- IONIC DIMERISATION OF TRIFLUOROPROPENENITRILE AND ITS ADDITION REACTIONS WITH METHYL TRIFLUOROPROPENOATE
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Dimerisation of trifluoropropenenitrile (I) in the presence of potassium fluoride and tertiary amines afforded a mixture of stereoisomeric perfluoro-4-methyl-2-pentenedinitriles (II), higherboiling compounds, and 2,3,3,3-tetrafluoropropanenitrile (III) which arises by proton transfer from the solvent molecule.Under optimum conditions, product II was obtained in about 50percent yield.Reaction of the nitrile I with methyl trifluoropropenoate (IV) gave, besides the dimers II and V, the product of addition of the nitrile I to the propenoate, IV, i.e. methyl 4-cyanoperfluoro-2-pentenoate (VI), and the addition product of the propenoate IV to the nitrile I, i.e. methyl 4-cyanoperfluoro-2-methyl-3-butenoate (VII).The relative reactivity of I and IV is discussed.The ratio of stereoisomers in II, V, VI and VII indicates that the magnitude of the steric substituent effect, operating in the reaction mechanism, decreases in the order -CFCF3(COOCH3)> -CFCF3(CN)> -COOCH3> -CN.
- Svoboda, Jiri,Paleta, Oldrich,Dedek, Vaclav
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p. 406 - 414
(2007/10/02)
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