bluuebunny/crossref_metadata_2025 huggingface dataset:
Recherches en série azabenzodiazépine VII. Synthése de pyrazolo[3,4‐b]diazépines‐1,4
Authors: Affane‐Nguema J.‐P. , Lavergne J.‐P. , Viallefont Ph.
Published: April 2009

Par action de l'acétylacétate d'éthyle ou de l'acétylacétone, sur des diamino‐4,5 pyrazoles, les pyrazolo[3,4‐b]diazépines‐1,4 sont synthétisées, soit directement, soit aprés cyclisation d'inter‐médiaires crotoniques ou cétoniques. Le sens de cyclisation et les structures des cycles diazépines sont démontrés. IIs correspondent á l'attaque initiale du carbonyle cétonique sur la fonction amine en position 4.
The photochemical synthesis of novel heterocyclic compounds from s‐triazolo [4,3‐b] pyridazine, III
Authors: Bradshaw Jerald S. , Tueller John E. , Baxter Steven L. , Maas Garren E. , Carlock John T.
Published: April 2009

s‐Triazolo[4,3‐b]pyridazine (I) reacted photochemieally with bieyélo[2.2.1] hepla‐2,5‐diene, 1,5‐cyclooctadiene, 1,3‐cyclooctadiene, methylene cyclohexane, diethyl cis‐1,2,3,6‐tetrahydro‐phthalate and ethyl 2‐cyclopentene‐1‐acetate to givt: the following products: the endo and exo isomers of 4a, 5, 8a, 9‐tetrahydro‐9‐rnethylene‐5,8‐rnethano‐8H‐s‐triuzolo[1, 5‐a]indole (II) and the endo and exo‐9‐cyanometliyl products (III and IV) from bicyclo[2.2.1] hepta‐2,5‐diene; 4a,5,‐9, 10, 10a, 11‐huxahydro‐11‐methylene‐6H‐cycloocta[4,5]pyrrolo[1,2‐b]‐s‐triazole (V) and the 11‐cyanomethyl product VI from 1,5‐cyclooctadiene: 4a,7,8,9,10,10a‐hexahydro‐11 ‐inethylene‐11H‐cycloocta[4,5]pyrrolo[1,2‐b]‐s‐triazole(VII),4a, 5, 7, 8, 10a, 11‐hexahydro‐11‐methylene‐6H‐cycloocta[4,5]pyrroIo[1,2‐b]‐s‐triazole (VIII) and their respective 9‐cyanomethyl products (X and 1X) from 1,3‐cyclooctadiene; 6′, 7′ ‐dihydro‐7′ ‐methylenespiro[cyclohexane‐1, 5′‐[5H] pyr‐rolo[1,2‐b]‐s‐triazole] (XI), 6′, 7′‐dihydro‐7′‐meth) lene. spiro cyclohexane‐1, 6′‐[5H]pyrrolo[1,2‐b]‐s‐triazole] (XII) and their respective 7 ‐eyanomethyl products (XIII and XIV) from melhylene cyclohexane; 6,7‐dicarbethoxy‐9‐cyanomelhyl‐4a, 5, 7, 8, 8a, 9‐hexahydro‐6H‐s‐triazolo[1,5‐a]indole (XV) from diethyl cis‐1, 2, 3, 6‐tetrahydrophlhalate: and 5‐earl)elhoxymethyl‐8‐eyanomethyl‐4a, 5, 6, 7, 7a, 8‐hexahydrocyclopenta[4,5]pyrrolo( 1, 2‐b]‐s‐triazole (XVI) from ethyl 2, 2‐cyclo‐pentene‐1‐acetate. Many other alkenes, particularly the phenyl ethylenes, did not react with compound 1. In general, more than one product was isolated for each reaction except in the case of the two ester alkenes where a single eyanomethyl product was observed.
Synthesis, photooxidation and Z ⇌ E photoisomerization of benzalpyrrolinones
Authors: Lightner D. A. , Park Y‐T.
Published: April 2009

In contrast to oxodipyrromethenes and bilirubin, benzalpyrrolinones (H, P‐OCH3, p‐Cl, p‐N(CH3)2 and o‐CH3) and α‐pyridalpyrrolinones appear not to undergo dye‐sensitized photo‐oxygenation. They do, however, undergo an unsensitized E ⇌ Z photoisomerization reminiscent of stilbene photoisomerization, and the photostationary state varies with substituent. Intramolecular H‐bonding is implicated in the α‐pyridalpyrrolinone isomerization. In each case, the Z isomers are the therrnodynamically more stable ones, but the corresponding E isomers have been isolated and characterized following photoirradialion.
Action de l'anhydride acétique sur les (aziridinyl‐1)‐2 tétra‐hydropyrannes et sur les dialkylamino‐2 tétrahydropyrannes: Influence des substituants de l'azote sur l'orientation de la réaction
Authors: Ricart Guy , Clacet Charles , Couturier Daniel
Published: April 2009

Les (aziridinyl‐1)‐2 tétrahydropyrannes sont obtenus par réaction d'Hofmann entre les α‐chlorotétrahydropyrannes et les aziridines; l'anhydride acétique les transforme en N‐(tétra‐hydropyrannyl‐2) N‐(β‐acétoxyéthyl) acélamides: il y a ouverture de l'hétérocycle azoté. Les dialkylamino‐2 tétrahydropyrannes avec le měme anhydride, réagissent ditféremment selon la nature des substituants alkyles de Tatome d'azote: les dérivés N‐diméthylés subissent la coupure carbone alpha‐azote pour donner un mélange d'acétoxy‐2 tétrahydropyrannes et de dimćthylacétamide; les composés N‐diéthylé's et autres fournissent des produits poly condensés, ayant vraisemblablement pour origine un clivage de la liaison carbone alpha‐oxygéne, et les dialkylacétamides correspondants. Une frontiére trés nette existe done entre les α‐aminotetra‐hydropyrannes N‐dimćthylés et N‐dialkylés.
Intramolecular cyclizations leading to bridgehead bicyclics 2. 5,5‐dialkylhydantoin derivatives
Authors: Okada Katsuhide , Kelley James A. , Driscoll John. S.
Published: April 2009

The effect of substituenls in the 5‐position on the course of hydantoin intramolecular alkylation reactions was studied. Dialkyl and diaryl substituted intermediates resulted in the same type product, 2,3‐dihydro‐6,6‐disubstituted imidazo[2,1‐b]oxazole‐5(6H)ones, indicating alkylation on oxygen rather than nitrogen. The mass spectral and nmr characteristics of these bicyclic compounds are discussed.
Pyrimidines. XIII. Novel pyrimidine to pyrimidine transformation reactions
Authors: Hirota Kosaku , Watanabe Kyoichi A. , Fox Jack J.
Published: April 2009

Novel pyrimidine to pyrimidine transformation reactions are described. 1,3‐Dimethyl‐(or diethyl)‐uracil(1) are converted into isocytosine, 2‐thiouracil or uracil derivatives by treatment with guanidine, thiourea or urea, respectively. The latter two cases require base catalysis. The effects of some substituents at C‐5 and C‐6 of 1,3‐dialkylated uracils (1a → 1e) on this transformation were examined and a plausible mechanism is offered for their reaction. The utility of this reaction is exemplified by the facile two‐step conversion of pseudouridine into the anlileukemic agent, pseudoisocytidine, in good overall yield.
Preparation of azapyrylocyanine dyes
Authors: Reynolds G. A. , Vanallan J. A.
Published: April 2009

