Divinyl Sulfoxide: XI. Selective Addition of Carbonodithioate Anions to Divinyl Sulfoxide in the Water-Benzene System

Selective monoaddition of carbonodithioate anions to divinyl sulfoxide gives rise to O-alkyl S-[2-(vinylsulfinyl)ethyl] carbonodithioates [ROC(S)SK, R = Et, Bu; 42–50°C, 6 h, NaHCO₃, aqueous benzene].     

Crystal and molecular structures of the complexes of cobalt dichloride with 1-isopropenylimidazole and 1-vinylimidazole

The crystal and molecular structures of bis(1-isopropenylimidazole)dichlorocobalt (C₁₂H₁₆Cl₂·N₄Co) [R 0.036 (R _W 0.089) for 3229 unique reflections with I > 2σ(I)] and tetra(1-vinylimidazole)dichlorocobalt (C₂₀H₂₄Cl₂N₈Co) [R 0.031 (R _W 0.072) for 1863 unique reflections with I > 2σ(I)] were determined. In these molecular complexes, the monodentate terminal 1-alkenylimidazole ligands coordinate to the metal via a “pyridine” nitrogen atom. In C₁₂H₁₆Cl₂N₄Co, the Co atom has a distorted tetrahedral 2N,2Cl coordination. The coordination polyhedron of cobalt in C₂₀H₂₄Cl₂N₈Co is a strongly elongated 4N,2Cl octahedron. The Co-N and Co-Cl bonds [Co-N 2.015(2) and 2.032(4) Å; Co-Cl 2.229(2) Å] in the tetrahedral complex C₁₂H₁₆Cl₂N₄Co are shorter than those in the octahedral complex C₂₀H₂₄Cl₂N₈Co [Co-N 2.134(2) and 2.157(2) Å; Co-Cl 2.518(1) Å]. In the structures of both complexes there are short contacts involving the Cl atoms.     

The radiation yields of radicals in solid organic substances containing heteroatoms

EPR has been used to measure the radiation yields of radicals (G_R) in various classes of organic compounds containing heteroatoms: dialkyl disulfides, diphenyl- and dibenzyl disulfide, alkyl derivatives of thiophene, thiophenecarboxylic acids, halogen derivatives of thiophene, and saturated heterocyclic compounds containing nitrogen, oxygen, and sulfur atoms. It has been shown that 1) G_R=0.2–1 per 100 eV in saturated disulfides and cyclic sulfides, while G_R=3–8 per 100 eV in the corresponding hydrocarbons, alcohols, oxides, and alkyleneimines; 2) the introduction of a sulfur atom into aromatic compounds does not alter the radiation stability; 3) disturbance of the conjugation of halogen atoms and of the carboxyl group with the thiophene ring leads to a decrease in the radiation stability. It is suggested that the increased stability of sulfur-containing compounds may be due to the excitation of the electrons in the S atom at the d-orbitals, which lie appreciably lower in the sulfur atom than in the atoms of oxygen, nitrogen, and carbon, and the subsequent dissipation of the excitation energy.     

NMR spectroscopic study of the effects of conjugation

Conclusions We have examined the¹³C NMR spectra of para- and meta-substituted alkylthiobenzenes. Steric disruption of the p, -conjugation of sulfur with the aromatic fragment on increase in the size of the alkyl substituents is typical of all the series. The degree of p,-conjugation and the molecular conformation also depend on the electronic effects of the para and meta substituents.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1525–1531, July, 1981.     

A new method for the synthesis of diorganylvinylphosphine oxides

Diorganylvinylphosphine oxides were synthesized in 31–38% yields on heating (50°C) diorganylphosphine oxides with vinyl sulfoxides or divinyl sulfone in the presence of KOH. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1895–1896, October, 1997.     

Interaction of 1, 3-dioxa-2-silacyclanes and their oligomers with alklymagnesium and arylmagnesium halides

Conclusions Cyclic alkoxysilanes — 1,3-dioxa-2-silacyclanes — and their oligomers are decomposed by organomagnesium compounds with the formation of the corresponding silanols (disiloxanes) and tetraalkylsilanols.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1283–1285, July, 1966.     

Cyanoacetylene and Its Derivatives: XXXIV. Nucleophilic Addition of Tetrazole to Cyanoacetylenes

Nucleophilic addition of tetrazole to 4-hydroxy-4-alkyl-2-alkynonitriles and to 3-phenyl-2-propynonitrile occurred regiospecifically and afforded E-, Z-4-hydroxy-4-methyl-3-tetrazolyl-2-alkenonitriles and 3-tetrazolyl-3-phenyl-2-propenonitrile [20–40°C, 13–50 h, 4–15 wt% MOH (M = Na, K), THF (or DMSO)] in up to 69% yield. The attempt to perform cyclization of the hydroxy-containing adducts into iminodihydrofurans (KOH, ethanol, 23-25°C) resulted in vinyl nucleophilic substitution of the tetrazole moiety by an ethoxy group.     

Reactions of Elemental Phosphorus and Phosphine with Electrophiles in Superbasic Systems: XVI. Phosphorylation of Benzyl Chloride with Elemental Phosphorus and Phosphine

The major product of the reaction of benzyl chloride with red phosphorus in the system concentrated aqueous KOH-dioxane-phase-transfer catalyst (43–95°C, Ar) is tribenzylphosphine oxide (yield up to 61%). Under similar conditions, phosphorylation of benzyl chloride with white phosphorus occurs differently, yielding dibenzylphosphine oxide as major product. Conditions are found for preparative synthesis of dibenzylphosphine from phosphine and benzyl chloride in the system KOH-DMSO.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005, pp. 724–728.Original Russian Text Copyright © 2005 by Trofimov, Gusarova, Malysheva, Shaikhudinova, Belogorlova, Kazantseva, Sukhov, Plotnikova.