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Taoiseach
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I've tried the synthesis of sodium bis-5,5'-diazoamintotetrazolate for the second time now and each time I failed 
First time I tried according to Engager's procedure in his excellent EDOT.pdf, second time I tried according to US pat. 3,064,827 "manufacture of
salts of diazotized tetrazole derivatives". The procedures are not much different except that the patent suggests a slightly lower temperature
(15°C). Aminoguanidine nitrate, acetic acid and sodium acetate was dissolved in water and NaNO2 added dropwise with cooling. The second time I
managed to keep the temperature perfectly within 14-16°C. Mixture turned yellow and produced much foaming upon warming to RT (lots of N2 I guess).
Yet even after standing for 1 week no crystals have deposited
Any suggestions/ideas?
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Engager
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I have no idea what can go wrong, but i know that products of this reaction are very dependent on pH of reaction mixture and temperature. Mechanism of
this reaction, and photos from my experiment can be found earlier in this thread: http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a.... However, your may examine references by yourself, to get more understanding about
process chemistry and attempt to locate your problem point. Excellent review of aminoguanidine chemistry by Lieber & Smith is attached to this
message (topic you may be interested at is in pages 232-243). Also i want to remember you that some substances have difficulties in crystallization,
as you can see on the photos i've provided from my experiment in pdf and earlier in this thread salt formed is in form of agglomerates witch are
microcrystaline or even amorphous, so tendency to difficult crystallization is evident. I remember some long time ago i tried to make some 5-ATZ by
Schtolle's method (from dicyandiamide and hydrogen azide) and was very disappointed then after week of standing no product crystallized and i thought
that experiment was a failure, but then i accidentally applied glass/glass friction in this solution i was very surprized, because product suddenly
crystallized in excelent yield. Solution was greatly supersaturated because of low solubility of 5-ATZ in water, but it not crystallized spontaneously
for a week! Pure chemicals, absence of dust, absence of uneven regions in reaction flask are aiding supersaturation greatly. So try to force
crystallization by friction of glass rod on the side of reaction flask (below liquid of course) and wait for some more time to make sure you got
nothing precipitated. Can you post photo of reaction mixture after standing so i can watch for difference with solution i got from my experiment?
Attachment: Chemistry_of_Aminoguanidine_And_Related_Substances.pdf (975kB)
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[Edited on 25-7-2010 by Engager]
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Taoiseach
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Rubbing with a glass rod to force crystallization has been tried but to no effect. Comparing your pictures with the solution I obtained it is obvious
that it is a much paler yellow. The first time I tried it according to your instructions, there were very very few crystals on the bottom which
closely resembled the coarse agglomerates in your picture. So some DATZ must have formed. Also the solution was a much darker yellow, just like in
your picture. This time the solution ist much lighter in color, which might be to the lower temperature. I kept the temperature 14-16°C and after the
reaction was over, the solution stayed at 15°C for 30 minutes. No N2 or heating was observed. I then started to swirl the flask and it immediatly
started foaming and a lot of gass was produced. It also heated up several degrees. This only happened when the flask was swirled; no reaction seemd to
take place when it stands still.
The aminoguanidine carbonate is p.a. material from a chemical supplier. Only the acetic acid and sodium acetate are technical grade. The instructions
never say wether the anhydrous or trihydrate salt is required, so yes the pH could be wrong.
Do you know the "ideal" pH for this reaction? I might try neutralizing some of the acetic acid with sodium bicarbonate.
Also I wonder if the diazoaminotetrazolic acid is stable under prolonged boiling.
[Edited on 26-7-2010 by Taoiseach]
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Inorganic
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Can you give a source where is described synthesis of biguanidine sulphate ?
I have been performed searching in SciFinder and I don't find any informations about biguanidine sulphate.
Name biguanidine = 1,2-Hydrazinedicarboximidamide CAS 6882-47-9
Quote: Originally posted by Engager  | Reciently i made some biguanide sulphate, and got an interesting idea, about how another interesting tetrazole can be made. How does it look? Someone
have synth procedure for biguanidine or it's salts (first made by Thiele in last century)?
