Pyridine-3,5-dicarboxylic acid esters

Systematic studies150,153 with CLX50, (7), decyl esters of pyridine monocarboxylic acids (8)-(10), and dipentyl esters of pyridine dicarboxylic acids (11)—(15) showed that extraction of Cu11 is strongly dependent on the activity of water and the total concentration of ionic and molecular species in the aqueous phase. For the monoesters, copper distribution is dependent on... 

The hydrolysis of esters by the nickel derivative (271) provided an early example of the use of a metal-capped cyclodextrin as a catalyst (shown here as its p-nitrophenyl acetate inclusion complex) (Breslow Overman, 1970 Breslow, 1971). The synthesis of this host involves the following steps (i) covalent binding of the pyridine dicarboxylic acid moiety to cyclodextrin, (ii) coordination of Ni(n) to this species, and (iii)... 

Catalytic groups other than imidazole have been covalently linked to cycloamyloses. Breslow and Overman 14) bound a pyridine dicarboxylic acid group to a secondary hydroxyl by means of the m-nitrophenyl ester. When this group is chelated to pyridine carboxaldoxime through Ni " ", an... 

Many other compounds are presendy in use a 1993 database search showed 27 active ingredients in 212 products registered by the U.S. EPA for human use as repellents or feeding depressants, including octyl bicycloheptene dicarboxamide (lV-2-ethylhexylbicyclo[2.2.1]-5-hepten-2,3-dicarboxamide), dipropyl isocinchomeronate (2,5-pyridine dicarboxylic acid, dipropyl ester), dimethyl phthalate, oil of citronella, cedarwood oil, pyrethrins, and pine tar oil (2). Repellent—toxicant or biting depressant systems are available which are reasonably comfortable for the user and can protect completely against a number of pests for an extended period of time (2). 

Los, M., Ladner, D. W., Cross, B. (2-lmidazolin-2-yl)thieno- and -furo[2,3-b]pyridines and Use of Said Compounds as Herbicidal Agents, U.S. Patent 4,752,323, 1988. Ciba-Geigy, 2-lmidazolinyl-pyridine-and -quinolinecarboxylic Acid Production by Reaction of Pyridine or Quinoline-2,3-dicarboxylic Acid Esters with a 2-Amino-alkanoic Acid Amide, EP 233-150A, 1986. 

Pvridine Dicarboxvlic Hvdrazide A mixture of 100 ml. of benzene, 15 g. of hydrazine hydrate, and 28 g. of 2,5-pyridine dicarboxylic acid methyl ester was heated at reflux on a steam bath for 24 hrs. The mixture was cooled and diluted with 200 ml. of methanol and the finely crystalline product collected. This was dissolved in 1500 ml. of water at the boil, and decolorized with charcoal. About half of the water was removed by evaporation and the product allowed to crystallize. The yield was 22.6 g. m.p. 279-280. Anal. Calcd. for C7H9O2N5 C, 42.9 H, 4.62 N, 35.7. Found ... 

The polyamide obtained by polycondensation of 2,6-diaminopyridine and 2,6-pyridine dicarboxylic acid was the first polymer to assemble itself into a double helix (DNA-type) in solution. The synthesis and physicochemical characterization of some polymer-supported rhodium catalysts based on polyamides containing 2,6- and 2,5-pyridine units were reported by Michalska and Strzelec (2000) these catalysts were used for the hydrosilylation of vinyl compounds such as phenylacetylene. Chevallier et al. (2002) prepared polyamide-esters from 2,6-pyridine dicarboxylic acid and thanolamine derivatives and investigated their polymer sorption behavior towards heavy metal ions. Finally, Scorlanu et al. (2006) also prepared a polymer with improved performance based on polyureas containing 2,6-pyridine moiety and polyparabanic acids, and polymethane-ureas containing 2,6-pyridine rings. 

Esters of pyridine-dicarboxylic acids are reduced to dihydro-compounds by aluminium and wet ether o s ... 

