Sciencemadness Discussion Board - 1,3,5-trichlorohexahydrotriazine

1,3,5-trichlorohexahydrotriazine

plante1999 - 2-6-2012 at 04:53

I made my first energetic compound!

I do not really like energetic compound but following a post of franklyn I found an energetic compound that I wanted to try.

http://www.sciencemadness.org/talk/viewthread.php?tid=2945&page=3

The process was not well explained, but the general idea was that if hexamine is reacted with NaOCl/CH3COOH mix it will make 1,3,5-trichlorohexahydrotriazine ( C3H6N3Cl3).

Experimental:
(I did all the process outside)
2.5g of hexamine from coleman fuel tablet was disolved in 25ml of water. Then 30ml of 10% sodium hypochlorite (pool chem) was mixed with 40ml of 10% acetic acid (cleaning vinegar). After pouring the NaOCl/CH3COOH mix in the hexamine sol. the solution turned cloudy white, I swirled and suddenly a yellow flocculent formed on top. I filtered it and take a pinch of it and try to dissolve in water but iit was insolube in water, so water was a perfect solvent to clean the product. I cleaned the product with water and I lets it dry. After drying I deflagrated some of it, It burn instantly making a pop sound, success!

Maybe I will try to make a salt with this compound.

Description of the product (from my own analyse):
Yellow material insoluble in water and smelling chloramine.

Thanks!

plante1999 - 2-6-2012 at 11:50

Sorry for the double post.

This compound seam to be very energetic when dry. The product take some time to dry but when it is completly dry it is quite impressing for someone that never made energetic compound. The compound is solube in methanol.

The most impressive with this compound is the OTC(ness) of its starting material.

edit:
I'm precipitating a bromo variant. More info on the process/reactivity soon.

[Edited on 2-6-2012 by plante1999]

franklyn - 2-6-2012 at 14:50

If you are willing to experiment , I'm wondering if RDX can be achieved by this
method. NaNO2 sodium nitrite is also very soluble in methanol. Mixed with the
compound you have made and promoted with some lewis acid catalyst such as
CuCl2 copper chloride , it could result that NaCl would precipitate out producing RDX.

. .NCl --- CH2
. . / . . . . . . . \
CH2 . . . . . NCl . . . . . + 3 NaNO2 => 3 NaCl + C3H6N6O6
. . \ . . . . . . . /
. .NCl --- CH2

Those of you with more knowledge of synthesis please contibute your opinion
and critique this. It's been a nagging thought for too long.

Hypothetically NaClO3 sodium chlorate is also worth trying , possibly yielding a
Perchloramide >NClO3

.

plante1999 - 3-6-2012 at 02:42

I'm willing to experiment but I do not have sodium nitrite. I have sodium chlorate.

The product generate chlorine when in 30%HCl probably this reaction is appening:

6HCl + C3H6N3Cl3 + 3H2O -) 3Cl2 + 3NH4Cl + 3CH2O

Ral123 - 3-6-2012 at 04:09

Just exactly how many explosive options hexamine gives you

? I'll remember-hexamine-NaClO-acetic acid for when I have NaClO

plante1999 - 3-6-2012 at 04:37

Quote: Originally posted by Ral123

Just exactly how many explosive options hexamine gives you

? I'll remember-hexamine-NaClO-acetic acid for when I have NaClO

NaOCl can by bougth at the hardware store as ''liquid chlorine''. If you cannot get some look for 65% calcium hypochlorite or '' shock chlorine'' for pool it should also work.

[Edited on 3-6-2012 by plante1999]

Ral123 - 3-6-2012 at 07:54

I can't afford basic lab equipment as scale and use mostly jars... At the price of the NaClO I'd buy 2kg of good AN...

AndersHoveland - 4-6-2012 at 03:45

Quote: Originally posted by franklyn

I'm wondering if RDX can be achieved by this
method.

Those of you with more knowledge of synthesis please contibute your opinion
and critique this. It's been a nagging thought for too long.

That is an intiguing question. One thing for certain, however, it would not work if there was any water present. The chloramine would act like a bleach and the nitrite would get oxidized to nitrate.

I am not entirely sure how the N-Cl bond would behave in nucleophilic substitution reactions. Although the N-Cl bond can readily hydrolyse in water, it could be much less reactive in an attempted substitution reaction with nitrite.

I believe this may be anologous to the reactions of haloalkanes with sodium nitrite. Chloroalkanes generally do not react, while bromoalkanes are much more reactive. Remember, the proper solvent needs to be used, which is both non-nucleophilic (generally water is not optimal) and can dissolve the sodium nitrite. DMSO is a good solvent for this. If trichlorotriazine is unreactive, you might try tribromotriazine.

You might see this reference:
http://www.sciencedirect.com/science/article/pii/S1044030500...
It mentions that nucleophilic substitution on chloramine to form chloride ions proceeds at a rate more than 100 times that of chloromethane, which may still be rather slow. Consider for example that the hydrolysis of chloromethane with water takes around a whole year!

