Reaction flavors sulfide

Sulfur Compounds of Beef Flavor. Methional, which results from the degradation of methionine, is an important contributor to flavor in meat. Thiolanes, formed during the cooking of beef, have peculiar oniony flavors that also augment the quality of the meaty flavor. Thiophenes and thiofurans are also important to meaty flavors. Sulfides, such as methyl sulfide, are oxidized to methyl sulfoxide and methyl sulfone. Condensation reactions of Maillard browning products also result in thiazoles such as benzothiazole, an important component of meat flavor. 

Recent reaction flavor work in our labs has lead to a recently GRAS listed material, natural 4-Mercapto-4-methyl-2-pentenone (FEMA 3997), from the reaction of natural Hydrogen Sulfide and natural 4-Methyl-3-penten-2-one (equation 12). While the flavor descriptors in the literature vary from catty, buchu, black currant, broom tree to cassis, we have found the material to have a meaty, Chinese pork type of flavor when used in savory applications. 

Mixed sulfides are prepared in the flavor industry by the reaction of thiols, 2inc oxide, and a bromoalkane (39). Some of these mixed sulfides are constituents of allium, asafetida, coffee, and meat flavors. A representative reaction is represented in equation 24. 

Ammonium sulfide, reaction with aldehydes with and without acetoin, 36-54 Animal fat, role in flavor of cook meat, 118... 

Cheese is ripened for 6 months to 1 year or longer at 5° to 15°C and 70-75% relative humidity. Cheese ripening is a complex process involving a combination of chemical, biochemical, and physical reactions. Proteolytic enzymes, e.g., rennet and lactic starter culture enzymes, hydrolyze caseins to produce flavor compounds and proper body. Lipase and lactase enzymes also hydrolyze their respective substrates to produce a large number of characteristic flavor compounds (Reiter and Sharpe 1971 Harper 1959 Law 1981 Schmidt etal. 1976), including free fatty acids, methanethiol, methanol, dimethyl sulfide, diacetyl, acetone, and others (Moskowitz 1980). 

Many desirable meat flavor volatiles are synthesized by heating water-soluble precursors such as amino acids and carbohydrates. These latter constituents interact to form intermediates which are converted to meat flavor compounds by oxidation, decarboxylation, condensation and cyclization. 0-, N-, and S-heterocyclics including furans, furanones, pyrazines, thiophenes, thiazoles, thiazolines and cyclic polysulfides contribute significantly to the overall desirable aroma impression of meat. The Maillard reaction, including formation of Strecker aldehydes, hydrogen sulfide and ammonia, is important in the mechanism of formation of these compounds. 

It is precisely to the production of meatlike flavors that the great majority of patents based on the Maillard reaction have been directed. Mos of them indicate cysteine or cystine as the essential sulfur-containing compound. Other patents claim alternative sources for sulfur, e.g., derivatives of mercaptoacetaldehyde (36), mercaptoalkylamines (37), S-acetylmercaptosuccinic acid (38), 2-thienvltetrasulfide (39), "a sulfide" (40), and hydrogen sulfide (heated with aqueous xylose without any amino acid) (41). 

Finally, heating of amino acids can produce volatiles Including aldehydes, amines and hydrogen sulfide. One minor, but Important, flavor generating pathway Involves the Strecker degradation of an amino acid as shown in Figure 2. In this reaction, an alpha amino acid reacts with an alpha dicarbonyl at an elevated temperature to produce an aldehyde (one carbon less than the amino acid) as well as an alpha amino ketone. These products can react further to yield Important heterocyclic aroma chemicals such as pyrazines, thlazoles, and dihydrofuranones. 

Many individual flavor chemicals which were isolated and identified from Maillard "side reactions" have been reported in the patent literature. It is evident from these patents that much work has been done to glean specific flavor chemicals from the complexities of the Maillard reaction. 3-Furyl alkyl sulfide, disulfide, and 0-chalcogenalkyl sulfide derivatives are claimed to provide bloody, meaty, and roasted notes to beef broth and beef products (64-66). 3-Methylcyclopent-2-en-l-one was declared for its flavor eiiEancement of beef bouillon (67). Firmenich claimed 2,6-dimethyl-2-octenal and its analogs as possessing meat flavor qualities (68). A method to produce disulfides for application to meat and savory flavors was patented (69). 

These reactions can lead to the formation of numerous heterocyclics associated with meat flavor as described by Vernin and Parkanyi (57), including furans, thiophenes, pyrroles, oxazoles, imidazoles, thiaz-oles, pyrans, pyridines, pyrazines, cyclic sulfides and polysulfides. 

Heterocyclic compounds are dominant among the aroma compounds produced in the Maillard reaction, and sulfur-containing heterocyclics have been shown to be particularly important in meat-like flavors. In a recent review, MacLeod (6) listed 78 compounds which have been reported in the literature as possessing meaty aromas seven are aliphatic sulfur compounds, the other 71 are heterocyclic of which 65 contain sulfur. The Strecker degradation of cysteine by dicarbonyls is an extremely important route for the formation of many heterocyclic sulfur compounds hydrogen sulfide and mercaptoacetaldehyde are formed by the decarboxylation and deamination of cysteine and provide reactive intermediates for interaction with other Maillard products. 

A mechanism has been reported for the formation of trithlolane from the reaction of aldehydes with hydorgen sulfide (51). The identification of 3-methyl-5-butyl-l,2,4-trithiolane and 3-methyl-5-pentyl-1,2,4-trithiolane in food flavor suggests that pentanal and hexanal were Involved in the formation of these compounds (Figure 5). Pentanal and hexanal are major thermal and oxidative decomposition products of lipids. 

DHA can be reduced to RAA by chemical agents, such as hydrogen sulfide or enzymatically, by dehydroascorbic acid reductase. The conversion of DHA to diketogulonic acid (DKG) is irreversible and occurs both aerobically and anaerobically, particularly during heating. This reaction results in loss of biological activity. The total oxidation of RAA may result in the formation of furfural by decarboxylation and dehydration. With subsequent polymerization, the formation of dark-colored pigments results. These compounds affect the color and flavor of certain foods, such as citrus juices, and decrease nutritive value. 

Van den Ouweland, G. A.M. Components contributing to beef flavor. Volatile compounds produced by the reaction of 4-hydroxy-5-methyl-3(2//)-fiiranone and its thio analog with hydrogen sulfide. J. Agric. Food Chem. 1975, 23, 501-505. 

The Maillard reaction plays an important role in flavor development, especially in meat and savory flavor (Buckholz, 1988). Products of the Maillard reaction are aldehydes, acids, sulfur compounds (e.g., hydrogen sulfide and methanethiol), nitrogen compounds (e.g., ammonia and amines), and heterocyclic compounds such as furans, pyrazines, pyrroles, pyridines, imidazoles, oxazoles, thiazoles, thiophenes, di- and trithiolanes, di- and trithianes, and furanthiols (Martins et al., 2001). Higher temperature results in production of more heterocyclic compounds, among which many have a roasty, toasty, or caramel-like aroma. 

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