Organic Syntheses Involving Reactions of Acetylenes with Elemental Sulfur and Selenium

涉及乙炔与元素硫和硒反应的有机合成

• 批准号: 03640437
• 负责人: HOSHINO Masamatsu
• 金额: $ 1.28万
• 依托单位: Saitama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03640437/
• 关键词: 1, 2-Dithietes; 1, 2-Dithiocarbonyl compounds; 1, 2-Dieselnoxo compounds; Tetraarylthiophenes; Tetraarylselenophenes; Thieno[3, 2-b]thiophenes; Selenolo[3, 2-b]selenophenes; Bis(diethylamino)carbeniumdithiocarboxylate; 単体硫黄; 単体セレン; チエノチオフェン; セレ

1) A convenient symthesis of 1, 2-dithietes, which involves reaction of elemental sulfur with acetylenes carrying bulky substituents such as tert-butyl and 1-adamantyl, has been established.2) It was found that ynamines such as bis(diethlamino)acetylene react with elemental sulfur to give the corresponding 1, 2-dithiocarbonyl compounds but not the 1, 2-dithietes. A similar reaction with elemental selenium was also found.3) Convenient and practical syntheses of tetraarylthiophenes and tetraarylselenophenes, which involve reactions of diarylacetylenes with elemental sulfur and selenium, respectively, have been deveised. Application of the above method allowed the preparation of a star-burst type of thiophene oliogomers.4) Acetylenediols such as 2, 5-dimethl-3-hexyne-2, 5-diol react with elemental sulfur to give substituted thieno[3, 2-b]shiophenes, thus providing a practical one-pot synthesis of thienothiophenes. The reaction is also applicable to the preparation of selenolo[3, 2-b]selenophenes.5) 2-Chloro and 2-phenoxy substituted 1, 1-bis(diethylamino)ethylenes react with elemental sulfur to afford an inner salt, bis(diethylamino)carbeniumdithiocarboxylate in excellent yields.

1)建立了一种简便的1,2 -二亚酯合成方法，该方法是由单质硫与带有大取代基的乙炔（如叔丁基和1-金刚烷基）反应而成。2)发现双（二乙胺）乙炔等动力胺与单质硫反应生成相应的1,2 -二硫羰基化合物，而不是1,2 -二硫基化合物。与硒元素也发现了类似的反应。3)设计了方便实用的四芳基噻吩和四芳基硒基噻吩的合成方法，它们分别由二芳基乙炔与单质硫和硒反应而成。应用上述方法可以制备星爆型噻吩寡聚物。4)乙炔二醇如2,5 -二甲基-3-己炔- 2,5 -二醇与单质硫反应生成取代噻吩[3,2 -b]，从而提供了一锅合成噻吩的实用方法。该反应也适用于硒罗[3,2 -b]硒烯的制备。5) 2-氯和2-苯氧基取代的1,1 -双（二乙基氨基）乙烯与单质硫反应生成内盐，双（二乙基氨基）羰基二硫代羧酸酯，收率高。

项目成果

Nakayama,Mizumura,Akiyama,Nishio,Iida: "Synthesis and Characterization of Tetraethylethanediselenoamide" Chemistry Letters. 77-80 (1994)

Nakayama、Mizumura、Akiyama、Nishio、Iida：“四乙基乙烷二硒酰胺的合成和表征”化学快报。

Sawada,Choi,Kuroda,Taniguchi,Ishii,Hoshino,Nakayama: "Preparation of Tetraarylthiophenes and Tetraarylselenophenes by Reactions of Diarylacetylenes with Elemental Sulfur and Selenium" Sulfur Letters. 15. 273-283 (1993)

Sawada、Choi、Kuroda、Taniguchi、Ishii、Hoshino、Nakayama：“通过二芳基乙炔与元素硫和硒的反应制备四芳基噻吩和四芳基硒吩”硫快报。

J.Nakayama,K.S.Choi,I.Akiyama,and M.Hoshino: "A Convenient Synthesis of 1,2ーDithietes and α-Dithiocarbonyl Compounds by Sulfuration of Acetylenic Compounds" Tetrahedron Letters. 34. 115-118 (1993)

J. Nakayama、K. S. Choi、I. Akiyama 和 M. Hoshino：“通过乙炔化合物的硫化来方便地合成 1,2-二硫代化合物和 α-二硫代羰基化合物”，Tetrahedron Letters 34. 115-118 (1993)。

J.Nakayama, A.Mizumura, I.Akiyama, T.Nishio, and I.Iida: "Synthesis and Characterization of Tetraarylethanediselenoamide" Chem.Lett.77-80 (1994)

J.Nakayama、A.Mizumura、I.Akiyama、T.Nishio 和 Iida：“四芳基乙烷二硒酰胺的合成和表征”Chem.Lett.77-80 (1994)

Sawada,Choi,Kuroda,Taniguchi,Ishii,Hoshino,Nakayama: "Preparation of Tetraarylthiophenes and Tetraarylselenophenes by Reactions of Diarylacetylenes with Elemental Sulfur and Selenium" Sulfur Letters. 16. (1993)

Sawada、Choi、Kuroda、Taniguchi、Ishii、Hoshino、Nakayama：“通过二芳基乙炔与元素硫和硒的反应制备四芳基噻吩和四芳基硒吩”硫快报。