Quote:

Anhydrous chloramine is an extremely hazardous (toxic and explosive) and unstable (decomposes at −50 °C) compound. Therefore, it was prepared in situ in an aqueous solution according to the modified Raschig method: Aqueous ammonia (30%) and a solution of sodium hypochlorite (11%–13% available chlorine), both chilled to −18 °C, were mixed in a 1:4 ratio by volume (a slight excess of hypochlorite) in an ice/NaCl bath. The resulting fresh solution of chloramine (10 mL, ≈3 M; kept in an ice/water bath at 0 °C) was immediately used for experiments

[Edited on 4-6-2012 by AndersHoveland]

plante1999 - 4-6-2012 at 04:11

Like I said earlier I'm willing to experiment but i do not have NaNO2 or DMSO solvent. I could buy some...

At least I could make anhydrous aluminium bromide as a catalyst.

I also tried to make bromo variant but it did not seam to work... I will make hypobromite soon and attempt to make it again.

[Edited on 4-6-2012 by plante1999]

AndersHoveland - 4-6-2012 at 04:32

Not sure if the below relates to this topic:

Quote:

The nitration of aliphatic secondary amides and of primary and secondary aliphatic amines has been studied extensively and some understanding of the reaction is now at hand. Firstly it has been found that the ease of nitration in acetic anhydride varies inversely in respect of increasing base strength. Secondly those strong amines which cannot be nitrated directly can be converted to their nitramines via the intermediate preparation of the chloramines, presumably because the chlorine substituent reduces the base strength of the amine. In many cases the chloramine may be prepared in situ in the acetic anhydride - nitric acid medium by adding a small amount of hydrogen chloride. The hypochlorous acid thus produced forms the chloramine and is regenerated when the chloramine is converted to the nitramine. A chain reaction is thus developed which is largely self-sustaining. Finally primary amines, which cannot be nitrated directly, may be converted to primary
nitramines via the primary dichloramine. The alkylchloronitramine (which can be converted separately to the alkylnitramine) is the actual product of the latter reaction. This is fortunate because primary nitramines decompose in nitration media, often violently, in strong sulphuric or nitric acid. In acetic anhydride or acetic acid the decomposition rate is dependent on the amount of excess nitric acid which is present.

MECHANISM OF GUANIDINE NITRATION
George F. Wright
Canadian Journal of Chemistry, Volume 30

Could someone look into this excert?

Quote:

The method was later worked out by Brian and Lamberton [38] to produce previously unobtainable nitramines. The formation of nitramines through chloramines

Urbanski

woelen - 20-6-2012 at 23:54

I tried this little experiment as well, but I obtained a white flocculent solid, on top of the liquid. As Plante1999 said, the liquid first becomes opaque and white, and after swirling a flocculent solid is formed which moves to the top of the liquid. This solid, however, is white in my case, white like snow.

@Plante1999: What kind of vinegar did you use? Was it clear colorless, or some colored and spicey stuff? In my experiment I used diluted acetic acid from a chemical supplier and I used plain household bleach for the hypochlorite. I used purified hexamine, recrystallized from so-called ESBIT solid fuel tablets. The hexamine I used has a fishy smell. Maybe the yellow color you observed is due to some impurity?

plante1999 - 21-6-2012 at 00:15

Quote: Originally posted by woelen

I tried this little experiment as well, but I obtained a white flocculent solid, on top of the liquid. As Plante1999 said, the liquid first becomes opaque and white, and after swirling a flocculent solid is formed which moves to the top of the liquid. This solid, however, is white in my case, white like snow.

@Plante1999: What kind of vinegar did you use? Was it clear colorless, or some colored and spicey stuff? In my experiment I used diluted acetic acid from a chemical supplier and I used plain household bleach for the hypochlorite. I used purified hexamine, recrystallized from so-called ESBIT solid fuel tablets. The hexamine I used has a fishy smell. Maybe the yellow color you observed is due to some impurity?

My hexamine was from Coleman fuel tablet, 12.5% sodium hypochlorite and 10% house hold vinegar. But I think you are right since washing the product with excess water give my a white floculent solid and a yellow solution. I think the impurity is chlorinated organic since they are quite volatile, the yellow solution turn colorless in a few hour after the reaction.

AndersHoveland - 21-6-2012 at 02:45

Quote: Originally posted by plante1999

12.5% sodium hypochlorite and 10% house hold vinegar.

I think it would be much preferable not to use vinegar. While vinegar and bleach certainly can form some hypochlorous acid in solution, the acetate (from the vinegar) may be vulnerable to oxidation.

woelen - 21-6-2012 at 04:15

The vinegar is essential. Without the vinegar, no precipitate is formed at all. I tried that as well. Any weak acid will do the job, as long as it is not oxidized by the bleach. Acetic acid is suitable, it resists oxidation very well.

niertap - 8-9-2012 at 22:33

[Edited on 9-9-2012 by niertap]

Motherload - 16-9-2012 at 12:46

Well I just scored some NaNO2.
I am going to try making some trichlorohexahydrotriazine.
Plante1999 and Woelen .... Did you find any significant gas evolution or fuming besides the smell of bleach ?
Reason I ask is .... I reside in a fairly populated area with houses and lots of neighbors.
Smell of bleach .... No one cares about.
I am going to use 5% vinegar and hypo and double the amounts.
Thanks

Sydenhams chorea - 23-9-2012 at 19:49

I am somewhat disappointed. It so happens I was at the uni library digging up papers on organic reactions with hexamine. My first thoughts were how closely it resembled trichlorotriazine (cyanuric chloride), a powerful chlorination reagent which can substitute for thionyl chloride and PCl3 and has the additional advantage of being a solid.

