1-溴-2-丙-1-烯-2-基苯 | 7073-70-3

• 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: 1-溴-2-丙-1-烯-2-基苯
• 英文名称: 1-bromo-2-isopropenylbenzene
• 英文别名: 1-bromo-2-(1-methylethenyl)benzene；1-bromo-2-(prop-1-en-2-yl)benzene；2-bromo-α-methylstyrene；1-bromo-2-prop-1-en-2-ylbenzene
• CAS: 7073-70-3
• 化学式: C₉H₉Br
• mdl: MFCD20384533
• 分子量: 197.074
• InChiKey: XAJLFMOXQLPTIL-UHFFFAOYSA-N

物化性质

• 沸点：
  56-57 °C(Press: 3 Torr)
• 密度：
  1.301±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.111
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 储存条件：
  2-8°C

反应信息

• 作为反应物：
  描述：

  1-溴-2-丙-1-烯-2-基苯 在 重铬酸吡啶 、 正丁基锂 、 偶氮二异丁腈 、 Celite 、 氧气 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 4.0h， 生成 1,4-Dimethyl-4-phenylsulfanylmethyl-1,4-dihydro-benzo[d][1,2]dioxin-1-ol
  参考文献：
  名称：

  环状过氧化物合成中的基态氧。第1部分：Benzo融合缩酮

  摘要：

  涉及基态分子氧的硫醇-烯烃-共加氧（TOCO）自由基链反应将2'-异丙烯基苯乙酮直接转化为具有三个新键的环状过氧半缩酮产物。从4-叔丁基苯硫醇开始，此TOCO方法以克为单位可重复进行，收率为86％。半缩酮→缩酮和硫化物→砜的转化最终提供了一系列磺酰基环过氧缩酮。据报道，其中一些结构简单的苯并稠合环过氧化物的体外抗疟活性。

  DOI：

  10.1016/j.tet.2006.02.008
• 作为产物：
  描述：

  methyl triphenylphosphonium bromide 在 potassium tert-butylate 作用下， 以 乙醚 为溶剂， 反应 0.5h， 生成 1-溴-2-丙-1-烯-2-基苯
  参考文献：
  名称：

  Cobalt-Catalyzed Enantioselective Intramolecular Hydroacylation of Ketones and Olefins

  摘要：

  Cobalt-chiral diphoshine catalytic systems promote intramolecular hydroacylation reactions of 2-acylbenzaldehydes and 2-alkenylbenzaldehydes to afford phthalide and indanone derivatives, respectively, in moderate to good yields with high enantioselectivities. The ketone hydroacylation did not exhibit a significant H/D kinetic isotope effect (KIE) with respect to the aldehyde C-H bond, indicating that C-H activation would not be involved in the rate-limiting step.

  DOI：

  10.1021/ja509919x

文献信息

• Decatungstate-mediated solar photooxidative cleavage of CC bonds using air as an oxidant in water
  作者：Pan Xie、Cheng Xue、Junfei Luo、Sanshan Shi、Dongdong Du

  DOI：10.1039/d1gc01234g

  日期：——

  With the increasing attention for green chemistry and sustainable development, there has been much interest in searching for greener methods and sources in organic synthesis. However, toxic additives or solvents are inevitably involved in most organic transformations. Herein, we first report the combination of direct utilization of solar energy, air as the oxidant and water as the solvent for the selective

  随着对绿色化学和可持续发展的日益关注，人们对寻找更绿色的有机合成方法和来源产生了浓厚的兴趣。然而，大多数有机转化都不可避免地涉及有毒添加剂或溶剂。在此，我们首先报道了直接利用太阳能、空气作为氧化剂和水作为溶剂选择性裂解 C 的组合。C 芳基烯烃中的双键。各种 α-甲基苯乙烯、二芳基烯烃以及末端苯乙烯在这种绿色和可持续的策略中具有良好的耐受性，并以令人满意的收率提供所需的羰基产品。与多相催化一样，这种均相催化体系也可以重复使用，重复3次后仍能保持良好的活性。机理研究表明，O 2 ˙ -和1 O 2都参与了反应。基于这些结果，提出了两种可能的机制，包括电子转移途径和能量转移途径。
• Synthesis of Dibenzoheteropines of Group 13–16 Elements via Ring-Closing Metathesis
  作者：Takanori Matsuda、Shinya Sato

  DOI：10.1021/jo4001993

  日期：2013.4.5

  The ring-closing metathesis (RCM) of bis(2-vinylphenyl)silanes in the presence of the second-generation Hoveyda–Grubbs catalyst in toluene at 100 °C afforded dibenzo[b,f]silepines in excellent yields. Other dibenzoheteropines of group 13–16 elements were also prepared via the RCM of the corresponding heteroatom-tethered dienes.

  在第二代Hoveyda-Grubbs催化剂存在下，在100°C的甲苯中，双（2-乙烯基苯基）硅烷的闭环复分解（RCM）提供了极好的收率的二苯并[ b，f ]西拉品。还通过相应的杂原子连接的二烯的RCM制备了第13-16组元素的其他二苯并杂庚因。
• ortho-Effect on the acid-catalyzed hydration of 2-substituted α-methylstyrenes
  作者：Ondřej Prusek、Filip Bureš、Oldřich Pytela

