2-(4-iodophenyl)-1,8a-dihydroazulene-1,1-dicarbonitrile | 298212-99-4

• 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: 2-(4-iodophenyl)-1,8a-dihydroazulene-1,1-dicarbonitrile
• 英文别名: 2-(4-(iodo)phenyl)azulene-1,1(8aH)-dicarbonitrile；2-(4-iodophenyl)-8aH-azulene-1,1-dicarbonitrile
• CAS: 298212-99-4
• 化学式: C₁₈H₁₁IN₂
• 分子量: 382.203
• InChiKey: LFISOURQMMEJTP-UHFFFAOYSA-N

物化性质

• 沸点：
  581.1±50.0 °C(Predicted)
• 密度：
  1.66±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(4-iodophenyl)-1,8a-dihydroazulene-1,1-dicarbonitrile 在 溴 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以95%的产率得到3-bromo-2-(4’-iodophenyl)azulene-1-carbonitrile
  参考文献：
  名称：

  二氢甘菊烯的溶剂依赖性溴化反应

  摘要：

  1,8a-dihydroazulene-1,1-dicarbonitriles (DHA) 的溴化然后消除 HBr 以前被证明是在七元环（在 C7）中功能化这些分子光开关的重要协议。在这里，我们系统地展示了溴化反应的结果如何取决于 DHA C2 位芳基取代基的电子特性，以及溶剂极性，因为反应可以导致加成产物或相应的 2-芳基-1 -bromo-3-cyanoazulene。

  DOI：

  10.1055/s-0035-1560823
• 作为产物：
  描述：

  2[1-(4-iodophenyl)ethylidene]propanedinitrile 在 trityl tetrafluoroborate 、 三乙胺 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 4.0h， 生成 2-(4-iodophenyl)-1,8a-dihydroazulene-1,1-dicarbonitrile
  参考文献：
  名称：

  Photoswitchable Tetraethynylethene-Dihydroazulene Chromophores

  摘要：

  The synthesis. characterization, and photophysical as well as electrochemical properties of the photochromic hybrid systems 11-16 and 18, which contain photoswitchable tetraethynylethene (TEE: 3,4-diethynylhex-3-ene-1,5-diyne) and dihydroazulene (DHA) moieties, are presented. The molecular photoswitches were synthesized by a Sonogashira cross-coupling reaction between an appropriate TEE precursor (6-10 and 17) and an iodinated DHA 1 or its vinylheptafulvene (VHF) isomer (4) (Schemes 5-7). X-Ray crystal structures of five DHA derivatives (1. trans-11a, cis-11a, 12, and 13) are discussed (Figs. 2-5). In all compounds, the cyclohexatriene moiety of the DHA chromophore adopts a clear boat conformation (Table I). presumably due to crystal-packing effects. the arylated TEE moieties in the hybrid systems show substantial distortions from planarity, with the dihedral angles between the plants of the central TEE core and thr adjacent aryl substituents amounting to 43. The switching properties were investigated by electronic absorption spectroscopy. Upon light absorption. DHAs 1. 12-16. and 18 underwent retro-electrocyclization in solution to give the corresponding VHFs( Figs h. II. and 12). The reaction is thermally reversible, with half-lives tau (1,2) between 3.9 and 5.8 h at 2.5 in CH2Cl2 (Figs. 7 and 13 and Table 3). A comparatively slower (E) - (Z) isomerization process about the central C=C bond of the TEE moiety was also observed. The N,N-dimethylanilino-(DMA) substituted TEE-DHA hybrid systems trans-11a and cis-11a did not react to the corresponding VHFs upon irradiation (Scheme 9). Instead. only the reversible (E) - (Z) photoisomerization of the TEE core occurred (Fig. 10 and Table S). This process was further investigated for photofatigue bq electronic-emission spectroscopy (Fig. 17). After protonation of the DMA group, the usual DHA - VHF photoreaction took place. Compound 11 represents a three-way chromophoric molecular switch with three addressable sub-units (TEE core, DHA/VHF moiety, and proton sensitive DMA group) that can undergo individual. reversible switching cycles (Scheme 9). A process modeling the function of an 'AND' logic gate (Fig. 19) and three writc/erase processes could be performed with this system. Cyclic and linear sweep-voltammetry studies in CH2Cl2 (+ Bu4NPF6) revealed the occurrence of characteristic first-reduction steps in the TEE-DHA hybrid systems between - 1.6 and - 1.8 V L'S. Fc/Fc. (ferrocene/ferricinium couple) (Table 5). Oxidations occur at cn. +1.10 V. After photoisomerization to the VHF derivatives. reduction steps at more positive and oxidation steps at mt,re negative potentials H ere recorded. No DHA - VHF isomerization took place upon electrochemical oxidation or reduction (Fig. 20).

