Ammonium Chloride → HCID 178448042, compound

HRID 989586Notes

Reaction equation

HRID 989586 reaction equation
[Mg].[F:2][C:3]1[C:8]([F:9])=[CH:7][CH:6]=[CH:5][C:4]=1Br.[CH2:11]([C@H:14]1[CH2:19][CH2:18][C@H:17]([C@H:20]2[CH2:25][CH2:24][C@H:23]([CH2:26][CH2:27][CH2:28][CH:29]=O)[CH2:22][CH2:21]2)[CH2:16][CH2:15]1)[CH2:12][CH3:13].[Cl-].[NH4+]>C1COCC1>[F:9][C:8]1[C:3]([F:2])=[C:4]([CH:29]=[CH:28][CH2:27][CH2:26][C@H:23]2[CH2:24][CH2:25][C@H:20]([C@H:17]3[CH2:16][CH2:15][C@H:14]([CH2:11][CH2:12][CH3:13])[CH2:19][CH2:18]3)[CH2:21][CH2:22]2)[CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 27332601-Bromo-2,3-difluorobenzeneHCID 5462224MagnesiumHCID 178448046HCID 178448046, compound

Product 1

HCID 178448042HCID 178448042, compoundYield 67.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
50 °C

Procedure

Under nitrogen gas stream, 8.05 g (331 mmol) of magnesium was added to 20.0 ml of THF, and a solution of 58.1 g (301 mmol) of 2,3-difluoro-1-bromobenzene in 600 ml of THF was added by drops thereto so that the reaction temperature was maintained at about 50° C. and then stirred at room temperature for 1 hour. To the reaction solution was added by drops a solution of 70.0 g (251 mmol) of the crude 4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butanal obtained by the same manner as in the fifth step of Example 1 in 700 ml of THF, stirred at 50 to 60° C. for 2 hours, and then 200 ml of saturated aqueous ammonium chloride solution was added thereto to terminate the reaction. The reaction mixture was filtered with Celite, the solvent was distilled off under a reduced pressure, and then the residue was extracted with 700 ml of toluene. The organic layer was washed with 400 ml of water thrice and then dried over anhydrous magnesium sulfate. After the anhydrous magnesium sulfate was filtered off, 3.56 g of p-toluenesulfonic acid monohydrate was added to the filtrate, and heated to reflux for 4 hours. The organic layer was washed with 300 ml of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 63.5 g of a crude 2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-1-butenyl)benzene.

Workup

  1. stirringstirred at 50 to 60° C. for 2 hours
  2. customto terminate
  3. customthe reaction
  4. filtrationThe reaction mixture was filtered with Celite
  5. distillationthe solvent was distilled off under a reduced pressure
  6. extractionthe residue was extracted with 700 ml of toluene
  7. washThe organic layer was washed with 400 ml of water thrice
  8. dry with materialdried over anhydrous magnesium sulfate
  9. filtrationAfter the anhydrous magnesium sulfate was filtered off
  10. addition3.56 g of p-toluenesulfonic acid monohydrate was added to the filtrate
  11. temperatureheated
  12. temperatureto reflux for 4 hours
  13. washThe organic layer was washed with 300 ml of water thrice
  14. dry with materialdried over anhydrous magnesium sulfate
  15. distillationThe solvent was distilled off under a reduced pressure

Sources & evidence

ORD record
ord-1a51bcf51c914b8fa342cbd54203196b
Source dataset
uspto-grants-2002_10
Patent number
US06458433B1

Reaction notes

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