Sciencemadness Discussion Board - Fifth grader discovers novel energetic compound

Fifth grader discovers novel energetic compound

gutter_ca - 2-2-2012 at 10:54

Playing with a molecular model kit, she got a co-author credit.

http://www.themarysue.com/clara-lazen-new-molecule/

AirCowPeaCock - 2-2-2012 at 11:00

Oh that's great! She has no clue what went on!!

Adas - 2-2-2012 at 12:31

Nice. What is the structure of the molecule?

quicksilver - 2-2-2012 at 13:04

I only hope some jerk doesn't tell the little girl that "Chemistry is hard" or that "it has a lot of math in it and that's very tough". We ruin young people with negative stereotypical messages about science or a confusion of theoretical mathematics with arithmetical issues.

AirCowPeaCock - 2-2-2012 at 13:23

But that's exactly why I liked chemistry when I was her age!

1,2,3,4-Tetra(nitratoxycarbon)methane.gif - 2kB

I believe it's something like this..

[Edited on 2-2-2012 by AirCowPeaCock]

Adas - 3-2-2012 at 04:08

Nitrogen bond to three oxygens? Insane

phlogiston - 3-2-2012 at 04:22

Also goes to show that toying with an old-fashioned molecular model kit can be insightful. If you can build it, things like the the bond strain etc are likely to be within the realm of the possible.

AirCowPeaCock - 3-2-2012 at 07:46

Does anyone know of other molecules with groups like those?!

killswitch - 4-2-2012 at 16:49

Without a cell phone camera, this might never have happened. Weird.

Anyhoo, the name is Tetrakis(nitratoxycarbon) methane.

Five bucks says Anders chimes in with a "theoretical" synthesis in the next couple of days.

killswitch - 4-2-2012 at 16:56

It looks like it has a positive oxygen balance, but damn if that thing doesn't look unstable. Not to mention that the negative charge will tend towards the outer edges, repelling the other molecules, plus a lack of hydrogen atoms for H-bonding and what appears to be a nonpolar structure, the density for this thing looks pretty bad.

But what the hell do I know; I've never seen the damned thing. Haha!

AndersHoveland - 12-2-2012 at 21:44

I think that molecule would be so chemically unstable that it would not be isolatable.
Not because of the bond strain, but because it would just spontaneously reform to carbonyl nitrite groups, for the same reason that polymerized CO2 only exists under extreme pressure.

[Edited on 13-2-2012 by AndersHoveland]

AirCowPeaCock - 13-2-2012 at 06:21

Quote: Originally posted by killswitch

Without a cell phone camera, this might never have happened. Weird.

Anyhoo, the name is Tetrakis(nitratoxycarbon) methane.

Five bucks says Anders chimes in with a "theoretical" synthesis in the next couple of days.

Fortunately for you, no one was willing to take that bet(;

arsphenamine - 13-2-2012 at 16:28

If you were in 5th grade, had a solid chemistry idea that a professional used as a starting point for publication,
then discovered you'd been included as an author, would you feel encouraged to continue in science?

I'd like to think so.

AndersHoveland - 14-2-2012 at 02:08

But the fact is that she did not invent anything!

Those nitratoxycarbon groups have never actually been prepared. And it is very doubtful they even exist.

Just another sensationalized news headline.

Show me an article mentioning a structure like trimethoxy orthonitrite, (CH3O)3N, then perhaps this type of thing could be possible.

Edit:
After doing some research, I am withdrawing my opinion!
Caged "nitratoxycarbon" groups might be possible.

Triethyl orthoformate exists:
http://en.wikipedia.org/wiki/Triethyl_orthoformate

And apparently orthonitrite esters exist (although not salts)...

Quote:

An Australian marine tunicate Aplidium sp. collected from the Great Australian Bight has been found to contain seven macrocyclic alkaloids, identified as the novel marine metabolites aplidites A-G (1)-(7). Each aplidite incorporates a hitherto undescribed orthonitrite functionality. Structures for the aplidites were secured by detailed spectroscopic analysis, derivatization and degradation.

