Acetic Acid → t-Butyl 2-oxo-4-(4-methylphenyl)-butanoate

HRID 1584083노트

반응식

HRID 1584083 반응식
[CH3:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][CH:3]=1.C(O)(=O)C.N1CCCCC1.[C:20]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])(=[O:24])[C:21]([CH3:23])=[O:22]>C1C=CC=CC=1.C(OCC)(=O)C.O>[O:22]=[C:21]([CH2:23][CH2:6][C:5]1[CH:8]=[CH:9][C:2]([CH3:1])=[CH:3][CH:4]=1)[C:20]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24]

참가 물질

8

반응물 4

HCID 176Acetic AcidHCID 77254-MethylbenzaldehydeHCID 8082PiperidineHCID 11309579t-butyl pyruvate

생성물 1

HCID 12065883t-Butyl 2-oxo-4-(4-methylphenyl)-butanoate

시약·촉매·용매 3

HCID 241Benzene용매2회HCID 962Water용매HCID 8857Ethyl Acetate용매

실험 절차

To a solution of 4-methylbenzaldehyde (2.5 mL, 21.2 mmol) in 25 mL of benzene was added 1 mL each of acetic acid and piperidine. The mixture was heated to reflux with azeotropic removal of water via a Dean-Stark trap. A solution of t-butyl pyruvate (3.36 g, 23.32 mmol) in 5 mL of benzene was added over 7 h by syringe pump. The mixture was cooled, diluted with ethyl acetate and washed three times with saturated aqueous sodium bicarbonate and three times with 1N hydrochloric acid. The organics were dried over sodium sulfate, filtered, and concentrated. The crude product was purified by MPLC on silica-gel eluting with 2.5% ethyl acetate in hexane to give the desired product as a yellow oil: 1H NMR (200 MHz, CDCl3) δ7.75 (d, 1H, J=16.19 Hz), 7.49 (d, 2H, J=8.25 Hz), 7.24 (m, 3H), 2.37 (s, 3H), 1.58 (s, 9H). The above product was dissolved in ethyl acetate and held under hydrogen in the presence of 100 mg of 10% palladium on carbon for 2 hours. The mixture was filtered and concentrated in vacuo to give 1.196 g of the title compound as a pale-yellow oil: 1H NMR (200 MHz, CDCl3) δ7.1-6.9 (m, 4H), 3.12 (t, 2H, J=6.8 Hz), 2.90 (t, 2H, J=7.3 Hz), 1.56 (s, 9H). ##STR29## N-[1(R)-Benzyloxycarbonyl-5-(1,3-dioxo-isoindolin-2-yl)pentyl]-α-(S)-(2-phenyl-ethyl)!glycine-(L)-leucine, N-phenylamide (5d')

후처리

  1. temperatureThe mixture was heated
  2. temperatureThe mixture was cooled
  3. washwashed three times with saturated aqueous sodium bicarbonate and three times with 1N hydrochloric acid
  4. dry with materialThe organics were dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude product was purified by MPLC on silica-gel
  8. washeluting with 2.5% ethyl acetate in hexane

출처 및 근거

ORD 기록
ord-76355f366bbe47dfb1a9a3fdaf36a8c6
출처 데이터셋
uspto-grants-1999_08
특허 번호
US05932551

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