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

摘要

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.Deprotec-tion 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 glycocymi-dine derivatives lla,b.Reaction of 2a with (2,3,4,6-tetra-O-acetyl-alpha-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.