Succinic acid, 290 Table

Efficient syntheses of substituted succinic acids (Table 2, Nos. 5, 6) have been developed in the past a more recent application is the coupling of 16 as part of a semi-bullvalene synthesis [130]. 

Twenty-five sorbents were screened for uptake of succinic acid. Table 1 lists the initial capacity for each of the sorbents as well as the type and manufacturer of the sorbents. 

Pyrrohdinone (2-pyrrohdone, butyrolactam or 2-Pyrol) (27) was first reported in 1889 as a product of the dehydration of 4-aminobutanoic acid (49). The synthesis used for commercial manufacture, ie, condensation of butyrolactone with ammonia at high temperatures, was first described in 1936 (50). Other synthetic routes include carbon monoxide insertion into allylamine (51,52), hydrolytic hydrogenation of succinonitnle (53,54), and hydrogenation of ammoniacal solutions of maleic or succinic acids (55—57). Properties of 2-pyrrohdinone are Hsted in Table 2. 2-Pyrrohdinone is completely miscible with water, lower alcohols, lower ketones, ether, ethyl acetate, chloroform, and benzene. It is soluble to ca 1 wt % in aUphatic hydrocarbons. 

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). 

Table 1. Physical Properties of Succinic Acid and Succinic Anhydride...

Commercial specifications of succinic acid and succinic anhydride are given in Table 2. 

Table 3 summarizes many of the uses mentioned in the literature. The main use of succinic acid in Japan is for bath preparations (314—322). This application in 1994 accounted for nearly 80% of total consumption. After recording a more than 10% yearly increase in the late 1980s, the growth of this apphcation has slowed down, and consumption is decreasing on account of the replacement of succinic acid by fumaric acid for economic reasons. This trend is expected to continue in the coming years. 

It IS interesting that the rates of elimination of hydrogen fluoride from all fluormated succinic acids span hardly 1 order of magnitude, whereas the rates of preferential dehydrofluorination of both a-bromo-a -fluorosuccimc acids are higher by almost 2 orders of magnitude [35, 36, 37, 38] (Table 3)... 

Table 5.1 Example of organic acids produced commercially by micro-organisms organic adds considered in this chapter are labelled with. A related add, a-oxoglutaric acid, is easy to produce microbiologically but has no current end use succinic acid is produced chemically. Amino adds are beyond the scope of this chapter.

Table VI.—Hydrolysis Rates at 25°C for the Esters op Glycol, Glycerol, and Succinic Acid ...

Table 1 Summary of succinic acid esterification results.

Table 15.13 Hydrogenation of succinic acid and anhydride using [Ru4H4(CO)g(P Bu3)4].a)...

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... 

EM for cyclization of succinamic acid assumed equal to that for cyclization of succinic esters (Table A.2 see text). Direct rate comparisons give EM s for substituted succinamic acids at 25°. No corrections for pX,... 

Table 4.4 shows the values of the proton-proton correlation for the three dicarboxylic acids maleic, fumaric, and succinic acids (Fig. 4.26). All the values of W(l, 1) are positive, i.e., negative cooperativity. Since the configuration of the first two acids is nearly rigid, one can expect that the larger the proton-proton distance, the weaker the cooperativity. Indeed, the ratio of W(l, 1) for the first two... 

One can easily adjust the values of the dielectric constants D(, and Dj to obtain the experimental values of W, as in Table 4.4. With a choice of = 19.6 and Dj. = 51.0 for water, and D. = 12.5 and Dj. = 31.8 for 50% water-ethanol, we obtain the experimental values of W. We now compute the total correlation function for the two-state model for succinic acid. Here the correlation cannot be computed as an average correlation of the two configurations (see Section 4.5). The total correlation of the equilibrated two-state model is... 

The quantity (5) is an average of the direct correlations S. and 5yin a hypothetical system, where the mole fractions of the two configurations are and respectively (see Section 4.5). As such, (S) is bound by and Sj, but y(l, 1) must be larger than unity and is not bound by and In Table 4.4 we see that both the experimental and calculated values of 11 (1,1) are closer to the fumaric rather than the maleic values. One could argue that since the ionized succinic acid would be most of the time in the trans configuration, we should expect that the value of IV for the succinie aeid be closer to the fumaric acid value. The faet that the IV (succinic) is indeed intermediate between IV (maleic) and IV (fumaric) is quite accidental. The value of IV (succinic) is determined by both the negative correlation (5) and the positive correlation y(l, 1). 

