99584-16-4Relevant articles and documents
Thiazolyl-phosphine hydrochloride salts: Effective auxiliary ligands for ruthenium-catalyzed nitrile hydration reactions and related amide bond forming processes in water
Garcia-Alvarez, Rocio,Zablocka, Maria,Crochet, Pascale,Duhayon, Carine,Majoral, Jean-Pierre,Cadierno, Victorio
, p. 2447 - 2456 (2013/09/12)
A series of water-soluble N-protonated thiazolyl-phosphine hydrochloride salts have been synthesized and coordinated to the ruthenium(ii) fragment [RuCl2(η6-p-cymene)]. The resulting complexes were evaluated as potential catalysts for the selective hydration of nitriles to primary amides in environmentally friendly aqueous medium. The best results in terms of activity were achieved when tris(5-(2-aminothiazolyl))phosphine trihydrochloride was used as ligand. Using the Ru(ii) complex 9 derived from this salt (3 mol%), the catalytic reactions proceeded cleanly in pure water at 100 °C without the assistance of any additive, affording the desired amides in high yields (>78%) after short reaction periods (0.5-7 h). The process was operative with both aromatic, heteroaromatic, α,β-unsaturated and aliphatic nitriles, and tolerated several functional groups. The utility of 9 in promoting the formation of primary amides in water by catalytic rearrangement of aldoximes and direct coupling of aldehydes with NH2OH·HCl has also been demonstrated.
Bis(allyl)ruthenium(rV) complexes containing water-soluble phosphane ligands: Synthesis, structure, and application as catalysts in the Selective hydration of organonitriles into amides
Cadierno, Victorio,Diez, Josefina,Francos, Javier,Gimeno, Jose
experimental part, p. 9808 - 9817 (2010/10/21)
The novel mononuclear ruthenium(IV) complexes [RuCl2(η 3: η3-C10H16)(L)] [L = (meta-sulfonatophenyl)diphenylphosphane sodium salt (TPPMS) (2a), 1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]decane (PTA) (2b), 1-benzyl-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.13,7]decane chloride (PTABn) (2c), 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) (2d), and 2,4,10-trimethyl-1,2,4,5,7,10-hexaaza-3-phosphatricyclo[3.3.1. 13,7]decane (THPA) (2e)] have been synthesized by treatment of the dimeric precursor [{RuCl(μ-Cl)((η3: η3-C 10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) (1) with two equivalents of the corresponding water-soluble phosphane. Reaction of 1 with one equivalent of the cage-type diphosphane ligand 2,3,5,6,7,8-hexamethyl-2,3,5,6,7,8-hexaaza-1,4- diphosphabicyclo[2.2.2]octane (THDP) allowed also the high-yield preparation of the dinuclear derivative [[RuCl2(η3: η3-C10H16)}2(μ-THDP)] (2f). All these new complexes have been analytically and spectroscopically (IR and multinuclear NMR) characterized. In addition, the structure of 2b, 2c, 2d, and 2 f was unequivocally confirmed by X-ray diffraction methods. Complexes 2a-f are active catalysts for the selective hydration of nitriles to amides in pure aqueous medium under neutral conditions. The wide scope of this catalytic transformation has been evaluated by using the most active catalysts [RuCl 2(η3: η3-C10H 16)(THPA)] (2e) and [{RuCl2(η3: η3-C10H16)}2(μ-THDP)] (2f). Advantages of using MW versus conventional thermal heating are also discussed.
PROCESS FOR THE PREPARATION OF SUBSTITUTED HETEROCYCLES
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Page/Page column 4, (2010/11/27)
The present disclosure generally relates to a process for the preparation of hydroxy-substituted heterocycles such as isoquinolines, naphthyridines, pyridopyridazines, and pyridopyrimidines.
