Sciencemadness Discussion Board

Halogenated Amines - the others

Axt - 2-12-2004 at 18:47

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]

neutrino - 2-12-2004 at 19:01

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>.

J_O_H_N_Q - 2-12-2004 at 20:45

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?

Axt - 2-12-2004 at 21:44

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.

chemoleo - 16-12-2004 at 15:22

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.

Axt - 16-12-2004 at 16:25

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.

Axt - 3-1-2005 at 16:10

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]

Axt - 9-1-2005 at 04:48

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 1100 times


chemoleo - 9-1-2005 at 19:31

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]

Axt - 10-1-2005 at 13:26

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 :o, Im not even sure is there are examples of that.

Axt - 18-1-2005 at 20:26

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]

Jome - 22-1-2005 at 18:31

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?

Axt - 22-1-2005 at 20:08

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?

Theoretic - 24-1-2005 at 06:29

How about replacing one of the chlorine atoms in C2H4(NCl2)2 with a perchlorate group? This would give it perfect OB.

Jome - 24-1-2005 at 07:57

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?

Axt - 24-1-2005 at 15:51

Quote:
Originally posted by Jome
How would H2C=N-NH2 be made, formaldehyde and hydrazine?


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.

Jome - 25-1-2005 at 10:26

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.

Axt - 26-1-2005 at 01:02

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.

S.C. Wack - 26-1-2005 at 09:59

Ger 301, 799

chemoleo - 26-1-2005 at 17:56

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]

chemoleo - 30-1-2005 at 16:22

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]

Myrol - 13-2-2005 at 02:39

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!

garage chemist - 13-2-2005 at 04:13

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.

Axt - 15-2-2005 at 01:15

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.

franklyn - 9-6-2006 at 16:36

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.

.

Axt - 9-6-2006 at 18:33

Quote:
Originally posted by franklyn
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.


No, urea, and probably guanidine form NCl3. Via what mechanism I'm not sure probably hydrolysis to CO2 & NHCl2 followed by further chlorination of dichloramine yielding the yellow oil of NCl3.

[Edited on 10-6-2006 by Axt]

12AX7 - 9-6-2006 at 20:42

Could it be analogous to the haloform reaction?

Tim

franklyn - 1-7-2006 at 17:33

http://www.wikimirror.com/Nitrogen_trichloride

Links and resources _

http://www.justnitrogen.com/nitrogentrichloride

U P D A T E

http://www.sciencemadness.org/talk/viewthread.php?tid=6717&a...

.

[Edited on 6-9-2007 by franklyn]

Zelot - 18-3-2008 at 14:38

Sorry to bring up this thread, but I am interested in franklyn's post about urea forming a primary explosive with chlorine. Could you tell me more about that?

chemoleo - 18-3-2008 at 15:18

Quote:
Originally posted by Axt
Quote:
Originally posted by franklyn
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.


No, urea, and probably guanidine form NCl3. Via what mechanism I'm not sure probably hydrolysis to CO2 & NHCl2 followed by further chlorination of dichloramine yielding the yellow oil of NCl3.

[Edited on 10-6-2006 by Axt]


How did you manage to not see this?
It is also very unlikely as a compound, due to the strongly eletronegative carbonyl in the centre, destabilising the putative tetrachloro urea even further.

Reply to Zelot

franklyn - 19-3-2008 at 05:07

Quote:
Originally posted by Axt - No, urea, and probably guanidine form - - the yellow oil of NCl3.

Quote:
Originally posted by chemoleo - It is also very unlikely as a compound, due to the strongly eletronegative carbonyl in the centre, destabilising the putative tetrachloro urea even further.

Apparently not since there is no mention of this in literature.
Dichlorourea has been known a long time
http://www.sciencemadness.org/talk/viewthread.php?action=att...
Not explosive itself, this decomposes slowly to form NCl3
which is very dangerous. http://www.lateralscience.co.uk/oil/index.html

.

Axt - 19-3-2008 at 15:00

Quote:
Originally posted by Axt - No, urea, and probably guanidine form NCl3. Via what mechanism I'm not sure probably hydrolysis to CO2 & NHCl2 followed by further chlorination of dichloramine yielding the yellow oil of NCl3.

Quote:
Originally posted by chemoleo - It is also very unlikely as a compound, due to the strongly eletronegative carbonyl in the centre, destabilising the putative tetrachloro urea even further.

Quote:
Originally posted by franklyn - Apparently not since there is no mention of this in literature.


From the article you just gave,

"... since, in the presence of HCl formed at the same time, hydrolysis so readily occurs and so much nitrogen chloride is produced..."

Apparently not? I'd say apparently it does, everything you gave supported it.

Scifinder when given the structure of tetrachlorourea provides no hits, though from memory I did find a pentachloroguanidine.

Interesting targets would be chlorinated products of glycine and sulphamic acid which would enable the inclusion of catalytic metal ions, it would at least be interesting to see if this has any effect on explodability. Though chlorination and precipitation with lead/silver for example would be difficult. Maybe a potassium salt depending on solubility. Both the free acids are known and freely soluble, HO-S(=O)2-NCl2 is probably susceptable to hydrolysis as well.

[Edited on 20-3-2008 by Axt]

Axt - 13-4-2008 at 09:34

Quote:
Originally posted by Axt... though from memory I did find a pentachloroguanidine.


