Sciencemadness Discussion Board

Ethylene diamine perchlorate

woelen - 26-12-2009 at 11:10

I made a funny compound, which burns with a beautiful pink flame.



I made this by taking 5 ml of 10% HClO4 and adding drops of an approximately 10% solution of ethylene diamine in water. I added around 1 ml of this 10% solution and then I added single drops. After each two or three drops I tested a tiny sample of the liquid with some NaHCO3 and if it still fizzled I added another drop of 10% ethylene diamine solution. I stopped adding ethylene diamine until the solution does not cause fizzling of NaHCO3 solution. In this situation there probably is a slight excess of ethylene diamine. In the process of sampling I have taken good care not to contaminate the liquid with NaHCO3.

Next, I poured the liquid in a hour glass and put it in a warm and dry place for a few days. This results in formation of a pale yellow solid, which still seemed slightly wet (no nice crystals but some sticky semicrystalline mass was produced).

When a small quantity of this sticky mass is put on a small spatula and kept in a flame then it first does some sputtering and bubbling and then at once it gives an intense flame of fire with a pink color.

The picture shows the end of the burst of fire (at the most intense point the camera was strongly overexposed).

I'll make a webpage with more pictures and more details but I already wanted to share this nice result with you.



[Edited on 26-12-09 by woelen]

Rosco Bodine - 26-12-2009 at 22:31

Betaine would probably also be an interesting titrant :D

woelen - 27-12-2009 at 05:36

This is the webpage in which the experiment is described in more detail. You can also see a video demonstrating the reaction.

http://woelen.homescience.net/science/chem/exps/NH2CH2CH2NH2...

franklyn - 27-12-2009 at 10:08

- very good woelen
It has a lot of merit for a " funny compound ", it is a serious explosive
( lead block performance 144 % to that of TNT ) as are all organic base
prechlorate adducts
See Federov , Page E 237 - Ethylenediamine Diperchlorate
The chelating property of Ethylenediamine also lets it make coordination
complexes with oxidizer salts.
See Federov , Page E 235 - Ethylenediamine Complexes

PHILOU Zrealone commented here _
http://www.sciencemadness.org/talk/viewthread.php?tid=10058#...
" Stangely hydrazine perchlorate is less powerfull than the nitrate, in the other cases
perchlorates are always higher performers on all aspects; ( maybe due to excess oxygen
content.) "

Rosco Bodine commented here _
http://www.sciencemadness.org/talk/viewthread.php?tid=4076#p...
" Mixtures of urea perchlorate , hexamine diperchlorate , and ammonium perchlorate
in some combination of binary or perhaps tertiary mixtures could also result in some
interesting compositions."
- on Methylamine Perchlorate , which is very similar
http://www.sciencemadness.org/talk/viewthread.php?tid=4076#p...
http://www.sciencemadness.org/talk/viewthread.php?tid=6791#p...

Related threads & post
Hexamine Diperchlorate
http://www.sciencemadness.org/talk/viewthread.php?tid=364
Urea Perchlorate
http://www.sciencemadness.org/talk/viewthread.php?tid=3286
TriperchloroTriaminobenzene
http://www.sciencemadness.org/talk/viewthread.php?tid=1081&a...
http://www.sciencemadness.org/talk/viewthread.php?tid=1081&a...

.

woelen - 20-2-2010 at 13:45

I made another somewhat related compound, N(CH3CH2)4ClO4. This can be made by dissolving tetraethylammonium bromide, N(CH3CH2)4Br, in water and adding a concentrated solution of a soluble perchlorate to this. I used 20% HClO4, but a concentrated solution of Mg(ClO4)2 or NaClO4 also will work. When the solutions are added to each other, a dense white somewhat flocculent precipitate is formed.

Next, I boiled the solution for a while and all of the precipitate dissolves when this is done. I continued boiling for a while so that appr. 50% of all water evaporated. Next, I allowed the liquid to cool down for two hours or so. After this, the liquid is filled with many needle-shaped crystals.

The wet mass of crystals and liquid were put on a sintered glass filter and the mass is rinsed three times on this filter with ice cold distilled water. Next, I put some paper tissue on the bottom side of the sintered glass filter, such that most of the liquid is absorbed. Then I scraped off the solid material and put it in a petri dish in a warm dry place for a few hours. The result is a purely dry feather-like solid which is not hygroscopic. The latter surprises me, because tetraethylammonium bromide is very hygroscopic.

When the material is kept in a flame, then it does not ignite at once. You have to keep it in the flame for a while just like the ethylene diamine perchlorate. But after a while it sets off white a deep orange flame and a strong whoosh sound, and a cloud of black soot is ejected from the explosion. The soot can be explained, because there is insufficient oxygen in the oxidizer. This material is less powerful than the ethylene diamine perchlorate, but the visual effect of setting off this compound is nice. I'll try to make a video of this tomorrow.

woelen - 6-4-2010 at 10:56

It has been some time since I made this compound, but the material is not really energetic. I made a video, but it is not really worth posting here. Just some crackling and sputtering, that's all. I can understand this, because the compound has four ethyl groups for roughly 4 O-atoms and there is a very strong oxygen deficiency in this compound.

I now also have tertramethyl chloride and with this compound I made [N(CH3)4]ClO4. This compound is much more energetic and much easier to ignite than [N(CH3CH2)4]ClO4. I also made the compound [N(CH3)4]IO4 and the latter is even easier to ignite, but the reactions seems to be somewhat less powerful. The smoke effect of [N(CH3)4]IO4 is nice though. It gives a mix of purple and yellow smoke. I already made a video of this and that video will follow soon.

woelen - 17-6-2010 at 12:08

Here is the promised video. It took some time, but I still think it is nice to share this with others. It is the burning of [N(CH3)4]IO4. This compound is ignited very easily and gives a lot of yellow smoke and purple iodine vapor on burning.

http://www.homescience.net/chem/exps/NH2CH2CH2NH2_HClO4/N(CH...

Here follows a single frame of the yellow smoke reaction:



This amazing amount of smoke is from just a few cubic mm of solid material!



___________________________________________________________________________

In the meantime I also made hydrazine perchlorate, N2H5ClO4. This compound also is quite interesting. You can read about that on my website as well.

http://woelen.homescience.net/science/chem/exps/hydrazine_pe...

Most special are the fairy-powder effects when boiling N2H5ClO4 sprays little droplets into the air, which explode with tiny specks of light and a crackling/hissing noise.





[Edited on 17-6-10 by woelen]

Anders Hoveland - 17-6-2010 at 16:14

Woelen: you might try the BH3NH2NH4ClO4 that is described in "stronger than Astrolite" post. The BH3 is much less reactive after it has become an adduct. There is also exists the di-nitrate of hydrazine, and therefore the di-perchlorate could probably be made.

Anyone wanting to make HClO4 might try first crystallizing out NH4ClO4, which has a low solubility in water (less than NaClO4),
and then reacting NH4ClO4 with chlorine gas, being careful to not use too much Cl2, otherwise NCl3 will form and cause an explosion. 2NH4ClO4 + 3Cl2 --> N2 + 6HCl gas + HClO4

If water is not used, one might get pure HClO4
I do not know why there is so much interest in N2H4 and not NH2OH. If there is some organic group attached to it, NH2OH can be more poweful than hydrazine, with much less toxicity. I believe that ONCH2CH2NO will react with bisulfite to form HONHCH2CH2NHOH, the sulfate of that compound anyway.

woelen - 18-6-2010 at 01:09

BH3NH2NH3ClO4 sounds like an interesting compound to play with, but making this is beyond my capabilities. I have no borane and cannot make it from chemicals available to me (remember, I am not a professional chemist, but am doing this as a hobby, as most of us do here).

Making the diperchlorate of hydrazine is not easy at all. I tried this, but the result is a wet and sticky mess and no crystals are obtained. This is what I also wrote in my webpage. In air, even at a warm place, the material simply does not want to dry.
I have the impression that N2H6(ClO4)2 and N2H5ClO4+HClO4 are in equilibrium with each other and in air, this mix is EXTREMELY hygroscopic. Maybe it can be prepared when it is dried in vacuum at somewhat elevated temperatures over P4O10 and/or H2SO4, but under such extreme conditions, the anhydrous HClO4 also is volatile and simply leaves the compound, or it ignites the whole mess. On the other hand, the mono-perchlorate is perfectly stable and non-hygroscopic.

The idea of making HClO4 from NH4ClO4 unfortunately does not work in practice. In the past I have done similar experiments with this. I attempted to make H2SO4 from (NH4)2SO4 (purified fertilizer, so-called "zwavelzure ammoniak" as we can buy it in the Netherlands). This reaction is not smooth at all. Cl2 and NH4(+) ion can coexist in aqueous solution fairly well and in no way is there a smooth reaction in which N2 and HCl are formed. Just try it yourself. At high concentrations of ammonium ion, indeed NCl3 can be formed. So, this method is not practical and gives a shitload of all kinds of side reactions, which are slow.

