Review on the Synthesis of Pyrazine and Its Derivatives

Abstract

Pyrazine is a kind of natural product which can be found in plants, animals, insects, marine organisms andmicroorganisms. The main function of pyrazine in living organisms is used as flavor of the raw foods. Pyrazine and its derivatives were also produced in industries mainly for fragrance, flavor and pharmaceutical applications. This review describes the historical development of pyrazine including the discovery and synthesis, to the recent synthetic approach of pyrazinium. In general, six synthetic approaches namely condensation reaction, ring closure, metal catalysis, green reaction, Maillard reaction and acid catalyst on N-substitution have been reviewed in this paper. The first five approaches are mainly aimed for the substitution at 2, 3, 5 and 6 positions in pyrazine ring, whereas the last approach is specifically for 1 and 4 positions in pyrazine.
 Keywords: Diazine, pyrazine, and Maillard reaction

Semibiocatalytic Approach toward Regioisomerically Enriched Ethyl Dimethylpyrazines Important in Flavor Industries

“…Also, the commercially available mixtures of 7 and 8 were chromatographically separated to show that each distinctly affected the behavioral response of fire ants in an electroantennogram study . Given the broad chemosensory application of EDMPs, several accounts highlight industrial syntheses and separation of these commodity compounds to address production bottlenecks. − …”

“…Today, AlkPyrs are assembled synthetically by condensation between dicarbonyls and diamino compounds (Scheme A) or biosynthetically between self-condensation of an aminocarbonyl ( 19 ), followed by oxidation on the proposed biosynthetic pathway to 325-EDMP ( 8 ) in Serratia marcescens (Scheme B). , Recently, 325-EDMP ( 8 ) was discovered as an active component with potential for plant disease management against oomycete pathogens . Given this broad chemosensory and potential antimicrobial applications of AlkPyrs, several studies highlight the synthesis and separation of these commodity chemicals. − For a while, natural EDMP isomers were thought to be available only as mixtures by extraction from resources, such as coffee beans, raw plants, vegetables, fish, poultry, and beef …”

“…If regioisomeric AlkPyrs are used as food additives, additional resources for accessing them as single isomers are desirable. AlkPyrs are often assembled synthetically by condensation between dicarbonyls and diamino compounds, where the symmetry in one reagent gives the best isomeric selectivity on the route to pyrazines . Several regiocontrolled condensation reactions have been aided by altering the metal catalysts or changing the organic solvent.…”

Catalytic transformations of glycerol via hydroxyacetone into nitrogen heterocycles of industrial interest

“…A number of old organic methodologies for synthesising pyrazine and its derivatives were reported more than two centuries ago. The self-condensation of α-ketoamines or the combination of α-diketones with vicinal diamines followed by dehydrogenation are among the oldest synthesis reactions to produce pyrazines that continue to be exploited [320].…”

“…Moreover, Park et al concluded that the cyclization of propylene glycol and ethylenediamine to give 2-methylpyrazine using CuO-ZnO-SiO2 catalyst showed outstanding results (84% of 2-metylpyrazine yield at ≈99% conversion) attributed to the combined effect of the dehydrogenation properties of CuO-SiO2 and the cyclization properties of ZnO-SiO2 [326]. Other catalytic systems with limited data in reference patents are based on copper-chromium, copper-zinc-chromium, or zinc phosphates with manganese [320]. In the same line, R. Anand et al reported the reaction of ethylenediamine and propylene glycol over ZnO-modified FER [327] and ZnO-modified ZSM-5 [328] catalysts, achieving yields close to 65% when working with an excess of ethylenediamine at 450 ºC.…”