1,2,3,4-Tetrachloro-9,9-dimethoxy-1α,4α,4aα,6,7,8aα-hexahydro-1,4-methanonaphthalene-5,8-dione | 114716-11-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2,3,4-Tetrachloro-9,9-dimethoxy-1α,4α,4aα,6,7,8aα-hexahydro-1,4-methanonaphthalene-5,8-dione
• 英文别名: (1S,2S,7R,8R)-1,8,9,10-tetrachloro-11,11-dimethoxytricyclo[6.2.1.02,7]undec-9-ene-3,6-dione
• CAS: 114716-11-9
• 化学式: C₁₃H₁₂Cl₄O₄
• 分子量: 374.048
• InChiKey: MPIXFRRYWBKHBN-ZTCHHREXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.69
• 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：

  1,2,3,4-Tetrachloro-9,9-dimethoxy-1α,4α,4aα,6,7,8aα-hexahydro-1,4-methanonaphthalene-5,8-dione 在 喹啉 、 copper(I) oxide 、 2,2'-联吡啶 、 水 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 丙酮 、 苯 为溶剂， 反应 77.0h， 生成 4,6,7,8-tetrachloro-5,5-dimethoxyhexacyclo[5.5.1.0^2,6.0^3,10.0^4,8.0^9,13]tridecane-11,12-diol
  参考文献：
  名称：

  Synthetic Approach Towards Hexaprismane. A Novel Entry to Homosecohexaprismane Skeleton by Cage Enlargement

  摘要：

  AbstractA series of caged 1,4‐diols, 26, 29a/29b, 31, were synthesized from the Diels‐Alder cycloadduct 21 of 1,2,3,4‐tetrachloro‐5,5‐dimethoxycyclopentadiene and 1,4‐benzoquinone. Reduction of enedione 21 with aqueous TiCl3, followed by base‐catalyzed enolization in the presence of acetic anhydride, gave diene 23b, which reacted with maleic anhydride and 1,4‐benzoquinone to produce the corresponding [4+2] cycloadducts 24b and 27, respectively. The adduct 24b was converted to birdcaged 1,4‐diol 26 by photocyclization followed by decarboxylative olefination of resulted caged anhydride 25b. The adduct 27 was photocyclized to cage compound 28, which was aromatized to dihydroquinone 29a by acid‐catalyzed enolization, or benzo‐annulated compound 31 by reduction and dehydration. The birdcaged 1,4‐diols 26 and 31 underwent fragmentation induced by (diacetoxyiodo)benzene to give enediones 38/39 and 41/42, respectively. Photocyclization of 38 and 39 produced the corresponding caged compounds 43 and 44, respectively, possessing homosecohexaprismane skeletons. The corresponding monohydrate 43a of 43 was structurally characterized by single‐crystal X‐ray diffraction.

  DOI：

  10.1002/jccs.199700073
• 作为产物：
  描述：

  (+/-)-(1R*,2R*,6R*,7S*,8S*)-1,8,9,10-Tetrachlor-11,11-dimethoxytricyclo-6-hydroxy<6.2.1.0^2.7>-undec-9-en-3-on 在 硫酸 作用下， 以 二氯甲烷 为溶剂， 反应 36.0h， 以80%的产率得到1,2,3,4-Tetrachloro-9,9-dimethoxy-1α,4α,4aα,6,7,8aα-hexahydro-1,4-methanonaphthalene-5,8-dione
  参考文献：
  名称：

  合成和碱促进 8-羟基-1,2,3,4-四氯-9,9-二甲氧基-1α,4α,4aα,6,7,8β,8aα-六氢-1,4-甲萘-的分子内亲核反应- 5(1H)-一

  摘要：

  两个取代的六氢-1,4-二甲萘-5,8-二酮的催化氢化导致烯二酮碳-碳双键的还原，同时两个化学等价的 C=O 基团中的一个也随之还原。一种部分还原产物与碱的反应导致碳-碳双键的分子内加成。

  DOI：

  10.1007/bf01665970

文献信息

• A Ruthenium-Catalyzed, Novel and Facile Procedure for the Conversion of Vicinal Dihaloalkenes to α-Diketones
  作者：Faiz Ahmed Khan、B. Prabhudas、Jyotirmayee Dash、Nilam Sahu

  DOI：10.1021/ja001956c

  日期：2000.10.1

  transition metal chemistry, used in the preparation of variety of heterocycles and natural products. α-Diketones also function as the key elements in the Weiss reaction and in the construction of rigid molecular assemblies (molecular wires, rods, etc.) based on ‘block’ chemistry. Some of the common methods to obtain α-diketones are: (i) oxidation of αhydroxyketones, (ii) oxidation of alkynes, and (iii)

  丰富的官能团以及在各种键形成反应中创建、相互转化和利用它们的大量方法是设计任何目标分子化学合成的重要资产。α-二酮是两个相邻羰基的强大组合，由于其广泛的应用而备受关注。α-二酮表现出有趣的光化学，用作调味剂，用作过渡金属化学中配体的前体，用于制备各种杂环和天然产物。α-二酮也是 Weiss 反应和基于“嵌段”化学的刚性分子组件（分子线、棒等）的构建中的关键元素。获得 α-二酮的一些常用方法是： (i) α-羟基酮的氧化，(ii) 炔烃的氧化，和 (iii) α-亚甲基酮的氧化。尽管烯烃的受控氧化很困难，但据报道，KMnO4/Ac2O 会产生低到中等产率的 α-二酮和副产物。但是，该方法不适用于小环（环辛烯以下）和双环系统。我们发现，邻位二卤代烯烃可以作为掩蔽的 α-二酮（方案 1）。我们特别选择了
• Goessinger E., Graupe M., Zimmermann K., Monatsh. Chem, 125 (1994) N 6-7, S 773-782
  作者：Goessinger E., Graupe M., Zimmermann K.

  DOI：——

  日期：——
• Synthese des all-cis-Perhydronaphtho[1,8-bc]furansystems durch Photocyclisierung
  作者：E. G�ssinger、M. Graupe、K. Zimmermann

  DOI：10.1007/bf01277639

  日期：1994.6

  The diketone 3 was reduced to the diol which then was transformed to the tetracyclic diketal 5 by treatment with sodium in ethanol. Protection of the remaining hydroxy group was followed by hydrolysis of the dimethylketal. The resulting ketone 7 was stereoselectively converted to the tertiary alcohol by methyl magnesium chloride. Acidic retrograde aldol reaction of the tertiary alcohol led to the decalindione 10, which was partially dehydrogenated by cupric chloride under basic conditions. The resulting endione 1 cyclized by light induced hydrogen abstraction and collapse of the resulting diradical to the perhydronaphtho[1,8-bc]furan derivative.
• A fragmentation-photocyclization approach towards homosecohexaprismane skeleton
  作者：Teh-Chang Chou、Yu-Lin Yeh、Gerng-Horng Lin

  DOI：10.1016/s0040-4039(96)02030-8

  日期：1996.11

  Birdcaged bicyclo[2.2.2]octene-1,4-diol 15 was prepared from Diels-Alder adduct of 5,5-dimethoxy-1,2,3,4-tetrachlorocyclopentadiene in five steps. This diol underwent DIB-promoted fragmentation to give tetracyclic dienes 16 and 17. Intramolecular [2+2]photocyclization of 16 and 17 furnished hexacyclic cage compounds 18 and 19 having homosecohexaprismane skeleton. Copyright (C) 1996 Elsevier Science Ltd