Sciencemadness Discussion Board - Hexanitrobenzene

Hexanitrobenzene

PrimoPyro - 24-10-2002 at 06:21

Would be pretty strong wouldn't it? One would think so. But hard to prepare. Couldn't be done by nitration of benzene.

But if one trinitrated benzene to 1,3,5-trinitrobenzene, then reduced all three nitro groups to amines, yielding 1,3,5-triaminobenzene, one should then be able to trinitrate this to 1,3,5-trinitro-2,4,6-triaminobenzene. This would then have to be re-oxidized to 1,2,3,4,5,6-hexanitrobenzene.

That's a lot of work. But there might be another way.

Acetylenes trimerize to benzenes in the presence of Ni+2 catalysts. Some acetylenes with electron-withdrawing groups don't even need catalysts at all. This reaction is not a minor one that has crappy yields, no no. These compounds want to trimerize.

Extremely sterically crowded benzenes have been prepared this way, ones that have yet to be prepared by any other method. Things like hexa-isopropylbenzene, and 1,2,3-trifluoro-4,5,6-tri-isobutylbenzene, the first time in history that three isobutyl functions had ever been placed next to each other on an aromatic ring.

Well, trimerization of 1,2-dinitroacetylene would yield 1,2,3,4,5,6-hexanitrobenzene. Hell, by all rights it should do it without a catalyst, but in reality that kind of statement can't be made without some experimentation, so I won't make it.

Dinitroacetylene should be VERY explosive, too, no? I would think that the aromatic compound would be much more stable than the acetylene when it comes to shock at least.

My main question that I would like input on, is how would one go about preparing 1,2-dinitroacetylene? This very simple compound seems to be quite difficult to prepare in any reasonable number of steps, and it is starting to frustrate me.

I got interested in this possibility after I heard of the reaction of 1,1,1-trichloroethane reacting with aluminum to form chloroacetylene. 'Hmm' I said to myself at the time.

I can think of a few different pathways to 1,2-dinitroacetylene, but they all suck. What idea do you have? I am interested in hearing them, as well as alternative ideas for the preparation of hexanitrobenzene, or any physical properties information on it, as well as explosive properties on it.

Whatever you can provide or take a wild stab at, I'd like to hear it.

PrimoPyro

madscientist - 24-10-2002 at 10:00

I was actually planning on giving 1,2,3,4,5,6-hexanitrobenzene synthesis a try sometime. There's a few ways it might be done without using benzene.

Nitration of 1-aminobenzene in mixed acid - I'm not sure if the nitration will go all the way to 1,2,3,4,5-pentanitro-6-aminobenzene. But if it did, the 1,2,3,4,5-pentanitro-6-aminobenzene would then be oxidized with Caro's acid to yield 1,2,3,4,5,6-hexanitrobenzene.

Nitration of 1,4-diaminobenzene in mixed acid. I'm fairly confident the nitration will go all the way to 2,3,5,6-tetranitro-1,4-diaminobenzene. 1,4-diaminobenzene might be prepared by oxidizing xylene to its dicarboxylic acid, then reacting with urea, then reacting with calcium hypochlorite. The 2,3,5,6-tetranitro-1,4-diaminobenzene would then be oxidized to 1,2,3,4,5,6-hexanitrobenzene with Caro's acid.

It is probably feasible to prepare 1,3,5-trinitrobenzene by oxidizing 2,4,6-trinitrotoluene's methyl group to a carboxyl group, then decarboxylating. I've heard mentions of the decarboxylation proceeding easily - it supposedly can be done by boiling an aqueous solution of the 2,4,6-trinitrobenzoic acid.

Nick F - 24-10-2002 at 10:22

As far as I'm aware, dinitroacetylene hasn't ever been isolated. It would make one hell of a (probably primary) explosive though...
I would bet a lot of money on the fact that it couldn't be done by direct nitration of acetylene though! A carbon-carbon triple bond, and electrophilic nitronium ions... I can't think of any feasable ways to do it.

I know that HNB can be made from TATB, but I forget how exactly.
Aminopentanitrobenzene can be made without too much difficulty:
toluene -nitration-> TNT -oxidation, decarboxylation-> TNB -reduction-> 1-amino-3,5-dinitrobenzene -nitration-> APNB.
The -NH2 on the ring directs further -NO2's ortho/para in relation to it, and also activates the ring to electrophilic attack, thus making further nitration MUCH easier than trying to nitrate sym-TNB.
And from APNB you're only some NaN3 away from CL-18, aminonitrobenzodifuroxan.

Nick F - 24-10-2002 at 10:26

Madscientist, are you sure about Caro's acid doing the -NH2 to -NO2 conversion on aminobenzenes?

madscientist - 24-10-2002 at 10:29

There is something that really interested me that PHILOU Zrealone mentioned in the trinitrotoluene preparation thread.

He said that nitration of an aminobenzene with sulfuric-free nitric acid will result in the nitration of the amine group to NHNO₂; and then the nitro group supposedly shifts onto the benzene ring, reforming the amine group. Has anyone heard about this?

madscientist - 24-10-2002 at 10:33

It seems that PHILOU Zrealone didn't post that in the trinitrotoluene preparation thread. I know I saw it somewhere though...

Here's a quote from him, which is what caused me to think that oxidation with Caro's acid of an amine group will probably yield a nitro group.

Quote:

How do you think it is possible to make hexanitrobenzene?
NH2-C6(NO2)4-CH3 -HNO3/H2SO4/H2O2(all 100%)-> C6(NO2)6 + CO2 + H2O

Triple post :D

madscientist - 24-10-2002 at 10:37

This is something that PHILOU Zrealone posted in the trinitromelamine thread:

Quote:

NH2-C6H5 + HNO3 (conc) --> O2N-NH-C6H5 + oxydation products (quinones)
As a mather of facts:
O2N-NH-C6H5 -rearranges-> NH2-C6H5-NO2 (para)
This proves an vicinal to aromatic ring nitramine is unstable!

