1,4-bis(4-chlorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene | 19215-48-6

• 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: 1,4-bis(4-chlorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene
• 英文别名: N-(3-(4-chlorophenylimino)butan-2-ylidene)-4-chlorobenzamine；biacetyl bis(4-chlorophenylimine)；(para-Cl(C6H4)NCMe)2；2-N,3-N-bis(4-chlorophenyl)butane-2,3-diimine
• CAS: 19215-48-6
• 化学式: C₁₆H₁₄Cl₂N₂
• 分子量: 305.207
• InChiKey: KLBSWRHIUJTGKZ-UHFFFAOYSA-N

物化性质

• 熔点：
  172.4-173.8 °C
• 沸点：
  429.2±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)：
  4.5
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-bis(4-chlorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene 在 溴 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以70%的产率得到N-(3-(2-bromo-4-chlorophenylimino)butan-2-ylidene)-2-bromo-4-chlorobenzenamine
  参考文献：
  名称：

  Potassium Tellurocyanate Mediated Coupling Reactions ofN-(1-Chloroethylidene)Arylamines

  摘要：

  The reaction of potassium tellurocyanate (prepared in situ) with N-(1-chloroethylidene)arylamines (i.e., 4-RC6H4N = C(CH3)Cl, where R = H, Cl, CH3 and NO2) in DMSO solution gave unexpectedly, after hydrolysis, the corresponding N-(3-(arylamino)butan-2-ylidene)arylamines in 63-78%. Reaction of N-(3-(arylamino)butan-2-ylidene)arylamines with SOCl2 or with Br-2 resulted in the substitution of a halogen on the aromatic rings. The presence of a water molecule within the structure of the synthesized diimines was rationalized theoretically by Density Functional Theory (DFT). All compounds were characterized by elemental analysis, IR, NMR and mass spectroscopic data.

  DOI：

  10.1080/10426507.2014.902830
• 作为产物：
  描述：

  N-(1-chloroethylidene)-4-chlorobenzenamine 在 potassium tellurocyanate 作用下， 以 二甲基亚砜 为溶剂， 反应 2.5h， 以63%的产率得到1,4-bis(4-chlorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene
  参考文献：
  名称：

  Potassium Tellurocyanate Mediated Coupling Reactions ofN-(1-Chloroethylidene)Arylamines

  摘要：

  The reaction of potassium tellurocyanate (prepared in situ) with N-(1-chloroethylidene)arylamines (i.e., 4-RC6H4N = C(CH3)Cl, where R = H, Cl, CH3 and NO2) in DMSO solution gave unexpectedly, after hydrolysis, the corresponding N-(3-(arylamino)butan-2-ylidene)arylamines in 63-78%. Reaction of N-(3-(arylamino)butan-2-ylidene)arylamines with SOCl2 or with Br-2 resulted in the substitution of a halogen on the aromatic rings. The presence of a water molecule within the structure of the synthesized diimines was rationalized theoretically by Density Functional Theory (DFT). All compounds were characterized by elemental analysis, IR, NMR and mass spectroscopic data.

  DOI：

  10.1080/10426507.2014.902830

文献信息

• Rhenium Chemistry of Diazabutadienes and Derived Iminoacetamides Spanning the Valence Domain II−VI. Synthesis, Characterization, and Metal-Promoted Regiospecific Imine Oxidation
  作者：Samir Das、Indranil Chakraborty、Animesh Chakravorty

  DOI：10.1021/ic034586c

  日期：2003.10.1

  4, respectively, where L' is the monoionized iminoacetamide ligand R'N=C(H)-C(=O)-NR'(-). Finally, the reaction of Re(V)O(OEt)X(2)(PPh(3))(2) with L has furnished bivalent species of type Re(II)X(2)(L)(2), 6(X = Cl, Br). The X-ray structures of 1 (R = Me, R' = Ph), 3 (R = H, R' = Ph, Ar = Ph), and 4 (R = H, R' = cycloheptyl, Ar = C(6)H(4)Cl) are reported revealing meridional geometry for the ReCl(3)

