1,4-bis(3,5-di-tert-butylphenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene | 404373-20-2

• 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(3,5-di-tert-butylphenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene
• 英文别名: (3,5-di-tert-butylphenyl)N=C(Me)-C(Me)=N(3,5-di-tert-butylphenyl)；(3,5-tBu2C6H3)NC(Me)C(Me)N(C6H3tBu2-3,5)；tBu2ArDABMe；2-N,3-N-bis(3,5-ditert-butylphenyl)butane-2,3-diimine
• CAS: 404373-20-2
• 化学式: C₃₂H₄₈N₂
• 分子量: 460.747
• InChiKey: QNFKHNABQVKTCA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 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(3,5-di-tert-butylphenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  甲烷、甲醇和二甲醚 CH 与亲电铂配合物活化的动力学和机制

  摘要：

  [(NN)PtMe(TFE-d(3))](+) ((NN) = ArN=C(Me)-C(Me)=NAr 对甲烷、甲醇和二甲醚的 CH 活化的相对速率;Ar = 3,5-二叔丁基苯基，TFE-d(3) = CF(3)CD(2)OD) (2(TFE))。甲烷活化动力学是通过在单晶蓝宝石 NMR 管中使 2(TFE)-(13)C 与 300-1000 psi 的甲烷反应来进行的；获得了干净的二阶行为（k = 1.6 +/- 0.4 x 10(-3) M(-1) s(-1) at 330 K；k = 2.7 +/- 0.2 x 10(-4) M( -1) s(-1) 在 313 K）。向 2(TFE) 溶液中添加甲醇会迅速建立甲醇 (2(MeOD)) 和三氟乙醇 (2(TFE)) 加合物之间的平衡，甲醇优先结合 (K(eq) = 0.0042 +/- 0.0006)。CH 活化产生 [(NN)Pt(CH(2)OD)(MeOD)](+)

  DOI：

  10.1021/ja056387t

文献信息

• Copper-Catalyzed Diastereoselective Arylation of Tryptophan Derivatives: Total Synthesis of (+)-Naseseazines A and B
  作者：Madeleine E. Kieffer、Kangway V. Chuang、Sarah E. Reisman

  DOI：10.1021/ja4023557

  日期：2013.4.17

  A copper-catalyzed arylation of tryptophan derivatives is reported. The reaction proceeds with high site- and diastereoselectivity to provide aryl pyrroloindoline products in one step from simple starting materials. The utility of this transformation is highlighted in the five-step syntheses of the natural products (+)-naseseazine A and B.

  报道了色氨酸衍生物的铜催化芳基化。该反应以高位点和非对映选择性进行，从简单的起始材料一步即可提供芳基吡咯并二氢吲哚产物。这种转化的效用在天然产物 (+)-naseseazine A 和 B 的五步合成中得到了强调。
• C−H Bond Activation by Cationic Platinum(II) Complexes:  Ligand Electronic and Steric Effects
  作者：H. Annita Zhong、Jay A. Labinger、John E. Bercaw

  DOI：10.1021/ja011189x

  日期：2002.2.1

  benzene with cationic Pt(II) complexes bearing 3,5-disubstituted aryl diimine ligands, the rate-determining step is C [bond] H activation, whereas for the more sterically crowded analogues with 2,6-dimethyl-substituted aryl groups, benzene coordination becomes rate-determining. This switch is manifested in distinctly different isotope scrambling and kinetic deuterium isotope effect patterns. The more electron-rich

  已经制备了一系列双（芳基）二亚胺连接的 Pt(II) 与各种取代芳基的甲基配合物。阳离子配合物 [(ArN=CR [bond] CR=NAr)PtMe(L)](+)[BF(4)](-) (Ar = 芳基；R = H，CH(3)；L = 水，三氟乙醇）在大约室温下在三氟乙醇溶剂中与苯平稳反应，通过 Pt(IV)-甲基-苯基-氢化中间体产生甲烷和相应的苯基 Pt(II) 阳离子。甲基取代苯的反应产物表明，芳香族比苄基 C [键] H 活化具有固有的反应性偏好，然而，这可能会被空间效应所覆盖。对于苯与带有 3,5-二取代芳基二亚胺配体的阳离子 Pt(II) 配合物的反应，决定速率的步骤是 C [键] H 活化，而对于具有 2 的空间上更拥挤的类似物，6-二甲基取代芳基，苯配位成为定速。这种转换表现为明显不同的同位素扰乱和动力学氘同位素效应模式。根据相应羰基阳离子复合物的 CO 伸缩频率测定，配体越富电子，C
• Arene C−H Bond Activation and Arene Oxidative Coupling by Cationic Palladium(II) Complexes
  作者：Lily J. Ackerman、Joseph P. Sadighi、David M. Kurtz、Jay A. Labinger、John E. Bercaw

