Sciencemadness Discussion Board - Quinone to make Energetic Compound

Quinone to make Energetic Compound

Anders Hoveland - 19-6-2010 at 21:40

Alternatively, one could begin with nitro-quinone. The oxidation with nitric acid is tricky. You must use just the right concentration, and and not use too much. Phenol would be a good solvent. The yield is low, as the nitric acid attacks the hydroxylamine group.

energetic.bmp - 227kB

psychokinetic - 20-6-2010 at 00:42

Reading this, I feel as though I just woke up in a lecture I didn't intend to be in.

Have you done this? What happened? Pictures?

What is this WIZardry?

/exit stage left.

bbartlog - 20-6-2010 at 07:02

Quote:

The oxidation with nitric acid is tricky. You must use just the right concentration, and and not use too much.

Ooh, trying even harder to make it sound like you've actually tried this. Frankly at this point I'm hoping you get banned. You haven't responded to any of the requests to document your speculation with references. And your main response to criticism that you are engaging in idle flights of fantasy seems to be to be deliberately vague as to whether what you're posting is experimental or hypothetical. It wouldn't be so bad if so much of your spew weren't related to energetic materials; sooner or later I'm sure you'll post some brain fart that happens to be a perfect recipe for disaster, and I don't really like to see the forums littered with such land mines.

Justin - 21-6-2010 at 18:41

Sadly I feel the same, your info would be much more useful if there were some references to the synthesis of these theoretical compunds, or atleast some experimental data done by you.

mfilip62 - 22-6-2010 at 11:17

Nitration of benzoquinones or hydroquinone might be interesting idea I had recently, anyone documented it!?
I assume that o and p isomers would have interestingly different properties.

Question for someone who is more in organics;
Is there even remote possibility to put -ONO2 group in place of -OH in hydoquinone just like in
alcohols!?
That sounds like a long shot,but I am pretty sore you could put both,-NO2 and -ONO2 on molecules
like safrole or any phenyl-alkene or phenyl-alkene with alk(a/e)ne bigger than 3 C.

Phenyl compound with -ONO2 would be interesting!

Anders Hoveland - 22-6-2010 at 17:59

No, you cannot put a NO3 in place of the OH, and still have another OH at the opposite end. This arrangement automatically would revert to HNO3 and quinone, sine the H on the OH would ionize and the electron on the O would move over to the NO3.

mfilip62 - 22-6-2010 at 18:20

No need for -OH on the opposite end,can you supstitute them both with -ONO2!?

In other case,can you put -NO2 on the phenyle and -ONO2 on the propene/propane group !?

Anders Hoveland - 22-6-2010 at 18:41

That is a difficult question. I am not completely sure. I highly doubt it could be done by a direct nitration. Perhaps para dibromobenzene and AgNO3 in benzene.
Even then the para dinitrate of benzene would hydrolyze and self oxidize in water.

[Edited on 23-6-2010 by Anders Hoveland]

mfilip62 - 23-6-2010 at 06:51

I just asked is it possible,I don't expect it ot be stable or useful.

Is there any documented phenyl compund with both -NO2 and -ONO2 groups!?

Anders Hoveland - 23-6-2010 at 09:20

Actually, benzene 1,4-dinitrate likely shares a resonance state, meaning it would have an equilibrium with 2 NO2 and quinone. The dinitrate might be stable under dry ice, but probably quinone is far too stable to revert back in any significant ammount.

mfilip62 - 23-6-2010 at 09:32

Why is it 1,4-dinitrate so unstable while 1,3,5-trinitrobenzene is not,by "stable" I mean it can be handled at room temperature.

PHILOU Zrealone - 23-6-2010 at 11:48

Maybe Ar-O-NO2 might exist but then it will be as a transcient species because it will be a kind of mixte anhydride of two acids, like acetyl nitrate (CH3-CO-O-NO2); but, unlike this later, it will display a reactive counterpart into the aromatic moety that will unvariably lead to ortho- or para-nitrophenol what are more stable thermodynamically.
Ar-O-NO2 <--==> Ar-O(-) + NO2(+)
H-C6H4-O(-) + NO2(+) <--==> O2N-C6H4-O(-) + H(+) <==> O2N-C6H4-OH

Same kind of phenomenon is observed with aniline...that yield sometimes a nitramine prior to rearangement into nitroanilin!

[Edited on 23-6-2010 by PHILOU Zrealone]

mfilip62 - 23-6-2010 at 12:07

OK,lets make it simple...

You can put -NO2 on the phenyle/(A) without problem.(TNT,TNP...)
You can put -ONO2 on alchohols/(B)without problem. (NG,ETN,EGDN...)

