Ethanol → Ethyl 2-(3-chlorophenyl)acetate

HRID 1411180Notes

Reaction equation

HRID 1411180 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH3:8])[CH:5]=[CH:6][CH:7]=1.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:3]=[C:4]([CH2:8][C:21]([O:14][CH2:15][CH3:18])=[O:23])[CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 4

HCID 702EthanolHCID 79313-ChlorotolueneHCID 8033Di-tert-butyl peroxideHCID 178418416HCID 178418416, compound2×

Product 1

HCID 8063366Ethyl 2-(3-chlorophenyl)acetateYield 83%

Conditions

Temperature
120 °C

Procedure

m-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 m-chlorophenylacetate was obtained by column chromatography, in a yield of 83%. 1HNMR (400 MHz, CDCl3) δ 1.24 (t, J=7.2 Hz, 3H), 3.58 (s, 2H), 4.13 (q, J=7.2 Hz, 2H), 7.15-7.18 (m, 1H), 7.24-7.26 (m, 1H), 7.29 (s, 1H); 13CNMR (100 MHz, CDCl3) δ 14.2, 40.9, 61.1, 127.3, 127.5, 129.5, 129.8, 134.3, 135.9, 170.9; HRMS (ESI) calcd. for C10H11ClNaO2 [M+Na]: 221.0340. found: 221.0342. The ethyl m-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, 64 mg product m-chlorophenylacetic acid was obtained by extraction with ethyl acetate, and the yield of hydrolysis was 91%.

Workup

  1. additionwas introduced

Sources & evidence

ORD record
ord-c4e4a094d2b54eed857248eb180ff88f
Source dataset
uspto-grants-2014_12
Patent number
US08921591B2

Reaction notes

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