Acetaldehyde → 3-(4-Chlorophenyl)-4,5-dihydro-N-(4-(methylthio)phenyl)-4-(5-trifluoromethyl-2-pyridinyl)-1H-pyrazole-1-carboxamide

HRID 1655244Notes

Reaction equation

HRID 1655244 reaction equation
[CH3:1][S:2][C:3]1[CH:8]=[CH:7][C:6]([N:9]=[C:10]=[O:11])=[CH:5][CH:4]=1.[Cl:12][C:13]1[CH:18]=[CH:17][C:16]([C:19]2[CH:23]([C:24]3[CH:29]=[CH:28][C:27]([C:30]([F:33])([F:32])[F:31])=[CH:26][N:25]=3)[CH2:22][NH:21][N:20]=2)=[CH:15][CH:14]=1.C(=O)C>C(Cl)Cl>[Cl:12][C:13]1[CH:18]=[CH:17][C:16]([C:19]2[CH:23]([C:24]3[CH:29]=[CH:28][C:27]([C:30]([F:31])([F:32])[F:33])=[CH:26][N:25]=3)[CH2:22][N:21]([C:10]([NH:9][C:6]3[CH:7]=[CH:8][C:3]([S:2][CH3:1])=[CH:4][CH:5]=3)=[O:11])[N:20]=2)=[CH:15][CH:14]=1

Participants

5

Reactant 3

HCID 177AcetaldehydeHCID 27333164-(Methylthio)phenyl isocyanateHCID 189876283-(4-Chlorophenyl)-4,5-dihydro-4-(5-trifluoromethyl-2-pyridinyl)-1H-pyrazole

Product 1

HCID 189876213-(4-Chlorophenyl)-4,5-dihydro-N-(4-(methylthio)phenyl)-4-(5-trifluoromethyl-2-pyridinyl)-1H-pyrazole-1-carboxamide

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

4-(Methylthio)phenyl isocyanate (2.8 g, 17 mmol) was added to a stirring slurry of 3.8 g (3.0 mmol) of the product of Example 6 in methylene chloride (25 mi) at 21° C. causing rapid formation of a pale precipitate. TLC showed complete conversion after 19 hr and the precipitate, which was the corresponding bisaryl urea, was removed by gravity filtration. The filtrate was diluted with saturated aqueous sodium bicarbonate and the layers separated. The organic layer was dried over sodium sulfate, filtered, and evaporated to obtain a red oil which solidified on standing. This was purified by column chromatography eluting with 100:0 to 90:10 methylene chloride/ethyl acetate solvent. The product was recrystallized by dissolving in ethyl acetate and then adding hexane to obtain 0.44 g (29 percent of theory; 9 percent from the ethanone) of the title compound as fine white needles melting at 225°-226° C.;

Workup

  1. customafter 19 hr
  2. customwas removed by gravity filtration
  3. additionThe filtrate was diluted with saturated aqueous sodium bicarbonate
  4. customthe layers separated
  5. dry with materialThe organic layer was dried over sodium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customto obtain a red oil which
  9. customThis was purified by column chromatography
  10. washeluting with 100:0 to 90:10 methylene chloride/ethyl acetate solvent
  11. customThe product was recrystallized
  12. dissolutionby dissolving in ethyl acetate
  13. customadding hexane to obtain 0.44 g (29 percent of theory

Sources & evidence

ORD record
ord-a849448178c4426ab666f014f0356818
Source dataset
uspto-grants-1993_10
Patent number
US05250532

Reaction notes

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