This research, being supported by the Organic and Macromolecular Chemistry Program, will develop the technique of flash vacuum pyrolysis (FVP) as a source of reactive intermediates that will permit the synthesis of a number of unusual structures. FVP permits the rapid assembly of complex molecules from relatively inexpensive starting materials in a reduced number of steps. This program will develop reactions of o-quinodimethanes and other reactive molecules that will be of use in the synthesis of complex organic molecules. Specific objectives include the development of: (a) reaction sequences involving o-quinodimethanes derived from the ferrocene and other metal pi-complexed ring systems which lead to stable organometallic compounds and nonorganometallic derivatives of them; (b) reaction sequences which start from the furan adduct of methylenecyclobutenone and lead to functionalized fused ring systems; (c) reaction sequences involving intramolecular reactions of bis-2,5-dimethylene-2,5-dihydrofurans that lead to cyclophanes and derivatives of them; (d) reaction sequences involving quinodimethanes with extended pi systems that lead to cyclophanes and other ring systems; and (e) a general reaction for the conversion of omega-halo N,N-dialkyl-amides to omega-formylnitriles. The project includes the following types of studies: (a) the preparation of novel reactive molecules such as o-quinodimethanes derived from less common aromatic systems; (b) study of the chemistry of selected reactive molecules; (c) development of "protected" forms of reactive molecules that will allow them to be handled more conveniently; and (d) development of pyrolytic reactions that involve unusual fragmentations or rearrangements. This project should result in reactions which have unique specificities and can be used to prepare ferrocenes and other metal pi-complexed ring systems, functionalized fused ring systems, cyclophanes, medium and large carbocycles and heterocycles, and omega-formylnitriles.
