3,4-dimethyl-cyclohex-3-enecarboxylic acid methyl ester | 5688-48-2

• 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: 3,4-dimethyl-cyclohex-3-enecarboxylic acid methyl ester
• 英文别名: (+/-)-methyl 3,4-dimethyl-3-cyclohexene-1-carboxylate；1,2-dimethyl-4-methoxycarbonylcyclohex-1-ene；methyl 3,4-dimethyl-3-cyclohexenecarboxylate；methyl 3,4-dimethylcyclohex-3-enecarboxylate；3,4-Dimethyl-cyclohex-3-encarbonsaeure-methylester；3,4-Dimethyl-cyclohex-3-en-1-carbonsaeuremethylester；3-Cyclohexene-1-carboxylic acid, 3,4-dimethyl-, methyl ester；methyl 3,4-dimethylcyclohex-3-ene-1-carboxylate
• CAS: 5688-48-2
• 化学式: C₁₀H₁₆O₂
• mdl: MFCD09032264
• 分子量: 168.236
• InChiKey: MLXHWXTWIQUFRX-UHFFFAOYSA-N

物化性质

• 沸点：
  105.5-106.5 °C(Press: 20 Torr)
• 密度：
  0.9669 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,4-dimethyl-cyclohex-3-enecarboxylic acid methyl ester 在 ruthenium trichloride 、 sodium periodate 作用下， 以 乙酸乙酯 、 乙腈 为溶剂， 反应 0.05h， 以80%的产率得到(+/-)-methyl cis-3,4-dihydroxy-3,4-dimethylcyclohexane-1-carboxylate
  参考文献：
  名称：

  Shing, Tony K. M.; Tam, Eric K. W.; Tai, Vincent W.-F., Chemistry - A European Journal, 1996, vol. 2, # 1, p. 50 - 57

  摘要：

  DOI：
• 作为产物：
  描述：

  ((methyl)2cyclohexenyl)(methoxymethylene)pentacarbonyltungsten 在 二甲基亚砜 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以91%的产率得到3,4-dimethyl-cyclohex-3-enecarboxylic acid methyl ester
  参考文献：
  名称：

  Wulff, William D.; Bauta, William E.; Kaesler, Ralph W., Journal of the American Chemical Society, 1990, vol. 112, # 9, p. 3642 - 3659

  摘要：

  DOI：

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。
• New Lewis acid catalysts for the Diels-Alder reaction
  作者：T. Ross Kelly、Sanat K. Maity、Premji Meghani、Nizal S. Chandrakumar

  DOI：10.1016/s0040-4039(00)99464-4

  日期：1989.1

  Catechol boron bromide (1) and ferrocenium hexafluorophosphate (2) function as Lewis acid catalysts for the Diels-Alder reaction.

  儿茶酚溴化硼（1）和六氟磷酸铯（2）充当Diels-Alder反应的路易斯酸催化剂。
• Dramatic acceleration of the Diels-Alder reaction by adsorption on chromatography adsorbents
  作者：V.V. Veselovsky、A.S. Gybin、A.V. Lozanova、A.M. Moiseenkov、W.A. Smit、R. Caple

  DOI：10.1016/s0040-4039(00)80045-3

  日期：1988.1

  The development of a new method for effecting [4+2] cycloadditions on the surface of chromatographic adsorbents in the absence of solvents that leads to a moderation of the reaction conditions and an increase in selectivity is described.

  描述了在不存在溶剂的情况下在色谱吸附剂表面进行[4 + 2]环加成反应的新方法的开发，该方法导致反应条件的缓和和选择性的提高。
• Taming the Silylium Ion for Low-Temperature Diels-Alder Reactions
  作者：Hendrik F. T. Klare、Klaus Bergander、Martin Oestreich

  DOI：10.1002/anie.200904520

  日期：2009.11.16

  trivalent silicon cation stabilized by an electron‐rich transition metal as the “hot” Lewis acidic site catalyzes challenging Diels–Alder reactions at low temperatures with excellent reaction rates and selectivities (see scheme). In addition to the chemical stability of the silylium ion catalyst (in CH2Cl2), the potential of these reactive compounds is also discussed.

  有些人喜欢它：一种新型的基于硅的路易斯酸，具有三价硅阳离子，该阳离子被富电子的过渡金属稳定，作为“热”路易斯酸性位点，可在低温下催化具有挑战性的Diels-Alder反应，并具有出色的反应速率和选择性（请参见方案）。除了硅离子催化剂的化学稳定性（在CH 2 Cl 2中）之外，还讨论了这些反应性化合物的潜力。
• Solvent-Free Diels–Alder Reaction in a Closed Batch System
  作者：Daolai Sun、Fumiya Sato、Yasuhiro Yamada、Satoshi Sato

  DOI：10.1246/bcsj.20120247

  日期：2013.2.15

  Solvent-free Diels–Alder reactions were carried out by heating a mixture of a volatile diene, such as 1,3-butadiene, isoprene, or 2,3-dimethyl-1,3-butadiene, and a dienophile, such as methyl vinyl ketone, methyl acrylate, or maleic anhydride, in a closed batch reactor. High yields of Diels–Alder products were obtained without using solvents and catalysts within a short reaction time in most of the reactions. In particular, several reactions of dienophiles with 1,3-butadiene, which is known as a diene with low reactivity because of its gaseous form, also proceeded with high yields of Diels–Alder products in the closed batch reactor under conditions pressured by the reactant vapor. Solvent-free reactions provided high yields compared to reactions in solvent since the reaction heat directly resulted in increasing the reaction temperature and pressure. Energy in the exothermic reaction was used effectively in the closed batch system under solvent-free conditions.

  无溶剂的Diels-Alder反应是在一个封闭的批式反应器中，通过加热混合挥发性的二烯烃（如1,3-丁二烯、异戊二烯或2,3-二甲基-1,3-丁二烯）与二烯亲电试剂（如甲基乙烯酮、甲基丙烯酸酯或马来酸酐）而进行的。大多数反应在短时间内在不使用溶剂和催化剂的情况下获得了高产率的Diels-Alder产物。特别是，一些公认由于其气态形式而反应活性较低的1,3-丁二烯与二烯亲电试剂的反应，在封闭批式反应器中，在反应物蒸气压力条件下，也以高产率进行了Diels-Alder产物生成。与溶剂中的反应相比，无溶剂反应提供了更高的产率，因为反应热直接导致了反应温度和压力的升高。在无溶剂条件下，封闭批式系统中有效地利用了放热反应的能量。