Azapyrylocyanine and thiopyrylocyanine dyes were prepared from a 4‐aminopyrylium or 4‐aminothiopyrylium perchlorate and a 4‐methoxypyrylium or thiopyrylium perchlorate in the presence of a tertiary amine. The Absorption spectra of these dyes was shifted 107–125 mm to shorter wavelength compared to the corresponding methine dyes.
Mass spectral fragmentation pattern of 2,2′‐bipyridyls. Part VIII. 2,2′‐Bipyridyl‐5‐carboxylic Acid and 2,2′‐bipyridyl‐5‐sulphonic acid
Authors: Keats N. G. , Summers L. A.
Published: April 2009

The mass spectra of 2,2′‐bipyridyl‐5‐carboxylic acid and 2,2′‐bipyridyl‐5‐sulphonic acid obtained by electron impact are described. The principal initial fragmentation routes from the molecular ion of the carboxylic acid involve loss of CO, CN˙, HCN, CO2, OH˙ and H2O. From the molecular ion of the sulphonic acid the principal fragmentations are accompanied by loss of HCN, O3, SO2 and SO3.
Addition von aldehyden an aktivierte doppelbindungen, XV . Synthese von γ‐diketonen mit heterocyclischen substituenten und deren umsetzung zu N‐methylpyrrolen und chinolizidin bzw. Indolizidin systemen
Authors: Stetter Hermann , Krasselt Joachim
Published: April 2009

Aliphatische, aromatische und heterocyclische Aldehyde können unter Cyanid‐ bzw. Thiazoliumsalz‐Katalyse erfolgreich an α,β‐ungesattigte Ketone addiert werden. Die erhaltenen γ‐Diketone lassen sich leicht zu Pyrrol‐, Chinolizidin‐ bzw. Indolizidin‐Systemen umsetzen.
Studies on the chemistry of 2,3,5,6‐Tetrahydro‐6‐phenylimidazo[2,1‐b]‐thiazole. I. The reaction of N‐Alkyl derivatives with nucleophiles
Authors: Bigg D. C. H. , Faull A. W. , Purvis S. R.
Published: April 2009

7‐Alkyl‐2,3,5,6‐tetrahydro‐6‐pheriylimidazo[2,1‐b]thiazoliurn salts behave as arnbident electro‐philes, which give ring‐opened products on reaction with a variety of nucleophiles. The results are rationalised in terms of thermodynamic or kinetic control.
Streptonigrin and related compounds III. Synthesis and microbiological activity of destrioxyphenylstreptonigrin and analogues
Authors: Rao Koppaka V.
Published: April 2009

Synthesis of three tricyclic analogues of streptonigrin, based on the 2‐(2′‐pyridyl)quinoline‐5,8‐dione system and with the characteristic substitution pattern of rings A and C of streptonigrin is described. The C‐ring precursor, in the form of a substituted 2‐acetylpyridine was condensed with either 3‐hydroxy‐5‐methoxy‐2‐nitrobenzaldehyde or 3‐hydroxy‐4‐methoxy‐2‐nitrobenzaldehyde, followed by reductive cyclization and oxidation to the corresponding quinones 12 and 29. The 7‐amino substitution was introduced in 12 via bromination and azidation. The 6‐amino substitution was introduced through direct reaction of 29 with sodium azide. Destrioxyphenylstreptonigrin 2 was twice as active and the 6‐amino‐7‐inethoxy analogue 4 was as active as streptonigrin in a microbiological assay. A 4′‐bromo analogue of 2 was 60% as active as streptonigrin.
Procedural refinements in the N‐Demethylation of morphine and codeine using phenyl chloroformate and hydrazine
Authors: Rice Kenner C. , May Everelte L.
Published: April 2009

A refined, rapid procedure for the preparation of normorphine and norcodeine in 80‐90% yields is described.
Abnormal behavior of nitropyridines in substitution reactions with anions
Authors: Kurita Keisuke , Williams R. L.
Published: April 2009

The reactions of the anions of isonicotinamide and 2‐amino‐5‐nitropyridine with 2‐chloro‐5‐nitropyridine and 3‐nitropyridine were observed to give rise to unexpected substitution products presumably via a radical anion mechanism.
A chemical synthesis of the nucleoside 1‐methylpseudouridine
Authors: Earl Robert A. , Townsend Leroy B.
Published: April 2009

A facile chemical synthesis of 1‐methylpseudouridine has been accomplished by direct methylation of pseudouridine.
Reaction of carbonyl compounds with dimethyl 3‐ketoglutarate. Synthesis of bicyclic furan derivatives
Authors: Campos Olivia , Cook James M.
Published: April 2009

Acid catalyzed reaction of cyelododecane‐1,2‐dione VI with dimethyl,3‐ketoglutarate II led to the formation of methyl (E)‐6,7,8,9,10,11,12,13‐octahydro‐3‐(methoxycarbonyl)cyclododeca‐[b]furan‐2‐aeetate IX, presumably formed through the dihydrodihydroxy furan VIII. This dihydrofuran intermediate VIII was shown to be characteristic of the reaction of 2‐substituted carbonyl‐compounds with 11 for both α‐chlorocyclohexanone and α‐chlorocyclopentanone furnished furans XVIa and XX, respectively, when treated with 11. The effect of dihydrodihydroxy‐furan intermediates on the course of such reactions is discussed.
Analogues azotés de dérivés de l'acide orotique
Authors: Daunis Jacques , Follet Michel
Published: April 2009

Les synthéses de deux nouveaux types de composés de structures oxo‐3 thioxo‐5 et dithioxo‐3,5 éthoxycarl)onyl‐6 tétrahydro‐2,3,4,5 triazines‐1,2,4 sont décrites; leur réactivite vis á vis d'agents alkylants et de I'hydrazine est examinée.
Studies on the furan series. Part VII. A preparation of 2,3‐Di(2‐furyl and thienyl)furans
Authors: Pennanen Seppo I.
Published: April 2009

Furoin reacts smoothly with dimethyl acetylenedicarboxylate via a Michael addition, which is followed by a dihydrofuran ring formation. After elimination of water the previously unknown 2,3‐di(2‐furyl)furan structure is produced. Thenoin gives a side reaction to yield a fumaric acid derivative in addition to the expected 2,3‐di(2‐thienyl)furan. A mechanism for the side reaction is suggested. The reactivities of the prepared new furan structures towards some oxidation, hydrogenation and electrophilic reagents were determined.
Hétérocycles contenant du phosphore. XXXII. Etude de l'action des phosphorhydrazides sur les orthoesters, l'anhydride acétique et l'acide formique
Authors: Majoral Jean Pierre , Revel Monique , Kraemer Raymond , Germa Héléne , Navech Jacques
Published: April 2009

L'action des phosphodi‐ ou trihydrazides sur les orthoesters permet, en général, d'obtenir des tétrahydro‐2,3,4,5 tétrazaphosphorines‐1,2,4,5,3. Cependant, dans certains cas, il y a formation de amino‐4 triazaphospholidines‐1,2,4,3. Les tétrazaphosphorines‐1,2,4,5,3 obtenues présentent parfois une prototropie. La présence de cette prototropie se traduit par une orientation de la réaction de certains de ces composés avec le formaldéhyde ou l'acétone. La structure des différents hétérocycles obtenus est établie par rmn.
Etude de la configuration d'oximes a activité cardiotrope
Authors: Laforest Jacqueline , Thuillier Germaine
Published: April 2009

