Cyclohexanone → 2-Cyclohexylidene-2-ortho-tolyl acetonitrile
Reaction equation
[C:1]1(=O)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[CH3:8][C:9]1[CH:17]=[CH:16][CH:15]=[CH:14][C:10]=1[CH2:11][C:12]#[N:13].[OH-].[K+]>>[C:1]1(=[C:11]([C:10]2[CH:14]=[CH:15][CH:16]=[CH:17][C:9]=2[CH3:8])[C:12]#[N:13])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1Participants
Conditions
- Temperature
- 140 °C
Procedure
The mixture of cyclohexanone (44.7 g, 0.46 mol) and 2-methyl benzylcyanide (41.9 g, 0.32 mol) is treated with KOH (3.58 g, 0064 mol) and the resulting mixture is heated to 120° C. (oilbath temperature 140° C.) for 2 h with concomitant distillation of H2O as an azeotrope with cyclohexanone. The temperature is raised to 130° C. (oilbath temperature 150° C.) for 30 min, before cooling to 60° C. and dilution of the viscous mixture with toluene (50 ml). Standard aqueous workup is effected with toluene, H2O, sat. aq. Na2CO3-solution and brine. The organic layer is dried over MgSO4 and the volatiles removed in vacuo. The crude product (67 g), which crystallizes upon standing, is subjected to a short path distillation at 0.05 mbar/120-127° C. to yield 42.6 g of crystalline product which is recrystallized three times from hexane. From this, 33.6 g of white crystalline product is obtained (50% yield), m.p. 65.2-66.0° C.
Workup
- distillationwith concomitant distillation of H2O as an azeotrope with cyclohexanone
- temperatureThe temperature is raised to 130° C. (oilbath temperature 150° C.) for 30 min
- temperaturebefore cooling to 60° C.
- dry with materialThe organic layer is dried over MgSO4
- customthe volatiles removed in vacuo
- customThe crude product (67 g), which crystallizes
- distillationis subjected to a short path distillation at 0.05 mbar/120-127° C.
Sources & evidence
- ORD record
- ord-4fdf2faccc1a4b36a2bf91eb27352701
- Source dataset
- uspto-grants-2010_02
- Patent number
- US07655701B2
Reaction notes
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