4-bromo-3,6-dibutoxyphthalonitrile | 320614-40-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-bromo-3,6-dibutoxyphthalonitrile
• 英文别名: 4-Bromo-3,6-dibutoxybenzene-1,2-dicarbonitrile
• CAS: 320614-40-2
• 化学式: C₁₆H₁₉BrN₂O₂
• 分子量: 351.243
• InChiKey: AYGKNJJGSMKDPA-UHFFFAOYSA-N

物化性质

• 沸点：
  461.8±45.0 °C(Predicted)
• 密度：
  1.32±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  66
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,4-苯二硼酸 、 4-bromo-3,6-dibutoxyphthalonitrile 在 四(三苯基膦)钯 、 sodium carbonate 作用下， 以 乙醇 、 水 、 甲苯 为溶剂， 反应 72.0h， 以70%的产率得到phenyl-4,4-di(3,6-dibutoxyphthalonitrile)
  参考文献：
  名称：

  A novel selective fluorescent chemosensor for Fe3+ ions based on phthalonitrile dimer: synthesis, analysis, and theoretical studies

  摘要：

  1,4- 苯基双硼酸（1）和 4-溴-3,6-二丁氧基邻苯二甲腈（2）通过铃木交叉偶联反应合成了苯基-4,4-二（3,6-二丁氧基邻苯二甲腈）（3）。新合成的化合物（3）通过傅立叶变换红外光谱、MALDI-MS、ESI-MS、1H-NMR、13C-NMR 和 13C-DEPT-135-NMR 进行了表征。荧光光谱研究了苯基-4,4-二（3,6-二丁氧基邻苯二甲腈）(3) 对各种金属离子的荧光特性，发现该化合物 (3) 对 Fe3+ 有明显的 "熄灭 "反应，这表明配体 (3) 与 Fe3+ 之间形成了 1:2 的络合物。还通过密度泛函理论计算对该化合物进行了研究，揭示了分子与 Fe3+ 离子的相互作用机制。

  DOI：

  10.3906/kim-2004-68
• 作为产物：
  描述：

  3,6-二羟基邻苯二甲腈 在 N-溴代丁二酰亚胺(NBS) 、 potassium carbonate 作用下， 生成 4-bromo-3,6-dibutoxyphthalonitrile
  参考文献：
  名称：

  一些 3,6-二取代邻苯二甲腈的路线和从中衍生的酞菁实例：概述

  摘要：

  本文回顾了一些合成途径，这些途径提供了 3,6-二取代酞腈，这是合成 1,4,8,11,15,18,22,25-八取代酞菁衍生物的前体。评价了使用 Diels-Alder 反应合成 3,6-二烷基、3,6-二烷氧基甲基、3,6-二烯基和 3,6-二苯基邻苯二甲腈的早期路线。然而，审查的重点集中在 2,3-二氰基氢醌作为获得 3,6-二取代邻苯二甲腈的起始原料的范围和应用。使用 2,3-二氰基氢醌的最早例子涉及其 O-烷基化以提供 3,6-二烷氧基邻苯二甲腈。这些是近红外吸收酞菁衍生物的直接前体。2,3-二氰基氢醌的三氟甲磺酸化扩展了该化合物用于合成酞菁的范围；ñAr 反应并容易与硫醇反应生成 3,6-双（烷基硫烷基）和 3,6-双（芳基硫烷基）邻苯二甲腈。3,6-双（苯基硒基）邻苯二甲腈最近也从相同的前体中获得。从中获得的酞菁衍生物通常表现出强烈的红移 Q 波段吸收，该吸收对中心金属离子特别敏感。2

  DOI：

  10.1142/s108842461330005x

文献信息

• X-Ray crystallographic studies of three substituted indium(iii) phthalocyanines: effect of ring substitution and the axial ligand on molecular geometry and packing
  作者：Aur�lien Auger、Paul M. Burnham、Isabelle Chambrier、Michael J. Cook、David L. Hughes

  DOI：10.1039/b413189b

  日期：——

  Crystal structure analyses of a series of three substituted indium phthalocyanines, viz., chloro[1,4,8,11,15,18,22,25-octakis(hexyl)phthalocyaninato]indium(III), 1, 4-fluorophenyl[1,4,8,11,15,18,22,25-octakis(hexyl)phthalocyaninato]indium(III), 2, and racemic chloro[2-bromo-1,4-dibutoxy-8,11,15,18,22,25-hexakis(hexyl)phthalocyaninato]indium(III), 3, are reported. Despite varying the axial ligand from a chloro group to the more space demanding 4-fluorophenyl group, and introducing somewhat different substituents onto one of the benzenoid rings of one of the derivatives, the three compounds form similar types of columnar stacks. Key components of the stack structure are concave–concave pairs of molecules. The molecules are offset but allow for a significant degree of overlap. Components of these pairs then participate in a lower area convex–convex overlap with adjacent pairs to form an offset column of pairs. However, one of the compounds, 1, shows a different type of global packing to the other two. For this compound, the molecules of one column are tilted with respect to those in an adjacent column and thus exhibit a type of herring bone arrangement; the molecules of the other two compounds pack with their central planes parallel. All three compounds form apparently even and transparent films by the spin coating method. UV-vis spectroscopy shows that the visible region absorption band is shifted to the red relative to the solution phase spectra.

