Studying the route of a three-component reaction of pyrrolo[3,2,1-ij]quinoline-1,2-dione with activated nitriles and resorcinol using HPLC-MS monitoring
DOI:
https://doi.org/10.17308/sorpchrom.2021.21/3780Keywords:
High-performance liquid chromatography, mass spectrometry, pyrrolo[3,2,1-ij]quinoline-1,2-dione, spiro-2-amino-4H-chromene, three-component reaction, multicomponent cascade reactionAbstract
The analysis of the composition and structure of intermediates, evaluation of the degree of conversion of reagents, identification of side products, and determining of the structure of products and the mechanisms of reactions in the liquid phase are now performed by means of their monitoring using mass spectrometry in combination with liquid chromatography. The article presents the results of HPLC-MS monitoring of a three-component cascade reaction of substituted 4H-pyrrolo[3,2,1-ij]quinoline-1,2-dione with activated nitrile (malononitrile and ethyl cyanoacetate) and resorcinol when boiled in ethanol in the presence of N-methylpiperazine as a catalyst. It also suggests a possible mechanism of this cyclocondensation.
The study determined that the route of this multicomponent process depends on the acceptor strength of the substituent in nitrile. For malononitrile, the interaction proceeds as a cascade of subsequent reactions: Knoevenagel-Michael-Thorpe-Ziegler. First, the condensation of β-carbonyl group of pyrrolo[3,2,1-ij]quinoline-1,2-dione with nitrile takes place. Then, resorcinol is added accompanied by the formation of a linear product of the three-component reaction. Further cyclisation and [1,3]-sigmatropic proton shift result in the final substituted 2-amino-7-hydroxy-2'-oxo-4'H-spiro[chromene-4,1'-pyrrolo[3,2,1-ij]quinoline]-3-carbonitrile. With a less reactive methylene component, ethyl cyanoacetate, the main cascade of reactions is accompanied by the formation of a product of attaching ethyl cyanoacetate to pyrrolo[3,2,1-ij]quinoline-1,2-dione, whose condensation with resorcinol results in a linear product of the three-component reaction. Another cascade reaction proceeds at the same time along the side route through the formation of a product of condensation of pyrroloquinolinedione with resorcinol. The latter one adds a ethyl cyanoacetate molecule and transforms through a linear product of the three-component reaction into ethyl 2-amino-7-hydroxy-2'-oxo-4'H-spiro[chromene-4,1'-pyrrolo[3,2,1-ij]quinoline]-3-carbonitrile.
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