trans-2'-Methyl-4-stilbazol | 5825-18-3

• 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: trans-2'-Methyl-4-stilbazol
• 英文别名: (E)-4-(2-methylstyryl)pyridine；4-[(E)-2-Methylstyryl]pyridine；4-[(E)-2-(2-methylphenyl)ethenyl]pyridine
• CAS: 5825-18-3；64632-64-0；7370-31-2
• 化学式: C₁₄H₁₃N
• 分子量: 195.264
• InChiKey: WVDCCQYDLFTGGH-VOTSOKGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  zinc(II) sulfate heptahydrate 、 trans-2'-Methyl-4-stilbazol 、 4,4'-二苯醚二甲酸 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 以89%的产率得到
  参考文献：
  名称：

  类拟轮烷MOF辅助的立体选择性固态合成取代的环戊二烯

  摘要：

  反式-4-苯乙烯基吡啶（4-spy）衍生物的区域选择性光二聚作用是使用类拟轮烷样的基于Zn的金属有机骨架MOF作为模板进行的。的形成rctt -HT（头对尾）二聚体是通过限制对六角窗内协调4-间谍衍生物配位体中，然后用UV光照射它们来实现的。在这样的MOF材料中包含两个不同的取代4间谍配体的光二聚反应也是可能的。醚键的形成来保护HO-间谍的敏感-OH基团和CH的甲基3 O型间谍在CH形成环丁烷衍生物的后随后去除3基于O间谍的MOF。在4间谍的苯基的2或3位引入取代基不会显着影响二聚反应的速率，除非强吸电子硝基的速率显着降低。这些结果与光产物的混合物形成鲜明对比，而光产物的混合物是通过在有机溶剂中进行非模板光二聚而获得的低收率。

  DOI：

  10.1002/anie.201806076
• 作为产物：
  描述：

  2-碘代甲苯 、 4-乙烯基吡啶 生成 trans-2'-Methyl-4-stilbazol
  参考文献：
  名称：

  ANDRIENKO, O. S., MOL. UCHENYE I SPETS.NAR. X-BY. 4 REGION. NAUCH.-PRAKT. KONF. XIMIYA, TOM+

  摘要：

  DOI：

文献信息

• Rationally Designed Pincer-Type Heck Catalysts Bearing Aminophosphine Substituents: Pd^IVIntermediates and Palladium Nanoparticles
  作者：Jeanne L. Bolliger、Olivier Blacque、Christian M. Frech

  DOI：10.1002/chem.200800441

  日期：2008.9.8

  catalytic cycle of the Heck reaction, their general existence as reactive intermediates (for example, in other reactions) cannot be excluded. On the contrary, they were shown to be thermally accessible. Compounds 1 and 2 show a smooth halide exchange with bromobenzene to yield their bromo derivatives in DMF at 100 degrees C. Experimental observations revealed that the halide exchange most probably proceeded

  氨基膦基钳形配合物[C6H3-2,6-（XP（哌啶基）2）2Pd（Cl）]（X = NH 1; X = O 2）可以很容易地由廉价的起始原料通过依次添加1,1在“一锅”中，在N 2下，将'，1''-膦三基三哌啶和1,3-二氨基苯或间苯二酚制得[Pd（cod）（Cl）2]（cod =环辛二烯）在甲苯中的溶液。事实证明，化合物1和2是出色的Heck催化剂，可以在很短的反应时间和较低的催化剂负载量下，在140℃下将数种电子失活和空间位阻的芳基溴化物与各种烯烃作为偶联伴侣进行定量偶联。升高的反应温度还使得在仅0.01mol％的催化剂存在下，烯烃能够与电子失活的和位阻的芳基氯有效地偶联。进行的机理研究排除了均相的Pd 0配合物是1和2的催化活性形式。另一方面，钯纳米颗粒参与催化循环得到了有力的实验支持。即使衍生自1（和2）的钳型Pd IV中间体不参与Heck反应的催化循环，也不能排除它们作为反应性中
• Aminophosphine Palladium Pincer Complexes for Suzuki and Heck Reactions
  作者：Jeanne L. Bolliger、Christian M. Frech

  DOI：10.2533/chimia.2009.23

  日期：——

  The aminophosphine-based pincer complexes [C6H3-2,6-NHP(piperidinyl)2}2Pd(Cl)] (2) and [C6H3-2,6-OP(piperidinyl)2}2Pd(Cl)] (3) are readily prepared from cheap starting materials by sequential addition of 1,1?,1?-phosphinetriyltripiperidine and 1,3-diaminobenzene or resorcinol to solutions of [Pd(cod)(Cl)2] (cod = cyclooctadiene) in toluene under N2 in 'one pot'. Compounds 2 and 3 proved to be not only excellent catalysts for the Suzuki and the Heck cross-coupling reactions, but they are also very convenient to use: The toluene solutions of the 'one-pot' syntheses can be used directly for the catalytic reactions, thereby saving the time-consuming isolation of the catalysts. The Suzuki cross-coupling reaction catalyzed by 2 and 3 can be performed in air at 100 °C in toluene of technical quality: in the presence of only 0.001mol% of catalyst, several electronically deactivated and sterically hindered aryl bromides are quantitatively coupled with phenylboronic acid within a few minutes of reaction time. Furthermore, complex 2 enables the use of activated and non-activated aryl chlorides as coupling partners in the Suzuki reaction. Compounds 2 and 3 have also been shown to be highly active and reliable Heck catalysts: Very low catalyst loadings and short reaction times are required for the quantitative coupling of several electronically deactivated and sterically hindered aryl bromides with various olefins at 140 °C. At increased temperatures, even electronically deactivated and sterically hindered aryl chlorides can be efficiently coupled with olefins in the presence of only 0.01 mol% of catalyst.

