Acetic acid, 2-(triphenylphosphoranylidene)-, methyl ester → Methyl 3-(5-chlorothiophen-2-yl)prop-2-enoate

HRID 1432871Notes

Reaction equation

HRID 1432871 reaction equation
[Cl:1][C:2]1[S:6][C:5]([CH:7]=O)=[CH:4][CH:3]=1.C1(P(=[CH:28][C:29]([O:31][CH3:32])=[O:30])(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[CH3:32][O:31][C:29](=[O:30])/[CH:28]=[CH:7]/[C:5]1[S:6][C:2]([Cl:1])=[CH:3][CH:4]=1

Participants

4

Reactant 2

HCID 17453Acetic acid, 2-(triphenylphosphoranylidene)-, methyl esterHCID 817002-Thiophenecarboxaldehyde, 5-chloro-

Product 1

HCID 69024911Methyl 3-(5-chlorothiophen-2-yl)prop-2-enoateYield 87.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 5-chloro-2-thiophene-carboxaldehyde (5.10 g, 34.8 mmol) in 100 mL of dry CH2Cl2 is added methyl (triphenylphosphoranylidene)acetate (11.8 g, 35.3 mmol). The resulting brown-green mixture is stirred for 19 h at room temperature. The mixture is filtered through a Celite pad, concentrated in vacuo and triturated with hexane. The white precipitate (triphenylphosphine oxide) is filtered off and the filtrate is concentrated. The crude residue is purified via flash column chromatography eluting with a gradient of 5% EtOAc/hexanes to 10% EtOAc/hexanes to provide the title compound (6.20 g, 30.6 mmol) as a yellow solid. 1H NMR (CDCl3, 300 MHz) δ7.65 (d, 1H), 7.05 (d, 1H), 6.89 (d, 1H), 6.10 (d, 1H), 3.80 (s, 3H).

Workup

  1. filtrationThe mixture is filtered through a Celite pad
  2. concentrationconcentrated in vacuo
  3. customtriturated with hexane
  4. filtrationThe white precipitate (triphenylphosphine oxide) is filtered off
  5. concentrationthe filtrate is concentrated
  6. customThe crude residue is purified via flash column chromatography
  7. washeluting with a gradient of 5% EtOAc/hexanes to 10% EtOAc/hexanes

Sources & evidence

ORD record
ord-c9c57ca99b3f45578bf5728c533a3cc4
Source dataset
uspto-grants-2009_11
Patent number
US07612075B2

Reaction notes

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