5,8-dimethoxy-6-methoxymethyl-7-methyl-1,4-methano-1,2,3,4-tetrahydronaphthalene | 157637-22-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: 5,8-dimethoxy-6-methoxymethyl-7-methyl-1,4-methano-1,2,3,4-tetrahydronaphthalene
• 英文别名: 3,6-Dimethoxy-4-(methoxymethyl)-5-methyltricyclo[6.2.1.02,7]undeca-2,4,6-triene
• CAS: 157637-22-4
• 化学式: C₁₆H₂₂O₃
• 分子量: 262.349
• InChiKey: KBMJIDFBICXTDZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5,8-dimethoxy-6-methoxymethyl-7-methyl-1,4-methano-1,2,3,4-tetrahydronaphthalene 以25%的产率得到
  参考文献：
  名称：

  Rathore R., Bosch E., Kochi J. K., Tetrahedron, 50 (1994) N 23, S 6727- 6758

  摘要：

  DOI：
• 作为产物：
  描述：

  4-(chloromethyl)-3,6-dimethoxy-5-methyltricyclo[6.2.1.02,7]undeca-2,4,6-triene 、 sodium methylate 生成 5,8-dimethoxy-6-methoxymethyl-7-methyl-1,4-methano-1,2,3,4-tetrahydronaphthalene
  参考文献：
  名称：

  Rathore R., Bosch E., Kochi J. K., Tetrahedron, 50 (1994) N 23, S 6727- 6758

  摘要：

  DOI：

文献信息

• Selective nitration versus oxidative dealkylation of hydroquinone ethers with nitrogen dioxide
  作者：R. Rathore、E. Bosch、J.K. Kochi

  DOI：10.1016/s0040-4020(01)81329-6

  日期：1994.1

  Various alkyl-substituted p-dialkoxybenzenes (ArH) react readily with nitrogen dioxide (NO2) in dichloromethane solution via either nitration (ArNO2) or oxidative dealkylation to quinones (Q). Spectral transients indicate that these coupled processes from the dialkoxybenzene radical cation (ArH+·) formed as the common reactive intermediate from electron-transfer in the disproprtionated precursor [ArH

  各种烷基取代的对二烷氧基苯（ArH）可以通过硝化（ArNO 2）或氧化脱烷基化成醌（Q）与二氯甲烷溶液中的二氧化氮（NO 2）反应。光谱瞬变指示来自二烷氧基苯自由基阳离子这些耦合过程（ARH +·形成为从disproprtionated前体电子转移常见的反应中间体）ARH，NO + ] N0 3 - 。在快速的后续步骤中。ARH +·经历均裂耦合与NO 2（这会导致芳烃硝化）和NO的亲核攻击3 -（这导致氧化脱烷基）。这样，通过溶剂极性和添加的硝酸盐可以有效地调节硝化和氧化脱烷基之间的竞争。
• Acid Catalysis vs. Electron-Transfer Catalysis via Organic Cations or Cation-Radicals as the Reactive Intermediate. Are These Distinctive Mechanisms?
  作者：Rajendra Rathore、Jay K. Kochi、Augusto Canavesi、Larry L. Miller、Giovanni V. Sebastiani、George W. Francis、József Szúnyog、Bengt Långström

  DOI：10.3891/acta.chem.scand.52-0114

  日期：——

  Proton transfer to aromatic and olefinic donors (D) lends to the facile interchange of transient carbocations (DH+) and cation-radical (D+.). The same types of cation and cation-radical are reactive intermediates in the acid catalysis and the electron-transfer catalysis of such organic transformations as benzylic coupling, epoxide.-pinacol rearrangements and cis-trans isomerization of stilbenes when they are both carried out under otherwise identical reaction conditions, However, the rapid exchange of diamagnetic cations and paramagnetic cation-radicals blurs the traditional view of sepal ate electrophilic and homolytic processes, and rigorous experimental evidence is required to establish whether acid catalysis and electron-transfer catalysis actually represent distinct mechanistic categories.
• Radical-Cation Catalysis in the Synthesis of Diphenylmethanes via the Dealkylative Coupling of Benzylic Ethers
  作者：Rajendra Rathore、Jay K. Kochi

  DOI：10.1021/jo00128a020

  日期：1995.11

  The dealkylative coupling of benzyl alkyl ethers (ArCH(2)OR) to yield the corresponding diarylmethanes (ArCH2Ar) together with dialkoxymethane (ROCH(2)OR) is catalyzed by small amounts of 1-electron oxidants (such as aromatic cation radicals, NO+, etc.) or py an equivalent electrochemical (anodic) method. The catalytic method is successfully employed for the facile synthesis of a novel macrocyclic crown ether 18 that contains a diarylmethane linkage. On the basis of the spectral observation of the radical cation ArCH(2)OR(.+) and the excellent catalytic efficiency with turnover numbers in excess of 10(2), an electron-transfer and an alternative electrophilic chain mechanism are discussed for the dealkylative coupling process.