I do have some NH2OH.HCl and I could try mixing a highly concentrated solution of this with 30% HClO4. If hydroxylammonium perchlorate also has relatively low solubility like ammonium perchlorate, I might be capable of isolating this from the liquid. I'll try that next weekend. If I obtain some dry powder from this, I could see how energetic this is. I do not expect too much of this, because of the really large excess oxygen balance in this compound. On the other hand, the endothermic character of NH2OH may add to the energetic properties of NH2OH.HClO4. To be continued....

Anders Hoveland - 18-6-2010 at 10:16

Hydroxylamine perchlorate would be LESS powerful than the hydrazine salt, however it is a better oxidizer, and can be more powerful if than the hydrazine salt if there are other groups to oxidize, or even if mixed with CH3NO2 to make a "cheddite".
Buy boric acid (available in many pharm. stores). Heat it to make B2O3. Burn with magnesium in the absence of air. You will get some magnesium boride.

[Edited on 18-6-2010 by Anders Hoveland]

woelen - 19-6-2010 at 02:59

I tried making the hydroxylammonium perchlorate. It is not that difficult to make, but it is not as easy as making N(CH3)4ClO4. The salt is soluble quite well in water and is not easily crystallized. I did the following:

Dissolve some NH2OH.HCl in a little amount of water. Some heating was required to get all of it dissolved.
To this, I added some 50% HClO4. When this is done, no crystals appear. Apparently NH2OH.HClO4 is soluble very well.

Next, I boiled down the solution, until the liquid became somewhat syruppy. I didn't want to go any further, because of fear of sudden violent decomposition. While boiling down, a lot of HCl-gas escapes!

On cooling down, crystals of NH2OH.HClO4 separated. I put the crystalline mass on a sintered glass fritte and sucked away liquid with a piece of tissue paper on the other side of the glass fritte. Next I rinsed the piece of paper with a lot of water (just to be sure no dangerous paper/HClO4 mixes are formed) and threw away the wet piece of paper. On the glass fritte a fairly dry white crystalline mass remains.
The crystals do not become really dry, they remain somewhat sticky, but they are useful for experimenting.

I put some of the crystals on a spatula and kept this above a flame. When this is done, the solid melts and starts sputtering and then suddenly it burns with a blue flame. The reaction is only marginally less energetic than the reaction of hydrazinium perchlorate.

I indeed can imagine that if a methyl group could be attached to the hydroxyl amine, then a more energetic compound can be prepared.

[Edited on 19-6-10 by woelen]

Anders Hoveland - 19-6-2010 at 18:21

And how to methylate NH2OH? Maybe start with the methyl group to begin with. I think HSO3- might reduce a nitroso group.

NH2OH mechanics.bmp - 306kB

Anders Hoveland - 23-6-2010 at 19:37

One might be able to do a "nitrosoation" on toluene with conc. H2SO4 and NaNO2. This would make CH3C6H2(NO)3.
Use the reaction in the above post with HSO3- and one might get
CH3C6H2(NHOH)3. This could be used to make an energetic salt.

[Edited on 24-6-2010 by Anders Hoveland]

[Edited on 24-6-2010 by Anders Hoveland]

mnick12 - 23-6-2010 at 20:16

I dont think so. Nitrous acid on aniline would give you the diazonium salt which would decompose into phenol and other things very easily. Also conc H2SO4 and sodium nitrite would give very conc HNO2 which would rapidly decompose into nitrogen oxides. The way I would do it is mononitrate benzene, then reduce with Zn and NH4Cl to phenylhydroxylamine. That could be oxidized using sodium or potassium dichromate to the nitrosobenzene. Alternatively you could oxidize aniline to nitrosobenzene.

But I dont even know why we are talking about this, the thread is on ethylenediamine perchlorate and related compounds...

woelen, interesting expiriments! Have you tried methylamine perchlorate? I was going to attempt this once I get some more conc HCl to make perchloric acid, but money is kinda tight right now. I have a feeling methylamine perchlorate would be pretty soluable, but also could be a good energetic oxidizer when mixed with other fuels.

franklyn - 4-9-2010 at 16:28

Referring to the previous posting above in this thread of this topic here _
http://www.sciencemadness.org/talk/viewthread.php?tid=13174#...
Amine base + acid explosophore adduct compounds applying this theme
are quite varied and a prolific area for investigation , as has been observed
before by me here _
http://www.sciencemadness.org/talk/viewthread.php?tid=10058#...
and here _
http://www.sciencemadness.org/talk/viewthread.php?tid=14033#...
NOTE * N,N-Dimethyl-2,4,6-Trinitroaniline is not basic enough to protonate
as Nicodem pointed out.


1,3,5-triaminobenzene
http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=6695...
http://cdb.ics.uci.edu/cgibin/ChemicalDetailWeb.py?chemical_...
Can readily be combined as a perchlorate salt and also with Trinitromethane
http://www.sciencemadness.org/talk/viewthread.php?tid=1081&a...
2 C6H3(NH2)3 • 3HClO4 => 3 CO2 + 9 CO + 9 H2O + 6 HCl + 3 N2
C6H3(NH2)3 • 3HC(NO2)3 => 3 CO2 + 6 CO + 6 H2O + 6 N2

Protonation of 1,3,5-triaminobenzenes in aqueous solutions
http://pubs.acs.org/doi/abs/10.1021/ja00230a034


1,2,4,5-Tetraaminobenzene
http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=7826...
http://cdb.ics.uci.edu/cgibin/ChemicalDetailWeb.py?chemical_...
The same as the triamino shown above but affords better oxygen balance.
It is readily oxidized in air as described in the attached excerpts , but
stable as the hydrochloride salt in which it is commercially available.
C6H2(NH2)4 • 4HClO4 => 5 CO2 + CO + 5 H2O + 4 HCl + 2 N2
C6H2(NH2)4 • 4HC(NO2)3 => 7 CO2 + 3 CO + 7 H2O + 8 N2


2,3,5,6-Tetraaminopyrazine
This is a recently isolated heterocyclic investigated mostly for polymer applications.
Due to a higher nitrogen content replacing carbon , a nearly oxygen balanced nitrate salt
makes sense. The rest have a positive oxygen balance.
C4N2(NH2)4 • 4HNO3 => 2 CO2 + 2 CO + 6 H2O + 5 N2
C4N2(NH2)4 • 4HClO4 => 4 CO2 + 4 H2O + 4 HCl + 3 N2 + 2 O2
C4N2(NH2)4 • 4HC(NO2)3 => 8 CO2 + 6 H2O + 9 N2 + O2

.

Tetraamino benzene.gif - 23kBTetraamino benzene.jpg - 32kB 2,3,5,6-tetraaminopyrazine.gif - 58kB

franklyn - 9-9-2010 at 12:00

2,3,5,6-Tetraaminopyrazine
This patent dates to 1974 so this material has been around for a while after all.
http://www.google.com/patents/download/3808209_DI__NITROPYRA...

2,3,5,6-Tetraaminopyridine Hydrochloride Preparation
http://www.mdpi.com/1420-3049/14/5/1652/pdf
2 C5HN(NH2)4 • 4HNO3 => CO2 + 9 CO + 13 H2O + 9 N2
4 C5HN(NH2)4 • 4HClO4 => 20 CO2 + 18 H2O + 16 HCl + 10 N2 + 3 O2
2 C5HN(NH2)4 • 4HC(NO2)3 => 17 CO2 + CO + 13 H2O + 17 N2

The WiZard is In
made this related post on previous work on this theme here _
http://www.sciencemadness.org/talk/viewthread.php?tid=4697#p...

______________________


Alternatively the amines of the precusors can be replaced directly with nitro groups

2,3,5,6-Tetranitropyrazine.gif - 2kB

2,3,5,6-Tetranitropyrazine
Theoretical Study on Polynitropyrazines and Their N-oxides
Available in the references section
http://www.sciencemadness.org/talk/files.php?pid=184713&...

2,4,6-Trinitropyridine & Related Compounds
Available in the references section
http://www.sciencemadness.org/talk/files.php?pid=112877&...

High Nitrogen Explosives Part 1 - 2,6-Dinitropyridines & Dibenzo-1,3a,4,6a-Tetraazapentalenes
http://handle.dtic.mil/100.2/ADA285388
re-directs to :
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA285388&Locati...

.

