meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane
• 英文别名: 7R,14R-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane；R,R-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane；(7R,14R)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetrazacyclotetradecane
• 化学式: C₁₆H₃₆N₄
• 分子量: 284.489
• InChiKey: XHCNINMOALIGKM-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  48.1
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,3-二碘丙烷 、 meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane 在 sodium carbonate 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 72.0h， 生成 meso-5,5,7,12,12,14-hexamethyl-1,8-diazonia-4,11-diazabicyclo[9.3.3]heptadecane chloride iodide
  参考文献：
  名称：

  A cyclam-like macrocycle side-bridged by a propyl chain

  摘要：

  The preparation and crystal structure of meso-5,5,7,12, 12,14-hexamethyl-1,8-diazonia-4,11-diazabicyclo[9.3.3]heptadecane chloride iodide 0.5-diethyl ether solvate, C19H42N42+. Cl-. I- . 0.5C(4)H(10)O, are described. The 14-membered macrocycle has an extended conformation with the -(CH2)(3)- bridge to one side. It contains two N-H ... Cl hydrogen bonds.

  DOI：

  10.1107/s0108270199011038
• 作为产物：
  描述：

  在 sodium tetrahydroborate 、 sodium hydroxide 作用下， 生成 meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane 、 meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane
  参考文献：
  名称：

  异构六甲基四氮杂氮杂环配体的N-齿双-（氰乙基）衍生物的铜（II）和镍（II）配合物：合成，表征，电解行为和抗菌研究

  摘要：

  摘要通过乙二胺与丙酮在定量高氯酸存在下的缩合反应，合成了十四元四氮杂大环的六甲基衍生物盐Me6 [14]二烯.2HClO4（L.2HClO4）。该二烯配体盐经NaBH4还原后，在pH高于12的条件下用CHCl3萃取，得到异构体配体Me6 [14]烷的混合物，通过分步结晶从二甲苯中分离出该混合物，并命名为'tet-a'和'tet- b'。'tet-b'与过量的丙烯腈的相互作用产生了一个N-pendent衍生物'tet-bx'，其中两个氰基乙基连接在较少拥挤的两个反式N原子上。乙酸镍（II）四水合物和高氯酸铜（II）六水合物与'tet-bx'的相互作用，随后添加NaClO4。在镍（II）产生方形橙色橙色[Ni（'tet-bx'）]（ClO4）2和六配位八面体红紫色[Cu（'tet-bx']（ClO4）2]络合物的情况下，6H2O和HClO4 。在[Ni（'tet-bx'）]（ClO4）2上与N

  DOI：

  10.1016/j.ica.2020.120172

文献信息

• Lewis-Base Adducts of Lead(II) Compounds. X. Synthetic and Structural Studies of Some 1:1 Adducts of 'tet-b' With Lead(II) (Pseudo-)Halides
  作者：JM Harrowfield、H Miyamae、BW Skelton、AA Soudi、AH White

