Ethyl Acrylate → (E)-ethyl 1-(3-(3-ethoxy-3-oxoprop-1-en-1-yl)phenyl)cyclopropanecarboxylate

HRID 931090Notes

Reaction equation

HRID 931090 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]2([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:10][CH2:9]2)[CH:5]=[CH:6][CH:7]=1.[C:16]([O:20][CH2:21][CH3:22])(=[O:19])[CH:17]=[CH2:18].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:21]([O:20][C:16](=[O:19])/[CH:17]=[CH:18]/[C:2]1[CH:3]=[C:4]([C:8]2([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:10][CH2:9]2)[CH:5]=[CH:6][CH:7]=1)[CH3:22]

Participants

6

Reactant 3

HCID 8821Ethyl AcrylateHCID 80271Tri-o-tolylphosphine2×HCID 66765078Ethyl 1-(3-bromophenyl)cyclopropanecarboxylate

Product 1

HCID 131735154(E)-ethyl 1-(3-(3-ethoxy-3-oxoprop-1-en-1-yl)phenyl)cyclopropanecarboxylateYield 55.2%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalyst2×HCID 6342AcetonitrileSolvent

Procedure

Ethyl 1-(3-bromophenyl)cyclopropanecarboxylate (740 mg, 2.75 mmol) was dissolved in acetonitrile (20 mL) and the solution was treated with ethyl acrylate (3.90 mL, 35.7 mmol) and tri-o-tolyl phosphine (83.7 mg, 0.275 mmol). The reaction mixture was stirred at room temperature until all of the tri-o-tolyl phosphine had dissolved. Palladium acetate (30.9 mg, 0.137 mmol) was added in a single portion and the reaction mixture was stirred at reflux for 16 hr. Palladium acetate was added (10 mg) and the reaction mixture was stirred for another 4 h. The solvent was removed under reduced pressure and the crude material was purified via flash chromatography (pentane/ethyl acetate 95/5 to 92/8) to afford (E)-ethyl 1-(3-(3-ethoxy-3-oxoprop-1-en-1-yl)phenyl)cyclopropanecarboxylate (438 mg, 55%). 1H NMR (400 MHz, CDCl3) δ 1.09-1.19 (m, 5H), 1.31 (t, 3H), 1.56-1.63 (m, 2H), 4.03-4.11 (m, 2H), 4.23 (q, 2H), 6.40 (d, 1H), 7.20-7.36 (m, 2H), 7.36-7.42 (m, 1H), 7.44-7.51 (m, 1H), 7.66 (d, 1H).

Workup

  1. dissolutionhad dissolved
  2. temperatureat reflux for 16 hr
  3. stirringthe reaction mixture was stirred for another 4 h
  4. customThe solvent was removed under reduced pressure
  5. customthe crude material was purified via flash chromatography (pentane/ethyl acetate 95/5 to 92/8)

Sources & evidence

ORD record
ord-6fece1b5f70542bcad129a332a61f7d0
Source dataset
uspto-grants-2016_03
Patent number
US09296745B2

Reaction notes

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