Hydrochloric Acid → Ethyl 4-[2,4-bis(benzyloxy)-6-(4-nitrophenoxy)phenyl]-2,4-dioxobutanoate

HRID 880351Notes

Reaction equation

HRID 880351 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[C:13]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:12]=[C:11]([O:23][C:24]2[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=2)[C:10]=1[C:33](=[O:35])[CH3:34])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Li].C[Si]([N-][Si](C)(C)C)(C)C.C1COCC1.[C:51](OCC)(=[O:57])[C:52]([O:54][CH2:55][CH3:56])=[O:53].Cl>C1COCC1.[Cl-].[Na+].O>[CH2:1]([O:8][C:9]1[CH:14]=[C:13]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:12]=[C:11]([O:23][C:24]2[CH:25]=[CH:26][C:27]([N+:30]([O-:32])=[O:31])=[CH:28][CH:29]=2)[C:10]=1[C:33](=[O:35])[CH2:34][C:51](=[O:57])[C:52]([O:54][CH2:55][CH3:56])=[O:53])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 7268Diethyl OxalateHCID 3028194LithiumHCID 667590791-[2,4-Bis(benzyloxy)-6-(4-nitrophenoxy)phenyl]ethanoneHCID 86662374bis trimethylsilylamide THF

Product 1

HCID 66758581Ethyl 4-[2,4-bis(benzyloxy)-6-(4-nitrophenoxy)phenyl]-2,4-dioxobutanoateYield 75%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 57417360Sodium chloride; waterSolvent

Procedure

To a stirred solution of 1-[2,4-bis(benzyloxy)-6-(4-nitrophenoxy)phenyl]ethanone (5.1 g, 11 mmol) in THF (50 mL) was added drop wise 1M lithium (bis trimethylsilylamide/THF solution (12 mL, 12 mmol) at −50° C. After 30 minutes, a solution of diethyl oxalate (1.7 mL) in THF (15 mL) was slowly added and the stirring was continued for 1 hours. The solution was taken up in brine (200 mL) and treated with 1 M HCl solution (13 mL), then extracted with ethyl acetate. The organic phase was dried and the solvent removed. The crude was filtered on a small pad of silica gel eluting with hexane/ethyl acetate 2/1 to afford the title compound (5.7 g, 75% yield).

Workup

  1. waitthe stirring was continued for 1 hours
  2. extractionextracted with ethyl acetate
  3. customThe organic phase was dried
  4. customthe solvent removed
  5. filtrationThe crude was filtered on a small pad of silica gel eluting with hexane/ethyl acetate 2/1

Sources & evidence

ORD record
ord-430885f51f524fd594f802e933952dd9
Source dataset
uspto-grants-2015_03
Patent number
US08993556B2

Reaction notes

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