Citric Acid → 5-Formylthiophene-2-Carbonitrile

HRID 432674

반응식

HRID 432674 반응식
C(NC(C)C)(C)C.C([Li])CCC.[S:13]1[CH:17]=[CH:16][CH:15]=[C:14]1[C:18]#[N:19].C(O)(=O)C[C:22](CC(O)=O)(C(O)=O)[OH:23]>O1CCCC1.O>[C:18]([C:14]1[S:13][C:17]([CH:22]=[O:23])=[CH:16][CH:15]=1)#[N:19]

참가 물질

7

반응물 4

HCID 311Citric AcidHCID 7912DiisopropylamineHCID 660872-ThiophenecarbonitrileHCID 178418339Butyllithium

생성물 1

HCID 122800045-Formylthiophene-2-Carbonitrile수율 55.3%

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매2회

실험 절차

A solution of diisopropylamine (35.3 ml, 0.251 moles) in tetrahydrofuran (500 ml) was cooled to −78° C. under a nitrogen blanket. To this was added 1.6M n-butyllithium in hexanes (157 ml, 0.251 moles) and allowed to stir for 5 min. Then slowly added thiopene-2-carbonitrile (21.33 ml, 0.229 moles) in tetrahydrofuran (115 ml) and allowed to stir. After 45 min. was added NN-dimethylformamide (88.66 ml, 1.145 moles) at −78° C. Citric acid (40 g) was added after 2 h. followed by water (240 ml) and stirred for 18 h. The reaction was concentrated in vacuo, transferred to a separatory funnel, diluted with brine, and extracted twice with ether. The combined ether layers were washed with brine, dried over magnesium sulfate, filtered, and the solvent removed in vacuo. Chromatography yielded 15.8 g (50%) of 2-cyano-5-formylthiophene (EX-55A) as a brown solid: 1H NMR (300 MHZ, CDCl3) d 10.02 (s, 1H), 7.79 (m, 1H), 7.30 (m, 1H).

후처리

  1. stirringto stir
  2. stirringstirred for 18 h
  3. concentrationThe reaction was concentrated in vacuo
  4. customtransferred to a separatory funnel
  5. additiondiluted with brine
  6. extractionextracted twice with ether
  7. washThe combined ether layers were washed with brine
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. customthe solvent removed in vacuo

출처 및 근거

ORD 기록
ord-a63caca2447a4727828166c5acef299b
출처 데이터셋
uspto-grants-2003_12
특허 번호
US06664255B1

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