4,6-dichloro-2-[[(2,6-diisopropylphenyl)imino]methyl]phenol | 210882-40-9

• 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: 4,6-dichloro-2-[[(2,6-diisopropylphenyl)imino]methyl]phenol
• 英文别名: 2,4-Cl2-6-(CH=N-2,6-(i)Pr2C6H3)-C6H2OH；[(Cl)ON(DIPP)]H；2,4-Dichloro-6-[[2,6-di(propan-2-yl)phenyl]iminomethyl]phenol
• CAS: 210882-40-9
• 化学式: C₁₉H₂₁Cl₂NO
• 分子量: 350.288
• InChiKey: SQEHJQUZMFQMNF-UHFFFAOYSA-N

物化性质

• 熔点：
  116-118 °C
• 沸点：
  489.7±45.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  32.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis(bis(trimethylsilyl)amido)zinc(II) 、 4,6-dichloro-2-[[(2,6-diisopropylphenyl)imino]methyl]phenol 以 正戊烷 为溶剂， 以94%的产率得到
  参考文献：
  名称：

  Bis-Salicylaldiminato Complexes of Zinc. Examination of the Catalyzed Epoxide/CO₂ Copolymerization

  摘要：

  A series of salicylaldimine ligands of the general formula ((NRC7H5-x)-C-2(R-1)(x)OH) [x = 1 or 2; R-1 = Me, (BU)-B-t, Cl, OMe: R-2 = 2 6-(Pr2C6H3)-Pr-1, or 3,5-(CF3)(2)C6H3] have been synthesized and characterized via H-1 and C-13 NMR, elemental analysis, and X-ray crystallography. The concomitant series of zinc bis(salicylaldiminato) complexes of the general formula ((NRC7H5-x)-C-2(R-1)(x)O)(2)Zn have been synthesized and characterized in the solid state by X-ray crystallography. All complexes crystallized as four coordinate monomers with distorted tetrahedral geometry about the zinc center. The O-Zn-O angles range between 105 and 112.5 degrees, and the N-Zn-N bond angles were more obtuse spanning the range 122.9-128.9 degrees The only deviation from distorted tetrahedral geometry occurred when R-2 = 3,5-(CF3)(2)C6H3 which crystallized as a distorted trigonal bipyramidal dimeric species with O-ax-Zn-O-ax bond angles of 165.00(15)degrees. The equatorial angles approach 120 degrees except for the N-eq-Zn-N-eq angle of 110.54(16)degrees which is attributed to the strain of the bridging ligands. The zinc bis(salicylaldiminato) complexes showed varying activities as catalyst precursors for the copolymerization of CO2 and cyclohexene oxide. Activation is proposed to occur via CO, insertion in the phenolic Zn-O bond with simultaneous ring-opening resulting in a site for epoxide binding. The difference in activity has been ascribed to the different steric/electronic effects provided by the R-1 and R-2 substituents an the various steps of the copolymerization mechanism, The activity of the zinc bis(salicyaldiminato) catalyst precursors (< 16 gpoly/m/g . Zn/hr) were similar to the activities of the previously reported zinc phenoxide complexes for this reaction: however, unlike; the zinc phenoxide catalysts, the zinc bis(salicylaldiminato) complexes produced poly(cyclohexane carbonate) with greater than 99% carbonate linkages.

