Английская Википедия:Chichibabin pyridine synthesis
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The Chichibabin pyridine synthesis (Шаблон:IPAc-en) is a method for synthesizing pyridine rings. The reaction involves the condensation reaction of aldehydes, ketones, α,β-Unsaturated carbonyl compounds, or any combination of the above, with ammonia.[1] It was reported by Aleksei Chichibabin in 1924.[2][3] Methyl-substituted pyridines, which show widespread uses among multiple fields of applied chemistry, are prepared by this methodology.[4]
Representative syntheses
The syntheses are presently conduced commercially in the presence of oxide catalysts such as modified alumina (Al2O3) or silica]] (SiO2). The reactants are passed over the catalyst at 350-500 °C. 2-Methylpyridine- and 4-methylpyridine are produced as a mixture from acetaldehyde and ammonia. 3-Methylpyridine and pyridine are produced from acrolein and ammonia. Acrolein and propionaldehyde react with ammonia affords mainly 3-methylpyridine. 5-Ethyl-2-methylpyridine is produced from paraldehyde and ammonia.[5]
Mechanism and optimizations
These syntheses involve many reactions such as imine synthesis, base-catalyzed aldol condensations, and Michael reactions.
Chichibabin pyridine synthesis
Many efforts have been made to improve the method.[6][1] Conducting the reaction in the gas phase in the presence of aluminium(III) oxide.[4] zeolite (yield 98.9% at 500 K),[7]
From nitriles
Of the many variations have been explored. one approach employs nitriles as the nitrogen source. For example, acrylonitrile and acetone affords 2-methylpyridine uncontaminated with the 4-methyl derivative. In another variation, alkynes and nitriles react in the presence of organocobalt catalysts, a reaction inspired by alkyne trimerization.[5]
See also
- Chichibabin reaction
- Gattermann–Skita synthesis
- Hantzsch pyridine synthesis
- Ciamician–Dennstedt rearrangement
References
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