Hexane → p-[4-(Methoxymethylene)cyclohexyl]benzonitrile

HRID 653353

Reaction equation

HRID 653353 reaction equation
[Cl-].C1([P+](C2C=CC=CC=2)(C2C=CC=CC=2)[CH2:9][O:10][CH3:11])C=CC=CC=1.[C:24]([C:26]1[CH:31]=[CH:30][C:29]([CH:32]2[CH2:37][CH2:36][C:35](=O)[CH2:34][CH2:33]2)=[CH:28][CH:27]=1)#[N:25].CCCCCC>COC(C)(C)C.O1CCCC1>[CH3:9][O:10][CH:11]=[C:35]1[CH2:36][CH2:37][CH:32]([C:29]2[CH:30]=[CH:31][C:26]([C:24]#[N:25])=[CH:27][CH:28]=2)[CH2:33][CH2:34]1

Participants

6

Reactant 3

HCID 8058HexaneHCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 157899134-(4-Oxocyclohexyl)benzonitrile

Product 1

HCID 19739357p-[4-(Methoxymethylene)cyclohexyl]benzonitrileYield 94%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 15413tert-Butyl methyl etherSolvent

Procedure

10.4 g of triphenyl-methoxymethyl-phosphonium chloride were suspended in 60 ml of t-butyl methyl ether while gassing with argon in a sulphonation flask provided with a thermometer, mechanical stirrer, dropping funnel and solid substance addition tube and treated at -10° C. within 10 minutes with 3.6 g of solid potassium t-butylate. After completion of the addition, the mixture was stirred at -10° C. to 0° C. for a further 30 minutes and then the deep orange, heterogenous mixture was treated dropwise at 0° C. with a solution of 4.2 g of 4-(p-cyanophenyl)cyclohexanone in 50 ml of absolute tetrahydrofuran. The mixture was subsequently stirred at room temperature for a further 2 hours, then poured into 500 ml of hexane and filtered. Low-pressure chromatography (0.5 bar) of the concentrated residue (7.1 g) on silica gel with ethyl acetate/petroleum ether (vol. 5:95) gave 4.5 g (94%) of p-[4-(methoxymethylene)cyclohexyl]benzonitrile as a colourless oil; purity 95%, Rf-value (ethyl acetate/petroleum ether vol. 1:9) 0.30.

Workup

  1. customwhile gassing with argon in a sulphonation flask
  2. customprovided with a thermometer, mechanical stirrer
  3. additionfunnel and solid substance addition tube
  4. additionAfter completion of the addition
  5. stirringThe mixture was subsequently stirred at room temperature for a further 2 hours
  6. filtrationfiltered

Sources & evidence

ORD record
ord-aee6e824fb9445fd843dd2aa988bb3df
Source dataset
uspto-grants-1987_06
Patent number
US04676604

Linked notes

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