Anders2 - 12-9-2010 at 00:30

If I am not mistaken, the compound in figure (92) can be oxidized with concentrated trifluoracetic acid and H2O2 to add an oxide to the heterocyclic nitrogen on the top, forming (after neutralization) a very insensitive explosive with ideal properties.
This was described on a site called "Energetic..." something, but now I cannot find it.
"Advances in Energetic Materials"?

http://www.scribd.com/doc/17087769/A-Review-of-Energetic-Mat...

http://pubs.acs.org/doi/abs/10.1021/ol049076g

"DNTZ" from Organic chemistry of explosives By Jai Prakash Agrawal, R. D. Hodgson
looks interesting, while the book is 150USD, the contents are irresistable and fascinating for anyone with a passion for advanced energetic materials.
DNTZ could be thermally stable, despite the two nitro groups, because the amine would be expected to be electron donating, through the aromatic resonance

On p15 of "Oxidation and Nitration of C-N bonds", for instance, it discusses gem-nitro groups, saying that oximes can be turned to dinitro with nitric acid and ammonium nitrate, but that then the psuedonitrole product needs treatment with H2O2 (or NO2) to yield the gem-dinitro


Bis-(triaminoguanidinium)-5,5′-azotetrazolate

[Edited on 12-9-2010 by Anders2]

franklyn - 14-9-2010 at 12:07

Heterocyclics available as base adducts with oxy acid groups is extensive.
Examples of basic media include :

- 5 member rings with one nitrogen, ranging from aromatic to saturated,
. such as pyrrole, 3-pyrroline, pyrrolidine.
- 5 member rings with two nitrogens, ranging from aromatic to saturated,
. such as Imidazole, pyrazole, 2-pyrazoline, pyrazolidine.
- 5 member rings with three nitrogens, such as 1,2,3-triazole, 1,2,4-triazole.
- 5 member rings with four nitrogens, tetrazole.

untitled.JPG - 8kB

- 6 member rings with one nitrogen, ranging from aromatic to saturated,
. such as pyridine, piperidine.
- 6 member rings with two nitrogens, ranging from aromatic to saturated,
. such as pyridazine, pyrimidine, pyrazine, piperazine

- 6 member rings with three nitrogens, ranging from aromatic
. 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, to saturated, Triazacyclohexane

- 6 member rings with four nitrogens, 1,2,3,4-tetrazine, 1,2,4,5-tetrazine

Additionally any of the rings containing an attached amine group
can also serve as base adducts with oxy acid groups.
Examples of these basic cyclic compounds include
- aminopyridine, diaminopyridine, triaminopyridine,
- aminopyridazine, diaminopyridazine, triaminopyridazine,
- aminopyrimidine, diaminopyrimidine, triaminopyrimidine,
- aminopyrazine, diaminopyrazine, triaminopyrazine,
- aminotriazine, diaminotriazine & triaminotriazine ( melamine )

Many of these have already been subject of investigation as propellants.
Substituted nitro derivatives of the rings is an ongoing effort for the
development of new explosives compounds.

Studies of Aminonitropyridines, Aminonitropyrimidines, and Their N-Oxides
http://www.mdpi.com/1422-0067/3/8/858/pdf

Synthesis, Characterization and Explosive Properties of
3,5-Dinitro-2,4,6-Triaminopyridine and Its 1-Oxide
http://handle.dtic.mil/100.2/ADA299641
Re-directs to:
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA299641&Locati...


[Edited on 15-9-2010 by franklyn]

Anders2 - 14-9-2010 at 14:31

I found the link. page 2, compound "LLM-105"
http://docs.google.com/viewer?a=v&q=cache:YUiQqbN8BYsJ:p...

Note that LLM-116 is stated to be calculated as having 90% the power of HMX. Now compare the with the molecular structure of DNTZ. This indicates that DNTZ is likely more powerful than HMX, and possibly more stable, since the nitrogens will serve as an electron donor through the aromatic ring.

"Vogl has patented an explosive prepared from ethylenediamine perchlorate, by forming an addition compound with picric acid."
(Perchlorates: Their Properties, Manufacture And Uses) p139

Message to the Moderators: Perhaps move some of these posts to the topic "New Energetic Materials - Current Research", starting with franklyn's post (which started with "2,3,5,6-Tetraaminopyrazine...This patent..."). Things started slowly drifting a little off topic before that, but the posts before franklyn's related to ethyldiamine perchlorate at least to some extent.

[Edited on 14-9-2010 by Anders2]

nitrocholine perchlorate

Rosco Bodine - 29-9-2010 at 06:43

It isn't clear if this material has any value or not and there is very little in the literature about it. The synthesis would seem simple enough but the hazards of synthesis are also unknown.

Choline forms a perchlorate salt , mp 273C

C5H14NO-ClO4

The perchlorate salt on being heated in water bath with 65% HNO3 does form a nitratoperchlorate mp 186C ,
sl sol water , explodes strongly when heated above mp .

C3H9N(ClO4)CH2CH2-ONO2

This compound is also called nitrocholine perchlorate .

Hofmann , K.A. and Hobold , K. , Ber. chem. Ges. 44 , 1766 (1911)

possible Mannich reaction ?

Rosco Bodine - 17-10-2010 at 22:25

This " hypothetical " ( exist ? ) compound has been puzzling me a bit lately so I am going to just throw it out there for consideration and comment. No search of the literature has been done to learn more about this possible reaction and no experiments either .....so this is purely a "shot in the dark" kind of an idea for a compound and a reaction route that may or may not work for the compound that also may or may not exist. Please humor me . Does this reaction work ?

It involves a Mannich reaction for nitromethane and formaldehyde and ammonium perchlorate :

CH3NO2 + HCHO + NH4ClO4 ----> CH2NO2CH2NH2 - HClO4 + H2O

As for nomenclature, perhaps the desired theoretical compound CH2NO2CH2NH2 - HClO4 would be called nitroethanolamine perchlorate

I can't find any reference to such a compound.

Nicodem - 18-10-2010 at 07:27

Quote: Originally posted by Rosco Bodine  
It involves a Mannich reaction for nitromethane and formaldehyde and ammonium perchlorate :

CH3NO2 + HCHO + NH4ClO4 ----> CH2NO2CH2NH2 - HClO4 + H2O

As for nomenclature, perhaps the desired theoretical compound CH2NO2CH2NH2 - HClO4 would be called nitroethanolamine perchlorate

I can't find any reference to such a compound.

You can not get a nitronate ester like that as the addition of the MeNO2 derived nitronate to the carbonyl is reversible. You can utmost get the normal Manich reaction product which would be O2N-CH2CH2-NH2*HClO4. However, I found no examples of Mannich reactions between nitromethane and ammonia. I would expect polysubstitution could and might occur at both sides, at the alpha-nitroalkane position and the nitrogen of ammonia. Already with normal Mannich reaction, when employing ammonia, one gets substitution products up to the tertiary amine. Otherwise the Mannich reaction with nitroalkanes is known and has been relatively well studied (for one example, see DOI: 10.1021/jo01019a069).
O2N-CH2CH2-NH2*HClO4 is only described in a patent (abstract bellow). O2N-CH2CH2-NH2 can be prepared via the Michael reaction (see second reference).
Quote:
Process of preparing 2-nitroalkylamines, preferably in the form of salts. Soroka, Miroslaw; Siwek, Andrzej. (Politechnika Wroclawska, Pol.). Pol. (2005), 6 pp. CODEN: POXXA7 PL 188456 B1 20050228 Patent written in Polish. Application: PL 98-324914 19980217. Priority: . CAN 144:128653 AN 2006:110575 CAPLUS

Patent Family Information

Patent No. Kind Date Application No. Date
PL 188456 B1 20050228 PL 1998-324914 19980217

Priority Application
PL 1998-324914 19980217


Abstract

The title compds. H2NCH2C(R1)(R2)NO2 [R1, R2 = H, alkyl] or preferably its salts H3N+CH2C(R1)(R2)NO2X- [I; R1, R2 = H, alkyl; X = chloride, sulfate, perchlorate, etc.] were prepd. by reacting N-(triarylmethyl)-1-amino-2-nitroalkane A3CNHCH2C(R1)(R2)NO2 [II; R1, R2 as above; A = aryl, preferably Ph] with hydrochloride acid or other inorg. acid in preferably org. solvent at 250-400K. Aq. solns. of I were also prepd. by acidolysis of II with hydrochloride acid or other inorg. acid in H2O at 250-400K. Thus, treating N-(triphenylmethyl)-1-amino-2-nitroethane with dry hydrogen chloride in Et2O at 273-310K afforded 100% 2-nitroethylamine hydrochloride.



