2-(N,N-dimethylthiocarbamato-S)-5-tert-butylisophthalaldehyde | 312962-45-1

• 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: 2-(N,N-dimethylthiocarbamato-S)-5-tert-butylisophthalaldehyde
• 英文别名: S-(2,6-diformyl-4-tert-butylphenyl) dimethylcarbamothioate；S-(2,6-diformyl-4-tert-butylphenyl) dimethylthiocarbamate；S-(2,6-diformyl-4-tert-butylphenyl)dimethylthiocarbamate；S-(2,6-diformyl-4-tert-butyl) dimethylthiocarbamate；5-tert-Butyl-2-(N,N-dimethylaminocarbonylthio)isophthalaldehyde；S-(4-tert-butyl-2,6-diformylphenyl) N,N-dimethylcarbamothioate
• CAS: 312962-45-1
• 化学式: C₁₅H₁₉NO₃S
• 分子量: 293.387
• InChiKey: DKUDRLMIHQGESW-UHFFFAOYSA-N

物化性质

• 熔点：
  132-133 °C
• 沸点：
  403.6±55.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  79.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(N,N-dimethylthiocarbamato-S)-5-tert-butylisophthalaldehyde 在 NH₄Cl 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 (10,23,36,49-tetra-tert-butyl-13,26,39,52-tetramercapto-2,6,15,19,28,32,41,45-octaaza-1,7,14,20,27,33,40,46-octaene[7.7.7.7]metacyclophane)dinickel(II)
  参考文献：
  名称：

  Controlled formation and topologies of thiophenolate-based macrocycles: rings, cylinders and bowls

  摘要：

  1,3-二氨基丙烷与保护的噻吩醇二醛在Ni²⁺、Pd²⁺或Zn²⁺存在下进行Schiff碱缩合反应，可以通过选择金属阳离子和对阴离子来控制产物是单核非环状复合物，还是2 + 2和4 + 4大环复合物。2 + 2大环的Ni²⁺复合物包含两个平面正方形的镍离子，且其排列类似于之前观察到的那种：噻吩醇盐基团的μ-S原子呈金字塔形，位于由大环中的四个氮原子定义的平面的同一侧，形成一个V形分子。相反，2 + 2大环的Zn²⁺复合物发生低聚反应，生成一个碗状的六核复合物，其中包含一个μ₃-碳酸根阴离子。该拓扑结构的重要特征是存在三个μ₃-S-噻吩醇基团，它们将三个大环单元连接在一起，形成一个Zn₃S₃环，密封碗的底部。在这种排列中，每个二核Zn²⁺复合物中一个金字塔形的μ₃-S原子相对于观察到的二镍复合物的排列是翻转的。分子模型显示，2 + 2大环复合物的μ-S原子翻转在室温下是很容易实现的，而对Ni²⁺和Zn²⁺复合物观察到的不同排列是各自金属阳离子能量上最有利的状态。稀有的4 + 4大环复合物作为中性二核复合物被分离出来用于Ni²⁺和Pd²⁺，而作为四核复合物阳离子用于Zn²⁺。这些体系的拓扑结构有显著的差异：具有两个平面正方形Ni²⁺或Pd²⁺离子的体系形成扩展环，而Zn²⁺的体系形成一个硫衬里的圆柱，在晶态下容纳了乙腈分子。反应条件也可以优化，以产生作为其单核Ni²⁺和Pd²⁺复合物的2 + 1非环状配体，为形成更复杂的大环和超分子体系提供潜在的有用构件。

  DOI：

  10.1039/b512068c
• 作为产物：
  描述：

  O-(2,6-diformyl-4-tert-butylphenyl) dimethylthiocarbamate 反应 1.0h， 以61%的产率得到2-(N,N-dimethylthiocarbamato-S)-5-tert-butylisophthalaldehyde
  参考文献：
  名称：

  Controlled formation and topologies of thiophenolate-based macrocycles: rings, cylinders and bowls

  摘要：

  1,3-二氨基丙烷与保护的噻吩醇二醛在Ni²⁺、Pd²⁺或Zn²⁺存在下进行Schiff碱缩合反应，可以通过选择金属阳离子和对阴离子来控制产物是单核非环状复合物，还是2 + 2和4 + 4大环复合物。2 + 2大环的Ni²⁺复合物包含两个平面正方形的镍离子，且其排列类似于之前观察到的那种：噻吩醇盐基团的μ-S原子呈金字塔形，位于由大环中的四个氮原子定义的平面的同一侧，形成一个V形分子。相反，2 + 2大环的Zn²⁺复合物发生低聚反应，生成一个碗状的六核复合物，其中包含一个μ₃-碳酸根阴离子。该拓扑结构的重要特征是存在三个μ₃-S-噻吩醇基团，它们将三个大环单元连接在一起，形成一个Zn₃S₃环，密封碗的底部。在这种排列中，每个二核Zn²⁺复合物中一个金字塔形的μ₃-S原子相对于观察到的二镍复合物的排列是翻转的。分子模型显示，2 + 2大环复合物的μ-S原子翻转在室温下是很容易实现的，而对Ni²⁺和Zn²⁺复合物观察到的不同排列是各自金属阳离子能量上最有利的状态。稀有的4 + 4大环复合物作为中性二核复合物被分离出来用于Ni²⁺和Pd²⁺，而作为四核复合物阳离子用于Zn²⁺。这些体系的拓扑结构有显著的差异：具有两个平面正方形Ni²⁺或Pd²⁺离子的体系形成扩展环，而Zn²⁺的体系形成一个硫衬里的圆柱，在晶态下容纳了乙腈分子。反应条件也可以优化，以产生作为其单核Ni²⁺和Pd²⁺复合物的2 + 1非环状配体，为形成更复杂的大环和超分子体系提供潜在的有用构件。

