2,3-Diaminopyridine → tert-Butyl 4-[(2-aminopyridin-3-yl)amino]piperidine-1-carboxylate

HRID 271865

反応式

HRID 271865 の反応式
C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].[NH2:15][C:16]1[C:21]([NH2:22])=[CH:20][CH:19]=[CH:18][N:17]=1.[C:23]([O:27][C:28]([N:30]1[CH2:35][CH2:34][C:33](=O)[CH2:32][CH2:31]1)=[O:29])([CH3:26])([CH3:25])[CH3:24]>ClC(Cl)C>[NH2:15][C:16]1[C:21]([NH:22][CH:33]2[CH2:34][CH2:35][N:30]([C:28]([O:27][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:29])[CH2:31][CH2:32]2)=[CH:20][CH:19]=[CH:18][N:17]=1

参加物

5

反応物 3

HCID 99562,3-DiaminopyridineHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 5049666Sodium triacetoxyborohydride2 回

生成物 1

HCID 22293217tert-Butyl 4-[(2-aminopyridin-3-yl)amino]piperidine-1-carboxylate収率 33.2%

試薬・触媒・溶媒 1

HCID 63651,1-Dichloroethane溶媒

実験手順

Sodium triacetoxyborohydride (14.5 g, 68.7 mmol) was added to a solution of 2,3-diaminopyridine (5.00 g, 45.8 mmol) and N-(t-butoxycarbonyl)-4-piperidone (9.58 g, 48.1 mmol) in dichloroethane (75 mL) at room temperature. After 5 h, additional sodium triacetoxyborohydride was added (1.8 g) and again after another 2.5 h. The reaction was stirred overnight, and quenched with 5% aqueous sodium hydroxide. This was extracted with I methylene chloride, and washed with 5% aqueous sodium hydroxide, water and saturated sodium chloride solution. After drying over sodium sulfate, the solution was filtered and evaporated to give the crude product. This was purified by chromatorgraphy (silica gel, 3 to 5% methanol in methylene chloride gradient elution), which gave the title compound (4.44 g). MS 293 (M+1) 1H NMR (500 MHz, CD3OD) δ 7.32 (dd, J=1, 5 Hz, 1H), 6.85 (dd, J=1, 8 Hz, 1H), 6.59 (dd, J=5, 8 Hz, 1H), 4.04 (d, J=13 Hz, 2H), 3.46 (m, 1H), 2.98 (br s, 2H), 2.01 (dd, J=2, 12 Hz, 2H), 1.46 (s, 9H), 1.37 (qd, J=4, 12 Hz, 2H).

後処理

  1. waitagain after another 2.5 h
  2. customquenched with 5% aqueous sodium hydroxide
  3. extractionThis was extracted with I methylene chloride
  4. washwashed with 5% aqueous sodium hydroxide, water and saturated sodium chloride solution
  5. dry with materialAfter drying over sodium sulfate
  6. filtrationthe solution was filtered
  7. customevaporated
  8. customto give the crude product
  9. customThis was purified by chromatorgraphy (silica gel, 3 to 5% methanol in methylene chloride gradient elution), which

出典と根拠

ORDレコード
ord-b1f7896f4f9d4c6d805de19ebe777ee8
出典データセット
uspto-grants-2008_11
特許番号
US07452903B2

関連ノート

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