Fumaric acid Structure

Structure X in Figure 300 shows interpenetrating tetrahedra with carbon centers and a single bond between these carbons. Van t Hoff correctly postulated that there is free rotation about such single bonds. Structures XIa, Xlb, XII, and XIII rationalize cis and Irons isomerism (e.g., the difference between maleic acid and fumaric acid). Structure XIV explains the widespread occurrence of six-membered rings in chemistry and aspects of Baeyer s strain theory. ... 

Both acids 3deld succinic acid, m.p. 185°, upon catalytic reduction (see Section 111,150), thus establishing their structures. Maleic and fumaric acids are examples of compounds exhibiting cis-trans isomerism (or geometric isomerism). Maleic acid has the cm structure since inter alia it readily 3delds the anhydride (compare Section 111,93). Fumaric acid possesses the trans structure it does not form an anhydride, but when heated to a high temperature gives maleic anhydride. 

Fumaric acid is converted to L-malic acid by hydration in the presence of the enzyme fumamse. From the structure of the substrate and the configuration of the product, it is apparent that the hydroxyl group has been added to the si fiice of one of the carbon atoms of the double bond. Each of the trigonal carbon atoms of an alkene has its fiice specified separately. The molecule of fumaric acid shown below is viewed fixjm the re-re fiice. 

Maleic acid and fumaric acid are the cis- and trans- isomers, respectively, of QH COOH) a dicarboxylic acid. Draw and label their structures. 

This intramolecular bonding in maleic acid, (8), halves its ability to form intermolecular bonds. In fumaric acid, on the other hand, all of the hydrogen bonds form between molecules (intermolecular bonds) to give a stronger, interlinked crystal structure. 

Fractional crystallization, 413 Freezing point lowering, 325, 393 Freon, 362 Frequency of light, 246 relation to wave length, 251 Fructose, 423 Fumaric acid, 428 properties, 308 structure, 316... 

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. 

Complexes. The iodine complexes of 1,5-naphthyridine and other heterocycles have been used under anhydrous conditions to estimate the pK.t values for such heterocycles.885 The structures of 1 1 complexes of 1,5-naphthyridine with oxalic acid,1024 fumaric acid,1024 or meso- 1,2-diphenyl- 1,2-ethane-diol1021 have been studied. Complexes of 1,5-naphthyridine with Co(II), Ni(II), Cu(II), Zn(II), and Ag(I) salts have been prepared 705 the mono- and... 

Brown, C. J. (1966). The crystal structure of fumaric acid. Acta Crystallogr. 21, 1. 

Hsiou, Y., Wang, Y. and Liu, L.-K. (1989). Structures of tetracarbonyl (2-3-r -maleic acid)iron, cA-[Fe(C4H404)(C0)4], and tetracarbonyl (2-3-r -fumaric acid)iron, trara-[Fe(C4H404)(C0)4]. Acta Crystallogr. C45,... 

Pedone, C. and Sirigu, A. (1968). Crystal structure and absolute configuration of (-)-tetracarbonyl(fumaric acid)iron. Inorg. Chem. 7, 2614. 

Although the free phenolic structures are oxidized faster, chlorine dioxide also destroys nonphenolic phenyl propane units and double bonds present in the pulp chromophores. After cleavage of the benzene ring various di-carboxylic acids are formed, such as oxalic, muconic, maleic, and fumaric acids in addition to products substituted with chlorine (Fig. 8-10). As a result of depolymerization and formation of carboxyl groups the modified lignin is dissolved during the chlorine dioxide treatment and in the sodium hydroxide extraction stage that usually follows. 

While these experiments stimulated other research, it is sad to relate that the proposed explanation is not correct. It required almost seventy years, however, before it was realized that the curare-like action of the onium salts was a result of their ionic character. Other examples of the role of spatial arrangement were discovered. For example, quoting Stewart Ishizuka (1897) found that maleic acid was a much stronger poison than its stereoisomer, fumaric acid 1.94 grammes for every kilogramme in a dog s weight was a fatal dose of the former acid, while the same dose of fumaric acid was harmless. Similarly these isomers were found to have differential effects on microorganisms. Stewart also rationalized the mydriatic action of tropine and the inactivity of pseudotropine in terms of three-dimensional formulae as shown below (1 and 2). In many ways, these structural representations are close to the present-day conformational structures (pseudotropine = 3, tropine = 4) ... 

Generally speaking, these distinctions have not been observed by biochemists. Stereoselective has been little used, and stereospecific has been used to cover almost all aspects of the impact of stereochemical influences on reactions in living tissues or enzyme systems. Consider, for instance, the enzymatic hydration of fumarate by the enzyme, fumarase. Since there is a relationship between the structure of the substrate and product, the process could be described as stereospecific. Yet the definition of stereospecific requires that it be shown that the isomer of fumaric acid gives rise to a product which is stereochemically different from L-malate. Since the enzyme, however, does not catalyze any reaction with the (Z)-isomer (maleic acid) it is not clear whether stereospecific actually applies. 

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