Water → 3,5-dibenzyloxyphenol

HRID 217542Notes

Reaction equation

HRID 217542 reaction equation
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

Participants

6

Reactant 4

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

Product 1

HCID 118229213,5-dibenzyloxyphenolYield 11%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
150 °C

Procedure

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, 2 H), 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.

Workup

  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)

Sources & evidence

ORD record
ord-5e7b1fa9df95497580ac703054e9265b
Source dataset
uspto-grants-2012_06
Patent number
US08193377B2

Reaction notes

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