Water → 3,5-dibenzyloxyphenol

HRID 1754592ノート

反応式

HRID 1754592 の反応式
C(S)C.[H-].[Na+].[CH2:6]([O:13][C:14]1[CH:19]=[C:18]([O:20]CC2C=CC=CC=2)[CH:17]=[C:16]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[CH:15]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.O>CN(C=O)C>[CH2:29]([O:28][C:16]1[CH:17]=[C:18]([OH:20])[CH:19]=[C:14]([O:13][CH2:6][C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[CH:15]=1)[C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1

参加物

6

反応物 4

HCID 962WaterHCID 6343EthanethiolHCID 24758Sodium hydrideHCID 10916273Benzene, 1,3,5-tris(phenylmethoxy)-

生成物 1

HCID 118229213,5-dibenzyloxyphenol収率 11%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
150 °C

実験手順

Ethanethiol (10 g, 216 mmol) was added dropwise to a stirred suspension of sodium hydride (60% dispersion in mineral oil, 2.4 g, 100 mmol) in dry DMF (120 mL) at 0° C. After 1 h, 1,3,5-tribenzyloxybezene (24 g, 60 mmol) was added in 10 batches and the mixture was heated to 150° C. for 1.5 h. After the reaction was cooled, water (500 mL) was added and the mixture was extracted with EtOAc. The combined organic layers were dried (MgSO4) and evaporated. The residue was purified by flash chromatography on silica gel (benzene) to give 3,5-dibenzyloxyphenol as white solid (11%) after recrystallization from carbon tetrachloride and product #d as white solid (56%) after recrystallization from EtOAc and hexane. Compound #d was identified by mp 107-109° C.; 1H NMR (CDCl3, 400 MHz) δ 7.36-7.23 (m, 15H), 6.25 (d, J=2.2 Hz, 1H), 6.07 (d, J=2.2 Hz, 1H), 4.96 (s, 2H), 4.92 (s, 2H), 3.99 (s, 2H); 13C NMR (CDCl3, 400 MHz) δ 158.4, 157.9, 154.9, 140.7, 136.7, 136.6, 128.4, 128.2, 128.1, 127.8, 127.5, 127.3, 127.0, 125.6, 108.5, 94.7, 93.3, 70.2, 69.9, 28.3; HRMS (ESI) calcd for C27H24O3Na (M+Na) 419.1623, found 419.1645.

後処理

  1. temperatureAfter the reaction was cooled
  2. extractionthe mixture was extracted with EtOAc
  3. dry with materialThe combined organic layers were dried (MgSO4)
  4. customevaporated
  5. customThe residue was purified by flash chromatography on silica gel (benzene)

出典と根拠

ORDレコード
ord-2c430b9461034176a75646960080cd75
出典データセット
uspto-grants-2015_10
特許番号
US09169230B2

反応ノート

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