Premium
Electrochemical Synthesis of Organophosphorus Compounds through Nucleophilic Aromatic Substitution: Mechanistic Investigations and Synthetic Scope
Author(s) -
Cruz Hugo,
Gallardo Iluminada,
Guirado Gonzalo
Publication year - 2011
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201101357
Subject(s) - chemistry , nucleophile , phosphonate , phosphorane , nucleophilic substitution , electrochemistry , tetrafluoroborate , reagent , electrophilic aromatic substitution , substitution reaction , nucleophilic aromatic substitution , organic chemistry , combinatorial chemistry , medicinal chemistry , ionic liquid , catalysis , electrode
Advantages of the electrochemical approach in the nucleophilic aromatic substitution reaction, such as (a) low cost and ready availability of reagents, (b) atom economy, and (c) high yields (approaching 100 %), are applied to rationalize the (polar or radical) mechanism and to develop new greener synthetic routes for the synthesis of substituted nitroaromatic organophosphorus compounds. The nucleophiles used to study the feasibility and viability of the reaction are the classical tervalent phosphorus nucleophiles: trimethylphosphane, triethylphosphane, triphenylphosphane, diphenylphosphane, trimethyl phosphite, triethyl phosphite, dimethyl phosphonate, diethyl phosphonate, oxo(diphenyl)phosphorane, with two nitroaromatic compounds 1,3,5‐trinitrobenzene and 1‐chloro‐2,4,6‐trinitrobenzene in a DMF solution containing 0.1 M tetrabutylammonium tetrafluoroborate. In all cases, in order to establish the feasibility or benefits of the electrochemical approach relative to the chemical approach, blank reactions were also performed.