Here it is,

Chlorination of guanidine and cyanamide. Davydov, A. V.; Kretov, A. E. USSR. Zhurnal Vsesoyuznogo Khimicheskogo Obshchestva im. D. I. Mendeleeva (1981), 26(4), 478-9. CODEN: ZVKOA6 ISSN: 0373-0247. Journal written in Russian. CAN 95:168503 AN 1981:568503 CAPLUS

Abstract

Guanidine nitrate was chlorinated in H2O-CHCl3 contg. finely divided marble and NaCl at -10° to give 37% ClN:C(NCl2)2. Chlorinating H2NCN with HOCl in H2O-CCl4 contg. NaCl at -10° yielded 65% ClC(:NCl)NCl2 (I). Treating I with dry HCl in CCl4 yielded 85% HN:CXNH2.HCl (II; X = Cl), which reacted with refluxing MeOH to give II (X = OMe).

They've been there done that

franklyn - 13-4-2008 at 15:00

Pentafluoroguanidine is known and quite a super explosive in terms of its energy
product ≈ 3300 Kcal/ Kg , I am uncertain as to how it's detonation properties
compare to more prosaic oxo group materials.
http://www.sciencemadness.org/talk/viewthread.php?tid=6717&a...
Fluoroamino groups in a boron heterocyclic compound was examined many years
ago either by Los Alamos or Livermore, the exact reference I discarded because
of the disappointingly poor performance exhibited in the actual tests , although
characteristically for this type of functional group it's energy is paradoxically quite high.
B - Tri ( difluoroamino ) - N -Tri - fluoroborazole
∆Hf (Heat of formation) = -184 Kcal/ mol
Density ( ρ ) ≈ 1.7 gm/cm³
Detonation pressure . P = 212 Kilobar
Velocity of detonation . VOD = 6400 Meters/sec

TDFTFB.jpg - 4kB

Axt - 14-4-2008 at 01:06

Quote:
Originally posted by franklyn
I am uncertain as to how it's detonation properties
compare to more prosaic oxo group materials.


The attachment gives comparison to CF4, CO2, HF, H2O, Al2O3 and AlF3 detonation products. The conclusion was that only HF showed promise over H2O where "blast over brisance" is desired, but then isnt that what aluminium is for. CF4 and AlF3 "do not seem to be worth the trouble".

EDIT: Was too big to attach.

[Edited on 14-4-2008 by Axt]

Formatik - 20-4-2008 at 14:02

Here's another from PATR:



This is from Beilstein (Vol. 1, p. 1154):



Diethylenedichlorodiamine C4H8Cl2N2 = ClN.C4H8.NCl. Prep.: from diethylenediamine and NaClO. The precipitate is suctioned off immediately. – Strong smelling columns (from alcohol). Melting point: 71 deg.C. Explodes at 80 deg.C. Sparingly soluble in water, barely soluble in ether, easily in alcohol. Upon standing in water, diethylenediamine hydrochloride forms.

[Edited on 20-4-2008 by Schockwave]

Formatik - 23-4-2008 at 21:11

Here's some more from Beil:



Chloropiperidine C5H10ClN = C5H10.NCl. Formation. By mixing clear, aqueous solutions of piperidine and chloride of lime. - Pungent smelling oil. After several hours (and through heat, explosively) it changes into piperidine chloride. It boils with some decomposition at 52 deg. at 25 mm. Very volatile with water vapours. By prolonged boiling with water, piperidine results. Warming it with conc. HCl releases chlorine.



Naphthoquinone chloroimide. C20H10NClO3 (?). Formation. By treating a-amido-a-napthalene with chloride of lime solution. - Bright-brown needles (from dilute acetic acid). Meltpnt.: 85 deg. Explodes at 130 deg. Barely soluble in water, easily in alcohol, ether and acetic acid.



... Diacetyl-o-bischloroaminobenzene C10H10O2N2Cl2 = C6H4(NCl.CO.CH3)2. Prep.: by shaking diacetyl-o-phenylenediamine (see above) with a potassium bicarbonate containing solution of hypochlorous acid. quadrilateral prisms. Melts at 94 deg. with a light explosion. It isomerizes in glacial acetic acid to form 1,2-bis-acetamino-4,5(?)-dichlorobenzene (see below).

chemoleo - 24-4-2008 at 16:58

Very interesting. I guess all these N-chloro amines have explosive properties, regardless the remainder attached to the nitrogen.
I'm just not clear on one thing - what is diethylene diamine? It's not diethylamine, so what is it?
Where do you get these references from? Beilstein yes, but where can you access this so far back? Are there affordable subscriber options?

By the way I found it interesting that in the patent above Ger 301, 799 (S.C.Wack) it mentioned that these alkylaminechlorides can be detonated 'especially' well with mercury fulminates and the like once they are soaked into 'Kieselgur' which is diatomaceous earth... It may be old school (similar to the NG that used to be absorbed in Kieselgur before making NC-based dynamite) but it may be of interest.

[Edited on 25-4-2008 by chemoleo]

Formatik - 24-4-2008 at 17:33

Quote:
Originally posted by chemoleo
Very interesting. I guess all these N-chloro amines have explosive properties, regardless the remainder attached to the nitrogen.


Not all of them are necessarily or readily explosive, e.g. chloroguanidine deflagrates according to Beil.

Quote:
I'm just not clear on one thing - what is diethylene diamine? It's not diethylamine, so what is it?


Diethylenediamine, a.k.a. piperazine (C2H4)2.(NH)2, made from ethylene chloride and alcoholic NH3, etc.

Quote:
Where do you get these references from? Beilstein yes, but where can you access this so far back? Are there affordable subscriber options?


