4-Dimethoxyboranylbenzonitrile | 161664-51-3

• 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-Dimethoxyboranylbenzonitrile
• 英文别名: 4-dimethoxyboranylbenzonitrile
• CAS: 161664-51-3
• 化学式: C₉H₁₀BNO₂
• 分子量: 174.995
• InChiKey: PIDLTJFQSWLCPF-UHFFFAOYSA-N

物化性质

• 沸点：
  271.1±23.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.55
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  42.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-Dimethoxyboranylbenzonitrile 在 盐酸 、 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 potassium phosphate 、 水 作用下， 以 水 、 异丙醇 为溶剂， 反应 15.5h， 生成 氰基联苯酚
  参考文献：
  名称：

  焓-熵补偿结合内聚自由能密度调节氰基联苯衍生物的熔融温度

  摘要：

  这项工作说明了4'-（十二烷氧基）-4-氰基联苯甲基化产生的微小结构扰动如何导致其熔融过程的焓-熵补偿，这种趋势可以在简单的分子间内聚模型的框架内进行分析。将在可变温度下收集的熔融热力学参数转换为在共同参考温度下表达的内聚自由能密度，将产生新颖的线性相关性，从中可以简单地从分子体积预测熔融温度。

  DOI：

  10.1002/chem.201300587
• 作为产物：
  描述：

  对氨基苯腈 在 tetrafluoroboric acid 作用下， 以 水 为溶剂， 反应 2.17h， 生成 4-Dimethoxyboranylbenzonitrile
  参考文献：
  名称：

  在温和条件下使用IV类茂金属进行硼酰化

  摘要：

  芳香重氮盐的硼酸酯化反应已使用钛茂和锆茂衍生物作为催化剂进行了优化。该反应使用二异丙基氨基硼烷作为硼化剂，并在室温下平稳进行，以在甲醇解和频哪醇酯交换后提供芳基硼酸酯。已经发现反应机理是通过自由基途径进行的。

  DOI：

  10.1016/j.tetlet.2014.01.080

文献信息

• Effects of substitution and terminal groups for liquid-crystallinity enhanced luminescence of disubstituted polyacetylenes carrying chromophoric terphenyl pendants
  作者：Dan Zhou、YiWang Chen、Lie Chen、Fan Li、HuaRong Nie、Kai Yao

  DOI：10.1007/s11426-010-3166-1

  日期：2010.6

  Liquid-crystalline and light-emitting poly(2-alkyne)s containing terphenyl cores with hexamethyleneoxy spacers, and cyano or n-propoxy tails −“[CH3C=C(CH2)6O-terphenyl-R]” n −, where R=CN, CH3PA6CN, R=OCH2CH2CH3, CH3PA6OPr, were synthesized. The effects of the substitution and terminal groups on the properties, especially the mesomorphic and optical properties of the polymers, were investigated. The disubstituted acetylene monomers (CH3A6CN, CH3A6OPr) were prepared through multistep reaction routes and were polymerized by WCl6-Ph4Sn in good yields (up to 82%). All the monomers and CH3PA6CN exhibited the enantiotropic SmA phase with a monolayer arrangement at elevated temperatures, whereas CH3PA6OPr formed a bilayer SmAd packing arrangement. Upon excitation at 330 nm, strong UV and blue emission peaks at 362 and 411 nm were observed in CH3PA6OPr and CH3PA6CN, respectively. The luminescent properties of CH3PA6CN and CH3PA6OPr have been improved by introducing the methyl substituted group, and the quantum yield of the polymer with cyano tail CH3PA6CN (Φ = 74%) was found to be higher than that of CH3PA6OPr (Φ = 60%). Compared to polyacetylene parents, both CH3PA6OPr and CH3PA6CN showed a narrower energy gap. This demonstrated that the electrical conductivities of polyacetylenes could be enhanced by attaching appropriate pendants to the conjugated polyene backbones.

