Chloro derivatives of 4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one

The chlorination of 4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one with N-chlorosuccinimide takes place at the methylene group to give mono and diehloro derivatives. In the reaction of the diazepinone with sulfuryl chloride chlorine is incorporated in the 1 or 3 position or in both the 1 and 3 positions, as well as in the para position of the phenyl substituent; in the presence of anhydrous aluminum chloride substitution takes place in the methylene group of the heteroring and in the 8 position of the annelated benzene ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 405–409, March, 1982.     

Reaction of 2,3-dihydro-4-phenyl-1H-1,5-benzodiazepinethione-2 with acetylhydrazine

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, p. 1430, October, 1991.     

Vilsmeier reaction with 4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one

4-Phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one reacts with the Vilsmeier reagent to give a 3-dimethylaminomethylidene derivative, the hydrolysis of which leads to 3-formyl-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepinone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 223–225, February, 1984.     

Synthesis and nitration of 4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one

Analysis of the UV spectra of the reaction products shows that in the nitration of 4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one the nitro group is directed to the benzodiazepine ring rather than to the phenyl ring to give a 7-nitro derivative.Translated from Khimiya Geterotsiklieheskikh Soedinenii, No. 4, pp. 525–528, April, 1977.     

Nitration of 8-substituted 2,3-dihydro-1H-1,5-benzodiazepin-2-ones

The nitration of a number of 8-R-4-R-2,3-dihydro-1H-1,5-benzodiazepin-2-ones with substituents in the diazepin (4-R=CH₃, C₆H₅, and C₆H₄OCH₃-p) and benzene (8-R=Cl, Br) rings takes place in the 7 position. The presence in the benzene ring of a strong electron-donor substituent (methoxy group), by determining the direction of electrophilic substitution in the ortho position with respect to it, leads to the formation of 7- and 9-nitro isomers in a ratio of 43.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 551–554, April, 1978.     

Formylation of 4-aryl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones

The formylation of 8-chloro- and 8-methoxy-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones with the Vilsmeier reagent leads to 3-dimethylaminomethylene derivatives which, in the case of the 8-chloro derivative, have been converted by hydrolysis in acetic acid into 8-chloro-3-formyl-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones.Translated from Khimiya Geterotsiklicheskaya Soedinenii, No. 9, pp. 1262–1265, September, 1984.     

Synthesis of 4-Pyridyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones

4-Pyridyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones were obtained by the condensation of ethyl nicotinoyl- or isonicotinoylacetates with o-phenylenediamine. Alkylation of the pyridylbenzodiazepinones with ethyl iodide under phase-transfer catalysis conditions occurred at the amide nitrogen of the heterocycle, whereas in nitromethane it occurred at the nitrogen of the pyridine substituent. Bromination with N-bromosuccinimide occurred at position 3 of the heterocycle. Pyridyldibenzodiazepinones underwent thermal rearrangement to derivatives of vinylbenzimidazole.     

Synthesis of 4-styryl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones

4-Styryl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones were synthesized and their structure was established by means of PMR spectra and mass spectroscopy.Dnepropetrovsk State University Named in Honor of 300th Anniversary of the Reunion of Ukraina and Russia, Dnepropetrovsk 320625. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1560–1562, November, 1987.     

Bromo derivatives of 4-phenyl-2,3-dihydro-1h-1,5-benzodiazepin-2-one

Monobromo and dibromo derivatives were synthesized by bromination of 4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one with bromine under various conditions and with N-bromosuccinimide in CCl₄. 7-Bromo- and 8-bromo-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones were obtained by condensation of 4-bromo-o-phenylenediamine with benzoylacetic ester in refluxing xylene. The UV and PMR spectra of the products are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 411–415, March, 1978.     

Synthesis of ethyl 2-oxo-2,3-dihydro-1H-1,5-benzodiazepine-4-carboxylate

300th Anniversary of the Reunification of the Ukraine with Russia Dnepropetrovsk State University, Dnepropetrovsk 320010. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, p. 854, June, 1991.     

