A remarkable selectivity in the N-functionalization of polyaza[n]paracyclophanes. Synthesis of N-(4-picolyl)-substituted 2,6,9,13-Tetraaza[14]paracyclophanes

✍ Scribed by M. Isabel Burguete; Beatriu Escuder; Juan C. Frías; Santiago V. Luis; Juan F. Miravet; Enrique García-España

• Publisher: Elsevier Science
• Year: 1997
• Tongue: French
• Weight: 442 KB
• Volume: 53
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(97)10075-8

✦ Synopsis

Interaction of cationic host species, in particular Zn 2+ salts, with polyaza[n]paracyclophanes (i.e. 2,9,paracyclophane, B323 (la)) directs their selective N-functionalization. In this way compounds mono-or difunctionalized with ARCH2-groups at the benzylic nitrogen atoms can be easily obtained. Direct reaction with the alkylating agent, in the absence of the Zn 2+ species, produces, in general, very complex mixtures of mono-and polyalkylated compounds except when 4picolyl chloride is used. In this case, mono-, di-, tri-and tetra N-substituted derivatives of D323 can be isolated depending on the amount of the alkylating agent used. In this case, the mono-and dialkylated products obtained differ from the ones prepared using the metal assisted synthesis.