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2001 Fiscal Year Final Research Report Summary

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

Research Project

Project/Area Number 12650843
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) 2000 – 2001
KeywordsReactive speicies / Dication / Transannular interaction / Oxidation / 1,5,3,7-Dichalcogenadiazocine / 1,2,4-Dichalcogenazolidine / 1,2,3,4,5,7-Pentathiazocine
Research Abstract

Current interest has been concentrated on the chalcogen atom-containing reactive species generated by the fragmentation of cyclic chalcogenoacetals. Especially, it was expected that oxidation of conformationally flexible eight membered aminochalcogenoacetals would cause 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 dichalcogenides by the attack of nuclephiles toward the methylene carbons of the dications. In this study, we carried out the investigation of a novel ring contraction of 3,7-Disubstituted 2H,6H-tetrahydro-1,5,3,7-dischalcogenadiazocines 1 to 1,2,4-dichalcogenazolidines 2 by treating with various oxidizing agents.
Treatment of diselenadiazocines and diteluradiazocines with oxidizing agents such as NBS, mCPBA, t-BuOOH, or CuCl_2 afforded the corresponding 4H-dihydro-1,2,4-dichalcogenazolidines in goodyields.
On the other hand, treatment of a CH_2Cl_2 solution of 1,5,3,7-dithiadiazocines with bromine at -78 ℃ afforded unexpected 6H-dihydro-1,2,3,4,5,7-pentathlazocines 3 in low yields along with insoluble products and no 1,2,4-dithiazolidines were obtained. Yields of 6H-dihydro-1,2,3,4,5,7-pentathiazocines were dramatically improved by treating 1,5,3,7-dithiadiazocines with Br_2/S_8 or S_2Cl_2.
It was assumed that 2(Se, Te) were formed from 1 through oxidative ring contraction via dication. Compound 3 would be formed by the sequent reaction of 1,2,4-dithiazolidines 2(S), which were generated by a similar manner, with elemental sulfur.

  • Research Products

    (4 results)

All Other

All Publications (4 results)

  • [Publications] Yuji Takikawa, Takamasa Yoshida, Yutaka Koyama, Yuko Shibata, Shigenobu Aoyagi, Kazuaki Shimada, Chizuko Kabuto: "Synthesis of 1,2,4-Ditellurazoridines by Oxidative Ring Contraction of 2H,6H-Tetrahydro-1,5,3,7-ditelluradiazocines"Chemistry Letters.. 870-871 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuaki Shimada, Takamasa Yoshida, Kenshiro Makino, Tatsuya Otsuka, Yuki Onoma, Shigenobu Aoyagi, Yuji Takikawa, Chizuko Kabuto: "Novel Synthesis and Thermal Ring Fission of 7-Aryl-1,2,3,4,5,7-pentathiazocanes"Chemistry Letters. 90-91 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yuji Takikawa, Takamasa Yoshida, Yutaka Koyama, Yuko Shibata, Shigenobu Aoyagi, Kazuaki Shimada, Chizuko Kabuto: "Synthesis of 1,2,4-Ditellurazoridines by Oxidative Ring Contraction of 2H,6H-Tetrahydro-1,5,3,7-ditelluradiazocines"Chemistry Letters. 870-871 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuaki Shimada, Takamasa Yoshida, Kenshiro Makino, Tatsuya Otsuka, Yuki Onuma, Shigenobu Aoyagi, Yuji Takikawa, Chizuko Kabuto: "Novel Synthesis and Thermal Ring Fission of 7-Aryl-1,2,3,4,5,7-pentathiazocanes"Chemistry Letters. 90-91 (2002)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2003-09-17  

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