N,N'-二均三甲苯基-2,3-丁烷二亚胺 | 202277-65-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: N,N'-二均三甲苯基-2,3-丁烷二亚胺
• 英文名称: 1,2-bis[(2,4,6-trimethylphenyl)imino]-1,2-dimethylethane
• 英文别名: N,N'-dimesityl-2,3-butanediimine；N,N′-dimesitylbutane-2,3-diimine；2-N,3-N-bis(2,4,6-trimethylphenyl)butane-2,3-diimine
• CAS: 202277-65-4
• 化学式: C₂₂H₂₈N₂
• 分子量: 320.478
• InChiKey: FJAOMTXFIFEIFY-UHFFFAOYSA-N

物化性质

• 熔点：
  187.4-188.2℃

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  N,N'-二均三甲苯基-2,3-丁烷二亚胺 在 环己烯 、 三溴化磷 、 二乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 以30%的产率得到
  参考文献：
  名称：

  用于Suzuki-Miyaura交叉偶联反应的杂原子取代的二级氧化膦

  摘要：

  制备并表征了几种二取代的二亚胺（3a - 3f）和杂原子取代的不饱和仲氧化膦（HASPO，6a - 6f）。化合物6a - 6f被认为是预配体，因为它们能够互变异构为杂原子取代的次膦酸（HAPA，7a - 7f）。从化合物6e与PdBr 2的反应中观察到出乎意料的3e-配位的二溴化钯8e。预配体6a，6c和6e的分子结构，以及钯配合物8e通过单晶X射线衍射法测定。当将预配体6a应用于钯催化的Suzuki-Miyaura交叉偶联反应时，可获得令人满意的产率。密度泛函理论被雇用来检查HASPO的电子性质6A-6F预配体，其相应的1,3-二- ñ -取代的互变异构体7A-7F，饱和对方7AS的7A。化合物7a是Suzuki-Miyaura反应中最有效和最可靠的配体，其高位孤对（LP）分子轨道（HOMO-1）证实了这一点。7c的LP轨道–7f位于较低的HOMO-5。对于每个7c – 7f，找到了两

  DOI：

  10.1016/j.jorganchem.2016.02.007
• 作为产物：
  描述：

  2,3-丁二酮 、 2,4,6-三甲基苯胺 在 甲酸 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以68%的产率得到N,N'-二均三甲苯基-2,3-丁烷二亚胺
  参考文献：
  名称：

  A more sustainable and efficient access to IMes·HCl and IPr·HCl by ball-milling

  摘要：

  一种用户友好型且环保的合成方法，通过机械化学方法实现了广泛使用的N-杂环卡宾（NHC）前体的合成。

  DOI：

  10.1039/c7gc03539j
• 作为试剂：
  描述：

  1-(3,5-dimethoxyphenyl)-2-(2-methoxyphenoxy)propane-1,3-diol 在 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 N,N'-二均三甲苯基-2,3-丁烷二亚胺 、 氧气 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 甲苯 为溶剂， 反应 18.0h， 以53%的产率得到3,5-二甲氧基苯甲醛
  参考文献：
  名称：

  β-O-4木质素模型化合物选择性CC键裂解的铜催化剂

  摘要：

  AbstractThe reactivity of homogeneous copper catalysts towards the selective CC bond cleavage of both phenolic and non‐phenolic arylglycerol β‐aryl ether lignin model compounds has been explored. Several copper precursors, nitrogen ligands, and solvents were evaluated in order to optimize the catalyst system. Using the optimized catalyst system, copper(I) trifluoromethanesulfonate [Cu(OTf)]/L/TEMPO (L=2,6‐lutidine, TEMPO=2,2,6,6‐tetramethyl‐piperidin‐1‐yl‐oxyl), aerobic oxidation of the non‐phenolic β‐O‐4 lignin model compound proceeded with good selectivity for CαCβ bond cleavage, affording 3,5‐dimethoxybenzaldehyde as the major product. Aerobic oxidation of the corresponding phenolic β‐O‐4 lignin model proceeded with different selectivity, affording 2,6‐dimethoxybenzoquinone and α,β‐unsaturated aldehyde products resulting from cleavage of the CαCaryl bond. At low catalyst concentrations, however, a change in selectivity was observed as oxidation of the benzylic secondary alcohol predominated with both substrates.magnified image

  DOI：

  10.1002/adsc.201400463

文献信息

• Cyclopentadienyl chromium diimine and pyridine-imine complexes: ligand-based radicals and metal-based redox chemistry
  作者：Wen Zhou、Linus Chiang、Brian O. Patrick、Tim Storr、Kevin M. Smith