Nick F - 24-10-2002 at 10:45

Ah, thanks for the quote. I looked in the TNT thread and couldn't find it! Although I did see the use of Caro's acid for -NH2 -> -NO2.
Damn, if it was meta then the C6H5-NH-NO2 --> O2N-C6H4-NH2 would be very useful for getting more nitrated aromatics, but since the product is para it's of little use, since nitration of aminobenzene will get you p/o ANB anyway

Replies:

PrimoPyro - 24-10-2002 at 13:35

Madscientist:

Quote:

Nitration of 1-aminobenzene in mixed acid - I'm not sure if the nitration will go all the way to 1,2,3,4,5-pentanitro-6-aminobenzene. But if it did, the 1,2,3,4,5-pentanitro-6-aminobenzene would then be oxidized with Caro's acid to yield 1,2,3,4,5,6-hexanitrobenzene.

This will not work all the way to the fully nitrated benzene. At best it will stop at 2,4,6-trinitroaniline. (aniline is aminobenzene) But thats ok too. I just wanted to point out that it will indeed not fully nitrate.

Quote:

Nitration of 1,4-diaminobenzene in mixed acid.

Now this, on the other hand, is a great idea. This *should* be possible to fully nitrate.

Quote:

1,4-diaminobenzene might be prepared by oxidizing xylene to its dicarboxylic acid, then reacting with urea, then reacting with calcium hypochlorite.

Won't work. Even if it did, it wouldnt work well. Firstly, terphthalic acid (p-benzenedicarboxylic acid) is cheap and available as is, or can be made via cheaper methods, and also, Hoffmann Degradation does not work well at all on multiple functions on a single molecule. Most organic reactions work horribly if multiple groups are worked on at the same time intramolecularly. This would be an example of such.

Quote:

It is probably feasible to prepare 1,3,5-trinitrobenzene by oxidizing 2,4,6-trinitrotoluene's methyl group to a carboxyl group, then decarboxylating. I've heard mentions of the decarboxylation proceeding easily - it supposedly can be done by boiling an aqueous solution of the 2,4,6-trinitrobenzoic acid.

Thats a lot of dangerous work to get somewhere you can get to more easily from other methods. Would you want to subject TNT to KMnO4, H2SO4, and then dry distill it with Ca(OH)2? I wouldn't.

Nick F:

Quote:

As far as I'm aware, dinitroacetylene hasn't ever been isolated. It would make one hell of a (probably primary) explosive though...

Damn damn damn, lol. I was afraid someone would say that (regarding its isolation). dinitroacetylene should be more powerful than HNB, gram for gram. Keep that in mind. It was just a novel idea, that really should never be attempted. But HNB needs to be made, so someone can say they pimped themselves some HNB just for the hell of it. [laugh]

Also, why go through all the trouble of ripping off that methyl of TNT when you can just trnitrate benzene? I understand that some of you cling to your OTC ways, but when making research explosives, isn't it ok to cheat and assume you can get some benzene?

Anyways, dont think Im dissatisfied, Im far from that.

I think the best method would be to mononitrate aniline with KNO3 (NaNO3 is not a reasonable substitute here, the K+ ion is crucial) to get p-mononitroaniline, and then reduce this to p-diaminobenzene with Fe/HCl which is easy, high yielding, and cheap as hell.

Then nitrate the shit out of it with NaNO3 or LiNO3 or HNO3, but not KNO3 (yields will be lower) to get 1,4-diamino-2,3,5,6-tetranitrobenzene. This could then be oxidized by several oxidizing agents to HNB.

PrimoPyro

HNB

obscura - 25-10-2002 at 00:54

You should stop the fucking post about
HNCHH ! :cool:

Nick F - 25-10-2002 at 03:30

TNB from benzene isn't easy (unless you do a Friedel-Crafts to make toluene!), it's much more economical to oxidise and decarboxylate TNT. That's the way it's done. Otherwise, you get to m-DNB and then you have to use loads of oleum and 100% HNO3 and reflux it for hours.
TNBenzoic acid decarboxylates very easily, as madscientist said it can be done in boiling water with a bit of NaOH. I suppose since -COOH directs -NO2 groups to the meta position, and TNBenzoic acid has -NO2 o/p to the -COOH, this makes it less stable and more prone to decarboxylation than 3,5-dinitrobenzoic acid. I don't really know why, I haven't been taught about directing effects on aromatics and haven't got round to reading about it yet.

[QUOTE]I think the best method would be to mononitrate aniline with KNO3 (NaNO3 is not a reasonable substitute here, the K+ ion is crucial) to get p-mononitroaniline, and then reduce this to p-diaminobenzene with Fe/HCl which is easy, high yielding, and cheap as hell.

Then nitrate the shit out of it with NaNO3 or LiNO3 or HNO3, but not KNO3 (yields will be lower) to get 1,4-diamino-2,3,5,6- tetranitrobenzene. This could then be oxidized by several oxidizing agents to HNB.[/QUOTE]

Start with p-DCB mothballs, nitrate as much as you can, then reflux with NH3, then nitrate more if necessary, then oxidise -NH2 to -NO2 with Caro's. Totally OTC HNB

I'm not sure if you'd be able to get 1,4-dichloro-2,3,5,6-tetranitrobenzene though, so more nitration might be necessary after the conversion of -Cl to -NH2. But you want to nitrate it as much as possible before doing that, because it'll make the substitution of the -Cl's easier, and p-diaminobenzene will be easy to oxidise if you try to nitrate it directly, so you'll probably end up with a high proportion of black tar, like when you rush a TNP synth. Lots of NO2 and some black tar are the products!

Nope

PrimoPyro - 25-10-2002 at 14:12

Quote:

Start with p-DCB mothballs, nitrate as much as you can, then reflux with NH3, then nitrate more if necessary, then oxidise -NH2 to -NO2 with Caro's. Totally OTC HNB [/qupte]

Wont work for the same reason that trinitration of benzene is hard.

