Ethyl chloroformate → 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-[N-ethoxycarbonyl-N-(3-ethylthiopropyl)amino]-4-trifluoromethylsulfonylpyrazole

HRID 2109917ノート

反応式

HRID 2109917 の反応式
[H-].[Na+].[Cl:3][C:4]1[CH:9]=[C:8]([C:10]([F:13])([F:12])[F:11])[CH:7]=[C:6]([Cl:14])[C:5]=1[N:15]1[C:19]([NH:20][CH2:21][CH2:22][CH2:23][S:24][CH2:25][CH3:26])=[C:18]([S:27]([C:30]([F:33])([F:32])[F:31])(=[O:29])=[O:28])[C:17]([C:34]#[N:35])=[N:16]1.Cl[C:37]([O:39][CH2:40][CH3:41])=[O:38].[Cl-].[NH4+]>O1CCCC1.C(OCC)(=O)C>[Cl:14][C:6]1[CH:7]=[C:8]([C:10]([F:13])([F:12])[F:11])[CH:9]=[C:4]([Cl:3])[C:5]=1[N:15]1[C:19]([N:20]([C:37]([O:39][CH2:40][CH3:41])=[O:38])[CH2:21][CH2:22][CH2:23][S:24][CH2:25][CH3:26])=[C:18]([S:27]([C:30]([F:33])([F:32])[F:31])(=[O:28])=[O:29])[C:17]([C:34]#[N:35])=[N:16]1

参加物

7

反応物 4

HCID 10928Ethyl chloroformateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 866002281-(2,6-Dichloro-4-trifluoromethylphenyl)-3-cyano-5-(3-ethylthiopropylamino)-4-trifluoromethylsulfonylpyrazole

生成物 1

HCID 866002311-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-[N-ethoxycarbonyl-N-(3-ethylthiopropyl)amino]-4-trifluoromethylsulfonylpyrazole収率 81%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
20 °C

実験手順

Sodium hydride (0.032 g, 60%, 0.8 mmol) was added to a solution of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-(3-ethylthiopropylamino)-4-trifluoromethylsulfonylpyrazole (0.3 g, 0.54 mmol) in tetrahydrofuran 20° C. under nitrogen. The mixture was stirred at 20° C. for one hour then ethyl chloroformate (0.121 g, 1.1 mmol) was added. The mixture was stirred at 20° C. for 5 hours, then poured into saturated ammonium chloride and ethyl acetate. The organic layer was washed with water and brine, dried (sodium sulfate), evaporated to provide and purified by chromatography on silica gel eluting with heptane-ethyl acetate (4:1) to give 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-[N-ethoxycarbonyl-N-(3-ethylthiopropyl)amino]-4-trifluoromethylsulfonylpyrazole as an oil (Compound number 3-14, 0.278 g, 81% yield), 19F: −63.9; −77.9.

後処理

  1. stirringThe mixture was stirred at 20° C. for 5 hours
  2. washThe organic layer was washed with water and brine
  3. dry with materialdried (sodium sulfate)
  4. customevaporated
  5. customto provide
  6. custompurified by chromatography on silica gel eluting with heptane-ethyl acetate (4:1)

出典と根拠

ORDレコード
ord-a67d097e7a6d4a7fb5c4e4a815b0eeeb
出典データセット
uspto-grants-2009_04
特許番号
US07517877B2

反応ノート

読み込み中…