Hydrochloric Acid → 5-(3,3-Dimethylbutyl)thiophene-2-carbaldehyde

HRID 629139

반응식

HRID 629139 반응식
[S:1]1[CH:5]=[CH:4][CH:3]=[CH:2]1.C([Li])CCC.Cl[CH2:12][CH2:13][C:14]([CH3:17])([CH3:16])[CH3:15].CN(C)[CH:20]=[O:21].Cl>CN(C)P(N(C)C)(N(C)C)=O.O1CCCC1>[CH3:15][C:14]([CH3:17])([CH3:16])[CH2:13][CH2:12][C:5]1[S:1][C:2]([CH:20]=[O:21])=[CH:3][CH:4]=1

참가 물질

8

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온도
-78 °C

실험 절차

To a solution of thiophene (300 mg, 3.57 mmol) in anhydrous 10% hexamethylphosphoramide in tetrahydrofuran (33 mL) under argon at −78° C. was added n-butyllithium (1.57 mL, 2.5 M in hexanes) dropwise. After stirring at −78° C. for 1 hour, 1-chloro-3,3-dimethylbutane (430 mg, 3.57 mmol) was added dropwise and the resulting solution allowed to warm to room temperature over 3 hours. The reaction mixture was re-cooled to −78° C., a second portion of n-butyllithium (1.78 mL, 4.46 mmol) was added dropwise over 5 minutes and the mixture was stirred for 1 hour at −78° C. before anhydrous dimethylformamide (1.38 mL, 17.8 mmol) was added dropwise and the resulting mixture allowed to warm to room temperature. The reaction mixture was poured into 1 N hydrochloric acid (150 mL) and organics were extracted with ether (3×100 mL), dried with magnesium sulfate, filtered and concentrated. The residue was purified by flash chromatography on silica gel with gradient elution (5%→20% ethyl acetate in hexanes) to give 5-(3,3-dimethylbutyl)thiophene-2-carbaldehyde (130 mg, 19%). Used without further characterization.

후처리

  1. temperatureto warm to room temperature over 3 hours
  2. temperatureThe reaction mixture was re-cooled to −78° C.
  3. additionwas added dropwise
  4. temperatureto warm to room temperature
  5. extractionorganics were extracted with ether (3×100 mL)
  6. dry with materialdried with magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by flash chromatography on silica gel with gradient elution (5%→20% ethyl acetate in hexanes)

출처 및 근거

ORD 기록
ord-217d810fc451467987b2a2654e9fb484
출처 데이터셋
uspto-grants-2016_04
특허 번호
US09315495B2

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