Methyl Acrylate → methyl (2E)-5-cyclopropyl-5-(2,2-diethoxyethoxyl)pent-2-enoate

HRID 1478728Notes

Reaction equation

HRID 1478728 reaction equation
[C:1]([O:5][CH3:6])(=[O:4])[CH:2]=[CH2:3].[CH2:7]([O:9][CH:10]([O:20][CH2:21][CH3:22])[CH2:11][O:12][CH:13]([CH:17]1[CH2:19][CH2:18]1)[CH2:14]C=C)[CH3:8]>ClCCl>[CH:17]1([CH:13]([O:12][CH2:11][CH:10]([O:9][CH2:7][CH3:8])[O:20][CH2:21][CH3:22])[CH2:14]/[CH:3]=[CH:2]/[C:1]([O:5][CH3:6])=[O:4])[CH2:19][CH2:18]1

Participants

4

Reactant 2

HCID 7294Methyl AcrylateHCID 86721304[1-(2,2-Diethoxyethoxy)but-3-en-1-yl]cyclopropane

Product 1

HCID 90253559methyl (2E)-5-cyclopropyl-5-(2,2-diethoxyethoxyl)pent-2-enoate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of methyl prop-2-enoate (69.5 mL, 767 mmol) and benzylidene[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]dichloro(tricyclohexylphosphine)ruthenium (Grubbs catalyst, second generation) (1.30 g, 1.53 mmol) in dichloromethane (102 mL) was added to a solution of [1-(2,2-diethoxyethoxyl)but-3-en-1-yl]cyclopropane (C15) (7.00 g, 30.7 mmol) in dichloromethane (102 mL), and the reaction mixture was stirred at room temperature for 3 hours. After removal of solvent under reduced pressure, the residue was mixed with diethyl ether and filtered through Celite. The filter pad was washed with additional diethyl ether, and the combined filtrates were concentrated in vacuo. Purification using silica gel chromatography (Gradient: 0% to 30% ethyl acetate in heptane) afforded the product as an oil. Yield: 6.0 g, 21 mmol, 68%. 1H NMR (400 MHz, CDCl3) δ 7.04 (dt, J=15.7, 7.4 Hz, 1H), 5.85-5.91 (m, 1H), 4.59 (dd, J=5.4, 5.2 Hz, 1H), 3.64-3.74 (m, 6H), 3.52-3.61 (m, 2H), 3.44 (dd, J=10.3, 5.5 Hz, 1H), 2.76 (dt, J=8.5, 5.9 Hz, 1H), 2.51 (ddd, J=7.3, 5.9, 1.4 Hz, 2H), 1.19-1.24 (m, 6H), 0.78-0.89 (m, 1H), 0.57-0.66 (m, 1H), 0.37-0.52 (m, 2H), 0.03-0.11 (m, 1H).

Workup

  1. customAfter removal of solvent under reduced pressure
  2. additionthe residue was mixed with diethyl ether
  3. filtrationfiltered through Celite
  4. washThe filter pad was washed with additional diethyl ether
  5. concentrationthe combined filtrates were concentrated in vacuo
  6. customPurification

Sources & evidence

ORD record
ord-cd060eb974f44bf98be6ad569f50a4f1
Source dataset
uspto-grants-2016_08
Patent number
US09403846B2

Reaction notes

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