Can you put B on the A and have both -NO2 and -ONO2 groups on the same molecules!?

For example...Safrole(or anything alike without metilen dioxy ring if it tempers with reaction)!?
Longer the A the better!

Anders Hoveland - 23-6-2010 at 19:14

To answer the three questions:
1,4 dinitrate would be unstable because of resonance. The benzene has delocalized bonding electrons, so the NO2's could break off without "breaking" any other bonds or creating radicals, because the two O atoms still on the benzene become doubly bonded onto the carbons.
1,4 dinitro benzene would be stable, because nothing can break off without creating radicals (with unpaired electrons).

"H-C6H4-O(-) + NO2(+) <--==> O2N-C6H4-O(-) + H(+) <==> O2N-C6H4-OH"
You forgot two of the equilibrium reactions;
(-)ON(+)=C6H4=O H(+)
O(-)

O2N--C6H5=O
One of these last two would probably be the most stable.
However, I am fairly sure that PhONO2 does not ionize. In contact with a concentrated strong acid, it would ionize in equilibrium, and the NO2+ would likely nitrate an adjacent position next to the now ---OH2+ group on the benzene. Thus you would get 2-nitrophenol.

The last post I did not understand. Yes, you can put a nitrate and nitro on the same compound. Now if you mean, can you make 1-nito, 4-nitrate benzene, the answer is: I am uncertain but my guess would be yes. This compound might share a resonance with (-)(-)O2N(+)=C6H4=O NO2(+),
but I doubt it would ionize without a strong acid.

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

PHILOU Zrealone - 24-6-2010 at 02:38

Quote: Originally posted by mfilip62

OK,lets make it simple...

You can put -NO2 on the phenyle/(A) without problem.(TNT,TNP...)
You can put -ONO2 on alchohols/(B)without problem. (NG,ETN,EGDN...)

Can you put B on the A and have both -NO2 and -ONO2 groups on the same molecules!?

For example...Safrole(or anything alike without metilen dioxy ring if it tempers with reaction)!?
Longer the A the better!

Off course you can get both nitro and nitrate groups in an aromatic ring! Especially if you have the alcoholic moety appart from the aromatic ring...
Typical examples are:
-2,4,5 trinitrophenethyle nitrate: O2NO-CH2-CH2-C6H2(NO2)3
-1,3,5 trimethylol-2,4,6 trinitrobenzene trinitrate: C6(NO2)3(-CH2-ONO2)3

It is possible than a phenyl nitrate exists longer than as a transcient species if the aromatic ring can't react further with the NO2(+)...I imagine it could be the case in pentamethylphenol.

PHILOU Zrealone - 24-6-2010 at 02:44

Quote: Originally posted by mfilip62

Nitration of benzoquinones or hydroquinone might be interesting idea I had recently, anyone documented it!?
I assume that o and p isomers would have interestingly different properties.
.....
Phenyl compound with -ONO2 would be interesting!

I think you should check into the nitranilate tread.

I also have very good ideas about o- and p- nitroquinones.

You have a very powerfull and beautifull molecule that is hexamethylolbenzene hexanitrate (C6(-CH2-NO3)6) that proves you are right in writting what you wrote.

PHILOU Zrealone - 24-6-2010 at 03:01

Quote: Originally posted by Anders Hoveland

"H-C6H4-O(-) + NO2(+) <--==> O2N-C6H4-O(-) + H(+) <==> O2N-C6H4-OH"
You forgot two of the equilibrium reactions;
(-)ON(+)=C6H4=O H(+)
O(-)

O2N--C6H5=O
One of these last two would probably be the most stable.

However, I am fairly sure that PhONO2 does not ionize. In contact with a concentrated strong acid, it would ionize in equilibrium, and the NO2+ would likely nitrate an adjacent position next to the now ---OH2+ group on the benzene. Thus you would get 2-nitrophenol.

The last post I did not understand. Yes, you can put a nitrate and nitro on the same compound. Now if you mean, can you make 1-nito, 4-nitrate benzene, the answer is: I am uncertain but my guess would be yes. This compound might share a resonance with (-)(-)O2N(+)=C6H4=O NO2(+),
but I doubt it would ionize without a strong acid.

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

Actually I didn't forgot, I simply did kept it simple...resonance forms and hybridations are often way to complex to write down here and doesn't say much or add much to the text.