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Engager
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Unfortunately this reaction path is likely to be failure since heating urea with hydrazine produces semicarbazide by replacement of NH2 group with
hydrazine group (with evolution of NH3). It seems that such substitution in compounds of urea group is very common, and that hydrazine is unable to
condense on urea carbonyl oxygen, like it does in some other cases for example with acetone:
(CH3)2C=O + NH2-NH2 => (CH3)2C=N-NH2 + H2O
In fact if urea can be reacted in such manner it would lead to formation of aminoguanidine:
(NH2)C=O + N2H4 => (NH2)2C=N-NH2 + H2O <=> NH2-C(=NH)-NH-NH2
However it is imposible for hydrazine to act like that on urea oxygen so this scheme is a failure in first step.
And by the way, substance you asked for exists i'm not sure how to name it properly but it can be obtained by reduction of azodicarbomidine - product
produced by oxidation of aminoguanidine with KMnO4 (Ref: Chem.Rev. "Chemistry of aminoguanidine and related substances" page 230).
[Edited on 31-8-2010 by Engager]
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Rosco Bodine
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| Quote: Originally posted by Engager | Unfortunately this reaction path is likely to be failure since heating urea with hydrazine produces semicarbazide by replacement of NH2 group with
hydrazine group (with evolution of NH3). It seems that such substitution in compounds of urea group is very common, and that
hydrazine is unable to condense on urea carbonyl oxygen, like it does in some other cases for example with acetone:
(CH3)2C=O + NH2-NH2 => (CH3)2C=N-NH2 + H2O
In fact if urea can be reacted in such manner it would lead to formation of aminoguanidine:
(NH2)C=O + N2H4 => (NH2)2C=N-NH2 + H2O <=> NH2-C(=NH)-NH-NH2
However it is imposible for hydrazine to act like that on urea oxygen so this scheme is a failure in first step.
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However, it may be possible that hydrazine will react with guanidine splitting off ammonia to give aminoguanidine.
The same mechanism is used in reaction of hydrazine with nitroguanidine to produce nitroaminoguanidine.
If twice the amount of hydrazine is present the product is the diamino derivative, and three hydrazines will yield the triamino derivative.
http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...
This reaction may provide a "shortcut" to aminoguanidine via possible reaction of hydrazine directly with guanidine.
One of the polyaminoguanidine salts of particular interest is triaminoguanidine perchlorate which is a fuse sensitive primary and initiating explosive
reportedly having high brisance. See attached patent US2929699 Also attached is the similar patent US2929698 regarding the diaminoguanidine compounds
which are also energetic.
These compounds are not tetrazoles but reside in a nearby branch of related compounds by virtue of the guanidine and hydrazine reactions.
Also of possible interest is US3293853 which shows a method of obtaining triaminoguandine perchlorate from guanidine perchlorate and hydrazine in
isopropanol. The reaction scheme may be adaptable to use of other guanidine salts and other alcohols as well as adaptable to formation of the
mono-aminoguanidine and di-aminoguanidine derivatives simply by varying the amount of hydrazine available for the reaction.
Also of possible interest is US3813439 which shows reaction of Calcium Cyanamide in aqueous solution with Hydrazine Nitrate, subsequently converting
and precipitating and filtering the Calcium as Carbonate. This process is used for producing Triaminoguanidine Nitrate. However, it is likewise
probably adaptable as an alternative method for mono-aminoguanidine or di-aminoguanidine derivatives, by varying the available hydrazine. The value
here is for a greater versatility in the use of Calcium Cyanamide. It is very easy to react Hydrazine Sulfate with Calcium Nitrate and filter to
obtain a Hydrazine Nitrate solution. Such a process variation may also be helpful for avoidance of the "sludge" and filtration issues which can arise
with Calcium Sulfate in other
parts of the reaction, if Hydrazine Sulfate is used differently.
The usual sludge does not seem to form but rather a granular precipitate from the reaction of Hydrazine Sulfate and Calcium Nitrate. So here is a
possible alternative manipulation of conditions which may be useful.
Additionally, a patent has recently issued related to some of the previously described "Green Primaries" which were being discussed early in this
thread. See US7741353 attached.
Attachment: US2929699 Triaminoguandine Perchlorate Initiating Explosive.pdf (143kB)
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Attachment: US2929698 diaminoguanidine salts.pdf (107kB)
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Attachment: US3293853_EUTECTICS_OF_TRIAMINOGUANIDINE_P.pdf (262kB)
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Attachment: US3813439_TRIAMINOGUANIDINE_SALTS.pdf (154kB)
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Attachment: US7741353_Lead_free_primary_explosives.pdf (67kB)
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Triaminoguandine Perchlorate is something which caught my notice a few years ago. Check the date on the last post on the following page.
http://ysatel.net/ftp/roguesci/www.roguesci.org/theforum/arc...
