Methyl Acrylate → HCID 23003539, compound

HRID 1424249Notes

Reaction equation

HRID 1424249 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:6]([C:9]([F:12])([F:11])[F:10])=[CH:5][C:3]=1[NH2:4].[C:13]([O:17][CH3:18])(=[O:16])[CH:14]=[CH2:15].CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)CC)C>CC([O-])=O.CC([O-])=O.[Pd+2].C(#N)C>[NH2:4][C:3]1[CH:5]=[C:6]([C:9]([F:12])([F:11])[F:10])[CH:7]=[CH:8][C:2]=1/[CH:15]=[CH:14]/[C:13]([O:17][CH3:18])=[O:16]

Participants

7

Reactant 4

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 679892-Bromo-5-(trifluoromethyl)benzenamineHCID 80271Tri-o-tolylphosphine

Product 1

HCID 23003539HCID 23003539, compoundYield 37%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
90 °C

Procedure

A 100 ml 3-neck flask with magnetic stirrer was charged with 2-bromo-5-(trifluoromethyl)aniline (500 mg, 2.08 mmol), methyl acrylate (538 mg, 6.25 mmol), Pd(OAc)2 (23.3 mg, 0.104 mmol), P(o-tolyl)3 (64 mg, 0.21 mmol), triethylamine (422 mg, 4.7 mmol) and acetonitrile (20 mL). The flask was purge with N2 and heated to 90° C. overnight. Saturated aqueous NH4Cl (40 mL) was added, and the mixture was extracted with ethyl acetate (10 mL×3). The combined organic layers were dried over Na2SO4, filtered and concentrated under reduce pressure. The crude product was purified by silica gel chromatography to give (E)-methyl 3-(2-amino-4-(trifluoromethyl)phenyl)acrylate (180.9 mg, 37%) as a light green solid. 1H NMR (400 MHz, CDCl3): δ 7.71 (d, J=16 Hz, 1H), δ 7.38 (d, J=8 Hz, 1H), δ 6.92 (d, J=8 Hz, 1H), δ 6.86 (s, 1H), δ 6.34 (d, J=8 Hz, 1H), δ 4.05 (s, 2H), δ 3.73 (s, 3H).

Workup

  1. customThe flask was purge with N2
  2. additionSaturated aqueous NH4Cl (40 mL) was added
  3. extractionthe mixture was extracted with ethyl acetate (10 mL×3)
  4. dry with materialThe combined organic layers were dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude product was purified by silica gel chromatography

Sources & evidence

ORD record
ord-7cd204552f7840b4b72d112a53254f65
Source dataset
uspto-grants-2015_01
Patent number
US08927577B2

Reaction notes

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