If following you Ar-O-NO2 doesn't ionise without a concentrated strong acid...how do you account for the fact acetyl nitrate is a strong NO2(+) generator?It is usually used without external acids

Also a simple experiment I have done is to mix toluen and 69% HNO3 (what is, you must admit, far from being a concentrated HNO3 full of NO2+); I found strange I was able to get after a very short while (minutes or hours) without agitation nor heating (ambiant temperature) an interfacial yellow colour that turned day after day darker and darker (orange, brown,black with a green shade)...in fine after a few monthes I got orange to yellow cristalls that filled all the toluene layer...this simple observation went in total contradiction with my belief (based on what I have learned at university or in books) that concentrated HNO3 is needed to achieve aromatic nitration.
I believe what I got is paranitrotoluen, maybe with some orthonitrotoluene and nitrobenzoic acid...but I have to make some tests on it...I did take a lot of pictures of the reactor and so I will try to post those down here later.

mfilip62 - 24-6-2010 at 07:02

Thanks!

If you have the whole synthesis and some info on properties of hexamethylolbenzene hexanitrate (C6(-CH2-NO3)6)
please post it! (or PM me at least)

I am glad someone confirmed my idea and this -CH2-NO3 has sense,it "widens" the molecule and gives enough space
for aditional -ONO2 gruops.

Anotherinteresting examle might be to put etilo,propilo,butilo or longer group(s) on phenyl (no need to max. number of six)
and than "grow" some nice -ONO2 groups on them like beries!

I don't want to be smart-ass and say some organic molecules name that are proably wrong,so here is
very fast and rough sketch where "Y" might be -ONO2 groups.

benz.jpg - 32kB

Anders Hoveland - 24-6-2010 at 08:50

If acetic nitrate can indeed introduce a NO2 group onto phenol, then I would not think that phenyl nitrate would be stable. Does anyone know why acetyl phenol would be able to nitrate toluene, but not itself? One would think it could react with acetic acid, generating nitroform or CO2. I could not find much information about the compound, or whether it is even just a transient species. Nitric acid oxidizes acetic anhydride,(see the topic about tetranitromethane) so why would acetyl nitrate be expected to exist?

mfilip62 - 24-6-2010 at 11:07

Define stable!?

Some people (like most of my professors) label every explosive as "unstable" molecule, even TNT !
In world of energetic materials, everything that can be handled without causing havoc is stable.
Molecules that tend to explode on tiniest provocation or they exist only under extreme circumstances
(P,T,light wavelength...) are unstable.

psychokinetic - 24-6-2010 at 12:55

Indeed, stability is relative to what you want it for!

PHILOU Zrealone - 24-6-2010 at 12:59

Quote: Originally posted by mfilip62

Thanks!

If you have the whole synthesis and some info on properties of hexamethylolbenzene hexanitrate (C6(-CH2-NO3)6)
please post it! (or PM me at least)

I am glad someone confirmed my idea and this -CH2-NO3 has sense,it "widens" the molecule and gives enough space
for aditional -ONO2 gruops.

Anotherinteresting examle might be to put etilo,propilo,butilo or longer group(s) on phenyl (no need to max. number of six)
and than "grow" some nice -ONO2 groups on them like beries!

I don't want to be smart-ass and say some organic molecules name that are proably wrong,so here is
very fast and rough sketch where "Y" might be -ONO2 groups.

The synthesis of hexamethylolbenzene hexanitrate (C6(-CH2-NO3)6) is not easy...I have a reference of this compound somewhere in books it is listed as relatively unsensitive (impact sensitivity less sensitive than PETN and as brisant has HMX) for a polynitrate ester...probably because there are no adjacent (vicinal) nitrate groups....PETN has nitrate groups on carbons separated by a carbon atom and are thus not vicinal...this accounts for its "unsensitivity" as compared to the other nitrate esters of the H-(CHONO2)n-H familly (with n = 1,2,3,4,5,6)....same occurs with CH3-CH2-ONO2 (ethyl nitrate) and CH3-CH(ONO2)-CH2-CH2ONO2 or O2N-CH2-CH2-CH2-CH2-ONO2 (butandiol dinitrate).

The synthesis goes from hexamethylbenzene, to hexakis-chloromethyl-benzene via a radicalar halogenation....then I suppose they hydrolise it to the alcool with a base and finally nitrate it with conc HNO3.

I would shortcut the hydrolyse and the nitration by methatesis with AgNO3..because chloromethylaromatics are benzilic halogen and thus very easily subsitued!
White unsoluble AgCl is easily collected and recycled!
AgCl -sunlight-> Ag + 1/2 Cl2 (g)
Ag + HNO3 --> AgONO2 + NOx
Ar-CH2-Cl + AgONO2 --> Ar-CH2-ONO2 + AgCl (s)

Thus from
C6(CH2Cl)6 + 6 AgONO2 ---> C6(CH2ONO2)6 + 6 AgCl

The molecule you designed O2NOCH2-(CH(ONO2)-)3-C6H4-(CH(ONO2)-)3-CH2ONO2 will be dense but less powerfull than, and as sensitive to shock as, mannitol hexanitrate (hexanhexol hexanitrate).

