# Does dinitratomethane exist?

In 2016 synthesis and structure of tetranitratoethane $$\ce{C2H2N4O12}$$ were reported [1]. Currently (as of 2017-Q4) this is the only dinitrato-carbon compound with the well-established crystal structure and composition:

This article also mentions dinitratomethane (reference number updated from 6 to 2):

While nitrate esters such as nitroglycerin (NG) and pentaerythritoltetranitrate (PETN) (Figure 2A and B) are well known, only very few examples of germinal C-nitrato compounds are known. The simplest one, dinitratomethane (Figure 2C) is a liquid which is obtained from nitration of 1,3,5-trioxane in a $$\ce{HNO3/H2SO4}$$ mixture [2].

Figure 2. Structural formula of nitroglycerin (A), PETN (B), and dinitratomethane (C).

However, I wasn't able neither to get the full-text of original paper from 1938, nor any more recent proofs of existence for dinitratomethane. Google Scholar returns only a couple of entries one of which is [1], and another one is a PhD thesis. There are also zero Ngrams for "dinitratomethane", which is unusual. ChemSpider also lists this compound as nitrooxymethyl nitrate (CAS 38483-28-2).

Can anyone approve or disapprove the existence of dinitratomethane $$\ce{CH2N2O6}$$ (feel free to utilize computational chemistry too)?

### References

1. Fischer, D.; Klapötke, T. M.; Stierstorfer, J. Chem. Comm. 2016, 52 (5), 916–918. DOI: 10.1039/C5CC09010E.
2. G. Travagli, Gazz. Chim. Ital., 1938, 68, 718.
• "dinitratomethane" sounds off to me, I'm afraid authors weren't too good in nomenclature-fu. Better names can be Methylene (or methanediyl) nitrate, or nitroxy instead of nitrato. Nitrato is used for inorganic nomenclature. – Mithoron Dec 16 '17 at 19:22
• For some reason I’m not surprised at all to see Klapōtke in that author list. (Same for Stierstorfer) – Jan Dec 16 '17 at 20:09

After some more research I'm pretty much convinced in its existence. As Mithoron noticed in the comments, the name dinitratomethane is somewhat confusing, and is indeed not preferred.

I suppose the most accurate IUPAC-compatible one would be (nitrooxy)methyl nitrate. It also turned out that in the literature (mostly on regulated and hazardous chemicals) this compound is generally known as methylene glycol dinitrate.

The second volume of a classic handbook "Chemistry and Technology of Explosives" [1, p. 155] gives the most extensive description I discovered (reference numbers are updated):

Methylene glycol dinitrate, or "nitromethylene glycol", is an oily liquid having a boiling point of $\pu{75-77 ^\circ C}$ at $\pu{20 mm Hg}$.

It is a strong explosive, capable of dissolving collodion cotton. However it is not stable, being readily hydrolysed and therefore it is of no practical significance.

A method of obtaining this explosive, by the nitration of moist paraformaldehyde was patented by Travagli and Torboli [2]. They utilised the well-known property of formaldehyde of reacting like methylene glycol in the presence of water.

According to Travagli [3,4] methylene glycol dinitrate is obtained as follows: paraformaldehyde is dissolved in sulphuric acid and added drop-wise at $\pu{3-5 ^\circ C}$ into a mixture of nitric and sulphuric acid. The resulting oil is separated and washed with water to give a final yield of $35\%$.

The recent handbook of liquid explosives from 2015 [5, p. 227] contains virtually the same information without any updates, which indicates there simply hasn't been much of an interest in this compound due to its instability and lack of possible applications.

### References

1. Tadeusz Urbanski. Chemistry and Technology of Explosives, 1st ed., Pergamon Press GmbH, 1965; Vol. 2.
2. G. O. Travagli and Torboli, Ital. Pat. 338080 1935.
3. G. O. Travagli, Gazz. Chim. Ital. 1938, 68, 718.
4. G. O. Travagli, Chimica ed Ind. 1938, 20, 389.
5. Jiping, L. Liquid explosives; Springer Berlin Heidelberg: New York, NY, 2015. ISBN 978-3-662-45847-1.
• Admit it: you knew this all along and just wanted to get two hats ;p – Jan Dec 18 '17 at 17:00
• @Jan No, I didn't know it at a time. The fact I might get two hats was a good enough carrot to do more research:) – andselisk Dec 18 '17 at 21:38