1,3,5-Cyclohexanetriamine, N,N',N"-tris(2-pyridinylmethyl)-, (1.α.,3.α.,5.α.)- | 177660-40-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 1,3,5-Cyclohexanetriamine, N,N',N"-tris(2-pyridinylmethyl)-, (1.α.,3.α.,5.α.)-
• 英文别名: N,N′,N″-tris(2-pyridylmethyl)-1,3,5-cis,cis-triamino-cyclohexane；N,N',N"-tris(2-pyridylmethyl)cyclohexane-cis,cis-1,3,5-triamine；N,N',N''-tris(2-pyridylmethyl)-cis,cis-1,3,5-triaminocyclohexane；N,N',N''-tris(2-pyridylmethyl)-cis-1,3,5-triaminocyclohexane；r-1,c-3,c-5-tris[(2-pyridylmethyl)amino]cyclohexane；tachpyr；tachpyridine
• CAS: 177660-40-1
• 化学式: C₂₄H₃₀N₆
• 分子量: 402.542
• InChiKey: ILHFCLNOTOJYHF-BKFWDETESA-N

物化性质

• 沸点：
  576.4±50.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.83
• 重原子数：
  30.0
• 可旋转键数：
  9.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  74.76
• 氢给体数：
  3.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  mercury(II) perchlorate 、 1,3,5-Cyclohexanetriamine, N,N',N"-tris(2-pyridinylmethyl)-, (1.α.,3.α.,5.α.)- 以 乙醇 为溶剂， 以52%的产率得到Λ-(N,N',N''-tris(2-pyridylmethyl)-cis,cis-1,3,5-triaminocyclohexane)mercury(II) perchlorate
  参考文献：
  名称：

  Effect of metal size on coordination geometry of N,N′,N″-tris(2-pyridylmethyl)-cis,cis-1,3,5-triaminocyclohexane: synthesis and structure of [MIIL](ClO4)2 (M=Zn, Cd and Hg)

  摘要：

  The hexadentate ligand N,N',N'-tris(2-pyridylmethyl)-cis,cis-1,3,5-triaminocyclohexane (tachpyr) forms stable metal complexes from the salts M(ClO4)(2) . 6H(2)O (M = Zn2+ and Cd2+) and Hg(ClO4)(2) in methanol or ethanol. The complexes [Zn(tachpyr)] (ClO4)(2) . CH3OH (1 . CH3OH), [Cd(tachpyr)] (ClO4)(2) (2) and [Hg(tachpyr)] (ClO4)(2) (3) have been isolated. and their solid state structures have been determined and analyzed. The coordination sphere changes from octahedral to trigonal-prismatic geometry with increasing metal radius. The trigonal twist angles (alpha) are 43.7(2)degrees in compound 1 . CH3OH, range between 11.0(4)degrees and 21.7(2)degrees in compound 2 and range between 3.1 (3)degrees and 5.5(2)degrees in compound 3. To accommodate larger metal ions there is also a slight outward expansion of the triaminocyclohexane nitrogens, which leads to a reduction in the average cyclohexyl ring C-C-C-C torsion angles (beta) with concomitant flattening of the ring. The torsion angles (beta) in 1 . CH3OH are 52.3(6)degrees and 52.4(6)degrees, range between 46.1(9)degrees and 52.7(9)degrees in compound 2 and range between 45.1 (6)degrees and 52.9(7)degrees in compound 3. (C) 2000 Elsevier Science Ltd All rights reserved.

  DOI：

  10.1016/s0277-5387(00)00380-6
• 作为产物：
  描述：

  cis,cis-1,3,5-triaminocyclohexane 在 sodium hydroxide 、 sodium tetrahydroborate 作用下， 以 水 、 苯 为溶剂， 生成 1,3,5-Cyclohexanetriamine, N,N',N"-tris(2-pyridinylmethyl)-, (1.α.,3.α.,5.α.)-
  参考文献：
  名称：

  An improved synthesis of cis,cis-1,3,5-triaminocyclohexane. Synthesis of novel hexadentate ligand derivatives for the preparation of gallium radiopharmaceuticals

  摘要：

  An improved synthesis of cis,cis-1,3,5-triaminocyclohexane in 82% yield involves reaction of the commercially available cis,cis-1,3,5-cyclohexanetricarboxylic acid with DPPA to afford the tri(benzylcarbamate) as the Curtius rearrangement product Deprotection yields the triamine which serves as a platform from which a variety of chelating structures may be assembled. Novel tris(2-methylenepyridyl)triamine and tris(2-methylenethienyl)triamine ligands are prepared to investigate their suitability for use as gallium radiopharmaceuticals.

