N,N-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine | 351415-87-7

• 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-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine
• 英文别名: N,N-bis(6-neopentylamino-2-pyridylmethyl)-N-(2-pyridylmethyl)amine；bis[(6-neopentylaminopyridin-2-yl)methyl](pyridin-2-ylmethyl)amine；bis((6-(neopentylamino)-2-pyridyl)methyl)(2-pyridylmethyl)amine；bis[(6-neopentylamino-2-pyridyl)methyl][(2-pyridyl)methyl]amine；N(CH2Py)(CH2Py-6-NHCH2(t)Bu)2；bnpapa；N-(2,2-dimethylpropyl)-6-[[[6-(2,2-dimethylpropylamino)pyridin-2-yl]methyl-(pyridin-2-ylmethyl)amino]methyl]pyridin-2-amine
• CAS: 351415-87-7
• 化学式: C₂₈H₄₀N₆
• 分子量: 460.666
• InChiKey: VMPQFHSUSRLJFV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  34
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  66
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  N,N-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine 以 甲醇 、 氘代乙腈 、 水 为溶剂， 生成 [(N,N-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine-d2)Ni(formato)]ClO4
  参考文献：
  名称：

  Carboxylate Coordination Chemistry of a Mononuclear Ni(II) Center in a Hydrophobic or Hydrogen Bond Donor Secondary Environment:  Relevance to Acireductone Dioxygenase

  摘要：

  A series of Ni(II) carboxylate complexes, supported by a chelate ligand having either secondary hydrophobic phenyl groups (6-Ph(2)TPA, N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine) or hydrogen bond donors (bnpapa, N,N-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine), have been prepared and characterized. X-ray crystallographic studies of [(6-Ph(2)TPA)Ni(O2C(CH2)(2)SCH3)]ClO4 center dot CH2Cl2 (4 center dot CH2Cl2) and [(6-Ph(2)TPA)Ni(O2CCH2SCH3)]ClO4 center dot 1.5CH(2)Cl(2) (5 center dot 1.5CH(2)Cl(2)) revealed that each complex contains a distorted octahedral Ni(II) center and a bidentate carboxylate ligand. A previously described benzoate complex ([(6-Ph(2)TPA)Ni(O2CPh)]ClO4 (3)) has similar structural characteristics. Recrystallization of dry powdered samples of 3, 4 center dot 0.5CH(2)Cl(2), and 5 from wet organic solvents yielded a second series of crystalline Ni(II) carboxylate complexes having a coordinated monodentate carboxylate ligand ([(6-Ph(2)TPA)Ni(H2O)(O2CPh)]ClO4 (6), [(6-Ph(2)TPA)Ni(H2O)(O2C(CH2)(2)SCH3)]ClO4 center dot 0.2CH(2)Cl(2) (7 center dot 0.2CH(2)Cl(2)), [(6-Ph(2)TPA)Ni(H2O)(O2CCH2SCH3)]ClO4 (8)) which is stabilized by a hydrogen-bonding interaction with a Ni(II)-bound water molecule. In the cationic portions of 7 center dot 0.2CH(2)Cl(2) and 8, weak CH/pi interactions are also present between the methylene units of the carboxylate ligands and the phenyl appendages of the 6-Ph(2)TPA ligands. A formate complex of the formulation [(6-Ph(2)TPA)Ni(H2O)(O2CH)]ClO4 (9) was isolated and characterized. The mononuclear Ni(II) carboxylate complexes [(bnpapa)Ni(O2CPh)]ClO4 (10), [(bnpapa)Ni(O2C(CH2)(2)SCH3)]ClO4 (11), [(bnpapa)Ni(O2CCH2SCH3)]ClO4 (12), and [(bnpapa)Ni(O2CH)]ClO4 (13) were isolated and characterized. Two crystalline solvate forms of 10(10 center dot CH3CN and 10 center dot CH2Cl2) were examined by X-ray crystallography. In both, the distorted octahedral Ni(II) center is ligated by a bidentate benzoate ligand, one Ni(II)-bound oxygen atom of which accepts two hydrogen bonds from the supporting bnpapa chelate ligand. Spectroscopic studies of 10-13 suggest that all contain a bidentate carboxylate ligand, even after exposure to water. The combined results of this work enable the formulation of a proposed pathway for carboxylate product release from the active site Ni(II) center in acireductone dioxygenase.

