Bromosuccinic acid

Malic acid crystallizes in colourless needles m.p. lOO C. It o- curs in many acid fruits, such as grapes, apples and gooseberries. It can be prepared by microbiological processes using various moulds or from ( + )-bromosuccinic acid by the action of NaOH. 

In a similar reaction, bromosuccinic acid and thiobenzamide in ethyl-acetate yielded an acyclic intermediate (229), Ri = Ph, R2 = CH2C02H, which by heating in water cyclizes to the thiazole (230), Rj = Ph and R2 = CH2C02H. (260). 

Antoracemisation has been observed with substances not only in solid or liquid states but also in their solutions, For Example (+)-phenyl bromoacetic acid after three years of storage becomes inactive, in its solid state. A liquid showing antoracemisation is the ethyl ester of bromosuccinic acid. 

Electrolytic Conductance of Lithium Bromide in Acetone and Acetone-Bromosuccinic Acid Solutions... 

The Fuoss-Onsager-Skinner equation satisfactorily describes the electrolytic conductance of lithium bromide in acetone. Values of 198.1 0.9 Q l cm2 eq l and (3.3 0.1) X I03 are established for A0 and KA, respectively, at 25°C furthermore, a value of 2.53 A is obtained for the sum of the ionic radii ( ). When bromosuccinic acid is added to 10 5 N lithium bromide in acetone, there is a decrease in the specific conductance of lithium bromide rather than the increase that is observed at higher concentrations. As the concentration of bromosuccinic acid is increased, the values obtained for A0 and KA decrease, while those for a increase when the bromosuccinic acid and acetone are considered to constitute a mixed solvent. These results do not permit any simple explanation. When bromosuccinic acid and acetone are considered a mixed solvent, the Fuoss-Onsager-Skinner theory does not describe the system. 

This study was undertaken to determine whether or not the electrolytic conductance of the lithium bromide-bromosuccinic acid-acetone system can be described by the Fuoss-Onsager-Skinner equation (FOS equation)—Equation 2—by treating the system as lithium bromide in a mixed solvent, and to establish values for Ao and KA for lithium bromide in anhydrous acetone with the same equation. The equation requires knowledge of the concentration and corresponding equivalent conductance along with the dielectric constant and viscosity of the solvent and the temperature that is,... 

This is an extremely complicated system for such a study, inasmuch as it is a three-component system consisting of an ionophore (lithium bromide) and an ionogen (bromosuccinic acid) in a smenogenic solvent (acetone). Further, the solvent has a high affinity for water and a comparatively high vapor pressure at 25°C. 

Olson and Cunningham (6) found that the specific conductance of 0.01m lithium bromide in acetone was increased by 30% when sufficient bromosuccinic acid, was added to make the solution 0.2m with respect to the acid. When dimethyl bromosuccinate was added in lieu of bromosuccinic acid, the specific conductance was diminished by 6% and when lithium perchlorate was substituted for lithium bromide, the specific conductance decreased linearly as bromosuccinic acid was added. These observations motivated Cunningham and his co-workers to continue work in the field. 

The mass spectrum of the bromosuccinic acid (K K Laboratories, Inc.), a snow-white powder which melted smoothly in the range of 160°-165°C, showed no peak corresponding to the parent compound. No impurities could be identified in particular, there were no peaks corresponding to fragments containing two bromine atoms. The mass spectrum for bromosuccinic acid was not found in the literature, but that of the prepared acid was analogous to the one for succinic acid, e.g., no parent peak (25). 

Dimethyl bromosuccinate was prepared from bromosuccinic acid by the diazomethane method (26) using the procedure of Eisenbraun, Morris, and Adolphen (27). It was distilled under vacuum (0.08-0.1 Torr) at 45°-49°C to yield a clear colorless oil. Thin layer chromatography with benzene as the solvent on SiC>2 yielded a symmetrical single spot, indicating either a pure compound or no separation with this particular solvent. Its mass spectrum had a very small peak corresponding to the parent compound, but none to a dibromo compound. The mass spectrum for dimethyl bromosuccinate was not found in the literature, but that for dimethyl succinate also has a small peak corresponding to the parent compound (25). 

