Preparation, Structure and Reactions of Novel Tellurium-Containing Heterocycles

新型含碲杂环化合物的制备、结构及反应

• 批准号: 12672073
• 负责人: SASHIDA Haruki
• 金额: $ 1.6万
• 依托单位: Hokuriku 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-12672073/
• 关键词: tellurium; 1-benzotellurepine; 1-benzotelluropyrylium Salt; 2-benzotelluropyrylium Salt; tellurochromen-4-one; tellurochromene; isotellurochromene; Te-Li exchange; 1-ペンゾセレノピリリウム塩; イソセレノクロメン; 2-ベンゾセレノピリリウム塩; 1-ベンゾスタネピン; 1-ベンゾスチベピン; 1-ベンゾボレピン /

1. The treatment of 1-benzotellurepines, novel seven-membered heterocycles, with t-BuLi followed by addition of a metal reagent (Cl_2SnBu_2, Cl_2SbPh and Cl_2SiMe_2) afforded the corresponding 1-benzostannepines, 1-benzostibepines and 1-benzosilepines, respectively, in one pot via the tellurium-lithium exchange.2. The 1-benzostannepines, which were prepared from (Z)-1-(o-bromophenyl) but-1-ene-3-ynes, were easily converted into the 1-benzostibepines and the 1-benzoborepines by tin-antimony and tin-boron exchange reactions in moderate to good yields, respectively.3. The general preparation of the unsubstituted and 2-substituted 1-benzoselenopyrylium salts from the selenochromen-4-ones via the selenochlomenes is investigated.4. The reactions of the stable 1-benzoselenopyrylium salts with several nucleophiles and also LiAlH_4 reduction are described ; comparison of the behavior of 1-benzotelluropyrylium salts is made.5. The treatment of the 1-benzoselenopyrylium salts with an alkyl(phenyl … More )magnesium halide resulted in nucleophilic addition at the C-4 position to give the corresponding 2,4-disubstituted 4H-selenochromenes in good yields, respectively. The obtained selenochromenes were men easily converted into the 2,4-disubstituted 1-benzoselenopyrylium salts.6. The treatment of the tellurochromen-4-ones with several Grignard reagents gave the 4-substituted 4-hydroxy-4H-tellurochromenes in good yields, respectively. The obtained compounds were readily transformed into the 2,4-disubstituted 1-benzotelluropyrylium salts.7. The regioselective and stereospecific intramolecular ring closure reactions of o-ethynylbenzyl tellurols and o-ethynylbenzyl selenols, which were readily. generated by the reaction of the o-ethynylbenzyl bromides with sodium hydrogen telluride (NaHTe) or sodium hydrogen selenide (NaHSe), produced the isotellurochromenes and isoselenochromenes together with (Z)-1-methylidene-2-tellurahidans and (Z)-1-methylidene-2-selenaindans, respectively. The obtained isochromenes and were transformed into the corresponding 2benzopyrylium tetratluoroborates, respectively. An X-ray structural analysis of the 2-tert-butyl denvatives is also described. Less

1. 用t-BuLi处理新型七元杂环化合物1-苯并telluleines，然后加入金属试剂Cl_2SnBu_2， Cl_2SbPh和Cl_2SiMe_2，通过碲锂交换，在一个锅中分别得到相应的1-苯并斯坦苯、1-苯并斯蒂比松和1-苯并西利平。以(Z)-1-（邻溴苯基）-1-烯-3-炔为原料制备的1-苯并二苯甲苯胺，通过锡-锑交换反应和锡-硼交换反应，分别以中优产率转化为1-苯并二苯甲苯胺和1-苯并二苯甲苯胺。研究了硒铬-4-酮经硒铬烯制备非取代和2取代的1-苯并硒吡啶盐的一般方法。描述了稳定的1-苯并硒代吡啶盐与几种亲核试剂的反应和LiAlH_4还原反应；比较了1-苯并-苯并telluropyryum盐的行为。用烷基（苯基）卤化镁处理1-苯并硒酰基盐，可在C-4位置发生亲核加成反应，得到相应的2,4-二取代4h -硒铬，产率较高。所得的硒铬很容易转化为2,4-二取代的1-苯并硒基盐。用几种格氏试剂处理4- 1型碲铬，分别得到了产率较高的4-取代4-羟基- 4h碲铬。得到的化合物很容易转化为2,4-二取代的1-苯并苯磺基吡啶盐。邻乙基苄基碲醇和邻乙基苄基硒醇具有区域选择性和立体特异性的分子内闭环反应。邻乙基苄基溴化物与碲化氢钠（NaHTe）或硒化氢钠（NaHSe）反应，分别与(Z)-1-甲基-2-tellurahidans和(Z)-1-甲基-2-selenaindans生成异碲铬烯和异硒铬烯。得到的同色胺和异色胺分别转化为相应的四氟硼酸二苯并吡啶。还描述了2-叔丁基衍生物的x射线结构分析。少

项目成果

指田 春喜: "テルロールおよび関連化合物の分子内三重結合への環化付加による複素環合成"有機合成化学協会誌. 59. 355-362 (2001)

Haruki Sashida：“通过碲醇和相关化合物与分子内三键的环加成合成杂环”，合成有机化学学会杂志 59. 355-362 (2001)。

Haruki Sashida and Atsuhiro Kuroda: "An alternative general preparation of 2-alkyl-1-benzostannepines and their conversion into 1-benzostibepines and 1-benzoborepines via a tin-metal exchange"J.Chem.Soc.,Perkin Trans.1. 1965-1969 (2000)

Haruki Sashida 和 Atsuhiro Kuroda：“2-烷基-1-苯并锡平的另一种通用制备方法及其通过锡-金属交换转化为 1-苯并烯平和 1-苯并硼庚烷”J.Chem.Soc.，Perkin Trans.1。

Haruki Sashida, Kazuo Ohyanagi, Mao Minoura, Kin-ya Akiba: "Studies on tellurium-containing heterocycles. Part 18. Preparation and structure of 2-benzotelluropyrylium salts and 2-benzoselenopyrylium salts"J. Chem. Soc., Perkin Transactions 1. 606-612 (200

Haruki Sashida、Kazuo Ohyanagi、Mao Minoura、Kin-ya Akiba：“含碲杂环的研究。第 18 部分。2-苯并碲吡咯盐和 2-苯并硒吡咯盐的制备和结构”J。

Haruki Sashida, Masahiro Yoshida: "A simple and practical preparation of 2,4-disubstituted 1-beuzotelluropyrylium salts"Heterocycles. 57. 649-656 (2002)

Haruki Sashida、Masahiro Yoshida：“一种简单实用的 2,4-二取代 1-beuzotelluropyrylium 盐的制备方法”杂环。

Haruki Sashida: "An alternative route for the preparation of 1-benzostannepines, 1-benzostibepines and 1-benzosilepines via Te-Li exchange of 1-benzotellurepines"Heterocycles. 53. 49-53 (2000)

Haruki Sashida：“通过 1-苯并碲平的 Te-Li 交换制备 1-苯并锡平、1-苯并斯蒂平和 1-苯并西平的替代路线”杂环。