Formation of N-cyclopropylhydrazones by azo coupling of cyclopropyldiazonium with aliphatic CH acids

Decomposition of N-cyclopropyl-N-nitrosourea under the action of K₂CO₃ or KOH containing 15—20% of H₂O at 0—7 °C gives rise to cyclopropyldiazonium, which reacts with some -diketones, methyl cyanoacetate, or malonodinitrile to form the corresponding cyclopropylhydrazones. The latter compounds are analogous to products of azo coupling and isomerization of aryldiazonium ions with the above-mentioned substrates. These transformations provide the first example of azo coupling of the cyclopropyldiazonium ion in the series of activated aliphatic CH acids.     

Acylation of norcarane and its derivatives by pivaloyl tetrafluoroborate

Conclusions The decomposition of the complex obtained in the reaction of pivaloyl tetrafluoroborate with norcarane and its 1-methyl and 1-phenyl derivatives by water gives 1-hydroxy-3-pivaloyl derivatives of cyclohexanes and the corresponding unsaturated ketones. The hydride decomposition of the same complex leads to derivatives of 6-oxabicyclo[3.2.1]octane.For preliminary report see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2512–2518, November, 1976.     

Regioselective catalytic addition of terminal acetylenes to methyl esters of 1-alkylcyclopropene-3-carboxylic acids

Conclusions Terminal acetylenes and HCN in the presence of CuCl add regioselectively as CH-acids to the unsaturated three-membered ring of methyl esters of 1-alkylcyclopropene-3-carboxylic acids to form the methyl esters of the corresponding 3-alken-5-ynoic acids or 4-cyano-3-alkyl-3-butenoic acids in yields up to 60%.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2401–2405, October, 1985.These results were partially reported at the Seventh All-Union Conference on the Chemistry of Acetylene [1].     

Synthesis and structure of <Emphasis Type="Italic">N</Emphasis>-(2-(1-adamantyl)-2-hydroxyethyl)cytisine diastereomers

Diastereomers of N-(2-(1-adamantyl)-2-hydroxyethyl)cytisine were synthesized by reduction of N-(2-(1-adamantyl)-2-oxoethyl)cytisine with NaBH₄. Their structures were established using x-ray structure analysis. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 244–247, May–June, 2007.     

Reaction of γ-nitroketones and methyl 4-nitrobutanoates with formaldehyde and primary amines

5-Nitropentan-2-one reacts with methylamine and formaldehyde according to the Mannich reaction pattern to give 5-hexahydropyrimidinylcarbonyl-substituted 1-nitro-3,7-diazabicyclo[3.3.1]nonane in one experimental stage. When methyl 3-R-4-nitrobutanoates are used, the reaction stops after the formation of substituted 5-nitrohexahydropyrimidines in 40–98% yields. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1687–1693, July, 2005.     

Generation of 1-aryl-3-methoxycarbonylnitrilimines and their reaction with halogen-containing unsaturated compounds

Thermal decomposition of 1-(4-methoxyphenyl)- and 1-(4-fluorophenyl)hepta(methoxycarbonyl)-3a,7a-dihydroindazoles at 135 °C in the presence of allyl or propargyl halides leads to the elimination of hexamethyl benzenehexacarboxylate and the formation of the corresponding pyrazolines or pyrazoles as the products of 1,3-dipolar cycloaddition of 1-aryl-3-methoxycarbonylnitrilimines to the multiple bonds of the substrates used. In the case of vinyl halides, the products of the target reactions are either obtained in low yields or nonexistent, with a side conversions taking place instead. Thus, for example, in the case of 1,1-dichloro-4-methylpenta-1,3-diene, besides hexamethyl benzenehexacarboxylate, 3,5,5-trichloro-2-methylpent-4-en-2-ol and arylchlorohydrazones MeO₂CC(Cl)=N-NHAr were unexpectedly isolated as the main products, as well.     

Electrochemical Synthesis of Organophosphorus Compounds on the Base of Elemental Phosphorus

Abstract

The straight synthesis of organophosphorus compounds on the base of white phosphorus may solve a lot of problems concerning with simplification technology proceeding as a whole. At present time we are investigating procedures for the electrochemical generation of organophosphorus compounds directly white phosphorus The ability to carry out this type of procedure in single step will have considerable environmental benefits. Thus procedure affording trialkylphosphates in a yield more than 90% and purity up to 98% for row material in undivided cell has been elaborated.     

Molecular structure of 3,7-dimethyl-9-thia-3,7-diazabicyclo[3.3.1]nonane-9,9-dioxide

By a single crystal X-ray diffraction study the molecular structure of 3,7-dimethyl-9-thia-3,7-diazabicyclo[3.3.1]nonane-9,9-dioxide having a chair-chair conformation with a diequatorial arrangement of methyl groups at nitrogen atoms is determined. Compound 1 C₈H₁₆N₂O₂S crystallizes in the space group Pnma with the following cell parameters: a = 11.0262(3) Å, b = 14.4490(3) Å, c = 6.1780(3) Å.