Synthesis of Polycyclic Hydrocarbons C₁₄H₂₀by Hydrogenation ofexo–exo-,exo–endo-,endo–exo-, andendo–endo-Hexacyclo[9.2.1.0^2,10.0^3,8.0^4,6.0^5,9]tetradec-12-enes with H₂SO₄and Isomerization of the Products to Diamantane Induced by Ionic Liquids

Abstract

A new method has been developed for the complete (full) hydrogenation of unsaturated hexacyclic norbornadiene dimers, namely, exo−exo-, exo−endo-, endo−exo-, endo−endo-hexacyclo[9.2.1.0 2,10 .0 3,8 .0 4,6 .0 5,9 ]tetradec-12-enes at the double bond and the cyclopropane ring using sulfuric acid (98%) to form pentacyclo[8.2.1.1 5.8 .0 2.9 .0 3.7 ]tetradecanes in 51−76% yield. Hydrogenolysis of exo−endo-and endo−endo-tetradecenes containing the most shielded cyclopropane cycle occurs with the skeletal rearrangement. Sulfuric acid is the hydrogen donor, cyclohexane is the solvent, and the hydrocarbons themselves are transformed into benzene and aromatic products of an unknown structure. It was found that under the action of the [Et 3 NH] + [Al 2 Cl 7 ] − -CuCl 2 ionic liquid, pentacyclo[8.2.1.1 5,8 .0 2,9 .0 3,7 ]tetradecanes are selectively isomerized to diamantane in 80−84% yield.

Hexacyclotetradecenes as Polycyclic Fused exo-Norbornene Monomers: Synthesis of Cyclic Olefin Copolymers via Ti-Catalyzed Controlled Polymerization

“…30,31 NBD has unique diene -bonds that chelate to the transition-metal center; hence, it undergoes various transition-metal-catalyzed cycloaddition reactions to yield polycyclic hydrocarbons. Among these reactions, the dimerizations of NBD afford various cyclic hydrocarbon products (a diene, 32,33 monoalkenes, [34][35][36][37][38] and saturated dimers 39 ), some of which yield reactive cyclopropane moieties. We have previously reported the synthesis of cyclopropane-containing COPs through the ROMP of four stereoisomeric NBD dimers containing a polymerizable norbornenyl group and a cyclopropane moiety.…”

Hexacyclotetradecenes as polycyclic fused exo-norbornene monomers: synthesis of cyclic olefin copolymers via Ti-catalyzed controlled polymerization

“…32,33 NBD has unique diene π-bonds that chelate to the transition-metal center; hence, it undergoes various transitionmetal-catalyzed cycloaddition reactions to yield polycyclic hydrocarbons. Among these reactions, the dimerizations of NBD afford various cyclic hydrocarbon products (a diene, 34,35 monoalkenes, [36][37][38][39][40] and saturated dimers 41 ), some of which yield reactive cyclopropane moieties. We have previously reported the synthesis of cyclopropane-containing COPs through the ROMP of four stereoisomeric NBD dimers containing a polymerizable norbornenyl group and a cyclopropane moiety.…”

Reactions of exo-exo-hexacyclo[9.2.1.02,10.03,8.04,6.05,9]tetradecane with Aliphatic Alcohols under the Action of Ionic Liquids

“…Ionic liquids (ILs) meet these requirements. For example, ILs based on aluminum, iron, and other metal halides are an alternative to traditional catalysts; in particular, they catalyze the Friedel-Crafts alkylation and the acylation reactions, hydrogenation, and isomerization of alkanes and polycyclic hydrocarbons [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16].…”