5,5-Bis(methoxymethyl)-14,17,20,23-tetraoxatricyclo[23.2.2.29,12]hentriaconta-1(28),9,11,25(29),26,30-hexaen-2,7-diyne | 1605284-09-0

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 5,5-Bis(methoxymethyl)-14,17,20,23-tetraoxatricyclo[23.2.2.29,12]hentriaconta-1(28),9,11,25(29),26,30-hexaen-2,7-diyne
• 英文别名: 5,5-bis(methoxymethyl)-14,17,20,23-tetraoxatricyclo[23.2.2.29,12]hentriaconta-1(28),9,11,25(29),26,30-hexaen-2,7-diyne
• CAS: 1605284-09-0
• 化学式: C₃₁H₃₈O₆
• 分子量: 506.639
• InChiKey: DEJLXLSSEIARRQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  37
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-戊炔 、 5,5-Bis(methoxymethyl)-14,17,20,23-tetraoxatricyclo[23.2.2.29,12]hentriaconta-1(28),9,11,25(29),26,30-hexaen-2,7-diyne 在 tris(triphenylphosphine)rhodium(l) chloride 作用下， 以 四氢呋喃 、 异丙醇 为溶剂， 反应 6.0h， 以64%的产率得到5,5-Bis(methoxymethyl)-9-propyl-16,19,22,25-tetraoxapentacyclo[25.2.2.211,14.02,10.03,7]tritriaconta-1(29),2,7,9,11(33),12,14(32),27,30-nonaene
  参考文献：
  名称：

  A Strain Induced Change of Mechanism from a [2 + 2 + 2] to a [2 + 1 + 2 + 1] Cycloaddition Reaction

  摘要：

  While investigating the [2 + 2 + 2] cycloaddition as a tool to build up strained oligophenyl systems with a diyne-ethylene glycol macrocyle, a surprising change of mechanism was observed. Instead of the expected [2 + 2 + 2] para-terphenyl, the ortho-terphenyl product explained by a formal [2 + 1 + 2 + 1] cycloaddition was formed. An eta(4)-coordinated metal-cyclobutadiene is proposed as the key structure in the catalytic cycle, which is formed to release the induced strain. The optical properties of the ortho-terphenyl products have been measured as well as the coordination ability of Na+ and K+.

  DOI：

  10.1021/ol5007604
• 作为产物：
  描述：

  4-碘苄醇 在 copper(l) iodide 、 四(三苯基膦)钯 、 sodium hydride 、 二异丙胺 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 3.0h， 生成 5,5-Bis(methoxymethyl)-14,17,20,23-tetraoxatricyclo[23.2.2.29,12]hentriaconta-1(28),9,11,25(29),26,30-hexaen-2,7-diyne
  参考文献：
  名称：

  A Strain Induced Change of Mechanism from a [2 + 2 + 2] to a [2 + 1 + 2 + 1] Cycloaddition Reaction

  摘要：

  While investigating the [2 + 2 + 2] cycloaddition as a tool to build up strained oligophenyl systems with a diyne-ethylene glycol macrocyle, a surprising change of mechanism was observed. Instead of the expected [2 + 2 + 2] para-terphenyl, the ortho-terphenyl product explained by a formal [2 + 1 + 2 + 1] cycloaddition was formed. An eta(4)-coordinated metal-cyclobutadiene is proposed as the key structure in the catalytic cycle, which is formed to release the induced strain. The optical properties of the ortho-terphenyl products have been measured as well as the coordination ability of Na+ and K+.

  DOI：

  10.1021/ol5007604

文献信息

• A Strain Induced Change of Mechanism from a [2 + 2 + 2] to a [2 + 1 + 2 + 1] Cycloaddition Reaction
  作者：Anne-Florence Tran-Van、Silas Götz、Markus Neuburger、Hermann A. Wegner

  DOI：10.1021/ol5007604

  日期：2014.5.2

  While investigating the [2 + 2 + 2] cycloaddition as a tool to build up strained oligophenyl systems with a diyne-ethylene glycol macrocyle, a surprising change of mechanism was observed. Instead of the expected [2 + 2 + 2] para-terphenyl, the ortho-terphenyl product explained by a formal [2 + 1 + 2 + 1] cycloaddition was formed. An eta(4)-coordinated metal-cyclobutadiene is proposed as the key structure in the catalytic cycle, which is formed to release the induced strain. The optical properties of the ortho-terphenyl products have been measured as well as the coordination ability of Na+ and K+.