Tetrahydrofuran → 2-Carbomethoxy-4-(p-chlorophenyl)-4-cyanocyclohexanone

HRID 543853Notes

Reaction equation

HRID 543853 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:19]#[N:20])([CH2:14][CH2:15][C:16]([OH:18])=O)[CH2:9][CH2:10][C:11]([OH:13])=[O:12])=[CH:4][CH:3]=1.O1CCC[CH2:22]1.CC(C)([O-])C.[K+]>C(O)(=O)C>[C:11]([CH:10]1[CH2:9][C:8]([C:5]2[CH:4]=[CH:3][C:2]([Cl:1])=[CH:7][CH:6]=2)([C:19]#[N:20])[CH2:14][CH2:15][C:16]1=[O:18])([O:13][CH3:22])=[O:12]

Participants

5

Reactant 3

HCID 8028TetrahydrofuranHCID 204534054-(p-Chlorophenyl)-4-cyanopimelic acidHCID 23665647Potassium tert-butoxide

Product 1

HCID 122302342-Carbomethoxy-4-(p-chlorophenyl)-4-cyanocyclohexanoneYield 96%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A reaction mixture consisting of 34.97 g. (0.108 mole) dimethyl ester of 4-(p-chlorophenyl)-4-cyanopimelic acid (prepared in Part a, above) dissolved in 700 ml. tetrahydrofuran with 24.4 gm. (0.218 mole) potassium tert-butoxide added is heated at the reflux temperature for 41/2 hours. After cooling, the reaction mixture is chilled in an ice-bath and 175 ml. 2.5 N acetic acid is added. The organic and aqueous phases separate and the organic phase is recovered. It is diluted with 600 ml. benzene before being washed successively with aqueous sodium bicarbonate, water, and brine. The organic solvents are then removed by distillation under reduced pressure. There is thus obtained 30.2 gm. (96% yield) of 2-carbomethoxy-4-(p-chlorophenyl)-4-cyanocyclohexanone having a melting point at 139° to 143° C.

Workup

  1. dissolutiondissolved in 700 ml
  2. temperatureis heated at the reflux temperature for 41/2 hours
  3. temperatureAfter cooling
  4. temperaturethe reaction mixture is chilled in an ice-bath
  5. customThe organic and aqueous phases separate
  6. customthe organic phase is recovered
  7. additionIt is diluted with 600 ml
  8. washbenzene before being washed successively with aqueous sodium bicarbonate, water, and brine
  9. customThe organic solvents are then removed by distillation under reduced pressure

Sources & evidence

ORD record
ord-fed60a51c4a5449b9510e5a7c3851e16
Source dataset
uspto-grants-1984_05
Patent number
US04447454

Reaction notes

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