5-Pyrenylidene-hydantoin, 2-thiohydantoin derivatives: synthesis,S- and N-alkylation

5-Pyrenylidene-2-thiohydantoin derivatives 2a–d were prepared by condensation of pyrene-1-carboxaldehyde with 2-thiohydantoin derivatives. Compounds 2a,b undergo Mannich reaction with formaldehyde and morpholine to give the corresponding Mannich products 3a,b respectively. S- and N-monoalkyl-5-pyrenylidene-hydantoin derivatives 5a,b and 6a,b were prepared by reaction of 5-pyrenylidene-2-thiohydantoin sodium salts with 1,3-dioxolan-methylsulfate derivatives. Deprotection of the products afforded 5-pyrenylidene-hydantoin (7), S- and N-dihydroxy derivatives 8a,b and 9a,b respectively. Reaction of 2a with methyl iodide afforded the corresponding S-methyl derivative 10, which reacted with secondary amines such as morpholine and piperidine afforded the glycocymidine derivatives 11a,b. Reaction of 2a with (2,3,4,6-tetra-O-acetyl-α-? D-glucopyranosyl)bromide afforded a mixture of S- and N-glucoside derivatives 12 and 13 respectively. Deprotection of 12 afforded compound 7, while deprotection of 13 furnished 5-Pyrenylidene-3-? D-glucopyranosyl-2-thiohydantoin (14). Reaction of 7 with propargyl chloride in DMF afforded the monoalkynyl- and bis-alkynyl-hydantoin derivatives 15 and 16, respectively. Reaction of 15 with p-bromophenyl-ether derivative 17 yielded the bis-alkynyl derivative 18.