La configuration des 2 isoméres de thiényl‐2, et furyl‐2, (dichloro‐2,3 methoxy‐4)phényl cétone oxime est déterminée, d'une part en étudiant les déplacements chimiques induits sur les spectres de résonance magnétique nucléaire par la formation d'un complexe avec un chélate de lanthanide et d'autre part par voie chimique. Les résultats obtenus permettent de définir la configuration des 2 isoméres de thiényl‐2, et furyl‐2, (dichloro‐2,3 méthoxy‐4)phényl O‐di‐éthylamino éthyl cétone oxime, composés dont l'activité cardiotrope est remarquable.
Ind‐N‐alkylation of rutaecarpine and synthesis of two novel related heterocyclic ring systems: Indolo[1′,2′:3,4]pyrazo[1,2‐α]quinazoline and indolo[1′,2′:3,4] [1,4] diazepino[ 1,2‐α]quinazoline
Authors: Danieli Bruno , Palrnisano Giovanni
Published: April 2009

The failure to obtain the N‐(13)alkylrutaecarpines (1d,e,f) by heating rutaecarpine (1a) with neat alkyl halides at 120° is discussed in comparison with the facile reaction with methyl iodide. In contrast, with alkyl halide‐potassium carbonate in acetone, the corresponding N‐(13)alkyl‐rutaeearpines (1d‐l) are obtained in good yield. By use of 1,3‐diiodopropane and 1,2‐dibromo‐ethane, this reaction provides a facile route to 12a and 13 which are derivatives of the heretofore unknown indolo[1,2′:3,4]pyrazo[1,2‐α]quinazoline and indolo[1,2 :3,4][1,4]diazepino[1,2‐α]quinazoline ring systems.
Reactivity of the A‐CH=N=NR‐CX‐B System. 1,3,4‐thiadiazoles and Δ2 ‐thiadiazolines
Authors: Werber Giuseppe , Buccheri Francesco , Gentile Manlio , Librici Luigi
Published: April 2009

The reactivity of the magnified image‐ system towards ferric chloride has been investigated. The cyclo‐oxidation reaction led to the formation of 2‐amino‐5‐thenoyl‐1,3,4‐thiadiazoles and 4‐methyl‐5‐imino‐2‐thenoyl‐Δ2‐1,3,4‐thiadiazolines. Their structures were proven spectro‐scopically and chemically (nucleophilic attack and formation of the related 2‐amino‐1,3,4‐thiadiazoles and 4‐methyl‐5‐imino‐Δ2‐1,3,4‐thiadiazolines).
Conversion of the carboxyl group to the corresponding trichloromethyl group in the quinoline series
Authors: Takahashi Kazuyuki , Mitsuhashi Keiryo
Published: April 2009

Various substituted quinaldinic acids were treated with phosphorus pentachloride in an excess of thionyl chloride. Carboxyl groups of quinaldinic acid, 6‐methyl‐, 6‐chloro‐, 4‐phenyl‐ and 4‐(p‐chlorophenyl)quinaldinic acids and benzo[f]quinoline‐3‐carboxylic acid were converted to the trichloromethyl group, while those of 8‐methyl‐, 4‐(3,4‐dichlorophenyl)‐, 4‐(p‐nitrophenyl)‐quinaldinic acids and benzo[h]quinoline‐2‐carboxylic acid were not. The difference is discussed on the basis of the effects of the basicity of ring nitrogen and steric factors.
Methylation and amination of folic acid
Authors: Temple Carroll , Kussner Conrad L. , Montgomery John A.
Published: April 2009

The methylation of folic acid (2) with excess methyl iodide resulted in the formation of dimethyl 1,3‐dimethylfolate (4), whereas, methylation of dimethyl folate (3) with an equimolar amount of methyl iodide gave mainly dimethyl 3‐methylfolate (6). Both 4 and 6 underwent the Dimroth rearrangement in base to give the corresponding 2‐deamino‐2‐methyiamino folic acids 5 and 7, respectively. Amination of 2 with hydroxylamine‐O‐sulfonic acid in dilute base gave a low yield of 3‐amino folic acid (8), which underwent Dimroth rearrangement to give 2‐deamino‐2‐hydrazino folic acid (9) in an acidic, but not a basic, medium.
Synthesis and 270 MHz Nmr structural studies of the isomers of 2,3,5‐trimethyl‐ and 2,3,6‐trimethylmorpholine
Authors: Hernestam Sven , Nilsson Bertil , Stenvall Gillis
Published: April 2009

The four isomers of 2,3,5‐trimethylmorpholine and those of 2,3,6‐trimethylmorpholine have been synthesized from appropriately substituted ethanolamines and separated by means of preparative gas‐liquid chromatography. The configuration of each isomer was determined from 270 MHz FT‐nmr studies of the magnitudes of the methine‐methine and methine‐methylene proton coupling constants. The evaluated chemical shifts of axial methyl groups are discussed.
Synthesis, phosphodiesterase inhibition and antiinflammatory activity of 2‐aryl‐3‐hydroxythieno[2,3‐b]quinoline 1,1‐dioxides. Application of sodium chlorite as a novel reagent for the (Stepwise) oxidation of sulfides to sulfones
Authors: Harrison Ernest A. , Rice Kenner C. , Rogers Michael E.
Published: April 2009

Synthesis of five 2‐aryl‐3‐hydroxythieno[2,3‐b]quinoline 1,1‐dioxides (38‐42) from 3‐formylquinoline‐2‐thiol (3) via a facile oxidation‐cyclization sequence is reported. Reaction of appropriate benzyl chlorides with the thiol (3) in the presence of sodium methoxide gave excellent yields of the corresponding benzyl 2‐(3‐formylquinolyl) sulfides (4‐8). Direct oxidation of these sulfides to the corresponding sulfones (23‐27) was effected with excess sodium chlorite in aqueous pyridine. Esterification of these sulfone‐acids followed by brief treatment of the resulting esters 28‐32 with sodium methoxide gave the desired compounds 38‐42 after acidification. The benzyl 2‐(3‐formylquinolyl) sulfides were also selectively oxidized to the corresponding sulfoxides (13‐17). Thus sodium chlorite has proved to be an effective reagent for the stepwise oxidation of sulfides to sulfones. The title compounds were potent inhibitors of cyclic AMP phosphodiesterase, but failed to display significant antiinflammatory effects in the carrageenan rat paw edema test or significant activity in the phenylquinone induced writhing test for analgesia.
A method for nitration of thiazoles
Authors: Grehn Leif
Published: April 2009

Nitrations of some sensitive thiazole derivatives with trifluoromethanesulfonic acid‐trifluoro‐methanesulfonic anhydride.‐potassium nitrate in 1,2‐dichloroethane gave significantly higher yields of the nitro compounds in comparison with nitrations in sulfuric acid‐nitric acid mixtures.
Condensation of o‐aminophenol and α‐dicarbonyl compounds. Part 1. Benzoxazines
Authors: Belgodere E. , Bossio R. , Parrini V. , Pepino R.
Published: April 2009

