3-均三甲苯基丙腈 | 27645-05-2

• 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: 3-均三甲苯基丙腈
• 英文名称: 3-mesitylpropanenitrile
• 英文别名: 3-(2,4,6-trimethylphenyl)propanenitrile
• CAS: 27645-05-2
• 化学式: C₁₂H₁₅N
• 分子量: 173.258
• InChiKey: DLSLPHKCRAOIEC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2926909090

反应信息

• 作为产物：
  描述：

  2,4,6-三甲基苯甲醛 在 sodium hydride 作用下， 以 四氢呋喃 、 乙醇 为溶剂， -10.0~110.0 ℃ 、1.33 Pa 条件下， 反应 1.0h， 生成 3-均三甲苯基丙腈
  参考文献：
  名称：

  LASER FLASH PHOTOLYSIS STUDY OF PHENYLCARBENE,o-TOLYLCARBENE AND MESITYLCARBENE

  摘要：

  Laser flash photolysis (LFP, XeCl, 308 nm, 20 ns) of phenyldiazomethane (PDM), o-tolydiazomethane (TDM) and mesitydiazomethane (MDM) produces phenylcarbene (PC), o-tolycarbene (TC) and mesitylcarbene (MSG), respectively, Transient spectra of PC and TC could not be detected in pentane at ambient temperature; however, these carbenes could be trapped with pyridine to form UV-Vis-active ylides, The rate of formation of these ylides was resolved in CF2ClCFCl2 (Freon-113) and yields, after analysis, values of k(pyr) and tau, where k(pyr) is the absolute rate constant of the reaction of the spin equilibrated carbene with pyridine and tau is the carbene lifetime in Freon-113 in the absence of pyridine, LFP of MDM produces the transient spectra of both triplet MSG and 3,5-dimethyl-1,2-benzoquinodimethane (3,5-BQM), The lifetime of (MSC)-M-3 in pentane is ca 500 ns. (MSC)-M-3 reacts with pyridine with an apparent rate constant of k(pyr) = 1.35 x 10(7) M-1 s(-1). The decay of (MSC)-M-3 in 3 variety of solvents does not lead to increased absorption of 3,5-BQM in solution, nor does the presence of a carbene scavenger (methanol) lead to a reduction in yield of 3,5-dimethyl-1,2-benzoquinodimethane upon LFP of precursor, Thus, the decay of (MSC)-M-3 in solution does not lead to the formation of quinodimethane. This species (3,5-BQM) is formed, instead, by a hydrogen atom transfer in the excited state of the precursor, Product analysis reveals that the excited state rearrangement which forms xylylene is a minor process, Photolysis of MDM in a nitrogen matrix at 10 K leads to the UV-Vis spectra of matrix isolated triplet mesitylcarbene and 3,5-BQM. The carbene rearranges slowly to 3,5-BQM in the cryogenic matrix, in contrast to its behavior in solution. (C) 1997 by John Wiley & Sons, Ltd.

  DOI：

  10.1002/(sici)1099-1395(199704)10:4<207::aid-poc883>3.0.co;2-8

文献信息

• A strategy for generating aryl radicals from arylborates through organic photoredox catalysis: photo-Meerwein type arylation of electron-deficient alkenes
  作者：Y. Iwata、Y. Tanaka、S. Kubosaki、T. Morita、Y. Yoshimi

  DOI：10.1039/c7cc09140k

  日期：——

  Photoinduced reactions of arylboronic acids with electron deficient alkenes under mild organic photoredox catalysis conditions lead to the formation of Meerwein arylation type adducts via the generation of aryl radicals.

  的温和的有机photoredox催化条件下芳基硼酸与缺电子烯烃的光诱导反应导致形成meerwein芳基化反应类型的加合物通过芳基的生成。
• Cooperative Palladium/Lewis Acid-Catalyzed Transfer Hydrocyanation of Alkenes and Alkynes Using 1-Methylcyclohexa-2,5-diene-1-carbonitrile
  作者：Anup Bhunia、Klaus Bergander、Armido Studer

  DOI：10.1021/jacs.8b10651

  日期：2018.11.28

  represents a clean and safe alternative to hydrocyanation processes using toxic HCN gas. Such reactions provide access to pharmaceutically important nitrile derivatives starting with alkenes and alkynes. Herein, an efficient and practical cooperative palladium/Lewis acid-catalyzed transfer hydrocyanation of alkenes and alkynes is presented using 1-methylcyclohexa-2,5-diene-1-carbonitrile as a benign and readily

