Synthesis of some alkaloids using the allyl derivatives of boron (review)

Data on the application of the allylic derivatives of boron for the synthesis of piperidine, indolizine, pyrrolizidine, and indole alkaloids are reviewed.A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1015–1027, August, 1999.     

Synthesis and properties of N-methylmorpholinium 4aryl-6-methyl-5-phenylcarbamoyl-3cyano-1,4dihydropyridine-2-thiolates. Molecular and crystalline structure of 2allylthio-6-methyl-5-phenylcarbamoyl-4-(2chlorophenyl)-3-cyano-1,4-dihydropyridine

By the condensation of an aromatic aldehyde, the anilide of acetoacetic acid, cyanothioacetamide, and Nmethylmorpholine, substituted N-methylmorpholinium 1,4-dihydropyridine-2-thiolates have been synthesized and subsequently used in the synthesis of the corresponding thiones, 2-alkylthiopyridines, thieno[2, 3b]pyridines, and disulfides. X-ray diffraction has been used to establish the structure of 2-allylthio-6-methyl-5phenylcarbamoyl-4-(2-chlorophenyl)-3-cyano-1, 4-dihydropyridine.T. G. Shevchenko Lugansk State Pedagogical Institute, Lugansk 348011. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, Moscow 117813. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1243–1251, September, 1996. Original article submitted May 13, 1996.     

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.     

Indolopyridines with a bridging heteroatom. 9. Synthesis,structure, and thermolysis of 5-hydroxy-5-(2-pyridyl)-fluorene and 4-azafluorene

Treatment of fluorenone or 4-azafluoren-9-one with 2-pyridyllithium gives 45-hydroxy-5-(2-pyridyl)fluorene and its aza analog. The structure of the former has been studied by x-ray crystallography. It was found that, in contrast to the non-condensed diaryl-2-pyridylcarbinols, these alcohols do not undergo acid catalyzed dehydration and heterocyclization. Under pyrolytic conditions. 5-pyridylfluorenol undergoes fission to form fluorenone.Russian University of National Friendship, Moscow 117198 and A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow 117813. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 955–959, July, 1996. Original article submitted March 18, 1996.     

Stereoselective synthesis and structure of 3,4-trans-6-amino-4-aryl-3-carbamoyl-5-cyano-1,2,3,4-tetrahydropyridin-2(1H)-thiones

Condensation of thiocarbamoylacetamide with arylidenemalononitrile or the three-component condensation of thiocarbamoylacetamide with aldehydes and malononitrile in the presence of triethylamine occurred regioselectively to give triethylammonium-6-amino-4-aryl-3-carbamoyl-5-cyano-1,4-dihydropyridine-2-thiolates. Protonation of the latter occurred stereoselectively to give 3,4-trans-6-aryl-3-carbamoyl-5-cyano-1,2,3,4-tetrahydropyridin-2(1H)-thiones. The¹H NMR spectrum and single x-ray crystallography indicate that the dihydropyridine ring has he sofa conformation with trans-pseudodiaxial orientation of the Ar and CONH₂ groups and trans-pseudoequatorial orientation of atoms 3-H and 4-H.N. D. Zelinskii Organic Chemistry Institute, Russian Academy of Sciences, Moscow, 117913. A. N. Nesmeyanov Institute of Elementoorganic Chemistry, Russian Academy of Sciences, Moscow, 117813. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1376–1382, Octoberm 1996. Original article submitted June 10, 1996.     

Synthesis of 4-trifluoromethyl-7-hydroxycoumarin derivatives. Structure of 3-cyano-4-trifluoromethyl-7-acetoxycoumarin

A method was developed for the production of derivatives of 4-trifluoromethyl-7-hydroxycoumarin with electron-withdrawing groups (CN, CF₃CO) at position 3. The structure of 3-cyano-4-trifluoromethyl-7-acetoxycoumarin was proved by x-ray crystallographic investigation. The effect of the substituents on the geometry of the molecule is discussed.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Institute of Biochemistry, Academy of Sciences of Armenia, 375044 Erevan. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1371–1375, June, 1992.     