Two electron withdrawing groups para to each other are highly deactivating. Even mononitration of p-DCB would be a difficult task, not to mention further nitrations, where the substitutions are even more difficult because:

1.Even less electrodense ring

2.The groups present are all meta directing, but only positions open are ortho, subsitutions will be strongly discouraged, so to speak.

2-nitro-p-dichlorobenzene could only be substituted in the 5 or 6 position, with the 6 being the more likely of the two, and even that is hard.

Only one nitro group on the ring will not sufficiently weaken any ring-Cl bonds present. p-DCB is very inert because those Cl's are bound tight as fuck to that ring.

But aniline is another story. NH2 is meta directing, I see no reason why nitration of aniline to p-nitroaniline would not be easy.

And p-diaminobenzene is extremely acitvated, and I do mean extremely. The VERY electron dense ring is vry suitable for aromatic electrophilic substitution, definitely to the dinitro stage, likely to the trinitro stage, and maybe possible even to the tetranitro, I don't know though.

PrimoPyro

Microtek - 26-10-2002 at 04:23

In patent number 4,248,798 pentanitroaniline is produced by reducing one nitro group of TNT with H2S and then nitrating the aminodinitrotoluene with mixed acids. A huge amount of H2SO4 is used, but only 3 mL HNO3 per gram ADNT and the product is extracted with CH2Cl2 so the sulfuric acid can probably be recycled without much trouble. No exotic conditions are employed.
Does anyone know what the properties of pentanitroaniline are? It seems to me that it must be extremely powerful but not as unstable as HNB.

pentanitroaniline

zodiac - 26-10-2002 at 10:57

Pentanitroaniline ?
Is it a stuff for HardcorePyro ?

Microtek - 27-10-2002 at 02:04

As was mentioned earlier, aniline is just another name for aminobenzene so pentanitroaniline is the same as aminopentanitrobenzene.

vulture - 27-10-2002 at 06:30

I wonder if there's no way to get those electrons of the benzene ring in a more active state by adding a strongly electrophilic specie or something.

Also, would further nitrating the NH2 group to NH(NO2) or even N(NO2)2 be possible from pentanitroaniline?
Maybe by oxidation with K2Cr2O7 or KMnO4?

Nick F - 1-11-2002 at 12:22

Sorry, this is a fairly pointless post in that it doesn't help us get to HNB, but I thought I'd post it to illustrate the difficulty of nitrating benzene to TNB:

"Hepp and Lobry de Bruyn improved the process, treating 60 grams of m-dinitrobenzene with a mixture of 1 kilo of fuming sulphuric acid and 500 grams of nitric acid (d. 1.52) for 1 day at 100*C and for 4 days at 110*C..."

Taken from COPAE. And that's the IMPROVED process!

Thats why you dont use HNO3 :P

PrimoPyro - 1-11-2002 at 19:45

Thats why you use N2O5 as the nitrating agent. Yields are better, but there are more side reactions as well, and more fumes of course.

Nick F - 2-11-2002 at 04:05

Ah, well yes if you can get N2O5 or those crazy nitronium salts then it could be more easy to nitrate... I was assuming OTC.

Of Course

PrimoPyro - 2-11-2002 at 06:53

And you are right, I was only being sarcastic. N2O5 could be put to much better use than nitration, using it for this would be retarded.

I do know that trinitrating aniline will be easier than trinitrating toluene. I think that phenol is the easiest monosubstituted benzene to trinitrate though. So if thats true, you can look at it as nitrating aniline to be between toluene and phenol in difficulty. Not bad at all.

PrimoPyro

IodineForLunch - 10-11-2002 at 18:25

In the TNT thread philou mentioned something about treating tetranitrotoluene with a mixture of H2SO4/H2O2/HNO3 to yeild HNB. Go find it, that may be a good method...

David Hansen

Ramiel - 16-11-2002 at 23:06

I also had the idea of trimerizing 1.2-dinitro-ethene to hexanitro benzene, but then dinitroethene is unstable. So, is it possible to create some kind of 1.2-diamino-ethene, then trimerize it to an aromatic, and then somehow oxidize the amine groups (how I don't know - someone mentioned Caro's acid).

potassiumcarbonmonoxide

vulture - 14-12-2002 at 09:30

What does this have to do with HNB you'll ask?
Well, looking at the structure it might be very useful. It can be prepared by reducing potassiumcarbonate with carbon.
The name will seem a bit odd when you look at the structure, but the formula is K6C6O6 and it can also be prepared by reacting potassium metal with hot CO gas.

potassiumcarbonmonoxide.gif - 2kB

Polverone - 14-12-2002 at 14:54

If you read old texts (say, Muspratt) about the carbothermic production of potassium you will be informed that this compound is a treacherous explosive. Just warning anybody who might be about to (ha!) synthesize it.

vulture - 15-12-2002 at 14:52

I don't see why this would be explosive, it's merely the salt of hexahydroxybenzene.
There is however another form of potassiumcarbonmonoxide with the formula K2C2O2, K - O - C = C - O - K
("=" is triple bond here). Maybe this is the explosive one because of the acetylene bond?

madscientist - 15-12-2002 at 18:39

I would think that it would be rather explosive, considering what the thermodynamics of decomposition would probably be.

Polverone - 15-12-2002 at 23:36

I don't know exactly what the composition of the explosive material is, given that Muspratt doesn't know and I don't have a good inorganic reference at my current location. I do know that texts on the carbothermic production of potassium warn that the black material you get along with potassium metal when you strongly heat carbon and potassium carbonate together is explosive and should be removed from the metal as soon as possible.

KABOOOM(pyrojustforfun) - 17-12-2002 at 17:48

I wonder why anybody is seeking for difficult methods when pentanitroaniline (probably) can be made starting with aniline (I am almost sure).
edit: added probably and almost

[Edited on 23-7-2003 by KABOOOM(pyrojustforfun)]

madscientist - 17-12-2002 at 20:39

Could you provide details on preparing pentanitroaniline from aniline?

