Triethylamine → N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenyloxy)-5-methylpyrazole-1-carboxamide

HRID 499997ノート

反応式

HRID 499997 の反応式
Cl[C:2](OC(Cl)(Cl)Cl)=[O:3].[Cl:9][C:10]1[CH:15]=[C:14]([C:16]([F:19])([F:18])[F:17])[CH:13]=[C:12]([F:20])[C:11]=1[O:21][C:22]1[CH:26]=[C:25]([CH3:27])[NH:24][N:23]=1.[CH2:28]([NH2:34])[CH:29]1[O:33][CH2:32][CH2:31][CH2:30]1.C(N(CC)CC)C>C(Cl)(Cl)Cl>[CH2:28]([NH:34][C:2]([N:24]1[C:25]([CH3:27])=[CH:26][C:22]([O:21][C:11]2[C:12]([F:20])=[CH:13][C:14]([C:16]([F:19])([F:17])[F:18])=[CH:15][C:10]=2[Cl:9])=[N:23]1)=[O:3])[CH:29]1[O:33][CH2:32][CH2:31][CH2:30]1

参加物

6

反応物 4

HCID 8471TriethylamineHCID 10426DiphosgeneHCID 253298TetrahydrofurfurylamineHCID 178624283-(2-Chloro-6-fluoro-4-trifluoromethylphenyloxy)-5-methylpyrazole

生成物 1

HCID 17862429N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenyloxy)-5-methylpyrazole-1-carboxamide収率 29.6%

試薬・触媒・溶媒 1

HCID 6212Chloroform溶媒

実験手順

Trichloromethyl chloroformate (0.39 g, 2.0 mmol) was added to a chloroform (10 mL) solution of 3-(2-chloro-6-fluoro-4-trifluoromethylphenyloxy)-5-methylpyrazole (0.59 g, 2.0 mmol) at 0° C., and while the mixture was allowed to gradually warm up to a room temperature, it was further stirred at room temperature for 3 hours. Tetrahydrofurfurylamine (0.61 g, 6.0 mmol) and triethylamine (0.4 g, 4.0 mmol) were added to the reaction mixture, and the mixture was refluxed under heating for 5 hours. After completion of the reaction, the reaction mixture was poured into ice and extracted with chloroform (20 mL×3 times). The organic layer was washed with water and dried over anhydrous magnesium sulfate, the desiccant was removed by filtering, and the solvent was distilled off the filtrate under reduced pressure. The resultant crude product was purified with a silica gel column (ethyl acetate/hexane= 1/10˜⅕) to give a colorless viscous substance of N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenyloxy)-5-methylpyrazole-1-carboxamide (0.25 g, yield: 29.6%). 1H-NMR (CDCl3, TMS, ppm): δ1.50-1.65 (m, 1H), 1.75˜2.05 (m, 3H), 2.58 (s, 3H), 3.32 (dt, J=6.3 and 13.9 Hz, 1H), 3.48 (ddd, J=3.7, 5.7 and 13.9 Hz, 1H), 3.74 (dq, J=7.0 and 8.6 Hz, 2H), 4.03 (dq, J=3.7 and 7.0 Hz, 1H), 5.79 (s, 1H), 6.85˜7.10 (m, 1H), 7.39 (dd, J=1.9 and JHF=9.3 Hz, 1H), 7.56 (s, 1H).

後処理

  1. temperaturethe mixture was refluxed
  2. temperatureunder heating for 5 hours
  3. customAfter completion of the reaction
  4. additionthe reaction mixture was poured into ice
  5. extractionextracted with chloroform (20 mL×3 times)
  6. washThe organic layer was washed with water
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customthe desiccant was removed
  9. filtrationby filtering
  10. distillationthe solvent was distilled off the filtrate under reduced pressure
  11. customThe resultant crude product was purified with a silica gel column (ethyl acetate/hexane= 1/10˜⅕)

出典と根拠

ORDレコード
ord-c28b1aa26c74445aa859a5d2e26e2a02
出典データセット
uspto-grants-2010_08
特許番号
US07767827B2

反応ノート

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