bluuebunny/crossref_metadata_2025 huggingface dataset:
Identification of the addition products formed in the chlorination of benzofuran
Authors: Baciocchi Enrico , Clementi Sergio , Sebastiani Giovanni V.
Published: April 2009

The cis and trans isomers of 2,3‐dichloro‐2,3‐dihydrohenzofuran have been prepared and their reactions studied in the presence and in the absence of bases. Some data on the influence of the experimental conditions on the stereochemical course of the reaction are also reported.
Synthesis and tautomeric structure of some 2H‐pyrazolo[3,4‐d]pyridazines
Authors: Shawali Ahmad Sami
Published: April 2009

A number of substituted 2H‐pyrazolo[3,4‐d]pyridazines, pyridazin‐7(6H)ones, and ‐pyrid‐azine‐4,7(5H,6H)diones have been prepared from the 3,4‐diacyl‐, 3‐carbethoxy‐4‐acyl‐, 3‐carbethoxy‐4‐cyano‐, and 3,4‐dicarbethoxy‐pyrazole derivatives and hydrazine hydrate. The structures of the compounds prepared were inferred from their elemental analyses and spectral data. On the basis of spectroscopic data it was concluded that pyrazolopyridazinones have the oxo form, whereas the monohydroxymono oxo structure is preferred for pyrazolopyridazine‐diones.
The mass spectrometric fragmentation patterns of some biologically active 1,3,4‐thiadiazoles
Authors: Kirkien‐Rzeszotarski Alicja M. , Rzeszotarski W. J.
Published: April 2009

Mass spectra of some twelve derivatives of 1,3,4‐thiadiazole are reported. The fragmentation scheme of the 1,3,4‐thiadiazole ring is specific and indicative as to the structure. Derivatives of 5‐phenyl‐1,3,4‐thiadiazoles show rearrangement to isothiocyanates.
Analogs of sparteine. IV. Mass spectral features of a series of N, N′‐disubstituted bispidines
Authors: Ruenitz Peter C. , Smissman Edward E. , Wright Deborah S.
Published: April 2009

The mass spectra of a series of N, N′‐disubstituted bispidinc derivatives have been investigated, and salient features analogous to those seen in the spectra of related azabieyelie compounds observed. The most important feature observed in the spectra is the common base peak (m/e 58), which results from the generation of N, N‐dimethylformimmonium ion 24. The pathway by which this ion originates is discussed.
Oxidation reactions of 3,4,5‐triamino‐1,2,6‐thiadiazine 1,1‐dioxide. Preparation of 3,5‐diamino‐4H‐1,2,6‐thiadiazin‐4‐one 1,1‐dioxide
Authors: Garcia‐Muñoz G. , Ochoa C. , Stud M.
Published: April 2009

Oxidation reactions of 3,4,5‐triamino‐1,2,6‐thiadiazine 1,1‐dioxidc with hydrogen peroxide and chromium trioxide are reported. 3, 5‐Diamino‐4H‐1,2,G‐thiadiazin‐4‐one 1,1‐dioxide is synthesized by different methods.
Anionotropic shift of the 3‐substituent in the reaction of 2‐methoxy‐2,3‐dihydro‐3‐benzofuranols with boron trifluoride
Authors: Caranti Luisa , Zecchi Gaetano , Pagnoni Ugo M.
Published: April 2009

The reaction of 2,3‐dihydro‐3‐benzofuranols 1a,c,d,f with boron trifluoride in boiling xylene gave 3‐(2H)benzofuranones 2a,c,d,f in 40‐85% yield. This reaction was not observed in the case of 1b,e.
Réactivité de l'hypochlorite de tertiobutyle dans l'oxydation du benzothiophene
Authors: Ceneste P. , Olivé J. L. , Ung S. N.
Published: April 2009

Dans la réaction avec le benzothiophéne, l'hypochlorite de tertiobulyle se comporte á la fois comme réactif d'oxydation et réaetif de chloration. On obtient un mélange de chloro‐3 benzothiophéne, de trois sulfoxydes isoméres du dichloro‐2,3 dihydro‐2,3 benzothiophéne (trans‐anti; trans‐syn; cis‐anti) et de sulfoxyde du chloro‐2 benzothiophéne. Avec un excés important d'hypochlorite, la réaction conduit au dichloro‐2,3 benzothiophene etaux sulfoxydes du dichloro‐2,3 benzothiophéne, du trichloro‐2,2,3 dihydro‐2,3 benzothiophéne et du dichloro‐2,2 oxo‐3 benzothiophéne. L'oxydation s'arrěte toujours au stade du sulfoxyde.
Synthése par deux voies différentes d'un systéme dihétérocyclique apparenté aux peltogynoides
Authors: Deschamps‐Vallet Colette , Meyer‐Dayan Michéle , Andrieux Jean , Riboulleau Jacques , Bodo Bernard , Molho Darius
Published: April 2009

Certaines plantes de la famille des Légumineuses contiennent des composés du type flavonique désignés par le terme “peltogynoides”, tous rattachés au squelette fondamental: [2]benzo‐pyrano[4,3‐b][1]benzopyranne, mais á divers degrés d'oxydation. Ce sont done, mis á part les substituants hydroxyles ou methoxyles des noyaux aromatiques, les dérivés de type 1:

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Condensation du méthane disulfochlorure avec quelques diamines 1,2 et 1, 3 études des hétérocycles obtenus
Authors: Vincent Michel , Remond Georges , Volland Jean‐Paul
Published: April 2009

En milieu dilué, la condensation du méthane disulfochlorure avec quelques orthophenyléne‐diamines conduit aux benzo [e] dithiadiazépines‐1,3,4,7 tétroxyde‐2,2,4,4. Dans les měmes conditions, l'amino‐2 chloro‐5 benzhydrylamine conduit á un hétérocycle homologue. L'un des composés a donné lieu á une fragmentation intéressante par spectrométrie de masse.
Base‐catalyzed hydrolysis of 6‐aminopenicillanic acid. The kinetic and thermodynamic products
Authors: Carroll R. D. , Jung S. , Sklavounos C. G.
Published: April 2009

In the presence of sodium hydroxide or a β‐lactamase, 6‐APA has been shown to hydrolyze rapidly at room temperature to penicic acid 3, the kinetic product of the reaction. In a subsequent equilibration 3 isomerizes at C‐5, by way of intermediate imine 4, affording 5‐epi‐penicic acid 6 as the major hydrolysis product (∼ 95% at equilibrium). The pH and temperature parameters of equilibration are discussed and HPLC, optical rotation, proton nmr and 13C nmr data are presented.
Lithiation of 1‐benzenesulfonylimidazole. Characterization of authentic 2‐lodoimidazole
Authors: Sundberg Richard J.
Published: April 2009

Lilhiulion of 1‐betizenesulfonylimidazole takes place readily at −20° or 0° in THE. The lithium reagent gives products of addition to typical carhonyl compounds but only in low yield, lodination occurs at the 2‐position, in low yield, and authentic 2‐iodoimidazole is obtained by cleavage ol the henzenesulfonyl group.
Reinvestigation of the synthesis of 5‐arylamino‐2‐picolines
Authors: Peterson Louis H. , Tolman Richard L.
Published: April 2009

