Anders Hoveland
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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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i always wondered what would happen if i mixed hydrazine with perchloric acid.
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JohnWW
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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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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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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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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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Quote: Originally posted by Anders Hoveland ![](images/xpblue/lastpost.gif) | 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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Quote: Originally posted by jon ![](images/xpblue/lastpost.gif) | 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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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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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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Quote: Originally posted by Nicodem ![](images/xpblue/lastpost.gif) |
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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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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Reference
Anders Hoveland
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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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Reference
Anders Hoveland
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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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Hoveland
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http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/aldk...
the condensation products of hydrazone and semicarbazone are mentioned
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