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]

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 1398 times

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]

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.

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.

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.