Chemistry of Sulfur-containing Heterocycles : from Three-membered to Macrocycles

含硫杂环化学：从三元环到大环

• 批准号: 09440213
• 负责人: NAKAYAMA Juzo
• 金额: $ 8.26万
• 依托单位: Saitama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440213/
• 关键词: episulfide; thiirene 1-oxide; tetrathiolane 3,4-dioxide; SィイD22ィエD2O; pentathiepane; thiophene 1-oxide; thiophene 1,1-dioxide; thiophenophane; テトラチオラン; 1,2-ジチエット; テトラチオラン2,3-ジオキシド; オリゴ(チオ-2,5-チエニレン); ジベンゾトリチオシン; テトラチオン; ジチエット; トリチオシン; ジメチル

The following are new results developed by the present project.1. Sulfuration of anti- and syn-9,9'-bibenzonorbornenylidenes by elemental sulfur produced episulfides in high yields with retention of the configuration of the original alkenes.2. Treatment of di-1-adamantylacetylene with disulfur dichloride furnished 2,3-di-1-adamantyl-thiirene 1-oxide, 3,4-di-1-adamantyl-1,2-dithiete, and 1,2-di-1-adamantyl-2-thioxoethanone.3. Oxidation of tetrathiolanes, carrying two bulky substituents at the 5-position, with dimethyldioxirane, produced the corresponding tetrathiolane 3,4-dioxides, the first vic-disulfoxide isolated in pure form. The 3,4-dioxides decomposed in solution at room temperature to give dithiirane 1-oxides and a reactive species "SィイD22ィエD2O". Deoxygenation of the dithiirane 1-oxides with Lawesson's reagent provided dithiiranes.4. Ring inversion energies of the trithiolane and pentathiepane rings were determined. A pair of conformational isomers was synthesized by making use of high inversion barrier of the pentathiepane ring.5. Monocyclic thiophene 1-oxides, 1-imides, and related species were synthesized, and their structures and reactivities were investigated.6. The parent thiophene 1,1-dioxide and monosubstitued derivatives were synthesized and isolated for the first time, and their spectroscopic properties and reactivities were fully characterized.7. A wide variety of sulfur-containing large-membered heterocycles, such as thiophenophanes and crown thioethers, were synthesized.

以下是本项目开发的新成果。反式和顺式-9，9 '-联苯并降冰片烯亚基通过元素硫的硫化反应以高产率生成环硫醚，并保留了原始烯的构型.用二氯化二硫处理二-1-金刚烷基乙炔得到2，3-二-1-金刚烷基-噻二烯1-氧化物、3，4-二-1-金刚烷基-1，2-二硫醚和1，2-二-1-金刚烷基-2-硫代乙酮.在5-位带有两个大取代基的四硫杂环戊烷与二甲基二氧杂环乙烷的氧化产生了相应的四硫杂环戊烷3，4-二氧化物，这是第一个以纯形式分离的vic-二亚砜。3，4-二氧化物在溶液中室温下分解生成二硫杂环丙烷1-氧化物和反应性物种“S二硫杂环丙烷D22二硫杂环丙烷D2 O”。用Lawesson试剂将二硫杂环丙烷1-氧化物脱氧得到二硫杂环丙烷。测定了三硫杂环戊烷和五硫杂环庚烷的环反转能。利用五硫杂环庚烷环的高反转势垒，合成了一对构象异构体.合成了单环噻吩1-氧化物、1-酰亚胺及相关化合物，并对其结构和反应性能进行了研究.首次合成并分离了噻吩1，1-二氧化物母体及其单取代衍生物，并对其光谱性质和反应活性进行了全面表征.合成了一系列含硫大环化合物，如噻吩并吩、冠硫醚等。

项目成果

Hidehiro Nagasawa: "Thiophene 1,1-DIoxide : Synthesis, Isolation, and Properties"Bulletin of the Chemical Society Of Japan. 72. 1919-1926 (1999)

Hidehiro Nagasawa：“噻吩 1,1-二氧化物：合成、分离和性质”日本化学会通报。

Akihiko Ishii: "1-Adamantyl-tert-butyltetrathiolane 2,3-Dioxide : First Isolable vic Disulfoxide and Efficient Precursor of S20"Journal of the American Chemical Society. 121. 7959-7960 (1999)

Akihiko Ishii：“1-金刚烷基-叔丁基四硫烷 2,3-二氧化物：第一个可分离的二亚砜和 S20 的有效前体”美国化学会杂志。

J. Nakayama, S. Tanaka, Y. Sugihara, A. Ishii: "Synthesis with Bis(o-mercapto)phenyl Sulfide : An Easy Access to Sulfur-containing 16- Membered Heterocycles"Heterocycle. 50. 103-108 (1999)

J. Nakayama、S. Tanaka、Y. Sugihara、A. Ishii：“用双（邻巯基）苯基硫醚合成：轻松获得含硫 16 元杂环”杂环。

A. Ishii, M. Nakabayashi, J. Nakayama: "1-Adamantyl-tert-butyltetrathiolane 2,3-Dioxide : First Isolable vic-Disulfoxide and Efficient Precursor of S2O"J. Am. Chem. Soc.. 121. 7959-7960 (1999)

A. Ishii，M. Nakabayashi，J. Nakayama：“1-金刚烷基-叔丁基四硫烷 2,3-二氧化物：第一个可分离的 vic-二亚砜和 S2O 的有效前体”J。

Takashi Otani: "1-Imino and 1,1-Diimino derivatives of 3,4-Di-tert-butylthiophene"Tetrahedron Letters. 40. 5549-5552 (1999)

Takashi Otani：“3,4-二叔丁基噻吩的1-亚氨基和1,1-二亚氨基衍生物”四面体字母。