As above mentioned compound, trichlorohexahydrotriazine, is very closely related I was hoping to find similar capabilities for ths product.

woelen - 23-9-2012 at 23:11

Quote: Originally posted by Motherload

Well I just scored some NaNO2.
I am going to try making some trichlorohexahydrotriazine.
Plante1999 and Woelen .... Did you find any significant gas evolution or fuming besides the smell of bleach ?
Reason I ask is .... I reside in a fairly populated area with houses and lots of neighbors.
Smell of bleach .... No one cares about.
I am going to use 5% vinegar and hypo and double the amounts.
Thanks

This process gives off quite some nasty smell. It is manageable, but I would not like to do it in a crowded area. There is a very peculiar smell, not like bleach, but much more pungent. It probably is due to formation of some chloro amines. The hexamine I used has a fishy smell (it always has, due to formation of trace amounts of methyl amines) and I think that the chlorination of these leads to the nasty and choking smell. You could try it on a testtube scale first (e.g. 1/10 of the amounts, used by plante1999).

Rosco Bodine - 24-9-2012 at 21:46

Quote: Originally posted by AndersHoveland

Not sure if the below relates to this topic:

Quote:

Could someone look into this excert?

Quote:

The method was later worked out by Brian and Lamberton [38] to produce previously unobtainable nitramines. The formation of nitramines through chloramines

Urbanski

This is off for AH regarding the George F. Wright article in the Canadian Journal of Chemistry here is the article pdf
http://www.nrcresearchpress.com/doi/pdf/10.1139/v52-008
and here is some information on the precursor azobisformamidine
http://www.sciencemadness.org/talk/viewthread.php?tid=8144&a...

Motherload - 25-9-2012 at 19:59

Woelen .... Thank you for the heads up.
I'll try just reacting a quarter tablet or something.
Will let you guys know what happens...
I have this weird gut feeling that only 1 or 2 out of 3 N-Cl will convert to N-NO2 by treatment with NaNO2 in MeOH.
Just seems too easy. Only one way to find out if it will work or not.

497 - 25-9-2012 at 23:09

http://www.researchgate.net/publication/27256427_Synthesis_o...

Bot0nist - 26-9-2012 at 14:51

I just reproduced the reaction with bleach and white vinigar using pure hexamine from a pyrotechnics suppliers. worked like a charm and produces a snow white product. drying now. A very fun and easy reaction. It was easy to manage, but i did notice a very pungent smell as woleon describs. Thanks guys.

[Edited on 26-9-2012 by Bot0nist]

franklyn - 27-9-2012 at 10:03

The related monomer
Chloroamine Reactions : Methylene Chloroamine
has also text on 1,3,5-trichlorohexahydrotriazine.pdf
www.sciencemadness.org/talk/viewthread.php?tid=9319&page...
You need to have access to the References section.

Yield is poorer due to perishability of chloramine precursor reagent.

From the SciMad Library Formaldehyde J. Frederic Walker page 123
When ammonium chloride and formaldehyde are added to hypochlorites.
the methylene derivative of monochloramine (CH2:NCl) is obtained in the
form of needle-like crystals.[ 21 ]
[ 21 ] J. Chem. Soc., 97, 2404-2406 (1910); Chem. Zentr., 1911, I, 236.
Cross, C. F . , Bevan, £ . J., and Bacon, W.

From the SciMad Library Formaldehyde J. Frederic Walker page 290
Reactions with Halogens and Inorganic Halides. Chlorine decomposes
hexamethylenetetramine in aqueous solution with formation of the explosive
nitrogen trichloride[ 29 ] With sodium hypochlorite, chloro derivatives are
obtained. These products are apparently unstable and may explode on storage.
According to Delepine[ 30 ], N-dichloropentamethylenetetramine, C5H10N4Cl2,
may be obtained in the form of thin leaflets by addition of a dilute sodium
hypochlorite solution to a solution of hexamethylenetetramine.
On heating to 78-82ºC, the product explodes. Leuher[ 29 ] reports a
dichlorohexamethylenetetramine (m.p. 77ºC) produced by addition of 8.4g
potassium bicarbonate and 45 cc sodium hypochlorite (72 g active chlorine
per liter) to 5 g hexamethylenetetramine in 40 cc water, claiming a yield of
77-80 per cent. A moist sample of this product prepared in the writer's
laboratory exploded violently on standing. A tetrachloro- derivative,
C6H8N4.Cl4 is claimed by Buratti[ 13 ].
[ 13 ] Buratti, R., Swiss Patent 90,703 (1921); Chem. Zentr., 1922, IV, 891.
[ 29 ] Delepine, M., Bull. soc. chim. France (3), 17,390.
[ 30 ] Delepine, M., Bull. soc. chim. France (4), 9,1025 (1911).

____________________________________________________

Substitution of the chlorine has been tried before

Some old bones _
www.sciencemadness.org/talk/viewthread.php?tid=9370#pid10889...
www.sciencemadness.org/talk/viewthread.php?tid=9370#pid10904...
www.sciencemadness.org/talk/viewthread.php?tid=9370#pid10906...
www.sciencemadness.org/talk/viewthread.php?tid=9370#pid10906...

related reference
www.sciencemadness.org/talk/viewthread.php?tid=4282&page...