  DOI：10.1021/om0303294

  日期：2003.9.1

  N,N'-Diaryl-alpha-diimine-ligated Pd(II) dimethyl complexes ((tBu2Ar)DAB(Me))PdMe2 and ((CF3)2Ar)DAB(Me)} PdMe2 (tBu2Ar)DAB(Me): ArN=C(CH3)-C(CH3)=NAr, Ar=3,5-di-tert-butylphenyl; ((CF3)2Ar) DAB(Me): Ar = 3,5-bis(trifluoromethyl)phenyl} undergo protonolysis with HBF4(aq) in trifluoroethanol (TFE) to form cationic complexes [(alpha-diimine)Pd(CH3)(H2O)][BF4]. The cations activate benzene C-H bonds at room temperature. Kinetic analyses reveal trends similar to those observed for the analogous platinum complexes: the C-H activation step is rate-determining (KIE = 4.1 +/- 0.5) and is inhibited by H2O. The kinetic data are consistent with a mechanism in which benzene substitution proceeds by a solvent-(TFE-) assisted associative pathway. Following benzene C-H activation under 1 atm O-2, the products of the reaction are biphenyl and a dimeric mu-hydroxide complex, [(alpha-diimine)Pd(OH)](2)[BF4](2). The Pd(0) formed in the reaction is reoxidized by O-2 to the dimeric mu-hydroxide complex after the oxidative C-C bond formation. The regioselectivity of arene coupling was investigated with toluene and alpha,alpha,alpha-trifluorotoluene as substrates.
• Controlled Benzylation of α-Diimine Ligands Bound to Zirconium and Hafnium: An Alternative Method for Preparing Mono- and Bis(amido)M(CH₂Ph)_<i>n</i> (<i>n</i> = 2, 3) Complexes as Catalyst Precursors for Isospecific Polymerization of α-Olefins
  作者：Hayato Tsurugi、Ryuji Ohnishi、Hiroshi Kaneko、Tarun K. Panda、Kazushi Mashima

  DOI：10.1021/om800880n

  日期：2009.2.9

  Reactions of M(CH2Ph)(4)(M = Zr, Hf) with various alpha-diimine ligands afforded amido-imino or diamido complexes through intramolecular benzylation of the C=N bonds of the ligands. Selective benzylation of alpha-diimine ligands, i.e., single- and double-benzylation, was accomplished by varying the substituent on the nitrogen atom of the imine moiety or the ligand backbone. Kinetic analysis of the second benzylation step indicated that the benzyl group migrated from the metal center to the C=N moiety via an ordered four-center transition state (Delta S-double dagger = -3(4) eu for 3a; -5(9) eu for 5b). Upon activation with B(C6F5)(3) or [Ph3C] [B(C6F5)(4)], amido-imino (3, 6) and diamido (2, 4) complexes became active catalysts for 1-hexene polymerization, and the resulting poly(1-hexene)s had moderate isotacticity ([mmmm], up to 90%). Polymerization of vinylcyclohexane was also catalyzed with moderate activity to give highly isotactic poly(vinylcyclohexane) ([mmmm] > 95%) via a chain-end control mechanism.
• Synthesis and characterization of cationic rhodium(I) dicarbonyl complexes
  作者：James Kovach、William W. Brennessel、William D. Jones

  DOI：10.1016/j.ica.2010.12.005

  日期：2011.2

  Treatment of Rh(acac)(CO)(2) (acac = acetoacetonate) with perchloric acid followed by addition of an alpha-diimine (alpha-diimine = 1,4-bis(Ar)-2,3-dimethyl-1,4-diaza-1,3-butadiene, Ar = 3,5-dimethylphenyl, 1; 3,5-ditert-butylphenyl, 2; and 3,4,5-trimethoxyphenyl, 3; phenyl, 4; and 4-chlorophenyl, 5) generates a series of complexes of the type [Rh(alpha-diimine)(CO)(2)][ClO4] 6-10 with varying electronic properties of the supporting diimine ligand. X-ray crystal structures have been determined for the alpha-diimine ligands 1-5, and complexes 6, 8, and 10. (C) 2010 Elsevier B.V. All rights reserved.