Aliphatic nitro compounds. VII. Preparation of 2-nitroalkylamines. Heath, Royden L.; Rose, J. D. Imperial Chem. Industries Ltd., Manchester, UK. Journal of the Chemical Society (1947), 1486-9. CODEN: JCSOA9 ISSN: 0368-1769. Journal language unavailable. CAN 42:23078 AN 1948:23078 CAPLUS

Abstract

NH3 and primary or secondary amines interact with a-nitro olefins to give 2-nitroalkylamines. Those formed from NH3 or aliph. amines are in general extremely unstable but can be reduced over Raney Ni to derivs. of (CH2NH2)2. N-(2-Nitroalkyl)arylamines from arom. amines are somewhat more stable but are best isolated and characterized as their salts. In many cases O2NCH2CH2NO3 (I) can be used as a convenient lab. substitute for O2NCH:CH2 and Me(O2NCH2)CHOAc (II) or Me(O2NCH2)CHNO3 (III) can replace MeCH:CHNO2 (IV). I (13.6 g.), added dropwise to 20 cc. MeOH satd. with dry NH3 at -5 and the mixt. stirred 4 h. at -5 to 0, gives 9 g. crude O2NCH2CH2NH2, which forms a black tar in 1-2 h. and does not yield cryst. salts but on redn. in MeOH gives (CH2NH2)2. IV and MeOH-NH3, stirred 3 h. at 0, give 55% 2-nitroisopropylamine, b10 50-5, decomp. within 24 h. (HCl salt, m. 114); redn. yields 52% MeCH(NH2)CH2NH2. III (30 g.) in 200 cc. dry ether, treated 1 h. with NH3, gives 12.7 g. bis(2-nitroisopropyl)amine, b0.5 60-2. MeCH:C(NO2)Me and MeOH-NH3, stirred 2 h. at 0, give 60% 2-nitro-3-aminobutane, b20 75-8, n18D 1.4720, decomp. in 2 days (HCl salt, m. 115 (decompn.), also unstable); redn. gives 40% [MeCH(NH2)]2. Me2C:CHNO2 in C6H6 gives 40% 1-nitro-2-amino-2-methylpropane, b11 62.5, decomp. in 3-4 days (HCl salt, m. 182 (decompn.)); redn. gives 75% Me2C(NH2)CH2NH2. I (6.8 g.), added to 7.3 g. Et2NH in 100 cc. ether at 0, gives diethyl(2-nitroethyl)amine, which could not be distd. at 15 mm. (violent decompn.); HCl salt, m. 72-5; picrate, m. 88. MeCH:C(NO2)Me gives 65% 2-nitro-3-diethylaminobutane, b11, 90-5, begins to decomp. in 12 h. (picrolonate, m. 267 (decompn.)). I (5.9 g.), added dropwise to 11.8 g. tetrahydroquinoline at a temp. below 30, the mixt. stirred 1 h., dissolved in 50 cc. ether, and treated with ether-HCl, gives 75% N-(2-nitroethyl)-1,2,3,4-tetrahydroquinoline-HCl, m. 132; CH2:CHNO2 gives 12.5%. I (27.2 g.), added dropwise to 37.2 g. PhNH2 in 250 cc. ether at room temp.
and stirred 2 h., gives 65% PhNHCH2CH2NO2, m. 37; HCl salt, m. 109; Ac deriv., m. 99; with CH2:CHNO2 this yields 50% %Ngr;,N-bis(2-nitroethyl)aniline, m. 64 (HCl salt, m. 128). PhNHMe and CH2:CHNO2 give 50% N-methyl-N-(2-nitroethyl)aniline, b0.2 110 (HCl salt, m. 82). N-Ethyl-N-(2-nitroethyl)aniline, pale green oil, b0.1 108, n19D 1.5597; HCl salt, m. 114, 70%; picrate, m. 106; CH2:CHNO2 gives 75% of the HCl salt. N-(2-Nitroisopropyl)aniline, yellow, m. 33. MeCH:CHNO2 (43 g.), treated dropwise with 53.5 g. PhNHMe at a temp. below 30 and the crude product in 500 cc. ether added to 500 cc. ether contg. 20 g. HCl, gives 92% of the HCl salt, m. 126, of N-methyl-N-(2-nitroisopropyl)aniline, pale green oil, b0.5 112-15; picrate, m. 116; perchlorate, m. 116; HCl salt of p-NO deriv., dark green, decomp. 160; II gives 50% of the HCl salt. N-Ethyl-N-(2-nitroisopropyl)aniline-HCl, m. 123, 90%. N-Ethyl-N-(2-nitropropyl)aniline-HCl, m. 126, 50%. N-(2-Nitro-1-methylpropyl)aniline, b0.5 86, n17D 1.5570, 72%; HCl salt, m. 122; perchlorate, explodes on warming.


Edit: A quote from the above mentioned DOI: 10.1021/jo01019a069 says: "Mannich bases, I (R = H), of nitromethane had not been reported, however, since all attempts to prepare them had led exclusively to the disubstitution products, II (R = H).[ref. 3-5]" Reference 5, which is DOI: 10.1021/ja01205a004, describes some Mannich reactions on nitromethane giving disubstituted products of the O2N-CH(CH2NR2)2 type. This explains why I could not find any example of the Mannich reaction between ammonia, formaldehyde and nitromethane. Most likely the condensation would give either a polycyclic compound, like 3,7,10-trinitro-1,5-diazabicyclo[3.3.3]undecane for example, or some cross-linked polymer or oligomer.

[Edited on 18/10/2010 by Nicodem]

Rosco Bodine - 18-10-2010 at 09:33

Nicodem, Thank you for your insight. I am still thinking about this possible reaction, even though it may be another method for "red goo".

My idea was that the proposed compound is possibly a variant "derivative" of methylamine perchlorate via an
intermediate methyleneimine derived from the initial reaction of the formaldehyde with the ammonium ...

NH4ClO4 + HCHO ---> CH2-NH(HClO4) + H2O

CH3NO2 + CH2-NH(HClO4) ----> CH2NO2CH2NH2(HClO4)

Your rewriting the formula as O2N-CH2CH2-NH2*HClO4
is probably better.



[Edited on 18-10-2010 by Rosco Bodine]

Nicodem - 18-10-2010 at 10:43

Quote: Originally posted by Rosco Bodine  
NH4ClO4 + HCHO ---> CH2-NH(HClO4) + H2O

CH3NO2 + CH2-NH(HClO4) ----> CH2NO2CH2NH2(HClO4)

Your rewriting the formula as O2N-CH2CH2-NH2*HClO4
is probably better.

You should also rewrite the second product above as it should be O2N-CH2CH2-NH-CH3*HClO4. Also, imines have a double bond, e.g. CH2=NH.

Anyway, that is indeed a Mannich reaction, but like the above mentioned references explain, the Mannich reaction on nitromethane does not stop on the monosubstitution stage, it instead gives disubstitution (the monosubstituted products can be obtained via the Michael addition instead). Furthermore, since Mannich reactions with ammonia usually give the tertiary amines I would expect the product of the Mannich condensation of nitromethane, formaldehyde and ammonia would be the already mentioned 3,7,10-trinitro-1,5-diazabicyclo[3.3.3]undecane (though more likely further condensation with HCHO is possible and this is probably why there is nothing in the literature). Unfortunately, SciFinder gives no hits on this compound, but it does give several references for its 3,7,10-triethyl substituted analogue which is obtained by the condensation of 1-nitropropane, formaldehyde and ammonia (for the synthesis, see DOI: 10.1016/S0040-4039(01)87863-1 and DOI: 10.1039/JR9580002319). 1-Nitrobutane gives the corresponding tripropyl analogue (with 1-nitropropane or -butane no further condensation with HCHO is possible).

Using primary amines instead of ammonia gives similar tricyclic structures. For example, ethylenediamine can be used to give an interesting compound (see abstract bellow).

The Mannich reaction between nitromethane, formaldehyde and methylamine is also possible and gives 3,7-dimethyl-1,5-dinitro-3,7-diazabicyclo[3.3.1]nonane (the Mannich base gets cross-linked with an additional HCHO via Henry condensation, though this might be only due to the basic conditions used). Similar products are obtained by using ethanolamine, benzylamine, t-butylamine and other primary amines (Russian Chemical Bulletin, 54 (2005) 414-420).

Interesting coordination compounds are obtained by the Mannich reaction of metal glycinates, nitromethane and formaldehyde (DOI:10.1016/j.poly.2007.03.018).

