Water → S-[(4-Formylphenyl)methyl] ethanethioate

HRID 2111454Notes

Reaction equation

HRID 2111454 reaction equation
Br[CH2:2][C:3]1[CH:10]=[CH:9][C:6]([CH:7]=[O:8])=[CH:5][CH:4]=1.BrCC1C=C(C=CC=1)C=O.[C:21]([O-:24])(=[S:23])[CH3:22].[K+].O>CC(C)=O>[C:21]([S:23][CH2:2][C:3]1[CH:10]=[CH:9][C:6]([CH:7]=[O:8])=[CH:5][CH:4]=1)(=[O:24])[CH3:22]

Participants

6

Reactant 4

HCID 962WaterHCID 71278253-(Bromomethyl)benzaldehydeHCID 112064214-(Bromomethyl)benzaldehydeHCID 23670855Potassium ethanethioate

Product 1

HCID 10559727S-[(4-Formylphenyl)methyl] ethanethioateYield 85%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

To a solution of 4-(bromomethyl)-benzaldehyde (Hsung et al. (1995) Organometallics, 14: 4808-4815; Bookser and Bruice (1991) Am. Chem. Soc. 113: 4208-4218; Wagner et al. (1997) Tetrahedron 53: 6755-6790 for the synthesis of 3-(bromomethyl)benzaldehyde) (0.43 g, 2.2 mmol) in acetone (10 mL) was added potassium thioacetate (280 mg, 2.5 mmol) under stirring at rt, then the mixture was refluxed. A precipitate formed after a few minutes. The reaction was monitored by TLC and cooled to rt when no starting material was detectable (3.5 h). Water (25 mL) was added, the mixture was extracted with ethyl acetate (3×30 mL), and the combined organic phases were dried (Na2SO4) and evaporated. Column chromatography over flash silica gel (ethyl ether/hexanes, 1:1) gave 359 mg (85% yield) of a brown oil which darkened upon standing (nonetheless elementary analysis four weeks after exposure to air at rt indicated a high level of purity as listed below). IR (neat): {tilde over (v)} 3052, 2923, 2830, 2737, 1694, 1606, 1576; 1H NMR δ 2.36 (s, 3H), 4.15 (s, 2H), 7.45, 7.81 (AA′BB′, 2×2H), 9.97 (s, 1H); 13C NMR (APT) δ 30.1 (−), 32.9 (+), 129.3 (−), 129.9 (−), 135.2 (+), 144.7 (+), 191.5 (−), 194.3 (+); GC-MS (EI) obsd 194, 152, 119, 91, 43; Anal. Calcd for C10H10O2S: C, 61.83; H, 5.19; S, 16.51. Found: C, 61.97; H, 5.20; S, 16.60.

Workup

  1. temperaturethe mixture was refluxed
  2. customA precipitate formed after a few minutes
  3. temperaturecooled to rt when no starting material
  4. custom(3.5 h)
  5. extractionthe mixture was extracted with ethyl acetate (3×30 mL)
  6. dry with materialthe combined organic phases were dried (Na2SO4)
  7. customevaporated

Sources & evidence

ORD record
ord-460b5c8e4a4e4370a13d954d872e7e2d
Source dataset
uspto-grants-2009_04
Patent number
US07518905B2

Reaction notes

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