tert-Butyl methyl ether → HCID 178444506, compound

HRID 1463746Notes

Reaction equation

HRID 1463746 reaction equation
[C:1]([C@H:3]1[CH2:8][CH2:7][C@H:6]([C@H:9]2[CH2:14][CH2:13][C@H:12]([CH2:15][CH2:16][CH2:17][CH:18]=O)[CH2:11][CH2:10]2)[CH2:5][CH2:4]1)#[N:2].[CH3:20]OC(C)(C)C>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>[CH2:15]([C@H:12]1[CH2:13][CH2:14][C@H:9]([C@H:6]2[CH2:7][CH2:8][C@H:3]([C:1]#[N:2])[CH2:4][CH2:5]2)[CH2:10][CH2:11]1)[CH2:16][CH2:17][CH:18]=[CH2:20]

Participants

5

Reactant 2

HCID 15413tert-Butyl methyl ether2×HCID 178511238HCID 178511238, compound

Product 1

HCID 178444506HCID 178444506, compound

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

3.28 g of methyltriphenylphosphonium bromide were suspended in 40 ml of tert.butyl methyl ether while gassing with argon. The suspension was treated at room temperature within 1 minute with 962 mg of potassium tert.butylate and stirred for I hour. The mixture was subsequently cooled to 0° C., treated dropwise within 3 minutes with a solution of 1.5 g of 4-[trans-4-(trans-4-cyanocyclohexyl)cyclohexyl]butyraldehyde in 20 ml of tert.butyl methyl ether and stirred at 0° C. for a further 45 minutes. Thereafter, the reaction mixture was diluted with 80 ml of water and extracted three times with 100 ml of petroleum ether each time. The organic phases were washed twice with 100 ml of water each time, dried over magnesium sulfate, filtered and concentrated. Chromatographic purification of the crude product (2.1 g) on silica gel at 0.5 bar with ethyl acetate/petroleum ether (vol. 2:98) and recrystallization from 20 ml of methanol gave 1.26 g of trans-4-[trans-4-(4-pentenyl)cyclohexyl]-cyclohexanecarbonitrile as colorless crystals with m.p. (C-SB) 20.1° C, SB -N 36.9° C., cl.p. (N-I) 54.8° C.

Workup

  1. stirringstirred at 0° C. for a further 45 minutes
  2. extractionextracted three times with 100 ml of petroleum ether each time
  3. washThe organic phases were washed twice with 100 ml of water each time
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customChromatographic purification of the crude product (2.1 g) on silica gel at 0.5 bar
  8. customwith ethyl acetate/petroleum ether (vol. 2:98) and recrystallization from 20 ml of methanol

Sources & evidence

ORD record
ord-40ef2e34367946d4b4e3555f37b04975
Source dataset
uspto-grants-1994_04
Patent number
US05302317

Reaction notes

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