KABOOOM(pyrojustforfun) - 20-1-2003 at 18:50

from my chemical dictionary:
trinitroaniline (picramide) C₆H₂NH₂(NO₂)₃.
Properties: Orange-red crystals; m.p. 188°C; b.p. explodes; sp.gr. 1.762.
Derivation: Nitrating aniline in glacial acetic acid solution or by the use of mixed nitric-sulfuric acid in limited amounts.
Hazard: Dangerous; explodes by heat or shock.
Use: Explosive compositions.
Shipping regulations: (Rail) Explosive A label. Not acceptable passenger. (Air) Not acceptable dry, or wet whith less than 10% water; Flammable Solid label when wet with not less than 10% water.
tetranitroaniline (TNA) C₆H(NO₂)₄NH₂. A nitration product of aniline which melts at 170°C and explodes at 237°C.
Hazard: Toxic. Dangerous fire and explosion risk.
Use: Manufacture of detonators and primers.
Shipping regulations: Detonating primers, (Rail) Explosive A label. Not acceptable passenger. (Air) Not acceptable.

so the usual mixed acid nitrates it to tetranitroaniline. the only -H which is not nitrated should be at 5th C. knowing that the 3d C is nitrated, it's perhaps possible that at hardrer conditions the symmetric position (5th C) could be nitrated.(I'm not completely sure)

I've thought of another method starting from chloranil (see the attachment)
sorry for late replying ,unfortunately I won't have many posts until summer. (those who had ICQ chat with me know why).

P.N.A.jpg - 29kB

Re:Hexanitrobenzene

solo - 21-1-2003 at 07:29

Hexanitrobenzene: Heat of formation: (in cal/g) 12, Density: 0.0717 in
lbm/in^3 -in NASA thermochemistry you would need to convert from
cal/g to cal/mol by multiplying these values by the molecular weight of
the compound. this info is taken from the good ol' Propulsion data
base:............................solo
http://roger.ecn.purdue.edu/~propulsi/propulsion/comb/propel...
which also has more valuble information like this on other compounds.

NO2
|
|
/ \
/ \
/ \
NO2¯¯¯¯| |¯¯¯¯NO2
| |
NO2¯¯¯¯ \ / ¯¯¯¯NO2
\ /
\ /
|
|
NO2

Hexanitrobenzene

KABOOOM(pyrojustforfun) - 22-1-2003 at 18:55

forget about chloranil method even if it could work untill the pentanitrophenol part. the next step probably won't work because amminolysis usually needs high temperature and PNP may decompose at that temp.

PHILOU Zrealone - 19-3-2003 at 04:54

The procedure to form HNB that I mentionned is from a book dedicated to pernitrocoumpounds
-TNMethane
-HNEthane
-TeNEthene
-HNB
Are discussed extensively but some unknown compounds were discussed too (ONC has been synthetised meanwhile)
-octanitropropane
-Dinitroacetylen
-octanitronaphtalene
-ONC
....

They mention that dinitrocetylen has been tried without succes for decades!
That HNB is very sensitive towards moisture in wich it turns fast into trinitrophloroglucidol
C6(NO2)6 + 3H2O --> C6(OH)3(NO2)3 + 3HNO2
This explains why the final step of the reaction of tetranitrotoluidine must be carried out in anhydrous HNO3/H2SO4/H2O2!

So one of the way to produce HNB is via Toluen!
C6H5-CH3 + HNO3 --> CH3-C6H4(NO2)
para nitrotoluene -Fe/HCl-> Paratoluidine
CH3-C6H4-NH2 -HNO3/H2SO4-> TetraNitroParaToluidine
CH3-C6(NO2)4-NH2 -HNO3/H2SO4/H2O2-> HNB + CO2
The final step is peroxydation of the amino group to a nitro one, oxydation of the CH3 into CO2H, decarboxyaltion and nitration of the resulting H!

I don't know if the ammonolyse of the nitrophenols is easy to perform at moderate T (under the T of detonation of such powerful and sensitive HE)!

Anyway, I have to correct some errors that I have seen along all this chat!
-NH2 is a ORTHO and PARA director with a favor to para depending on the substituant!
-NH3(+) is a meta director (this explains why some TeNA is formed in the TNA process!
-Aminobenzene will produce very little TNA,TeNA or PNA by direct nitration without any protection since aniline readily oxydises to para quinone.This is circumvented in the case of paratoluidine because of the CH3!
-In the same order of idea paradiaminobenzene will perform very bad (as pararesorcinol) in nitrations; usually you get complete decomposition (oxydation in quinone and then water and CO2 + nitrous fumes)!
-It is possible to make paradiaminotetranitrobenzene via paradichlorotetranitrobenzene! The fact two groups are para to each other is absolutely not a problem!Thus nitrating pDCB is as simple as nitrating MonoCB and a little less than metaDCB.In the case of paratoluidine the NH2 is stronger activator than CH3 and will rule the two first nitro in ortho to the NH2; then the CH3 activates the position in ortho to itself; the two effects are not concertative but doesn't oppose really on each other!

To understand this:
speed of nitration of benzene is 1
speed of nitration of toluene is 10
speed of nitration of metaxylen is 30
speed of nitration of orthoxylen is 15
speed of nitration of paraxylen is 20
speed of nitration of mesitylene is 100

Thus no mather the position of the activating group towards each other, they activate more when there are more and even more if they are concertative (in meta of each other)!

Chlorobenzen nitrates almost as fast as benzen so DCB will do aswel and as in the case of benzen to go high in NO2, you need SO3 oleum and anhydrous HNO3!