Table 4.6 shows some experimental data on a-a dialkyl succinic acids. The most remarkable finding is that some of these molecules have a very large negative cooperativity, far beyond what could be explained by electrostatic theories. These molecules exist in two isomers—the meso and racemic forms. The latter exists in two optically active enantiomers that are mirror images of each other—only one of these is shown in Fig. 4.29. 

Using the model described above with dielectric constant Dj. = 34.2 and D(, = 12, and with Xq = 3.62 x 10, we can reproduce the experimental values of and kj for succinic acid. These are shown in Table 4.7. Note that the dielectric constant for the trans form is very close to the macroscopic dielectric constant of 50% mixture of water and ethanol (Hamed and Owen, 1958) (for which D = 49 at 25 °C the experimental values of pKi and pK2 reported in Table 4.6 are at 20 °C). As expected, the fitted dielectric constant for the cis configuration is far smaller than the macroscopic dielectric constant. Once we determined Dj and Xq, they were... 

In the case of dialkylated succinic acid, we have seen that, due to the occurrence of two barriers in the rotational potential of the racemic form (and not of the meso form) with the bulkier alkyl groups (and not the smaller ones), it is likely that the system will freeze-in into a mixture of two components. This is exactly where we observed very large negative cooperativity in the experimental data shown in Table 4.6. One cannot avoid the conclusion that at least a substantial part of the observed cooperativity is spurious. 

A group of related siderophores comprises the desferri- or deferriferrioxamines (occasionally abbreviated as desferrioxamines) or proferrioxamines. Originally they were obtained from Actinomycetes, mainly Nocardia and Streptomyces spp. (187) and later found to be produced also by Erwinia spp. (several representatives) (e.g. (30a, 113,115,180)), Arthrobacter simplex (B), Chromobacterium violaceum (E) (246a), and by Pseudomonas stutzeri (several) (229a, 246,398). They consist of three (or in rare cases four) mono-N-hydroxy-l,4-diaminobutane (putrescine), mono-iV-hydroxy-l,5-diaminopentane (cadaverine) or (rarely) mono-N-hydroxy-1,3-diaminopropane units connected by succinic acid links. The hydroxylated terminus carries an acetyl or a succinyl (as in the structural formula heading Table 6)... 

TABLE 2-9 Gel Point Determinations for Mixture of 1,2,3-Propanetricarboxylic Acid, Diethylene Glycol, and Either Adipic or Succinic Acid"... 

Neutron diffraction has been used occasionally to determine the absolute configuration of deuterium-labeled stereogenic centers, such as R -CHD-R2 (Table 6) and R -C(CH3)(CD3)—R2 82, by internal comparison, i.e, determination of configuration relative to a second stereogenic center of known absolute configuration in the same compound (see Section 4.2.2 3.). For example, the absolute configuration of (-)-(2R)-butane-2-d-dioic acid (succinic acid), prepared from (-)-(25,37 )-2-hydroxybutane-3-rf-dioic acid (malic acid), was determined on the corresponding 1-phenylethylammonium salt (Table 6)83. 

The extremely short duration of action of succinylcholine (5-10 minutes) is due to its rapid hydrolysis by butyrylcholinesterase and pseudocholinesterase in the liver and plasma, respectively. Plasma cholinesterase metabolism is the predominant pathway for succinylcholine elimination. Since succinylcholine is more rapidly metabolized than mivacurium, its duration of action is shorter than that of mivacurium (Table 27-1). The primary metabolite of succinylcholine, succinylmonocholine, is rapidly broken down to succinic acid and choline. Because plasma cholinesterase has an enormous capacity to hydrolyze succinylcholine, only a small percentage of the original intravenous dose ever reaches the neuromuscular junction. In addition, as there is little if any plasma cholinesterase at the motor end plate, a succinylcholine-induced blockade is terminated by its diffusion away from the end plate into extracellular fluid. Therefore, the circulating levels of plasma cholinesterase influence the duration of action of succinylcholine by determining the amount of the drug that reaches the motor end plate. 

Many formation constants involve polycarboxylates Table 28 summarizes the data. Nagyp l and Fabian s report on the oxalic and malonic systems seems the most complete as hydrolysis of both metal ion and complexes has been included.584 A concentration distribution of the complexes in the malonic system is shown in Figure 25. The order of basicities is succinic > citraconic > itaconic > maleic > malonic acid and log /3U0 should follow the same order. However, from Table 28, the order of stabilities is citraconic > malonic > maleic > itaconic > succinic acid.608... 

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