  DOI：

  10.1002/1522-2675(20010418)84:4<743::aid-hlca743>3.0.co;2-1

文献信息

• Syntheses of Donor–Acceptor-Functionalized Dihydroazulenes
  作者：Søren Lindbæk Broman、Martyn Jevric、Andrew D. Bond、Mogens Brøndsted Nielsen

  DOI：10.1021/jo4020326

  日期：2014.1.3

  properties relies on ready access to new derivatives via efficient synthetic protocols. The central DHA core is conveniently prepared in a four-step synthesis starting from acetophenone and tropylium substrates. Here, the outcome of this reaction as a function of the nature of the substituent group on the phenyl unit of acetophenone is investigated in detail. A wide variety of functional groups (nitro, cyano

  二氢氮杂烯（DHA）/乙烯基庚二烯（VHF）光电/热敏开关已被广泛用于分子电子学和高级材料中。先前已经发现两种异构体之间的转换很大程度上取决于供体和受体基团的存在。光学和开关特性的微调取决于通过有效的合成协议对新衍生物的便捷访问。中心DHA核心可方便地以四步合成的方式从苯乙酮和对苯二铵底物开始制备。在此，根据苯乙酮的苯基单元上的取代基的性质，对该反应的结果进行了详细研究。可以耐受多种官能团（硝基，氰基，卤素，烷基，酰胺基和硫醚），并且该路线为人们提供了更多选择的DHA衍生物（DHA的位置2）。通过区域选择性溴化-消除方案研究了这些化合物在七元环中随后进行官能化的能力，并在位置7引入了溴取代基。对卤代DHA进行了钯催化的氰化反应，Sonogashira，Cadiot-Chodkiewicz ，铃木联轴器以及后者的反应；通过改变钯催化剂开发了最佳条件。总的来说，我们的重点是减少完全不饱和的z烯
• Palladium-Mediated Strategies for Functionalizing the Dihydroazulene Photoswitch: Paving the Way for Its Exploitation in Molecular Electronics
  作者：Martyn Jevric、Søren Lindbæk Broman、Mogens Brøndsted Nielsen

  DOI：10.1021/jo400362u

  日期：2013.5.3

  The dihydroazulene (DHA)/vinylheptafulvene (VHF) photo/thermoswitch has attracted interest as a molecular switch for advanced materials and molecular electronics. We report here two synthetic approaches using palladium catalysis for synthesizing dihydroazulene (DHA) photoswitches with thioacetate anchoring groups intended for molecular electronics applications. The first methodology involves a Suzuki

  作为先进材料和分子电子学的分子开关，二氢azulene（DHA）/乙烯基庚二烯（VHF）光/热开关引起了人们的兴趣。我们在这里报告了两种使用钯催化的合成方法，用于合成打算用于分子电子应用的具有硫代乙酸酯锚定基团的二氢氮杂烯（DHA）光开关。第一种方法涉及使用叔叔的铃木耦合-丁基硫醚保护基。使用三溴化硼/乙酰氯转化为硫代乙酸酯导致产物形成为由开环反应介导的区域异构体的混合物。第二种方法是通过合成锡烷作为中间体来规避异构化及其在Stille偶联中的应用。尽管在DHA锡烷的合成过程中形成了完全不饱和的天青石副产物，但该方法允许在两个末端之一（位置2或7）或两个末端选择性结合硫代乙酸酯锚定基团。
• Liquid crystalline dihydroazulene photoswitches
  作者：Anne Ugleholdt Petersen、Martyn Jevric、Richard J. Mandle、Edward J. Davis、Stephen J. Cowling、John W. Goodby、Mogens Brøndsted Nielsen

  DOI：10.1039/c5ra18649h

  日期：——

  A large selection of photochromic dihydroazulene (DHA) molecules incorporating various substituents at position 2 of the DHA core was prepared and investigated for their ability to form liquid crystalline phases. Incorporation of an octyloxy-substituted biphenyl substituent resulted in nematic phase behavior and it was possible to convert one such compound partly into its vinylheptafulvene (VHF) isomer

