DubaiAmateurRocketry
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DTTO synthesis discussion
Going straight from NO2 > tBu azoxy was too hard and almost impossible.
So I changed thing around, what about this ?
This seems pretty promising. However I am not sure of the stability of the intermediates compounds in this method, especially the NO version of the
FOX-7.
What are your thoughts ?
[Edited on 18-11-2013 by DubaiAmateurRocketry]
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Marvin
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Unfounded speculation is worthless, experiments are valuable when done well, literature searches are essential.
If you are going to speculate, base the steps on existing chemistry. Reference the reactions. Read and learn.
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DubaiAmateurRocketry
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reference
https://sites.google.com/site/ecpreparation/dtto
I'm not 100% sure of the first 2 step, but the last 2 step is almost confirmed since it is already repeated by others.
If we can get the NO version of FOX-7, then DTTO could be made.
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Marvin
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Doesn't matter what level you are at, science is all about evidence. Go back and find out how much evidence you can find to support every step.
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DubaiAmateurRocketry
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Marvin:
Alright I apologize for not showing any refernce at all. However here it is.
This reaction pulled me to FOX-7 which already has the C=C bonds and NH2 and NO2 on both sides, already 2 semi rings are there.
And this reaction is in the paper, which I have no access to, however the publisher of
''https://sites.google.com/site/ecpreparation/dtto'' this website has, I believe.
and the paper was.
"The Tetrazole 3-N-Oxide Synthesis" Tal Harel, Shlomo Rozen, School of Chemistry, Tel-Aviv University, Tel-Aviv, Israel. J. Org. Chem., 2010, 75 (9),
pp 3141–3143
Journal of the Chemical Society, Volume 75 (Great Britain) p.976 also cited this reaction.
and this
"Oxidation of phenylhydrazine with nitrosobenzene", Hiroshi Minato, Akiko Kusuoka, J. Org. Chem., 1974, 39 (23), pp 3419–3421
For the first two reaction, I am not 100% sure, however it obeys some rules which I lost the source to, I will attach it also when I find it
@Dany have a lot of knowledge and I think he might know if the first 2 reaction is possible. Any ways, if the NO2 becomes N=O, DTTO
seems possible.
And finally the paper for the first reaction is here.
Attachment: The Synthesis and Energetic Properties of 5,7 Dinitrobenzo-1,2,3,4-tetrazine-1,3-dioxide (DNBTDO) DTTO related.pdf (582kB)
This file has been downloaded 1313 times
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DubaiAmateurRocketry
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Alright sorry for the OP reaction which will probably not work.
Here is another way, first changing the NH2 to N=O, then add tbu to it so when SnCl2 reduce the NO2, the it will not be effected, then its is left
with NO2BF4 to close the rings.
Reference
Step 1: Synthesis of polynitro compounds. Peroxydisulfuric acid oxidation of polynitroarylamines to polynitro aromatics Arnold T. Nielsen , Ronald L.
Atkins , William P. Norris , Clifford L. Coon , Michael E. Sitzmann
J. Org. Chem., 1980, 45 (12), pp 2341–2347
The Synthesis and Energetic Properties of 5,7 Dinitrobenzo-1,2,3,4-tetrazine-1,3-dioxide (DNBTDO) Thomas M. Klapçtke,*[a, b] Davin G. Piercey,[a]
Jçrg Stierstorfer,[a] and Michael Weyrauther[a] Propellants, Explosives, Pyrotechnics
step 2: ^
Step 3: ^
Step 4:Oxidation of phenylhydrazine with nitrosobenzene", Hiroshi Minato, Akiko Kusuoka, J. Org. Chem., 1974, 39 (23), pp 3419–3421
The Tetrazole 3-N-Oxide Synthesis" Tal Harel, Shlomo Rozen, School of Chemistry, Tel-Aviv University, Tel-Aviv, Israel. J. Org. Chem., 2010, 75 (9),
pp 3141–3143
https://sites.google.com/site/ecpreparation/dtto
And again, the 2nd compound might not be stable.
