Sodium Bicarbonate → 5-Amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-propanoylpyrazole

HRID 2288562Notes

Reaction equation

HRID 2288562 reaction equation
O.C1(C)C=CC(S(O)(=O)=[O:9])=CC=1.[NH2:13][C:14]1[N:18]([C:19]2[C:24]([Cl:25])=[CH:23][C:22]([C:26]([F:29])([F:28])[F:27])=[CH:21][C:20]=2[Cl:30])[N:17]=[C:16]([C:31]#[N:32])[C:15]=1[C:33]#[C:34][CH3:35].C(=O)(O)[O-].[Na+]>C(#N)C>[NH2:13][C:14]1[N:18]([C:19]2[C:20]([Cl:30])=[CH:21][C:22]([C:26]([F:28])([F:27])[F:29])=[CH:23][C:24]=2[Cl:25])[N:17]=[C:16]([C:31]#[N:32])[C:15]=1[C:33](=[O:9])[CH2:34][CH3:35]

Participants

5

Reactant 3

HCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrate3×HCID 221733795-Amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-(prop-1-ynyl)pyrazole

Product 1

HCID 186994405-Amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-propanoylpyrazole

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

p-Toluenesulphonic acid monohydrate (2.92 g) was added to a stirred solution of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-(prop-1-yn-1-yl)pyrazole (WO-A-97/07102; 2.1 g) in acetonitrile (40 ml) and the mixture stirred at room temperature for 1 hour. Further p-toluenesulphonic acid monohydrate (1.0) was added and this mixture stirred at room temperature for 16 hours. Further acetonitrile (20 ml) and yet more p-toluenesulphonic acid monohydrate (1.0 g) were added and stirring continued for 1 hour, then the reaction mixture was poured into saturated aqueous sodium bicarbonate solution (500 ml) and extracted with ether (2×100 ml). The combined organic extracts were washed with brine (100 ml), dried (Na2SO4) and evaporated under reduced pressure, then the residue purified by column chromatography on silica gel (70 g), using dichloromethane as eluant, to yield the title compound as a pale brown solid, m.p. 167-169° C. δ (CDCl3): 1.26 (t,3H), 3.03 (q,2H), 5.83 (br.s,2H), 7.80 (s,2H). MS (thermospray): M/Z [M+H] 377.2; C14H9Cl2F3N4O+H requires 377.0.

Workup

  1. stirringthis mixture stirred at room temperature for 16 hours
  2. stirringstirring
  3. waitcontinued for 1 hour
  4. extractionextracted with ether (2×100 ml)
  5. washThe combined organic extracts were washed with brine (100 ml)
  6. dry with materialdried (Na2SO4)
  7. customevaporated under reduced pressure
  8. customthe residue purified by column chromatography on silica gel (70 g)

Sources & evidence

ORD record
ord-c5c6e31bb54b480e94c20ecafd329665
Source dataset
uspto-grants-2000_07
Patent number
US06090394

Reaction notes

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