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Study on the Conversion of 1,5,3,7-Dichalcogenadiazocines to Cyclic Polychalcogenides

Research Project

Project/Area Number 09650946
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionIwate University

Principal Investigator

TAKIKAWA Yuji  Iwate University Faculty of Engineering Professor, 工学部, 教授 (00003848)

Co-Investigator(Kenkyū-buntansha) AOYAGI Shigenobu  Iwate University Faculty of Engineering Assistant, 工学部, 助手 (90271840)
SHIMADA Kazuaki  Iwate University Faculty of Engineering Associate Professor, 工学部, 助教授 (10142887)
Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1998: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1997: ¥2,200,000 (Direct Cost: ¥2,200,000)
KeywordsDichalcogenadiazocine / Dichalcogenazolidine / Oxidation / Transannular interaction / Cyclic polychalcogenide / Dication / Pentathiazocine / 渡環反応 / 環縮小反応
Research Abstract

Current interest has been concentrated on the chalcogen atom-containing reactive species generated by the fragmentation of cyclic chalcogenoacetals. However, few studies on the oxidation of cyclic polyaminopolychalcogenoacetals have been achieved in spite of the expectation to give various chalcogen-containing heterocycles through the oxidative ring contraction. Especially, it was expected that oxidation of conformationally flexible eight membered aminochalcogenoacetals would cause spontaneous transannular Ch-Ch interaction to give 1,5,3,7-dichalcogenadiazabicyclo[3.3.0]octane-type dichalcogena dications which would undergo further fragmentation to give novel cyclic dichalcogenidesby the attack of nucleophiles toward the methylene carbons of the dications, In this paper, we would like to describe a novelring contraction of 3,7-Disubstituted 2 H,6H-tetrahydro-1,5,3,7-dichalcogenadiazocines to 1,2,4-dichalcogenazolidines by treating with various oxidizing agents.
Treatment of 3,7-disubstituted 2 H,6H-tetrahydro-1,5,3,7-dithiadiazocines with bromine afforded 6H-dihydro-1,2,3,4,5,7-pentathiazocines in moderate yield and the addition of elemental sulfur in this reaction systems resulted in an increase of the yields of pentathiazocines. Reaction with sulfur chloride resulted in a good yield.
On the other hand, treatment of diselenadiazocines and ditelluradiazocines with various oxidizing agents afforded the corresponding 3H-dihydro-1,2,4-chalcogenazolidines in good yields. The intermediates of the reactions were supposed to be diselena or ditellura dications possessing 1,5,3,7-dichalcogenadiazabicyclo[3.3.0]octane skeleton generatedtransiently by the transannular interaction of two chalcogen atoms.
In conclusion, 2H,6H-tetrahydro-1,5,3,7-dichalcogenadiazocines subjected to selective ring contraction by treating with various oxidizing agents gave 1,2,3,4,5,7-pentathiazocines and 1,2,4-diselena- or ditellurazolidines, respectively.

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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