149508-58-7Relevant academic research and scientific papers
Synthesis and reactivity of 3-chloro-3-trifluoromethylacroleins: stabilisation of the tetrahedral intermediate in a nucleophilic vinylic "substitution"
Alvernhe, Gerard,Greif, Dieter,Langlois, Bernard,Laurent, Andre,Drean, Isabelle Le,et al.
, p. 167 - 172 (2007/10/02)
Trifluoromethyl ketones 1a-d reacted with the Vilsmeier reagent to give CF3-substituted β-chloro-vinylaldehydes 2a-d in good yields.Using 2-amino-ethanethiol as a nucleophile, a different regiochemistry of cyclization that depends on a methyl or trifluoromethyl substituent was observed.The cyclization of trifluoromethyl compounds 2a and 2e into thiazolidines 7 or 24 results in the stabilization of the tetrahedral intermediate by the captodative effect.We report the first direct substitution of a tetrahedral intermediate (instead of elimination) in a nucleophilic vinylic reaction. trifluoromethylacroleins / Michael addition / tetrahedral intermediate
Trifluoromethyl Substitution Affects the Regiochemistry of Cyclising Condensation in 1,4 Substitution Processes
Alvernhe, Gerard M.,Laurent, Andre J.,Drean, Isabelle M. Le,Selmi, Abdelaziz
, p. 2483 - 2486 (2007/10/02)
β-Trifluoromethyl β-chloroacrolein 2 reacts with 2-mercaptoethylamine 3 to produce thiazolidine 5 instead of the expected thiazepine 8.The reason of this behaviour is the formation of the tetrahedral intermediate 6 because of stabilisation by the trifluoromethyl group; an intramolecular substitution takes place faster than a 1,4 addition-elimination process. Key Words: Trifluoromethyl; Michael reaction; regiochemistry; thiazolidine; thiazepine
