3-Methyl-cyclohexen-(4)-carbonsaeure-(1)-methylester | 67201-22-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-Methyl-cyclohexen-(4)-carbonsaeure-(1)-methylester
• 英文别名: Methyl 5-methylcyclohex-3-ene-1-carboxylate
• CAS: 67201-22-3
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: VZAIBLBJANAOTQ-UHFFFAOYSA-N

物化性质

• 沸点：
  188.7±19.0 °C(Predicted)
• 密度：
  0.980±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  反-1,3-戊二烯 、 丁烯酮 在 silica gel 作用下， 以 二氧化碳 为溶剂， 反应 24.0h， 生成 2-methyl-cyclohex-3-enecarboxylic acid methyl ester 、 3-Methyl-cyclohexen-(4)-carbonsaeure-(1)-methylester
  参考文献：
  名称：

  Silica-Promoted Diels−Alder Reactions in Carbon Dioxide from Gaseous to Supercritical Conditions

  摘要：

  Amorphous fumed silica (SiO(2)) was shown to increase yields and selectivities of several Diels-Alder reactions in gaseous and supercritical CO(2). Pressure effects on the Diels-Alder reaction were explored using methyl vinyl ketone and penta-1,3-diene at 80 degrees C. The selectivity of the reaction was not affected by pressure/density. As pressure was increased, the yield decreased. At the reaction temperature, adsorption isotherms at various pressures were obtained for the reactants and the Diels-Alder adduct. As expected when pressure is increased, the ratio of the amount of reactants adsorbed to the amount of reactants in the fluid phase decreases, thus causing the yield to decrease. The Langmuir adsorption model fit the adsorption data. The Langmuir equilibrium partitioning constants all decreased with increasing pressure. The effect of temperature on adsorption was experimentally determined and traditional heats of adsorption were calculated. However, since supercritical CO(2) is a highly compressible fluid, it is logical to examine the effect of temperature at constant density. In this case, entropies of adsorption were obtained. The thermodynamic properties that influence the real enthalpy and entropy of adsorption were derived. Methods of doping the silica and improving yields and selectivities were also explored.

  DOI：

  10.1021/jp984227g

文献信息

• Use of functionalized onium salts as a soluble support for organic synthesis
  申请人：Vaultier Michel

  公开号：US20070043234A1

  公开（公告）日：2007-02-22

  The invention relates to the use of a onium salt functionalized by at least one organic function, as a soluble support, in the presence of at least one organic solvent, for organic synthesis of a molecule, in a homogenous phase, by at least one transformation of said organic function. The onium salt enables the synthesized molecule to be released. The onium salt is present in liquid or solid form at room temperature and corresponds to formula A 1 + , X 1 − , wherein A 1 + represents a cation and X 1 − represents an anion.

  该发明涉及使用至少一个有机功能官能化的离子盐作为可溶性支持体，在至少一个有机溶剂的存在下，用于在均相相中通过至少一个所述有机功能的转化对分子进行有机合成。该离子盐使合成的分子能够被释放。该离子盐在室温下以液态或固态形式存在，符合以下公式A1+，X1−，其中A1+代表阳离子，X1−代表阴离子。
• Mechanism of Di-<i>tert</i>-Butylsilylene Transfer from a Silacyclopropane to an Alkene
  作者：Tom G. Driver、K. A. Woerpel

  DOI：10.1021/ja0301370

  日期：2003.9.1

  Kinetic and thermodynamic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes suggested a possible mechanism for di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 and cyclohexene were determined to be 1 and -1, respectively. Saturation kinetic behavior in monosubstituted alkene concentration was observed. Competition experiments between

  环己烯硅杂环丙烷 1 和单取代烯烃反应的动力学和热力学研究表明了二叔丁基亚甲硅烷基转移的可能机制。环己烯硅杂环丙烷 1 和环己烯的动力学顺序分别确定为 1 和 -1。观察到单取代烯烃浓度下的饱和动力学行为。取代的苯乙烯和 1 的不足量的二叔丁基亚甲硅烷之间的竞争实验与哈米特方程很好地相关，并使用 sigma(p) 常数提供了 -0.666 +/- 0.008 的 rho 值。这些数据支持两步机制，包括从 1 中可逆地挤出二叔丁基亚甲硅烷，然后是亚甲硅烷对单取代烯烃的不可逆协同亲电攻击。发现 Eyring 激活参数为 DeltaH++ = 22.1 +/- 0.9 kcal.mol(-1) 和 DeltaS++ = -15 +/- 2 eu。环烯烃和烯丙苯之间的竞争实验确定环烯烃是更有效的亚甲硅烷陷阱 (k(rel) =1.3，DeltaDeltaG++ = 0.200 kcal.mol(-
• Highly regioselective diels-alder reactions of 2-trimethylsilylmethyl- and 2-trimethylstannylmethyl-1,3-butadiene
  作者：Akira Hosomi、Masaki Saito、Hideki Sakurai

  DOI：10.1016/s0040-4039(01)85471-x

  日期：1980.1