Succinic acid derivatives from

Identified by Schormuller et al. (1961) in a commercial coffee extract (0.28 %, 6% of the acid content) and later by Woodman et al. (1968) in a Santos roasted coffee. It was also found by Feldman et al. (1969) in concentrations of 55 160 ppm in medium and dark-roasted arabica and robusta coffees. Van der Stegen and van Duijn (1988) found higher values for which they did not have a definite explanation up to 0.15%in green arabicas, 0.05 0.35 % in robustas and 0.19-0.8% (d.m.) in commercial roasted coffee. The quantity increased in a brew left at high temperature. Maier (1987,1988) mentioned the presence of succinic acid in a Santos green arabica (180 ppm) and with other minor acids in roasted coffee (50-100 ppm). Bahre and Maier (1999) (see E.29) found only 40-50 ppm in green arabicas and about 80 ppm after roasting. Succinic acid derives from citric acid. 

When the 1-position is substituted, 3- and 5-aminopyrazoles react at the C-4 carbon atom, the reactivity of which is enhanced by the amino group. Thus pyrazolo[3,4-Z ]pyridines (545) are obtained either by the Skraup synthesis or from 1,3-diifunctional compounds. Here also aminopyrazolinones have been used instead of aminopyrazoles to prepare (545 R = OH). If 1,4-ketoesters (succinic acid derivatives) are used instead of /3-ketoesters, pyrazolo[3,4-Z ]azepinones (546) are obtained. 

The second relevant set of data is for the formation of the anhydride from substituted succinic acid derivatives. Equilibrium constants for the formation of the anhydride from the acid are available for the various methyl-substituted compounds (Table A.l) and the derived EM s are compared in Table 5 with those for intramolecular nucleophilic catalysis in the hydrolysis of half-esters... 

The synthesis of succinic acid derivatives, /3-alkoxy esters, and a,j3-unsaturated esters from olefins by palladium catalyzed carbonylation reactions in alcohol have been reported (24, 25, 26, 27), but full experimental details of the syntheses are incomplete and in most cases the yields of yS-alkoxy ester and diester products are low. A similar reaction employing stoichiometric amounts of palladium (II) has also been reported (28). In order to explore the scope of this reaction for the syntheses of yS-alkoxy esters and succinic acid derivatives, representative cyclic and acyclic olefins were carbonylated under these same conditions (Table I). The reactions were carried out in methanol at room temperature using catalytic amounts of palladium (II) chloride and stoichiometric amounts of copper (II) chloride under 2 atm of carbon monoxide. The methoxypalladation reaction of 1-pentene affords a good conversion (55% ) of olefin to methyl 3-methoxyhexanoate, the product of Markov-nikov addition. In the carbonylation of other 1-olefins, f3-methoxy methyl esters were obtained in high yields however, substitution of a methyl group on the double bond reduced the yield of ester markedly. For example, the carbonylation of 2-methyl-l-butene afforded < 10% yield of methyl 3-methyl-3-methoxypentanoate. This suggests that unsubstituted 1-olefins may be preferentially carbonylated in the presence of substituted 1-olefins or internal olefins. The reactivities of the olefins fall in the order RCH =CHo ]> ci -RCH=CHR > trans-RCH =CHR >... 

The strategy for the development of products from biomass needs to be twofold. One approach is to identify those opportunities where we can compete economically with existing petrochemical products. Succinic acid-derived materials fit into this category (Fig. 1). The second approach must include the identification of products with novel functionality that cannot easily or cost effectively be derived from petrochemical building blocks. The challenge with developing new materials is that the market for these products must also be developed and the time and cost can be significant however, the reward may also be substantial. 

Succinic acid is a potential platform chemical that is expected to be commercialised in a few years. Although the production capacity of petrochemically derived succinic acid is on the scale of 15 000 tonnes per year (Zeikus etal., 1999), the production capacity of succinic acid derivatives is over 270 000 tonnes per year (Willke and Vorlop, 2004). Fermentative production of succinic acid could offer a viable route to bulk chemical production. Figure 4.4 presents potential routes for chemical production from succinic acid (McKinlay et al., 2007). Another advantage of succinic acid microbial production is the simultaneous requirement for CO2 consumption, which reduces the emission of the most important greenhouse gas and makes fermentative succinic acid production a process of significantly low environmental impact. 

The cyclization of carbamic acid 34 into NCA was supposed to correspond to an equilibrium constant that would not be very different from the values reported for the cyclization of succinic acid derivatives 36 (Kcyc = 0.7 x 10-5 and 4 x 10 5 for R = H and Me, respectively [216]). The value of Kcyc = 1 x 10-5 was therefore selected for carbamic acid 34. 

In the polycondensation of aliphatic dicarboxylic acids with diols, DCC is used to mediate the reaction. In this manner biodegradable and surface active aliphatic polyesters are obtained. Also, hydroxycarboxylic acids derived from maleic or succinic acid are ho-mopolymerized in the presence of EDCCl in DMF at room temperature. In this manner... 

Dibenzylidene succinic acid derivatives are examples of substrates with a direct link between the a-carbons. Voltammetry of dimethyl dibenzylidenesuccinate shows two reduction peaks separated by 200 mV, and preparative-scale reduction under a variety of conditions gave none of the cyclobutane derivatives expected from intramolecular cyclization. Monomeric products (2 F or 4 F depending on the working potential) were found together with varying amounts of oligomers [122],... 