This reaction consists of the condensation of two molecular equivalents of a 1,3 diketone (or a J3-keto-ester) with one equivalent of an aldehyde and one of ammonia. Thus the interaction of ethyl acetoacetate and acetaldehyde and ammonia affords the 1,4-dihy dro-pyridine derivative (1), which when boiled with dilute nitric acid readily undergoes dehydrogenation and aromatisation" to gb e the diethyl ester of collidine (or 2,4,6-trimethyl-pyridine-3,5 dicarboxylic acid (II)). For the initial condensation the solid aldehyde-ammonia can conveniently be used in place of the separate reagents. 

Pyrazolo[l,5-a]pyridine-2,3-dicarboxylic acid dimethyl ester synthesis, 5, 153 Pyrazolopyridines acylation, 5, 311 6-fused... 

Unexpectedly strong intermolecular hydrogen bonding has been reported by IR spectroscopic studies for tetrahydro-4,7-phenanthroline-l,10-dione-3,8-dicarboxylic acids, which exist in the oxo-hydroxy form 165 in both solid state and in solution [78JCS(CC)369].Tlie conclusion was based on comparison of B-, C-, and D-type bands for 165 and their dimethyl esters (detection of hydrogen bonding) and on analysis of IR spectra in the 6 /xm region (pyridine- and pyridone-like bands). 

The scope of this reaction is similar to that of 10-21. Though anhydrides are somewhat less reactive than acyl halides, they are often used to prepare carboxylic esters. Acids, Lewis acids, and bases are often used as catalysts—most often, pyridine. Catalysis by pyridine is of the nucleophilic type (see 10-9). 4-(A,A-Dimethylamino)pyridine is a better catalyst than pyridine and can be used in cases where pyridine fails. " Nonbasic catalysts are cobalt(II) chloride " and TaCls—Si02. " Formic anhydride is not a stable compound but esters of formic acid can be prepared by treating alcohols " or phenols " with acetic-formic anhydride. Cyclic anhydrides give monoesterified dicarboxylic acids, for example,... 

The Ni - and Zn " " -complexes of phenyl and salicyl esters of pyridine-2,6-dicarboxylic acid [50a and b] hydrolyse much faster than the uncomplexed esters (Breslow and McAllister, 1971) the rate of hydroxide ion catalysis of the Ni " -complexes increases 9300... 

Reaction of the m-nitrophenyl ester of pyridine-2,5-dicarboxylic acid with cyclodextrin (see Section 3) gives a picolinate ester [52] of a cyclodextrin secondary hydroxyl group (Breslow, 1971 Breslow and Overman, 1970) which will bind metal ions or a metal ion-pyridine carboxaldoxime complex. Such a complex will catalyse hydrolysis of p-nitrophenyl acetate bound within the cyclodextrin cavity leading to a rate constant approximately 2000-fold greater at... 

Dimethyl-4-phenyl-l,4-dihydro-pyridine-3,5-dicarboxylic acid diethyl ester... 

A mixture of the oxazole (I) with two moles of diethyl maleate (Ila) is heated and the adduct cleaved with ethanolic hydrogen chloride to form the diethyl ester of 2-methyl-3-hydroxy-pyridine-4,5-dicarboxylic acid hydrochloride (Ilia) (85%). This diester is reduced with lithium aluminum hydride to pyridoxine (41-42) isolated as its hydrochloride. 

Derivatives of pyridine-3,5-dicarboxylic acid have been shown to undergo reaction with lithium aluminum hydride by attack on the pyridine ring to form 1,4-dihydropyridines.57,58 Presumably the decrease in electron-density at the ring carbon atoms due to these substituents causes the ring to be extremely susceptible to hydride attack. Similar results were obtained with 3,5-dicyanopyridine derivatives. Methyl nicotinate, however, underwent reaction with LAH with exclusive reduction of the ester function.57 Recently the 3,5-dicyanopyridines have been reported to give mixtures of 1,2- and 1,4-dihydropyridines on reduction with LAH or sodium boro-hydride.20 ... 

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