Procedure. Equation 1 indicates that it is necessary to determine the concentration, resistance, dielectric constant, viscosity, and temperature of the system. These data were acquired for five different solvent systems. A series of measurements, in which the concentration of lithium bromide was varied from about 10 5N to 10 3N, was made on each system. The solvents used were acetone (I), 0.02063m bromosuccinic acid in acetone (II), 0.05009m bromosuccinic acid in acetone (III), 0.09958m bromosuccinic acid in acetone (IV), and 0.05047m dimethyl bromosuccinate in acetone(V). Each solvent was used to prepare stock solutions of 10-2 and 10 3m lithium bromide. All mixed solvents and solutions were prepared in the dry box. 

The viscosities of the acetone-bromosuccinic acid mixed solvents were derived from the Jones-Dole (33) equation and data acquired by Muller, who used the special viscometer described by Tuan and Fuoss (34). The values used for the viscosities (in poise) of solvents I-V were 3.02 X 10 3, 3.05 X 10-3, 3.08 X 10-3, 3.13 X 10-3, and 3.02 X 10-3, respectively. The literature value for the dielectric constant of acetone, 20.7, was used as the dielectric constant for each solvent. This is justified because at the highest concentration of bromosuccinic acid its mole fraction is less than 0.004. 

Figure 5 indicates this holds true up to a concentration of about 2-3 X 10 4N lithium bromide, whereas above about 5 X 10 4N the specific conductance is enhanced by the addition of bromosuccinic acid. On the basis of the divergence of the curves at these concentrations, it is reasonable to assume that if the concentration of lithium bromide is further increased, the enhancement of the specific conductance from the addition of the bromosuccinic acid should be still greater. This is consistent with the results of Bjornson, who measured the specific conductance of solutions containing 0.01m lithium bromide in acetone and varying amounts of bromosuccinic acid. He found the specific conductance of the solution to be 3.0 X 10 4 Q l cm-1 in the absence of bromosuccinic acid for 0.02m, 0.05m, 0.1m, and 0.2m bromosuccinic acid in the solution, the specific conductances were (Q-1 cm-1) 3.4 X 10 4,4.0 X 10 4,4.4 X 10 4, and 4.6 X 10 4,... 

It is to be noted from Table II that, as in Series I, the standard deviation of Ao is small, that of L is large, and that of K is intermediate for Series II-IV. These large standard deviations can be rationalized as in the preceding section. The table shows that Ao and K decrease systematically while a increases with increasing bromosuccinic acid concentration. 

Table I shows that y decreases with increasing concentration of lithium bromide for each series, but that the decrease becomes smaller as the bromosuccinic acid concentration gets larger. The effect of lithium bromide and bromosuccinic acid concentration on y is also demonstrated in Figure 1. All the terms listed in Table I diminish the equivalent conductance from Aq for Series II-IV and the magnitude of the reduction for each term increases with increasing...

If the system behaved ideally, the specific conductances should be additive. Figure 7 shows the specific conductance of the solution corrected (by subtraction) for the specific conductances of the acetone and lithium bromide for various fixed amounts of lithium bromide as a function of bromosuccinic acid concentration. Inasmuch as this should be equal to the equivalent conductance of bromosuccinic acid, if there were no interaction among the conducting species all four curves should coincide with the curve for no lithium bromide. Clearly, some type of interaction must occur. 

Figure 7. Specific conductance of solution minus specific conductance of acetone and lithium bromide as a function of bromosuccinic acid concentration for various fixed amounts of lithium bromide...

