Conclusions
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1.
The addition of thiols (CH3SH, t-C4H9SH) to methyl ethynyl ketone in methanol, in the presence of Triton B, leads to the unstable hemithioketal, the 1,2-addition product. The hemithioketal decomposes at −20°, with the resultant formation of the addition products of the thiol to the C=C bond as a mixture of the cis- and trans-alkylthiovihyl alkyl ketones.
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2.
Within the framework of the self-consistent MO LCAO method, taking into account all of the valence electrons (CNDO/2), we calculated the energies of the two “transition” complexes that characterize the possible competing attack of alcoholate ion on the fourth or second C atom of methyl ethynyl ketone. The results of the calculation disclosed that attack on the C4 atom should be more probable in the case of the simple bimolecular reaction scheme, despite the seeming disadvantage from the standpoint of the distribution of the charges in the methyl ethynyl ketone molecule.
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See [1] for Communication 4.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 890–897, April, 1975.
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Mikhelashvili-Fioliya, I.L., Bogdanov, V.S., Chuvylkin, N.D. et al. Stereochemistey of nucleophilic addition reactions to ketones with acetylene bonds. Russ Chem Bull 24, 806–811 (1975). https://doi.org/10.1007/BF00920698
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DOI: https://doi.org/10.1007/BF00920698