Methyl chloroformate → 1H-Pyrazole-4-carboxylic acid, 3-(4-chlorophenyl)-1-(((4-chlorophenyl)amino)carbonyl)-4,5-dihydro-4-methyl-, methyl ester

HRID 978168Notes

Reaction equation

HRID 978168 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]([N:11]2[CH2:15][CH:14]([CH3:16])[C:13]([C:17]3[CH:22]=[CH:21][C:20]([Cl:23])=[CH:19][CH:18]=3)=[N:12]2)=[O:10])=[CH:4][CH:3]=1.C(NC(C)C)(C)C.C([Li])CCC.Cl[C:37]([O:39][CH3:40])=[O:38]>O1CCCC1.CCCCCC>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9]([N:11]2[CH2:15][C:14]([C:37]([O:39][CH3:40])=[O:38])([CH3:16])[C:13]([C:17]3[CH:18]=[CH:19][C:20]([Cl:23])=[CH:21][CH:22]=3)=[N:12]2)=[O:10])=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 6586Methyl chloroformateHCID 7912DiisopropylamineHCID 13752557N,3-bis-(4-chlorophenyl)-4-methyl-4,5-dihydro-1H-pyrazole-1-carboxamideHCID 178418339Butyllithium

Product 1

HCID 1758551H-Pyrazole-4-carboxylic acid, 3-(4-chlorophenyl)-1-(((4-chlorophenyl)amino)carbonyl)-4,5-dihydro-4-methyl-, methyl ester

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-20 °C

Procedure

To 3.4 g of N,3-bis-(4-chlorophenyl)-4-methyl-4,5-dihydro-1H-pyrazole-1-carboxamide and 1.1 g of diisopropylamine dissolved in 20 ml of tetrahydrofuran and cooled in an acetone bath maintained at -20° C., was added 8.0 ml of a 2.7 molar solution of butyllithium in hexane. The resulting solution was stirred for 20 minutes and then cooled to -70° C. To this solution was added 0.9 ml of methyl chloroformate. The reaction was allowed to stir for 10 minutes and then allowed to warm to room temperature over 10 minutes. The reaction was quenched with 1.0 ml of acetic acid and the reaction mixture was partitioned between diethyl ether and water and the organic layer was dried over anhydrous magnesium sulfate. The resulting solution was filtered evaporated in vacuo to give 2.9 g of N,3-bis-(4-chlorophenyl)-4-carbomethoxy-4-methyl-4,5-dihydro-1H-pyrazole-1-carboxamide. NMR and IR data were consistent with the structure.

Workup

  1. temperaturecooled in an acetone bath
  2. temperaturecooled to -70° C
  3. stirringto stir for 10 minutes
  4. temperatureto warm to room temperature over 10 minutes
  5. customThe reaction was quenched with 1.0 ml of acetic acid
  6. customthe reaction mixture was partitioned between diethyl ether and water
  7. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
  8. filtrationThe resulting solution was filtered
  9. customevaporated in vacuo

Sources & evidence

ORD record
ord-dc2c67269bc2469683eaa28f3a594278
Source dataset
uspto-grants-1987_05
Patent number
US04663341

Reaction notes

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