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Precipitates
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Quote: Originally posted by Yorty2040  | | Does anyone have any information on melamine diperchlorate? Solubility, handling, decomposition temp, sensitivity, shelf life, etc?
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I could only really find this article on Melamine Diperchlorate Hydrate.
I assume reasonable solubility, not ridiculously sensitive and relatively stable.
[Edited on 25-5-2024 by Precipitates]
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dettoo456
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Has anyone carried out a destructive nitration procedure on a ketone before? I couldn’t find much information on them; it seems Russian chemists
were messing around with the principles and kinetics in the mid 90s, but those journal entries are very hard to find, let alone translate.
As far as I can tell, it’s basically the same conditions as for the preparation of Nitroform from Acetone (or from the dehydration of IPA and
subsequent nitration). Carbonyls, mainly ketones but apparently carboxylic acids as well, undergo decarboxylative nitration to yield the
trinitromethyl or dinitromethyl derivative at the alpha position relative to the carbonyl.
This polynitromethyl product though, can be generated by the action of WFNA/H2SO4 with the ketone at 0C, and Hexanitroethane can even be prepared like
this in up to a 75% yield from the terminal-trinitro ketone (authors reported using trinitropentanone, though I believe this was a mistake, and
trinitrobutanone might have been used instead).
https://www.researchgate.net/publication/250556009_ChemInfor...
This abstract does not provide much insight as to the conditions (molar equivalent, addition rate, extraction), and I couldn’t find the article in
the Russian Org Chem journal.
In short, is it plausible that this reaction could be applied to something like MEK, to yield 1,1,1-trinitroethane?
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Yorty2040
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So methazonic acid (2-nitroacetaldoxime) can be produced by the base-catalyzed self-condensation of nitromethane, followed by acid workup.
Is there any info on using sodium perborate + glacial AcOH to convert it to 1,2-dinitroethane? The procedure should work, but the devil (and
yield) is in the details of the procedure and subsequent workup.
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dettoo456
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I’m assuming you’re referencing this paper (linked below) for the oxidation with perborate. As you mentioned though, the preparation will suffer
in yields with the scope being so wide (small chain aldoxime already with a nitro substitutient compared to mainly aryl ketoximes reported being
used).
A more sketchy method to yield 1,1,2-TRInitroethane could be the ponzio reaction; NO2 or N2O4 in ether or a suitable polar nonprotic at low
temperature).
Or, some other, cleaner oxidizer like oxone or H2O2. Though, in any case, including the Perborate/GAA method, oxidation of the aldehyde to carboxylic
acid and oxime to carbonyl is probably the reason for such low reported yields.
[Edited on 15-6-2024 by dettoo456]
Attachment: Oxime Oxidation to NO2.pdf (159kB)
This file has been downloaded 16 times
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Yorty2040
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What's the technical, physicochemical explanation for why complexing the oxoacid salt of a nitrogenous base with a transition metal typically
increases sensitivity compared to the uncomplexated salt?
[Edited on 18-6-2024 by Yorty2040]
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dettoo456
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The acidity of the acid itself may contribute to instability (the free H+). Or, since the main decomposition pathway of energetics is based on BDEs
(bond disassociation energies) of different groups and bonds on a molecule, if the oxoacid has a lower BDE than other groups in the complex (ionic
bonds between the metal and anion), it could kickstart a decomposition process. C, O, and N intermediates may also simply be easier for a group like
ClO4-, NO3-, etc to oxidize than the metal itself too. OB% factors in to this as well, along with perhaps higher densities of the materials due to
packing of the nitrogenous oxoacids in the complex’s lattice; such higher densities can affect sensitivity too.
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