Water → HCID 178495003, compound

HRID 2254963Notes

Reaction equation

HRID 2254963 reaction equation
[Cl-].[CH3:2][O:3][CH2:4][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[C:24]([C:26]1[CH:31]=[CH:30][C:29]([C@H:32]2[CH2:37][CH2:36][C@H:35]([CH2:38][CH:39]=O)[CH2:34][CH2:33]2)=[CH:28][CH:27]=1)#[N:25].O>COC(C)(C)C>[CH3:2][O:3][CH:4]=[CH:39][CH2:38][C@H:35]1[CH2:34][CH2:33][C@H:32]([C:29]2[CH:28]=[CH:27][C:26]([C:24]#[N:25])=[CH:31][CH:30]=2)[CH2:37][CH2:36]1

Participants

5

Reactant 3

HCID 962WaterHCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 178509798HCID 178509798, compound

Product 1

HCID 178495003HCID 178495003, compoundYield 91%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent2×

Procedure

A suspension of 4.5 g of methoxymethyl-triphenylphosphonium chloride in 40 ml of t-butyl methyl ether was treated within 3 minutes with 1.5 g of potassium t-butylate while gassing with argon at -10° C. and the solution was stirred for a further 1 hour at 0°-5° C. The suspension was then treated dropwise within 5 minutes at 0° C. with a solution of 2.0 g of [trans-4-(p-cyanophenyl)cyclohexyl]-acetaldehyde in 20 ml of t-butyl methyl ether and the mixture was stirred for a further 2 hours at room temperature. The reaction mixture was subsequently poured into 100 ml of water and extracted three times with 100 ml of diethyl ether each time. The organic phases were washed twice with 100 ml of water each time, dried over magnesium sulphate and concentrated. The resulting, viscous oil was dissolved in 15 ml of ethyl acetate and the clear solution was treated with 250 ml of petroleum ether. After leaving to stand for 10 minutes at -20° C. the precipitated triphenylphosphine oxide was filtered off and the filtrate was concentrated to dryness. Low-pressure chromatography (0.5 bar) of the residue (3.3 g) on silica gel with ethyl acetate/petroleum ether (vol. 5:95) gave 2.04 g (91%) of p-[trans-4-(3-methoxy-2-propenyl)cyclohexyl]benzonitrile as a colourless oil; Rf-value (ethyl acetate/petroleum ether vol. 10:90) 0.33.

Workup

  1. customwhile gassing with argon at -10° C.
  2. stirringthe mixture was stirred for a further 2 hours at room temperature
  3. extractionextracted three times with 100 ml of diethyl ether each time
  4. washThe organic phases were washed twice with 100 ml of water each time
  5. dry with materialdried over magnesium sulphate
  6. concentrationconcentrated
  7. dissolutionThe resulting, viscous oil was dissolved in 15 ml of ethyl acetate
  8. additionthe clear solution was treated with 250 ml of petroleum ether
  9. customAfter leaving
  10. waitto stand for 10 minutes at -20° C.
  11. filtrationthe precipitated triphenylphosphine oxide was filtered off
  12. concentrationthe filtrate was concentrated to dryness

Sources & evidence

ORD record
ord-71e6736b6d79439e9708f1260272954b
Source dataset
uspto-grants-1993_08
Patent number
US05238602

Reaction notes

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