  含六甲ylene氧间隔基和氰基或n-丙氧基尾的特苯核心的液晶和发光聚（2-炔）（"-[CH3C=C（CH2）6O-特苯基-R]n-"，其中 R=CN，CH3PA6CN，R=OCH2CH2CH3，CH3PA6OPr）被合成。研究了取代基和末端基团对聚合物特性，特别是液晶和光学特性的影响。通过多步反应路线制备了二取代乙炔单体（CH3A6CN，CH3A6OPr），并通过 WCl6-Ph4Sn 聚合得到了良好的产率（高达 82%）。所有单体和 CH3PA6CN 在升高温度下表现出单层排列的反向 SmA 相，而 CH3PA6OPr 形成了双层 SmAd 堆积排列。在 330 nm 激发下，CH3PA6OPr 和 CH3PA6CN 分别观察到 362 和 411 nm 的强 UV 和蓝光发射峰。通过引入甲基取代基团，CH3PA6CN 和 CH3PA6OPr 的发光特性得到了改善，氰基尾聚合物 CH3PA6CN 的量子产率（Φ = 74%）被发现高于 CH3PA6OPr（Φ = 60%）。与聚乙炔母体相比，CH3PA6OPr 和 CH3PA6CN 都显示出更窄的能隙。这表明通过将适当的支链附着到共轭多烯骨架上，可以提高聚乙炔的电导率。
• Synthesis and thermal analysis of disubstituted propiolates bearing terphenylene mesogen
  作者：Lie Chen、Yiwang Chen、Weihua Zhou、Xiaohui He、Yanlin Song、Zhijie Zhang

  DOI：10.1007/s10973-009-0199-9

  日期：2010.2

  Novel disubstituted propiolates bearing chromophoric terphenylene mesogenic groups, namely, 4′-cyano-4-terphenylyl-2-octynate M(CN) and 4′-methoxyl-4-terphenylyl-2-octynate M(OCH3) are synthesized, where the terphenyl groups are connected to the C≡C through ester linkage directly. Using transition-metal catalysts such as the classical MoCl5- and WCl6-based metathesis catalysts, the polymerization of the M(CN) and M(OCH3) are carried out in a series of different solution, however, did not obtain any products. It suggests that the WCl6- and MoCl5-based catalysts are poisoned by the polar groups, on the other hand, the bulk terphenyl groups and the long alkyl chain around the C≡C bond might inhibit the reaction. M(CN) displays monotropic nematicity, whereas M(OCH3) exhibits enantiotropic nematicity and smecticity (SmAd) with a bilayer arrangement when cooled and heated. Ultraviolet spectroscopy and photoluminescence measurements also show that the terphenyl groups endow disubstituted propiolates with strong UV light absorption and high photoluminescence.

  合成了具有色品特苯介质基团的新型二取代丙炔酸酯，分别为4′-氰基-4-特苯基-2-辛酸酯M(CN)和4′-甲氧基-4-特苯基-2-辛酸酯M(OCH3)，其中特苯基团通过酯键直接与C≡C连接。通过使用过渡金属催化剂，如经典的基于MoCl5和WCl6的复分解催化剂，在一系列不同的溶液中进行M(CN)和M(OCH3)的聚合实验，然而未能获得任何产物。这表明WCl6和MoCl5基催化剂被极性基团毒化，另一方面，体积较大的特苯基团和C≡C键周围的长烷基链可能抑制了反应。M(CN)显示出单向性向列相，而M(OCH3)在冷却和加热时则表现出对称性向列相和层状相（SmAd），呈双层排列。紫外光谱和光致发光测量结果也表明，特苯基团赋予了二取代丙炔酸酯强烈的紫外光吸收和高光致发光性能。
• Full-colour luminescent compounds based on anthracene and 2,2′-dipyridylamine
  作者：Bin Chen、Gang Yu、Xin Li、Yubin Ding、Cheng Wang、Zhiwei Liu、Yongshu Xie

  DOI：10.1039/c3tc31751j

  日期：——

  Starting from two simple units of anthracene and 2,2′-dipyridylamine, a series of new luminescent compounds 1–8 were designed and synthesized by a combined strategy of changing the connection mode between the two units, extending the conjugation size, and introducing an additional electron donor. Photophysical properties of 1–8 were investigated and discussed on the basis of solvatochromic behaviour, theoretical calculations, crystal structure, and optimized structures. Interestingly, the emission wavelengths of these compounds could be successfully tuned from violet to red both in solutions and the solid-state, and prominent positive solvatochromism was observed for the compounds with a D–π–A framework. Consider compound 7 as an example, it shows peaks at 526 nm and 627 nm in cyclohexane and DMSO, respectively. Meanwhile, the quantum yield was decreased from 0.80 in cyclohexane to 0.12 in DMSO. The introduction of bulky groups was demonstrated to be effective for suppressing the aggregation effect and thus improving the solid state emission quantum yield. These results indicate that the combined structure modulation strategy offers a powerful tool for tuning the emission behaviour. To demonstrate the possibility of practical applications, 2 was employed as the emitting material for the fabrication of deep-blue organic light-emitting diodes (OLEDs), which showed a maximum external quantum efficiency of 2.2%. The CIE coordinates of (0.15, 0.08) are indicative of excellent blue color purity.

