Flavors or the very low levels of bromophenols that occur in aquacultured shrimp result in indistinet or bland flavors that lack traditional marine- or sea-like flavor notes. 10.7 DEVELOPMENT OF PROCESS OR REACTION FLAVOR VOLATILES ‘Many flavor compounds found in cocked or processed foods occur asthe result of reactions common (o all types of foods regardless of whether they are of animal, plant or microbial derivation. These reactions take place when suitable reactants are present and appropriate conditions (heat, pH, ligh!) exist, Process or reaction flavors are discussed separately in this section because of their broad importance to all foods, and because they comprise a large volume of natural flavor concentrates that are used widely in foods, especially when meat or savory flavors are desired, Related information ‘can be found in discussions dealing with carbohydrates (Chapter 3), lipids (Chapter 4) and vitamins (Chapter 7). 10.7.1 THERMALLY INDUCED PROCESS FLAVORS ‘Traditionally, these flavors have been broadly viewed as products from browning reactions because of eatly discoveries showing the role of reducing sugars and amino compounds in the induction of a process that ultimately leads to the formation of brown pigments (see Chapters 3 and 4 for deuils of Maillard browaing reactions). Although browning reactions are almost always involved in the development of process flavors in foods, the interactions between products of the browning reaction and other food constituents are also important and extensive, By taking a broad approach to discussions of thermally induced flavors, the aforementioned interactions, as well as reactions that occur following heat treatment, can be appropriately considered. Although many of the compounds associated with process favors possess potent and pleasant aromas, relatively few of these compounds seem to provide truly distinguishing characterimpact flavoretects. Instead they often consibute general nutty, meaty roasted toasted, burnt, floral, plant, or caramel odors. Some process flavor compounds are acyclic, but many ate heterocyclic, with nitcogen, sulfur, o oxygen substituents common (Figure 10.32). These process flavor compounds occur in many foods and beverages, such as roasted meats, boiled meats, cafe, roasted nuts, bee, bread, crackers, snack foods, cocoa, and most other processed foods. The distribution of individual compounds, however, depends on factors such asthe availablity of precursors, temperature, time, and water activity Production of process flavor concentrates is accomplished by selecting reaction mixtures and conditions so that those reactions occurring in normal food processing are duplicated. Selected ingredients (Table 10.5), usually including a reducing sugar, amino acids, and compounds with sulfur atoms, are processed under elevated temperatures to produce a distinctive profile of flavor compounds [35]. Thiamine isa popular ingredient because it provides both nitrogen and sulfur atoms already in ring structures (see Chapter 7) ‘Because of the large number of process flavor compounds produced during normal food pro- cessing or process simulation, itis unrealistic to cover the chemistry oftheir formation in depth. Rather, examples are given to illustrate some of the more important flavor volatiles formed and the mechanisms of their formation, Alkyl pyrazines were among the first compounds tobe recognized as important contributors othe flavors ofall roasted, toasted or similarly thermally processed foods. ‘The most direct route to their formation results from the interaction of a-dicarbonyl compounds (intermediate products in the Mallard reaction) with amino acids through the Strecker degrada- tion reaction (Figure 10:33). Transfer ofthe amino group to the dicarbonyl provides a means for Integrating amino acid nitrogen into small compounds destined for any ofthe condensation reaction sechanisms envisioned in these reactions. Methionine has been selected asthe aminoacid involvedoe Fennema’s Food Chemistry C 4 “yf ) ) aU UO YUL FIGURE 10.32 Some heterocyclic molecular skeletons found commonly in flavor compounds associated ‘with thermally induced or browning favors. TABLE 10.5, Some Common Ingredients Used in Process Flavor Reaction Systems for the Development of Meat-like Flavors Hiydrolyzed Vegetable Protein Thiamine ‘Yeast atoysste Cysteine Beef exit Giutathione Specte animal fats ose (Chicken et solids Arsbinote Giyeerat 5 -Ribonueleotides ‘Monosodium gloamate Methionine in the Strecker degradation reaction because it contains a sulfur atom and it leads to formation of ‘methional, which isan important character-impact compound in boiling potatoes and cheese-cracker flavors. Methional also readily decomposes further to yield methanethiol (methyl mercaptan) that oxidizes to dimethyl disulfide, thus providing a source of reactive, low molecular weight sulfur ‘compounds that contribute to the overall system of flavor development. Hydrogen sulfide and ammonia are very reactive ingredients in mixtures intended for the devel- ‘opment of process flavors, and they are often included in model systems and assist in promoting certain reaction mechanisms, Thermal degradation of cysteine (Figure 10.34) yields both ammonia and hydrogen sulfide as well as acetaldehyde. Subsequent reaction of acetaldehyde with a mercaplo derivative of acetoin (from the Maillard reaction) gives rise to thiszoline that contributes to the flavor of boiled beef [57] Some heterocyclic favor compounds are quite reactive and tend to degrade or interact further ‘with components of foods or reaction mixtures. An interesting example of flavor stability and carry through in foods is provided by the compounds shown in Equation 10.2, both of which provideFlavors oo Reducing sugars Caranetzaion he 20 tee SORBET 21 \e/Voon I Merionine degradston HAP HS. cup cig ie HHsc-cH,-c-C—oHy rig oF ScHy wot Len, (aninectoony)| Seis” | ° eoctnn Nay YE ONG 60 EM ‘eh bateapntote seen) || (0s oo Ngis7 N’ * Dineb 25:Dmetyh on sebyiprese (ecm ou goatee Sine, FIGURE 10.33 Formation ofan alkyl pyrazine and small sulfur compounds through reactions occuring in the development of process favors thems F A A segadaton