1998 Fiscal Year Final Research Report Summary
Syntheses and Reactivities of Thiophenetriptycenesulfenic and selenenic acids
| Project/Area Number |
09640624
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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 | Saitama University |
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Principal Investigator |
ISHII Akihiko Saitama University, Department of Chemistry, Associate Professor, 理学部, 助教授 (90193242)
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| Co-Investigator(Kenkyū-buntansha) |
SUGIHARA Yoshiaki Saitama University, Department of Chemistry, Assistant Professor, 理学部, 助手 (00272279)
NAKAYAMA Juzo Saitama University, Department of Chemistry, Professor, 理学部, 教授 (90092022)
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| Project Period (FY) |
1997 – 1998
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| Keywords | sulfenic acid / selenenic acid / thiophenetriptycene / triptycene / selenoseleninate / dimethyldioxirane / oxidation / beta-elimination |
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| Research Abstract |
Syntheses and reactivities of thiophenetriptycenesulfenic (Thtrip-SOH) and selenenic acids (Thtrip-SeOH) and triptycneneselenenic acid (Trip-SeOH) were investigated.
1. Attempted synthesis of Thtrip-SeOH The oxidation of Thtrip-Se-n-Bu with dimethyldioxirane (DMD) gave the corresponding selenoxide [Thtrip-Se(O)-n-Bu] . The thermal beta-elimination of the selenoxide yielded Thtrip-Se(O)Se-Thtrip, instead of the desired selenenic acid (ThtripSeOH). Thtrip-Se(O)Se-Thtrip is the first isolable selenoseleninates and the structure was determined by X-ray crystallography.
2. Synthesis of Trip-SeOH The oxidation of Trip-Se-n-Bu with DMD gave the corresponding selenoxide [Trip-Se(O)-n-Bu], the beta-elimination of which yielded the desired Trip-SeOH in a good yield. Trip-SeOH is the first isolable alkancselenenic acid and the structure was determined by X-ray crystallography.
3. Reactions of Trip-SeOH Heating a solution of Trip-SeOH in dichloromethane yielded the selenoseleninate, Trip-Se(O)Se-Trip. The dimerization was not accelerated by an acid. The treatment of Trip-Se(O)Se-Trip with Et^c_3N furnished a mixture of TripSe(O)SeTrip, Trip-SeSe-Trip, and Trip-SeO_2HEt_3N, the molar ratio of which was 1 : 1 : 1. Acid-catalized hydrolysis of TripSe(O)SeTrip gave TripSeOH quantitatively.
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