  DOI：

  10.1016/0960-894x(96)00110-2

文献信息

• Steric effects caused by N-alkylation of the tripodal chelator N,N′,N″-tris(2-pyridylmethyl)-cis,cis-1,3,5-triaminocyclohexane (tachpyr): structural and electronic properties of the Mn(ii), Co(ii), Ni(ii), Cu(ii) and Zn(ii) complexes
  作者：Gyungse Park、Ann M. Przyborowska、Neng Ye、Nicole M. Tsoupas、Cary B. Bauer、Grant A. Broker、Robin D. Rogers、Martin W. Brechbiel、Roy P. Planalp

  DOI：10.1039/b209228j

  日期：2003.1.29

  demonstrate weakened bonding in the complexes of (N–R)3tachpyr relative to tachpyr, due to steric effects of methyl or ethyl groups on coordinated tach amines. Structures of [Zn(tachpyr)]2+ and [Ni(tachpyr)]2+ indicate a clear preference of tachpyr and derivatives for octahedral geometry, while [Cu((N–Me)3tachpyr)]2+ exhibits a classic Jahn–Teller tetragonal distortion. The complex [Mn(tachpyr)](ClO4)2 demonstrates

  位阻对锰（Ⅱ），钴（Ⅱ），镍（Ⅱ），铜（Ⅱ）和锌（Ⅱ）络合的影响。螯合剂 基于 顺式，顺式-1,3,5-三氨基环己烷（tach）已被研究。这螯合剂研究是转速的2-甲基吡啶基侧基臂衍生物，“tachpyr”（Ñ，Ñ '，Ñ “ -三（2-吡啶基甲基） -顺式，顺式-1,3,5-三氨基），并且Ñ烷基化类似物'（N-Me）的3 tachpyr'（ñ，ñ '，ñ “ -三甲基- ñ，ñ '，ñ ” -三（2-吡啶基甲基） -顺式，顺式-1,3,5-三氨基）和' （N–Et）3 tachpyr'（N，N '，N ''-三乙基-N，N′，N ″-三（2-吡啶基甲基）-顺式，顺式-1,3,5-三氨基环己烷）。六配位络合物[M II L] X 2是由适当的金属离子盐与L在酒精介质中反应生成的（M = Mn，Co，Ni，Cu，Zn； L = tachpyr，（N–Me）3 tachpyr，（的N- ET）3
• Pyridine‐Ring Alkylation of Cytotoxic <i>r</i> ‐1, <i>c</i> ‐3, <i>c</i> ‐5‐Tris[(2‐pyridylmethyl)amino]cyclohexane Chelators: Structural and Electronic Properties of the Mn ^II , Fe ^II , Ni ^II , Cu ^II and Zn ^II Complexes
  作者：Matt L. Childers、Fan Su、Ann M. Przyborowska、Bimjhana Bishwokarma、Gyungse Park、Martin W. Brechbiel、Suzy V. Torti、Frank M. Torti、Grant Broker、Jacob S. Alexander、Robin D. Rogers、Karin Ruhlandt‐Senge、Roy P. Planalp