Beilstein exists in any decent library, but you can also find a couple volumes online (e.g. Internet archive or google books). I'm not sure if there is an online system of subscription to access of all of the volumes, possibly.

Quote:
By the way I found it interesting that in the patent above Ger 301, 799 (S.C.Wack) it mentioned that these alkylaminechlorides can be detonated 'especially' well with mercury fulminates and the like once they are soaked into 'Kieselgur' which is diatomaceous earth... It may be old school (similar to the NG that used to be absorbed in Kieselgur before making NC-based dynamite) but it may be of interest.


Certainly the case.

Formatik - 25-4-2008 at 16:15

I think Riedel's suggestion would have been engaged in if these N-chloroamines were not suspected genotoxins (e.g. N-chloropiperidine) and most of them didn't hydrolyse or decompose.

Axt - 27-4-2008 at 01:02

I have some doubt as to their definition of "explosive", maybe it detonates when touched with a hot wire or explodes when a glass vial containing it is thrown into a fire its not clear. My guess is that the examples given deflagrate.

One thing that it does show though is the very low ignition points of the chloramines (particularly the secondary alkyl chloramines). Below 100 degrees C. The chloramine analogues of RDX and DPT from memory also have this low ignition point. The chloronitramine of EDNA also very low ignition point.

1,4,5,8-Tetrachloro-1,4,5,8-tetraazadecalin (the chloramine analogue of TNAD) would be a better choice of simular structure, and more easily produced via glyoxal + ethylenediamine. I was planning to try that one but never got around to it.

Another OTC possiblility is the dichloramine of isopropylamine, which is available as "roundup" weed killer as the glyphosate salt. The chlorinated products of glyphosate (which is a secondary amine) should remain in solution.

AND heres reference to tetrachlorourea damnit, though I still not willing to accept that it exists so readily (not that I can read it), possibly non-explosive or at least insensitive considering the amounts hes producing. Its from patent DE720206.

And lastly an abstract regarding the conversion of chloramines to bromamines via a bromide salt.

Zawalski, Robert; Kovacic, Peter. "Chemistry of N-halo compounds. 29. A convenient preparation of N,N-dibromoamines" Synthetic Communications (1978), 8(8), 549-62.

Abstract

Ten N,N-dibromoamines, e.g., N,N-dibromocyclohexylamine, Me2CHNBr2, Me3CCH2NBr2, Me3CNBr2, were prepd. in 60-90% yields by treatment of the resp. N,N-dichloroamine in MeCN or MeOH at 0-5 with a water sol. bromide salt. Several attempts were made to prep. a mixed N,N-dihalo compd., e.g., by reaction involving an excess of N,N-dichloro-.alpha.-aminoisobutyronitrile with various sources of bromide.

[Edited on 27-4-2008 by Axt]

tetrachlorourea.jpg - 22kB

Formatik - 27-4-2008 at 16:33

Quote:
Originally posted by Axt
I have some doubt as to their definition of "explosive", maybe it detonates when touched with a hot wire or explodes when a glass vial containing it is thrown into a fire its not clear. My guess is that the examples given deflagrate.


Beilstein said chloroguanidine deflagrates in a capillary tube when heated to 150 deg. and bromoguanidine in the same instance deflagrates without melting at 110 deg., different than explosions readily obtained from other related compounds. That doesn't tell us though if they are or aren't detonable / explodable. They might also just be decomposable though.

Quote:
1,4,5,8-Tetrachloro-1,4,5,8-tetraazadecalin (the chloramine analogue of TNAD) would be a better choice of simular structure, and more easily produced via glyoxal + ethylenediamine. I was planning to try that one but never got around to it.

Another OTC possiblility is the dichloramine of isopropylamine, which is available as "roundup" weed killer as the glyphosate salt. The chlorinated products of glyphosate (which is a secondary amine) should remain in solution.


There seems to be many possiblities from various nitrogenous bases and the range is wide from aromatic and aliphatic bases like the alkylamines (bases with one nitrogen atom of the variety, C(n)H(2n + 3)N) - how about compounds from amines with a triple bond? Propargylamine, aminoacetylene, etc. And compounds from bases with two nitrogen atoms of the variety C(n)H(2n + 4)N2), e.g. aliphatic hydrazines (methyl or ethylhydrazine), tetramethyltetrazone, etc. must get some hellish unstable and toxic compounds. Also bases of the kind C(n)H(2n)N4 like tetrazine, N(CH.NH.NH:CH)N, or C(n)H(2n+4)N4 like piperazyldihydrazine, NH2.N(CH2.CH2)2N.NH2, etc.

Quote:
AND heres reference to tetrachlorourea damnit, though I still not willing to accept that it exists so readily (not that I can read it),


The patent mentions that tri- and tetrachlorourea can not be prepared from urea and chlorine directly because what results is from further addition of chlorine is NCl3. They say this can be avoided when the urea molecule is bound and protected with an additional molecule group (so salts from urea, or nitrogen-atom substituted deriatives like monoacyl-, monoalkyl or monoarylureas) in a solubilized form and then treated with a calculated amount of chlorine, etc.

Quote:
possibly non-explosive or at least insensitive considering the amounts hes producing.


I know dichlorourea deflagrates when heated, but formed NCl3 explodes if the urea is heated in a covered or closed container, not sure about tetrachlorourea. Dichlorourea also hydrolyzes from water to give NCl3, tetrachlorourea maybe. About stability, the patent mentions trichlorourea is too easily decomposed, monochlorourea and a-symmetrical dichlorourea can only be stored for a short time, and say sym-dichlorourea and sym-tetrachlorourea are stable when pure.

