Isocinchomeronic Acid Research Articles

Preparation and thermal reactivity of hydrazinium 2,n-pyridinedicarboxylates (n=3, 4, 5 and 6)

Hydrazinium 2,n-pyridinedicarboxylates of general compositions N2H5HA, (N2H5)2A·H2O and N2H5HA·H2A, where H 2 A=2,n-pyridinedicarboxylic acid (n=3, quinolinic acid;n=4, lutidinic acid; n=5, isocinchomeronic acid and n=6, dipicolinic acid) have been prepared by the neutralisation of aqueous solution of hydrazine hydrate with the respective acids, in stoichiometric ratios. Formation of these hydrazinium derivatives has been confirmed by analytical, IR spectral and thermal studies. Among these, the monohydrazinium salts are anhydrous whereas the dihydrazinium salts are monohydrated. While lutidinic and dipicolinic acids form all the three types of salts, the quinolinic and isocinchomeronic acids do not form N2H5HA·H2A and N2H5HA, respectively, except the other two types. Infrared spectra of these salts reveal N-N stretching frequencies of the hydrazinium ion in the region 970-950 cm-1. The simultaneous TG and DTA of these salts show that all of them decompose without clear melting and lose hydrazine endothermically between 200 and 280°C, except dihydrazinium isocinchomeronate monohydrate in which half of the hydrazine molecule is lost exothermically, to give pyridinemono- or dicarboxylic acid intermediate which further decomposes exothermically to gaseous products.

Proton pump activation and growth promotion by cinchomeronic acid in radish

Cinchomeronic acid (CA, 3,4-dicarboxypyridine or 4-carboxynicotinic acid) promoted hypocotyl elongation of radish seedlings when added to the medium or applied to the hypocotyls. On microscopic observation of epidermal cells of the plant, the length of each cell was elongated several times when compared to those of the controls. The mechanism of the plant-growth promotion by CA was investigated with plasma membrane vesicle prepared from radish seedlings. CA elevated the Vmax of vanadate-sensitive H +-ATPase in plasma membrane vesicle by 1.8 times. It was found that CA and quinolinic acid were activators, and isocinchomeronic acid and 2,4-lutidinic acid were inhibitors for the H +-ATPase. These results reflected the effects of these compounds on plant growth. It is suggested that CA activates ATP-dependent proton transport and leads to plant-growth promotion by acid.

Preparation and characterization of some metal(II) complexes of isocinchomeronic acid and X-ray crystal structure ofcis-diaquabis(hydrogen isocinchomeronato)manganese(II)

The reactions between Mn(II), Co(II), Ni(II), and Zn(II) ions with isocinchomeronic acid (H2-isocin) afforded complexes of the general formula M(H-isocin)2-2H2O, whereas Fe(II) gives both red and deep red-brown products of the same formula. Various physical measurements suggest that the complexes of M = Co, Ni, Zn, and Fe (brown) are octahedrally coordinated by two aqua ligands and twotrans-N,O-bidentate H-isocin− anions with dimeric hydrogen bonding. Those for M = Mn and Fe (red) are the correspondingcis isomers. The structure of the manganese complex as determined by X-ray crystallography exhibitsC 2 molecular symmetry with Mn-N = 2.279(2), Mn-O(H-isocin)− = 2.196(2), and Mn-O(aqua) = 2.137(2) A. Each aqua ligand forms two donor O-H ⋯ O hydrogen bonds with carboxy groups of different molecules in adjacent chains.

