killswitch
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1,1’-azobis-1,2,3-triazole
Preparation of 1,1’-azobis-1,2,3-triazole
1-amino-1,2,3-triazole (1.68 g, 20 mmol)* was dissolved in 40 ml CH3CN. The solution was cooled at -2~0 °C and a solution of sodium
dichloroisocyanurate (SDCI, 4.44 g, 20 mmol) in 10 ml water and 5.0 ml CH3COOH was added dropwise. The reaction mixture was further stirred at 0 °C
for 30 min. The solution was neutralised with NaHCO3, then filtrated to remove insoluble solids. The solution was concentrated, and the product
isolated as a little yellow solid was obtained after recrystallization from acetone. Yield 78%. Mp: 193.8 °C (dec.).
A very similar procedure with 1-aminotetrazole gives 1,1'-azobis(tetrazole), but only Klapötke is that crazy (I hope).
Now, with regards to getting a bigger bang, perhaps nitrating it?
Or a more advanced derivative like 1,1'-azobis(1,2,3-triazolyl tetrazine dioxide)?
Which would be more sensitive? I've heard very strange things about tetrazine oxides. How much conjugation is present after the oxygen is added? And
what kind of absorption and cis-trans behavior would the nitro-azobistriazole display?
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Boffis
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Have you actually tried this and if so how did you prepare the precursor?
I am looking at this reaction, its high on my "to do list". The main problem is getting a decent yield of the glyoxal dihydrazone precursor without
anhydrous hydrazine. I don't think the later is essential but the reaction appears to be an equilibrium in which water favours the individual reactant
and my hydrazine is only 40% solution like the glyoxal solution. I am experimenting with various ways of removing water from the reaction mixture at
present such a s vacuum concentration in my roatvap. Which oxidizing agent did you use?
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killswitch
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Sodium dichloroisocyanurate, per Klapotke's work. I've only done the 1,2,3 compound, though.
And aqueous hydrazine doesn't seem to be a problem.
This is actually sold as a pool chemical in 99% purity in huge tubs. I'm also pretty sure it can be made from cyanuric acid and sodium hypochlorite,
though I'm not entirely sure how one would go about separating and purifying it.
EDIT: I'm rather excited about the possibilities of a salt or adduct of the dinitrate, like this one:
[Edited on 6-12-2012 by killswitch]
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Davin
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Glyoxal bishydrazone can be made by refluxing glyoxal and hydrazine in water. After evaporation and extraction with ethyl acetate, pure
glyoxalbishydrazone is obtained. http://www.freepatentsonline.com/EP0727418B1.html
Trans will be more favorable than cis, illumination may cause isomerization.
The tetrazine dioxide would be more sensitive. But good luck making it.
And by the way: Hi. I made the 1,1'-azobis(tetrazole)
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killswitch
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-------------------------------------
Glyoxal to triazole
REFERENCE EXAMPLE 1
preparation of Glyoxal Bishydrazone (I)
In a reactor were charged a 40% aqueous solution of 1.45 g of glyoxal (VI), 1.00 g of hydrazine monohydrate, and 10 ml of water, and the mixture was
stirred at room temperature for 1 hour and then at 100° C. for 3 hours. After completion of the reaction, the solvent was evaporated under reduced
pressure, the residue was extracted with ethyl acetate, and the extract was dried over anhydrous sodium sulfate. The solvent was evaporated under
reduced pressure, and the residue was purified by silica gel column chromatography to obtain 813 mg (94%) of glyoxal bishydrazone (I).
Melting point: 85°-87° C. 1 H-NMR (DMSO-d6): 7.31 (s, 2H), 6.57 (s, 4H) Mass (EI) m/e: 86 (M+) IR (KBr) cm-1 : 3344, 3161, 1577, 1075, 919
Summary of the rest of the crap: MnO2 is the only catalyst you should bother with.
EXAMPLE 8
Synthesis of 1-Amino-1,2,3-triazole (III)
In a reactor were charged 813 mg of glyoxal bishydrazone (I) obtained in Reference Example 1 and 1.0 ml of ethanol, and the mixture was stirred at
room temperature. To the mixture was added 2.0 g of manganese dioxide for ferrite (a product of Tosoh Corp.; effective oxygen content; 94% or more;
hereinafter the same), followed by stirring at the same temperature for 2 hours. Then, 0.5 g of manganese dioxide for ferrite was further added
thereto, and the stirring was continued at that temperature for 5 hours. After completion of the reaction, any insoluble matter was removed by
filtration, and the solvent was evaporated under reduced pressure to give 720 mg (yield: 91%) of 1-amino-1,2,3-triazole (III).
It's rather sad when even chemical patents are no longer immune to product placement.
[Edited on 6-12-2012 by killswitch]
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killswitch
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I'm working on an over-the-counter prep for the bistriazole.
Ethanol from everclear+drierite
Sodium dichromate (or ammonium dichromate and NaOH) from fireworks supplier. I am wondering if KMnO4 (from greensand iron filter recharge packs) might
work as well.
Sulfuric acid from Rooto (cleaned up with H2O2).
