1α,2β,5α,6β-tricyclo[4.2.1.0^2,5]nona-3,7-diene-3,4-dicarbonyl chloride | 869645-09-0

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 英文名称: 1α,2β,5α,6β-tricyclo[4.2.1.0^2,5]nona-3,7-diene-3,4-dicarbonyl chloride
• 英文别名: (1R,2R,5S,6S)-tricyclo[4.2.1.02,5]nona-3,7-diene-3,4-dicarbonyl chloride
• CAS: 869645-09-0
• 化学式: C₁₁H₈Cl₂O₂
• 分子量: 243.089
• InChiKey: ZQYIZXNYVWEZQQ-RNGGSSJXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1α,2β,5α,6β-tricyclo[4.2.1.0^2,5]nona-3,7-diene-3,4-dicarbonyl chloride 在 sodium hydroxide 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 14.0h， 生成 1α,2β,4β,5α,8α,9β,11β,12α-Hexacyclo[10.2.1.15,8.02,11.03,10.04,9]hexadeca-6,13-diene-3,10-dicarboxylic acid
  参考文献：
  名称：

  Reactivity increase of dienophiles by change of the ester substituents into the acid chlorides: cycloaddition reaction of the diacid chloride of 3,10-hexacyclo[10.2.1.15,8.02,11.03,10.04,9]hexadeca-6,13-diene-3,10-dicarboxylic acid with quadricyclane

  摘要：

  Conversion of the ester substituents on the cyclobutene it-bond of dimethyl tricyclo[4.2.1.0(2,5)]nona-3,7-diene-3,4-dicarboxylate to the corresponding acid chloride increases the cycloaddition reactivity toward quadricyclane so dramatically that the reaction temperature can be dropped from 180 degrees C (preparation of title 3,10-diester) to room temperature (preparation of the title 3,10-diacid chloride). The cycloadduct product, an acid chloride of the title ring system, is extremely docile and can be recrystallized unchanged from hot methanol. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.06.057
• 作为产物：
  描述：

  二甲基(1R,2R,5S,6S)-三环[4.2.1.02,5]壬-3,7-二烯-3,4-二羧酸酯 在 氯化亚砜 、 potassium hydroxide 作用下， 以 甲醇 、 氯仿 、 水 为溶剂， 反应 21.0h， 生成 1α,2β,5α,6β-tricyclo[4.2.1.0^2,5]nona-3,7-diene-3,4-dicarbonyl chloride
  参考文献：
  名称：

  Reactivity increase of dienophiles by change of the ester substituents into the acid chlorides: cycloaddition reaction of the diacid chloride of 3,10-hexacyclo[10.2.1.15,8.02,11.03,10.04,9]hexadeca-6,13-diene-3,10-dicarboxylic acid with quadricyclane

  摘要：

  Conversion of the ester substituents on the cyclobutene it-bond of dimethyl tricyclo[4.2.1.0(2,5)]nona-3,7-diene-3,4-dicarboxylate to the corresponding acid chloride increases the cycloaddition reactivity toward quadricyclane so dramatically that the reaction temperature can be dropped from 180 degrees C (preparation of title 3,10-diester) to room temperature (preparation of the title 3,10-diacid chloride). The cycloadduct product, an acid chloride of the title ring system, is extremely docile and can be recrystallized unchanged from hot methanol. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.06.057

文献信息

• Container Systems II: An Experimental Study of the High-Pressure Intramolecular Cycloaddition of Tethered Furans and Anthracenes onto Norbornane Cyclobutene-1,2-diesters
  作者：Davor Margetić、Ronald N. Warrener

  DOI：10.1002/jhet.2015

  日期：2014.9

  single 1:1‐adduct was obtained in which one furfuryl moiety was intramolecularly cyclized and the other present as the DMAD adduct; again this product underwent retro‐DA reaction at 40°C. Similar intermolecular cyclization was observed with the bis‐anthracenyl esters. The stereoselectivity of the intermolecular attack of the furfuryl diene with the dienophilic cyclobutene gave a single adduct by endo‐face

  描述了一种新型的容器分子，并报道了产生原型的第一步。该方法的中心是在末端的环丁烯-1，2-二糠基酯或在中央降冰片烷亚基的桥头处具有类似官能团的聚降冰片烷的形成。描述了糠基起始原料及其蒽基对应物的合成。转换为容器系统涉及糠醛或蒽的分子间连接，方法是在Diels-Alder（DA）方案中，在热或高压（HP）条件下，用二甲基乙炔二甲酸二甲酯（DMAD）处理。实际上，降冰片烷底物之间没有发生分子间连接，仅产生了DA 1：1加DMAD的产物。在高压条件下检测到糠基单元之一在环丁烯π键上的分子内加成，该分子间产物能够通过在室温或低于室温的条件下进行分离和表征，但在室温以上仍可恢复为起始原料。当在DMAD存在下进行时，获得了一个1：1-加合物，其中一个糠基部分被分子内环化，另一个作为DMAD加合物存在。该产品再次在40°C进行逆转录DA反应。双蒽基酯也观察到类似的分子间环化反应。糠基二烯与双亲亲环丁烯的
• Reactivity increase of dienophiles by change of the ester substituents into the acid chlorides: cycloaddition reaction of the diacid chloride of 3,10-hexacyclo[10.2.1.15,8.02,11.03,10.04,9]hexadeca-6,13-diene-3,10-dicarboxylic acid with quadricyclane
  作者：Davor Margetić、Anamarija Briš、Ronald N. Warrener、Douglas N. Butler

  DOI：10.1016/j.tet.2013.06.057

  日期：2013.9

  Conversion of the ester substituents on the cyclobutene it-bond of dimethyl tricyclo[4.2.1.0(2,5)]nona-3,7-diene-3,4-dicarboxylate to the corresponding acid chloride increases the cycloaddition reactivity toward quadricyclane so dramatically that the reaction temperature can be dropped from 180 degrees C (preparation of title 3,10-diester) to room temperature (preparation of the title 3,10-diacid chloride). The cycloadduct product, an acid chloride of the title ring system, is extremely docile and can be recrystallized unchanged from hot methanol. (C) 2013 Elsevier Ltd. All rights reserved.