Pyridoxine derivatives

Diels-Alder reactions.2 This vinyl sulfone has been used as an acetylene equivalent in a new synthesis of vitamin Be. Thus 1 undergoes a Diels-Alder reaction with 4-methyloxazole (2) to give a pyridoxine derivative (3) with elimination of mcthanesulfinic acid. The product is converted into the vitamin (4) in three simple steps. 

Aksenova and Messineva (A2) investigated the excretion of 4-pyridoxic acid in 63 patients affected by different forms of leukemia and hypoplastic anemia. Since all pyridoxine derivatives are oxidized to 4-pyridoxic acid, such a compound was considered an index of vitamin Be balance. These patients showed a deficiency of pyridoxine, which increased with simultaneous loadings of tryptophan and pyridoxine (A2). 

Examples of such a behaviour have been observed for maleic and fumaric acids (Hanu and BrdiCka, 1950), phthalic acid (Ryvolova and HanuS, 1956) and pyridoxine derivatives (ManouSek and Zuman, 1964). 

Maeno, M., Morimoto, Y., Hayakawa, T., Suzuki, Y., and Tsuge, H., 1997. Feeding experiments of pyridoxine derivatives as vitamin Bg. International Journal for Vitamin and Nutrition Research. 61 444-449. 

T.G. Nam, J.M. Ku, C.L. Rector, H. Chjopi, N.A. Porter, and B.S. Jeong. Pyridoxine-derived licyche aminopyridinal antioxidants Synthesis and their antioxidant activities. Org. Biomal. Ghent. 9 8475-8452 (2011). 

Fat-soluble vitamins are vitamin A, D, E and K. Water soluble vitamins include the B group vitamins or vitamin B complex (which refers to all of the known essential water-soluble vitamins except for vitamin C) and vitamin C. The B group vitamins are thiamine, riboflavin, niacin, pyridoxinal derivatives, pantothenic acid, biotin, folacin and the corrinoids. 

Moller, J. and Bitsch, R., Einsatz der Hochleistungs-fliissigchromatographie (HPLC) zur simultanen Bestimmung der Pyridoxin-derivate aus Biologischen Materialien, Emah-ning. Umsch., 35(9), 324-328, 1988. 

Thus a thiamine derivative plays a metabolic role as cocarboxylase, which has been found to be inactivated by a specific phosphatase of yeast (122,123). The inactivation was inhibited by thiamine itself and to a lesser degree by thiamine monophosphate and the pyrimidine constituent of the thiamine molecule. Synthesis and breakdown of thiamine by Phycomyces species have also been studied (9,45,98). Pyridoxine derivatives are now known to catalyze two t3T)cs of bacterial reactions, involving transamination and decarboxylation of amino acids (4,32,35,59). Interconversion between members of the group of substances of natural occurrence which are related to pyridoxine has been observed in microorganisms and appears likely to afford a series of changes comparable to those observed in nicotinic acid dreivatives. Production of folic acid from chemically defined precursors by bacterial suspensions has also been observed (110,111). 

Table 1. Properties of Pyridoxine, Pyridoxamine, Pyridoxal, and Derivatives...

Most amino acids lose their nitrogen atom by a transamination reaction in which the -NH2 group of the amino acid changes places with the keto group of ct-ketoglutarate. The products are a new a-keto acid plus glutamate. The overall process occurs in two parts, is catalyzed by aminotransferase enzymes, and involves participation of the coenzyme pyridoxal phosphate (PLP), a derivative of pyridoxine (vitamin UJ. Different aminotransferases differ in their specificity for amino acids, but the mechanism remains the same. 

Plants contain to some extent less bioavailable forms of vitamin B6, e.g., glycosylates, or biologically inactive metabolites, e.g., e-pyridoxin-lysin-complexes. In addition, the release of vitamin B6 from foods rich in fiber is assumed to be delayed. The bioavailability of vitamin B6 from animal-derived foods is therefore overall higher than from plant-derived foods. Good dietary sources of vitamin B6 include chicken, fish, pork, beans, and pulses [1]. 

Pyridoxal 157,158,253 Pyridoxamine 253 Pyridoxine 253 Pyrimidines 266,438, 439 Pyrocatechol see 1,2-Dihydroxybenzene I ocatecholsulfophthalein 398 I ocatechol violet reagent 398 Pyrolysis of organic compounds 92, 96 a,y-Pyrone derivatives 288 Pyrrole alkaloids 66 Pyrrole derivatives 266, 269, 270 Pyruvic acid 426... 

Purpuric acid lb 174 Pyrazolidine derivatives la 426 3,5-Pyrazolidindione derivatives lb 20 Pyrazolinone derivatives lb 277 Pyrazolin-5-one derivatives lb 327,329 Pyrazone lb 332 Pyrene lb 379 PyrethrinI lb 18 Pyrethrin II lb 18 Pyrethroids lb 86,87 Pyrethroid insecticides la 359 Pyridine alkaloids la 66 lb 279 Pyridine derivatives lb 119,244 Pyridinium carbinols lb 65 Pyridinium glycols lb 65 Pyridoxal la 157,158,253 Pyridoxamine la 253 Pyridoxine la 253... 

Brousmiche, D. W. Wan, P. Photogeneration of quinone methide-type intermediates from pyridoxine and derivatives. J. Photochem. Photobiol. A Chem. 2002, 149, 71-81. 

