Methoxymethyl-triphenylphosphonium chloride → HCID 178495003, compound

HRID 1285069Notes

Reaction equation

HRID 1285069 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]>COC(C)(C)C.O1CCCC1>[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 2

HCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 178509798HCID 178509798, compound

Product 1

HCID 178495003HCID 178495003, compoundYield 96%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
0 °C

Procedure

A suspension of 22.2 g of methoxymethyl-triphenylphosphonium chloride in 150 ml of t-butyl methyl ether was treated with 7.4 g of solid potassium t-butylate at 0° C. within 3 minutes while gassing with argon in a sulphonation flask provided with a mechanical stirrer. The orange suspension was stirred at 0° C. for 1 hour and then treated dropwise within 10 minutes with a solution of 9.8 g of 2-[trans-4-(p-cyanophenyl)cyclohexyl]acetaldehyde in 100 ml of tetrahydrofuran. Subsequently, the suspension was left to warm slowly to room temperature while stirring. After 15 hours, the suspension was 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 resulting, yellowish oil (13.7 g) on silica gel with ethyl acetate/petroleum ether (vol. 5:95) gave 10.5 g (96%) of p-[trans-4-(3-methoxy-2-propenyl)cyclohexyl]benzonitrile as a colourless oil.

Workup

  1. customwhile gassing with argon in a sulphonation flask
  2. customprovided with a mechanical stirrer
  3. waitSubsequently, the suspension was left
  4. temperatureto warm slowly to room temperature
  5. stirringwhile stirring
  6. waitAfter 15 hours
  7. customthe suspension was partitioned three times in diethyl ether/water
  8. washThe organic extracts were washed twice with water
  9. dry with materialdried over magnesium sulphate
  10. filtrationfiltered
  11. customevaporated
  12. customIn order to separate triphenylphosphine oxide
  13. dissolutionthe residue was dissolved in ethyl acetate
  14. additionthe solution was diluted with petroleum ether
  15. filtrationfiltered
  16. customevaporated
  17. customChromatographic separation of the resulting, yellowish oil (13.7 g) on silica gel with ethyl acetate/petroleum ether (vol. 5:95)

Sources & evidence

ORD record
ord-b39d169891704f8f8456092b043d2ce1
Source dataset
uspto-grants-1986_01
Patent number
US04565425

Reaction notes

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