By condensation with o‐aminophenol of a series of phenylglyoxal derivatives two species of products were obtained, namely 2‐hydroxy‐(2H)‐1,4‐benzoxazines (I) and 2′ ‐aryl‐2,2′ ‐dibenzoxa‐zolines (II). The structure of compounds I was investigated by ir, uv and pmr spectroscopy and a reaction mechanism was proposed. J. Chem. Soc., 14, 997 (1977)
Reaction of dichloroketene and sulfene with N,N‐disubstituted 6‐amino‐methylene‐b,7,8,9 ‐tetrahydro‐5H‐benzocyclohepten‐5‐ones. Synthesis of 6‐(2,2‐Dichloroethylidene)‐b,7,8,9‐tetrahydro‐5H‐benzocyclohepten‐5‐one and of 5H‐benzo[3,4]cyclohepta[2,l‐b]pyran and 5H‐Benzo[3,4]cyclo‐hepta[1,2‐e]‐1,2‐oxathiin derivatives
Authors: Bignardi Gaetano , Mosti Luisa , Schenone Pietro , Menozzi Giulia
Published: April 2009

The 1,4‐cycloaddition of dichloroketene to N,N‐disubstituted 6‐aminomethylene‐b,7,8,9‐tetra‐hydro‐5H‐benzocyclohepten‐5‐ones afforded N,N‐disubstituted 4‐amino‐3,3‐dichloro‐3,4,6,7‐tetrahydro‐5H‐benzo[3,4]cyclohepta[2,l‐b]pyran‐2‐ones only in the case of aromatic or strong hindering aliphatic N‐substitution. The adducts gave N,N‐disubstituted 4‐amino‐3‐chloro‐b,7‐dihydro‐5H‐benzo[3,4]cyclohepta[2,l‐b]pyran‐2‐ones by dehydrochlorination with collidine. Upon chromatography on neutral alumina, two products were instead isolated in the case of usual aliphatic N‐substitution (diethylamine, piperidine), namely 6‐(2,2‐dichloroethylidene)‐6,7,8,9‐tetrahydro‐5H‐benzocyclohepten‐5‐one and the dehydrochlorinated 2‐pyrone; this latter was the sole product in the case of pyrrolidine substitution. The 1,4‐cycloaddition of sulfene occurred readily to give N,N‐disubstituted 4‐amino‐3,4,6,7‐tetrahydro‐5H‐benzo[3,4]cyclohepta‐[1,2‐e]‐1,2‐oxathiin 2,2‐dioxidesin the case of both aliphatic and partially aromatic N‐substitution.
1,3‐Dioxolan‐4‐ones and 1,3‐oxathiolan‐5‐ones. Configuration of cis and trans isomers
Authors: Pilgram Kurt , Zupan Mike
Published: April 2009

The attempted acid‐catalyzed azeotropic removal of water from a mixture containing lactamide and chloral in refluxing toluene lead to the elimination of ammonia; both cis‐ and trans‐5‐methyi‐2‐(trichloromethyl)‐1,3‐dioxolan‐4‐one were isolated. A number of 1,3‐dioxolan‐4‐ones and 1,3‐oxathiolan‐5‐ones were obtained by cyclodehydration of aldehydes with α‐hydroxy‐ and α‐mercapto‐carboxylic acids in the presence of boron trifluoride etherate. Geometric isomers were separated, and their configurations were determined by nuclear magnetic resonance.
Azido‐tetrazolo isomerizations of some thiazolopyridines
Authors: Petrič A. , Stanovnik B. , Tišler M.
Published: April 2009

2‐Azidothiazolo[5,4‐b]pyridine and 2‐azidothiazolo[4,5‐c]pyridine were synthesized. Azido‐tetrazolo isomerizations of these compounds were investigated and in both cases also the tetrazolo form could be obtained. In solution, equilibria at different temperatures were determined.
Experimental antiulcer drugs. 3. Some unusual transformations of the cyclopenta[c] pyrroles
Authors: Bell Malcolm R. , Oesterlin Rudolf , Geolotte Karl O. , Hlavac Allan G. , Crain Alfred V. R.
Published: April 2009

The cyclopenta[c]pyrrole‐4‐carbonitrile (3) is transformed by hyrlroxylamine in hot alcohol to 4,5,6,6a‐tetrahydro‐l‐imino‐3,5,5,6a‐tetramethyl‐4‐cyclopenta[c]pyrrole methyl ketone oxime (5) in contrast to the cyclopentapyrrole 10 which afforded 1,2‐diacetyl‐3,3,5,5‐tetramethyl‐cyclopentene dioxime (11). The cyclopenta[c]pyrrole‐4‐carboxamide 1 (R = C6H5) yielded the isomeric 2a,3,4,4a,5,6,6a,6b‐octahydro‐2a,4,4,6a‐tetramethyl‐5‐(phenylimino)pentaleno[1,6‐bc]‐pyrrol‐2‐(1H)one (12) in hot dilute hydrochloric acid or hot 99% phosphoric acid. The amide 1 (R = C6H5) was transformed in the solid state by oxygen over a period of several months to a mixture of the isomeric anils, 13 and 14 of 1,7‐diacetyl‐7‐hydroxy‐4,6,6‐trimethyl‐2‐azabicyclo‐[2.2.l.]heptan‐3‐one(16).
1,2‐Benzothiazines VIII. A novel semmler‐wolff type transformation of 2‐methyl‐2H‐1,2‐benzothiazin‐4‐one 1,1‐dioxide oxime
Authors: Zinnes Harold , Comes Roger A. , Shavel John
Published: April 2009

Refluxing the oxime (1) of 2‐methyl‐2H‐1,2‐benzothiazin‐4(3H)one 1,1‐dioxide with tri‐fluoroacetic acid or with boron trifluoride in acetic acid gives the corresponding N‐acyl derivative (2 or 3) of 4‐amino‐2‐methyl‐2H‐1,2‐benzothiazin‐3(4H)one 1,1‐dioxide. This transformation appears to be related to the acid catalyzed conversion of α‐tetralone oxime to α‐naphthylamine.
Ring‐opening of heterocyclic organometallics. XII. Rates of the ring‐opening of some 3‐thienyllithium derivatives
Authors: Frejd Torbjörn
Published: April 2009

The ring‐opening rates of some substituted 3‐thienyllithium derivatives have been measured and the activation parameters calculated for the ring‐opening of 2,5‐dimethyl‐3‐thienyllithium. Steric and electronic effects are discussed. J. Chem. Soc., 14, 1085 (1977)
Synthesis of 2‐substituted benzylidene‐6‐b‐nitrothiazolo[3,2‐α]benzimidazol‐3(2H)ones as possible anticonvulsants
Authors: Singh S. P. , Parmar S. S. , Pandey B. R.
Published: April 2009

Several 2‐substituted benzylidene‐b‐nitrothiazolo[3,2‐α]benzimidazol‐3(2H)ones were prepared by the condensation of 6‐nitrothiazolo[3,2‐α]benzimidazol‐3(2H)one with suitable aryl aldehydes as possible anticonvulsants. Amongst these benzimidazoles, two compounds possessed anticonvulsant activity and provided 60% protection against pentylene‐tetrazol‐induced seizures in mice.J. Heterocyclic Chem., 14, 1093 (1977)
Mass spectral fragmentation pattern of 2,2′‐bipyridyls Part XI. 2,2′‐Iminodipyridine
Authors: Keats N. G. , Summers L. A.
Published: April 2009

The base peak in the mass spectrum of 2,2′‐iminodipyridine is due to the M‐1 ion. There are several minor fragmentation routes from the molecular ion but the principal pathway involves rupture of the central bonds. J. Heterocyclic Chem., 14, 1103 (1977)
A semi‐micro synthesis of selenophene
Authors: Jacobs P. M. , Davis M. A. , Norton H.
Published: April 2009