However, if the purpose is to get something energetic then the Mannich reaction of dinitromethane, formaldehyde and ammonia to potentially give 3,3,7,7,10,10-hexanitro-1,5-diazabicyclo[3.3.3]undecane or its salts would be more interesting. Or the reaction of dinitromethane, formaldehyde and ethylenediamine to potentially give 3,3,7,7-tetranitro-1,5-diazabicyclo[3.3.2]decane. Or their perchlorate salts as in the spirit of this thread. Unfortunately, there is nothing in the literature on these.
Quote:
Reactions of aliphatic nitro compounds. XXI. Products of reaction of 1-nitropropane with formaldehyde and ethylenediamine. Urbanski, T.; Kolinski, R. Inst. Technol., Warsaw, Roczniki Chemii (1956), 30 201-13. CODEN: ROCHAC ISSN: 0035-7677. Journal written in English. CAN 51:5540 AN 1957:5540 CAPLUS

Abstract

cf. C.A. 51, 421a. 1-Nitropropane (I) reacts with CH2O (II) and NH2CH2CH2NH2 (III) to give 3,7-dinitro-3,7-diethyl-1,5-diazabicyclo[3.3.2]decane (IV). The reactions of IV and of its degradation products are described. To 9.8 g. 77% aq. III 50 ml. 30% II was added with cooling and then 22.3 g. I, and the mixt. kept 24 hrs. The product was a yellow gum and an aq. layer. The gum was dissolved in 75 ml. EtOH and slowly crystd. to give 11.0 g. crude IV and 23.5 g. brown gum. Pure IV m. 104-6; hydrochloride, m. 140-1. From the aq. layer there was obtained 0.5 g. tertiary amine, m. 137-9 [hydrochloride, m. 212-14 (decompn.)], and 2 g. 6-nitro-6-ethyl-1,4-diazacycloheptane (V) (isolated as the hydrochloride), an oil (hydrochloride, charring at about 300; picrate, m. 149-51; nitroso deriv., m. 122-3 ). Refluxing IV hydrochloride (3.2 g.) in 96% EtOH gives besides 2 g. unchanged IV, II, and 0.5 g. 1-(2-nitrobutyl)-6-nitro-6-ethyl-1,4-diazacycloheptane hydrochloride (VI), m. 160-2 (decompn.) (free base and nitroso deriv. are oils). Heating 2.9 g. IV in 10 ml. concd. HCl gives 1.3 g. V hydrochloride, while ethanolic HCl gives VI in addn. to V hydrochloride. Refluxing 3.1 g. VI in 10 ml. concd. HCl gives a primary nitroparaffin, II, and V hydrochloride. The structure of IV is confirmed by its synthesis from V hydrochloride and 2-nitro-2-ethyl-1,3-propanediol (VII) in which V and VII react at room temp. in aq. soln. at pH 8. The synthesis of the 1,4-di-p-toluenesulfonyl deriv. of V from ethylene-N,N-di-p-toluenesulfonamide and 1,3-dichloro-2-nitro-2-ethylpropane (VIII) failed. VIII (9.5 g.), m. 48-50, was obtained by reaction of 15 g. VII in 20 ml. pyridine with 15 ml. SOCl2; 1 g. of cyclic sulfite of 2-nitro-2-ethyl-1,3-propanediol, m. 68-70, was obtained as a by-product.

Conformational behavior of 3,7-dimethyl-1,5-dinitro-3,7-diazabicyclo[3.3.1]nonane. Zefirov, N. S.; Palyulin, V. A.; Efimov, G. A.; Subbotin, O. A.; Levina, O. I.; Potekhin, K. A.; Struchkov, Yu. T. Mosk. Gos. Univ., Moscow, USSR. Doklady Akademii Nauk SSSR (1991), 320(6), 1392-5 [Chem.]. CODEN: DANKAS ISSN: 0002-3264. Journal written in Russian. CAN 116:127882 AN 1992:127882 CAPLUS

Abstract

The title compd. I was prepd. by the cyclocondensation reaction of MeNH2.HCl, H2CO, and MeNO2 in the presence of NaOH, and its conformation investigated in the solid state by x-ray crystallog. and in the liq. state by low-temp. 13C NMR. In the solid state the conformation of I was couch-tub; couch-tub .dblarw. tub-couch conformational equil. was obsd. in soln., with an activation barrier of 6.5 kcal/mol. A barrier of 8.7 kcal/mol was detd. for diazabicyclononanone deriv. II, indicating that the couch-tub .dblarw. tub-couch process is synchronous with N inversion.


[Edited on 18/10/2010 by Nicodem]

Rosco Bodine - 18-10-2010 at 12:41

Quote: Originally posted by Nicodem  
Quote: Originally posted by Rosco Bodine  
NH4ClO4 + HCHO ---> CH2-NH(HClO4) + H2O

CH3NO2 + CH2-NH(HClO4) ----> CH2NO2CH2NH2(HClO4)

Your rewriting the formula as O2N-CH2CH2-NH2*HClO4
is probably better.

You should also rewrite the second product above as it should be O2N-CH2CH2-NH-CH3*HClO4.
[Edited on 18/10/2010 by Nicodem]


You just lost me there ...where is the final CH3 coming from ?

As for the other .... ( amending the bond symbol for methyleneimime )

NH4ClO4 + HCHO ---> CH2=NH(HClO4) + H2O

CH3NO2 + CH2=NH(HClO4) ----> CH2NO2CH2NH2(HClO4)

Possibly the shorter chain would not cyclize and the reaction would proceed if the formaldehyde was added gradually or there was simultaneous addition so formaldehyde was not present in excess ?

The energetic salt if it exists would be isomeric with ethylnitramine or ethylnitramide (plus perchloric acid)

[Edited on 18-10-2010 by Rosco Bodine]

1-Amino,2-Nitro Ethane

AH-Poster - 18-10-2010 at 15:29

Quote: Originally posted by Rosco Bodine  

NH4ClO4 + HCHO ---> CH2=NH(HClO4) + H2O

CH3NO2 + CH2=NH(HClO4) ----> CH2NO2CH2NH2(HClO4)
[Edited on 18-10-2010 by Rosco Bodine]


This is potentially a good idea!

It should be noted that aldehydes actually disproportionate upon reaction with salts of ammonia. Also note that NH4ClO4 is one of the least soluble ammonia salts.

To perform the reaction, formaldehyde could be slowly added over the period of 1h, in several small additions, to a 60% alcohol solution of ammonium perchlorate and nitromethane.

There should be doubts about whether this could work, however. CH2O reacts with ammonia salts, the reaction can be written as:
(2)CH2O + NH4ClO4 ==> CH3NH2*HClO4 + HCO2H

Also note that methylene imine quickly loses ammonia and condenses into hexamine. Whether a solution of hexamine and ammonia could be used in an addtion reaction with nitromethane is not known.

Whether CH3NO2 could react with the intermediate imine (not shown) before it gets reduced is doubtful. It is, however, more likely that such an addition reaction could take place under alkaline conditions.

Nitromethane only reacts to form addition compounds through its "aci-form", and this tautomer only dominates under alkaline conditions. Formaldehyde actually disproportionates into methyl formate ester under very strongly alkaline conditions (sodium methoxide). Michael reactions, of the type between CH2O and CH3NO2, usually require a strong base to catalyze them.

Ammonium "nitromethanate" could possibly exist under normal pressure. Cold anhydrous NH3 would be bubbled into liquid nitromethane cooled to (minus) -25degC.
The salt of hydrazine and nitromethane, which is a liquid mixture, is mentioned on wikipedia: "With nitromethane, hydrazine forms an explosive salt..." The explanation is ellaborated upon in another forum: "nitromethane proton is "acidic" enough to be removed by a relatively weak base such as hydrazine (indeed forming a salt) and thus can act as an acid." http://webcache.googleusercontent.com/search?q=cache:20uotFw...

The formation of the salt of ammonia and nitromethane will probably raise the boiling point of the ammonia, in the same way that NH3 can be handled as a liquid in the form of concentrated NH4OH. This "salt"/ liquid mixture, may react with formaldehyde in a Michael reaction to form the desired product, NH2CH2CH2NO2. The formaldehyde, in this case, should be solid trioxane dissolved in an excess of pure alcohol, and the resulting solution very slowly added to the NH3-CH3NO2 mixture.

However, nitromethane is known to react with formalin (CH2O) under alkaline conditions to form Tris(hydroxymethyl)nitromethane (not sure if this reaction requires heat). To summarize, CH2O and CH3NO2 may react to form an undesirable byproduct under basic conditions, while
CH2O and ammonia condense together into hexamine, or under acidic conditions, will form undesirable byproducts . It is unknown what product(s) would form if CH2O was added to a mixture of ammonia and nitromethane. Not having any formalin, this reaction cannot be investigated by me.

If too much CH2O present, it likely will react with the imine before the imine has a chance to react with CH3NO2.

NH4+ and CH2O ==> CH2=NH2+

CH2=NO2- and CH2=NH2+ ==> O2NCH2CH2NH2

[Edited on 19-10-2010 by AH-Poster]

Rosco Bodine - 18-10-2010 at 15:51

Actually I have my own strong skepticism that it would work, however it does seem plausible so it continues to be intriguing. Yes nitromethane is reactive towards formaldehyde ....however the formaldehyde is reactive also towards the ammonium and it would seem more favorably so in acidic medium. So I thought
the formation of the methyleneimine might be preferential ...and that then the
nitromethane would couple directly with it. It was my thinking that solubility might drive this route for a reaction in aqueous methanol particularly if the desired product had low solubility as its perchlorate salt....the product desired may simply drop out of solution as fast as it was formed. Of course there are a whole lot of "ifs" there .....but sometimes such things do occur.

I was hoping that Nicodem may propose an alternative route as he mentioned using the Michael reaction. Paraformaldehyde is what I have on hand and
will doubtlessly convert some of it to methylamine perchlorate as I have no doubt that simpler well known reaction will work. I was simply intrigued by the considered and described possibility that the same unsaturated methyleneimine intermediate in that known reaction might combine directly with nitromethane leading to a possibly even more energetic derivative.

