Synthesis of new substituted pyridines via Vilsmeier-Haack reagent

Q4 Chemistry

Voprosy Khimii i Khimicheskoi Tekhnologii Pub Date : 2023-03-01 DOI:10.32434/0321-4095-2023-146-1-34-39

N. Smetanin, S. Varenichenko, A. V. Kharchenko, O. Farat, V. Markov

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Abstract

New substituted pyridines were synthesized by the reaction of spiroimidazolidinones with the Vilsmeier-Haack reagent (PBr3/DMF) with satisfactory yields. The reaction proceeds as an electrophilic trigger process according to the push-pull mechanism due to the anomeric effect of two nitrogen atoms with an increase in the primary heterocycle. An explanation is proposed for the different chemical behavior of 5',6',7',8'-tetrahydro-1'H-spiro[cyclohexane-1,2'-quinazolin]-4'(3'H)-one and spiroimidazolidinones under Vilsmeier-Haack reaction conditions. The likely reason is the hybridization of the amine (enamine) nitrogen atom in the structure of heterocycles. The reaction of spiroimidazolidinones with the Vilsmeier-Haack reagent results in formylation of the ammine nitrogen atom with subsequent reaction steps; and in the case of 5',6',7',8'-tetrahydro-1'H-spiro[cyclohexane-1,2'-quinazolin]-4'(3'H)-one, the reaction results in formylation of carbon atom followed by heterocycle opening and its intramolecular cyclization. The synthesized new pyridine derivatives, due to the presence of several reaction centers in them, are of interest not only as potential pharmacologically active compounds, but also as low-molecular building blocks for organic synthesis.

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用维斯迈耶-哈克试剂合成新取代吡啶

以螺咪唑烷酮为原料，在Vilsmeier-Haack试剂(PBr3/DMF)的催化下合成了新的取代吡啶。随着原生杂环的增加，由于两个氮原子的异构效应，反应按照推拉机制进行亲电触发过程。对5'，6'，7'，8'-四氢-1' h -螺[环己烷-1,2'-喹唑啉]-4'(3'H)- 1和螺咪唑烷酮在Vilsmeier-Haack反应条件下的不同化学行为进行了解释。其原因可能是杂环结构中胺(烯胺)氮原子的杂化。螺咪唑烷酮与Vilsmeier-Haack试剂反应后，氨基氮原子甲酰化;对于5'，6'，7'，8'-四氢-1' - h -螺[环己烷-1,2'-喹唑啉]-4'(3'H)- 1，反应的结果是碳原子甲酰化，杂环开环和分子内环化。所合成的新的吡啶衍生物，由于其中存在几个反应中心，不仅是潜在的药理活性化合物，而且是有机合成的低分子基础。

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来源期刊

Voprosy Khimii i Khimicheskoi Tekhnologii Chemical Engineering-Chemical Engineering (all)

CiteScore

0.90

自引率

0.00%

发文量

期刊介绍： Voprosy Khimii i Khimicheskoi Tekhnologii (Issues of Chemistry and Chemical Technology) is published bimonthly by the Ukrainian State University of Chemical Technology and accepts Ukrainian- or English language high-quality original articles and reviews concerning various fields of research in chemistry and chemical engineering. Our unusual title “Voprosy khimii i khimicheskoi tekhnologii” originates from the transliterated initial Russian title “Issues of Chemistry and Chemical Technology“. The fact of the matter is that Voprosy khimii i khimicheskoi tekhnologii was founded in 1965 as a scientific journal mainly for Russian-reading and Russian-speaking readership when «the Iron Curtain» existed. Since 1991, after Ukraine declared its independence, our Journal began to publish the articles in Ukrainian and English. Multilingualism is our established tradition. We remember and cherish our traditions, but we follow the latest trends in modern science. Papers that are multidisciplinary or address new or emerging areas of chemistry and chemical engineering are particularly encouraged. Thus, the scope is dynamic. It includes but is not limited to the traditional areas of general, inorganic, organic, analytical, physical chemistry and electrochemistry, as well as all conventional areas of chemical engineering (chemistry of high molecular compounds, technology of inorganic and organic substances, processing of combustible minerals, chemical technology of silicates, processes and apparatus of chemical productions, etc.). The Journal publishes papers dealing with newer interdisciplinary areas such as materials science, nano-science, catalysis, computational and theoretical chemistry, surface phenomenon and colloidal systems, environmental chemistry, green chemistry.