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

HRID 396592Notes

Reaction equation

HRID 396592 reaction equation
[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]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 12184Ethyl GlycolateHCID 17198AcetosyringoneHCID 5462977Diethyl azodicarboxylate

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-6cc53d3207e44a8786c8088c01149b00
Source dataset
uspto-grants-2003_08
Patent number
US06608101B1

Reaction notes

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