1,1-dimethyl-3-phenylgermacyclopent-3-ene | 115126-53-9

• 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: 1,1-dimethyl-3-phenylgermacyclopent-3-ene
• 英文别名: 3；1,1-Dimethyl-3-phenyl-2,5-dihydrogermole
• CAS: 115126-53-9
• 化学式: C₁₂H₁₆Ge
• 分子量: 232.849
• InChiKey: XIYBRLVUMOIZEB-UHFFFAOYSA-N

物化性质

• 沸点：
  271.0±50.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.79
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  四氢呋喃 、 1,1-dimethyl-3-phenylgermacyclopent-3-ene 以 正己烷 为溶剂， 生成 tetramethyldigermene
  参考文献：
  名称：

  溶液中二芳基和二烷基亚锗烷基二甲醚与醇和醚反应的动力学和机理

  摘要：

  甲醇，叔丁醇和THF与一系列简单的亚二甲基衍生物二甲基-（GeMe 2），二苯基-（GePh 2）和二聚三苯甲基亚甲基（GeMes 2； Mes = 2,4,6-三甲基苯基）的反应已经进行。在25°C的己烷溶液中通过激光闪光光解方法进行了研究。结果与快速，可逆反应形成弱稳定的路易斯酸碱配合物一致，路易斯酸碱配合物在290-360 nm范围内表现出最大的UV吸收，并随着混合阶动力学的衰减而伴随着相应的Digermene Ge 2 R 4的形成（ R = Me，Ph或Mes）。可以测量GePh 2形成配合物的绝对速率常数对于所有三种底物，GeMe 2均具有四氢呋喃，发现在（4-10）×10 9 M -1 s -1范围内变化。在所有情况下均测量平衡常数。对于GeMes 2，它们的变化范围为1.2到15 M -1，以MeOH> t-BuOH> THF的顺序降低，而GeMe 2和GePh 2的则为2-4个数量级，并且以THF>

  DOI：

  10.1021/om060595s
• 作为产物：
  描述：

  7,7-dimethyl-2,3,5,6-tetraphenyl-7-germabicyclo[2.2.1]hepta-2,5-diene 、 丁-1,3-二烯-2-基苯 以63%的产率得到
  参考文献：
  名称：

  NEUMANN, WILHELM P.;MICHELS, ERHARD;KOCHER, JURGEN, TETRAHEDRON LETT., 28,(1987) N 33, 3783-3786

  摘要：

  DOI：

文献信息

• Fast Kinetic Studies of the Reactivities of Transient Germylenes in Methanol and Tetrahydrofuran Solution
  作者：Farahnaz Lollmahomed、Lawrence A. Huck、Cameron R. Harrington、Saurabh S. Chitnis、William J. Leigh

  DOI：10.1021/om8010323

  日期：2009.3.9

  Laser flash photolysis techniques have been employed to study the reactivities of dimethylgermylene (GeMe2), diphenylgermylene (GePh2), and a series of ring-substituted diarylgermylenes (GeAr2) in methanol (MeOH) and tetrahydrofuran (THF) solution, where the germylenes exist as the corresponding Lewis acid−base complexes with the O-donor solvents. Dimerization to the corresponding digermene is a significant

  激光闪光光解技术已被用于研究二甲基亚锗烯（GeMe 2），二苯锗烯（GePh 2）以及一系列环取代的二芳基锗烯（GeAr 2）在甲醇（MeOH）和四氢呋喃（THF）溶液中的反应性。亚二甲苯基作为与O-供体溶剂的相应路易斯酸碱配合物而存在。在THF溶液中，二聚化为相应的二锗烯是一种重要的衰变模式，特别是对于GeMe 2 -THF配合物，尽管对于二芳基体系而言，与己烷溶液相比，其降解速度显着降低。另一方面，在MeOH中检测不到二聚化，其中GeAr 2-MeOH配合物在低激光强度和20-50μs范围内的寿命下以伪一级动力学衰减。GeMe 2 -MeOH络合物的寿命约为 在类似条件下为4μs。溶剂的动力学同位素效应与溶剂催化的质子转移相一致，从而产生相应的烷氧基氢化锗烷，这是导致二甲苯-MeOH配合物衰变的过程。它们的衰变分别由强酸和强碱（例如甲磺酸和甲醇钠）加速，它们以大约0.2的速率常数淬灭GePh
• Electronic and Steric Effects on the Lewis Acidities of Transient Silylenes and Germylenes: Equilibrium Constants for Complexation with Chalcogen and Pnictogen Donors
  作者：Svetlana S. Kostina、Tishaan Singh、William J. Leigh

