Generation of benzocyclobutadiene derivatives from zirconaindene derivatives

Zirconaindene derivatives produced benzocyclobutadiene derivatives in situ in the presence of CuCl and 1,4-naphthoquinone, which afforded their dimers, 6a,10b-dihydrobenzo[a]biphenylenes and dibenzosemibullvalenes or dibenzo[a,e]cycloctenes.     

Azaindole derivatives

It is shown that it is possible to synthesize 1-acyl-4-methyl-7-azatryptamines from ethyl (4-methyl-7-aza-3-indolyl)acetate through 3-(-chloroethyl)-4-methyl-7-azaindole with subsequent acylation by replacement of halogen by a nitro group and reduction. The N-acetyl group is cleaved in the reaction of 1-acetyl-3-(-chloroethyl)-4-methyl-7-azaindole with ammonia, bis (dimethylmethoxysilyl)amide potassium salt, and potassium phthalimide (with subsequent removal of the phthalimide protective group).See [1] for communication XLII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1370–1373, October, 1973.     

Isoquinoline derivatives

Condensation of p-alkoxybenzoyl chlorides with 1-phenyl-1-aminomethylcyclopentane affords the amides V. Subsequent cyclization and hydrogenation gives the corresponding tetrahydroisoquinoline derivatives VIII and secondary amines VI. The hydrochlorides of compounds VIII and VI possess moderate hypotensive activity, and also reduce by an average of 50% the spasms of segments of intestine, induced by barium chloride.     

Indole derivatives

The behavior of some 3-nitrovinyl indoles in their reactions with nitrogen-containing nucleophilic reagents is examined. It is shown that hydroxylamine, phenylhydrazine, hydrazine, and semicarbazide react with 3--nitrovinyl indole to give the corresponding oxime, phenylhydrazone, azine, and semicarbazone of indole-3-aldehyde, possibly by decomposition of intermediates formed by the addition of the nucleophilic reagents to the nitrovinyl indole. 3--Nitropropenyl indole and N-methyl-3--nitrovinyl indole react similarly. Only the addition products of phenylhydrazine with N-acetyl-3-nitrovinyl indole and N-acetyl-3--nitropropenyl indole are stable. The reaction conditions and constants of the compounds prepared are given, and explanations are offered for the results obtained.For part XXXV, see [14].     

Indole derivatives

Depending on the pH, 1-(1-indolinyl)-3-aryltriazenes (I) or 5-arylazoindolines (II) are formed in the reaction of indoline with aryldiazonium salts. In acid media, I are rearranged to II. The dehydrogenation of I or II with chloranil gives 5-arylazoindoles.See [1] for communication LXXVI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 648–651, May, 1972.     

Acetylene derivatives

Summary The conditions were found for the hydration of 4-alken-2-ynylamines, and by this means several previously inaccessible -amino ketones were synthesized in high yield; such amino ketones are of interest for the synthesis of 4-piperidones and of some physiologically active compounds, in particular anesthetics.     

Cubane derivatives

New substituted cubane-1,4-dicarboxamides and 4-bromocubanecarboxamides containing the nitroxyl group and amino acid fragments along with the cubane skeleton were synthesized. The cardiac pharmacological activity (both the effect on aorta relaxation and the calcium channel blocking activity) of most of nitroxyalkyl derivatives is equal to or higher than that of N-(2-nitroxyethyl)nicotinamide (nicorandil).     

Cubane derivatives

A precision X-ray structural investigation of 1,4-dimethoxycarbonylcubane at 218 K was carried out. Analysis of the experimental maps of deformational electron density indicates the existence of partial electron density transfer from the cage bonds to the C_cubane-COOR bonds and the shift of the electron density to the symmetrical (relative to the COOMe planes) cube faces.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1210–1213, July, 1993.     

Azaindole derivatives

1-Benzyl-6-hydroxy-7-cyano-5-azaindoline, which was converted to 6-chloro-5-azaindoline through 6-hydroxy-5-azaindoline, was synthesized from O-methylbutyrolactim through 1-benzyl-2-pyrrolidone, 1-benzyl-2-cyano (carbamoylmethylene)-pyrrolidine, and the product of its condensation with dimethylformamide diethylacetal.See [1] for communication LII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 355–358, March, 1978.     

Indole derivatives

2-(1-Octen-1-yl)indole was obtained by the Wittig reaction, and the product was used to prepare ethyl 7-[2-(1-octen-1-yl)-3-indolyl]-7-ketoheptanoate and the acid itself, which are possible model compounds in the synthesis of indole analogs of prostaglandins.     

Indole derivatives

A method for the introduction of a 3-indolyl group in compounds with an active methylene group was developed. The corresponding 3-indolyl diketones were obtained by condensation of 1-acetyl-3-indolinone with dimedone, 4-hydroxycoumarin, 1,2-diphenyl-3,5-pyrazolinedione, and barbituric and thiobarbituric acids and subsequent alkaline hydrolysis of the condensation products. The existence of cyclic six-membered 3-indolyl diketones in the enol form and of cyclic five-membered 3-indoly diketones in the keto form was shown by IR and UV spectroscopy. Depending on the conditions, (1-acetyl-3-indolyl)cyanoacetamide, 1,3-bis(1-acetyl-3-indolyl)-1,3,3-tricyano-2-amino-1-propene, and 1-acetyl-3-indolylmalononitrile are obtained in the condensation of 1-acetyl-3-indolinone with malononitrile. 1-Acetyl-3-indolylmalononitrile exists in equilibrium with the keteneimine form and in protic solvents is converted to 3-cyano-8-acetylpyrrolo[2,3-b]indole by intramolecular cyclization.See [1] for communication CX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 360–368, March, 1977.     

