Sauron - 1-5-2007 at 12:36
This is a relatively accessible room temperature nitrating agent that was developed by Emmons et al as an offshoot of Olah's work with methyl nitrate
as a nitrating agent for amines catalyzed by BF3-etherate. Emmons reasoned that a methyl nitrate derivative with no alpha hydrogens and with an
electronegative substituent would be superior to the unstable and difficultly prepared methyl nitrate.
Besides nitrating at mild conditions, ACN is also unusual in that it nitrates under neutral to basic conditions rather than the usual strongly acidic
conditions normally required.
Acetone cyanohydrin is readily prepared from acetone and alkili cyanide (Org.Syn. and Vogel) and is also commercially available. It is nitrated with
the white fuming nitric acid/Ac2O system. The white fuming nitric acid is 90% HNO3 d1.48 - 1.50 decolorized with urea and air sparged. This is a
procedure well known to the members who mess with energetics. Details are given in Emmons' original paper and in an Org.Syn. prep of N-nitromorpholine
exemplifying the use of this reagent for nitramines. The acetone cyanohydrin nitrate, previously unknown, was purified by vacuum distillation.
Org.Syn. describes it as moderately explosive. In the Olin drop-block test ACN scored 40 kg-cm to nitromethane's 60 kg-cm and propyl nitrate's 10
kg-cm.
I am attaching the fundamental papers on this reagent and its uses. These include efficient room temperature preparations of nitramines, nitrate
esters of malonic and acetoacetic esters, and nitration of aromatics.
There does not seem to have been any alternative preparative method developed for ACN possibly because of its limited use. Might there not be some
more user-friendly system than WFNA/Ac2O that will do this job?
This zip file is 1.4 Mb so I put it on my 4shared acct linked below rather than use the forum storage
http://www.4shared.com/dir/2245331/5a78115f/sharing.html
[Edited on 2-5-2007 by Sauron]