(E)-1,1'-(diazene-1,2-diyl)bis(1,3-phenylene)bis(ethan-1-one) | 151224-49-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 偶氮苯
• 英文名称: (E)-1,1'-(diazene-1,2-diyl)bis(1,3-phenylene)bis(ethan-1-one)
• 英文别名: 3,3'-diacetyl-trans-azobenzene；(E)-1,1'-(diazene-1,2-diylbis(3,1-phenylene))bis(ethan-1-one)
• CAS: 151224-49-6
• 化学式: C₁₆H₁₄N₂O₂
• 分子量: 266.299
• InChiKey: DOIWHHWUHOVBBP-ISLYRVAYSA-N

物化性质

• 沸点：
  450.6±30.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.51
• 重原子数：
  20.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  58.86
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (E)-1,1'-(diazene-1,2-diyl)bis(1,3-phenylene)bis(ethan-1-one) 在 镍 、 hydrazinium monoformate 作用下， 以 甲醇 为溶剂， 反应 0.15h， 以90%的产率得到间氨基苯乙酮
  参考文献：
  名称：

  使用雷尼镍和单甲酸肼将偶氮化合物轻松转移氢化为偶氮化合物和苯胺

  摘要：

  摘要 根据反应条件，通过在单甲酸肼鎓存在下使用雷尼镍，可以方便地将偶氮化合物还原为部分还原的偶氮化合物或完全还原的苯胺。可以容忍其他可还原部分，如 ‒COOH 和卤素。还原过程具有选择性、快速和高产。

  DOI：

  10.1081/scc-120027231
• 作为产物：
  描述：

  3,3'-diacetyl-cis-azobenzene 在 2,4-bis(cyclohexylamino)-6-methoxy-1,3,5-triazine 作用下， 以 二氯甲烷 为溶剂， 生成 (E)-1,1'-(diazene-1,2-diyl)bis(1,3-phenylene)bis(ethan-1-one)
  参考文献：
  名称：

  Effects of the hydrogen-bonded interactions on the thermal cis to trans isomerization of 3,3′-diacetylazobenzene

  摘要：

  在 2,4-双（环己基氨基）-6-甲氧基-l,3,5-三嗪的存在下，3,3â²-二乙酰基-顺式偶氮苯 1b 的热异构化会因分子间氢键组装的形成而减慢。

  DOI：

  10.1039/c39930001044

文献信息

• Structure and Reactivity of Half-Sandwich Rh(+3) and Ir(+3) Carbene Complexes. Catalytic Metathesis of Azobenzene Derivatives
  作者：Daniel J. Tindall、Christophe Werlé、Richard Goddard、Petra Philipps、Christophe Farès、Alois Fürstner

  DOI：10.1021/jacs.7b12673

  日期：2018.2.7

  Specifically, the donor/acceptor carbene 10a derived from ArC(═N2)COOMe and [Cp*RhCl2]2 undergoes spontaneous 1,2-migratory insertion of the emerging carbene unit into the Rh-Cl bond with formation of the C-metalated rhodium enolate 11. In contrast, the analogous complexes 10b,c derived from [Cp*RhX2]2 (X = Br, I) as well as the iridium species 13 and 14 derived from [Cp*IrCl2]2 are sufficiently stable

  传统的铑卡宾化学依赖于重氮衍生物与 [Rh2(OAc)4] 或相关双核 Rh(+2) 配合物的受控分解，而其他铑源的使用则要少得多。现在表明，源自 [Cp*MX2]2（M = Rh、Ir；X = Cl、Br、I，Cp* = 五甲基环戊二烯基）的半夹心卡宾物种也表现出良好的应用特性。有趣的是，在环丙烷化、环氧化物形成和以前未知的偶氮苯衍生物催化复分解的情况下，阴离子配体 X 被证明是反应性的关键决定因素，而 X 的性质在 -OH 插入反应中没有发挥任何重要作用。这种令人困惑的差异可以根据一组具有代表性的此类卡宾配合物的光谱和晶体学数据来解释，尽管它们具有明显的亲电性，但仍可以将其分离。具体而言，衍生自 ArC(=N2)COOMe 和 [Cp*RhCl2]2 的供体/受体卡宾 10a 经历了出现的卡宾单元自发的 1,2-迁移插入到 Rh-Cl 键中，形成了 C-金属化的铑enolate 11.
• Convergent Paired Electrochemical Synthesis of Azoxy and Azo Compounds: An Insight into the Reaction Mechanism
  作者：Ali Sadatnabi、Niloofar Mohamadighader、Davood Nematollahi

