Water → Ethyl 2-(3-methylbenzyl)-propionate

HRID 1073058

반응식

HRID 1073058 반응식
[CH3:1][C:2]([CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([CH3:20])[CH:15]=1)(C(OCC)=O)[C:3]([O:5][CH2:6][CH3:7])=[O:4].[OH-].[Na+].O>[Br-].C([N+](C)(C)C)CCCCCCCCCCCCC.C(O)C>[CH3:20][C:16]1[CH:15]=[C:14]([CH:19]=[CH:18][CH:17]=1)[CH2:13][CH:2]([CH3:1])[C:3]([O:5][CH2:6][CH3:7])=[O:4]

참가 물질

6

반응물 3

HCID 962WaterHCID 14798Sodium HydroxideHCID 22157936Diethyl 2-methyl-2-(3-methylbenzyl)-malonate

생성물 1

HCID 22157933Ethyl 2-(3-methylbenzyl)-propionate

시약·촉매·용매 2

HCID 14250Tetradecyltrimethylammonium bromide촉매HCID 702Ethanol용매

실험 절차

500 ml of toluene, 207 g of ground potassium carbonate, 8 g of potassium iodide, 7 g of 18-crown-6 and 209 g of diethyl methylmalonate were initially introduced into a 2 l four-necked flask. The mixture was heated to 85° C. with stirring. 141 g of 3-methylbenzyl chloride were added dropwise in the course of half an hour and the mixture was then stirred at 90° C. for 8 hours. After cooling, the salts were removed by repeatedly shaking with water and the organic layer was distilled. 184 g of diethyl 2-methyl-2-(3-methylbenzyl)-malonate were obtained at a boiling point of 120° C. and a pressure of about 0.02 mbar. For hydrolysis, the ester was boiled under reflux with stirring for 16 hours with 60 g of NaOH, 170 ml of water and a spatula tip-full of tetradecyltrimethylammonium bromide, ethanol which formed in the meantime being distilled off. The dicarboxylic acid was liberated by acidifying with hydrochloric acid, separated off and heated in xylene for 4 hours under reflux for decarboxylation. The monocarboxylic acid was then esterified with ethanol (p-toluenesulfonic acid as catalyst, cyclohexane as entraining agent for water). 115 g of ethyl 2-(3-methylbenzyl)-propionate (boiling point 70°-73° C. at 0.03 mbar) were obtained. For hydrogenation, 21 g of LiAlH4 were dissolved or suspended in 800 ml of tetrahydrofuran in a 2 l four-necked flask under nitrogen. A mixture of 110 g of ethyl 2-(3-methylbenzyl)-propionate and 100 ml of tetrahydrofuran were then added dropwise with ice cooling. The mixture was then decomposed with ice and hydrochloric acid, extracted with ether and dried over K2CO3, and 75 g of 2-methyl-3-(3-methylphenyl)propan-1-ol (boiling point 68°-70° C. at 0.1 mbar) were obtained by distillation.

후처리

  1. customFor hydrolysis
  2. temperatureunder reflux
  3. distillationbeing distilled off
  4. customseparated off
  5. temperatureheated in xylene for 4 hours
  6. temperatureunder reflux for decarboxylation

출처 및 근거

ORD 기록
ord-7c19d5b8b72f4d788fc1a8c577a81036
출처 데이터셋
uspto-grants-1990_11
특허 번호
US04968668

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