That last reaction equation which you show is not balanced.

For that last reaction you mean 3 CH2O rather than 2 CH2O
and the balanced reaction would actually be

3 CH2O + 2 NH4ClO4 ----> CH3NH2*HClO4 + H2O + HCO2H + CH2=NH*HClO4

If that does happen, then a methylamine perchlorate mixed product or double salt is possible if the methyleneimine does indeed conjugate with the CH3NO2.

[Edited on 19-10-2010 by Rosco Bodine]

Nicodem - 19-10-2010 at 09:47

Quote: Originally posted by Rosco Bodine  

You just lost me there ...where is the final CH3 coming from ?

As for the other .... ( amending the bond symbol for methyleneimime )

Never mind that. With all those methyls and methylenes I mistakenly believed you are presenting a new reaction using methylamine.
Quote:
Possibly the shorter chain would not cyclize and the reaction would proceed if the formaldehyde was added gradually or there was simultaneous addition so formaldehyde was not present in excess ?

No, the disubstitution Mannich reaction on nitromethane is the consequence of the inherent property of nitroalkanes which tautomerize more easily when they are RCH2CH2NO2 or R2CHNO2 compared to nitromethane (for example, compare the pKa of nitromethane and nitroethane to see the difference). So, once the monosubstituted Mannich product forms, it will be a much better substrate for another Mannich reaction compared to nitromethane itself. The initial product of monusubstitution is an amine and can efficiently participate as bifunctional substrate for the Mannich, thus leading toward cyclization or oligomerization. Essentially, you can forget about forming 2-nitroethylamine this way. If you check the references above, you can see that enough effort was already put into this and it does not work. The only route that actually worked was alkylating ammonia with nitroethene via Michael reaction.
Quote: Originally posted by AH-Poster  
To perform the reaction, formaldehyde could be slowly added over the period of 1h, in several small additions, to a 60% alcohol solution of ammonium perchlorate and nitromethane.

There should be doubts about whether this could work, however. CH2O reacts with ammonia salts, the reaction can be written as:
(2)CH2O + NH4ClO4 ==> CH3NH2*HClO4 + HCO2H

... ...

Instead of diving in idle speculation and off road wilderness, why don't you put some effort and actually read the preceding posts and the references provided? You were already explicitly told to change your ways several times. Don't you think it is about time you change? Why do you insist in ignoring theory and literature? Such attitude can cost a chemist his life and this forum does not promote carelessness or ignorance.

Rosco Bodine - 19-10-2010 at 11:54

Thanks Nicodem,

Yeah, if the reaction continues for the ( first ) Mannich base, as is likely, rather than it dropping out of solution as a salt ....then the hoped reaction fails and a more complex product results. Oh well, it wasn't a totally dumb idea and it was fun while it lasted :D

aminoacetonitrile perchlorate ....exist?

Rosco Bodine - 25-11-2010 at 12:33

Further contemplation has been done about a possible similar compound which may have potential usefulness as an energetic perchorate, and with regards to this hypothetical
compound, I also welcome any thoughts from you all.

The organic perchlorate being contemplated is "glycine nitrile" perchlorate, or aminoacetonitrile perchlorate

NH2CH2CN-HClO4

proposed synthetic route

NH2CH2CN-HCl + NaClO4 ----> NaCl + NH2CH2CN-HClO4

Perhaps for the hydrochloride precursor is possible to use a method using TCCA and glycine, reacted in aqueous medium for a half hour at 5C and basic conditions as per description on page 3 of attached paper, reaction following the example
details on page 5 as for the conversion of phenylalanine to phenylacetonitrile: The synthesis could be simplified as there would be no need for isolation of the aminoacetonitrile hydrochloride.

General One-Pot Procedure for the Preparation of
Nitriles from a-Aminoacids. The reported procedure is
representative: L-Phenylalanine (1.20 g, 7.6 mmol) was
dissolved in an aq solution of 2 N NaOH (3.8 mL) and
treated with TCCA (1.17 g, 5.1 mmol) at 25 °C. After 10
min, when TLC analysis showed the complete absence of the
L-phenylalanine, the reaction mixture was treated with HCl
(15 mL), followed by an aq solution of 3 N HCl (2.5 mL).
After 10 min the mixture was extracted twice with Et2O (15
mL). The organic layers were washed with H2O (10 mL),
dried on Na2SO4, filtered and concentrated in vacuo to yield
2-phenylacetonitrile (20, 0.87 g, 98%). 1H NMR: d = 7.38
(m, 5 H), 3.75 (s, 2 H). 13C NMR: d = 142.1, 129.1, 127.9,
127.8, 117.8, 23.5.

A bit of scientific trivia perhaps is that aminoacetonitrile is a material detected in the far reaches of interstellar space ...... (see link) ........
http://medgadget.com/archives/2008/04/scientists_spot_amino_...

http://www.youtube.com/watch?v=3hEfcawx6Fc&feature=relat...

http://www.youtube.com/watch?v=DNjzzDNIJWw&fmt=18

Attachment: An Insight of the Reactions of Amines with Trichloroisocyanuric Acid.pdf (160kB)
This file has been downloaded 1429 times

[Edited on 26-11-2010 by Rosco Bodine]

nitro-genes - 26-11-2010 at 01:12

Sort of OT:

What would happen if NH3 was used under the same conditions? Presumably it would form nitrogen nitrille. (a fancy word for nitrogen gas) I was wondering what makes the formation of Cl-NH2 more favorable in the the hydrazine synthesis, while Cl2-NH (Cl3-N?) is apparently the result of the direct reaction of TCCA.

[Edited on 26-11-2010 by nitro-genes]

Rosco Bodine - 26-11-2010 at 01:41

Ummm ....
I think for a nitrile there must be a C having a triple bond to N as a CN .....
nitrile being synonymous with cyanide .....right ?

therefore, your nitrogen nitrile would be NCN ??

( because if it was CNN .... then it would be a TV station )

And yes I am a blonde :P , or I used to be long ago before I became a silver :D

Ummm....anyway there is a unusual amount of energy contained (and releasable) from a CN group ....so it seemed like as a fuel component of an energetic organic perchlorate that it may provide excellent performance.

[Edited on 26-11-2010 by Rosco Bodine]

nitro-genes - 26-11-2010 at 08:48

( because if it was CNN .... then it would be a TV station )

Haha, you may have lost your blonde manes, but clearly not your humor! :D

It's been a while since I've done anything even remotely chemistry related. I increasingly tend to write brain-fart-inspired posts and then think about it later, srry about that...

Rosco Bodine - 26-11-2010 at 09:20

No problem, I have my moments too when things get kind of foggy. I drink way too much coffee just to try to keep from sleeping excessively....I'm like an old lion who wakes up when hungry, eats too much and then goes back to sleep till hungry again.

http://www.youtube.com/watch?v=THWgH85TyJQ Bungle In The Jungle

Anyway .....
what about the speculative and hypothetical cyanoglycine perchlorate ?

Seems worth an experiment and simple enough. It would be great if it is stable and non-hygroscopic.
The stuff could even be a primary and the energy potential there is probably somewhere around that of tetryl or better.

[Edited on 26-11-2010 by Rosco Bodine]

Rosco Bodine - 1-12-2010 at 21:25

It looks like the actual precursor required for oxidation to aminoacetonitrile would be aminoglycine since the amino is the source of nitrogen for the formation of the nitrile. Glycine would be oxidized to acetonitrile. I have been looking at this for a few days and that is my conclusion. Aminoglycine is mentioned as a component of hair treatments.

It may be interesting also to see what would be the oxidation product of hydantoic acid (ureidoacetic acid) NH2CONHCH2COOH .

[Edited on 2-12-2010 by Rosco Bodine]

Diammonium Hydrazinium Tetraperchlorate

Rosco Bodine - 8-2-2011 at 09:31

Diammonium Hydrazinium Tetraperchlorate US4053566

This is interesting because of the numerous possible different synthetic routes and the likelihood it is energetic,
along with an absence of literature references to the material. It suggests that other complex double salt perchlorates involving substituted ammonias and/or substituted hydrazines are also possible. For example perhaps a methylamine perchlorate with semicarbazide perchlorate would form an analogous double salt.

Good luck trying to find any further information. It appears this may be obscure or in the realm of purely experimental.

According to a Dow Chemical research report this is not an actual compound, but is a physical mixture which has been misidentified.
http://oai.dtic.mil/oai/oai?verb=getRecord&metadataPrefi...

An additional patent US3743701 (attached) subsequent to the Dow Chemical report evidently disputes the Dow finding.

Attachment: US4053566 Diammonium Hydrazinium (tetra)Perchlorate.pdf (151kB)
This file has been downloaded 968 times

Attachment: US3743701_DIAMMONIUM_HYDRAZINIUM_TETRAPERC.pdf (378kB)
This file has been downloaded 1116 times

Thiokol is the patent holder for what indeed does appear to be an actual compound.