  R'N = C（R）-C（R）= NR'，L（R = H，Me; R'=环烷基，芳基）类型的二氮杂丁二烯与Re（V）OCl（3）（AsPh（ 3））（2）提供了Re（V）OCl（3）（L），1，其中Re（III）（OPPh（3））Cl（3）（L），2和Re（V）（ NAr）Cl（3）（L），3，已经合成。由H（2）O（2）水溶液对2（R = H）进行化学氧化，由稀HNO（3）对3（R = H）进行化学氧化，产生Re（IV）（OPPh（3））Cl（3）（ L'），5和Re（VI）（NAr）Cl（3）（L'），4，其中L'是单离子化亚氨基乙酰胺配体R'N = C（H）-C（= O）- NR'（-）。最后，Re（V）O（OEt）X（2）（PPh（3））（2）与L的反应提供了Re（II）X（2）（L）（2），6型二价物质（X ＝ Cl，Br）。1（R = Me，R'= Ph），3（R = H，R'=
• Lysosome-targeted potent half-sandwich iridium(III) α-diimine antitumor complexes
  作者：Deliang Kong、Lihua Guo、Meng Tian、Shumiao Zhang、Zhenzhen Tian、Huayun Yang、Ye Tian、Zhe Liu

  DOI：10.1002/aoc.4633

  日期：2019.1

  F6 (Cpx = Cp*, tetramethyl(phenyl)cyclopentadienyl (Cpxph) or tetramethyl(biphenyl)cyclopentadienyl (Cpxbiph); N^N = diamine) have been synthesized and characterized. The molecular structure of 1A was determined using single‐crystal X‐ray diffraction analysis. The hydrolysis of 1A–5C was monitored using UV–visible spectra. Complexes 3A–3C showed catalytic activity for the oxidation of NADH to NAD+

  十五有机金属铱（III）半夹心络合物（1A - 5C）具有通式[（η 5 -Cp X）IR（N ^ N）CL] PF 6（CP X =的Cp *，四甲基（苯基）环戊二烯基（已经合成并表征了Cp xph）或四甲基（联苯）环戊二烯基（Cp xbiph； N ^ N =二胺）。1A的分子结构使用单晶X射线衍射分析确定。1A – 5C的水解使用紫外可见光谱进行监测。配合物3A – 3C显示出将NADH氧化为NAD的催化活性+，其中3C在450分钟内显示最高的29.9营业额。在药物治疗24或48小时后，针对两种人类癌细胞系（HeLa和A549）进行了MTT分析的细胞毒性检查。该复合物显示出高效能，其中最有效的复合物（3C； IC 50  = 3.4μM）在暴露24小时后对A549细胞的活性是顺铂的六倍。随着Cp环上的苯基取代，对A549细胞的细胞毒性作用增强：Cp xbiph > Cp xph > Cp
• One‐Step Access to Heteroatom‐Functionalized Imidazol(in)ium Salts
  作者：Dmitry V. Pasyukov、Maxim A. Shevchenko、Konstantin E. Shepelenko、Oleg V. Khazipov、Julia V. Burykina、Evgeniy G. Gordeev、Mikhail E. Minyaev、Victor M. Chernyshev、Valentine P. Ananikov

  DOI：10.1002/anie.202116131

  日期：2022.2.21

  and imidazolinium salts in one step via cascade reactions of easily available 1,4-diaza-1,3-butadienes with trialkyl orthoformates and heteroatomic nucleophiles was developed. Feasibility of the new imidazol(in)ium salts for direct metallation to give M/NHC complexes (M=Pd, Ni, Cu, Ag, Au) was demonstrated.

