Photogenerated o-Azaxylylenes: Mechanistic Studies and Synthetic Applications

This research sets out to build upon excited state o-azaxylylene cycloaddition. The mechanism behind the excitation and cycloaddition process of photogenerated o-azaxylylenes was determined experimentally. Time-correlated single-photon counting, steady-state spectroscopy, triplet quenching experiments, and quantum yield studies provided evidence suggesting that excited state intramolecular proton transfer is followed by intersystem crossing and stepwise addition to the tethered unsaturated pendant. In keeping with the principles of diversity oriented synthesis, a modular approach was taken to gain access to a diverse array of N,O,S-Polyheterocycles which were modified postphotochemically via Suzuki coupling to yield fused biaryls. Cycloaddition products, outfitted with halogens in the aromatic ring of the o-azaxylylene, proved to be reactive with a variety of boronic acids resulting in a rapid growth in structural complexity. A novel procedure was developed that utilized multiple o-azaxylylene cores in a photochemical cascade transformation yielding complex scaffolds of unprecedented topology. The photoprecursors were produced in a one-pot two-step sequence from commercially available starting materials, and upon irradiation yield structures containing up to five fused hetrocyclic rings, and showed complete diastereoselectivity.

Compliance Strategies for Gasoline Distribution Facilities

Gasoline Distribution Generally Available Control Technology (GD GACT) is a Federal environmental regulation that is specifically written and enforced to reduce HAP emissions from gasoline distribution (GD) facilities. The regulation targets four specific types of GD facilities: bulk gasoline terminals, bulk gasoline plants, pipeline breakout stations, and pipeline pumping stations. A GD GACT compliance plan was developed for a particular, representative example of each type of GD facility affected by the regulation. Each facility in the study is owned and operated by a single company. The compliance plans were developed to meet the regulatory requirements contained within GD GACT. The compliance plans will be implemented at each facility prior to the January 10, 2011 compliance date.