3-trimethylethylenediaminomethyl-5-bromosalicyldehyde | 155857-86-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-trimethylethylenediaminomethyl-5-bromosalicyldehyde
• 英文别名: 5-bromo-3-[[2-(dimethylamino)ethyl-methylamino]methyl]-2-hydroxybenzaldehyde
• CAS: 155857-86-6
• 化学式: C₁₃H₁₉BrN₂O₂
• 分子量: 315.21
• InChiKey: ZCCCEWPMSBUOEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.96
• 重原子数：
  18.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  43.78
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  3-trimethylethylenediaminomethyl-5-bromosalicyldehyde 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 24.0h， 生成 2-{[N-(2-dimethylaminoethyl)-N-methyl]-aminomethyl}-4-bromo-6-[[N'-2-(2'-pyridyl)-ethyl]-aminomethyl]phenol
  参考文献：
  名称：

  Hydrolysis of β-Lactam Antibiotics Catalyzed by Dinuclear Zinc(II) Complexes:  Functional Mimics of Metallo-β-lactamases

  摘要：

  Three stable dinuclear zinc(II) complexes, [Zn2L1(mu-NO3)(NO3)(2)] and [Zn2L1(mu-OMe)(NO3)(2)], where L-1 is 2,6-bis {{N-(2-dimethylaminoethyl)-N-methyl]aminomethyl}-4-methylphenolate, and [Zn2L2(NO3)(3)], where L-2 is 2-{[N-(2-dimethylaminoethyl)-N-methyl]aminomethyl}-4-bromo-6-{[N'-2-(2'-pyridyl)ethyl]aminomethyl}phenolate, were synthesized and characterized in the solid stare and in aqueous solution. These complexes catalyze the hydrolysis of penicillin G and nitrocefin, serving as functional synthetic analogues of the metallo-beta-lactamases, bacterial enzymes responsible for antibiotic resistance. The mechanism of the hydrolysis was studied in detail for the catalyst precursor [Zn2L1(mu-NO3)(NO3)(2)], which converts into [Zn2L1(mu-OH)(NO3), (sol)(2-n)]((2-n)+) in the presence of water. The complex [Zn2L1(mu-OH)(No-3)(2)] (n = 2) was characterized in the solid state. Initial coordination of the substrate carboxylate group is followed by the rate-limiting nucleophilic attack of the bridging hydroxide at the beta-lactam carbonyl group in aqueous solution. The product is formed upon fast protonation of the intermediate. Mononuclear complexes Zn(cyclen)(NO3)(2) and Zn(bpta)(NO3)(2) are as reactive in the beta-lactam hydrolysis as the dinuclear complexes. Consequently, the second zinc ion is not required for catalytic activity.

  DOI：

  10.1021/ja993704l
• 作为产物：
  描述：

  N,N,N'-三甲基乙二胺 、 5-溴水杨醛 、 alkaline earth salt of/the/ methylsulfuric acid 以 乙醇 为溶剂， 反应 20.0h， 以89%的产率得到3-trimethylethylenediaminomethyl-5-bromosalicyldehyde
  参考文献：
  名称：

  Hydrolysis of β-Lactam Antibiotics Catalyzed by Dinuclear Zinc(II) Complexes:  Functional Mimics of Metallo-β-lactamases

  摘要：

  Three stable dinuclear zinc(II) complexes, [Zn2L1(mu-NO3)(NO3)(2)] and [Zn2L1(mu-OMe)(NO3)(2)], where L-1 is 2,6-bis {{N-(2-dimethylaminoethyl)-N-methyl]aminomethyl}-4-methylphenolate, and [Zn2L2(NO3)(3)], where L-2 is 2-{[N-(2-dimethylaminoethyl)-N-methyl]aminomethyl}-4-bromo-6-{[N'-2-(2'-pyridyl)ethyl]aminomethyl}phenolate, were synthesized and characterized in the solid stare and in aqueous solution. These complexes catalyze the hydrolysis of penicillin G and nitrocefin, serving as functional synthetic analogues of the metallo-beta-lactamases, bacterial enzymes responsible for antibiotic resistance. The mechanism of the hydrolysis was studied in detail for the catalyst precursor [Zn2L1(mu-NO3)(NO3)(2)], which converts into [Zn2L1(mu-OH)(NO3), (sol)(2-n)]((2-n)+) in the presence of water. The complex [Zn2L1(mu-OH)(No-3)(2)] (n = 2) was characterized in the solid state. Initial coordination of the substrate carboxylate group is followed by the rate-limiting nucleophilic attack of the bridging hydroxide at the beta-lactam carbonyl group in aqueous solution. The product is formed upon fast protonation of the intermediate. Mononuclear complexes Zn(cyclen)(NO3)(2) and Zn(bpta)(NO3)(2) are as reactive in the beta-lactam hydrolysis as the dinuclear complexes. Consequently, the second zinc ion is not required for catalytic activity.