The synthesis of Cl-C#C-H from CCl3-CH3 and Al seems doubtfull since Al in polyhalide is a wish for a detonation (heat sensitive)...so dehalogenation in explosive Cl-C#C-H seems very dangerous...even more if applied to the hypothetical (di)nitroacetylen synthesis!
Anyway one might attempt to "condensate" chloropicrin with Al...?
2O2N-CCl3 + 2Al --> O2N-C#C-NO2 + 2AlCl3

Nitroacetylen and dinitroacetylen are more than certainly subject of strong instability due to nitronate resonance and nitrito resonance!This effect explains the poor stability of tetranitroethylene!
O2N-C#C-H <-->O=N-O-C#C-H <--> HO-C#C-N=O <-->
O=C=C=N-OH

I personnally would be very cautious with any attempts to produce dinitroacetylen since most precusor are already explosives!
I could think to
O2N-C#C-NO2 from I-C#C-I and AgNO2, from C2H2 and I-NO2 to form I-C#C-NO2 and then subsequent action of AgNO2
Cl2C(NO2)-C(NO2)Cl2 refluxed with Zn in an inert solvant!
Note that pernitrocompounds are strong nitrating agents so solvant has to be very unreactive!They also display a positive OB and free NOx so they are panclastite like HE mixes with combustible solvants!!!!Heat, shock have to be avoided at any costs!

vulture - 15-6-2003 at 12:50

If hexanitrobenzene is so sensitive to moisture, nitrating in dichloromethane might be an interesting option. An abstract and a patient mention DCM as a relatively safe and inert nitrating solvent which also seems to promote yields in aromatic nitrations.

Hexanitrobenzene

R-Salt - 17-6-2003 at 11:06

Simplest would seem to be :- follow standard method to 1,3,5-triamino 2,4,6-trinitrobenzene then use 98%h2o2 in oleum to oxidise -nh2 to -no2. An interesting alternative would be starting from hexanitrosobenzene (available ) which is a tautomer of benzene trifuroxide. Furoxides are known to be oxidisable to nitro with peracids.
Does anyone happen to know if the pyridine equivalent of HNB has been made?. pentanitropyridine

Hexanitrobenzene

R-Salt - 17-6-2003 at 12:16

It occurs to me that it might be possible from triaminotrinitrobenzene as follows:-
RNO2 to diazotise the three NH2 then replace N2+ with NO2. The "normal" NaNO2 / HNO2 aqueous would obviously be no good as HNB is unstable to water, but alkyl nitrite then a non aqueous NO2 replacement might work.?

KABOOOM(pyrojustforfun) - 22-7-2003 at 18:54

as -NO2 groups increase in the ring, diazotation of the amino group becomes harder for example diazotation of picramide needs conc sulfuric acid. if TATB could be diazotated the othere amino groups will become very hard/impossible to diazotate. there are many disadvantages in oxidization of TATB, firstly it's insoluble in most (any?) solvents. secondly @ least three times more H2O2 & H2SO4 is needed than the usual method (using PNA as starting material) . TATB is rather hard and expensive to make (although the VNS method via NH2OH makes it cheap & easy).
I'm very hopeful that VNS amination of TeNA is possible . this will yield 1,3-diamino 2,4,5,6-tetranitrobenzene. DATeB is a very powerful explosive on its own (definitely more powerful than TATB). its oxidation hopefully results HNB. a alternative method for oxidization step is to add porassium persulfate in H2SO4 instead of adding conc H2O2 in it.

[Edited on 23-7-2003 by KABOOOM(pyrojustforfun)]

Mendeleev - 25-12-2003 at 14:56

US patent 4,262,148 describes the process for synthesizing HNB from pentanitroaniline, here's the abstract, followed by a summary of the process:

Hexanitrobenzene is prepared by oxidizing the amine group of pentanitroaniline with H2O2 in H2SO4 The compound is a high density explosive.

The process is something like dissolve 1 gram of pentanitroaniline in H2SO4 with 20% dissolved SO3 content. After cooling to 5 degrees C, slowly add 5 mL of 98% or higher H2O2 keeping the temperature under 30 degrees C. The solution is protected by a drying tube and kept at 25 degrees C for 24 hours, then at 0 degrees Celsius for one hour, after which the precipitate is removed.

US patent 4,248,798 describes how to prepare pentanitro aniline from TNT here is the abstract, followed by a somewhat lengthier summary of the process:

Trinitrotoluene is selectively reduced by reaction with H2S in p-dine to produce 4-amino-2,6-dinitrotoluene. This latter compound is then nitrated with HNO3 in H2SO4 to produce pentanitroaniline.

This process involves dissolving 25 g of TNT in 50 mL of p-dioxane that contains 1 mL of NH4OH as a catalyst. H2S is bubbled through for 30 minutes, and there should be a precipitate. The soution is filtered and the precipitate which is a mixture 4-amino-2,6-dinitrotoluene and 2,6-dinitro-4-hydroxylaminotoluene is recrystallized from methanol to get the 4-amino-2,6-dinitrotoluene. 1 gram of 4-amino-2,6-dinitrotoluene is dissolved in 40 mL of 96% H2SO4 and 3 mL of 90% HNO3 are added dropwise, while the reaction temperature rises to 40 degrees Celsius. It is then heated for one hour at 70 degrees Celsius. The solution is then cooled to room temperature after which the acids are extracted with methylene chloride and the extract is dried over MgSO4. After the methylene chloride has evaporated a 62.4% yield of pentanitroaniline is obtained.

Read the patents if you want all the gritty details, but that was most of them.

[Edited on 25-12-2003 by Mendeleev]

KABOOOM(pyrojustforfun) - 26-12-2003 at 19:50

Mendeleev: we knew both patents. fully read the thread?

Mendeleev - 27-12-2003 at 09:03

Whoops... Terribly sorry about that, sort of missed that first page there

. Thanks for telling me otherwise I would have gone on in ignorance.

polyhydroxycyclohexanes as intermediates

halogen - 19-4-2004 at 04:23

Has anyone thought of using hydrogen peroxide in any of this?
resocinol and H2O2?
I think that the H2O2 will split the double bonds in a benzene like structure.
C6H4(OH)2+3H2O2-->C6H4(OH)8
From ther you can nitrate it.
It's not hexanitrobenzene, but its similar

.
Also, p-nitrophenol+gallic acid. Oooh! Add H2O2 and nitrate! Wowwwww!

No

Turel - 19-4-2004 at 10:01

Peroxide will not effect benzenoids that way. Aromaticity complicates matters (or simplifies them, depending on how familiar you are with organic chemistry).