  DOI：10.1039/c2dt30160a

  日期：——

  Paramagnetic CpCr(III) complexes with antiferromagnetically-coupled anionic radical diimine and pyridine-imine ligands were prepared and characterized. The diimine chloro CpCr[(ArNCR)2]Cl complexes (1: Ar = 2,6-iPr2C6H3 (Dpp), R = H; 2: Ar = 2,6-Me2C6H3 (Xyl), R = Me; 3: Ar = 2,4,6-Me3C6H2 (Mes), R = Me) were synthesized by treatment of previously reported Cr(diimine)(THF)2Cl2 precursors with NaCp. Reduction of 1 with Zn gives CpCr[(DppNCH)2], 4, resulting from reduction of Cr(III) to Cr(II) with retention of the ligand-based radical. Alkoxide complexes CpCr[(DppNCH)2](OCR2R′) (5: R = Me, R′ = Ph; 6: R = iPr, R′ = H) were synthesized by protonolysis of Cp2Cr with HOCR2R′ in the presence of the neutral diimine and catalytic base. The corresponding radical pyridine-imine complexes CpCr(PyCHNMes)Cl (9), CpCr(PyCHNMes) (8), and CpCr(PyCHNMes)(OCMe2Ph) (11), were prepared by analogous routes. Oxidation of 8 with iodine gives CpCr(PyCHNMes)I (10) where oxidation of Cr(II) to Cr(III) again occurs with retention of the anionic pyridine-imine radical ligand. The molecular structures of complexes 1, 2, 4–8, 10 and 11 were determined by single-crystal X-ray diffraction. Unusual low energy bands were observed in the UV-vis spectra of the reported complexes, with particularly strong transitions observed for the Cr(II) complexes 4 and 8. The electronic structure of pyridine-imine complexes 8 and 10 were investigated by theoretical calculations.

  制备并表征了具有反铁磁偶联的阴离子自由基二亚胺和吡啶亚胺配体的顺磁性 CpCr(III) 配合物。二亚胺氯 CpCr[(ArNCR)2]Cl 配合物（1: Ar = 2,6-iPr2C6H3 (Dpp), R = H; 2: Ar = 2,6-Me2C6H3 (Xyl), R = Me; 3: Ar = 2,4,6-Me3C6H2 (Mes), R = Me）通过对先前报道的 Cr(二亚胺)(THF)2Cl2 前驱体进行 NaCp 处理合成。用 Zn 还原 1 得到 CpCr[(DppNCH)2]，4，其源于 Cr(III) 还原为 Cr(II) 并保留了配体基自由基。烷氧化物配合物 CpCr[(DppNCH)2](OCR2R′)（5: R = Me, R′ = Ph; 6: R = iPr, R′ = H）通过中性二亚胺和催化碱存在下 Cp2Cr 与 HOCR2R′ 的质子解反应合成。相应的自由基吡啶亚胺配合物 CpCr(PyCHNMes)Cl (9)、CpCr(PyCHNMes) (8) 和 CpCr(PyCHNMes)(OCMe2Ph) (11) 通过类似方法制备。用碘氧化 8 得到 CpCr(PyCHNMes)I (10)，其中 Cr(II) 氧化为 Cr(III) 再次保留了阴离子吡啶亚胺配体。通过单晶 X 射线衍射确定了配合物 1、2、4-8、10 和 11 的分子结构。在报道的配合物的 UV-vis 光谱中观察到异常的低能带，尤其是 Cr(II) 配合物 4 和 8 的强跃迁。通过理论计算研究了吡啶亚胺配合物 8 和 10 的电子结构。
• Synthesis of pentafluorobenzene-based NHC adducts and their catalytic activity in the microwave-assisted reactions of aldehydes
  作者：Evanthia Papadaki、Victoria Magrioti

  DOI：10.1016/j.tetlet.2019.151419

  日期：2020.1

  as standalone organocatalysts in various reactions, mostly using aromatic aldehydes as substrates. We have previously demonstrated the efficiency of azolium-2-carboxylate zwitterions in the hydroxymethylation of aldehydes, especially aliphatic aldehydes, under microwave irradiation. In the present work, we report a series of pentafluorobenzene-based NHC adducts and their efficiency in the hydroxymethylation

