2,2'-bis(3,5-dichloro-2-hydroxybenzylideneamino)-1,1'-binaphthyl | 175133-27-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2,2'-bis(3,5-dichloro-2-hydroxybenzylideneamino)-1,1'-binaphthyl
• 英文别名: 2,2'-Bis(3,5-dichloro-2-hydroxybenzylideneamino)1,1'-binaphthyl；2,4-dichloro-6-[[1-[2-[(3,5-dichloro-2-hydroxyphenyl)methylideneamino]naphthalen-1-yl]naphthalen-2-yl]iminomethyl]phenol
• CAS: 175133-27-4；736969-85-0；175133-28-5；166986-31-8；199280-96-1
• 化学式: C₃₄H₂₀Cl₄N₂O₂
• 分子量: 630.357
• InChiKey: KZPDEKFPTFERPD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.4
• 重原子数：
  42
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  65.2
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  iron(III)-acetylacetonate 、 2,2'-bis(3,5-dichloro-2-hydroxybenzylideneamino)-1,1'-binaphthyl 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Chiral manganese and iron complexes of binaphthyl Schiff bases: syntheses, crystal structures and asymmetric epoxidation of alkenes

  摘要：

  手性二萘Schiff碱锰配合物 [MnL(X)] [H2L = 2,2′-双(3-R1-5-R2-2-羟基苄亚胺)-1,1′-二萘；R1 = R2 = Cl, X = O2CMe 1；R1 = Et, R2 = NO2, X = O2CMe 2；R1 = R2 = Cl, X = acac（乙酰丙酮）3] 及其铁类似物 [FeL(acac)] 4（R1 = R2 = Cl）已被合成。这些化合物的外消旋形式的晶体结构3·CH2Cl2和4·2H2O显示出非平面cis-β构型，两个萘环之间的二面角分别为85.5°和72.1°。配合物(R)-1至3是通过PhIO催化不对称环氧化烯烃的活性催化剂。在-20°C下，(R)-2在甲苯中氧化cis-β-甲基苯乙烯得到76%的对映体过量。

  DOI：

  10.1039/a700712d
• 作为产物：
  描述：

  [1,1’-联萘]-2,2’-二胺 、 3,5-二氯水杨醛 以 乙醇 为溶剂， 反应 4.0h， 生成 2,2'-bis(3,5-dichloro-2-hydroxybenzylideneamino)-1,1'-binaphthyl
  参考文献：
  名称：

  具有四齿萨伦配体的螺旋铂（II）配合物的异常圆偏振和聚集诱导的近红外磷光。

  摘要：

  合成并表征了一系列具有1,1'-联萘基连接基的手性和螺旋Pt II -Salen配合物。由于中心1,1'-联萘的分子内运动受到限制，这些配合物表现出不同寻常的近红外聚集诱导的磷光（AIP）。（R）/（S）对映纯配合物通过X射线衍射，圆二色性光谱，随时间变化的密度泛函理论计算和圆偏振发光（CPL）进行表征。本工作探讨了可以容易地从市售对映纯化合物制备四齿配体的方法，以及随后制备稳定的CPL活性方平面Pt II的方法。 具有AIP效果的复合物，可能在许多应用中引起关注。

  DOI：

  10.1002/chem.201801414

文献信息

• Preparation and reactivities of chiral manganese(III) and copper(II) complexes of binaphthyl Schiff bases
  作者：Chun-Wah Ho、Wing-Chi Cheng、Ming-Chuan Cheng、Shie-Ming Peng、Kin-Fai Cheng、Chi-Ming Che

  DOI：10.1039/dt9960000405

  日期：——

  A series of chiral Schiff bases, 2,2′-bis(3-R1-5-R2-2-hydroxybenzylideneamino)-1,1′-binaphthyl H2L (R2= Cl, R1= Cl, Me, Et or NO2; R2= Me, R1= But; R2= NO2, R1= H, Me, Et, Pri, But or Cl), and their complexes [CuL1]1 and [Mn2L12(OMe)2]2(R1= R2= Cl) have been prepared. The crystal structure of the racemic form of 1 has been determined. Complex 1 is an active catalyst for the oxidation of alkenes by tert-butyl hydroperoxide. On the contrary, 2 is inert towards alkene epoxidation by PhIO. However, upon mixing Mn(O2CMe)3·xH2O and H2L in acetonitrile a green solution was obtained which could effect asymmetric epoxidation of alkenes by PhIO. The effects of the steric and electronic effects of the R1 and R2 substituents, temperature, and the addition of donors like N-methyl- and 2-methyl-imidazole and pyridine N-oxide on the catalytic activity of the MnIII+(S)-H2L systems towards alkene epoxidation have been investigated. When R1= Et and R2= NO2 the best enantiomeric excesses of 58 and 43% were found for epoxidation of cis-β-methylstyrene to (1S,2R)-cis-β-methylstyrene oxide and 4-chlorostyrene to 4-(S)-chlorostyrene oxide respectively.

