Sciencemadness Discussion Board

3 - Nitroanilinediazonium perchlorate and derivatives

garage chemist - 20-2-2005 at 04:24

In the paper (referring to thread 3432), why didn't they mention
3-nitroanilinediazonium perchlorate?
It's a very powerful primary, 3,5mg (IIRC) are enough to detonate PETN.
There is a very good thread about it on the E&W, named "My favourite primary".

The production of the compound is very simple, if you have 3-nitroaniline, NaNO2 and perchloric acid.

3- nitroaniline could be prepared by nitrating methyl benzoate to the 3-nitro derivate, then amidation to nitrobenzamide and finally hofmann degradation to nitroaniline.

The 3,5-dinitro is of course even more powerful, but its production is more difficult, requiring nitrosyl sulfuric acid for the diazotation.


[Edited on 7-6-2005 by chemoleo]

Axt - 20-2-2005 at 05:49

Urbanski/COPAE make mention of nitrobenzenediazonium perchlorate but say its too unstable, and hygroscopic for commercial use. It's patent GB27198 contradicts this by saying its not susceptible to moisture, and that actually its mononitro is the prefered initiating explosive. Personally I'll believe any reference over a patent. So, yeh. initiating ability isn't the most important aspect of primary explosives, stability comes first, especially for commercial use.

I've been trying to find a solvent that will allow the precipitation of a nitrobenzenediazonium-MEDNA salt, which should have interesting properties, but no luck as yet.

A one pot diazotization of nitroaniline & acetone with Nitrogen oxide would be very convenient. However it precipitates as some diazo coupled molecule between the nitroanilines. Creating an intermediate salt such as a nitrate that remains soluble. By including HNO3 in the reaction vessel may be the way to go. but excess HNO3 and no MEDNA will form. What is a solvent for nitroaniline nitrate?

NOTE: I have no idea if a diazonium -MEDNA salt is even possible, but I think its worth trying.

Jome - 20-2-2005 at 08:07

Couldn't H2SO4 and then Ba(ClO4)2 be used instead of perchloric acid?

garage chemist - 20-2-2005 at 08:39

Quote:
Originally posted by Jome
Couldn't H2SO4 and then Ba(ClO4)2 be used instead of perchloric acid?


Yes, but barium sulfate would precipitate.

Barium perchlorate soln. should first be mixed stochiometrically with dilute H2SO4 and the formed barium sulphate filtered. The filtrate is dilute perchloric acid, which can be concentrated to 72% by boiling it down until it fumes, just as you would do with sulfuric acid.

Did you make the Ba(ClO4)2 yourself? If yes, how?

Mumbles - 20-2-2005 at 20:11

The easiest way to make Barium Perchlorate would probably be ammonium perchlorate and Barium carbonate or hydroxide. It is coming down in price from pyro suppliers. It can be had for about $5-$10 a pound, or less than $2 a pound if you happen to want a drum of it and have a BATF licence.

garage chemist - 21-2-2005 at 09:47

Yes, ammonium perchlorate is needed, thats the problem.
I just realized how useless KClO4 is as a precursor for other perchlorates...

Jome - 22-2-2005 at 16:11

I dont follow, how could NH4ClO4 be made with BaCO3? Ba(ClO4)2 seems quite soluble.

Ba(ClO4)2 here is f*ing expensive, so if im getting it, I'll have to make it myself.

Could HClO4 be concentrated to 72% by running it in a vacuum dessicator?

EDIT: wrong word.

[Edited on 23-2-2005 by Jome]

Mumbles - 23-2-2005 at 19:59

Perhaps barium hydroxide would be better. In either case Ammonium hydroxide or carbonate both decompose in boiling water. I chose barium carbonate because it is very cheap.

And yes, I assume Barium Perchlorate to be quite soluble. I can't find any values, but if the chlorate is soluble(which it is), the perchlorate is always souble too. Actually, Barium Perchlorate would make and excellent pyro chemical. I may have to make a bit to just test it out as a green colorant.

3-nitroanilinediazonium perchlorate?

Bert - 23-2-2005 at 20:39

Quote:

Actually, Barium Perchlorate would make and excellent pyro chemical.