[Edited on 2-9-2010 by Rosco Bodine]
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Rosco Bodine
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Triaminoguanidine nitrate synthesis kinetics
Attached is a journal article which studies some of the reaction kinetics that are applicable in one reaction scheme for synthesis of
triaminoguanidine nitrate. The study is limited to one reaction system, and provides some insight into the reaction, but is not very helpful in
shedding light on the intermediate reactions for the mono-aminoguanidine and the di-aminoguanidine, nor does it explore alternative methods.
There is some parallel I would think for observations made with respect to the hydazinolysis of nitroguanidine to form nitroaminoguanidine, and the
general reactions involving hydrazinolysis of guanidine, and vice versa.
Kinetics of triaminoguanidine nitrate synthesis
Chan Yuan Ho, Tai Kang Liu, Wen Hai Wu
Ind. Eng. Chem. Res., 1989, 28 (4), pp 431–437
DOI: 10.1021/ie00088a010
Publication Date: April 1989
Attachment: Kinetics of triaminoguanidine nitrate synthesis.pdf (770kB)
This file has been downloaded 1601 times
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Taoiseach
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Suprise suprise, the DATZ did crystallize after 1 month  Sometimes patience pays
off.
Here's a picture of small samples (few miligrams) of several azotetrazolate salts.
From lef to right: disodium-5,5-azotetrazolate, diammonium-5,5-azotetrazolate, dihydrazinium-5,5-azotetrazolate-pentahydrate,
diguanidinium-5,5-azotetrazolate-dihydrate, basic lead 5,5-azotetrazolate; the rightmost picture shows tetrazolylguanyltetracene-hydrate.
The ammonium and hydrazinium salts were made by metathesis reaction of barium azotetrazolate with the corresponding sulphates. The guanidinium salt
was made by neutralizing guanidinium carbonate with dilute HCl and adding sodium azotetrazolate to the boiling solution. The solution was then
filtered and rapidly cooled in an ice bath. After 30 minutes the salt was precipated as fur-like needle shaped crystals. Yield seems to be excellent
due to low solubility in ice cold water (remaining solution was almost colorless).
The basic lead salt was prepared according to GB pat. 986631.
Explosive properties: I only tested heat sensitivity. The guanidinium and hydrazinium salts deflagrate mildly upon flame contact. The carefully dried
ammonium and sodium salt react more violently but only a few crystals will explode, spilling the remaining crystals across the table. The sodium salt
when heated over the flame first turns pale yellow and then explodes incompletely. The ammonium salt crystallizes without water and thus explodes more
readily (without the dehydration stage) when ignited but the explosion is incomplete as well.
The basic lead salt reacts very mildly to flame contact, comparable to lead picrate. A tidbit of confinement will make it DDT tough. 50mg wrapped
tightly into 2 layers of aluminium foil caused a sharp report.
Anyways this is far from what I had expected from compounds with such incredibly high nitrogen content. They look good on the paper but propagation is
poor (maybe due to low density). Its useless stuff IMHO except maybe for special purpose like smokeless rocket fuel. Maybe ammonium/hydrazinium
5,5-diazoaminotetrazolate has better properties.
Someone gotta find a good route to triaminoguanidine perchlorate, that stuff sounds interesting.
[Edited on 2-9-2010 by Taoiseach]
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Rosco Bodine
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Here's an interesting paper
Synthesis and Characterization of the Energetic
Compounds Aminoguanidinium-, Triaminoguanidinium and
Azidoformamidinium Perchlorate
Central European Journal of Energetic Materials, 2008, 5(1), 13-30
Note:
Azidoformamidinium Perchlorate = Guanyl Azide Perchlorate
Alternate routes would seem possible. For example it may be possible to react Hydrazine Sulfate with Barium Perchlorate or Calcium Perchlorate and
filter out the relatively insoluble sulfate to leave a solution of Hydrazine Perchlorate. The hydrazinolysis of Calcium Cyanamide or Cyanamide or
perhaps Sodium Cyanamide, perhaps in the presence of ammonium perchlorate, could then lead to the monoaminoguanidine perchlorate, or diaminoguanidine
perchlorate, or triaminoguanidine perchlorate. Likewise hydrazinolysis of a guanidine salt may work as well. Possibly a nitrosation of the
monoaminoguanidine intermediate would produce Guanyl Azide Perchlorate. The possible reactions are certainly interesting  This should help explain my interest expressed early in this thread about the
potential usefulness of polyaminoguanidines and guanyl azide. These are something like an unexplored "branch" of potentially useful energetic
compounds which reside on the "reaction tree" associated with tetrazoles.