  DOI：10.1071/ch9961067

  日期：——

  Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 1 : 1 adducts of (7R*,14R*)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (' tet -b') with a variety of lead(II) salts. [( tet -b)PbCl2] is monoclinic, P 21/c, a 7.183(3), b 12.425(2), c 24.418(2) Ǻ, β 95.32(3)°, Z = 4; conventional R on |F| was 0.044 for 3188 independent, 'observed' (I > 3σ(I)) reflections. [( tet -b)PbI2] is monoclinic, P 21/c, a 19.920(5), b 7.772(5), c 15.605(6) Ǻ, β 108.39(2)°, Z = 4; R 0.051 for No 2507. [( tet -b) Pb (NCS)2] is orthorhombic, P 212121, a 36.99(1), b 8.996(5), c 6.964(3) Ǻ, Z = 4; R 0.043 for No 2100. All are discrete mononuclear [( tet -b)PbX2] entities in which the macrocyclic N4 ligand occupies one 'face' of the N4PbX2 coordination sphere, the thiocyanate ligands being N-bonded, with Pb -N-C angles of 116(2) and 118(1)°; interesting hydrogen-bonding interactions are found, columns of molecules being formed by way of hydrogen bonding between the coordinated (pseudo-)halides and the NH hydrogen atoms which project to the 'rear' face of the ligand of the next molecule, opposite the metal. In contrast to these, the bromide analogue, monoclinic, P21, a 9.342(3), b 12.720(5), c 18.845(5) Ǻ, β 103.17(2)°, Z = 4, R 0.035 for No 3593, is best formulated as [( tet -b) PbBr ] Br, one only of the bromide entities being bound to the lead, the other being fully dissociated by hydrogen bonding/ion pairing to the 'rear' side of adjacent ligands , forming hydrogen-bonded sheets rather than columns. This formulation has been extended to provide a description of an analogous mixed chloride- perchlorate 'double salt', [( tet -b) PbCl ] (ClO4).CH3OH, which is orthorhombic, P 212121, a 19.475(2), b 18.73(1), c 6.820(2) Ǻ, Z = 4, R 0.054 for No 3075. However, another double salt, modelled in refinement as Pb ( tet -b)Cl0.5(ClO4)1.5.H2O, orthorhombic Pnma , a 20.640(5), b 26.16(1), c 8.937(4) Ǻ, Z = 4 dimers , R 0.074 for No 1769, is in this case more appropriately described as [( tet -b) Pb (OClO2O)2Pb( tet -b)] (ClO4) Cl.H2O with perchlorate rather than halide coordinated, and an incipiently dimeric cation, as in the parent [( tet -b) Pb (OClO3)]2 (ClO4)2.2H2O.

  记录了 (7R*,14R*)-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷（"tet -b"）与多种铅（II）盐的 1 : 1 加合物的合成和室温单晶 X 射线结构测定。[( tet -b)PbCl2] 呈单斜，P 21/c，a 7.183(3)，b 12.425(2)，c 24.418(2)Ǻ，β 95.32(3)°，Z = 4；对于 3188 个独立的 "观察到的"（I > 3σ(I)）反射，|F|上的常规 R 值为 0.044。[( tet -b)PbI2] 呈单斜，P 21/c，a 19.920(5)，b 7.772(5)，c 15.605(6)Ǻ，β 108.39(2)°，Z = 4；No 2507 的 R 值为 0.051。[Pb (NCS)2] 为正方体，P 212121，a 36.99(1)，b 8.996(5)，c 6.964(3)Ǻ，Z = 4；No 2100 的 R 值为 0.043。所有这些都是离散的单核 [( tet -b)PbX2] 实体，其中大环 N4 配体占据 N4PbX2 配位层的一个 "面"，硫氰酸配体以 N 键相连，Pb -N-C 角分别为 116(2) 和 118(1)°；发现了有趣的氢键相互作用，配位的（假）卤化物和 NH 氢原子之间通过氢键形成分子列，NH 氢原子突出到下一个分子配体的 "后 "面，与金属相对。与此相反，溴化物类似物，单斜，P21，a 9.342(3)，b 12.720(5)，c 18.845(5)Ǻ，β 103.17(2)°，Z = 4，R 0.035 表示 No 3593，最好表述为 [( tet -b) PbBr ] Br，其中只有一个溴实体与铅结合，另一个通过氢键/离子配对完全解离到相邻配体的 "后 "面，形成氢键片而不是柱。这一公式已被扩展用于描述一种类似的氯-高氯酸盐混合 "双盐"，即[( tet -b) PbCl ] (ClO4).CH3OH，它是正方体，P 212121，a 19.475(2)，b 18.73(1)，c 6.820(2)Ǻ，Z = 4，R 0.054（No 3075）。然而，另一种双盐在细化过程中被模拟为 Pb ( tet -b)Cl0.5(ClO4)1.5.H2O, orthorhombic Pnma , a 20.640(5), b 26.16(1), c 8.937(4) Ǻ, Z = 4 二甲基，R 0.074 表示 No 1769，在这种情况下，将其描述为[( tet -b) Pb (OClO2O)2Pb( tet -b)] (ClO4) Cl.H2O 更为恰当，因为它配位的是高氯酸盐而不是卤化物，并且与母体中的[( tet -b) Pb (OClO3)]2 (ClO4)2.2H2O 一样，是一个初生二聚阳离子。
• Lewis-Base Adducts of Lead(II) Compounds. IX. Synthetic and Structural Studies of Some 1:1 Adducts of 'cyclam' and Its Hexamethylated Derivative 'tet-b' With Lead(II) Oxoanion Salts
  作者：JM Harrowfield、H Miyamae、TM Shand、BW Skelton、AA Soudi、AH White