[Edited on 9-2-2011 by Rosco Bodine]

DougTheMapper - 9-2-2011 at 12:56

This is some really neat stuff. The diammonium hydrazinium tetraperchlorate isn't all that far out of reach for those with perchlorate salts, esp. pertaining to the first patent.

If the compound is able to sustain detonation it might find use when plasticized since the relatively large amount of binder needed for plasticization could bring the overly-positive oxygen balance into check. Of course, this would then serve to reduce sensitivity (which is probably pretty low anyway since the patent talks about using it as a propellant) as well as increase power but probably reduce brisance.

Decomp seems to be (NH4)2(N2H6)(ClO4)4 --> 2N2 + 6H2O + 2HCl + 5O2 with a whopping oxygen balance of +40.3 wt%!

For that matter, this compound could probably be used to make oxygen candles once the HCl has been scrubbed.

Rosco Bodine - 9-2-2011 at 13:52

DAHTP could be useful as an energetic oxidizing perchlorate explosive component, especially if compatable with another energetic oxygen deficient perchlorate based explosive fuel in a mixture achieving oxygen balance. It would be a bonus if such a mixture was a nonhygroscopic eutectic....such a composition could be very stable, and dense and powerful. It is good to have valid alternative compositions to the more usual nitration products used as energetic materials.
Of course DAHTP could be an interesting component also with the usual fuels
which might be used with other energetic oxidizers, fuels like nitronaphthalene, dinitrotoluene, ect. It would be my expectation that such mixtures would be
cap sensitive and would be brisant and powerful, although more expensive than more usual nitrate oxidizer based analogues.

DougTheMapper - 9-2-2011 at 21:34

If the perchlorate double salt forms in perchloric acid, why not the picrate salt in picric acid? Instead of ammonium perchlorate and perchloric acid, ammonium picrate in picric acid with a halide hydrazine salt. Or is picric too weak of an acid? I don't know much about this sort of chemistry but the TNP anions might be too bulky to "stick." Starting with chlorides might be a bad idea since the reaction might favor chloropicrin... bromopicrin wouldn't be unnecessarily hazardous though.

Diammonium hydrazinium tetrapicrate? That would be quite a compound.

(NH3)2(N2H6)(C6H3N3O7)4 --> 8N2 + 10CO2 + 24CO2 + H2O + 11H2

And with a terrible lack of oxidants, possibly the answer to what to mix with the DAHTP. I wonder if there's a reliable way to estimate the density of such a compound?

By the way, do you think this would favor the water and tend to produce more elemental C to keep the oxygen deficit? Like TNT, I think because of the similar structure and already existent C=C bonds. Hm.

Possibly impossible to manufacture but maybe split it 50/50 and do Diammonium hydrazinium dipicrate diperchlorate... what a mess. Heck, mixing perchloric acid with picric acid sounds like a positively terrible idea.

Theoretically:

(NH3)2(N2H6)(C6H3N3O7)2(ClO4)2 --> 5N2 + 8H2O + 7CO2 + 5C + 2HCl

Or diammonium hydrazinium picrate triperchlorate. I guess anything could exist on paper.

I think the general theme here is that much like a mixture of explosive compounds is usually better than a mix of an explosive and a fuel (NC gelled NG vs. ANFO for instance), molecules made of two explosive ions are usually better than an explosive ion with a metal or something. (Like pentazenium azide vs. NaN3) The main problem is finding the salts which are stable enough to exist for any useful length of time.

[Edited on 10-2-2011 by DougTheMapper]

Rosco Bodine - 10-2-2011 at 03:07

The OB mixture of DAHTP with Triaminoguandine Perchlorate would be something that comes to mind as a possible candidate mixture. Betaine Perchlorate, Choline Perchlorate, Trimethylamine Perchlorate, and Tetramethylammonium Perchlorate
in OB mix with DAHTP or some complex mixture in specific proportions of these compounds could result in one or more eutectics having desirable properties.

In my last post above immediately before the subject of DAHTP, there is my speculation concerning a nitrile derivative gotten by oxidation of hydantoic acid, also having a perchlorate of potential interest. In an earlier thread regarding glycine nitrate,
http://www.sciencemadness.org/talk/viewthread.php?tid=2642&a...
hydantoic acid was mentioned by Axt in a related interest as an intermediate. And a simple synthesis of the hydantoic acid was described, taken from GB991644. See example 1 of the patent attached. It is also possible that hydantoic acid itself may form an energetic perchlorate, properties also unknown.

Attachment: GB991644 Hydantoic Acid and derivatives.pdf (146kB)
This file has been downloaded 1491 times


[Edited on 10-2-2011 by Rosco Bodine]

Rosco Bodine - 26-9-2011 at 13:02

Here's an interesting find and perhaps a useful method for simultaneously getting the water out and putting the fuel into molecular explosive compositions where otherwise a hydrated oxidizing salt could be problematic. Basically it appears that the water of crystallization can be azeotroped from DMSO solution of the hydrated oxidizer salt and then DMSO of crystallization substitutes for the previous water of crystallization, this substitution resulting in an energetic material instead of what was before a benign hydrated oxidizer salt.

US3463684 DMSO substituted Hydrate Oxidizer Salt Molecular Explosives

Attachment: US3463684_Explosive DMSO substituted Hydrates of Perchlorates and Nitrates.pdf (156kB)
This file has been downloaded 1261 times

AndersHoveland - 26-9-2011 at 17:40

That may not be necessary. Organic amine perchlorates tend not to be hygroscopic, and indeed they have much lower solubilities than the corresponding nitrates.

Rosco Bodine - 26-9-2011 at 18:07

I was thinking more in terms of producing an energetic fuel component for another possible chemically compatible candidate mixture with DAHTP, which could achieve OB for the mixture. Such a DMSO adduct could also possibly be used with other oxidizers in mixture to achieve OB.

Ethylenediamine Perchlorate Picrate

Rosco Bodine - 13-2-2012 at 23:12

Here's something interesting I found. US2406573 describes that a complex salt can be formed by half neutralization of ethylenediamine to form the monoperchlorate can be followed by another half neutralization with picric acid
resulting in a perchlorate-picrate ethylenediamine salt which has explosive properties. Other similar combination salts may also be possible.

Attachment: US2406573 Ethylenediamine Perchlorate Picrate.pdf (123kB)
This file has been downloaded 1020 times

Rosco Bodine - 15-2-2012 at 14:27

Among the similar possible combination salts which might be worth investigation
is a possible Ethylenediamine Hydrazine Tetraperchlorate similar to the DAHTP described in the other patents posted earlier. Ethylenediamine and hydrazine both should displace ammonia from ammonium perchlorate, the ammonia being volatile. Therefore it might be possible to form the speculated Ethylenediamine Hydrazine Tetraperchlorate easily if indeed it does exist as speculated. It would seem possible the result could also be a triperchlorate or other multiple salt as opposed to a tetraperchlorate.

[Edited on 15-2-2012 by Rosco Bodine]

AndersHoveland - 16-2-2012 at 13:57

Both hydrazinium di-nitrate and di-perchlorate hydrolyse in water. So it would not be possible to obtain the di-perchlorate by reacting hydrazinium perchlorate with an aqueous solution of perchloric acid.

More information about hydrazinium di-perchlorate:
Quote:

Not only is the monoperchlorate much less energetic as an oxidizer than the hydrazinium diperchlorate, but it is much more sensitive to detonation by shock than the diperchlorate.

Preparation of hydrazinium diperchlorate using sodium perchlorate and hydrazinium dichloride In a reaction vessel equipped with stirring means, a cooling device and inlets for supplying nitrogen and liquid hydrogen fluoride, the following reactants are added; a pulverized and intimately admixed mixture of 2.45 parts by weight of anhydrous sodium perchlorate and 1.05 parts by weight of hydrazinium. dichloride. The mixture is chilled to -80' C., purged with a nitrogen atmosphere, evacuated and 9.88 parts by weight of anhydrous liquid hydrogen fluoride is added to the reaction mixture. The system is brought back to atmospheric pressure by reintroducing nitrogen to the system and the reaction is initiated by allowing the reaction mixture to warm to room temperature. The solvolysis of the hydrazinium dichloride to the fluoride salt is evidenced by the evolution of bubbles of hydrogen chloride gas. The hydrogen fluoride suspension is stirred vigorously for 5 hours and allowed to settle. The insoluble fraction is hydrazinium. diperchlorate and the soluble fraction is principally sodium fluoride, which has a solubility in hydrogen fluoride.

Preparation of hydrazinium diperchlorate using potassium perchlorate and hydrazinium dibromide as reactants. In this example the same equipment and procedure is followed as described in before, except that 2.77 parts by weight of anhydrous potassium perchlorate, 1.94 parts by weight of hydrazinium dibromide and 10.65 parts by weight of anhydrous liquid hydrogen fluoride are used as reactants.

