N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-propanediamine | 142177-95-5

• 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: N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-propanediamine
• 英文别名: N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-propylenediamine；N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-diaminopropane；N,N,N',N'-tetrakis(2-pyridylmethyl)propylenediamine；N,N,N',N'-tetrakis(2-pyridylmethyl)-(R,S)-propylenediamine；tetrakis(2-pyridylmethyl)-1,2-propylenediamine；tppn；N~1~,N~1~,N~2~,N~2~-Tetrakis[(pyridin-2-yl)methyl]propane-1,2-diamine；1-N,1-N,2-N,2-N-tetrakis(pyridin-2-ylmethyl)propane-1,2-diamine
• CAS: 142177-95-5
• 化学式: C₂₇H₃₀N₆
• 分子量: 438.575
• InChiKey: AFOZQFFQJIQFBV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  33
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  58
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  nickel(II) perchlorate hexahydrate 、 N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-propanediamine 以 甲醇 为溶剂， 以80%的产率得到[Ni(N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-diaminopropane)](ClO4)2
  参考文献：
  名称：

  Mercaptoethanesulfonic acid studies with nickel(II) complexes of tetra- and hexadentate ligands containing pyridyl groups: synthesis, structure, spectra and redox behavior

  摘要：

  Nickel(II)complexes of N,N,N'N'-tetrakis(2-pyridylmethyl)ethylenediamine (L-1), N,N,N'N'-tetrakis(2-pyridylmethyl)-1,2-diaminopropane (L-2), N,N,N'N'-tetrakis(2-pyridylmethyl)-1,3-diaminopropane (L-3), N,N'-bis(2-pyridylmethyl)ethylenediamine (L-4), N,N'-bis(2-pyridylmethyl)-1,2-diaminopropane (L-5) and N,N'-bis(2-pyridylmethyl)-1,3-diaminopropane (L-6) were prepared and their spectroscopic and redox behaviors studied. The distorted octahedral geometry was determined for [NiL2](ClO4)2 by using Xray crystallography. The electronic spectral bands ((3)A(2g) --> T-3(2g) and (3)A(2g) --> E-1(g) transitions) of NiN6 and NiN4O2 were analyzed; it shows that the former complexes possess well-resolved bands compared to the latter compounds. In addition, the ligand field parameter Dq found for NiN4O2 complexes was much lower than that of NiN6 compounds; thereby, a more positive redox potential was detected for NiN4O2 complexes in electrochemistry over the NiN6 compounds. Further, the coordination studies of 2-mercaptoethanesulfonic acid as a simulator of coenzyme M reductase (CoM) with NiN4 or NiN6 chromophores were discussed. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01194-5
• 作为产物：
  描述：

  2-氯甲基吡啶盐酸盐 、 1,2-丙二胺 在 sodium hydroxide 、 十六烷基三甲基氯化铵 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 24.0h， 以77%的产率得到N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-propanediamine
  参考文献：
  名称：

  Convenient Synthesis ofN,N,N′,N′-Tetrakis (2-pyridylmethyl)-α,ω-alkanediamines Using a Phase-Transfer Catalyst

  摘要：

  在十六烷基三甲基氯化铵作为相转移催化剂的存在下，用 2-(氯甲基)氯化吡啶鎓对 δ、Ï-烷二胺及其 N,N′-二取代衍生物进行烷基化反应，可以方便地得到相应的 N,N,N′,N′-四(2-吡啶基甲基)-δ、Ï-烷二胺，收率良好。 同样也得到了 N,N′-双（2-吡啶基甲基）-N,N′-双（2-噻吩基甲基）-1,2-乙二胺。

  DOI：

  10.1055/s-1992-26157

文献信息

• Chiral Distortion of Di(μ-sulfido)bis[oxomolybdenum(V)] Complexes of a Hexadentate Ligand<i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-Tetrakis(2-pyridylmethyl)-<i>R</i>-propylenediamine and Its Analogs
  作者：Hai-Ying Jin、Ryoichi Hazama、Mikio Yamasaki、Keisuke Umakoshi、Kiyoshi Tsuge、Yoichi Sasaki

