Chloroacetic Acid → 2-Cyclohexylideneacetic acid

A mixture of 4.0 ml (0.031 mole) of diethyl phosphite and 4.46 g (0.093 mole) of 50% sodium hydride in mineral oil in 100 ml of 1,2-dimethoxyethane under nitrogen was treated with a solution of 2.93 g (0.031 mole) of chloroacetic acid in 30 ml of 1,2-dimethoxyethane, and the mixture was stirred until hydrogen gas evolution ceased. Then 3.20 ml (0.031 mole) of cyclohexanone was added and the mixture was stirred for 1 h, after which it was quenched by the addition of 5 ml of ethanol and then poured into 500 ml of water. The strongly basic solution was washed with ether to remove mineral oil (ether extract discarded), then acidified to pH 4 with conc hydrochloric acid and extracted with ether. The ether extract was dried (over MgSO4) and evaporated in vacuo to yield 2.35 g (54%) of cyclohexylideneacetic acid which was recrystallized from methanol/water; mp 90°-91.5° (literature mp 90°-92°, Beesley, Thorpe, and Ingold, J. Chem. Soc., 107, 1099 (1915)); Ir (CHCl3) 3600-2400 (--OH), 1700 (C=O), and 1650 (C=C) cm-1 ; 1H NMR (CDCl3) δ 1.60 (6, s, CH2CH2CH2CH 2 CH2C=), ##STR8## 5.50 (1, s, =CHCO2H), and 11.40 (1, s, --CO2H); Anal Calcd for C8H12O2 : C, 68.55; H, 8.63; Found: C, 68.45; H, 8.61.

1. customafter which it was quenched by the addition of 5 ml of ethanol
2. additionpoured into 500 ml of water
3. washThe strongly basic solution was washed with ether
4. customto remove
5. extractionmineral oil (ether extract discarded)
6. extractionextracted with ether
7. extractionThe ether extract
8. dry with materialwas dried (over MgSO4)
9. customevaporated in vacuo

ORDレコード

ord-ac5aafcc020a40d0a95eaca95dd4b245

出典データセット

uspto-grants-1981_12

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US04307232