Sa Nd ony 5 cop We "'Coon cystine ¢ oH 9 wye—bbiow, 6 es Fae Te Ebay 245-Tomethyt ‘hazaline FIGURE10.34 Formation of thiazoline oundin cooked beef through the and sugar-amino browning, ction of fragments fromeysteine distinct, but different meat-like aromas [20]. A roasting meat aroma is exhibited by su s— 2 — ut wy (10.2) oH oP Os HONG. 2alotyatanbl say uni ele 2-methyl-3-furanthiol (reduced form), but upon oxidation to the disulfide form, the flavor becomes mote characteristic of fully cooked meat that has been held for some time, Chemical reactions, such as the one just mentioned, are responsible for the subtle changes in meat flavor that ‘occur because of the degree of cooking and the time interval alter cooking, During processing of complex systems, sulfur as such, or as thiols or polysulfides, can be incorporated in various compounds, resulting in the generation of new flavors, However, even680 Fennema’s Food Chemistry we omc) ge \o/V soon Bonnnastl 2 Veoo Neen S-Metnylmethionine a” Hso7 o “aes FIGURE 10.35 Formation of dimethyl sulfide from thermal degradation of S-methylmethionine sulfonium salt, gen vt chs ‘oe ° ate! orator oyettenes ee) Oyo Heo wh Sy wed es, HAAS OHS Metnk 401.250 20H-4 5 Dinety Sietranone ‘t2Hitranone 25Dhysrotuar-one ‘tuaneoi, aagarteanone) FIGURE 10.36 Structures of some important caramel-like favor compounds derived from reactions occurring during processing ‘though dimethyl sulfide is often found in processed foods, it does not react readily. In plant foods, dimethyl sulfide originates from biologically synthesized molecules, especially S-methylmethionine sulfonium sats (Figure 10.35). S-Methylmethionine salts are quite labile to heat, and dimethyl sulfide is readily released during cooking. In the case of plant-derived foods, dimethyl sulfide provides especially characterizing top notes to the flavors of freshly boiled and canned sweet com as well as to tomato juice and other cooked tomato products. ‘Some of the most pleasant aromas derived from process reactions are provided by the compounds shown in Figure 10.36. These compounds exhibit caramel-like aromas and have been found in many. processed foods. Cyclotene is used widely asa synthesized maple syrup flavor substance, and maltol is used widely as a flavor enhancer for sweet foods and beverages (Section 10.2.6). 4-Hydroxy-2,5- ddimethyl-3(2H)-furanone (Furaneol) is sometimes known as the “pineapple compound” because it ‘was first isolated from processed pineapple, where it contributes strongly to its characteristic flavor. Furancol is also produced in biological systems, and it contributes a very ripe strawberry note that can, be detected over freshly picked fruit, 3-OH-4,5-Dimetbyl-2,5-dihydrofuran-2-one is often referred as sugar faranone because its highly characterizing aroma can casily be detected in the gases above bulk refined sugars (sucrose). Additionally, furanones are found in cooked meats, such as boiled beef, where they apparently enhance meatiness. ‘The planar enol-cyclic-ketone structure for the compounds shown in Figure 10.36 is typic~ ally derived from the sugar precursors, and this structural component appears responsible for their ccaramel-like aroma quality [61]. As shown in Equation 10.3 for maltol, the planar enolone form isFlavors 681 ‘herp 2enenal FIGURE 10.37 Formation of an important cocoa toma Volatile through an aldol condensation of wo Stwecket reaction-derived aldehydes largely favored over the cyclic diketone form because the enolone form allows strong intramolecular H-bonding to occur : (Stable orton fom) ‘The flavor of chocolate and cocoa has received much attention because of the high demand for these flavors. After harvesting, cocoa beans are often fermented under somewhat poorly controlled conditions. The beans are then roasted, sometimes with an intervening alkali treatment that darkens the color and yields a less harsh flavor. The fermentation hydrolyzes sucrose to reducing sugars, frees amino acids, and oxidizes some polyphenols. During roasting, many pyrazines and other heterocy. lics are formed, but the unique flavor of cocoa is derived from an interaction between aldehydes from the Strecker degradation reaction, The reaction shown in Figure 10.37 between phenylacetaldehyde (dom phenylalanine) and 3-methylbutanal (from leucine) constitutes an important flavor-forming reaction in cocoa. The product of this aldol condensation, S-methyl-2-phenyl-2-hexenal, exhibits a character-impact persistent chocolate aroma. This example also serves to show that reactions in the development of process flavors do not always yield heterocyclic aroma compounds. 10.7.2. VoLanites DeRiven FROM OXIDATIVE CLEAVAGES OF Carorenoms (Oxidations focusing on tiacylglycerols and faty acids were discussed in previous sections, but some extremely important flavor compounds that are oxidatively derived from carotenoid precursors have not been covered and deserve mention here. Some of these reactions requite singlet oxygen through chlorophyll sensitization; others are photooxidation processes. A large number of flavor compounds, derived from oxidizing carotenoids (orisoprenoids), have been identified in curing tobacco [18], and many of these are considered important for characterizing tobacco flavors, However, relatively few compounds in this category (three representative compounds are shown in Figure 10.38) are currently considered highly important as food flavors, Each of these compounds exhibits unique sweet, floral, and fruit-like characteristics that vary greatly with concentration. They also blend nicely with aromas of foods to produce subtle effects that may be highly desirable or very undesirable. f-Damascenone exerts very positive effects on fresh apple aromas. It also enhances the flavor of wines, but in beer this compound at only a few parts per billion results ina stale, raisin-like note, B-Tonone also exhibits pleasant violet, floral aroma compatible with frit-type flavors, but itis also the principal off-lavor compound present in oxidized, freeze-dried carrots. Furthermore, these compounds have been found inbblack tea, where they make positive contributions tothe flavor. Theaspirane and related derivatives