Water → tert-Butyl 3-(4'-Hydroxyphenyl)mercaptopivaloate

HRID 1586768Notes

Reaction equation

HRID 1586768 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([SH:8])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].Cl[CH2:16][C:17]([CH3:26])([CH3:25])[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19].O>CN(C=O)C.CCOCC>[OH:1][C:2]1[CH:7]=[CH:6][C:5]([S:8][CH2:16][C:17]([CH3:26])([CH3:25])[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 2401474-MercaptophenolHCID 22590969Tert-butyl 3-chloropivaloate

Product 1

HCID 21695402tert-Butyl 3-(4'-Hydroxyphenyl)mercaptopivaloateYield 60%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

To a slurry of 4-hydroxythiophenol (259.4 g, 2.06 mol) and potassium carbonate (284.2 g, 2.06 mol) in 500 mL of DMF at 0° C. was added tert-butyl 3-chloropivaloate (373.8 g, 1.94 mol) dropwise over 2 hours. After stirring to room temperature overnight, the reaction was heated to 110° C. for 3 hours. The reaction was allowed to cool for room temperature and water and ether were added. The layers were separated and the organic layer washed with water and 5% NaOH, dried over MgSO4 and concentrated. The resulting oil was recrystallized from 1:3 CH2Cl2 /pet. ether to afford 328.0 g (60%) of the desired product. mp 100°-100.5° C.; 1H NMR (CDCl3) δ1.22 (s,6H), 1.44 (s,9H), 3.07 (s,2H), 5.42 (br s,1H,--OH), 6.77 (d,2H,J=8.7 Hz); 13C NMR (CDCl3) δ 24.62, 27.73, 44.58, 46.86, 81.00, 116.2, 127.7, 133.5, 155.4, 176.7; IR (KBr, film) 3362, 2971, 1720, 1693, 1600, 1583, 1495, 1472, 1366, 1320, 1223, 1150(s), 835, 817 cm-1.

Workup

  1. temperaturethe reaction was heated to 110° C. for 3 hours
  2. temperatureto cool for room temperature
  3. customThe layers were separated
  4. washthe organic layer washed with water and 5% NaOH
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customThe resulting oil was recrystallized from 1:3 CH2Cl2 /pet. ether

Sources & evidence

ORD record
ord-a9bcf706e32c4a55bdeb718fa017de7b
Source dataset
uspto-grants-1993_06
Patent number
US05216022

Reaction notes

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