3,4-Dimethoxybenzene-1-thiol → t-Butyl-3-(3,4-dimethoxyphenyl)sulfanyl-7-phenylheptanoate

HRID 1107167Notes

Reaction equation

HRID 1107167 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([SH:11])[CH:6]=[CH:7][C:8]=1[O:9][CH3:10].[C:12]1([CH2:18][CH2:19][CH2:20][CH2:21][CH:22]=[CH:23][C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1>C1COCC1.O.[Li]CCCC>[C:27]([O:26][C:24](=[O:25])[CH2:23][CH:22]([S:11][C:5]1[CH:6]=[CH:7][C:8]([O:9][CH3:10])=[C:3]([O:2][CH3:1])[CH:4]=1)[CH2:21][CH2:20][CH2:19][CH2:18][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)([CH3:30])([CH3:28])[CH3:29]

Participants

6

Reactant 2

HCID 1365393,4-Dimethoxybenzene-1-thiolHCID 54541139t-Butyl 7-phenyl-2-heptenoate

Product 1

HCID 10670305t-Butyl-3-(3,4-dimethoxyphenyl)sulfanyl-7-phenylheptanoateYield 90.1%

Reagents, catalysts & solvents 3

HCID 178418339ButyllithiumCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 3,4-dimethoxythiophenol (8.25 mL, 57.6 mmol) in anhydrous THF (100 mL) at 0° C., is added n-BuLi (2.5 M in hexane, 0.77 mL, 1.92 mmol) and the solution is stirred for 15 minutes under a nitrogen atmosphere. t-butyl 7-phenyl-2-heptenoate (10 g, 38.4 mmol) in THF (100 mL) is added dropwise and the mixture is allowed to warm to room temperature and stir overnight. TLC analysis indicated complete reaction. The reaction mixture is diluted with water (300 mL) and extracted with ether (3×250 mL). Combined organic extracts are washed successively with sat. Na2CO3 solution (4×200 mL), water (200 mL) and brine (200 mL) then dried over MgSO4 and concentrated to afford a pale yellow oil which is chromatographed on silica gel (pet-ether/EtOAc, 9:1) to afford 14.9 g of (±)-t-butyl-3-(3,4-dimethoxyphenyl)sulfanyl-7-phenylheptanoate (90%) as a colorless oil. TLC analysis [pet-ether/EtOAc, 9:1, Rf (heptenoate)=0.80, Rf (heptanoate)=0.50]. 1H NMR (300 MHz, CDCl3) δ 1.44 (s, 9H), 1.48-1.68 (m, 6H), 2.42 (dABq, 2H), 2.60 (t, 2H), 3.28 (t, 1H), 3.85 (d, 6H), 6.75 (d, 1H), 7.0 (dd, 2H), 7.15 (d, 3H), 7.25 (t, 2H) ppm. Mass spectrum (FAB) m/z 447 (M+H)+.

Workup

  1. stirringstir overnight
  2. customreaction
  3. extractionextracted with ether (3×250 mL)
  4. washCombined organic extracts are washed successively with sat. Na2CO3 solution (4×200 mL), water (200 mL) and brine (200 mL)
  5. dry with materialthen dried over MgSO4
  6. concentrationconcentrated
  7. customto afford a pale yellow oil which
  8. customis chromatographed on silica gel (pet-ether/EtOAc, 9:1)

Sources & evidence

ORD record
ord-5b9c18a8e5d8433398e2819571ed61a7
Source dataset
uspto-grants-2000_05
Patent number
US06057369

Reaction notes

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