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 -phenylene- p -phenylene-33-crown-10 derivatives has been synthesized. Cyclization of m - and p -bis(ω-chlorotetraethyleneoxy)benzenes ( 6 ) with 5-substituted resorcinols 1 using pseudo-high dilution conditions in DMF and either CsF or K 2 CO 3 as base afforded 5-carbomethoxy-1,3-phenylene- m -phenylene-32-crown-10 ( 7a, 46%), 5-carbomethoxy-1,3-phenylene- p -phenylene-33-crown-10 ( 7b, 48%), 5-(benzyloxy)-1,3-phenylene- m -phenylene-32-crown-10 ( 11a, 42%) and 5-(benzyloxy)-1,3-phenylene- p -phenylene-33-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 ), 5-(hydroxymethyl)-1,3-phenylene- m -phenylene-32-crown-10 ( 9a ), 5-(bromomethyl)-1,3-phenylene- m -phenylene-32-crown-10 ( 10a ), 5-hydroxy-1,3-phenylene- m -phenylene-32-crown-10 ( 12a ), 5-hydroxy-1,3-phenylene- p -phenylene-33-crown-10 ( 12b ), 5-(phthalimidomethyl)-1,3-phenylene- m -phenylene-32-crown-10 ( 13a ), and 5-(aminomethyl)-1,3-phenylene- m -phenylene-32-crown-10 ( 14a ). Similarly 5-carbomethoxy-1,3-phenylene-16-crown-5 ( 4 ) was transformed to the corresponding acid ( 16 ), hydroxymethyl ( 17 ), formyl ( 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.