  DOI：10.1246/bcsj.78.2161

  日期：2005.12

  Chiral distortion of the basal four pyridyl nitrogen donors of the titled complex [Mo 2 (O) 2 (μ-S) 2 μ-N,N,N',N'-tetrakis(2-pyridylmethyl)-R-propylenediamine}] 2 + has been found to be the reverse to that of the corresponding di-μ-oxo complex, on the basis of the inverse pattern of the circular dichroism spectra. Asymmetric distortion of the dimolybdenum(III) dimer [Mo 2 (μ-OH) 2 (μ--CH3COO)μ-N

  标题复合物 [Mo 2 (O) 2 (μ-S) 2 μ-N,N,N',N'-tetrakis(2-pyridylmethyl)-R-丙二胺} 的基础四个吡啶基氮供体的手性畸变] 2 + 已被发现与相应的 di-μ-oxo 配合物的相反，基于圆二色光谱的逆模式。二钼(III)二聚体[Mo 2 (μ-OH) 2 (μ--CH3COO)μ-N,N,N',N'-四(2-吡啶基甲基)乙二胺}] 3 + 的不对称畸变也有进行了讨论。
• Hazama, Ryoichi; Umakoshi, Keisuke; Ichimura, Akio, Bulletin of the Chemical Society of Japan, 1995, vol. 68, p. 456 - 468
  作者：Hazama, Ryoichi、Umakoshi, Keisuke、Ichimura, Akio、Ikari, Shinji、Sasaki, Yoichi、et al.

  DOI：——

  日期：——
• McCusker, James K.; Walda, Kevin N.; Magde, Douglas, Inorganic Chemistry, 1993, vol. 32, # 4, p. 394 - 399
  作者：McCusker, James K.、Walda, Kevin N.、Magde, Douglas、Hendrickson, David N.

  DOI：——

  日期：——
• Variable-Temperature Studies of Laser-Initiated ⁵T₂ → ¹A₁ Intersystem Crossing in Spin-Crossover Complexes:  Empirical Correlations between Activation Parameters and Ligand Structure in a Series of Polypyridyl Ferrous Complexes
  作者：James K. McCusker、Arnold L. Rheingold、David N. Hendrickson

