Electrochemical synthesis of aliphatic 1,3-dinitro compounds

Citation
Zi. Niazimbetova et al., Electrochemical synthesis of aliphatic 1,3-dinitro compounds, J ELCHEM SO, 147(1), 2000, pp. 256-259
Citations number
8
Categorie Soggetti
Physical Chemistry/Chemical Physics","Material Science & Engineering
Journal title
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
ISSN journal
00134651 → ACNP
Volume
147
Issue
1
Year of publication
2000
Pages
256 - 259
Database
ISI
SICI code
0013-4651(200001)147:1<256:ESOA1C>2.0.ZU;2-D
Abstract
A one-step electrochemical synthesis of 1,3-dinitro compounds from aromatic and heteroaromatic aldehydes and nitromethane has been developed. in the p rocedure. an electrogenerated base is prepared by cathodic reduction of air -saturated nitromethane solutions. Then the aldehyde is added and allowed t o react. The reaction presumably proceeds in thrice base-catalyzed steps: a ddition of nitromethane to the aldehyde to form a nitroalcohol, dehydration of the nitroalcohol to produce nitroolefin. and Michael addition of nitrom ethane to the nitroolefin. The synthesis produces the 1.3-dinitro products in very good yields when the aryl group is electron-donating in character. For less strongly electron-donating groups, only moderate yields are obtain ed and with electron-withdrawing groups the reaction tends to stop at the s tags of the nitroalcohol. For purposes of comparison, four of the products were prepared in a multistep synthesis with the last step being the cathodi cally promoted Michael addition of nitromethane to the nitroolefin. It was found that this last procedure was also successful in forming the 1,3-dinit ro derivative from 2-thiophenecarbox-aldehyde and nitroethane in good yield and ail three isomers of the product were separated and characterized. The stereochemical identity of one isomer was proved by X-ray crystallography whereas that of the other two was established by comparison of. nuclear mag netic resonance spectra with those of the isomers of an analogous compound of known stereochemistry. (C) 2000 The Electrochemical Society. S0013-4651( 99)06-092-9. All rights reserved.