Quote:
Its from patent DE720206.


That procedure should look something like this:

100 g of urea are - just as in example 1 - converted to urea chloride*. The solution is warmed to 30 deg., and 473 g of chlorine are passed into it. After about half of the chlorine has been passed through, there is an evolution of gases which ceases if chlorine is further added. Due to any danger of the possible formation of nitrogen trichloride at this stage, some chloroform is added, which can be later let off. The aqueous solution does not give any crystals. After the evaporation and then resolubilization of the evaporation residue in distilled water, the determination of freely produced iodine from KI, shows the formation of 205 g tetrachlorourea (62% of the theory).

* ... Example 1: 100 g urea are solubilized in a small amount of water and are converted to the chloride salt through the addition of hydrochloric acid which contains 59 g HCl. ...


Quote:
And lastly an abstract regarding the conversion of chloramines to bromamines via a bromide salt.

Zawalski, Robert; Kovacic, Peter. "Chemistry of N-halo compounds. 29. A convenient preparation of N,N-dibromoamines" Synthetic Communications (1978), 8(8), 549-62.

Abstract

Ten N,N-dibromoamines, e.g., N,N-dibromocyclohexylamine, Me2CHNBr2, Me3CCH2NBr2, Me3CNBr2, were prepd. in 60-90% yields by treatment of the resp. N,N-dichloroamine in MeCN or MeOH at 0-5 with a water sol. bromide salt. Several attempts were made to prep. a mixed N,N-dihalo compd., e.g., by reaction involving an excess of N,N-dichloro-.alpha.-aminoisobutyronitrile with various sources of bromide.


A simple displacement then.


Note: B. [1895], 28, 1683 states the explosion product of dichloromethylamine is: CH3.NCl2 -> HCN + 2 HCl, just another reason why it likley never found application.

Formatik - 27-4-2008 at 18:29

Quote:
Originally posted by Schockwave ... Naphthoquinone chloroimide. C20H10NClO3 (?). Formation. By treating a-amido-a-napthalene with chloride of lime solution. - Bright-brown needles (from dilute acetic acid). Meltpnt.: 85 deg. Explodes at 130 deg. Barely soluble in water, easily in alcohol, ether and acetic acid.


Note: this should read a-amido-a-napthol chloride.

[Edited on 27-4-2008 by Schockwave]

Axt - 28-4-2008 at 03:36

Quote:
Originally posted by Schockwave

There seems to be many possiblities from various nitrogenous bases and the range is wide from aromatic and aliphatic bases ...

how about compounds from amines with a triple bond?...


Aromatic chloramines are particularly unstable, due to them wanting to rearange to chlorinate the benzene ring. N,N-2,4,6-pentachloroaniline is said to be somewhat stable (Acad. Sci. Munich. Ber. (1914), 46 2728-36). Chlorination(oxidation) of the the likes of <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=5813">DAF</a> results in coupling through a azoic bridge.

Chloraminoalkynes would be hard to do, at least through direct chlorination of the amine. I would think trying to chlorinate an aminoalkyne will result in addition across the triple bond.

An interesting explosive moiety would be -O-NCl2, giving the chloramine analogue of the nitrates. The prep of H2N-O-C2H4-O-NH2 is in PEP (2006), 31(3), 196-204. I cant view it right now but from memory I think it refers its preparation to another article which I'm sure I attached at some time into this forum though I cant find it now. The "oxydichloramine" group is not known to scifinder.

Thanks for the translation, it seems quite odd that tetrachlorourea as the patent says is so soluble and stable. Also considering that only one reference refers to such a simple compound :/ its hard to trust a patent.

Formatik - 28-4-2008 at 19:11

Quote:
Originally posted by Axt Aromatic chloramines are particularly unstable, due to them wanting to rearange to chlorinate the benzene ring. N,N-2,4,6-pentachloroaniline is said to be somewhat stable (Acad. Sci. Munich. Ber. (1914), 46 2728-36). Chlorination(oxidation) of the the likes of <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=5813">DAF</a> results in coupling through a azoic bridge.


I've also found an aromatic chloroamine, N-chloro deriative of aceto-p-chloroanilide:


This is described as being sheets from petrol ether having a melting point of 82 deg. and decomposes explosively at 165 deg. to form aceto-2,4-dichloroanilide.

There are also quite a few more like N-chloroderiatives of nitroanilines e.g. 4-nitro-2-chloroanilide N-chloroderiative (NO2.C6H3Cl.NCl.CO.CH3, regular bright yellow prisms, Meltpnt. 106 deg. in B. 33, 3060), but not much beyond their pretty low melting points and some general descriptions.


Quote:
Chloraminoalkynes would be hard to do, at least through direct chlorination of the amine. I would think trying to chlorinate an aminoalkyne will result in addition across the triple bond.


Alkynes seem to survive hypochlorites, but forms highly unstable compounds.

Quote:
An interesting explosive moiety would be -O-NCl2, giving the chloramine analogue of the nitrates. The prep of H2N-O-C2H4-O-NH2 is in PEP (2006), 31(3), 196-204. I cant view it right now but from memory I think it refers its preparation to another article which I'm sure I attached at some time into this forum though I cant find it now. The "oxydichloramine" group is not known to scifinder.


The closest I've been able to find to this is trichlorooxypropylamine [OH.CH2.CH(CH2Cl)-]3N mentioned in Beil and they basically just say it has a melting point of 92-93 deg and is made from epichlorohydrin and ammonia (B. 21 [2] 646), according to that structure it doesn't look like an analogous -O-NCl2 though.

