Microbiological transformation of derivatives of 4-phenyl-2-pyrrolidone by mycelial fungi

In the microbiological transformation of 4-phenylpyrrolidine by growing strains of the fungi Cunninghamella,Beauveria, andPenicillium, its 1-ethyl and 1-acetyl derivatives are formed; these are subsequently oxidized at positions 2 and 3. In contrast, 1-benzoyl-4-phenylpyrrolidine is hydroxylated by those same cultures in positions 3 and 5. For the corresponding 2-pyrrolidone derivatives, the 4-phenyl-2-pyrrolidone is not transformed by these fungi, while the 1-benzoyl-2-pyrrolidone is hydrolyzed at the benzamide group under the same conditions. The structures of the products from these transformations were determined by mass spectrometry.Chemistry Department, M. V. Lomonosov Moscow State University, Moscow 199899. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 607–610, May, 1997.     

Heterocycles with a bridging nitrogen atom. 9. Recyclization of an oxazole fragment to a pyrrole fragment. Synthesis and crystal structure of 5-hexamethylenimino-2-p-nitrophenylindolyzine

X-ray diffraction structural analysis was used to determine the structure of 5-hexamethylenimino-2-p-nitrophenylindolyzine formed in the reaction of 5-methyl-2-p-nitrophenyloxazolo[3,2-a]pyridinium perchlorate with hexamethylenimine.For Communication 8, see [1].M. V. Lomonosov Moscow State University, 119899 Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 983–985, July, 1998.     

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.     

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.     

Hetarenes with a bridge nitrogen atom. 6. Ambident properties of the oxazolo[3,2-a]pyridinium nucleus in reactions with nucleophiles: Prediction and experiment

We have studied the problem of ambident opening of five-membered and six-membered rings of the heteroaromatic oxazolo[3,2-a]pyridinium cation. A quantum chemical SINDO1 calculation of the energies of isomeric adducts of this cation with nucleophiles predicts preferential formation of the C₉-adduct in the case of OH and SH ions with opening of the oxazole fragment, while for nitrogen-containing nucleophiles (NH₂, NMe₂) attack at the C₍₅₎ atom is also likely with opening of the pyridine fragment. We have experimentally observed that this cation undergoes opening of the five-membered ring in reaction with NaSH, opening of the six-membered ring in reaction with piperidine, and opening of both rings in reaction with ammonia.For communication 5, see [1].M. V. Lomonosov Moscow State University, Moscow 119899. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 397–402, March, 1997.     

S-tosylsulfene chloride — The first representative of a new class of sulfene halides

A representative of a previously unknown class of S-sulfonylsulfene halides — S-tosylsulfene chloride (1) — was prepared for the first time. It was shown that the reaction of sulfene chloride1 with cyclohexene yieldstrans-2-chlorocyclohexyl-p-toluene thiosulfonate, and the reaction with 1-hexene yields a mixture of 2-chlorohexyl-p-toluene thiosulfonate and 1-chloro-2-hexyl-p-toluene thiosulfonate.M. V. Lomonosov Moscow State University, 119899 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1217–1218, May, 1992.     

Synthesis of N-methylmorpholinium 6-oxo-3,5-dicyano-1,4,5,6-tetrahydro-4-(spirocyclopentane)pyridine-2-thiolate with the Michael reaction

N-Methylmorpholinium 6-oxo-3,5-dicyano-1,4,5,6-tetrahydro-4-(spirocyclopentane)pyridine-2-thiolate was obtained by reaction of cyclopentylidenecyanoacetic ester with cyanothioacetamide or cyclopentylidenecyanothioacetamide with cyanoacetic ester in the presence of N-methylmorpholine; it is used in synthesis of substituted 2-alkylthiotetrahydropyridines, 5-oxo-6,8-dicyano-2,3,6,7-tetrahydro-(5H)-7-(spirocyclopentane)-thiazolo[3,2-a]pyridine, 5-allyl-2-methylthio-3,5-dicyano-4,5-dihydro-4-(spirocyclo-pentane)pyridin-6(1H)-one, and 3-amino-6-oxo-5-cyano-4,5-dihydro-4-(spirocyclopentane)-2H-pyrazolo[5,4-b]pyridin-6(7H)-one. T. G. Shevchenko Lugansk State Pedagogical Institute, Lugansk 348011, Ukraine, N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 208–212, February, 1998.     

