry L. , Sowinski Francis , Spitzmiller Ervin R.
Published: March 2009

6,11‐Dihydro‐12H‐dibenzo[b,f][1,4]thiazocine, 4, and its 2‐chloro, 7, and 2‐(trifluoromethyl)‐, 1, derivatives, were prepared by the reaction of an o‐aminobenzenethiol and α,α‐dibromo‐o‐xylene. Acylation and alkylation at position‐12 gave a series of ω‐haloacyl‐, ω‐amino‐acyl, and ω‐aminoalkyl derivatives of these heterocycles. The conformations, proton magnetic resonance spectra, and x‐ray crystallographic studies of these compounds are discussed.
Malonic ester derivatives of s‐Triazine
Authors: Fredric Reynolds C. , Berner Robert , Boutwell William
Published: March 2009

Reaction of cyanuric chloride with solutions of sodium diethyl malonate led to three products, 2,4,6‐tris(dicarbethoxymethylene)hexahydro‐s‐triazine, 2,4‐bis(dicarbethoxymethylene)‐6‐oxohexahydro‐s‐triazine, and 2‐dicarbethoxymethylene‐4,6‐dioxohexahydro‐s‐triazine. The preferred structures (IV,V,VI) are stabilized by chelated N‐H‐O protons in six membered rings. The assignment of structures was made on the basis of ir, nmr, uv and mass spectral data.
Pyrido[2,3‐H]‐2,6‐naphthyridines. I. Synthesis and thermal reactions of the 2,2′bisacylazide of 3,3′ bipyridine
Authors: Williams R. L. , Elfayoumy M. G.
Published: March 2009

2 The2′‐bisacylazide of 3,3′‐bipyridine (1) has been synthesized from the (4,7)‐phenantholine‐5,6‐dione (3) and the thermal decomposition of this new bisacylazide has been shown to give rise to the Curtius rearrangement and subsequent cyclization to the pyrido[2,3‐h]‐2,6‐naph‐thridinone ring system 8.
Heterocycles from substituted amides II. Novel behavior of a reactive thiophene in some cyelo‐ and acyclo‐addition reactions
Authors: Chupp John P.
Published: March 2009

N,N'‐Diisopropyl‐N,N'‐diphenyl‐2,4‐thiophenediamine (1) has demonstrated its remarkable electron‐donating abilities and atypical behavior as a thiophene, by its facile reaction with a number of electron deficient dienophiles. Thus, β‐nitrostyrene, ethoxymethylene malononitrile, diethyl azodicarboxylate and dimethyl acetylenedicarboxylate undergo Michael‐type addition at the 5‐position of 1 to form adducts 2, 3, 4, and 5. Alternatively, the dienophiles, acrylonitrile, N‐phenylrnaleimide and phenyl‐1,2,4‐triazoline‐3,5‐dione gave novel cyclic materials 6, 9, and 11, not necessarily arising from simple Diels Alder addition. Structure proofs for the products as well as alternative mechanisms for their formation are discussed.
The reaction of N‐Acyl imines with t‐Butyl isocyanide
Authors: Deyrup J. A. , Killion K. K.
Published: March 2009

N‐Acylimines and their derivatives react with t‐butyl isocyanide only the in presence of acid catalysis. The major products of these; reactions are 5‐aminooxazoles and 5‐iminooxazolines. The structure of these compounds and some of their degradative chemistry is discussed.
Syntheses of analgesics. Part XXX.. Conformational studies of diastereoisomeric quaternary ammonium salts of 1,2,3,4,5,6‐Hexahydro‐2,6‐methano‐3‐benzazocines
Authors: Kametani Tetsuji , Kigasawa Kazuo , Hiiragi Mineharu , Satoh Fumio , Saito Setsu , Sugi Hideo , Uryu Tsuneo
Published: March 2009

The configuration of the quaternary ammonium salts (Va and Vb) from 3‐benzyl‐1,2,3,4,5,6‐hexahydro‐8‐hydroxy‐6,11‐dimethyl‐2,6‐methano‐3‐benzazocine. (II) and 3‐methyl‐2‐butenyl bromide was determined spectroscopically. Moreover, configurational studies on 3‐benzyl (VIa and VIb) and 3‐(3‐methyl‐2‐butenyl)benzazocinium bromides (VIIa and VIIb) were also achieved.
Studies on the syntheses of analgesics. Part XXXII. An alternative synthesis of 1,2,3,4,5,6‐Hexahydro‐8‐hydroxy‐6,11‐dimethyl‐3‐(3‐methyl‐2‐butenyl)‐2,6‐methano‐3‐benzazoeine [Studies on the syntheses of heterocyclic compounds. Part CDLXXX]
Authors: Kamelani Tetsuji , Kigasawa Kazuo , Hiiragi Mineharu , Satoh Fumio , Sugi Hideo , Uryu Tsuneo
Published: March 2009