  DOI：

  10.1021/ic061316w
• 作为产物：
  描述：

  N,N-bis(6-pivaloylamido-2-pyridylmethyl)-N-(2-pyridylmethyl)amine 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 13.0h， 以63%的产率得到N,N-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine
  参考文献：
  名称：

  通过合成模拟化学定量分析锌（II）-水酸度中氢键和疏水环境以及配位基团的相对贡献。

  摘要：

  源自通式（6-RNHpyCH2）nN（CH2py）（3-n）（R = H，n = 1-3 L（1的三脚架N4配体三（吡啶甲基）胺（（pyCH2）3N，tpa）的配体-3）； R =新戊基，n = 1-3 L'（1-3））用于阐明和量化氢键和疏水环境在其配合物的锌-水酸度中所产生作用的大小。[（L（1-3））Zn（OH2）] 2+和[（L'（1-3））Zn（OH2）] 2+ 1'-3'与锌结合的水分子的pKa为通过在水（1-3）或水-乙醇（1：1）（1'-3'）中的电位pH滴定法测定。锌（II）水的酸性随着与水分子相邻的-NH2氢键基团数量的增加而逐渐增加。因此，[（L3）Zn（OH2）] 2+和[（tpa）Zn（OH2）] 2+的锌结合水去质子化，其pKa值分别为6.0和8.0。水分子的pKa 但是，仅从[（tpa）Zn（OH2）] 2+中的8.0升高到[[bpg）Zn（OH2）] +中的9

  DOI：

  10.1039/b402084g

文献信息

• Preparation, Structure Characterization, and Oxidation Activity of Ruthenium Complexes with Tripodal Ligands Bearing Noncovalent Interaction Sites
  作者：Koichiro Jitsukawa、Yoshiyuki Oka、Syuhei Yamaguchi、Hideki Masuda

  DOI：10.1021/ic0494399

  日期：2004.12.1

  geometry with the tripodal ligand and some monodentate ligands. The amide-series ligands prefer to form a Ru(II) complex, while the amine-series ones give a Ru(III) complex. In the presence of PhIO oxidant, the catalytic activities for epoxidation of olefins, hydroxylation of alkane, and dehydrogenation of alcohol have been investigated using the six ruthenium complexes [Ru(II)(tppa)Cl(2)] (1), [Ru(I

  钌（II / III）与带有一个，两个或三个新酰胺基（MPPA，BPPA，TPPA：酰胺类配体）或新戊胺类（MNPA，BNPA，TNPA：胺类配体）的三脚架三（吡啶基甲基）胺配体的配合物）已经合成并在结构上表征了在吡啶环的6-位上的）。这些配合物的单晶的X射线结构分析表明，它们通过三脚架配体和一些单齿配体完成了八面体的几何形状。酰胺系列配体倾向于形成Ru（II）配合物，而胺系列配体则提供Ru（III）配合物。在PhIO氧化剂的存在下，使用六种钌络合物[Ru（II）（tppa）Cl（2）]（1），[Ru （III）（tnpa）Cl（2）] PF（6）（2），[Ru（II）（bppa）Cl] PF（6）（3），[Ru（III）（bnpa）Cl（2）] PF（6）（4），[Ru（II）（mppa）Cl] PF （6）（5）和[Ru（III）（mnpa）Cl（2）] PF（6）（6）。其中，酰胺系
• The strength of hydrogen bonding to metal-bound ligands can contribute to changes in the redox behaviour of metal centres
  作者：Juan C. Mareque Rivas、Sarah L. Hinchley、Laurent Metteau、Simon Parsons

  DOI：10.1039/b516234c

  日期：——

  [(L(Piv-1,2,3))Cu(I)Cl] and [(L(Piv-1,2,3))Cu(II)Cl]+ complexes in acetonitrile show that the intramolecular N-H...Cl-Cu hydrogen bonding weakens in the order L(Piv-1) > L(Piv-2) > L(Piv-3), and that it is stronger in the Cu(I) complexes. The 1H NMR spectra of the [(L(Piv1,2,3))Cu(I)Cl] complexes are in complete agreement with the IR data, and reveal that the stability of the Cu(I) complexes to oxidation

  一系列基于三（吡啶基-2-甲基）胺TPA的九个三脚架四齿配体，在一个，两个和三个吡啶6位中具有氢键供体R（R = NH2氨基，L（Am-1,2， 3）; NHCH2（t）Bu新戊基氨基，L（Np-1,2,3）; NHCO（t）Bu pivaloylamido，L（Piv-1,2,3））和TPA用于研究不同氢的影响键合微环境对其LCuCl配合物的电化学性能的影响。氢键供体是刚性预组织的，并适合于分子内NH ... Cl-Cu氢键的取向。循环伏安法研究表明，作为配体的函数，Cu（II）/ Cu（I）对的还原电位遵循以下顺序：TPA L（Piv-2）> L（Piv-3）的顺序减弱，并且在Cu（I）配合物中更强。[（L（Piv1,2,3））Cu（I）Cl]配合物的1H NMR光谱与IR数据完全一致，并且揭示了Cu（I）配合物对空气中氧化的稳定性增加顺序为L（Piv-1）
• LZnX complexes of tripodal ligands with intramolecular RN–H hydrogen bonding groups: structural implications of a hydrogen bonding cavity, and of X/R in the hydrogen bonding geometry/strength
  作者：Juan C. Mareque Rivas、Ravi Prabaharan、Rafael Torres Martín de Rosales、Laurent Metteau、Simon Parsons

