4-甲基偶氮苯 | 57573-52-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 4-甲基偶氮苯
• 英文名称: 4-methylbenzene diazonium
• 英文别名: 4-methyl-benzenediazonium ion；p-methylbenzenediazonium；4-methylbenzenadiazonium；4MBD；4-methyl-benzenediazonium cation；Toluol-4-diazonium-Salz；4-Methylbenzenediazonium
• CAS: 57573-52-1
• 化学式: C₇H₇N₂
• 分子量: 119.146
• InChiKey: LWYMLCYZEMSNBK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-甲基偶氮苯 在 tin 、 盐酸 、 copper(II) nitrate 作用下， 以 水 为溶剂， 以80%的产率得到对氯甲苯
  参考文献：
  名称：

  Sn +2或抗坏血酸对重氮盐反应的刺激

  摘要：

  使用温和的还原剂和配体转移将重氮盐转化为芳基卤化物提供了Sandmeyer方法的替代方法。

  DOI：

  10.1016/s0040-4039(00)74537-0
• 作为产物：
  描述：

  乙烷,三氯氟- 在 氢氟酸 、 sodium nitrite 作用下， 反应 2.0h， 以80%的产率得到4-甲基偶氮苯
  参考文献：
  名称：

  使用 HF 或 HF 碱在氨基芳烃的一锅重氮化和氟去重氮中制备氟芳烃。HF溶液中碱的作用

  摘要：

  在苯胺的一锅重氮化，然后使用 HF 或 HF 以碱 (HF-Base) 作为溶剂进行原位氟代重氮化中，已发现重氮化阶段对有效产生氟芳烃起到最重要的作用。HF 溶液的组成对苯胺的重氮化有很大的影响，并通过使用适量的碱，如吡啶，大大增强了苯胺的重氮化。另一方面，重氮盐的氟脱重氮一旦形成，就很容易在 HF 或 HF-碱中发生，以高产率生产氟芳烃，尽管这些碱在一定程度上减缓了重氮盐的分解速度。

  DOI：

  10.1246/bcsj.63.2058
• 作为试剂：
  描述：

  4-oxo-3-p-tolyl-4,5-dihydro-[1,2,3]thiadiazolium betaine 在 吡啶 、 4-甲基偶氮苯 作用下， 生成 4-oxo-3,5-di-p-tolyl-4,5-dihydro-[1,2,3]thiadiazolium betaine
  参考文献：
  名称：

  612.巯基乙酸（巯基乙酸）的含氮衍生物制成的脱水化合物。第三部分 芳偶氮化合物

  摘要：

  DOI：

  10.1039/jr9560003189

文献信息

• The effect of <i>ortho</i> and <i>para</i> substituents on the formation of the <i>E</i> and <i>Z</i> isomers of the arylhydrazones obtained from diazonium coupling with methyl 3-aminocrotonate and 3-aminocrotononitrile
  作者：Jason V. Jollimore、Marc Vacheresse、Keith Vaughan、Donald L. Hooper

  DOI：10.1139/v96-029

  日期：1996.2.1

  Reaction of arene diazonium salts with 3-aminocrotononitrile or methyl 3-aminocrotonate affords the 2-aryl-hydrazono-3-oxobutanenitrile (1 or 3 and 3′) or the methyl 2-arylhydrazono-3-oxobutanoate (2 and 2′ or 4 and 4′). A series of these hydrazones has been prepared with a range of electron-withdrawing and -donating substituents in the ortho or para position of the aryl moiety. The hydrazones have been characterized by spectroscopic methods, with emphasis on the ¹H NMR spectra, which have been used to determine the configuration of the hydrazones as E or Z or a mixture of the two. The para-substituted hydrazononitriles (1) are formed as a single species, namely the Z isomer, whereas the ortho isomers are formed as a mixture of E and Z configurations (3 and 3′). The hydrazonobutanoates (2 and 2′ or 4 and 4′) are formed as E/Z mixtures regardless of the position of the substituent in the aryl moiety. Complete assignments of all signals in the ¹H NMR spectra have been made on the basis of the ability of the various substituents to participate in intramolecular hydrogen bonding and a mechanism is proposed to account for the variations in the proportions of E and Z isomers and the effect of the nature of the substituent on this ratio. ¹³C NMR spectra of selected hydrazones have been recorded as an aid to structure assignment. Key words: hydrazone, diazonium, NMR spectroscopy, E/Z isomers, crotonic acid derivatives.

