Fumaric acid, addition

Fumaric Aero Inhibition. Another means of preventing malo-lactic fermentation is to add fumaric acid after alcoholic fermentation is complete (45, 46, 47,48). The inhibition is relative and its extent is dependent on the amount added. The susceptibility to fumaric acid is also dependent on the strain of malo-lactic bacteria tested (49). However, we know of no case where fumaric acid addition at the levels suggested by Cofran and Meyer (45) (about 0.05%) did not delay malo-lactic fermentation under normal winemaking conditions. This includes several experiments from our pilot winery (50). Nevertheless, we have not been hasty to recommend the use of fumaric acid as an inhibitor because 1) of the difficulty in solubilizing the acid in wine 2) we do not know the mechanism of action of its inhibition [Pilone (47, 48) has shown that the bacteria metabolize low levels of fumaric acid to lactic acid but, at inhibitory levels at wine pH, the acid is bactericidal] and 3) of the desirability of minimizing the use of chemical additives. 

Additives acting on the pour point also modify the crystal size and, in addition, decrease the cohesive forces between crystals, allowing flow at lower temperatures. These additives are also copolymers containing vinyl esters, alkyl acrylates, or alkyl fumarates. In addition, formulations containing surfactants, such as the amides or fatty acid salts and long-chain dialkyl-amines, have an effect both on the cold filter plugging point and the pour point. 

Description of Method. Salt substitutes, which are used in place of table salt for individuals on a low-sodium diet, contain KCI. Depending on the brand, fumaric acid, calcium hydrogen phosphate, or potassium tartrate also may be present. Typically, the concentration of sodium in a salt substitute is about 100 ppm. The concentration of sodium is easily determined by flame atomic emission. Because it is difficult to match the matrix of the standards to that of the sample, the analysis is accomplished by the method of standard additions. 

Isomerization. Maleic acid is isomerized to fumaric acid by thermal treatment and a variety of catalytic species. Isomerization occurs above the 130 to 140°C melting point range for maleic acid but below 230°C, at which point fumaric acid is dehydrated to maleic anhydride. Derivatives of maleic acid can also be isomerized. Kinetic data are available for both the uncatalyzed (73) and thiourea catalyzed (74) isomerizations of the cis to trans diacids. These data suggest that neither carbonium ion nor succinate intermediates are involved in the isomerization. Rather, conjugate addition imparts sufficient single bond character to afford rotation about the central C—C bond of the diacid (75). 

Fumaric acid and malic acid [6915-15-7] are produced from maleic anhydride. The primary use for fumaric acid is in the manufacture of paper siting products (see Papermaking additives). Fumaric acid is also used to acidify food as is malic acid. Malic acid is a particularly desirable acidulant in certain beverage selections, specifically those sweetened with the artificial sweetener aspartame [22839-47-0]. 

A solution of 3-dimethylsulfamoylphenthiazine (5 g) in anhydrous xylene (100 cc) is heated under reflux for 1 hour with sodamide (0.67 g). 3-(4-methyl-1-piperazinyl)-1 heated under reflux for 5 hours. After treatment of the reaction products, a crude oily base (2.5 g) is obtained after treatment. By the addition of a solution of fumaric acid in ethanol to an ethanolic solution of the base, 3-dimethylsulfamoyl-10-(3-4 -methyl-1 -piperazinylpropyD-phenthiazine diacid fumarate (2.6 g) is obtained, melting point 182°C. The base recrystallized from ethyl acetate melts at about 140°C. 

An example of intramolecular hydrogen bonding is provided by the cis- and trans- forms of the acid HOOC—CH=CH—COOH. The trans- form, fumaric acid, has a higher melting point than the cis- form, maleic acid. In addition to the general effect of molecular shape (mentioned earlier in this chapter), another reason for... 

