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.     

New synthesis of 9-alkylguanines and their N2-substituted derivatives

A new method of synthesizing 9-alkyl guanines and their N²-substituted derivatives from 7-benzylguanine and its N²-substituted derivatives has been developed by quaternization with alkyl halides, dialkyl sulfates, or arenesulfonic acid esters, and subsequent removal of the benzyl protection by hydrogenation of the intermediate quaternary salts or of the betaines obtained from them.Center for Drug Chemistry, All-Russian Scientific Research Institute for Pharmaceutical Chemistry, Moscow 119815. State Institute for Blood Substitutes and Medicinal Preparations, Moscow 109044, Russia. Zaporozhe State Medical Institute. Zaporozhe 330074, Ukraine. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 542–546, April, 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.     

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.     

Furocoumarins ofKomarovia anisospermum

Summary Three furocoumarins have been isolated from the roots ofKomarovia anisospermum Korov.: isoimperatorin, phellopterin, and 8-geranyloxy-5-methoxypsoralen. This is the first time that the last-mentioned of these substances has been isolated in the pure state.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Moscow State University. Botanical Garden, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 166–169, March–April, 1976.     

Chemical investigation of the herbage ofMelissa officinalis

Samara State Medical Institute; All-Russian Scientific-Research Institute of Medicinal and Aromatic Plants, Scientific Production Combine, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 318–320, March-April, 1995. Original article submitted November 22, 1994.     

Structure and stereochemistry of galbanic acid

On the basis of the¹H NMR spectrum at 300 MHz and the results of chemical degradation, the structure of 7-[6-(β-carboxyethyl)-5-isopropylidene-1,2-dimethylcyclo-hexylmethoxy]coumarin has been proposed for galbanic acid. V. L. Komarov Institute of Botany, Academy of Sciences of the Azerbaidzhan SSR, Baku. All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 620–623, September–October, 1980.     

The structure and stereochemistry of tavicone

Summary It has been established from H¹ NMR spectra in CDCl₃ with additions of Eu(FOD)₃ as paramagnetic shift reagent that tavicone must be ascribed the structure of 7-(1,1,3a,5-tetramethyl-2-oxo- ₅ ⁵ -hexahydroinden-4-ylmethoxy) coumarin. The stereochemistry of this compound has been determined.Institute of Botany, Academy of Sciences of the Azerbaidzhan SSR, Baku. All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 452–455, July–August, 1976.     

Synthesis of bicyclo-heptane, 6-oxabicyclo-octane and 3-azabicyclo-nonene derivatives in the course of 1,2,4-trimethyl-4-isopropenylcyclohexene cyclization

Carbocyclic and heterocyclic compounds of the bicyclo[2.2.1]-heptane, 6-oxabicyclo[3.2.1]octane, and 3-azabicyclo[3.3.1]-nonene series were obtained from the reaction between 1, 2, 4-trimethyl-4-isopropenylcyclohexene (a dimer of 2, 3-dimethyl-buta-1, 3-diene) and CH₃CN in the presence of H₂SO₄ which was accompanied by intramolecular cyclization.M. V. Lomonosov Moscow State University, Institute of Chemical and Biological Physics, Estonian Academy of Sciences, Tallin. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 754–759, June, 1996. Original article submitted April 11, 1996.     

The stereochemistry of nevskin

Summary The relative configurations of the substituents in nevskin have been determined from the H¹ NMR spectra in CDCl₃ with additions of Eu(FOD)₃ as paramagnetic shift reagent.Institute of Botany, Academy of Sciences of the Azerbaidzhan SSR, Baku. All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 450–452, July–August, 1976.     

Dicaffeolyquinic acids from Helichrysum italicum and Achillea cartilaginea

The quinic acid caffeates of the flowers ofHelichrysum italicum and the herbage ofAchillea cartilaginea have been studied with the use of HPLC,¹³H NMR spectroscopy, and chemical transformations.All-Union Research Institute of Medicinal Plants Scientific-Production Association, Moscow. Translated from Bioorganicheskaya Khimiya, No. 1, pp. 50–55, January–February, 1992.     

Lactones ofFerula gigantea

The following substances have been isolated from an acetone extract ofFerula gigantea B. Fedtsch.: a coumarin — umbelliferone, C₉H₆O₂, mp 230–233°C; and sesquiterpene lactones — talassin A, C₂₅H₃₀O₇, mp 188–191°C; malaphyllinin, C₂₄H₂₄O₇, mp 231–235°C; malaphyll, C₂₉H₃₂O₉, mp 212–213°C; and malaphyllin, C₂₆H₂₈O₉, mp 216–218°C. Structures have been proposed for three new sesquiterpene lactones on the basis of an analysis of their spectral characteristics.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. M. V. Lomonosov Moscow State University, Botanical Garden, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 490–495, July–August, 1979.     

