Potassium Hydroxide → 6-(5-Ethoxycarbonyl-5-phenylhexylsulfanyl)-2-methyl-2-phenylhexanoic acid ethyl ester

HRID 48314Notes

Reaction equation

HRID 48314 reaction equation
Br[CH2:2][CH2:3][CH2:4][CH2:5][C:6]([CH3:18])([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:7]([O:9][CH2:10][CH3:11])=[O:8].N[C:20](N)=[S:21].[OH-:23].[K+]>C(O)C>[CH2:10]([O:9][C:7](=[O:8])[C:6]([CH3:18])([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:5][CH2:4][CH2:3][CH2:2][S:21][CH2:20][CH2:3][CH2:4][CH2:5][C:6]([C:7]([O:9][CH2:10][CH3:11])=[O:23])([C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)[CH3:18])[CH3:11]

Participants

5

Reactant 3

HCID 14797Potassium HydroxideHCID 2723790ThioureaHCID 11174430Ethyl 6-bromo-2-methyl-2-phenylhexanoate

Product 1

HCID 116418176-(5-Ethoxycarbonyl-5-phenylhexylsulfanyl)-2-methyl-2-phenylhexanoic acid ethyl esterYield 85%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A solution of ethyl 6-bromo-2-methyl-2-phenyl-hexanoate (18.5 g, 59.0 mmol), thiourea (7.0 g, 91.0 mmol), and potassium hydroxide (6.1 g, 92.0 mmol) in ethanol (200 mL) was heated to 40-50° C. overnight. The mixture was cooled to rt, poured into an ice/water/HCl mixture (150 g/150 mL/150 mL), and stirred for 20 min. The mixture was extracted with dichloromethane (4′ 60 mL) and the combined organic layers were washed with sat. NaHCO3 solution (100 mL) and sat. NH4Cl solution (100 mL). The dichloromethane solution was dried over MgSO4 and concentrated in vacuo. The crude product was purified by column chromatography on silica gel (hexanes/ethyl acetate=10/1) to give 6-(5-ethoxycarbonyl-5-phenylhexylsulfanyl)-2-methyl-2-phenyl-hexanoic acid ethyl ester (12.5 g, 85%) as a yellow oil. 1H NMR (300 MHz, CDCl3/TMS): d (ppm): 7.42-7.15 (m, 10H), 4.20-4.05 (q, 4H, J=7.1 Hz), 2.44 (t, J=7.6 Hz, 4H), 2.15-1.95 (m, 2H), 1.95-1.75 (m, 2H), 1.62-1.40 (m, 10H), 1.35-1.10 (m, 4H), 1.18 (t, 6H, J=7.1 Hz). 13C NMR (75 MHz, CDCl3/TMS): d (ppm): 176.06, 143.89, 128.25, 126.52, 125.84, 60.65, 50.04, 38.77, 31.80, 30.11, 24.06, 22.61, 14.01. HRMS (LSIMS, nba): Calcd. for C30H43O4S1 (MH+): 499.2882, found 499.2868.

Workup

  1. extractionThe mixture was extracted with dichloromethane (4′ 60 mL) and the combined organic layers
  2. washwere washed with sat. NaHCO3 solution (100 mL) and sat. NH4Cl solution (100 mL)
  3. dry with materialThe dichloromethane solution was dried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customThe crude product was purified by column chromatography on silica gel (hexanes/ethyl acetate=10/1)

Sources & evidence

ORD record
ord-41768f3d41914157b0838f585da9dbce
Source dataset
uspto-grants-2004_03
Patent number
US06703422B2

Reaction notes

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