Novel Syntheses of N-Pivot Lariat Diaza-Crown Ethers from 4,13-Bis(benzotriazolylmethyl)-4,13-diaza-1,7,10,16-tetraoxacyclooctadecane.
4,13-Bis(benzotriazolylmethyl)-4,13-diaza-1,7,10,16-tetraoxacyclooctadecane (6) was synthesized as a versatile intermediate in the preparation of bis(lariats) of diaza-18-crown-6. N,N'-Bis(umbelliferon-8-ylmethyl) derivative 8, bis(lariats) with terminal unsaturated groups (11c,e), ester functionalities (11d), N,N'-di-beta-aralkyl derivatives (11a,b), and gamma-oxy-substituted (13, 14) and gamma-amino-substituted (17-19) propylene-side-armed derivatives were thus prepared in moderate to excellent yields. The X-ray structure of bis(lariat) 6 and stability constants for several of the complexes of bis(lariats), derivatives of 6, with metal cations are discussed.
Katritzky
Alan R.
AR
Department of Molecular Biology and Pharmacology, Washington University School of Medicine, Washington University, St. Louis, Missouri 63110.
Belyakov
Sergei A.
SA
Sorochinsky
Alexander E.
AE
Steel
Peter J.
PJ
Schall
Otto F.
OF
Gokel
George W.
GW