539-23-1Relevant articles and documents
Preparation of highly reactive pyridine- and pyrimidine-containing diarylamine antioxidants
Hanthorn, Jason J.,Valgimigli, Luca,Pratt, Derek A.
experimental part, p. 6908 - 6916 (2012/10/08)
We recently reported a preliminary account of our efforts to develop novel diarylamine radical-trapping antioxidants (Hanthorn, J. J. et al. J. Am. Chem. Soc. 2012, 134, 8306-8309) wherein we demonstrated that the incorporation of ring nitrogens into diphenylamines affords compounds which display a compromise between H-atom transfer reactivity to peroxyl radicals and stability to one-electron oxidation. Herein we provide the details of the synthetic efforts associated with that report, which have been substantially expanded to produce a library of substituted heterocyclic diarylamines that we have used to provide further insight into the structure-reactivity relationships of these compounds as antioxidants (see the accompanying paper, DOI: 10.1021/jo301012x). The diarylamines were prepared in short, modular sequences from 2-aminopyridine and 2-aminopyrimidine wherein aminations of intermediate pyri(mi)dyl bromides and then Pd-catalyzed cross-coupling reactions of the amines and precursor bromides were the key steps to yield the diarylamines. The cross-coupling reactions were found to proceed best with Pd(η3-1-PhC3H 4)(η5-C5H5) as precatalyst, which gave higher yields than the conventional Pd source, Pd2(dba) 3.
Liquid Crystalline Compounds Bearing Pyridine Ring: 3-(4-Alkoxyphenylazoxy)-6-alkoxypyridines
Kamogawa, Hiroyoshi,Kasai, Tsuneharu
, p. 69 - 78 (2007/10/02)
3-(4-Alkoxyphenylazo)-6-alkoxypyridines (6) with n-alkoxyl (C1-C6) groups were synthesized by the coupling reaction of phenol with 6-alkoxy-3-pyridine diazonium chloride prepared from 2-chloro-5-nitropyridine via 2-alkoxy-5-nitro and 2-alkoxy-5-aminopyridines and subsequent etherification with n-alkyl iodides.Mild oxidation of 6 with hydrogen peroxide in acetic acid provided 3-6-alkoxy-pyridines (7) containing nearly equimolar amounts of ONN (8) and NNO (8') isomers.Centrifugal liquid chromatography satisfactorily separated these two isomers.Mesomorphic behaviors of 8 and 8' are characteristic in that the pyridine ring exerts polar effects and 8 are more balanced in polarity than 8'.Compounds 7 possess rather lower mesomorphic ranges than 8 and 8'.Some of compounds 6 indicate mesomorphic ranges but generally azo compounds are inferior to azoxy ones.
