2,3-二氨基吡啶 → 4-(2-氨基吡啶-3-基氨基)哌啶-1-羧酸叔丁酯

HRID 14379

反应方程式

HRID 14379 反应方程式
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

参与物

5

反应物 3

HCID 99562,3-二氨基吡啶HCID 735900N-叔丁氧羰基-4-哌啶酮HCID 5049666三乙酰氧基硼氢化钠2 次

产物 1

HCID 222932174-(2-氨基吡啶-3-基氨基)哌啶-1-羧酸叔丁酯收率 33.2%

试剂、催化剂与溶剂 1

HCID 63651,1-二氯乙烷溶剂

实验过程

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-(tert-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 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 chromatography (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=5, 1 Hz, 1H), 6.85 (dd, J=8, 1 Hz, 1H), 6.59 (dd, J=8, 5 Hz, 1H), 4.04 (d, J=13 Hz, 2H), 3.46 (m, 1H), 2.98 (br s, 2H), 2.01 (dd, J=12, 2 Hz, 2H), 1.46 (s, 9H), 1.37 (qd, J=12, 4 Hz, 2H).

后处理

  1. waitagain after another 2.5 h
  2. customquenched with 5% aqueous sodium hydroxide
  3. extractionThis was extracted with 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 chromatography (silica gel, 3 to 5% methanol in methylene chloride gradient elution), which

来源与证据

ORD记录
ord-9a838bdd34ad464698717d23dc8fc819
来源数据集
uspto-grants-2010_06
专利号
US07732438B2

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