Acetic Acid → Methyl 5-cyano-2-oxo-5-phenylcyclohexanecarboxylate

HRID 1095491Notes

Reaction equation

HRID 1095491 reaction equation
CO[C:3](=[O:21])[CH2:4][CH2:5][C:6]([C:19]#[N:20])([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[CH2:7][CH2:8][C:9]([O:11][CH3:12])=[O:10].C(O)(=O)C.C1(C)C=CC=CC=1>O1CCCC1>[CH3:12][O:11][C:9]([CH:8]1[CH2:7][C:6]([C:19]#[N:20])([C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[CH2:5][CH2:4][C:3]1=[O:21])=[O:10]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 1140TolueneHCID 283742dimethyl 4-cyano-4-phenylheptanedioate

Product 1

HCID 582396Methyl 5-cyano-2-oxo-5-phenylcyclohexanecarboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

4-Cyano-4-phenylheptanedioic acid dimethyl ester (14.45 g, 0.05 mol) was dissolved in dry tetrahydrofuran (350 ml). Sodium tert-butylate (9.6 g, 0.1 mol) was then added in portions. During this addition the reaction mixture became orange in colour. Thereafter, the mixture was boiled under reflux for 5 h. During the boiling a beige-colouring, slurry-like suspension formed. The reaction mixture was cooled to room temperature overnight. 2.5 N glacial acetic acid (170 ml) was slowly added dropwise to the reaction mixture, while cooling with ice. Toluene (100 ml) was then added to the mixture. The organic phase was separated off and washed with saturated sodium bicarbonate solution (3×70 ml), water (3×50 ml) and sodium chloride solution (1×70 ml). After drying with Na2SO4, the solvent was distilled off on a rotary evaporator and the residue was recrystallized from methanol. It was possible to obtain the desired product in a yield of 10.7 g (83%) as a yellow solid with a melting point of 75-80° C.

Workup

  1. additionDuring this addition the reaction mixture
  2. temperatureunder reflux for 5 h
  3. customformed
  4. temperaturewhile cooling with ice
  5. customThe organic phase was separated off
  6. washwashed with saturated sodium bicarbonate solution (3×70 ml), water (3×50 ml) and sodium chloride solution (1×70 ml)
  7. dry with materialAfter drying with Na2SO4
  8. distillationthe solvent was distilled off on a rotary evaporator
  9. customthe residue was recrystallized from methanol

Sources & evidence

ORD record
ord-8463e27dc3004d4d877a26ff4618b288
Source dataset
uspto-grants-2012_03
Patent number
US08138187B2

Reaction notes

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