  制备了大量在DHA核的2位掺入各种取代基的光致变色二氢氮杂（DHA）分子，并研究了它们形成液晶相的能力。辛氧基取代的联苯取代基的引入导致向列相行为，并且当在液晶相中被光照射时，可以将一种这样的化合物部分地转化为其乙烯基庚二烯（VHF）异构体。该转化导致相的分子排列增加。随着时间的流逝，亚稳定的VHF返回到DHA，并在此处保持对齐。系统的结构变化表明，DHA和烷基链之间需要一个联芳基间隔基，以实现液晶性，并且该间隔基中的一个芳环不能被三唑取代。
• Dihydroazulene Photoswitch Operating in Sequential Tunneling Regime: Synthesis and Single-Molecule Junction Studies
  作者：Søren Lindbaek Broman、Samuel Lara-Avila、Christine Lindbjerg Thisted、Andrew D. Bond、Sergey Kubatkin、Andrey Danilov、Mogens Brøndsted Nielsen

  DOI：10.1002/adfm.201200897

  日期：2012.10.23

  assure weak coupling, the DHA switching kernel is modified by incorporating p‐MeSC6H4 end‐groups. Molecules are prepared by Suzuki cross‐couplings on suitable halogenated derivatives of DHA. The synthesis presents an expansion of our previously reported bromination–elimination–cross‐coupling protocol for functionalization of the DHA core. For all new derivatives the kinetics of DHA/VHF transition has

  分子开关在分子电子学的发展中起着核心作用。在这项工作中，证明了如果开关核与电极弱耦合，则单分子二氢azulene（DHA）/乙烯基庚富烯（VHF）开关的重现性和耐用性可以得到显着增强，从而电子传输可以通过顺序隧穿进行。为了确保弱耦合，通过合并p- MeSC 6 H 4对DHA交换内核进行了修改。端组。分子是通过Suzuki交叉偶联在合适的DHA卤代衍生物上制备的。该合成显示了我们先前报道的用于DHA核心功能化的溴化-消除-交叉偶联方案的扩展。对于所有新的衍生物，已经在溶液中彻底研究了DHA / VHF跃迁的动力学。动力学揭示了硫端基对VHF热闭环的影响。一种包含p- MeSC 6 H 4的导数锚定基团的一端，已被放置在银纳米间隙中。电导率测量证明，通过DHA（高电阻率）和VHF（低电阻率）两种形式的传输都是通过顺序隧穿进行的。切换是相当可逆和可重入的；经过20多次“ ON-OFF”切换后，
• Multistate Switches: Ruthenium Alkynyl–Dihydroazulene/Vinylheptafulvene Conjugates
  作者：Alexandru Vlasceanu、Cecilie L. Andersen、Christian R. Parker、Ole Hammerich、Thorbjørn J. Morsing、Martyn Jevric、Søren Lindbæk Broman、Anders Kadziola、Mogens Brøndsted Nielsen

  DOI：10.1002/chem.201600178

  日期：2016.5.23

  dependent on the electronic communication between the metal center and the organic photoswitch in these [Ru*]–DHA conjugates. Detailed electrochemical, spectroscopic (UV/Vis, IR, NMR), and X‐ray crystallographic studies indeed reveal significant electronic interactions between the two moieties. When in direct conjugation, the ruthenium metal center was found to quench the photochemical ring‐opening of

  包含独特且可独立寻址的功能组件的多模分子开关具有潜在的应用，如分子电子和存储器存储设备的高级开关和逻辑门。在本文中，我们描述了基于以二氢氮杂烯/乙烯基庚二烯（DHA / VHF）光电/热开关对为基础的四个开关的合成和表征，该对基于钌的Cp *（dppe）Ru（[Ru *]）金属配合物（dppe = 1 ，2-双（二苯基膦基）乙烷； Cp * ＝五甲基环戊二烯基）。[Ru *] – DHA共轭物可能以六种不同状态存在，可通过DHA / VHF，Ru II / Ru III之间的交替访问和炔基/亚乙烯基，可以通过使用光/热，氧化/还原和酸/碱分别进行刺激。发现在这些[Ru *]-DHA共轭物中，进入所有状态的过程很大程度上取决于金属中心与有机光电开关之间的电子通信。详细的电化学，光谱学（UV / Vis，IR，NMR）和X射线晶体学研究确实揭示了两个部分之间的重要电子相互作用。在直接结合时，发