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Author: Subject: Critique my synthesis
a nitrogen rich explosive
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[*] posted on 30-4-2016 at 12:55
Critique my synthesis


Just so everyone knows: this is NOT a synthesis that has been attempted. It is a synthesis that I will run, once I have made sure that all processes involved are correct. Once I have attempted this synthesis, I will put the write up on pre-publications.

Diazonium compounds and their properties

By a nitrogen rich explosive

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Basics of diazonium compounds
Diazonium compounds are compounds synthesised from primary amines that contain a chain of 2 or more nitrogen atoms. A prime example of this is benzenediazonium, a compound comprising of a benzene ring and 2 nitrogen atoms. Most diazonium salts are extremely unstable and usually highly explosive. Diazonium compounds do not exist by themselves, but instead exist as salts (mostly) of mineral acids (x diazonium chlorate, nitrate etc.)
Take the example of benzenediazonium salts. This is a typical diazonium compound, synthesised by the reaction of aniline with nitrous acid. Nitrous acid (HNO2) is a very unstable acid that is only capable of existing in solution. Because of this, nitrous acid is only ever prepared in situ by the reaction of a nitride salt with a mineral acid. In the case of benzenediazonium, it is synthesised by the reaction of sodium nitrite and (for the sake of example) perchloric acid, forming nitrous acid and leaving a free perchlorate ion. To this solution is added aniline. The nitrous acid reacts with the RNH2 and free H+ ions in solution, forming benzenediazonium and 2H2O. Given that benzenediazonium cannot exist on its own, it instantly reacts with the free perchlorate ions to form benzenediazonium perchlorate, as in the process below.
C6H5NH2 + HNO2 + H + ClO4- = C6H5N2ClO4 + 2H2O
Benzenediazonium perchlorate is one of the more energetic of the diazonium salts, and has found occasional use as a primary explosive in detonators. It is flame sensitive, reasonably impact sensitive and slightly friction sensitive, due to the stability incurred by the mildly coordinating perchlorate ion. However, solid diazonium halides are dangerously explosive and highly unstable. Particularly, diazonium fluorides are dangerously sensitive to any kind of energy, reportedly exploding at the lowest possible ratings for shock and friction tests (although I have not tested this personally, due to obvious reasons.



Section 1 – synthesis of benzenediazonium salts
Chemicals required (all quantities shown here 1/10 mol)

6.9 g sodium nitrite
33.3 g 30% perchloric acid
to form 4.7 g HNO2 according to molar ratio
9.3g pure aniline

Synthesis
An ice bath is prepared, containing no less than 500 grams of ice. A magnetic stirrer is placed at the bottom, and turned on. A 250ml flask was added to the centre of the ice bath, and cooled. To this is added 6.9 grams of sodium nitrite and 33.3 grams of 30% perchloric acid. The mixture is stirred gently until all the sodium nitrite is dissolved. Immediately after all the sodium nitrite is visibly dissolved, the magnetic stirrer is turned off and the mixture is left to cool for a few minutes. 9.3 grams of pure aniline is then added slowly dropwise, with the mixture being gently stirred by hand between every drop. The mixture is monitored with a thermometer. During this process, the mixture must be maintained at below 5 degrees Celsius, or the reaction will just yield a oily black mixture of phenol and other compounds. After all the aniline is added, the mixture is gently stirred by hand for a few minutes, with the temperature being constantly maintained at below 5 degrees Celsius. Another flask is added to the ice bath, and cooled to below 5º. A funnel is prepared with filter paper, and inserted into the empty flask. The aniline mixture is left for a few hours for a precipitate to form, with the ice bath being periodically topped up. After this, the mixture is filtered, yielding a crop of white crystals of benzenediazonium perchlorate.

Benzenediazonium nitrate can also be prepared using a similar method by substituting the 33.3 grams of 30% perchloric acid for 21 grams of 30% nitric acid.