  催化转移氢氰化是使用有毒 HCN 气体的氢氰化工艺的一种清洁和安全的替代方法。此类反应提供了获得以烯烃和炔烃为原料的药学上重要的腈衍生物的途径。在此，使用 1-甲基环己-2,5-二烯-1-腈作为良性且易于获得的 HCN 来源，提出了一种高效实用的钯/路易斯酸催化的烯烃和炔烃转移氢氰化反应。大量腈衍生物（> 50 个例子）是由脂肪族和芳香族烯烃制备的，具有良好到优异的抗马尔科夫尼科夫选择性。一系列脂肪族烯烃参与选择性氢氰化反应以提供相应的腈。所介绍的方法可用于内烯烃的链式氢氰化反应，以提供具有良好区域选择性的末端腈。该协议也适用于生物活性分子的后期修饰。
• Zeolites as equilibrium-shifting agents in shuttle catalysis
  作者：Jesse Dallenes、Jonas Wuyts、Niels Van Velthoven、Andraž Krajnc、Gregor Mali、Oleg A. Usoltsev、Aram L. Bugaev、Dirk De Vos

  DOI：10.1038/s41929-023-00967-8

  日期：——

  we show an approach that harnesses the shape-selective and catalytic properties of zeolites to drive the shuttling equilibrium of transfer hydrocyanation and transfer hydroformylation reactions to near-completion. The zeolites irreversibly convert the transfer reaction co-products in an exergonic tandem reaction while excluding the substrates via pore size restrictions. Through fine-tuning of the zeolite’s

  功能部分的催化穿梭已成为替代和多样化传统氢化功能化技术的有前途的策略。然而，由于它们的等渗性质，这些反应是可逆的，这限制了它们对选定的供体和受体分子阵列的适用性，并在原子经济性和实用性方面提出了重大挑战。在这里，我们展示了一种利用沸石的形状选择性和催化特性来驱动转移氢氰化和转移加氢甲酰化反应接近完成的穿梭平衡的方法。沸石在放能串联反应中不可逆地转化转移反应副产物，同时通过孔径限制排除底物。通过微调沸石的特性，可以实现高达 80% 的产率增加，从而使腈供体多样化为丙腈，醛受体多样化为未活化的烯烃。机械和光谱研究突出了沸石和均相转移催化剂之间独特的协同作用。
• LASER FLASH PHOTOLYSIS STUDY OF PHENYLCARBENE,o-TOLYLCARBENE AND MESITYLCARBENE
  作者：Atnaf Admasu、Matthew S. Platz、Andrzej Marjcinek、Jacek Michalak、Anna D�ra Gudmundsd�ttir、Jerzy Gebicki

  DOI：10.1002/(sici)1099-1395(199704)10:4<207::aid-poc883>3.0.co;2-8

  日期：1997.4

  Laser flash photolysis (LFP, XeCl, 308 nm, 20 ns) of phenyldiazomethane (PDM), o-tolydiazomethane (TDM) and mesitydiazomethane (MDM) produces phenylcarbene (PC), o-tolycarbene (TC) and mesitylcarbene (MSG), respectively, Transient spectra of PC and TC could not be detected in pentane at ambient temperature; however, these carbenes could be trapped with pyridine to form UV-Vis-active ylides, The rate of formation of these ylides was resolved in CF2ClCFCl2 (Freon-113) and yields, after analysis, values of k(pyr) and tau, where k(pyr) is the absolute rate constant of the reaction of the spin equilibrated carbene with pyridine and tau is the carbene lifetime in Freon-113 in the absence of pyridine, LFP of MDM produces the transient spectra of both triplet MSG and 3,5-dimethyl-1,2-benzoquinodimethane (3,5-BQM), The lifetime of (MSC)-M-3 in pentane is ca 500 ns. (MSC)-M-3 reacts with pyridine with an apparent rate constant of k(pyr) = 1.35 x 10(7) M-1 s(-1). The decay of (MSC)-M-3 in 3 variety of solvents does not lead to increased absorption of 3,5-BQM in solution, nor does the presence of a carbene scavenger (methanol) lead to a reduction in yield of 3,5-dimethyl-1,2-benzoquinodimethane upon LFP of precursor, Thus, the decay of (MSC)-M-3 in solution does not lead to the formation of quinodimethane. This species (3,5-BQM) is formed, instead, by a hydrogen atom transfer in the excited state of the precursor, Product analysis reveals that the excited state rearrangement which forms xylylene is a minor process, Photolysis of MDM in a nitrogen matrix at 10 K leads to the UV-Vis spectra of matrix isolated triplet mesitylcarbene and 3,5-BQM. The carbene rearranges slowly to 3,5-BQM in the cryogenic matrix, in contrast to its behavior in solution. (C) 1997 by John Wiley & Sons, Ltd.