Abstract
2-Phenylalkanenitriles 1 react under PTC conditions with 1,1or cis-dichloroethylene giving ethynylated products 2. Nitriles 1, α-substituted desoxybenzoines 6, 2-substituted phenylacetaldehydes 8, 1,3-dialkylindene 10 and substituted diethylmalonates 12 afford with trichloroethylene 1,2-dichlorovinylated derivatives, respectively 3, 7, enol ethers 9, 11 and 13. PTC reaction of trans-dichloroethylene with 1 or 10 lead to formation of 2-chlorovinylated 14 or ethynylated 16 products, respectively. In majority of cases the products were formed in good yield. The course of these reactions is rationalized.
Highlights
1,1-Dichloroethylene, cis-1,2-dichloroethylene or trichloroethylene (TRI) eliminate hydrogen chloride with formation of chloroacetylene (CA) 1 or dichloroacetylene (DCA), 2,3 respectively when treated with alkali metal hydroxide in the presence of a catalyst, a quaternary ammonium salt 1,2 or in aprotic dipolar solvent 3
PTC technique was successfully applied to reactions of TRI with oxygen,[8] selenium 9-11 and nitrogen 2,12-15 nucleophiles leading to formation of the corresponding 1,2-dichlorovinyl substituted derivatives and/or other products
Nucleophiles, including carbanions, add to mono substituted triple bond usually in trans-fashion with formation of cis-products.[16,17,18] cis-Adducts formed from carbanions and CA should eliminate hydrogen chloride giving ethynylated C-H acids
Summary
Dedicated to Professor Mieczysław Mąkosza on his 70th birthday (received 27 Sep 03; accepted 20 Feb 04; published on the web 27 Feb 04). Abstract 2-Phenylalkanenitriles 1 react under PTC conditions with 1,1- or cis-dichloroethylene giving ethynylated products 2. Nitriles 1, α-substituted desoxybenzoines 6, 2-substituted phenylacetaldehydes 8, 1,3-dialkylindene 10 and substituted diethylmalonates 12 afford with trichloroethylene 1,2-dichlorovinylated derivatives, respectively 3, 7, enol ethers 9, 11 and 13. PTC reaction of trans-dichloroethylene with 1 or 10 lead to formation of 2-chlorovinylated 14 or ethynylated 16 products, respectively. In majority of cases the products were formed in good yield. The course of these reactions is rationalized
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