Hydrochloric Acid → HCID 178447839, compound

HRID 1936330Notes

Reaction equation

HRID 1936330 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[F:8].C([Li])CCC.[CH2:14]([C@H:17]1[CH2:22][CH2:21][C@H:20]([CH:23]2[CH2:28][CH2:27][CH2:26][CH2:25][CH2:24]2)[CH2:19][CH2:18]1)[CH2:15][CH3:16].Cl>C1(C)C=CC=CC=1.O1CCCC1.CCCCCC>[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([C:26]2[CH2:27][CH2:28][CH:23]([C@H:20]3[CH2:21][CH2:22][C@H:17]([CH2:14][CH2:15][CH3:16])[CH2:18][CH2:19]3)[CH2:24][CH:25]=2)[C:3]=1[F:8]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 97061,2-DifluorobenzeneHCID 178418339ButyllithiumHCID 178447858HCID 178447858, compound

Product 1

HCID 178447839HCID 178447839, compoundYield 48.6%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-60 °C

Procedure

First, 46 g of 1,2-difluorobenzene and 240 ml of dehydrated tetrahydrofuran were put in an argon-replaced 2 flask, and cooled to −60° C. Then 315 ml of a hexane solution containing n-butyllithium at a concentration of 1.6 mol/l was dropped into the resultant mixture while being stirred for one hour, and further stirred keeping the same temperature for two hours. Subsequently, 470 ml of dehydrated tetrahydrofuran containing 80 g of 4-(trans-4-propylcyclohexyl)cyclohexane dissolved therein was dropped and stirred keeping the same temperature for two hours. The resultant mixtures was left to gradually resume room temperature, stirred for eight hours and cooled again to 0° C. The reaction solution was poured into dilute hydrochloric acid to acidify the reaction solution. Toluene was added to the resultant solution for extraction. The resultant toluene layer was washed with a saturated brine and dried with sodium sulfate. The solvent was then distilled off. The residue, 2 g of p-toluenesulfonic acid, and 1 of toluene were put in a 2 flask provided with a water content quantitative tube, and subjected to azeotropic dehydration under reflux for five hours. After the reaction, the reaction solution was washed with a saturated brine and dried with sodium sulfate. The solvent was then distilled off. The residue was distilled (b.p. 151° C./16 Pa) and recrystallized from acetone to obtain 55.7 g (Y: 48.6%) of 1,2-difluoro-3-[4-(trans-4-propylcyclohexyl)cyclohexenyl]benzene. The purity of the resultant compound was 98.0% as measured by GC.

Workup

  1. stirringfurther stirred
  2. customfor two hours
  3. additiontherein was dropped
  4. stirringstirred
  5. customfor two hours
  6. waitThe resultant mixtures was left to gradually resume room temperature
  7. stirringstirred for eight hours
  8. temperaturecooled again to 0° C
  9. washThe resultant toluene layer was washed with a saturated brine
  10. dry with materialdried with sodium sulfate
  11. distillationThe solvent was then distilled off
  12. customprovided with a water content quantitative tube
  13. temperatureunder reflux for five hours
  14. customAfter the reaction
  15. washthe reaction solution was washed with a saturated brine
  16. dry with materialdried with sodium sulfate
  17. distillationThe solvent was then distilled off
  18. distillationThe residue was distilled (b.p. 151° C./16 Pa)
  19. customrecrystallized from acetone

Sources & evidence

ORD record
ord-7bc63e3cacdd4c0cbf2d879107b69c9d
Source dataset
uspto-grants-2002_05
Patent number
US06388146B1

Reaction notes

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