Attachment: Aminoguanidine Perchlorate, Triaminoguanidine Perchlorate, Guanyl Azide Perchlorate.pdf (316kB)
This file has been downloaded 1560 times
[Edited on 3-9-2010 by Rosco Bodine]
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Engager
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| Quote: Originally posted by Taoiseach | Anyways this is far from what I had expected from compounds with such incredibly high nitrogen content. They look good on the paper but propagation is
poor (maybe due to low density). Its useless stuff IMHO except maybe for special purpose like smokeless rocket fuel. Maybe ammonium/hydrazinium
5,5-diazoaminotetrazolate has better properties. Someone gotta find a good route to triaminoguanidine perchlorate, that stuff sounds interesting.
[Edited on 2-9-2010 by Taoiseach] |
Diazoaminotetrazolates and azotetrazolates are significantly less powerful explosives then for example 5-nitro and 5-azidotetrazolates, however they
also form nasty explosive salts with heavy metals - for example try silver azotetrazolate. Anyways azotetrazole is not much of interest by itself - it
is useful as intermediate product for some other good derivatives such as 5-azidotetrazole or isocyanogen tetraazide compounds, some
5-hydrazotetrazole complex derivatives are also of interest since they poses high sensitivity vs laser. As it comes to 5-nitrotetrazolates they have
behaviour somethat similar to heavy metal azides, they explode very violently. Remember that explosive properties of tetrazoles are very dependant on
nature of group attached to carbon atom at 5 position and from cations in the salts. Some Na,K hydrated salts may behave as you described, then some
heavy metal salts (Hg, Cu, Ag) can explode underwater and some even spontaneously.
[Edited on 3-9-2010 by Engager]
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mnick12
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Well today I thought I would test some 5-atz.
I mixed a small amount of 5-atz with enough ethyleneglycol dinitrate to make it clump together. 350mg of this mix was packed into and empty .22 shell
that still had the priming in it. The shell was placed on concrete then half a gram of Zn/S mix was placed around the base of the .22 (to ignite the
primer). Then a tomato sauce can was placed ontop of the the shell. The thing was ignited using a piece of visco. It gave a very loud crack and sent
the can flying. Here is a pick of the damage.
keep in mind that is only 350mg.
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Rosco Bodine
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| Quote: Originally posted by Rosco Bodine | | Quote: Originally posted by The_Davster | About the azidotetrazoles and ethyleneditetrazyl azide mentioned in the early parts of this thread. Looks like the old patent made something else or,
they the patent made an impure oil of a product. The following paper states the ethylene bridged azidotetrazole to be a solid.
http://www3.interscience.wiley.com/journal/122512017/abstrac...
(This is not the first instance of something being discussed on this board being published a few years later...  ) |
If you have the complete article please post it. It could be the temperature is low for which crystal data is referenced, or it could be a different
isomer, or something different entirely from the material referenced in the patent.
Edit: Thanks to solo for the article attached
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@The Davster
With regards to what we were discussing a few months ago, it would seem possible that more specifically what we are talking in circles around but not
quite explicitly stating, is that there is probable optical activity which may be found as a dextro or a levo or a dextro-levo (dl-racemic) isomeric
forms for certain of these tetrazoles.
Mention of biguanide recently has interest parallel with guanyl azide, triaminoguanidine and guanidine with regards to the perchlorates and here is
the link to the biguanide thread
http://www.sciencemadness.org/talk/viewthread.php?tid=10829#...
Possibly also of interest is an expedient method for sodium perchlorate which could be useful for double decomposition or other reactions in pursuit
of perchlorate derivatives. I found a patent procedure describing thermal decomposition of sodium chlorate to sodium perchlorate followed by
extraction of the sodium perchlorate by acetone. The sodium chlorate precursor is relatively easily gotten by thermal disproportionation of ordinary
bleach or electrolysis of sodium chloride using graphite or mmo anodes. So here attached is a thermal decomposition method for obtaining modest
quantities of perchlorate, US3151935 Thermal Conversion of Sodium Chlorate to Perchlorate.