  DOI：10.1039/b407790c

  日期：——

  Tripodal ligands N(CH2Py)3−n(CH2Py-6-NHR)n (R = H, n = 1–3 L1–31–31–3, n = 0 tpa; R = CH2tBu, n = 1–3 L′1–3′1–3′1–3) are used to investigate the effect of different hydrogen bonding microenvironments on structural features of their LZnX complexes (X = Cl−, NO3−, OH−). The X-ray structures of [(L222)Zn(Cl)](BPh4) 2·0.5(H2O·CH3CN), [(L333)Zn(Cl)](BPh4) 3·CH3CN, [(L′111)Zn(Cl)](BPh4) 1′, [(L′222)Zn(Cl)](BPh4) 2′·CH3OH, and [(L′333)Zn(Cl)](BPh4) 3′ have been determined and exhibit trigonal bipyramidal geometries with intramolecular (internal) N–H⋯Cl–Zn hydrogen bonds. The structure of [(L′222)Zn(ONO2)]NO34′·H2O with two internal N–H⋯O–Zn hydrogen bonds has also been determined. The axial Zn–Cl distance lengthens from 2.275 Å in [(tpa)Zn(Cl)](BPh4) to 2.280–2.347 Å in 1–3, 1′–3′. Notably, the average Zn–Npy distance is also progressively lengthened from 2.069 Å in [(tpa)Zn(Cl)](BPh4) to 2.159 and 2.182 Å in the triply hydrogen bonding cavity of 3 and 3′, respectively. Lengthening of the Zn–Cl and Zn–Npy bonds is accompanied by a progressive shortening of the trans Zn–N bond from 2.271 Å in [(tpa)Zn(Cl)](BPh4) to 2.115 Å in 3 (2.113 Å in 3′). As a result of the triply hydrogen bonding microenvironment the Zn–Cl and Zn–Npy distances of 3 are at the upper end of the range observed for axial Zn–Cl bonds, whereas the axial Zn–N distance is one of shortest among N4 ligands that induce a trigonal bipyramidal geometry. Despite the rigidity of these tripodal ligands, the geometry of the intramolecular RN–H⋯X–Zn hydrogen bonds (X = Cl−, OH−, NO3−) is strongly dependent on the nature of X, however, on average, similar for R = H, CH2tBu.

  利用三足配体 N(CH2Py)3ân(CH2Py-6-NHR)n（R = H，n = 1â3 L1â31â31â3，n = 0 tpa；R = CH2tBu，n = 1â3 Lâ²1â3â²1â3â²1â3）研究了不同氢键微环境对其 LZnX 复合物（X = Clâ、NO3â、OHâ）结构特征的影响。(L222)Zn(Cl)](BPh4) 2Â-0.5(H2OÂ-CH3CN)、[(L333)Zn(Cl)](BPh4) 3Â-CH3CN、[(Lâ²111)Zn(Cl)](BPh4) 1â²、[(Lâ²222)Zn(Cl)](BPh4) 2â²Â-CH3OH、和[(Lâ²333)Zn(Cl)](BPh4) 3â²的结构已经确定，它们呈现出具有分子内（内部）NâHâ¯ClâZn氢键的三叉双锥体几何结构。此外，还确定了具有两个内部 NâHâ¯OâZn 氢键的 [(Lâ²222)Zn(ONO2)]NO34â²Â-H2O 结构。ZnâCl的轴向距离从[(tpa)Zn(Cl)](BPh4)中的2.275 Ã延长到1â3, 1â²â3â²中的2.280â2.347 Ã。值得注意的是，ZnâNpy的平均距离也从[(tpa)Zn(Cl)](BPh4)中的2.069 Ã逐渐延长到3和3â²的三氢键空腔中的2.159 Ã和2.182 Ã。随着 ZnâCl 和 ZnâNpy 键的延长，反式 ZnâN 键也逐渐缩短，从[(tpa)Zn(Cl)](BPh4) 中的 2.271 à 到 3 中的 2.115 Ã（3â² 中为 2.113 Ã）。由于存在三重氢键微环境，3 的 ZnâCl 和 ZnâNpy 间距处于轴向 ZnâCl 键所观察到的范围的上限，而轴向 ZnâN 间距则是诱导出三叉双锥几何结构的 N4 配体中最短的距离之一。尽管这些三足配体具有刚性，但分子内 RNâHâ¯XâZn 氢键（X = Clâ、OHâ、NO3â）的几何形状在很大程度上取决于 X 的性质，但平均而言，R = H、CH2tBu 时的几何形状相似。
• Preparation of a Hydroperoxo Zinc(II) Intermediate
  作者：Akira Wada、Syuhei Yamaguchi、Koichiro Jitsukawa、Hideki Masuda

  DOI：10.1002/anie.200501157

  日期：2005.9.5
• JP2004256419A
  申请人：——

  公开号：JP2004256419A

  公开（公告）日：2004-09-16