2-methyl-4'-(methylsulfanyl)biphenyl

• 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-methyl-4'-(methylsulfanyl)biphenyl
• 英文别名: 4-(2-methylphenyl)thioanisole；4-(2-tolyl)thioanisole；2-Methyl-4'-(methylsulfanyl)-1,1'-biphenyl；1-methyl-2-(4-methylsulfanylphenyl)benzene
• 化学式: C₁₄H₁₄S
• 分子量: 214.331
• InChiKey: DYICUMLQKUTTGW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  4-溴茴香硫醚 、 O-甲苯基氯化镁 在 ((Cy₂POH)2PdCl)2 zinc(II) chloride 作用下， 以 N-甲基吡咯烷酮 、 乙醚 为溶剂， 反应 3.33h， 以92%的产率得到2-methyl-4'-(methylsulfanyl)biphenyl
  参考文献：
  名称：

  钯亚膦酸催化的芳基和酰基卤与芳基，烷基和乙烯基锌试剂的交叉偶联。

  摘要：

  已经制备了几种钯次膦酸，并将其用于芳基或酰基卤与脂族和芳族有机锌试剂的交叉偶联反应。发现POPd7催化的芳基卤化物（包括富含电子的芳基氯化物）和芳基锌试剂的反应可提供具有烷氧基，烷硫基，氨基，酮，氰基，硝基，酯基和杂芳基基团的联芳基，产率为75-93％。使用位阻受阻的底物可获得优异的结果，该底物以高达92％的收率得到二和三邻位取代的联芳基。在温和条件下，芳基卤化物也经历POPd7催化的芳基-乙烯基和芳基-烷基键的形成。由芳基卤化物和乙烯基或烷基锌试剂制备苯乙烯和烷基芳烃的产率为79-93％。用酰基卤取代芳基卤化物可得到酮，当使用POPd作为催化剂时，酮的产率可高达98％。该方法克服了传统的Friedel-Crafts酰化方法的受限底物范围，降低的区域控制和较低的官能团耐受性。

  DOI：

  10.1021/jo801445y

文献信息

• General Copper-Catalyzed Coupling of Alkyl-, Aryl-, and Alkynylaluminum Reagents with Organohalides
  作者：Bijay Shrestha、Surendra Thapa、Santosh K. Gurung、Ryan A. S. Pike、Ramesh Giri

  DOI：10.1021/acs.joc.5b02077

  日期：2016.2.5

  We report the first example of a very general Cu-catalyzed cross-coupling of organoaluminum reagents with organohalides. The reactions proceed for the couplings of alkyl-, aryl-, and alkynylaluminum reagents with aryl and heteroaryl halides and vinyl bromides, affording the cross-coupled products in good to excellent yields. Both primary and secondary alkylaluminum reagents can be utilized as organometallic

  我们报道了有机铝试剂与有机卤化物非常普通的铜催化交叉偶联的第一个例子。进行反应以使烷基铝，芳基铝和炔基铝试剂与芳基和杂芳基卤化物和乙烯基溴化物偶联，从而以良好或优异的收率提供交叉偶联的产物。伯烷基铝试剂和仲烷基铝试剂都可用作有机金属偶联剂。这些反应不会因β-氢化物的消除而复杂化，因此，即使在“无配体”条件下与杂芳基卤化物偶合，也不会用仲烷基铝试剂观察到重排产物。自由基探针的自由基时钟实验和Ph 3的相对反应性研究具有两个不同氧化还原电位的具有两个卤代芳烃1-溴萘和4-氯苄腈的Al表明该反应不涉及作为中间体的游离芳基和自由基阴离子。这些结果与通过使Ph 3 Al与含有p -H，p -Me，p -F和p -CF 3取代基的碘代芳烃反应获得的哈米特图的结果结合在一起，该曲线显示出一条线性曲线（R 2 = 0.99）。 ρ值为+1.06，表明电流转换遵循氧化加减还原途径。
• Synthesis of biaryls via nickel-catalyzed cross-coupling reaction of arylboronic acids and aryl mesylates
  作者：Masato Ueda、Atsushi Saitoh、Saori Oh-tani、Norio Miyaura

