SYNTHESES OF CROWN ETHER-ESTERS WITH (BENZYLOXY)METHYL SIDE ARMS USING SBPH(3) AND BIPH(3) AS TEMPLATES

New crown ether-esters 3a, 3b, 4a, 4b, 4c and 5a with side arms are sy nthesized by the treatment of (benzyloxy)methyl-substituted diols (1 a nd 2) with acid chlorides [malonyl chloride and diglycolyl chloride (2 ,2'-oxydiacetyl chloride)]. SbPh(3) and BiPh(3) are effective template s for the synthesis of 14-crown-4 ether-esters with (benzyloxy)methyl side arms, and the template effect depends on the structures of both t he diols and acid chlorides. Also, it was revealed that the key step i n the template synthesis is the formation of a complex between 1 and M Ph(3) (M = Sb and Bi) by IR and mass spectral studies. The order of co mplexing ability between 1 and MPh(3) is: 1 + BiPh(3) much greater tha n 1 + SbPh(3) > 1 + AsPh(3). In particular, BiPh(3) can form stable 1: 1 and 2:1 complexes with 1.