Resorcinol could be oxidized in small yields with H2O2 to meta-benzoquinone. Resorcinol is rather inert to H2O2 in low concentrations. If benzenoids were nonaromatic, you would still produce a different compound using this method. (cyclohexan-1,2,3,4,5,6-hexol hexanitrate).

hexanitro derivates ???

Spawn - 7-5-2004 at 09:10

Hexanitrobenzene:

Hexachlorobenzene + ammonia + Soium Acetate
---> Hexaaminobenzene

Hexaaminobenzene + H2SO4 + H2O2 (Caros Acid)
--->Hexanitrobenzene

Hexanitrocyclohexane:

Hexachlorocyclohexane + ammonia + Soium Acetate
---> Hexaaminocyclohexane

Hexaaminocyclohexane + H2SO4 + H2O2 (Caros Acid)
--->Hexanitrocyclohexane

:cool:

Different Nitrobenzene

rsgpit - 22-5-2006 at 14:52

Would it be possible to have a nitro group of each carbon in a benzene ring. I know regular NB has only one Nitro group and 5 hydrogen. Has it ever been done? If it has, its surely very powerful, yeilding only CO2 and N2.

Mr. Wizard - 22-5-2006 at 15:15

Wouldn't that be hexanitrobenzene? The first search returned in Google, a very useful tool, gave this:
http://en.wikipedia.org/wiki/Hexanitrobenzene
It is a powerful explosive, but is apparently sensitive to light !

Chris The Great - 22-5-2006 at 15:53

Also susceptable to hydrolysis in the presence of moisture... it is not chemically stable, however it is possible to prepare as long as moisture is avoided and it is not left in the light.

It's explosive properties are amoung the most powerful of any explosive prepared to date. I believe it is more powerful than CL-20 by a decent margin, though don't have any refs at the moment.

quicksilver - 22-5-2006 at 16:19

I was always put off by benzene as Gerald Hurst was one of the people back in the early 1990's who claimed it was possibly one of the things that contributed to his health issues. I remember having received some from a chem supplier a long time back and it's MSDS was one of the only ones that claimed that it (in and of itself) was a very serious carsinogen; that it was a prooven cause. Jerry claimed that he used it to clean up with and his liver funtion tests in his mid 50's was very seriously poor. That being said I believe that Marshall has some information about it's extended nitration. Obtaining it today may be even more difficult than 10years back. Way back then I was interested and may have some direct info re same - will post if I can dig it up.

JohnWW - 23-5-2006 at 21:02

How would one prepare hexanitrobenzene, presumably starting with nitrobenzene, and especially given its sensitivity to light and hydrolysis moisture? It would be very difficult to nitrate it beyond 1,3,5--trinitrobenzene, because after that the less favorable electrostatic charge distribution, and steric strain, makes further electrophilic substitution with further -NO2s unfavorable. To avoid moisture, one would have to use something like N2O5 or NO2ClO4, rather than HNO3 with H2SO4.

Chris The Great - 23-5-2006 at 23:30

Toluene -> TNT, selective reduction of the 4-nitro with H2S, then oxidation/nitration to tetranitroaniline (high temps to oxidize the methyl to COOH and then de-carboxylate it), and finally oxidation with H2SO4/H2O2 (100% or fuming and 98% concentrations respectively).
I think the final oxidation step could be improved and made more simple, for example a H2SO4/Na2WO4/H2O2 mixture, which is more active and efficient at oxidizing NH2 groups, especially deactivated ones. It would require much less oxidizing mixture, and give higher yields as well. Maybe toss some SO3 in the form of fuming sulfuric acid to improve the yield by removing all traces of water.
Also, thinking to picric -> picramic reductions, perhaps ascorbic acid (vitamin C) could be used to selectively reduce the TNT without the horrid smell and chance of death.

Then, after isolation, it's time to brag big time on the internet

Madandcrazy - 2-6-2006 at 10:15

Nice idea hexanitrobenzene by TNT, but how prepared PNT (pentanitrotoluene) and how oxidized/substituted to HNB ?
Are oxidzing around a good method, i think it is some wasteful and poisonous.
TNT -->
1-methyl-2-amino-4,6-dinitrobenzene -->
1-methyl-2-amino-3,4,6-trinitrobenzene -->
1-methyl-2-3,4,6-tetranitrobenzene -->
1-methyl-5-amino-2-3,4,6-tetranitrobenzene -->
PNT

But how oxidized PNT to HNB (PNA), with a mix of a hyposulfide/chloroamin or NH4OH/hyposulfide ?

Maybe TNT is strong treated in a vessel in low amounts with HNO3/H2SO4 to PNT or to trichlorotrinitrotoluene

.
NaN3 is evantually useful as a buffer subtsance for substitution/nitration.
Is trinitrobenzene not even treated by this method to HNB ?

More capabilities maybe:
chloropicrin is treated to chloropentanitrobenzene and this is continued with ammonium acetate to pentanitroaniline.
hexachlorobenzene is treated with the same.

I think some interest applies to for syntheses of pentanitrophenol or some salts like ammoniumpentacrate

, but some of this high nitrated salts still stable ?

Excuse me, when some nomenclatura not correcly in this long post.

[Edited on 2-6-2006 by Madandcrazy]

K6C6O6

Zinc - 15-6-2006 at 12:26

Quote:

Originally posted by Polverone
If you read old texts (say, Muspratt) about the carbothermic production of potassium you will be informed that this compound is a treacherous explosive.

Does it detonate? If yes what is the VOD? Can it be initiated by a fuse?

[Edited on 16-6-2006 by Zinc]

franklyn - 21-6-2010 at 15:35

http://www.sciencemadness.org/talk/viewthread.php?tid=1226#p...

.

The WiZard is In - 22-6-2010 at 08:57

Quote: Originally posted by Polverone

I don't know exactly what the composition of the explosive material is, given that Muspratt doesn't know and I don't have a good inorganic reference at my current location. I do know that texts on the carbothermic production of potassium warn that the black material you get along with potassium metal when you strongly heat carbon and potassium carbonate together is explosive and should be removed from the metal as soon as possible.

