9319419 Bentrude New free radical and photochemical reactions of tri- and penta-coordinate phosphorous molecules will be studied with attention directed to reaction mechanisms and synthetic applications. The reactions will include the use of organophosphorous molecules as free radical trapping agents and the chemistry of cation radicals produced from tri- coordinate phosphorous derivatives by single-electron transfer. Photochemical studies will include photorearrangements of allyl phosphite triesters and photo- Abruzov rearrangements of benzyl phosphites. Questions of 1,3-biradical intermediates in the allylic rearrangement and of singlet or triplet excited states in the photo-Abruzov rearrangement will be explored. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Wesley G. Bentrude at the University of Utah. New reactions of molecules containing phosphorous atoms with three and four other atoms or groups attached will be studied. The groups will contain carbon, hydrogen, oxygen, and other atoms. The reactions will include trapping of carbon free radicals (e.g., carbon bonding to three other atoms and possessing one non-bonded electron) and ultraviolet-light induced reactions. Attention will be given to the detailed steps in these reactions and synthetic applications. This work provides potential impact in areas such as antitumor and antiviral agents, fuel additives, pesticides, and key biochemical intermediates. ***