  DOI：10.1021/acs.orglett.1c02304

  日期：2021.8.20

  convergent paired electrochemical method was developed for the synthesis of azoxy and azo compounds starting from the corresponding nitroarenes. We propose a unique mechanism for electrosynthesis of azoxy and azo compounds. We find that both anodic and cathodic reactions are responsible for the synthesis of these compounds. The synthesis of azoxy and azo derivatives have been successfully performed in an undivided

  开发了一种收敛配对电化学方法，用于从相应的硝基芳烃开始合成偶氮和偶氮化合物。我们提出了一种独特的偶氮和偶氮化合物电合成机制。我们发现阳极和阴极反应都负责这些化合物的合成。偶氮和偶氮衍生物的合成已在未分隔的电池中成功进行，使用碳棒电极，在室温下通过恒流电解。
• Palladium-Catalyzed Direct <i>ortho</i> Alkoxylation of Aromatic Azo Compounds with Alcohols
  作者：Zhangwei Yin、Xiaoqing Jiang、Peipei Sun

  DOI：10.1021/jo401623j

  日期：2013.10.4

  highly regioselective synthesis of 2-alkoxy aromatic azo compounds via palladium(II)-catalyzed alkoxylation of azobenzene derivatives directed by the azo group using alcohols as the alkoxylation reagents and PhI(OAc)2 as the oxidant has been developed. The method is applicable to both primary and secondary alcohols and affords moderate to good yields.

  通过使用醇作为烷氧基化试剂和PhI（OAc）2作为氧化剂，通过钯（II）催化由偶氮基团引导的偶氮苯衍生物的偶氮苯衍生物的烷氧基化，可以高效且高度区域选择性地合成2-烷氧基芳族偶氮化合物。该方法适用于伯醇和仲醇，收率中等至良好。
• Behavior of organic compounds confined in monoliths of sol–gel silica glass. Effects of guest–host hydrogen bonding on uptake, release, and isomerization of the guest compounds
  作者：Jovica D. Badjić、Nenad M. Kostić

  DOI：10.1039/b005823h

  日期：——

  Various proteins, catalysts, and other compounds can be encapsulated or diffused into porous sol–gel glasses, but little is known about their interactions with the glass matrix. We report unexpectedly large effects that hydrogen bonding between organic compounds and sol–gel silica has on equilibria and reactions involving these guest compounds. Silica monolith immersed in a solution takes up the organic solute. Styrene, which is incapable of hydrogen bonding, becomes evenly distributed between external solution and the glass. Aniline and N,N-diethyl-p-methoxybenzamide, which are capable of hydrogen bonding, become extracted into the glass when the solvent (neat CCl4) does not interfere with their hydrogen bonding with silica. They become evenly distributed between the solution and the glass when a component of the solvent (DMF added to CCl4) or chemical modification (trimethylsilylation) of the silica surface suppresses hydrogen bonding of the guests with the surface. Ultraviolet spectra show that silica–guest interactions are present when the guest uptake is excessive and absent when this uptake is balanced. Ultraviolet spectra of aniline show that the hydrogen atoms are donated by silica to the guest. Not only the extent, but also the rate, of uptake is enhanced when the guest makes hydrogen bonds to the silica matrix; suppression of these bonds lowers the uptake rate. Silica monolith extracts trans-3,3′-diacetylazobenzene from a CCl4 solution 1250-fold. Upon addition of DMF, hydrogen bonds are broken, and the monolith completely releases the solute into the external solution. Five derivatives of azobenzene (3,3′-dimethyl-, 3-acetyl-, 3,3′-diacetyl-, 3,5-diacetyl-, and 3,3′,5,5′-tetraacetylazobenzene), which differ in the propensity for accepting hydrogen atoms, served as photochromic probes and showed the effect of hydrogen bonding on reactivity. Both the photoinduced (trans-to-cis) and the subsequent thermal (cis-to-trans) isomerizations of the five derivatives obey the first-order law in glass as well as in free solution. When the solvent (neat CCl4) allows hydrogen bonding, the proportion of the isomers in the photostationary state differs between the glass and solution, and the rate constant for the thermal reaction is two to four times (in different derivatives) smaller in the glass than in solution. Evidently, hydrogen bonding retards the rearrangement of the probe molecules in the silica matrix. When hydrogen bonding is abolished (by addition of DMF to CCl4), the compositions of the photostationary state in the glass and in solution become equal, and so do the rate constants. Effects of hydrogen bonding on enzymes encapsulated in sol–gel glass and on the distribution of analytes between the glass monolith and the sample solution should be taken into consideration when designing accurate biosensors.

