p-Nitrophenyl-2-aminothiazol-5-ylsulphone → 5-[(4-Nitrophenyl)sulfonyl]thiazole

HRID 327174

反応式

HRID 327174 の反応式
N[C:2]1[S:3][C:4]([S:7]([C:10]2[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][CH:11]=2)(=[O:9])=[O:8])=[CH:5][N:6]=1.N([O-])=O.[Na+].P(P(O)(O)=O)(O)(O)=O.[OH-].[NH4+]>P(=O)(O)(O)O.O>[N+:16]([C:13]1[CH:12]=[CH:11][C:10]([S:7]([C:4]2[S:3][CH:2]=[N:6][CH:5]=2)(=[O:9])=[O:8])=[CH:15][CH:14]=1)([O-:18])=[O:17]

参加物

7

反応物 4

HCID 1535p-Nitrophenyl-2-aminothiazol-5-ylsulphoneHCID 14923Ammonium HydroxideHCID 24536Hypophosphoric acidHCID 23668193Sodium Nitrite

生成物 1

HCID 107071535-[(4-Nitrophenyl)sulfonyl]thiazole収率 35.2%

試薬・触媒・溶媒 2

HCID 962Water溶媒2 回HCID 1004Phosphoric Acid溶媒

反応条件

温度
-5 °C

実験手順

To a cooled (-5° C.), stirred solution of 2-amino-5-[(4-nitrophenyl)sulfonyl]thiazole (5.15 g, 18.1 mmol) in 85% phosphoric acid (200 mL) was added dropwise a solution of sodium nitrite (1.56 g, 22.6 mmol) in distilled water (10 mL) at such a rate to maintain the internal temperature between -5° and 5° C. When the addition was complete the reaction mixture was stirred for 1 hour at 0° C. then treated dropwise with 50% hypophosphoric acid (15 mL). After the addition, the ice bath was removed and reaction mixture stirred at room temperature for 3 hours during which time moderate frothing occurred. The brown solution was diluted with water (total volume=1 L), neutralized with 28% ammonium hydroxide and filtered. Flash chromatography of the resulting brown solid (eluted with 5% v/v ethyl acetate in methylene chloride) yielded the title thiazole (1.72 g, 35%) as a yellow solid; mp 168°-170° C. 1H--NMR (250 MHz, d6 --DMSO): 8.32 (d, 2H, J=12.6 Hz, aromatic), 8.45 (d, 2H, J=12.8 Hz, aromatic), 8.74 (s, 1H, aromatic), 9.578 (s, 1H, aromatic). MS (CI, CH4): 271(M+1).

後処理

  1. temperatureto maintain the internal temperature between -5° and 5° C
  2. additionWhen the addition
  3. additionAfter the addition
  4. customthe ice bath was removed
  5. customreaction mixture
  6. stirringstirred at room temperature for 3 hours during which time moderate frothing
  7. filtrationfiltered
  8. washFlash chromatography of the resulting brown solid (eluted with 5% v/v ethyl acetate in methylene chloride)

出典と根拠

ORDレコード
ord-94ed8af1edb24399b0998ff8dde550fc
出典データセット
uspto-grants-1993_12
特許番号
US05272163

関連ノート

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