Abstract: The key to the syntheses of selenacrown ethers is the syntheses of selenium-con-taining intermediates, This paper described an improved method to prepare poly(o-diselenobenzene), and poly(o-diselenobenzene) was used as the intermediate for the syntheses of o-benzene diselenium type of selenacrown ether compounds: under an alkaline condition,poly(o-diselenobenzene) was reduced by potassium borohydride into o-benzenediselenolateanion, which condensed with dihalides, and seven selenacrown compounds were obtained.Besides[1+1] products,[2+2] products were also isolated. All the selenacrown compounds were identified by elemental analysis, MS,¹HNMR and IR, and their syntheti methods and spectral characteristics were discussed.

Key words: Crown ether, Selenacrown ether, Poly(o-diselenobenzene)