Section 2 - synthesis of semi-carbazide salts

6.2 g urea
9.4 g 35% hydrazine
6.9 g sodium nitrite
33.3 g 30% perchloric acid

A small flask is prepared. 9.4 grams of 35% hydrazine (available on Sigma-Aldrich) is added. A magnetic stirrer is set up. 6.2 grams of urea is slowly added to the hydrazine, with stirring. After all the urea has been added and dissolved, the stirrer is turned off. Once a precipitate is formed, the mixture is gravity filtered, yielding around 7.5 grams of a white, crystalline solid (semicarbazide.)
An ice bath is prepared, containing no less than 500 grams of ice. A flask with a stir bar is set up in the ice bath, and left to cool. 6.9 grams of sodium nitrite is added to the flask, followed by perchloric acid under stirring. The reaction is strongly exothermic. After this reaction has finished, the magnetic stirrer is turned off and the mixture is then left to cool down in the ice bath. Once the mixture has cooled below 5 degrees Celsius, the ice bath is topped up. The stir bar is turned on again, and 7.5 grams of semicarbazide is gradually added to the flask. Between each addition, the mixture is monitored with a thermometer - as before, it is vital that the mixture doesn't go above 5 degrees Celsius. Once all the semicarbazide has dissolved, the mixture is left for a few hours, for the reactions below to take place.

CH5N3O + HNO2 + H = CH2N4O + 2H2O

CH2N4O + ClO4 = CH2N4ClO5

Once a precipitate has formed, the reaction is gravity filtered to yield a crop of white crystals.

[Edited on 30-4-2016 by a nitrogen rich explosive]

[Edited on 30-4-2016 by a nitrogen rich explosive]

[Edited on 1-5-2016 by a nitrogen rich explosive]




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[*] posted on 30-4-2016 at 12:57


If you haven't tried it yet, write it in the present imperative rather than the past tense.



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[*] posted on 30-4-2016 at 12:59


Sorry about this...
I can edit it out.




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[*] posted on 30-4-2016 at 15:14


Do you even have any aniline?
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[*] posted on 30-4-2016 at 18:17


Quote: Originally posted by Rosco Bodine  
Do you even have any aniline?


Aniline isnt too hard to synthesize, I think there's a video on YouTube about it. Not really worth criticizing the procedure based on that.

In other news, I think this is really great. Perhaps some more background and history might be nice, (ie: weren't diazo compounds used as dyes?).
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[*] posted on 30-4-2016 at 22:48


Yes, there were. I believe that a diazo- complex was used as a 'mauve' dye to dye Victorian ladies' dresses purple.



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[*] posted on 1-5-2016 at 09:32


Isn't 20g benzenediazonium perchlorate a bit much for a first trial? :mad:

Hints:
-diazoniums salts are usually made very dilluted to avoid presence of solid salt crystals
-aniline upon contact with HClO4 will heat a lot, maybe forming the aniline perchlorate first would allow most of the heat to be taken away prior to the NaNO2 addition...
-HClO4 and NaNO2 will exhaust all HONO in fumes before you had the time to introduce your aniline

Is the magnetic mixing or hand mixing of a concentrated solution of sensitive primary suspended benzodiazonium perchlorate crystals a good idea? :mad:




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[*] posted on 1-5-2016 at 09:47


Halve the quantities.
16.7 grams of 30% HClO4 contains 12 grams of water, diluting 10g of benzendiazonium perchlorate.
Synthesising aniline perchlorate first would be a very good idea.




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[*] posted on 1-5-2016 at 16:23


Quote: Originally posted by a nitrogen rich explosive  
Halve the quantities.
16.7 grams of 30% HClO4 contains 12 grams of water, diluting 10g of benzendiazonium perchlorate.
Synthesising aniline perchlorate first would be a very good idea.

