Sodium hydride → Bis(1,1-dimethylethyl) [2-fluoro-3-(1-naphthalenyloxy)-4-nitrophenyl]propanedioate

HRID 1875043Notes

Reaction equation

HRID 1875043 reaction equation
[H-].[Na+].[C:3]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])(=[O:12])[CH2:4][C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6].[F:18][C:19]1[C:24](F)=[CH:23][CH:22]=[C:21]([N+:26]([O-:28])=[O:27])[C:20]=1[O:29][C:30]1[C:39]2[C:34](=[CH:35][CH:36]=[CH:37][CH:38]=2)[CH:33]=[CH:32][CH:31]=1>C1COCC1>[F:18][C:19]1[C:20]([O:29][C:30]2[C:39]3[C:34](=[CH:35][CH:36]=[CH:37][CH:38]=3)[CH:33]=[CH:32][CH:31]=2)=[C:21]([N+:26]([O-:28])=[O:27])[CH:22]=[CH:23][C:24]=1[CH:4]([C:5]([O:7][C:8]([CH3:9])([CH3:10])[CH3:11])=[O:6])[C:3]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 68324Di-tert-butyl malonateHCID 684878651-[(2,3-Difluoro-6-nitrophenyl)oxy]naphthalene

Product 1

HCID 68483921Bis(1,1-dimethylethyl) [2-fluoro-3-(1-naphthalenyloxy)-4-nitrophenyl]propanedioateYield 115.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Sodium hydride (60% oil dispersion) (4.07 g, 102 mmol) was added in portions to a solution of di-t-butyl malonate (11.01 g, 50.9 mmol) in THF (200 mL) at room temperature. After gas evolution ceased, 1-[(2,3-difluoro-6-nitrophenyl)oxy]naphthalene (13.94 g, 46.3 mmol), dissolved in THF (100 mL), was added. The reaction mixture was stirred at room temperature for 2 hrs and then poured on to ice and extracted with ethyl acetate. The organic layer was dried over sodium sulfate. The solvent was evaporated to give the title compound (26.59 g, 102%) as a yellow oil. 1H NMR (400 MHz, chloroform-d) δ ppm 8.33-8.44 (m, 1H), 7.83-7.95 (m, 2H), 7.51-7.65 (m, 4H), 7.23-7.34 (m, 1H), 6.60 (d, 1H), 4.82 (s, 1H), 1.49 (s, 18H). ESMS: m/z 497.

Workup

  1. additionwas added
  2. additionpoured on to ice
  3. extractionextracted with ethyl acetate
  4. dry with materialThe organic layer was dried over sodium sulfate
  5. customThe solvent was evaporated

Sources & evidence

ORD record
ord-8135c088c4b9436f9614272d3b5e8c47
Source dataset
uspto-grants-2012_11
Patent number
US08304419B2

Reaction notes

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