  各种蛋白质、催化剂和其他化合物都可以封装或扩散到多孔溶胶玻璃中，但人们对它们与玻璃基质的相互作用却知之甚少。我们报告了有机化合物与溶胶二氧化硅之间的氢键作用对涉及这些客体化合物的平衡和反应产生的意想不到的巨大影响。浸入溶液中的二氧化硅整体吸收有机溶质。不能发生氢键作用的苯乙烯会均匀地分布在外部溶液和玻璃之间。苯胺和 N,N-二乙基对甲氧基苯甲酰胺能够形成氢键，当溶剂（纯净的 CCl4）不干扰它们与二氧化硅的氢键结合时，它们就会被萃取到玻璃中。当溶剂中的某种成分（在 中加入 DMF）或二氧化硅表面的化学修饰（三甲基硅烷化）抑制了客体与二氧化硅表面的氢键结合时，它们就会在溶液和玻璃之间均匀分布。紫外光谱显示，当客体吸收过多时，二氧化硅与客体之间存在相互作用，而当这种吸收平衡时，则不存在相互作用。苯胺的紫外光谱显示，二氧化硅向客体提供了氢原子。当客体与二氧化硅基质形成氢键时，吸收的程度和速度都会提高；抑制这些氢键则会降低吸收速度。二氧化硅整体从 溶液中萃取反式-3,3â²-二乙酰偶氮苯的能力提高了 1250 倍。加入 DMF 后，氢键断裂，硅石将溶质完全释放到外部溶液中。偶氮苯的五种衍生物（3,3â²-二甲基偶氮苯、3-乙酰基偶氮苯、3,3â²-二乙酰基偶氮苯、3,5-二乙酰基偶氮苯和 3,3â²,5,5â²-四乙酰基偶氮苯）接受氢原子的倾向各不相同，它们可用作光致变色探针，并显示了氢键对反应活性的影响。这五种衍生物的光诱导异构化（反式-顺式）和随后的热异构化（顺式-反式）在玻璃中和自由溶液中都符合一阶定律。当溶剂（纯净的 ）允许氢键作用时，玻璃和溶液中处于光静止状态的异构体比例不同，热反应的速率常数在玻璃中比在溶液中小 2 到 4 倍（对于不同的衍生物）。显然，氢键阻碍了探针分子在二氧化硅基质中的重新排列。当氢键被取消时（在 中加入 DMF），玻璃中的光静止态成分与溶液中的光静止态成分相等，速率常数也相等。在设计精确的生物传感器时，应考虑到氢键对封装在溶胶玻璃中的酶以及分析物在玻璃整体和样品溶液之间分布的影响。
• Control of the thermalcis totrans isomerizations of azobenzene and thioindigo derivatives by the formation of supramolecular H-bonded assemblies
  作者：Jacqueline Rosengaus、Itamar Willner

  DOI：10.1002/poc.610080111

  日期：1995.1

  (association constants K = 4.9 × 104 and 3.5 × 105 1 mol−1, respectively). The thermal cis→trans isomerization of 4b and 5b to 3,3′-diacetyl-trans-azobenzene (4a), and 6,6′-diethoxy-trans-thioindigo (5a), is inhibited in the intermolecular complex 1a–4b and 1a–5b. Molecular mechanics calculations support the formation of the intermolecular H-bonded complexes between 1a and 4b or 5b.

  2,3-双（氨基环己基）-6-甲氧基-1,3,5-三嗪（1a）与3,3'-二乙酰基-顺式-偶氮烯（4）和6,6'-二乙氧基形成分子间H键合的配合物-顺式-硫靛蓝（5b），（缔合常数K分别为4.9×10 4和3.5×10 5 1 mol -1）。4b和5b的热顺→反异构化为3,3'-二乙酰基-反-偶氮苯（4a）和6,6'-二乙氧基-反-硫代靛蓝（5a）在分子间复合物1a–4b和1a-5b。分子力学计算支持在1a和4b或5b之间形成分子间H键合的配合物。