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Axt
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Halogenated Amines - the others
Nitrogen trichloride and nitrogen triiodide are well known. but what of the others?
Below is some references to some explosive halogenated amines, top left is from a JACS article, other two from PATR 2700.
<center><img src="http://www.sciencemadness.org/scipics/axt/tetrachlorodiaminoethane.jpg"></center>
Noting the "explodes with great violence", I tried to create the ethylenediamine derivative NCl2-CH2-CH2-NCl2, using the process in the JACS article.
20g baking soda was dissolved into 200ml water and 2.5g ethylenediamine was added. Chlorine from MnO2/HCl was bubbled through the solution. Within a
few minutes a yellow liquid formed in the bottom of the vessel, chlorine was bubbled for 30min. A decent quantity of milky yellow liquid was formed.
this was extracted with DCM. Below is the first time I tried it, in smaller quantities, note the yellow liquid in the bottom of the test tube.
<center><img src="http://www.sciencemadness.org/scipics/axt/ethylchloro.jpg"></center>
Trying to freeze the extract out of the DCM didnt work, so it was evaporated off in the sun. The bright yellow liquid that was left DOESN'T EXPLODE!
It will burn after heating with an orange flame leaving black residue. Very disappointing, as "its" very easily made unlike NCl3 which Ive never been
able to do.
According to the references, this should be far more energetic then what it seems to be. Though considerably safer then NCl3, and maybe more powerful
(from HCl formation). Especially where an explosive with comparatively bad OB is said to be an equivalent to NG.
Have to try its tetraiodo.
[Edited on 9-12-2005 by Axt]
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neutrino
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NF<sub>3</sub> is stable because the fluorine atoms are small and bind very tightly to the nitrogen atom. NBr<sub>3</sub> is
very unstable: somewhere between NCl<sub>3</sub> and dry NI<sub>3</sub>.
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J_O_H_N_Q
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AXT, what kind of initiation did you try?
Did you burn it, or have you tried a det. yet?
Maybe it requires shock to be set off?
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Axt
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From the reference: "explodes violently on heating". I hit it with a MAPP torch, and even then it took a few seconds to ignite. Maybe its
not fully chlorinated, I dont know but I cant see any other way of getting there.
I just tried to form a complex of a DCM solution with copper sulphate, but ... nope.
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chemoleo
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Strange, I never noticed this thread.
Anyway, did you try to heat it on a heating plate? I.e. a 0.5 ml, on a piece of metal, on a plate? Maybe it behaves differently then.
It's strange nonetheless that the torch didn't do the job.
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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Axt
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I havn't tried slow heating, but I have dropped it onto a hotplate, in which case it puffs off simular to what NG does at the same heat but
accompanied by an awful stinky smell (realy... really awful!). Im going to try track down its original reference, it could be that it was heated in
an enclosed vessel to "explode violently".
By pouring 98% ethylenediamine over iodine it gives an exothermic reaction, and eats the iodine leaving nothing, so the tetraiodo is either a clear
liquid, soluble in ethylenediame (it doesnt precipitate when diluted) or this method just doesn't work. I'll try cold dilute ethylenediamine
to see if its decomposing due to the heat of the reaction.
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Axt
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Anyway, 9ml of this yellow oil was compared to (true) PLX, charges were in plastic vials, taped onto a vertical 3mm steel plate held in a vice. 0.5g
PETN used for initiation. On detonation the N,N,N',N'-tetrachloroethylenediamine gave the expected black smoke from free carbon with a cloud of HCl
(stand upwind!). C2H4N2Cl4 --> 2 C + 4 HCl + N2
<center><img src="http://www.sciencemadness.org/scipics/axt/endet.jpg"></a>
<a href="http://www.geocities.com/roguemovies8/index.html">MOVIE</a></center>
Its effect was nearly identical to the PLX charge.
<center><img src="http://www.sciencemadness.org/scipics/axt/plx-ntceddent.jpg"></a>
PLX on left, NTCED on right</center>
The movie above also shows it puffing off as its dropped onto a hotplate.
[Edited on 1-11-2007 by Axt]
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Axt
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I now have the original "explodes with great violence" reference. Indeed, it was heated under confinement (in capillary tube) to have this
property. It mentions that heating causes decomposition, sometimes explosion under atmospheric pressure, so it's now all adding up.
It's mentioned that it's stable, not undergoing decomposition. Gives off a pungent, irritating odour which attacks the eyes (this I can
confirm!). The evidence seems to suggest that its reasonably stable, and not unduly sensitive.