  从两个简单的单元——蒽和2,2'-二吡啶胺出发，设计并合成了一系列新的发光化合物1-8，通过改变两个单元之间的连接方式、扩展共轭尺寸以及引入额外的电子给体的综合策略。对1-8的光物理特性进行了研究，并根据溶液色变行为、理论计算、晶体结构和优化结构进行了讨论。有趣的是，这些化合物的发射波长在溶液和固态中都成功地从紫光调谐到红光，并且在具有D-π-A框架的化合物中观察到显著的正溶剂色变。以化合物7为例，它在环己烷和DMSO中分别显示出526 nm和627 nm的峰值。同时，量子产率在环己烷中从0.80降低到DMSO中的0.12。引入大体积基团被证明对抑制聚集效应有效，从而提高固态发射量子产率。这些结果表明，结合结构调制策略为调节发射行为提供了强大的工具。为了展示实际应用的可能性，化合物2被用作深蓝色有机发光二极管（OLED）制造的发光材料，显示出最大外量子效率为2.2%。其CIE坐标（0.15，0.08）表明良好的蓝色纯度。
• Flow synthesis of arylboronic esters bearing electrophilic functional groups and space integration with Suzuki–Miyaura coupling without intentionally added base
  作者：Aiichiro Nagaki、Yuya Moriwaki、Jun-ichi Yoshida

  DOI：10.1039/c2cc36197c

  日期：——

  We found that an integrated flow microreactor system enables the preparation of boronic esters bearing electrophilic functional groups using organolithium chemistry and that it allows for their use in Suzuki-Miyaura cross-coupling without intentionally added base. Based on this method, cross-coupling of two aryl halides bearing electrophilic functional groups was accomplished to obtain the corresponding

  我们发现，集成的流动微反应器系统能够使用有机锂化学方法制备带有亲电官能团的硼酸酯，并且可以将其用于Suzuki-Miyaura交叉偶联中而无需故意添加碱。基于此方法，完成了两个带有亲电官能团的芳基卤化物的交叉偶联，以一次获得相应的联芳基化合物。
• Functionalization of (2S)-Isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones by a Suzuki-Miyaura Cross-Coupling Reaction Using Aryltrifluoroborate Salts: Convenient Enantioselective Preparation of α-Substituted β-Amino Acids
  作者：Hélio A. Stefani、Monica F. Z. J. Amaral、Gloria Reyes-Rangel、Jorge Vargas-Caporali、Eusebio Juaristi

  DOI：10.1002/ejoc.201000852

  日期：2010.11

  -OMe, -SEt, -CN, -CHO, -Cl, -Cbz, -NCbz, -OH, -CO 2 H) could be tolerated. Hydrogenation of the endocyclic double bonds in the Suzuki-Miyaura products followed by acid hydrolysis afforded highly enantioenriched α-aryl-substituted β-Amino acids.

  Pd(OAc) 2 催化的 1-苯甲酰基-(2S)-isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones 与芳基三氟硼酸钾交叉偶联反应的简单方案已开发。该反应在 110 °C 下使用无配体催化剂进行。在所有情况下，观察到 1-苯甲酰基-(2S)-isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones 和芳基三氟硼酸盐完全转化为 CC 偶联产物在 30- 360 分钟 值得注意的是，芳基三氟硼酸钾中存在的多种基团（-CF 3 、-OMe、-SEt、-CN、-CHO、-Cl、-Cbz、-NCbz、-OH、-CO 2 H）可能是容忍。Suzuki-Miyaura 产品中的环内双键氢化，然后酸水解，得到高度对映体富集的 α-芳基取代的 β-氨基酸。