Cholroxysulfurpentafluoride & derivatives

franklyn - 29-4-2008 at 09:59

Quote:
Originally posted by Schockwave
Quote:
Originally posted by Axt
An interesting explosive moiety would be -O-NCl2, giving the chloramine analogue of the nitrates. The prep of H2N-O-C2H4-O-NH2 is in PEP (2006), 31(3), 196-204. I cant view it right now but from memory I think it refers its preparation to another article which I'm sure I attached at some time into this forum though I cant find it now. The "oxydichloramine" group is not known to scifinder.


US 3582292
View _
http://www.google.com/patents?id=XVVlAAAAEBAJ&pg=PA1971&...
Download _
http://www.google.com/patents/pdf/ULTRA_VIOLET_RADIATION.pdf...

Some nerve agent precursors having a similar chemistry.

.

Axt - 29-4-2008 at 21:18

Theres quite a few references to oxydifluoramines, though there always attached to fluorocarbons, not so great for explosive performance, well unless you include Al in the mix. Along with the sulfur compound mentioned above the simplest one trifluoromethane derivative is described in the following.

Hale, William H., Jr.; Williamson, Stanley M. Pentafluorosulfur and trifluoromethyl oxydifluoramines. Preparations and properties. Inorg. Chem. (1965), 4(9), 1342-6. [attached]

And CF2(ONF2)2 is detailed in US3663588. As a possible oxidant in rocket fuel.

And this, which may be of more interest though I haven't seen it.

Fokin, A. V.; Studnev, Yu. N.; Stolyarov, V. P.; Valiev, R. Sh. Organic compounds bearing a difluoroaminooxy group. Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya) (1999), 48(1), 131-135.

Fluorine chemistry is a bit inaccessable. The only citation given for chlorine is as the dichloronitronium ion +O-NCl2, none for its compounds.

And I'll just chuck in a couple more citations regarding the preparation of some explosive dibromamines, available online but not to me;

"Dibromamin: Alkylderivate" , Journal Monatshefte für Chemie / Chemical Monthly, Issue Volume 104, Number 6 / November, 1973, Pages 1681-1689, DOI 10.1007/BF00909655

"Dibromamin: Acylderivate", Journal Monatshefte für Chemie / Chemical Monthly, Issue Volume 104, Number 2 / March, 1973, Pages 421-432, DOI 10.1007/BF00903106

[Edited on 30-4-2008 by Axt]

Attachment: Pentafluorosulfur and trifluoromethyl oxydifluoramines. Preparations and properties.pdf (591kB)
This file has been downloaded 685 times


Axt - 30-4-2008 at 23:32

Okay, regarding halogenation of the oxyamines I've been going over stuff that I've already posted before but forgotten about. I posted it off topic in the <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=3681&page=1#pid40653">diazonium salt</a> thread. The reaction of the oxyamines with hypobromic acid does not result in the separation of an oxydibromamine but rather (like DAF) is coupled through an azoic group forming a hyponitrite ester. So for example CH3-O-NH2 + HOBr --> CH3-O-N=N-O-CH3.

Axt - 12-5-2008 at 13:27

I mentioned previously in this thread that iodine under ethylenediamine turned red. Heres an article that gives the preparation of the tetraiodoethylenediamine.

<b>Nitrogen-iodine compounds. VIII. N-Iodo compounds of some aliphatic and alicyclic diamines.</b> Jander, J.; Knuth, K.; Trommsdorff, K. U. Anorg.-Chem. Inst., Univ. Heidelberg, Heidelberg, Fed. Rep. Ger. Zeitschrift fuer Anorganische und Allgemeine Chemie (1972), 394(3), 225-32.

Abstract

Reaction of H2NCH2CH2NH2, MeNHCH2CH2NHMe, Me2NCH2CH2NH2, or piperazine with NI3.NH3 or iodine chloride gave I2NCH2CH2NI2, IMeNCH2CH2NMeI, Me2NCH2CH2NI2, or N,N'-diiodopiperazine, resp.

12AX7 - 12-5-2008 at 13:48

Wow, a synthesis using NI3.NH3, crazy!

Formatik - 14-5-2008 at 00:41

Quote:
Originally posted by 12AX7
Wow, a synthesis using NI3.NH3, crazy!


I've found NI3.NH3 explodes readily like when being touched directly, bumped or scraped even under a lot of water. At some point, the weight of its own crystals should explode it in suspension. Iodine chloride would be the safer, albeit more toxic choice in a synthesis.

Axt - 14-5-2008 at 04:57

I've seen reference to NI3.NH3 being used to convert acetylene to tetraiodoethylene as well.