Yes. Both Barium and Strontium perchlorates were used to some extent in pyrotechny, particularly before WWII. The modern tendency is to use Barium or Strontium nitrate with an admixture of Potassium perchlorate and a high temperature fuel such as magnesium/Aluminum alloy.

nitrobenzenediazonium experience

pdb - 30-3-2005 at 04:33

Axt: I agree patents are not always trustable. However, my own experience with this compound (which I have been using for more than 15 years) does match the characteristics you mentioned:

- it is not hygroscopic: it is still free flowing after months and years of storage in an open-air case

- I prepared the diazoperchlorate salt of dinitroanilin, and found out it would deflagrate without DDT in tiny amounts, when nitrobenzenediazonium does detonate very violently. However, the results (dents on Al plate) are similar when considering hand-pressed 20mg charges in a straw.

I've never tried preparing a diazonium-MEDNA salt. But why not ?

Axt - 30-3-2005 at 15:15

I too made the diazo-perchlorates (after reading your thread), derived from aniline, 1,3-phenylenediamine, 3-nitroaniline and 2,4-dinitroaniline. I put a movie up <a href="http://geocities.com/roguemovies8/">here</a>, which parallel your experiances with the mono/dinitro salts. The dinitro only flashes where the others detonate in the quantities used in the movie. The mononitro also required more then the two "non-nitros" to DDT unconfined.

Though I did find them all susceptable to direct sunlight. the aniline/phenylenediamine/nitroaniline derivatives, which were white turned a medium brown and the dinitro went dark browny orange. No change was seen if they were dried inside (Thats @ sunny ~25°C weather).

The benzene(bis)diazonium perchlorate was detonated by placing it on pine wood board and tapping it lightly with the back of a spoon and the benzenediazonium perchlorate detonated by itself when dried in the sun (I didnt place the bis(diazonium) salt in sun). They are both horridly sensitive. The precipitated bis(diazonium) salt actally started crackling and popping when the reaction vessel was swirled! You can imagine how it scared me :)

Quote:
- it is not hygroscopic: it is still free flowing after months and years of storage in an open-air case


Mine was never free flowing, and you mentioned on E&W that yours isn't either? To be "distinctly hygroscopic" only requires a few percent weight change, but I agree that its not going to draw enough moisture in to dampen its extreme "detonatability".

[Edited on 30-3-2005 by Axt]

Thread splitting!

chemoleo - 30-3-2005 at 17:04

Very interesting, I wonder how melamin would behave... :D
I doubt it'd survive diazotation.

Anyway, I split the above posts from the DAHA primary thread, they don't really belong there.

Axt - 30-3-2005 at 18:00

Its actually hard enough to get a bis(diazonium) or "tetrazonium" salt, as it requires large concentrations of relatively concentrated acids.

I'll attach two references, one for p-phenylenediamine, and one for m-phenylenediamine. I used the synth given for the p-phenylenediamine only later did I find the reference to same authors attempt at the m-phenylenediamine derivative. He blew himself up, not suprising considering the quantities he was using combined with electric stirring.

<a href="http://ww1.altlist.com/~58717/pulse.altlist.com/banners/benzenetetrazonium-perchlorate.pdf">Tetrazotization of p-Phenylenediamine in Hydrochloric Acid and Perchloric Acid</a>

<a href="http://pulse.altlist.com/banners/benzenebis(diazo)-perchlorate.pdf">A New Synthesis of m-Phenylenedihydrazine via Tetrazonium Salt</a>

First I used only HClO4, but I decomposed the precipitate by trying to wash it with water, then I used the HCl and precipitated with HClO4, with no washing to limit the quantity of HClO4 needed.

Also, heres some references to diazoethoxane, which is the ester of hyponitrous acid, which dimerises through a diazo group. A liquid primary of no practical interest (decomposes), but still interesting.

<a href="http://pulse.altlist.com/banners/oxylamines.pdf">Synthesis of oxylamines</a> (precursor of hyponitrous esters warning-2.32MB in German)

<a href="http://pulse.altlist.com/banners/hyponitrous-esters.pdf">Preperation of Esters of Hyponitrous Acid</a>

[Edited on 31-3-2005 by Axt]

pdb - 31-3-2005 at 00:15

Quote:

Mine was never free flowing, and you mentioned on E&W that yours isn't either?


That's a matter of vocabulary; I mean together:
- still "free-flowing" after months/years storage, which shows it didn't capture moisture
- not enough "free-flowing" to make caps preparation an easy routine.
Sorry for the confusion.

BTW how did you prepare the bis(diazonium) salt ?

Axt - 31-3-2005 at 01:49

Quote:
Originally posted by pdb
BTW how did you prepare the bis(diazonium) salt ?