If this reaction scheme can be made to work it opens
new areas of investigation for high nitrogen content
compounds such as terazole _

_ other ways to get it.
www.organic-chemistry.org/synthesis/heterocycles/tetrazoles....
http://heterocyclist.com/2012/02/13/tetrazole-synthesis-part...
http://heterocyclist.com/2012/02/15/tetrazole-synthesis-part...

________________________________________________

This is off topic , but while on the subject here is another
way to Tetrazole by way of methylenediamine precursor.

From the SciMad Library Formaldehyde J. Frederic Walker page 207
the preparation of methylenediamine salts* by the action of an excess of strong acid
on methylenediformamide at low temperatures. When 77 grams methylenediformamide
were added to 500 grams concentrated hydrochloric acid at approximately 12°C,
[ Knudsen 64 ] obtained 57 grams methylenediamine hydrochloride, CH2(NH2)2-2HCl
as a crystalline precipitate. Formic acid is obtained as a by-product of this reaction:
* Methylenediamine is of particular interest since it is the ammono- analog of
methylene glycol. Knudsen found that salts of this diamine are stable in the dry state
and, in addition to the hydrochloride, prepared the nitrate [ CH2(NH2)2.2HNO3 ]
and the sulfate [ CH2(NH2).H2S04 ] by reacting methylenediformamide with an excess
of concentrated nitric acid and 50 per cent sulfuric acid, respectively, at low temperatures.
The nitrate of methylenediamine crystallizes in prisms, which melt and then explode
when heated on platinum foil. Attempts to prepare methylenediamine itself by the action
of alkali on the hydrochloride were unsuccessful, since the pure base is apparently
unstable in the free state. However, when it is liberated in the presence of alcohol,
solutions of methylenediamine are obtained and, according to Knudsen, are sufficiently
stable for use in chemical reactions.
[ 64 ] Knudsen, P., Ber., 47, 2698-2701 (1914).

.

[Edited on 27-9-2012 by franklyn]

AndersHoveland - 28-9-2012 at 06:23

If 1,3,5-trichlorohexahydrotriazine is energetic, it makes me wonder why 1,3,5-trichloro-1,3,5-triazine (TCCA) cannot be detonated.

Adas - 28-9-2012 at 08:00

Quote: Originally posted by AndersHoveland

If 1,3,5-trichlorohexahydrotriazine is energetic, it makes me wonder why 1,3,5-trichloro-1,3,5-triazine (TCCA) cannot be detonated.

Probably the oxygen atoms instead of hydrogen can stabilise the molecule.

franklyn - 28-9-2012 at 17:06

Quote: Originally posted by AndersHoveland

If 1,3,5-trichlorohexahydrotriazine is energetic, it makes me wonder why 1,3,5-trichloro-1,3,5-triazine (TCCA) cannot be detonated.

Earth to AndersHoveland , earth to AndersHoveland ,
you're not making sense ,
circulate your air through the CO2 scrubber.

_______________________________

www.sciencemadness.org/talk/viewthread.php?tid=9486#pid11027...

Trichlorotriazine (TCT) is not TCCA , alias
- Trichloroisocyanuric acid
- 1,3,5-Trichloroisocyanuric acid
- 1,3,5-Trichloro-S-triazine-2,4,6-trione
- 1,3,5-Trichloro-1,3,5-triazine-2,4,6(1H,3H,5H)-trione
etc. etc.

While admittedly 2,4,6-Trichloro-s-triazine has a positive heat of formation
http://webbook.nist.gov/cgi/cbook.cgi?Formula=C3Cl3N3&Un...
Anything that can be written on the right side of a balanced equation for this C3Cl3N3 =>
will have a more positive heat of formation.

We've been down this road before ,
www.sciencemadness.org/talk/viewthread.php?tid=17012&pag...

in this case TCT is the trimer of Cyanogen chloride ClCN , it is even more endothermic
http://webbook.nist.gov/cgi/cbook.cgi?ID=C506774&Units=S...
this cannot explode into something else because that will have again a more positive
heat of formation , why it instead condenses into the trimer. ( clue , hint , hint )

It's not too poor an oxidizer though and may make
something approaching a bang if finely mixed with a
suitable reducing agent such as cesium.

.

Adas - 29-9-2012 at 09:46

Wouldn't it be cool to use NaHSO4 instead of acetic acid? It is stronger acid and you can get it pure (not 8% like vinegar) easily.

franklyn - 29-9-2012 at 10:37

Quote: Originally posted by Adas

Wouldn't it be cool to use NaHSO4 instead of acetic acid?
It is stronger acid and you can get it pure (not 8% like vinegar) easily.

Why would this be cool ? When white vinegar is all that is called for
and only serves as a catalytic activator. " It is a stronger acid " which
means hypochlorous acid is formed instead of the hypochlorite ion.
See _
www.sciencemadness.org/talk/viewthread.php?tid=20296#pid2520...

Commercial grade sodium bisulfate is anything but pure containing
many impurities since it is intended to unclog drains , or adjust the
pH of a pool at enormous dilution.

.

Motherload - 8-10-2012 at 18:16

Ok..
I tried to make this .... I do get a fluffy white filterate but it will not ignite !!
Does it have to be absolutely dry ?
Damp filterate with a chloramine odour just melts and smokes.. No deflagration !!
I am itching to react it with some NaNO2 and hopefully (95% sure not gonna happen) and produce RDX. (That 5% chance is worth it)
Also wont mind trying it with some NaN3 soln and have a =N-N3 bond.
Chances of that happening seem higher than -NO2 as we have cyanurictriazide but no trinitrocyanauric acid .... Loosely speaking.