[Edited on 19-11-2013 by DubaiAmateurRocketry]
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Marvin
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I've not gone, I just have a lot to read. Your original synthesis had some problems but also some chemistry of which I was previously ignorant.
That scheme seems plausible. My main problem with it, is that it's TOO plausible for a compound that has never been successfully made before. The
starting material is available, all the steps apart from the first are high yielding when attached to stabilising rings. My hunch is that reading
through the papers will give hints as to which step will fail and why.
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exoto
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If you good at computational chemistry, you ll notice that amino group and nitro group on FOX-7 are not functional groups in a conventional sense. The
shape of HOMO and LUMO well illustrates the point. So i don't even think some of these ideas will work.
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exoto
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Quote: Originally posted by exoto  | | If you good at computational chemistry, you ll notice that amino group and nitro group on FOX-7 are not functional groups in a conventional sense. The
shape of HOMO and LUMO well illustrates the point. So i don't even think some of these ideas will work. |
What I mean is that you can't treat them as a NH2 or NO2 group because on FOX-7 they are not what they look like. They won't show any reactivitiy that
you expect in a conventional sense.
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plante1999
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Dubai posts of the 18 have a diagram in which I find some errors. I never heard of N2O6. Although mostly everything seams possible, the diagram is
doubtful.
I never asked for this.
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bismuthate
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N2O6 is dinitrogen hexoxide.
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plante1999
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I know nomenclature bismuthate, it was more about the fact that such a compound do not exist.
I never asked for this.
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bismuthate
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http://books.google.com/books?id=lTcNk8MsHrkC&pg=SA6-PA1...
Here's a link to a book that very strongly indicates it exists. I also saw plenty more.
[Edited on 24-11-2013 by bismuthate]
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plante1999
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Permit me to doubt of the sources. Two nitro groups linked by a peroxidic bonds seams the kind of molecules that spectrometer researcher works with,
if it exist.
I never asked for this.
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bismuthate
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From what I've seen in research and predicted I believe that it is very unstable and rare, so it probably is mostly talked about in spectrometry
although I did find this.
http://books.google.com/books?id=nao5AQAAMAAJ&q=dinitrog...
If this source is truthfull that would be very interesting.
(unfortunatly I have my doubts I thought that the reaction would proceed differently)
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DubaiAmateurRocketry
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| Quote: Originally posted by exoto | If you good at computational chemistry, you ll notice that amino group and nitro group on FOX-7 are not functional groups in a conventional sense. The
shape of HOMO and LUMO well illustrates the point. So i don't even think some of these ideas will work.
What I mean is that you can't treat them as a NH2 or NO2 group because on FOX-7 they are not what they look like. They won't show any reactivitiy that
you expect in a conventional sense.
|
Thank you for that information.
Any ways, DTTO's density has been predicted to go down to a 1.9 which is extremely depressing for such a structure. VOD go down to 9700.
Thank dany for this paper.
http://www.wydawnictwa.ipo.waw.pl/cejem/vol-10-1-2013/Politz...
However DTTO it is still interesting because it have very low sensitivity while having much performance over HMX in detonation pressure and velocity,
and producing only nitrogen and CO2 which is more clean.
Any ways, If TATB was used as the starting material, following the exact same step on my post ''posted on 19-11-2013 at 19:04''
http://en.wikipedia.org/wiki/TATB
Maybe it would form tris-tetrazinedioxide ? However its performance might be lower
| Quote: Originally posted by plante1999 | | Dubai posts of the 18 have a diagram in which I find some errors. I never heard of N2O6. Although mostly everything seams possible, the diagram is
doubtful. |
ugh, It must be N2O5 and is that was just a old diagram that i ''screen shot'' so the quality went down.
I apologize for misleading.
A similar reaction on this site is done with N2O5.
https://sites.google.com/site/ecpreparation/dtto
The original file is not very clear either but Im pretty sure it is N2O5.
[Edited on 24-11-2013 by DubaiAmateurRocketry]
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bismuthate
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That makes more sense. N2O6 would be very hard to make.
[Edited on 24-11-2013 by bismuthate]
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