Tributylvinyltin → HCID 66789861, compound

HRID 1672297Notes

Reaction equation

HRID 1672297 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.[CH2:25]([Sn](CCCC)(CCCC)C=C)[CH2:26]CC>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.O1CCOCC1>[F:21][C:18]1[CH:19]=[CH:20][C:15]([N:8]2[C:7]3[C:2]([CH:25]=[CH2:26])=[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

5

Reactant 2

HCID 81998TributylvinyltinHCID 66789667HCID 66789667, compound

Product 1

HCID 66789861HCID 66789861, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

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); 100 mg), tributyl(vinyl)tin (78 μL) and tetrakis(triphenylphosphine)palladium(0) (59 mg) and dioxane was refluxed under argon atmosphere for 6 hours. After cooling, the reaction mixture was concentrated in vacuo, and the resultant residue was diluted with acetonitrile and n-hexane. The n-hexane layer was removed from the mixture, and the acetonitrile layer was concentrated in vacuo. The resultant residue was purified by column chromatography on silica gel (solvent; n-hexane/ethyl acetate=8/1→4/1) and filtered through NH-silica gel. The filtrate was concentrated in vacuo to give 4-(4-fluorophenyl)-2,2-dimethyl-7-nitro-5-vinyl-2H-1,4-benzoxazin-3(4H)-one (40 mg) as a pale yellow oil.

Workup

  1. temperaturewas refluxed under argon atmosphere for 6 hours
  2. temperatureAfter cooling
  3. concentrationthe reaction mixture was concentrated in vacuo
  4. additionthe resultant residue was diluted with acetonitrile and n-hexane
  5. customThe n-hexane layer was removed from the mixture
  6. concentrationthe acetonitrile layer was concentrated in vacuo
  7. customThe resultant residue was purified by column chromatography on silica gel (solvent; n-hexane/ethyl acetate=8/1→4/1)
  8. filtrationfiltered through NH-silica gel
  9. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-ef15ea42f03d4954b252129ea181959f
Source dataset
uspto-grants-2011_08
Patent number
US07998956B2

Reaction notes

Loading…