Hydrochloric Acid → HCID 178495618, compound

HRID 2290484Notes

Reaction equation

HRID 2290484 reaction equation
[CH3:1][O:2][CH2:3][C@H:4]1[CH2:9][CH2:8][C@H:7]([C:10]2[CH:15]=[CH:14][C:13](I)=[CH:12][CH:11]=2)[CH2:6][CH2:5]1.[CH2:17]([Li])CCC.C([CH:25]1[CH2:30][CH2:29][C:28](=O)[CH2:27][CH2:26]1)CC.Cl>O.CCCCCC.C1(C)C=CC=CC=1>[CH3:1][O:2][CH2:3][C@H:4]1[CH2:9][CH2:8][C@H:7]([C:10]2([C:25]3[CH2:30][CH2:29][CH2:28][CH2:27][CH:26]=3)[CH:15]=[CH:14][C:13]([CH3:17])=[CH:12][CH2:11]2)[CH2:6][CH2:5]1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 1424824-PropylcyclohexanoneHCID 178418339ButyllithiumHCID 178495623HCID 178495623, compound

Product 1

HCID 178495618HCID 178495618, compoundYield 27.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8058HexaneSolvent

Conditions

Temperature
5 °C

Procedure

Into a 500 ml three-neck flask were placed the compound (VI) (21 g, 0.064 mol) obtained at the fourth step and dry toluene (40 ml) in dry nitrogen atmosphere, followed by dissolving with stirring. To the solution was dropwise added a commercially available 1.67N hexane solution (42.7 ml) of n-butyllithium (0.067 mol) over about 10 minutes at a liquid temperature kept at 20° to 25° C. After completion of the addition, the mixture was kept at 25° C. for 30 minutes, and then cooled to 5° C., followed by dropwise adding 4-propylcyclohexanone (11.2 g, 0.08 mol) over 20 minutes while the temperature was kept at 5° to 10° C., further keeping the temperature at 45° C. for 30 minutes, dropwise adding water (20 ml), further dropwise adding 6N-HCl (40 ml) while the temperature was kept at 30° C. or lower, separating off the resulting organic layer, adding potassium hydrogen sulfate (KHSO4) (2 g), distilling off the solvent on heating, concentrating until the liquid temperature reached 110° C., during which dehydration reaction proceeded, cooling, transferring into a separating funnel, washing the resulting organic layer with water, distilling off the solvent, recrystallizing the residue from ethyl alcohol (10 c.c.) to obtain trans-4-methyloxymethyl-1-(4'-methyl-1-cyclohexenylphenyl)cyclohexane (VII) (5.3 g) having a melting point (C-S point) of 64° C., a S-N point of 93.4° C. and a clearing point (N-I point) of 14.3° C.

Workup

  1. customInto a 500 ml three-neck flask were placed
  2. dissolutionby dissolving
  3. customkept at 20° to 25° C
  4. additionAfter completion of the addition
  5. customwas kept at 5° to 10° C.
  6. customat 45° C.
  7. customfor 30 minutes
  8. customwas kept at 30° C.
  9. customlower, separating off the resulting organic layer
  10. additionadding potassium hydrogen sulfate (KHSO4) (2 g)
  11. distillationdistilling off the solvent
  12. temperatureon heating
  13. concentrationconcentrating until the liquid temperature
  14. customreached 110° C., during which dehydration reaction
  15. temperaturecooling
  16. customtransferring into a separating funnel
  17. washwashing the resulting organic layer with water
  18. distillationdistilling off the solvent
  19. customrecrystallizing the residue from ethyl alcohol (10 c.c.)

Sources & evidence

ORD record
ord-0677db9ea37142e6b9ad5c44f0a11bc5
Source dataset
uspto-grants-1986_10
Patent number
US04617141

Reaction notes

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