  DOI：

  10.1021/ja993704l

文献信息

• Instant Detection of Hydrogen Cyanide Gas and Cyanide Salts in Solid Matrices and Water by using Cu^II and Ni^II Complexes of Intramolecularly Hydrogen Bonded Zwitterions
  作者：Ratish R. Nair、M. Raju、Kalyanashis Jana、Dhrubajyoti Mondal、E. Suresh、Bishwajit Ganguly、Pabitra B. Chatterjee

  DOI：10.1002/chem.201800894

  日期：2018.7.25

  remains intact in aqueous and organic solutions. Grinding of HL1 and HL2 with Cu2+/Ni2+ salts develop turn‐on probes 1–4. Compounds 1 and 4 are dinuclear CuII and NiII species, respectively. Compound 2 is a tetranuclear CuII complex. Interestingly, compound 3 is a mononuclear NiII species in which both nitrogen atoms in the pendant diamine arm are protonated and, therefore, not coordinated to the NiII

  本文报道了一系列分子内氢键的两性离子间隔配体HL1 - HL4，其含有一个单质子化的侧挂二胺臂和一个4-卤代苯酚的两个不同邻位的醛官能度。单晶X射线衍射（SXRD）为在室温下鉴定这类质子转移的两性离子提供了有说服力的证据。这些两性离子的固态光致发光性质在水溶液和有机溶液中保持不变。的磨削HL1和HL2与铜2+ /镍2+盐开发接通探针1 - 4。化合物1和4分别是双核Cu II和Ni II物种。化合物2是四核Cu II配合物。有趣的是，化合物3是单核Ni II物种，其中二胺侧链上的两个氮原子都质子化，因此不与Ni II中心配位。所有这些探针（1 – 4）对固体基质和水溶液（100％水）中都存在的有毒气体氰化氢（HCN）和氰化物盐具有即时响应。选择性的和在固体/土壤/水相HCN气体和氰化物盐的快速感测，没有任何干扰，由mechanosynthesized络合物1 - 4可以很容易地用肉眼手持式UV灯下被感知。
• A chimeric design of heterospin 2p–3d, 2p–4f, and 2p–3d–4f complexes using a novel family of paramagnetic dissymmetric compartmental ligands
  作者：Andrei A. Patrascu、Sergiu Calancea、Matteo Briganti、Stéphane Soriano、Augustin M. Madalan、Rafael A. Allão Cassaro、Andrea Caneschi、Federico Totti、Maria G. F. Vaz、Marius Andruh

  DOI：10.1039/c7cc03236f

  日期：——

  End-off bicompartmental ligands bearing a nitronyl–nitroxide arm have been designed for synthesizing various heterospin molecular systems. These ligands can selectively interact with 3d and 4f metal ions, leading to 2p–4f, 2p–3d, and 2p–3d–4f complexes. The magnetic properties of the 2p–4f and 2p–3d–4f complexes have been investigated and rationalized by theoretical calculations.