Semi-hindered phenols. 1. Synthesis of 3,5-di-tert-butylsalicylic aldehyde

Some differences were observed in the solid- and liquid-phase benzylic oxidation of 2-(hydroxy- or dialkylamino)-methyl-4,6-di-tert-butylphenols. Oxidation of these semi-hindered phenols with lead tetraacetate gave a new compound: 3,5-di-tert-butyl-ortho-benzoquinone diacylal.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Institute of Synthetic Polymeric Materials, Russian Academy of Sciences, 117393 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2380–2384, October, 1992.     

Synthesis of heterocycles from the products of the addition of polyhaloalkanes to unsaturated systems

4-Methyl-5-(2,2,2-trichloroethyl) derivatives of 2-thiazolethione and 2-amino-3-hydroxythiazolium chloride were synthesized from 3-thiocyanato-5,5,5-trichloro-2-pentanone. The structures of these derivatives were determined using spectral data and x-ray diffraction structural analysis.For Communication 7, see [1]N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117813. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences Moscow 117813. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 832–838, June, 1998.     

Trisubstituted 1,3,5-triazines. 2. Synthesis of 1,3,5-triazines from 2,4,6-tris[di(tert-butoxycarbonyl)methylene]hexahydro-1,3,5-triazine

A study was carried out on electrophilic addition and hydrolytic dissociation of 2,4,6-tris[di(tert-butoxycarbonyl)methylene]hexahydro-1,3,5-triazine. Chloro, bromo, and methyl derivatives of tris[di(tert-butoxycarbonyl)methyl]-1,3,5-triazine were synthesized for the first time as well as 2,4,6-tris-(tert-butoxycarbonylmethyl)-1,3,5-triazine. For Communication 1, see ref. [1]. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow and Institute of Chemical Physics, Russian Academy of Sciences at Chernogolovka, 142432 Chernogolovka, Moscow Oblast. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1404–1407, October, 1998.     

Formation of 1,2-oxazine derivatives: A novel type of reaction between 2-aminooxazoles and maleic acid imide

N,N-Disubstituted 2-aminooxazoles in acetic acid at 20°C undergo addition of maleinimide, converting to alkylidene succinimides or 1,2-oxazine derivatives.N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913; e-mail: zhulin@cacr.ioc.ac.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1128–1131, August, 2000.     

Dehydrogenation of isobutane with carbon dioxide on manganese-containing catalysts

Institute of Petrochemical Processes, Azerbaidzhan Academy of Sciences, 370025 Baku; N. N. Semenova Institute of Chemical Physics, Russian Academy of Sciences, 117334 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1230–1231, May, 1992.     

Convenient method for synthesis of functionally substituted hexahydroquinolines. Molecular and crystal structure of 4-isopropyl-7,7-dimethyl-5-oxo-3-cyano-2-cyanomethylthio-1,4,5,6,7,8-hexahydroquinoline

We have obtained 2-alkylthio-7,7-dimethyl-5-oxo-4-ethyl(isopropyl)-3-cyano-1,4,5,6,7,8-hexahydroquinolines by reaction of 5,5-dimethylcyclohexane-1,3-dione, propionic (or isobutyric) aldehyde, cyanothioacetamide, and alkyl halides. We have established the structure of 4-isopropyl-7,7-dimethyl-5-oxo-3-cyano-2-cyanomethylthio-1,4,5,6,7,8-hexahydroquinoline by x-ray diffraction.T. G. Shevchenko Lugansk State Pedagogical Institute, Lugansk 348011. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, Moscow 117813. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 785–792, June, 1997.     

Nitromethyl derivatives of 1,3,5-triazine. Synthesis and properties

The destructive nitration of 2,4,6-tris[di(carboxy)methylene]hexahydro-1,3,5-triazine and its esters has been investigated. A first representative of the nitromethyl derivatives of 1,3,5-triazine, viz. 2,4,6-tris(nitromethyl)-1,3,5-triazine, has been synthesized.Deceased.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, Chernogolovka 142432. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1254–1259, September, 1997.     

