Oxidation of Cyclic Oligosulfides and Structures and Decomposition Reactions of the Oxides

环状低硫醚的氧化及其氧化物的结构和分解反应

• 批准号: 12440174
• 负责人: ISHII Akihiko
• 金额: $ 3.26万
• 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: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440174/
• 关键词: Dithiiranes; Tetrathiolanes; Pentathianes; 1,2,4-trithiolanes; Elemental sulfur; Dimethyldioxirane; Oxidation; Platinum complex; 1,2-ジオキシド; 硫黄酸化物; 一酸化二硫黄; X線結晶構造解析; ジチイランオキシド; トリフルオロ過酢酸; 二原子硫黄; ジアゾアルカン

1. The chemistry of Dithiiranes. (i) The reaction of S_8O, prepared by oxidation of elemental sulfur, with diazo compounds yielded the desired dithiirane 1-oxides. (ii) The dithiirane 1-oxides were reduced with Lawesson's reagent to give unoxidized dithiiranes. (iii) The reaction of the dithiirane 1-oxides and the dithiiranes thus obtained with (Ph_3P)_2Pt(C_2H_4) produced the Pt-insertion products in high yields.2. The chemistry of tetrathiolanes. (i) Oxidation of a tetrathiolane with dimethyldioxirane (DMD) gave the 2-oxide and then 2,3-dioxide. The 2,3-dioxide decomposed in solution over -20℃ to give the dithiirane 1-oxide and disulfur monoxide. (ii) The reactions of the 2-oxide and the 2,3-dioxide with (Ph_3P)_2Pt(C_2H_4) produced the identical Pt-S_2O complex. The Pt-S_2O complex further reacted with (Ph_3P)_2 Pt(C_2H_4) to give the novel platinum dinuclear complex in high yield.3. The chemistry of pentathianes. (i) Oxidation of a pentathiane with trifluoroperacetic acid and DMD g … More ave the 3-oxide and the 1-oxide, respectively. (ii) The reaction of the 3-oxide with (Ph_3P)_2 Pt(C_2H_4) yielded the cyclic (dithiolato-thiolato)-Pt complex and the Pt-S_2O complex in high yields.4. The chemistry of 1,2,4-trithiolanes. (i) a cis-tetrasubstituted 1,2,4-trithiolane was allowed to react with DMD to give two 1-oxides. Oxidation of one of the 1-oxides yielded the desired 1,2-dioxide, while that of the other 1-oxide gave the 1,1-dioxide. The 1,1-dioxide decomposed in solution at room temperature to give two molar equiv of the thioketone. Similarly, the 1,2-dioxide decomposed to two molar equiv of the thioketone in refluxing chloroform, while the two 1-oxides decomposed to the identical thiirane in refluxing xylene. (ii) Oxidation of a trans-tetrasubstituted 1,2,4-trithiolane with MCPBA produced two 1-oxides. Further oxidation of one of the 1-oxides with DMD yielded two diastereoroeric 1,2-dioxdes and 1,1-dioxide, while that of the other 1-oxide gave only one of the 1,2-dioxides. We observed equilibrium between the two 1,2-dioxides. Less