Derivation Occurs naturally in wine lees made synthetically from maleic anhydride and hydrogen peroxide and by an enzymatic reaction with a succinic acid derivative. 

Alcaligenes faecalis has a hydroxylamine-oxidizing enzyme which differs from the enzyme of other heterotrophic nitrifying bacteria. In this bacterium, hydroxylamine is oxidized through pyruvic oxime (Fig. 3.6). Pyruvic acid derived from lactate, succinate, and other carboxylates reacts nonenzymatically with hydroxylamine formed from ammonia to form pyruvic oxime. This compound is oxidized to nitrite and pyruvic acid by the catalysis of pyruvic oxime dioxygenase (Ono et al., 1996, 1999). 

The alkaloid avadharidine differs from delsemine only in that it is a succinic acid derivative, whereas XXXIII is a methylsuccinic acid derivative. Acid cleavage of avadharidine produces anthranoyllycoctonine (XXX) thus, the structure of avadharidine is XXXVI. 

Starting from these substituted dienes, asymmetric syntheses of optically active polymers are possible, since the chirality of the asymmetric carbon atoms of the main chain is determined by the local environment. Indeed these syntheses have been successfully carried out with many of them. The synthesis of optically active polysorbates by Natta et al. dates back to 1960 (228), and is the first example of an asymmetric synthesis of homopolymers. A conclusive proof of the asymmetric induction was obtained by oxidative degradation of the polymers to succinic acid derivatives (229). This synthesis, as well as those performed with trans 1,3-pentadiene (230), 1-phenyl-butadiene (231), and l-phenyl-4-methy1-butadiene (146) have been carried out using optically active initiators. A new kind of asymmetric polymerization was obtained by Farina et al (232) by y-irradiation of trans-1,3-pentadiene included in (-)perhydrotriphenylene (XIX). 

Succinic and malic acids are listed among the top 15 platform chemical opportunities to be produced from biorefinery carbohydrates by the US Department of Energy (DoE Werpy et al., 2004 Bozell and Petersen, 2010). Succinic acid is traditionally produced by the catalytic hydrogenation of petrochemical maleic acid or anhydride (de Jong et al., 2012). Its market value potential has been projected as 245 x 10 tons per year, while an additional market size of 25 X10 tons per year is expected for succinic acid-derived polymers (Bozell and Petersen, 2010). Therefore biosuccinic acid production from microbial processes is anticipated to increase progressively in the near future. 

The sulfosuccinimdes may be of two varieties, one analogous to the previously mentioned succinic acid derivatives, where the sulfonate group is added across the double bond of maleic acid and subsequently reacted to produce the cyclic imide. The second variety requires a different synthetic approach, since the locations of their hydrophilic and hydrophobic groups are reversed from those of the succinic acid derivatives. In this case, the starting material is a 2-alkyl, alkenyl, or similar succinic anhydride, which is reacted with the appropriate sulfoalkylamine to produce the amide acid, followed by dehydration to the imide. Similar reaction schemes can be used to prepare di- and higher polyesters and amides of malonic acid, itaconic acid, and other polycarboxylic acids. 

With some acids (e.g., succinic acid and sulplianilic acid) more satisfactory results are obtained by reversing the order of mixing, i.e., by adding the solution of the so um salt of the acid to the reagent. It should be pointed out that the melting points of the derivatives as determined on the electric hot plate (Fig. II, 11, 1) may differ by 2-3° from those obtained by the capillary tube method. In view of the proximity of the melting points of the derivatives of many acids, the mixed m.p. test (Section 1,17) should be applied. 

Cydopentane reagents used in synthesis are usually derived from cyclopentanone (R.A. Ellison, 1973). Classically they are made by base-catalyzed intramolecular aldol or ester condensations (see also p. 55). An important example is 2-methylcydopentane-l,3-dione. It is synthesized by intramolecular acylation of diethyl propionylsucdnate dianion followed by saponification and decarboxylation. This cyclization only worked with potassium t-butoxide in boiling xylene (R. Bucourt, 1965). Faster routes to this diketone start with succinic acid or its anhydride. A Friedel-Crafts acylation with 2-acetoxy-2-butene in nitrobenzene or with pro-pionyl chloride in nitromethane leads to acylated adducts, which are deacylated in aqueous acids (V.J. Grenda, 1967 L.E. Schick, 1969). A new promising route to substituted cyclopent-2-enones makes use of intermediate 5-nitro-l,3-diones (D. Seebach, 1977). 

Succinyl-CoA derived from propionyl-CoA can enter the TCA cycle. Oxidation of succinate to oxaloacetate provides a substrate for glucose synthesis. Thus, although the acetate units produced in /3-oxidation cannot be utilized in glu-coneogenesis by animals, the occasional propionate produced from oxidation of odd-carbon fatty acids can be used for sugar synthesis. Alternatively, succinate introduced to the TCA cycle from odd-carbon fatty acid oxidation may be oxidized to COg. However, all of the 4-carbon intermediates in the TCA cycle are regenerated in the cycle and thus should be viewed as catalytic species. Net consumption of succinyl-CoA thus does not occur directly in the TCA cycle. Rather, the succinyl-CoA generated from /3-oxidation of odd-carbon fatty acids must be converted to pyruvate and then to acetyl-CoA (which is completely oxidized in the TCA cycle). To follow this latter route, succinyl-CoA entering the TCA cycle must be first converted to malate in the usual way, and then transported from the mitochondrial matrix to the cytosol, where it is oxida-... 

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