  一系列三种取代的铟酞菁，即氯[1,4,8,11,15,18,22,25-八(己基)酞菁]铟(III), 1, 4-氟苯基[ 1,4,8,11,15,18,22,25-八(己基)酞菁]铟(III),2,和外消旋氯[2-溴-1,4-二丁氧基-8,11,15,18报道了22,25-六(己基)酞菁]铟(III), 3。尽管将轴向配体从氯基团改变为需要更多空间的4-氟苯基基团，并且在其中一种衍生物的苯环之一上引入稍微不同的取代基，但这三种化合物形成相似类型的柱状堆叠。堆叠结构的关键组成部分是凹-凹分子对。分子是偏移的，但允许很大程度的重叠。然后，这些对的组件参与与相邻对的较低区域凸凸重叠，以形成对的偏移列。然而，其中一种化合物 1 表现出与其他两种不同类型的全局堆积。对于这种化合物，一列的分子相对于相邻列中的分子倾斜，因此表现出一种人字形排列；其他两种化合物的分子以其中心平面平行排列。所有三种化合物均通过旋涂方法形成明显均匀且透明的薄膜。紫外-可见光谱表明，可见区吸收带相对于溶液相光谱向红色移动。
• Phthalocyaninodehydroannulenes
  作者：Michael J. Cook、Martin J. Heeney

  DOI：10.1002/1521-3765(20001103)6:21<3958::aid-chem3958>3.0.co;2-y

  日期：2000.11.3

  4-Bromo- and 4,5-dibromo-3,6-dibutoxyphthalonitrile have been prepared and treated with 3,6-didecylphthalonitrile in cross tetramerisation reactions in the presence of nickel acetate to afford monobromo- and dibromo-dibutoxyhexadecylphthalocyaninato nickel(II) complexes. Sonogashira and Stille coupling reactions on these compounds displaced the bromine substituents by ethynyl groups. Oxidative coupling of the monoethynyl derivatised nickel phthalocyanine afforded a butadiynyl-linked dinuclear phthalocyanine. The corresponding coupling reaction of the diethynylated phthalocyanine gave a mixture of phthalocyaninodehydroannulenes. Separation of the mixture yielded the diphthalocyaninodehydro[12]annulene as the major product. Electrospray mass spectrometry provides evidence for its aggregation in solution. The corresponding cyclic trimer, the triphthalocyaninodehydro[18]annulene. has been identified as a minor product. Both compounds show a large splitting of the Q-band absorption in the visible region spectrum, Most of the mononuclear phthalocyanine precursors exhibit discotic liquid crystal behaviour. The diphthalocyaninodehydro[12]annulene also enters a mobile phase on heating, hut undergoes an irreversible change at 220 degreesC. MALDI-TOF mass spectrometry of the product reveals that the compound undergoes oligomerisation at this temperature.
• Elongation of the π-System of Phthalocyanines by Introduction of Thienyl Substituents at the Peripheral <i>β</i> Positions. Synthesis and Characterization
  作者：Tsuyoshi Muto、Tetsuji Temma、Mutsumi Kimura、Kenji Hanabusa、Hirofusa Shirai

  DOI：10.1021/jo010384r

  日期：2001.9.1

  1,4,8,11,15,18,22,25-Octabutoxyphthalocyanines ((OBu)(8)Pcs) having eight 2-thienyl (1) and [2,2 ' -bithiophene] -5-yl (2) groups at beta positions and their zinc(II) and cobalt(II) derivatives were prepared from 2-thienyl- (3) or [2,2 ' -bithiophenel-5-yl (4)-substituted phthalonitriles in moderate to good yields. The electronic absorption spectra of the Pes showed red-shifted Q-bands relative to P-unsubstituted (OBu)8Pcs. The longer substituent, the [2,2 ' -bithiophene]-5-yl group, is more effective than the 2-thienyl group in enlarging the a-conjugated system of the Pcs. The ring oxidation potential obtained by cyclic voltammetry shifted cathodically with increasing chain length, indicating destabilization of the HOMOs. Due to the shift of the Q-band, 2-thienyl- and [2,2 ' -bithiophene]-5-yl-substituted Pes exhibit a remarkable color change from the original green color.
• SUBSTITUTED PHTHALOCYANINES AND THEIR PRECURSORS
  申请人：Gentian AS

  公开号：EP1238016A1

  公开（公告）日：2002-09-11
• [EN] SUBSTITUTED PHTHALOCYANINES AND THEIR PRECURSORS<br/>[FR] PHTALOCYANINES SUBSTITUEES ET LEURS PRECURSEURS
  申请人：GENTIAN AS

  公开号：WO2001042368A1

  公开（公告）日：2001-06-14

  This invention relates to a process for the preparation of phthalonitrile sulfonate esters, a process for the preparation of substituted phthalonitriles using said phthalonitrile sulfonate esters, a process for the preparation of substituted phthalocyanines using said substituted phthalonitriles, a process for the preparation of phthalonitrile halides, a process for the preparation of substituted phthalocyanines using said phthalonitrile halides, novel phthalonitrile sulfonate esters, novel substituted phthalonitriles, novel substituted phthalocyanines and certain uses of said novel substituted phthalocyanines.