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

HRID 613212노트

반응식

HRID 613212 반응식
[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]

참가 물질

6

반응물 3

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

생성물 1

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

시약·촉매·용매 2

HCID 1140Toluene용매HCID 8028Tetrahydrofuran용매

실험 절차

Triphenylmethylmercaptan (362.94 g, 1.31 mol, 100 mol %) dissolved in anhydrous THF (tetrahydrafuran; 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:

후처리

  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

출처 및 근거

ORD 기록
ord-a8d023961bc541869655852f83822888
출처 데이터셋
uspto-grants-1999_12
특허 번호
US06007792

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