7-苯基甲基-1,4-二噁-7-氮杂螺[4.5]癸烷-8-甲腈 | 132462-23-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 中文名称: 7-苯基甲基-1,4-二噁-7-氮杂螺[4.5]癸烷-8-甲腈
• 中文别名: 1-苄基-5,5-(伸乙二氧基)-2-氰基哌啶；1-苄基-5,5-(亚乙氧基)-2-哌啶腈
• 英文名称: 1-Benzyl-5,5-(ethylenedioxy)-2-piperidinecarbonitrile
• 英文别名: 1-benzyl-5-(ethylenedioxy)-2-piperidinecarbonitrile；7-Benzyl-1,4-dioxa-7-azaspiro[4.5]decane-8-carbonitrile；9-benzyl-1,4-dioxa-9-azaspiro[4.5]decane-8-carbonitrile
• CAS: 132462-23-8
• 化学式: C₁₅H₁₈N₂O₂
• 分子量: 258.32
• InChiKey: GSRMGPHDKVTGIE-UHFFFAOYSA-N

物化性质

• 熔点：
  95 °C(Solv: chloroform (67-66-3))
• 沸点：
  411.7±45.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  45.5
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2934999090

反应信息

• 作为反应物：
  描述：

  7-苯基甲基-1,4-二噁-7-氮杂螺[4.5]癸烷-8-甲腈 在 盐酸 、 lithium aluminium tetrahydride 、 四丁基溴化铵 、 sodium cyanoborohydride 、 lithium triethoxyaluminum hydride 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 邻二氯苯 为溶剂， 反应 7.42h， 生成 Hexahydro-2-(2-methoxyphenyl)-2H-pyrido<1,2-a>pyrazin-7(6H)-one
  参考文献：
  名称：

  Synthesis of 2,5-substituted piperidines and their bicyclic piperazine analogs: the 2,7-substituted octahydro-2H-pyrido[1,2-a]pyrazines

  摘要：

  Partial and complete reduction of the key compound 1-benzyl-5-(ethylenedioxy)-2-piperidinecarbonitrile (1) was applied to generate the corresponding aldehyde 2 and primary amine 3. These were transformed into bicyclic 7-(ethylenedioxy)-2(R)-octahydro-2H-pyrido[1,2-a]pyrazines 7 (R = H) and 15 (R = aryl) through the following sequence: (i) chloroacetylation of 3 and of arylamines derived from 2, (ii) cyclization to give the intermediate lactams 5 and 14, and (iii) reduction with LiAlH4. Deprotection of the N-aryl compounds 15 yielded the corresponding ketone model compounds 16. From amino acetal 7, a complementary ketone synthon 11 was prepared via N-benzylation and cleavage of the acetal group, providing a general route to piperidine-bridged analogues of 1,4-substituted piperazine drugs.

  DOI：

  10.1021/jo00017a036
• 作为产物：
  描述：

  1-Benzyl-3,3-(ethylenedioxy)piperidine 在 lithium aluminium tetrahydride 、 mercury(II) diacetate 、 edetate disodium 作用下， 以 溶剂黄146 为溶剂， 反应 4.5h， 生成 7-苯基甲基-1,4-二噁-7-氮杂螺[4.5]癸烷-8-甲腈
  参考文献：
  名称：

  Regioselective oxidation of piperidine-3 derivatives: a synthetic route to 2,5-substituted piperidines

  摘要：

  Mercuric acetate oxidation of 1-benzyl-3,3-(ethylenedioxy)piperidine (1) and of 3-CO2Et- and 3-CH2OH-substituted piperidines 7-9 was shown to occur regioselectively at the 6-position. Trapping of the resulting 6-iminium ions with cyanide yielded the corresponding 5-substituted 2-piperidinecarbonitriles 5, 10, and 11. However, the 2-iminium ion was formed in the reaction of the N-oxide of 1 with trifluoroacetic anydride; with cyanide this afforded the regioisomeric 3,3-(ethylenedioxy)-2-piperidinecarbonitrile (2). Plausible mechanisms are advanved to explain this contrasting behavior. 1-Benzyl-5,5-(ethylenedioxy)-2-piperidinecarbonitrile (5) was transformed into other piperidine-2,5 derivatives by reaction of the alpha-amino nitrile anion with electrophoresis, followed by reductive decyanation.

  DOI：

  10.1021/jo00007a025

文献信息

• COMPERNOLLE, FRANS;SALEH, M. ASHTY;DEN, BRANDEN STEFAN VAN;TOPPET, SUZANN+, J. ORG. CHEM., 56,(1991) N, C. 2386-2390
  作者：COMPERNOLLE, FRANS、SALEH, M. ASHTY、DEN, BRANDEN STEFAN VAN、TOPPET, SUZANN+

  DOI：——

  日期：——
• Regioselective oxidation of piperidine-3 derivatives: a synthetic route to 2,5-substituted piperidines
  作者：Frans Compernolle、M. Ashty Saleh、Stefan Van den Branden、Suzanne Toppet、Georges Hoornaert

  DOI：10.1021/jo00007a025

  日期：1991.3

  Mercuric acetate oxidation of 1-benzyl-3,3-(ethylenedioxy)piperidine (1) and of 3-CO2Et- and 3-CH2OH-substituted piperidines 7-9 was shown to occur regioselectively at the 6-position. Trapping of the resulting 6-iminium ions with cyanide yielded the corresponding 5-substituted 2-piperidinecarbonitriles 5, 10, and 11. However, the 2-iminium ion was formed in the reaction of the N-oxide of 1 with trifluoroacetic anydride; with cyanide this afforded the regioisomeric 3,3-(ethylenedioxy)-2-piperidinecarbonitrile (2). Plausible mechanisms are advanved to explain this contrasting behavior. 1-Benzyl-5,5-(ethylenedioxy)-2-piperidinecarbonitrile (5) was transformed into other piperidine-2,5 derivatives by reaction of the alpha-amino nitrile anion with electrophoresis, followed by reductive decyanation.
• Synthesis of 2,5-substituted piperidines and their bicyclic piperazine analogs: the 2,7-substituted octahydro-2H-pyrido[1,2-a]pyrazines
  作者：Frans Compernolle、M. Ashty Saleh、Suzanne Toppet、Georges Hoornaert

  DOI：10.1021/jo00017a036

  日期：1991.8

  Partial and complete reduction of the key compound 1-benzyl-5-(ethylenedioxy)-2-piperidinecarbonitrile (1) was applied to generate the corresponding aldehyde 2 and primary amine 3. These were transformed into bicyclic 7-(ethylenedioxy)-2(R)-octahydro-2H-pyrido[1,2-a]pyrazines 7 (R = H) and 15 (R = aryl) through the following sequence: (i) chloroacetylation of 3 and of arylamines derived from 2, (ii) cyclization to give the intermediate lactams 5 and 14, and (iii) reduction with LiAlH4. Deprotection of the N-aryl compounds 15 yielded the corresponding ketone model compounds 16. From amino acetal 7, a complementary ketone synthon 11 was prepared via N-benzylation and cleavage of the acetal group, providing a general route to piperidine-bridged analogues of 1,4-substituted piperazine drugs.