116241-61-3Relevant articles and documents
Ruthenium (II) and iridium (III) complexes of N-heterocyclic carbene and pyridinol derived bidentate chelates: Synthesis, characterization, and reactivity
Gerlach, Deidra L.,Siek, Sopheavy,Burks, Dalton B.,Tesh, Jamie M.,Thompson, Courtney R.,Vasquez, Robert M.,White, Nicholas J.,Zeller, Matthias,Grotjahn, Douglas B.,Papish, Elizabeth T.
, p. 442 - 450 (2017)
We report the synthesis and characterization of new ruthenium(II) and iridium(III) complexes of a new bidentate chelate, NHCR′-pyOR (OR?=?OMe, OtBu, OH and R′?=?Me, Et). Synthesis and characterization studies were done on the following compounds: four ligand precursors (1–4); two silver complexes of these NHCR′-pyOR ligands (5–7); six ruthenium complexes of the type [η6-(p-cymene)Ru(NHCR′-pyOR)Cl]X with R′?=?Me, Et and R?=?Me, tBu, H and X?=?OTf?, PF6? and PO2F2? (8–13); and two iridium complexes, [Cp?Ir(NHCMe-pyOtBu)Cl]PF6 (14) and [Cp?Ir(NHCMe-pyOH)Cl]PO2F2 (15). The complexes are air stable and were isolated in moderate yield. However, for the PF6? salts, hydrolysis of the PF6? counter anion to PO2F2? during t-butyl ether deprotection was observed. Most of the complexes were characterized by 1H and 13C NMR, MS, IR, and X-ray diffraction. The ruthenium complexes [η6-(p-cymene)Ru(NHCMe-pyOR)Cl]OTf (R?=?Me (8) and tBu (9)) were tested for their ability to accelerate CO2 hydrogenation and formic acid dehydrogenation. However, our studies show that the complexes transform during the reaction and these complexes are best thought of as pre-catalysts.
Novel synthesis method for ortho-alkane superseded pyridine
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Paragraph 0018; 0019; 0020; 0021, (2017/07/19)
The invention relates to a novel synthesis method for ortho-alkane superseded pyridine. According to the method, ortho halogenated pyridine serves as raw materials, the ortho halogenated pyridine and corresponding alcohol react to obtain the ortho-alkane superseded pyridine under the action of sodium hydroxide. The reaction has universality for the ortho halogenated pyridine, and the method is simple and practical. Influence of consumption of the sodium hydroxide on mono-substitution and di-substitution in the reaction is inspected, alkoxy mono-substitution products and alkoxy di-substitution production are acquired, and a novel simply-operated, economical and favorable process for synthesis ortho-alkane superseded pyridine is provided.
Selective C-H fluorination of pyridines and diazines inspired by a classic amination reaction
Fier, Patrick S.,Hartwig, John F.
, p. 956 - 960 (2013/12/04)
Fluorinated heterocycles are prevalent in pharmaceuticals, agrochemicals, and materials. However, reactions that incorporate fluorine into heteroarenes are limited in scope and can be hazardous. We present a broadly applicable and safe method for the site-selective fluorination of a single carbon-hydrogen bond in pyridines and diazines using commercially available silver(II) fluoride. The reactions occur at ambient temperature within 1 hour with exclusive selectivity for fluorination adjacent to nitrogen. The mild conditions allow access to fluorinated derivatives of medicinally important compounds, as well as a range of 2-substituted pyridines prepared by subsequent nucleophilic displacement of fluoride. Mechanistic studies demonstrate that the pathway of a classic pyridine amination can be adapted for selective fluorination of a broad range of nitrogen heterocycles.
