2',4'-Dihydroxyacetophenone → HCID 12016857, compound

HRID 1868578Notes

Reaction equation

HRID 1868578 reaction equation
C[Si](C)(C)N[Si](C)(C)C.[Li].C([O:13][C:14](=O)[C:15]1[CH:20]=[CH:19][C:18]([O:21][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[C:17]([O:29][CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[CH:16]=1)C.[CH3:38][C:39]([C:41]1[CH:42]=[CH:43][C:44]([OH:48])=[CH:45][C:46]=1[OH:47])=[O:40]>O1CCCC1>[CH2:30]([O:29][C:17]1[CH:16]=[C:15]([C:14](=[O:13])[CH2:38][C:39]([C:41]2[CH:42]=[CH:43][C:44]([OH:48])=[CH:45][C:46]=2[OH:47])=[O:40])[CH:20]=[CH:19][C:18]=1[O:21][CH2:22][C:23]1[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1)[C:31]1[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=1

Participants

5

Reactant 3

HCID 69902',4'-DihydroxyacetophenoneHCID 11325933ethyl-3,4-dibenzyloxybenzoateHCID 57426343Lithium bis(trimethylsilyl)amide

Product 1

HCID 12016857HCID 12016857, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of 20% lithiumhexamethyldisilazane in tetrahydrofuran (200.8 mL, 240 mmol), 2,4-dihydroxy acetophenone, 14 (9.12 g, 60 mmol) in tetrahydrofuran (150 mL) and ethyl-3,4-dibenzyloxy benzoate, 9 (21.7 g, 60 mmol) in tetrahydrofuran (100 mL) were reacted to afford 17, 1-(3,4-bis-benzyloxy-phenyl)-3-(2,4-dihydroxy-phenyl)-propane-1,3-dione (55 g), which was then cyclized with Dowex-H+ (12 g) in 2-propanol (400 mL) in a similar way as described for 22 to afford 23 (Frederique, A. A. A.; Hageman, J. A.; Guido, R. M. M. H.; Van Der Vijgh, W. J. F.; Bast, A.; Menge, W. M. P. B. J. Med. Chem. 2000, 43, 3752.). Yield 24 g (89%); mp 245-247° C. (lit. 244-245° C.); MS (FAB) 451 (M++1); IR (KBr) 3426, 1607; 1H NMR (200 MHz, DMSO-d6) δ 10.79 (s, 1H), 7.86 (d, J=8.6 Hz, 1H), 7.68 (s, 1H), 7.60 (d, J=8.8 Hz, 1H), 7.51-7.30 (m, 10H), 7.18 (d, J=8.5 Hz, 1H), 6.98 (s, 1H), 6.91 (d, J=8.8 Hz, 1H), 6.83 (s, 1H), 5.26 (s, 2H), 5.21 (s, 2H).

Sources & evidence

ORD record
ord-76a3a86635b640d1998507159cd50c6b
Source dataset
uspto-grants-2009_12
Patent number
US07635779B2

Reaction notes

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