Sodium hydride → 6-(diphenylmethyl)-2,3-dihydro-6H-[1,4]dioxino[2,3-f]indole-7,8-dione

HRID 1965339Notes

Reaction equation

HRID 1965339 reaction equation
[O:1]1[C:6]2=[CH:7][C:8]3[C:9](=[O:15])[C:10](=[O:14])[NH:11][C:12]=3[CH:13]=[C:5]2[O:4][CH2:3][CH2:2]1.[H-].[Na+].Br[CH:19]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>CN(C)C=O.O.C(OCC)(=O)C>[C:20]1([CH:19]([C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[N:11]2[C:12]3[CH:13]=[C:5]4[O:4][CH2:3][CH2:2][O:1][C:6]4=[CH:7][C:8]=3[C:9](=[O:15])[C:10]2=[O:14])[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1

Participants

7

Reactant 3

HCID 24758Sodium hydrideHCID 236603Bromodiphenylmethane2×HCID 20298022,3-dihydro-6H-[1,4]dioxino[2,3-f]indole-7,8-dione

Product 1

HCID 673802436-(diphenylmethyl)-2,3-dihydro-6H-[1,4]dioxino[2,3-f]indole-7,8-dioneYield 22.4%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a cooled (0° C.) solution of 2,3-dihydro-6H-[1,4]dioxino[2,3-f]indole-7,8-dione (Lackey and Sternbach, Synthesis 1993:993-997) (1.73 g, 8.42 mmol) in anhydrous N,N-dimethylformamide (28 mL) was added sodium hydride (60% in mineral oil, 0.37 g, 9.26 mmol). The mixture was stirred at ambient temperature for 1 h and bromodiphenylmethane (2.39 g, 9.69 mmol) was added. After stirring at ambient temperature for 16 h, further bromodiphenylmethane (0.42 g, 1.68 mmol) was added. The mixture was stirred at ambient temperature for 8 h and then diluted with water (200 mL) and ethyl acetate (200 mL). The layers were separated and the aqueous layer was extracted with ethyl acetate (2×100 mL). The combined organic layers were washed with brine (150 mL), dried over anhydrous magnesium sulfate, filtered, concentrated in vacuo. The residue was purified by column chromatography, eluted with a 35% to 50% gradient of ethyl acetate in hexanes to afford 6-(diphenylmethyl)-2,3-dihydro-6H-[1,4]dioxino[2,3-f]indole-7,8-dione (0.7 g, 22%) as a red solid: 1H NMR (300 MHz, CDCl3) δ 7.41-7.28 (m, 10H), 7.16 (s, 1H), 6.94-6.91 (m, 1H), 5.96 (s, 1H), 4.27-4.14 (m, 4H); MS (ES+) m/z 371.9 (M+1).

Workup

  1. stirringAfter stirring at ambient temperature for 16 h
  2. stirringThe mixture was stirred at ambient temperature for 8 h
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with ethyl acetate (2×100 mL)
  5. washThe combined organic layers were washed with brine (150 mL)
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by column chromatography
  10. washeluted with a 35% to 50% gradient of ethyl acetate in hexanes

Sources & evidence

ORD record
ord-8fdb0ae9cec048e783694a41471cf3d8
Source dataset
uspto-grants-2013_04
Patent number
US08415370B2

Reaction notes

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