Reaction of 5‐bromo‐ or 3‐bromo‐2‐methylpyridine with o‐nitroaniline gave the corresponding N‐[2‐methyl‐5(or 3)pyridyl]‐o‐nitroanilines. Reduction to the corresponding amino derivatives and ring closure to 1‐[2‐methyl‐5(or 3)pyridyl]benzotriazole allowed the structures to be confirmed and an earlier literature report to be corrected. Displacement of bromide by anthranilic acid from 5‐bromo‐2‐methylpyridine and decarboxylation gave N‐(2‐methyl‐5‐pyridyl)aniline.
Neighboring group participation in cyclodehydration. A regiospecific isoxazole synthesis
Authors: Crawley L. S. , Fanshawe W. J.
Published: April 2009

The regiospecific synthesis of isoxazoles 2, 11, 14, and 15 is explained in terms of neighboring group participation of the ortho nitrogen of the heterocyclic ring in the cyclodehydration step.
1,2,3‐Selenadiazolyl‐1,3,4‐oxadiazole, 1,2,3‐Thiadiazolyl‐1,3,4‐oxadiazole and 5‐(1,2,3‐Thiadiazolyl)‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazoles
Authors: Shafiee A. , Lalezari I. , Mirrashed M. , Nercesian D.
Published: April 2009

A series of 5‐substituted‐2‐(4‐alkyl or phenyl‐1,2,3‐thia(or selena)diazol‐5‐yl)‐1,3,4‐oxadiazoles were prepared. 5‐Substituted‐2‐(4‐phenyl‐1,2,3‐selenadiazol‐5‐yl)‐1,3,4‐oxadiazoles upon pyrolysis afforded the corresponding alkynes. Also, a series of 5‐substituted‐4‐amino‐3‐(1,2,3‐thiadiazol‐5‐yl)‐s‐triazoles and 5‐(1,2,3‐thiadiazolyl)‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazoles were prepared.
Synthèse et structure de triazoline‐1,2,4 thiones‐5 possédant en 3 ou 4 un substituant dialkylaminoèthyle
Authors: Hénichart Jean‐Pierre , Houssin Raymond , Lablanche Brigitte
Published: April 2009

L'addition d'un hydrazide sur un isothiocyanate conduit à la formation d'un acylthiosemi‐earbazide. Lorsque I'un des composés de départ posséde une chaǐne dialkylaminoéthyle, une hétérocyclisation en triazolinethione s'effectue d'emblée.

Une étude physicochimique de quelques‐uns de ces composés de cyclisation est reportée et un mécanisme permettant d'interpréter leur fragmentation en spectrographie de masse est proposé.
6‐ And 7‐Substituted 4H‐Pyrido[1,2‐a] pyrimidin‐4‐ones. Synthesis via the Acid‐catalyzed Isomerization of 2‐(Acetoacetamido)pyridines
Authors: Yale Harry L. , Spitzmiller E. R.
Published: April 2009

A novel procedure has been developed for converting a variety of substituted 2‐(aceto‐acetamido)pyridines into substituted 4H‐pyrido[1,2‐a]pyrimidin‐4‐ones. The reaction involves an acid‐catalyzed isomerization of the 2‐(acetoacetamido)pyridine derivatives into the corresponding enamines, under conditions that permit the latter to undergo cyclization to the 4‐one, in situ. The method has been employed to prepare a number of hitherto unknown 2,6‐ and 2,7‐di‐ and 2,7,9‐trisubstituted 4H‐pyrido[1,2‐a]pyrimidin‐4‐ones.
An Investigation on the thermolytic conversions of 5‐Diazouracils into 1,2,3‐Triazoles
Authors: Thurber T. Craig , Townsend Leroy B.
Published: April 2009

The thermolysis of 5‐diazo‐6‐methoxy‐1‐methyl‐1,6‐dihydrouracil (1) has afforded methyl N‐(1‐methyl‐1,2,3‐triazol‐4‐oyl)carbamate (2), bis‐(1‐methyl‐1,2,3‐triazol‐4‐oyl)amine (3) and di‐methylcarbimate (4). The reaction was shown to proceed with the initial formation of 2 followed by a subsequent disproportionation of 2 to give 3 and 4. A similar thermolysis of 5‐diazo‐6‐ethoxy‐1‐methyl‐1,6‐dihydrouracil (9) gave ethyl N‐(1‐methyl‐1,2,3‐triazol‐4‐oyl)car‐bamate (10) as the sole product. Double labeling experiments have indicated that a major pathway for these reactions involves an intermolecular transfer of the C‐6 substituent to the C‐2 position.
N‐substitution in the 2‐amino‐ and 2,7‐diaminophenoxazin‐3‐one ring system. Application to the preparation of actinomycin D analogs
Authors: Chaykovsky Michael , Modest Edward J. , Sengupta Sisir K.
Published: April 2009

A method is described for the direct N2‐monoalkylation of the 2‐aminophenoxazin‐3‐one system by treatment with dimethylsulfonium methylide in DMSO‐THF, which acts as a base by abstracting a proton from the 2‐amino function to form a stabilized anion, which is then alkylated by reaction with an alkyl halide. Selective N7‐monoalkylation of the 2,7‐diaminophenoxazin‐3‐one system can be accomplished by reaction with aromatic aldehydes in glacial acetic acid to give Schiff bases, which are then reduced with dimethylamine borane. These reactions have been applied to the preparation of N2‐benzyl‐ and 7‐benzylaminoactinomycin D.
Synthesis of tris and tetraisoxazole compounds
Authors: Auricchio S. , Ricca A. , De Pava O. Vajna
Published: April 2009

The syntheses of new tris (XII) and tetraisoxazole compounds (XIII and XIV) are reported; all synthons have been described. New isoxazole chlorooximes (V and VIII) have been prepared for this purpose and their behavior was examined.
Fused s‐Triazino heterocycles. VI. 1,9,9b‐Triazaphenalenes
Authors: Shaw John T. , Prem Suzanne
Published: April 2009

Derivatives of 1,9,b‐triazaphenalene have been prepared by reacting alkyl‐N‐cyanoimidates with 2,6‐bis(cyanomethyl)pyridine.
The reaction of 1,2‐dioxo‐1,2‐dihydropyrrolo‐[3,2,1‐kl] phenothiazine with amines
Authors: Pinto Ângelo C. , Hollins Richard A.
Published: April 2009

The title compound I reacts with aliphatic amines producing ring‐opened keto‐amides of structure VII and with anilines forming imines of structure VIII.
Fused‐s‐triazino heterocycles. VII. 1,3,5,7,9b‐Pentaazaphenalene and 1,3,4,6,8,9b‐hexaazaphenalene
Authors: Shaw John T. , Kyler Keith S. , Anderson Mark D.
Published: April 2009

Cyclization of 2,6‐diaminopyrazine to two new heterocyclic ring systems, 1,3,5,7,9b‐pentaazaphenalene and 1,3,4,6,8,9b‐hexaazaphenalene is reported.
A simple synthesis of 8‐(trifluoromethyl)‐2,3,5,6,11,12,14,15‐octahydro‐1H,4H,10H, 13H‐diquinolizino[9,9a,1‐bc:9′,9a',1‐hi] xanthylium perchlorate, an efficient dye
Authors: Haley Laser N. F.
Published: April 2009