  芳香族重氮盐与3-氨基丙烯腈或甲基3-氨基丙烯酸酯反应，得到2-芳基-叠氮基-3-氧代丁腈（1或3和3'）或甲基2-芳基叠氮基-3-氧代丁酸酯（2和2'或4和4'）。已制备了一系列这些叠氮基化合物，其中芳基部分的邻位或对位具有一系列电子吸引或供给取代基。这些叠氮基化合物已通过光谱方法进行表征，重点放在¹H NMR谱上，该谱已用于确定叠氮基的构型为E或Z或两者的混合物。对位取代的叠氮基腈（1）形成为单一种类，即Z异构体，而邻位异构体形成为E和Z构型的混合物（3和3'）。叠氮基丁酸酯（2和2'或4和4'）无论芳基部分的取代基位置如何，都形成为E/Z混合物。基于各种取代基参与分子内氢键形成的能力，已对¹H NMR谱中所有信号进行了完整的指认，并提出了一种机制来解释E和Z异构体的比例变化以及取代基性质对此比例的影响。已记录了选定叠氮基的¹³C NMR谱，以帮助结构指认。关键词：叠氮基，重氮盐，NMR光谱，E/Z异构体，丙烯酸衍生物。
• Nano-Fe₃O₄ encapsulated-silica supported boron trifluoride as a novel heterogeneous solid acid for solvent-free synthesis of arylazo-1-naphthol derivatives
  作者：Abdolhamid Bamoniri、Naimeh Moshtael-Arani

  DOI：10.1039/c4ra12604a

  日期：——

  Fe₃O₄@SiO₂–BF₃ nanoparticles were prepared as a novel solid acid and effectively applied for the solvent-free synthesis of arylazo-1-naphthols at room temperature.

  Fe₃O₄@SiO₂-BF₃纳米颗粒被制备为一种新型固体酸，并有效地应用于室温下的无溶剂合成芳基偶氮基-1-萘酚。
• pH Effects on Ethanolysis of Some Arenediazonium Ions: Evidence for Homolytic Dediazoniation Proceeding through Formation of Transient Diazo Ethers
  作者：Roman Pazo-Llorente、Carlos Bravo-Diaz、Elisa Gonzalez-Romero

  DOI：10.1002/ejoc.200400170

  日期：2004.8

  inflection points at pH ≈ 3.6, depending on solvent composition. With increasing pH, kobsd. values increase by factors of up to about 4 (2MBD), about 3 (3MBD), and about 50 (4MBD) with respect to the kobsd. values at low pH. HPLC analyses of the reaction mixtures show that only heterolytic products are obtained at low pH, indicating that solvolytic dediazoniation takes place through an ionic mechanism

  pH 值对观察到的速率常数 (kobsd.) 和 2-、3- 和 4-甲基苯重氮离子（分别为 2MBD、3MBD 和 4MBD）乙醇分解的溶剂解脱重氮产物分布的影响由以下组合确定分光光度法 (UV/Vis) 和色谱 (HPLC) 技术。两个 kobsd 的变化。和产物产率随 pH 值呈 S 形曲线，拐点在 pH ≈ 3.6，具体取决于溶剂组成。随着 pH 值的增加，kobsd。值相对于 kobsd 增加了大约 4 (2MBD)、大约 3 (3MBD) 和大约 50 (4MBD)。低 pH 值。反应混合物的 HPLC 分析表明，在低 pH 值下仅获得异溶产物，表明溶剂分解脱重氮是通过离子机制发生的，但 pH 值的增加有利于均裂脱重氮作用，在 pH ⩾ 6 (4MBD) 下定量转化为还原产物甲苯，表明在 EtO 含量微不足道的实验条件下，发生了从异裂机制到均裂机制的转变- 或 OH- 应存在于溶液中。获得的
• Predominance of 2-arylhydrazones of 1,3-diphenylpropane-1,2,3-trione over its proton-transfer products
  作者：Ryszard Gawinecki、Erkki Kolehmainen、Henryk Janota、Reijo Kauppinen、Maija Nissinen、Borys O?mia?owski

