Possible route to 1,4-Dinitrotetrazol-5-One ?

This post presents synthesis routes to a theoretical compound 1,4-Dinitro-1,2,3,4-tetrazol-5-one(DNTO). Density, heat of formation, and impact sensitivity was calculated by various equations from papers Dany sent me. DNTO have the advantages of very high density, oxygen balance, and heat of formation, while having lower calculated sensitivity than other future oxidizer candidates such as ADN and HNF. DNTO also have 6 catenated nitrogen chain which have large amount of stored chemical energy for high efficiency propellants. DNTO is expected to provide advantagesover traditional oxidizers such as ammonium perchlorate, and even the future candidates of oxidizers such as ammonium dinitramide(ADN) and hydrazine nitroformate(HNF). Tetrazolone was chosen because of its high density, oxygen balance, and the insensitivity of the carbonyl group.



Possible synthesis of DNTO. The route starting from semicarbazide is only guessed, however if possible, would make tetrazolone a very cheap chemical.

Density calculations
The calculated density using molecular fragment method was 2.09g/cm3. Surprised by the high value it gave, a second method for calculating the density of DNTO was used[4]. The second method gave a density of 2.095 g/cm3 from Mohammad Hossein Keshavarz's equation. (Maximum diviation observed in this equation is 4.71%. Therefore, the maximum and minimum possible value for the density of this compound will most likely be 2.095 ± 0.099, which is between 1.996-2.193g/cm3.)[5]

Heat of formation
Heat of formation on DNTO was calculated to be +326kJ/mol. The maximum error found for the used equation is 91kJ/mol[6].

Sensitivity toward external stimuli.
Impact sensitivity of this compound might be very high since it has 6 catenated nitrogen bonds on a tetraozle ring. However, it does include a high density low energy carbonyl fragment which is insensitive alone and can contribute to overall sensitivity, thermal stability, and density of the compound[6]. The highly positive oxygen balance might also decrease the impact sensitivity.

The calculated (H50) for DNTO is 20.5cm (5J). However the prediction for sensitivity is hard and the deviation for this equation can be large[7]. Friction sensitivity might be of a problem because most azole energetic compounds are more sensitive to friction than other energetic compound. A similar structure to DNTO, 1,4,5-triamino-1,2,3,4-tetrazolium cation and its salts are highly sensitive to friction[8]. Problems associated with friction sensitivity could be solved when mixed with a binder. Finally, since this compound does not have hydrogen at all, it is most likely that DNTO will not form salts.

Properties
CON4(NO2)2 or empirically [CN6O5]
Elemental analysis: Carbon: 6.822% Nitrogen: 47.737% Oxygen: 45.4405%
Molarmass:176.0482
Oxygen balance: (CO2 = +27.3%, CO= +36.4%)
Heat of formation: ~+326kJ/mol
Density: 2.0947 ± 0.09866, (1.996-2.193g/cm3)
Impact sensitivity(H50): 20cm
VOD at 2.08g/cm3 and +326kj/mol : 9160m/s
Detonation pressure: 437 kbar (Wow thats higher than HMX)
Temperature of explosion: 4000K
Products: CO2, 3N2, 1.5O2
Explosive properties were calculated by member Dornier.

References
[1]Dennis Fischer, Thomas M. Klapçtke,* and Jçrg Stierstorfer Salts of Tetrazolone – Synthesis and Properties of Insensitive Energetic Materials- Propellants Explos. Pyrotech. 2012, 37, 156 – 166
[2] Sevil Ozcan, Zeynep Ekmekci, Berk Mujde, Metin Balci - Synthesis of fused tetrazolone derivatives - Turkish Journal of Chemistry (2013) 37: 610-618
[3]Si-Ping Pang -Yong-Zhong Yu, Xin-Qi Zhao - A Novel Synthetic Route to Hexanitrohexaazaisowurtzitane - Propellants, Explosives, Pyrotechnics 30, No. 6 (2005)
[4]A. A. Kotomin and A. S. Kozlov- Calculation of Densities of Organic Compounds
from Contributions of Molecular Fragments- Russian Journal of Applied Chemistry Vol.69 No.6 2006
[5]Mohammad Hossein Keshavarz- New method for calculating densities of nitroaromatic
explosive compounds- Journal of Hazardous Materials 145 (2007) 263–269
[6]Mohammad Hossein Keshavarz- Theoretical prediction of condensed phase heat of formation of nitramines, nitrate esters, nitroaliphatics and related energetic compounds.- Journal of Hazardous Materials A136 (2006) 145–150
[7] Mohammad Hossein Keshavarz - A New General Correlation for Predicting Impact Sensitivity of Energetic Compounds - Propellants Explos. Pyrotech. 2013, 35, 1 – 7]
[8]Thomas M. Klapötke*,Davin G. Piercey, and Jörg Stierstorfer - The 1,4,5-Triaminotetrazolium Cation (CN7H6+): A Highly Nitrogen-Rich Moiety - Eur. J. Inorg. Chem. 2012, 5694–5700



[Edited on 27-1-2014 by DubaiAmateurRocketry]

You might aswel try via DNU, chlorination then azidation? but no water allowed!

