Tributylvinyltin → 5-Bromo-4-chloro-2-vinylbenzenamine

HRID 588803Notes

Reaction equation

HRID 588803 reaction equation
[Br:1][C:2]1[C:3]([Cl:10])=[CH:4][C:5](I)=[C:6]([NH2:8])[CH:7]=1.[CH2:11]([Sn](CCCC)(CCCC)C=C)[CH2:12]CC>C1(C)C=CC=CC=1.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>[Br:1][C:2]1[C:3]([Cl:10])=[CH:4][C:5]([CH:11]=[CH2:12])=[C:6]([NH2:8])[CH:7]=1

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 50999508HCID 50999508, compound

Product 1

HCID 1176071655-Bromo-4-chloro-2-vinylbenzenamineYield 57.4%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

A mixture of 5-bromo-4-chloro-2-iodobenzenamine (2.5 g, 7.51 mmol), tributyl(vinyl)stannane (2.4 g, 7.51 mmol), Pd(PPh3)4 (867 mg, 0.75 mmol) in toluene (25 mL) was stirred at reflux under argon for 16 h. The reaction mixture was allowed to cool to room temperature and quenched with aqueous KF solution. The mixture was partitioned between ethyl acetate and water. The organic layer was washed with brine, dried over Na2SO4 and concentrated. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate=20:1) to afford the desired product (1.0 g, 57.4% yield). ESI-MS m/z: 232.2[M+H]+.

Workup

  1. temperatureat reflux under argon for 16 h
  2. customquenched with aqueous KF solution
  3. customThe mixture was partitioned between ethyl acetate and water
  4. washThe organic layer was washed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate=20:1)

Sources & evidence

ORD record
ord-7a3b333c223d478bb5f4a64b0dcafe7f
Source dataset
uspto-grants-2016_01
Patent number
US09227978B2

Reaction notes

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