Reaction of 1-pyridyl-1,3-butanediones and 1,3-dipyridyl-1,3-propanediones

Ferles, M.; Kafka, Stanislav; Silhankova, A.; Šputová, Michaela

doi:10.1135/cccc19811167

Cited by 13 publications

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“…A. Synthesis and Properties of Palladium Complexes. Pyridinylpyrazole ligands 3a (MePPH) and 3b (tBuPPH) were easily obtained by Claisen condensation of ethyl pyridinecarboxylate with methyl ketones and subsequent formation of the pyrazole ring with hydrazine (Scheme ). Reaction of 3a and η 3 -allylpalladium chloride dimer in the presence of AgBF 4 in dichloromethane gave air-stable complex 1a in 89% yield as a white powder (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

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Novel η³-Allylpalladium−Pyridinylpyrazole Complex: Synthesis, Reactivity, and Catalytic Activity for Cyclopropanation of Ketene Silyl Acetal with Allylic Acetates

1998

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Novel cationic η3-allylpalladium−pyridinylpyrazole complexes 1a and 1b were synthesized from 3-alkyl-5-(2-pyridinyl)pyrazole and η3-allylpalladium chloride dimer in the presence of AgBF4. Cationic complexes 1a and 1b were converted into neutral complexes 2a and 2b under basic conditions. These complexes were characterized by 1H, 13C, and 15N NMR studies. Neutral complexes 2a and 2b have high catalytic activity for cyclopropanation of ketene silyl acetals with allylic acetates. Comparison of the cationic and neutral complexes and the reaction mechanism of cyclopropanation were discussed.

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Section: Resultsmentioning

confidence: 99%

“…2-H-3-Methyl-5-(2-pyridynyl)pyrazole (MePPH, 3a). To a suspension of NaH (60 wt % in mineral oil, 5.2 g, 130 mmol) in THF (50 mL) at 0 °C was added acetone (9.54 mL, 130 mmol). The mixture was stirred at room temperature for 20 min, and then allowed to heat to 60 °C.…”

Section: Methodsmentioning

confidence: 99%

Novel η³-Allylpalladium−Pyridinylpyrazole Complex: Synthesis, Reactivity, and Catalytic Activity for Cyclopropanation of Ketene Silyl Acetal with Allylic Acetates

1998

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“…As starting materials the symmetrical 1,3-diketones 1a and 1b were employed, which were obtained by condensation of ethyl 2- or 3-pyridinecarboxylates with the appropriate 2- or 3-acetylpyridines following known procedures [ 25 – 26 ]. Reaction of 1a and 1b with 2-hydrazinopyridine and phenylhydrazine, respectively, afforded the tri(hetero)arylpyrazoles 2a–d which were further converted into the corresponding 4-iodopyrazole derivatives 3a–d by treatment with I 2 /HIO 3 in acetic acid at 80 °C ( Scheme 2 ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of tetrasubstituted pyrazoles containing pyridinyl substituents

Jansa¹,

Schmidt²,

Mamuye³

et al. 2017

Beilstein J. Org. Chem.

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A synthesis of tetrasubstituted pyrazoles containing two, three or four pyridinyl substituents is described. Hence, the reaction of 1,3-dipyridinyl-1,3-propanediones with 2-hydrazinopyridine or phenylhydrazine, respectively, affords the corresponding 1,3,5-trisubstituted pyrazoles. Iodination at the 4-position of the pyrazole nucleus by treatment with I2/HIO3 gives the appropriate 4-iodopyrazoles which served as starting materials for different cross-coupling reactions. Finally, Negishi cross-coupling employing organozinc halides and Pd catalysts turned out to be the method of choice to obtain the desired tetrasubstituted pyrazoles. The formation of different unexpected reaction products is described. Detailed NMR spectroscopic investigations (1H, 13C, 15N) were undertaken with all products prepared. Moreover, the structure of a condensation product was confirmed by crystal structure analysis.

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“…1,3-Diketones and keto aldehydes produced by the Claisen condensation were used a precursors, but unfortunately the product yields were not indicated. A large volume of the research was done by the authors [7,8], who synthesized a series of symmetrical and unsymmetrical 3,5-dipyridyl-substituted pyrazoles and also a few 3,5-dipyridyl-substituted isoxazoles ( The starting materials were 1,3-dipyridylpropanediones. The structures of all the compounds were proved unambiguously, and the yields are the preparatively useful.…”

Section: Pyrazolesmentioning

confidence: 99%

Synthesis of Azoles with Two Pyridine Substituents at Carbon Atoms and Their Use in Coordination Chemistry. (Review)

