1-benzyl-4-formyl-1,4,7-triazacyclononane | 112498-58-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-benzyl-4-formyl-1,4,7-triazacyclononane
• 英文别名: 4-Benzyl-1,4,7-triazonane-1-carbaldehyde
• CAS: 112498-58-5
• 化学式: C₁₄H₂₁N₃O
• 分子量: 247.34
• InChiKey: MNAGPTXMJUMNJY-UHFFFAOYSA-N

物化性质

• 沸点：
  413.9±40.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  35.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-benzyl-4-formyl-1,4,7-triazacyclononane 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 生成 1-benzyl-4-(2-hydroxy-2-methylpropyl)-1,4,7-triazacyclononane
  参考文献：
  名称：

  Stacked amido macrocyclic complexes: synthesis and single crystal X-ray structure of Na[Cu(L)(NCMe)](BF₄)₂(NO₃)[L = 1-formyl-4,7-bis(2-hydroxy-2-methylpropyl)-1,4,7-triazacyclononane]

  摘要：

  介绍了 [9]aneN3 的双功能衍生物的合成过程；Na[Cu(L)(NCMe)](BF4)2(NO3) 的结构显示了一个中心[Na(BF4)2]-核心，连续的[Cu(L)(NCMe)]2+阳离子的酰胺分子的 O-单体与 Na+ 结合，形成叠层结构。

  DOI：

  10.1039/c39940002467
• 作为产物：
  描述：

  溴甲苯 在 sodium hydroxide 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 27.5h， 生成 1-benzyl-4-formyl-1,4,7-triazacyclononane
  参考文献：
  名称：

  中环三胺的选择性N保护

  摘要：

  1,4,7-三氮杂环壬烷和1,5,9-三氮杂环十二烷的选择性N-保护以及相关双-冠冕的合成的有效方案是基于三环原酰胺的合成中间体。

  DOI：

  10.1039/c39870000886

文献信息

• Selective derivatisation of aza macrocycles
  作者：Alexander J. Blake、Ian A. Fallis、Robert O. Gould、Simon Parsons、Steven A. Ross、Martin Schröder

  DOI：10.1039/dt9960004379

  日期：——

  short Cu–O(16) bond of 1.963(3)Å and one long Cu–O(21) bond of 2.252(3)Å. There is also a sixth longer-range interaction of the copper(II) centre with the amide N [N(1)] of H2L1 at a distance of 2.611(5)Å, confirmed by the loss of planarity of the C(2)–C(9)–N(1)–C(10)–O(11)–H(10) amide fragment to give a dihedral angle between the planes defined by C(2)–C(9)–N(1) and N(1)–C(10)–O(11)–H(10) of 27.1(4)°

  一系列衍生自1,4,7-三氮杂环壬烷（[9] aneN 3）的选择性官能化化合物，包括4,7-双（2-羟基-2-甲基丙基）-1,4,7-三氮杂环壬烷-1-甲醛（H 2 L 1），1-苄基-4,7-双（2-羟基-2-甲基丙基）-1,4,7-三氮杂环壬烷（H 2 L 2）和1,4-双（2-羟基-已经制备了2-甲基丙基）-1,4,7-三氮杂环壬烷（H 2 L 3）。H 2 L 3 ·CHCl 3的结构显示无序的大环环，其主要构象异构体精炼至位点占有率为0.663（8），两个无序环均采用[333]构象。悬垂的醇臂没有紊乱，发现氢键合到CHCl 3溶剂化物分子上，H⋯O（1）和H⋯O（4）的距离分别为1.73和1.81Å。Na [Cu（H 2 L 1）（NCMe）] [BF 4 ] 2 [NO 3 ]的结构显示在[Cu（H 2 L 1）（NCMe）] 2+阳离子结合中的铜（II）中心到H 2 L 1
• Molecular structure and hydrolytic stability amidinium salts derived from triazatricyclo[5.2.1.04,10]decane
  作者：Andrew R. Battle、Leone Spiccia

  DOI：10.1016/j.tet.2005.05.049

  日期：2005.8

  lo[5.2.1.04,10]decane, confirmed that these amidinium salts hydrolyse in aqueous solution, the latter 60 times faster than the former. Tacnoa, which has C–N distances typical of single bonds, showed no evidence of hydrolysis after several days at 80 °C. Molecular modeling calculations indicate that the preferred gas phase structure of the salts is one where the positive charge is delocalised over the

