An Efficient and Chemoselective Method for Oximination of β-Diketones Under Mild and Heterogeneous Conditions

Mohammad Ali Zolfigol

doi:10.3390/60800694

Abstract

A combination of oxalic acid dihydrate and sodium nitrite in the presence of wet SiO2 was used as an effective nitrosating agent for the nitrosation of β-diketones to their corresponding α-oximinoketones in moderate to excellent yields under mild and heterogenous conditions.

Highlights

The α-oximinoketones are known to be important intermediates for the synthesis of aminoacids [1], nitrosopyrazoles [2], 2-vinylimidazoles [3] and so on
Nitrous acid or one of its esters [4], alkyl thionitrite or thionitrate [5], nitrosyl halides [6] and sodium nitrite in acetic acid [7] are all used for the synthesis of α-oximinoketones, the yields, selectivity for mono oximination and chemoselectivity on the methylene carbon where there are two possible sites of nitrosation are low [5]
It was observed that exclusive nitrosation of acetylacetone occurred, whereas the 2,5-hexadione remained intact in the reaction mixture, even after 5 hours (Scheme 2)

Summary

Introduction

The α-oximinoketones are known to be important intermediates for the synthesis of aminoacids [1], nitrosopyrazoles [2], 2-vinylimidazoles [3] and so on. Nitrous acid or one of its esters [4], alkyl thionitrite or thionitrate [5], nitrosyl halides [6] and sodium nitrite in acetic acid [7] are all used for the synthesis of α-oximinoketones, the yields, selectivity for mono oximination and chemoselectivity on the methylene carbon where there are two possible sites of nitrosation are low [5]. We wish to report a one-pot heterogeneous procedure for Molecules 2001, 6 chemoselective mono oximination of β-diketones by oxalic acid dihydrate (C2H2O4·2H2O, Pka~2) and sodium nitrite.

Results

Conclusion