  设计了带有硝酰基-硝基氧根臂的末端双室配体，用于合成各种异旋分子系统。这些配体可以选择性地与3d和4f金属离子相互作用，从而形成2p–4f，2p–3d和2p–3d–4f络合物。2p–4f和2p–3d–4f配合物的磁性已经通过理论计算得到了研究和合理化。
• Studies on the interaction between oxido/dioxidovanadium(V) compounds and reactive oxygen species: Synthesis, characterization, and photophysical investigation
  作者：Riya Ghosh、Snehasish Debnath、Arnab Bhattacharya、Debjani Pradhan、Pabitra B. Chatterjee

  DOI：10.1016/j.jinorgbio.2022.111845

  日期：2022.8

  fluorescent nature of 1 and 2. Protonation of the hanging amine moiety of the ligand remained unchanged in the vanadium complexes 1 and 2. However, the intramolecular H-bonding is not present in 1 and 2. Hydrophilicity and luminescent nature of the vanadium complexes provided us the opportunity to study the interaction of 1 and 2 with different ROS. Excited state photophysical investigations revealed

  单线态氧 ( 1 O 2 ) 和次氯酸盐 (OCl ˉ ) 是两种主要的非自由基活性氧 (ROS)，它们在许多生化过程中产生。在细胞系统中，这些分析物发挥着各种重要作用。在本文中，我们报告了分子内氢键发光两性离子配体 (HL) 的两种单核氧化钒和二氧化钒 (V) 化合物 1 和 2。单晶 X 射线衍射分析和多核 ( 1 H 和51V) NMR 光谱提供了 1 和 2 在固态和溶液状态下的身份，分别。1 和 2 都是水溶性和荧光的。配体 HL 的荧光是造成 1 和 2 的荧光性质的原因。配体的悬挂胺部分的质子化在钒配合物 1 和 2 中保持不变。但是，分子内氢键不存在于 1 和 2 中。钒配合物的亲水性和发光性质为我们提供了研究 1 和 2 与不同 ROS 相互作用的机会。激发态光物理研究揭示了探针 1 和 2 对单线态氧和次氯酸盐的高度选择性即时响应。在存在其他具有挑战性的 ROS 的情况下，二氧化钒
• Label‐Free Detection of Unbound Bilirubin and Nitrophenol Explosives in Water by a Mechanosynthesized Dual Functional Zinc Complex: Recognition of Picric Acid in Various Common Organic Media
  作者：Ratish R. Nair、Snehasish Debnath、Riya Ghosh、Arnab Bhattacharya、M. Raju、Pabitra B. Chatterjee

  DOI：10.1002/chem.202303068

  日期：2024.2.12

  High levels of unconjugated bilirubin (UB) in serum lead to asymptomatic and neonatal jaundice and brain dysfunctions. Herein, we have reported the detection of UB at as low as 1 μM in an aqueous alkaline medium using a Zn(II) complex. The specificity of the complex has been validated by the HPLC in the concentration window 6–90 μM, which is rare. The sensory response of the probe at physiological pH against nitro explosives developed it as an instant‐acting fluorosensor for picric acid (PA) and 2,4‐dinitrophenol (2,4‐DNP). Spectroscopic titration provided a binding constant of 4×10⁵ M⁻¹ with PA. The naked eye detection was found to be 15 μM. The solid‐state photoluminescent nature of the complex enabled it for PA sensing in the solid phase. Interestingly, the probe remained fluorescent in various volatile and non‐volatile organic solvents. As a result, it can also detect PA and 2,4‐DNP in a wide range of common organic media. NMR studies revealed the coordination of PA, 2,4‐DNP, and UB to the Zn(II) center of the probe, which is responsible for the observed quenching of the probe with the analytes.

  摘要 血清中高含量的未结合胆红素（UB）会导致无症状黄疸和新生儿黄疸以及脑功能障碍。在此，我们报告了利用锌（II）复合物在碱性水介质中检测低至 1 μM 的未结合胆红素的方法。在 6-90 μM 的浓度范围内，HPLC 验证了该复合物的特异性。该探针在生理 pH 值下对硝基爆炸物的感官反应使其成为苦味酸（PA）和 2,4-二硝基苯酚（2,4-DNP）的瞬效荧光传感器。通过光谱滴定，它与 PA 的结合常数为 4×105 M-1。肉眼检测结果为 15 μM。该复合物的固态光致发光特性使其能够在固相中感测 PA。有趣的是，该探针在各种挥发性和非挥发性有机溶剂中都能保持荧光。因此，它还能在多种常见有机介质中检测 PA 和 2,4-DNP。核磁共振研究显示 PA、2,4-DNP 和 UB 与探针的 Zn（II）中心配位，这也是探针与分析物发生淬灭的原因。
• Dinuclear Nickel(II) Complexes of Phenol-Based “End-Off” Compartmental Ligands and Their Urea Adducts Relevant to the Urease Active Site
  作者：Takeichiro Koga、Hideki Furutachi、Takako Nakamura、Nobuo Fukita、Masaaki Ohba、Kazuhiro Takahashi、Hisashi Ōkawa

