Methoxymethyl-triphenylphosphonium chloride → HCID 178495106, compound

HRID 1285067Notes

Reaction equation

HRID 1285067 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]([CH:38]=O)[CH2:34][CH2:33]2)=[CH:28][CH:27]=1)#[N:25]>COC(C)(C)C>[CH3:2][O:3][CH:4]=[CH: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

4

Reactant 2

HCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 178509803HCID 178509803, compound

Product 1

HCID 178495106HCID 178495106, compoundYield 74.4%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent2×

Conditions

Temperature
0 °C

Procedure

A suspension of 29.0 g of methoxymethyl-triphenylphosphonium-chloride in 200 ml of t-butyl methyl ether was treated with 9.7 g of potassium t-butylate at -10° C. within 3 minutes while gassing with argon in a sulphonation flask provided with a mechanical stirrer. The orange suspension was stirred at about 0° C. for 1 hour, then treated dropwise at -10° C. within 10 minutes with a solution of 12.0 g of trans-4-(p-cyanophenyl)cyclohexanecarboxaldehyde in 90 ml of t-butyl methyl ether and stirred at 0° C. for a further 45 minutes. The mixture was subsequently partitioned three times in diethyl ether/water. The organic extracts were washed twice with water, dried over magnesium sulphate, filtered and evaporated. In order to separate triphenylphosphine oxide, the residue was dissolved in ethyl acetate and the solution was diluted with petroleum ether, filtered and evaporated. Chromatographic separation of the yellowish, crystalline residue (16.3 g) on silica gel with ethyl acetate/petroleum ether (vol. 5:95) gave 10.1 g (74%) of p-[trans-4-(2-methoxyvinyl)cyclohexyl]benzonitrile as white crystals.

Workup

  1. customwhile gassing with argon in a sulphonation flask
  2. customprovided with a mechanical stirrer
  3. stirringstirred at 0° C. for a further 45 minutes
  4. customThe mixture was subsequently partitioned three times in diethyl ether/water
  5. washThe organic extracts were washed twice with water
  6. dry with materialdried over magnesium sulphate
  7. filtrationfiltered
  8. customevaporated
  9. customIn order to separate triphenylphosphine oxide
  10. dissolutionthe residue was dissolved in ethyl acetate
  11. additionthe solution was diluted with petroleum ether
  12. filtrationfiltered
  13. customevaporated
  14. customChromatographic separation of the yellowish, crystalline residue (16.3 g) on silica gel with ethyl acetate/petroleum ether (vol. 5:95)

Sources & evidence

ORD record
ord-2174a8fc55804fef9cc41abb6bc9bda2
Source dataset
uspto-grants-1986_01
Patent number
US04565425

Reaction notes

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