Bot0nist - 8-10-2012 at 18:41

Must be very dry, and dry it fast. Mine decomposes even after a good wash into a yellow stain when left on the filter.

Motherload - 8-10-2012 at 18:53

Thanks Bot0nist.
I shall dry it ASAP.
Anyone have access to NaN3 ? If you do .... Please try a few mg qty
I will try dissolving dry filtrate in anhydrous MeOH and adding a MeOH/NaNO2 soln.

AndersHoveland - 9-10-2012 at 23:59

Quote: Originally posted by Motherload

Anyone have access to NaN3 ?

I really do not think an azide group could be substituted onto a nitrogen atom. Reacting NaN3 with 1,3,5-trichlorohexahydrotriazine would most likely just form diazomethane, or possibly a trimer thereof, in addition to liberating nitrogen gas. This would be rather dangerous.

franklyn - 11-10-2012 at 02:56

http://www.sciencemadness.org/talk/files.php?pid=260440&...

Just as the azidamine of methylene can reform into terazole ,
a trimer of tetrazole can result from 1,3,5-triazidohexahydrotriazine.

Tetrazole Trimer.gif - 2kB

In the same way Cyanuric Triazide is isomeric with Benzotrifuroxan
www.sciencemadness.org/talk/viewthread.php?tid=4094#pid13473...

known organic azide derivations
http://www.sciencemadness.org/talk/viewthread.php?tid=217#pi...

________________________________________________

This post is a summary of the various ideas by forum members and myself on
the notion of substituting labile Chlorine in the above shown Triazine analogs
with an Azide or Nitro group by metathesis with an alkali salt such as Sodium
Azide or Sodium Nitrite. Considering each in turn.

TCCA

http://www.sciencemadness.org/talk/viewthread.php?tid=4282&a...
1,3,5-Trinitro-1,3,5-Triazine-2,4,6-trione , or triketo RDX is apparently according
to member PHILOU Zrealone a known compound
http://www.sciencemadness.org/talk/viewthread.php?tid=4282&a...
niertap unknowingly suggested the same thing here _
http://www.sciencemadness.org/talk/viewthread.php?tid=21453
The Azide variant has been unsuccessfully attempted by Formatik
http://www.sciencemadness.org/talk/viewthread.php?tid=21453#...

Solubility of TCCA in water is meager and enables hydrolysis of any resulting
product which is the central problem with producing what amounts to an
acid anhydride , necessitating use of non aqueous solvation.

Trichlorohexahydrotriazine

Axt first broached the present topic in this thread
http://www.sciencemadness.org/talk/viewthread.php?tid=9370
The_Davster observed that =>
http://www.sciencemadness.org/talk/viewthread.php?tid=9370#p...
http://www.sciencemadness.org/talk/viewthread.php?tid=9370#p...
The reference cited from
Chemistry and Technology of Explosives vol 3 by Urbanski

TCT

The_Davster
" Not to get off topic, but the reaction of cyanuric chloride and nitrite was tried and failed ?
...fascinating, I had always wondered about that reaction."
http://www.sciencemadness.org/talk/viewthread.php?tid=9370#p...
The intended Trinitrotriazine has not resulted by this means , however
Cyanuric triazide is well known and readily prepared this way =>
http://www.sciencemadness.org/talk/viewthread.php?tid=4094#p...
Often the expected or rather hoped for result never does and something
unanticipated occurs instead. This paper notes different results occur depending
on the solvent and reaction conditions. For example TCT ( here called CC) with NaN3
Recent Applications of 2,4,6-Trichloro-1,3,5-Triazine & its Derivatives in Organic Synthesis
www.sciencemadness.org/talk/files.php?pid=94971&aid=3046
Carbon Nitride was synthesized by heating Cyanuric Chloride and Sodium Azide
in benzene at 220 ºC, which forms high quality nanotubes 14 ( Fig. 4 ) ,
by self assembly. Guo, Q.; Xie, Y.; Wang, X.; Zhang, S.; Hou, T.; Lv, S. Chem.
Commun. 2004, 26–27.

.

[Edited on 12-10-2012 by franklyn]

franklyn - 15-10-2012 at 00:41

Here 's a thread that relates to TCCT , concluding there is
scant prospect of successfully obtaining the hypothetical
1,3,5-Trinitro-1,3,5-Triazine-2,4,6-trione
http://www.sciencemadness.org/talk/viewthread.php?tid=18690#...

.

That's TCCA , sorry about that

franklyn - 16-10-2012 at 08:10

PHILOU Zrealone - 19-10-2012 at 05:06

The unstability of NN'N''-trichloro-s-triazane is due to the presence of hydrogen fuel to burn aside on the carbons.
See the tread on chloramines by Axt.

The chlorine atoms are reactive chlorine atoms of the kind Cl(+) (due to the electronegativity of the N atoms), like what is found in hypochlorites and chloramines.
HOCl --> HO(-) + Cl(+)
A contrario, cyanuric chloride displays chlorine atoms of the kind Cl(-) because they are fixed on a carbon and are thus exchangeable with negatively charged anions (like OH(-) to get cyanuric acid)).

This might explain that nitrite anion can't subsitute easily the chlorine atom, but that HNO3 (what is a NO2(+) generator) is able to convert it into nitramine.

