1987 Fiscal Year Final Research Report Summary
Reactivities of Nitrenium Ion Intermediates and the Application to Organic Syntheses
| Project/Area Number |
60490007
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
広領域
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| Research Institution | Shinshu University |
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Principal Investigator |
TAKEUCHI Hiroshi Shinshu University, 工学部, 助教授 (00029258)
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| Co-Investigator(Kenkyū-buntansha) |
TSUCHIDA teruko Shinshu University, 工学部, 教務員
MITANI Michiharu Shunshu University, 工学部, 助教授 (20021016)
KOYOMA Kikuhiko Shinshu University, 工学部, 教授 (40029012)
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| Project Period (FY) |
1985 – 1987
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| Keywords | Arylnitrenium ions / Aryl azides / Trifluoroacetic acid / Dearylamines / Alkyl thioanilines / Parent nitrenium ion / Vinylnirenium ions / イソオキサゾール誘導体 |
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| Research Abstract |
The chemistry of nitrenium ions has been actively investigated in recent years since they are not only reactive metabolites of some carcinogens but also important intermediates for organic syntheses.
Arylnitrenium ions (ArN.^H or ArN^+-^-AlCl_3) are generated from aryl azides in the presence of trifluoroacetic acid (TFA), trifluoromethanesulfonic acid (TFSA), or aluminium chloride. The singlet arylnitrenium ions are capable of bringing about inter- and intra-molecular aromatic N-substitutions and stereospecific additions to olefins, whereas the triplet nitrenium ions lead only to hydrogen abstraction. The substitutions afforded diarylamines, carbazoles, and 9,10-dihydroacridine. The reaction of alkyl sulfides with phrnylnitrenium ion generated from phenyl azide in the presence of both TFA and TFSA gave a new synthetic method for alkyl thioaniline dirivatives (i.e. aminophenyl sulfides).
Phenylnitrenium ion, parent nitrenium ion, and alkylnitrenium ions are generated in the thermolysis or photolysis of 1-(phenylamino, amino, and alkylamino)-pyridinium salts in the presence of TFA. Direct aromatic N-substitutions are also allowed to occur by these ions in singlet states. The parent nitrenium ion is also formed in the photolysis of S-aminophenylsulfonium salts.
The reaction of <beta>-azidostyrene in the presence of TFA, difluoroacetic acid, trichloroacetic acid, dichloroacetic acid, or chloroacetic acid produced a novel compound 4-pheny1-5-halomethylisoxazole, respectively. On the contrary, the reaction of <alpha>-azidostyrene instead of <beta>-azidostyrene did not give isozazole but acetophenone imide. Mechanistic study suggests that the reactions proceed via vinylnitrenium ion intermediates.
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Research Products
(11 results)