Bjornson worked at sufficiently high concentration (0.01m lithium bromide) to observe only the increase in specific conductance due to the addition of bromosuccinic acid to a lithium bromide-acetone solution. Lithium bromide is an ionophore and in acetone exists as lithium ions and bromide ions (conductors) in equilibrium with associated lithium bromide ion pairs (nonconductors), while bromosuccinic acid is an ionogen which exists in acetone as bromosuccinic acid molecules (nonconductors) in equilibrium with hydrogen ions and bromosucci-nate ions (conductors). In order to explain the anomalous increase in specific conductance, Bjornson proposed that when bromosuccinic acid is added to the lithium bromide-acetone solution, bromide ion from the lithium bromide combines with the hydrogen ion from the bromosuccinic acid and forms molecular hydrogen bromide (a nonconductor). This would result in a decrease in concentration of these ions however, as bromide ions and bromosuccinate ions... 

Bjornson also measured the specific conductance of a solution of 0.01m lithium bromide in acetone with various amounts of dimethyl bromosuccinate added and found a slight linear decrease in specific conductance with addition of dimethyl bromosuccinate. These results, along with those of Olson and Cunningham, lent support to Bjornson s postulate, in that when the acidic hydrogens of bromosuccinic acid were replaced with methyl groups, or the bromide ions of lithium bromide were replaced with perchlorate ions, the increase in specific conductance was not observed. 

The decrease in K and Ao with increase in concentration of bromosuccinic acid observed in this work is consistent with the trend observed by Nilsson and Beronius (22) for water and acetone and by Nilsson (23) for methanol and acetone. However, the a values obtained from these data do not match too well with those obtained for the water-acetone and water-methanol systems, but it should be noted that these a values are not calculated in the same manner. With acetone and bromosuccinic acid the change in the a values is just the reverse of what was observed for the other systems as the concentration of the second solvent is increased. 

In any event, it can be concluded that in acetone there are strong associations between bromosuccinic acid and lithium bromide ions. The largest concentration of bromosuccinic acid studied (Series IV) is approximately equal to the lowest concentration studied for the acetone-water and acetone-methanol systems. As expected, the data show the association with the acid to be much greater than with either the methanol or the water. From the K and a values it is evident that the association between the salt and dimethyl bromosuccinate is much less than the association of the salt with bromosuccinic acid but greater than the salt-acetone association. In view of this, it is concluded that the association between the bromide ion and the second solvent accounts for the change in K. Knowledge of the precise nature of the association will have to await further investigations. 

V-Thiomalic acid can be prepared from bromosuccinic acid by reaction with KiS. The two enantiomers can be obtained from the corresponding optically active potassium hromosuccinales. 

Fumaric acid has been prepared from bromosuccinic acid by heating with water,1 or dilute hydrobromic add,2 and by heating the acid above its melting point.3 It has also been prepared by heating malic acid,4 by transmutation of maleic acid 5 and by the reduction of tartaric acid with phosphorus and iodine.6 The procedure described is the most satisfactory for laboratory use, and is a slight modification of one recently described in the literature.7... 

C4H204 3,4-dihydroxy-3-cyclobutene-1,2-dione 2892-51-5 25.00 1.4720 2 2631 C4H5Br04 DL-bromosuccinic acid 923-06-8 25.00 1.7770 2... 

Bromosuccinic Acid. Bromobutanedioic acid mouobromosuccinic acid. C1H,Br01, mol wt 197.00. C 24.39%, H 2.56%, Br 40.57%, O 32.49%, HOOCCHjCHBr-COOH, Prepn of tfl-form by bromination of succinic add Kekule, Ann. 117, 120 (l861) from fumaric acid and HBr Fittig. Ann. 188, 42 (]877) by bromination of succinyl bromide or succinic anhydride Hughes, Watson, J. Chem. Soc. 1930, 1733. Prepn of J-form from (-aspartic acid Walden, Ber. 29, 133 (1896) Karrer et al, Hetv. Chim. Acta 30, 271 (1947). 

Dicarboxylic acids of maleic-fumaric acid type are almost always obtained from halogenated succinic acids fumaric acid is easily formed from mono-bromosuccinic acid, which loses 1 equivalent of hydrogen bromide when merely boiled with water63 or heated above its melting point.64... 

The preparation of fumaric acid by treating bromosuccinic acid with potassium hydroxide is another illustration of a general method which is much used to establish a double bond in a compound —... 

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