Synthesis of substituted 14‐crown‐4 compounds

Seventeen new substituted 14‐crown‐4 derivatives 3‐10, 35‐40, 42, 45 and 46 are described. A series of nine compounds 2‐10 with two, three or four substituents in the 6‐ and/or 13‐positions was synthesized in good yields from the appropriate diols and ditosylates using improved cyclization conditions. The solid state structures of 6,6,13,13‐tetra(benzyloxymethyl)‐14‐crown‐4 (8) and lithium thiocyanate complexes of trans‐ and cis‐6,13‐bis(spiro‐2,2‐dichlorocyclopropyl)‐14‐crown‐4 (45) and (46), respectively, have been determined.