Diazotisation of phenylenediamine, Which is the same thing as the tetrazonium salts in the references above, its usually named "bis(diazonium)" which I think is more descriptive of its structure.

<center><img src="http://www.sciencemadness.org/scipics/axt/benzenebis(diazonium)-perchloratex.jpg"></center>

Heres what I did anyway, essentually its the synth given for p-phenylenediamine above, just reduced quantities, and precipitating from the chloride with perchloric acid, to save on HClO4. Note that it can't be washed with water, diluting the acid results in immediate decomposition to dark brown crud (though still exposive!).

Into 0.5g 1,3-phenylenediamine under 5ml water is added 0.5g HCl and stired until dissolved. Into this is then added 50g 32% HCl, and temperature reduced to -10°C which results in a fine suspension of phenylenediamine dihydrochloride. Maintaining the solution at -10°C a solution of 0.8g sodium nitrite in 5ml water is added over the course of 30 minutes. The solution of now benzenebis(diazonium) chloride still holds some solids, these were then filtered out. With the temperature brought back down to -10°C a solution of 2g 70% perchloric acid in 5ml water was added slowly with swirling of the solution, almost immediately a suspension of the diazo perchlorate formed which started crackling and popping as the solution was swirled. The solution was cautiously poured into a filter paper. A small portion of the precipitate was placed on some absorbent paper to dry and the rest disposed of by watering it into the lawn.

I only aquired the syth of for the m-phenylenediamine derivative after doing the above. Thats why I didnt follow it, though its much the same.

[Edited on 9-12-2005 by Axt]

Axt - 12-5-2005 at 11:01

Is anyone capable of translating the Russian text in the comparison table in this patent? What are the 6 explosives that are compared?

<a href="http://ww1.altlist.com/~58717/pulse.altlist.com/banners/diazo-perchlorate-russian.pdf">russian patent 2080320</a>

artem - 14-5-2005 at 20:10

This link don't work:( If you give me full text, I'll translate it.

Rosco Bodine - 14-5-2005 at 20:44

Try this attached file

Attachment: RU2080320 diazo-perchlorate-russian.pdf (128kB)
This file has been downloaded 1026 times


artem - 16-5-2005 at 22:44

It seems to me suspicious the minimal mass for tetryl - table 3 (for 2.4-dinitrodiazo it equal the value for TNT, table 2)
translated tables look here:

Attachment: RU2080320.doc (34kB)
This file has been downloaded 1004 times


Axt - 18-5-2005 at 23:05

Thanks Artem, The 2g MF having the same effect on lead plate as the 1.5g MF/RDX dets doesn't look right either, especially on the basis of weight.

Patents have no reason at all to give unbiased & correct results. Careful pulling "facts" from them.

artem - 19-5-2005 at 09:25

I think, 90 % information in this patent are not the data of authors, and was collected from different sources. Novelty as far as I have understood, that 2,4-isomer is the most suitable, and its properties were studied by authors seriously.
As for detonators with 2gMF and 1.5gMF+Tetryl/RDX -most likely, as they are(were) a batch production, there were a standard test (for example, the detonator should punch 5mm lead). And all of them punch. But for a subj authors were not too lazy and have measured a MAXIMUM depth.

Axt - 19-5-2005 at 18:18

Yep, I understand Artem. So one can say dinitrobenzenediazonium perchlorate = 7mm, the others = >5mm :P Thus table 1 provides no useful info whatsoever!, other then its at least comparable to the other dets.

Thanks.

a couple of patents for the m-nitroaniline precursor

Rosco Bodine - 18-1-2007 at 11:31

Should probably accompany these references with
descriptions of the synthesis for dinitrobenzene
and posibly also for dinitrotoluene .....
which I will try to find and provide later .


Also I think these reduction methods are possibly
applicable to the production of picramic acid ,
and also to reductions of other nitro compounds .

I think the use of a solvent like xylene could also be
useful in polysulfide reductions where the reduction
is done at lower pH and free sulfur is allowable as
a byproduct .....since the sulfur should dissolve into
the xylene ( or toluene ) , while amino derivative
of the nitroaromatic would be soluble in the aqueous phase .
This would tend to produce a purer product from reductions
using polysulfides , where occluded sulfur or a microfine
colloidal " milk of sulfur " which passes right through a filter
paper too easily as a physically inseparable byproduct can be a troublesome impurity in the reduction product .