An easier and less extreme conditions method for conversion of chlorate to perchlorate in about 30% yield via heating with ordinary concentration HNO3
is described in the following thread http://www.sciencemadness.org/talk/viewthread.php?tid=11849&...
Attachment: US3151935 Thermal Conversion of Sodium Chlorate to Perchlorate.pdf (243kB)
This file has been downloaded 1423 times
[Edited on 29-9-2010 by Rosco Bodine]
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Rosco Bodine
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2,4-dinitrobenzenediazonium perchlorate would likely be compatible in mixture with triaminoguanidine perchlorate or guanyl azide perchlorate and
perhaps may even form double or multiple salts of interest as energetic materials. In parallel with the possibility of compatible mixtures or adduct
or double / multiple salts with the guanidine / "tetrazole vicinity" related perchlorate compounds, it is also possible that similar compatibility may
exist towards other organic perchlorates including Guanidine Perchlorate, Biguanide Diperchlorate, as well as many other perchlorates of a
non-guanidine relation, such as Methylamine Perchlorate, Betaine Perchlorate, Nitrocholine Perchlorate, and possibly others. By virtue of the common
perchlorate component, there should be good chemical compatibility, with no attendant problems of organic perchlorate / organic nitrate
"transesterfication" or double decomposition as could occur involving mixtures of perchlorate and nitrate or nitroester compounds. A parallel
compatabilty may also exist for (mono) 3-nitrobezenediazonium perchlorate as I am hypothesizing for the 2,4-dinitrobenzenediazonium perchlorate.
There is a thread regarding the 2,4-dinitrobenzene diazonium perchlorate and 3-nitrobenzenediazonium perchlorate including synthesis of the
nitroaniline and dinitroaniline precursors
http://www.sciencemadness.org/talk/viewthread.php?tid=3681&a...
It would seem likely that there are possible combinations among these energetic perchlorates which would be useful as detonators, having desirable
properties in regards to storage stability, performance, and reasonable economy.
[Edited on 8-10-2010 by Rosco Bodine]
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AH-Poster
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There is also 1,5-Diamino Tetrazole.
https://sites.google.com/site/energeticchemical/diamino-tetr...
5-DinitroMethylTetrazole also exists. It can actually be made using DADNE is a precursor, although better routes exist.
https://sites.google.com/site/energeticchemical/5-dinitromet...
These two compounds together would form an interesting adduct/ salt, since the first acts like a base and the second as an acid.
[Edited on 17-10-2010 by AH-Poster]
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Rosco Bodine
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I am curious about the original article regarding the second synthesis described on the page linked above. Could you please identify the reference.
Edit: never mind, I found it. You simply copy and pasted the synthesis for thiosemicarbazide from this forum
http://www.sciencemadness.org/talk/viewthread.php?tid=12995
[Edited on 21-10-2010 by Rosco Bodine]
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Rosco Bodine
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| Quote: Originally posted by Engager | Finaly i got all chemicals i need for synth of DAT (1,5-diaminotetrazole), i found reference on path from thiosemicarbazide via desulfurization and
reaction of intermediate with ammonium azide in dimethylformamide solution:
Synth from reference, attached to this message (translated from russian): 18g (0.2 mol) thiosemicarbazide, 16.3g (0.25 mol) sodium azide, 13.4g (0.25
mol) NH4Cl and 89.2g (0.4) PbO are mixed in 350 ml of dimethylformamide on boiling water bath for 6 hours. Mixture is filtered hot, and filtrate is
evaporated to dryness in vacuum. Residue is dissolved in 50 ml of hot water, filtered hot and slowly cooled. Precipitate is filtered, washed with cold
water and dried. Yield is 11.8g (59%), white crystals, melting point 186-187C with decomposition (from water). Good soluble in hot water, and
water-ethanol mixtures, acids, dimethylformamide, moderately soluble in cold water, ethanol, insoluble in tetrahydrofuran, ethylacetate, methylene
chloride, either.
However, side reaction of HN3 and PbO surely exists and some lead azide will also form.
