2003 Fiscal Year Final Research Report Summary
Generalization of New Synthetic Methods of Macrocyclic compounds Utilizing Characteristic Bonding Properties of Hypervalent Atom and Their Applications
| Project/Area Number |
14540502
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Osaka Prefecture University |
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Principal Investigator |
MATSUMURA Noboru Osaka Prefecture University, Graduate School, Assoc.Professor, 大学院・工学研究科, 助教授 (40125274)
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| Co-Investigator(Kenkyū-buntansha) |
KAZUHIKO Mizuno Osaka Prefecture University, Graduate School, Professor, 大学院・工学研究科, 教授 (10109879)
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| Project Period (FY) |
2002 – 2003
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| Keywords | Tetraazathiapentalene / Hypervalent Sulfur / Macrocyclic Compound / Ring-Opening / Anion Receptor / Molecular Recognition |
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| Research Abstract |
We report new methods for the synthesis of novel macrocyclic compounds by utilizing characteristic bonding properties of hypervalent sulfur. The results are summarized as follows: 1)Treatment of 2,3-dimethyltetraazathiapentalene derivative (1)with 1 equiv. of p-xylilene diisothiocyanate in refluxing benzene gives the macrocyclic compound 2 which has two tetraazathiapentalene skeletons in the compound. 2)The reaction of compund 3 which has two pentalene rings in the molecule with p-xylilene diisothiocyanate affords macrocyclic compound 4 which has four tetraazathiapentalene rings, these rings being situated in a laminate form. 3)The reaction of 3 with 3,6,9-trioxaundecane-1,11-diisothiocyanate affords macrocyclic compound 5 which has having two rings containing oligoethyleneglycol chain and pentalene ring. 4)The reaction of 2,4 and 5 with NaBH_4 gives ring-expanded 26-35-membered macrocycles 6,7 and 8, respectively, via the reductive elimination of hypervalent sulfur. 5)Treatment of 2,4 and 5 with aqueous potassium hydroxide gives 4045 membered macrocyclic compound 9, 10 and 11, respectively, which have thiourea moieties via the elimnation of C=S^<IV> moiety. 6) The macrocyclic compound 6 -8 serve as an anionm receptor for H_2PO_4. The reactions described here would provide the useful methods for the variety of macrocyclic compounds.
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