Ethanol → Ethyl (4-chlorophenyl)acetate

HRID 1411178Notes

Reaction equation

HRID 1411178 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=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:7]=[CH:6][C:5]([CH2:8][C:21]([O:14][CH2:15][CH3:18])=[O:23])=[CH:4][CH:3]=1

Participants

5

Reactant 4

HCID 702EthanolHCID 78104-ChlorotolueneHCID 8033Di-tert-butyl peroxideHCID 178418416HCID 178418416, compound2×

Product 1

HCID 84177Ethyl (4-chlorophenyl)acetateYield 90%

Conditions

Temperature
120 °C

Procedure

p-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 89 mg ethyl p-chlorophenylacetate was obtained by column chromatography, in a yield of 90%. 1HNMR (400 MHz, CDCl3) δ 1.23 (t, J=7.2 Hz, 3H), 3.57 (s, 2H), 4.12 (q, J=7.2 Hz, 2H), 7.19-7.23 (m, 2H), 7.27-7.30 (m, 2H); 13CNMR (100 MHz, CDCl3) δ 14.2, 40.7, 61.0, 128.7, 130.7, 132.6, 133.0, 171.2; HRMS (ESI) calcd. for C10H11ClNaO2 [M+Na]: 221.0340. found: 221.0342. The ethyl p-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, 75 mg product p-chlorophenylacetic acid was obtained by extraction with ethyl acetate, and the yield of hydrolysis was 98%.

Workup

  1. additionwas introduced

Sources & evidence

ORD record
ord-0e80ad73dce34b16b73156572e751ace
Source dataset
uspto-grants-2014_12
Patent number
US08921591B2

Reaction notes

Loading…