Hexane → p-[2-(4-Methoxymethylenecyclohexyl)ethyl]benzonitrile

HRID 247679Notes

Reaction equation

HRID 247679 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]([CH2:32][CH2:33][CH:34]2[CH2:39][CH2:38][C:37](=O)[CH2:36][CH2:35]2)=[CH:28][CH:27]=1)#[N:25].CCCCCC.CCCCCC.C(Cl)Cl>COC(C)(C)C.O1CCCC1.C(Cl)Cl>[CH3:2][O:3][CH:4]=[C:37]1[CH2:38][CH2:39][CH:34]([CH2:33][CH2:32][C:29]2[CH:30]=[CH:31][C:26]([C:24]#[N:25])=[CH:27][CH:28]=2)[CH2:35][CH2:36]1

Participants

8

Reactant 4

HCID 8058HexaneHCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 197393184-[2-(p-Cyanophenyl)ethyl]cyclohexanoneHCID 21226440Methylenechloride Hexane

Product 1

HCID 20159862p-[2-(4-Methoxymethylenecyclohexyl)ethyl]benzonitrileYield 74.5%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
0 °C

Procedure

A suspension of 54.4 g of methoxymethyl-triphenylphosphonium chloride in 315 ml of t-butyl methyl ether was treated with 18.8 g of potassium t-butylate while gassing with argon at -10° C. and the orange suspension was stirred for a further 30 minutes at 0° C. The mixture was subsequently treated dropwise within 30 minutes at 0° C. with a solution of 25.1 g of 4-[2-(p-cyanophenyl)ethyl]cyclohexanone in 260 ml of tetrahydrofuran and the mixture was stirred for a further 3 hours at room temperature. Thereafter, the reaction mixture was poured into 2.6 l of hexane, stirred for 10 minutes and suction filtered (rinsing with hexane). The filtrate was concentrated in vacuo at 50° C., whereby 47.7 g of yellow, partially crystalline residue were obtained. Low-pressure chromatography (0.3 bar) of the residue on silica gel with hexane/methylene chloride (vol. 4:1) and methylene chloride gave 21.0 g of p-[2-(4-methoxymethylenecyclohexyl)ethyl]benzonitrile as a yellowish oil; Rf-value (methylene chloride) 0.43.

Workup

  1. customwhile gassing with argon at -10° C.
  2. stirringthe mixture was stirred for a further 3 hours at room temperature
  3. stirringstirred for 10 minutes
  4. filtrationsuction filtered
  5. wash(rinsing with hexane)
  6. concentrationThe filtrate was concentrated in vacuo at 50° C.
  7. customwhereby 47.7 g of yellow, partially crystalline residue were obtained

Sources & evidence

ORD record
ord-faafb626e3104f9da090dde714296be5
Source dataset
uspto-grants-1987_11
Patent number
US04709030

Reaction notes

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