Ethanol → Ethyl 2-(2-chlorophenyl)acetate

反応式

[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH3:8].C(O[O:14][C:15]([CH3:18])(C)C)(C)(C)C.[C]=O.[CH2:21]([OH:23])C>>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][C:21]([O:14][CH2:15][CH3:18])=[O:23]

参加物

反応物 4

HCID 702Ethanol

HCID 72382-Chlorotoluene

HCID 8033Di-tert-butyl peroxide

HCID 178418416HCID 178418416、化合物2 回

生成物 1

HCID 10081468Ethyl 2-(2-chlorophenyl)acetate収率 83%

反応条件

温度: 120 °C

実験手順

o-Chlorotoluene (1.89 g), ethanol (46 mg), di-tert-butyl peroxide (73 mg, 1 equivalent), and Pd(Xantphos)Cl2 (3.8 mg, 1 mol %) were added into a reaction kettle, into which 10 atm carbon monoxide was introduced. The reaction was heated to 120° C., and stirred at this constant temperature for 16 h. After the reaction was completed, carbon monoxide was discharged, and 82 mg ethyl o-chlorophenylacetate was obtained by column chromatography, in a yield of 83%. 1HNMR (400 MHz, CDCl3) δ 1.24 (t, J=7.2 Hz, 3H), 3.77 (s, 2H), 4.15 (q, J=7.2 Hz, 2H), 7.21-7.24 (m, 2H), 7.28-7.30 (m, 1H), 7.36-7.40 (m, 1H); 13CNMR (100 MHz, CDCl3) δ 14.2, 39.2, 61.0, 126.9, 128.6, 129.5, 131.4, 132.6, 134.6, 170.6; HRMS (ESI) calcd. for C10H11ClNaO2 [M+Na]: 221.0340. found: 221.0343. The ethyl o-chlorophenylacetate obtained was dissolved in 1,4-dioxane. 6 N sodium hydroxide solution was added, and the reaction was heated to 60° C. After 2 h of reaction, the pH value was adjusted to 1 by adding 2 N hydrochloric acid. After removing the organic solvent under reduced pressure, 66 mg product o-chlorophenylacetic acid was obtained by extraction with ethyl acetate, and the yield of hydrolysis was 94%.