One can think that nitroniums salts or F-NO2 will work because F is so électronegative that only NO2(+) can result. Also for the perchloryl one must use F-ClO3

Maybe by inversion of polarity NN'N''-trifluoro-s-triazane may react with NaNO2 or NaClO3...

Maybe that AgNO2 (owing to AgCl precipitation as driving force) will lead to some conversion with NN'N''-trichloro-s-triazane but both reactants are not very soluble and the solvent is the problem because it must be unreactive towards positive chlorine.
Also the nitrite-nitro rearrangement is 50/50 and if R2N-NO2 is stable R2-N-O-N=O shouldn't be...thus leading to unstable parts in the molecule... with spontaneous decomposition reactions.

[Edited on 19-10-2012 by PHILOU Zrealone]

[Edited on 19-10-2012 by PHILOU Zrealone]

plante1999 - 28-6-2013 at 07:01

I just made a test, and it seams that the chlorine can't be substitued by nitrite. I made a solution of the 1,3,5-trichlorohexahydrotriazine in methanol, and did the same with sodium nitrite. When mixed, the two solution did, well, nothing. They simply looked like a normal solution. I also did a test with silver nitrite, without succes etheir.

A warning note for 1,3,5-trichlorohexahydrotriazine, I had stored a gram of it in a semi-closed vial for the night. When I came back in the moring, the vial had closed for some reason, a pitch black material was on the bottom of the vial, and when opened, and hydrochloric acid smell was made. Decomposition should look something like this:

2C3H6N3Cl3-) 6HCl + 3N2 + CxHx+y + yC

AndersHoveland - 28-6-2013 at 10:09

Quote: Originally posted by plante1999

I just made a test, and it seams that the chlorine can't be substitued by nitrite. I made a solution of the 1,3,5-trichlorohexahydrotriazine in methanol, and did the same with sodium nitrite. When mixed, the two solution did, well, nothing. They simply looked like a normal solution. I also did a test with silver nitrite, without succes either.

Most likely, the trichlorohexahydrotriazine just oxidized the nitrite to nitrate. Aqueous solutions of these N-Cl compounds act as oxidizers, because of partial hydrolysis to hypochlorous acid (there is equilibrium in the solution). You would have to try the substitution reaction with a non-aqueous solvent. (usually I would recommend DMSO, but I recently read that DMSO violently reacts with acetyl chloride, so this solvent may not work here)

papaya - 28-6-2013 at 11:32

Anders he used methanol. But I don't get what one should expect from Cl+ + Ag+ --> ??? type reaction, as the chlorine is positive here. What if you tried xxN-Cl + HONO2 -> xxN-NO2 + HOCL reaction, is there a chance for this to happen?

plante1999 - 28-6-2013 at 11:45

It is not exactly my type of thing to try many reaction to make a new process for energetic material synthesis.

People where asking me to try it, so did I, but I think I completed my part of the conctract, finding nitrite, remaking the chloramine etc...

papaya - 28-6-2013 at 11:54

Ok,ok, I asked to see what the more competent people think about my suggestion, but if you have nitric acid you could try that (may be quite dangerous, little amounts only). And if you have TCCA also to try it directly with nitric in the hope to get keto-RDX .

AndersHoveland - 28-6-2013 at 22:02

It might be prohibitively dangerous, but I have read reactions where the solution is heated, severing the N-Cl bond, and leaving radicals that can then react. I will describe this references at the bottom of this post.

I am not sure if a R₂N• radical could react with NO2 to make a nitramine.

It is more complicated than I care to explain, but there is more reason to believe this might work with trichlorohexahydrotriazine than with TCCA (and even if it did work with TCCA, there would just be immediate hydrolysis to the free nitramine).

References:

R.A. Carboni, J.C. Kauer, J. American Chem. Society, volume 89, p2633, (1967) describes a reaction where an azide group on an organic scaffold is decomposed, leaving behind a nitrogen radical that was then able to react the central (2-) nitrogen of a 1(N)-substituted 1,2,3-triazole. What is remarkable about this is that the nitrogen atom becoming bonded was already in a 3-valence state. But just as tertiary amines can still be oxidized to form the N-oxide, so too here was the nitrogen atom in the aromatic ring able to bond with an additional nitrogen radical.

In another reaction, N,N-dibromo-tert-butylamine, tBu-NBr₂, was heated, driving off the bromines and leaving a nitrogen radical that was able to react with another nitroso compound to leave an azoxy bridge.

tBu-N• + O=N-R --> tBu-N=N(-O)-R

(sorry, I do not have the exact reference for this reaction, this is just from my notes, I think it was A. M. Churakov published in Tetrahedron), but I remember reading in a paper another investigator questioned the procedure as originally described by the original russian investigators)

I think chlorine would also work instead of the bromine here.

In another investigation, they describe the preparation of dibromoamines in situ from tribromocyanuric acid and the amine. Obviously the HOBr hydrolyzes off the TBCA and preferentially condenses with the amine, could be described as an equilibrium reaction. I just wanted to point out that, even though it can be considered an "oxidation reaction", the bromine atoms are not actually oxidizing the amine.

Sorry, I do not like elaborating on long tangents, but I also want to preemptively address potential misconceptions and questions in a single post. It can be frustrating having to explain everything later, and I would prefer nothing be misunderstood.

