The preparation of pyridine derivatives from halogenopyridines by means of the Grignard Reaction IV: Synthesis of bis‐(pyridyl‐2) ketone

Jonge, A. P. de; Hertog, H. J. den; Wibaut, J. P.

doi:10.1002/recl.19510701107

Cited by 20 publications

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“…Tris(2-pyridyl)carbinol (TPC) is a facial-capping, trinitrogen ligand which has rarely been used since its original synthesis. TPC was first characterized as a low-yield byproduct in the formation of bis(2-pyridyl)ketone from 2-pyridylmagnesium iodide and ethyl picolinate . The overall yield of TPC has been increased to 25% by a stepwise synthesis of bis(2-pyridyl)ketone from 2-lithiopyridine and 2-cyanopyridine (40%), followed by nucleophilic attack of the ketone with 2-lithiopyridine (60%) (Scheme ). , Synthesis of TPC using 3 equiv of 2-lithiopyridine with either ethylchloroformate or carbonyldiimidazole (CDI) also proceeds in extremely low yields (<10%).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of a Family of Systematically Varied Tris(2-pyridyl)methoxymethane Ligands: Copper(I) and Copper(II) Complexes

Jonas

Stack

1998

Inorg. Chem.

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An efficient modular protocol for synthesizing a series of facial-capping tris-pyridyl ligands, based on the tris(2-pyridyl)methoxymethane backbone, has been developed which allows for systematic variations of the steric demands at the periphery of the ligand. The coordination chemistry of one such family of ligands that positions 0-->3 methoxy groups at the periphery with Cu(I) and Cu(II) is presented. The ligands are tris(2-pyridyl)methoxymethane (L(0)()), bis(2-pyridyl)(2-(6-methoxy)pyridyl)methoxymethane (L(1)()), bis(2-(6-methoxy)pyridyl)(2-pyridyl)methoxymethane (L(2)()), and tris(2-(6-methoxy)pyridyl)methoxymethane (L(3)()). The ligand exchange behavior and, to a lesser extent, the structures of the these complexes vary dramatically given the small perturbation of introducing methoxy substituents. Two distinct coordination modes are observed for the Cu(I) complexes, both in solution and the solid state. One is a pseudo-tetrahedral coordination comprised of the facial-capping, tris-pyridyl ligand and a monodentate ligand such as CH(3)CN, CO, or PPh(3). The other structural type is also a pseudo-tetrahedral Cu(I) monomer formed by two tris-pyridyl ligands coordinated in a bidentate manner with preferable binding by the nonmethoxy pyridyl subunits. With the exception of the most sterically hindered ligand, L(3)(), which only displays monoligation to Cu(I), all ligands form both types of Cu(I) complexes, and the formation is controlled by stoichiometry. Both competitive ligand binding experiments and ligand substitution with CO(g) show that the [(L(0)())(2)Cu](+) and [(L(1)())(2)Cu](+) complexes have nearly equivalent stability in aprotic solvent, and greater stability than the [(L(2)())(2)Cu](+) complex due to inclusion of bulky methoxypyridines into the Cu(I) coordination sphere. The Cu(II) complexes of the ligand series generate "bis-tris", [(L(0)()(-->)(3)())(2)Cu](2+), complexes, with the Cu(II) ligated in a tetragonally distorted octahedral coordination environment. The degree of bulk at the ligand periphery dictates the Cu(II)-ligand bond lengths both in solution and the solid state. In these complexes, the bulky pyridyl ring prefers to bind in the axial position. For the most sterically encumbered ligand, L(3)(), the bisligated Cu(II) complex is moisture sensitive, reacting to give a monoligated, tris-aqua species, [L(3)()Cu(H(2)O)(3)](2+).

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Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of a Family of Systematically Varied Tris(2-pyridyl)methoxymethane Ligands: Copper(I) and Copper(II) Complexes

Jonas

Stack

1998

Inorg. Chem.

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“…Bromohydrins and ketones are the principal products in the reaction of a-bromoaldehydes with organomagnesium compounds as pointed out by Kirrmann and Chancel (118). The preparation of pyridine derivatives from halopyridines by means of the Grignard reaction was presented in an article by de Jonge, den Hertog, and Wibaut (111). Maginnity and Cloke (142) have investigated the action of methylmagnesium iodide on substituted pyrrolines and related substances.…”

Section: Carbon-carbon Alkylations Grignard Reagentmentioning

confidence: 99%

Alkylation

Shreve¹

1953

Ind. Eng. Chem.

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Alkylation is classified this year entirely under the bonding-i.e., carbon to carbon, carbon to oxygen, carbon to nitrogen, carbon to sulfur, carbon to silicon, and carbon to metal. Supplementing this classification, some of the references are arranged under dealkylation. Under these subheads, there are various catalyst divisions. As was true last year, there has been found increasing study of alkylation involving carbon to sulfur, carbon to silicon, and carbon to various metals. Also in this past year patents continue to be a very important part of the compilation. INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 45, No. 9 ALUMINUM CHLORIDE CATALYST EHvell (73) uses aluminum chloride in concentrations of 0.015

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Halopyridines

Mertal

1961

Chemistry of Heterocyclic Compounds: A Series of Monographs

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It is hoped that the organization of this monograph will prove to be selfexplanatory, but a few general observations are in order.Chemical compounds are tabulated exhaustively by the principle of latest position. Thus halogenated pyridinecarboxylic acids are found in Chapter X rather than VI, but hydroxy acids in Chapter XII. The principal exceptions are the quaternary compounds, which proved too numerous to be catalogued, and the N-oxides, which are included in Chapter IV irrespective of nuclear substitution. Other exceptions are explained where they occur.The principle of latest position does not apply to reactions. All reactions for obtaining pyridine derivatives from non-pyridinoid starting materials are covered in Chapter I1 irrespective of substitution. If the starting material is a pyridine derivative, the reaction is discussed instead in the appropriate later chapter or chapters. Thus the conversion of aminopyridines to pyridinols is discussed in Chapters IX and XII.Nomenclature follows Chemical Abstracts.The editor wishes to express his gratitude to Prof. D. S . Tarbell of the University of Rochester for the impetus he gave to this undertaking, to the chemists in many parts of the world who have been so generous with reprints, to the staff of Interscience Publishers for their cooperation, and finally to Dr. R. S. Long and Dr. J. J. Leavitt of American Cyanamid for their patience. ERWINKLINCSBERG vii Contents of Other Parts Part One I. Properties and Reactions of Pyridine and Its Hydrogenated Derivatives. By 11. Synthetic and Natural Sources of the Pyridine Ring.

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The preparation of pyridine derivatives from halogenopyridines by means of the Grignard Reaction IV: Synthesis of bis‐(pyridyl‐2) ketone

Cited by 20 publications

References 13 publications

Synthesis and Characterization of a Family of Systematically Varied Tris(2-pyridyl)methoxymethane Ligands: Copper(I) and Copper(II) Complexes

Synthesis and Characterization of a Family of Systematically Varied Tris(2-pyridyl)methoxymethane Ligands: Copper(I) and Copper(II) Complexes

Alkylation

Halopyridines

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