Summary
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1.
Under mild nucleophilic conditions (60–70° in alcoholic solution) alkanethiols add to butenyne predominantly at the triple bond. The cis-1-(alkylthio)-1,3-butadiene is formed stereospecifically, and only a small amount (0–12%) of the 2-(alkylthio)-1,3-butadiene is detected.
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2.
The addition of the thiolate ion to the conjugated double bond of butenyne with formation of the 4-(alkylthiol-1,2-butadiene and the 4-(alkylthio)-1-butyne is of secondary importance.
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3.
The isomerization of the allene compounds RSCH2C=C=CH2 at 125–135° in presence of alkalies gives cis-and trans-1-(alkylthio)-1,3-butadienes in equimolecular proportions. On the basis of this a method was developed for the preparation of cis-1-(alkylthio)-1,3-butadienes (containing up to 15% of the trans isomers) from the mixture of products of the nucleophilic addition of thiols to butenyne.
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4.
The structures of the products were proved by means of analytical gas-liquid chromatography, the IR spectra, the study of their reactions, and independent syntheses.
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This article is published in accordance with a resolution of the Conference of Editors-in-Chief of Journals of the USSR Academy of Sciences of July 12, 1962, as a dissertation paper by V. N. Petrov.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2180–2188, December, 1966.
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Petrov, V.N., Andrianova, G.M. & Prilezhaeva, E.N. Structural and steric orientation in nucleophilic additions of thiols to butenyne. Russ Chem Bull 15, 2109–2114 (1966). https://doi.org/10.1007/BF00867710
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DOI: https://doi.org/10.1007/BF00867710