Recherches en série diazépine-1,4 et triazépine-1,2,4. XI—etude en spectrométrie de masse des fragmentations de triazépines-1,2,4

The mass spectra of eleven 1,2,4-triazepines with oxo, thioxo, methoxy and methylmercapto groups in the 3 and 5 positions are reported and analysed. Each of the five structures of the triazepine ring present is characterized by a particular group of fragmentations.     

Recherches en série diazépine-1,4 et triazépine-1,2,4. XV. Syntlièse d'halogéno-3(7)-s-triazolo[4,3-b] triazépinones

Halogenation of s-triazolo[4,3-b]triazepinones gas been accomplished by several methods. According to the agents used it has been possible to halogenate the triazepine ring (C-7 carbon) or (and) the triazole ring (C-3 carbon). Thus eighteen halogeno triazolotriazepines have been synthesized and their structures established from the spectral data.     

Recherches en série diazépine-1,4 et triazépine-1,2,4. X. Réductions et méthylations de pyrazolo[3,4-b]diazépines-1,4

Reduction and methylation of pyrazolo[ 3,4-b ]diazepines have been effected by several methods. According to the reducing agents used, it has been possible to reduce selectively the C?N double bond, the carbonyl group, to reduce the diazepinone rings completely and to reduce partially or completely the insaturated parts of the (6H)pyrazolodiazepines. Methylation on the amide nitrogen, on oxygen of the same function, and in a few cases on the C₆ carbon of the pyrazolodiazepinones and finally on the 4 position in tetrahydropyrazolodiazepinones have been obtained.     

Recherches en série triazépine-1,2,4: II — Etude de la réaction de l'acétylacétate d'éthyle avec les diamino-3,4 oxo-5 dihydro-4,5 triazines-1,2,4

The reaction of 3,4-diamino-5-oxo-4,5-dihydro-l,2,4-triazine or its 6-methyl or 6-phenyl substituted derivatives and ethyl acetoacetate gave three compounds: 4,7-dioxo-9-methyl-1,4,6,7-tetrahydro-as-triazino[4,3-b]-1,2,4-triazepine in poor yield, isomeric 4,9-dioxo-7-methyl-1,4,8,9-tetrahydro-as -triazino[4,3-b]-1,2,4-triazepine and by competitive cyclisation, 2-methyl-7-oxo-3,7-dihydro-s-triazolo[3,2-c]-1,2,4-triazine. By condensation of 3-methylamino-4-amino-5-oxo-4,5-dihydro-1,2,4-triazine with ethyl acetoacetate, the formation of 4,9-dioxo-7,10-dimethyl-4,8,9,10-tetrahydro-as-triazino[4,3-b]-1,2,4-triazepine was strongly favored.     

Régio et périsélectivité de réactions de diels-alder et des cycloadditions dipolaires-1,3 avec une triazépine-1,2,4: Approche théorique

e.s The cycloaddition of 1,3-dipoles (mesitonitrile, C,N-dimethylnitrone) and various dienophiles (DMAD, maleic anhydride) to 1,2,4-triazepine 1 are peri and regiospecific. Nitrone excepted the preferred orientation of addition is predicted correctly by FMO/MNDO calculation.     

Nouvelles synthèses de systèmes bicycliques hétéroaromatiques. I. Cycloaddition [4 + 2]π de la diméthyl-2,7 diméthylthio-3,5 triazépine-1,2,4

The cycloaddition of 3,5-dimethylthio-1,2,4-triazepine (1) to various dienophiles has been studied. 4-Phenyl-1,2,4-triazoline-3,5-dione, dimethyl acetylene dicarboxylate and meleic anhydride react with I to give the [4+2]π cycloadduct. The heterocyclic products were found to be formed via 1,3-sigmatropic rearrangement of this cycloadduct.     

Synthèse spécifique de pyrimidines. Formation conccurentielle de pyrimidines et de triazépines

Nucleophilic displacement of ethyl cyanoacetic ester on compounds 1 or 2 with hydrazines yielded only pyrimidines 3, 4 or 11 . Triethyl orthoformate (or triethyl orthoacetate) reacting with o-aminohydrazides produced a mixture of pyrimidines 3 or 11 and the triazepine 10 .     

Nouveaux types de sucres triazotés: triazènes et phénylimino-2-oxadiazoles-1,3,4. Communication préliminaire

Novel types of sugars bearing three nitrogen atoms: triazenes and 2-phenylimino-1, 3, 4-oxadiazoles . A series of aminodeoxysugars treated with p-nitrobenzenediazonium tetrafluoroborate led to the corresponding triazenes, each of which in chloroform solution existing as an equilibrium between its two tautomeric forms. The free energy of activation of the exchange of the proton between the two nitrogen atoms has been estimated by variable temperature ¹H-NMR. measurements. Each triazenylsugar gave on acetylation an unique positional isomer bearing its acyl group on the nitrogen atom directly attached to the glycosyl group. Phenylsemicarbazones of two keto-sugars were oxidized with El Khadem's reagent (I₂, HgO, MgO) to give the corresponding spiro-2-phenylimino-1, 3, 4-oxadiazoles.     

