Synthesis of n2-alkyl(aryl,dialkyl, cycloalkyl)guanines

Novel N²-alkyl(aryl, dialkyl, cycloalkyl)guanines have been synthesized by treating 2-chloro-7-benzylhypozanthine with amines and debenzylation of the N²-substituted 7-benzylguanine products by means of palladium catalyzed hydrogenation.DeceasedCenter for the Chemistry of Medicinal Compounds. All Russian Chemico-Pharmaceutical Science Research Institute, Moscow, 119815. State Institute for Blood Substitutes and Medicinal Preparations, Moscow, 109044. Zaporozh'e State Medicinal Institute, Zaporozhe'e, 330074. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 391–394, March, 1996. Original article submitted January 6, 1996.     

Synthesis of n2-guanylcarboxylic acids

A novel method has been developed for synthesizing N²-guanylcarboxylic acids by reaction of 2-chloro-7-benzyl-hypoxanthine with amino acids and debenzylation of the 7-benzyl-N²-guanylcarboxylic add products by means of palladium catalyzed hydrogenation.Center for the Chemistry of Medicinal Compounds. All-Russian Chemico-Pharmaceutical Science Research Institute, Moscow 119815. State Institute for Blood Substitutes and Medicinal Preparations, Moscow 109044. Zaporozh'e State Medicinal Institute, Zaporozh'e 330074. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 395–398, March, 1996. Original article submitted January 17, 1996.     

Branched polycyclic tetrazole systems. 1. Synthesis and structure of 2-(5-tetrazolyl)ethyl derivatives of some CH-, OH-, and NH-acids

The cycloaddition of dimethylammonium azide to the nitrile groups of 2-cyanoethyl derivatives of CH-, OH-, and NH-acids leads to open-chain branched structures containing terminal NH-tetrazolyl groups. An x-ray diffraction structural analysis of tris[2-(5-tetrazolyl)ethyl]nitromethane revealed steric access of the equivalent NH-tetrazolyl rings of the branched system. In going from the branched nitrile substrates to the corresponding tetrazoles, the PMR spectra show a breakdown in the resolution of the multiplet components, which had not been observed previously for monocyclic 5-substituted tetrazoles. A dependence was found for the¹³C NMR chemical shifts on the pK_a values, reflecting the NH-acidity of the branched polycyclic tetrazoles in water. Dedicated to the memory of I. N. Goncharova. St. Petersburg State Technological Institute, 198013 St. Petersburg. V. A. éngel'gart Institute of Molecular Biology, Russian Academy of Sciences, 117984 Moscow. L. Ya. Karpov Physics and Chemistry Research Institute, 103062 Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1494–1501, November, 1997.     

Synthesis of 2-(3-hydroxyacetonyl)malonic aldehyde and its derivatives. Their reactions with 5-aminotetrazole

2-(3-Hydroxyacetonyl)malonic aldehyde and its derivatives were prepared for the first time by the hydrolysis of 2-substituted 2,5-dimethoxy-4-formyltetrahydrofuranes. Their interaction with 5-aminotetrazole gave functionally substituted 6-tetrazolo[1,5-a]pyrimidines.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Hexagon Chemistry Consultants, DK-1460 Copenhagen. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, 807–810, June, 1997.     

Reaction of trifluoromethyl-containing enones with thiophenol derivatives

The reaction of trifluoromethyl-containing enones with thiophenol derivatives has been studied. Reactions with 4-methylthiophenol proceed with the formation of either ketosulfides or a pyran derivative. Reactions of trifluoromethyl-containing enones with 2-mercaptobenzaldehyde lead to 3-trifluoroacetyl-substituted 2H-thiochromenes. M. V. Lomonosov Moscow State University, Moscow 119899, Russia N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 117907, Russia. Department of Chemistry, University of Durham, South Road, Durham, Great Britain, DH1 3LE. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 618–626, May, 1999.     

Structure of cyanoethylation products of 1,2,3-triazolecarboxylic acid derivatives

The cyanoethylation of derivatives of 5-chloro-1,2,3-triazolecarboxylic acids was studied, and it was shown by mass spectrometry and¹H NMR spectroscopy that the only products of this reaction are 2-N-cyanoethyl derivatives.Center for the Chemistry of Drugs, All-Russian Chemicopharmaceutical Scientific-Research Institute, Moscow, 119021. Translated from Khimiya Geterotsiklicheskikh Soedienii, No. 10, pp. 1369–1374, October 1994. Original article submitted October 14, 1994.     

Nα,Nim-di-tert-alkoxycarbonyl derivatives of histidine

The acylation of histidine with di-tert-butyl and di-tert-amyl pyrocarbonates has given the corresponding N,N_im-di-tert-alkoxycarbonyl derivatives. The N,N^im-di-tert-butoxycarbonyl derivative was obtained in the crystalline form by crystallization from benzene or carbon tetrachloride, or in the form of salts with cyclohexylamine, dicyclohexylamine, and diethylamine. N,N^im-di-tert-amyloxycarbonyl-histidine was characterized in the form of the salt with dicyclohexylamine.Institute of Biological and Medicinal Chemistry, Academy of Medical Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 379–383, May–June, 1980.     