  DOI：

  10.1021/ic0006403
• 作为产物：
  描述：

  2,6-二异丙基苯胺 、 3,5-二氯水杨醛 以 甲醇 为溶剂， 反应 0.5h， 生成 4,6-dichloro-2-[[(2,6-diisopropylphenyl)imino]methyl]phenol
  参考文献：
  名称：

  锌 (II) 均相和异相及其在 rac-丙交酯开环聚合中的应用

  摘要：

  席夫碱配体 (L1H–L8H) 已制备并与 ZnII 中心络合。所有八种配合物都通过单晶 X 射线衍射方法、多核 NMR 光谱和元素分析进行​​了表征。结果表明，分离出 Zn3(OAc)4(L1-2)2 形式的 L1H 和 L2H 三金属配合物。然而，对于形成 L3H 到 L7H 的单金属配合物，Zn(L3-7)2。对于 L8H，也分离出与 Zn3(OAc)4(L1-2)2 具有相同化学计量的三金属配合物，但检测到不同的配位基序。席夫碱配体 L1H 被固定在二氧化硅上并用 Zn(OAc)2·2H2O 处理形成非均相 ZnII 系统。这通过 13 C{1H} CP/MAS NMR 光谱表征。使用未升华的单体，在没有溶剂的情况下，在 130°C 下评估所有均相和非均相催化剂的外消旋丙交酯的开环聚合反应。所有催化剂都提供了良好的转化率和中等程度的控制。（© Wiley-VCH Verlag GmbH

  DOI：

  10.1002/ejic.200801049

文献信息

• Bidentate salicylaldiminato tin(ii) complexes and their use as lactide polymerisation initiators
  作者：Nonsee Nimitsiriwat、Vernon C. Gibson、Edward L. Marshall、Mark R. J. Elsegood

  DOI：10.1039/b812877d

  日期：——

  A study of the reactions of several salicylaldimines (ortho-iminophenols) with Sn(NMe2)2 reveals that the sterics and electronics of the N-substituent play a principal role in determining the product mixture. Thus mono(chelate) tin(II) amides have only been isolated with bulky N-anilido substituents, including [2,4-X2-6-CHN-2,6-iPr2C6H3}-C6H2O]Sn(-NMe2)]2, X = Cl, 1; X = I, 2 and [2,4-Cl2-6-CHN-2

  对几种水杨醛亚胺（邻亚氨基苯酚）与Sn（NMe2）2的反应的研究表明，N-取代基的空间和电子学在确定产物混合物中起主要作用。因此，单（螯合物）锡（II）酰胺仅用大的N-苯胺基取代基分离，包括[2,4-X2-6- CHN-2,6-iPr2C6H3} -C6H2O] Sn（-NMe2）] 2 ，X = Cl，1; X = I，2和[2,4-Cl2-6- CHN-2,4,6-tBu3C6H2} -C6H2O] Sn（NMe2），3。具有较小的N-芳基和N-烷基取代的水杨醛亚胺，的混合物即使酚盐环带有大的叔丁基取代基，也会形成单螯合物和双螯合物。此外，当苯胺基基团带有吸电子取代基时，亚氨基碳被活化而趋向亲核攻击（如[2,4-tBu2-6- CH（NMe2）N-2,4,6-Br3C6H2的形成所证明} -C6H2O] Sn，4）；当卤素取代基位于酚环上时，没有观察到这样的反应性。还研究了配合物
• Synthesis and Structures of Nickel and Palladium Salicylaldiminato 1,3,5-Triaza-7-phosphaadamantane (PTA) Complexes
  作者：Donald J. Darensbourg、Cesar G. Ortiz、Jason C. Yarbrough

  DOI：10.1021/ic0341284

  日期：2003.10.1

  The synthesis of nickel(II) and palladium(II) salicylaldiminato complexes incorporating the water-soluble phosphine 1,3,5-triaza-7-phosphaadamantane(PTA) has been achieved employing two preparative routes. Reaction of the original ethylene polymerization catalyst developed by Grubbs and co-workers (Organometallics 1998, 17, 3149), (salicylaldiminato)Ni(Ph)PPh(3), with PTA using a homogeneous methanol/toluene

