In recent years, we have used the photocyclizations of diarylethylenes to synthesize a number of [n]phenacenes in the hope that they might be useful as the bridging groups for electron transfer processes in donor-bridge-acceptor molecules. Because [n]phenacenes with n > 5 are very insoluble, their synthesis and characterization has required the attachment of solubilizing substituents such as tert-butyl. The studies of Pascal and co-workers of some large polynuclear aromatic compounds having multiple phenyl substituents prompted us to explore the use of phenyls as alternative solubilizing groups for [n]phenacenes. Although phenyl groups turned out to provide significantly less solubilization than tert-butyl groups in these compounds, we found some interesting structural comparisons of the phenyl-substituted and tert-butyl-substituted [n]phenacenes.

The in-solution oxidative photocyclization of stilbenes to phenanthrenes is a well-known and synthetically valuable reaction. We report here our discovery that the oxidative photocyclization of several tert-butyl-substituted 1-styrylphenanthrenes resulted not only in the expected formation of tert-butyl-substituted picenes but also in the previously unknown rearrangement leading to the formation of tert-butyl-substituted pentahelicenes.

The reaction of ketenimines with ketene in anhydrous liquid sulfur dioxide gave substituted l,2-oxathiane-4one 2-oxides. The structures of these compounds were verified by both chemical and spectral methods, p-Tolylsulfonyl isocyanate reacted with ketene in liquid sulfur dioxide to yield A-(p-tolylsulfonyl)-3-thiazolidine-2,4-dione 1,1-dioxide. In addition, substituted 2,l,5-benzothiadiazepin-4-one 2-oxides were obtained from the corresponding o-phenylenediamine, ketene, and sulfur dioxide. The mechanisms of these reactions were believed to involve a ketene-sulfur dioxide adduct as a common intermediate. This reactive species was isolated and intercepted at low temperatures. During the course of this investigation, ketene was also found to react with jV-sulfinylaniline to give jV-phenyl-l,2-thiazetidin-3-one 1-oxide.

experiments allow us to observe the temperature dependence of the parameters that characterize methyl group rotation in both compounds and in mixtures of the two compounds. In the mixtures, both types of methyl groups (that is, molecules of 1 and 2) can be observed independently and simultaneously at low temperatures because the solid state 1 H spin-lattice relaxation is appropriately described by a double exponential. We have followed the conversion 1 → 2 over periods of two years. The solid state 1 H spin-lattice relaxation experiments in pure samples of 1 and 2 indicate that there is a distribution of NMR activation energies for methyl group rotation in 1 but not in 2 and we are able to explain this in terms of the particle sizes seen in the field emission scanning electron microscopy images.

No abstract