Synthesis and properties of N-methylmorpholinium 6-methyl-4-(4-pyridyl)-5-phenylcarbamoyl-3-cyano-1,4-dihydropyridine-2-thiolate

Condensation of acetoacetic acid anilide, 4-pyridyl aldehyde, cyanothioacetamide and N-methylmorpholine gave N-methylmorpholinium 6-methyl-4-(4-pyridyl)-5-phenylcarbamoyl-3-cyano-1,4-dihydropyridine-2-thiolate from which were obtained the corresponding substituted pyridinethiones, 2-alkylthio-1,4-dihydropyridines and 3-amino-2-benzoyl-6-methyl-4-(4-pyridyl)-5-phenylcarbamoylthieno[2,3-b]pyridine.T. G. Shevchenko Lugansk Pedagogical Institute, Lugansk 348011. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 672–675, May, 1997.     

Synthesis of 4-alkyl-substituted 1,2,3,4-tetrahydropyrimidin-2-ones by the Biginelli reaction

p-Toluenesulfinic acid is an effective catalyst for condensation of acetoacetic ester with urea and aliphatic or aromatic aldehydes, leading to formation of 4-substituted 6-methyl-5-ethoxycarbonyl-1,2,3,4-tetrahydropyrimidin-2-ones.M. V. Lomonosov State Academy of Fine Chemical Technology, Moscow 117571, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 979–982, July, 1998.     

2-Bromo-i-phenylethylidenemalononitrile in the synthesis of thieno[3,2-b]pyridines and thiazolo[4,5-b]pyridines

A novel regioselective synthesis of thieno[3, 2-blpyridines and thiazolo[4,5-blpyridines from 2-bromo-I-phenyl ethylidenemalononitrile is proposed. In the case of the thiazolo[4, 5-b]pyridines, the intermediate 5-(2, 2-dicyano-l-phenylvinyl)thiazoles were separated. Formation of the thiazolo(4,5-b]pyridines was confirmed by x-ray analysis.A. D. Zelinski Institute of Organic Synthesis, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 413–419, March, 1996. Original article submitted December 22, 1995.     

Indolopyridines with a bridging heteroatom

Reaction of 2-acetylpyridine with 4-[2.2]paracyclophanyllithium or 4-acetyl[2.2]paracyclophane with 2-pyridllithium gives 1-([2.2]paracyclophan-4-yl)-1-(2-pyridyl)ethanol. Its molecular and crystalline structures have been studied by x-ray analysis. It was found that heating this alcohol in acid medium causes dehydration and heterocyclization to give 1-paracyclophanyl-1-pyridylethylene and 10-methyl[2.2]paracyclophano[4,5-bindolizine.For communication 9 see [1]. This report is also communication [5] in the series Synthesis, Structure, and Biological Activity of [2.2]Paracyclophanes (for communication 4 see [2]).Russian University of National Friendship, Moscow 117198. A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow 117813. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 793–800, June, 1997.     

Synthesis, structure, and biological activity of [2.2]paracyclophanes. 6. Synthesis of 2-([2.2]paracyclophan-4-yl)(benzo[g])indoles

Cyclocondensation of 2-([2.2]paracyclophan-4-yl)-2-oxoethyltriethylammonium bromide with aniline and -naphthylamine gives 2-(paracyclophan-4-yl)indoles and benzo[g]indole respectively.For Communication 5, see [1].Russian University of National Friendship, Moscow 117198. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1065–1068, August, 1997.     

13C NMR spectra of azolopyridines and their quaternary salts

¹³ C NMR spectra of some azole series have been investigated: 2-pyridylbenzimidazoles, 2-pyridylimidazo [4,5-b]-pyridines, 2-pyridylimidazo[4,5-c]-pyridines, analogous oxazole compounds, as well as their mono- and bisquaternary salts. Some problems, related to the structure of these compounds in solution, have been discussed.V. I. Vernadskii Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Moscow 117975. Torino University, Italy. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 866–872, April, 1992.     