A method for the preparation of nicotinic acid and its amide from 2-methyl-5-ethylpyridine

Potassium permanganate is a suitable agent for the preparative-scale synthesis of carbonic acids with a variety of structures. Such agents are also quite frequently used in technology, for example, for the preparation of nicotinic acid from 13picoline. We have shown that the permanganate method of oxidation can successfully be used for preparing nicotinic acid from such widely available raw materials as 2-methyl-5-ethylpyridine (MEP), although additional stages must be included, to extract and decarboxylate isocinchomeronic acid (ICA). The first stage of the reaction is carried out using 6 moles of KMnO 4 for each mole of MEP. Addition of the correct quantity of oxidizing agent to the reaction vessel in a single aliquot or as 2-3 portions results in the reaction occurring too violently and with excessively low selectivity, and ICA is then formed with yields close to those described in the literature, i.e., not greater than 45% [1]. During experiments to identify the optimal reaction conditions it was found that the KMn04 dosing should be changed, reducing the amount of oxidizing agent to 0.5-1 moles per mole of pyridine base, and each portion should only be added after complete utilization of the preceding portion, which is easily detected because of the decolorization of the reaction solution. MEP itself has an extensive tendency to oxidize: even at 80~ the first 2-3 portions of KMnO 4 are entirely utilized within 10-15 min. As shown in Table 1, the reaction product at this time point consists of three pyridinecarboxylic acids, namely, 6-methylnicotinic, 5-ethylpicolinic, and isocinchomeronic acids, though the ftrst of these is predominant. As more oxidizing agent is added, the total rate of the process decreases, and the content of 6-methylnicotinic acid in the reaction mix decreases, and the proportion of isocinchomeronic acid increases. Side reactions occur simultaneously, accompanied by breakage of the pyrimidine ring, profound oxidation of the organic material, and correspondingly unexpected degradation of the oxidizing agent. Thus, both 6-methylnicotinic acid and the initial MEP are present in the decolorized oxidation reaction after addition of 6 moles of KMnO4. Increasing the temperaatre of the reaction and addition of excess oxidizing agent promote ICA accumulation. At 90~ and at boiling temperature, addition of 7 moles of KMnO 4 results in completion of the oxidation process within 3-3.5 h. By this time, MEP and pyrimidine monocarboxylic acids are completely consumed, and the ICA yield is 68-72% of the theoretical maximum. Excess utilization of the oxidizing agent is no more than 15% of the amount required for the quantity of MEP used. Experiments with greater excess quantities of KMnO 4 did not give positive results: oxidation of the ICA product started, though all sources of ICA were exhausted before this started. Experiments with increased quantities of oxidizable material and oxidizing agent present risks of overheating, especially in the initial phases of the reaction. In order to avoid complications, the first portions of KMnO 4 should be made smaller, the intervals between addition of KMn04 portions should be increased, the mixing of the reaction should be improved, removal of heat from the reaction area should be efficient, and the oxidizing agent should be added as an aqueous solution. It should also be noted that losses during extraction of ICA from the reaction are small, because its water solubility is low, i.e., 0.05-0.1 at pH 1.3-2.8 [2]. The stage producing nicotinic acid consists of decarboxylation of ICA, which is carried out by heating ICA in a steel autoclave at 230-250~ for 2 h in the presence of a minimal quantity of water: up to 15 mmoles per mole of initial substance [3]. In these conditions, the desired product is obtained with a yield of 98-99%.

Effects of Cinchomeronic Acid and Related Compounds on the Growth of Radish Seedlings

Cinchomeronic acid (CA) at 10–100mM enlarged the leaf area of radish seedlings, and at 10 mM, it increased stem elongation. CA was found in free form in the plants. The effects of CA analogs on the growth of radish seedlings were investigated. Quinolinic acid and dinicotinic acid increased stem elongation, but at 10 mM, isocinchomeronic acid, dipicolinic acid, lutidinic acid, pyridine monocarboxylic acids, and pyrazine monocarboxylate inhibited elongation. Two carboxyl groups, one at the C-3 position of the pyridine ring and the other at the C-2, C-4, or C-5 position, seem to be required for increased growth. Growth was inhibited by pyridine monocarboxylic acids regardless of the position of the carboxyl group, and growth was also inhibitory by pyridine dicarboxylic acids with one carboxyl group at C-2 and the other at a position other than C-3.

