Sodium hydride → 2-Methyl-2-(triphenylmethylthio)propanal

HRID 581636Notes

Reaction equation

HRID 581636 reaction equation
[C:1]1([C:7]([SH:20])([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[H-].[Na+].Br[C:24]([CH3:28])([CH3:27])[CH:25]=[O:26]>C1COCC1.C1(C)C=CC=CC=1>[CH3:27][C:24]([S:20][C:7]([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)([C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)[C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)([CH3:28])[CH:25]=[O:26]

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 77281Benzenemethanethiol, alpha,alpha-diphenyl-HCID 5783772-Bromo-2-methylpropanal

Product 1

HCID 211921942-Methyl-2-(triphenylmethylthio)propanalYield 59%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Triphenylmethylmercaptan (362.94 g, 1.31 mol, 100 mol %) dissolved in anhydrous THF (2 L) was cooled in an ice bath under argon. Sodium hydride (60% in oil; 54.39 g, 1.35 mol, 104 mol %) was added in portions over 20 min. 2-bromo-2-methylpropanal (206.06 g, 1.36 mol, 104 mol %; see Stevens & Gillis, 1957, J. Amer. Chem. Soc. 79: 3448-51) was then added slowly over 20 min. The reaction mixture was allowed to warm to room temperature and stirred for 12 hours. The reaction was quenched with water (1 L) and extracted with diethyl ether (3×1 L). The ether extracts were combined, washed with saturated NaCl solution (500 mL), dried over Na2SO4 and filtered. The solvent was removed under reduced pressure to afford a thick orange oil. The crude oil was dissolved in toluene (200 mL) and diluted to 2 L with hot hexanes. The mixture was filtered through a sintered glass funnel and cooled at -5° C. for 12 hours. The white crystalline solid which formed was removed by filtration to afford 266.36 g (59% yield) of the title compound. The melting point of the resulting compound was determined to be 83-85° C. Nuclear magnetic resonance characterization experiments yielded the following molecular signature:

Workup

  1. temperaturewas cooled in an ice bath under argon
  2. customThe reaction was quenched with water (1 L)
  3. extractionextracted with diethyl ether (3×1 L)
  4. washwashed with saturated NaCl solution (500 mL)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. customThe solvent was removed under reduced pressure
  8. customto afford a thick orange oil
  9. filtrationThe mixture was filtered through a sintered glass funnel
  10. temperaturecooled at -5° C. for 12 hours
  11. customThe white crystalline solid which formed
  12. customwas removed by filtration

Sources & evidence

ORD record
ord-c5aa0298eeae4effbc76e5106a2023f6
Source dataset
uspto-grants-1999_07
Patent number
US05922303

Reaction notes

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