1,2-二(苄氧基)-4,5-二溴苯 | 206995-42-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 中文名称: 1,2-二(苄氧基)-4,5-二溴苯
• 中文别名: 苯,1,2-二溴-4,5-二(苄氧基)-
• 英文名称: 1,2-dibenzyloxy-4,5-dibromobenzene
• 英文别名: 1,2-bis(benzyloxy)-4,5-dibromobenzene；Benzene, 1,2-dibromo-4,5-bis(phenylmethoxy)-；1,2-dibromo-4,5-bis(phenylmethoxy)benzene
• CAS: 206995-42-8
• 化学式: C₂₀H₁₆Br₂O₂
• 分子量: 448.154
• InChiKey: VYAHNTUWPGULOB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,2-二(苄氧基)-4,5-二溴苯 在 palladium on activated charcoal 正丁基锂 、 dibromo[1,2-bis(diphenylphosphino)ethane]nickel(II) 、 氢气 、 锌 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 12.0h， 生成 3,4-dihydroxy-7,8-dimethoxy-6H-naphtho[1,2-b]benzo[d]pyran-6-one
  参考文献：
  名称：

  Nickel-Catalyzed Synthesis of Benzocoumarins:  Application to the Total Synthesis of Arnottin I

  摘要：

  The ring-opening addition of methyl 2,3-dimethoxy-6-iodobenzoate to oxabenzonorbornadienes followed by cyclization in the presence of NiBr2( dppe) and Zn metal powder in acetonitrile at 80 C to give the corresponding benzocoumarin derivatives is described. This methodology was then applied to the synthesis of natural product arnottin I, first isolated from Xanthoxylum arnottianum Maxim, using protecting group chemistry. After deprotection and subsequent ring closure, arnottin I was obtained in 21% overall yield after six steps starting from catechol.

  DOI：

  10.1021/jo061477h
• 作为产物：
  描述：

  2-苄基-2,4-环己二酮 在 溴 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以92%的产率得到1,2-二(苄氧基)-4,5-二溴苯
  参考文献：
  名称：

  Hydroxyphthalocyanines as Potential Photodynamic Agents for Cancer Therapy

  摘要：

  A series of benzyl-substituted phthalonitriles, substituted at the 3-, 4-, and 4,5-positions, underwent varied condensations with phthalonitrile to give a series of protected (monohydroxy- and polyhydroxyphthalocyaninato)zinc(II) derivatives which were readily cleaved to give several hydroxyphthalocyanines (ZnPc) (phthalocyanine phenol analogues). Their efficacy as sensitizers for the photodynamic therapy (PDT) of cancer was evaluated on the EMT-B mammary tumor cell line. In vitro, the 2-hydroxy ZnPc (32) was the most active, followed by the 2,3- and 2,9-dihydroxy ZnPc (39 and 45), with the 2,9,16-trihydroxy ZnPc (33) exhibiting the least activity. In vivo, the monohydroxy derivative 32 and the 2,3-dihydroxy derivative 39 were both efficient in inducing tumor necrosis at 1 mu mol kg(-1), but complete tumor regression was poor, even at 2 mu mol/kg. In contrast, the 2,9-dihydroxy isomer 45, at 2 mu mol kg(-1), induced tumor necrosis in all animals treated, with 75% complete regression. These results underline the importance of the position of the substituents on the Pc macrocycle to optimize tumor response and confirm the PDT potential of the unsymmetrical Pcs bearing functional groups on adjacent benzene rings.

  DOI：

  10.1021/jm970336s

文献信息

• Synthesis of Crowned Triazolephthalocyanines
  作者：Beatriz Cabezón、Ernesto Quesada、Sagrario Esperanza、Tomás Torres

  DOI：10.1002/1099-0690(200008)2000:15<2767::aid-ejoc2767>3.0.co;2-2

  日期：2000.8

  The synthesis of triazolephthalocyanines bearing crown ether and aza-crown ether substituents is described. Different substituents have been introduced on the nitrogen atom of the aza-crown moiety to improve the solubility and the intrinsic amphiphilic character of these macrocycles. The crowned triazolephthalocyanines described have been prepared by a statistical procedure, and also by different variations

  描述了带有冠醚和氮杂冠醚取代基的三唑酞菁的合成。在氮杂冠部分的氮原子上引入了不同的取代基，以提高这些大环的溶解度和固有的两亲性。所描述的加冠三唑酞菁已通过统计程序以及逐步方法的不同变体制备。还对这一新化合物家族的一个代表的聚集特性进行了初步研究。展示了对三唑酞菁的相应二氰基衍生物前体合成的详尽研究。为此目的使用了两种不同的方法：第一种方法在合成冠醚部分之前插入氰基，而第二个在氰化过程之前构建分子的冠醚部分。Rosemund-von-Braun氰化条件的不相容性和分子中氮原子的存在是这些前体合成的主要难点。
• Hexadecabenzyloxy(diphthalocyanines) of rare-earth elements: synthesis and spectroscopic and electrochemical characteristics
  作者：I. P. Kalashnikova、I. V. Zhukov、L. G. Tomilova、N. S. Zefirov

  DOI：10.1007/s11172-006-0082-9

  日期：2005.9

  elements afforded symmetrical lutetium, dysprosium, samarium, and neodymium complexes with hexadecabenzyloxy(diphthalocyanine), which are well soluble in organic solvents. The spectroscopic and electrochemical characteristics of the complexes obtained were studied.

