(4-Cyanobenzyl)triphenylphosphonium chloride → 4-[2-(p-Cyanophenyl)vinyl]cyclohexanone

HRID 2254975Notes

Reaction equation

HRID 2254975 reaction equation
[Cl-].[C:2]([C:4]1[CH:29]=[CH:28][C:7]([CH2:8][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=[CH:6][CH:5]=1)#[N:3].[CH:30]([CH:32]1[CH2:37][CH2:36][C:35](=[O:38])[CH2:34][CH2:33]1)=O>COCCOC>[C:2]([C:4]1[CH:5]=[CH:6][C:7]([CH:8]=[CH:30][CH:32]2[CH2:37][CH2:36][C:35](=[O:38])[CH2:34][CH2:33]2)=[CH:28][CH:29]=1)#[N:3]

Participants

4

Reactant 2

HCID 2724468(4-Cyanobenzyl)triphenylphosphonium chlorideHCID 111709734-Oxocyclohexane-1-carbaldehyde

Product 1

HCID 542443444-[2-(p-Cyanophenyl)vinyl]cyclohexanoneYield 110.7%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

63.3 g of p-cyanobenzyl-triphenylphosphonium chloride, 17.2 g of potassium t-butylate and 195 ml of ethylene glycol dimethyl ether were placed in a sulphonation flask while stirring and gassing with nitrogen, whereby the internal temperature rose to 44° C. The brown suspension was cooled to 0° C. and treated within 2 minutes with a solution of 16.7 g of 4-formylcyclohexanone in 100 ml of ethylene glycol dimethyl ether. Thereafter, the cooling bath was removed and the reaction mixture was stirred for a further 3.5 hours at room temperature. The suspension was subsequently poured into 500 ml of water and extracted three times with 600 ml of methylene chloride each time. The organic phases were washed twice with 500 ml of 10 percent (wt./vol.) sodium chloride solution each time, dried over sodium sulphate, filtered and concentrated, whereby 76.9 g of a brownish paste remained behind. Chromatographic separation of this crude product on silica gel with methylene chloride as the eluent gave 33.0 g of 4 -[2-(p-cyanophenyl)vinyl]cyclohexanone as a yellow-brownish oil.

Workup

  1. customrose to 44° C
  2. customThereafter, the cooling bath was removed
  3. stirringthe reaction mixture was stirred for a further 3.5 hours at room temperature
  4. additionThe suspension was subsequently poured into 500 ml of water
  5. extractionextracted three times with 600 ml of methylene chloride each time
  6. washThe organic phases were washed twice with 500 ml of 10 percent (wt./vol.) sodium chloride solution each time
  7. dry with materialdried over sodium sulphate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customChromatographic separation of this crude product on silica gel with methylene chloride as the eluent

Sources & evidence

ORD record
ord-9bab1e4db88343de9250fa8207835fcb
Source dataset
uspto-grants-1993_08
Patent number
US05238602

Reaction notes

Loading…