Acetaldehyde from ethanol, sodium dichromate and sulfuric acid (per the rhodium archive on erowid), or perhaps just ethanol and aqueous permanganate.
At first this looked promising for Glyoxal, but it's in freaking Mandarin.
Hydrazine from the methyl ethyl ketazine process.
bishydrazone from glyoxal, and hydrazine
1-amino-1,2,3-triazole from bishydrazone, ethanol, and MnO2.
sodium dichloroisocyanurate from pool supply
glacial acetic from ethanol and acidic permanganate, or if desperate, boiled-down white vinegar cleaned up with concentrated H2O2. (Can't recommend
that last one).
acetonitrile from ammonium acetate and glacial acetic.
Then perform the synthesis of the azobistriazole as above.
But I know I missed one step, and I might be missing others. Anyone speak Mandarin?
[Edited on 6-12-2012 by killswitch]
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Boffis
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That patent is interesting; as I suspected removal of the water is sufficient to give the glyoxaldihydrazone so I'll give this a try in the near
future. The paper I have also give MnO2 as the preferred oxidizing agent to oxidize the hydrazone to the triazole derivative.
OTC? it depends where you are. Here in the UK 40% glyoxal solution and 40% hydrazine solution can usually be obtained from ebay and hydrazine sulphate
also crops up fairly regularly along with acetaldehyde. Selenium and 70% nitric acid (=selenium dioxide) are always available and with these you can
oxidize acetaldehyde and paraldehyde to glyoxal. Glacial acetic acid, acetonitrile, Na dichlorocyanurate and various grades of MnO2 are likewise
easily available.
I presume that your source of the synthesis of the azo compound was from the paper:
1,1'-azobis-1,2,3-triazole: A High Nitrogen Compound with a Stable N8 Structure and Photochromism; Yu-Chuan Li et al; JACS 2010.
The actual preperative details can be downloaded free.
The synthesis of glyoxal dihyradrazone that I am working with is from:
H. M. Fisher and R. C. Stoufer; Inorg Chem.; Vol 5, No7 (1966)
And the synthesis of 1-amino-1,2,3-triazole was from this paper
Attachment: 1-amino-1,2,3-triazole & derivatives synthesis ADA433942.pdf (804kB)
This file has been downloaded 769 times
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AndersHoveland
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You will not be able to just nitrate it. 1,2,3-triazole cannot be directly nitrated, even "under rigorous conditions". It is thought that the reason
for this phenomena is a charge sheilding effect, as the nitrogens pull electron charge distribution away from the carbon atoms, effectively giving
them a partial positive charge, and repeling nitronium cations that are the mechanism through which nitration reactions proceed.
(4-nitro-1,2,3-triazole can however be further nitrated, as the nitro group on the carbon apparently defeats the shielding effect) This is
the same reason why 5-methyl tetrazole cannot be nitrated (at least not directly). Radical nitration may be a possible way around this problem.
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
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killswitch
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Quote: Originally posted by AndersHoveland  |
You will not be able to just nitrate it. 1,2,3-triazole cannot be directly nitrated, even "under rigorous conditions". It is thought that the reason
for this phenomena is a charge sheilding effect, as the nitrogens pull electron charge distribution away from the carbon atoms, effectively giving
them a partial positive charge, and repeling nitronium cations that are the mechanism through which nitration reactions proceed.
(4-nitro-1,2,3-triazole can however be further nitrated, as the nitro group on the carbon apparently defeats the shielding effect) This is
the same reason why 5-methyl tetrazole cannot be nitrated (at least not directly). Radical nitration may be a possible way around this problem.
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Your handle has changed again...
Seriously. Mods. Most of his shit works, and he's even more clued in than some of the spooks at China Lake and Thiokol. Yeah, he once suggested a
solvent choice that would have ignited in the reaction in question. I assume that was quickly rectified via the power of peer review. If he makes an
obvious typo, just correct it. And off-site business is off-site business.
And regarding nitration, what would be the best radical mechanism? Nitric acid+hydrogen peroxide? hydroxylamine/peroxone? Nitrous acid in Caro's acid?
This is an aspect of chemistry I have very little knowledge of.
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AndersHoveland
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The formation of intermediate radicals would bypass the charge shielding effect. One idea would be to to just add a small quantity of NHPI as a
catalyst.
| Quote: |
Catalytic nitration of alkanes with nitric acid was first successfully achieved by the use of N-hydroxyphthalimide (NHPI) under mild conditions; the
key to the present nitration was found to be the in situ generation of NO2 and phthalimide N-oxyl radical by the reaction of NHPI with nitric acid.
"Nitration of alkanes with nitric acid catalyzed by N-hydroxyphthalimide", Shinji Isozaki, Yoshiki Nishiwaki, Satoshi Sakaguchi, and Yasutaka
Ishii, Kansai University, Osaka, Japan
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NHPI basically has the structure:
HON(CO)2C6H4
the molecule as basically a pentagonal ring adjoining a hexagonal benzene ring. It is basically the equivalent of phthalic acid condensed with a
molecule of hydroxylamine.