  4,5-二苄氧基邻苯二甲腈与稀土元素的盐反应生成对称的镥、镝、钐和钕与十六苄氧基（二酞菁）的配合物，这些配合物在有机溶剂中具有良好的溶解性。研究了所得配合物的光谱和电化学特性。
• A New Class of Inhibitors for the Malarial Aspartic Protease Plasmepsin II Based on a Central 11-Azatricyclo[6.2.1.02,7]undeca-2,4,6-triene Scaffold
  作者：David A. Carcache、Simone R. Hörtner、Andreas Bertogg、François Diederich、Arnulf Dorn、Hans Peter Märki、Christoph Binkert、Daniel Bur

  DOI：10.1002/hlca.200390177

  日期：2003.6

  4-arylpiperidines – including the unlocking of a new hydrophobic (flap) pocket – were modeled. The sequence identity of 35% between mature renin and PMII had prompted us to hypothesize that an induced-fit adaptation around the active site as observed in renin might also be effective in PMII. The new inhibitors contain a central 11-azatricyclo[6.2.1.02,7]undeca-2(7),3,5-triene core, which, in protonated form,

  通过基于结构的从头设计，开发了一种新型的，高达单个数微摩尔活性（IC 50值）的疟疾天冬氨酸蛋白酶-纤溶酶II（PMII）的非肽类抑制剂。设计中使用的活性部位基质基于PMII的X射线晶体结构，在4-芳基哌啶络合后，肾素结构上看到的主要构象变化–包括解锁新的疏水性（瓣）口袋–被建模。成熟的肾素和PMII之间35％的序列同一性促使我们假设，如在肾素中观察到的，围绕活性位点的诱导适应适应在PMII中也可能有效。新的抑制剂含有一个中心的11-氮杂三环[6.2.1.0 2,7] undeca-2（7），3,5-三烯核，质子化形式，与两个PMII活性位点的催化Asp残基进行离子H键合（图1和2）。通过活化的吡咯和就地产生的苯并species物质之间的狄尔斯-阿尔德反应，可以容易地制备该三环支架（方案1）。两个与萘基或1,3-苯并噻唑基部分取代基连接到中央芯体（方案1 - 4），用于容纳在疏水襟翼和S1
• Hydrophobic‐Driven, Metallomacrocyclic Assembly – Towards Quantitative Construction
  作者：Ting‐Zheng Xie、Jing‐Yi Li、Zaihong Guo、James M. Ludlow、Xiaocun Lu、Charles N. Moorefield、Chrys Wesdemiotis、George R. Newkome

  DOI：10.1002/ejic.201600048

  日期：2016.4

  resulting complexes were characterized by NMR spectroscopy and ESI-MS coupled with travelling wave ion mobility spectrometry (ESI-TWIM-MS) experiments. The desired bis-macrocycles were obtained in quantitative yields through the use of long alkyl-chain substituents, in contrast to the lower yields obtained for smaller alkyl moieties.

  通过将四（三联吡啶基）噻蒽和双联三联吡啶、60°定向、Ru2+二聚体相结合，设计并构建了一系列配位驱动、杂配自组装、领结形双大环。所得配合物通过 NMR 光谱和 ESI-MS 结合行波离子迁移谱 (ESI-TWIM-MS) 实验进行表征。通过使用长烷基链取代基以定量产率获得所需的双大环，而较小烷基部分的产率较低。
• From supramolecular triangle to heteroleptic rhombus: a simple bridge can make a difference
  作者：Xiaocun Lu、Xiaopeng Li、Jin-Liang Wang、Charles N. Moorefield、Chrys Wesdemiotis、George R. Newkome

  DOI：10.1039/c2cc35510h

  日期：——

  Multicomponent, self-assembled rhomboidal constructs are reported, in which bis-terpyridines possessing 120° or 60° directionality and ZnII or CdII in a stoichiometric ratio (1 : 1 : 2) initially form rhomboid and triangle mixtures; whereas, a tris-terpyridine reacts with the 60°-based bis-ligand and metal to quantitatively form a heteroleptic, centrally fused, rhomboidal structure.

  报道了一种多组分自组装的菱形结构，其中具有120°或60°方向性的双吡啶和ZnII或CdII以化学计量比（1:1:2）初步形成菱形和三角形混合物；而三吡啶与60°基双配体和金属反应，定量形成一种异配位的、中心融合的菱形结构。