dimethyl tricyclo[4.2.2.0^2,5]deca-3,7,9-triene-7,8-dicarboxylate | 25157-95-3

• 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: dimethyl tricyclo[4.2.2.0^2,5]deca-3,7,9-triene-7,8-dicarboxylate
• 英文别名: dimethyl tricyclo<4.2.2.0^2,5>deca-3,7,9-triene-9,10-dicarboxylate；dimethyl ester of tricyclo<4.2.2.0^2,5>deca-3,7,9-triene-9,10-dicarboxylic acid；9,10-dimethoxycarbonyltricyclo<4.2.2.0^2,5>deca-3,7,9-triene；dimethyl tricyclo<4.2.2.0^2,5>deca-3,7,9-triene-7,8-dicarboxylate；rel-7,8-Dimethyl (1R,2R,5S,6S)-tricyclo[4.2.2.02,5]deca-3,7,9-triene-7,8-dicarboxylate；dimethyl (1R,2R,5S,6S)-tricyclo[4.2.2.02,5]deca-3,7,9-triene-7,8-dicarboxylate
• CAS: 25157-95-3
• 化学式: C₁₄H₁₄O₄
• 分子量: 246.263
• InChiKey: PPINETRWBOZSGM-YNFQOJQRSA-N

物化性质

• 沸点：
  362.2±42.0 °C(Predicted)
• 密度：
  1.292±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dimethyl tricyclo[4.2.2.0^2,5]deca-3,7,9-triene-7,8-dicarboxylate 在 palladium diacetate 、 四丁基氯化铵 、 sodium acetate 作用下， 以 乙腈 为溶剂， 反应 72.0h， 以30%的产率得到邻苯二甲酸二甲酯
  参考文献：
  名称：

  ortho-Disubstitution reactions of aromatic rings with homo-conjugated bicyclo[2.2.2]octa-2,5-diene derivatives in the presence of palladium(II) acetate

  摘要：

  Bicyclo[2.2.2]octa-2,5-diene derivatives 5 and 7 reacted with aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, and tropone in the presence of Pd(OAc)(2) to afford ortho-disubstituted aromatics 6 and 8-12. Since the yields and regioselectivity were generally low, the reaction conditions were optimized by using iodoarenes as reagents to provide sufficient yields and regioselectivity. In order to investigate reactivities of diene moieties, several kinds of homo-conjugated dienes were surveyed for the reaction. Only dienes containing a bicyclo[2.2.2]octa-2,5-diene skeleton gave the ortho-disubstituted aromatics. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)01126-2
• 作为产物：
  描述：

  dimethyl (1S,2R,5R,6S)-tricyclo[4.2.2.02,5]deca-3,7,9-triene-1,8-dicarboxylate 生成 dimethyl tricyclo[4.2.2.0^2,5]deca-3,7,9-triene-7,8-dicarboxylate
  参考文献：
  名称：

  DINULESCU I. G.; GEORGESCU E. G.; STANESCU L.; AVRAM M., TETRAHEDRON, 1981, 37, SUPPL. NO 9, 55-59

  摘要：

  DOI：

文献信息

• High-Pressure Diels–Alder Reaction of Cyclooctatetraene with Dimethyl 1,4-Dimethyl-7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate. Single Crystalline State Valence Isomerization of a<i>syn</i>-Tricyclo[4.2.0.0^2,5]octane Derivative
  作者：Hitoshi Takeshita、Akira Mori、Nobuo Kato、Yoichi Kurahashi、Masahito Ito

  DOI：10.1246/bcsj.68.2669

  日期：1995.9

  High-pressure Diels–Alder reaction of cyclooctatetraene with dimethyl 1,4-dimethyl-7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate afforded six products, one of which was shown to be a 2 : 2-adduct having a syn-tricyclo[4.2.0.02,5]octane framework. Upon radiation with X-rays, the tricyclooctane derivative isomerized to a cyclooctadiene derivative.

  在高压条件下，环辛四烯与二甲基1,4-二甲基-7-氧杂双环[2.2.1]庚-2,5-二烯-2,3-二羧酸酯发生Diels-Alder反应，生成了六种产物，其中之一被证实为具有顺式三环[4.2.0.02,5]辛烷骨架的2:2加合物。经X射线辐射后，三环辛烷衍生物异构化为环辛二烯衍生物。
• 2-Isoxazoline derivatives—III
  作者：G. Bianchi、R. Gandolfi、P. Grünanger

  DOI：10.1016/s0040-4020(01)93164-3

  日期：1970.1

  The structure and the stereochemistry of the mono-adducts, obtained by 1,3-dipolar cycloaddition of nitrile oxides to cyclooctatetraene, have been elucidated on chemical evidence. Thermolysis of their Diels-Alder adducts with acetylenedicarboxylate yielded 4-aryl (or alkyl)-2,3-oxazabicyclo[3.2.0]hepta-3,6-dienes. Some reactions of this new heterocyclic condensed system are described.

