Synthesis of n-(2-chloro-5-bromo-4-pyrimidyl)- and N-(2-chloro-5-iodo-4-pyrimidyl)amino acids

The previously unreported N-(2-chloro-5-bromo-4-pyrimidyl)- and N-(2-chloro-5-iodo-4-pyrimidyl) amino acids were synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 527–529, April, 1971.     

Reaction of ethynylsilanes with perfluoroiodoalkanes

Conclusion The addition of iodotrifluoromethane, 1-iodoperfluoropropane, and 1-iodo-1,1,2,2,3,3,4,4-octafluorobutane to alkylethynyl- and alkylalkoxyethynylsilanes gave the 1-iodo-3,3,3-trifluoropropen-1-ylsilanes, 1-iodo-3,3,3,4,5-5,5-heptafluoropenten-1-ylsilanes, and 1-iodo-3,3,4,4,5,5,6,6-octafluorohexen-1-ylsilane. The corresponding fluorosilanes were synthesized by reacting the latter with 40% aqueous HF solution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1424–1428, June, 1982.     

Substituted 6-ethynyl-1.4-naphthoquinones

Conclusions Syntheses are reported for substituted 6-ethynyl-1,4-naphthoquinone by the condensation of 6-iodo-1,4-dimethoxynaphthalene or 6-iodo-1-naphthol with terminal acetylenes and subsequent oxidation using Ce(NH₅)₂(NO₃)₆ and ON(SO₃K)₂.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 485–488, February, 1988.     

Azaindole derivatives. 59. Synthesis and chemical properties of 1-benzyl-4-dimethylamino-6-chloro-7-cyano-5-azaindoline

The condensation of 1-benzyl-2-cyanocarbamoylmethylene-pyrrolidine with tetramethylurea diethylacetal and subsequent cyclization gave 1-benzyl-4-dimethyl-amino-6-chloro-7-cyano-5-azaindoline, for which nucleophilic substitution and dehydrogenation reactions are described. The reactivity of this product is compared with that of 1-benzyl-6-chloro-7-cyano-5-azaindoline.See [1] for Communication 58.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 215–220, February, 1981.     

Reactions of 3-iodo-7-dialkylaminocoumarins with secondary amines

The reaction of 3-iodo-7-diethylaminocoumarin and 2,3,6,7-tetrahydro-10-iodo-1H,5H-quinolizino[9,9a,1-gh]coumarin with secondary amines (diethylamine, piperidine, morpholine, imidazole, and benzimidazole) leads to 4,7-diaminocoumarins. The corresponding 3-iodo-4-chloro-7-dialkylaminocoumarins under similar conditions give 3-iodo-4,7-diaminocoumarins. 4-Aminomethyl derivatives of coumarins are formed in the reactions of 3-iodo-4-methyl-7-diethylaminocoumarin and 2,3,6,7-tetrahydro-9-methyl-10-iodo-1H,5H-quinolizino[9,9a,1-gh]coumarin with these secondary amines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 609–618, May, 1991.     

Reaction of chloro-symm-triazines with thioacetic acid

Conclusions The reaction of cyanogen chloride and 2-chloro-4,6-bis-(alkylamino)- and 2-chloro-4,6-bis(dialkylamino)-symm-triazines with sodium thioacetate gave the corresponding symm-triazinethiols.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1432–1434, June, 1986.     

Synthesis of B-halobarenes from halodecaboranes and order of substitution in the electrophilic halogenation of barenes

Conclusions The corresponding B-halobarenes, with a definite position of the halogen atom in the barene nucleus, were synthesized from the 1-chloro-, 2-chloro-, 2-bromo-, 1-iodo- and 2-iododecaboranes by reaction with acetylene, phenylacetylene and propargyl bromide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2014–2016, November, 1966.     

Synthesis of 6-substituted 9-(dihydroxyalkyl) purines

5-Amino-6-chloro-4-dihydroxyalkylaminopyrimidines, which are cyclized to 6-chloro-9-(dihydroxyalkyl)purines, were obtained by the condensation of 5-amino-4,6-dichloropyrimidine with 2-amino-1,3-dihydroxypropane or with 2-amino-1,4-dihydroxybutane. The corresponding 6-hydroxy and 6-amino derivatives were obtained by replacement of the chlorine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 262–264, February, 1971.     

Synthesis and structure of 6-substituted 9-(2-ethoxy-1,3-dioxan-5-yl)purines

The reaction of 4-chloro-5-amino-6-(1,3-dihydroxy-2-propyl)aminopyrimidine with excess ethyl orthoformate gave a cyclic acetal, viz., 6-chloro-9-(2-ethoxy-1,3-dioxan-5-yl)purine, amination of which yielded 6-amino-9-(2-ethoxy-1,3-dioxan-5-yl)purine. The presence of two configurational isomers with a diaxial orientation of the purine ring and the ethoxy group in the trans isomer and an equatorial orientation of the ethoxy group in the cis isomer was established for these compounds by ¹H and ¹³C NMR and IR spectroscopy. The three-dimensional structure of trans-6-chloro-9-(2-ethoxy-1,3-dioxan-5-yl)purine was determined by an x-ray difraction study, and the trans-diaxial orientation of the purine ring and the ethoxy group was confirmed; it is shown that the dioxane ring is in an anti conformation relative to the purine ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 976–983, July, 1979.     

