Benzyl Alcohol → 3-benzyloxycarbonylamino-1-(2-chlorophenyl)-5-(4-chlorophenyl)-4-methoxy-1H-pyrazole

HRID 253059Notes

Reaction equation

HRID 253059 reaction equation
C([C:4]1[C:8]([O:9][CH3:10])=[C:7]([C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)[N:6]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[Cl:24])[N:5]=1)(O)=O.C1(P([N:39]=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.[CH2:42]([OH:49])[C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1.[C:50](=[O:53])([O-])O.[Na+]>C1(C)C=CC=CC=1.CN(C)C1C=CN=CC=1.C(N(CC)CC)C>[CH2:42]([O:49][C:50]([NH:39][C:4]1[C:8]([O:9][CH3:10])=[C:7]([C:11]2[CH:12]=[CH:13][C:14]([Cl:17])=[CH:15][CH:16]=2)[N:6]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[Cl:24])[N:5]=1)=[O:53])[C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1

Participants

8

Reactant 4

HCID 244Benzyl AlcoholHCID 199401P,P-Diphenylphosphinic azideHCID 516892Sodium BicarbonateHCID 668627343-carboxy-1-(2-chlorophenyl)-5-(4-chlorophenyl)-4-methoxy-1H-pyrazole

Product 1

HCID 668622843-benzyloxycarbonylamino-1-(2-chlorophenyl)-5-(4-chlorophenyl)-4-methoxy-1H-pyrazoleYield 89%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1140TolueneSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 3-carboxy-1-(2-chlorophenyl)-5-(4-chlorophenyl)-4-methoxy-1H-pyrazole (3.63 g) in toluene (30 mL) was added diphenylphosphorylazide (2.37 mL) and triethylamine (1.67 mL) at 0° C. under nitrogen-gas atmosphere and the mixture was stirred at the same temperature for 30 minutes and at 80° C. for 3 hours. After cooling to 0° C., to the reaction mixture was added benzyl alcohol (1.86 mL) and 4-dimethylaminopyridine (61 mg) and the mixture was stirred at 80° C. overnight. After cooling to room temperature, to the reaction mixture was added an aqueous sodium hydrogencarbonate solution. After stirring, the mixture was extracted with ethyl acetate and the extract was dried over magnesium sulfate and filtered. The filtrate was concentrated in vacuo and the resultant crude product was purified by column chromatography on silica gel (solvent: hexane/ethyl acetate=80/20 to 60/40) to obtain 3-benzyloxycarbonylamino-1-(2-chlorophenyl)-5-(4-chlorophenyl)-4-methoxy-1H-pyrazole (4.15 g, yield: 89%) as a pale yellow viscidity.

Workup

  1. temperatureAfter cooling to 0° C., to the reaction mixture
  2. stirringthe mixture was stirred at 80° C. overnight
  3. temperatureAfter cooling to room temperature, to the reaction mixture
  4. stirringAfter stirring
  5. extractionthe mixture was extracted with ethyl acetate
  6. dry with materialthe extract was dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated in vacuo
  9. customthe resultant crude product was purified by column chromatography on silica gel (solvent: hexane/ethyl acetate=80/20 to 60/40)

Sources & evidence

ORD record
ord-d6abdf684d344ab996135a9f769bfe92
Source dataset
uspto-grants-2011_01
Patent number
US07872006B2

Reaction notes

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