A one‐step procedure is described for the preparation of the title compound I, an efficient laser dye operating in the red region.
2,3‐Fused 1,8‐Naphthyridines
Authors: Thummel Randolph P. , Kohli Dalip K.
Published: April 2009

The Friedlander condensation of 2‐aminonicotinaldehyde with cyclic ketones leads to the preparation of 2,3‐fused 1,8‐naphthyridines. The spectral properties and basicities of these molecules are discussed.
Synthesis of 2‐amino‐5,6‐dihydro‐4H‐1,3‐thiazines and related compounds by acid catalyzed cyclization of allylic isothiuronium salts
Authors: Cohen Noal , Banner Bruce L.
Published: April 2009

Several allylic isothiuronium salts 6 have been shown to yield 4‐substituted 2‐amino‐5,6‐dihydro‐4H‐1,3‐thiazines (2; R3 = H) and the 2‐phenylimino compound 10 on exposure to trifluoroacetic acid or trifluoroacetic acid‐stannic chloride. The overall process constitutes a convenient transformation of readily available ketones or aldehydes 3 into the target hetero‐cycles. The scope and limitations of this approach are discussed in terms of carbenium ion intermediates (7). Whereas this method successfully led to the imidazo[2,l‐b][1,3]thiazine 13 (93% from 12), its application to the synthesis of 2‐amino‐2‐thiazolines (eg. 14→ 15) or imidazo‐[2,1‐b]thiazoles (eg. 16 → 17) was unsuccessful. The 2‐acetylimino derivatives 9 were found to be useful for purification of the 2‐aminothiazines.
Tetrazoles from N‐(4‐dimethylaminophenyl)nitrones and hydrogen azide
Authors: Moderhack Dietrich
Published: April 2009

The reaction of N‐(4‐dimethylaminophenyl)nitrones, 1, with hydrogen azide proceeds via three distinct pathways to give a mixture of two tetrazoles, 5 and 9, and a 2‐azido‐4‐dimethyl‐aminoaniline derivative, 6. The proportions largely depend on the electron‐withdrawing force resident in the function R attached to nitrone carbon. The formation of 5 constitutes a new synthetic approach to 1,5‐disubstituted tetrazoles.
[1] Benzofuro [2,3‐d] pyridazines II. Etude des benzofuropyridazones
Authors: De Sévricourt Michel Cugnon , Robba Max
Published: April 2009

La dihydro‐1,2 oxo‐1 [1] benzofuro [2,3‐d] pyridazine et la dihydro‐3,4 oxo‐4 [1] benzofuro [2,3‐d] pyridazine sont synthétisées par cyclisation de I'hydrazine avec des dérivés benzofuran‐niques earbonylés. Une autre voie d'accés, mettant en oeuvre la tétrabydro‐1,2,3,4 dioxo‐1,4 [1] benzofuro [2,3‐d] pyridazine et la tetrahydro‐1,2,3,4 oxo‐4 [1] benzofuro [2,3‐d] pyridazine, a été mise en oeuvre. La strueture d'une benzofuropyridazone‐4 nitrée sur l'homoeyele a été établie par application de l'effet Overhauser.
Recherches sur le benzofuranne, LVII. Sur une chloration inhabituelle de l'hétérocycle au cours de la réduction des (nitro‐4 phényl)‐2 ou ‐3 benzo‐furannes par le chlorure stanneux
Authors: Demerseman Pierre , Flad Geneviéve , Platzer Nicole , Royer Et René
Published: April 2009

Les réductions des (nitro‐4 phényl)‐2 et (nitro‐4 phényl)‐3 benzofurannes par le chlorure stanneux en présence d'acide chlorhydrique fournissent non seulement les (amino‐4 phényl)‐2 et (amino‐4 phényl)‐3 benzofurannes attendus mais aussi les (amino‐4 phényl)‐2 chloro‐3 et (amino‐4 phényl)‐3 chloro‐2 benzofurannes dont les structures sont démontrées notamment par leurs spectres de rmn du 13C établis en comparaison de ceux des phényl‐2 et phényl‐3 benzofurannes. Ces chlorations parasites á la réduction precédent vraisemblablement d'un mécanisme radical aire.
Reaction of piperidine and morpholine with 2H‐pyran‐2‐ones, 2H‐thiopyran‐2‐ones, 2H‐pyran‐2‐thiones, and 2H‐thiopyran‐2‐thiones. A novel route to thiophene derivatives
Authors: El‐Kkoly Ibrahim El‐Sayed , Mishrikey Morcos Michael , Fuid‐Alla Hassan Mostafa
Published: April 2009

The reaction of piperidine or morpholine with 2H‐pyran‐2‐ones was found to give open chain δ‐oxoamides, while with 2H‐thiopyran‐2‐ones, thiophene derivatives were formed. For 2H‐pyran‐2‐thiones, either open chain δ‐oxothioamides or thiophene derivatives were obtained. From the 1 H nmr data of the pyran derivatives, the effect of the replacement of ring and carbonyl oxygens with sulphur on the chemical shift of the H‐3 proton could be studied.
The crystal and molecular structure of the cycloadduct from an activated carbodiimide and methyl isothiocyanate
Authors: Schaumann Ernst , Kausch Erwin , Klaska Karl‐Heinz , Klaska Rolf , Jarchow Otto
Published: April 2009

The crystal and molecular structures of the cycloadduct from isopropyl[α‐(dimethylthio‐carbamoyl)isopropyl]carbodiimide and methyl isothiocyanate were determined by single‐crystal X‐ray methods. The product was established to be 2‐(1‐isopropyl‐3,5‐dimethyl‐4,6‐dithioxo‐hexahydro‐1,3,5‐triazine‐2‐ylidenamino)‐N,N‐dimethylthioisoburyramide, in which contrary to expectations based on hybridisation the heterocyclic ring adopts a boat conformation.
Recherches sur le benzofuranne. LIX. Orientation de l'aroylation de l'éthyl‐2 benzofuranne selon la nature du chlorure d'aroyle utilise
Authors: Astoin Jacques , Demerseman Pierre , Platzer Nicole , Royer Et René
Published: April 2009

Contrairement aux chlorures d'alcanoyle et á certains chlorures d'aroylt: trés agressifs ou encombrés au voisinage du carbonyle qui réagissent exclusivement en 3 avec l'éthyl‐2 benzofuranne, la plupart des autres chlorures d'aroyles l'attaquent egalement en 6 et accessoirement en 4.
Synthesis of dimethoxybenz[g]isoquinolines
Authors: Menon C. S. , Zee‐Cheng Robert K.‐Y. , Cheng C. C.
Published: April 2009

