m-methylbenzenediazonium tetrafluoroborate | 1422-76-0

• 英文名称: m-methylbenzenediazonium tetrafluoroborate
• 英文别名: 3-methylbenzenediazonium tetrafluoroborate；3-methylbenzene-1-diazonium tetrafluoroborate；3-methylphenyldiazonium tetrafluoroborate；3-methylphenyldiazonium fluoroborate；m-toluenediazonium tetrafluoroborate
• CAS: 1422-76-0
• 化学式: BF₄*C₇H₇N₂
• 分子量: 205.951
• InChiKey: UWSQPXMWXDVLHS-UHFFFAOYSA-N

物化性质

• 熔点：
  108 °C (decomp)

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

安全信息

• 海关编码：
  2927000090

反应信息

• 作为反应物：
  描述：

  m-methylbenzenediazonium tetrafluoroborate 在 sodiumsulfide nonahydrate 作用下， 以 水 为溶剂， 反应 0.25h， 以81%的产率得到di-m-tolyl sulfide
  参考文献：
  名称：

  对称和不对称硫化物的合成及纳米钯催化的化学选择氧化

  摘要：

  已经开发出一种高度化学选择性，高效和纳米钯催化的方案，分别通过使用H 2 O 2作为氧化剂，通过对称和不对称硫化物的氧化来快速构建亚砜和砜。起始材料的可用性，催化剂的易于回收和再利用，广泛的底物范围以及高收率使得该方案成为有吸引力的替代方案。该方法还涉及无金属和微波促进的对称的二芳基硫醚的合成，以及FeCl 3介导的芳族重氮四氟硼酸盐与Na 2 S·9H 2的反应制备对称的二芳基二硫化物。O作为硫源。另外，经由K 2 CO 3介导的四氟硼酸壬二唑鎓与对称的二硫化物的反应产生了不对称的硫化物。

  DOI：

  10.1039/c8ob03209b
• 作为产物：
  描述：

  在 亚硝酸特丁酯 作用下， 以 四氢呋喃 为溶剂， 生成 m-methylbenzenediazonium tetrafluoroborate
  参考文献：
  名称：

  Discovery and structure-activity relationship studies of 1-aryl-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione derivatives as potent dual inhibitors of indoleamine 2,3-dioxygenase 1 (IDO1) and trytophan 2,3-dioxygenase (TDO)

  摘要：

  Indoleamine 2,3-dioxygenase 1 (IDO1) and tryptophan 2,3-dioxygenase (TDO), which mediate kynurenine pathway of tryptophan degradation, have emerged as potential new targets in immunotherapy for treatment of cancer because of their critical role in immunosuppression in the tumor microenvironment. In this investigation, we report the structural optimization and structure-activity relationship studies of 1-phenyl-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione derivatives as a new class of IDO1/TDO dual inhibitors. Among all the obtained dual inhibitors, 1-(3-chloro-4-fluorophenyl)-6-fluoro-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione (38) displayed the most potent IDO1 and TDO inhibitory activities with IC₅₀ (half-maximal inhibitory concentration) values of 5 nM for IDO1 and 4 nM for TDO. It turned out that compound 38 was not a PAINS compound. Compound 38 could efficiently inhibit the biofunction of IDO1 and TDO in intact cells. In LL2 (Lewis lung cancer) and Hepa1-6 (hepatic carcinoma) allograft mouse models, this compound also showed considerable in vivo anti-tumor activity and no obvious toxicity was observed. Therefore, 38 could be a good lead compound for cancer immunotherapy and deserving further investigation.

  DOI：

  10.1016/j.ejmech.2020.112703

文献信息

• A general electrochemical strategy for the Sandmeyer reaction
  作者：Qianyi Liu、Beiqi Sun、Zheng Liu、Yi Kao、Bo-Wei Dong、Shang-Da Jiang、Feng Li、Guoquan Liu、Yang Yang、Fanyang Mo

  DOI：10.1039/c8sc03346c

  日期：——

  Herein we report a general electrochemical strategy for the Sandmeyer reaction. Using electricity as the driving force, this protocol employs a simple and inexpensive halogen source, such as NBS, CBrCl3, CH2I2, CCl4, LiCl and NaBr for the halogenation of aryl diazonium salts. In addition, we found that these electrochemical reactions could be performed using anilines as the starting material in a one-pot

  本文中，我们报告了桑德迈尔反应的一般电化学策略。使用电作为驱动力，该协议采用一种简单且廉价的卤素源，例如NBS，CBrCl 3，CH 2 I 2，CCl 4，LiCl和NaBr进行芳基重氮盐的卤化。另外，我们发现这些电化学反应可以以一锅的方式使用苯胺作为起始原料来进行。此外，该方法的实用性在使用非常便宜的石墨作为电极的多克规模的芳基卤化物的合成中得到了证明。已经进行了一系列详细的机理研究，包括自由基时钟和自由基清除剂研究，循环伏安分析和原位电子顺磁共振（EPR）分析。
• Sandmeyer reactions. Part 7.1 An investigation into the reduction steps of Sandmeyer hydroxylation and chlorination reactions
  作者：Peter Hanson、Jason R. Jones、Alec B. Taylor、Paul H. Walton、Allan W. Timms