Solid-phase synthesis of 1,2-benzophenazine and some fused imidazole derivatives

The solid-phase synthesis of 1,2-benzophenazine and various N-methylbenzimidazoles using o-diaminoarenes is very promising and permits the synthesis of 1-methyl-4,5-[b]naphtho-1H-imidazole, which could not be obtained by the condensation of o-diaminoarenes with paraformaldehyde using the standard liquid-phase method.M. V. Lomonosov Moscow State University, 119899, Moscow, Institute for Synthetic Polymer Materials, 117461, Moscow, and Institute of Physiologically Active Compounds, Russian Academy of Sciences, Chernogolovka, 1424432, Moscow Oblast. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 672–674, May, 1996. Original article submitted April 3, 1996.     

Synthesis and transformations of 6-amino-3,5-dicyano-4ethylpyridine-2(1H)-thione

The condensation of propionaldehyde with cyanothioacetamide gives 6-amino-3,5-dicyano-4-ethylpyridine-2(1H)-thione, which was used to obtain substituted 2-alkylthiopyridines, 2-ethylthio-6- ethylaminopyridine, and pyrazolo[3,4-b]pyridine.T. G. Shevchenko Lugansk State Pedagogical Institute, 348011 Lugansk. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Science, 117913 Moscow. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1094–1098, August, 1996. Original article submitted March 4, 1996; revision submitted July 1, 1996.     

Production of a pyridine derivative of grosshemin

Summary The reaction of pyridine and hydrochloric acid with grosshemin in the presence of acetic anhydride forms a substance with the composition C₂₀H₂₄O₄NCl · H₂O, mp 160–165°C, [] ₂₀ ^D + 71.23 (c 1.33; water), for which structure (II) is proposed.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 306–309, May–June, 1976.     

6-Chloroapigenin fromEquisetum arvense L.

A new compound 6-chloroapigenin, C₁₅H₉C10₅, M⁺ 304, mp 305–306°C, _max 274, 336 (methanol) has been isolated from the ether-soluble fraction of a methanolic extract of the field horsetail. On the basis of the results of UV and PMR spectroscopy and mass spectrometry, the structure of 6-chloro-4,5,7-trihydroxyflavone has been established for this compound.Irkutsk Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR, All-Union Scientific-Research Institute of Medicinal Plants, Moscow. I. M. Sechenov First Moscow Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 499–501, July–August, 1980.     

Reaction of substituted 7-cyclopropyl-1,4-benzodioxanes with dinitrogen tetraoxide

The reaction of 6-bromo-7-cyclopropyl-1,4-benzodioxane with N₂O₄ in methylene chloride does not affect the cyclopropane ring and forms the nitrodebrominated product (ipso-substitution). The same reaction of 6-nitro- and 5,6-dinitro-7-cyclopropyl-1,4-benzodioxanes produces only the products with an modified threemembered ring. The difference in the reaction paths of the studied cyclopropylbenzodioxanes with N₂O₄ is explained by the different ratio of substrate to one-electron oxidant, the nitrosyl cation.M. V. Lomonosov Moscow State University, Moscow 119899Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 324–329, March, 1999.     

Composition,structure, and ir spectra of acid trialkylmethylammonium acetates in CCl4+HAc solutions

The composition and structure of neutral and acid trialkyl(C₈-C₁₀)methylammonium acetates in CCl₄+HAc solutions formed by the reaction R₃CH₃N⁺Ac⁻+nHAc⇔R₃CH₃N⁺(Ac·nAc)⁻ are investigated by IR spectroscopy. As the molar ratio HAc/R₃CH₃N⁺Ac⁻ increases in solutions, complex anions Ac·nAc⁻ (I) with n=1, 2, 3, 4 are formed in sequence. The curves of formation of anions with n=0, 1, 2 are plotted. One terminal COO group of anions I is bonded to (“blocked” by) the R₃CH₃N⁺ cation, and another group sequentially adds H-bonded HAc molecules as the concentration of HAc in solutions increases. The sequence of IR spectral changes in the series of anions I with n=0, 1, 2, 3, 4 is discussed. Institute of Catalysis, Siberian Branch, Russian Academy of Sciences. Novosibirsk State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 2, pp. 310–318, March–April, 1996. Translated by L. Smolina     

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.