Investigations in the imidazole series 97. Synthesis and some transformations of 5-nitro-5-hydroxyalkylamino- and 4-hydroxy-alkylamino-5-nitroimidazoles

A series of 1-alkyl(1,2-dialkyl)-substituted 4-nitro-5-hydroxyalkylamino- and 4-hydroxyalkylamino-5-nitro-imidazoles were obtained by the reaction of 1-alkyl(1,2-dialkyl)-substituted 4-nitro-5-chloro(bromo)imidazoles with amino alcohols. Their reactions with thionyl chloride and carboxylic acid halides and their catalytic hydrogenation were studied. For Communication 96, see [1]. Center of the Chemistry of Medicinal Agents, All-Russia Scientific-Research Chemical-Pharmaceutical Institute, Moscow 119815. Novokuznetsk Scientific-Research Chemical-Pharmaceutical Institute, Novokuznets 654034, Russia. Zaporozh'e State Medical University, Zaporozh'e 33074. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10. pp. 1346–1351, October, 1998.     

Asymmetric synthesis of heteroorganic analogs of natural products. 6. (S)-α-amino-ω-phosphonocarboxylic acids

Alkylation, by -haloalkylphosphonates, of the Ni(II) complex of the Schiff base formed from glycine and (S)-2-N-(N¹-benzylprolyl)-o-aminobenzophenone has been used for the asymmetric synthesis of (S)-2-amino-4-phosphonobutyric and (S)-2-amino-5-phosphonovaleric acids.Institute of Bioorganic Chemistry and Oil Chemistry, Ukrainian Academy of Sciences, 250800 Kiev. A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 397–402, February, 1992.     

Investigations on imidazoles 98. Reactions of nitrohaloimidazoles with amino acids

The reaction of 5-chloro(bromo)-1-methyl(1,2-dimethyl)-4-nitroimidazoles and 4-chloro-1-methyl-5-nitroimidazole with amino acids has been studied. This has enabled a series of N-(4-nitro-5-imidazolyl)- and N-(5-nitro-4-imidazolyl)-substituted amino acids to be synthesized. Esters of some of these acids have been obtained.For Part 97 see [1].Center for Drug Chemistry, All-Russian Research Institute for Pharmaceutical Chemistry, Moscow 119815. Novokuznetsk Research Institute for Pharmaceutical Chemistry, Novokuznetsk 654034, Russia. Zaporozhye State Medical University, Zaporozhye 330074, Ukraine. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 48–53, January, 1999.     

Quantum chemical study of 2-substituted 4-oxo-and 4-thioxospiro(benzo[h]quinazoline-5,1′-cycloalkanes) in alkylation reactions

The steric and electronic structures of 2-substituted 4-oxo- and 4-thioxospiro(benzo[h]quinazoline-5,1-cycloalkanes and their deprotonated forms have been calculated by the semiempirical PM-3 quantum chemical method. Using the conclusions of limiting orbital theory, a quantum chemical explanation has been derived, based on the calculations made, for the selectivity of alkylation of the systems investigated.A. L. Mndzhoyan Institute of Fine Organic Chemistry, Armenian Academy of Sciences, Erevan 375014, Armenia. M. V. Lomonosov Moscow State University, Moscow 119899, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1118–1124, August, 1998.     

Synthesis of guanine from 3-methylxanthine

Summary A new preparative method of obtaining guanine from 3-methylxanthine has been developed.L. A. Gutorov and V. S. Aleksandrova are Deceased.Center for Drug Chemistry, All-Russian Scientific-Research Institute for Pharmaceutical Chemistry, Moscow 114815, State Institute for Blood Substitutes and Drugs, Moscow 109044. Zaporozhe State Medical Institute, Zaporozhe 330074. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 388–390, March, 1995.Original article submitted February 4, 1995.     

Stereochemistry, absolute configuration, and crystal structure ofcis-(4S,9S,10R)-1-(S-1-phenylethyl)decahydroquinolin-4-ol. Relative stereochemistry of cycloalkano-2,3-piperidin-4-ols

According to x-ray crystallographic data, thecis-isomer of 1-(1-phenylethyl)decahydroquinolin-4-ol, the predominant product of the stereoselective hydrogenation of1-(1--phenylethyl)-^{9, 10} -octahydroquinoline-4-one with sodium tetrahydroborate, has the (4S, 9S, 10R) configuration. The x-ray crystallographic data for this cisdecahydroquinolin-4-ol have been compared with the previously studied piperidin-4-ones of known absolute configuration. The stereochemical rules for cycloalkano-2,3-piperidine-4-ols are discussed.M. V. Lomonosov Moscow State University, Chemistry Faculty, Moscow 119899, A. N. Nesmeyanov Institute of Elementoorganic Chemistry, Russian Academy of Sciences, Moscow 117813. A. B. Bekturov Institute of Chemical Science, Kazakhstan Academy of Sciences, Alma-Ata 480100. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 526–534, April, 1998.     