  DOI：10.1071/ch9961051

  日期：——

  Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 1 : 1 adducts of (1,4,8,11-tetraazacyclotetradecane) ('cyclam') with lead(II) perchlorate and (7R*,14R*)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ('tet -b') with lead(II) nitrate, perchlorate and acetate ('ac'). [( cyclam ) Pb (ClO4)2] is orthorhombic, Pb21a, a 16.024(7), b 13.595(4), c 8.6810(5) Ǻ, Z = 4 f.u .; R was 0.055 for No 1318 independent 'observed' (I > 3σ(I)) reflections. [( tet -b) Pb (NO3)2]2 is monoclinic. P 21/a, a 16.15(2), b 14.550(6), c 19.775(2) Ǻ, β 90.86(5)°, Z = 4 dimers ; R 0.074 for No 3184. [( tet -b) Pb (ClO4)2]2.H2O is monoclinic, P 21/c, a 13.663(9), b 9.031(3). c 20.61(1) Ǻ, β 100.40(3)°, Z = 4 f.u .; R 0.044 for No 2857. [( tet -b) Pb (ac)2].2H2O is triclinic, Pī , a 13.138(5), b 10.924(4), c 10.518(3) Ǻ, α 115.48(3), β 91.95(2), γ 102.38(2)°, Z = 2 f.u .; R 0.031 for No 6485. In all complexes, the macrocycle-N4 ligand occupies one 'side' of the coordination sphere of the lead atom, with anionic oxygens opposed; the cyclam/perchlorate complex is, like the nitrate, mononuclear with seven-coordinate (N4)PbO3 with a bidentate O,O'- and a unidentate O- perchlorate . In the tet-b acetate, the anionic oxygen atoms are surprisingly sparse, comprising simply a bidentate acetate in a mononuclear (N4)PbO2 environment with the other (lattice) acetate bonded to the macrocycle axial NH hydrogens . The nitrate and perchlorate complexes involve bridging anions: in the nitrate. a central centrosymmetric PbO2Pb array is found, the lead atoms being bridged by one oxygen of a bidentate nitrate, the other nitrate being unidentate and the coordination sphere (N4)PbO4: in the perchlorate , again a centrosymmetric dimer is found, the lead atoms being linked by O,O'-bridging perchlorates (again with (N4)PbO2 coordination environments), the complex being essentially [( tet -b) Pb (OClO2O)2Pb( tet -b)](ClO4)2H2O. The structure of [cyclamH4]4+ (NO3-)4.2H2O is also recorded [triclinic, Pī , a 8.626(2), b 8.549(1), c 8.400(2) Ǻ, α 80.60(2), β 76.62(2), γ 65.06(1)°, Z = 1; R 0.044 for No 1539], together with that of the diprotonated hexamethyl derivative [tet-bH2]2+(ClO4-)2.CH3OH [monoclinic, P21/c, a 11.296(3), b 8.834(8), c 26.22(1) Ǻ, β 99.05(3)°, Z = 4 f.u .; R 0.063 for No 2583].

