13-(2-hydroxybenzyl)-1,4,8,11-tetraazacyclotetradecane-12,14-dione | 175443-54-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂卓
• 英文名称: 13-(2-hydroxybenzyl)-1,4,8,11-tetraazacyclotetradecane-12,14-dione
• 英文别名: 6-[(2-Hydroxyphenyl)methyl]-1,4,8,11-tetrazacyclotetradecane-5,7-dione
• CAS: 175443-54-6
• 化学式: C₁₇H₂₆N₄O₃
• 分子量: 334.418
• InChiKey: IXEJFXDQPVTEOV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  103
• 氢给体数：
  5
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  13-(2-hydroxybenzyl)-1,4,8,11-tetraazacyclotetradecane-12,14-dione 、 copper(II) perchlorate 在 NaOH 作用下， 以 水 为溶剂， 以60%的产率得到
  参考文献：
  名称：

  Synthesis of Novel Macrocyclic Polyamines with a Pendant Phenol Group and Properties and Structures of Their Copper(II) Complexes

  摘要：

  A series of new dioxocyclams with pendant phenol groups has been synthesized from coumarin 3-carboxylic ester and linear polyamines in refluxing methanol/ethanol. Corresponding saturated cyclam derivatives were obtained by B-2 H-6 . THF reduction. Reaction of a dioxocylam derivative with Cu(ClO4)(2) in aqueous solution yields a singly deprotonated dioxotetraamine copper(II) complex, whose X-ray crystal structure has shown that the enolic tautomer of an amido group was coordinated to copper(II). X-ray crystal data for [C17H25N4O3Cu]- ClO4 . H2O: monoclinic, space group P2(1)/a, a 15.554(3) Angstrom, b = 8.478(2) Angstrom, c = 17.250(3) Angstrom, beta = 111.4(1)degrees, V = 2117(1) Angstrom(3), Z = 4, D-c = 1.614 mg/mm(3), F(000) = 1068, R = 0.040 and R(w) = 0.044. When coordinated to copper(II), the amido group deprotonates with pK(a) = 4.3. Potentiometric, electrochemical, and EPR spectral data of the complexes were studied. In the pH region 3-9, the substituent phenol does not coordinate to the copper(II) ion; however, substituents do have some effect on their Cu(II)/Cu(III) potential and complex stability. In this study, we show that, besides doubly deprotonated copper(II) complexes, singly deprotonated dioxotetraamine complexes also exist both in aqueous solution and in the solid state with considerable stability. The existence of the singly deprotonated dioxotetraamine copper(II) complex undoubtedly indicates that the complex deprotonates stepwise and not simutaneous. This is a new conceptual discovery. The results provide us critical evidence for a discussion of the detailed mechanism of complex formation and acid dissociation.

  DOI：

  10.1021/ic951250x
• 作为产物：
  描述：

  氢气 、 以 further solvent(s) 为溶剂， 生成 铜 、 13-(2-hydroxybenzyl)-1,4,8,11-tetraazacyclotetradecane-12,14-dione
  参考文献：
  名称：

  Kinetics and mechanism of the acid dissociation of copper(II) complex of novel C-functionalized macrocylcic dioxotetramines

  摘要：

  The kinetics of the acid dissociation of copper(II) complex of a novel C-functionalized macrocyclic dioxotetraamine has been studied using a stopped-flow spectrophotometer. It was proven that substituents decrease the acid dissociation rates. The dissociation rate follows the law upsilon(d) = C(com)kK(1)K(2)H(2)/(1 + K1H + K1K2H2). On the intermediates we have obtained, the dissociation kinetics are interpreted by a mechanism involving the negatively charged carbonyl oxygen of the complex being rapidly protonated in a pre-equilibrium step, the rate-determining step being intramolecular hydrogen(enolic tautomer) migration(to imine nitrogen). The dissociation rate reached a plateau in strongly acidic solution. By means of temperatures coefficient method, K-1, K-2 of the pre-equilibrium step and Delta H-not equal and Delta S not equal of the rate-determining step were obtained and the results discussed. It is the strong in-plane ligand held that increased Delta H of the rate-determining step and thus decreases the dissociation rate constant. The Bronsted type linear free energy relationships do exist in this C-functionalized dioxotetraamine copper(II) complex. The results clarify insights into acid dissociation mechanisms for the 14-membered macrocyclic dioxotetraamine copper(II) complex. (C) 1997 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0277-5387(96)00516-5

文献信息

• Novel structure of a macrocyclic dioxotetraamine copper(II) complex
  作者：Fuping Kou、Shourong Zhu、Huakuan Lin、Yunti Chen、Honggen Wang、Xinkai Yao

  DOI：10.1039/cc9960000059

  日期：——

  An unprecedented singly deprotonated macrocyclic dioxotetraamine copper(II) complex is prepared and characterized by IR, UV–VIS, EPR and X-ray crystallography; it is established that the enolic tautomer of the amide is present; two double deprotonated copper(II) complexes are prepared for comparison.

  制备了一种前所未有的单去质子化大环二氧四胺铜(II)络合物，并通过红外光谱、紫外可见光谱、电致发光光谱和 X 射线晶体学对其进行了表征；确定了其中存在酰胺的烯醇同系物；制备了两种双去质子化铜(II)络合物进行比较。