  DOI：10.1021/ic971209p

  日期：1998.3.9

  Two phenol-based compartmental ligands of the "end-off" type, 2,6-bisN-[2-(dimethylamino)ethyl]iminomethyl}-4-methylphenol (HL1) and 2-N-[2-(dimethylamino)ethyl]iminomethyl}-6-N-methyl-N-[2-(dimethylamino)ethyl]aminomethyl}-4-bromophenol (HL2), have been used to form [Ni-2(L-1)(AcO)(NCS)(2)(MeOH)] (1), [Nh(L-1)(AcO)(2)-(MeOH)]BPh4 (2), [Ni-2(L-2)(AcO)(NCS)(2)(MeOH)] (3), [Ni-2(L-2)(AcO)(2)]BPh4 (4), and [Ni-2(L-2)(NCS)(3)(MeOH)] (5). X-ray crystallographic studies were done for 2-5. 2: triclinic, space group P (1) over bar, a 13.613(3) Angstrom, b = 16.475(4) Angstrom, c = 11.307(4) Angstrom, alpha = 99.90(2)degrees, beta = 104.16(2)degrees, gamma = 109.01(2)degrees, V = 2253(1) Angstrom(3), Z = 2. The complex cation has a dinuclear core triply bridged by the phenolic oxygen of (L-1)- and two acetate groups in the syn-syn mode. One Ni has a six-coordinate geometry together with a methanol oxygen. 3: triclinic, space group P (1) over bar, a = 10.167(1) Angstrom, b = 16.119(2) Angstrom, c = 9.472(3) Angstrom, alpha = 103.53(2)degrees, beta = 100.91(1)degrees, gamma = 85.62(1)degrees, V = 1481(1) Angstrom(3), Z = 2. A pair of Ni ions are bridged by the phenolic oxygen of (L-2)(-), an isothiocyanate nitrogen, and an acetate group. The sixth position of one Ni is occupied by a methanol oxygen and that of the other Ni by isothiocyanate nitrogen. 4: monoclinic, space group P2(1)/n, a = 15.146(2) Angstrom, b = 9.442(3) a, c = 30.844(2) Angstrom, beta = 93.427(9)degrees, V = 4402(1) Angstrom(3), Z = 4. TWO Ni ions are bridged by the phenolic oxygen of (L-2)(-) and an acetate group. The Ni bound to the iminic pendant arm is nearly planar whereas the Ni bound to the aminic pendant arm is of six-coordination together with a bidentate acetate group. 5: monoclinic, space group C2/c, a = 26.744(5), b = 10.323(4) Angstrom, c = 21.785(6) Angstrom, beta = 94.73(2)degrees, V = 5993(3) Angstrom(3), Z = 8. TWO Ni ions are bridged by the phenolic oxygen of (L-2)(-) and an isothiocyanate nitrogen. The Ni bound to the iminic pendant arm is of five-coordination along with an isothiocyanate nitrogen. The Ni bound to the aminic pendant arm has a six-coordinate geometry together with a methanol oxygen and an isothiocyanate nitrogen. 1-5 were examined regarding their ability to bind urea, and 4 and 5 were shown to form [Ni-2(L-2)(AcO)(2)(urea)]BPh4 (4') and [Ni-2(L-2)(NCS)(3)(urea)] (5'), respectively. 5' crystallizes in the monoclinic system, space group P2(1)/n, with a = 11.709(5), b = 15.100(4), c = 17.548(5) Angstrom, beta = 95.58(3)degrees, V = 3087(1) Angstrom(3), and Z = 4. Its dinuclear core is very similar to that of 5 except that the methanol of 5 is replaced by a urea molecule.