2-phenyl-1,5,9-triazacyclotridecan-4-one | 73397-35-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: 2-phenyl-1,5,9-triazacyclotridecan-4-one
• 英文别名: 12-phenyl-2,6,11-triazacyclotridecanone；3-phenyl-4,9-diazadodecanelactam
• CAS: 73397-35-0
• 化学式: C₁₆H₂₅N₃O
• 分子量: 275.394
• InChiKey: PKWPVMYYBCGGEB-UHFFFAOYSA-N

物化性质

• 沸点：
  493.5±45.0 °C(Predicted)
• 密度：
  0.985±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  53.2
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-phenyl-1,5,9-triazacyclotridecan-4-one 在 4-二甲氨基吡啶 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 反应 36.5h， 生成 N-acetyl-(+/-)-celacinnine
  参考文献：
  名称：

  Total synthesis of (.+-.)-celacinnine, (.+-.)-celallocinnine, (.+-.)-celafurine, and (.+-.)-celabenzine

  摘要：

  DOI：

  10.1021/ja00410a025
• 作为产物：
  描述：

  亚精胺 在 哌啶 、 丙二酸单乙酯 、 sodium cyanoborohydride 、 儿萘酚硼烷 作用下， 以 吡啶 、 乙醇 、 水 为溶剂， 反应 0.67h， 生成 2-phenyl-1,5,9-triazacyclotridecan-4-one
  参考文献：
  名称：

  The chemistry of naturally occurring polyamines. 1. Total synthesis of celacinnine, celabenzine and maytenine

  摘要：

  DOI：

  10.1021/jo01298a073

文献信息

• β-Lactams as building blocks in the synthesis of macrocyclic spermine and spermidine alkaloids
  作者：Harry H Wasserman、Haruo Matsuyama、Ralph P Robinson

  DOI：10.1016/s0040-4020(02)00731-7

  日期：2002.8

  Syntheses of the macrocyclic spermidine alkaloids (±)-celacinnine (1) and (±)-dihydroperiphylline (2) as well as the related spermine alkaloid (±)-verbascenine (3) were accomplished by means of sequential ring expansions of smaller lactam rings. Three ring expansion methods were employed: (1) transamidation of N-(aminoalkyl)lactams, (2) β-lactam-lactim ether condensation followed by reductive cleavage

  大环亚精胺生物碱（±）-celacinnine（1）和（±）-二氢茶碱（2）以及相关的亚精胺生物碱（±）-verbascenine（3）的合成是通过较小内酰胺环的连续环扩展来完成的。使用了三种扩环方法：（1）N-（氨基烷基）内酰胺的转酰胺基化，（2）β-内酰胺-内酰胺醚缩合，然后用NaBH 3 CN / AcOH还原双环4-氧代四氢嘧啶产物和（3）形成双环酰基肼，然后用Na / NH 3裂解N–N键。每个合成均以4-苯基氮杂环丁烷-2-酮中间体的扩环为特征，该中间体会发生酰胺基扩环或内酰胺醚缩合反应。
• Transamidation reactions in the formation of macrocyclic lactams. A total synthesis of celacinnine
  作者：Harry H. Wasserman、Ralph P. Robinson、Haruo Matsuyama

  DOI：10.1016/s0040-4039(00)78723-5

  日期：1980.1

  The macrocyclic spermidine alkaloid, celacinnine, has been synthesized by methods involving successive ring expansion reactions. One route starts with 4-phenyl-2-azetidinone; another, with piperidazine.

  大环亚精胺生物碱，塞拉西宁，已经通过涉及连续环扩环反应的方法合成。一种途径是从4-苯基-2-氮杂环丁酮开始；另一个，与哌啶嗪。
• Lithium and proton templated ω-polyazamacrolactamization, new general routes to macrocyclic polyamines
  作者：Konstantin Drandarov、Manfred Hesse

  DOI：10.1016/s0040-4039(02)01660-x

  日期：2002.9

  A general, lithium templated/catalyzed ω-polyazamacrolactamization method for the synthesis of macrocyclic polyamines including spermidine and spermine alkaloids is presented. The formation of 12-, 13-, 16-, 17-, and 19-membered N3, N4, N5, and N6 containing rings is described. A proton templated/catalyzed macrolactamization of some ω-polyazaaminoesters is also observed.

  提出了一种通用的锂模板化/催化的ω-聚ama杂内酰胺化方法，用于合成大环多胺，包括亚精胺和亚精胺生物碱。描述了含12、13、16、17和19元N 3，N 4，N 5和N 6的含环的形成。还观察到一些ω-聚氮杂氨基酯的质子模板化/催化的大内酰胺化。
• Wasserman, Harry H.; Robinson, Ralph P., Heterocycles, 1984, vol. 21, # 1, p. 279 - 288
  作者：Wasserman, Harry H.、Robinson, Ralph P.

  DOI：——

  日期：——
• Synthesis of the spermidine alkaloid (±)-N-acetyl-N(1)-deoxymayfoline
  作者：Bassem F. Tawil、Armin Guggisberg、Manfred Hesse

  DOI：10.1016/s0040-4020(01)92268-9

  日期：1992.1

  The total synthesis of the spermidine alkaloid (+/-)-N(1)-acetyl-N(1)-deoxymayfoline ((+/-)-1) was achieved by expansion of rings. The 5-membered cyclic compound 2 was fused with butadiene by intermolecular Diels-Alder cycloaddition. The resulting 7-phenyl-1,6-diazabicyclo[4.3.0]nona-3,7-dien-9-one (4) was reductively cleaved with Raney-Ni in alcoholic KOH to afford the mono-cyclic lactam 6. This was selectively alkylated in high yields to the cyano derivative 7. Reduction of the nitrile group to the amine derivative 8 went smoothly by use of Adam's catalyst in the presence of acid. Intramolecular transamidation was then accomplished by acid catalysis with TsOH to furnish the 13-membered diazalactam 9. The synthesis of (+/-)-1 was completed by the selective acetylation of the more nucleophilic amino group.