  DOI：10.1021/om3002558

  日期：2012.5.14

  calculations of thermochemical parameters for the complexation of SiMe2 and GeMe2 with 17 O, S, N, and P donors, which are shown to agree with experiment to within 1 kcal mol–1 for the 6 systems that have also been studied experimentally. The calculations confirm that, in general, trialkylphosphines bind most strongly, followed by amines, sulfides, and then ethers and alcohols. SiMe2 and GeMe2 are borderline-soft

  二甲基甲硅烷基，二苯基二甲硅烷基和二甲基苯乙烯硅（分别为SiMe 2，SiPh 2和SiMES 2）及其锗同系物（GEMe 2，GePh 2和GEMa href=https://www.molaid.com/MS_310095 target="_blank">MES 2）的路易斯酸碱络合反应与乙醚（Et 2 O），四氢噻吩（THT），三乙基膦（Et 3 P）和三环己基膦（Cy 3 P）已在25°C的烃类溶剂中通过激光闪光光解法进行了表征。连同先前报道的（和一些新的）数据，分析了六种瞬态四甲苯与甲醇（MeOH），四氢呋喃（THF）以及二乙胺和三乙胺（Et 2分别为NH和Et 3 N），这些结果可以对溶液中硫属元素和光生原供体的简单二烷基和二芳基亚甲硅烷基及其锗同系物的路易斯酸碱络合的热​​力学进行第一个系统的评估。这6种物质与Et 2 O络合的平衡常数（K C）范围约为ca。10 5中号-1，在为了降低SIPH 2 >森达2 > GePh 2 > GEME 2 »SIMES 2 > GEMa href=https://www.molaid.com/MS_310095 target="_blank">MES 2。对于每个同源MR
• Time-Resolved Spectroscopic Studies of the Reactivities of Dimethylgermylene and Tetramethyldigermene in Solution
  作者：William J. Leigh、Farahnaz Lollmahomed、Cameron R. Harrington

  DOI：10.1021/om0600083

  日期：2006.4.1

  Dimethylgermylene (GeMe2) has been generated and studied by laser flash photolysis of 1,1-dimethyl-and 1,1,4-trimethyl-3-phenylgermacyclopent-3-ene (3a and 3b, respectively) in hexane solution, where it exhibits lambda(max) = 470 nm and decays on the microsecond time scale with second-order kinetics. In the absence of scavengers the decay of GeMe2 is accompanied by the growth of absorptions due to tetramethyldigermene (Ge2Me4; lambda(max) = 370 nm), which decays over the next ca. 100 mu s. Absolute rate constants for reaction of GeMe2 with several reagents have been determined, including acetic acid, CCl4, oxygen, n-butyl- and triethylamine, a terminal alkene and alkyne, two dienes, and the group 14 trialkymetallyl hydrides R3MH (M = Si, Ge, Sn; R = Et or n-Bu). The rate constants agree closely with gas-phase values for the same or similar substrates. The data are compared to those for reaction of GePh2 with the same set of reagents, showing GeMe2 to be significantly more reactive than its phenylated analogue in every case. Evidence of reversibility is obtained for the reactions with the alkene and dienes, which are thought to yield the corresponding three-membered germanocycles as primary products; the equilibrium constants for these reactions are also considerably higher than those for reaction of GePh2. Comparisons are also made with published data for SiMe2 in solution. Absolute rate constants for reaction of Ge2Me4 have also been measured or assigned upper limits and are compared to those for the tetraphenyl analogue (Ge2Ph4), providing the first quantitative assessment of the effects of substituents on the reactivity of the Ge=Ge bond.