Gregorovich, Basil V.2009-04-172009-04-1719661966Source: Dissertation Abstracts International, Volume: 68-07, Section: B, page: 4485.http://hdl.handle.net/10393/10696http://dx.doi.org/10.20381/ruor-8414Part I. 2-Butynoic acid, which was synthesized by the reaction of carbon dioxide with lithio methylacetylide, was converted to the methyl ester with diazomethane. This ester, when photolysed in benzene, gave 2-carbomethoxy-1-methylcyclooctatetraene. Hydrogenation of 2-carbomethoxy-1-methylcyclooctatetraene confirmed the presence of four double bonds and gave a single product, cis-2-carbomethoxy-1-methylcyclooctane. 2-Carbomethoxy-1-methylcyclooctatetraene was converted to the alcohol by metal hydride in ether. It was found that aluminum hydride gave better yields than lithium aluminum hydride. The reaction of phosphorus tribromide with this alcohol gave the bromo compound which, when treated with trimethylamine in methanolhexane, gave 1-methyl-2-N,N,N-trimethylaminomethylcyclooctatetraene bromide, This quaternary bromide on treatment with an aqueous slurry of silver oxide gave the quaternary hydroxide, which was readily converted to 1,2-dimethylenecyclooctatriene by pyrolysis at reduced pressure. The mass spectra of 2-carbomethoxy-1-methylcyclooctatetraene, 2-hydroxymethyl-1-methylcyclooctatetraene, and 1,2-dimethylenecyclooctatriene were obtained and breakdown patterns were proposed. 1,2-Dimethylenecyclooctatriene was shown to be monocyclic by the n.m.r. spectrum, although the possibility that the monocyclic form is in equilibrium with a small amount of a bicyclic form is not excluded. An attempt to obtain a bicyclic form by photolysis was unsuccessful. 1,2-Dimethylenecyclooctatriene was shown to be fairly stable thermally but extremely sensitive to oxygen. The infrared spectrum indicated that the molecule is not highly strained. Molecular orbital calculations were performed on planar 1,2-dimethylenecyclooctatriene. The total pi energy, the delocalization energy, the bond orders and the free valences were calculated. Despite a high calculated delocalization energy for the planar form, the molecule apparently prefers a less strained non-planar shape as is shown by the ultraviolet spectrum. The reactions of a variety of pi systems with dienophiles were compared with the reaction of 1,2-dimethylenecyclooctatriene with tetracyanoethylene. Part II. The addition of ketene to cis, trans-1,3-cyclooctadiene gave trans-bicyclo[6.2.0]dec-2-en-9-one. Arguments were presented supporting the assignment of the position of the double bond as gammadelta to the carbonyl group and the fusion of the rings as trans. The reduced product, bicyclo[6.2.0]dec-9-one was prepared. The reduction confirmed that the original product had only one double bond. cis-Bicyclo[6.2.0]dec-2-en-9-one was obtained by passing a dilute solution of trans-bicyclo[6.2.0]dec-2-en-9-one in pentane through an alumina column. Wolff-Kishner reduction gave bicyclo[6.2.0]dec-2-ene which was used for dehydrogenation studies. Dehydrogenation by rhodium on alumina gave a small amount of azulene but none of the desired bicyclo[6.2.0]decapentaene.148 p.Chemistry, Organic.Thesis