Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester → Ethyl-3-(5'-fluoro-2'-methoxyphenyl)acrylate

HRID 1919532Notes

Reaction equation

HRID 1919532 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]([O:10][CH3:11])=[C:6]([CH:9]=1)[CH:7]=O.[C:12]([CH:17]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:14][CH2:15][CH3:16])=[O:13]>C(Cl)Cl>[CH2:15]([O:14][C:12](=[O:13])[CH:17]=[CH:7][C:6]1[CH:9]=[C:2]([F:1])[CH:3]=[CH:4][C:5]=1[O:10][CH3:11])[CH3:16]

Participants

4

Reactant 2

HCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 27349435-Fluoro-2-methoxybenzaldehyde

Product 1

HCID 67499726Ethyl-3-(5'-fluoro-2'-methoxyphenyl)acrylateYield 95.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 5-fluoro-2-methoxybenzaldehyde (4.3 g, 28.0 mmol) in dry CH2Cl2 (30 mL) at 0° C. was added carbethoxymethylenetriphenylphosphorane (10.7 g, 30.1 mmol) portion-wise and the reaction was warmed to room temperature and stirred for 12 h. The solvent was then removed in vacuo and the residue was purified by flash column chromatography (EtOAc/hexane, 10:90, v:v, Rf=0.2) to yield the product (6.0 g, 95%) as a 4:1 mixture of trans:cis diastereomers; 1H NMR (CDCl3, 500 MHz): δ 7.93 (d, J=16.2 Hz, 0.8 H), 7.33 (dd, J=3.1, 9.2 Hz, 0.2 H), 7.21 (dd, J=3.1, 9.2, Hz, 0.8 H), 7.08 (d, J=12.5 Hz, 0.2 H), 7.03 (dt, J=3.0, 8.8 Hz, 0.8 H), 6.99 (dt, J=3.0, 8.8 Hz, 0.2 H), 6.84 (dd, J=3.1, 8.6 Hz, 0.8 H), 6.79 (dd, J=3.3, 9.1 Hz, 0.2 H), 6.47 (d, J=16.2 Hz, 0.8 H), 5.99 (d, J=12.5 hz, 0.2 H), 4.25 (q, J=7.1 Hz, 1.6 H), 4.15 (q, J=7.0 Hz, 0.4 H), 3.86 (s, 2.4H), 3.81 (s, 0.6 H), 1.34 (t, J=7.1 Hz, 2.4 H), 1.22 (t, J=7.0 Hz, 0.6 H).

Workup

  1. customThe solvent was then removed in vacuo
  2. customthe residue was purified by flash column chromatography (EtOAc/hexane, 10:90, v:v, Rf=0.2)

Sources & evidence

ORD record
ord-738251e246b14daca25303336d46a6f7
Source dataset
uspto-grants-2012_05
Patent number
US08168635B2

Reaction notes

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