Stobbe condensation of 2,3‐dimethoxybenzaldehyde with diethyl succinate, followed by reduction and cyclization, gave 3‐carbethoxy‐5,6‐dimethoxy‐l‐tetralone (7a). Subsequent reduction, aromatization and side chain conversion yielded the key intermediate 7,8‐dimethoxy‐2‐naphthalenecarboxaldehyde (8c). 6,7‐Dimethoxybenz[g]isoquinoline (1) was prepared from 8c via condensation with nitromethane, reduction, formylation, cyclization, and aromatization reactions; the isomeric 8,9‐dimethoxybenz[g]isoquinoline (2) was obtained by the condensation of 8c with the diethyl acetal of aminoacetaldehyde (12) followed by reduction, tosylation, cyclization and aromatization. The methiodides of both compounds were also prepared.
Synthesis of 1‐amino‐5‐phenyl‐4,5‐dihydro‐3H‐2‐benzazepines and the isomeric 2‐amino‐1‐benzazepines
Authors: Kukla Michael J.
Published: April 2009

The title amidines (1 and 2) were synthesized. A synthesis of lactam 10 free of isomeric 4 is described. An interesting rate difference in displacement of thiomethyl ether intermediates 5 and 11 with amines was observed.
2‐(Methylpyridyl or quinolyl)benz‐X‐azoles
Authors: Barni Ermanno , Savarino Piero
Published: April 2009

In view of the preparation of heterocyclic polymethine dyes, 2‐(methylpyridyl or quinolyl)‐benz‐X‐azoles were synthesized with the general reaction between carboxylic acids (or derivatives) and o‐bifunctional compounds. The electronic spectra and the methyl proton chemical shifts are briefly discussed.
Quaternization of 2‐aziridino‐5‐chlorobenzophenone, an efficient synthesis of medazepam
Authors: Mihalić M. , Šunjić V. , Kajfež F. , Žinić M.
Published: April 2009

Quaternization of 2‐aziridino‐5‐chlorobenzophenone (1) with methyl iodide resulted in formation of 2‐(N‐β‐iodoethyl‐N‐methyl)aminobenzophenone (2), via an unstable quaternary compound. Rate constants for 1 → 2 conversion, as determined by an nmr method at 35 ± 0.1°, varied between 0.22 × 10−3 sec−1 in DMSO‐d6, and 0.95 × 10−6 sec−1 in methanol‐d4. Ammonolysis with hexamine, and subsequent cyclization afforded 7‐chloro‐l‐methyl‐5‐phenyl‐2,3‐dihydro‐lH‐1,4‐benzodiazepine (3, generic name medazepam) in 92% over‐all yield.
Stacked double‐macrocyclic ligands II. Synthesis of cofacial diporphyrins
Authors: Chang C. K. , Kuo Ming‐Shang , Wang Ching‐Bore
Published: April 2009

A new class of dimeric porphyrin ligands and their metal complexes have been prepared by an unambiguous and high‐yield synthetic scheme.
Condensation of o‐aminophenol and α‐dicarbonyl compounds. Part 2. Dibenzoxazolines
Authors: Belgodere E. , Bossio R. , Parrini V. , Pepino R.
Published: April 2009

The study of 2′‐aryl‐2,2′‐dibenzoxazolines (II), obtained together with 2‐hydroxy‐(2H)‐1,4‐benzoxazines (1) by condensation of o‐aminophenol with a series of phenylglyoxal derivatives, emphasized that these compounds are an equilibrium mixture of dibenzoxazolines and related tautomeric ketimine forms. This behaviour was widely investigated by ir, uv and pmr spectroscopy. J. Heterocyclic Chem., 14, 957 (1977)
Cycloadditions dipolaires 1,3. XXIX. Addition de deux esters nitroniques isomères à diverses défines. Etude de la régiosélectivitè et du mode d'approche du dipolarophile par le dipôle
Authors: Grée René , Carrié Robert
Published: April 2009

Les cycloadditions dipolaires 1,3 de deux esters nitroniques isomères géométriques à diverses oléfines mono, di et trisubstituées sont áetudiées. Pour chaque réaction, rorientation e la cycloaddition est unique et conforme aux prévisions théoriques. Les modes d'approche de ces dipolarophiles par les deux esters nitroniques sont établis dans la plupart des cas. IIs sont discutès a l'aide de propriétés des orbitales frontières des réactifs. J. Heterocyclic Chem., 14, 965 (1977)
Synthesis of a tetraazacyclotetradecadiene and a pentaazacyclotetradecatriene
Authors: Griffiths David , Hull Roy
Published: April 2009

Useful procedures for preparing a novel tetraazacyclotetradecadiene and a pentaazacyclotetradecatriene are reported. J. Heterocyclic Chem., 14, 1097 (1977)
The reaction of indole and the indole grignard reagent with phosgene. A facile synthesis of indole‐3‐carboxylic acid derivatives
Authors: Bergman Jan , Carlsson René , Sjöberg Birger
Published: April 2009

Indole‐3‐carboxylic acid (as well as indole‐3‐glyoxylic acid) derivatives are readily prepared from indoles (including oxindoles) and phosgene (oxalyl chloride), respectively. The interaction of these reagents with the indole Grignard reagent afforded several products including the cyclo‐tetramers, 21 and 30. Indolo‐fused heterocycles can be readily prepared from the reaction of phosgene (or oxalyl chloride) with suitable reactants. Thus e.g., phosgene and 2‐(2‐hydroxy‐phenyl)‐N‐methylindole readily gave 5,6‐dihydro‐11‐methyl‐6‐oxobenzo[a]pyrano[4,3‐b] indole (33).
Synthesis of 4‐substituted 1,4‐benzodiazepine‐3,5‐diones
Authors: Stavropoulos G. , Theodoropoulos D.
Published: April 2009

Synthetic routes leading to the preparation of 4‐substituted 1,4‐benzodiazepine‐3,5‐diones are described. Thus, 2‐carbobenzoxyaminobenzoic acid was converted to its p‐nitrobenzyl ester (I) and the decarbobenzoxylated product (II) gave, with ethyl α‐bromoacetate, N‐(2‐carboxy p‐nitrobenzylate)phenylglycine ethyl ester (III). The latter was hydrogenolyzed to N‐(2‐car‐boxy)phenylglycine ethyl ester (IV), which was coupled with benzylamine to give N‐(2‐carboxy‐benzylamido)phenylglycine ethyl ester (VIa). Saponification of VIa afforded N‐(2‐carboxy‐benzylamido)phenylglycine (VIIa) which was cyclized with DCCI to produce 4‐benzyl‐2H‐1,4‐benzodiazepine‐3,5(lH,4H)dione (VIIIa). Alternatively, 2‐nitro‐N‐phenylbenzamide (Xb) was reduced to 2‐amino‐N‐phenylbenzamide (XIb) which was converted to N‐(2‐carboxanih'do)‐phenylglycine ethyl ester (VIb). The latter was converted to 4‐phenyl‐2H‐1,4‐benzodiazepine‐3,5(1H,4H)dione (VIIIb) in an analogous fashion described for VIIIa.
Synthesis of 2‐amino‐3‐carbethoxy‐1‐hydroxyindoles
Authors: Munshi K. L. , Kohl H. , De Souza N. J.
Published: April 2009

A general method is described for the synthesis of 2‐amino‐3‐carbethoxy‐l‐hydroxyindoles by the reductive cyclization of 2‐nitrophenylcyanoacetates using zinc and acetic acid at temperatures of 15–28°.
Synthesis of 2,4,6‐trinitrophenyl derivatives of heterocyclic compounds
Authors: Dacons Joseph C. , Sitzmann Michael E.
Published: April 2009