Also, if you are going to attempt N-Cl nitrite substitution reactions, I would recommend propylene carbonate as an ideal solvent, since it can dissolve ionic compounds, and would also be unreactive here.

[Edited on 29-6-2013 by AndersHoveland]

franklyn - 29-6-2013 at 02:27

@ plante1999

Examining the supposed reaction we see that the formation of NaCl is favored by
the enthalpy of reaction being negative. This is determined from the bond energies.

Starting materials total bond energies is 125 kcal _
Chloramine : H2N-Cl , 60 kcal
Sodium Nitrite : Na-ONO , 65 kcal

Reaction result bond energies is 139 kcal _
Nitramine : (CH2)2N-NO2 , ~ 41 kcal
Sodium Chloride : Na-Cl , 98 kcal

A catalyst seems to be called for to reduce the activation energy. The Problem
as I see it , is that NaONO is soluble as ions whereas the organic Chloramine is
solvated as a covalent molecule , so there is no basis for metathesis.

Electronic character of Sodium Nitrite , NaONO
Electronegativity Na = 0.9
Electronegativity -O = 3.4
the difference is , 3.4 - 0.9 = 2.5 > 2 , an ionic bond

Electronic character of Chloramine , =N-Cl , a covalent bond

Electronic character of Sodium Chloride , NaCl
Electronegativity Na = 0.9
Electronegativity Cl = 3.0
the difference is , 3.0 - 0.9 = 2.1 > 2 , an ionic bond

However _

Electronic character of , Magnesium Chloride , MgCl2
Electronegativity Mg = 1.3
Electronegativity Cl = 3.0
the difference is , 3.0 - 1.3 = 1.7 < 2 , a polar covalent bond

Electronic character of Magnesium Nitrite , Mg(NO2)2
Electronegativity Mg = 1.3
Electronegativity -O = 3.4
the difference is , 3.4 - 1.3 = 2.1 > 2 , an ionic bond ( although weaker than with sodium )

MgCl2 and Magnesium Nitrite are soluble in Methanol

The addition of some MgCl2 ( de-icing salt ) to the solution will procede as follows _

2 NaNO2 + MgCl2 => 2 NaCl + Mg(NO2)2 , , 2(-98 ) - (-154 ) = - 43 kcal
MgCl2 = ∆Hf -154 Kcal/mol
NaCl = ∆Hf - 98 Kcal/mol

Encyclopedia of the Alkaline Earth Compounds from page 210[/size][/font]
http://books.google.com/books?id=yZ786vEild0C&pg=PA210&a...

Magnesium Nitrite is not stable and re-formation of MgCl2 favors exchange
with the organic Chloramine. Mg(NO2)2 + 2 ( =NCl ) => MgCl2 + 2 ( =NNO2 )

Starting materials total bond energies is 102 kcal _
Chloramine : H2N-Cl , 60 kcal
Magnesium Nitrite : NO2Mg-ONO , 42 kcal

Reaction result total bond energies is 118 kcal _
Nitramine : (CH2)2N-NO2 , ~ 41 kcal
Magnesium Chloride : ClMg-Cl , 77 kcal

MgCl2 does form a complex with Methanol

Magnesium Chloride forms hydrates with 2, 4, 6, 8, and 12 molecules of water.
Both the anhydrous and hexahydrate salt are deliquescent and need to be stored
under dry cool conditions. Magnesium Chloride is very soluble in water 54.6 gm
100 ml, and the hexahydrate is the only stable hydrate between 0 and 100 °C.
The anhydrous salt is also soluble in Methanol ( 20.4 gm at 60 °C) and Ethanol
(15.9 gm at 60 °C). On cooling , these solutions crystallize the alcoholate addition
compound , such as Magnesium Chloride hexamethanolate , MgCI2 •6CH30H ,
and Magnesium Chloride hexaethanolate , MgCI2 •6C2H5OH

The Chemistry and Technology of Magnesia from page 216
http://books.google.com/books?id=0ShuV4W0V2gC&pg=PA216&a...

Heating MgCl2•6H2O yields the basic salt, Mg(OH)Cl
MgCl2•6H2O => Mg(OH)Cl + HCl + 5H2O

Pure anhydrous chloride can be prepared by heating the double salt
MgCl2•NH4Cl•6H2O

MgCl2•NH4Cl•6H2O => MgCl2•NH4Cl + 6H2O
Ammonium Chloride sublimes on further heating , leaving pure anhydrous MgCl2
MgCl2•NH4Cl => MgCl2 + NH4Cl

— Some observations _

An issue that is troubling is that the bond energy of Chloramine is 60 Kcal ,
19 Kcal more than the Nitramine bond of 41 Kcal , an endothermic substitution.
One can suppose that the solution temperature will drive the reaction.

The best solvents for RDX are Dimethyl Formamide , Acetonitrile , Acetone , in
descending order. RDX is sparingly soluble in methanol , so it and everything else
it seems will drop out of solution upon completion of the reaction , also driving
the reaction to completion.

Stability of Choramines is pH dependent. Acid low pH accelerates decomposition.
The problem then is that nitrous acid is formed from the nitrite salt and this reacts
with the Methanol to produce Methyl Nitrite. pH needs to be neutral or basic.

The application of a lewis acid such as Aluminum Choride , Zinc Chloride , does
facilitate breaking covalent bonds , but in the present case it will react first with
the ionic Sodium Nitrite just as well as the Magnesium Choride wil. But these
have a lower enthalpy of reaction and then inhibit the reaction from going forward.

