Benzyl Alcohol → HCID 10376962, compound

HRID 327696Notes

Reaction equation

HRID 327696 reaction equation
Cl[S:2]([N:5]=C=O)(=[O:4])=[O:3].C(O)C1C=CC=CC=1.[N:16]1([C:21]2[CH:26]=[CH:25][C:24]([OH:27])=[CH:23][CH:22]=2)[CH:20]=[CH:19][N:18]=[CH:17]1.C(N(CC)CC)C.C(O)(C)C>C(Cl)Cl.CO.[Pd]>[N:16]1([C:21]2[CH:26]=[CH:25][C:24]([O:27][S:2](=[O:3])(=[O:4])[NH2:5])=[CH:23][CH:22]=2)[CH:20]=[CH:19][N:18]=[CH:17]1

Participants

9

Reactant 5

HCID 244Benzyl AlcoholHCID 3776IsopropanolHCID 8471TriethylamineHCID 70918Chlorosulfonyl isocyanateHCID 823151-(p-Hydroxyphenyl)imidazole

Product 1

HCID 10376962HCID 10376962, compoundYield 55.7%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a chilled solution of chlorosulfonyl isocyanate (8.7 ml, 0.10 mole) in 50 ml of methylene chloride was added a solution of 10.8 g (0.10 mole) of benzyl alcohol in 200 ml of methylene chloride over a period of 6 minutes at 3°-15° C. The reaction was then stirred at ambient temperature for 2 hours and then chilled in an ice-water bath. To this solution was added 4-(imidazol-1-yl)phenol (12 g, 0.075 mole) as a solid, and the mixture was stirred at room temperature for 45 minutes. Triethylamine (14 ml, 0.1 mole) was then added to the suspension, and the reaction became a dark brown solution. The mixture was stirred for two days, and the solid was collected by filtration, stirred in water for half an hour, and filtered again, rinsed with isopropyl alcohol and isopropyl ether. This solid intermediate weighed 18.24 g (65%) and 1H NMR showed it exists as zwitterion. The zwitterion (18 g) was added to a solution of isopropyl alcohol containing 0.05 mole hydrogen chloride and diluted with 100 ml methanol. The resultant solution was mixed with 1.8 g Pd-C (5%) and hydrogenated until there was no further absorption of hydrogen. The catalyst was removed, and the solution was concentrated to give 10 g solid. Part of the solid was recrystallized by dissolving in excess amount of methanol, filtering, and concentrating to crystallize out about 5 g solid. The solid was dried in vacuum oven at 80° C. overnight, mp 198°-200° C.

Workup

  1. temperaturechilled in an ice-water bath
  2. stirringthe mixture was stirred at room temperature for 45 minutes
  3. stirringThe mixture was stirred for two days
  4. filtrationthe solid was collected by filtration
  5. stirringstirred in water for half an hour
  6. filtrationfiltered again
  7. washrinsed with isopropyl alcohol and isopropyl ether
  8. customno further absorption of hydrogen
  9. customThe catalyst was removed
  10. concentrationthe solution was concentrated

Sources & evidence

ORD record
ord-6c464110c97c4c0aaa506b0834f442e9
Source dataset
uspto-grants-1993_12
Patent number
US05273993

Reaction notes

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