Hydroxylamine derivatives

The condensation of urethane and ethyl acetohydroximate with 2-chloromethyl-1-methylbenzimidazole has given, respectively, N-ethoxycarbonyl-O-(1-methylbenzimidazol-2-ylmethyl)hydroxylamine and ethyl N-(1-methylbenzimidazol-2-ylmethoxy)acetimidate. Acid hydrolysis of the latter has given O-(1-methylbenzimidazol-2-ylmethyl)hydroxylamine. The reactions of its derivatives with HCl have been studied, and it has been shown that 1-methylbenzimidazole-2-aldehyde O-(1-methylbenzimidazole-2-methyl)oxime is formed. The structure of the latter has been shown by an analysis of its PMR spectra.For part II, see ¦1¦.     

Quinoline derivatives

A number of difficult-to-obtain heterocyclic compounds — tetrahydroquinolino- and quinolinopyrazines — were synthesized from o-dinitrotetrahydroquinolines. The UV spectra of the synthesized compounds were studied.See [1] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 525–527, April, 1973.     

Tetramethylcyclopentadienylselenium derivatives

Bis(1,2,3,4-tetramethylcyclopentadienyl)selane (1) has been prepared by the reaction of tetramethylcyclopentadienyllithium (Cp(t)Li) with selenium bis(diethyldithiocarbamate). Treatment of Cp(t)Li with elemental selenium, followed by air oxidation, led to loss of the allylic hydrogen atom, and formation of the novel tricyclic compound 1,4,5,6,7,10,11,12-octamethyltricyclo[7.3.0.0]-2,8-diselenadodeca-3,5,9,11-tetraene (2). The sulfur analogue of 2 has been obtained by a similar procedure. The X-ray crystal structures of compounds 1 and 2 have been determined, and the molecular geometry observed for has been probed using DFT calculations.     

Benzimidazole derivatives

Benzoquinonyl derivatives of azoles were obtained by the Meerwein reaction of 1,4-benzoquinone with heterocyclic diazo compounds. Reactions involving the addition of hydrogen chloride, reduction of the quinoid ring, and quaternization of the heteroring were carried out for these compounds. A method for the preparation of 1-quinonylbenzimidazoles was developed.See [1] for communication XXXII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1402–1404, October, 1974.     

Tetrazole derivatives

The polarographic reduction of tetrazolyl-containing tetrazolium salts with betaine structures and various substituents attached to the C(s) and N(s) atoms was investigated. It is shown that the depolarization of the tetrazolium salts proceeds in three electrochemically irreversible steps. In the first step one observes two-electron reduction to a formazan dianion without the consumption of protons. Electron-donor substituents facilitate the reduction, whereas electron-acceptor substituents hinder it. The substituent effect is manifested to a greater extent from the 3 position of the tetrazolium ring.See [1] for communication XVI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1686–1690, December, 1977.     

Tetrazole derivatives

The corresponding leucoverdazyl and 1-methyl-5--benzoylhydrazidotetrazole are formed in the reaction of 1-(1-methyl-5-tetrazolyl)-3,5-diphenylformazan with formaldehyde in acidic media. 1,3-Diphenyl-1,2,4-triazole is formed when the reaction is carried out in alkaline media. According to the PMR spectral data, prototropic tautomerism is characteristic for the leucoverdazyl. The verdazyl radical derivative has the ability to undergo recyclization with conversion of the tetrazine ring to a triazole ring either spontaneously or when it is heated.Translated from Geterotsiklicheskikh Soedinenii, No. 8, pp. 1137–1140, August, 1978.     

Hydroxylamine derivatives

Conclusions Various O-substituted hydroxylamines were synthesized by the method proposed by us.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1820–1823, August, 1967.     

Cubane derivatives

The reduction of 1-bromo-9,9-ethylenedioxypentacyclo[4.3.0.0^2,5.0^3,8.0^4,7]nonane-4-carboxylic acid (2) with lithium aluminum hydride and aluminum hydride in THF was studied. A new effective method for preparing 1-bromo-9,9-ethylenedioxypentacyclo[4.3.0.0^2,5.0^3,8.0^4,7]-non-4-ylcarbinol (1) based on reduction of2 with AlH₃ under mild conditions was developed.     

Benzimidazole derivatives

The alkylation of benzimidazole and its derivatives with propargyl bromide was studied. 1-(2-Propynyl)benzimidazoles are readily formed in liquid ammonia in the presence of sodium amide. The alkylation of 1-ethyl-2-aminobenzimidazole leads to a mixture of 2-(N-mono)- and 2-(N,N-2-propynyl)amino-1-ethylbenzimidazoles.See [1] for communication XXX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 551–552, April, 1973.