However, if both maleic and fumaric acid gave the dl pair or a mixture in which the dl pair predominated, the reaction would be stereoselective but not stereospecific. If more or less equal amounts of dl and meso forms were produced in each case, the reaction would be nonstereoselective. A consequence of these definitions is that if a reaction is carried out on a compound that has no stereoisomers, it cannot be stereospecific, but at most stereoselective. For example, addition of bromine to methylacetylene could (and does) result in preferential formation of trans-1,2-dibromopropene, but this can be only a stereoselective, not a stereospecific reaction. 

There is much evidence that when the attack is by Br (or a carrier of it), the bromonium ion (2) is often an intermediate and the addition is anti. As long ago as 1911, McKenzie and Fischer independently showed that treatment of maleic acid with bromine gave the dl pair of 2,3-dibromosuccinic acid, while fumaric acid (the... 

Principles and Characteristics Mass spectrometry can provide the accurate mass determination in a direct measurement mode. For a properly calibrated mass spectrometer the mass accuracy should be expected to be good to at least 0.1 Da. Accurate mass measurements can be made at any resolution (resolution matters only when separating masses). For polymer/additive deformulation the nominal molecular weight of an analyte, as determined with an accuracy of 0.1 Da from the mass spectrum, is generally insufficient to characterise the sample, in view of the small mass differences in commercial additives. With the thousands of additives, it is obvious that the same nominal mass often corresponds to quite a number of possible additive types, e.g. NPG dibenzoate, Tinuvin 312, Uvistat 247, Flexricin P-1, isobutylpalmitate and fumaric acid for m = 312 Da see also Table 6.7 for m = 268 Da. Accurate mass measurements are most often made in El mode, since the sensitivity is high, and reference mass peaks are readily available (using various fluorinated reference materials). Accurate mass measurements can also be made in Cl... 

Many enzymes have absolute specificity for a substrate and will not attack the molecules with common structural features. The enzyme aspartase, found in many plants and bacteria, is such an enzyme [57], It catalyzes the formation of L-aspartate by reversible addition of ammonia to the double bond of fumaric acid. Aspartase, however, does not take part in the addition of ammonia to any other unsaturated acid requiring specific optical and geometrical characteristics. At the other end of the spectrum are enzymes which do not have specificity for a given substrate and act on many molecules with similar structural characteristics. A good example is the enzyme chymotrypsin, which catalyzes hydrolysis of many different peptides or polypeptides as well as amides and esters. 

In addition to the reactions mentioned, ethyl diazoacetate takes part in many condensations with acetylene and ethylene derivatives, when the nitrogen is retained in the molecule. Thus, with esters of fumaric acid, for example, pyrazoline tricarboxylic esters are produced ... 

Development of the third class, i.e. unsaturated polyester resins, remained rather slow until the late 1930s, but after commercial production of maleic anhydride by catalytic oxidation of benzene began in 1933, maleic anhydride and fumaric acid rapidly became the most important sources of unsaturated groups in polyesters. The mechanism of drying of these resins on their own and with the addition of drying oils (i.e. unsaturated compounds such as linseed oil) was... 

The enzyme fumarase catalyses the stereospecific iram -addition of water to fumaric acid giving (5)-malic acid, and the reverse reaction, the rrans-elimination of water from (S )-malic acid ... 

An attempted synthesis of biotin using thiocarbonyl ylide cycloaddition was carried out (131,133,134). The crucial step involves the formation of the tetrahydrothiophene ring by [3 + 2] cycloaddition of a properly substituted thiocarbonyl ylide with a maleic or fumaric acid derivative (Scheme 5.27). As precursors of the thiocarbonyl ylides, compounds 25a, 72, and 73 were used. Further conversion of cycloadducts 74 into biotin (75) required several additional steps including a Curtius rearrangement to replace the carboxylic groups at C(3) and C(4) by amino moieties. 

L-aspartic acid by ammonia addition to fumaric acid by aspartase (from E. coli)... 

L-malic acid by addition of water to fumaric acid by fumarase from Brevibacterium... 

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