A semi‐micro preparation of selenophene is described which offers a convenient technique for the production of milligram quantities of the heterocycle. Selenophene is synthesized from bis‐(trimethylsilyl)‐1,3‐butadiyne and sodium hydrogen selenide generated in situ from selenium and sodium borohydride in DMF‐water. J. Chem. Soc., 14, 1115 (1977)
Fused indoles. 1. Synthesis of the 1,9‐dihydrothiazino[3,4‐b] indole ring system
Authors: Coppola Gary M. , Hardtmann Goetz E.
Published: April 2009

The title compounds were prepared by treating 2‐chloroindole‐3‐carboxaldehydes and 3‐acetyl‐2‐chloroindole with N‐methylmethanesulfonamide and cyclizing the resulting intermediates with sodium hydride. Spectral data of the products are also discussed. J. Chem. Soc., 14, 1117 (1977)
Synthesis and antiinflammatory activity of the sulfoxides of 4‐[3‐(dimethylamino)propyl] ‐ 3,4‐ dihydro‐ 2‐(1‐hydroxyethyl)‐3‐phenyl‐2H‐1,4‐benzothiazine
Authors: Turk Chester F. , Egli Peter , Krapcho John
Published: April 2009

Oxidation of 4‐[3‐(dimethylamino)propyl]‐3,4‐dihydro‐2‐(1‐hydroxyethyl)‐3‐phenyl‐2H‐1,4‐benzothiazine, hydrochloride (I) with hydrogen peroxide yielded a mixture of two sulfoxides (II). Since this mixture exhibited antiinflammatory activity, the two components (Isomers A and B) were prepared in purified form by oxidation of I withN‐chlorosuccinimide and hydrogen peroxide, respectively. Isomer A was more potent than Isomer B in the carrageenin‐induced edema test.
Quinazolines and 1,4‐benzodiazepines. LXXVIII Pyrazolo[1,5‐a] [1,4]‐benzodiazepines and Imidazo[1,5‐a] [1,4]benzodiazepinones
Authors: Gilman Norman W. , Holland Betty C. , Fryer R. Ian
Published: April 2009

The syntheses of novel 8‐chloropyrazolo[1,5‐a][1,4]benzodiazepines and of an imidazo‐benzodiazepinone utilizing products from the nucleophilic substitution of fluorine in 2‐fluoro‐5‐nitrobenzophenone (1) by pyrazole‐3,5‐dicarboxylic acid, dimethyl ester (2) and by 2‐methyl‐imidazole‐4,5‐dicarboxylic acid, diethyl ester (30) are described.
Synthetic studies on chemotherapeutics. III. Synthesis of the 6,9‐dihydro‐9‐oxo‐1H‐ and 2H‐pyrazolo[3,4‐f]quinoline‐8‐carboxylic acid derivatives [studies on the syntheses of heterocyclic compounds. Part 718 ]
Authors: Kametani Tetsuji , Kigasawa Kazuo , Hiiragi Mineharu , Wakisaka Kikuo , Kusama Osamu , Sugi Hideo , Kawasaki Kumeo
Published: April 2009

1H‐ and 2H‐Pyrazolo[3,4‐f]quinolines were synthesized in order to get an antibacterial compound by two different methods from 6‐nitro‐ and 6‐aminoindazole.
Potentiell tumorhemmende wirkstoffe. IX. 4,5,6‐trialkylierte 2‐methoxy‐ und 2‐(methylthio)pyrimidine
Authors: Kreutzberger Alfred , Tesch Uwe‐Hartmut
Published: April 2009

Aus der Umsetzung des O‐Methylisoharnstoff‐sulfats (1a) bzw. des S‐Methylisothioharnstoff‐sulfats (1b) mit 3‐Methyl‐2,4‐pentandion (2a) resultieren das 2‐Methoxy‐ (3a) und das 2‐Methyl‐thio‐4,5,6‐trimethylpyrimidin (3b). Die aus den analogen Umsetzungen mit 3‐Äthyl‐2,4‐pen‐tandion (2b) erhältlichen 5‐Äthylpyrimidine (3c und 3d) tendieren in Kontakt mit der Luft unter Abspaltung der 5‐Äthylgruppe zum Übergang in 4,6‐Dimethyl‐2‐methoxypyrimidin (4a) und 4,6‐Dimethyl‐2‐(methylthio)pyrimidin (4b).
The structure of thiophene sesquioxide: Syn, endo‐3a,4,7,7a‐tetrahydro‐4,7‐epithiobenzo[b] thiophene 1,1,8‐trioxide
Authors: Merrill Ronald E. , Sherwood Gary
Published: April 2009

Thiophene sesquioxide is shown to be syn, endo‐3a,4,7,7a‐tetrahydro‐4,7‐epithiobenzo[b]‐thiophene 1,1,8‐trioxide (I) by 1 H and 13 C nmr evidence. Assignment of the 13 C spectrum was facilitated by a cross‐ring long‐range 13 C‐1 H coupling. The mass spectrum of I is dominated by an unusual break‐down to give benzene radical cation.
1,5‐Dipolar cycloaddition reactions. Semicarbazone bromides, 5‐alkyl (or aryl)amino‐1,3,4‐oxadiazole‐2‐carboxylic acids and their esters
Authors: Werber Giuseppe , Buccheri Francesco , Noto Renato , Gentile Manlio
Published: April 2009

The synthesis of the title compounds from semicarbazones of glyoxylic ester is reported.
Carbon‐13 NMR investigation of the structure of hydroxy‐azoloazines with a bridgehead nitrogen
Authors: Pugmire Ronald J. , Smith James C. , Grant David M. , Stanovnik Branko , Tisler Miha , Polanc Slvenko
Published: April 2009

Carbon‐13 nmr data has been obtained on four hydroxy‐azoloazines containing a bridgehead nitrogen atom, on the corresponding methoxide derivatives, and on selected anionic and cationic derivatives. These results have been interpreted in terms of the site of protonation of the parent hydroxy‐compounds. A comparison of the anionic derivatives with those of the parent compounds demonstrate that the neutral parent hydroxy‐species exist predominately in the “hydroxy form” rather than as the ionized species. The chemical shift data also provides information on the conformation of the hydroxy‐ and methoxy‐groups in 8‐hydroxy‐6‐methyl‐s‐triazolo[4,3‐6]‐pyridazine and 8‐rnethoxy‐6‐methyl‐s‐triazolo[4,3‐6]pyridazine.
Réactions induites par les halogénures de pyridinium. XXIV. Sur la synthése de dibenzofurannes à partir de diméthoxy‐2,2′ biphényles
Authors: Bachelet Jean‐Pierre , Demerseman Pierre , Royer René
Published: April 2009

Certains dibenzofurannes peuvent ětre obtenus par hétéroeyclisation au moyen du bromure de pyridinium des dihydroxy‐2,2′ biaryles formés par déméthylation au moyen du chlorure de pyridinium des diméthoxy‐2,2′ biaryles. La desalcoylation suivie d'hétérocyclisation en dibenzofurannes des diméthoxy‐2,2′ biaryles par le bromure de pyridinium se complique d'une trans‐methylation indireete. Les dérivés acylés des diméthoxy‐2,2′ biaryles perdent leur groupe acyle lors de leur désalcoylation, suivie ou non d'hétérocyclisation, par les halogénures de pyridinium.
A facile synthesis of some pyrazolo[1,5‐b] ‐1,2,4‐benzothiadiazepin 5(4H)ones 10,10‐dioxides. A new ring system
Authors: Plescia S. , Agozzino P. , Fabra I.
Published: April 2009

