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.     

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.     

ESR study of the reversible dimerization of phosphonylfullerenyl radicals

A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1936–1937, August, 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.     

An ESR study of the adducts of phosphonyl radicals with fullerene-70

A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1938–1940, August, 1992.     

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.     

Cycloaddition of bis(trifluoromethyl)diazomethane to activated alkenes and alkynes

Bis(Trifluoromethyl)diazomethane undergoes [3+2] cycloaddition with activated alkenes and alkynes regiospecifically to give substituted pyrazolines and pyrazoles.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 452–455, February, 1992.     

Synthesis of fluorovinyl fluorosulfonates

A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, p. 1451, June, 1992.     

An efficient dehydrofluorinating system for polyvinylidene fluoride

A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1223–1225, May, 1992.     

Reactions of highly electrophilic polyfluoro unsaturated compounds with pyrazole derivatives

Pyrazole derivatives were hydroxyalkylated at the C⁴ atom by hexafluoroacetate and methyl trifluoropyruvate. The products of the hydroxyalkylation were dehydrated to the corresponding alkylidene derivatives which were reacted with nucleophiles. Dicyanoethylenes, obtained from polyfluorocarbonyl compounds, alkylated pyrazol-5-ones with the formation of pyrazolopyran derivatives.A. N. Nesmeyanov Institute for Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2617–2623, November, 1992.     

Epr investigation of the adducts of element-centered radicals with polyhedral carbon clusters (fullerenes)

A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1457–1458, June, 1992.     

Effects of formation of an adduct of trialkylpyrazole with CdBr2 in15N NMR

The¹⁵N NMR chemical shifts for the analogous diamagnetic adduct of 3,5-dipropyl-4-ethylpyrazole with cadmium dibromide were measured to obtain reference data for estimating the isotropic paramagnetic NMR shifts of nitrogen in paramagnetic adducts of alkylpyrazoles with transition metal salts. The¹³C and¹H NMR spectra were obtained for the same adduct in conditions of frozen protometallotropic rearrangement of the hydrogen in the NH group and the temperature-dependent NMR spectra of isotopes of Cd were made.A. N. Nesmeyanov Institute of Organoelemental 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. 756–761, June, 1998.     

Synthesis,molecular, and crystalline structure of 3-benzoyl-1,2-di(ethylsulfonyl)indolizine

Reaction of pyridiniumbenzoyl methylide with (E)-1,2-di(ethylsulfonyl)-1,2-dichloroethene (which has four nucleophilic groups) occurs via a 1,3-dipolar stereo- and regio directed cycloaddition to give 3-benzoyl-1,2-di(ethylsulfonyl)indolizine the structure of which was established using x-ray crystallography. The rotation of the phenyl substituted by 72.6° relative to the indolizine ring plane and the geometry of the ethylsulfonyl groups can be explained by steric hindrance due to shortened intramolecular non-valence contacts.Deceased.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow 117813. N. D. Zelinski Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 950–954, July, 1996. Original article submitted May 5, 1996.     

Anomalous addition of trifluoroacetic acid to 2,3-difluorobicyclohepta[2.2.1]diene-2,5

Trifluoroacetic acid adds to 2,3-difluorobicyclohepta[2.2.1]diene-2,5 at the FC=CF bond to give mainly the cis-exo adduct.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 450–452, February, 1992.     

Aliphatic aldehydes in the synthesis of condensed 4-alkyl(cycloalkyl)-2-amino-3-cyano-4H-pyrans

Substituted 4-alkyl(cycloalkyl)-2-amino-3-cyano-4H-pyrans have been obtained from the reaction of aliphatic aldehydes with malononitrile and some other CH acids in the presence of N-methylmorpholine. T. G. Shevchenko Lugansk State Pedagogical University, Lugansk 348011, Ukraine. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117813, Russia; Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1363–1366, October, 1999.     

Metallization of 1-substituted 1-benzyl-o-carboranes with n-butyllithium and some conversions of 1-R-2-benzyllithium-o-carboranes

It was shown that 1-R-2-benzyl-o-carboranes (R=Me, i-Pr, Ph, PhCH₂) and other derivatives of o-carborane containing an ArCH₂ group in positions 1 and 2 are readily metallized by n-butyllithium, forming the corresponding benzyllithium derivatives, which react with electrophilic reagents like the usual organolithium compounds, permitting the synthesis of various C-substituted 1-o-carboranes.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 431–435, February, 1992.     

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.     

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.     

Salts of α-cyanoacrylic acid with sterically hindered tertiary amines

Syntheses are reported for representatives of a new class of derivatives of -cyanoacrylic acid, namely, its salts with brucine, tert-butyldimethylamine, and diisopropylmethylamine.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 212–214, January, 1992.     

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.