  DOI：10.1002/poc.435

  日期：2001.11

  substituent effect is transmitted effectively only to the hydrazone nitrogen and hydrogen atoms. Ab initio calculations show that the ketohydrazone tautomer is really very much favoured over its proton-transfer products in chloroform solution. The same tautomer was also detected in the crystal state by X-ray crystallography. Copyright © 2001 John Wiley & Sons, Ltd.

  通过15 N NMR化学位移在氯仿溶液中检测到1,3-二苯基-1,2,3-三酮的2-苯hydr是主要的互变异构形式。苯hydr部分中的取代基不影响该互变异构偏好。取代基效应仅有效地传递至的氮和氢原子。从头算计算表明，酮hydr互变异构体确实比氯仿溶液中的质子转移产物更受青睐。还通过X射线晶体学在晶体状态下检测到相同的互变异构体。版权所有©2001 John Wiley＆Sons，Ltd.
• Genetic variability and expression of phenological and morphological differences in populations of <i>Delia radicum</i> (Diptera: Anthomyiidae)
  作者：D.G. Biron、D. Coderre、G. Boivin、E. Brunel、J.P. Nénon

  DOI：10.4039/ent134311-3

  日期：2002.6

  In this study, survival to adult stage, duration of development of the immature stages, egg micromorphology, DNA polymorphism, and reproductive compatibility were measured for early- and late-emerging phenotypes of Delia radicum Linneaus to determine whether both phenotypes had evolved differences other than the duration of puparial development and to find the most likely genetic system controlling the expression of both phenotypes. Survival to adult stage was not significantly different between the early- and late-emerging phenotypes. Random amplified polymorphic DNA (RAPD) primers tested suggest that it is possible to distinguish an early-emerging fly from a late-emerging fly. Furthermore, the results suggest that the early- and late-emerging phenotypes differ not only in the timing of adult emergence but also in their egg structure (egg micromorphology) and in their larval and puparial mortality. These two phenotypes are not reproductively or ecologically isolated. The genetic system controlling the expression of early and late emergers in a population of D. radicum is probably an adaptive strategy reducing predator and parasitoid pressures, optimizing resource utilization, and ensuring survival of D. radicum during atypical winters. This strategy could eventually lead to temporal sympatric speciation if there are changes in a few key loci responsible for host plant selection and fitness on a new host.

  摘要 本研究测定了林尼厄斯蝇（Delia radicum Linneaus）早龄和晚龄表型的成虫存活率、未成熟期发育持续时间、卵微形态、DNA多态性和生殖相容性，以确定这两种表型是否存在除蛹发育持续时间以外的进化差异，并找到控制这两种表型表达的最可能的遗传系统。早发和晚发表型在成虫阶段的存活率没有显著差异。测试的随机扩增多态性 DNA（RAPD）引物表明，可以区分早出蝇和晚出蝇。此外，研究结果表明，早发和晚发表型不仅在成虫出现的时间上不同，而且在卵的结构（卵微形态）以及幼虫和蛹的死亡率上也不同。这两种表型在生殖或生态上并不隔离。控制滇金丝猴种群中早期和晚期成虫表达的遗传系统可能是一种适应性策略，可减少捕食者和寄生虫的压力，优化资源利用，确保滇金丝猴在非典型冬季存活。如果负责寄主植物选择和在新寄主上的适应性的几个关键基因座发生变化，这种策略最终可能会导致时间上的同域物种分化。