Regarding other Nitrites , electronegativity of Silver Ag 1.93 and Copper Cu 1.9
exhibit pronounced polar covalency in their bonds. A low activation energy is the
likely reason Silver Nitrite at least has found success in this type of reaction. The
use of Copper in this scheme might be worth investigating , since Copper Nitrite
is not a stable compound , with Nitrogen dioxide faintly bound to it. Copper Sulfate
can be tried used instead of Magnesium Chloride.

Finally the use of solvent or more usefully a mixture of solvents is well known to
enhance or inhibit reactions. Dimethyl Sulfoxide is unsurpassed for aiding in the
placement of a nitro group onto an organic compound from a Nitrite salt. This
is so far only cited for carbon bonds , and is essentially a Finkelstein SN2 type
reaction.

.

[Edited on 29-6-2013 by franklyn]

AndersHoveland - 29-6-2013 at 02:56

Quote: Originally posted by franklyn

The Problem
as I see it , is that NaONO is soluble as ions whereas the organic Chloramine is solvated as a covalent molecule , so there is no basis for metathesis.

The N-Cl bond is weaker than the C-Cl bond. Chloramines can be protonated which leads to easy hydrolysis of the chlorine off the amine.

Trying to perform a substitution reaction in this situation has several potential problems, but getting the chlorine to come off is not really one of them.

One investigation mentions that nucleophilic substitution on chloramine to form chloride ions proceeds at a rate more than 100 times that of chloromethane (which may still be rather slow, considering that the hydrolysis of chloromethane with water takes around a whole year)
"Gas phase reactions of NH2Cl with anionic nucleophiles: nucleophilic substitution at neutral nitrogen", Roustam Gareyeva, Shuji Katoa, Veronica M. Bierbauma

Organic Chemistry of Explosives, p234, claims:

Quote:

Metathesis reactions between N-chloramines and silver nitrite in alkaline solution are reported to give the silver salt of the corresponding primary nitramine.

There are some other threads in this forum about nitrogen trichloride, where you can read about how it reversibly hydrolyzes at low pH to ammonium ions and hypochlorous acid. At higher pH, it can hydrolyze to chloramine, though such solutions can be unstable if not highly diluted. It is much too complicated to try to get into the details of the reaction here, but the point is that the N-Cl bond can easily be hydrolyzed.

There has been similar discussion on this forum several times before. Typically what happens is some topic is being discussed, and then some member brings up this idea of making RDX by metathesis with NaNO2 or AgNO2 . I have seen it happen at least 3 times before. Someone should really start a specific thread for this idea.

I would suggest trying to react trichlorohexahydrotriazine with sodium nitrite in the absence of water, using propylene carbonate as the solvent. If there is any water, the nitrite will just be oxidized.

Even using alcohol, there might be undesirable reaction. Methanol apparently seems to be fairly inert to TCCA, but I would not completely discount the possibility of the solution containing some equilibrium of methyl hypochlorite, which could potentially be a reaction pathway for the oxidation of the nitrite. And I am not even sure how soluble NaNO2 is in alcohol.

[Edited on 29-6-2013 by AndersHoveland]

papaya - 29-6-2013 at 12:42

Quote: Originally posted by AndersHoveland

I would suggest trying to react trichlorohexahydrotriazine with sodium nitrite in the absence of water, using propylene carbonate as the solvent. If there is any water, the nitrite will just be oxidized.

Again this, then explain me how are you going to make Cl- from Cl+ (in chloramine, which when hydrolyzed with water gives HOCL, again Cl+ here) without some sort of redox reaction, I mean no exchange is possible to form AgCL or am I missing something?

[Edited on 30-6-2013 by papaya]

Motherload - 5-5-2014 at 11:50

Sorry to bring up and old thread..
Does anyone have yields on this ?
If the efficiency is high on the conversion of hexamine to trichlorohexahydrotriazine then the reaction with NaNO2 should go to completion forming R-Salt.
As previously speculated .... I don't see RDX forming.

kratomiter - 16-8-2015 at 02:58

Recently I try to synthesize 1,3,5-trichlorohexahydrotriazine without success, using NaDCC instead of hypochlorite. Somebody knows why it doesn't work?
Without any acid (basic pH in mix, no hypochlorous acid formed) I get a white, non-flammable precipitate. Using acetic acid, just hexamine decomposition (strong formaldehyde odor).

njl - 15-1-2021 at 08:10

As mentioned above, the electrophilic Cl+ is needed for this reaction. I'm guessing NaDCC is less labile than OCl- when it comes to generating Cl+. This reaction and product seem useful though. If the product can in fact generate radical species maybe it would be useful as a chlorinating agent. It would probably give triazine with elimination of HCl.

It's a shame that the NaNO2 displacement doesn't work. Maybe a more typical nitration with H2SO4/HNO3 would work, since the electrophilic NO2+ is generated. Alternatively, directly gassing a heated solution of the product with NO2 might work, with the release of chlorine gas.

clearly_not_atara - 15-1-2021 at 15:15

Quote:

It would probably give triazine with elimination of HCl.

This was the first thing I thought of when I read this thread. Unsubstituted s-triazine is a difficult target; controlled oligomerization of hydrogen cyanide has been done, but has obvious downsides.