Synthèse de nouvelles amidines bicycliques . Dérivés de la pyrimidine,de la quinazoline et de la diazépine-1,3

The synthesis of pyrrolo[1,2-α] pyrimidines is described. Several homologous compounds contain pyridine or azepine instead of pyrrole ring. They are obtained by cyclization of iminolactams with β-ketoesters, αβ-unsaturated esters, aldehydes or ketones, or diketene. The possibility of obtaining isomers is discussed.     

Pyrrolo[1,2-d]triazines-1,2,4. I. Dérivés pyrroliques

Pyrrole hydrazides and hydrazones were synthesized from pyrrole-2-carboxylic acid and pyrrole-2-carboxaldehyde, The 2-pyrrolyloxadiazoles and thiadiazoles were obtained by cyclising the pyrrole hydrazides with phosphorus oxychloride and tetraphosphorus decasulphide. These derivatives have been used for the synthesis of pyrrolo[1,2-d]-1,2,4-triazines by cyclisation or rearrangement.     

Pyrazolo[1,5-d]triazines-1,2,4. I. Dérivés pyrazoliques

Pyrazole hydrazides and hydrazines were synthesized from pyrazole-5-carboxylic acid, 4-bromopyrazole-5-carboxylic acid and pyrazole-5-carboxaldehyde. The 5-pyrazolyloxadiazoles and 5-pyrazolylthiadiazoles were obtained by cyclising the pyrazole hydrazides with phosphorus oxychloride and tetraphosphorus decasulphide. Cyclisations in 1,2-dihydro-1-oxo- (or l-thioxo)pyrazolo[1,5-d]-1,2,4-triazines were eventually observed. The structures were assignated by nmr.     

Hexahydro-5,6,6a,7,12,14 isoquino[2,3-b]benzazépine-2. Nouvelle voie d'accès

Several hexahydroisoquino[2,3-b][2]benzazepines 1b-e variously substituted at positions 9,10,11 by alkoxy groups have been prepared by the Pictet-Spengler cyclization between formaldehyde and 3-alkoxybenzyl-2,3,4,5-tetrahydro-1H-2-benzazepines 12b-e. The compounds did not show any antitumor activity against leukemia L-1210 cells.     

Etude en série triazénique. IV. Synthèse et réactivité d'aryl-3-(diméthyl-3,4-isoxazolyl-5)-1-triazènes et d'arylazo-4-diméthyl-3,4-isoxazolones-5

Synthesis and reactivity of 3-aryl-1-(3,4-dimethyl-5-isoxazolyl)-triazenes and 4-arylazo-3,4-dimethylisoxazol-5-ones According to the experimental conditions and the nature of the substituents on the aromatic ring, aryldiazonium salts react with 5-amino-3,4-dimethylisoxazole ( 3 ) leading to either 3-aryl-1 (3,4-dimethyl-5-isoxazolyl)-triazenes ( 1A ) or 4-arylazo-3,4-dimethylisoxazol-5-ones ( 4 ). Analyses of the products resulting from thermal decomposition of these triazenes in aromatic substrates and in DMSO and their behaviour in acidic medium show that it is essentially the arylazo form 1B which is reactive.     

Cyclisations par l'intermédiaire de fonctions phénylthioet phénoxy-carbamyle. I. Diphényl-1,2-alcoyl-5-dioxo-3,6-hexahydro-triazines-1,2,4

The N-(p-nitrophenoxy-carbonyl) and N-(phenylthio-carbonyl) derivatives of α-amino-acyl-hydrazides cyclize in presence of diazomethane, yielding hexahydro-1, 2, 4-triazines with simultaneous formation of p-nitro-anisole or thio-anisole respectively. The molecules with a phenoxycarbonyl function such as N-(phenoxycarbonyl)-glycyl-(N, N′-diphenylhydrazide) give the corresponding ring products and anisole only in solvents with high dielectric constant (e.g. nitromethane). The phenylthio-carbonyl derivatives give the same ring products in presence of lead acetate by the intervention of HO^?. The p-nitrophenoxycarbonyl derivatives give rise to the same cyclisations in the presence of pyridine by the intermediate of carbamyle-pyridinium ion acting as electrophile. These different types of intramolecular reactions are illustrated by the formation of 1, 2-diphenyl-5-alcoyl-3, 6-dioxo-1, 2, 4-hexahydro-triazines.