Acrylonitrile → 3-(3,4-Dimethoxyphenyl)acrylonitrile

HRID 1624861Notes

Reaction equation

HRID 1624861 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[C:4]([O:10][CH3:11])[CH:3]=1.[C:12](#[N:15])[CH:13]=[CH2:14].C([O-])(=O)C.[Na+].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CC(N(C)C)=O.[Pd]>[CH3:11][O:10][C:4]1[CH:3]=[C:2](/[CH:14]=[CH:13]/[C:12]#[N:15])[CH:7]=[CH:6][C:5]=1[O:8][CH3:9]

Participants

8

Reactant 4

HCID 7855AcrylonitrileHCID 76114Benzene, 4-bromo-1,2-dimethoxy-HCID 80271Tri-o-tolylphosphineHCID 517045Sodium Acetate

Product 1

HCID 15509583-(3,4-Dimethoxyphenyl)acrylonitrileYield 33%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 74236Tetrabutylammonium BromideCatalystHCID 31374DimethylacetamideSolvent

Procedure

A mixture of 5 g of 4-bromo-1,2-dimethoxybenzene (3.31 mL, 23 mmoles), 3.2 g of acrylonitrile (3.9 mL, 60 mmoles, 2.6 eq.), 2.3 g of sodium acetate (27.6 mmoles, 1.2 eq.), 7.4 g of tetrabutylammonium bromide (23 mmoles, 1 eq.), 0.7 g of tri(o-tolyl)phosphine (2.3 mmoles, 0.1 eq.) and 4.9 g of palladium 5% on carbon (2.3 mmoles, 0.1 eq.) in 25 mL of DMAC is prepared. The black suspension is stirred at reflux for 12 hours. The reaction mixture is brought back to ambient temperature and filtered. The solid residue is rinsed twice with toluene. The filtrates are combined and evaporated under reduced pressure. The crude reaction product is purified on a silica column (eluant: methylcyclohexane:ethyl acetate 6:4) to yield 1.4 g of the expected product.

Workup

  1. customis prepared
  2. temperatureat reflux for 12 hours
  3. customis brought back to ambient temperature
  4. filtrationfiltered
  5. washThe solid residue is rinsed twice with toluene
  6. customevaporated under reduced pressure
  7. customThe crude reaction product
  8. customis purified on a silica column (eluant: methylcyclohexane:ethyl acetate 6:4)

Sources & evidence

ORD record
ord-c264b99add834f12b63cc811da55c07f
Source dataset
uspto-grants-2014_07
Patent number
US08779122B2

Reaction notes

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