Carbonyl are discussed in Mellor's 16 volume opus. 5:950-62.

And by da .... [Mellor] "The corresponding sodium
carbonyl,Na2C2O2 is obtained in a similar manner as a white
owder with a lilac tint. It detonates at 90o in vacuo, or when
rought in contact with air or water.... When it detonates, very
little gas is evolved, and a small quantity of sodium cyanide is
formed, but the principal reaction is represented by the equation
2NaC2O2 = NaCO3 + Na2O + 3C. "

I own an original copy of Muspratt and to fill in the blanks would quote him.

p. 725
The grey powder is possessed of most powerfully explosive
properties, and if the greatest care not be exercised in removing it
from the apparatus—such as carefully excluding it form the
atmosphere until quite cool, and soaking well in naphtha previous
to attempting its removal — the most dangerous accidents may
occur.

The WiZard is In - 22-6-2010 at 09:20

Quote: Originally posted by Polverone

If you read old texts (say, Muspratt) about the carbothermic production of potassium you will be informed that this compound is a treacherous explosive. Just warning anybody who might be about to (ha!) synthesize it.

Production of potassium from potassium carbonate and charcoal
with calcium carbonate is discussed with sufficient detail in —

ENCYCLOPÆDIA OF CHEMISTRY THEORETICAL, PRACTICAL, AND
ANALYTICAL AS APPLIED TO THE ARTS AND MANUFACTURES.
BY WRITERS OF EMINENCE.
ILLUSTRATED WITH NUMEROUS WOOD-CUTS AND STEEL-PLATE ENGRAVINGS.
VOL. II.
GLASS - ZINC.
PHILADELPHIA:
J. B. LIPPINCOTT & CO.
1879.

I own the 1880 version, you can read/DL yours at/from Google.com/books

http://tinyurl.com/287p7zh

p. 672 Search for Curaudau.

The WiZard is In - 22-6-2010 at 09:26

Quote: Originally posted by The WiZard is In

Noted in passing... This 2-volume American edition is a reprint of
the original 8-volume English edition.

JohnWW - 22-6-2010 at 17:53

Quote: Originally posted by The WiZard is In

Quote: Originally posted by Polverone

Production of potassium from potassium carbonate and charcoal with calcium carbonate is discussed with sufficient detail in —
ENCYCLOPÆDIA OF CHEMISTRY THEORETICAL, PRACTICAL, AND
ANALYTICAL AS APPLIED TO THE ARTS AND MANUFACTURES.
BY WRITERS OF EMINENCE.
ILLUSTRATED WITH NUMEROUS WOOD-CUTS AND STEEL-PLATE ENGRAVINGS.
VOL. II. GLASS - ZINC.
PHILADELPHIA: J. B. LIPPINCOTT & CO. 1879.

I own the 1880 version, you can read/DL yours at/from Google.com/books
http://tinyurl.com/287p7zh
p. 672 Search for Curaudau.

It cannot be downloaded, or even read online, from that page, or from any link on it. However, I think Muspratt's volumess may be available from archive.org and elsewhere.

The WiZard is In - 22-6-2010 at 17:58

Quote: Originally posted by JohnWW

ENCYCLOPÆDIA OF CHEMISTRY THEORETICAL, PRACTICAL, AND
ANALYTICAL AS APPLIED TO THE ARTS AND MANUFACTURES.
BY WRITERS OF EMINENCE.
ILLUSTRATED WITH NUMEROUS WOOD-CUTS AND STEEL-PLATE ENGRAVINGS.
VOL. II. GLASS - ZINC.
PHILADELPHIA: J. B. LIPPINCOTT & CO. 1879.

I own the 1880 version, you can read/DL yours at/from Google.com/books
http://tinyurl.com/287p7zh
p. 672 Search for Curaudau.[/rquote]

It cannot be downloaded, or even read online, from that page, or from any link on it. However, I think Muspratt's volumess may be available from archive.org and elsewhere.

Did you as I instructed search for — Curaudau?

On the left side of the page - "Search in this book."

Anders Hoveland - 23-6-2010 at 19:57

To answer the original question on the post, ICCI might react with a polyvinyl-trimethylammonium nitrite to make a low yield of dinitroacetylene.

--CH2CH(N(+)[CH3]3)---

--CH2CH(N[CH3]2)-- can be turned into the above with a methylating agent such as CH3SO3F methyl fluorosulfonate, which acts as a CH3+ carbenium cation, but methylating agents are highly toxic.

Or possibly (NO2)BrHCCBrH(NO2) and anyhydrous liquid tetramethylammonium hydroxide will make dinitroacetylene, since 2HBr's will be pulled off.

As a sidenote: hexa nitroso (NO) benzene shares resonance states with the trifuroxan.

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

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

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

PHILOU Zrealone - 24-6-2010 at 03:26

Quote: Originally posted by Anders Hoveland

To answer the original question on the post, ICCI might react with a polyvinyl-trimethylammonium nitrite to make a low yield of dinitroacetylene.

--CH2CH(N(+)[CH3]3)---

--CH2CH(N[CH3]2)-- can be turned into the above with a methylating agent such as CH3SO3F methyl fluorosulfonate, which acts as a CH3+ carbenium cation, but methylating agents are highly toxic.

Or possibly (NO2)BrHCCBrH(NO2) and anyhydrous liquid tetramethylammonium hydroxide will make dinitroacetylene, since 2HBr's will be pulled off.

As a sidenote: hexa nitroso (NO) benzene shares resonance states with the trifuroxan.