The preparation of 2,4,6‐trinitrophenyl (picryl) derivatives of triazine, pyrimidine, thiophene, furan, thiazole, 1,3,4‐oxadiazole and 1,3,4‐thiadiazole is described. The picryl derivatives are prepared by the Ullmann reaction and by cyclization reactions to form the heterocyclic ring.
Novel fused‐ring derivatives of 2‐methyl‐3‐o‐tolyl‐4(3H)quinazolone; Quinazolino [3,2‐a] [1,4] benzodiazepines
Authors: Harrison D. R. , Kennewell P. D. , Taylor J. B.
Published: April 2009

The synthesis of some quinazolino[3,2‐a][1,4]benzodiazepines from 2‐bromomethyl‐3‐o‐carbomethoxyphenyl‐4(3H)quinazolone is described. Alkylation and acylation of N‐6 led to a series of novel derivatives of this ring system.
Novel bicyclo[2.2.2]octanyl‐1,4‐benzodiazepinones. Their syntheses and rearrangement to bicyclooct‐2‐enylbenzimidazoles
Authors: Fairhurst J. , Horwell D. C. , Timms G. H.
Published: April 2009

The synthesis of the novel bicyclo[2.2.2]octanyl[1,4]benzodiazepinone ring system (IV) and its facile acid catalysed rearrangement to the corresponding bicyclo[2.2.2]oct‐2‐enylbenzirnid‐azole system (IX) is described.
The synthesis and spectra of new (E)‐(trans) and (Z)‐(cis)‐1‐alkyl‐2‐aryl (alkyl) ‐ 3 ‐aroylaziridines
Authors: Tarburton Philip , Wolpa Lori J. , Loerch Robert K. , Folsom Thomas L. , Cromwell Norman H.
Published: April 2009

The synthetic scope of the reaction of primary amines with α,β‐dibromochalones to form aroylaziridines is explored and found to require at least one hydrogen on the α‐carbon of the amine. Fourteen new epimeric l‐alkyl‐2‐aryl(alkyl)‐3‐aroylaziridines are synthesized accordingly. Next, representative aroylaziridines are investigated by infra‐red spectroscopy in solvents of ambient polarity to assess the relative populations of the gauche and cisoid conformers present in the (Z)‐(cis) series.
Synthesis of some 7‐α‐carboxyethyl‐1,3‐dihydro‐(2H)‐1,4‐benzodiazepin‐2‐ones
Authors: Žinić M. , Kolbah D. , Blažević N. , Kajfež F. , Šunjić V.
Published: April 2009

1,4‐Benzodiazepin‐2‐ones possessing an α‐carboxyethyl group in 7‐position (21‐25) were prepared from a key compound, 2‐amino‐5‐α‐carboxyethylbenzophenone (8) or from its O‐benzyl derivative 14, using methods developed previously. An optimized route to 8 starting from 2‐nitro‐5‐chlorobenzophenone (1), as well as some unsuccessful attempts are described. Compound 8 was deaminated into racemic α‐(3‐benzoyl)‐phenylpropionic acid (9), a well‐known antiinflammatory agent.
The diazotization of 1‐aminophenazine
Authors: Olson Edwin S.
Published: April 2009

An investigation of why 1‐aminophenazine fails to form a diazonium salt which will couple with β‐naphthol revealed that the phenazine‐1‐diazonium cation reacts rapidly with water to give l‐diazo‐2(lH)phenazinone (1), whose coupling ability has been demonstrated to be very weak. A similar reaction occurred with 2‐aminophenazine.
A convenient synthesis of 2‐chromonecarboxylic acids
Authors: Pifferi Giorgio , Gaviraghi Giovanni , Pinza Mario , Ventura Paolo
Published: April 2009

Knoevenagel condensation of the β‐ketosulfinyl intermediate II with butyl glyoxylate afforded the butyl 2‐hydroxy‐4‐(2‐hydroxyphenyl)‐3‐methylsulfinyl‐4‐oxobutyrates (III). Compounds III are versatile intermediates for the synthesis of either 2‐chromonecarboxylates (V) or 2‐carboxy‐methylene‐3‐coumaranone esters (VII).
Synthesis of Bi‐ and tridentate imidazole ligands
Authors: Sundberg Richard J. , Mente Donald C. , Yilmaz Ibrahim , Gupta Goutam
Published: April 2009

A number of imidazole derivatives were prepared in the course of studying the limits of carbon‐metal bond formation in complexes of imidazole with first‐row transition metals. Seven of the compounds were new. The 4‐ and 5‐methyl and 4,5‐dimethyl derivatives of l‐(2‐pyridyl)‐imidazole were prepared by reaction of the appropriate imidazole with 2‐bromopyridine. Alkylation of imidazole, 4,5‐dimethylimidazole, and benzimidazole with 2‐chloromethylpyridine gave a series of 1‐(2‐pyridylmethyl)imidazoles. 1‐(2,3‐Diaminopropyl)imidazole was prepared in six steps via a Gabriel sequence.
Syntheses of “oxidized” hemopyrrole and kryptopyrrole: Porphyric monopyrroles
Authors: Wooldridge T. A. , Lightner D. A
Published: April 2009

Straightforward, short synthetic procedures have been developed to produce gram quantities of 4,5‐dimethyl‐3‐ethyl‐5‐hydroxy‐3‐pyrrolin‐2‐one (1) and 3,5‐dimethyl‐4‐ethyl‐5‐hydroxy‐3‐pyrrolin‐2‐one (2), which are, respectively, the oxidized hemopyrrole and kryptopyrrole factors associated with psychiatric and prophyric disorders.
Stacked double‐macrocyclic ligands III. Spectral properties of cofacial diporphyrins as a function of the inter‐chromophore separation
Authors: Chang C. K.
Published: April 2009

Three homologous cofacial diporphyrins that have interplanar distances ranging from 6.4Å to 4.2Å have been synthesized. Their absorption and emission spectra revealed strong exciton coupling in the diporphyrin. Magnesium complexes of diporphyrins were studied and their application as a model for P700 photoactive center was discussed.
Reaction of vinyl ketoximes with N‐bromosuccinimide. Synthesis of isoxazoles and 4‐bromoisoxazolines
Authors: Hansen John F. , Strong Scott A.
Published: April 2009

The reaction of some selected α,β‐unsaturated oximes with N‐bromosuccinimide gave isoxazoles or 4‐bromoisoxazolines in moderate to good yields.
1H‐pyrrolo[3,2‐c]pyridin‐4,6(5H,7H)dione(3,7‐dideazaxanthine)
Authors: Schneller S. W. , Hosmane R. S.
Published: April 2009

A facile chemical synthesis of 1H‐pyrrolo[3,2‐c]pyridin‐4,6(5H,7H)dione (3,7‐dideazaxanthine) has been accomplished from ethyl 3‐ethoxycarbonylpyrrole‐2‐acetate.
An improved synthesis of 3‐deazaeytosine, 3‐deazauracil, 3‐deazacytidine, and 3‐deazauridine
Authors: Dan Cook P. , Day Robert T. , Robins Roland K.
Published: April 2009