Question is how safe is to boil this miture on water bath? Do anyone have references on energetic materials whitch can be made from DAT? (I heard that
some complexes such as with Fe(ClO4)2 are proposed as lead azide replacement primaries). Any known properties of DAT salts with strong acids?
[Edited on 12-6-2008 by Engager] |
In earlier discussion about the possible synthesis routes for aminoguanidine, desulfurization of thiourea was mentioned, and a suggestion was made by
me that sodium zincate could possibly be useful. I will need to look at those reactions and structures again, but it would appear there may be worth
considering other parallels of reactivity for cyanamide and aminocyanamide to see if there are any interesting analogues. Reportedly the
diazotization schemes for aminocyanamide are dangerously pH sensitive (and probably concentration and temperature sensitive) as eight laboratory
explosions were reported while trying to identify the proper reaction conditions. It may be an idea worth experimentation to determine if a
simultaneous desulfurization and diazotization is possible via reaction with strontium nitrite. Desulfurization alone might be possible by reaction
with strontium nitrate. These are purely ideas and no experiments or references have been seen by me concerning these possible uses of strontium
compounds.
Interesting file for test data from the following link
http://www.serdp.org/content/download/6513/86128/file/PP-136...
See US7592462 attached
See Hirlinger research paper attached
See essay explosives attached
Diaminotetrazole Chloride article attached
Attachment: essay explosives.pdf (1.2MB)
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Attachment: US7592462_Explosive_complexes.pdf (142kB)
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Attachment: Hirlinger research paper.pdf (789kB)
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Attachment: Diaminotetrazole Chloride.pdf (283kB)
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[Edited on 22-10-2010 by Rosco Bodine]
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almaz
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Obviously what as a result of reaction cyanamide and hydrazine -reaction product aminoguanidine. But i have in its dictation dicyandiamide and
hydrazine sulphate. How, in what way you out of dicyandiamide and hydrazine sulphate prepare aminoguanidine bicarbonate? publish the reference.
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Hydrazinium
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<b> The Usage of 5-ATZ as a nucleophile </b>
Having kept an eye on the topic concerning 5-ATZ, I have been wondering, has anyone tested the strength of 5-ATZ as a nucleophile? For example, I have
been looking at the possibility of using it in a nucleophilic substitution with chloromethane.
Has anyone attempted any similar procedures?
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zhanghaodong
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 擦的
果然是疯狂的东西 5AT硝酸盐不可小视……
擦的……英文水平太低 有中国的疯子们么？
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quicksilver
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"英文水平太低 有中国的疯子们么？"
保留尝试! 某人将回答。我们有中国成员。
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The_Davster
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| Quote: Originally posted by Hydrazinium | <b> The Usage of 5-ATZ as a nucleophile </b>
Having kept an eye on the topic concerning 5-ATZ, I have been wondering, has anyone tested the strength of 5-ATZ as a nucleophile? For example, I have
been looking at the possibility of using it in a nucleophilic substitution with chloromethane.
Has anyone attempted any similar procedures? |
Not sure about chloromethane, but MeI or Me2SO4 methylates to a mix of 1 and 2 methyl aminotetrazoles.
Ethyl bromide does similar.
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Rosco Bodine
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| Quote: Originally posted by almaz | | Obviously what as a result of reaction cyanamide and hydrazine -reaction product aminoguanidine. But i have in its dictation dicyandiamide and
hydrazine sulphate. How, in what way you out of dicyandiamide and hydrazine sulphate prepare aminoguanidine bicarbonate? publish the reference.
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There is no specific reference to this reaction which I know.
What I understand you are asking about is the possible
depolymerization of dicyandiamide under basic conditions
to then react with hydrazine hydrate and a hydrazine salt in solution. It may be possible to limit this known reaction progress to the
monoaminoguanidine stage, by limiting the amount of hydrazine available for reaction to one third the proportion as would lead to the
triaminoguanidine derivative, however this is unconfirmed. The reactions of interest are on page 2 of this thread where the desired product is a
triaminoguanidine derivative, described in US3285958. Also of interest is US5041661. As a starting point for an experiment it would seem likely the
lower reaction temperature and 1/3 the molar amounts of hydrazine values used in Example 2 (table 1 experiment 10)
of US3285958 would be reasonable, with attempted precipitation of the end product using sodium bicarbonate.