You wrote 33g of 30% HClO4, 6.9g of NaNO2 and 9.3g aniline
So from there:
MM aniline (C6H5-NH2) = 93g/mole
MM HClO4 = 100,4g/mole
MM NaNO2 = 69 g/mole

6.9g NaNO2 is 1/10 of mole
9.3g aniline is 1/10 of mole
33g *30/100 of HClO4 is 0,0986 mole (you actually need twice that amount to make the perchlorate of diazonium since your NaNO2 will catch 1/10 of mole of HClO4 for making HNO2 and NaClO4...you stil need 1/10 of mole to neutralize the 1/10 of mole of diazonium)

This would make 1/10 of mole of BDAP (MM=204,4 g/mol) --> 20.44 g

Even half that is way to much for a first trial...do you really think your poor 12g water will prevent an explosion and glass shrapnells? Water gap between detonating crystals since relatively uncompressible will propagate detonation to neightbourghood crystals for a sympathetic detonation.




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[*] posted on 1-5-2016 at 17:54


Here is the relevant page from Chemical Abstracts, Volume 1, January 1907

And the relevant pages from PATR plus some pages for closely related compounds

Attachment: Benzenediazonium pages PATR Vol. 2 B-C.pdf (754kB)
This file has been downloaded 359 times

Attachment: Page 59 Chemical_Abstracts Volume 1.pdf (172kB)
This file has been downloaded 337 times
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[*] posted on 1-5-2016 at 23:32


Thanks to both. You saved me (possibly.)



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[*] posted on 2-5-2016 at 08:55


Would diaminofurazan work as well?
C2-N-O-N-NH2-NH2 + HNO2 + ClO4 + H = C2-N-O-N-NH2-N-N-ClO4 + 2H2O




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[*] posted on 3-5-2016 at 14:28


Quote: Originally posted by a nitrogen rich explosive  
Would diaminofurazan work as well?
C2-N-O-N-NH2-NH2 + HNO2 + ClO4 + H = C2-N-O-N-NH2-N-N-ClO4 + 2H2O

Diaminofurazan on its own with HClO4 would be interestings HE
--> DAF monoperchlorate (C2H5N4ClO5) or if possible diperchlorate (C2H6N4Cl2O9)
(H2N-)2C2N2O + HClO4 --> H2N-(C2N2O)-NH3OClO3
H2N-(C2N2O)-NH3OClO3 + HClO4 --> (C2N2O)(-NH3OClO3)2

Diaminofurazan will make bisdiazoniums with difficulty because ortho NH2-s tends to cyclise faster into a triazole ring... what is acidic and can't catch the perchlorate anion...and form a salt of it...




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[*] posted on 4-5-2016 at 05:17


Ditriazolefurazan might also be interesting. Would it be possible to cyclise the triazoles further into tetrazole rings?



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[*] posted on 4-5-2016 at 05:23


Quote: Originally posted by a nitrogen rich explosive  
Ditriazolefurazan might also be interesting. Would it be possible to cyclise the triazoles further into tetrazole rings?

Just to see...try to draw your Ditriazolefurazan and post your conclusions back!

Making tetrazoles out of triazoles has not yet been done IIRC-IMO...but maybe one day




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[*] posted on 4-5-2016 at 09:05


No, not going to happen!
This compound won't work.

[Edited on 4-5-2016 by a nitrogen rich explosive]




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[*] posted on 5-5-2016 at 04:16


Quote: Originally posted by a nitrogen rich explosive  
No, not going to happen!
This compound won't work.

[Edited on 4-5-2016 by a nitrogen rich explosive]

You see you answered your question by yourself...

But spelling is important in chemistry...while ditriazolefurazan doesn't exist...on the other hand the following might exist (at least on paper what is a good start):
-diazidofurazan (N3-(C2N2O)-N3)
-ditriazenofurazan (H2N-N=N-(C2N2O)-N=N-NH2)
-triazolofurazan (HN3=C2N2O)
-ditriazolylfurazan((HN3C2H)-(C2N2O)-(HC2N3H))
But those are bad at OB...so to improve OB and density, better work with furoxans or theorical furdioxans ...
and for the last molecule to replace the external H's atoms from triazolyl's C=C-H by nitroformyl's --> C=C-C(NO2)3




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