This is regardig the chloramine analogue of PETN:

<b>Attempts toward the preparation of tetracyanomethane. Tetrakis(N, N-dichloroaminomethyl)methane, a very powerful explosive</b>. Gryszkiewicz-Trochimowski, Eustache; Gryszkiewicz-Trochimowski, Oleg; Levy, Robert S. Memorial des Poudres (1958), 40 109-12.
Abstract
C(CH2Br)4 was treated with p-MeC6H4SO2NH2, the resulting tetramide recrystd. with AcOH and hydrolyzed with H2SO4 to C(CH2NH2)4.4H2SO4 (I), m. 302-3. Treating I with a BaCl2 soln. and distg. the mixt. with solid KOH gave 54% C(CH2NH2)4.H2O (II), b15 147-9, m. 40-1. Heating slowly a mixt. of 6.2 g. II and 32 g. PhCHO (III) to 100 and keeping it at 100 1 hr. gave a yellow oil which solidified after H2O and excess III were removed in vacuo. Grinding with EtOH, drying, and washing several times with EtOH and petr. ether gave 16 g. C(CH2N:CHPh)4 (IV), m. 172-3 (1:1 tetrahydrofuran-Me2CO). NaOCl was prepd. by introducing the calcd. amt. of Cl into a cooled soln. of 18 g. NaOH in 85 cc. H2O. (Caution! Any free Cl must be removed by an air stream, otherwise spontaneous fires result on adding I.) To the cooled soln. was added 15 cc. glacial AcOH and then, with hand stirring, the total amt. of 4.5 g. I. The temp. was very slowly raised to 70-5 (it must not exceed 80). After several min., I dissolved and an oil formed. On rapid cooling in cold H2O, the oil solidified and the aq. layer was decanted. Washing with H2O, and drying first on paper then in a desiccator contg. H2SO4 gave 5.25 g. C(CH2NCl2)4 (V), m. 54-4.5 (Et2O-petr. ether). In storage, IV decompd. above -15 with evolution of Cl. It was believed that V exploded more vigorously on heating than Hg fulminate. Attempts to convert IV into C(CN)4 (VI) on heating to 300 in the presence of Pd gave only a small amt. of PhMe and an intractable residue. Attempts to convert V into VI by various dehydrochlorination procedures were fruitless. Thermal decompn. of V in (CH2Br)2 gave rise to the evolution of Cl instead of the expected HCl.

Axt - 10-7-2008 at 14:35

Quote:
Originally posted by Axt
Another OTC possiblility is the dichloramine of isopropylamine, which is available as "roundup" weed killer as the glyphosate salt. The chlorinated products of glyphosate (which is a secondary amine) should remain in solution.


The chlorination of monoisopropylamine glyphosate (roundup) failed. Roundup in 50% acetic acid was added to 12.5% NaOCl, a lot of gassing and foaming resulted with the distict smell of chloramine. No product separated, temperature wasnt monitored, but it only got slightly warm to the touch on addition. Isopropyldichloramine is known and its preparation is in JACS, 69 1539-40 (1947):

"i-Propyldichloramine was prepared by a modification of the above procedures. To an ice-cooled concentrated aqueous solution of 95 g. (I mole) of i-propylamine hydrochloride (prepared in situ) was added slowly 2.25 moles of aqueous sodium hypochlorite (prepared by adding chlorine to cold 15% aqueous sodium hydroxide, 1.6 moles hypochlorous acid per liter). Simultaneously with this addition over two to three hours was added 6 N hydrochloric acid at such a rate that the acidity was maintained between pH 5.6 and 6.6. Bromcresol green and chlorphenol red papers can be used as criteria if the solution is allowed to creep into the paper so as to give an indicator zone ahead of the bleached zone. After two hours' subsequent stirring in the cold, the heavy oil was separated, washed once with 30 cc. cold water, twice with 50-cc. portions of 5% sodium thiosulfate, once with cold water, twice with cold 50% sulfuric acid and finally twice with cold water. The crude yield (97 g., 76% of theoretical) contained 94% of the theoretical electropositive chlorine content. Distillation at 41-43' (15 mm.) resulted in 70% recovery of yellow oil (d20/4 1.165; n23D 1.4572) which contained 99.8% of the calculated electropositive chlorine content."

Depending on how readily glyphosate is chlorinated it might just be a case of it using up all the NaOCl. http://cat.inist.fr/?aModele=afficheN&cpsidt=18092577

Axt - 10-7-2008 at 14:56

The tetrabrominated derivative of ethylenediamine was prepared. Its mentioned in the JCS article I attached into this thread, by adding ethylenediamine to hypobromous acid. I formed this in situ by adding NaBr to NaOCl.

12g acetic acid was added to 2g ethylenediamine in 12ml water. This was then slowly poured into a cooled solution of 28g sodium bromide in 140ml 12.5% sodium hypochlorite. An orange precipitate formed immediately on addition that was filtered. Dissolving the precipitate in DCM in which it is very soluble and evaporating gave brilliant orange crystals having the melting point reported in the literature (62°C).

It ignited with a fssht with a fair quantity of smoke. Heating on a spoon it first melted the puffed off. It explodes readily when struck with a hammer on steel. I wasnt prepared to heat more then a pinch at a time since the JCS article mentions a "very violent detonation" on heating, they dont mention the conditions but thats likely under confinement.

[Edited on 11-7-2008 by Axt]

tetrabromoethylenediamine-precip.jpg - 30kB

Formatik - 10-7-2008 at 22:54

Concerning the literature descriptions, many times small details are left out, this is the thing I hate most about it. Nice crystals.

Formatik - 11-9-2008 at 00:50

Taking it to another level of power and instability are N-perchlorylamines. There are not many are well known, besides N-perchlorylpiperidine, C5H10NClO3, which US 3332955 describes as a dangerously sensitive oil and perchlorylamide salts.

Reactions of Dichlorine Heptoxide with Amines:
http://pubs.acs.org/cgi-bin/abstract.cgi/jacsat/1974/96/i10/...

Taoiseach - 19-10-2008 at 09:55

Does N-tetrabromoethylenediamine work as a complexing agent? I figure each of the 4 N atoms has a lone electron pair.
[(Br2N-CH2-CH2-NBr2)2Cu](ClO4)2 looks interesting...

