p-Fluoronitrobenzene → HCID 58914732, compound

HRID 1297768Notes

Reaction equation

HRID 1297768 reaction equation
[Cl:1][C:2]1[CH:28]=[CH:27][CH:26]=[CH:25][C:3]=1[CH2:4][N:5]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[CH:7]([C:14]2[CH:19]=[C:18]([CH3:20])[C:17]([O:21][CH3:22])=[C:16]([CH3:23])[CH:15]=2)[C:6]1=[O:24].C[Si]([N-][Si](C)(C)C)(C)C.[K+].F[C:40]1[CH:45]=[CH:44][C:43]([N+:46]([O-:48])=[O:47])=[CH:42][CH:41]=1>CN(C=O)C>[Cl:1][C:2]1[CH:28]=[CH:27][CH:26]=[CH:25][C:3]=1[CH2:4][N:5]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[C:7]([C:14]2[CH:19]=[C:18]([CH3:20])[C:17]([O:21][CH3:22])=[C:16]([CH3:23])[CH:15]=2)([C:40]2[CH:45]=[CH:44][C:43]([N+:46]([O-:48])=[O:47])=[CH:42][CH:41]=2)[C:6]1=[O:24]

Participants

5

Reactant 3

HCID 9590p-FluoronitrobenzeneHCID 3251421Potassium bis(trimethylsilyl)amideHCID 58914677HCID 58914677, compound

Product 1

HCID 58914732HCID 58914732, compoundYield 240.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
20 °C

Procedure

Dissolve 1-(2-chloro-benzyl)-3-(4-methoxy-3,5-dimethyl-phenyl)-1,3-dihydro-indol-2-one (222 mg, 0.57 mmol) in anhydrous DMF (5 mL) under nitrogen. Cool in an ice bath and add at 5-8° C. a 0.5M solution of potassium bis(trimethylsilyl)amide (1.2 mL, 0.6 mmol). After 10 min. remove the ice bath and allow to warm to 20° C. over 30 min. Add 1-fluoro-4-nitrobenzene (0.21 mL, 2 mmol) and heat at 80° C. for 3 h. Allow to cool to room temperature and partition between saturated NH4Cl solution (25 mL) and ethyl acetate (50 mL). Separate, dilute aqueous portion with water (25 mL) and extract with ethyl acetate (2×50 mL). Combine all organic portions and wash with 1N HCl (50 mL) and brine (50 mL). Dry (MgSO4), filter and concentrate in vacuo to give 704 mg of a yellow oil. Purify by flash chromatography (gradient of 50% hexanes/CH2Cl2 to 100% CH2Cl2) to give 259 mg (89%) of the title compound as a light yellow foam. MS (FAB, M+1): calcd for C30H25ClN2O4 513.1581. found 513.1577; 1H NMR(DMSO-d6): □8.23 (m, 2H), 7.55-4.63 (m, 4H), 7.35-7.27 (m, 3H), 7.16 (t, J=7.5, 6.8 Hz, 1H), 7.02 (m, 2H), 6.86 (s, 2H), 5.11 (s, 2H), 3.65 (s, 3H), 2.16 (s, 6H). Anal. Calcd for C30H25ClN2O4: C, 70.24; H, 4.91; N, 5.47. Found C, 70.05; H, 5.19; N, 5.42.

Workup

  1. temperatureCool in an ice bath
  2. customAfter 10 min. remove the ice bath
  3. temperatureto cool to room temperature
  4. custompartition between saturated NH4Cl solution (25 mL) and ethyl acetate (50 mL)
  5. customSeparate
  6. extractiondilute aqueous portion with water (25 mL) and extract with ethyl acetate (2×50 mL)
  7. washCombine all organic portions and wash with 1N HCl (50 mL) and brine (50 mL)
  8. dry with materialDry (MgSO4)
  9. filtrationfilter
  10. concentrationconcentrate in vacuo

Sources & evidence

ORD record
ord-f4d45df85fd141beb6ffcc7ce2b80666
Source dataset
uspto-grants-2007_07
Patent number
US07250442B2

Reaction notes

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