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首页> 外文期刊>Chemistry: A European journal >Completely Spirocyclopropanated Macrocyclic Oligodiacetylenes and Their Permethylated Analogues: Preparation and Properties
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Completely Spirocyclopropanated Macrocyclic Oligodiacetylenes and Their Permethylated Analogues: Preparation and Properties

机译：完全螺环丙烷化的大环齐二炔及其全甲基化类似物：制备与性能

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摘要

The acyclic dehydrotrimer (12) and -hexamer (28) or 1,3-diethynyl-2,2,3,3-tetramethylcyclopropane were prepared from 1-chloro-1-(trimethylsilylethynyl)-2,2,3,3-tetramethylcyclopropane (4) in six ans nine steps, respectively, in 36 and 8% overall yield, respectively, using Cadiot-Chodkiewicz or Hay coupling procedures as key steps. Mono-tert-butyldimethylsilyl (TBDMS) protection of the acylic dehydrotrimer (20) and-hexamer (23) of 1,1-diethynylcyclopropane followed by Hay coupling and protiodensilylation furnished the acyclic dehydrohexamer (23) and -dodecamer (29) in 35 and 56% overall yield, respectively. Subsequent cyclizing oxidative dimerization of 12 or cyclization of 28 using a modified Glaser protocol produced the first completely permethylspirocyclopropanated macrocyclic oligodiacetylene, compound 30 in 49 and 21% yield, respectively. The cyclic dehydrohexa- (31) and dehydrododecamer (32) have been prepared from 23 and 29 in 49 and 7% yield by applying the same protocol. The macrocycle 32 is particularly interesting in that it contains 60 carbon atoms in the inner ring, and indeed a decomposition mode consecutively cleaving off ethylene units from it as well as from 31 and tetramethylethylene from the permethylated exp-[6] rotane 30 has been proved by differential scanning calorimetry with evolved gas analysis. The thermal decomposition of these "exploding" [6] rotanes 31 and 30 set on at 100 and 135 deg C, respectively, and release energies of 478 and 285 kcal ·mol~(-1), respectively, significantly more than the energy release of the explosive hexogen with 143 kcal mol~(-1).
机译：由1-氯-1-（三甲基甲硅烷基乙炔基）-2,2,3,3-四甲基环丙烷制备无环脱氢三聚体（12）和-六聚体（28）或1,3-二乙炔基-2,2,3,3-四甲基环丙烷（4）使用Cadiot-Chodkiewicz或Hay偶联步骤作为关键步骤，分别在六个步骤和九个步骤中，总收率分别为36和8％。 1，1-二乙炔基环丙烷的酰基脱氢三聚体（20）和六聚体（23）的单叔丁基二甲基甲硅烷基（TBDMS）保护，然后进行Hay偶联和脯烯基甲硅烷基化，从而在35和总产率分别为56％。随后使用改良的Glaser方案进行环氧化12的氧化二聚或环化28的反应，分别制得第一个完全被全甲基螺环丙烷化的大环低聚二乙炔，化合物30的产率分别为49％和21％。通过应用相同的方案，由23和29以49和7％的收率制备了环状脱氢六氢（31）和脱氢十二烷基（32）。大环32的特别有趣之处在于它的内环中含有60个碳原子，并且确实证明了一种分解模式可从中连续分解乙烯单元以及从全甲基化exp- [6]旋转烷烃30中脱除31和四甲基乙烯。通过差示扫描量热法和析出气体分析。这些“爆炸” [6]的罗丹酮31和30分别在100和135℃时发生热分解，释放出的能量分别为478和285 kcal·mol〜（-1），远大于能量释放。 143 kcal mol〜（-1）的爆炸性含氧化合物的含量。

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