Nitrogen- and sulfur-containing heterocycles

4-Chloro-5-amino- and 4-chloro-5-methylamino-6-phenacylmercaptopyrimidines (II–V and XVI–XX) were obtained by the reaction of 4-chloro-5-amino- and 4-chloro-5-methylamino-6-mercaptopyrimidines (I and XV) with phenacyl halides. It is shown that II–V are cyclized by alkalis to 4-chloro-6-aryl-6-hydroxy-5,6-dihydropyrimido[4,5-b][1,4]thiazines (VI–IXa), while both II–IXa and XVI–XIX, respectively, are converted to 7H-4-chloro-6-aryl- (X–XIII) and 5H-4-chloro-5-methyl-6-arylpyrimido[4,5-b][1,4]thiazines (XX–XXIII) under the influence of acidic reagents.See [5] for communication XVIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 73–77, January, 1971.     

Synthesis of 2,3-dioxo-2,3-dihydro-4-methyl-6-chloro-1H-pyrrolo[2,3-b]pyridine and its 1-α-L-arabinopyranoside

A new type of isatin analog-2,3-dioxo-2,3-dihydro-4-methyl-6-chloro-1H-pyrrolo[2,3-b]pyridine — was obtained by oxidation of 4-methyl-6-chloro-1H-pyrrolo(2,3-b]pyridine. Condensation of L-arabinose with 4-methyl-6-chloro-2,3-dihydropyrrolo[2,3-b]pyridine and subsequent acetylation and dehydrogenation gave 1-(2,3,4-tri-O-acetyl--L-arabinopyranosyl)-4-methyl-6-chloropyrrolo[2,3-b]pyridine, which served as the starting compound for the synthesis of 1--L-arabinopyranosyl-4-methyl-6-chloropyrrolo[2,3-b]pyridine. Oxidation of 1-(2,3,4-tri-O-acetyl-L-arabinopyranosyl)-4-methyl-6-chloropyrrolo[2,3-b]pyridine gave 1-(2,3.4-tri-O-acetyl--L-arabinopyranosyl)-2,3-dioxo-2,3-dihydro-4-methyl-6-chloropyrrolo [2,3-b]pyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1083–1086, August, 1977.     

Synthesis of 6-nitro-8-chloro-2,3-dieydro-4(1H)-quinolone

6-Nitro-8-chloro-2,3-dihydro-4(1H)-quinolone and its dehydrogenation product-6-nitro-8-chloro-4-hydroxyquinoline — were isolated in the cyclization of N-(2-chloro-4-nitrophenyl--alanine in polyphosphoric acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 954–956, July, 1978.     

(2-Chlorovinyl)chlorocarbenes: Generation and reactions with alkenes

The treatment of Z-1,1,3-trichloro-4,4-dimethyl-2-pentene (Ia) with t-C₄H₉OK in boiling hexane or benzene gave rise to (Z-2-chloro-3,3-dimethyl-1-butenyl)chlorocarbene (IVa), which reacted with alkenes to give the cyclopropane derivatives (V) in 44–57% yields. Dichloro-(2-chloro-1-alkenyl)methanes (Ib-d), which have a hydrogen atom at the C₃ position of the alkenyl substituent, were also used as carbene precursors under these conditions. These compounds gave rise to mixtures of the cyclopropanes (VI)–(VIII) (obtained in up to 57% yields) and the dienes (IX)–(XI) (yields up to 54%). The reaction of cis-2-butene with (2-chloro-1-cyclopentenyl)chlorocarbene (IVd) was found to be completely stereospecific, indicating that this carbene exists in a singlet ground state.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2552–2558, November, 1991.     

Reactions of 3-methyl-1-(2-pyridyl)-4-chloro-5-formyl-6,7-dihydroindazole

The reactions of 3-methyl-1-(2-pyridyl)-, 3-methyl-1-phenyl-, and 3-methyl-1,6-diphenyl-4-chloro-5-formyl-6,7-dihydroindazoles with guanidine and benzo- and 3- and 4-pyridinecarbamidines gave the corresponding 8-substituted 1-methyl-3-(2-pyridyl)-and 1-methyl-3-phenyl-4,5-dihydropyrazolo[5,4-h]quinazolines. With acetic anhydride the same indazole derivatives gave the 4-acetoxy-5-formyl derivatives, and with hydroxylamine they gave4-chloro-5-hydroxyiminomethyl-6,7-dihydroindazoles. Thereactionof4-acetoxyl-1-(2-pyridyl)-5-formyl-6,7-dihydroindazole with hydroxylamine gave 8-methyl-6-(2-pyridyl)-4,5-dihydroisoxazolo[5,4-e]indazole, while dehydration of 5-hydroxyiminomethyl-3-methyl-4-chloro-6,7-dihydroindazole gave the 4-chloro-5-cyano derivative. The reaction of the latter with nucleophilic reagents was investigated.Riga Technical University, Riga, Latvia LV-1658. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1209–1213, September, 1998.     