Axt - 29-10-2008 at 03:44

I had tried to complex the tetrachloro compound, but to no avail. I mentioned the attempt on first page of this thread by mixing a DCM solution of TCED with a water solution of copper sulphate, there was no noticable change in the two layers.

Formatik - 24-12-2008 at 01:23

Here's another one. It is the most basic organic chloramine from what I can tell and quite unstable. Methylenechloroamine CH2=NCl made from action of formaldehyde onto chloramine in water solution which results from NH4Cl and NaClO (Cross, Bevan, Bacon, Journal of the Chemical Soc. of London. 97, 2406). Needles (from CHCl3). It is very unstable in air. Decomposes at 50-60°C explosively under formation of NH4Cl. Soluble in 20-30 parts ether at room temperature. In benzene it appears to polymerize.

Formatik - 25-12-2008 at 16:34

More references on the above here and here (pg. 12).

Axt - 25-12-2008 at 19:57

I have the original french article for what that is the abstract of. I have tried to form the RDX analogue once, though failed. I no longer know the exact process I tried.

I OCR'ed and added the machine translation to the end.

Attachment: Cyclotrimethylenetrichloramine - Bull. Soc. Chim. Fr., 9, 1025 (1911) w translation.pdf (280kB)
This file has been downloaded 873 times


Formatik - 26-12-2008 at 00:52

Thank you for that paper. I forgot to add that Cross also patented a method for the preparation of the monomer compound in English pat. 15303 (1909). No idea where to get this though.

franklyn - 22-1-2009 at 13:01

From the citation above by Formatik
http://www.rsc.org/delivery/_ArticleLinking/DisplayArticleFo...
on pg 12

Action of Sodium Hypochlorite on Hexamethylenetetramine.

MARCEL DELEPINE ( Bull. Soc. chim., 1911, [IV], 9, 1025--1029 ).
Sodium hypochlorite reacts with aqueous solutions of
hexamethylenetetramine to form N-Dichloropentamethylenetetramine,
but in presence of acetic acid gives N-trichlorotrimethylenetriamine
( 1,3,5-trichlorohexahydrotriazine ), which is isomeric with Cross,
Bevan, and Bacon's methylenechloroamine ( Trans,, 1910, 97, 2404).
N-Dichloropentamethyenetetramine, C5H10N4CI2, crystallises in brilliant
lamellae: from water, or in octahedra from ether, possesses the odour
peculiar to compounds containing chlorine and nitrogen, is sparingly
soluble in water, and moderately so in ether or benzene, and deflagrates
at 78-82', giving an odour of carbylamines. It can be kept for long
periods in sealed tubes, but decomposes in the course of a, few days on
exposure to air, forming ammonium chloride and hexnmethylenetetramine
hydrochloride. With sodium hydroxide in alcohol, ammonia is produced,
and the chlorine is removed as alkali chloride.
1,3,5-Trichlorohexahydrotriazine ( Abstr., 1899, i, 326 ),
. .NCl --- CH2
. . / . . . . . . . \
CH2 . . . . . NCl
. . \ . . . . . . . /
. .NCl --- CH2
crystallises in brilliant needles, has a slight odour of chlorine, is nearly
insoluble in water, but soluble in alcohol or chloroform, and deflagrates at
78 º, evolving fumes having the odour of hydrogen cyanide and carbylamines,
and leaving a residue of ammonium chloride. It decomposes in air, or when
kept in solution in organic solvents. With sodium hydroxide in alcohol,
it yelds ammonia and sodium chloride, and the residue on distillation
with a dilute acid gives formic acid : this decomposition
appears to take place in accordance with the equations :
(1) (CH,:NCl), + 3NaOEt = 3NaC1+ 3CH(NH)*OEt ;
(2) CH(NH)*OEt + 2H20 = H*CO2H + EtOH + NH2.
T. A. H.

_________________________________________


The above cited paper on Methylenechloramine was obtained for me by solo some time ago,
Chloroamine Reactions :Methylene chloroamine
http://www.sciencemadness.org/talk/viewthread.php?tid=9319&a...
it is also available here. http://ifile.it/yjwc4in

My research on chloramine production
http://www.sciencemadness.org/talk/viewthread.php?tid=6042&a...
Ironically I just found this thread relating experiences with a likely method
for production of choramine (NH4)2SO4 + Ca(ClO)2 -> CaSO4•2H2O + 2 H2NCl
http://www.sciencemadness.org/talk/viewthread.php?tid=2567
I had independently thought of using the measured amount of this in a chlorinated
organic solvent for anhydrous production of chloramine, to then react with formaldehyde
to form Methylenechloramine as described in the paper above. A small beaker of the
wetted mixture would be placed inside a larger canister with a airtight lid
( something like tupperware ) containing about two centimeters deep of formaldehyde.

I thought that the method described in this paper here for C - nitration could
perhaps be also applied to N - nitration
A New Method for the Synthesis of Aliphatic Nitro Compounds1, 2.
http://sciencemadness.org/talk/viewthread.php?action=attachm...
Another german paper on just this idea posted by Axt in his Azidamine thread
Nukleophile Substitutionen an N-Chlor-aminen
http://www.sciencemadness.org/talk/viewthread.php?action=att...

Additionally here is a theoretical study on Methylene Nitroamine
the supposed monomer of the familiar RDX trimer. It has not been isolated
and is supposed a decomposition intermediate of RDX.
Analytical Potential Energy Surface for Methylene Nitramine (CH2NNO2)
Re-direct > http://handle.dtic.mil/100.2/ADA291247
to this download link _
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA291247&Locati...