3‐Dcazacytosine (4‐amino‐2‐pyridone, 3), 3‐doazauracil (4‐hydroxy‐2‐pyridone, 5), 3‐deaza‐cytidine (4‐amino‐1‐β‐D‐ribofuranosyl‐2‐pyridonc, 9), and 3‐deazauridine (4‐hydroxy‐1‐β‐D‐ribo‐furanosyl‐2‐pyridone, 11) were prepared in high overall yields from 1‐methoxy‐1‐buten‐3‐yne (1). Ethyl 3,5,5‐triethoxy‐3‐pentenoate (2), obtained from acylatioti of 1 with diethyl carbonate and subsequent in situ conjugate addition of ethoxide, was cyelized with ammonia to provide 3. Diazotization of 3 and subsequent in situ hydroxydediazotization afforded 5. Nucleoside 9 was obtained from the stannic chloride‐catalyzed condensation of bis‐trimethylsilylated 3 and 1‐O‐acetyl‐2,3,5‐tri‐O‐benzoyl‐β‐D‐ribofuranose (7), followed by ammonolysis of the blocking groups. Diazotization of 9 and subsequent in situ hydroxydediazotization afforded nucleosidc 11.
Etude expérimentale et théorique de la substitution de N‐méthyl‐halogéno‐triazoles‐1,2,4 par les réactifs nucléophiles
Authors: Maury Georges , Fkih‐Tétouani Souad , Arriau Jean , Sauvaǐtre Henri , Bernardini Antoine
Published: April 2009

L'étude cinétique de la substitution des N‐méthyl‐halogénotriazoles‐1,2,4 isoméres par la pipéridine et l'ion méthoxyde rnontre que l'isomère méthyl‐1 halogéno‐5 est plus réactif que lisomère mèthyl‐4 halogéno‐3, le moins réactif étant l'isomère mèthyl‐1 halogéno‐3. L'applica‐tion de diverses méthodes de calcul théoriques montre que l'examen des charges frontières et le modèle à liaison délocalisée traduisctit le mieux les différences tie réuetivité constatées expéri‐mentalement.
Synthesis of some benzimidazole, benzoxazole and benzothiazole derivatives. Action of aliphatic selenonesters on some o‐phenylenediamine, o‐amino‐phenol and o‐aminothiophenol and their derivatives
Authors: Cohen Victor Israel , Pourabass Soraya
Published: April 2009

Aliphatic selenonesters react with o‐phenylenediamine, o‐aminophenol and o‐aminothiophenol and their derivatives to form benzimidazole, benzoxazole and benzothiazole derivatives, respectively. The mass and nmr spectra of the mentioned compounds were studied.
Cyclization of ylidenemalononitriles. X. Synthesis of benzazapropellane derivatives from α‐Cyano‐β‐chloroalkylcinnamonitriles
Authors: Campaigne E. , Mehra Ravindra K.
Published: April 2009

The reaction of nucleophilic and non‐nucleophilic bases wtih 2‐carbamoyl‐3‐(γ‐chloropropyl)‐1‐indenone (5) have been investigated. Condensation of γ‐chlorobutyrophenone with malono‐nitrile afforded α‐cyano‐β‐(3‐ehloropropyl)cinnamonitrile which was cyclized in concentrated sulfurie acid to produce 5. Two other products obtained from the cyclization reaction were 2‐carbamoyl‐3‐(γ‐ehloropropylidene)‐1‐indanone (4) and α‐carbamoyl‐β‐(3‐chloropropyl)cinnam‐amide.

Treatment of a solution of 4 in ethyl acetate with piperidine resulted in cyclization of the γ‐chloropropyl side chain to give 2‐carbamoyl‐3‐cycIopropyl‐1‐indanone. The same compound was obtained in improved yield by the treatment of 4 or 5 with sodium hydroxide solution. The reaction of dirnethylamine with 5 in benzene gave initial Michael addition of the amine followed by internal alkylation of the carbanion so formed to yield 3a‐dimethylamino‐2,3,3a,8‐tetrahydro‐8‐oxoeyclopent[a]indene‐8a(lH)earboxamide (7a). Similarly addition of ammonia, pyrrolidine, piperidine, benzenethiol, p‐toluenethiol, 2‐naphthalenethiol and nitromethane to the indenone I gave respective analogs of type 7.

Treatment of 5 with sodium cyanide in aqueous t‐butyl alcohol resulted in a similar Michael addition followed by internal alkylation. In addition, cyclization between the nitrile and the carbamoyl functions occurred in the same step to give 2‐oxo‐4‐imino‐7,8‐benzo‐3‐aza[3.3.3]‐propellan‐6‐one (13a). Hydrolysis of the iminopyrrolido ring in 13a to the corresponding suecin‐irnide gave 2,4‐dioxo‐7,8‐benzo‐3‐aza[3.3.3]propellan‐6‐one (13b). Reactión of 13b with methyl iodide, allyl bromide, benzyl bromide, and diethyluminoethyl chloride afforded the corresponding N‐alkylated products. A similar sequence starling with δ‐ehlorovalerophenone led to 5,6‐fused ring systems, including a [4.3.3]propellane. 2,9‐Dioxo‐4‐methyl‐7,8‐benzo‐3‐aza[4.3.3]propell‐4‐ene was obtained by the reaction of 5 with acetone in dilute alkali.
Condensation of ethyl phenylpropiolate with some cyanoacetyl and cyanomethylene heterocycles
Authors: Al‐Jallo Hikmat N. , Al‐Biaty Ibtisam A. , Al‐Azawi Fatin N.
Published: April 2009

N‐Cyanoacetyl pyrrolidine, piperidine and morpholine reacted with ethyl phenylpropiolate to give the rearranged Michael addition products III. Some interesting results obtained from the bromination, hydrolysis and reduction of III are reported. 2‐Thiophene and 2‐furaneaceto‐nitriles reacted with ethyl phenylpropiolate to give the Claisen addition products XVIII. Reaction of either III or XVIII with hydrazine hydrate, phenylhydrazine and hydroxylamine hydrochloride afforded 3‐phenylpyrazol‐5‐one, 1,3‐diphenylpyrazol‐5‐one and 3‐phenylisoxazol‐5‐one together with the appropriate starting cyanoacetyl or cyanomethylene compounds, respectively. The mechanism for the formation of the various reaction products beside the ir and nmr spectral results are discussed.
Substituted 2,3‐dihydro‐4(1H)quinazoIinones, 2
Authors: Yale Harry L.
Published: April 2009

Details are given for the reaction of isatoic anhydrides with different primary aromatic amines to give several new N‐aryl‐o‐aminobenzamides. The latter were annulated with a variety of dialkyl and alkyl aryl ketones to give 2,3‐dihydro‐4(1H)quinazolinones. Several novel and efficient procedures for effecting the cyclization are described.
Synthetische untersuchungen zum reaktionsverhalten von 2‐phenyl‐5‐oxo‐5H‐naphtho[1,8‐bc] thiophen — thia‐pseudophenalenon
Authors: Neidlein R. , Kraemer A. D.
Published: April 2009