  记录了 1 ：1,4,8,11-四氮杂环十四烷）（"cyclam"）与高氯酸铅（II）的 1 : 1 加合物，以及(7R*,14R*)-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷（"tet -b"）与硝酸铅（II）、高氯酸铅和醋酸铅（"ac"）的 1 : 1 加合物。[Pb21a, a 16.024(7), b 13.595(4), c 8.6810(5) Ǻ, Z = 4 f.u .[( tet -b) Pb (NO3)2]2 为单斜面。P 21/a, a 16.15(2), b 14.550(6), c 19.775(2) Ǻ, β 90.86(5)°, Z = 4 个二聚体；No 3184 的 R 值为 0.074。[(四-b) Pb (ClO4)2]2.H2O 呈单斜，P 21/c，a 13.663(9)，b 9.031(3)。[( tet -b) Pb (ac)2].2H2O 为三棱体，Pī ，a 13.138(5)，b 10.924(4)，c 10.518(3)Ǻ，α 115.48(3)，β 91.95(2)，γ 102.38(2)°，Z = 2 f.u .；No 6485 的 R 为 0.031。在所有配合物中，大环-N4 配体都占据了铅原子配位层的一个 "边"，阴离子氧原子与之相对；环/高氯酸盐配合物与硝酸盐一样，是单核的七配位 (N4)PbO3，具有双齿 O、O'- 和单齿 O- 高氯酸盐。在四溴醋酸酯中，阴离子氧原子出奇地稀少，仅包括单核 (N4)PbO2 环境中的一个双叉醋酸酯，另一个（晶格）醋酸酯与大循环轴向 NH 氢键结合。硝酸盐和高氯酸盐配合物涉及桥接阴离子：在硝酸盐中，发现了一个中心对称的 PbO2Pb 阵列，铅原子被一个双叉硝酸盐的一个氧桥接，另一个硝酸盐为非同位，配位球为 (N4)PbO4：在高氯酸盐中，同样发现了一个中心对称的二聚体，铅原子被 O、O'桥接的高氯酸盐连接（配位环境同样为 (N4)PbO2 配位环境）连接在一起，复合物本质上是[( tet -b) Pb (OClO2O)2Pb( tet -b)](ClO4)2H2O 。还记录了[cyclamH4]4+ (NO3-)4.2H2O的结构[三棱，Pī ，a 8.626(2)，b 8.549(1)，c 8.400(2) Ǻ，α 80.60(2)，β 76.62(2)，γ 65.06(1)°，Z = 1；R 0.044 for No 1539]，以及二质子化六甲基衍生物 [tet-bH2]2+(ClO4-)2.CH3OH [monoclinic, P21/c, a 11.296(3), b 8.834(8), c 26.22(1) Ǻ, β 99.05(3)°, Z = 4 f.u .］
• Synthesis, characterization and antibacterial studies of zinc(II) complexes with hexamethyl-tetraazacyclotetradecadiene Me6[14]diene and C-chiral isomers of its reduced analogue
  作者：Sabina Yasmin、Saswata Rabi、Foni Bushon Biswas、Tapashi Ghosh Roy、Falk Olbrich、Dieter Rehder

  DOI：10.1007/s10847-017-0693-9

  日期：2017.4

  this diene ligand salt, L·2HClO4 with sodium borohydride, the two isomeric ligands, ‘tet-a’ and ‘tet-b’ were produced. The ligands, on reaction with ZnX2 (X=Cl, ClO4, NO3 or CH3COO) and ZnSO4 produced the corresponding complexes. These complexes have been characterized on the basis of elemental analyses; IR, UV–Vis and 1H-NMR spectroscopies; magnetic and conductance data. Based on these data, all of the

