Methyl Methacrylate → methyl (2E)-3-[4-(dimethylamino)phenyl]-2-methylprop-2-enoate

HRID 13877

Reaction equation

HRID 13877 reaction equation
[CH3:1][N:2]([CH3:10])[C:3]1[CH:8]=[CH:7][C:6](Br)=[CH:5][CH:4]=1.[C:11]([O:16][CH3:17])(=[O:15])[C:12]([CH3:14])=[CH2:13].C1(C(N)C2CCCCC2)CCCCC1>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].C1([B-](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C.O1CCCC1>[CH3:17][O:16][C:11](=[O:15])/[C:12](/[CH3:14])=[CH:13]/[C:6]1[CH:7]=[CH:8][C:3]([N:2]([CH3:10])[CH3:1])=[CH:4][CH:5]=1

Participants

7

Reactant 3

HCID 6658Methyl MethacrylateHCID 114654-bromo-N,N-dimethylanilineHCID 10774245alpha-Cyclohexylcyclohexanemethanamine

Product 1

HCID 11390367methyl (2E)-3-[4-(dimethylamino)phenyl]-2-methylprop-2-enoateYield 86.7%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 23136663Tri-tert-butylphosphonium TetraphenylborateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 1.000 g (5 mmol) of 4-dimethylaminobromobenzene, 1.001 g (10 mmol) of methyl methacrylate, 0.011 g (0.012 mmol) of tris (dibenzylideneacetone)dipalladium (0), 1.074 g (5.5mmol) of dicyclohexylmethylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.026 g (0.05 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 25 hours. After the completion of the reaction, 5 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.951 g of (E)-3-(4-dimethylaminophenyl)-2-methylacrylic acid methyl ester (yield: 87 mol % based on 4-dimethylaminobromobenzene). The identification of the product was made by 1H-NMR and 13C-NMR.

Workup

  1. customA 30-ml four-necked flask was equipped with a stirrer
  2. additionadded into the flask
  3. customThe flask was purged with argon
  4. stirringby stirring at 30° C. for 25 hours
  5. customAfter the completion of the reaction, 5 ml of toluene and 10 ml of saturated sodium chloride solution
  6. additionwere added
  7. customfollowed by separation
  8. customThe organic phase was purified by column chromatography

Sources & evidence

ORD record
ord-daee0aff2ff34360b22fd00fcb8d4709
Source dataset
uspto-grants-2010_06
Patent number
US07728176B2

Linked notes

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