2,4,6-trinitro-1,3,5-triazine (TNTA)

[A.Q. Square]

According to a 1996 computational chemistry paper available at
(http://www.sciencemadness.org/talk/viewthread.php?action=attachment&tid=173&pid=93255), 2,4,6-trinitro-1,3,5-triazine could be as energetic as the related RDX but at a density of 2.1 g/cm^3. This seems plausible for a hydrogen-free compound with perfect oxygen balance.

The Wikipedia article for TNTA (http://en.wikipedia.org/wiki/Trinitrotriazine) claims that s-triazine can be nitrated with nitric and sulfuric acid to produce it, but s-triazine costs $111/5g (sigma-aldrich.com). Melamine (1,3,5-triazine-2,4,6-triamine) and cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) are cheap, so I would like to know whether TNTA can be made from these (or another cheap precursor).

My chemistry professor suggested that the amino groups on melamine might be oxidized to nitro groups to yield TNTA, and the abstract at (http://www3.interscience.wiley.com/cgi-bin/abstract/27551/ABSTRACT) makes me wonder if this could be done with t-butyl hydroperoxide and a zirconium-based catalyst. (I don't have access to the full-text, and I don't know what zirconium tetra-tert-butylate does, but could what works on aliphatic amines work for melamine?)

Any approach with a cheap precursor, cheap reagents, and a simple procedure would be great. I would also be grateful for information on the actual properties of TNTA, as I have found so little about these that I wonder if the research is classified.:confused:

[Enkidu]

Maybe cyanuric chloride + a nitrite? But that's 1+1 chemistry, I don't have any refs to back that up...

[simply RED]

According to my information this compound has not been synthesized as yet.

[megalomania]

Ahh, a niche theoretical material that other chemists have given up on. One of my professors said that's a good way to get published if you are a small school. Indeed the article you mentioned, J. Am. Chem. Soc., 118 (48), 12244 -12245, 1996. 10.1021/ja962744b S0002-7863(96)02744-8. "Theoretical Prediction of 2,4,6-Trinitro-1,3,5-triazine (TNTA). A New, Powerful, High-Energy Density Material?" (http://dx.doi.org/10.1021/ja962744b) even says there is only one obscure reference to it dating back to 1907.

I doubt this explosive is top secret because every nation in the world would have to be in on it considering there have been no other publications. Knowledge of this substance is no secret thanks to the JACS article.

I would not read too much into theoretical studies. They are often close in their properties, although never accurate yet, but they get too far ahead of synthetic methodologies. If you want my esteemed opinion no one knows how to make this compound and no one is interested in figuring out how.

Not that figuring out the synthesis of novel energetic materials is useless, far from it, it is just there are so many other candidates with superior properties that need better synthetic methods, and so few chemists specifically working on developing energetic materials, that spending time on every molecule that the computer spits out is not productive.

Research on heterocyclic triazines has some importance to the pharmaceutical industry. It is likely there that a synthesis will emerge, although they may not specifically trying to produce trinitro compounds. If you can find methodologies used by those chemists to produce similar compounds, derivatives of TNTA with different functional groups, you may be able to devise a synthesis.

Attached are the relevant files, "Zirconium-Catalyzed Oxidation of Primary Aliphatic Amines to Nitro Compounds with tert-Butyl Hydroperoxide" and the JACS article.

[A.Q. Square]

Thanks to Mega for his input and the full-text of the Zr-catalyzed oxidation paper, which suggests other approaches as well. I would like to see the "communication" (K. Krohn, J. Küpke, H. Rieger, J. Prakt. Chem. 1997, 339, 335-339.) mentioned at the beginning of the paper as demonstrating the ability of the same process to oxidize primary aromatic amines to aromatic nitro compounds (a description which I believe applies to 2,4,6-trinitro-1,3,5-triazine).

Are you sure that it has not been synthesized? A post (by "PHILOU Zrealone" at 09:37 on 2-6-2003) on the Sciencemadness thread (http://www.sciencemadness.org/talk/viewthread.php?fid=3&tid=173&action=printable) linked to the JACS article claims "Action of AgNO2 in an appropriate solvant[sic] allows cyanuric iodide (-CI=N-)3 to form in a very exothermic reaction the trinitro brother of TNB (-C(NO2)=N-)3 and AgI.".

TNTA is not an entirely specific designator; the abstract found at (http://doi.wiley.com/10.1002/1521-4087(200101)26:1%3C43::AID-PREP43%3E3.0.CO;2-H) concerns drophammer tests involving "1,3,5- trinitro-2,4,6-triazidobenzene" which they abbreviate as TNTA, and Googling this brings up other papers. This complicates the matter of finding references in the literature.

[megalomania]

Oops, I cut off the last line of my above post where I said I only did a name search for the compound, not a full search by CAS number and such, so there could very well be some methods of synthesis developed in the last decade. I would also do a search for the authors of the JACS article to see if they have published any follow up work related to the compound, and search for any citations of that paper to see if any other researchers have used it in their own work.

Google is a piss poor way to find scientific information. At least try Google Scholar to limit the infochaff from blogs and spammers. The compound is a non standard name, meaning researchers can call it whatever they want until there is a consensus as to what to call it. Anyone can use whatever acronym they want too, as many research groups do. You can run searches freely at the major journal publishers websites, but it will be hard to find the compound if it is called by a different name.