ChemInform Abstract: A New Synthesis of (±)‐Lysergic Acid.

AbstractDie N‐benzoylierten Lysergsäureester (VIa) und (VIb) werden ausgehend vom Keton (I) in der im Formelschema skizzierten Weise hergestellt.

Partial Purification and Characterization of Dihydrodipicolinic Acid Reductase from Maize

Dihydrodipicolinic acid reductase, an enzyme which catalyzes the pyridine nucleotide-linked reduction of dihydrodipicolinic acid to tetrahydrodipicolinic acid in the biosynthetic pathway leading to l-lysine, has been partially purified from maize (Zea mays cv Pioneer 3145) kernels. The crude maize extract and the partially purified enzyme were assayed for dihydrodipicolinic acid reductase by their ability to restore the capability of crude extracts of a mutant Escherichia coli (CGSC 4549; defective in dihydrodipicolinic acid reductase) to synthesize diaminopimelic acid from aspartic acid and pyruvic acid.In a study of its properties, the Michaelis constant obtained for dihydrodipicolinic acid was 4.3 x 10(-4) and for NADPH the K(m) was 4.6 x 10(-5). The enzyme had a pH optimum close to 7 and was much more temperature labile than the bacterial enzyme. Its molecular weight was 8.0 x 10(4).Several compounds, viz., alpha-picolinic acid, l-pipecolic acid, isophthalic acid, and isocinchomeronic acid, with structures similar to dihydrodipicolinic acid inhibited the reductase reaction. Dipicolinic acid, the most potent of these inhibitors, acted as a competitive inhibitor with a K(i) of 9.0 x 10(-4). The competitive inhibition of the reductase reaction by dipicolinic acid (oxidized dihydrodipicolinic acid) suggests that the substrate for this enzyme was in the ring rather than the open chain form. Oxidized pyridine nucleotide inhibited the activity slightly.

A thermoanalytical study of dipicolinic acid acting as a terdentate ligand in coordination compounds of divalent metal ions

The coordination compounds obtained by reaction of hot solutions of dipicolinic acid with the carbonates of the divalent metal ions manganese(II), iron(II), cobalt(II), nickel(II), copper(II) and zinc(II) are studied using TG, DSC and HTRS techniques. For the thermal stability a sequence Mn > Fe > Zn > Co > Ni > Cu may be observed. This series is compared with the similar series obtained with isocinchomeronic acid. The thermal stability is, for each metal of the series, isocinchomeronic > dipicolinic. Thermal stability is discussed in terms of the intermolecular bonds, of the structures and of the stability constants of the complexes examined.

Thermal properties of some complexes of quinolinic acid with divalent metal ions

Studies of the complexes of pyridinecarboxylic acids with divalent metal ions as a function of the position of the carboxyl groups were extended. The thermal properties of the complexes of quinoline acid (pyridine-2,3-dicarboxylic acid) with several divalent metal ions were determined by thermogravimetry (TG) and differential thermal analysis (DTA). A correlation between these compounds and others obtained by reaction between the studied metal ions with similar acids (lutidinic acid (pyridine-2,4-dicarboxylic acid) and isocinchomeronic acid (pyridine-2,5-di-carboxylic acid) is discussed in terms of the position of the carboxyl group far from the aza group. The thermal stability of the metal complexes is in the order Mn(II) > Fe(II) > Zn(II) ⋍ Co(II) > Ni(II) > Cu(II).

Effect of ammonium ions on the polarographic behavior of nitriles and amides of some pyridinecarboxylic acids

The character of the polarographic reduction of picolinonitrile, nicotinonitrile, isonicotinonitrile, isocinchomeronic acid dinitrile, picolinamide, and nicotinamide on a dropping mercury electrode with a buffer-solution base electrolyte in the presence of ammonium ions depends on the concentration of the ammonium ions, which interact with the ring nitrogen.

