1993 Fiscal Year Final Research Report Summary
The Chemistry of Novel[7]Annulene Compounds
| Project/Area Number |
04640489
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Saitama University |
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Principal Investigator |
MACHIGUCHI Takahisa Saitama University, College of Liberal Arts and Science, Professor, 教養部, 教授 (00008864)
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| Co-Investigator(Kenkyū-buntansha) |
YAMABE Shinichi Nara University of Education, Educaitional Technology Center, Professor, 教育学部, 教授 (00109117)
HASEGAWA Toshio Saitama University, College of Liberal Arts and Science, Technical Official Mini, 教養部, 教務職員 (00237976)
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| Project Period (FY) |
1992 – 1993
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| Keywords | [7]Annulene / [7]Annulenethione / Fulvene / Cycloaddition / Cage Molecule / [7]Annulenimine / S-Oxide / Sulfine |
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| Research Abstract |
We have found the following results,
1.The absorption bands of tropothione are assigned by a new method "magnetic circular-dichroism".
2.[7]Annulenthione, which is valence isoelectronic with tropone, reacts concertedly with fulvene to give 1 : 1[8 + 2]cycloadducts. The product configuration is sharply different from that of the initially formed[6 + 4]cycloadduct between tropone and fulvene. The reaction mechanism are studies kinetically and by molecular orbital calculations. The obtained endo form of the[8 + 2]product is found to arise from the secondary orbital interaction in the course of the intrinsic reaction coordinate.
3.Thermally stable[7]annulenthiones have been synthesized by direct thiocarbonylation of the corresponding tropones in polar solvents. The products are characterized by IR, UV-visible, and ^1H, ^<13>C, ^<14>N NMR spectroscopies.
4.The reaction of 8, 8-dicyanoheptafulvene and cyclopentadienide anion affords under mild condition two unusual tetracyclic cage molecules. The structures are elucidated using various modern NMR spectroscopic techniques and deuterium-labeling experiments. The easy formation of the considerably strained molecules is ascribed to a nucleophilic addition, followed by protonation and an intramolecular Diels-Alder reaction with normal electron demand. MNDO-MO calculations suggest a possible mechanism.
5.[7]Annulenthione S-oxide have been synthesized as stable dark red needles (mp 68ﾟC)in high yield. The structure and chemical behaviors of the sulfur are investigated both by X-ray analysis and ^<13>C, ^<17>O, ^<33>S NMR spectroscopies and this compound is found to be the first exmaple of a sulfine charge reversion(umpoulung).
2-Amino[7]annulenimine is conveniently synthesized in high yield and is isolated in pure form.
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