  DOI：10.1021/ic9507880

  日期：1996.1.1

  Results are presented from a variable-temperature solution-phase laser photolysis study of the T-5(2) --> (1)A(1) intersystem crossing in a series of related complexes: [Fe(tpen)](ClO4)(2), [Fe(tppn)](ClO4)(2), [Fe(tptn)](ClO4)(2), [Fe(t-tpchxn)](ClO4)(2), and [Fe(dpa)(2)](ClO4)(2). The hexadentate ligands are formed with four 2-pyridylmethyl arms attached to ethylenediamine (tpen), 1,2-diaminopropylene (tppn), 1,3-diaminopropylene (tptn), or trans-1,2-diaminocyclohexane (t-tpchxn). The dpa ligand is a tridentate analogue of these ligands, namely, bis(2-pyridylmethyl)amine. The complex [Fe(mtpen)](ClO4)(2) .(2)/(3) H2O, where mtpen is the same as tpen except one of the pyridyl rings has a 6-methyl substituent, crystallizes in the space group C2/c, which at 173 K has a unit cell with a = 41.390(13) Angstrom, b = 9.5239(16) Angstrom, c = 24.016(6) Angstrom, beta = 108.24(3)degrees, and Z = 12, Refinement with 2844 observed [F > 5.0 sigma(F)] reflections gave R = 0.075 and R(w) = 0.076. The complex [Fe(tppn)](ClO4)(2) .(2)/3H2O crystallizes in the space group P2(1)/n, which at 296 K has a unit cell with a = 12.979(4) Angstrom, b = 12.624(4) Angstrom, c = 19.475(6) Angstrom, beta = 108.17(2)degrees, and Z = 4. Refinement with 2357 observed [F > 5.0 sigma(F)] reflections gave R = 0.1198 and R(w) = 0.1141. The mtpen complex is a high-spin Fe-II complex at all temperatures (4.2-400 K). The hydrated tpen complex is a spin-crossover complex with the temperature where there are 50% high-spin complexes (T-1/2) is similar or equal to 385 K, the hydrated tppn complex is also spin-crossover with a higher T-1/2 value, and the hydrated tptn complex is low spin up to 400 K. The present crystallographic results, together with previously reported structural results for the tpen complex at two temperatures, are used to show that the conversion from low spin to high spin leads to an increase in the trigonal twist of these distorted octahedral complexes. The influence of this variation in trigonal twist on the rate of T-5(2) --> (1)A(1) intersystem crossing is examined with variable-temperature laser-flash photolysis. Data collected for the tpen complex in MeOH in the 190-294 K range give a linear Arrhenius plot with an activation energy of E(a) = 767 +/- 22 cm(-1) and a preexponential term of A = (1.35 +/- 0.2) x 10(9) s(-1). The tppn complex gives similar results of E(a) = 771 +/- 17 cm(-1) and A = (1.45 +/- 0.2) x 10(9) s(-1). At 294 K the rate (k(-1)) for the T-5(2) --> (1)A(1) intersystem crossing is 2.87 x 10(7) s(-1) for the tpen complex, and 3.21 x 10(7) s(-1) for the tppn complex. On the other hand the tptn complex has k(-1) = 6.25 x 10(8) s(-1) at 295 K as measured with a picosecond spectrometer, and together with nanosecond data measured in the 186-210 K range gives an Arrhenius activation energy of E(a) = 777 +/- 50 cm(-1) with A = (2.6 +/- 0.8) x 10(10) s(-1). The bis(tridentate) complex [Fe(dpa)(2)](ClO4)(2) in MeOH is found to give k(-1) = 4.59 x 10(7) s(-1) at 282 K and with the 191-282 K data gives Arrhenius values of E(a) = 339 +/- 13 cm(-1) and A = (2.5 +/- 0.25) x 10(8) s(-1). The terpyridine complex [Fe(terpy)(2)](ClO4)(2) is found to have k(-1) = 1.0 x 10(8) s(-1) in MeOH at 239 K, and the analysis of 190-239 K data gives E(a) = 532 +/- 36 cm(-1) and A = (2.4 +/- 0.4) x 10(9) s(-1). Previous studies have shown that the greater the trigonal twist, the lower in energy is the T-3(1) state which facilitates the spin-orbit interaction between the T-5(2) high-spin and (1)A(1) low-spin states. It is suggested that the trigonal twist is a vibrational coordinate strongly coupled to the T-5(2) --> (1)A(1) intersystem crossing. It is additionally shown that the data are consistent with a model wherein the ''intrinsic'' rate of T-5(2) --> (1)A(1) intersystem crossing, as gauged by the preexponential term, is a function of how far along the reaction coordinate a complex proceeds.
• Convenient Synthesis of<i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-Tetrakis (2-pyridylmethyl)-α,ω-alkanediamines Using a Phase-Transfer Catalyst
  作者：Masaru Sato、Yutaka Mori、Takeaki Iida

  DOI：10.1055/s-1992-26157

  日期：——

  Alkylation of α,ω-alkanediamines and their N,N′-disubstituted derivatives with 2-(chloromethyl)pyridinium chloride in the presence of hexadecyltrimethylammonium chloride as a phase-transfer catalyst gave conveniently the corresponding N,N,N′,N′-tetrakis (2-pyridylmethyl)-α,ω-alkanediamines in good yields. N,N′-Bis(2-pyridylmethyl)-N,N′-bis (2-thienylmethyl)-1,2-ethanediamine was similarly obtained.

  在十六烷基三甲基氯化铵作为相转移催化剂的存在下，用 2-(氯甲基)氯化吡啶鎓对 δ、Ï-烷二胺及其 N,N′-二取代衍生物进行烷基化反应，可以方便地得到相应的 N,N,N′,N′-四(2-吡啶基甲基)-δ、Ï-烷二胺，收率良好。 同样也得到了 N,N′-双（2-吡啶基甲基）-N,N′-双（2-噻吩基甲基）-1,2-乙二胺。