Triphenylphosphine → 4'-Ethoxycarbonyl-methoxy-3',5'-dimethoxyacetophenone

HRID 396592

반응식

HRID 396592 반응식
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:12](=[O:14])[CH3:13])[CH:6]=[C:7]([O:10][CH3:11])[C:8]=1O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:34]([O:38][CH2:39][CH3:40])(=[O:37])CO.C[CH2:42][O:43]C(/N=N/C(OCC)=O)=O>O1CCCC1>[CH2:39]([O:38][C:34]([C:8]1[C:7]([O:10][CH3:11])=[CH:6][C:5]([C:12](=[O:14])[CH2:13][O:43][CH3:42])=[CH:4][C:3]=1[O:2][CH3:1])=[O:37])[CH3:40]

참가 물질

6

반응물 4

HCID 11776TriphenylphosphineHCID 12184Ethyl GlycolateHCID 17198AcetosyringoneHCID 5462977Diethyl azodicarboxylate

생성물 1

HCID 220255854'-Ethoxycarbonyl-methoxy-3',5'-dimethoxyacetophenone수율 35.9%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

Ex-61A: 3′,5′-Dimethoxy-4′-hydroxyacetophenone (6.03 g, 31 mmol) and triphenylphosphine (8.05 g, 31 mmol) were stirred in 124 mL of tetrahydrofuran (THF). The mixture was treated with ethyl glycolate (3.2 g, 31 mmol) and diethylazodicarboxylate (4.83 mL, 31 mmol). The reaction mixture was stirred under reflux for about 3.5 h and then evaporated. The residue was crystallized from hexane/ethyl acetate. The mother liquor was concentrated to give a crude product which was purified by recrystallization from EtOH twice to give 3.14 g of 4′-ethoxycarbonyl-methoxy-3′,5′-dimethoxyacetophenone. Solvent removal from the mother liquor provided additional crude product which was purified by silica gel chromatography (hexane/ethyl acetate, 1:1) to give additional product (4.2 g). The total amount of pure material isolated was 7.34 g (90% yield). mp. 81-83° C.; Anal. Calcd. for C14H18O6: C, 59.57; H, 6.43; Found: C, 59.60; H, 6.34; MS (direct probe): Calcd for C14H18O6: m/z=282, found: m/z=282.

후처리

  1. temperatureunder reflux for about 3.5 h
  2. customevaporated
  3. customThe residue was crystallized from hexane/ethyl acetate
  4. concentrationThe mother liquor was concentrated
  5. customto give a crude product which
  6. customwas purified by recrystallization from EtOH twice

출처 및 근거

ORD 기록
ord-6cc53d3207e44a8786c8088c01149b00
출처 데이터셋
uspto-grants-2003_08
특허 번호
US06608101B1

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