Cyclohexanone → 2-Cyclohexylideneheptanenitrile

HRID 263161

Reaktionsgleichung

Reaktionsgleichung von HRID 263161
S([O-])([O-])(=O)=O.[Ca+2].[C:7]1(=O)[CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]1.[C:14](#[N:21])[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20].[OH-].[K+]>C(O)CO.CCCCCC>[C:7]1(=[C:15]([CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])[C:14]#[N:21])[CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]1

Komponenten

7

Edukt 4

HCID 7967CyclohexanoneHCID 12372Heptanenitrile2×HCID 14797Potassium HydroxideHCID 24497Calcium Sulfate

Produkt 1

HCID 538246262-Cyclohexylideneheptanenitrile

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 174Ethylene GlycolLösungsmittelHCID 8058HexaneLösungsmittel

Versuchsvorschrift

Into a 25 ml. flask, equipped with magnetic stirrer, heating mantle, condensor, calcium sulfate drying tube, constant temperature controller and thermometer, was charged 0.98 g. of cyclohexanone (0.01 M), 11.1 g. of heptanonitrile (0.10 M) and 0.66 g. of 85% potassium hydroxide flakes. The mixture was heated cooled, 30 ml. of hexane was added, and the mixture washed six times with 30 ml. portions of water and once with saturated brine. The washes were each in succession, cross-extracted with two 15 ml. portions of hexane. The combined organic and hexane phases were dried over anhydrous sodium sulfate and solvent evaporated on a rotary evaporator at ~30 mm. Hg to give 6.7 g. of oil. Gas chromatographic analysis (6' × 1/4" column, 20% Carbowax 20 m. on Chromasorb W, programmed 135° C. to 220° C. at 4°/minute, He flow ~60 ml./minute) showed product nitrile peaks at 17.8 minutes (10.3%) and 20.1 minutes (4.1%) with heptanonitrile at 4.3 minutes (85.5%). The product peaks which eluted together at 17.6 minutes on a 20% SE30 column (6' × 1/4") under the same operating parameters were trapped out for odor evaluation. An IR spectrum on the trapping of combined isomers showed a nitrile band at 4.5 microns and an olefin band at 6.27 microns. The product was described by perfumers as having an interesting, fruity, floral, salicylate quality.

Aufarbeitung

  1. customflask, equipped with magnetic stirrer
  2. additionwas charged 0.98 g
  3. temperatureThe mixture was heated
  4. temperaturecooled
  5. washthe mixture washed six times with 30 ml
  6. extractioncross-extracted with two 15 ml
  7. dry with materialThe combined organic and hexane phases were dried over anhydrous sodium sulfate and solvent
  8. customevaporated on a rotary evaporator at ~30 mm. Hg
  9. customto give 6.7 g
  10. customprogrammed 135° C. to 220° C. at 4°/minute, He
  11. customat 17.8 minutes
  12. custom(10.3%) and 20.1 minutes (4.1%)
  13. customat 4.3 minutes
  14. washThe product peaks which eluted together at 17.6 minutes on a 20% SE30 column (6' × 1/4") under the same operating parameters

Quellen und Nachweise

ORD-Eintrag
ord-d2c8e71457b242359025849429f42090
Quelldatensatz
uspto-grants-1979_05
Patentnummer
US04156690

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