An effective and mild method for the conversion of oximes to secondary nitro compounds

✍ Scribed by E.J. Corey; Herbert Estreicher

• Book ID: 104236144
• Publisher: Elsevier Science
• Year: 1980
• Tongue: French
• Weight: 304 KB
• Volume: 21
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)83928-9

✦ Synopsis

The carbonyl and nitro functional groups play a major role in organic synthesis.

I, 2 The efficient replacement of one by the other, which enhances this utility, is readily accomplished in the nitro to carbonyl direction. However, the conversion of carbonyl to nitro groups, which is generally effected via oximes using very strong and non-selective oxidants (CF3CO3H, 3a and ozone, 3b principally), is at present only narrowly applicable. This paper reports an especially mild method for the carbonyl to nitro transformation, which should greatly broaden the scope and use of this process.

Upon initial examination, a number of reagents (e. g. tert-butyl hydroperoxide/VO(acac)2 in tetrahydrofuran, pyridinium dichromate in dimethylformamide -(DMF), or lithium hypochlorite in DMF) were found to be inapplicable for conversion of oxime to nitro, since they yielded only ketone. Attention was then turned to the use of IfSand's* o-halonitroso intermediates, despite the problems previously encountered in their efficient synthesis and use, 5 with excellent results. It was found ' C-Cl bend hydromolysiswith H2/pd-C in methanol-water (4: 1) ccntainfng sodium hydroxi& (lo-20 equiv). j Zu dust in THF-water (3:l) containing either ammmium chloride or hydroxylamfne hydrochloride as protcn source k Mixture of cis and trans isomers. _-