Hydrochloric Acid → HCID 19857690, compound

HRID 1283992Notes

Reaction equation

HRID 1283992 reaction equation
BrBr.Cl.[CH3:4][C:5]1[CH:10]=[CH:9][CH2:8][C:7]([CH3:12])([CH3:11])[C:6]=1[CH2:13][CH2:14][C:15](=[O:17])[CH3:16]>C(Cl)(Cl)Cl>[CH3:11][C:7]1([CH3:12])[CH:6]([CH2:13][CH2:14][C:15](=[O:17])[CH3:16])[C:5](=[CH2:4])[CH:10]=[CH:9][CH2:8]1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 24408BromineHCID 5771262-Butanone, 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-

Product 1

HCID 19857690HCID 19857690, compoundYield 8.8%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

The resulting mixture is cooled in an ice-sodium chloride bath and a mixture of 3.2 grams of bromine and 9 ml chloroform is added drop-wise with stirring over a half hour period. The reaction mass is then stirred at 5°C for a period of 5 hours and then concentrated under reduced pressure. The resulting residue is then heated on a steam bath for a period of 3 hours after 11 ml of N,N-Diethyl-aniline has been added to the residue. After 3 hours 2.5 ml pyridine is then added to the reaction mass and heating is continued for 1/2 hour longer. To the cooled reaction mixture are added 50 ml of 5 N Hydrochloric acid. The aqueous layer is then extracted with three 100 ml portions of n-pentane. The combined pentane extracts are washed with two 50 ml portions of 5 N hydrochloric acid, then two 50 ml 10% sodium bicarbonate solution portions and two 100 ml portions of distilled water. The pentane extracts are then evaporated after drying over anhydrous sodium sulfate yielding (confirmed by infrared and mass spectral analysis) a mixture containing 90% 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanone and 10% 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanone (over-all yield: 8.8%). The 90:10 mixture of 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanone and 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanone distills at 65°C and at 15 mm Hg. pressure.

Workup

  1. temperatureThe resulting mixture is cooled in an ice-sodium chloride bath
  2. additionis added drop-wise
  3. stirringThe reaction mass is then stirred at 5°C for a period of 5 hours
  4. concentrationconcentrated under reduced pressure
  5. temperatureThe resulting residue is then heated on a steam bath for a period of 3 hours after 11 ml of N,N-Diethyl-aniline
  6. additionhas been added to the residue
  7. additionAfter 3 hours 2.5 ml pyridine is then added to the reaction mass
  8. temperatureheating
  9. customTo the cooled reaction mixture
  10. extractionThe aqueous layer is then extracted with three 100 ml portions of n-pentane
  11. washThe combined pentane extracts are washed with two 50 ml portions of 5 N hydrochloric acid
  12. customThe pentane extracts are then evaporated
  13. dry with materialafter drying over anhydrous sodium sulfate yielding (confirmed by infrared and mass spectral analysis) a mixture

Sources & evidence

ORD record
ord-139af3b9244542e7adfbccd2e47a2640
Source dataset
uspto-grants-1976_08
Patent number
US03977419

Reaction notes

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