Completely spirocyclopropanated macrocyclic oligodiacetylenes and their permethylated analogues: Preparation and properties

Abstract

The acyclic dehydrotrimer (12) and -hexamer (28) of 1,1-diethynyl-2,2,3,3-tetramethylcyclopropane were prepared from 1-chloro-l-(trimethylsilylethynyl)-2,2,3,3-tetramethylcyclopropane (4) in six and 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 acyclic dehydrotrimer (20) and -hexamer (23) of 1,1-diethynylcyclopropane followed by Hay coupling and protiodesilylation 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 135degreesC, 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).