Вацадзе

Nuriev

Зык

2005

Chem Heterocycl Compd

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Published data on the synthesis of azoles containing two pyridine substituents are analyzed in relation to the type of central five-membered ring. The applications of such molecules as ligands in coordination chemistry are discussed.The design of coordination polymers having unique structures and valuable functional characteristics is one of the most rapidly developing regions of modern chemistry and materials science [1,2]. Most of the employed exo-dentate ligands belong to the bipyridine class with the general formula Py-X-Py, where X is a conjugated disubstituted fragment. The parent of such ligands is 4,4'-bipyridine (X is absent), which has been widely used for a long time in the construction of coordination polymers [3]. The most widely used bridges X include double and triple carbon-carbon bonds, azo and imino groups, and benzene, pyridine, triazine, and tetrazine rings or combinations of these fragments [4].One modern trend in the synthesis of coordination polymers is to use ligands of the Py-X-Py type, where X is a meta-or ortho-substituted azole. The interest in such compounds is due, first, to their electronic characteristics and, second, to the ability of the pyridine nitrogen atom of the azole ring to coordinate with the metal ion. This fact significantly extends the possibilities of the ligands in coordination, enhancing the practical characteristics of the complexes. At the moment the coordination characteristics of a small group of dipyridylazoles have been studied. It is important to emphasize that at this time there has been no systematic treatment of data on the design and synthesis of such compounds. In view of the foregoing it seemed to us important and timely to clarify some of the problems that arise in the synthesis of dipyridylazoles for the systems that are finding use in coordination chemistry.It should be noted that in this paper we restrict ourselves to examination of the synthesis and coordination characteristics of azoles containing not less than one nitrogen atom of the pyridine type. Consequently, we do not consider five-membered donating heterocycles with one heteroatom. The second restriction is the fact that we decided to examine only azoles substituted by pyridine groups at carbon atoms, and the range of compounds studied does not therefore include tetrazoles.The review is divided up according to the types of central five-membered heterocycles. In each section the synthetic aspects and questions concerning the use of specific ligands in coordination chemistry are examined. _______ * Dedicated to Academician Nikolai Serafimovich Zefirov in honor of his seventieth birthday. __________________________________________________________________________________________

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Reaction of 1-pyridyl-1,3-butanediones and 1,3-dipyridyl-1,3-propanediones

Abstract: Reduction of diketones I with zinc and formic acid gives monoketones II. Diketones Ia, IIIb, IIIc are converted with hydrazines to pyrazoles VIa, IVa, IVb, V. Methiodides VII are reduced with sodium borohydride to derivatives of 1-methyl-3-piperideine VIII-X.

Cited by 13 publications

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Novel η³-Allylpalladium−Pyridinylpyrazole Complex: Synthesis, Reactivity, and Catalytic Activity for Cyclopropanation of Ketene Silyl Acetal with Allylic Acetates

Novel η³-Allylpalladium−Pyridinylpyrazole Complex: Synthesis, Reactivity, and Catalytic Activity for Cyclopropanation of Ketene Silyl Acetal with Allylic Acetates

Synthesis of tetrasubstituted pyrazoles containing pyridinyl substituents

Synthesis of Azoles with Two Pyridine Substituents at Carbon Atoms and Their Use in Coordination Chemistry. (Review)

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Reaction of 1-pyridyl-1,3-butanediones and 1,3-dipyridyl-1,3-propanediones

Abstract: Reduction of diketones I with zinc and formic acid gives monoketones II. Diketones Ia, IIIb, IIIc are converted with hydrazines to pyrazoles VIa, IVa, IVb, V. Methiodides VII are reduced with sodium borohydride to derivatives of 1-methyl-3-piperideine VIII-X.

Cited by 13 publications

References 0 publications

Novel η3-Allylpalladium−Pyridinylpyrazole Complex: Synthesis, Reactivity, and Catalytic Activity for Cyclopropanation of Ketene Silyl Acetal with Allylic Acetates

Novel η3-Allylpalladium−Pyridinylpyrazole Complex: Synthesis, Reactivity, and Catalytic Activity for Cyclopropanation of Ketene Silyl Acetal with Allylic Acetates

Synthesis of tetrasubstituted pyrazoles containing pyridinyl substituents

Synthesis of Azoles with Two Pyridine Substituents at Carbon Atoms and Their Use in Coordination Chemistry. (Review)

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Novel η³-Allylpalladium−Pyridinylpyrazole Complex: Synthesis, Reactivity, and Catalytic Activity for Cyclopropanation of Ketene Silyl Acetal with Allylic Acetates

Novel η³-Allylpalladium−Pyridinylpyrazole Complex: Synthesis, Reactivity, and Catalytic Activity for Cyclopropanation of Ketene Silyl Acetal with Allylic Acetates