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Author: Subject: High Yield Hydrazine Synthesis?
Anders Hoveland
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[*] posted on 19-6-2010 at 18:06
High Yield Hydrazine Synthesis?


I have not actually tried this one.
Trichloroisocyanuric acid is available at pool supply stores in big buckets. If reacted with Dimethylamine, it would likely make
((CH3)2N)3N3C3O3, where the chlorine atoms get replaced by N(CH3)2, and dimethylamine chloride is also formed. ((CH3)2N)3N3C3O3 should hydrolyze with either NaOH or NH4OH
to make isocyanate or carbonate and dimethyl hydrazine (CH3)2N. This should allow a much higher yield because the hydrazine derivitive, once formed, is resistant against being oxidized. The perchlorate, or diperchlorate would be expected to be very powerful. The diperchlorate, if it is deliquescent, could likely be made by using concentrated HClO4 on the monoperchlorate. Alternatively, the monoperchlorate should from coordination salts with cupric perchlorate, to increase the oxygen balance.
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jon
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[*] posted on 25-6-2010 at 13:48


i always wondered what would happen if i mixed hydrazine with perchloric acid.
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JohnWW
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[*] posted on 25-6-2010 at 14:03


You would have to bubble the hydrazine, or add it in aqueous solution, slowly into a cold reasonably dilute solution of HClO4. The hydrazinium perchlorate formed would be with the evolution of a fair amount of heat. After the HClO4 has all been neutralized, you could then evaporate slowly (which may be aided by reduced pressure, but not at elevated temperature) to crystallize out the hydrazinium perchlorate, which is an high explosive.

[Edited on 25-6-10 by JohnWW]
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jon
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[*] posted on 25-6-2010 at 14:37


i thought i would get the darwin award.
sounds like it might be unstable just a hunch, is it shock sensitive???
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Anders Hoveland
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[*] posted on 27-6-2010 at 13:02


You can find that information elsewhere on this forum, but to answer your question, yes, hydrazinium perchlorate is moderately shock sensitive, more so than RDX, but not enough that it will explode if accidently dropped. It is fairly powerful. If detonated by a booster charge, it is more powerful than nitroglycerine, but if detonated by flame or a weak primary explosive, it will undergo a lower velocity detonation, characteristic of hydrazine explosives. If perchloric acid dihydrate is added to a warm solution of hydrazinium perchlorate in excess glacial acetic acid, and then acetic anhydride is slowly added, you might be able to precipitate hydrazinium diperchlorate. The diperchlorate is acidic and should be less soluble in an acidic solution.
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Anders Hoveland
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[*] posted on 27-6-2010 at 16:30


Some of you might immediately be turned off by the need for dimethylamine.
This site gives information on the synthesis: http://www.lycaeum.org/rhodium/chemistry/methylamine.html

Also, will adding a solution of NaOCl to dimethylamine make N,N-dimethyl hydroxylamine or will it make tetramethyl hydrazine? Both N,N-dimethyl hydroxylamine andTetramethyl hydrazine should be unreactive with NaOCl right?
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Nicodem
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[*] posted on 28-6-2010 at 00:35


Quote: Originally posted by Anders Hoveland  
I have not actually tried this one.
Trichloroisocyanuric acid is available at pool supply stores in big buckets. If reacted with Dimethylamine, it would likely make
((CH3)2N)3N3C3O3, where the chlorine atoms get replaced by N(CH3)2, and dimethylamine chloride is also formed.

Trichloroisocyanuric acid is not an acid chloride! It's reaction with dimethylamine gives N-chlorodimethylamine and cyanuric acid. Why don't you first search the literature and then post something that actually makes some sense and is supported by references?
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woelen
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[*] posted on 28-6-2010 at 02:08


Quote: Originally posted by jon  
i thought i would get the darwin award.
sounds like it might be unstable just a hunch, is it shock sensitive???

Didn't you read my experiences with hydrazinium perchlorate? It is in the energetic materials section of the forum. I made this compound, and used the method as outlined by JohnWW: simply mixing dilute solutions of both chemicals, using slight excess of hydrazine and then slowly evaporating in a dry warm place. This compound can be handled without problems, no Darwin award will be given for making this compound ;).