Bischler‐Napieralski reaction of the amides (VIII and IX), derived from the 3‐methyl‐3‐pentenylamine (III) with the phenylacetic acid derivatives (V ∼ VII), gave the 5,6‐dihydropyridines (XII and XIII), which were reduced, followed by N‐benzylation, to afford the 1,2,5,6‐tetrahydropyridines (XIX ∼ XXI). Grewe‐type cyclization of these compounds gave 3‐benzyl‐3‐benzazocine (II), which was already converted into pentazocine (Ic). Moreover, the 1,2,5,6‐tetrahydropyridines (XIX ∼ XXI) were also obtained from the 2‐benzylidene‐1,2,5,6‐tetrahydropyridine (XVII ∼ XVIII) from the N‐benzylamine (IV) of III via the amides (X and XI).
Reaction of ketenes with N,N‐Disubstituted 2‐Aminomethylenecycloalkanones III. Synthesis of N,N‐Disubstituted 3,3‐Diehloro‐4‐amino‐5,6‐polymethylene‐3,4‐dihydro‐α‐pyrones
Authors: Bignardi G. , Fvangelisti F. , Schenone P. , Bargagna A.
Published: March 2009

The reaction of dichloroketene with N,N‐Disubstituted 2‐aminomethylenecyclopentanones, cyclohexanones, cycloheptanones and cyclooctanones gave the 1,4‐cycloadducts, namely N,N‐Disubstituted 3,3‐dichloro‐4‐amino‐5,6‐polymethylene‐3,4‐dihydro‐α‐pyrones. The structures of these products were determined by uv, ir and nmr spectral data, as well as by dehydrochlorination of the adduct, 3,3‐dichloro‐4‐diphenylamino‐5,6‐tetramethylene‐3,4‐dihydro‐α‐pyrone, which led to 3‐chloro‐4‐diphenylamino‐5,6‐tetramethylene‐α‐pyrone.

The by‐product of the cycloaddition reaction was the N,N‐Disubstituted dichloroacetamide, the formation of which varies according to the substituents on the nitrogen atom.
The use of enamines in the synthesis of heterocycles
Authors: Montgomery John A. , Laseter Anne G.
Published: March 2009

The reaction of the enamine N‐styryl pyrrolidine with 4,6‐dichloro‐5‐nitropyrimidine and 4‐amino‐6‐chloro‐5‐nitropyrimidine was investigated. Reduction of resultant compounds was followed by spontaneous ring closure to the pyrrolo[3,2‐d]pyrimidine ring system. This reaction sequence should provide a general method for the preparation of 4,7‐disubstituted pyrrolo[3,2‐d]‐pyrimidines.
The reactions of pyranylidenemethylpyrylium salts with sodium sulfide
Authors: Reynolds G. A. , Van Allan J. A.
Published: March 2009

Symmetrical pyranylidenemethylpyrylium salts react with sodium sulfide to give, after acidification, pyranylidenemethylthiapyrylium salts. In the case of unsymmetrical salts in which the methylene group is joined at the 2‐position of one ring and the 4‐position of the other, the ortho oxygen atom is displaced by sulfur. An unsymmetrical dye which is substituted in the 2,6‐positions of one ring with phenyl groups and with alkyl groups in the other ring gave a product which contained the sulfur atom in the aryl‐substituted ring.
Rearrangements of 5‐isoxazolylhydrazines: 1‐amino‐ and 4‐aminopyrazolin‐5‐ones
Authors: Adembri G. , Ponticelli F. , Tedeschi P.
Published: March 2009

5‐Isoxazolylhydrazines rearranged to 1‐aminopyrazolin‐5‐ones on heating. Under the same conditions, 5‐(3‐methyl‐4‐phenylisoxazolyl)hydrazine also gave 3‐methyl‐4‐amino‐4‐phenylpyra‐zolin‐5‐one. The structures of aminopyrazolones were assigned on the basis of spectroscopic properties and chemical behavior.
Benzo[b] thiophene derivatives. XVIII. The sulfur isosteres of harmaline, harmine and related isomers
Authors: Bosin T. R. , Maickel R. P. , Dinner A. , Snell A. , Campaigne E.
Published: March 2009