The patent also gives some further insight into a ratio
of sulfur to sodium which is found to be useful as a polysulfide , also in a reported quantity which gives good
yields for this type of reduction . This is a matter which
I looked at to some extent , evaluating the formation and
usefulness of a polysulfide made directly from the highly exothermic reaction of solid NaOH and sulfur which forms a
melt , reacting quickly to form a polysulfide reagent then
gradually diluted with perhaps four times its volume water ,
and used in reduction of sodium picrate to sodium picramate
under alkaline conditions .

[Edited on 18-1-2007 by Rosco Bodine]

Attachment: US1878950 Sodium Polysulfide reduction of nitroaromatics.pdf (316kB)
This file has been downloaded 755 times


Rosco Bodine - 18-1-2007 at 11:37

This second patent is a variation which utilizes ferrous
sulfate in a way which I have not seen described before ,
interesting since ferrous sulfate is itself a reducing agent
evidently modified by conversion to ferrous sulfide upon
addition of an alkaline sulfide . I'll have to study this method
further to understand this better why this is done , probably better yield or selectivity is achieved by the combination
of reductants applied together in a way that one reagent
augments or attenuates the action of the other .

Attachment: US1689014 Synthesis of m-nitroaniline and other reductions of nitroaromatic.pdf (185kB)
This file has been downloaded 943 times


Rosco Bodine - 19-1-2007 at 07:29

Following is a one pot synthesis of what is a good yield of
reasonably high purity "technical grade" m-dinitrobenzene under mild conditions .

Attachment: US2643271 m-dinitrobenzene.pdf (190kB)
This file has been downloaded 952 times


Rosco Bodine - 19-1-2007 at 07:32

Attached is a simple method for purification to reagent grade
of the technical grade m-nitrobenzene from the nitration above .

Attachment: US1665005 alkali purification of m-dinitrobenzene.pdf (201kB)
This file has been downloaded 769 times


another sulfide reduction reagent

Rosco Bodine - 24-1-2007 at 08:03

Earlier a patent , US1689014 , was posted concerning the use of ferrous sulfide produced in situ from addition of sodium sulfide or sodium polysulfide to a solution of ferrous sulfate , as a selective reducing reagent for nitroaromatic compounds .

A similar later patent has been found describing the analogous usefulness also for manganous sulfide , produced the same way as described in the earlier patent for the ferrous compound .

US1765660

[Edited on 24-1-2007 by Rosco Bodine]

Attachment: US1765660 Manganous Sulfide reduction of nitroaromatics.pdf (94kB)
This file has been downloaded 677 times


2,4-dinitroaniline

Rosco Bodine - 7-10-2010 at 16:09

Here is a synthetic method for 2,4-dinitroaniline via dinitrochlorobenzene reacted with urea.

Recently I have suggested in the tetrazole thread a possible usefulness for the 2,4-dinitrobenzene diazonium perchlorate in combination or mixture with other energetic perchlorates.



Attachment: US1752998 2,4-dinitroaniline via 2,4-dinitrochlorobenzene plus urea.pdf (66kB)
This file has been downloaded 620 times


3-nitroanaline, nitrous acid with aniline

AndersHoveland - 29-7-2011 at 14:37

The 3-nitroaniline is an important precursor for the preparation of diazoperchlorate-3-nitroaniline.
NO2—C6H4—N[+]ΞN ClO4[-]


From 3-chloronitrobenzene

Apparently, 3-chloronitrobenzene can be prepared by the electrophilic chlorination of nitrobenzene with chlorine in the presence of ferric chloride FeCl3.
Varnholt, J. prakt. Chem. (2) 36, 25 (1887).
The reaction was also mentioned in another forum
http://www.thenakedscientists.com/forum/index.php?topic=1844...
Unfortunately, nitration of chlorobenzene does not result in 3-nitroaniline.

Both 2- and 4-chloronitrobenzene react with anhydrous ammonia at 200degC to form the corresponding nitroaniline, whereas 3-chloronitrobenzene did not react under these conditions.
V. A. Tarasevich, M. F. Rusak, A. B. Tereshko, and N. G. Kozlov, Zh. Obshch. Khim. 67, 671 (1997); Chem. Abstr. 128, 2701275r (1998)

In the presence of the iodide ion, dry NH3, dissolved in pure alcohol, reacts rapidly with 2- and 4-chloronitrobenzene at 100degC. 1-chloro-2,4-dinitrobenzene reacted with alcoholic ammonia at room temperature. V. A. Tarasevich, M. F. Rusak, A. B. Tereshko, and N. G. Kozlov, Zh. Obshch. Khim, 67, 457 (1997); Chem. Abstr., 128, 270275r (1998)

So basically, nitrobenzene would have to halogenated with bromine in the presence of ferric bromide FeBr3 (in the absence of water obviously) to 3-bromonitrobenzene, which could then be reacted with anhydrous ammonia at room temperature to form 3-nitroaniline, since bromine substitutes off much more easily.

for readers without knowledge of organic terminology, the different structures of the isomers of nitroanaline can be seen:
https://7007983270460794965-a-1802744773732722657-s-sites.go...