Isopropyl‐2‐chlorosulfonylbenzoate was treated with some 3(5)aminopyrazoles. A new ring system, pyrazolo[1,5‐b]‐1,2,4‐benzothiadiazepin‐5(4H)one 10,10‐dioxide, was directly obtained.
Carbon‐13 nuclear magnetic resonance spectra of anti‐inflammatory drugs: Phenylbutazone, oxyphenbutazone and indomethacin
Authors: Singh S. P. , Parmar S. S. , Stenberg V. I. , Farnum S. A.
Published: April 2009

The 13C nmr chemical shifts of phenylbutazone, oxyphenbutazone, indomethacin and indole‐3‐acetic acid are reported. The assignments of various carbon resonances are made on the basis of the substitution effects on benzene shifts, multiplicities generated in SFORD spectra, nuclear overhauser enhancement for protonated carbons, and the comparison with analogous compounds.
Synthesis of 5‐methylfuro[3,2‐b]pyridine‐2‐carboxylic acid
Authors: Weis C. D.
Published: April 2009

Oxidation of 3‐hydroxy‐6‐methyl‐2‐hydroxymethylpyridine with manganese dioxide yielded the corresponding aldehyde, the condensation of which with diethyl bromomalonate furnished hydroxydihydrofuro[3,2‐b]pyridinediearboxylie acid ester. Saponification of the diester with concentrated hydrochloric acid afforded the hydrochloride of 5‐methylfuro[3,2‐b]pyrjdine car‐boxylic acid.
Carbon‐13 nuclear magnetic resonance spectrum of methaqualone
Authors: Singh S. P. , Parmar S. S. , Stenberg V. I. , Akers T. K.
Published: April 2009

13C nmr chemical shifts of methaqualone, 2‐methyl‐3‐propyl‐4‐quinazolone, 2‐methyl‐3‐phenyl‐4‐quinazolone and their precursor, acetanthranil, are reported. The signals are assigned on the basis of suhstituent effects on benzene shifts, intensities, multiplicities in SFORD, and comparison with structurally related compounds.
An anomalous acylation of an aminobenzenesulfonamide
Authors: Friary R.
Published: April 2009

Acylation of 2‐amino‐4‐chlorobenzenesulfonamide by 2‐acetoxyisobutyryl chloride under acidic conditions unexpectedly gave 6‐chloro‐3‐methyl‐4H‐1,2,4‐benzothiadiazine 1,1‐dioxide and 8‐ehloro‐2,2,3a‐trimethyl‐3a,4‐dihydrooxazolo[2,3‐b] [1,2,4]benzothiadiazin‐1‐one 5,5‐dioxide, the skeletons of which incorporate the carbon atom of the acetoxyl carbonyl group of the acid chloride.
Recherches en série diazépine‐1,4 et triazépine‐1,2,4. IX. Synthéses de nouvelles triazépines‐1,2,4
Authors: Hasnaoui A. , Lavergne J.‐P. , Viallefont Ph.
Published: April 2009

Les méthodes de préparation de triazépines‐1,2,4 présentant cinq types de structure, disubstituées dans les positions 3 et 5 par des groupes oxo, thioxo, méthoxy ou méthylthio, sont décrites. Onze triazépines ont ainsi été synthétisées et leurs structures établies à partir de I'ensemble des données spectrales.
The coordination chemistry of simple phospholes: Complexes of nickel(II), palladium(II) and platinum(II)
Authors: Holah David G. , Hughes Alan N. , Hui Benjamin C. , Tse Pui‐Kwan
Published: April 2009

The reactions between four very simply substituted phospholes and the chlorides of Ni(II), Pd(II) and Pt(II) are described. The phospholes 1‐phenylphosphole, 3‐methyl‐1‐phenyl‐phosphole and 3,4dimethyl‐1‐phenylphosphole all readily form bis‐complexes of formula L2MCl2 [L = phosphole ligand and M = Ni(II), Pd(II) or Pt(II)] or tris‐complexes of formula L3MCI2. 1‐n‐Butyl‐3,4‐dimethylphosphole appears to form stable complexes only with Ni(II). Evidence is put forward which indicates that the L2MCl2 complexes exist in a four‐coordinate, square‐planar monomeric/five coordinate equilibrium while the L3MCl2 complexes are primarily the ionic species [L3MCl]+ Cl− in solution. Comparisons are made with the behaviour of other simple phospholes which do not form Ni(II) complexes and the results are discussed briefly in terms of both aromatic and non‐aromatic phosphole models.
Acetylenic ketones. Part V. Reaction of acetylenic ketones with thiourea and some of its derivatives
Authors: Baddar F. G. , Al‐Hajjar F. H. , El‐Rayyes N. R.
Published: April 2009

Aroylphenylacetylenes (I) reacted with thiourea and S‐benzylisothiourea to give 4,6‐diaryl‐pyrimidine‐2(1H)thiones (IV) and α‐aroyl‐β‐benzylmercaptostyrenes (X), respectively. Methyla‐tion and acetylation of the thiones (IV) gave the corresponding S‐methyl‐ (V) and S‐acetyl‐ (VI) derivatives, respectively. The oxidation of these thiones gave the corresponding disulfide derivatives (VII). Reaction of α‐aroyl‐β‐benzylmercaptostyrenes (X) with hydrazine hydrate and phenylhydrazine gave 3(5)‐aryl‐5(3)‐phenylpyrazoles (XI) and 3‐aryl‐1,5‐diphenylpyrazoles (XIII), respectively. Reaction of aroylphenylacetylenes (1) with N‐allylthiourea gave 1‐allyl‐4,6‐diaryl‐pyrimidine‐2‐thiones (XVI).
Synthesis via pummerer intermediates. II.. Disproportionation reactions of 3‐(methylsulfinyl)chromones and 3‐(methyl‐sulfinyl)quinolinones with hydrochloric acid
Authors: Connor David T. , von Strandtmann Maximillian
Published: April 2009

Sulfoxides (1 and 10) gave oxidation‐reduction products when treated with 5N hydrochloric acid. 8‐Methoxy‐3‐(methylsulfinyl)‐4H‐benzopyran‐4‐one (1) gave 8‐methoxy‐3‐(methylthio)‐4H‐1‐benisopyran‐4‐one (4) and 8‐methoxy‐3‐(methylsulfonyl)‐4H‐1‐benzopyran‐4‐one (5), whereas 1‐melhyl‐3‐(methylsulfinyl)‐4(1H)quinolinone (10) gave 1‐methyl‐3‐(methylthio)‐4(1H)‐quinolinone (12) and 1‐methyl‐4(1H)‐quinolinone (13).
Studies on mesoionic compounds, II. The solvent effect on the electronic absorption spectra of mesoionic 2,3‐diaryl‐2H‐tetrazolium‐5‐thiolate derivatives
Authors: Kiwan A. M. , Kassim A. Y.
Published: April 2009