Maybe the base will be so strong it will exchange one of the NO2 for a OH...this could also occure from the H2O that was set free by the base catching the HBr and forming a salt.
Remember that hexanitrobenzene is very prompt to hydrolisis, amonolysis... because two vicinal NO2 groups separated by a double bond (thus on sp2 carbons) tends to favourise nitro-nitrite rearangement.This effect might be event stronger in the case of tripple bonding (sp) explaining the relative unstability of acetylenic compounds vs ethylenic ones.
O2N-C#C-NO2 <==> O2N-C#C-O-N=O
O2N-C#C-O-N=O + H2O <--==> O2N-C#C-OH + HO-NO
O2N-C#C-OH <==> O2N-CH=C=O
Then it can be very complex because you have so many reactants that can interfere that the course of the reaction is uncertain (H2O, H(+), N=O(+))

You mighte even consider internal oxydoredox like from HNO3, mercury and ethanol that end up with a fulminic acid.
O2N-CH=C=O <==> HO-N=C + CO2

[Edited on 24-6-2010 by PHILOU Zrealone]

Anders Hoveland - 27-6-2010 at 14:52

I wonder if the nitrosyl NO+ would react with acetylene H2C2 and conserve the triple bond? H2C2 + 2NO(+) --> C2(NO)2 + 2 H(+)
I cannot envison how NO+ would react with a triple bond, as nitric oxide is a reducing agent and the positive charge will not take to a carbon.
Trimerized, this would make hexanitrosobenzene.
Reduced with HSO3- , this would make HONHCCNHOH which would become dinitrosoethylene ONCH=CHNO. This in turn could be further reduced by HSO3- to
dihydroxylaminoethane HONHCH2CH2NHOH. These reductions are not direct hydrogenations of double bonds, but come about through more complex intermediates. Bisulfite will not hydrogenate acetylene, for example.
Somebody correct my chemical name mistakes. What exactly are the correct names for ONCH=CHNO and ONCH2CH2NO ?

Dinitroacetylene from the Diiodo-

Anders2 - 17-9-2010 at 14:29

Let me refer your attention to the prepublication section:
http://www.sciencemadness.org/talk/viewthread.php?tid=4915#p...

[Edited on 17-9-2010 by Anders2]

DubaiAmateurRocketry - 2-1-2014 at 22:41

Quote: Originally posted by madscientist

Nitration of 1,4-diaminobenzene in mixed acid. I'm fairly confident the nitration will go all the way to 2,3,5,6-tetranitro-1,4-diaminobenzene. 1,4-diaminobenzene might be prepared by oxidizing xylene to its dicarboxylic acid, then reacting with urea, then reacting with calcium hypochlorite. The 2,3,5,6-tetranitro-1,4-diaminobenzene would then be oxidized to 1,2,3,4,5,6-hexanitrobenzene with Caro's acid.

that compound you mentioned 2,3,5,6-tetranitro-1,4-diaminobenzene sound interesting as a high density insensitive explosive. 1,4-diaminobenzene Do exist, http://en.wikipedia.org/wiki/P-Phenylenediamine

eidolonicaurum - 7-1-2014 at 03:31

I do know of this method of making HNB, however, I have never tried it, nor know how it works. It is from a (almost certainly) reliable source. It is from a book that details the preparation of several different explosives, but I do not have its title.

Chemicals required:
Methanol - 317 ubw
Ethyl acetate - 45 ubw
TNT - 50 ubw
Sodium hypochlorite (5% solution) - 145 ubw
Sodium hydroxide - 2 ubw

Other materials required:
Heat/acid resistant container
2 acid resistant containers
Heat source
Stirring rod

1. Pour the ethyl acetate into the heat/acid resistant container and then add 250 pbv of methanol.
2. Put the TNT into the benzene/methanol mixture and stir the mixture.
3. Put the heat/acid resistant container on the heat source and heat it to 50oC to completely dissolve the
TNT.
4. Pour the sodium hypochlorite solution into the first acid resistant container, and then add the sodium hy-
roxide. Stir it to dissolve the sodium hydroxide.
5. When the benzene/methanol/TNT mixture reaches 50oC, add the sodium hypochlorite/sodium hydroxide
mixture to it drop-wise, one drop every 10 seconds. Stir the benzene/methanol/TNT mixture and maintain the temperature around 50oC the whole time.
6. Once all the sodium hypochlorite/sodium hydroxide mixture has been added, immediately remove the
heat/acid resistant container from the heat source.
7. Filter off the crystals, and while they are still in the filter paper, pour 75 pbv of methanol over them to
wash them.
8. Pour another 75 pbv of methanol over them to wash them.
9. Pour 500 pbv of COLD water over the crystals 3 times.
10. Let the crystals, which are HNB, air dry.

ALTERNATIVE METHOD OF MANUFACTURE

Chemicals required:
Benzene - 20 pbv
Methanol - 260 pbv
TNT - 20 ubw
Sodium hydroxide - 1 ubw
Sodium hypochlorite solution (5% solution) - 70 pbv

Other materials required:
Heat/acid resistant container
2 acid resistant containers
Heat source
Stirring rod

1. Pour the benzene into the heat/acid resistant container and then add 160 pbv of methanol.
2. Put the TNT into the benzene/methanol mixture and stir the mixture.
3. Put the heat/acid resistant container on the heat source and heat it to 40oC to completely dissolve the
TNT.
4. Pour the sodium hypochlorite solution into the first acid resistant container, and then add the sodium hydroxide. Stir it to dissolve the sodium hydroxide.
5. When the benzene/methanol/TNT mixture reaches 40oC, add the sodium hypochlorite/sodium hydroxide
mixture to it drop-wise, one drop every 5 seconds. Stir the benzene/methanol/TNT mixture and maintain
the temperature at 40oC the whole time.
6. Once all the sodium hypochlorite/sodium hydroxide mixture has been added, continue heating the mix-
ture for 1 hour, stirring every 5 minutes.
7. Remove the heat/acid resistant container from the heat source, and allow the mixture to cool to room
temperature.
8. Filter off the crystals, and while they are still in the filter paper, pour 100 pbv of methanol over them to
wash them.
9. Let the crystals, which are HNB, air dry.

PHILOU Zrealone - 10-1-2014 at 08:06

@eidolonicaurum
The preparations mentionned are likely not to work...and obviously from a dubbious source.

This because of the extreme sensitivity of HNB towards moisture and thus dilluted water solutions (and especially strong bases like aqueous NaOH) would all end up with TNPhloroglucidol...