Investigations on imidazoles 99. Synthesis and some conversions of esters of 4-nitro-5-imidazolylmalonic,-acetoacetic, and-cyanoacetic acids

Some esters of 1-alkyl(1,2-dialkyl)-4-nitro-5-imidazolylmalonic,-acetoacetic, and-cyanoacetic acids have been synthesized by the reaction of 5-chloro(bromo)-1-alkyl(1,2-dialkyl)-4-nitroimidazoles with ethyl esters of carboxylic acids indicated. Some conversions of the compounds obtained have been studied, including ketone and acid decomposition, synthesis of derivatives at the COOH and CO groups, and hydrogenation to 4-aminoimidazole derivatives.For Part 98 see [1].Center for Drug Chemistry, All-Russian Research Institute for Pharmaceutical Chemistry, Moscow 119815. Novokuznetsk Research Institute for Pharmaceutical Chemistry, Novokuznetsk 654034, Russia. Zaporozhye State Medical University, Zaporozhye 330074, Ukraine. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 54–60, January, 1999.     

Synthesis and some properties of 6-(ω-aroylbutylthio)purines

A series of 6-(ω-aroylthio)purines, which have not been described in the literature, has been obtained by the reaction of 6-purinethione with ω-chlorovalerophenone and its substituted derivatives. Some properties of the compounds synthesized have been studied, viz. reaction at the carbonyl group, methylation, and hydrolysis. All-Russian Scientific Center for the Safety of Biologically Active Substances, Staraya Kupavna, Moscow region 142450. Zaporozhe State Medical University, Zaporozhe 330074, Ukraine. Center for Drug Chemistry, All-Russian Pharmaceutical Chemistry Research Institute, Moscow 119815. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1407–1411, October, 1999.     

Crystal structure of [ZnCl·15-crown-5·H2O]2Zn2Cl6

State Scientific-Research Institute of Chemistry and Technology of Organometallic Compounds. L. Ya. Karpov Scientific-Research Physical Chemistry Institute, M. V. Lomonosov Moscow State University. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 3, pp. 161–164, May–June, 1989.     

Asymmetric synthesis of organoelemental analogs of natural compounds. 7. (2R,3S)-2-amino-3-hydroxy-5-phosphonovaleric acid

The reaction of the Ni(II) complex of the Schiff base of glycine with (S)-2-N-(N¹-benzylprolyl)-o-aminobenzophenone with diethyl-3-bromo-2-hydroxypropyl phosphonate yields the corresponding complex from which (2R, 3S)-2-amino-3-hydroxy-5-phosphonovaleric acid is separated with HCl.See [1] for Communication 6.Institute of Bioorganic Chemistry and Petrochemistry, Ukrainian Academy of Sciences, 252660 Kiev; N. A. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1172–1175, May, 1992.     

Synthesis of pyrazolo[1,5-a]pyrimidines by the reaction of β-dicarbonyl compounds with 3,5-diamino-4-nitropyrazole

The reaction of 3,5-diamino-4-nitropyrazole with asymmetrical β-dicarbonyl compounds gave polysubstituted pyrazolo[1,5-a]pyrimidines, which are used in reactions with both nucleophilic and electrophilic reagents. The structure of the compounds obtained was demonstrated by x-ray diffraction structural analysis. Center for Pharmacological Chemistry, All-Russian Pharmaceutical Chemistry Institute, 119815 Moscow and M. V. Lomonosov Moscow State University, 119899 Moscow, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1676–1681, December, 1998.     

Mass-spectrometric study of the sesquiterpene lactone grossmisin and its derivatives

Summary The dissociative ionization of grossmisin [O–D]grossmisin, and two of its derivatives have been studied. The appearance of the main fragments in the mass spectrum of grossmisin is due to the elimination by the M⁺ ion of H₂O and CO molecules and CH₃ and OH radicals in various sequences. The hypothesis has been put forward that in the splitting off of a CH₃COOH molecule by the M^+° ion of acetylgrossmisin a rearrangement of the lactone ring takes place with its reclosure at the C₆ carbon atom of the seven-membered ring.M. V. Lomonosov Moscow State University. Patrice Lumumba International Friendship University, Moscow. All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 344–349, May–June, 1977.     

Electron diffraction investigation of the structure of the 3,3-dimethyl-3-silathiophane molecule

Chemistry Faculty, M. V. Lomonosov Moscow State University. Irkutsk Institute of Organic Chemistry. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 2, pp. 148–151, March–April, 1991.