Reaction of methylmagnesium iodide with perfluorocarboxylate esters

Conclusions In the reaction of methylmagnesium iodide with esters of perfluorocarboxylic acids, the magnesium salt of the hemiketal was found to be more stable and the ketone yield was found to be higher with increasing bulk of the alkoxy group of the ester.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1163–1165, May, 1988.     

Reaction of methylmagnesium iodide with dibutylcyanamide and dibutylnitrosamine

The reaction of methylmagnesium iodide with di(n-butyl)cyanamide results in dibutylamine, dibutylisopropylamine, and acetonitrile, while the reaction with di(n-butyl)nitrosamine affords acetaldehyde dibutylhydrazone. Formaldehyde, acetone, and 2-butanone dibutylhydrazones, as well as acetaldehyde butyl(1-methylbutyl)hydrazone, 2-butanone butyl(1-methylbutyl)hydrazone, 1,1-dibutyl-2,2-dimethylhydrazine, and 1,1-dibutyl-2-ethyl-2-methylhydrazine were also identified in minor amounts. Di(n-butyl)nitramine reacts with methylmagnesium iodide to give di(n-butyl)nitrosamine.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2078–2081, December, 1993.     

Reaction of keto alcohols with organophosphorus compounds

Conclusions Trialkyl(aryl) phosphites and phosphonites react with 3-ketobutanol to give, respectively,-ketobutylphosphonic and phosphinic acids, while the phosphinites react to give the oxides of tertiary phosphines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimieheskaya, No. 5, pp. 1087–1092, May, 1970.     

Reaction of sulfolene oxides with thiocyanates

The reaction of oxides of sulfolene and its methyl derivative with potassium and sodium thiocyanates was studied. It is shown that under the influence of potassium thiocyanate these oxides undergo isomerization to the corresponding unsaturated alcohols. In the presence of sulfuric acid, however, the oxides react with sodium thiocyanate to give addition products, viz., hydroxythiocyanatosulfolanes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1333–1334, October, 1982.     

Reaction of methyl iodide with organylethynyl silatranylmethyl chalcogenides

The reactivity of organylethynyl silatranylmethyl chalcogenides RC=CYCH₂Si(OCH₂CH₂)₃N (R=Ph, Me₃Si; Y=S, Se, Te) in the reaction with methyl iodide depending on the nature of the chalcogen Y, the substituent R at the triple bond, and the reaction conditions was studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2550–2551, December, 1998.     

Reaction of CCl4 with o- and m-carboranylmagnesium iodides,and with phenyl- and methylmagnesium iodides

Conclusions Together with RCl, substantial amounts of RI are formed when RMgI (o- and m-carboranylmagnesium iodides, C₆H₅MgI and CH₃MgI) is reacted with CCl₄. A mixture of o-, m-RCB₁₀H₁₀CCl and o-, m-RCB₁₀·H₁₀CBr is formed when o- and m-RCB₁₀H₁₀CMgBr is reacted with CCl₄.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2312–2314, October, 1971.     

Reaction of alkene oxides with aromatic thionylimines

The oxides of ethylene and propene, and epichlorohydrin, react with thionylanilines (ArN=S=O) in the presence of tetraethylammonium bromide catalyst at 95°–100° C to give N-arylalkeneamidosulfites, whose structures are confirmed by retrosynthesis from the corresponding N-phenylamino alcohols, and thionyl chloride, as well as by their IR spectra.     

Reaction of secondary phosphine oxides with acylacetylenes

Secondary phosphine oxides reacted with 1-alkanoyl-2-phenylacetylenes in chemoselective fashion under mild conditions (20°C, THF) in the absence of a catalyst (diphenylphosphine oxide) or in the presence of potassium hydroxide [bis(2-phenylethyl)phosphine oxide] to give 1-alkyl-1-diphenyl(or 2-phenylethyl)-phosphoryl-3-phenylprop-2-yn-1-ols in up to 96% yield. The reaction of diphenylphosphine oxide with 1-alkanoyl-2-phenylacetylenes in the system KOH-THF (20°C) afforded not only adducts at the carbonyl group but also products of double α,β-addition at the triple bond, 2,3-bis(diphenylphosphoryl)-3-phenylpropan-1-ones.     

Reaction of some aromatic nitrile oxides with dimedone

1,3-Dipolar cycloaddition of benzonitrile and m-nitrobenzonitrile oxides to the enol form of dimedone gives the corresponding 4-oxotetrahydrobenzisoxazoles. A second reaction path — nucleophilic addition of the enol to the N-oxide to give a hydroxamic acid derivative — is observed in the case of m-nitrobenzonitrile oxide. The tetrahydrobenzisoxazoles are converted to enamine derivatives of benzoyldimedone under catalytic hydrogenation conditions.     

Reaction of cyclic phosphorus selenoacids with alkene oxides

Conclusions The alkylene glycol selenophosphoric acids react with alkene oxides in the same way as the analogous thiophosphoric acids. The selenophosphoric acid derivatives are less stable than the thio analogs when stored or heated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 677–680, March, 1983.