As far as TFSE showed this reaction hasn´t been given much notice at the Hive. Undeservingly, I might say,because it seems to have a great potencial for clandestine chemistry.
It is related to the Schmidt rearrangement (although it only applies to aldehydes and ketones) in the sense that the intermediate product is the same, but it doesn´t involve the use of NaN3 or HN3.
It consists on turning a Ketoxime or an aldoxime into an N-alkyl amide, using a Lewis acid like H
2SO
4 or PCl5 according to the following scheme:
+H
+ -H
2O
(R)
2-C=N-OH -------> R-C
+=N-R
H
2O
-H
+ -------> R-(C=O)-NH-R
The book where I took this from says that, for unsimetrical ketones, the rate of migration of the R groups should be similar to the Schmidt rearrangement:
t-C4H9 > C6H5 ~ i-C3H7 > C2H5 > CH3
or, as a general rule, that the bulkier R group will migrate preferentialy.
So, if I´m not mistaken, this offers the possiblity of turning, for example:
-acetone oxime into N-methylacetamide(hydrolyse to get methylamine)
-
acetaldoxime into N-methyl formamide(you can also hydrolyse this one, if you want
)
-any phenylpropanal oxime into the corresponding N-formyl phenethylamine
Unfortunately the only experimental procedures the book uses to "ilustrate" the rearrangement are for caprolactam from ciclohexanone oxime and Isatine from aniline and cloral hydrate and I don´t know how general these are. But some searching should dig up more usefull material. They also give some references:
F. Möller, Houben-Weyl, Vol XI/1 page 872-876, 899-903 (1957)
L. G. Donaruma and W. Z. Heldt, Org. reactions 11, 1-156 (1960)
and another one, a russian paper, I think, but it is written in cyrilic.