Chisholm
Hazard to Self
Posts: 62
Registered: 2-4-2017
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Mood: No Mood
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tetrazine and diazotization
Attempts to isolate freebase aminoguanidine under most lab conditions result instead in the formation of 1,4-diaminotetrazine.
Is this compound explosive? Can it form salts with oxoacid anions that are explosive?
How does the freebase tetrazine react to nitrous acid? Does it polymerize by forming diazo-couplings, does it become a diazonium salt, or does it just
fall apart?
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PHILOU Zrealone
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
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Mood: Bis-diazo-dinitro-hydroquinonic
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This comes from the tendency of carboaminohydrazide (R-C(=NH)-NH-NH2) to selfcondense and eliminate NH3 as a gas; then after isomerisation the oxygen
of the air oxydizes the C-NH-NH-C sequence into C-N=N-C to complete aromatization into tetrazine.
In principle it must display a low basicity based onto similar structured molecule like melamine (pKa = 5) thus tetrazine must be close to the pKa of
acetic acid (4-4,5) ; and second pKa function must be 3 pKa units lower (1-1,5) thus quite acidic.
For example melamine has 3 NH2 groups but when submitted to HC(NO3)2 only lead to a monosubstitued salt (with a power close to TNT...while one would
expect disubsitued or even trisubsitued salts (melamine bis-nitroformiate and tris-nitroformiate) the last one would be a killer salt outperforming
most HE...but it doesn't exist as such.
So here maybe a mono-nitroformiate or bis-nitroformiate (if possible) may be worth making and quite powerful.
H2N-C(N2)2C-NH2. HC(NO2)3
H2N-C(N2)2C-NH2. 2 HC(NO2)3
To ensure the protonation of second and third amino of the melamine one would need to use very strong acids like HNO3 or even better HClO4 even then
the third protonation might be hard to acheive.
For tetrazine is would be easier since there is only two NH2 so the second protonation should be in reach of HNO3 and for sure of HClO4.
The resulting salts will be quite powerful and dense; the bis-perchlorate must be quite sensitive too.
H2N-C(N2)2C-NH2. HNO3
H2N-C(N2)2C-NH2. 2 HNO3
H2N-C(N2)2C-NH2. HClO4
H2N-C(N2)2C-NH2. 2 HClO4
All must be more powerful and denser than their aminoguanidine analogues (nitrate and perchlorate).
Those may be quite hygroscopic and hard to get anhydrous (or not with nitrates and perchlorates of amines hard to figure out without doing it).
I was asking myself the same question last year, so I have already a lot of ideas to share about it...must depend on the surrounding media and
process...such diazonium must be quite reactive with the solvent (water)...
I was interested into the resulting putative polymeric energetic material 
1°) (-(CN4C)-N=N-)n this must be colorfull and probably violet, red, brown or even black
Sadly the density will not be exceptionnal due to loss of H bondings vs its hydrazine brother (-(CN4C)-NH-NH-), but stil decent and the energy content
wil be very good for this new carbo-nitrogen allotrope so maybe a very good energy fuel for binary mixes...must be a hell hot burning stuf. Organic
electric conductor?
2°) By loss of N2 and radical fusion kind of polytetrazaphenyls
(-CN4C-)n...same blabal as above very good potential superfuel probably quite dark.
3°) By loss of N2 and reaction with water
HO-N=N-CN4C-N=N-OH --> 2 N2(g) + HO-CN4C-OH
This dihydrotetraazaquinon must be quite acidic (--> energetic salts?) and oxydable owing to keto-enol equilibrium (into the later reaction part of
the N2 is left aside for convenience purpose)
HO-C-N=N-C-OH <==> O=C-NH-NH-C=O --O2--> O=C(-N=N-)2C=O (probably very unstable) + H2O
4°) Anion addition by N2 elimination...like common Sandmeyer reaction of diazoniums
--> Cl-CN4C-Cl
very interesting compound owing to the halide lability just like for trichlorotrinitrobenzene or cyanuric (tri)chloride (-C(Cl)=N-)3 possible
interesting substitutions when submitted to N2H4, NaN3, AgNO2, CH3-NNa-NO2 or CH2(NO2Na)2 and maybe AgC(NO2)3...
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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