  DOI：10.1039/b200748g

  日期：2002.5.22

  aqueous solution, the reduction steps have been investigated by means of correlation analyses of the effects of diazonium ion substitution on the rates of reduction. For simple hydroxylation, a change of behaviour between diazonium ions substituted by electron donor groups and those substituted by electron acceptor groups is interpreted as a change within an inner-sphere process from rate-determining electron

  对于桑德迈尔水溶液中的羟基化和氯化反应，通过相关分析重氮离子取代对还原速率的影响，研究了还原步骤。对于简单的羟基化，被电子给体基团取代的重氮离子与被电子受体基团取代的重氮离子之间的行为变化被解释为内球过程中从速率确定电子转移到反应物速率确定缔合的变化。相比之下，对于柠檬酸盐促进的羟基化，类似的行为变化可解释为内层和外层电子转移之间的变化。对于氯化作用，在所检查的取代基范围内没有机理上的变化，但其行为方式与内球机理一致。根据重氮离子取代和催化剂连接对各种反应性氧化还原对的还原电势和自交换速率的影响，合理化了各种行为方式。重氮离子的还原反应和其他亲电反应的比较相关性分析用于支持关于Sandmeyer还原步骤的高级论证。建议铜我还原剂反应经由亲核桥连配体的重氮Ñ β以得到瞬变ž-adducts其为前体配合物和活化用于电子转移包括关于N-N键的旋转。
• Preparation of <i>N</i>-Arylquinazolinium Salts via a Cascade Approach
  作者：Mani Ramanathan、Jing Wan、Shiuh-Tzung Liu

  DOI：10.1021/acs.joc.9b00601

  日期：2019.6.7

  readily available aryldiazonium salts, nitriles, and 2-aminoarylketones in a one-pot operation. This method relies on the in situ generation of the N-arylnitrilium intermediate from the reaction of aryldiazonium salt with nitrile, which undergoes amination/cascade cyclization/aromatization, leading to N-arylquinazolinium salts in excellent yields. Nucleophilic addition of alkoxide to these N-arylquinazolinium

  从一锅操作中容易获得的芳基重氮盐，腈和2-氨基芳基酮描述了一种制备N-芳基喹唑啉鎓盐的简便方法。该方法依赖于芳基重氮盐与腈反应的原位生成N-芳基腈中间体，该胺经历胺化/级联环化/芳构化，从而以极高的收率得到N-芳基喹唑啉盐。将醇盐向这些N-芳基喹唑啉鎓盐的亲核加成提供官能化的二氢-N-芳基喹唑啉。
• Highly efficient palladium-catalyzed cross-coupling of diarylborinic acids with arenediazoniums for practical diaryl synthesis
  作者：Fengze Wang、Chen Wang、Guoping Sun、Gang Zou

  DOI：10.1016/j.tetlet.2019.151491

  日期：2020.2

  A highly efficient cross-coupling of cost-effective diarylborinic acids with both isolatable and latent arenediazoniums, i.e. tetrafluoroborates and aryltriazenes, respectively, has been developed with a practical palladium catalyst system under base-free conditions in open flask at room temperature. A variety of electronically and sterically various biaryls, in particular, those bearing a coordinative

  低成本的二芳基硼酸与可分离的和潜在的芳族重氮鎓（即四氟硼酸酯和芳基三氮烯）的高效交叉偶联已在实用的钯催化剂体系下，在无碱条件下于室温下在敞口烧瓶中开发出来。通过使用0.3mol％的乙酸钯作为催化剂，可以以良好或优异的产率获得多种电子和空间上不同的联芳基，特别是那些带有配位邻位取代基的联芳基。该方案的特征包括二芳基硼酸的成本效益，对杂原子邻位取代底物的功效以及对芳基氯化物的高化学选择性，已在杀菌剂Boscalid的实际合成中得到了明确证明。
• Catalytic Sandmeyer Bromination
  作者：Irina Beletskaya、Alexander Sigeev、Alexander Peregudov、Pavel Petrovskii

  DOI：10.1055/s-2007-983784

  日期：2007.8

  An efficient catalyst system for Sandmeyer bromination is proposed. Aryl bromides and dibromides can be obtained with excellent yield by this synthetic protocol.

  提出了一种高效的Sandmeyer溴化催化体系。通过这一合成方案，可以获得产率极佳的芳基溴和二溴化合物。