methyl 2-endo-methylbicyclo[2.2.1]hept-5-ene-2-exo-carboxylate | 7167-28-4

• 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: methyl 2-endo-methylbicyclo[2.2.1]hept-5-ene-2-exo-carboxylate
• 英文别名: methyl 5-methyl-bicyclo[2.2.1]hept-2-ene-5-carboxylate；(+/-)-2endo-methyl-norbornene-(5)-carboxylic acid-(2exo)-methyl ester；(+/-)-2endo-Methyl-norbornen-(5)-carbonsaeure-(2exo)-methylester；methyl (1R,2S,4R)-2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate
• CAS: 7167-28-4
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: AEBDJCUTXUYLDC-WEDXCCLWSA-N

物化性质

• 保留指数：
  1130

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• 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：

  methyl 2-endo-methylbicyclo[2.2.1]hept-5-ene-2-exo-carboxylate 生成 methyl (1S,2S,4R,5R,6R)-6-methyl-3-oxatricyclo[3.2.1.02,4]octane-6-carboxylate
  参考文献：
  名称：

  KASYAN L. I.; SAMITOV YU. YU., V SB. ZHPOKSID. MONOMERY I EHPOKSID. SMOLY. ZHAKU, ZHLM, 1975, 87-91

  摘要：

  DOI：
• 作为产物：
  描述：

  exo-5-norbornene-2-carboxylic acid 在 正丁基锂 、 二异丙胺 作用下， 生成 methyl 2-endo-methylbicyclo[2.2.1]hept-5-ene-2-exo-carboxylate
  参考文献：
  名称：

  Stereochemistry of alkylation of carboxylic acid salt and ester .alpha. anions derived from cyclic systems

  摘要：

  DOI：

  10.1021/jo01304a019

文献信息

• Hydrogen-bond-rich ionic liquids as effective organocatalysts for Diels–Alder reactions
  作者：Karol Erfurt、Ilona Wandzik、Krzysztof Walczak、Karolina Matuszek、Anna Chrobok

  DOI：10.1039/c4gc00380b

  日期：——

  characterisation of new hydrogen-bond-rich ionic liquids and studies of their catalytic performance in Diels–Alder reactions are described. D-Glucose and chloroalcohols were used as the raw materials and as the sources of hydroxyl groups for the synthesis of ionic-liquid cations, whereas weakly coordinating bis(trifluoromethylsulfonyl)imide was used as the anion. The new ionic liquids were analysed by 1H and 13C

  描述了新型富氢键离子液体的合成，表征以及它们在Diels–Alder反应中的催化性能的研究。D-葡萄糖和氯醇被用作合成离子-液体阳离子的原料和羟基的来源，而弱配位的双（三氟甲基磺酰基）酰亚胺被用作阴离子。用1 H和13分析新的离子液体通过13 C NMR光谱和ESI-MS实验，证实了它们的结构。此外，通过差示扫描量热法和热重分析法测得的离子液体的热数据表明，这些化合物在-29°C至-16°C的温度范围内倾向于形成玻璃，并且在环境温度下具有热稳定性。到至少430°C，最有可能是因为存在双（三氟甲基磺酰基）酰亚胺阴离子。研究了离子液体在环戊二烯与马来酸二乙酯或丙烯酸甲酯的模型反应中的性能。所研究的离子液体即使以催化量存在（相对于亲双烯体为4摩尔％）也显示出高活性。离子液体结构中存在的羟基数目的增加导致更高的反应速率。
• Nanoporous Solid Acid Catalyst for the Diels-Alder Reaction of 1,3-Dienes with Acrylates
  作者：Makoto Onaka、Naoki Hashimoto、Ryota Yamasaki、Yasuyoshi Kitabata

  DOI：10.1246/cl.2002.166

  日期：2002.2

  Nanoporous aluminosilicate, Al-HMS with a high aluminum content, strong acidity, and nanoporosity was found to catalyze the Diels-Alder reaction of 1,3-dienes with methacrylate and acrylate, and turned out to be a green alternative to homogeneous acid catalysts.

  发现具有高铝含量、强酸性和纳米多孔性的纳米多孔铝硅酸盐 Al-HMS 可以催化 1,3-二烯与甲基丙烯酸酯和丙烯酸酯的 Diels-Alder 反应，并被证明是均相酸催化剂的绿色替代品。
• Total Synthesis of (±)-2-Isocyanoallopupukeanane
  作者：Tse-Lok Ho、Liang-Ren Kung、Rong-Jie Chein

  DOI：10.1021/jo000668w

  日期：2000.9.1

  addition, S(N)2' displacement, chain extension, and elaboration of the unsaturated ketone 12c which underwent an intramolecular hetero-Diels-Alder reaction to afford 13 containing all the skeletal carbon atoms. The dihydropyran unit was cleaved by ozonolysis to give the tricarbocyclic intermediate which required seven more steps to complete the synthesis.

  通过二溴卡宾加成，S（N）2'取代，链增长，外消旋形式从2-exo-methylbicyclo [2.2.1] hept-5-ene-2-endo-carboxylate甲基获得2-异氰基铝环庚烷烷（4）。并进行不饱和酮12c的合成，该不饱和酮经过分子内的杂-Diels-Alder反应，得​​到含有所有骨架碳原子的13。通过臭氧分解将二氢吡喃单元裂解，得到三碳环中间体，这需要另外七个步骤来完成合成。
• Methylalumoxane as a Highly Lewis Acidic Reagent for Organic Synthesis
  作者：Matsujiro Akakura、Hisashi Yamamoto

  DOI：10.1055/s-1997-762

  日期：1997.3

  Methylalumoxane (MAO) is an extremely strong Lewis acid and is a useful reagent for organic reactions such as the Diels-Alder reaction and the amidation of esters. Reactions using MAO proceed much faster than those using Me3Al.

  甲基铝氧烷（MAO）是一种极强的路易斯酸，是有机反应中的重要试剂，例如达尔斯-阿尔德反应和酯的酰胺化反应。使用MAO的反应进行得比使用Me3Al的反应快得多。
• Salt effect on the endo/exo ratio of the reaction of cyclopentadiene with methyl methacrylate
  作者：Suvarna S. Deshpande、Usha D. Phalgune、Anil Kumar

  DOI：10.1016/s0040-4020(02)01055-4

  日期：2002.10

  The salt effect on the stereoselectivity of the reaction of cyclopentadiene with methyl methacrylate has been investigated. CaCl2, Na2SO4, KCl and LiCl enhance the endo/exo ratios, while guanidinium chloride (GnCl) and LiClO4 decrease them. The results are supported by independent calculations of salting-out and in coefficients.

  研究了盐对环戊二烯与甲基丙烯酸甲酯反应的立体选择性的影响。CaCl 2，Na 2 SO 4，KCl和LiCl可以提高内/外比，而氯化胍（GnCl）和LiClO 4可以降低内/外比。结果得到盐析和系数的独立计算的支持。