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franklyn
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[*] posted on 29-6-2010 at 15:37


Regarding Hydrazine Perchlorate :
In concentrated solution it is a variant of Astrolite.
Iin that state it is actually more shock sensitive if
there are bubbles present. It crystalizes as a semi
hydrate which is insensitive to shock. See H - 200
PATR - 2700

.
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Anders Hoveland
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[*] posted on 1-7-2010 at 21:05


Quote: Originally posted by Nicodem  

Trichloroisocyanuric acid is not an acid chloride! It's reaction with dimethylamine gives N-chlorodimethylamine and cyanuric acid. Why don't you first search the literature and then post something that actually makes some sense and is supported by references?


Consider that chloramine reacts with dimethylamine to make dimethyl-hydrazine and dimethylamine-HCl. Chloramine is not an acid chloride. When the Cl oxidizes the H, it will create radicals on both the nitrogens. The radical is unlikely to shift to the oxygen in the cyanic acid ring.

Trichloroisocyanuric "acid" can be made by fusing urea, which gives off NH3, and leaves the trimer of Cyanuric acid. (Further heating will vaporize HOCN which is poisonous) Then dissolve the cyanuric trimer in water and bubble in chlorine. It is fairly easy to make.

(CH3)2NN(COR)2 + 2NH4OH --> (CH3)2NNH2 + 2NH4OCOR
This is the hydrolysis reaction, freeing the hydrazine derivitive.

(CH3)2NH + ClN(COR)2 --> (CH3)2NN(COR)2 + HCl
(CH3)2NH + ClNH2 --> (CH3)2NNH2 + HCl
comparing the reaction with chloramine to the reaction with
Trichloroisocyanuric acid.

I think Trichloroisocyanuric "acid" (there are no H atoms in the compound) would actually act like an acid chloride in many ways; but whether it would or not has no bearing on the reaction I describe.


[Edited on 2-7-2010 by Anders Hoveland]

[Edited on 2-7-2010 by Anders Hoveland]
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Anders Hoveland
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[*] posted on 7-7-2010 at 16:33


I found this
"Our results indicate that NDMA formation can occur through the slow formation of 1,1-dimethylhydrazine (UDMH) produced from the reaction of monochloramine and dimethylamine." (PT289) Formation of N-Nitrosodimethylamine (NDMA) During Chlorination of Wastewater Effluent. Sedlak, David1, Mitch, William1, 1
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[*] posted on 14-7-2010 at 12:24


P. J. Sohestakov (J. Russ. Phys. Chem. Soc., 1905, 37, p. 1) obtained hydrazine by oxidizing urea with sodium hypochlorite in the presence of benzaldehyde, which, by combining with the hydrazine, protected it from oxidation. F. Raschig (German Patent 198307, 1908)
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Anders Hoveland
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[*] posted on 18-7-2010 at 01:49


While researching nitrosamines, I came across something interesting:
"dimethylnitrosamine to unsymmetrical dimethylhydrazine has prompted the current report on the hydrogenation of nitrosamines to unsymmetrical hydrazines."

So apparently, nitrous acid mixed with dimethylamine makes dimethyl nitrosamine, which then can be reduced to dimethyl hydrazine. Maybe with vinegar and zinc dust?

Urea Hydrochloride and dissolved trioxane (formaldehyde) with more added hydrochloric acid react to produce methyl-urea, this is a simple methylation with an aldehyde. Formic acid is also made. The acidified Methyl-urea might react with sodium hypochlorite to form a hydrazine compound that would be protected from further oxidation. If this works, the dimethyl hydrazine could be freed by raising the pH. In this case it would be SYMETRICAL dimethyl hydrazine.
+NH3-CO-N(Me)-N(Me)-CO-NH3+
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[*] posted on 23-7-2010 at 01:09


http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/aldk...

the condensation products of hydrazone and semicarbazone are mentioned
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