Thermal properties of some compounds of lutidinic acid with divalent metals

The thermal properties of the complexes of lutidinic acid with several divalent metal ions were determined by thermogravimetry (TG) and differential thermal analysis (DTA). The complexes precipitate from aqueous solution as hydrated 1:1 complexes. On heating in air, hydrate water is lost first, followed by total disruption of the anhydrous complex to yield the metal oxide; in a nitrogen atmosphere, the pattern is similar, but final weight constancy is not achieved. The thermal stability of the metal complexes is in the order: Mn(II)>Fe(II)>Co(II)≅ Zn(II)>Ni(II)>Cu(II) The different metal-ligand ratio in the solid state for analogous compounds with isocinchomeronic acid is discussed.

The system aluminium(III)-isocinchomeronic acidin aqueous 0·5 M sodium perchlorate medium

Complex formation between isocinchomeronic (2,5-pyridinedicarboxylic) acid and the aluminium ion, at 25°C in aqueous 0·5 M NaClO 4, was studied potentiometrically by measuring the hydrogen-ion concentration. The cumulative formation constants of the acid species HL − and H 2 L were determined at the same temperature and for the same ionic medium: logβ 1L=4·58±0·01 logβ 2L=6·75±0·01 At pH between 2 and 3·5 and in the concentration range, 2·48 ≤ C M ≤ 7·43 mM, 2·27 ≤ C L ≤ 12·5 mM, the potentiometric results can be explained by the formation of two mononuclear complexes according to the equilibria: Al 3 + +L 2 − ⇌ AlL + logβ 1=3·95±0·02 Al 3 + +2L 2 − ⇌ AlL 2 − logβ 2=7·24±0·02 . Paper-electrophoretic and conductometric investigations confirmed the presence of the complexes. It is impossible to study the system by spectrophotometric methods, which cannot in this case give precise results.

Properties of glucose dehydrogenase from vegetative cells of Bacillus subtilis and effect of dipicolinic acid and its chemical analogues on the enzyme.

The glucose dehydrogenase from vegetative cells of Bacillus subtilis PCI 219 strain was partially purified through two ammonium sulfate fractionations and a filtration on Sephadex G-200. The optimal pH for stability of this enzyme was 6.0 and the optimal pH for the reaction catalyzed was 6.8. The Michaelis constant for glucose was 5.1×10−3 M at pH 6.8. High concentrations of lutidinic acid and isocinchomeronic acid remarkably protected the enzyme from heat inactivation, while dipicolinic acid showed a moderate protecting effect. Other chemical analogues of dipicolinic acid, such as quinolinic acid, nicotinic acid and isonicotinic acid, had less effect than dipicolinic acid, and phthalic acid had no effect. These effects of dipicolinic acid and other chemicals on the activity of glucose dehydrogenase from the vegetative cells were same with those on the activity of glucose dehydrogenase from the spores.

Synthetical Applications of Activated Metal Catalysts. XVIII. The Formation of 2,2',5',2'-Terpyridyl in the Reaction of Pyridine with Degassed Raney Nickel

2,2?,5?,2"-Terpyridyl has been isolated in c. 0.1 % yield from the reaction between pyridine and degassed Raney nickel. The structure of this terpyridine has been proved by degradation to picolinic acid and isocinchomeronic acid.

2-メチル,5-エチルピリジンの酸化によるイソシンコメロン酸の合成

2-メチル,5-エチルピリジンの酸化によるイソシンコメロン酸の合成

Effect of niacin precursors on the excretion of niacin metabolites.

Conclusions1. The effect of tryptophan, quinolinic acid, ornithine, isocinchomeronic acid, and anthranilic acid on the ability of the rat to form niacin derivatives has been determined.2. Isocinchomeronic acid does not appear to be an intermediate in the synthesis of niacin.3. Ornithine and anthranilic acid seem to stimulate the synthesis of niacin in the intestinal tract only.4. The results neither prove nor refute the theory that quinolinic acid is a possible intermediate in the tryptophan niacin synthesis scheme.