10-(4-methylphenyl)sulfonyl-11,12-diazahexacyclo[5.5.1.02,6.03,10.04,8.09,13]tridec-11-en-1-ol | 130762-18-4

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 10-(4-methylphenyl)sulfonyl-11,12-diazahexacyclo[5.5.1.02,6.03,10.04,8.09,13]tridec-11-en-1-ol
• CAS: 130762-18-4
• 化学式: C₁₈H₁₈N₂O₃S
• 分子量: 342.419
• InChiKey: LDKWOYYYSMPCES-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.01
• 重原子数：
  24.0
• 可旋转键数：
  2.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  79.09
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  10-(4-methylphenyl)sulfonyl-11,12-diazahexacyclo[5.5.1.02,6.03,10.04,8.09,13]tridec-11-en-1-ol 以 苯 为溶剂， 反应 12.0h， 以48%的产率得到exo-(p-tolylsulfonyl)-pentacyclo<5.4.0.0^2,6.0^3,10.0^5,9>undecane-8-one
  参考文献：
  名称：

  Synthesis and chemistry of a new, functionalized polycyclic azoalkane. A novel entry into the homopentaprismane ring system

  摘要：

  Reaction of pentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecane-8,11-dione, 1) with (p-tolylsulfonyl)hydrazine (1 equiv) followed by in situ reduction of the product thereby obtained with sodium borohydride afforded two products, i.e., hexacyclic azoalkane 3 (34%) and exo-3-(p-tolylsulfonyl)tetracyclo[6.3.0.0(4,11).0(5,9)]undecan-endo-6-ol (4, 19%). The structure of 3 was established via X-ray crystallographic analysis of its corresponding O-benzoyl derivative 5a. Reaction of 4 with acetic anhydride-pyridine gave the corresponding O-acetyl derivative 6, whose structure wa established by X-ray crystallographic methods. The corresponding reaction of 1 with (p-tolysulfonyl)hydrazine alone afforded 3 as the exclusive reaction product in 66% yield. Subsequent reduction of 3 with sodium borohydride afforded 4 (84%). The results of mechanistic studies revealed that the conversion of 3 to 4 proceeds stepwise, i.e., with loss of nitrogen from 3 to form 3-(p-tolylsulfonyl)tetracylo[6.3.0.0(4,11).0(5,9)]undec-2-en-6-one (7), which is subsequently reduced in situ by sodium borohydride. Irradiation of a benzene solution of 3 (Pyrex filter) afforded exo-(p-tolylsulfonyl)-PCUD-8-one (9, 48%). Similar irradiation of 5a produced the corresponding substituted homopentaprismane (11a, 71%), whereas irradiation of 5c (i.e., the O-acetyl derivative of 3) gave a mixture of two products, i.e., homopentaprismane 11b (52%) and the corresponding homohypostrophene 12 (14%), along with recovered 5c (15%). The results of a control study revealed that 12 is not an intermediate in the formation of 11b from 5c. Structures of 9 and of 11a were determined by X-ray crystallographic methods.

  DOI：

  10.1021/jo00001a053
• 作为产物：
  描述：

  五环[5.4.0.02,6.03,10.05,9]十一烷-8,11-二酮 、 对甲苯磺酰肼 以 四氢呋喃 为溶剂， 反应 8.0h， 以66%的产率得到10-(4-methylphenyl)sulfonyl-11,12-diazahexacyclo[5.5.1.02,6.03,10.04,8.09,13]tridec-11-en-1-ol
  参考文献：
  名称：

  Synthesis and chemistry of a new, functionalized polycyclic azoalkane. A novel entry into the homopentaprismane ring system

  摘要：

  Reaction of pentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecane-8,11-dione, 1) with (p-tolylsulfonyl)hydrazine (1 equiv) followed by in situ reduction of the product thereby obtained with sodium borohydride afforded two products, i.e., hexacyclic azoalkane 3 (34%) and exo-3-(p-tolylsulfonyl)tetracyclo[6.3.0.0(4,11).0(5,9)]undecan-endo-6-ol (4, 19%). The structure of 3 was established via X-ray crystallographic analysis of its corresponding O-benzoyl derivative 5a. Reaction of 4 with acetic anhydride-pyridine gave the corresponding O-acetyl derivative 6, whose structure wa established by X-ray crystallographic methods. The corresponding reaction of 1 with (p-tolysulfonyl)hydrazine alone afforded 3 as the exclusive reaction product in 66% yield. Subsequent reduction of 3 with sodium borohydride afforded 4 (84%). The results of mechanistic studies revealed that the conversion of 3 to 4 proceeds stepwise, i.e., with loss of nitrogen from 3 to form 3-(p-tolylsulfonyl)tetracylo[6.3.0.0(4,11).0(5,9)]undec-2-en-6-one (7), which is subsequently reduced in situ by sodium borohydride. Irradiation of a benzene solution of 3 (Pyrex filter) afforded exo-(p-tolylsulfonyl)-PCUD-8-one (9, 48%). Similar irradiation of 5a produced the corresponding substituted homopentaprismane (11a, 71%), whereas irradiation of 5c (i.e., the O-acetyl derivative of 3) gave a mixture of two products, i.e., homopentaprismane 11b (52%) and the corresponding homohypostrophene 12 (14%), along with recovered 5c (15%). The results of a control study revealed that 12 is not an intermediate in the formation of 11b from 5c. Structures of 9 and of 11a were determined by X-ray crystallographic methods.

  DOI：

  10.1021/jo00001a053