Methanol → HCID 72956942, compound

Participants

Reaction Steps

At 0° C., a solution of 62.9 g (185 mmol) of J, 2-(2-benzyloxyethyl)-1-chloro-1-(1,2,2-trichlorovinyl)cyclopropane, in 50 ml of anhydrous methanol is slowly added dropwise with stirring to a freshly prepared solution of 34.0 g of sodium (1.48 mol, 8 equivalents) in 250 ml of methanol. The mixture is then heated at reflux for 2 d. After cooling to room temperature, the mixture is admixed with 700 ml of water and extracted with diethyl ether. The combined organic phases are concentrated under reduced pressure and the residue is taken up in 300 ml of methanol. 25 ml of 10 per cent hydrochloric acid are added and the reaction mixture is stirred for 45 min. The mixture is then admixed with 300 ml of saturated sodium bicarbonate solution and extracted with diethyl ether. The ether extracts are dried over calcium chloride. Removal of the solvent under reduced pressure gives a dark-brown oil. Filtration through 300 g of silica gel (PE:diethyl ether 10:1) gives 24.4 g (47%) of K methyl [2-(2-benzyloxyethyl)cyclo-propylidene]chloroacetate in the form of a pale yellow liquid as a mixture of two diastereomers in the ratio of 1:1.6.-13C-NMR (62.9 MHz, CDCl3, additionally DEPT), isomer A: δ=11.6 (−), 20.3 (+), 31.6 (−), 52.8 (+), 68.8 (−), 72.9 (−), 115.3 (Cquart), 127.49 (+), 127.53 (+), 128.3 (+), 138.3 (Cquart), 143.8 (Cquart), 162.4 (Cquart). -isomer B: δ=15.6 (−), 16.1 (+), 31.5 (−), 52.8 (+), 69.3 (−), 73.0 (−), 114.6 (Cquart), 127.49 (+), 127.53 (+), 128.3 (+), 143.3 (Cquart), 162-7 (Cquart). MS (70 eV), m/z (%): 280 (<1) [M+], 245 (1) [M+—Cl], 189 (2) [M+—CH2Ph], 91 (100) [CH2Ph+]. —C15H17ClO3 (280.8): calc. C, 64.17 H, 6.10; found C, 63.24, H, 5.97.

Provenance & Evidence