  DOI：10.1135/cccc2008115

  日期：——

  α-Methylstyrene and nine ortho-substituted analogs have been synthesized and the kinetics of their acid-catalyzed hydration in aqueous solutions of sulfuric acid at 25 °C have been investigated. The kinetic acidity function H_S has been constructed from the dependence of the observed rate constants k_obs on the sulfuric acid concentration. The catalytic rate constants of the acid-catalyzed hydration k_ortho have been calculated as well. The identical shape of the kinetic acidity functions for ortho- and para-derivatives confirms what the consistent mechanism A-SE2 of the acid-catalyzed hydration has already proved for the corresponding para-derivatives. The A-SE2 mechanism involves a rate-determining proton transfer of the hydrated proton to the substrate. From the dependence of the catalytic rate constants of the ortho-derivatives on the catalytic rate constants of the para-derivatives, it is seen that the logarithm of the catalytic rate constant for hydrogen as a substituent is markedly out of the range of the other substituents and, simultaneously, that the ortho-derivatives react significantly slower than the corresponding para-derivatives. In correlation with the substitent constants σ_p⁺, a reaction constant of ρ⁺ = –1.45 have been found. The constant is, in absolute value, considerably smaller than that for para-derivatives (ρ⁺ = –3.07). In parallel, the steric effects are enforced more significantly for the monoatomic substituents (slope of the Charton’s constants 3.92) than for substituents including more atoms (slope of the Charton’s constants 2.09). A small value of the reaction constant ρ⁺ has been elucidated due to the lower conjugation between the reaction centre and the benzene ring as a consequence of the geometric twist of the reaction centre out of the main aromatic plane accompanied by fading mesomeric interaction between the reaction centre and the substituents attached to the benzene ring. The isopropyl group in the carbocation is twisted less out of the aromatic plane for the monoatomic substituents and, therefore, also a small difference in the bulk of substituents has considerable steric influence on the conjugation between the carbocation and the benzene ring bearing substituents. On the contrary, the isopropyl group in the carbocations with polyatomic substituents is twisted to such a degree that changes in the bulk of substituents affect the resonant stabilization negligibly. Similar conclusions were also deduced from the correlations of the substitution constants σI and σ_R⁺.

  α-甲基苯乙烯和九个邻位取代物已经合成，并研究了它们在25°C硫酸水溶液中酸催化水合的动力学。动力学酸度函数HS已经根据观察到的速率常数kobs对硫酸浓度的依赖关系构建。酸催化水合的催化速率常数kortho也已计算。邻位取代物和对位取代物的动力学酸度函数的相同形状证实了酸催化水合的一致机制A-SE2已经为相应的对位取代物证明。A-SE2机制涉及水合质子向底物的速率决定性质子转移。从邻位取代物的催化速率常数依赖于对位取代物的催化速率常数的关系中可以看出，氢作为取代基的催化速率常数的对数明显超出了其他取代基的范围，并且同时，邻位取代物的反应速度明显比相应的对位取代物慢。与取代基常数σp+的相关性，发现了一个反应常数ρ+ = -1.45。该常数的绝对值比对位取代物的常数（ρ+ = -3.07）要小得多。与取代基常数的斜率3.92相比，对于包含更多原子的取代基（Charton常数的斜率为2.09），单原子取代基的立体效应更为显著。由于反应中心与苯环之间的共轭减弱，导致反应中心扭曲出主要芳香平面并伴随着与连接到苯环的取代基之间的消退的共轭作用，解释了反应常数ρ+的小值。对于单原子取代基，卡宾离子中的异丙基团扭曲得较少，因此，取代基的体积差异对卡宾离子与携带取代基的苯环之间的共轭影响很大。相反，对于具有多原子取代基的卡宾离子中的异丙基团扭曲程度较大，因此，取代基体积的变化对共振稳定化的影响微乎其微。类似的结论也可以从取代常数σI和σR+的相关性推导出。
• Rhodium-Catalyzed Intermolecular Cyclopropanation of Benzofurans, Indoles, and Alkenes via Cyclopropene Ring Opening
  作者：Rachel J. Ross、Rubaishan Jeyaseelan、Mark Lautens

  DOI：10.1021/acs.orglett.0c01655

  日期：2020.6.19

  The generation of metal carbenoids via ring opening of cyclopropenes by transition metals offers a simple entry into highly reactive intermediates. Herein, we describe a diastereoselective intermolecular rhodium-catalyzed cyclopropanation of heterocycles and alkenes using cyclopropenes as carbene precursors with a low loading of a commercially available rhodium catalyst. The reported method is scalable

  通过过渡金属通过环丙烯的开环生成金属类化合物，可轻松进入高反应性中间体。在本文中，我们描述了使用环丙烯作为卡宾前体并以低载量的市售铑催化剂进行非对映选择性分子间铑催化的杂环和烯烃的环丙烷化。所报道的方法是可扩展的，并且可以在低至0.2mol％的催化剂载量下进行，而对反应产率或选择性没有影响。
• Annulation of Aromatic Imines via Directed C−H Bond Activation
  作者：Reema K. Thalji、Kateri A. Ahrendt、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/jo050757e

  日期：2005.8.1

  dihydroindoles, and other polycyclic aromatic compounds is presented. Cyclization of aromatic ketimines and aldimines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using (PPh3)3RhCl (Wilkinson's catalyst). The cyclization of a range of aromatic ketimines and aldimines provides bi- and tricyclic ring systems with good regioselectivity. Different ring

  提出了一种直接的CH键活化方法，用于合成茚满，四氢萘，二氢呋喃，二氢吲哚和其他多环芳族化合物。使用（PPh 3）3 RhCl（Wilkinson's催化剂）已经实现了在相对于亚胺定向基团的间位上束缚有链烯基的芳族酮亚胺和醛亚胺的环化。一系列芳香酮亚胺和醛亚胺的环化为双环和三环系统提供了良好的区域选择性。可以通过单取代的1，1-或1,2-二取代的和三取代的烯烃同时带有富电子和缺电子的官能团来获得不同的环尺寸和取代方式。