The synthetic methods reported in the literature for the preparation of sulfonylureas tend to be restricted in scope or unsuitable for use in parallel synthesis. We have developed a method for preparing sterically congested sulfonylureas based on N,N'-sulfuryldiimidazole that is both convenient and amenable to parallel synthesis. Sequential activation by way of alkylation of the imidazole group using methyl triflate followed by nucleophilic displacement with a variety of amines and anilines afford the unsymmetrical sulfonylurea. Sulfonylureas prepared from anilines were obtained in high yields using N,N'-sulfuryldiimidazole, while the somewhat more sterically congested analogue, N,N'-sulfurylbis-2-methylimidazole, proved to be superior for alkylamines.

A method for the synthesis of soluble polyphenylenes that involves the polymerization of l-halo-4-lithiobenzenes, l-halo-3-lithiobenzenes, and 1,3-and 1,4-dilithiobenzenes in ethereal solvents is described. The lithiobenzenes are prepared from the corresponding dihalogenated benzenes using tertbutyllithium . By varying the monomers and conditions used, a variety of soluble halogenated polyphenylenes can be obtained with weight average molecular weights (Afw) as high as 6000 with polydispersities (Mw/M") equal to ~2.8. The prequenched polymers can exist as multilithiated polymers if 2.0 equiv of tert-butyllithium is used to form the aryllithium intermediates. The polymers are usually amorphous and contain significant amounts of phenylated polyphenylene units capped with halogens. The polymers are soluble in organic solvents such as THF, chloroform, and methylene chloride. Several of the polymers exhibited low melting and glass transition temperatures. The brominated polymers are easily dehalogenated upon treatment with tert-butyllithium in THF at -78 °C followed by quenching with water. The molecular weights of several of the brominated polymers increased upon debromination with tert-butyllithium. When the polymerizations were carried out in the presence of 1,3-diphenylisobenzofuran, o-benzyne intermediates were trapped as their Diels-Alder adducts. LiH appears to be present in significant amounts upon completion of the polymerization.

LC/MS traces of the crude reaction for the preparation of: 9a, using 6a S34 9b using 6b S35 9d using 6a. S36 9e using 6a S37 16d using 6a S38 S2 1,2-Dimethyl-3-(2-methyl-imidazole-1-sulfonyl)-3H-imidazol-1-ium Triflate (4b):Using the method described for 4a, this compound (7.85 g, 91%) was obtained as a white solid from 3b (5.00 g, 22.1 mmol) and methyl triflate (3.61 g, 22.1 mmol). This compound is hygroscopic and could be used without loss of reactivity. 1 H-NMR (300