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2-氯丙烯硫代酰胺与二烷基乙炔二羧酸酯的新型环加成反应：二烷基 2-[4,5-双（烷氧基羰基）-2-（芳基（烷基）亚氨基）-3（2）-噻吩基] -1,3-二硫杂环戊烯-4,5-二羧酸酯的合成。

New Cycloadditon Reaction of 2-Chloroprop-2-enethioamides with Dialkyl Acetylenedicarboxylates: Synthesis of Dialkyl 2-[4,5-bis(alkoxycarbonyl)-2-(aryl{alkyl}imino)-3(2)-thienylidene]-1,3-dithiole-4,5-dicarboxylates.

机构信息

N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russia.

出版信息

Molecules. 2022 Oct 14;27(20):6887. doi: 10.3390/molecules27206887.

DOI:10.3390/molecules27206887
PMID:36296480
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9610143/
Abstract

The 1,3-dipolar cycloaddition of 1,2-dithiole-3-thiones with alkynes to form 1,3-dithioles is one of the most studied reactions in this class of polysulfur-containing heterocycles. Nucleophilic substitution of chlorine atoms in dimethyl 2-(1,2-dichloro-2-thioxoethylidene)-1,3-dithiole-4,5-dicarboxylate, which was obtained by addition one molecules of DMAD to 4,5-dichloro-3-1,2-dithiole-3-thione, led to a series of 2-chloro-2-(1,3-dithiol-2-ylidene)ethanethioamides. Cycloaddition reaction of 2-chloro-2-(1,3-dithiol-2-ylidene)ethanethioamides with activated alkynes led to the unexpected formation of 2-(thiophen-3(2)-ylidene)-1,3-dithioles via new intermediate, 1-(1,3-dithiol-2-ylidene)--phenylethan-1-yliumimidothioate. Structure of dimethyl 2-(4,5-bis(methoxycarbonyl)-2-(phenylimino)thiophen-3(2)-ylidene)-1,3-dithiole-4,5-dicarboxylate was finally proven by single crystal X-ray diffraction study. Optimized reaction conditions and a mechanistic rationale for the 1,3-dipolar cycloaddition of novel intermediate are presented.

摘要

1,2-二硫戊环-3-硫酮与炔烃的 1,3-偶极环加成反应生成 1,3-二硫戊环是这类含多硫杂环化合物中研究最多的反应之一。通过将一个 DMAD 分子加成到 4,5-二氯-3-1,2-二硫戊环-3-硫酮上，得到的二甲基 2-(1,2-二氯-2-亚乙基)-1,3-二硫戊环-4,5-二羧酸酯的氯原子的亲核取代反应，导致一系列 2-氯-2-(1,3-二硫代-2-亚乙烯基)乙硫酰胺的生成。2-氯-2-(1,3-二硫代-2-亚乙烯基)乙硫酰胺与活化炔烃的环加成反应导致通过新的中间体，1-(1,3-二硫代-2-亚乙烯基)-苯乙-1-基-1-硫代氨基甲酸盐，意外地形成了 2-(噻吩-3(2)-亚基)-1,3-二硫戊环。通过单晶 X 射线衍射研究最终证明了二甲基 2-(4,5-双(甲氧基羰基)-2-(苯基亚氨基)噻吩-3(2)-亚基)-1,3-二硫戊环-4,5-二羧酸酯的结构。提出了优化的反应条件和新型中间体的 1,3-偶极环加成反应的机理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/ddc6705513c1/molecules-27-06887-sch006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/51a144b05766/molecules-27-06887-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/30b869dfa41e/molecules-27-06887-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/7bd963684191/molecules-27-06887-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/3c36b6f39588/molecules-27-06887-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/7d6b18715687/molecules-27-06887-sch004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/253aefa94af2/molecules-27-06887-sch005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/ddc6705513c1/molecules-27-06887-sch006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/51a144b05766/molecules-27-06887-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/30b869dfa41e/molecules-27-06887-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/7bd963684191/molecules-27-06887-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/3c36b6f39588/molecules-27-06887-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/7d6b18715687/molecules-27-06887-sch004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/253aefa94af2/molecules-27-06887-sch005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7aa/9610143/ddc6705513c1/molecules-27-06887-sch006.jpg

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