  通过化学证据阐明了通过腈类化合物的1，3-偶极环加成反应获得的单加合物的结构和立体化学。用乙炔二羧酸酯对其Diels-Alder加合物进行热解，得到4-芳基（或烷基）-2,3-氧杂双环[3.2.0]庚3,6-二烯。描述了这种新的杂环缩合系统的一些反应。
• Cycloaddition reactions of nitrones to cyclooctatetraene and its derivatives
  作者：G. Bianchi、A. Gamba、R. Gandolfi

  DOI：10.1016/0040-4020(72)88042-6

  日期：1972.1

  The cycloaddition of acyclic nitrones to the Diels-Alder adduct cyclooctatetraene-acetylenedicarboxylate yields three different monoadducts, whose structures are assured through NMR spectroscopy and chemical transformations. Thermolysis of these monoadducts to the new heterocyclic system of 2,3-oxazabicyclo[3.2.0]hepta-6-ene is described. Depending on the nature of the substituents on the N atom and

  无环硝酮与Diels-Alder加合物的环加成环辛酸酯-烯基-乙二羧酸酯可产生三种不同的单加合物，其结构可通过NMR光谱和化学转化得到保证。描述了将这些单加合物热解为2,3-氧杂双环[3.2.0]庚-6-烯的新杂环系统。取决于N原子上取代基的性质以及异恶唑烷C-3的立体化学，还获得了不同量的吡咯醛。
• Reactions of cyclo-octatetraene and its derivatives—IX
  作者：Iqbal A. Akhtar、Richard J. Atkins、Gordon I. Fray、Graham R. Geen、Trevor J. King

  DOI：10.1016/0040-4020(80)88029-x

  日期：1980.1

  Tetracyclol[8.2.2.02,9.03,8]tetradeca-4,6,11-trienes 5 are produced from tricyclo[4.2.2.02,5]deca-3,7-dienes 1 by reaction with cyclopentadienones 2 (or equiv) followed by thermal decarbonylation. With tetraphenylcyclopentadienone, however, the product 5e rearranges under the conditions required for its formation to give the dihydrosemibullvalene 11. The rearrangement evidently proceeds via the cyclo-octa-1

  四环[8.2.2.0 2,9 .0 3,8 ]十四烷-4,6,11-三烯5是由三环[4.2.2.0 2,5 ] deca-3,7-二烯1与环戊二烯酮2（或当量），然后进行热脱羰。然而，对于四苯基环戊二烯酮，产物5e在其形成所需的条件下重排以得到二氢半牛缬烯11。显然，重排通过环辛-1,3,5-三烯14，开环5e→14进行苯基共轭效应促进了这一作用，这在涉及环戊二烯酮与三环[4.2.1.0 2,5 ] nona-3,7-diene 16的另一系列实验中未发现。因此，四苯环己基-1,3-二烯18c在回流的二甲苯中经历开环反应，得到环庚-1,3,5-三烯烃21a，而二甲基二苯基类似物18b在这些条件下抵抗化合价。
• Reactions of cyclo-octatetraene and its derivatives—VIII
  作者：R.J. Atkins、G.I. Fray

  DOI：10.1016/s0040-4020(01)93742-1

  日期：1979.1

  thermal decarbonylation of the product. Reaction of the mixture of cyclo-octatetraenes with bromine gave the (separable) dibromo-derivatives 17 and 18. On attempted debromination with zinc, the dibromodiene 17 formed the benzocyclobutadiene dimer 12, together with the benzobiphenylene 13; these compounds were also produced directly from the cyclo-octatetraene mixture by the action of zinc. In contrast

  描述了早期合成1,2,3,8-四氯环辛酸酯4的尝试。一个CA。通过缩酮15的水解（使用96％三氟乙酸），然后将产物热脱羰，最终获得1,2,3,8-和1,2,3,4-四氯环辛酸酯的2：1混合物。环辛酸酯与溴的混合物反应，得到（可分离的）二溴衍生物17和18。在尝试用锌脱溴时，二溴二烯17与苯并联亚苯基13一起形成了苯并环丁二烯二聚体12。; 这些化合物也可以通过锌的作用直接由环辛八烯混合物生产。相比之下，对二溴二烯18的类似处理导致生成E-溴苯乙烯22。环辛酸酯的混合物与马来酸酐反应得到加合物27，而与烯则获得加合物28。