  基于氨基膦的夹环配合物[C6H3-2,6-NHP(哌啶基)2}2Pd(Cl)]（2）和[C6H3-2,6-OP(哌啶基)2}2Pd(Cl)]（3）可以通过将1,1',1''-膦三哌啶和1,3-二氨基苯或间苯二酚依次加入苯甲醛溶液中[Pd(cod)(Cl)2]（cod = 环辛二烯）在N2气氛下在甲苯中进行'一锅法'合成而得。化合物2和3不仅被证明是苏酞基和赫克交叉偶联反应的优秀催化剂，而且它们也非常方便使用：'一锅法'合成的甲苯溶液可以直接用于催化反应，从而节省了耗时的催化剂分离过程。由2和3催化的苏酞基交叉偶联反应可以在技术质量的甲苯中在空气中以100°C进行：在只有0.001mol%催化剂存在的情况下，几种电子失活和立体位阻的芳基溴化物可以在几分钟内与苯硼酸定量偶联。此外，化合物2使得在苏酞基反应中可以使用活化和非活化的芳基氯化物作为偶联伙伴。化合物2和3也被证明是高活性和可靠的赫克催化剂：在140°C下，对于几种电子失活和立体位阻的芳基溴化物与各种烯烃的定量偶联，需要非常低的催化剂负载和短的反应时间。在提高的温度下，即使是电子失活和立体位阻的芳基氯化物也可以在只有0.01mol%催化剂存在的情况下与烯烃高效偶联。
• Ligand-Free Palladium-Catalysed Oxidative Heck Reaction of 4-Vinylpyridine with Arylboronic Acids: Selective Synthesis of (E)-4-Styrylpyridines
  作者：Chuanli Shi、Jinchang Ding、Jun Jiang、Jiuxi Chen、Huayue Wu、Miaochang Liu

  DOI：10.3184/174751912x13352864811920

  日期：2012.6

  A ligand-free palladium-catalysed oxidative Heck reaction of various arylboronic acids with 4-vinylpyridine has been developed, achieving (E)-4-styrylpyridines with high selectively in moderate to good yields. A plausible mechanism for the formation of (E)-4-styrylpyridines has been proposed.

  我们开发了一种无配体钯催化的芳基硼酸与 4-乙烯基吡啶的氧化 Heck 反应，以中等至良好的收率高选择性地获得了 (E)-4-苯乙烯基吡啶。提出了形成 (E)-4-styrylpyridines 的合理机制。
• Regiospecific [2 + 2] photocyclodimerization of trans-4-styrylpyridines templated by cucurbit[8]uril
  作者：Asao Nakamura、Hiromi Irie、Shuhei Hara、Mai Sugawara、Shinji Yamada

  DOI：10.1039/c1pp05079f

  日期：2011.9

  Addition of HCl accelerated the photocyclodimerization of trans-4-styrylpyridine 1a in methanol and increased the yield of syn-head-to-tail (syn-HT) dimer 2a through the effect of cation-π interactions between the pyridinium ion of one molecule and the phenyl group of the other. We examined the photoirradiation products of derivatives of 1a having alkyl substituents on the phenyl group (1b–1f). The effect of the alkyl substituent on product distribution was rather limited for the photoreaction in MeOH solutions. However, the substituents had a distinct effect on the product distribution for the photoreaction of the inclusion complexes of hydrochloride salts of trans-4-styrylpyridines with cucurbit[8]uril in aqueous solutions. Introducing an alkyl group at the 2- or 3-position of the phenyl group completely shifted the major product from the syn-HT dimer to the syn-head-to-head (syn-HH) dimer. By adjusting the balance of host–guest interactions and cation-p interactions between guest molecules through systematic changes in the substituents on the phenyl ring of trans-4-styrylpyridine, we could change the orientation of the reactant molecules in the host cavity, resulting in a change of the major regioisomer of the photocyclodimerization products.

  通过一个分子中的吡啶离子与另一个分子中的苯基之间的阳离子-π相互作用的影响，加入盐酸加速了反式-4-苯乙烯吡啶 1a 在甲醇中的光环二聚化，并增加了合成头尾（syn-HT）二聚体 2a 的产率。我们研究了苯基上有烷基取代基的 1a 衍生物（1b-1f）的光辐射产物。在 MeOH 溶液中进行光反应时，烷基取代基对产物分布的影响相当有限。但是，对于反式-4-苯乙烯吡啶盐酸盐与葫芦[8]脲的包合物在水溶液中的光反应，取代基对产物分布有明显的影响。在苯基的 2- 位或 3- 位引入一个烷基，会使主要产物从 syn-HT 二聚体完全转变为 syn-head-to-head (syn-HH) 二聚体。通过系统地改变反式-4-苯乙烯吡啶苯环上的取代基，调整客体分子之间的主-客体相互作用和阳离子-阳离子相互作用的平衡，我们可以改变反应物分子在主腔中的取向，从而改变光环二聚产物的主要区域异构体。