100795-50-4Relevant academic research and scientific papers
A new prearranged tripodant ligand N,N′,N″-trimethyl-N,N′,N″-tris(3-pyridyl)-1,3, 5-benzene tricarboxamide is easily obtained via the N-methyl amide effect
Jorgensen, Mikkel,Krebs, Frederik C.
, p. 4717 - 4720 (2001)
The N-methyl amide cis generating effect has been utilised to create a new prearranged tripodant ligand in two synthetic steps from benzene-1,3,5-tricarboxylic acid. Crystals of the ligand itself and of complexes with metal salts such as silver(I) triflate, copper(I) and copper(II) chloride and ruthenium(II) chloride have been prepared and the crystal structures solved by analysis of X-ray diffraction data.
Acceleration of Pd-Catalyzed Amide N-Arylations Using Cocatalytic Metal Triflates: Substrate Scope and Mechanistic Study
Becica, Joseph,Dobereiner, Graham E.
, p. 5862 - 5870 (2017)
The Pd/xantphos-catalyzed cross-coupling of amides and aryl halides is accelerated by cocatalytic metal triflate additives. A survey of nitrogen nucleophiles reveals improved yields for a variety of N-aryl amide products when Al(OTf)3 is employed as a catalytic additive, with some exceptions. Initial rates of catalysis indicate that the Lewis acid acceleration is more pronounced when bromobenzene (PhBr) is used in comparison with iodobenzene (PhI). The observation of an aryl halide dependence on rate and various qualitative kinetic experiments are consistent with a mechanism in which ligand exchange of halide for amide ("transmetalation") is turnover limiting. The mechanism may be different depending on whether PhBr or PhI is used as a coupling partner. Oxidative addition complexes (xantphos)Pd(Ph)(X) (X = Br, I; xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene), likely intermediates in catalysis, have been prepared; their differing interactions with Yb(OTf)3 in solution resemble the halide dependence of the catalytic mechanism, which we propose originates from a reversible Lewis acid mediated halide abstraction during catalysis.
Cross coupling of 3-bromopyridine and sulfonamides (R1NHSO2R2·R1 = H, Me, alkyl; R2 = alkyl and aryl) catalyzed by CuI/1,3-di(pyridin-2-yl)propane-1,3-dione
Han, Xiaojun
experimental part, p. 360 - 362 (2010/03/24)
N-(3-Pyridinyl)-substituted secondary and tertiary sulfonamides have been synthesized in good to excellent yields by the reaction of 3-bromopyridine with primary and secondary alkyl and aryl sulfonamides (MeSO2NH2, MeSO2NHMe, TolSO2NH2, TolSO2NHMe, 1,3-propanesultam, and 1,4-butanesultam), catalyzed by CuI (20 mol %) and 1,3-di(pyridin-2-yl)propane-1,3-dione (20 mol %) with K2CO3 (200 mol %) in DMF (0.17 M for ArBr) at 110-120 °C over 36-40 h. 2-Bromopyridine, 4-bromopyridine, and a wide variety of substituted phenyl bromides can also be successfully coupled with sulfonamides under these reaction conditions.
Reactions of N-Heteroaromatic Bases with Nitrous Acid. Part 7. Kinetics of the Nitrosation of the Secondary and of the Daizotisation of Primary β-Aminopyridines
Kalatzis, Evangelos,Papadopoulos, Panayiotis
, p. 248 - 255 (2007/10/02)
The nitrosation of 3-methylaminopyridine and 3-methylaminopyridine 1-oxide and the diazotisation of 3-amino-, 3-amino-2-chloro-, and 3-amino-6-methoxy-pyridine in 0.002-0.50M-perchloric acid are first-order in both the amine and nitrous acid.The rate coefficients of these reactions increase in the with an increase in the concentration perchloric acid and of sodium perchlorate.In perchloric acid solutions whose ionic strength is maintained constant by the addition of sodium perchlorate the rate coefficients of the nitrosation of 3-methylaminopyridine and of the diazotisation of 3-aminopyridine show only a rectilinear dependence on the +> of the medium.The nitrosation of 3-methylaminopyridine and the diazotisation of 3-amino, and 3-amino-6-methoxy-pyridine proceed mainly by the interaction of the nitrous acidium ion with the monoprotonated form of these amines whilst the nitrosation of 3-methylaminopyridine 1-oxide and diazotisation of 3-amino-2-chloropyridine proceed by the simultaneous interaction of the nitrous acidium ion with the protonated and the free form of both amines.The nitrosation and diazotisation of the free β-aminopyridines involve an initial interaction between the nitrous acidium ion and the heteroaromatic nucleus whilst the nitrosation and diazotisation of the monoprotonated β-aminopyridines proceed by direct interaction between the nitrous acidium ion and the amino group.These results are contrary to those of the nitrosation and diazotisation of the free and the protonated aromatic amines.Furthermore the nitrous acidium iom seems to show a distinct discrimination in its reaction with the free β-aminopyridines as is evident from a rectilinear relationship between the rate coefficients of their nitrosation and diazotisation and their Ka values.The similarity between the nitrosation and diazotisation results show that the formation of the nitrosamines is the rate-determining stage of the diazotisation of the β-aminopyridines in the acid range examined. pKa Values are recorded.
