Dimethylformamide → HCID 66790940, compound

HRID 1929449Notes

Reaction equation

HRID 1929449 reaction equation
Br[C:2]1[C:7]2[N:8]([C:15]3[CH:20]=[CH:19][C:18]([F:21])=[CH:17][CH:16]=3)[C:9](=[O:14])[C:10]([CH3:13])([CH3:12])[O:11][C:6]=2[CH:5]=[C:4]([N+:22]([O-:24])=[O:23])[CH:3]=1.[CH3:25][N:26](C)C=O>[C-]#N.[Zn+2].[C-]#N.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[F:21][C:18]1[CH:19]=[CH:20][C:15]([N:8]2[C:7]3=[C:2]([C:25]#[N:26])[CH:3]=[C:4]([N+:22]([O-:24])=[O:23])[CH:5]=[C:6]3[O:11][C:10]([CH3:13])([CH3:12])[C:9]2=[O:14])=[CH:16][CH:17]=1

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 66789667HCID 66789667, compound

Product 1

HCID 66790940HCID 66790940, compound

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
175 °C

Procedure

A mixture of 5-bromo-4-(4-fluorophenyl)-2,2-dimethyl-7-nitro-2H-1,4-benzoxazin-3(4H)-one (compound obtained in Reference Example 53(6), 2.00 g), zinc cyanide (0.60 g), tetrakis(triphenylphosphine)palladium(0) (0.60 g) and N,N-dimethyl-formamide (30 mL) was heated at 175° C. under microwave irradiation for 5 minutes under argon atmosphere. After cooling, to the reaction mixture was added water, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over sodium sulfate and concentrated in vacuo. The resultant residue was purified by column chromatography on silica gel (Solvent; n-hexane/ethyl acetate=95/5→65/35) to give 4-(4-fluorophenyl)-2,2-dimethyl-7-nitro-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-5-carbonitrile (1.42 g) as a pale yellow powder.

Workup

  1. temperatureAfter cooling, to the reaction mixture
  2. extractionthe mixture was extracted with ethyl acetate
  3. washThe organic layer was washed with water and brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe resultant residue was purified by column chromatography on silica gel (Solvent; n-hexane/ethyl acetate=95/5→65/35)

Sources & evidence

ORD record
ord-1e0ae82a177e47779ff2260ee5c4a07b
Source dataset
uspto-grants-2012_05
Patent number
US08188073B2

Reaction notes

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