  一系列手性席夫碱，2,2'-双（3-R1-5-R2-2-羟基亚苄胺基）-1,1'-联萘H2L（R2=Cl，R1=Cl、Me、Et或NO2；R2=Me，R1=But；R2= ，R1=H、Me、Et、Pri、But或Cl）及其配合物[CuL1]1和[Mn2L12(OMe)2]2（R1=R2=Cl）已被制备。1的外消旋形式的晶体结构已被确定。配合物1是叔丁基过氧化氢氧化烯烃的活性催化剂。相反，2对PhIO引发的烯烃环氧化是无活性的。然而，将Mn(O2CMe)3·xH2O和H2L混合在乙腈中，获得了一种绿色溶液，这种溶液可以催化PhIO引发的对烯烃的不对称环氧化。已经研究了R1和R2取代基的立体和电子效应对MnIII+(S)-H2L体系催化烯烃环氧化的影响，以及温度和加入供体如N-甲基-和2-甲基咪唑以及吡啶N-氧化物的影响。当R1=Et和R2= 时，烯烃环氧化过程得到了最好的对映体过剩，分别为：将顺-β-甲基苯乙烯环氧化成(1S,2R)-顺-β-甲基苯乙烯氧化物，对映体过剩为58%；将4-氯苯乙烯环氧化成4-(S)-氯苯乙烯氧化物，对映体过剩为43%。
• Titanium and ruthenium binaphthyl Schiff base complexes as catalysts for asymmetric trimethylsilylcyanation of aldehydes
  作者：Xiang-Ge Zhou、Jie-Sheng Huang、Po-Hung Ko、Kung-Kai Cheung、Chi-Ming Che

  DOI：10.1039/a904330f

  日期：——

  1′-binaphthyl, toward the asymmetric trimethylsilylcyanation of some aromatic and aliphatic aldehydes demonstrated that the titanium complex of the binaphthyl Schiff base with R1 = R2 = But is one of the best catalysts for such a process, with an enantiomeric excess (e.e.) as high as 96% obtained for m-tolualdehyde. Crystal structure determination of a nitrosylruthenium complex, [RuII(L)(NO)Cl] (L is the

  Ti（OPr i）4和多种席夫碱原位形成的钛配合物的催化行为研究，主要是双萘基衍生物2,2'-双（3-R 1 -5-R 2 -2-羟基苄基亚氨基） -1,1'-联萘基对某些芳族和脂族醛的不对称三甲基甲硅烷基氰化反应表明，联萘基席夫碱的钛配合物R 1  = R 2  = Bu t是该方法的最佳催化剂，其中对于得到的对映体过量（ee），为高达96％米-tolualdehyde。亚硝酰基钌配合物[Ru II的晶体结构测定（L）（NO）Cl]（L是联萘基席夫碱的二价阴离子，R 1  ＝ R 2  ＝ Cl），表明该络合物呈顺-β构型，联萘基的二面角为70.2°。用AgPF 6处理后，钌配合物对苯甲醛的三甲基甲硅烷基氰化也显示出良好的催化性能，尽管ee较低（24％）。
• Binaphthyl Schiff base complexes of palladium(II). Structures and reactivities toward alkene epoxidation
  作者：Xiang-Ge Zhou、Jie-Sheng Huang、Xiao-Qi Yu、Zhong-Yuan Zhou、Chi-Ming Che