The reactivity of 2‐phenyl‐5‐oxo‐5H‐naphtho[1,8‐bc]thiophene (1) with the N‐sulfonyl‐heterokumulenes (2a‐2c, 2d‐2e. 2f‐2k) was of interest. We obtained the N‐sulfonylimino‐pseudophenalenones (5a‐5k). Phenylisocyanate and m‐chlorophenylisocyanate reacted with 1 only in the presence of the Lewis acid anhydrous aluminum chloride to give the derivatives 6a and 6b. From diphenylketene (7) and 1 we obtained the pseudophenafulvene 8, and from the fluorenketene (9) and 1 we obtained the pentapseudophenafulvalene 10.
Reaktionsverhalten von 2‐brom‐thiapseudophenalenon und 2‐brom‐thia‐pseudophenaleniumtetrafluoroborat
Authors: Neidlein R. , Seel H.
Published: April 2009

The reactivity of the 2‐bromothiapseudophenalenone (1) 2‐bromo‐5H‐naphtho[1,8‐bc]‐thiophen‐5‐one and of the 2‐bromothiapseudophenalenium salt (2) 2‐bromo‐5‐ethoxynaphtho‐[1,8‐bc]thiolium‐tetrafluoroborate towards the N‐nucleophilic compounds R‐NH2 (3) or R‐NH‐NH2 and the C‐nucleophilic molecules e.g., malonodinitrile, barbituric acid was of interest. We obtained the substituted hydroxyiminothiapseudophenalenone derivatives 4a‐g, 6a‐g, 7, 8, 9, 11a‐o, 12 and 14.
Mass spectra of some 1,2,4‐triazine 1‐ and 2‐oxides
Authors: Radel Robert J. , Keen Brian T. , Paudler William W.
Published: April 2009

A study of the fragmentation patterns of a variety of substituted 1,2,4‐triazine 1‐ and 2‐oxides has been undertaken. It is shown that the fragmentation patterns of the 1‐ and 2‐oxides are extremely similar with the relative peak intensities varying with the type of substituents present.
Conjugate acid structure for oxaziridines bearing primary and secondary 2‐alky 1 groups
Authors: Challis Brian C. , Lobo Ana M.
Published: April 2009

The protonation of five representative oxaziridines is reported for inert solvents (deuterio‐chloroform or carbon tetrachloride) where conjugate acid formation may be effected by the addition of about 20% (v/v) TFA. Comparison of the 1H nmr chemical shifts for neutral and conjugate acid forms suggests that oxaziridines usually undergo protonation on the N‐atom under these conditions. For one compound studied, 2‐ethyl‐3‐p‐nitrophenyloxaziridine, there is a possibility that protonation occurs on the alternative O‐atom. The relevance of these findings to the mechanism of the acid‐catalysed hydrolysis of oxaziridines is discussed.
Synthesis of bis(arylsuh'onyl)furoxans from aryl nitromethyl sulfones
Authors: Kelley James L. , Mclean Ed W. , Williard K. F.
Published: April 2009

The synthesis of some symmetrically substituted bis(arylsulfonyl)furoxans from aryl nitromethyl sulfones is reported.
13C Nmr analysis of 5‐amino‐1,2,3,4‐thiatriazoles and thiatriazolinethione
Authors: L'Abbé Gerrit , Toppet Suzanne , Willocx André , Mathys Georges
Published: April 2009

The usefulness of 13C nmr spectroscopy in the tautomeric assignment of 5‐(monosubstituted)‐amino‐1,2,3,4‐thiatriazoles is demonstrated. The reaction products, derived therefrom by alkylation, acylation and sulfonylation, are also readily characterized by an inspection of the 13C5 signal shift. For thiatriazolinethione, the 13C nmr spectrum indicates the presence of a thioketone function (6, δ 193.1 ppm) instead of a thiol function (7).
2‐Pyridylenamines via transenamination
Authors: Yale Harry L. , Spitzmiller E. R.
Published: April 2009

Transenamination, a reaction apparently not previously described in the literature, has been employed to prepare a series of 2‐pyridylenamines. The products were formed in 11‐78% yield by the reaction of substituted 2‐arninopyridines, 1a‐g, and either methyl 3‐aminocrotonate, 2, or ethyl 3‐aminocinnamate, 3, in anhydrous toluene, under reflux. Data from these reactions would suggest that the reaction rates and consequently, the yields, were adversely affected by substitution that served to decrease the basicity of the amino group in either reactant.
Derivatives of 2‐sulfonamido‐4.5‐dimetlioxyphenylacetic acid and their oxazolines and aminoesters
Authors: Catsoulacos P. , Camoutsis Ch.
Published: April 2009

Series of variously substituted aminoesters and oxazolines of 2‐sulfonamido‐4,5‐clirnethoxy‐phenylacetic acid have been prepared and some of them screened for biological activity.
The origin of syn/anti selectivity in the cycloaddition reactions of 7‐substituted norbornadienes
Authors: Alston P. V. , Ottenbrite R. M.
Published: April 2009

Generalizations which permit the prediction of the syn/anti selectivity in the [π4s + π2s] cyeloadditions of 7‐substituted norbornadienes has been developed from perturbation molecular orbital theory. These theoretical predictions are in excellent agreement with all the experimental results reported in the literature. Furthermore, the effect of the 7‐substituent of norbornenes on the double bond has been explained by the “through‐space” interactions between the substituent and the syn‐double bond.
Carbon‐13 nuclear magnetic resonance spectra of potent antimalarials: Primaquine and chloroquine
Authors: Singh S. P. , Parmar S. S. , Stenberg Virgil I.
Published: April 2009

C13 Nmr chemical shits of primaquine and chloroquine are reported. The signals are assigned on the basis of substituent effects on benzene shifts, intensities, multiplicities in SFORI) and the comparison with structurally related compounds.
Cyclic imides. XI. Bisimide charge‐transfer polymers
Authors: Caswell Lyman R. , Palacios Patricia , Schmidt Suzanne J. , Anvar Roya , García Anabel
Published: April 2009

Condensation of two equivalents of an aromatic cyclic anhydride with an aromatic diamine, or of two equivalents of an aromatic amine with an aromatic bisanhydride, results in the formation of an aromatic bisimide. Thirty‐one such bisimides were prepared. The bisimides in which the two imide groups arc connected by a fully coplanar system show extremely low solubilities and high melting and decomposition temperatures. Many are also strongly colored. It is suggested that these properties may result from intermolecular charge‐transfer effects in the solid slate, giving charge‐transfer polymers.
Reaction of substituted selenoureas with dimethyl acetylenedicarboxylate
Authors: Shafiee A. , Assadi F. , Cohen V. I.
Published: April 2009

Mono and 1,3‐disubstituted selenoureas react with dimethyl acetylenedicarboxylate to give in high yield substituted 3,4‐dihydro‐4‐oxo‐2H‐1,3‐selenazines whose structures were established by speclroscopic methods.
The insertion and extrusion of heterosulfur bridges. V. Desulfurization of dibenzothiophene by means of methanol and molybdena catalysts
Authors: Klemm L. H. , Karchesy Joseph J.
Published: April 2009

