Abstract
3-Cyano-1-methyl-4-trifluoromethyl-3-pyrroline, as well as 4-cyano-1-methyl-3-trifluoromethyl- and 3-cyano-1-methyl-4-trifluoromethyl-2-pyrrolines were synthesized under DBU catalysis by heating of Z-3-cyano-4-ethoxy-1-methyl-4-trifluoromethyl-pyrrolidine in vacuo. 3-Cyano-1-methyl-4-trifluoromethyl-3-pyrroline undergoes redox disproportionation catalyzed by potassium tert-butoxide to form 2,4-bis(2-cyano-1-trifluoromethylprop-2-enylidene)-1,3-dimethyl-1,3-diazetidine and E-/Z-isomers of 3-cyano-1-methyl-4-trifluoromethylpyrrolidine. The same 1,3-diazetidine is formed by oxidation of 3-cyano-1-methyl-4-trifluoromethyl-3-pyrroline with atmospheric oxygen. Individual E- and Z-isomers of 3-cyano-1-methyl-4-trifluoromethylpyrrolidine were obtained by stereospecific 1,3-dipolar cycloaddition of E- and Z-isomers of 4,4,4-trifluorobut-2-enonitrile to N-methyl(methaniminio)-N-methylide generated in situ.
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This work was performed under financial support of the Ministry of Science and Higher Education of the Russian Federation in the framework of state task No. 075-00697-22-00 with the use of equipment of the Center for molecule composition studies of INEOS RAS.
No human or animal subjects were used in this research.
The authors declare no competing interests.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, Vol. 72, No. 7, pp. 1560–1568, July, 2023.
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Volkonskii, A.Y., Kagramanov, N.D. Synthesis and transformations of trifluoromethyl-substituted cyanopyrrolines. Russ Chem Bull 72, 1560–1568 (2023). https://doi.org/10.1007/s11172-023-3934-7
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DOI: https://doi.org/10.1007/s11172-023-3934-7