New method for the synthesis of 1,2,3-triazole 1-oxides

A general method is proposed for the synthesis of 1,2,3-triazole 1-oxides using 3,4-dinitro- or 4-amino-3-nitrofuroxanes.Deceased.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913, Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 675–679, May, 1996. Original article submitted February 22, 1996. Resubmitted after revision April 5, 1996.     

Isomerization of dichloro- and difluorobenzenes: A quantum-chemical consideration

The AM-1 method with full optimization of geometry was used to study several proposed isomerization mechanisms for dichloro- and difluorobenzenes on active centers as proton donors. Preferred positions of proton addition in dihalobenzenes were studied and protonation and activation energies for intramolecular migration of hydrogen and halogen atoms were determined. It was shown that the isomerization mechanisms are the same for dichloro-and difluorobenzenes and result from a 1,2-shift of the halogen. The activation energy for migration of a fluorine atom in difluorobenzenonium cations is substantially higher than for a chlorine atom in dichlorobenzenonium cations. The data obtained on the mechanism have experimental verification.A. N. Nesmeyanov Institute Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117433 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 731–737, March, 1992.     

Nucleophilic substitution reactions of 2,4,6-tris(trinitromethyl)-1,3,5-triazine. 1. Interaction of 2,4,6-tris(trinitromethyl)-1,3,5-triazine with alcohols,diols, ammonia,and secondary amines

A study has been made of nucleophilic substitution reactions of 2,4,6-tris(trinitromethyl)-1,3,5-triazine with certain nucleophiles. The possibility of replacing one, two, or three trinitromethyl groups in this compound has been demonstrated.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 674–678, May, 1995. Original article submitted February 28, 1995.     

Recyclization of substituted furoxans into 1,2,3-triazol-1-oxide derivatives

The effect of the position and nature of substituents on the recyclization of substituted furoxans has been established.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences (RAN), Moscow 117913, Russia Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences (RAN), Chernogolovka 142432, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 202–209, February, 1999.     

Intramolecular cyclization of 2-(o-carboran-1-yl) methylthio-3-cyanopyridines in basic conditions

Substituted 2-(o-carboran-1-yl)methylthio-3-cyanopyridines and-pyrimidines undergo Thorpe-Ziegler cyclization under the influence of KOH in DMF to give the corresponding thienopyridines and thienopyrimidines. The reaction is complicated by a side reaction in which thecloso-carborane nucleus is converted to anido-system. The yield of thienopyridines containing acloso-carborane unit is increased by introduction of an acceptor substituent in the pyridine ring. Destruction of thecloso-carborane nucleus is not observed with the pyrimidine derivatives. The structures of the series of new carborane-containing thienopyridines and pyrimidines was confirmed by spectroscopic methods.A. N. Nesmeyanov Institute of Elementoorganic Chemistry, Russian Academy of Sciences, Moscow 117813. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 790–793, June, 1998.     

Trisubstituted 1,3,5-triazines 3. Synthesis of substituted 2,4,6-tris(hydroxyiminomethyl)-1,3,5-triazines

Previously undescribed substituted 2,4,6-tris(hydroxyiminomethyl)-1,3,5-triazines, including 2,4,6-(1,3,5-triazinetriyl)trinitrolic acid, have been synthesized.For Communication 2, see [1].N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 117913. Institute of Chemical Physics in Chernoglovka, Chernoglovka, Moscow Oblast, 142432, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 76–78, January, 1999.     

Peroxide-initiated condensation of carboranes-12 with 1,2-dichloroethylene

The interaction of carboranes-12 with 1,2-dichloroethylene was investigated at 150–200°C in the presence oftert-butyl peroxide as an initiator.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, Moscow 117813. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 1017–1019, April, 1992.