Ethanol → Ethyl p-tolylacetate

HRID 1411170Notes

Reaction equation

HRID 1411170 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:8])=[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>>[CH3:1][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 7809P-XyleneHCID 8033Di-tert-butyl peroxideHCID 178418416HCID 178418416, compound2×

Product 1

HCID 84175Ethyl p-tolylacetateYield 96%

Conditions

Temperature
120 °C

Procedure

p-Xylene (1.59 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 85 mg ethyl p-methylphenylacetate was obtained by column chromatography, in a yield of 96%. 1HNMR (400 MHz, CDCl3) δ 1.23 (t, J=7.2 Hz, 3H), 2.33 (s, 3H), 3.57 (s, 2H), 4.11 (q, J=7.2 Hz, 2H), 7.11-7.18 (m, 4H); 13CNMR (100 MHz, CDCl3) δ 14.2, 21.1, 41.0, 60.8, 129.1, 139.3, 131.1, 136.6, 171.8; HRMS (ESI) calcd. for C11H14NaO2 [M+Na]: 201.0886. found: 201.0882. The ethyl p-methylphenylacetate 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, 69 mg product p-methylphenylacetic acid was obtained by extraction with ethyl acetate, and the yield of hydrolysis was 96%.

Workup

  1. additionwas introduced

Sources & evidence

ORD record
ord-c645362700054102b00622d016de2416
Source dataset
uspto-grants-2014_12
Patent number
US08921591B2

Reaction notes

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