Acetic Acid → 2-Cyano-4,4,8-trimethyl-non-2-enoic acid benzyl ester

HRID 1829849Notes

Reaction equation

HRID 1829849 reaction equation
[CH3:1][C:2]([CH3:11])([CH2:5][CH2:6][CH2:7][CH:8]([CH3:10])[CH3:9])[CH:3]=O.N1CCCCC1.[C:18]([CH2:20][C:21]([O:23][CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)=[O:22])#[N:19].C(O)(=O)C.Cl>C1(C)C=CC=CC=1>[CH2:24]([O:23][C:21](=[O:22])[C:20]([C:18]#[N:19])=[CH:3][C:2]([CH3:11])([CH3:1])[CH2:5][CH2:6][CH2:7][CH:8]([CH3:10])[CH3:9])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 8082PiperidineHCID 560818Benzyl 2-cyanoacetateHCID 219436612,2,6-Trimethyl-heptanal

Product 1

HCID 688724612-Cyano-4,4,8-trimethyl-non-2-enoic acid benzyl esterYield 61.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a mixture of 2,2,6-Trimethyl-heptanal (1.05 g, 6.73 mmol), piperidine (0.19 mL, 2.01 mmol) and benzyl cyanoacetate (1.29 g, 7.4 mmol) in toluene (50 mL) was added glacial acetic acid (0.72 g, 12.1 mmol). The flask was fitted with a Dean-Stark trap, and the mixture was heated at reflux for 18. The mixture was cooled, treated with dilute HCl, and the layers were separated. The organics were washed with a saturated sodium bicarbonate solution followed by brine, and dried (MgSO4), filtered and concentrated. The residual oil was purified by silica gel chromatography (98/2 hexane/EtOAc) to give 1.3 g of 2-Cyano-4,4,8-trimethyl-non-2-enoic acid benzyl ester m/z 314 (M+).

Workup

  1. customThe flask was fitted with a Dean-Stark trap
  2. temperaturethe mixture was heated
  3. temperatureat reflux for 18
  4. temperatureThe mixture was cooled
  5. customthe layers were separated
  6. washThe organics were washed with a saturated sodium bicarbonate solution
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe residual oil was purified by silica gel chromatography (98/2 hexane/EtOAc)

Sources & evidence

ORD record
ord-e10faeada7a445ccb1482b5c4eb0141b
Source dataset
uspto-grants-2006_06
Patent number
US07064147B2

Reaction notes

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