Synthesis of 2-amino-6-(nitroimidazolyl)thiopurines

We have synthesized a series of novel 2-amino-6-(nitroimidazolyl)thiopurines by reaction of thioguanine with 1-alkyl(1,2-dialkyl)-5-chloro-4-nitro-, 2-alkyl(1,2-dialkyl)-5-bromo-4-nitro-, and 1-alkyl(1,2-dialkyl)-4-chloro-5-nitroimidazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 221–224, February, 2000.     

Halogenation of Imidazo[4,5-<Emphasis Type="Italic">b</Emphasis>]pyridin-2-one Derivatives

Chlorination and bromination of 2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one and its N-methyl-substituted derivatives in acetic acid at 90–95°C leads to formation of the corresponding 5,6-dichloro(dibromo)-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones. Iodination of the same substrates with ICl under analogous conditions yields 6-iodo derivatives. Chlorination of 6-iodo-1,3-dimethyl-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one is accompanied by replacement of the iodine atom by chlorine with formation of 5,6-dichloro-1,3-dimethyl-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one. Bromination of 6-bromo- and 6-chloro-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones gives 5,6-dibromo- and 5-bromo-6-chloro-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones, respectively.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 586–589.Original Russian Text Copyright © 2005 by Yutilov, Lopatinskaya, Smolyar, Gres’ko.     

Acylation and oxidation of 4-chloro-6-hydroxyaminopyrimidines. Synthesis of 4-chloro-6-nitro(nitroso)pyrimidines

Treatment of 2-R-4,6-dichloropyrimidines with hydroxylamine gives 2-R-4-chloro-6-hydroxyaminopyrimidines, which are converted to mono- and diacyl derivatives upon acylation. Oxidation of 4-chloro-6-hydroxyaminopyrimidines with manganese dioxide or ozone gives the first reported synthesis of 4-chlorine-containing 6-nitroso- or 6-nitropyrimidines, respectively.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1088–1093, August, 1989.     

Nondegenerate tautomerism in 4-triphenylmethyl6-tert-butyl-3-chloro-2-hydroxyphenoxyl

Fast nondegenerate tautomeric transitions in the substituted ortho-hydroxy-phenoxy radical 4-triphenylmethyl-6-tert-butyl-3-chloro-2-hydroxyphenoxyl were detected by the ESR method. The kinetic and thermodynamic parameters of hydrogenotropy were determined. It was shown that the radical has stronger protolytic power than the familiar ortho-semiquinone radicals 3,6-di-tertbutyl-2-hydroxyphenoxyl and 4,6-di-tert-butyl-3-chloro-2-hydroxyphenoxyl.Karaganda University. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No. 2, pp. 244–248, March–April, 1991. Original article submitted January 5, 1987.     

Purinenucleoside analogs. 2. 9-(1-Alkoxyethyl-1)-6-substituted purines

Vinyl ethers react with 6-chloro- and 6-methylthiopurines in acid medium to give 9-(1-alkoxyethyl-1)-6-chloro- and 6-methylthiopurines. The 6-chloro compounds were used to prepare 9-(1-alkoxyethyl-1)-6-mercaptopurines. All the synthesized compounds proved to be inactive against lympholeucosis P 388, and Lewis carcinona grafted under kidney capsules in mice.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 403–406, March, 1986.     

Synthesis and reactions of 1-(4-chloro-, 3-chloro-, 2-chloro-, 2,4-dichloro-, and 2,4-difluorophenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazoles

Reaction of the potassium salt of 2-formyldimedone with hydrochlorides of 4-chloro-, 3-chloro-, 2-chloro-, 2,4-dichloro-, and 2,4-difluorophenylhydrazines gave the corresponding 2-arylhydrazinomethylene-dimedones which cyclized in acid media to 1-substituted 6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazoles. Oxidation of the latter with selenious acid gave the corresponding 4,5-dioxo-4,5,6,7-tetrahydroindazoles which were further converted into 3-aryl-5,5-dimethyl-4,5-dihydro-3H-pyrazolo[4,3-a]phenazines and 2,6-diaryl-4,4-dimethyl-4,5-dihydro-1H(3H)-indazolo[4,5-g]imidazoles.Riga Technical University, Riga LV-1658, Latvia; e-mail: marina@osi.lv. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, 533–539, April, 2000.