Synthesis, Property, and Reactivity of Novel π-Electron System Linked with Hetero Atoms

杂原子连接的新型π电子体系的合成、性质和反应性

• 批准号: 10640527
• 负责人: SHIMIZU Toshio
• 金额: $ 1.86万
• 依托单位: TOKYO METOROPOLITAN UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640527/
• 关键词: Organic Sulfur Compound; Unsaturated Cyclic Compound; 1,2-Dithiete; 1,2,5,6-Tetrathiocin; Disulfide Bond; Crystal Structure; Ring Conversion Reaction; Hetero Diels-Alder Reaction; 1,2-ジチェット; ジスルフィド結合

3,4-Bis(methoxycarbonyl)-1, 2-dithiete (1), 3,4,7,8-tetra(methoxycarbonyl)-1,2,5,6-tetrathiocin (2), and (Z,Z,Z,Z)-3,4,7,8,11,12,15,16-octa(methoxycarbonyl)-1,2,5,6,9.10,13,14-octathiacyclohexadeca-3,7,11,15-tetrraene (3) were synthesized by oxidation of corresponding titanocene dithiolene complex with sulfuryl chloride, and the crystal structures of 1 and 2 were characterized by X-ray crystallographic analysis which revealed planar and twist geometries, respectively. Hydrogen-substituted tetrathiocim 4 and sixteen-membered cyclic compound 5 were also obtained by oxidation of the corresponding dithiolate or dithiolene complex. 1,2-Dithiete 1 underwent tetramerization selectively to give sixteen-membered cyclic compound 3 even at room temperature. Ring conversion reactions also proceeded among the four-, eight-, and sixteen-membered unsaturated cyclic compounds possessing disulfide linkage under various conditions, such as in polar solvent or in the presence of silica-gel. The ring-size … More selectivity of these ring conversion reactions was studied using ab initio molecular orbital calculations. Reactions of 1,2-dithiete 1 with various alkenes or alkynes formed 2,3-dihydro-1,4-dithiins of thiophenes, respectively. The reactions with alkenes were stereospecific, which indicates the concerted reaction between 1,2-dithione 6, valence isomer of the 1,2-dithiete, and the dienophiles. Theoretical study confirmed the reactions of & with alkenes and alkynes are reverse electron demand hetero Diels-Alder reaction. The MO calculations showed the 1,2-dithiete 1 was 5.8 kcal molィイD1-1ィエD1 more stable than the corresponding ehane-1, 2-dithione 6, and the tautomerizaion energy between the 1,2-dithiete and the ethane-1, 2-dithione was also calculated to be 28.5 kcal molィイD1-1ィエD1 from the 1,2-dithiete, which suggests the tautomerization from 1,2-dithiete 1 to ethane-1, 2-dithioe 6 is possible at least at high temperature. Reaction of 1,2,5,6-tetrathiocim 2 or sixteen-membered cyclic compound 3 with ethyl vinyl ether also formed the 2,3-dihydro-1,4-dithiin derivative, which is the same compound obtained by the reaction of 1,2-dithiete 1 with the ether. Tetrathiocin 2 and sixteen-membered cyclic compound 3 also reacted with diphenylacetylene to give the thiophene derivative. Less

合成了3，4-二(甲氧基羰基)-1，2-二硫杂环戊二烯(1)、3，4，7，8-tetra(methoxycarbonyl)-1，2，5，6-tetrathiocin(2)和(Z，Z)-3，4，7，8，11，12，15，16-octa(methoxycarbonyl)-1，2，5，6，9.10，13，14-octathiacyclohexadeca-3，7，11，15-tetrraene)(3)，并用X-射线单晶衍射法对其结构进行了表征。氢取代的四硫代环化合物4和16元环状化合物5也是通过相应的二硫代硫酸盐或二硫代烯化合物氧化得到的。1，2-二硫杂环戊二烯1在室温下仍选择性地进行四聚反应，得到十六元环化合物3。具有二硫键的四元、八元和十六元不饱和环状化合物也可以在不同的条件下进行环转化反应，例如在极性溶剂中或在硅胶存在下。环形大小的…用从头算分子轨道计算方法研究了这些环转化反应的选择性。1，2-二硫杂环戊二烯分别与不同的烯烃或炔烃反应生成2，3-二氢-1，4-二硫杂环戊二烯。与烯烃的反应是立体专一性的，这表明1，2-二硫杂环的价异构体1，2-二硫酮6与双烯基团发生了协同反应。理论研究证实了&与烯烃和炔烃的反应是电子需求相反的Diels-Alder反应。分子轨道计算表明，1，2-二硫杂环己烷1比乙烷-1，2-二硫杂环己烯6更稳定，1，2-二硫杂环己烷与乙烷-1，2-二硫杂环己烷之间的互变异构化能为28.5kcalィイd1-1ィエd1，表明1，2-二硫杂环己烷与乙烷-1，2-二硫杂环己烷的互变异构化至少在高温下是可能的。1，2，5，6-四硫杂环化合物2或16元环状化合物3也与乙基乙烯基醚反应生成2，3-二氢-1，4-二硫杂环戊烷衍生物，该化合物与1，2-二硫杂环戊烷与乙基乙基醚反应得到的化合物相同。四硫杂环化合物2和十六元环化合物3还与二苯乙炔反应得到了噻吩衍生物。较少

项目成果

T. Shimizu K. Sakamaki, D. Miyasaka, N. Kamigata: "Preparation and Reactivity of 1,3-Bis(alkylthio)-allenes and Tetrathiacyclic Bisallenes"J. Org. Chem.. 65 in press. (2000)

T. Shimizu K. Sakamaki、D. Miyasaka、N. Kamigata：“1,3-双(烷硫基)-丙二烯和四硫环双三烯的制备和反应性”J。

T. Shimizu, h. Murakami, Y. Kobayashi, K. Iwata, N. Kamigata: "Synthesis, Structure, and Ring Conversion of 1,2-Dithiete- and Related Compounds"J. Org. Chem.. 63. 8192-8199 (1998)

T.清水，h。

T. Shimizu, H. Murakami, N. Kamigata: "Reaction of 1,2-Dithiete with Alkenes and Alkynes: Experimental and Theoretical Study"J. Org. Chem.. 64. 8489-8494 (1999)

T. Shimizu、H. Murakami、N. Kamigata：“1,2-二硫醚与烯烃和炔烃的反应：实验和理论研究”J。

Toshio Shimizu: "Reaction of 1,2-Dithiete with Alkenes and AlKynes : experimental and Theoretical Study"The Journal of Organic Chemistry. 64(23). 8489-8494 (1999)

Toshio Shimizu：“1,2-二硫醚与烯烃和炔烃的反应：实验和理论研究”有机化学杂志。

Toshio Shimizu: "Synthesis, Structure, and Ring Conversion of 1,2-Dithiete and Related Compounds"The Journal of Organic Chemistry. 63(23). 8192-8199 (1998)

Toshio Shimizu：“1,2-二硫醚及相关化合物的合成、结构和环转化”有机化学杂志。