  DOI：

  10.1039/b512068c

文献信息

• Conversion of some substituted phenols to the corresponding masked thiophenols, synthesis of a dinickel(II) dithiolate macrocyclic complex and isolation of some metal- and ligand-based oxidation products
  作者：Sally Brooker、Graham B. Caygill、Paul D. Croucher、Tony C. Davidson、Derrick L. J. Clive、Stephen R. Magnuson、Stephen P. Cramer、Corie Y. Ralston

  DOI：10.1039/b004214p

  日期：——

  preparation of the masked thiolate head unit S-(2,6-diformyl-4-methylphenyl) dimethylthiocarbamate 6 is detailed and two new masked thiolate head units, S-(2,6-diformyl-4-tert-butylphenyl) dimethylthiocarbamate 7 and S-(2-formylphenyl) dimethylthiocarbamate 8, are prepared by this method. The synthesis, crystal structure, NMR spectra and electrochemical properties of the first macrocyclic complex to be derived

  的一种改进的制备硫醇盐掩蔽头单元小号- （2,6-二甲酰基-4-甲基苯基）二甲基硫代氨基甲酸酯6中详述和两个新的掩蔽硫醇头单元，小号- （2,6-二甲酰基-4-叔丁基苯基）二甲基硫代氨基甲酸酯7和S-（2-甲酰基苯基）二甲基硫代氨基甲酸酯 通过这种方法准备图8。合成，晶体结构，核磁共振谱讨论了由7 [[Ni 2 L1]（ClO 4）2衍生的第一大环配合物的电化学性质。氧化作用[Ni 2 L2]（CF 3 SO 3）2（L2 2-是由6和1,3-二氨基丙烷）与硝酸铈（IV）铵引起的黑色络合物[Ni 2 L2] [Ce（NO 3）6 ]沉淀，据信其中含有一个镍（III）中心。该配合物在DMF中随时间（约24小时）分解而形成红色二镍（II）配合物[Ni 2 L2]（NO 3）2 ·2DMF，其结构已得到表征。氧化作用[Ni 2 L3]（CF 3 SO 3）2（L3 2-是由6和1,4-二氨基丁烷）与I
• Dimetal complexes of a bibrachial 2+2 thiolate-based macrocycle
  作者：Anders Lennartson、Vickie McKee、Jane Nelson、Michael Arthurs、Christine J. McKenzie

  DOI：10.1080/10610278.2012.701302

  日期：2012.8.1

  Protocols for accessing the [2 + 3] and [2 + 2] tren + thiophenolate-based cryptands and macrocycles, respectively, have been devised; however, a propensity towards incomplete crypt formation is clear: Cd(II)(2), Mn(II)(2), Ni(II)(2) and Pd(II)(2) complexes of the [2 + 2] bibrachial systems in which one arm of each of the tren head groups is pendant were isolated in attempts to make the crypts. The Mn(II) 2 complex can be used in transmetallation reactions and these probably occur in a stepwise fashion for the heavier, softer metal ions since the plausible intermediates Mn(II) M(II), M = Cd, Pd, were identified. There is evidence for the formation of [2 + 3] cryptand systems using templating Ag(I) and Cd(II); however, reaction conditions need to be strictly controlled to ensure isolation of either the [2 + 3] cryptand or the [2 + 2] macrocyclic complex since ensuing reactions leading to intractable oligomers are competing. The template and transmetallation experiments described here emphasise the relatively greater hydrolytic sensitivity of the thiophenol-derived imino macrocycles and crypts than their better-known phenol-based counterparts.
• Synthesis and crystal structures of a series of (μ-thiophenolato)(μ-pyrazolato-N,N′) double bridged dipalladium(II) complexes and their application in Mizoroki–Heck reaction as highly efficient catalysts
  作者：Narjes Khadir、Ghazal Tavakoli、Abdeljalil Assoud、Mojtaba Bagherzadeh、Davar M. Boghaei

  DOI：10.1016/j.ica.2015.10.035

  日期：2016.1

  Three new binucleating S-protected ligand precursors, 2-(N, N-dimethylthiocarbamato)-5-methylisophthalaldehyde di-2'-hydroxy 5'-methylanil (1b), 2-(N, N-dimethylthiocarbamato)-5-tert-butylisophthalaldehyde di-2'-hydroxyanil (2a) and 2-(N, N-dimethylthiocarbamato)-5-tert-butylisophthalaldehyde di-2'-hydroxy 5'-methylanil (2b), have been synthesized. The reaction of these ligand precursors with PdCl2 in the presence of pyrazole under Pd-mediated S-C cleavage yielded a series of binuclear palladium( II) complexes of general formula [LPd2(pz)], where pz is the exogenous bridging pyrazolyl ligand and L-3 represents a series of pentadentate thiophenol-based bridging ligands originated from their corresponding ligand precursors. All the compounds were characterized by elemental analysis, IR, H-1 NMR and UV-Vis spectroscopies. The binuclear mu-thiophenolato-mu-pyrazolato palladium(II) complexes have also been characterized by single crystal X-ray diffraction analysis. Crystal structure analyses of the complexes show that two Pd-II centers are located in distorted square-planar environments, arranged in binuclear units with Pd center dot center dot center dot Pd distance of 3.57 angstrom. The catalytic activity of these new binuclear palladium complexes was studied in Mizoroki-Heck C-C coupling reaction of methyl- and n-butyl acrylate with various types of aryl iodides and bromides. All reactions were completed for very short times with very excellent yield. Reactions were stereoselective and only trans isomers were obtained in each case. (C) 2015 Elsevier B.V. All rights reserved.