5-Aminopyridine-2-carbonitrile → 6-Cyanopyridine-3-sulfonyl chloride

HRID 331183

反応式

HRID 331183 の反応式
N[C:2]1[CH:3]=[CH:4][C:5]([C:8]#[N:9])=[N:6][CH:7]=1.N([O-])=O.[Na+].[S:14]([Cl:17])(Cl)=[O:15].[OH2:18]>Cl.O>[C:8]([C:5]1[N:6]=[CH:7][C:2]([S:14]([Cl:17])(=[O:15])=[O:18])=[CH:3][CH:4]=1)#[N:9]

参加物

6

反応物 3

HCID 38713955-Aminopyridine-2-carbonitrileHCID 23668193Sodium NitriteHCID 86607486Thionylchloride water

生成物 1

HCID 470031906-Cyanopyridine-3-sulfonyl chloride収率 73.5%

試薬・触媒・溶媒 2

HCID 313Hydrochloric Acid溶媒HCID 962Water溶媒

反応条件

温度
-5 °C

実験手順

In parallel, 5-amino-2-cyano pyridine (10 g, 0.084 mol) is dissolved in concentrated HCl (98 ml) and the mixture is cooled to −5° C. To this mixture is added dropwise over a period of 1 h a solution of NaNO2 (8.2 g, 0.118 mol) in water (50 ml), maintaining the reaction temperature between −5° C. and 0° C. This slurry is then added dropwise over a period of 1 h to the above reaction mixture (thionylchloride/water mixture), maintaining the reaction temperature between −5° C. and 0° C. (Note: The diazotized mixture should be also kept at −5° C. throughout the addition). As the addition proceeds, a white solid precipitates. When the addition is over, the reaction mixture is stirred for an additional hour. The precipitate is collected by filtration, washed with cold water and dried under vacuum to afford the title compound as light yellow solid (12.5 g, Yield 73.5%). 1H NMR (DMSO-d6:400 MHz) δ 14.49 (1H, s), 8.87 (1H, s), 8.11-8.14(1H, d), 8.0-8.03 (1H, d); HPLC (max plot) 97% Rt 1.155 min; LC/MS: m/z, M+, 202.8.

後処理

  1. temperaturemaintaining the reaction temperature between −5° C. and 0° C
  2. temperaturemaintaining the reaction temperature between −5° C. and 0° C. (Note
  3. additionThe diazotized mixture should be also kept at −5° C. throughout the addition)
  4. additionAs the addition proceeds
  5. customa white solid precipitates
  6. additionWhen the addition
  7. filtrationThe precipitate is collected by filtration
  8. washwashed with cold water
  9. customdried under vacuum

出典と根拠

ORDレコード
ord-61891c2d11db4648bce15139c7c65684
出典データセット
uspto-grants-2014_11
特許番号
US08877757B2

関連ノート

読み込み中…