p-Toluenesulfonic acid → 4-[[(Ethoxycarbonyl)methyl]methylamino]-4-phenylcyclohexanone

HRID 1462509Notes

Reaction equation

HRID 1462509 reaction equation
[CH3:1][NH:2][C:3]1([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH2:8][CH2:7][C:6](=[O:9])[CH2:5][CH2:4]1.Br[CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19].C(=O)([O-])[O-].[K+].[K+].C1(C)C=CC(S(O)(=O)=O)=CC=1>C(OCC)C.C1C=CC=CC=1.O.CN(C)C=O>[CH2:21]([O:20][C:18]([CH2:17][N:2]([CH3:1])[C:3]1([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH2:4][CH2:5][C:6](=[O:9])[CH2:7][CH2:8]1)=[O:19])[CH3:22]

Participants

9

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 7748Ethyl bromoacetateHCID 11430Potassium CarbonateHCID 133452704-Methylamino-4-phenylcyclohexanone

Product 1

HCID 213909514-[[(Ethoxycarbonyl)methyl]methylamino]-4-phenylcyclohexanoneYield 63%

Reagents, catalysts & solvents 4

HCID 241BenzeneSolvent2×HCID 962WaterSolventHCID 3283Diethyl EtherSolvent3×HCID 6228DimethylformamideSolvent

Procedure

A reaction mixture consisting of 8.77 gm. (0.031 mole) of 4-methylamino-4-phenylcyclohexanone, ethylene ketal hydrochloride (prepared as in Example 17, Part G, above), 5.16 gm. (3.42 ml.) ethyl bromoacetate, 4.29 gm. potassium carbonate, and 120 ml. dimethylformamide is heated in an oil bath to 100° C. and then held at that temperature with stirring for eighteen (18) hours. After removing the solvent medium by evaporation under reduced pressure, the residue obtained is dissolved in a mixture of 25 ml. water and 150 ml. benzene. The benzene layer is allowed to separate from the water and is recovered. It is washed with water and then with brine. The benzene is then removed by evaporation under reduced pressure. The residue thus obtained is dissolved in diethyl ether and to the ether solution is added 5.9 gm. p-toluenesulfonic acid dissolved in the minimum possible amount of diethyl ether. A gummy precipitate forms which is recrystallized two times from a mixture of methylene chloride and ethyl acetate. There is thus obtained 10.0 gm. (63% yield) of 4-[[(ethoxycarbonyl)methyl]methylamino]-4-phenylcyclohexanone, ethylene ketal, p-tetrenesulfonate having a melting range from 108° to 115° C. An analytical sample melts from 115° to 117° C.

Workup

  1. customAfter removing the solvent medium
  2. customby evaporation under reduced pressure
  3. customthe residue obtained
  4. dissolutionis dissolved in a mixture of 25 ml
  5. customto separate from the water
  6. customis recovered
  7. washIt is washed with water
  8. customThe benzene is then removed by evaporation under reduced pressure
  9. customThe residue thus obtained
  10. additionis added 5.9 gm
  11. customA gummy precipitate forms which is recrystallized two times
  12. additionfrom a mixture of methylene chloride and ethyl acetate

Sources & evidence

ORD record
ord-417fd04cef6f4dffa7f8728818a9e1ae
Source dataset
uspto-grants-1984_07
Patent number
US04460604

Reaction notes

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