1. 二硫杂环己烷的化学性质。 (i)通过元素硫的氧化制备的S_8O与重氮化合物的反应产生所需的二硫丙环1-氧化物。 (ii)用劳森试剂还原二硫杂丙环1-氧化物，得到未氧化的二硫杂丙环。 (iii)二硫杂丙环1-氧化物和由此获得的二硫杂丙环与(Ph_3P)_2Pt(C_2H_4)的反应以高收率产生Pt插入产物。2．四硫杂环戊烷的化学性质。 (i)用二甲基二环氧乙烷(DMD)氧化四硫杂环戊烷，得到2-氧化物，然后得到2,3-二氧化物。 2,3-二氧化物在-20℃下在溶液中分解，得到二硫丙环1-氧化物和一氧化二硫。 (ii) 2-氧化物和2,3-二氧化物与(Ph_3P)_2Pt(C_2H_4)的反应产生相同的Pt-S_2O络合物。 Pt-S_2O配合物进一步与(Ph_3P)_2 Pt(C_2H_4)反应，高产率地得到新型铂双核配合物。 3．戊硫烷的化学。 (i) 用三氟过乙酸和 DMD 分别氧化五硫烷，得到 3-氧化物和 1-氧化物。 (ii)3-氧化物与(Ph_3P)_2 Pt(C_2H_4)反应高产率地生成了环状(二硫醇-硫醇)-Pt配合物和Pt-S_2O配合物。 4． 1,2,4-三硫戊环的化学性质。 (i)使顺式四取代的1,2,4-三硫戊环与DMD反应，得到两个1-氧化物。一种1-氧化物的氧化产生所需的1,2-二氧化物，而另一种1-氧化物的氧化产生1,1-二氧化物。 1,1-二氧化物在室温下在溶液中分解，得到两摩尔当量的硫酮。类似地，1,2-二氧化物在回流氯仿中分解为两摩尔当量的硫酮，而两种1-氧化物在回流二甲苯中分解为相同的硫丙环。 (ii)用MCPBA氧化反式四取代的1,2,4-三硫戊环产生两个1-氧化物。用DMD进一步氧化其中一种1-氧化物产生两种非对映异构体1,2-二氧化物和1,1-二氧化物，而另一种1-氧化物仅产生一种1,2-二氧化物。我们观察到两种 1,2-二氧化物之间的平衡。较少的

项目成果

A.Ishii, M.Saito, M.Murata, J.Nakayama: "Reaction of Dithiirane 1-Oxides with a Platinum(O) Complex"Eur. J. Org. Chem.. 979-982 (2002)

A.Ishii、M.Saito、M.Murata、J.Nakayama：“Dithiirane 1-氧化物与铂（O）络合物的反应”Eur。

Akihiko Ishii, Masashi Saito, Tetsuhiko Kawai, Masami Murata, Juzo Nakayama: "Physical and Chemical Properties of Four-Membered Bis(Triphenylphospane)platinum(II) Sulfenato Thiolato Complexes"Phosphorus, Sulfur and Silicon. vol.177. 2025-2026 (2002)

Akihiko Ishii、Masashi Saito、Tetsuhiko Kawai、Masami Murata、Juzo Nakayama：“四元双（三苯基膦）铂（II）磺基硫醇配合物的物理和化学性质”磷、硫和硅。

A.Ishii, H.Oshida, J.Nakayama: "Structure Elucidation of 6-tert-Butyl-6-phenylpentathiane Monoxides by X-ray Crystallography and DFT Calculations"Bull. Chem. Soc. Jpn.. 75. 319-328 (2002)

A.Ishii、H.Oshida、J.Nakayama：“通过 X 射线晶体学和 DFT 计算解析 6-叔丁基-6-苯基五硫烷一氧化物的结构”公牛。

H.Oshida, A.Ishii, J.Nakayama: "Oxidation of cis-3,5-Di-tert-alkyl-3,5-diphenyl-1,2,4-trithiolanes : Isolation and Some Properties of the 1-Oxides and the 1,2-Dioxides"Tetrahedron Lett.. 43. 5033-5037 (2002)

H.Oshida、A.Ishii、J.Nakayama：“顺式 3,5-二叔烷基-3,5-二苯基-1,2,4-三硫戊环的氧化：1-氧化物的分离和一些性质

A. Ishii, H. Oshida, J. Nakayama: "Structure Elucidation of 6-tert-Butyl-6-phenylpentathiane Monoxides by X-ray Crystallography and DFT Calculations"Bull. Chem. Soc. Jpn.. 75. 319-328 (2002)

A. Ishii、H. Oshida、J. Nakayama：“通过 X 射线晶体学和 DFT 计算对 6-叔丁基-6-苯基五硫烷一氧化物进行结构解析”公牛。