Abstract Mnogo lishnego!

Readily available Tricyclooctadiene 1 was prepared from dicyclopropylethyne in two steps stages. In first operation was obtained adduct syn-2 in 67% yield, witch solution in pentane upon irradiation was entered involved an intramolecular [2+2] cycloaddition to give octacyclopropylcubane (3) in 48% yield. This new cubane derivative have very high overall strain energy (ca., 390 kcal mol^–1), also it have specific physical and chemical properties.

Abstract Mnogo lishnego!

Successful methodology for the synthesis of highly nitrated cubanes was developed. Four of the eight nitro groups of octanitrocubane 1 are introduced by dimethyldioxirane oxidation of the

tetraamine derived from Curtius-type transformations of the corresponding tetraacid; three more by the astonishingly rapid, low-temperature N₂O₄ nitration of sequentially formed polynitrocubyl anions via 4 equiv of NaN(TMS)₂ at -78.8°C; and last by addition of excess nitrosyl chloride to a solution of the lithium salt of heptanitrocubane (from 4 and LiN(TMS)₂) in CH₂Cl₂ at -78.8°C followed by ozonation. Application of the Kamlett-Jacobs equations to octanitrocubane leads to calculated detonation velocities and pressures much higher than classic C-nitro explosive TNT, N-nitro compound HMX, and polycyclic nitramine CL-20.

Date: 2014-12-22; view: 966