DFliyerz - 12-3-2015 at 12:33
After messing around with drawing random organic compounds like pentanitrotoluene and tetranitro-para-xylene (with both actually turned out to exist),
and seeing how they require extremely powerful nitrating agents to be made such as nitronium tetrafluoroborate, I was wondering (not for actual use in
my garage, of course) what is a very powerful yet relatively safe nitration agent?
Molecular Manipulations - 12-3-2015 at 14:09
Practically anything stronger than nitric and sulfuric acids will be more dangerous than them. Have you done any nitrations with nitric and sulfuric
before?
APO - 12-3-2015 at 15:33
In my opinion, it really depends on what kind of equipment you have to define what would be considered "safe". Level of experience and clumsiness also
comes into play. If I remember right, while refluxing, sometimes a nitrate salt (or combination of salts) dissolved in an aromatic solvent (presumably
very dry) can be used for mild nitration, which in some sense is slightly safer. But, it's not very easy to nitrate (at least for toluene) more than
three positions without using something ridiculously strong like what you mentioned.
Loptr - 12-3-2015 at 16:08
If I recall correctly, copper(ii) nitrate can be an efficient nitrating agent for aromatic rings under dehydrating conditions, which I believe was
referred to as Menke conditions. I recall acetic anhydride being used, but I am not sure if it was required. It also acted as the solvent.
DFliyerz - 13-3-2015 at 10:09
Speaking of insanely nitrated compounds, it's kind of scary of hexanitrobenzene is a thing.
kecskesajt - 14-3-2015 at 23:37
Acetic anhydride + Anh. Cu(NO3)2.
careysub - 15-3-2015 at 08:12
How about the scenario where you are not cooking up energetic molecules, but just doing synthetic organic chemistry and want to just mono-nitrate
toluene (dinitration would be an undesirable side product). Are there unusual mild nitration agents that will accomplish that (a nitrate salt
preparation perhaps)?
Here is an article about microwave mono-nitrations using metal salt catalysts that complete in 6 minutes for toluene at high yield for the para
product. They are using 69% nitric acid, but no sulfuric; sodium tungstate is an example catalyst. Not exactly the same thing as "mild" perhaps, but
still illustrating the possibilities for different nitration conditions.
Attachment: IJOC20120300015_46985024.pdf (1.6MB)
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