  结合了水溶性膦1,3,5-三氮杂-7-磷金刚烷（PTA）的水杨基铝亚氨基镍（II）和钯（II）配合物的合成已通过两种制备途径完成。由Grubbs及其同事开发的原始乙烯聚合催化剂（Organometallics 1998，17，3149）（（水杨基铝二氨基）Ni（Ph）PPh（3））与PTA的反应使用均相甲醇/甲苯溶剂系统进行PTA类似物的收率很高。或者，可以使用（tmeda）M（CH（3））（2）（M = Ni，Pd），相应的水杨醛亚胺和PTA通过直接方法合成此类复合物。通过这种方法的产率通常接近定量。在溶液中通过（1）H /（13）C /（31）P NMR光谱表征络合物，在固态下通过X射线晶体学表征。所有衍生物均表现出正方形平面的几何形状，苯胺上的庞大异丙基垂直于金属中心及其四个配体形成的平面。这些空间支配基团的这种取向负责烯烃聚合过程中聚合物链的生长，有利于通过β-氢化物消除的链终止。
• Vinyl Polymerization of Norbornene with Neutral Salicylaldiminato Nickel(II) Complexes
  作者：Wen-Hua Sun、Haijian Yang、Zilong Li、Yan Li

  DOI：10.1021/om030018t

  日期：2003.9.1

  A series of neutral salicylaldiminato Ni(II) complexes have been synthesized and characterized, and complexes a and e have been confirmed by X-ray single-crystal analyses. These compounds show highly catalytic activities for the vinyl polymerization of norbornene with MAO cocatalyst, which could be up to 2.86 × 108 g PNB/(mol Ni·h), and also lead to various activities, molecular weights, and distributions

  合成和表征了一系列中性的水杨醛亚氨基Ni（II）配合物，并通过X射线单晶分析证实了配合物a和e。这些化合物对降冰片烯与MAO助催化剂的乙烯基聚合反应显示出很高的催化活性，最高可达2.86×10 8 g PNB /（mol Ni·h），还导致聚降冰片烯的各种活性，分子量和分布。不同的反应条件。
• A New Water-Soluble Phosphine Derived from 1,3,5-Triaza-7-phosphaadamantane (PTA), 3,7-Diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane. Structural, Bonding, and Solubility Properties
  作者：Donald J. Darensbourg、Cesar G. Ortiz、Justin W. Kamplain

  DOI：10.1021/om0343059

  日期：2004.4.1

  The phosphine 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane, which we will condense to DAPTA, and its oxide have been fully characterized both in solution and in the solid state. These compounds were prepared by acylation of 1,3,5-triaza-7-phosphaadaman-tane (PTA) and its oxide with acetic anhydride. The nonionic compounds were found to be soluble in most common organic solvents, in addition to possessing extremely large molar solubilities in water. Indeed, the molar solubility of DAPTA was shown to be 7.4 M, which is 4 time more soluble than the commonly utilized water-soluble phosplaine, triply meta-sulfonated triphenylphosphine (TPPTS). In the case of DAPTA this enhanced water solubility is attributed to a strong interaction of water with the amide nitrogen-CO bond dipole as revealed by a large red shift of the nu(C=O) vibration on going from a weakly interacting solvent such as CH2Cl2 to water. This latter observation is supported by the short average amide nitrogen-carbonyl carbon bond distance of 1.375 Angstrom as determined via X-ray crystallography, indicative of a strong Coulombic interaction between the nitrogen and carbon atoms. To assess the metal to phosphorus binding characteristics of DAPTA, several group 10 and group 6 complexes were prepared and their M-P bond distances were shown to be quite similar with those of their PTA analogues. For examples, the W-P bond distance in W(CO)(5)DAPTA of 2.492(3) Angstrom is comparable to that previously reported for W(CO)(5)PTA of 2.4976(15) Angstrom and slighter shorter than that found in W(CO)(5)PMe3 (2.516(2) Angstrom). Accordingly, the PTA ligand has generally been characterized as possessing donor properties similar to that of PMe3. Consistent with these bonding parameters determined in the solid state, all three tungsten pentacarbonyl complexes have nearly identical v(CO) frequencies in solution.