It's extract was dried over calcium chloride before evaporating off the solvent (chloroform) to give an anhydrous product.
The reference provided also gives other halogenated amines, though the derivatives of ethylenediamine seem to be the only mentions with standout
explosive characteristics.
I've a couple more points to add:
If an excess of ethylenediamine is used in the synth, the product turns into some crystaline mass once dried, maybe due to interference from
ethylenediamine dihydrochloride. Its important to use the ratio's as stated. The NaOCl/acetic acid/ethylenediamine method in this reference
should be easier, not that its hard but the insolubility of bicarb limits the synth to a few grams at a time.
Iodine under dilute ethylenediamine turns red, presumably the tetraiodo derivative. But on drying it seemed to disappear, whether it decomposed,
exploded, blew away etc. I dont know. I'll try it again.
Attachment: halogenated amines.pdf (545kB)
This file has been downloaded 1367 times
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chemoleo
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Interesting.
Regarding the iodine derivative, possibly it is indeed too unstable to be isolatable, as the reference quotes the bromo-derivative to decompose at RT
with time, while the chloro-derivative is stable.
Hence, maybe the iodo-derivative only exists transiently.
What I like in particular about the method in the reference is that NaOCl is employed rather than chlorine gas - making handling easier.
Chloroform extraction does seem a must though - it also is a good way of getting rid of water.
Anyway, I was thinking that Cl2N-CH2-CH2-NCl2 may be a great starting compound for further syntheses!
For instance, I could see this reacting with NaNO2 under the right conditions, yielding the tetrabisnitro derivative, which should be highly
energetic!
Given the ease at which the tetrachloro ethylene diamine is produced, this might be worth investigating!
[Edited on 10-1-2005 by chemoleo]
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Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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Axt
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Looking at both the references a few things just dont add up!
Look at the yield in the first reference, 30g forms 70g with 92% yield, theoretically thats only a 71% yield. Also the freezing points are
significantly different, 4-4.5°C in the first and doesn't freeze in ice/salt in the second. Mine doesn't freeze at -15°C.
It reports a density of 1.544g, mine come in at ~1.5g so thats the only agreement, but taking into account all the other discrepancies, is probably
meaningless.
Are you saying N(NO2)2 groups  , Im not even sure is there are examples of that.
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Axt
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I just used the acetic/en/NaOCl route, with this result.
6g ethylenediamine was added to 36g acetic acid in 36g water. The resultant exotherm was allowed to return to room temperature. This solution was then
slowly poured into 480g of cool 12.5% NaOCl solution (liquid pool chlorinator). The solution turned milky and become warm to the touch. A yellow oil
fomed immediately and sank to the bottom.
The solution was left for 30min, and decanted to retrieve the yellow oil, as shown below.
<center><img src="http://www.sciencemadness.org/scipics/axt/NTCED.jpg"></center>
Yield was 11.5ml or 16.8g therefore density of 1.46g/cm<sup>3</sup>. This is 85% of theory. Its a quick and very easy synth, also it
didn't form as an emulsion but as the nice clear yellow oil as shown above.<br><br>
[Edited on 9-12-2005 by Axt]
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Jome
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This is extremely interesting....I'd never think NCl explosives would exist!
How sensitive is this material? IIRC Axt you have a weight-dropper (or what they're called), how about some tests?
Would chlorination of guanidine give yet another explosive or would it just wreck the molecule?
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Axt
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I havn't taken the impact sensitivity, though will do. I exhausted the last lot by eating it with H2O2, which left non-explosive clear crystals.
Guanidine may be interesting, I have no idea what the likely outcome is (anyone else?). I guess you know that urea falls apart leaving NCl3. Maybe
some derivatives of hydrazine would outperform the ethylenediamine derivative, CH2=N-N-Cl2?
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Theoretic
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How about replacing one of the chlorine atoms in C2H4(NCl2)2 with a perchlorate group? This would give it perfect OB.
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Jome
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How would H2C=N-NH2 be made, formaldehyde and hydrazine?
I have tons of "chlorine" (muriatic and MnO2) but no access to any amine. However their manufacture is OT here so I'll post a new
thread in the organic-section.
I doubt the molecule would still act as a organic base with the hydrogens replaced with chlorine, but perhaps Im not getting what you mean?
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Axt
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| Quote: | Originally posted by Jome
How would H2C=N-NH2 be made, formaldehyde and hydrazine?