The sulfur analogs of harmaline, 7‐methoxy‐3,4‐dihydro‐1‐methyl[1]benzothieno[2,3‐c]‐pyridine (Ib), harmine, 7‐methoxy‐1‐methyl[1]benzothieno[2,3‐c]pyridine (IIb), and corresponding 6‐methoxy isomers (Ic and IIc) have been synthesized for pharmacological evaluation as monoamine oxidase inhibitors.
Investigation of the preparation of pyrimidine isocyanates
Authors: Dyer Elizabeth , Nycz Thomas J. , Long Michael B.
Published: March 2009

Uracil‐5‐yl isocyanate and 1,3‐dimethyluracil‐5‐yl isocyanate were prepared from the corresponding new carboazides. 1,3‐Dimethyluracil‐5‐ylmethyl isocyanate obtained from the chloro compound and silver cyanate, was polymerized with an anionic initiator to the cyclic trimer. Attempts to isolate uracil‐6‐yl isocyanate, 1,3‐dimethyluracil‐6‐yl isocyanate, pyrimidinyl‐4‐isocyanate, and 2,6‐dichloropyrimidinyl‐4‐isocyanate were unsuccessful. Ethyl carbamate derivatives were made from all new azides and isocyanates. Other new pyrimidine derivatives included N,N'‐bis(pyrimidine‐4‐carbonyl)hydrazine, N,N'‐bis(1,3‐dimethyluracil‐5‐yl)urea, N,N'‐bis(1,3‐dimethyluracil‐6‐yl)urea and N,N'‐bis(2,5,6‐trichloro‐4‐pyrimidinyl)oxamide.
The crystal and molecular structure of 3,7‐dicyano‐3,5,7‐triaza‐1‐phosphabicyclo[3.3.1]nonane
Authors: Trefonas L. M. , Brown J. N.
Published: March 2009

The crystal and molecular structure of the title compound has been determined by a single crystal x‐ray diffraction study using counter‐data. The compound crystallizes in the monoclinic space group, P21/c, with a = 8.657 ± .001Å, b = 10.513 ± .001Å, c = 10.378 ± .001Å, β = 99.68 ± .01° for Z = 4. The structure was solved by the symbolic addition procedure and refined by block‐diagonal least‐squares to R = 0.052 for 1479 statistically significant reflections. The geometry of the bicyclic ring system is discussed.
Base‐catalyzed redox reactions of α‐hydroxyalkylazaaromatic N‐oxides
Authors: Muth Chester W. , Patton Jesse C. , Bhattacharya Bhabatosh , Giberson David L. , Ferguson Christopher A.
Published: March 2009

The (α‐hydroxybenzyl)pyridine 1‐oxides on heating with aqueous sodium hydroxide yielded the corresponding benzoylpyridines in redox reactions. When the phenyl groups of the foregoing compounds was replaced by hydrogen or methyl the redox reactions occurred less readily. A kinetic isotope effect of 3 was found for 4‐(α‐deuterio‐α‐hydroxybenzyl)pyridine 1‐oxide on reaction with sodium hydroxide. The removal of the α‐deuterio group is non‐reversible. A mechanism consistent with these observations is given. 6‐Acetoxyphenanthridine 5‐oxide yielded with concentrated hydrochloric acid a redox product, 6‐formylphenanthridine hydrochloride, whereas under the same conditions neither (α‐hydroxybenzyl)pyridine 1‐oxides nor 2‐hydroxy‐methylquinoline 1‐oxide yielded a redox product.
Synthesis in the diazasteroid group. I. A new synthesis of 8,13‐diaza‐2,3‐dimethoxygona‐1,3,5(10)triene and its mercuric acetate oxidation
Authors: Matoba Katsuhide , Isomura Kazumasa , Nagata Masanori , Yamazaki Takao , Castle Raymond N.
Published: March 2009

From the condensation reaction of methyl butyrolactim (I) with 1‐ethoxycarbonylmethyl‐6,7‐dimethoxy‐l,2,3,4‐tetrahydroisoquinoline (II), 8,13‐diaza‐2,3‐dimethoxygona‐l,3,5(10)trien‐12‐one (VI) and 8,13‐diaza‐2,3‐dimethoxygona‐l,3,5(10)triene (VII) were obtained in good yield. The oxidation of VI and VII with mercuric acetate was examined.
Pyrazoles XI. The synthesis of 1,1′‐dimethylbipyrazolyls
Authors: Timmermans Pieter B. M. W. M. , Uijttewaal Arnold P. , Habraken Clarisse L.
Published: March 2009

