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

HRID 396592

反応式

HRID 396592 の反応式
[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]

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 12184Ethyl GlycolateHCID 17198AcetosyringoneHCID 5462977Diethyl azodicarboxylate

生成物 1

HCID 220255854'-Ethoxycarbonyl-methoxy-3',5'-dimethoxyacetophenone収率 35.9%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-6cc53d3207e44a8786c8088c01149b00
出典データセット
uspto-grants-2003_08
特許番号
US06608101B1

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