3-(2-CARBOETHOXYPHENYL)-2-CHLORO-1-PROPENE synthesis

Yield:-

Reaction Conditions:

Stage #1: ethyl 2-iodobenzoatewith isopropylmagnesium bromide in tetrahydrofuran at -40; for 0.5 h;Inert atmosphere;
Stage #2: with copper(l) cyanide;lithium chloride in tetrahydrofuran at -40; for 0.0833333 h;Inert atmosphere;
Stage #3: 3-iodo-2-chloropropene in tetrahydrofuran at -40 - 20;Inert atmosphere;

Steps:

Typical experimental procedure for 2-(2-chloroallyl)-benzoic acid formation 1

General procedure: A dry, N₂ flushed 25 mL round-bottomed flask, equipped with a magnetic stirring bar, was charged with aryl iodide 3 (1 mmol) in anhydrous THF (5 mL), and cooled to -40 °C. i-PrMgCl (2 M in THF, 2 mmol) was slowly added. After 0.5 h, CuCN·2LiCl (premixed CuCN and 1 M LiCl in THF) (0.1 mmol) was added. After 5 min, at the same temperature, 2-chloro-3-iodo-propene (2 mmol) was added and the reaction mixture allowed to warm to rt. The reaction mixture was quenched with sat. NH₄Cl (20 mL) and extracted with MTBE (2 × 20 mL). The combined organic fractions were washed with brine (10 mL), then dried over Na₂SO₄, and concentrated in vacuo. The crude product was used in the next step after a silica plug treatment or without further purification.

References:

Linghu, Xin;McLaughlin, Mark;Chen, Cheng-Yi;Reamer, Robert A.;Dimichele, Lisa;Davies, Ian W. [Tetrahedron Letters,2012,vol. 53,# 13,p. 1550 - 1552] Location in patent:experimental part