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

HRID 1948587Notes

Reaction equation

HRID 1948587 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 mole) was dissolved in dry tetrahydrofuran (350 ml). Sodium tert-butylate (9.6 g, 0.1 mole) was then added in portions. During this addition the reaction mixture turned an orange colour. The reaction mixture was then boiled under reflux for 5 hours. During the boiling a beige-coloured pasty suspension was formed. The reaction mixture was cooled to room temperature overnight. 2.5N acetic acid (170 ml) was slowly added dropwise to the reaction mixture while cooling with ice. Toluene (100 ml) was then added to the reaction mixture. The organic phase was separated and washed with saturated sodium hydrogen carbonate solution (3×70 ml), water (3×50 ml) and sodium chloride solution (1×70 ml). After drying over Na2SO4, the solvent was distilled off on a rotary evaporator and the residue was recrystallised from methanol. The desired product was obtained 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 hours
  3. customDuring the boiling a beige-coloured pasty suspension was formed
  4. temperaturewhile cooling with ice
  5. customThe organic phase was separated
  6. washwashed with saturated sodium hydrogen carbonate solution (3×70 ml), water (3×50 ml) and sodium chloride solution (1×70 ml)
  7. dry with materialAfter drying over Na2SO4
  8. distillationthe solvent was distilled off on a rotary evaporator
  9. customthe residue was recrystallised from methanol

Sources & evidence

ORD record
ord-d6dd1b83332948c2b0611f75e264b1f4
Source dataset
uspto-grants-2013_03
Patent number
US08399503B2

Reaction notes

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