1-(1,7-octadiynyl)-2-methylcarboxybenzene | 138753-39-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(1,7-octadiynyl)-2-methylcarboxybenzene
• 英文别名: methyl 2-(1,7-octadiynyl)benzoate；methyl 2-octa-1,7-diynylbenzoate
• CAS: 138753-39-6
• 化学式: C₁₆H₁₆O₂
• 分子量: 240.302
• InChiKey: MPQDPTXPCUYGHH-UHFFFAOYSA-N

物化性质

• 沸点：
  371.8±27.0 °C(Predicted)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  重氮甲烷 、 1-(1,7-octadiynyl)-2-methylcarboxybenzene 生成 o-(1,7-octadiynyl)-α-diazoacetophenone
  参考文献：
  名称：

  Cyclization Reactions of Rhodium Carbene Complexes. Effect of Composition and Oxidation State of the Metal

  摘要：

  Treatment of o-(1,7-octadiynyl)benzoyldiazoethane with rhodium(II) octanoate in pentane resulted in a double internal/internal alkyne insertion reaction producing a labile bicyclo[4.1.0]hept-1(7)ene derivative which readily undergoes a Diels-Alder reaction with diphenylisobenzofuran. Changing the solvent from pentane to CH2Cl2 afforded a 2:1 mixture of cis- and trans-alkenyl-substituted indenones. Stepwise cyclization involving a set of dipolar intermediates occurs in CH2Cl2 whereas metallocyclobutenes are involved when pentane is used as the solvent. The rhodium(II) carboxylate catalyzed reaction of unsymmetrically substituted cyclopropenes gives substituted furans derived from cleavage of the less substituted beta-bond. Thus, treatment of 3-benzoyl-3-methyl-1-(n-butyl)cyclopropene with Rh2OAc4 afforded a 26:1 mixture of 2-phenyl-3-methyl-4-(n-butyl)- and 2-phenyl-3-methyl-5-(n-butyl)furan. In contrast, the [ClRh(CO)(2)](2)-catalyzed reaction resulted in cleavage of the more substituted sigma-bond producing only 2-phenyl-3-methyl-5-(n-butyl)furan. Both reactions involve electrophilic attack of the rhodium metal on the less substituted carbon atom of the cyclopropene pi-bond to give the most stabilized cyclopropyl carbocation. Ring opening followed by rapid electrocyclization to the furan occurs with the Rh(IH) catalyst. With the Rh(I) catalyst, the ring-opened species preferentially cyclizes to a metallocyclobutene intermediate which then equilibrates with the thermodynamically more stable isomer prior to furan formation. The Rh(I)-catalyzed reaction of 3-benzoyl-1-propylcyclopropene with various terminal alkynes gives 4-alkyl-4-propyl-7-phenyloxepins in good yield. These reactions involve electrophilic attack of the rhodium metal on the more substituted carbon of the cyclopropene; pi-bond to give a rhodium carbene complex, This metallo carbenoid undergoes a subsequent [2 + 2] cycloaddition with terminal acetylenes, The resulting rhodacycle rearranges by a formal 1,5-sigmatropic shift, and this is followed by reductive elimination of rhodium to produce the observed oxepin.

  DOI：

  10.1021/jo962271r
• 作为产物：
  描述：

  1,7-辛二炔 、 2-碘苯甲酸甲酯 在 copper(l) iodide 双(乙腈)氯化钯(II) 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 以63%的产率得到1-(1,7-octadiynyl)-2-methylcarboxybenzene
  参考文献：
  名称：

  钴催化的二炔与苄腈的共环三聚反应合成阻转异构吡啶

  摘要：

  芳基吡啶（潜在的有机催化剂的前体）可通过邻位取代的1-芳基-1,7-辛二炔与苄腈的钴催化共环三聚反应轻松获得。研究了关于邻位取代基（OMe，Me，COOMe，NHCOMe，F等）的反应范围。制备了三种潜在的对位异构体芳基吡啶，并将其中一种转化为相应的N-氧化物并拆分为其对映异构体。通过X射线晶体结构分析确定了N-氧化物的绝对构型。介绍了其在不对称有机催化中的初步应用结果。

