Succinic acid formation

In the previous studies, it was reported that initial concentration of carbon source could influence the cell growth and succinic acid production throughout the fermentation [20]. The effect of initial cheese whey concentrations on succinic acid formation was shown in Fig. 1 Maximum succinic acid concentration of 27.9 g/L was obtained at 48 h when the initial concentration of cheese whey was 100 g/L. The succinic acid concentration increased rapidly from 6 to 24 h corresponding to the rapid consumption of lactose during this period. 

The weak organic acids such as acetic acid and formic acid both have positive and negative effects on the bioethanol produetion proeess. In fermentations using S. cerevisiae NCYC 2592, an addition of aeetie acid in a concentration of 20 mM increased the ethanol produetivity (unpublished data). The low acetic acid concentrations (lower than 20 mM) did not have an impact on the yeast viability. At fermentations with higher acid concentration, the intracellular pH decreases, requiring plasma membrane ATPase to pump protons out of the cell. The depletion of ATP affected the biomass formation. In comparison with acetic acid, formic acid has a more severe inhibitory effect, which has also been observed in other biosynthesis processes, e.g. succinic acid formation. ... 

Wood HG and Workman CH (1940) The relationship of bacterial utilization of CO2 to succinic acid formation. Biochem J 34 129-137 Wood HG, Stone RW and Workman CH (1937) The intermediate metabolism of the propionic acid bacteria. Biochem J 31 349-359 Wood HG, Allen SHG, Stjemholm R and Jacobson B (1963) Transcarboxylase. III. Purification and properties of methylmalonyl-oxaloacetic transcarboxylase containing tntiated biotin. J Biol Chem 238 547-556... 

Although some dibasic acids, e.g, succinic acid and phthalic acid, readily lose water on heating with the formation of cyclic anhydrides, most monobasic... 

The fluorescein test for succinic acid (p. 349) and the phthalein and fluorescein tests for phthalic acid (p. 351) are obviously given also by succinic anhydride and phthalic anhydride, as these tests depend upon the initial formation of the anhy dride in each case. 

Method B. In a 500 ml. round-bottomed flask, provided with a reflux condenser protected by a cotton wool (or calcium chloride) drying tube, place 59 g. of succinic acid and 102 g. (94-5 ml.) of redistilled acetic anhydride. Reflux the mixture gently on a water bath with occasional shaking until a clear solution is obtamed ca. 1 hour), and then for a further hour to ensure the completeness of the reaction. Remove the complete assembly from the water bath, allow it to cool (observe the formation of crystals), and finally cool in ice. Collect the succinic anhydride as in Method A. The yield is 45 g., m.p. 119-120°. 

N). This area of the process has received considerable attention in recent years as companies strive to improve efficiency and reduce waste. Patents have appeared describing addition of SO2 to improve ion-exchange recovery of vanadium (111), improved separation of glutaric and succinic acids by dehydration and distillation of anhydrides (112), formation of imides (113), improved nitric acid removal prior to dibasic acid recovery (114), and other claims (115). 

V-Phenylsuccinimide [83-25-0] (succanil) is obtained in essentially quantitative yield by heating equivalent amounts of succinic acid and aniline at 140—150°C (25). The reaction of a primary aromatic amine with phosgene leads to formation of an arylcarbamoyl chloride, that when heated loses hydrogen chloride to form an isocyanate. Commercially important isocyanates are obtained from aromatic primary diamines. 

Physical properties of the acid and its anhydride are summarized in Table 1. Other references for more data on specific physical properties of succinic acid are as follows solubiUty in water at 278.15—338.15 K (12) water-enhanced solubiUty in organic solvents (13) dissociation constants in water—acetone (10 vol %) at 30—60°C (14), water—methanol mixtures (10—50 vol %) at 25°C (15,16), water—dioxane mixtures (10—50 vol %) at 25°C (15), and water—dioxane—methanol mixtures at 25°C (17) nucleation and crystal growth (18—20) calculation of the enthalpy of formation using semiempitical methods (21) enthalpy of solution (22,23) and enthalpy of dilution (23). For succinic anhydride, the enthalpies of combustion and sublimation have been reported (24). 

Heat. When heated, succinic acid loses water and forms an internal anhydride with a stable ring stmcture. Dehydration starts at 170°C and becomes rapid at 190—210°C (25). Further heating of succinic anhydride causes decarboxylation and the formation of the dilactone of gamma ketopimelic acid (26) (eq. 1). The same reaction takes place at lower temperatures in the presence of alkaU. 

Succinic anhydride is stabilized against the deteriorative effects of heat by the addition of small amounts (0.5 wt %) of boric acid (27), the presence of which also decreases the formation of the dilactone of gamma ketopimelic acid (28). Compared with argon, CO2 has an inhibiting effect on the thermal decomposition of succinic acid, whereas air has an accelerating effect (29,30). 

Halogenation. Succinic acid and succinic anhydride react with halogens through the active methylene groups. Succinic acid heated in a closed vessel at 100°C with bromine yields 2,3-dibromosuccinic acid almost quantitatively. The yield is reduced in the presence of excess water as a result of the formation of brominated hydrocarbons. The anhydride gives the mono- or dibromo derivative, depending on the equivalents of bromine used. 

As the mechanism, a radical and a cationic pathway are conceivable (Eq. 31). The stereochemical results with rac- or mcjo-1,2-diphenyl succinic acid, both yield only trans-stilbene [321], and the formation of a tricyclic lactone 51 in the decarboxylation of norbornene dicarboxylic acid 50 (Eq. 32) [309] support a cation (path b, Eq. 31) rather than a biradical as intermediate (path a). 

Alternative routes to -amino acids have also been explored and involve, stereoselective alkylation of chiral derivatives of y9-alanine [136-140], Curtius rearrangement of enantiomerically pure and regioselectively protected substituted-succinic acids [134, 141, 142] (the approach is also suitable for the synthesis of y9 -amino acids [143]), or the formation of chiral isoxazolidinone intermediates [144]. 

Detailed studies of 1 1 complex formation between and maleic and fumaric acids, which precedes reduction to succinic acid, cis-trans isomerisation and exchange of the double bond hydrogens, are relevant to the complex kinetics (A = substrate)... 

The principles set forth above account reasonably well for the course of bifunctional condensations under ordinary conditions and for the relative difficulty of ring formation with units of less than five or more than seven members. They do not explain the formation of cyclic monomers from five-atom units to the total exclusion of linear polymers. Thus 7-hydroxy acids condense exclusively to lactones such as I, 7-amino acids give the lactams II, succinic acid yields the cyclic anhydride III, and ethylene carbonate and ethylene formal occur only in the cyclic forms IV and V. 

In the hydroxycyclopropanation of alkenes, esters may be more reactive than N,N-dialkylcarboxamides, as is illustrated by the exclusive formation of the disubstituted cyclopropanol 75 from the succinic acid monoester monoamide 73 (Scheme 11.21) [91]. However, the reactivities of both ester- as well as amide-carbonyl groups can be significantly influenced by the steric bulk around them [81,91]. Thus, in intermolecular competitions for reaction with the titanacydopropane intermediate derived from an alkylmagnesium halide and titanium tetraisopropoxide or methyltitanium triisoprop-oxide, between N,N-dibenzylformamide (48) and tert-butyl acetate (76) as well as between N,N-dibenzylacetamide (78) and tert-butyl acetate (76), the amide won in both cases and only the corresponding cyclopropylamines 77 and 79, respectively, were obtained (Scheme 11.21) [62,119]. 

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... 

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