Aromatic derivatives of 2,3-dihydro-1H-1,5-benzodiazepine

The formation of 2,2,4-trisubstituted 2,3-dihydro-1H-1,5-benzodiazepines in the reactions of acetylarenes with 4-ethoxy- and 3,5-dimethyl-1,2-phenylenediamine was studied. The effect of the substituents on the individual stages of the reactions is discussed. A quantum-chemical calculation of the relative nucleophilicity of 1,2-phenylenediamine, 2,3-diaminopyridine, and 3,4-diaminofurazan was undertaken.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 370–375, March, 1987.     

Synthesis of nitro-substituted 4-methyl-2,3-dihydro- and 2,3,4,5-tetrahydro-1H-1,5-benzo-2-diazepinones

The nitration of 4-methyl-2,3-dihydro-1H-1,5-benzo-2-diazepinone gives the 7 nitro derivative. The 8-nitro isomer was obtained from 4-nitro-1,2-phenylenediamine. The catalytic hydrogenation of the nitrobenzodiazepinones gives the 7- and 8-amino derivatives. The nitrobenzodiazepinones exist in the enol form in alkaline media.     

Synthesis and mass spectra of 2,3-dihydro-1H-1,5-benzodiazepine-2-thiones

2,3-Dihydro-1H-1,5-benzodiazepine-2-thiones and their N-methyl and S-methyl derivatives were synthesized. It was demonstrated by means of the IR, UV, PMR, and mass spectra that in solutions with different polarities 1,5-benzodiazepine-2-thiones exist primarily in the thione form; the thione and enamino-thiol forms are the most probable forms in the gas phase.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 396–400, March, 1990.     

A convenient synthesis of 3-alkyl-2,3-dihydro-2,4-dioxo-6-phenyl-, 3-alkyl-2,3-dihydro-4-oxo-6-phenyl-2-thioxo-, and 3-alkyl-2-arylimino-2,3-dihydro-4-oxo-6-phenyl-4H-1,3-thiazines

The reactions of 1-alkylamino-1-alkylthio-3-phenylpropene-3-thiones 3 with thiophosgene and phosgene in toluene, followed by treatment of the reaction mixture with triethylamine gave 3-alkyl-2,3-dihydro-4-oxo-6-phenyl-2-thioxo- 4 , 3-alkyl-2,3-dihydro-2,4-dioxo-6-phenyl-4H-1,3-thiazines 5 , respectively in good to excellent yields. Similarly treatment of compounds 3 with N-arylimidoyl dichloride in benzene at room temperature gave 3-alkyl-2-arylimino-2,3-dihydro-4-oxo-6-phenyl-4H-1,3-thiazines 6 in excellent yields. The reactions of compounds 3 with oxalyl chloride in toluene gave also 5 in good yields.     

Chemical properties of 2,2,4-trisubstituted 2,3-dihydro-1H-1,5-benzodiazepines

Acetylation and nitrosation of 2,4-diaryl-2-methyl-2,3-dihydro-1H-1,5-benzodiazepines take place at the azomethyne nitrogen. Reduction is stereoselective.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1122–1126, August, 1987     

Chlorination of 4-methyl-8-methoxy-2,3-dihydro-1H,1,5-benzodiazepin-2-one

The results of the chlorination of 4-methyl-8-methoxy-2,3-dihydro-1H,1,5-benzodiazepin-2-ones are compared with the results of quantum-chemical calculations of 4-methyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones with various substituents in the benzene ring in the case of homolytic halogenation. The chlorination of 4-methyl-8-methoxy-2,3-dihydro-1H-1,5-benzodiazepin-2-one (I) with N-chlorosuccinimide leads to 3-chloro- and 3,3-dichloro-4-methyl-8-methoxy-2,3-dihydro-1H-1,5-benzodiazepin-2-ones, whereas chlorination with sulfuryl chloride leads to 4-chloromethyl and 3,3-dichloro-4-methyl derivatives. The IR, PMR, and mass spectra of the synthesized compounds are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1272–1274, September, 1981.