  DOI：10.1039/a908917i

  日期：——

  Palladium(II) binaphthyl Schiff base complexes [PdII(L)] (1: H2L = (racemic or R)-2,2′-bis(3,5-dichloro-2-hydroxybenzylideneamino)-1,1′-binaphthyl (H2L2); 2: H2L = (R)-2,2′-bis(3,5-dichloro-2-hydroxylbenzylideneamino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl (H2L3)) were prepared from sequential reactions of H2L with sodium methoxide and palladium(II) acetate in methanol in about 70% yields. Both complexes 1 and 2 have been characterised by X-ray crystallography as well as 1H NMR, IR, UV/VIS and MS spectroscopy. The structures of 1 and 2 feature a pseudo planar N2O2 arrangement with the Schiff base ligands adopting a stepped conformation, in contrast to the non-planar N2O2 geometry usually observed for this type of Schiff base bound to various metal ions. The catalytic behaviour of complexes 1 and 2 toward asymmetric epoxidation of styrenes was investigated. With 2 as a catalyst, a 71% ee was obtained for the epoxidation of p-fluorostyrene by tBuOOH.

  钯（II）二萘基希夫碱配合物[PdII(L)]（1: H2L = (外消旋或 R)-2,2′-bis(3,5-dichloro-2-hydroxybenzylideneamino)-1,1′-binaphthyl (H2L2); 2：H2L = (R)-2,2′-双(3,5-二氯-2-羟基亚苄基氨基)-5,5′,6,6′,7,7′,8,8′-八氢-1、1′-binaphthyl (H2L3)）是由 H2L 与甲醇钠和乙酸钯（II）在甲醇中的顺序反应制备的，收率约为 70%。复合物 1 和 2 均已通过 X 射线晶体学以及 1H NMR、IR、UV/VIS 和 MS 光谱进行了表征。1 和 2 的结构具有伪平面 N2O2 排列特征，希夫碱配体呈阶梯状构象，这与通常观察到的与各种金属离子结合的此类希夫碱的非平面 几何形状截然不同。研究了配合物 1 和 2 对苯乙烯不对称环氧化的催化作用。以 2 作为催化剂，tBuOOH 对对氟苯乙烯的环氧化反应获得了 71% 的ee。
• Pairing-Enhanced Regioselectivity: Synthesis of Alternating Poly(lactic-<i>co</i>-glycolic acid) from Racemic Methyl-Glycolide
  作者：Yiye Lu、Geoffrey W. Coates

  DOI：10.1021/jacs.3c05941

  日期：2023.10.18

  established the synthesis of isotactic, alternating PLGA from enantiopure starting materials. Here, to fill in the gap of the current field, we have developed the synthesis of syndioenriched, alternating PLGA from racemic methyl-glycolide (rac-MeG). The synthesis of alternating PLGA is accomplished by a highly regioselective ring-opening polymerization of rac-MeG with an optimized racemic aluminum catalyst

  聚乳酸乙醇酸(PLGA)在体内用于各种生物医学应用。由于其生物降解性和生物相容性，PLGA 特别适合肠胃外给药的受控药物输送。此前，我们建立了从对映体纯起始材料合成全同立构、交替 PLGA 的方法。在这里，为了填补当前领域的空白，我们开发了从外消旋甲基乙交酯（rac-MeG ）合成间二富集的交替PLGA的方法。交替PLGA的合成是通过外消旋-MeG与优化的外消旋铝催化剂的高度区域选择性开环聚合来完成的。进行机理研究以阐明配对增强催化剂的区域控制和立体控制。聚合物序列保真度已通过核磁共振研究确定，证实了主链立体构型内共聚单体序列的高度交替和中等的间同立构规整度。所得间二富集材料是无定形的，这将有利于药物络合行为。
• Polymerization of ethylene and propene promoted by binaphthyl-bridged Schiff base complexes of titanium
  作者：Maria Strianese、Marina Lamberti、Mina Mazzeo、Consiglia Tedesco、Claudio Pellecchia

  DOI：10.1016/j.molcata.2006.05.046

  日期：2006.10

  Three new binaphthyl-bridged Schiff base complexes featuring different phenolate substituents (meta-Me, orthopara-di-Cl, orthopara-di-Br) were synthesized. H-1 and C-13 NMR analyses indicated that the cis-beta isomers are preferentially formed in any case. These complexes were tested as precatalysts for ethylene and propene polymerization comparing their behaviour to that of related titanium and zirconium complexes previously reported.The beneficial effect on polymerization activity of halogen atoms in the ortho, para positions of the phenolate rings was also demonstrated. (c) 2006 Elsevier B.V. All rights reserved.