  DOI：

  10.1016/j.tet.2005.10.034

文献信息

• Cyclization Reactions of Rhodium Carbene Complexes. Effect of Composition and Oxidation State of the Metal
  作者：Albert Padwa、Jamal M. Kassir、Simon L. Xu

  DOI：10.1021/jo962271r

  日期：1997.3.1

  Treatment of o-(1,7-octadiynyl)benzoyldiazoethane with rhodium(II) octanoate in pentane resulted in a double internal/internal alkyne insertion reaction producing a labile bicyclo[4.1.0]hept-1(7)ene derivative which readily undergoes a Diels-Alder reaction with diphenylisobenzofuran. Changing the solvent from pentane to CH2Cl2 afforded a 2:1 mixture of cis- and trans-alkenyl-substituted indenones. Stepwise cyclization involving a set of dipolar intermediates occurs in CH2Cl2 whereas metallocyclobutenes are involved when pentane is used as the solvent. The rhodium(II) carboxylate catalyzed reaction of unsymmetrically substituted cyclopropenes gives substituted furans derived from cleavage of the less substituted beta-bond. Thus, treatment of 3-benzoyl-3-methyl-1-(n-butyl)cyclopropene with Rh2OAc4 afforded a 26:1 mixture of 2-phenyl-3-methyl-4-(n-butyl)- and 2-phenyl-3-methyl-5-(n-butyl)furan. In contrast, the [ClRh(CO)(2)](2)-catalyzed reaction resulted in cleavage of the more substituted sigma-bond producing only 2-phenyl-3-methyl-5-(n-butyl)furan. Both reactions involve electrophilic attack of the rhodium metal on the less substituted carbon atom of the cyclopropene pi-bond to give the most stabilized cyclopropyl carbocation. Ring opening followed by rapid electrocyclization to the furan occurs with the Rh(IH) catalyst. With the Rh(I) catalyst, the ring-opened species preferentially cyclizes to a metallocyclobutene intermediate which then equilibrates with the thermodynamically more stable isomer prior to furan formation. The Rh(I)-catalyzed reaction of 3-benzoyl-1-propylcyclopropene with various terminal alkynes gives 4-alkyl-4-propyl-7-phenyloxepins in good yield. These reactions involve electrophilic attack of the rhodium metal on the more substituted carbon of the cyclopropene; pi-bond to give a rhodium carbene complex, This metallo carbenoid undergoes a subsequent [2 + 2] cycloaddition with terminal acetylenes, The resulting rhodacycle rearranges by a formal 1,5-sigmatropic shift, and this is followed by reductive elimination of rhodium to produce the observed oxepin.
• Synthesis of atropoisomeric pyridines via cobalt-catalyzed cocyclotrimerization of diynes with benzonitrile
  作者：Radim Hrdina、Irena G. Stará、Lenka Dufková、Scott Mitchel、Ivana Císařová、Martin Kotora

  DOI：10.1016/j.tet.2005.10.034

  日期：2006.1

  benzonitrile. The scope of the reaction with respect to the ortho substituents (OMe, Me, COOMe, NHCOMe, F, etc.) was investigated. Three potentially atropoisomeric arylpyridines were prepared and one of them was converted into the corresponding N-oxide and resolved into its enantiomers. The absolute configuration of the N-oxide was established by X-ray crystal structure analysis. Preliminary results

  芳基吡啶（潜在的有机催化剂的前体）可通过邻位取代的1-芳基-1,7-辛二炔与苄腈的钴催化共环三聚反应轻松获得。研究了关于邻位取代基（OMe，Me，COOMe，NHCOMe，F等）的反应范围。制备了三种潜在的对位异构体芳基吡啶，并将其中一种转化为相应的N-氧化物并拆分为其对映异构体。通过X射线晶体结构分析确定了N-氧化物的绝对构型。介绍了其在不对称有机催化中的初步应用结果。