4-Methylcyclohexanone → 2-(4-Methylcyclohexylidene)heptanenitrile

HRID 263162

Reaction equation

HRID 263162 reaction equation
S([O-])([O-])(=O)=O.[Ca+2].[CH3:7][CH:8]1[CH2:13][CH2:12][C:11](=O)[CH2:10][CH2:9]1.[C:15](#[N:22])[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH3:21].[OH-].[K+].OCC1OC1(C)CCC=C(C)C>CCCCCC>[CH3:7][CH:8]1[CH2:13][CH2:12][C:11](=[C:16]([CH2:17][CH2:18][CH2:19][CH2:20][CH3:21])[C:15]#[N:22])[CH2:10][CH2:9]1

Participants

7

Reactant 5

HCID 115254-MethylcyclohexanoneHCID 12372Heptanenitrile2×HCID 14797Potassium HydroxideHCID 24497Calcium SulfateHCID 530403Oxiranemethanol, 3-methyl-3-(4-methyl-3-pentenyl)-

Product 1

HCID 536490532-(4-Methylcyclohexylidene)heptanenitrile

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Conditions

Temperature
83 °C

Procedure

Into a 25 ml. flask, equipped with magnetic stirrer, heating mantle, thermometer, condensor and calcium sulfate drying tube, was charged 1.12 g. of 4-methyl cyclohexanone (0.01 M), 11.1 g. of heptanonitrile, and 0.66 g. of 85% KOH. The mixture was heated to reflux with stirring at about 83° C. for a total of 32 hours. After cooling, 30 ml. of hexane was added and the mixture washed seven times with 30 ml. of H2O, each washing being back-extracted twice with 30 ml. portions of hexane. The combined organic phase and hexane extracts were dried over anhydrous sodium sulfate and the solvent removed by rotary evaporation at about 15 mm. Hg to give 6.3 g. of crude oil. Gas chromatographic analysis (6' × 1/4" stainless steel column packed with 20% SE30 on chromasorb W, programmed at 135° to 220° C., 4°/minute, He flow ~60 ml./minute) showed two product peaks at RF 19.0 and 20.2 minutes, which were 6.9% in ratio to heptanonitrile. An IR spectrum of the product peaks, trapped as a group from the gas chromatograph, showed a nitrile band at 4.5 microns and an olefinic band at 6.25 microns. The product was evaluated by perfumers as having a jasminic nitrile type odor with a strong, nerol oxide note.

Workup

  1. customflask, equipped with magnetic stirrer
  2. temperatureheating mantle
  3. temperatureThe mixture was heated
  4. temperatureto reflux
  5. temperatureAfter cooling
  6. washthe mixture washed seven times with 30 ml
  7. extractionof H2O, each washing being back-extracted twice with 30 ml
  8. dry with materialThe combined organic phase and hexane extracts were dried over anhydrous sodium sulfate
  9. customthe solvent removed by rotary evaporation at about 15 mm. Hg
  10. customto give 6.3 g
  11. customprogrammed at 135° to 220° C.
  12. customat RF 19.0 and 20.2 minutes, which

Sources & evidence

ORD record
ord-42f1cd57afbb48e5b952f5be51393bcd
Source dataset
uspto-grants-1979_05
Patent number
US04156690

Linked notes

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