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

1,5,3,7-二硫属元素重氮辛转化为环状多硫属化合物的研究

• 批准号: 12650843
• 负责人: TAKIKAWA Yuji
• 金额: $ 2.11万
• 依托单位: Iwate University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650843/
• 关键词: Reactive speicies; Dication; Transannular interaction; Oxidation; 1,5,3,7-Dichalcogenadiazocine; 1,2,4-Dichalcogenazolidine; 1,2,3,4,5,7-Pentathiazocine; 酸化剤; ジテルラゾリジン

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.

目前的兴趣集中在含硫原子的反应物质上，这些反应物质是由环硫缩醛的断裂产生的。特别是，构象柔顺的八元氨基缩醛的氧化会引起跨环Ch-Ch相互作用，得到1,5,3,7-二硫代二氮二双环[3.3.0]辛烷型二硫代化合物，这些二硫代化合物会在亲核试剂对亚甲基碳的攻击下进一步破碎，得到新的环状二硫代化合物。本研究研究了3,7-二取代2H， 6h -四氢-1,5,3,7-二硫代二氮杂嗪1在不同氧化剂作用下缩合成1,2,4-二硫代二氮杂烷2的新环。用NBS、mCPBA、t-BuOOH或CuCl_2等氧化剂处理二烯二氮和二烯二氮，可得到相应的4h -二氢-1,2,4-二氯基偶氮烷，产量较高。另一方面，在-78℃下，用溴处理1,5,3,7-二噻二氮嘧啶CH_2Cl_2溶液，得到了意想不到的低产率的6h -二氢-1,2,3,4,5,7-五噻二氮嘧啶3，并得到了不溶产物和1,2,4-二噻唑烷。用Br_2/S_8或S_2Cl_2处理1,5,3,7-二噻唑嘧啶，可显著提高6 - h -二氢-1,2,3,4,5,7-五噻唑嘧啶的收率。假设2（Se, Te）是由1通过催化氧化环收缩形成的。化合物3是由以类似方式生成的1,2,4-二噻唑烷2(S)与单质硫依次反应形成的。

项目成果

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. 870-87

Yuji Takikawa、Takamasa Yoshida、Yutaka Koyama、Yuko Shibata、Shigenobu Aoyagi、Kazuaki Shimada、Chizuko Kabuto：“通过 2H,6H-四氢-1,5,3,7- 的氧化环收缩合成 1,2,4-Ditellurazoridines

kazuaki Shimada, Takamasa Yoshida, kennshiro Makino, Taisuya 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)

kazuaki Shimada、Takamasa Yoshida、kennshiro Makino、Taisuya Otsuka、Yuki Onuma、Shigenobu Aoyagi Yuji Takikawa.、Chizuko Kabuto：“7-芳基-1,2,3,4,5,7-五噻唑烷的新颖合成和热环裂变”

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.. 870-8

Yuji Takikawa、Takamasa Yoshida、Yutaka Koyama、Yuko Shibata、Shigenobu Aoyagi、Kazuaki Shimada、Chizuko Kabuto：“通过 2H,6H-四氢-1,5,3,7- 的氧化环收缩合成 1,2,4-Ditellurazoridines

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)

Kazuaki Shimada、Takamasa Yoshida、Kenshiro Makino、Tatsuya Otsuka、Yuki Onoma、Shigenobu Aoyagi、Yuji Takikawa、Chizuko Kabuto：“7-芳基-1,2,3,4,5,7-五噻唑烷的新颖合成和热环裂变”

Yuji Takikawa,Takamasa Yoshida,Yutaka Koyama,Kazuto Sato,Yuko Shibata,Shigenobu Aoyagi.Kazuaki Shimada,Chizuko Kabuto: "Synthesis of1,2,4-Ditellurazolidines by Oxidative Ring Contraction of 2H,6H-Tetrahydro-1,5,3,7-ditelluradiazocines"Chemistry Letters. 8

Yuji Takikawa、Takamasa Yoshida、Yutaka Koyama、Kazuto Sato、Yuko Shibata、Shigenobu Aoyagi.Kazuaki Shimada、Chizuko Kabuto：“通过 2H,6H-四氢-1,5,3 的氧化环收缩合成 1,2,4-二碲唑烷，