Also contained in the zip file below with three other patents is this one , Perchloramide NClO3 US pat3295933
The literature on this substance is scant, but the described double salt NH4.HNClO3•NH4F
should react with formaldehyde in the expected manner forming an organic compound.

Nicodem provided this abstract for chlorinating Melamine in my Amine Methathesis thread
http://www.sciencemadness.org/talk/viewthread.php?tid=6717&a...
This zip file contains the above cited patent and these following patents relating to Hexachloromelamine.
Hexachloramine prep GB815682 , Hexachloromelamine US2472361 , Hexachloromelamine US3364214
http://ifile.it/tbvopum

len1 details proceedures for chlorine production
http://www.sciencemadness.org/talk/viewthread.php?tid=9713
The applicable chlorine threads
http://www.sciencemadness.org/talk/viewthread.php?tid=1305
http://www.sciencemadness.org/talk/viewthread.php?tid=730

.

AndersHoveland - 7-6-2011 at 19:06

Would reacting difluoramine, HNF2, with methyl perchlorate, CH3OClO3, dissolved in a solvent to prevent it from exploding, produce (CH3)2NF2[+] [-]ClO4 ?
Might be an interesting energetic compound, decent oxygen balance.

Dimethyl sulfate is known to be a potent alkylating agent, easily methylating amines to quaternary amines, so one would think methyl perchlorate, despite being extremely sensitive, would also work.

Some more information about HNF2,
http://pubs.acs.org/doi/abs/10.1021/ja01505a009

http://docs.google.com/viewer?a=v&q=cache:UuOX44kUhKgJ:w...

Also some articles about alkylating fluoramine and difluroamine:
http://www.springerlink.com/content/x032141571015122/

http://pubs.acs.org/doi/abs/10.1021/ja01003a021

http://pubs.acs.org/doi/abs/10.1021/jo01259a004

this is not really a direct alkylation, but also perhaps interesting:
http://docs.google.com/viewer?a=v&q=cache:RvwI9l1J6sEJ:w...

[Edited on 8-6-2011 by AndersHoveland]

PHILOU Zrealone - 8-6-2011 at 03:03

I wonder what is the result of the action of a base on such chloramines...
Does someone have infos on that?

R-NCl2 + 2 NaOH --> R-N(OH)2 + 2 NaCl
R-N(OH)2 --> R-N=O + H2O

Might be very valuable if it works... :cool:
H2N-CH2-CH2-NH2 -Cl2-> Cl2N-CH2-CH2-NCl2
Cl2N-CH2-CH2-NCl2 -NaOH-> O=N-CH2-CH2-N=O
O=N-CH2-CH2-N=O <==> HO-N=CH-CH=N-OH

AndersHoveland - 9-6-2011 at 13:46

The reaction between a base and chloramines is likely very slow without heating. Hypochlorite is produced, which would likely oxidize any intermediate nitroso groups to nitro.
For example, I think the reaction between nitrogen trichloride and aqueous base is:
(4)NCl3 + (18)OH[-] --> (3)Cl[-] + (9)OCl[-] + (9)H2O + (2)N2

Nitrogen trichloride is hydrolyzed by hot water.
Nitrogen trifluoride is inert to pure water at 133° C but reacts slowly with aqueous base at 100° C to give nitrite and fluoride. NF3 is also hydrolyzed by hot salt water, or hot hydrochloric acid, but not by dilute sulfuric acid.
http://docs.google.com/viewer?a=v&q=cache:vkG5Vh7ZuWEJ:w...

Information about the preparation of compounds containing the tris(difluoramino)methyl group:
http://www.freepatentsonline.com/3758555.html

Although --NF2 groups make energetic compounds more sensitive, geminal --NF2 groups (two difluoramino groups on the same carbon atom) are much more thermally stable than geminal nitro groups.

Preparation of Difluoramine HNF2
The aqueous fluorination of urea to N,N-difluorourea (H2NCONF2) gives highest yields at a pH range between 4 to 8. Using highly concentrated alkaline solutions instead gave tetrafluorohydrazine (N2F4), wheras only moderately basic solutions did not favor formation of any products that contained N-F bonds.
Difluorourea was isolated from the reaction mixture by five successive extractions of the cold, aqueous solution of fluorinated guanidinium hydrofluoride with ethyl acetate. After the first extraction, only one fourth of the volume of initial solvent is used. The combined portions of extraction solvent were dried with anhydrous sodium sulfate and the solvent evaporated at room temperature. The residue remaining after evaporation of the solvent was subjected to reduced pressures of less than 1 mm Hg, the difluorourea evaporated from the residue and was condensed at (minus) -15 degC. Through repetition of the sublimation process and using fractional condensation of the evaporating material to effect separation from water and acetic acid, difluorourea was isolated as a white, crystalline solid, with a melting point of 42 - 44 degC.

The difluorourea is not isolated, but is converted to difluoramine by direct addition of mineral acid to the aqueous solution of fluorinated guanidine hydrofluoride (or of fluorinated urea) followed by heating the solution to drive off the difluoramine, which is then collected by cold condensation. The yields of pure difluoramine from this procedure are 10 - 15% of the theoretical amount. Traces of perfluoroguanidine gas, which could later be condensed at around -195 degC, are also given off by the reaction. V. Grakauskas, K. Baum. Journal American Chem. society. volume 92, p2096. (1970)

[Edited on 9-6-2011 by AndersHoveland]