Synthesis Of Pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9] Undecane And Their Derivatives

Pentacyclo [5.4.0.02’6.03,10.05,9] undecane and their derivatives have been attracting considerable attentions in the fields of aviation fuel, energetic materials and pharmaceutical industry, due to their unqiue structures, high tension energy and high density. However, few studies have been reported about the synthesis of pentacyclo [5.4.0.02’6.03’10.05,9] undecane and their derivatives in recent years resulted from the harsh conditions and complicated steps. Therefore, the synthesis of pentacyclo [5.4.0.02,6.03,10.05,9] undecane and their derivatives has been explored in this study. The main points of this paper are listed as follows:synthesis of pentacyclo [5.4.0.02,6.03,10.05,9] undecane, pentacyclo [5.4.0.02,6.03,10.05,9]undecane dimers and8,8-dinitropentacyclo [5.4.0.02,6.03,10.05,9] undecane.I Pentacyclo [5.4.0.02,6.03,10.05,9] undecane was designed and synthesized. At the beginning, cyclopentadiene was prepared from its dimeric form by pyrolysis at200℃. By using cyclopentadiene and1,4-benzoquinone as starting materials, pentacyclo [5.4.0.02,6.03,10.05,9] undecane was synthesized with the total yield of51.6%successively via Diels-Alder,[2+2]photo-cycloaddition and Huang-Minlong reduction. The product was characterized by melting point,1H NMR,13CNMR, IR spectra and MS.II Pentacyclo [5.4.0.02,6.03,10.05’9] undecane dimers was designed and synthesized. By using pentacyclo [5.4.0.02,6.03,10.05,9]undecane-8,11-dione as starting material, pentacyclo [5.4.0.02,6.03,10.05,9] undecane dimers was synthesized with the total yield of23.54%successively via [2+2]photo-cycloaddition, carbonyl protecting, lithium aluminium hydride reduction, hydrolysis, Huang-Minlong reduction, oxidation and McMurry reaction. This method has the advantages of facilely available starting materials, simply conducted procedures, relatively high yield and easy purification. Therefore, it is more suitable for scale-up production.Ⅲ8,8-dinitropentacyclo [5.4.0.02,6.03,10.05,9] undecane was designed and first synthesized. By using pentacyclo [5.4.0.02,6.03,10.05,9]undecane-8-one as starting material,8,8-dinitropentacyclo [5.4.0.02,6.03,10.05,9] undecane was synthesized with the total yield of29.15%via oximation and nitrification reaction. This compound has potential application in the field of energy materials.