3-Chlorobenzaldehyde → Ethyl 3-(3-chlorophenyl)-2-propenoate
Reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=O.C1(P(=[CH:29][C:30]([O:32][CH2:33][CH3:34])=[O:31])(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1COCC1>[Cl:1][C:2]1[CH:3]=[C:4]([CH:5]=[CH:29][C:30]([O:32][CH2:33][CH3:34])=[O:31])[CH:7]=[CH:8][CH:9]=1Participants
Reactant 2
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 0 °C
Procedure
In a 2 l three necked flask fitted with mechanical stirrer and dropping funnel under inert atmosphere, 106.2 g (755 mmoles, 1 eq) of 3-chlorobenzaldehyde are dissolved in 1 l of THF and cooled down to 0° C. 341.9 g (980 mmoles, 1.3 eq) of ethyl (triphenylphosphoranylidene)acetate are then added under efficient stirring, the temperature raising to 10° C. The mixture is kept under stirring one hour at 0° C., and then overnight at room temperature. The mixture is concentrated to dryness, the residue suspended in diethyl ether, the triphenylphospine oxide is filtered off and the filtrate concentrated to dryness. The residue is purified by PrepLC (1 kg SiO2, pet. ether/EtOAc, 75:35) to give 191.8 g of pure 375, 92% yield. 1H NMR (250 MHz, (CD3)2SO): 1.30 (t, 3H), 4.25 (q, 2H), 6.70 (d, 1H), 7.40 (m, 2H), 7.50-7.70 (m, 2H), 7.85 (s(broad), 1H).
Workup
- temperaturethe temperature raising to 10° C
- customovernight
- customat room temperature
- concentrationThe mixture is concentrated to dryness
- filtrationthe triphenylphospine oxide is filtered off
- concentrationthe filtrate concentrated to dryness
- customThe residue is purified by PrepLC (1 kg SiO2, pet. ether/EtOAc, 75:35)
- customto give 191.8 g of pure 375, 92% yield
Sources & evidence
- ORD record
- ord-e26c1222770e4e76b62cb08c6f4bda0c
- Source dataset
- uspto-grants-2013_07
- Patent number
- US08492416B2
Reaction notes
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