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.     

Transformation of dihydro-1,5-benzodiazepin-2-ones under the influence of acetic anhydride

The acylation of 4-R-2,3-dihydro-1H-1,5-benzodiazepin-2-ones leads to isomerization or opening of the heteroring with subsequent acylation. 1-Acyl-2,3-dihydro-1,5-benzodiazepin-2-ones are not formed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 24, No. 3, pp. 380–385, March, 1988.     

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.     

Tautomerism of the Thioamide Group in 4-Methyl-7-nitro-2,3,4,5-tetrahydro-1,5-benzodiazepine-2-thione

When 4-methyl-7-nitro-2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-2-one were reacted with phosphorus pentasulfide, the corresponding benzodiazepine-2-thione and its thiol tautomer were formed, which via the 2-methylmercapto derivative were converted to 4-(2-acetylhydrazino)-2-methyl-8-nitro-2,3-dihydro-1H-1,5-benzodiazepine.     

On the reaction of 3-nitro-1,2-phenylenediamine with ethyl acetoacetate. Condensed dihydrodiazepinones

Condensation of 3-nitro-1,2-phenylenediamine with ethyl acetoacetate in boiling xylene gave two isomeric 2,3-dihydro-4-methyl-9-nitro- and 2,5-dihydro-4-methyl-6-nitro-1H-1,5-benzodiazepin-2-ones, the 9-nitro derivative thermal rearrangement product N-isopropenyl-4-nitrobenzimidazolone and a non cyclic acetoacetamide derivative. At room temperature these reactants afforded 2,3-dihydro-2-ethoxycarbonyl-methyl-2-methyl-4-nitrobenzimidazole.     

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 spectral properties of n-alkyl-4-methyl-7(8)-nitro-2,3,4,5-tetrahydro-(1h)-1,5-benzodiazepin-2-ones

Alkylation of 4-methyl-7(8)-nitro-2,3,4,5-tetrahydrobenzodiazepin-2-ones under phase transfer catalytic conditions or in dry acetone occurs only at position 1. The 5-alkyl isomers are obtained by reductive alkylation of 4-methyl-7(8)-nitro-2,3-dihydro-1,5-benzodiazepin-2-ones. The UV, IR, PMR, and mass spectra of the isomeric compounds are reported.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 959–963, July, 1992.     

Nucleophilic Substitution in 1,5-Benzodiazepin-2-ones

The reaction of 3-bromo-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one with cyclic amines gives 3-aminoalkyl-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one. Thiazolo[4,5-b][1,5]benzodiazepine was isolated along with the substitution product when thiourea was used.     

5,6,7,8-Tetrafluoro-4-hydroxycoumarin derivatives in reactions with o-phenylenediamine

The reactions of 5,6,7,8-tetrafluoro-4-hydroxycoumarin derivatives with o-phenylenediamine occur with pyrone heterocycle cleavage and formation of substituted benzodiazepin-2-ones. 5,6,7,8-Tetrafluoro-4-hydroxycoumarin affords 4-(3,4,5,6-tetrafluoro-2-hydroxyphenyl)-2,3-dihydro-1H-1,5-benzodiazepin-2-one, 3-acetimidoyl-5,6,7,8-tetrafluoro-4-hydroxycoumarin produces 3-(3,4,5,6-tetrafluoro-2-hydroxybenzoyl)-4-methyl-1,2-dihydro-1H-1,5-benzodiazepin-2-one, and 3-acetyl-5,6,7,8-tetrafluoro-4-hydroxycoumarin yields both these heterocycles.     

Reaction of o-phenylenediamine with acetoacetic and α-chloroacetoacetic esters

The reactivities of acetoacetic and -chloroacetoacetic esters in the reaction with o-phenylenediamine are compared. In contrast to the available data, it was established that in polyphosphoric aicd (PPA) acetoacetic ester is converted to 4-methyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one and ethyl 3-(2-aminoanilino)-crotonate, while chloroacetoacetic ester is converted to 2-methylbenzimidazole. At 20 °C chloroacetoacetic ester is converted to ethyl 2-chloro-3-(2-aminoanilino)crotonate. The conversion of this ester to 2-methyl-3-ethoxy-2,3-dihydro-1H-1,5-benzodiazepin-2-one was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1255–1259, September, 1981.     

Reaction of 2,3-Dihydro-1,5-benzothiazepines and Phenylacetyl Chloride in the Presence of Triethylamine： A New Aspect on the Formation Mechanism of Dihydro-1,3-oxazin-4-one Derivatives

2a,4-Disubstituted 2,2a,3,4-tetrahydro-2-phenyl-1H-azeto[2,1-d][ 1,5]benzothiazepin-1-ones, as well as 2-substi-tuted 2,3-dihydro-3-phenylacetyl-2-styryl-benzothiazoles and 4a,6-disubstituted 3- .benzyl-4a,5-d/hydro-2-phenyl-1H,6H-[1,3]oxazino[2,3-d][1,5]benzothiazepin-1-ones, were obtained from the reaction of 2,4-disubstituted 2,3-dihydro-1,5-benzothiazepines with phenylacetyl chloride in the presence of triethylamine. The mechanism for the formation of 4a,5-dihydro-1H,6H-[1,3]oxazino[2,3-d][1,5]benzothiazepin-1-ones, 2,3-dihydro-1,3-oxazin-4-one derivatives, was suggested.     