It would seem possible that the the required mixture of hydrazine hydrate and hydrazine sulfate in solution needed for the initial reaction for
depolymerization of the dicyandiamide could be gotten by partial freebasing of
hydrazine sulfate using NaOH. Poor solubility of hydrazine sulfate would make it a poor choice for this experiment and
it would seem better to use hydrazine nitrate gotten by
reaction of calcium nitrate with the hydrazine sulfate and
filtering out calcium sulfate, followed by partial freebasing
of the hydrazine using NaOH. If the reaction proceeds as hoped, the dicyandiamide will depolymerize and react with the hydrazine nitrate and
hydrazine hydrate with evolution of ammonia, to form monoaminoguanidine nitrate. The
soluble aminoguanidine nitrate, if it has formed, should precipitate as aminoguanidine bicarbonate when sodium bicarbonate is used to basify the
reaction mixture. Note:
The basic reaction mixture containing unreacted hydrazine hydrate should probably be first neutralized with HCl before being made basic with sodium
bicarbonate, for precipitation
of the desired aminoguanidine bicarbonate.
Pure hypothesis is what you are asking about .....
so this is the only reference I can publish
This may work fine, or it may not work at all ....I do not know.
[Edited on 24-5-2011 by Rosco Bodine]
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Jimbo Jones
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Direct hydrazine sulfate & calcium nitrate reaction will need too much water. Is there any way to convert the sulfate to more soluble salt?
P.S.
By the way Rosco, is it safe to perform your hydrazine sulfate synthesis under ordinary kitchen aspirator?
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Rosco Bodine
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The process is not really thought out completely so it may be workable or not, but a half neutralization of the hydrazine sulfate would result in the
highly soluble
dihydrazine sulfate which could then further be reacted with the calcium nitrate.
I haven't drawn this out on paper to try to analyze it or what complications may be encountered. Sodium hydroxide or ammonium hydroxide or sodium
hydroxide or sodium carbonate plus ammonium nitrate may be useful followed by the calcium nitrate ...I'll think about these contemplated scenarios
further.
A "kitchen" nothing is what should be used there I would think for what is not
really a kitchen process. I use a four inch flexible duct like is used for a clothes dryer mounted in a ring on a ringstand which has its open end
positioned a couple of inches away from the opening of a reaction vessel, and pulls a local draft
into that 4 inch intake duct. That duct is twenty feet long and attached to a flange on the intake of a speed controlled centrifugal blower the
outlet of which
goes to another thirty feet of 4 inch duct for remote discharge. Additionally is a
shop fan which pulls a lateral draft diagonally across the entire area. I use
lighted sticks of incense as visual smoke streamers to show the draft same
as is done in a wind tunnel. If the draft is effective there is no smelling of the
incense only a visual indicator that ventilation is effective. If incense can be smelled at any time, then there is a problem of turbulent air mixing
and the work area is compromised.
With toxic fumes don't play, then you can live another day .....
It is much less challenging to analyze your last experiment,
while you still have a pulse and respiration
That is the method I use for safety when dealing with fumes that are real nasties .....but it isn't IMO the case for low aqueous concentrations of
hydrazine. Really the greater concern there is air ingress into the reaction, moreso than
concern over hydrazine fume egress countercurrent to the
usual flow. Hydrazine is a getter for atmospheric oxygen
so keeping air out of your hydrazine is more likely to be the problem than keeping hydrazine out of your air. Truthfully,
the synthesis is in my opinion relatively low risk with ordinary caution and no extraordinary measures are required beyond
ordinary manipulation and common sense. Some people
seem to think chemistry is "cooking" where they should
deliberately smell the "stew" to see if it needs something....
go figure.....and that is Darwin award behavior in progress, but people will do it. Just use common sense and you will be okay, and don't use common
sense with chemistry and you are guaranteed to get hurt acting recklessly, sooner or later, and probably not too much later.
[Edited on 29-5-2011 by Rosco Bodine]
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Jimbo Jones
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Thanks for the fast reply.I also suspected that the low concentrations of hydrazine in the solution and his boiling point will make the process safe
enough to be performed in the “kitchen”. Don’t get me wrong. I’m not stupid or ignorant and take my hobby very seriously. The aspirator
question was bring to the table just because I move to new place, where every foaming flask on my porch will immidietly catch the attention of mine
sweet, brainwashed neighbours.
P.S.
Funny thing is that I’m indeed a chef. Cheers.
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