Acetic Acid → Cyanocyclohexylideneacetic acid

HRID 622859Notes

Reaction equation

HRID 622859 reaction equation
[C:1]([CH2:3][C:4]([OH:6])=[O:5])#[N:2].[C:7]1(=O)[CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]1.C(O)(=O)C.C1C=CC=CC=1>C([O-])(=O)C.[NH4+].O>[C:7]1(=[C:3]([C:1]#[N:2])[C:4]([OH:6])=[O:5])[CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 241BenzeneHCID 7967CyclohexanoneHCID 9740Cyanoacetic acid

Product 1

HCID 97457Cyanocyclohexylideneacetic acidYield 90%

Reagents, catalysts & solvents 2

HCID 517165Ammonium AcetateCatalystHCID 962WaterSolvent

Procedure

170 grams (2 moles) of cyanoacetic acid, 196 grams (2 moles) of cyclohexanone, 10 grams (0.13 moles) of ammonium acetate, 24 grams (0.4 moles) of acetic acid, and 380 milliliters of benzene were combined in a 2-liter round-bottomed flask equipped with a reflux condensor and a water separator, and the mixture heated (with reflux) for 6 hours. Upon cooling, the volatile compounds were removed in vacuo, and the residue washed with water to give 360 grams (1.8 moles, 90% yield) of cyclohexylidene cyanoacetic acid. The cyanoacetic acid was distilled under a vacuum of 50 Torricellis (torr.) thereby producing 196 grams (1.6 moles, 81% yield based on cyclohexanone, or 90% yield based on cyclohexylidene cyanoacetic acid) of cyclohexenyl acetic acid nitrile, which had a boiling point of between 115°-120° C. at 50 torr. (As an alternative to distilling the cyanoacetic acid under vacuum in the lastmentioned step, another portion of the cyclohexylidene cyanoacetic acid when heated to 140°-150° C. under a vacuum of 50-70 torr. for 2.5 hours was found to be readily convertible to an impure cyclohexenyl acetic acid nitrile.)

Workup

  1. customequipped with a reflux condensor
  2. temperature(with reflux) for 6 hours
  3. temperatureUpon cooling
  4. customthe volatile compounds were removed in vacuo
  5. washthe residue washed with water

Sources & evidence

ORD record
ord-a430b8788cb244ef9e10ca40a04c80cb
Source dataset
uspto-grants-1988_09
Patent number
US04772728

Reaction notes

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