Desuliurization of dibenzothiophene is effected in 82% yield by means of methanol and a sulfidcd cohaltous oxide‐molylxlic oxide‐aluminum oxide catalyst at 450° and ca. one atmosphere pressure in a flow system. The methanol serves as a hydrogen donor and methylating agent to form biphenyl (main product), 3‐ and 4‐methylbiphenyls, and fluorene.
Chemistry of the phenoxathiins. III. Synthesis of benzo[1″,2″:5,6:5″,4″:5′,6′]bis[1,4]oxathiino[3,2‐b:3′,2′‐b']dipyridine
Authors: Martin Gary E. , Turley James C. , Miller Richard F. , Schram Karl H. , Williams Louis
Published: April 2009

As a result of studies dealing with the synthesis of 1‐azaphenoxathiins, the synthesis of benzo[1″,2″:5,6:5″,4″:5′,6′]bis[1,4]oxathiino[3,2‐b:3′,2′‐b']dipyridine was examined. Unique evidence of solvent participation in the synthesis of these compounds by the structure elucidation of a novel minor by‐product formed during the synthesis of the title compound is also reported.
Synthesis of 4H‐furo[3,2‐b]indoles. II. Bromination, acylation and nitration of 4H‐ and 4‐benzoylfuro[3,2‐b]indoles
Authors: Tanaka Akira , Yakushijin Kenichi , Yoshina Shigetaka
Published: April 2009

Monobromination and monoacylation at the 2‐position of 4H‐furo[3,2‐b]indole ring (III) were facilitated by the benzoyl group in the 4‐position; subsequent nitration attempts were unsuccessful.
Oxazolo analogs of the actinomycin D chromophore
Authors: Sengupta Sisir K. , Tinter S. Karin , Modest Edward J.
Published: April 2009

Condensation of a tricyclic phenoxazin‐2‐amino‐3‐one (a model for the actinomycin D ring system) with acetaldehyde or benzaldehyde or with pyruvic acid as an acetaldehyde precursor gave tetracyclic 5H‐oxazolo[4,5‐b]phenoxazines. The pyruvic acid reaction proceeds efficiently in one step. The latter compounds were oxidized in a novel reaction by 2,3‐dichloro‐5,6‐dicyano‐benzoquinone exclusively at position 8 in the benzenoid ring. Uv, ir, nmr, and mass spectrometric data are reported.
Influence d'une fonction ester ou acide portée par la chaîne alcoxyle sur la réactivité des sels de N‐alcoxypyridinium envers les ions cyanures
Authors: Sliwa Henri , Tartar André
Published: April 2009

L'étude de la réactivité, vis à vis des ions cyanures, de sels de N‐alcoxypyridinium portant une, fonction ester en ‐α dans leur chaine alcoxyle, montre que la formation de cyanopyridines est concurrencée par une décomposition en pyridine et ester α‐carbonylé, dont l'importance croît avec l'acidité de l'hydrogène‐α de cette chaîne alcoxyle. Une réactivité normale s'observe pour le sel 3 à carbone ‐α tertiaire, malgré l'encombrement stérique qu'il présente, et qui entraîne un accroissement de la proportion de cyano‐4 pyridine formée, au détriment de la cyano‐2 pyridine isomère. Les sels à fonction acide en ‐α ou en ‐β présentent une réactivité considérable‐ment plus faible, résultant d'une diminution du pH du milieu réactionnel et de la formation d'une bétaïne, moins réactive que l'ion pyridinium. L'existence de cette bétaïne sous une conformation repliée rendrait compte d'une réactivité relative plus grande du sommet −4 du cycle par rapport au sommet −2.
Alcoylation d'acridanone‐9. Premiers exemples de O‐alcoylation dans cette série de composés
Authors: Blanchard Christiane , Fabre Jean‐Marc , Montginoul Claude , Chaffia Brat Ali , Torreilles Eliane , Giral Louis
Published: April 2009

Les résultats de différentes réactions de substitution de la méthoxy‐2 acridanone‐9 ont été interprétés sur la base d'une compétition entre les deux sites nucléophiles N et O de la molécule. Ils constituent les premiers exemples de O‐alcoylation d'acridanone‐9 substituéte.
Reduction studies on benzaza[3.3.3]propellanc derivatives
Authors: Campaigne E. , Mehra R. K.
Published: April 2009

Sodium borohydride reduction of 3‐methyl‐2,3‐dioxo‐7,8‐benzo‐3‐aza[3.3.3]propellan‐6‐one (1b) gave 2,4‐dioxo‐3‐methyl‐7,8‐benzo‐3‐aza[3.3.3]propellan‐6‐ol, while lithium aluminum hydride reduction gave 3‐methyl‐7,8‐benzo‐3‐aza[3.3.3]propellan‐6‐ol, which on oxidation, gave the corresponding ketone. This ketone formed the corresponding thioketal upon reaction with 1,2‐ethanedithiol. Raney nickel desulfurization of the thioketal provided 3‐methyl‐6,7‐benzo‐3‐aza[3.3.3]propellane. The same compound was also obtained in poor yield by forming the thioketal of Ib followed by lithium aluminum hydride reduction and Raney nickel desulfurization of the product. Desulfurization of the thioketal of Ib gave 2,4‐dioxo‐6,7‐Benzo‐3‐aza[3.3.3]propellane.
Photochemistry of some quinoxaline 1,4‐dioxides
Authors: Jarrar Adil A.
Published: April 2009

The photochemical reactions of some 2,3‐diarylquinoxaline 1, 4‐dioxides are described. A mechanistic interpretation of the experimental results is also offered.
Structure moléculaire et propriétés moléculaires de quatre isomères de formule C8H10N4
Authors: Delettré Jean , Bally Renée , Mornon Jean‐Paul , Alcalde Ermitas , De Mendosa Javier , Faure Robert , Vincent Emile‐Jean , Elguero José
Published: April 2009

Les structures moléculaires de trois isomères décrits par Meyer [méthyl‐3 (amino‐5′ rnéthyl‐3′ pyrazolyl‐1)‐3 acrylonitrile; azine de l'acétylacétonitrile; diméthyl‐2,5 amino‐7 pyrazolo[1,5‐a]pyrimidine] ont été déterminées et comparées à celle du quatrième isomère, dimèthyl‐2,7 amino‐5 pyrazolo[1,5‐a]pyrimidine. Des calculs CNDO/2 et CNDO/S ont été effectués utilisant comme base ces géométrìes pour déterminer les paramètres suivants: transitions électroniques, moments dipolaires, potentiels d'ionisation, charges et indices de liaison, énergies totales. On compare les valeurs calculées à une série de grandeurs expérimentales: spectres uv, déplacements chimiques 13C, constantes de couplage JHH et stabilité relative des quatre isomères.
Benzomorphan related compounds. V. Synthesis of thienomorphans
Authors: Alvarez M. , Bosch J. , Cranados R. , López F.
Published: April 2009

A series of thieno [2,3‐ƒ]‐, [3,2‐ƒ]‐ and [3,4‐ƒ]morphans prepared both by the Grewe synthesis and by the reaction of 2‐cyanopyridines with 3‐thienyllithium is described. Furthermore, a new synthetic route to thieno [2,3‐ƒ] morphans from 3‐ketotetrahydrolhiophene is reported. Separation and assignment of the α‐ and β‐diastereomerie structures by means of nmr data is reported. Some side products were isolated and their structures were confirmed on the basis of their spectral data. Mechanisms for their formation are proposed.