N,N'-Dimethylethylenediamine → N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)acetamide

HRID 512746ノート

反応式

HRID 512746 の反応式
[Cl:1][C:2]1[C:6]([NH:7][C:8](=[O:10])[CH3:9])=[CH:5][NH:4][N:3]=1.I[C:12]1[CH:13]=[N:14][CH:15]=[CH:16][CH:17]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].CNCCNC>[Cu](Cl)Cl.C(OCC)(=O)C.C(#N)C>[Cl:1][C:2]1[C:6]([NH:7][C:8](=[O:10])[CH3:9])=[CH:5][N:4]([C:12]2[CH:13]=[N:14][CH:15]=[CH:16][CH:17]=2)[N:3]=1

参加物

8

反応物 4

HCID 8070N,N'-DimethylethylenediamineHCID 62657Potassium Phosphate, TribasicHCID 707143-IodopyridineHCID 178474372N-(3-chloro-1H-pyrazol-4-yl)acetamide

生成物 1

HCID 118023019N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)acetamide収率 65%

試薬・触媒・溶媒 3

HCID 24014Cupric Chloride触媒HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A 250-mL, 3-neck round bottom flask was charged with N-(3-chloro-1H-pyrazol-4-yl)acetamide (4.8 g, 30.1 mmol), copper(II) chloride (0.404 g, 3.01 mmol), 3-iodopyridine (7.40 g, 36.1 mmol), potassium phosphate (7.66 g, 36.1 mmol) and acetonitrile (100 mL). N,N′-Dimethylethane-1,2-diamine (1.33 g, 15.0 mmol) was added and the mixture was heated at 80° C. for 18 hours, at which point thin layer chromatography analysis [Eluent: ethyl acetate] indicated that a trace amount of starting material remained and a major product formed. It was filtered through a pad of Celite® and the Celite® pad rinsed with acetonitrile (50 mL). Water (300 mL) was added to the filtrate and the resulting suspension was stirred for 2 hours and filtered. The resulting solid was rinsed with water (2×20 mL) and dried under vacuum at room temperature to afford a white solid (4.60 g, 65%): mp 169-172° C.; 1H NMR (400 MHz, DMSO-d6) δ 9.84 (s, 1H), 9.05 (dd, J=2.8, 0.8 Hz, 1H), 8.82 (s, 1H), 8.54 (dd, J=4.7, 1.4 Hz, 1H), 8.20 (ddd, J=8.4, 2.8, 1.4 Hz, 1H), 7.54, (ddd, J=8.3, 4.7, 0.8 Hz, 1H), 2.11 (s, 3H); 13C NMR (101 MHz, DMSO-d6) δ 168.12, 147.46, 139.42, 135.46, 133.60, 125.47, 124.21, 122.21, 120.16, 22.62; EIMS m/z 236 ([M]+).

後処理

  1. customa major product formed
  2. filtrationIt was filtered through a pad of Celite®
  3. washthe Celite® pad rinsed with acetonitrile (50 mL)
  4. additionWater (300 mL) was added to the filtrate
  5. filtrationfiltered
  6. washThe resulting solid was rinsed with water (2×20 mL)
  7. customdried under vacuum at room temperature

出典と根拠

ORDレコード
ord-62a3500717c349b082120ee159f5c8f0
出典データセット
uspto-grants-2015_08
特許番号
US09102655B2

反応ノート

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