Nitration of Aniline

Nitration of analine with the usual mixture of concentrated nitric/sulfuric acids is very problematic, because of both charring, and oxidation of the analine to nitrobenzene
(using a large excess of sulfuric acid helps minimize formation of nitrobenzene). It is true, however, that low yields of 3-nitroanaline (without significant formation of other isomers) can be obtained, however. Even the use of 60% nitric acid can result in some charring of analine, and this can be partially reduced by cooling the nitration bath. With 75% concentrated nitric acid added to excess analine, charring takes place fairly quickly.

Adding an acetyl group to the analine, using acetic anhydride, before nitration will make the reaction run much smoother without the byproducts, the acetyl group later being hydrolyzed off with a mildly strong base, but in this case mostly 4-nitroanaline is produced, with some lesser formation of 2-nitroanaline.


Reaction of Nitrous Acid (HNO2) with Aniline

Nitrous acid (NaNO2 and acid) can be used to nitrate phenol or analine. If concentrated mineral acids are present with the nitrous acid, mostly the para-nitro will be produced (91% yield), but if glacial acetic acid (concentrated) is present with the nitrous acid, yields of 74% ortho-nitro are possible. Ortho means the nitro is in the 2-position, adjacent to whatever other group is on the ring. Para means the nitro is on the opposite end of the ring from the other group.
The theory is that a nitrosyl ion (NO+) initially nitrates the ring, and then the resulting nitroso group gets oxidized to a nitro. ("Aromatic nitration", K. Schofield. 1980)
However, this nitrosyl ion equilibrium with nitrous acid is only present under strongly acidic conditions, certainly not when nitrous acid is in an alkaline envirorment., where it is mostly in the form of nitrite.

One source mentions that reaction of analine with nitrosonium hydrogen sulfate NO[+] [-]SO4H produces nitrobenzenediazonium salts.
NO2C6H4–N[+]ΞN
First, the nitro group is added to the analine. It is only after the acids have been somewhat diluted with water that the amino group can be diazotized, as diazotization cannot take place in extremely concentrated sulfuric acid.
"Interaction of Analine with diazotizing and nitrating Agents in Concentrated sulfuric Acid"
Mikhail V. Gorelik, Vera I. Lomzakova, Elena A. Khamidova
Research Institute of Organic Intermediates and Dyes, Moscow, Russian Federation


nitrosonium hydrogen sulfate is the same thing as nitrosyl sulfuric acid, which may be prepared by bubbling mixed nitric oxide/nitrogen dioxide gases into concentrated sulfuric acid.
(3)H2SO4 + NO2 + NO --> (2)NO[+]SO4H[-] + H3O[+]SO4H[-]

Whereas 3-nitroanaline can be easily diazotized with dilute nitrous acid, both 2-nitroanaline and 3,5-dinitroanaline require moderately concentrated sulfuric acid to be present, for formation of nitrosonium ions.

Treatment of a 1:1 ratio of nitrosylsulfuric acid to analine, using 92.5% concentrated sulfuric acid, leads to formation of about three times as much 4-nitrodiazonium salt as 3-nitrodiazonium salt. Using 95.5% sulfuric acid leads to a 6 to 4 ratio of the isomers, while 100% concentration leads to equal formation of both. The treatment of previously prepared benzenediazonium salt with nitric acid does add any nitro group.

you can see a bottle of nitrosylsulfuric acid:
https://7007983270460794965-a-1802744773732722657-s-sites.go...



[Edited on 29-7-2011 by AndersHoveland]

AndersHoveland - 21-9-2011 at 16:35

Nitration of aniline unexpectedly gives 47% yields of meta-nitroaniline (with nitro group in the 3-position). This is because analine under acidic conditions forms the anilinium ion,
C6H5NH3[+], which is meta-directing towards the addition of the nitro group.