  开发了一种通过容易获得的1,4-二氮杂-1,3-丁二烯与原甲酸三烷基酯和杂原子亲核试剂的级联反应一步合成多种杂原子官能化咪唑鎓和咪唑啉鎓盐的新策略。证明了新的咪唑（in）鎓盐直接金属化以产生 M/NHC 配合物（M=Pd、Ni、Cu、Ag、Au）的可行性。
• Highly active and cis-1,4 selective polymerization of 1,3-butadiene catalyzed by cobalt(II) complexes bearing α-diimine ligands
  作者：Xiangyu Jia、Heng Liu、Yanming Hu、Quanquan Dai、Jifu Bi、Chenxi Bai、Xuequan Zhang

  DOI：10.1016/s1872-2067(12)60625-1

  日期：2013.8

  synthesized for comparison. The structures of complexes 3i, 3k, and 4a were further analyzed by X‐ray crystallography. When the Co(II) complexes were activated with ethylaluminum sesquichloride, they exhibited high catalytic activity for 1,3‐butadiene polymerization. The polymers produced have high cis‐1,4 stereoregularity (up to 98.0%) and high molecular weights (Mn = 1×10^4 - 1×10^5). The substituent ligand

  合成了一系列带有α-二亚胺配体的钴（II）配合物，并通过元素和光谱分析对其进行了表征。这些配合物的通式为 [ArN = C(Me)-(Me)C = NAr]CoCl2 (Ar = C6H5, 3a; 4-MeC6H4, 3b; 4-MeOC6H4, 3c; 4-FC6H4, 3d; 4-ClC6H4 , 3e; 2-MeC6H4, 3f; 2-EtC6H4, 3g; 2-iPrC6H4, 3h; 2, 4, 6-Me3C6H2, 3i; 2, 6-Et2C6H3, 3j; 2, 6-iPrC6H3). 还合成了 2,6-双[(2,6-二异丙基苯基亚氨基)乙基]吡啶 CoCl2 (4a) 以进行比较。通过X射线晶体学进一步分析了配合物3i、3k和4a的结构。当 Co(II) 配合物用倍半氯化乙基铝活化时，它们对 1,3-丁二烯聚合表现出很高的催化活性。生产的聚合物具有高顺 1,4 立体规整度（高达
• Synthesis and Characterization of Neutral Ligand α-Diimine Complexes of Aluminum with Tunable Redox Energetics
  作者：Henry H. Wilson、Connor A. Koellner、Zain M. Hannan、Caroline B. Endy、Mark W. Bezpalko、Nicholas A. Piro、W. Scott Kassel、Matthew D. Sonntag、Christopher R. Graves

  DOI：10.1021/acs.inorgchem.8b00045

  日期：2018.8.20

  (5)] and electron-withdrawing [R = Cl (6), CF3 (7), and NO2 (8)] substituents in the aryl side arm of the ligand. UV–vis absorption spectroscopy and electrochemistry were used to access the optical and electrochemical properties, respectively, of the complexes. Both sets of properties are shown to be dependent on the R substituent. Density functional theory calculations performed on the [Al(LPh)2Cl2)][AlCl4]

  报道了一系列铝的中性配体α-二亚胺配合物的合成和完整表征。化合物[Al（L Ar）2 Cl 2）] [AlCl 4 ] [L Ar = N，N'-双（4-RC 6 H 4）-2,3-二甲基-1,4-二氮杂丁二烯]在结构上通过多核NMR光谱法和固态X射线衍射测定，在给电子体的整个范围内类似[R = Me（2），t Bu（3），OMe（4）和NMe 2（5）]和吸电子[R = Cl（6），CF 3（7）和NO 2（8）]取代基在配体的芳基侧臂中。紫外可见吸收光谱和电化学分别用于检测配合物的光学和电化学性质。两组性能均显示为取决于R取代基。在[Al（L Ph）2 Cl 2）] [AlCl 4 ]配合物（1）上进行的密度泛函理论计算主要表明基于配体的前沿轨道，并用于帮助支持我们对光谱和电化学数据的讨论。我们还报告了L Ph配体与两种AlBr的反应图3和A1 3示出了较重的卤化物相对于组中较轻的成员的不同反应性曲线。