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Products of the Reaction of 2a and la with 2-Methyl-2propanethiol. Selenenic anhydride 2a (0.29 g, 0.70 mmol) was dissolved in 15 mL of dioxane. To this was then added 0.5 mL of a 3 M solution of 2-methyl-2-propanethiol (1.40 mmol) in dioxane and 0.515 mL of 0.97 M aqueous perchloric acid, followed by enough water to bring the final volume of the solution to 25 mL. The solution was allowed to stand at room temperature. Periodically 2.5-µ aliquots were removed and diluted to 3.0 mL with 60% dioxane, and their ultraviolet spectrum was scanned between 320 and 460 nm. When the scan indicated that the reaction was complete, the solution was poured into 100 mL of water and extracted three times with 10-mL portions of chloroform. The chloroform was dried (Na2S04), the solvent was removed under reduced pressure at room temperature, and the residue was subjected to an oil pump vacuum for several hours to remove the last traces of solvent and dioxane. The residue, a yellow oil, was shown by TLC to consist of a single compound that was identified as tert-butyl o-nitrobenzeneselenenyl sulfide, í-BuSSeC6H4N02-o, 0.39 g (94%): NMR (CDC13) S 7.2-S.5 (m, 4 ), 1.38 (s, 9 H); mass spectrum, m/e 291 (M+, "Se), 289 (M+,

Solution thermolysis of 2,6-dichloro-d-phenethyl-and 2,6-dimethyl-d-phenethylsulfonyl azide leads to the formation of the corresponding 5,8-disubstituted 3,4-dihydro-2,l-benzothiazine 2,2-dioxides resulting from a 1,2-chlorine and -methyl shift, respectively, in the intermediates. No insertion into the phenethyl side chain, or into the side-chain methyl group in the 2,6-dimethyl case, was detected. Attempted cyclization of ethenesulfonanilides to 2,1-benzothiazine 2,2-dioxide failed. The orientation of the dichlorosultam was established unambiguously by its FVP to 4,7-dichloroindoline and by the synthesis of an authentic sample. Solution thermolysis of ß-styrenesulfonyl azide gave only hydrogen abstraction (32) and solvent insertion (33) products, but FVP gave indole, phenylacetonitrile, and phenylacetylene.

SynopsisCopolyesters containing pendent vinylidine groups were prepared in a one-step synthesis by reacting either chloro-or bromoacetic acid with 2-(bromomethyl)acrylc acid and triethylamine in diethyl ether. Polymers were characterized by IR, 'H-and 13C-NMR, DSC, and TGA. Copolymer formation supports a mechanism involving a triethylammonium carboxylate salt acting as an active nucleophilic species in a manner analogous to that seen in phase transfer catalysis involving carboxylate anions. Comparison of I3C-NMR spectra intensities indicates that 2-(bromomethy1)acrylic acid is much more reactive than the haloacetic acids leading to higher copolymer incorporation than in the monomer feed. Unsaturation in the copolymers provides a site for crosslinking during radical polymerization with an added vinyl monomer, similar to the way unsaturated polyesters function in commercial fiberglass formulations. This was confirmed by polymerization of both styrene and methyl methacrylate in the presence of an unsaturated copolymer giving insoluble semi-interpenetrating networks. These unsaturated copolymers are the first examples of soluble biodegradable glycolic acid polyesters containing such reactive functionality.