  由三氮杂三环[5.2.1.0 4,10 ]癸烷（tacnoa）制备了五种idi盐，并通过质谱，NMR光谱和X射线晶体学进行了表征。X射线结构显示次甲基碳与铵态氮之间的距离很长，即C–N距离为1.64–1.70Å，比照。其他C–N距离为1.40–1.50Å。1-乙基-4,7-二氮杂-1- azoniatricyclo [5.2.1.0的NMR研究4,10 ]癸烷和1-苄基-4,7-二氮杂-1- azoniatricyclo [5.2.1.0 4,10癸烷，证实这些am盐在水溶液中水解，后者比前者快60倍。Tacnoa具有典型的单键C–N距离，在80°C几天后没有显示水解的迹象。分子模型计算表明，盐的优选气相结构是其中正电荷在两个仲胺和次甲基碳上离域的结构。该碳与铵态氮之间的计算距离比晶体结构长0.15-0.4Å。优选的气相和固态构象之间的能量差为2 kJ mol -1对次甲基碳的亲核攻击几乎
• Synthesis of Novel Derivatives of 1,4,7-Triazacyclononane
  作者：Andrew Warden、Bim Graham、Milton T. W. Hearn、Leone Spiccia

  DOI：10.1021/ol016291d

  日期：2001.9.1

  [GRAPHICS]The coordination environment of 1,4,7-triazacyclononane can be adapted, through sequential functionalization of two secondary amines, to generate ligands applicable in biomimetic studies. Two "amino acids" and an amino derivative have been prepared from 1,4,7-triazatricyclo-[5.2.1.0(4,10)]decane. This synthon allows efficient attachment of one functional group to the macrocyclic ring, forming a monoamidinium salt. Hydrolysis generates a formyl derivative, which was further functionalized at the secondary amino and hydrolyzed in strong acid to generate ligands 1-3.
• Asymmetric functionalisation of aza macrocycles. Syntheses, crystal structures and electrochemistry of [Ni(Bz[9]aneN₃)₂][PF₆]₂and [Pd(Bz[9]aneN₃)₂][PF₆]₂·2MeCN (Bz[9]aneN₃= 1-benzyl-1,4,7-triazacyclononane)
  作者：Alexander J. Blake、Ian A. Fallis、Simon Parsons、Steven A. Ross、Martin Schröder

  DOI：10.1039/dt9960000525

  日期：——

  1-Benzyl-1,4,7-triazacyclononane (Bz[9]aneN(3)) has been prepared and its co-ordination chemistry with Ni-II and Pd-II investigated. The crystal structure Df the complex [Ni(Bz[9]aneN(3))(2)] [PF6](2) revealed Six independent Ni-N distances, affording a distorted-octahedral co-ordination geometry. Four lie in the range 2.089(4)-2.123(4) Angstrom, while the distances to the benzyl amine N-donors are significantly longer at 2.262(4) and 2.251(4) Angstrom. The benzyl amine N-donors occupy adjacent sites at the metal centre affording a syn geometry. Cyclic voltammetry of [Ni(Bz[9]aneN(3))(2)][PF6](2) in MeCN at a platinum electrode showed a reversible Ni-II-Ni-III oxidation at E(1/2) = +0.76 V vs. ferrocene-ferrocenium at 235 K. This process was irreversible at higher temperatures. The ESR spectrum of [Ni(Bz[9]aneN(3))(2)](3) c exhibits an axial signal, with g(parallel to) = 2.03 and g(perpendicular to) = 2.15, consistent with a tetragonally elongated octahedral co-ordination geometry at Ni-III. The crystal structure of [Pd(Bz[9]aneN(3))(2)] [PF6](2) . MeCN revealed the Pd atom on an inversion centre with the ligands bound via two N-donors from each, Pd-N 2.0588(19) and 2.0605(19) A. The benzyl amine N-donors do not interact with the metal centre, Pd ... N 3.402(4) Angstrom. Cyclic voltammetry of [Pd(Bz[9]aneN(3))(2)][PF6](2) in MeCN showed a reversible Pd-II-Pd-III couple at E(1/2) = +0.36 V at 298K. The ESR spectrum of [Pd(Bz[9]aneN(3))(2)](3+) exhibits an axial signal, with g(parallel to) = 2.007 and g(perpendicular to) = 2.117. Superhyperfine coupling (A (parallel to); = 26.9 G) is observed to two N-donors in the axial component consistent with a tetragonally elongated octahedral co-ordination geometry at the Pd-III.
• WEISMAN G. R.; VACHON D. J.; JOHNSON V. B.; GRONBECK D. A., J. CHEM. SOC. CHEM. COMMUN.,(1987) N 12, 886-887
  作者：WEISMAN G. R.、 VACHON D. J.、 JOHNSON V. B.、 GRONBECK D. A.

  DOI：——

  日期：——