| Project/Area Number |
09440213
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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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 | Saitama University |
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Principal Investigator |
NAKAYAMA Juzo Faculty of Science, Saitama University Professor, 理学部, 教授 (90092022)
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| Co-Investigator(Kenkyū-buntansha) |
NAGASAWA Akira Faculty of Science, Saitama University Professor, 理学部, 教授 (40108452)
SUGIHARA Yoshiaki Faculty of Science, Saitama University Associate Professor, 理学部, 助教授 (00272279)
ISHII Akihiko Faculty of Science, Saitama University Associate Professor, 理学部, 助教授 (90193242)
SAITO Hideki Faculty of Science, Saitama University Assistant Professor, 理学部, 助手 (90272278)
KUMAKURA Shigekazu Faculty of Science, Saitama University Associate Professor, 理学部, 助教授 (50008843)
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| Project Period (FY) |
1997 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥12,900,000 (Direct Cost: ¥12,900,000)
Fiscal Year 1999: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1998: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 1997: ¥7,500,000 (Direct Cost: ¥7,500,000)
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| Keywords | episulfide / thiirene 1-oxide / tetrathiolane 3,4-dioxide / SィイD22ィエD2O / pentathiepane / thiophene 1-oxide / thiophene 1,1-dioxide / thiophenophane / テトラチオラン / 1,2-ジチエット / テトラチオラン2,3-ジオキシド / オリゴ(チオ-2,5-チエニレン) / ジベンゾトリチオシン / テトラチオン / ジチエット / トリチオシン / ジメチルジオキシラン / カリックスチオフェン |
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| Research Abstract |
The following are new results developed by the present project.
1. Sulfuration of anti- and syn-9,9'-bibenzonorbornenylidenes by elemental sulfur produced episulfides in high yields with retention of the configuration of the original alkenes.
2. Treatment of di-1-adamantylacetylene with disulfur dichloride furnished 2,3-di-1-adamantyl-thiirene 1-oxide, 3,4-di-1-adamantyl-1,2-dithiete, and 1,2-di-1-adamantyl-2-thioxoethanone.
3. Oxidation of tetrathiolanes, carrying two bulky substituents at the 5-position, with dimethyldioxirane, produced the corresponding tetrathiolane 3,4-dioxides, the first vic-disulfoxide isolated in pure form. The 3,4-dioxides decomposed in solution at room temperature to give dithiirane 1-oxides and a reactive species "SィイD22ィエD2O". Deoxygenation of the dithiirane 1-oxides with Lawesson's reagent provided dithiiranes.
4. Ring inversion energies of the trithiolane and pentathiepane rings were determined. A pair of conformational isomers was synthesized by making use of high inversion barrier of the pentathiepane ring.
5. Monocyclic thiophene 1-oxides, 1-imides, and related species were synthesized, and their structures and reactivities were investigated.
6. The parent thiophene 1,1-dioxide and monosubstitued derivatives were synthesized and isolated for the first time, and their spectroscopic properties and reactivities were fully characterized.
7. A wide variety of sulfur-containing large-membered heterocycles, such as thiophenophanes and crown thioethers, were synthesized.
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