Dichloromethane → 3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoroacetylpyrazole

HRID 1421278Notes

Reaction equation

HRID 1421278 reaction equation
N(OC(C)(C)C)=O.N[C:9]1[N:13]([C:14]2[C:19]([Cl:20])=[CH:18][C:17]([C:21]([F:24])([F:23])[F:22])=[CH:16][C:15]=2[Cl:25])[N:12]=[C:11]([C:26]#[N:27])[C:10]=1[C:28](=[O:33])[C:29]([F:32])([F:31])[F:30].CCCCCC.ClCCl>O1CCCC1>[C:26]([C:11]1[C:10]([C:28](=[O:33])[C:29]([F:30])([F:31])[F:32])=[CH:9][N:13]([C:14]2[C:19]([Cl:20])=[CH:18][C:17]([C:21]([F:24])([F:22])[F:23])=[CH:16][C:15]=2[Cl:25])[N:12]=1)#[N:27]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 8058HexaneHCID 10906Tert-Butyl nitrite2×HCID 186994595-Amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoroacetylpyrazole

Product 1

HCID 186994613-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoroacetylpyrazole

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
55 °C

Procedure

t-Butyl nitrite (12.45 ml) was added dropwise to a stirred solution of 5-amino-3-cyano-1-(2,6dichloro-4-trifluoromethylphenyl)-4-trifluoroacetylpyrazole (JP-A-8-311036; 30 g) in tetrahydrofuran (250 ml) and the mixture stirred at 55° C. for 16 hours. Further quantities of t-butyl nitrite added/subsequent periods of stirring at 55° C. were as follows: 9 ml/7 hours, 6 ml/16 hours, 9 ml/6 hours, 4.75 ml/16 hours, 6 ml/6 hours and 3.5 ml/22 hours. The reaction mixture was allowed to cool and evaporated under reduced pressure, then the residue combined with those obtained from three identical preparations. Purification by column chromatography on silica gel (1 Kg), using hexane:dichloromethane (6:4) and then dichloromethane as eluants, gave a yellow oil which, on trituration with hexane (3×50 ml) followed by dichloromethane (100 ml), provided the title compound as a white solid, m.p. 124-125° C. δ(CDCl3): 7.83 (s,2H), 8.30 (s,1H). MS (thermospray): M/Z [M+H] 401.7; C13H3Cl2F6N3O+H requires 401.96.

Workup

  1. custom9 ml/7 hours, 6 ml/16 hours, 9 ml/6 hours, 4.75 ml/16 hours, 6 ml/6 hours and 3.5 ml/22 hours
  2. temperatureto cool
  3. customevaporated under reduced pressure
  4. customthose obtained from three identical preparations
  5. customPurification by column chromatography on silica gel (1 Kg)
  6. customdichloromethane as eluants, gave a yellow oil which

Sources & evidence

ORD record
ord-1db7d03dcfc847cd8e3302495713950f
Source dataset
uspto-grants-2000_06
Patent number
US06075043

Reaction notes

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