Carbon Dioxide → 4-{[(Tert-butoxy)carbonyl]amino}pyridine-3-carboxylic acid

HRID 901294

反応式

HRID 901294 の反応式
CN(CCN(C)C)C.[C:9]([O:13][C:14](=[O:22])[NH:15][C:16]1[CH:21]=[CH:20][N:19]=[CH:18][CH:17]=1)([CH3:12])([CH3:11])[CH3:10].[C:23](=[O:25])=[O:24].[OH-].[Na+]>C1COCC1>[C:9]([O:13][C:14]([NH:15][C:16]1[C:21]([C:23]([OH:25])=[O:24])=[CH:20][N:19]=[CH:18][CH:17]=1)=[O:22])([CH3:12])([CH3:10])[CH3:11]

参加物

6

反応物 4

HCID 280Carbon DioxideHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 14798Sodium HydroxideHCID 99902104-(Boc-amino)pyridine

生成物 1

HCID 221726234-{[(Tert-butoxy)carbonyl]amino}pyridine-3-carboxylic acid収率 30%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

n-Buli (1.6 M soln, 155 mL, 249 mmol) was added to a stirred solution of TMEDA (37.36 mL, 249 mmol) in THF at −40° C. The solution was allowed to come at room temperature over 10 min and stirred for another 10 min. The solution was cooled to −78° C. A solution of pyridine-4-yl-carbamic acid-tert-butyl ester (117) (22 g, 113.26 mmol) in THF was added slowly. The solution was allowed to come at room temperature within 3 h. After stirring at room temperature for 15 min the solution was again cooled to −78° C. and a freshly crushed dry ice was added. The solution was allowed to come at room temperature, stirred for 30 min and poured into ice cold 10% NH4Cl solution. The solution was basified by 1N NaOH solution and washed by dichloromethane. The pH of aqueous phase was adjusted to 4 by cold 10% HCl solution. The solids formed were filtered, washed by water and dried under vacuum at room temperature to yield 16.3 g (30%) 4-tert-butoxycarbonylamino-nicotinic acid (118) as white solids. MP: 260° C.; 1H-NMR (DMSO-d6): δ 1.49 (s, 9H), 8.23 (d, J=6.0 Hz, 1H), 8.55 (d, J=6.0 Hz, 1H), 8.96 (s, 1H); EIMS m/z 238 (M+1).

後処理

  1. waitto come at room temperature within 3 h
  2. stirringAfter stirring at room temperature for 15 min the solution
  3. temperaturewas again cooled to −78° C.
  4. customto come at room temperature
  5. stirringstirred for 30 min
  6. washwashed by dichloromethane
  7. customThe solids formed
  8. filtrationwere filtered
  9. washwashed by water
  10. customdried under vacuum at room temperature

出典と根拠

ORDレコード
ord-5aa9006f4d4f4fdf9c83d169eef854be
出典データセット
uspto-grants-2008_04
特許番号
US07361760B2

関連ノート

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