  DOI：10.1016/s0040-4020(98)00809-6

  日期：1998.10

  The cross-coupling reaction of arylboronic acids (1.3 equivs) with aryl methane-sulfonates was carried out in the presence of a nickel(0) catalyst (3 mol%) and K3PO4·nH2O (3 equivs). The use of toluene as the solvent and the nickel(0)-dppf catalyst prepared from NiCl2(dppf) plus dppf with BuLi were recognized to be the most efficient to achieve both high yields and high selectivity. The reaction can

  在镍（0）催化剂（3摩尔％）和K 3 PO 4 ·nH 2 O（3当量）的存在下，进行芳基硼酸（1.3当量）与芳基甲烷磺酸盐的交叉偶联反应。公认使用甲苯作为溶剂以及由NiCl 2（dppf）加dppf与BuLi制备的镍（0）-dppf催化剂是实现高收率和高选择性的最有效方法。该反应可用于各种电子不足和富集的芳基甲磺酸盐，以得到高产率。
• The 1,3-Diaminobenzene-Derived Aminophosphine Palladium Pincer Complex {C6H3[NHP(piperidinyl)2]2Pd(Cl)} - A Highly Active Suzuki-Miyaura Catalyst with Excellent Functional Group Tolerance
  作者：Jeanne L. Bolliger、Christian M. Frech

  DOI：10.1002/adsc.200900848

  日期：——

  The rapidly prepared 1,3‐diaminobenzene‐derived aminophosphine pincer complex C6H3[NHP(piperidinyl)2]2Pd(Cl)} (1) is an effective Suzuki catalyst with excellent functional group tolerance. Side‐product formations, such as homocoupling, debromation or protodeboration have only rarely been detected and if so, were in all cases below the 5% level. The presented reaction protocol is universally applicable

  快速制备的1,3-二氨基苯衍生的氨基膦钳形配合物C 6 H 3 [NHP（哌啶基）2 ] 2 Pd（Cl）}（1）是一种有效的Suzuki催化剂，具有出色的官能团耐受性。仅很少检测到副产物形成，例如均偶联，去溴化或原去硼，如果这样，在所有情况下均低于5％的水平。提出的反应方案是普遍适用的。实验观察表明，钯纳米颗粒的催化活性形式1。
• Pyrazole-4-Carboxamide Derivatives as Microbiocides
  申请人：Lamberth Clemens

  公开号：US20080188442A1

  公开（公告）日：2008-08-07

  Compounds of the formula I in which the substituents are as defined in claim 1 are suitable for use as microbiocides.

  式I中的化合物，其中取代基如权利要求1所定义的那样，适用于用作微生物杀菌剂。
• Highly Active, Air-Stable Palladium Catalysts for the C−C and C−S Bond-Forming Reactions of Vinyl and Aryl Chlorides:  Use of Commercially Available [(<i>t</i>-Bu)₂P(OH)]₂PdCl₂, [(<i>t</i>-Bu)₂P(OH)PdCl₂]₂, and [[(<i>t</i>-Bu)₂PO···H···OP(<i>t</i>-Bu)₂]PdCl]₂ as Catalysts
  作者：George Y. Li

  DOI：10.1021/jo010983y

  日期：2002.5.1

  Air-stable palladium complexes [(t-BU)(2)P(OH)](2)PdCl2, [(t-BU)(2)P(OH)PdCl2](2), and [[(t-Bu)(2)PO...H...OP(t-Bu)(2)]PdCl](2) serve as efficient catalysts for a variety of cross-coupling reactions of vinyl and aryl chlorides with arylboronic acids, arylzinc reagents, and thiols to yield the corresponding styrene derivatives, biaryls, and thioethers. P-31 NMR and mechanistic studies argue that the phosphinous acid ligands in the complexes can be deprotonated in the presence of a base to yield an electron-rich anionic species, which is likely a catalyst intermediate, and dimeric [[(t-BU)(2)PO...H...OP(t-Bu)(2)]PdCl](2) was isolated and cystallographically characterized. These anionic complexes are anticipated not only to accelerate the rate-determining oxidative addition of aryl chlorides but also to stabilize the palladium complexes in the catalytic cycle.