  DOI：10.1002/ejic.200500382

  日期：2005.10

  AbstractEffects of pyridyl‐ring alkylation on complexation of MnII, FeII, NiII, CuII and ZnII by chelators based on r‐1,c‐3,c‐5‐triaminocyclohexane (tach) have been studied. The chelators studied are N,N′,N′′‐tris[(x‐alkyl‐2‐pyridyl)methyl] derivatives of tach, where the ring substituents are 3‐Me, 4‐Me, 5‐Me, 6‐Me or 6‐MeO (“tach‐x‐Rpyr”). Dicationic complexes were synthesized for most combinations of the above five metals and five chelators, using ClO4−, NO3−, Cl−, or CF3SO3− as counterions. Their bonding, structure, and aqueous lability were analyzed by UV/Vis/NIR spectroscopy, magnetic moment determination, HPLC, and single‐crystal X‐ray crystallography. The striking features are seen in the 6‐alkylated complexes, where steric repulsions between the 6‐substituents at the threefold axis of the pseudo‐octahedral coordination sphere result in a substantially weakened metal–ligand interaction. In the [M(tach‐6‐Rpyr)]2+ series of divalent Mn, Ni, Cu and Zn, effects of these repulsions include bond angle and length distortions, decrease of the coordination number to five, shifts of d‐d electronic transitions to lower energies, and spin‐free complexes of the bound metal ion. Aqueous lability studies by HPLC agree with the spectroscopic findings. The bonding properties of the other tach‐x‐Mepyr chelators (x = 3, 4, 5) closely resemble the unalkylated parent tachpyr in solution. Similarly in the X‐ray studies, [Zn(tach‐3‐Mepyr)]2+ resembles [Zn(tachpyr)]2+. The cytotoxicities of the chelators toward human breast cancer cells (MCF7) at a fixed chelator concentration of 16 µM show time‐dependent induction of cell death in the order tach‐3‐Mepyr >≈ tach‐4‐Mepyr > tach‐5‐Mepyr > tachpyr, whereas tach‐6‐Mepyr and tach‐6‐MeOpyr had no effect on the cells. The depressed cytotoxicities of the latter two are attributed to inability to bind FeII or ZnII strongly. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Effect of metal size on coordination geometry of N,N′,N″-tris(2-pyridylmethyl)-cis,cis-1,3,5-triaminocyclohexane: synthesis and structure of [MIIL](ClO4)2 (M=Zn, Cd and Hg)
  作者：G Park、N Ye、R.D Rogers、M.W Brechbiel、R.P Planalp

  DOI：10.1016/s0277-5387(00)00380-6

  日期：2000.5

  The hexadentate ligand N,N',N'-tris(2-pyridylmethyl)-cis,cis-1,3,5-triaminocyclohexane (tachpyr) forms stable metal complexes from the salts M(ClO4)(2) . 6H(2)O (M = Zn2+ and Cd2+) and Hg(ClO4)(2) in methanol or ethanol. The complexes [Zn(tachpyr)] (ClO4)(2) . CH3OH (1 . CH3OH), [Cd(tachpyr)] (ClO4)(2) (2) and [Hg(tachpyr)] (ClO4)(2) (3) have been isolated. and their solid state structures have been determined and analyzed. The coordination sphere changes from octahedral to trigonal-prismatic geometry with increasing metal radius. The trigonal twist angles (alpha) are 43.7(2)degrees in compound 1 . CH3OH, range between 11.0(4)degrees and 21.7(2)degrees in compound 2 and range between 3.1 (3)degrees and 5.5(2)degrees in compound 3. To accommodate larger metal ions there is also a slight outward expansion of the triaminocyclohexane nitrogens, which leads to a reduction in the average cyclohexyl ring C-C-C-C torsion angles (beta) with concomitant flattening of the ring. The torsion angles (beta) in 1 . CH3OH are 52.3(6)degrees and 52.4(6)degrees, range between 46.1(9)degrees and 52.7(9)degrees in compound 2 and range between 45.1 (6)degrees and 52.9(7)degrees in compound 3. (C) 2000 Elsevier Science Ltd All rights reserved.
• Hilfiker, Kerry A.; Brechbiel, Martin W.; Rogers, Robin D., Inorganic Chemistry, 1997, vol. 36, p. 4600 - 4603
  作者：Hilfiker, Kerry A.、Brechbiel, Martin W.、Rogers, Robin D.、Planalp, Roy P.

  DOI：——

  日期：——
• An improved synthesis of cis,cis-1,3,5-triaminocyclohexane. Synthesis of novel hexadentate ligand derivatives for the preparation of gallium radiopharmaceuticals
  作者：Tom Bowen、Roy P. Planalp、Martin W. Brechbiel

  DOI：10.1016/0960-894x(96)00110-2

  日期：1996.4

  An improved synthesis of cis,cis-1,3,5-triaminocyclohexane in 82% yield involves reaction of the commercially available cis,cis-1,3,5-cyclohexanetricarboxylic acid with DPPA to afford the tri(benzylcarbamate) as the Curtius rearrangement product Deprotection yields the triamine which serves as a platform from which a variety of chelating structures may be assembled. Novel tris(2-methylenepyridyl)triamine and tris(2-methylenethienyl)triamine ligands are prepared to investigate their suitability for use as gallium radiopharmaceuticals.