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Yes, off topic but when condensed with 4M formaldehyde its peroxide should be good as well, better then HMTD. I have a journal article on this, though
I think their conclusion was that it will only condense with 3M, thus H2C=N-N(CH2-O-O-CH2)2N-N=CH2.
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Jome
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The compound listed below the one you prepared, ethyldichloroformamide, do you have any details on its preparation?
Wonder if it could be as easy as bubbling chlorine through the amide... Amides seems quite easy to make as opposed to amines.
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Axt
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No idea Jome, the original reference that was cut from the extract is "J.D. Rideal, Ger 301, 799 & CA 15, 1966 (1921)". I dont know what
"Ger" refers to, but chemical abstracts might help. Looking at the performance of the ethylenediamine derivative, I cant see how
N,N-Ethyldichloroformamide can have perfomance anywhere near NG, not to mention all those nasty fumes.
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S.C. Wack
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Ger 301, 799
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chemoleo
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THis patent that you list is interesting, or rather the references therein.
The patent states that alkylamine chlorides (the alkyl being methyl here)can be explosive substitutes that are NO2-free, they bring the methyl
dichloroamine together with Kieselgur (diatomaceous earth), to form a putty, which can be exploded with fulminate.
The references therein all debate the production of ethyl dichloroamine, and the reactions with Zn-Et. He makes it with CaOCl, and the amine
hydrochloride, and destills off the product.
Unfortuantley it does not mention the amide-chlorides, even though I more or less read through the whole first reference, and the other refs seemed
even less relevant. While the patent doesn't mention the dichloro amide at all. Hmmm....wonder where it's hiding!
PS seems the amine chlorides are good syntheons, i.e. with Zn-ethyl they made triethyl amine (etheric solution). I bet numerous intersting derivatives
could be made with ease as the chlorine is so happy to leave the nitrogen (Znethyl added to ethyldichloroamine lead to an immediate explosion)!
[Edited on 27-1-2005 by chemoleo]
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chemoleo
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On the note of nitrogen trichloride, which I believe someone had trouble making, here's an interesting website that details it somewhat:
http://www.lateralscience.co.uk/oil/
I love those old articles!
This is essentially the simplest of all halogenated amines 
[Edited on 31-1-2005 by chemoleo]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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Myrol
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I'm pretty new here but the Sciencemadness look's very cool!
Well, Axt, you've made TCED often enough to tell something about the ODOR.
I want to make this stuff too, but hey.....how worse is the smell of TCED really? I dropped all my intrest in MEKP just because it smells soo horrible
(and the cancerogenity...... )
The power looks impressive and I think you could even improve it with AN (to burn all the Carbon to CO2). Hope it isn't to unstable, because the
price is quite low!
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garage chemist
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I once suceeded in making an extremely small amount of NCl3.
By far the safest method of making it is the electrolysis of a SATURATED solution of ammonium chloride with two graphite electrodes (I used rods from
old zinc- carbon batteries). With dilute solutions, NCl3 doesn't form.
A current of 0,5- 1 A was used.
The amount of NCl3 produced is proportional to the charge (current*time) that has passed through the cell, making control of the formed amount of NCl3
easy.
The NCl3 collects as tiny yellow droplets on the anode. The drops explode with a sharp crack when the carbon rods are brought into contact with each
other at the place where a drop is (creating a short circuit and therefore heating the drops), sometimes splashing around the NH4Cl solution.
Its a fun little experiment, and safe if the current and electrolysis time is kept low.
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Axt
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If you dont like the odor of MEKP, ya aint going to like the <i>stench</i> of TCED. Though smells are always a matter of opinion. You
wouldnt want to make it inside.
I left a portion of TCED in the freezer (-15°C) and it did eventually freeze. though it took over 1 week. Its 4-4.5°C freezing point given in the
reference may be true, but it takes considerable time below this point to solidify, in this respect its simular to NG.
I've made very small amounts of NCl3 by urea/CaOCl/HCl, but it rapidly decomposes, i've never been able to extract and explode it. If you
pour a saturated solution of urea over solid CaOCl it will react violently with pops, bangs and explosions.
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franklyn
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| Quote: | Originally posted by Axt
Nitrogen trichloride and nitrogen triiodide are well known. but what of the others?
references to some explosive halogenated amines |
One of the simplest of improvised primary explosives
is prepared by the action of chlorine from the electrolysis
of salt water ( brine ) on urea ( urine ) precipitating
NCl2_CO_NCl2 . I suppose the same holds true for guanidine
yielding NCl_CNCl_NCL2, or any organic having primary amines.
.
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