Cyclic Polyolefins. XXIX. Cycloöctatetraene Derivatives from Copolymerization and Side Chain Modification¹

Abstract

7-Cyclooctatetraenyl-ro-propyl alcohol (I), 7-cyclooctatetraenyl-ro•propyl cyanide (V), cyclooctatetraenylmethylcarbinol (VIII), cyclooctatetraenyl methyl ketone (IX) and cycloóctatetraenyldimethylcarbinol (XI) have been prepared by copolymerization of acetylene with functionally substituted acetylenes. N.N-Dimethyl-y-cyclooctatetraenyl-re-propylamine (IV) and 7-cyclooctatetraenyl-M-propyl cyanide (V) were prepared by displacement reactions of the ^-toluenesulfonate III of the alcohol I, and -cycloóctatetraenyl-M-butylamine (VI) and 7-cyclooctatetraenyl-n-butyric acid (VII) by reduction and saponification, respectively, of the cyanide V. The structures of several of the new cyclooctatetraene derivatives were established by conversion to, or preparation from, known cycloóctatetraenes: The primary alcohol I was oxidized to ßcycloóctatetraenylpropionic acid (II); cycloóctatetraenylmethylcarbinol (VIII) was oxidized with sodium hypobromite to cyclooctatetraenecarboxylic acid; cyclooctatetraenyl methyl ketone (IX) was prepared by oxidation of the carbinol VIII; and cycloóctatetraenyldimethylcarbinol (XI) was prepared from methyl cycloóctatetraenecarboxylate and methylmagnesium iodide.

Substituted Cyclooctatetraenes as Ligands inf-Metal Chemistry

“…Alkyl cyclooctatetraenes can be obtained either by the reaction of C 8 H 8 with alkyllithium reagents,13,14 by the reaction of C 8 H 7 ‐Br with the corresponding dialkylcuprates,20,21 or by a modified Reppe synthesis (the cyclization of ethyne with the corresponding substituted alkyne) 15,16. Many functionalized cyclooctatetraenes such as C 8 H 7 ‐(CH 2 ) 3 NMe 2 were prepared starting from C 8 H 7 ‐(CH 2 ) 3 OH, which itself was obtained by copolymerization of ethyne with HC≡C‐(CH 2 ) 3 OH 16,1722…”

Statistical Analyses of a Class of Random Cyclooctatetraene Chain Networks with Respect to Several Topological Properties

“…The physical and chemical properties of compounds are key areas of concern for theoretical chemists [2,3]. Polygonal chemicals have a wide diversity of molecular structures and their physical and chemical properties are becoming increasingly significant, which is referenced in [4][5][6][7].…”