  配体盐 Me6[14]二烯·2HClO4 (L·2HClO4) 是由丙酮和乙二胺在高氯酸存在下缩合制备的。在用硼氢化钠还原这种二烯配体盐 L·2HClO4 时，产生了两种异构配体“tet-a”和“tet-b”。配体与 ZnX2（X=Cl、ClO4、NO3 或 CH3COO）和 ZnSO4 反应生成相应的配合物。这些配合物已在元素分析的基础上进行了表征；IR、UV-Vis 和 1H-NMR 光谱；磁和电导数据。基于这些数据，二烯配体 L 的所有配合物以及所有配体的高氯酸盐配合物都获得了方形锥体排列，而 'tet-a' 和 'tet-b' 的配合物，与X=NO3、Cl 或 CH3COO 和 ZnSO4 盐，呈八面体。而且，所有配合物都是单金属的，除了硝基配合物 [(ZnL)2(µ-NO3)](ClO4)3 是双金属的。[(ZnL)2(μ-NO3)](ClO4)3 的结构已通过 X 射线晶体学证实。在这个复合物中，锌中心位于
• Directional Electron Transfer in Crystals of [CrCo] Dinuclear Complexes Achieved by Chirality-Assisted Preparative Method
  作者：Shinji Kanegawa、Yoshihito Shiota、Soonchul Kang、Kazuyuki Takahashi、Hajime Okajima、Akira Sakamoto、Tatsuya Iwata、Hideki Kandori、Kazunari Yoshizawa、Osamu Sato

  DOI：10.1021/jacs.6b05089

  日期：2016.11.2

  polarization switching in the valence tautomeric compound. Mixing Cr and Co complexes with enantiopure chiral ligands resulted in the selective formation of only pseudosymmetric [CrCo] heterometallic complexes. Furthermore, the left-handed chiral ligands preferentially interacted with their right-handed counterparts, enabling molecules to form a polar crystal structure.

  极化切换机制用于各种设备，例如热释电传感器和存储设备。极化的变化主要通过离子置换发生。开发通过电子转移来切换极化以提高操作速度的材料是一个挑战。我们设计了一种合成和晶体工程策略，能够选择性合成具有极性晶体结构的 [CrCo] 异金属双核配合物，其中极化变化源于 Co 和配体之间的分子内电荷转移。偏振可以通过可见光照射和温度变化来调制。手性配体的引入对于价互变异构化合物中成功的极化转换至关重要。将 Cr 和 Co 配合物与对映纯手性配体混合导致仅选择性形成假对称 [CrCo] 异金属配合物。此外，左手手性配体优先与其右手手性配体相互作用，使分子能够形成极性晶体结构。
• Palladium complexes with hexamethyl tetraazacyclotetradecadiene (L) and isomers of its reduced form (‘tet-a’ & ‘tet-b’): synthesis, characterization and antimicrobial studies
  作者：Shawon Barua、Saswata Rabi、Anup Kumar Datta、Eshita Debanath、Ratul Kumar Shil、Tapashi Ghosh Roy

  DOI：10.1007/s10847-016-0667-3

  日期：2016.12

  complex of isomeric ligands [PdL′][PdCl4] underwent substitution reactions with KCNS and KNO2 to form tetrathiocyanato dipalladium(II) and tetranitrodipalladium(II) complexes, [PdL′][Pd(NCS)4] and [PdL′][Pd(NO2)4] respectively. However the same tetrachloro complexes underwent axial addition reactions with KBr and KI to form dibromidopalladium(IV) dibromide and diiodidopalladium(IV) diiodide complexes

  六甲基四氮杂环十四二烯二氢高氯酸Me6[14]二烯。2HClO4 (L·2HClO4) 还原产生两种异构的C-手性配体“tet-a”和“tet-b”。这些异构配体与 PdCl2 的反应产生方形平面四氯二钯 (II) 复合物，[PdL'][PdCl4]（L' = 'tet-a' 或 'tet-b'）。L·2HClO4 与不同钯(II) 盐、K2Pd(SCN)4、K2PdBr4 和K2PdI4 的类似反应生成八面体钯(IV) 硫氰酸盐、溴化物和碘化物配合物。异构配体的四氯二钯(II)配合物[PdL'][PdCl4]与KCNS和KNO2发生取代反应，形成四硫氰酸根合二钯(II)和四硝基二钯(II)配合物[PdL'][Pd(NCS)4]和[PdL] '][Pd(NO2)4]。然而，相同的四氯配合物与 KBr 和 KI 发生轴向加成反应，分别形成二溴化二溴化钯 (IV) 和二碘化钯 (IV) 配合物，[PdL'][PdBr2]Br2