1998 Fiscal Year Final Research Report Summary

CONSTRUCTION OF SELF-ASSEMBLY CAPSULE TYPE HOST COMPOUND : METAL ION PROMOTED CAPTURE AND RELEASE OF THE GUEST.

Research Project

Project/Area Number	08640744
Research Category	Grant-in-Aid for Scientific Research (C)
Allocation Type	Single-year Grants
Section	一般
Research Field	機能・物性・材料
Research Institution	KYUSHU UNIVERSITY
Principal Investigator	TAKEMURA Hiroyuki KYUSHU UNIVERSITY,DEPARTMENT OF CHEMISTRY,FUCULTY OF SCIENCE,RESEARCH ASSOCIATE, 理学部, 助手 (60183456)
Project Period (FY)	1996 – 1998
Keywords	Macrocyclic Compounds / Azacyclophandes / Calixarenes / Host-Guest Chemmistry / Supramolecular Chemistry / Self-Assembly
Research Abstract	Azacalixarenes which have various side arms were synthesized in a convenient method. The condensation reaction of para-substituted 2,6-bis(hydroxymethyl)-phenol derivatives and amines gave cyclic trimers, hexahomotriazacalix[3]arenes in good yields. Starting from 2,2-methylene-bis(4-methyl-6-hydroxymethylphenol) and amines, tetrahomodiaza-calix[4]arenes, were obtained in moderate to excellent yields. The cyclization procedure is very simple : bis(hydroxymethyl)phenol derivatives and amines are reacted in refluxing toluene or xylene, In this cyclization method, the high dilution technique is not required since the template effect of hydrogen bonds between phenolic OH groups and amines is present in the aprotic solvents. Novel self-filled azacalixarenes were synthesized following a simple method. The structure of a p-xylylene-bridged compound was investigated by X-ray crystallographic analysis. Dynamic NMR and MM3 calculations were also employed to study the structures in solution. Azacalix [4] skeletons are rigidly fixed in shallow cone conformations and bridging xylylene units (p- and in-) are located in the cavities of the cyclic skeletons. Intra-cavity hydrogen bonds between OH and N atoms localize at low temperatures. The free energy of the localization was estimated to be 10.8 and 11.2kcal mol^<-1> for p- and m-xylylene-bridged compounds, respectively. A new synthetic method of N-methylazacalixarenes was developed. One-pot reaction employing methylamine, formaline, and phenol afforded the mixture of N-methylazacalixarenes. N-alkylation of N-Me-azacalix[4]arene afforded betain-type macrocyclic molecule.