Sustainable synthesis of aldehydes, ketones or acids from neat alcohols using nitrogen dioxide gas, and related reactions.
Benzylic alcohols are quantitatively oxidized by gaseous nitrogen dioxide to give pure aromatic aldehydes. The reaction gas mixtures are transformed to nitric acid, which renders the processes free of waste. The exothermic gas-liquid or gas-solid reactions profit from the solubility of nitrogen dioxide in the neat benzylic alcohols. The acid formed impedes further oxidation of the benzaldehydes. The neat isolated benzaldehydes and nitrogen dioxide quantitatively give the benzoic acids. Solid long-chain primary alcohols are directly and quantitatively oxidized with nitrogen dioxide gas to give the fatty acids in the solid state. The oxidations with ubiquitous nitrogen dioxide are extended to solid heterocyclic thioamides, which gives disulfides, and to diphenylamine, which gives tetraphenylhydrazine. These sustainable (green) specific oxidation procedures produce no dangerous residues from the oxidizing agent or from auxiliaries.
Naimi-Jamal
M Reza
MR
Department of Chemistry, Iran University of Science and Technology, Tehran, Iran. naimi@iust.ac.ir
Hamzeali
Hamideh
H
Mokhtari
Javad
J
Boy
Jürgen
J
Kaupp
Gerd
G
D000438:Alcohols / Q000737:chemistry*; D000447:Aldehydes / Q000138:chemical synthesis*; D001547:Benzaldehydes / Q000737:chemistry; D004159:Diphenylamine / Q000737:chemistry; D005227:Fatty Acids / Q000138:chemical synthesis* / Q000737:chemistry; D005740:Gases / Q000737:chemistry*; D055772:Green Chemistry Technology / Q000379:methods*; D007659:Ketones / Q000138:chemical synthesis*; D009585:Nitrogen Dioxide / Q000737:chemistry*; D010084:Oxidation-Reduction; D013379:Substrate Specificity; D013854:Thioamides / Q000737:chemistry
D000438:Alcohols; D000447:Aldehydes; D001547:Benzaldehydes; D005227:Fatty Acids; D005740:Gases; D007659:Ketones; D013854:Thioamides; D004159:Diphenylamine; D009585:Nitrogen Dioxide; C032175:benzaldehyde