Nitration of 7- and 8-methyl-4-R-1H-2, 3-dihydro-1,5-benzodiazepin-2-ones

4-R-8-Methyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones are nitrated in the 7 position, whereas their 7-methyl analogs are nitrated in the 1, 8, or 9 position. The nitration of 4,8-dimethyldihydrobenzodiazepinone proceeds as primary substitution at the N₁ atom of the amide group. The resulting N₁-nitroamide undergoes prototropic rearrangement to the 9-nitro isomer in strongly acidic media.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 122–126, January, 1978.     

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.     

Quinazolines and 1,4-benzodiazepines XXXVI . The formation of 1,3-dihydro and 1,5-dihydro-1,4-benzodiazepines from tosyl and Mesyl - substituted 1,3,4,5-tetrahydro-5-phenyl- 1,4-benzodiazepine derivatives

The treatment of 4-sulfonyl derivatives of 5-phenyl-1,3,4,5-tetrahydro-1,4-benzodiazepin-2-ones (I) with base was shown to result in the formation of 1,3-dihydro or 1,5-dihydro-1,4-benzodiazepin-2-ones (III and II respectively) depending upon the conditions used. The base treatment of 1-sulfonyl substituted 2,3-dihydro-1,4-benzodiazepines (V) was shown to give the vinylimines VI.     

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.     

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.     

Synthesis of 5(and 6)-nitro-4-methyl-2,3-dihydro-1h-1,5-benzo-2-diazepinones

The reaction of 4-nitro-o-phenylenediamine (I) with acetoacetic ester at room temperature under acid catalysis gives ethyl 3-(2-amino-5-nitrophenylamino)crotonate (II), which is readily cyclized to 7-nitro-4-methyl-2,3-dihydro-1H-1,5-benzo-2-diazepinone (III) on heating with alkaline agents. The reaction of I with acetoacetic ester in refluxing xylene gives isomeric 8-nitro-4-methyl-2,5-dihydro-1H-1,5-benzo-2-diazepinone (IVa) or 8-nitro-4-methyl-2,3-dihydro-1H-1,5-benzo-2-diazepinone (IVb), which are readily interconverted. The synthesis of IV is complicated by the side formation of 5-nitro-2-methylbenzimidazole (V) and thermal rearrangement of IVa and IVb to 5-nitro-1-isopropenylbenzimidazolone (VI). 6-Nitro-1-isopropenylbenzimidazolone (VII) is similarly obtained on heating III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 696–699, May, 1972.     

1,4-benzodiazepines and their cyclic homdlogs and analogs

The transformations (acylation, condensation with aldehydes, and diazotization) of 7- and 3-amino-5-phenyl-1,2-dihydro-3H-1,4-benzodiazepin-2-ones are examined. It is shown that the action of P₂S₅ on 3-acetamidobenzodiazepinone leads to replacement of the oxygen atom of the acetyl group by a sulfur atom. The polarographic reduction of 7-arylideneamino-5-phenyl-1,2-dihydro-3H-1,4-benzodiazepin-2-ones was studied.See [8] for communication 29.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 4, pp. 545–549, April, 1979.     

Schmidt Reaction on 2-Aryl-1,2,3,4-tetrahydro-4-quinolone

Synthesis and stereochemistry of 2-aryl-1,2,3,4-tetrahydro-5H-1,4-benzodiazepin-5-one and 2-aryl-2,3-dihydro-4H-tetrazolo [1,5-d]-1H-1,4-benzodiazepine is reported by the Schmidt reaction on 2-aryl-1,2,3,4-tetrahydro-4-quinolone.     

Synthesis and some heterocyclization reactions of new diethyl (1,1-difluoro-3,3-dicyano-2-trifluoromethylallyl)phosphonate and ethyl 3,3-dicyano-2-[(diethoxyphosphoryl)difluoromethyl]acrylate

A new CF₂X-analogue of 1,1-bis(trifluoromethyl)-2,2-dicyanoethylene (X = P(O)(OEt)₂), diethyl (1,1-difluoro-3,3-dicyano-2-trifluoromethylallyl)phosphonate, has been synthesized from diethoxyphosphoryl pentafluoroacetone 1. A similar phosphoryl analogue of ethyl 3,3-dicyano-2-trifluoromethylacrylate, ethyl 3,3-dicyano-2-[(diethoxyphosphoryl)difluoromethyl]acrylate, has been obtained from ethyl 3-(diethoxyphosphoryl)-3,3-difluoro-2-oxopropionate 2. By heterocyclization of these new ethylenes with 3-methyl-2-pyrazoline-5-ones, 3(5)-aminopyrazoles, dimedone, 2-aminopyridines, 1-aryl-3-methyl-5-aminopyrazoles, 1,3,3-trimethylisoquinolines, as well as by condensation with anilines and ketones, the difluoromethylphosphonate-substituted derivatives of 1,4-dihydropyrano[2,3-c]pyrazole, 4,5-dihydropyrazolo[1,5-a]pyrimidine, 5,6,7,8-tetrahydro-4H-chromene, 2H-pyrido[1,2-a]pyrimidine, 4,7-dihydro-1H-pyrazolo[3,4-b]pyridine, 1,4-dihydropyridine, 4,5,6,7-tetrahydro-1H-[1]pyrindine, 1,4,5,6,7,8-hexahydroquinoline, and 6,7-dihydro-2H-pyrido[2,1-a]isoquinoline have been obtained in one stage.