The synthesis of al six isomers of 1,1′‐dimethylbipyrazolyl is reported. Their structure assignments were based on mnr data. Nmr spectra were determined in widely different solvents and structure assignments were based on these data, particularly on the found solvent effect. Uv spectral data are also reported.
Mechanism of the stereoseleetive formation of 1,4‐dithiafulvens from 1,2,3‐thiadiazoles and base
Authors: Shafiee A. , Lalezari I.
Published: March 2009

4‐Sul>stituted‐1,2,3‐thiadiazoles were found to react with base to form cis‐2,ω‐disubstituted‐1,4‐dithialulvenes. The mechanism lor the stereoselective formation of the product is discussed.
Studies on the syntheses of heteroeyelie compounds. Part DVI . Synthesis of oxynilidine and nitidine
Authors: Kametani Tetsuji , Kigasawa Kazuo , Hiiragi Mineharu , Kusama Osamu
Published: March 2009

A benzyne type reaction of 1‐bromo‐3,4‐dimethoxybenzene (V) with 3,4‐dihydro‐6,7‐methylenedioxy‐I(2H)naphthalenone (VI) gave the tetralone derivative VII, which was converted into the amine IX via the oxime VIII. A Mannich reaction of IX afforded the benzo[c]phen‐anthridine II which was then transformed into oxynitidine (I) and nitidine (IV).
Acyl Indoles. III. The synthesis of [1,4] diazcpino [6,5‐b ] indoles
Authors: Garcia E. E. , Benjamin L. E. , Fryer R. Ian
Published: March 2009

The synthesis of 1,3,4,6‐letrahydro‐6‐metliy]‐2H,5H‐[1,4]diazepino[6,5‐b] indole‐2,5‐diones and 5‐phenyl‐3,6‐dihydro[1,4]diazepino[6,5‐b ]indole‐2(lH)one is described. Also detailed is the, preparation of a 3‐amino‐2‐benzoylindole.
Synthesis of Indolo and benzimidazoquinazolines and benzodiazepines
Authors: Duncan Robert L. , Helsley Grover C. , Boswell Robert F.
Published: March 2009

Indolo[1,2‐c] quinazolines, indolo[1,2‐d] [1,4]benzodiazepines, indolo [1,2‐d] [1,4]benzodi‐azepin‐6‐ones and benzimidazo[1,2‐d] [1,4] benzodiazepin‐6‐ones were synthesized. In an acid medium, the indoloquinazolines were produced from 2‐(o‐aminophenyl)indole and acyl halides. However, in the presence of sodium acetate, the acylated amine was obtained and was cyclized to the indolobenzodiazepinones using sodium hydride. The syntheses are described in detail and characterization data are given.
The reactions of 2‐ethoxy‐2,3‐dihydro‐4H‐1,3‐benzothiazin‐4‐one (6), 4,4‐diphenyl‐2‐ethoxyoxazolidin‐5‐one (10), and l‐benzyl‐2‐methoxyimidazolidine‐4,5‐dione (12) with dienes
Authors: Ben‐Hhai D. , Gillon I. , Warshansky A.
Published: March 2009

2‐Ethoxy‐1,3‐benzothiazin‐4‐one (6), 4,4‐diphenyl‐2‐ethoxyoxazolin‐5‐one (10) and 1‐benzyl‐2‐methoxyimidazolidine‐4,5‐dione (12) were prepared and were found to react with 1,1‐bicyclo‐hexenyl, 1,2,3,4‐tetramethylbutadiene and 2,4‐dimethyl‐1,3‐pentadiene to give Diels‐Alder ad‐ducts ( 8, 9, 13‐18).
Picrylamino‐substituted heterocycles. VI. Pyrimidines
Authors: Harris Betty W. , Singleton Jannie L. , Coburn Michael D.
Published: March 2009

The condensation of various aminopyrimidines with picryl chloride and picryl fluoride has been investigated as part of our continuing effort in the field of picrylamino‐substituted heterocycles. Most of the aminopyrimidines that can tautomerize reacted with picryl fluoride to form picryl derivatives of their imino forms, but they gave picrylamino derivatives when they condensed with picryl chloride.
Synthesis of substituted pyrrolo[1,2‐α]pyrimidines
Authors: Sowell J. Walter , Dewitt Blanton C.
Published: March 2009

A facile route for the synthesis of pyrrolo[ 1,2‐α]pyrimidine derivatives and data for structural assignment are reported.