The electronic absorption spectra of 2,3‐di(2‐fluorophenyl)‐, 2,3‐di(4‐fluorophenyl)‐, 2,3‐di‐(2‐chlorophenyl)‐, 2,3‐di(2‐methylphenyl)‐, 2,3‐di(4‐methylphenyl)‐ and 2,3‐di(2‐methoxyphenyl)‐2H‐tetrazolium‐5‐thiolates have been measured in pure and mixed solvents. They were found to exhibit three characteristic absorption bands at 480‐380 nm, near 250 and near 210; the longest wavenlength band of which was assigned to an n → π* transition.
Reactions of 2 ‐dichloromethylbenzimidazole with certain primary amines
Authors: Pascal Robert A. , Jungk Steven , Risinger G. E.
Published: April 2009

An investigation of the reactions of 2,2‐dichloromethylbenzimidazole with primary amines has led to the synthesis of 2(N‐t‐butylformimidoyl)benzimidazole, 2‐N‐(2‐phenylethyl)formimdoylbenzimidazole, and 1‐(ethoxyearbonylmethyl)‐2‐(N‐t‐butylformimidoyl)benzimidazole. Under mild alkali conditions, 2,2‐dichloromethylbenzimidazole was rapidly converted into a dimer, namely, 6H,13H‐pyrazino[1,2‐a:4,5‐a']bisbenzimidazole‐6,13‐diol.
Quinazolines and 1,4‐benzodiazepines LXXXII. Reaction of 2‐hydrazino‐benzodiazepines with 1,3‐diearbonyl compounds
Authors: Walser Armin , Zenchoff Gladys
Published: April 2009

The 2‐hydrazinobenzodiazepines 1 were reacted with acelylacelone to form the hydroxy‐pyrazolines 2 which were converted to the triazolobenzodiazcpines 6 and the 2‐pyrazolyl‐benzodiazepine 4. Ring cleavage of the hydrazone 8 obtained from cyclohexane‐1,3‐dione and 1a led similarly to the 1‐(4‐oxopentyl)triazolol)enzodiazepine 12.
Synthesis of 10‐(substituted phenylhydrazonoacetyl)phenothiazines as possible anticonvulsants
Authors: Singh S. P. , Kumar S. , Pandey B. R. , Parmar S. S.
Published: April 2009

Some 10‐(substituted phenylhydrazonoacetyl)phenothiazines were synthesized as possible anticonvulsants. These compounds were investigated for their anticonvulsant activity and inhibitory effects on the oxidation of pyruvic acid by rat brain homogenates.
Syntheses of pyrimidine and purine analogs derived from 1,2,6‐thiadiazine 1,1‐dioxide
Authors: Ochoa C. , Stud M.
Published: April 2009

5‐Amino‐3‐oxo‐2H, 4H‐1,2,6‐thiadiazine 1,1‐dioxide and the monopotassium salt of 3,5‐dioxo‐2H, 4H,6H‐1,2,6‐thiadiazine 1,1‐dioxide was obtained by condensation of sulfamide and ethyl cyanacetate and diethyl malonate, respectively. 7‐Oxo‐1H,4H,6H‐imidazo[2,3‐c]‐1,2,6‐thia‐diazine 5,5‐dioxide was prepared by a multi‐step reaction sequence from 5‐amino‐3‐oxo‐2H, 4H‐1,2,6‐thiadiazine 1,1‐dioxide.
Synthetic approaches to fused heteroaromatic compounds by the condensation reactions of functional pyrroles
Authors: Uchida Takane
Published: April 2009

Condensation reactions ol the “functionalized” pyrroles which were obtained by one pot synthesis of aziridines and acetylenic dipolarophiles were discussed. On treatments of 3,4‐di‐ and 2,3,4‐tribenzoylpyrroles with hydrazine hydrate and phosphorus pentasulfide, the several pyrrolo‐pyridazine derivatives and fused thiophenes, respectively, were prepared. The structure proofs for the products of the reaction of the 2,3,4‐tribenzoylpyrrole (9a) with hydrazine hydrate were based on the 13C FT‐nmr spectrum of the corresponding 13C‐enriched compounds.
Synthesis of 4‐substituted 3‐hydroxy‐and 3‐amino‐6H‐1,2,6‐thiadiazine 1,1‐dioxides
Authors: Goya P. , Stud M.
Published: April 2009

Reaction of sulfamide with ethoxymethylene derivatives yielded 4‐ethoxycarbonyl‐, 4‐cyano‐, and 4‐nitro‐2H,6H‐1,2,6‐thiadiazine 1,1‐dioxide. In some cases, the corresponding open chain sulfamidomethylene derivatives were isolated. Preparation of 4‐amino‐ and 4‐amino‐5‐methyl‐2H,6H‐1,2,6‐thiadiazin‐3‐one 1,1‐dioxide is also described. Reaction of sulfamide with ethyl 3,3‐ethoxypropionate afforded 3,7‐bis(etlioxycarbonylmethyl)perhydro‐1,5,2,4,6,8‐dithiatetra‐zocine 1,1,5,5‐tetroxide.
Synthesis of 5,6‐dihydro‐2H‐thiopyrans
Authors: Chen C. H. , Reynolds G. A. , Zumbulyadis N. , Van Allan J. A.
Published: April 2009

Synthesis of 5,6‐dihydro‐2H‐lhiopyrans by mild dehydromesylation of the corresponding tetrahydro‐4H‐thiopyran‐4‐mesylates using commercial grade Woelrn W‐200 (activity, Super 1) neutral alumina is described.Cis‐ andtrans‐stereoisomers of 2,6‐diphenyl‐5,6‐dihydro‐2H‐thiopyrans were prepared for the first lime without isomerization.
Synthesis of Furo[2,3‐c]isoquinoline Derivatives
Authors: Ito Kazuo , Yakushijin Kenichi , Yoshina Shigetaka , Tanaka Akira , Yamamoto Katsumi
Published: April 2009

2‐Methylfuro [2,3‐c] isoquinolin‐5(4H)one (X) and 1‐phenylfuro[2,3‐c] isoquinolin‐5(4H)one (XI) were prepared from thermal cyelization via the Curtius rearrangement of 5‐methyl‐3‐phenyl‐2‐furoyl azide (VI) and 3,4‐diphenyl‐2‐furoyl azide (VII), respectively. Stability against acid, alkylation and conversion of the NHCO group to a C=N double bond of X and XI, which were synthesized, are described. Also, 5‐substituted furo[2,3‐c] isoquinolines (XVIIIa‐c) and (XIXa‐c) were prepared.
A new method for the synthesis of fused 3‐amino‐s‐triazole ring systems
Authors: Lin Yang‐i , Fields T. L. , Lang S. A.
Published: April 2009

Reaction of 2‐methyl‐2‐thiopseudourea sulfate with 1‐hydrazinophthalazine gave 3‐amino‐s‐triazolo[3,4‐a] phthalazine in good yield. 1‐Amino‐4‐methyl‐s‐triazolo[4,3‐a]quinoxaline and 1‐amino‐s‐triazolo[4,3‐a]quinoxalin‐4(5H)one were similarly perpared.
Steroidal pyrazolines
Authors: Catsoulacos Panayotis , Stassinopoulou C. I.
Published: April 2009

