Strecker degradation reaction

It has been found that AAs do not react with 3,4-disubstituted o-benzo-quinones in the expected Strecker degradation reaction instead, a decar-boxylative condensation reaction afforded the corresponding benzoxazoles. A mechanistic explanation has been advanced for this transformation. It should be mentioned, however, that other quinones or diones did not react in the described manner (78JOC509). 

Figure 2. Strecker degradation reactions and products. (Reprinted with permission from ref. 13. Copyright 1976 Marcel Dekker.)...

Phospholipids contribute specific aroma to heated milk, meat and other cooked foods through lipid oxidation derived volatile compounds and interaction with Maillard reaction products. Most of the aroma significant volatiles from soybean lecithin are derived from lipid decomposition and Maillard reaction products including short-chain fatty acids, 2-heptanone, hexanal, and short-chain branched aldehydes formed by Strecker degradation (reactions of a-dicarbonyl compounds with amino acids). The most odor-active volatiles identified from aqueous dispersions of phosphatidylcholine and phos-phatidylethanolamine include fra 5 -4,5-epoxy-c/5-2-decenal, fran5,fran5-2,4-decadienal, hexanal, fra 5, d5, d5 -2,4,7-tridecatrienal (Table 11.9). Upon heating, these phospholipids produced cis- and franj-2-decenal and fra 5-2-undecenal. Besides fatty acid composition, other unknown factors apparently affect the formation of carbonyl compounds from heated phospholipids. 

Aroma development during fermentation is accompanied by an increase in the volatile compounds typical of black tea. They are produced by Strecker degradation reactions of amino acids with oxidized flavanols (Formula 21.7) and by oxidation of unsaturated fatty acids and the caroti-noid neoxanthin. 

The first group contains compounds produced in the early stages of the reaction by the breakdown of the Amadori or Heynes intermediates, and includes similar compounds to those found in the caramelisation of sugars. Many of these compounds possess aromas that could contribute to food flavour, but they are also important intermediates for other compounds. The second group comprises simple aldehydes, hydrogen sulphide or amino compounds that result from the Strecker degradation occurring between amino acids and dicarbonyl compounds. 

Hydrogen sulphide is a key intermediate in the formation of many heterocyclic sulphur compounds. It is produced from cysteine by hydrolysis or by Strecker degradation ammonia, acetaldehyde and mercaptoacetaldehyde are also formed (Scheme 12.4). All of these are reactive compounds, providing an important source of reactants for a wide range of flavour compounds. Scheme 12.6 summarises the reactions between hydrogen sulphide and other simple intermediates formed in other parts of the Maillard reaction. 

Figure 232 Strecker degradation of L-valine by reaction with 2,3-butadione.

Both the ninhydrin reaction and pyridoxal phosphate-catalyzed decarboxylation of amino acids (Chapter 14) are examples of the Strecker degradation. Strecker reported in 1862 that alloxan causes the decarboxylation of alanine to acetaldehyde, C02, and ammonia.c... 

Two branches of the above reaction pathways provide active reagents for the degradation of a-amino acids to aldehydes and ketones of one less carbon atom (Strecker degradation), which is another arm of the Maillard reaction. Strecker aldehydes from these reactions are important flavor compounds (18). 

Several mechanisms have been reported for pyrazine formation by Maillard reactions (21,52,53). The carbon skeletons of pyrazines come from a-dicarbonyl (Strecker) compounds which can react with ammonia to produce ot-amino ketones as described by Flament, et al. (54) which condense by dehydration and oxidize to pyrazines (Figure 6), or the dicarbonyl compounds can initiate Strecker degradation of amino acids to form ot-amino ketones which are hydrolyzed to carbonyl amines, condensed and are oxidized to substituted... 

Figure 5. Formation of secondary reaction products involved in production of l-(methylthio)ethanethiol by Strecker degradation of amino acids. (Reproduced from Ref. 49. Copyright 1972, American Chemical Society.)...

Rohan had suggested that the operative reaction in the development of chocolate aroma might be a Strecker degradation of the amino acid fraction. Bailey et al. (8) demonstrated quantitatively that three aldehydes, which could be related to leucine, valine, and alanine, were prominent in the volatiles from a typical sample of roasted, ground cacao beans. 

In former experiments (5) we have shown that chemical analysis for Amadori compounds (mainly consisting of fructose-glutamic acid) and isovaleralde-hyde, formed by Strecker degradation of the amino acids leucine and isoleucine, can be used for an early detection of undesirable quality changes caused by the Maillard reaction. In order to demonstrate the usefulness of these compounds as indicator substances for quality improvement of dried products, we performed drying experiments with carrots as an example of plant products. 

Table I shows that an increase of Amadori compounds occurs parallel with an increase of isovaleraldehyde formed by Strecker degradation of the amino acid leucine (18 ). It becomes evident from Table I that the flavor impression "burnt arises if certain concentrations of isovaleraldehyde are exceeded this flavor change is increased by increasing isovaleraldehyde concentrations. By this means an analytical control of undesirable sensory changes caused by the Maillard reaction in carrots is available.

The imidazole part of the IQ-compounds suggests creatinine as a common precursor. The remaining parts of the IQ-compounds could arise from Maillard reaction products, e.g., 2-methylpyri-dine or 2,5-dimethylpyrazine. These two compounds could be formed through Strecker degradation. In Maillard reactions, this is induced by a-dicarbonyl compounds derived from carbohydrates, which are thereby converted to pyrroles, pyridines, pyrazines, etc. (8). 

Thus, IQ may arise from creatinine, 2-methylpyridine and formaldehyde or a related Schiff base, formed from glycine through Strecker degradation. The initial step may be a Mannich reaction or an aldol condensation. By analogy MelQ may arise from creatinine, alanine and 2-methylpyridine, and MelQx from creatinine, glycine and 2,5-dimethylpyrazine according to the scheme in Figure 1. 

Figure 2.10. Strecker degradation of amino acids and a-dicarbonyls to form heterocyclic compounds. For glycine, R = H. Reprinted with permission from Wong, J. W., and Shib-amoto, T. (1996). Geotoxicity of the Maillard reaction products. In The Maillard Reaction. Consequences for the Chemical and Life Sciences, Ikan, R., ed., John Wiley Sons, Chichester, UK, 129-159.

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. 

Also acetic acid may arise from a reaction of this type. Most important compounds of this pathway are pyruvic aldehyde, diacetyl, hydro-oxyacetone and hydroxydiacetyl which can easily react with amino acids. The Strecker degradation is a reaction where the amino acid is de-carboxylated and loses its amino group. Reaction products are the Strecker aldehyde and - as an intermediate - an aminoketone which forms a pyrazine by dimerization. This pathway is considered to be most important for the origin of pyrazines in thermal aromas. However, only limited knowledge is available about the fate of the Strecker aldehydes. As we will demonstrate they are very reactive. 

Pyridines and pyrroles can be formed in different pathways by Mail-lard reaction. The formation of 5-methyl pyrrole aldehyde and 6-methyl-3-pyridinole has been observed by Nyhammar et al (17) by the reaction of isotope labelled 3-deoxyosone with glycine. The 3-deoxy-hexosone represents an -dicarbonyl compound and in this way the Strecker degradation occurs. Another pathway is the reaction of fu-rans with ammonia. Under roast conditions, we have obtained primarily the corresponding pyrrole, whereas we found the corresponding py-... 

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