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

HRID 653360Notes

Reaction equation

HRID 653360 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 while stirring and gassing with nitrogen in a sulphonation flask, 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. The cooling bath was then removed and the mixture was stirred at room temperature for a further 3.5 hours. 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% (wt./vol.) sodium chloride solution each time, dried over sodium sulphate, filtered and concentrated, there being obtained 76.9 g of a brownish paste. 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. customgassing with nitrogen in a sulphonation flask
  2. customrose to 44° C
  3. customThe cooling bath was then removed
  4. stirringthe mixture was stirred at room temperature for a further 3.5 hours
  5. additionThe suspension was subsequently poured into 500 ml of water
  6. extractionextracted three times with 600 ml of methylene chloride each time
  7. washThe organic phases were washed twice with 500 ml of 10% (wt./vol.) sodium chloride solution each time
  8. dry with materialdried over sodium sulphate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customthere being obtained 76.9 g of a brownish paste
  12. customChromatographic separation of this crude product on silica gel with methylene chloride as the eluent

Sources & evidence

ORD record
ord-a2b695aa91114400823dfbae443a95fb
Source dataset
uspto-grants-1987_06
Patent number
US04676604

Reaction notes

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