O2N-NH-CO-NH-NO2 + 2 (CH3)3C-O-Cl --> O2N-NCl-CO-NCl-NO2 + 2 (CH3)3C-OH
O2N-NCl-CO-NCl-NO2 + NaN3 --> O2N-N(N3)-CO-N(N3)-NO2 + 2 NaCl
O2N-N(N3)-CO-N(N3)-NO2 --> cyclo (-N(NO2)-CO-N(NO2)-N=N-) + 2 N2(g)

It is also possible you get chain polymer
(-N(NO2)-CO-N(NO2)-N=N-)n + 2 N2
or
(-N(NO2)-CO-N(NO2)-N=N-N=N-)n + N2
or
and (-N(NO2)-CO-N(NO2)-N=N-N=N-N=N-)n

And if you ozonize 1,4-Dinitrotetrazol-5-One you may end up with tetranitrourea (O2N)2N-CO-N(NO2)2 by oxydation of the -N=N-...


No!
All this is pure speculation...Dinitrotetrazolone will be too unstable to exist...too much electron withdrawing group in the vicinity of the two -NO2 will lead them to nitro-nitrite rearrangement and spontaneous decomposition also extreme sensitivity to water!

Good similitudes can be seen in DNU; HNB; Trinitro-sym-triazine; 1,3,5-trinitrobiuret; 2,3,5,6-tetranitro-p-quinone and trinitro-isocyanuric acid (cyclo(-CO-N(NO2)-)3): this 1,4-dinitrotetrazol-5-one will be really unstable...

[Edited on 26-1-2014 by PHILOU Zrealone]

Quote: Originally posted by Dany

It is wrong to put 2.0947 ± 0.09866...

Quote: Originally posted by PHILOU Zrealone

You might aswel try via DNU, chlorination then azidation? but no water allowed! O2N-NH-CO-NH-NO2 + 2 (CH3)3C-O-Cl --> O2N-NCl-CO-NCl-NO2 + 2 (CH3)3C-OH O2N-NCl-CO-NCl-NO2 + NaN3 --> O2N-N(N3)-CO-N(N3)-NO2 + 2 NaCl O2N-N(N3)-CO-N(N3)-NO2 --> cyclo (-N(NO2)-CO-N(NO2)-N=N-) + 2 N2(g) ______________________________________________________________________________________________________ Good similitudes can be seen in DNU; HNB; Trinitro-sym-triazine; 1,3,5-trinitrobiuret; 2,3,5,6-tetranitro-p-quinone and trinitro-isocyanuric acid (cyclo(-CO-N(NO2)-)3): this 1,4-dinitrotetrazol-5-one will be really unstable... [Edited on 26-1-2014 by PHILOU Zrealone]

I think going from Urea might be too hard, not saying your guess was impossible. I dont think N-Cl can undergo azadation ? 4 aliphatic Nitrogen, is it possible ? Might be more un-stable than dinitrotetrazolone.

Also, I do not think 2 azide groups could come together for a tetrazole ring, however, what about inserting the azo bridge into DNU ?

Any ways, I just want to point out that the (O2N)N-CO-N(NO2) is stable. However those NNO2 are joined by -N=N- so It might just be sensitive and not up to a point to decomposing at rt. The carbon is in-active due to the carbonyl group, the carbonyl group have high heat of formation that give much less heat than most other carbon linked bonds. Therefore the nitro groups can barely contribute to the overall energy except the bond that connects the NO2 to tetrazole.

Some good example of a stable struture related to my compound is Trinitro-triazolone, A compound that is nitrated NTO using long or extreme process such as N2O5. And also HHTDD.





Comparism between DNTO, DTNTO, HHTDD shows possible stability, high density in DNTO.
DNTO also does not contain hydrogen it will most likely not formation of salts/reactivity toward bases/acids.

Quote: Originally posted by Dany

try to be homogenous in writing the numbers in the text, for example all the density should be to the second decimal place.