Bifunctional basic ionic liquid and water-phase catalytic synthesis of substituted pyridinium compound by using same

Abstract

The invention discloses a bifunctional basic ionic liquid and a novel water-phase catalytic synthesis method of a substituted pyridinium compound by using the same. In the method, a used catalyst is the bifunctional ionic liquid simultaneously containing a Lewis base and a Bronsted base; aromatic aldehyde, malononitrile and a sulfhydryl compound are used as raw materials; water is used as a reaction medium; and a multi-substituted pyridinium compound is obtained through catalytic synthesis. Compared with the prior art, the invention has the following advantages: (1) the raw materials are wide in sources, the preparation process is convenient, and the double-base catalyst has high activity, is hydrostable and can not be deactivated; (2) the reaction can be performed at room temperature, thereby ensuring that the conditions are mild; (3) the water solution containing the catalyst can be recycled and is environment-friendly; and (4) water is used instead of an organic solvent, thereby achieving environment and economic double benefits. Thus, the synthesis method of a multi-substituted pyridinium compound is efficient and environment-friendly, and is beneficial to large-scale industrial production.

Description

a technical field [0001] The invention relates to a dual-functional alkaline ionic liquid and a new method for synthesizing substituted pyridine compounds through water-phase catalysis, and belongs to the technical field of chemical material preparation. This method is suitable for the occasion of synthesizing multi-substituted pyridine compounds with aromatic aldehydes, malononitrile and mercapto compounds as raw materials. Two background technology [0002] Multi-substituted pyridine compounds are an important class of drug intermediates. Their skeleton structures are widely found in many natural compounds with biological activity. They are intermediates for the synthesis of various drugs. Different spatial structures show different biological activities. The 6-substituted thiol-2-amino-3,5-dicyanopyridine compound obtained by introducing a mercapto compound at the 6-position of its pyridine ring has antitumor, antiviral, antibacterial, anti-inflammatory and anti-HIV effec...

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Problems solved by technology

These methods have the following one or more disadvantages: low yield, many side reactions; complex catalyst preparation process; catalyst can not be recycled; serious equipment corrosion; complex operation process; only suitable for laboratories or Small-scale operation, no large-scale industrial application, etc.

Ranu etc. used [BMIM]OH to catalyze aromatic aldehydes, malononitrile, and mercapto compounds to synthesize 6-substituted thio-2-amino-4-phenyl-3,5-dicyanopyridines (Ranu, B.C.; Jana, R.; Sowmiah, S.J.Org.Chem.2007, 72, 3152-3154), but subsequent research shows that the ionic liquid catalyst used in this method has poor stability and is very easy to decompose. The rate is only 25-35% (Guo, K.; Chen, B.N.J.Org.Chem.2009, 74, 6999-7006); domestic researchers found that in ionic liquid 1-n-butyl-3-methylimidazolium tetrafluoroboric acid salt ([bmim]BF 4 ) medium, reacted at 50°C to obtain 2-amino-4-phenyl-6-(phenylthio)-3,5-dicyanopyridine derivatives (Tian, ​​J.J.; Guo, H.Y.Chin. J.Org.Chem.2012, 32, 193-196)

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