2',4'-Dihydroxyacetophenone → 1-(3,4-Dimethoxy-phenyl)-3-(2,4-dihydroxy-phenyl)-propane-1,3-dione

HRID 1868581Notes

Reaction equation

HRID 1868581 reaction equation
C[Si](C)(C)N[Si](C)(C)C.[Li].C(O[C:14](=[O:25])[C:15]1[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[C:17]([O:23][CH3:24])[CH:16]=1)C.[CH3:26][C:27]([C:29]1[CH:30]=[CH:31][C:32]([OH:36])=[CH:33][C:34]=1[OH:35])=[O:28]>O1CCCC1>[CH3:24][O:23][C:17]1[CH:16]=[C:15]([C:14](=[O:25])[CH2:26][C:27]([C:29]2[CH:30]=[CH:31][C:32]([OH:36])=[CH:33][C:34]=2[OH:35])=[O:28])[CH:20]=[CH:19][C:18]=1[O:21][CH3:22]

Participants

5

Reactant 3

HCID 69902',4'-DihydroxyacetophenoneHCID 77546Benzoic acid, 3,4-dimethoxy-, ethyl esterHCID 57426343Lithium bis(trimethylsilyl)amide

Product 1

HCID 694128701-(3,4-Dimethoxy-phenyl)-3-(2,4-dihydroxy-phenyl)-propane-1,3-dione

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of 20% lithiumhexamethyldisilazane in tetrahydrofuran (335 mL, 400 mmol), 2,4-dihydroxy acetophenone, 14 (15.2 g, 100 mmol) in tetrahydrofuran (150 mL) and ethyl-3,4-dimethoxy benzoate, 7 (21 g, 100 mmol) in tetrahydrofuran (100 mL) were reacted to afford 21, 1-(3,4-dimethoxy-phenyl)-3-(2,4-dihydroxy-phenyl)-propane-1,3-dione (37 g), which was cyclized with Dowex-H+ (15 g) in 2-propanol (250 mL) in a similar way as described for 22 to afford 27. Yield 15.4 g, (52%); mp 263-265° C.; MS (FAB) 299 (M++1); IR (KBr) 3452, 1625; 1H NMR (200 MHz, CDCl3+DMSO-d6) δ 9.83 (s, 1H), 7.32 (d, J=8.5 Hz, 1H), 6.97 (dd, J=8.5 Hz, 1.7 Hz, 1H), 6.83 (d, J=1.7 Hz, 1H), 6.43 (d, J=8.5 Hz, 1H), 6.34 (s, 1H), 6.30 (dd, J=9.7 Hz, 2.0 Hz, 1H), 6.08 (s, 1H), 3.35 (s, 3H), 3.32 (s, 3H).

Sources & evidence

ORD record
ord-63337d96b9e344e99a012382a6f6b80a
Source dataset
uspto-grants-2009_12
Patent number
US07635779B2

Reaction notes

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