Dimethylformamide → Tyclopyrazoflor

HRID 55743

反応式

HRID 55743 の反応式
C(=O)([O-])[O-].[Cs+].[Cs+].[Cl:7][C:8]1[C:12]([NH:13][C:14](=[O:24])[CH2:15][CH2:16][S:17][CH2:18][CH2:19][C:20]([F:23])([F:22])[F:21])=[CH:11][N:10]([C:25]2[CH:26]=[N:27][CH:28]=[CH:29][CH:30]=2)[N:9]=1.CN(C)C=O.I[CH2:37][CH3:38]>O.C(OCC)(=O)C>[Cl:7][C:8]1[C:12]([N:13]([CH2:37][CH3:38])[C:14](=[O:24])[CH2:15][CH2:16][S:17][CH2:18][CH2:19][C:20]([F:22])([F:21])[F:23])=[CH:11][N:10]([C:25]2[CH:26]=[N:27][CH:28]=[CH:29][CH:30]=2)[N:9]=1

参加物

7

反応物 4

HCID 6228DimethylformamideHCID 6340IodoethaneHCID 10796Cesium carbonateHCID 86700584N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide

生成物 1

HCID 86700627Tyclopyrazoflor収率 66.4%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
40 °C

実験手順

A 100 mL, 3-neck round bottom flask, equipped with mechanical stirrer, temperature probe and nitrogen inlet was charged with cesium carbonate (654 mg, 2.01 mmol), N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide (380 mg, 1.00 mmol) and N,N-dimethylformamide, (5 mL). Iodoethane (0.089 mL, 1.10 mmol) was added dropwise. The reaction was stirred at 40° C. for 2 hours, at which point thin layer chromatography analysis [((Eluent: ethyl acetate] indicated that only a trace of starting material remained. The reaction mixture was cooled to 20° C. and water (20 mL) was added. It was extracted with ethyl acetate (2×20 mL) and the combined organic layers were concentrated to dryness at <40° C. The residue was purified by flash column chromatography using 0-100% ethyl acetate/hexane as eluent. The fractions containing pure product were concentrated to dryness to afford a colorless oil (270 mg, 66%): 1H NMR (400 MHz, DMSO-d6) δ 9.11 (d, J=2.7 Hz, 1H), 8.97 (s, 1H), 8.60 (dd, J=4.8, 1.4 Hz, 1H), 8.24 (ddd, J=8.4, 2.8, 1.4 Hz, 1H), 7.60 (ddd, J=8.4, 4.7, 0.8 Hz, 1H), 3.62 (q, J=7.1 Hz, 2H), 2.75 (t, J=7.0 Hz, 2H), 2.66-2.57 (m, 2H), 2.57-2.44 (m, 2H), 2.41 (t, J=7.0 Hz, 2H), 1.08 (t, J=7.1 Hz, 3H); EIMS m/z 406 ([M]+).

後処理

  1. customA 100 mL, 3-neck round bottom flask, equipped with mechanical stirrer
  2. temperatureThe reaction mixture was cooled to 20° C.
  3. extractionIt was extracted with ethyl acetate (2×20 mL)
  4. concentrationthe combined organic layers were concentrated to dryness at <40° C
  5. customThe residue was purified by flash column chromatography
  6. additionThe fractions containing pure product
  7. concentrationwere concentrated to dryness

出典と根拠

ORDレコード
ord-6d0b65df60a34cc083ee6081165960bc
出典データセット
uspto-grants-2016_09
特許番号
US09433215B2

関連ノート

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