A "dirtier" method of radical nitration might involve dissolving the starting reactant in carbon tetrachloride, with plenty of excess nitrogen dioxide
dissolved, and then a very limited quantity of chlorine (or bromine) slowly/gradually added in the presence of sunlight. Molecular chlorine easily
breaks apart into radicals in the presence of blue/UV light. These atomic chlorine radicals can then attack otherwise inert hydrocarbons, abstracting
a hydrogen atom, and leaving a carbon radical. If there is a great excess of nitrogen dioxide, a nitroalkane is likely to form before the organic
radical can react with more chlorine. Of course, this type of radical reaction is much more complicated, I just wanted to mention it.
(also obviously there cannot be any water in the reaction)
Radical nitrations are also possible in the presence of nitrite simultaneously being oxidized by H2O2 (this transiently forms the powerful oxidizing
species peroxynitrite), but for reasons I will not go into this reaction would be entirely unsuitable in this situation.
Nitrous acid cannot exist in Caro's acid. No doubt you meant nitric acid. Yes, mixtures of concentrated sulfuric acid, nitric acid, and hydrogen
peroxide have been successful in further nitrating trinitrobenzene. I am not sure if it has ever been tried on 1,2,3-triazole. The reaction might be
more complicated.
Unlike with nitrobenzene, while plain 1,2,3-triazole is nearly impossible to nitrate, once the first nitro group has been introduced, subsequent
nitration is easy. In fact, not only does the [nitric acid] nitration of 4-nitro-1,2,3-triazole add another nitro group, it also oxidizes one of the
nitrogen atoms in the ring! The product is 4,5-dinitro-1,2,3-triazole-3N-oxide.
Some more information: while 1,2,3-triazole can be detonated, the liquid is surprisingly safe to handle (at least in terms of explosion danger), and
very resistant to explosion.
Also, do not quote me on this, but I think a route to preparing 4-nitro-1,2,3-triazole might have involved nitration of
1,2,3-triazole-4-carboxylic acid (I can't remember, probably wrong).
[Edited on 10-12-2012 by AndersHoveland]
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
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killswitch
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So, any ideas on the bis(tetrazinedioxide) compound?
There would probably be an easier synthesis pathway starting from the beginning, but if the azobistriazole is the starting point...
Condensation with four equivalents of an asymmetric hydrazine derivative, then a ring forming step that oxidizes off the organic group and forms a
bond between the transient hydrazide anions, followed by oxidation of the tetrazine?
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DubaiAmateurRocketry
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Nice post and guess killswitch, I actually drew the compound and searched for it and found this. I think the compound you drew definately is very
energetic however the azo link often give a low density, azoxy might be better, however maybe fused rings are best ?
Back to tetrazine dioxides, I realized it can be made in 4 steps when you have R=CH-CNH2=R or doubble bond between two carbon, heres a reaction,
Ill just call this reaction the process 1 so i dont need to draw for all other theoretically possible guesses
[1], [2], [3]
With this reaction, or the one in [2],[4], or [5]. we can make tetrazine oxides out of the above structure.
The tetrazino-azete-tetraoxide might seem interesting since the ring pressure contains a lot of energy.
The benzo tetrazine dioxide, or di tetrazine tetraoxide have been synthesized. In the uploaded.
The last compound should have very high density, and perfect oxygen balance. The first compound from left second line also looks like to have a good
density.
Reference for some guesses
[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
[2]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
[3]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
[4]Org. Lett 1999 Sep 9;1(5):721-4.Synthesis of 1,2,3,4-tetrazino[5,6-g]benzo-1,2,3,4-tetrazine 1,3,7,9-tetra-N-oxides. Frumkin AE, Churakov
AM, Strelenko YA, Kachala VV, Tartakovsky VA.
[5]Synthesis of 1,2,3,4-Tetrazino[5,6-f]benzo-1,2,3,4-tetrazine 1,3,7,9-Tetra-N-oxides
Aleksandr E. Frumkin,Aleksandr M. Churakov,*Yuri A. Strelenko ,Vadim V. Kachala , and Vladimir A. Tartakovsky DOI:10.1021/ol990713q
[6]Pyrazines. I. Pyrazine-N-oxides. Preparation and Spectral Characteristics BY BERNARDKL EINA ND JUDITH BERKOWIT 1957
[7]The Tetrazole 3-N-Oxide Synthesis Tal Harel and Shlomo Rozen* 2010
Attachment: [4]Synthesis of 1,2,3,4-tetrazino[5,6-g]benzo-1,2,3,4-tetrazine 1,3,7,9-tetraoxide.pdf (380kB)
This file has been downloaded 680 times
Attachment: [5]Synthesis of 1,2,3,4-Tetrazino[5,6-f]benzo-1,2,3,4-tetrazine 1,3,7,9-tetra-N-oxide.pdf (30kB)
This file has been downloaded 486 times
[Edited on 18-12-2013 by DubaiAmateurRocketry]
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Davin
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Improved prep of 1-amino-1,2,3-triazole
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