Vitamin B6 (pyridoxine) and its derivative pyridoxamine are apparently able to inhibit superoxide production, reduce lipid peroxidation and glycosylation in high glucose-exposed erythrocytes [353], It was suggested that the suppression of oxidative stress in erythrocytes may be a new mechanism by which these natural compounds inhibit the development of complication in diabetes mellitus. 

Vitamin Ba (pyridoxine, pyridoxal, pyridoxamine) like nicotinic acid is a pyridine derivative. Its phosphorylated form is the coenzyme in enzymes that decarboxylate amino acids, e.g., tyrosine, arginine, glycine, glutamic acid, and dihydroxyphenylalanine. Vitamin B participates as coenzyme in various transaminations. It also functions in the conversion of tryptophan to nicotinic acid and amide. It is generally concerned with protein metabolism, e.g., the vitamin B8 requirement is increased in rats during increased protein intake. Vitamin B6 is also involved in the formation of unsaturated fatty acids. 

Group-transfer reactions often involve vitamins3, which humans need to have in then-diet, since we are incapable of realizing their synthesis. These include nicotinamide (derived from the vitamin nicotinic acid) and riboflavin (vitamin B2) derivatives, required for electron transfer reactions, biotin for the transfer of C02, pantothenate for acyl group transfer, thiamine (vitamin as thiamine pyrophosphate) for transfer of aldehyde groups and folic acid (as tetrahydrofolate) for exchange of one-carbon fragments. Lipoic acid (not a vitamin) is both an acyl and an electron carrier. In addition, vitamins such as pyridoxine (vitamin B6, as pyridoxal phosphate), vitamin B12 and vitamin C (ascorbic acid) participate as cofactors in an important number of metabolic reactions. 

This enzyme [EC 2.7.1.35] (also known as pyridoxine kinase, pyridoxamine kinase, and vitamin kinase) catalyzes the reaction of ATP with pyridoxal to produce ADP and pyridoxal 5 -phosphate. Pyridoxine, pyridoxamine, and various other derivatives can also act as substrates. 

Vitamin Bg is a mixture of six interrelated forms pyridoxine (or pyridoxol) (Figure 19.23), pyri-doxal, pyridoxamine, and their 5 -phosphates derivatives. Interconversion is possible between all forms. The active form of the vitamin is pyridoxal phosphate, which is a coenzyme correlated with the function of more than 60 enzymes involved in transamination, deamination, decarboxylation, or desulfuration reactions. 

The B-group is a heterogeneous collection of water-soluble vitamins, most of which function as co-enzymes or are precursors of co-enzymes. The B-group vitamins are thiamin, riboflavin, niacin, biotin, pantothenic acid, pyridoxine (and related substances, vitamin B6), folate and cobalamin (and its derivatives, vitamin B12). 

There are two major disposal pathways for homocysteine. Conversion to methionine requires folate and vitamin B12-derived cofactors. The formation of cysteine requires vitamin B6(pyridoxine). 

Vitamin B6 is a collective term for pyridoxine, pyridoxal, and pyridox amine, all derivatives of pyridine. They differ only in the nature of the functional group attached to the ring (Figure 28.10). Pyridoxine occurs primarily in plants, whereas pyridoxal and pyridoxamine are found in foods obtained from animals. All three compounds can serve as precur sors of the biologically active coenzyme, pyridoxal phosphate. Pyridoxal phosphate functions as a coenzyme for a large number of enzymes, par ticularly those that catalyze reactions involving amino acids. 

Isoniazid (isonicotinic acid hydrazide), a drug frequently used to treat tuberculosis, can induce a B6 deficiency by forming an iiactive derivative with pyridoxal phosphate. Dietary supplementation with B is, thus, an adjunct to isoniazide treatment. Otherwise, cletary deficiencies in pyridoxine are rare but have been observed in newborn infants fed formulas low in vitamin B6, in women taking oral contraceptives, and in alcoholics. 

Two vitamins, nicotinamide and pyridoxine (vitamin B6), are pyridine derivatives. Nicotinamide participates in two coenzymes, coenzyme I (65 R = H) which is known variously as nicotinamide adenine dinucleotide (NAD) or diphosphopyridine nucleotide (DPN), and coenzyme II (65 R = P03H2) also called triphosphopyridine nucleotide (TPN) or nicotinamide adenine dinucleotide phosphate (NADP). These are involved in many oxidation-reduction processes, the quaternized pyridine system acting as a hydrogen acceptor and hydrogen donor. Deficiency of nicotinamide causes pellagra, a disease associated with an inadequately supplemented maize diet. Nicotinic acid (niacin) and its amide are... 

The most important derivatives of 2,5-dihydrofuran are the 2,5-dialkoxy and 2,5-diacetoxy compounds which are easily prepared from furans (Section 3.11.2.3). Their vast utility is as synthetic equivalents of malealdehyde and its derivatives (60MI31100). Suitable intermediates for Robinson-Schopf synthesis have been obtained in this way. Pyridazines are readily obtained (Scheme 121), and 3-pyridinols are available from 2-furylmethanamines (Scheme 122). This approach has been used in a synthesis of pyridoxine. The 2,5-diacetoxy... 

Several Hi antagonist drugs have been studied for possible use in treating "morning sickness." The piperazine derivatives were withdrawn from such use when it was demonstrated that they have teratogenic effects in rodents. Doxylamine, an ethanolamine Hi antagonist, was promoted for this application as a component of Bendectin, a prescription medication that also contained pyridoxine. Possible teratogenic effects of doxylamine were widely publicized in the lay press after 1978 as a... 

---