Reaction of 21‐benzal‐5‐pregnen‐3β‐ol‐20‐one acetate with phenylhydrazine or p‐methoxy‐phenylhydrazine in the presence of hydrochloric acid yielded 3β‐aeetoxy‐1′,5′ ‐diphenyl‐5‐preg‐neno[20,21‐c]pyrazoline. Alkaline hydrolysis of the 3β‐acetoxy group followed by Oppenauer oxidation furnished the 3‐oxo‐1′,5′‐diphenyl‐4‐pregneno[20, 21‐c]pyrazoline. The ir, nrar and mass spectra are described.
Acetylenic ketones. Part VI. Reaction of aroylphenylacetylenes with hydrazine derivatives
Authors: Baddar F. G. , Al‐Hajjar F. H. , El‐Rayyes N. R.
Published: April 2009

The reaction of aroylphenylacetylenes (I) with acyl‐ or aroylhydrazines (II) gave ω‐aroyl‐acetophenone‐N‐acyl or N‐aroylhydrazones (IV). The latter gave upon treatment with methanolic potassium hydroxide and with acetic anhydride in the presence of sodium acetate, the corresponding pyrazoles (V) and the N‐acetylpyrazoles (VII and VIII), respectively. The acetylenic ketones (1) also reacted with methylhydrazine and 1,1‐dimethylhydrazine to give 5‐aryl‐1‐methyl‐3‐phenylpyrazoles (XII), and 1,1‐dimethylhydrazine derivatives (XIII), respectively. When the latter compounds were heated with acetic anhydride, they gave the N‐methylpyrazoles (XII).
Thiocyanation of indoles
Authors: Tamura Yasumitsu , Kwon Sundo , Chun Moon Woo , Ikeda Masazumi
Published: April 2009

Treatment of indole, 2‐phenylindole, 2‐methylindole, and ethyl indole‐2‐carboxylate with thiocyanogen in acetic acid at 0° afforded the corresponding 3‐thiocyanatoindoles in quantitative yields, whereas similar treatment of 3‐methyl‐2‐phenylindoles and 2,3‐diphenylindoles gave the corresponding 6‐thiocyanatoindoles in high yields.
Reissert compound studies. XXX. Synthesis and alkylation of some new reissert compounds
Authors: Popp Frank D. , Buhts Robert E. , Chesney Dennis K.
Published: April 2009

The synthesis of several new isoquinoline Reissert compounds is described. Alkylation reactions of the anions of these new Reissert compounds and a rearrangement reaction are reported.
Synthesis and reactivity of indolylmethyl cations
Authors: Berti C. , Greci L. , Marchetti L.
Published: April 2009

The synthesis of diindolylmethyl cations by reaction of aldehydes and indoles is described, and their reaction with Grignard reagents, organo‐lithium compounds and sodium borohydride, giving the corresponding diindolyl methanes, is reported. The analogous phenyl indolylmethyl cations could never be isolated, but their formation was proved indirectly.
SN(ANRORC) mechanism XX. Degenerate ring transformations in reactions of 1,2,4,5‐tetrazines with hydrazine
Authors: Counotte‐Potman A. D. , van der Plas H. C.
Published: April 2009

Evidence is presented that the hydrazinolysis of 3‐amino‐ (5) and 3‐bromo‐6‐methyl‐1,2,4,5‐tetrazine (7) into the 3‐hydrazino‐6‐methyl‐1,2,4,5‐tetrazine (6*) with15N‐labelled hydrazine leads to incorporation of15N in the 1,2,4,5‐tetrazine ring. Thus in the hydrazino‐deamination and hydrazino‐debromination a SN(ANRORC) mechanism is operative. Based on quantitative mass spectrometry it was found that 20‐25% of both5and7reacts according to this SN‐(ANRORC) mechanism. The mechanism of these degenerate ring transformations is discussed.
Synthèse et étude conformationnelle de dioxa‐1,3 aza‐9 spiro[5,5]undecanes
Authors: Bassus J. , Anker D. , Pacheco H. , Duplan J. C.
Published: April 2009

La synthèse de nouveaux cycles dioxa‐1,3 aza‐9 spiro[5,5]undécane a été réalisée suivant le schèma représenté dans la figure 2. Les butyrophénones 6 obtenues, ont une activité neuro‐leptique voisine de celle de l'halopéridol. Leur étude pharmacologique fait l'objet d'une publication à part (2). L'étude conformationnelle des dioxa‐1,3 aza‐9 spiro[5,5]undécanes permed de mettre en évidence quatre conformations A, B, C et D, comme le montre la figure 4. L'existence de ces conformations dépend de la nature des substituants R et R' du cycle dioxanne. Ainsi, pour les composés où R ≠ H et R' = H, les quatre conformations sont possibles avec prédominance des formes A et B. Si R et R' sont différents de H, seule la conformation A existe à plus de 99%. Enfin, dans le cas où R = R' = H, les quatre conformations sont possibles avec égalité de population pour les conformères A et B d'une part et C et D d'autre part, A et B étant majoritaires. La présence de la chaîne fluorophénylbutyrique sur l'azote pipéridinique, ne semble pas apporter de modifications stéréochimiques dans la partie hétérocy clique.
The reactions of ethyl 3,4‐dihydro‐4‐quinazolylacetate and its derivatives with cyclopentanone. An attempt at the synthesis of the 6,8‐diazasteroid system VII
Authors: Yamazaki Takao , Matoba Katsuhide , Shirokawa Atsuko , Castle Raymond N.
Published: April 2009

The reaction of ethyl 3,4‐dihydro‐4‐quinazolylacetate (1a) with cyclopentanone in the presence of trifluoroacetic acid gave mainly two decomposition products, carbostyril (VIII) and ethyl 2‐aminocinnamate (IX). Two compounds which are suggested to have the 6,8‐diazasteroid skeleton were also obtained in poor yield. Ethyl 3,4‐dihydro‐2‐p‐methoxyphenyl‐4‐quinazolylacetate (1b), however, gave 2‐p‐methoxyphenylquinazoline (XII) as a decomposition product and did not condense with cyclopentanone. Furthermore, two ethyl 3,4‐dihydroquinazolylacetates substituted at the 2‐position with cyclohexyl (1c) and methyl (1d) groups could not be converted to the expected diazasteroid system.
Substituted 5‐aryl‐ or 5‐diphenylmethyl‐3‐alkyl‐2‐oxazolidones as anticonvulsants
Authors: Jaiswal R. K. , Parmar S. S.
Published: April 2009

Several 5‐aryl‐ or 5‐diphenylmethylhydracrylyl hydrazides were synthesized and converted into 5‐aryl‐ or diphenylmethyl‐2‐oxazolidones. The latter compounds were further alkylated into their corresponding 5‐aryl‐ or 5‐diphenylmethyl‐3‐alkyl‐2‐oxazolidones as possible anticon‐vusants.
Photoinduced fragmentation and rearrangement of phenyl substituted epoxyethylphosphonates
Authors: Griffin Claibourne E. , Kraas Ekkehard , Terasawa Hirofumi , Griffin Gary W. , Lankin David C.
Published: April 2009

An alternative source to phosphonocarbenes is described using phosphorus substituted oxiranes as precursors which compliments the conventional diazo route to these transient species. The results are in accord with previous theories advanced to rationalize the mode of photocyclo‐elimination of a variety of other unsymmetrically substituted oxiranes.
Regiospecific photohydroxyalkylation of pentafluoropyridine
Authors: Sket Boris , Zupan Marko
Published: April 2009

Irradiation of 1‐hydroxyalkane solutions of pentafluoropyridine in the presence of benzo‐phenone resulted in regiospecific substitution at position 4, thus forming 2,3,5,6‐tetrafluoro‐4‐(1‐hydroxyalkyl)pyridine.