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Trichloroacetyl chloride → 4-(4-Bromo-2-fluorobenzyl)-3-n-butyl-1-(2-chloro-5-nitrophenyl)-1H-pyrazole-5-carbonitrile

HRID 257565
ノート
印刷プレビュー

反応式

HRID 257565 の反応式
[Br:1][C:2]1[CH:30]=[CH:29][C:5]([CH2:6][C:7]2[C:8]([CH2:25][CH2:26][CH2:27][CH3:28])=[N:9][N:10]([C:15]3[CH:20]=[C:19]([N+:21]([O-:23])=[O:22])[CH:18]=[CH:17][C:16]=3[Cl:24])[C:11]=2[C:12]([NH2:14])=O)=[C:4]([F:31])[CH:3]=1.C(N(CC)CC)C.ClC(Cl)(Cl)C(Cl)=O>C(Cl)Cl>[Br:1][C:2]1[CH:30]=[CH:29][C:5]([CH2:6][C:7]2[C:8]([CH2:25][CH2:26][CH2:27][CH3:28])=[N:9][N:10]([C:15]3[CH:20]=[C:19]([N+:21]([O-:23])=[O:22])[CH:18]=[CH:17][C:16]=3[Cl:24])[C:11]=2[C:12]#[N:14])=[C:4]([F:31])[CH:3]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

HCID 6420Trichloroacetyl chlorideHCID 8471TriethylamineHCID 542034724-(4-Bromo-2-fluorobenzyl)-3-n-butyl-1-(2-chloro-5-nitrophenyl)-1H-pyrazole-5-carboxamide

生成物 1

HCID 197832514-(4-Bromo-2-fluorobenzyl)-3-n-butyl-1-(2-chloro-5-nitrophenyl)-1H-pyrazole-5-carbonitrile収率 69%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane
溶媒

反応条件

温度
0 °C

実験手順

A mixture of 600 mg (1.18 mmol) of 4-(4-bromo-2-fluorobenzyl)-3-n-butyl-1-(2-chloro-5-nitrophenyl)-1H-pyrazole-5-carboxamide (from Step E), 330 μL (238 mg, 2.35 mmol) of triethylamine, and 7 mL of methylene chloride was cooled to 0° C. and treated with 145 μL of trichloroacetyl chloride. The mixture was stirred under N2 and allowed to warm to room temperature. After 3 hours, the mixture was concentrated to dryness. The orange residue was triturated with ether. The insoluble material was removed by filtration. The filtrate was washed with 0.2N HCl followed by 0.25N NaOH. The organic layer, after being dried over Na2SO4, was filtered and concentrated. The orange residual oil was flash chromatographed on silica gel (elution with 4:1 and then 3:1 hexane-EtOAc) to give 399 mg (69%) of the title compound as a yellow oil; nearly homogeneous by TLC in 3:1 hexane-EtOAc; mass spectrum (FAB) m/e 491, 493 (M+1)+. 200 MHz 1H NMR (CDCl3) δ0.91 (t, J=7.1 Hz, 3H), 1.36 (m, 2H), 1.61 (m, 2H, partially obscured by H2O peak), 2.61 (t, J=7.7 Hz, 2H), 3.97 (s, 2H), 7.07 (dd, J=8, 8 Hz, 1H), 7.26-7.31 (m, 2H), 7.78 (d, J=8.8 Hz, 1H), 8.31-8.39 (m, 2H).

後処理

  1. temperatureto warm to room temperature
  2. concentrationthe mixture was concentrated to dryness
  3. customThe orange residue was triturated with ether
  4. customThe insoluble material was removed by filtration
  5. washThe filtrate was washed with 0.2N HCl
  6. dry with materialThe organic layer, after being dried over Na2SO4
  7. filtrationwas filtered
  8. concentrationconcentrated
  9. customchromatographed on silica gel (
  10. washelution with 4:1

出典と根拠

ORDレコード
ord-ce6d4c531ac343d580b5f5ffb99e385a
出典データセット
uspto-grants-1993_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05262412

反応ノート

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