SYNTHESES OF MONOFUNCTIONAL DERIVATIVES OF M-PHENYLENE-16-CROWN-5, BIS(M-PHENYLENE)-32-CROWN-10, AND M-PHENYLENE-P-PHENYLENE-33-CROWN-10

A series of monofunctional bis(m-phenylene)-32-crown-10 and m-phenylen e-p-phenylene-33-crown-10 derivatives has been synthesized. Cyclizatio n of m- and p-bis(omega-chlorotetraethyleneoxy)benzenes (6) with 5-sub stituted resorcinols 1 using pseudo-high dilution conditions in DMF an d either CsF or K2CO3 as base afforded carbomethoxy-1,3-phenylene-m-ph enylene-32-crown-10 (7a, 46%), carbomethoxy-1,3-phenylene-p-phenylene- 33-crown-10 (7b, 48%), 5-(benzyloxy)-1,3-phenylen-m-phenylene-32-crown -10 (11b, 51%). Unsubstituted m-phenylene-p-phenylene-33-crown-10 (15) was also made (29%) in this way. Functional group conversions of the bis-phenylene macrocycles yielded 5-carboxy-1,3-phenylene-m-phenylene- 32-crown-10 (8a), droxymethyl)-1,3-phenylene-m-phenylene-32-crawn-10 ( 9a), bromomethyl)-1,3-phenylene-m-phenylene-32-crown-10 (10a), 5-hydro xy-1,3-phenylene-m-phenylene-32-crown-10 (12a), 5-hydroxy-1,3-phenylen e-p-phenylene-33-crown-10 (12b), imidomethyl)-1,3-phenylene-m-phenylen e-32-crown-10 (13a), and aminomethyl)-1,3-phenylene-m-phenylene-32-cro wn-10 (14a). Similarly 5-carbomethoxy-1,3-phenylene-16-crown-5 (4) was transformed to the corresponding acid (16), hydroxymethyl (17), formy l(18), bromomethyl (19), phthalimidomethyl (20), azidomethyl (21), and aminomethyl (22) derivatives. These compounds are building blocks for supramolecular assemblies (as shown by the synthesis of a Schiff base (23) from 18 and a diester (24) from 4,4'-biphenol and 17) and useful endcapping or pendant host components of macromolecules.