Treatment of bis(methyl4,6-0-benzylidene-2,3-dideoxy-cu-D-glucopyranosido [2,3-~][2',3'-~])-1.4,7,lO,l3,16-hexaoxacyclo-octadecane (1) with aqueous acetic acid gave bis(methyl 2,3-dideoxy-cY-D-glucopyranosido[2,3-bl[2',3'-~])-1,4,7,10,13,16-hexaoxacyclo-octadecane (2). With LiAlH,-AlCl,, 1 gave a mixture of three 0-benzyl derivatives in which bis(methy1 4-O-benzyl-2,3-dideoxy-n-Dglucopyranosido[2,3-~][2',3'-~])-1,4,7,10,13,16-hexaoxacyclo-octadecane preponderated. Methylation and butylation of 2 in a two-phase system gave the tetramethoxy and tetrabutoxy crowns. Bis(methy1 4-O-acetyl-2,3-dideoxy-6-O-trityl-a-D-glucopyranosido[2,3-~][2',3'-~])-1,4,7,10,13,16-hexaoxacyclo-octadecane (5) was obtained from 2 by tritylation and acetylation. Detritylation of 5 with acetic acid-hydrogen bromide gave bis(methyl 4-O-acetyl-2,3-dideoxy-o-o-glucopyranosido[2,3-b][2',3'-k])-1,4,7,10,13,16-hexaoxacyclo-octadecane.
Treatment of 1 with N-bromosuccinimide gave the 4-benzoyl-6-bromo-6-deoxy compound which was suitable for making a new ring with a trans-annular connection.
The complex stability constant of each new crown has been measured and evaluated.