  N-杂环卡宾（NHC）已广泛用于有机金属化学中作为配体，以及在各种反应中用作独立的有机催化剂，主要使用芳族醛作为底物。先前我们已经证明了在微波辐射下，-2-羧酸偶氮鎓两性离子在醛尤其是脂肪族醛的羟甲基化中的效率。在目前的工作中，我们报告了一系列基于五氟苯的NHC加合物及其在微波辐射下脂族和芳族醛的羟甲基化和自缩合反应中的效率。在反应条件下释放出游离的羧苯甲酸酯，并且1,3-二甲基1,2-（全氟苯基）咪唑烷和1,3-双（2,6-二甲基苯基）-2-（全氟苯基）咪唑烷被证明是最有效的前催化剂。
• Expanding the Scope of Ligand Substitution from [M(S₂C₂Ph₂] (M = Ni²⁺, Pd²⁺, Pt²⁺) To Afford New Heteroleptic Dithiolene Complexes
  作者：Antony Obanda、Kristina Martinez、Russell H. Schmehl、Joel T. Mague、Igor V. Rubtsov、Samantha N. MacMillan、Kyle M. Lancaster、Stephen Sproules、James P. Donahue

  DOI：10.1021/acs.inorgchem.7b00971

  日期：2017.9.5

  decomposition identify soft σ donors as the ligand type capable of dithiolene substitution. Substitution of MeNC from [Ni(S2C2Ph2)(CNMe)2] by L provides access to a variety of heteroleptic dithiolene complexes not accessible from 1. Substitution of a dithiolene ligand from 1 involves net redox disproportionation of the ligands from radical monoanions, –S•SC2Ph2, to enedithiolate and dithione, the latter of which

  从[M（S 2 C 2 Ph 2）2 ] [M = Ni 2+（1），Pd 2+（2），Pt 2+（3）]直接取代二硫代烯配体以产生杂配物的范围[M（S 2 C 2 Ph 2）2 L n ]（n = 1，2）已扩大，除膦和二亚胺外还包括异腈和二硫代草酰胺。关于干净产生[M（S 2 C 2 Ph 2）L的配体的集体观察n ]，根本不反应，或导致不确定的分解，将软σ供体识别为能够进行二硫代烯取代的配体类型。L从[Ni（S 2 C 2 Ph 2）（CNMe） 2 ]取代MeNC可提供从1无法获得的多种杂二硫代二硫杂环戊烯络合物的访问权限。二硫代烯配体从1取代涉及配体从自由基单阴离子– S • SC 2 Ph 2到烯二硫代和二硫酮的净氧化还原歧化，后者是增强的离去基团，会进一步发生不可逆的反应。
• Electrophilic RhI catalysts for arene H/D exchange in acidic media: Evidence for an electrophilic aromatic substitution mechanism
  作者：Michael S. Webster-Gardiner、Paige E. Piszel、Ross Fu、Bradley A. McKeown、Robert J. Nielsen、William A. Goddard、T. Brent Gunnoe

  DOI：10.1016/j.molcata.2016.07.045

  日期：2017.1

  of new rhodium (I) complexes supported by bidentate nitrogen-donor ligands with varying electronic and steric properties were synthesized in situ and evaluated for catalytic arene C–H/D activation. In trifluoroacetic acid (HTFA), these complexes are proposed to mediate H/D exchange of arene C–H/D bonds by an electrophilic aromatic substitution mechanism that involves Rh-mediated activation of HTFA

  在原位合成了一系列具有不同电子和空间特性的双齿氮供体配体所支持的一系列新的铑（I）配合物，并对其催化芳烃的C–H / D活化进行了评估。在三氟乙酸（HTFA）中，提出了这些络合物通过亲电芳族取代机制（涉及Rh介导的HTFA（或DTFA）活化）介导芳烃C-H / D键的H / D交换。DFT计算支持H / D交换反应的拟议途径。
• Unraveling the synthesis of homoleptic [Ag(N,N-diaryl-NHC)₂]Y (Y = BF₄, PF₆) complexes by ball-milling
  作者：Audrey Beillard、Xavier Bantreil、Thomas-Xavier Métro、Jean Martinez、Frédéric Lamaty

  DOI：10.1039/c6dt03564g

  日期：——

  A user-friendly and general mechanochemical method was developed to access rarely described NHC (N-heterocyclic carbene) silver(I) complexes featuring N,N-diarylimidazol(idin)ene ligands and non-coordinating tetrafluoroborate or hexafluorophosphate counter anions. Comparison with syntheses in solution clearly demonstrated the superiority of the ball-milling conditions.

  开发了一种用户友好的通用机械化学方法，以访问很少描述的NHC（N-杂环卡宾）银（I）配合物，其特征在于N，N-二芳基咪唑（idin）烯配体和非配位四氟硼酸根或六氟磷酸抗衡阴离子。与溶液中合成方法的比较清楚地表明了球磨条件的优越性。