1-(2-pyridinyl)-4,7,10-tris(t-butyloxycarbonyl)-1,4,7,10-tetraazacyclododecane

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1-(2-pyridinyl)-4,7,10-tris(t-butyloxycarbonyl)-1,4,7,10-tetraazacyclododecane
• 英文别名: 1-(2-pyridyl)-4,7,10-tris(tert-butyloxycarbonyl)-1,4,7,10-tetraazacyclododecane；1,4,7-tris(tert-butoxycarbonyl)-10-(2-pyridinyl)-1,4,7,10-tetraazacyclododecane；Tritert-butyl 10-pyridin-2-yl-1,4,7,10-tetrazacyclododecane-1,4,7-tricarboxylate；tritert-butyl 10-pyridin-2-yl-1,4,7,10-tetrazacyclododecane-1,4,7-tricarboxylate
• 化学式: C₂₈H₄₇N₅O₆
• 分子量: 549.711
• InChiKey: AMTJHLFVIUHKNG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  39
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1-(2-pyridinyl)-4,7,10-tris(t-butyloxycarbonyl)-1,4,7,10-tetraazacyclododecane 在 盐酸 作用下， 以 乙醇 为溶剂， 以79%的产率得到1-(2-pyridyl)-1,4,7,10-tetraazacyclododecane trihydrochloride
  参考文献：
  名称：

  Metal Chelation-Controlled Twisted Intramolecular Charge Transfer and Its Application to Fluorescent Sensing of Metal Ions and Anions

  摘要：

  Two fluorescent ligands, N-(2-(5-cyanopyridyl))cyclen (L5) and N-(2-pyridyl)cyclen (L6) (cyclen = 1,4,7,10-tetraazacyclododecane), were designed and synthesized to control twisted intramolecular charge transfer (TICT) by metal chelation in aqueous solution. By complexation with Zn2+, L6 exhibited TICT emissions at 430 nm (excitation at 270 nm) in 10 mM HEPES (pH 7.0) with l = 0.1 (NaNO3) at 25 degreesC due to the perpendicular conformation of a pyridine ring with respect to a dialkylamino group, which was fixed by Zn2+-N(pyridine) coordination, as proven by potentiometric pH, UV, and fluorescence titrations and X-ray crystal structure analysis. We further describe that the 1:1 complexation of ZnL6 with guests such as succinimide, phosphates, thiolates, and dicarboxylates, which compete with a nitrogen in the pyridine ring for Zn2+ in ZnL6, induces considerable emission shift from TICT emissions (at 430 nm) to locally excited emissions (at ca. 350 nm) in neutral aqueous solution at 25 degreesC.

  DOI：

  10.1021/ja040095v
• 作为产物：
  描述：

  2-溴吡啶 、 1,4,7-三叔丁氧羰基-1,4,7,10-四氮杂环十二烷 在 palladium diacetate 三苯基膦 作用下， 以 甲苯 为溶剂， 反应 65.0h， 以55%的产率得到1-(2-pyridinyl)-4,7,10-tris(t-butyloxycarbonyl)-1,4,7,10-tetraazacyclododecane
  参考文献：
  名称：

  N-Arylation of 1,4,7,10-Tetraazacyclododecanes

  摘要：

  铂催化的N-芳基化反应可获得N-芳基取代和N-芳基桥接的1,4,7,10-四氮杂环十二烷。使用简单的卤代芳烃时，芳基化产物的产率较低，而与吡啶衍生物反应则可获得中等至满意的取代环烷产物。

  DOI：

  10.1055/s-2001-17531

文献信息

• N-Arylation of Protected Azamacrocycles
  作者：Máté Erdélyi、Alberte Veiga、Sven Arenz

  DOI：10.1055/s-0032-1318307

  日期：——

  A rapid method for efficient palladium-catalyzed N-arylation of polynitrogenated macrocycles is presented. Its applicability for functionalization of protected azamacrocycles of various sizes with substituted aryl bromides of optional electronic properties is demonstrated. The compatibility of the protocol with common N-protecting schemes as well as the impact of electronic versus steric factors is discussed. Using a commercially available catalytic system and easily available alkoxide or phenoxide base, the method provides moderate to excellent yields of N-arylated azamacrocycles (45-96%).