Hydroxylation of Nitroarenes with Alkyl Hydroperoxide Anions via Vicarious Nucleophilic Substitution of Hydrogen
摘要:
Carbo- -and heterocyclic nitroarenes react with anions of tert-butyl and cumyl hydroperoxides in the presence of strong bases to form substituted o- and p-nitrophenols. The reaction usually proceeds in high yields and is of practical value as a method of synthesis and manufacturing of nitrophenols. Orientation of the hydroxylation can be controlled to a substantial extent by selection of the proper conditions. Basic mechanistic features of this process were clarified.
Treatment of 2-ethoxycarbonylprop-2-enyl peroxides with potassium alkylperoxylate, the sodium enolate of diethyl malonate and a primary or secondary amine yields epoxides via a two-step process: (i) addition of the nucleophile to the acrylic unsaturated bond and (ii) intramolecular anionic substitution on the peroxidic bond.
Reaction of cationic palladium(II) and rhodium(I) complexes with the t-butylperoxy anion: Preparation of t-butylperoxo-palladium(II) and -rhodium(I) complexes
Treatment of the coordinatively unsaturated cationiccomplexes, [(η-C3H5)(Ph3P)2PdII]PF6 and [(1,5-COD)2RhI]BF4, with potassium t-butylperoxide in dichloromethane gives the t-butylperoxometal complexes; (η-C3H5)(Ph3P)(t-BuOO)PdII and [(1,5-COD)(t-BuOO)RhI](KBF4), via nucleophilic attack by t-BuOO− on the cationic metal center.
的配位不饱和阳离子络合物的治疗,[(η-C 3 H ^ 5)(PH 3 P)2钯II ] PF 6和[(1,5-COD)2的Rh我] BF 4,用叔丁醇钾,丁基过氧化物中二氯甲烷得到叔丁基过氧金属配合物。(η-C 3 H ^ 5)(PH 3 P)(叔BuOO)的Pd II和[(1,5-COD)(叔BuOO)的Rh我](KBF 4),通过由叔BuOO亲核攻击-在阳离子金属中心。
Chemiluminescence in the reaction of a sulfurane with alkyl hydroperoxides
作者:Paul D. Bartlett、Tetsuo Aida、Hsien-Kun Chu、Tai-Shan Fang
DOI:10.1021/ja00530a035
日期:1980.5
A synthesis of mixed dialkylperoxides via reaction of an alkylhydroperoxide with alkyl trifluoromethane sulfonates
作者:Mary F. Salomon、Robert G. Salomon、Robert D. Gleim