V. A. Budylin

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.

Reaction of 3-indolylphenyliodonium betaine with electrophilic agents

Abstract3-Indolylphenyliodonium chloride and bromide, respectively, were obtained by the action of hydrochloric and hydrobromic acids on 3-indolylphenyliodonium betaine. Pyrolysis of the chloride leads to a mixture of 2- and 3-chloroindoles, while pyrolysis of the bromide leads only to 3-bromoindole. 1-Benzyl-2-chloroindole is obtained in the reaction of the betaine with benzyl chloride. The betaine reacts with dimethyl sulfate to give an iodonium salt, the reaction of which with lithium chloride and ammonium chloride leads to 1-methyl-2-chloroindole.

Ring formation during the reaction of aromatic diamines with acetoacetic acid esters

It is shown that the reaction of aromatic o-diamines having a nitro group in the para position relative to one of the amino groups with acetoacetic esters under mild conditions gives arylaminocrotonates, which are isomerized to ketimines under the influence of acid, are cyclized to dihydro-1,5-benzodiazepinones on heating, and are converted to 1-isopropenylbenzimidazolones under more severe conditions. If the condensation of the nitrodiamine with the acetoacetic acid esters is carried out under severe conditions, the isomeric dihydro-1,5-benzodiazepinone is obtained. Splitting out of an alkylacetate ester to give the corresponding 2-methylbenzimidazole occurs in the condensation of various o-diamines with 2-alkylacetoacetic esters.

Preparation of opticaly active 3-(1-methyl-1-phenylpropyl)indole and investigation of its chiral-optical properties

Optically active 3-(1-methyl-1-phenylpropyl)indole was obtained by dehydrogenation of the resolved [by means of (L)-10-camphorsulfonic acid] 3-(1-methyl-1-phenylpropyl)indoline. The chiral-optical properties of this product were investigated, and the possibility of the use of circular dichroism data for the identification of the chiral indole chromophore was demonstrated.

Peculiarities of nucleophilic substitution in indolyliodonium salts

Abstract3-Indolylphenyliodonium trifluoroacetate reacts with ammonium bromide and lithium chloride and bromide to give 3-haloindoles. The reaction with ammonium chloride and tetrabutylammonium chloride leads to a mixture of 2- and 3-chloroindoles. The same mixture of chloroindoles is also formed by the action of lithium chloride but in the presence of 15-crown-5 ether. The course of the reaction is explained by ambident reaction of the cation of the iodonium salt.

Mechanism of migration of an acyl group in the pyrrole ring of indole

The isomerization of deuterium-labeled (in position 3) 2-acylindoles in polyphosphoric and trifluoroacetic acids was studied. It is shown that migration of the acyl group from position 2 to position 3 is accompanied by an intramolecular hydride shift.

Synthesis and spectral properties of 1-aryl-2-formylpyrroles

Various 1-aryl-2-formylpyrroles were synthesized by reaction of furfurol with substituted anilines. For p-bromo- and p-chlorophenylsubstituents, the intermediate Schiff bases were isolated.

Spatial structure of derivatives of 1-nitrophenylpyrroles

Combined 1H and 13C NMR data were used to show that 2-carbonyl derivatives of 1-nitrophenylpyrroles (aldehydes, acids, esters, and amides) have primarily the S-trans-configuration. Oximes of 1-nitrophenyl-2-formylpyrroles exist as a mixture of S-trans-syn- and S-cis-anti-isomers.

Asymmetrical alkylation of 1-[(s)-α-phenylethyl]-azethidinone-2

The methylation of the lithium derivative of azethidinone-2 which has a chiral substituent at the nitrogen atom is asymmetrical and leads, with an optical yield of 35%, to diastereomeric 3-methylated azethidinones-2. The reaction of these compounds with Na in liquid ammonia gives enantiomeric 3-methylazethidinones which confirms that an asymmetrical synthesis has taken place.

Synthesis of 1-(α-phenylethyl)azetidin-2-ones

Phase-transfer catalyzed cyclization of racemic and optically active N-substituted β-aminoacids has given racemic and optically active 2-azetidinones, the spatial structures of which have been established by NMR spectroscopy. The original β-aminoacids were obtained by adding α-phenylethylamine to substituted acrylic acids.