1-Chloro-2,6-dinitrobenzene → 1,3-Dinitro-2-vinylbenzene

HRID 1370808Notes

Reaction equation

HRID 1370808 reaction equation
Cl[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12].O1C=C[CH:16]=[C:15]1P(C1OC=CC=1)C1OC=CC=1.[Cl-].[Li+].C([Sn](CCCC)(CCCC)C=C)CCC>CN(C)C=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].[Cu]I>[N+:11]([C:3]1[CH:4]=[CH:5][CH:6]=[C:7]([N+:8]([O-:10])=[O:9])[C:2]=1[CH:15]=[CH2:16])([O-:13])=[O:12]

Participants

8

Reactant 4

HCID 118141-Chloro-2,6-dinitrobenzeneHCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 521585Tris(furan-2-yl)phosphane

Product 1

HCID 107264561,3-Dinitro-2-vinylbenzeneYield 349.1%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6228DimethylformamideSolvent

Procedure

1-Chloro-2,6-dinitrobenzene (1.00 g, 4.94 mmoles, purchased from Lancaster) tris(dibenzylideneacetone)dipalladium (0.113 g, 0.123 mmoles), tri-2-furylphosphine (0.229 g, 0.987 mmoles), copper(I) iodide (0.094 g, 0.494 mmoles), and lithium chloride (0.628 g, 14.8 mmoles) in N,N-dimethylformamide (15 mL) were treated with tributylethenylstannane (2.90 mL, 9.87 mmoles). The reaction mixture was degassed with nitrogen, stirred overnight at room temperature and then heated at 80° C. for 4 hours. The reaction mixture was then diluted with ethyl acetate and washed with water and brine. The organic phase was dried with sodium sulfate, filtered and the filtrate concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, 10% ethyl acetate/hexanes) to provide the title compound (0.669 g, 70%). MS (DCI) m/z 194 (M+H)+.

Workup

  1. customThe reaction mixture was degassed with nitrogen
  2. temperatureheated at 80° C. for 4 hours
  3. additionThe reaction mixture was then diluted with ethyl acetate
  4. washwashed with water and brine
  5. dry with materialThe organic phase was dried with sodium sulfate
  6. filtrationfiltered
  7. concentrationthe filtrate concentrated under reduced pressure
  8. customThe residue was purified by flash chromatography (silica gel, 10% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-906ff23129fc4887aebe52f6984931f6
Source dataset
uspto-grants-2003_06
Patent number
US06583180B2

Reaction notes

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