Quote:

The chlorination of acyclic N,N-dialkoxyamines under the action of tert-BuOCl results in the formation of unstable N-chloro-N,N-dialkoxyamines which in situ react with sodium methoxide to give previously unknown trialkoxyamines (orthonitrites). The properties of the N-chloro-N,N-dialkoxy-and trialkoxyamines have been demonstrated to be similar to those of their carbon analogues: dialkoxyalkylchlorides and orthoesters, respectively.
Vladimir F. Rudchenko, Sergei M. Ignatov, Ivan I. Chervin, Remir G. Kostyanovsky
Institute of Chemical Physics, Academy of Sciences, Moscow, Russia (1988)

Better get to work on that "theoretic synthesis"...

(Too bad killswitch was not able to find anyone to take that bet!

)

[Edited on 14-2-2012 by AndersHoveland]

arsphenamine - 14-2-2012 at 06:03

Quote: Originally posted by AndersHoveland

But the fact is that she did not invent anything!

Nor did she have to, nor did Zoellner, the article's primary author.
That's why they call it Computational and Theoretical chemistry.

A computational study of novel nitratoxycarbon, nitritocarbonyl, and nitrate compounds and their potential as high energy materials
http://www.sciencedirect.com/science/article/pii/S2210271X11...

If you're computationally-minded when you read the abstract, you notice
Zoellner's use of primitive basis sets and well-worn correlation energy theory.

"B3LYP/6-31G(d)?"
"BFD!", you may sneer (which I did).

Oops.

Correlation energy of 28 non-bonding electron pairs costs a lot,
with B3LYP scaling N^5 where N is the orbital count .
The bis compound alone costs 30 minutes on a fast SMP machine.
If you scale for the tetrakis homolog, you nearly double the orbital count on an N^5 computation ... (cough!)

No *way* will a more sophisticated theory/basis set computation finish by next semester.

"Gosh, that approximate but blazingly fast semi-empirical PM6 method is starting to look pretty good," I thought to meselfs.

Anders, in one post, you go from a "sensationalist headline" derisiveness to a more thoughtful "might be possible".

THAT is the value of theoretical chemistry -- if offers you new places to look for discoveries.

Lay off da kid. She done good.

PHILOU Zrealone - 15-2-2012 at 12:28

Orthoformate as stated by AndersHoveland do exist... HC(OR)3.

But in the present case, there is no hydrogen present and so it is more like an orthoacetate structure that must be searched for... CH3-C(OR)3
This do also exist and is referenced as orthoesters...http://en.wikipedia.org/wiki/Orthoester
The later can be done from nitrile alcoolysis under acidic conditions.
In the later link they express that orthoformate can be done from chloroform, alcool and sodium...
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=CV1...
One might expect that it would work the same with 1,1,1-trichlorethane...to get an orthoacetate ester.

So, to get the pentaeritritol structure designed by the little girl, we must start:
1°)from tetracyanomethane... C(C#N)4
C(C#N)4 +12 R-OH --> C(C(OR)3)4 + 4 NH3
2°)from perchloroneopentane (duodecachloroneopentane)... C(CCl3)4
3°)from any mix between nitrile and trichloro groups on a central carbon core (in the case the first idea is too hard because of the lability of the cyanide on tetracyanomethane.

The final step is hard because action of ammonia on such orthoformiates or orthoacetates doesn't lead to the desired compound but lead instead to formamidines or acetamidines...
HC(OR)3 + 3 NH3 --> HC(NH2)3 + 3 ROH
HC(NH2)3 --> H2N-CH=NH + NH3
In the present case we must expect C(C(=NH)NH2)4 what is also an interesting target molecule (tetraformamidylmethane).

The desired molecule might maybe result from the action of nitrogen trifluoride on the orthoester.... :cool:

R-C(OCH3)3 + NF3 -?-> R-C(O)3N + 3 CH3F
C(C(OCH3)3)4 + 4NF3 -?-> C(C(O)3N)4 + 12 CH3F

AndersHoveland - 18-2-2012 at 23:40

Although orthocarboxyl ethers and orthonitrite ethers apparently both exist, I still have doubts as to whether a mixed orthocarboxyl-orthonitrite anhydride (which is what nitratoxycarbon groups are) could exist. It may likely be that orthonitrite is only stabilized by the alkyl groups holding the oxygen atoms, the same phenomena for orthoformate.