US 317459210 (1973)

Rosco Bodine - 16-2-2012 at 16:00

Agreed, from an aqueous system and ammonia displacement reaction from ammonium perchlorate, a triperchlorate product consisting of Ethylenediamine Diperchorate + Hydrazine Monoperchlorate is about all that would be likely.
And it is unknown if such a triple perchlorate exists or what would be its properties......other than it would likely be highly energetic.

woelen - 12-5-2019 at 12:22

Quote: Originally posted by mnick12  
[...]woelen, interesting expiriments! Have you tried methylamine perchlorate? I was going to attempt this once I get some more conc HCl to make perchloric acid, but money is kinda tight right now. I have a feeling methylamine perchlorate would be pretty soluable, but also could be a good energetic oxidizer when mixed with other fuels.
I just received my order of methylamine (40% in water) and I remembered this thread, so I looked it up again. I have done the experiment with methylamine. Making methylammonium perchlorate is remarkably easy.

I took 2 ml of 40% methylamine in water and added appr. 3 ml of water. The resulting liquid is around 15% of methylamine and has a fairly strong smell, but it is not pungent anymore at this lower concentration. I took appr. 2.5 ml of 50% perchloric acid and added 3 ml water to this to make it more dilute.

Using these amounts, the methylamine is in excess amount. I slowly mixed the liquids (some heat is produced, but not as much as I expected). After mixing, a clear and colorless liquid is obtained. No crystals are formed.

I poured the liquid in a petri dish and put this aside in a dry warm place without dust (40 C or so). The next day, I had a nice amount of crystalline mass, which I scraped off the glass and crushed somewhat. Then I put the petri dish on the same place for another day. After that I had a perfectly dry snow-white solid.

I assured in this experiment that I had excess methylamine. On drying, the methylamine evaporates, together with the water, and simply disappears. This allows me to prepare a nice dry solid. If there is some excess HClO4, then you will get an ugly sticky and humid mess, which never gets dry. HClO4 does not evaporate (like H2SO4) and is very hygroscopic. You can easily check whether you have excess methylamine. If the liquid has a "yummy" smell, then there is free methylamine :D
The white salt is totally odourless.

Next, I tried ignition of this compound. It is comparable with the ethylene diamine complex, described at the start of this thread. The color of combustion, however is a beautiful blue.

I also tried a small amount of this material in a test tube (only 10 mg or so, DO NOT SCALE UP!). Put it in a test tube, and then heat the test tube in the flame of a bunsen burner. The material starts to fizzle a little, and then suddenly it decomposes with a blue flame and a kind of whistling noise. After cooling down of the test tube, I added some water. On addition of the water, very dense fumes are formed in the test tube (I think due to formation of HCl).

I have a camera which can make high speed movies at 1000 frames per second. I'll try to make a movie with this camera of the decomposition reaction. Lighting is a difficult thing, however, with such high frame rates, the base/background lighting must be such that you get a meaningful image at at most 1/1250 seconds expposure time.

fusso - 12-5-2019 at 13:57

Wont the excess MeNH2 absorb CO2 from air and form some methylamine bicarbonate?

Laboratory of Liptakov - 13-5-2019 at 11:36

@ woelen
All about perchlorates + some fuel (or anything) in interesting. Because here can be something for replace classic primary substances. But I am afraid, that methylamine (commerce solution 40%) can be difficult available. Also HCLO4 is not some easily available. OIf course, that both compound is possible prepare. Any way, very easy reaction and clear result. I think, that testing on Anvil is necessary for basic properties.... :cool:...LL

woelen - 14-5-2019 at 00:19

MeNH2 does not form a carbonate (at least not in appreciable amounts). I once tried this by putting a little 40% methylamine in a petri dish and allowing it to evaporate. Hardly any residue is formed, the glass only is a little frosty at the place which was wet. That may also be due to impurity of the methylamine solution.

I also tried this with ethylamine (70% by weight) and with ethylene diamine. The ethylamine also does not form any residue. The ethylene diamine leaves behind quite a lot of yellowish solid. It is somewhat oxidized and it forms a carbonate.

You can see the difference already when you keep the liquid in contact with air. Methylamine and ethylamine do not give off any visible fumes, ethylene diamone gives off dense white fumes in contact with air.

--------------------------------------------------------------------------------

I tried the same experiment with HClO4 and methylammonium chloride (a.k.a. methylamine HCl, CH3NH2.HCl). The latter is a salt. I tried dissolving this in a small amount of water and then adding 50% HClO4 to it. I used a slight excess amount of methylamine HCl.

When this liquid is allowed to stand in a warm place, you don't get any crystals. A colorless somewhat viscous liquid is produced, which does not dry further. This liquid is strongly acidic.
I tried heating some of this liquid, trying to drive off water and HCl. To some extent this works, but I could not get a clean dry solid compound. Before making it completely dry, it decomposes violently, with a blue flame and a loud WHOOSH sound. I think that the liquid invisibly goes from the aqueous solution form to a molten form and then it decomposes.
I dared not try the boiling down of a larger volume than a few drops. I can imagine that a few ml of this liquid, suddenly starting the violent decomposition reaction may lead to an explosion, due to self-confinement. I do not want pieces of glass flying around at high speed.

-------------------------------------------------------------------------------------------------

Methylamine is easy to obtain in the EU, either as its salt methylamine HCl, or as 40% solution in water. I ordered both of them, no questions asked. Use of methylamine for making crystal meth is not a problem in NL. Here we have quite some illicit drugmakers, but they make other drugs than crystal meth (eg. GHB, XTC, purified THC).

HClO4 is not that difficult to obtain as 60% solution, but it is expensive. A price of 70 euros per liter is not uncommon. For my small-scale experiments with 1 gram quantities this is not a real problem. Half a liter of acid goes a long way. Making KClO4 or NaClO4 from the acid is easy, but economically not feasible if you want quantities useful for a serious explosive device. So, there was no need to make HClO4 a forbidden chemical, it is not interesting for terrorists trying to make bombs.
The compound NH4ClO4 is available in NL as well (only the sodium and potassium salt are forbidden), and probably it also is available in the USA. It can be used to make (somewhat impure) HClO4. In order to do so, you first need to mix solid NaOH with solid NH4ClO4 in a 1 : 1 stoichiometric ratio. Dissolve the NaOH in as little as possible of water. Once you have a solution, slowly add the NH4ClO4 in small batches. In the beginning, after each addition you get a lot of NH3 gas. At the end of the reaction, you may need to heat to get all of it dissolved and to drive off all NH3. Keep on heating, until all NH3 is gone.
Next, allow to cool down. If any crystals are formed, add a tiny amount of water in order to dissolve them. Afther that, pour the solution slowly in concentrated HCl, while stirring. You get a precipitate of NaCl. Filter the solution from the NaCl. Allow to cool down to remove more NaCl.
Next, boil down until the liquid is 150 C or so and then allow to cool down again. You most likely get another small amount of solid NaCl.
The remaining liquid is fairly pure HClO4 (50% by weight or so), containing only a small amount of sodium ions and it may be colored a little, due to colored impurities of your HCl. If you use reagent grade reagents, then your HClO4 should be (nearly) colorless. This acid is perfectly suitable for experiments as described in this thread.


[Edited on 14-5-19 by woelen]

Laboratory of Liptakov - 14-5-2019 at 01:59

Incredibly comprehensive and detailed answer. In particular, the preparation of HClO 4 appears to be more advantageous, cheaper when using NaOH. I tried NH4ClO4 + HNO3 + HCl method. It works. In HClO4 remains NH4ClO4 as reziduum. With your NaCl method. The second part of the reaction is almost identical, thus increase temperature to 150 ° C. In this step excess HCl is evaporated. HClO4 remains. Good method, thank you....:cool:...LL

woelen - 14-5-2019 at 03:38

I know of the HNO3 method, but nitric acid is forbidden in the EU since 2016. You cannot purchase it anymore.
Hence, I worked out the method with NaOH. NaOH can be obtained in any hardware store and conc. HCl also is no problem.

In the past, before HNO3 was forbidden, I have tried the HCl/HNO3 method myself. It didn't work for me very well. I got a lot of left-over NH4ClO4, I had the impression that even after prolonged boiling not all NH4(+) ions were oxidized, while at the same time tons of Cl2 and ONCl were released. Very unpleasant! Maybe my acids were not sufficiently concentrated at that time (I used 30% HCl and 53% HNO3).



[Edited on 14-5-19 by woelen]

Laboratory of Liptakov - 14-5-2019 at 08:57

Your method is clearly better. NaCl has (I estimate) smaller solubility in HClO4 than NH4ClO4. Therefore is final product purity better. A lot experimentators has problem with availability HClO4. Your method is base key for much attempts. Easy and cheap. Almost the invent.....Thanks.....:cool:...LL