Reactions of 4,4,9-trimethyl-4,9-dihydro-4-silanaphtho[3,2-b]thiophen-9-one with nucleophilic and electrophilic reagents

We have studied the reaction of 4,4,9-trimethyl-4,9-dihydro-4-silanaphtho[3,2-b]-thiophen-9-one with organometallic compounds, lithium aluminum hydride, sodium borohydride, aniline, and acetyl nitrate. We have obtained secondary and tertiary dihydrosilanaphtho[3,2-b]thiophen-9-ols and 9-phenyliminodihydrosilanaphtho[3,2-b]thiophene. We have established that nitration of dihydrosilanaphthothiophen-9-one occurs at the position of the thiophene moiety.Russian University of International Friendship, Moscow 117923. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 621–625, May, 1998.     

Crystal structures of bis(quinidinium) molybdate hydrate and quinidinium chloride hydrate: The question of the stable conformation of quinidine

Anx-ray structural study of [QndH⁺]₂[MoO ₄ ^2– ]H₂O (1) and [QndH⁺]Cl^–H₂O (2), where Qnd = quinidine, was conducted. The structures have an ionic structure, and the ions are joined by hydrogen bonds into chains (1) and layers (2). Quinidinium cations protonated at the quinuclidine N atom have a conformation with agauche position of the N atom and OH group (as in neutral quinidine) corresponding to the local, and not the global, minimum of the calculated conformational energy.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1073–1078, May, 1992.     

An EPR and molecular mechanics study of radical adducts of phosphonyl radicals with 2-hydroperfluoro-4-methyl-and 4,4-dimethyl-2-pentene

EPR spectra of radical adducts of phosphonyl radicals with 2-hydroperfluoro-4-methyl- and 4,4-dimethyl-2-pentene have been studied. The molecular mechanics method has been used to determine the preferred conformation of the (CF₃)₂CF-CF-HCF₃P(O)(OMe)₂ radical. The eclipsed conformation of the C–P bond and 2p _z -orbital of an unpaired electron is stabilized due to steric factor and hyperconjugation.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2550–2554, November, 1992.     

Electrochemical and chemical oxidation of alcohols in a two-phase system using N-oxopiperidinium salt: Synthesis of 4-chlorobutanal,formylcyclopropanes, andm-phenoxybenzaldehyde

Oxidation of 4-chlorobutanol-1, cyclopropylcarbinols, andm-phenoxybenzyl alcohol with electrogenerated bromine, molecular bromine, and sodium hypochlorite using N-oxopiperidinium salt in the two-phase system CH ₂ Cl ₂ —water gave the corresponding carbonyl compounds with good yields.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 941–946, April, 1992.     

Formation of pyrrolo[2,3-f]quinolines from substituted 5-methyl-6-aminomoles by the combes reaction

It is shown that the reaction of 2, 3, 5-trimethyl-6-amino-indole with 1, 3-diketones is a convenient method for the preparation of angular IH-pyrrolo[2,3-f]quinolines, while the presence of a methyl group on the pyrrolic nitrogen atom of the initial indole as a result of steric hindrance completely blocks cyclization to the corresponding pyrroloquinolines.Mordovskii State Educational Institute, Saransk 430007. Moscow State University, Moscow 119899. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No 11, pp. 1499–1501, November, 1995. Original article submitted May 23, 1995.     

Di- and triphenylphosphonites of 2,2-di-(p-hydroxyphenyl)propane

Starting from 2,2-di-(p-hydroxyphenyl)propane and phenylphosphonic acid tetraethylamide we have prepared the first oligoarylenephosphonites with spatially separated phosphorus functionalities. We have studied the principal chemical properties of these compounds. We have shown the capacity of oligoarylenediphosphonites to coordinate with transition metals through one or all phosphorus atoms with formation of mono- and oligo complexes. We have found that monocomplexes can undergo degenerated metallotropic rearrangements.V. I. Lenin Moscow Pedagogical State University, 119883 Moscow, Russia. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2777–2784, December, 1992.     

Determination of copper, lead, and cadmium ions and the KF-91 flocculant in natural and waste waters by alternating-current stripping voltammetry

Procedures for determining copper, lead, and cadmium ions have been developed based on alternating-current stripping voltammetry with the use of a mercury-graphite electrode. These procedures are suitable for control of natural and waste waters containing surfactants. The procedures have been applied to the control of water purification and the determination of both heavy-metal ions and the KF-91 flocculant (2-methyl-N-methylpiridinium-5-polyvinyl methyl sulfate). Presented at the V All-Russian Conference with the Participation of CIS Countries on Electrochemical Methods of Analysis (EMA-99), Moscow, December 6–8, 1999.