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

mfilip62 - 24-6-2010 at 14:19

Damn, you are really got at this!

I just give example how phenyl might have both -ONO2 and -NO2 groups.
I didn't draw them,but -NO2 might be added also,
Just put those alkane groups on benzene so they make enough space to add -ONO2
on them and -NO2 on phenyl rign.

I have another idea how to remove vicinal distortion and have 12 -ONO2 groups.
Of course this might be extremely difficult to do,but rotation of propane groups may be just enough
to generate enough space for -ONO2 groups.

ben.jpg - 53kB

Anders Hoveland - 24-6-2010 at 20:53

All this seems pointless to me. Why not distribute those nitates over all 12 of the carbons to make it more stable? Even if two nitrate groups on the same carbon would not oxidize a C--H bond, your compound would be very unstable, violently decomposing in even the slightest trace of water, as the dinitrate would hydrolyze to become 2HNO3 and O=CH---R, as the concentrated HNO3 would readily oxidize everything.

Something like O2NOCH2CH(NO3)CH(NO3)...etc

[Edited on 25-6-2010 by Anders Hoveland]

mfilip62 - 25-6-2010 at 05:20

Sorry,I made a little mistake in drawning,but I tough exactly that.

Those "Y" groups are actually 1,3-Propanediol conected to the phenyl with middle C atom,while two other (end) C atoms
that had -OH on them are nitrated,times 6.

PHILOU Zrealone - 25-6-2010 at 13:50

Here is what you tried to draw

I think it is too bulky to be easy to do but who knows...experiment is the rule before rejecting.
Anyway it will be non ideal because of its negative OB (not enough O2 to burn all the carbon and hydrogen.

For some weird reason the hydrogens are lacking...they increases the bulky feeling...

[Edited on 25-6-2010 by PHILOU Zrealone]

[Edited on 26-6-2010 by PHILOU Zrealone]

PHILOU Zrealone - 25-6-2010 at 13:52

And here is what I was refering to slightly above

This compound exists and is also a bit on the negative side for OB...but stil possible if carbon monoxide is formed.
Maybe an extra oxygen provider would enhance its power!

[Edited on 25-6-2010 by PHILOU Zrealone]

JohnWW - 25-6-2010 at 13:52

Has anyone actually synthesized those two molecules, and lived to tell the tale?

[Edited on 25-6-10 by JohnWW]

mfilip62 - 25-6-2010 at 15:23

Zealone that was allmost EXACTLY what I tried to do!
Only difference being that propane dinitrate groups aren't paralel like l l l l l l,but more like l - l - l -.
Don't know if this is possible,but this might be natural aragement of the groups on the molecule if there is disturbance omong neighbour groups,you can't really do anything about that,rather than observe it.

They are both beautiful!

Nice idea to solve space problem with "hackenkreutz geometry"
(that is lousy translation,don't know to translate this into English, but I think you know what I mean)

OB is more like statistical than actual problem.
Actually it is more advantage than opposites.
For example TNT, you can add some significant mass by mixing with oxidants, while power of mix remains as pure explosive!
Some other explosives with negative OB, like some peroxides actually gain power, mass and stability by mixing them with oxidants (such as AN,KNO3...)
Another thing is war, all you want to do is to hurt enemy, so some CO can only be a good thing!

Stuff like these are way to exotic and powerful for civilian application where you need to take care of toxic fumes.

Only thing that might be tricky is their yield and sensitivity, but most phenyl nitrates are far from unstable.

If you have any documented and "high" yielding (relatively speaking) synthesis,please let us know!

[Edited on 25-6-2010 by mfilip62]

PHILOU Zrealone - 26-6-2010 at 02:32

Hexakis methylolbenzene was synthetised by trimerisation of butyne-1,4-diol (HO-CH2-C#C-CH2OH); but this implies rare catalysts. The butyne glycol itself can be synthetised from acetylen and formaldehyde; but it also require specific catalysts...

H-C#C-H + 2 CH2=O -cat 1-> HO-CH2-C#C-CH2-OH
3 HO-CH2-C#C-CH2-OH -cat 2-> C6(-CH2-OH)6

The butyne glycol could also lead to a powerful dinitrate ester but I wonder which of the two will be denser...the linear alcyne (richer at energy) or the cyclic planar aromatic.
In theory the later, but in practice I don't know...

[Edited on 26-6-2010 by PHILOU Zrealone]

mfilip62 - 26-6-2010 at 04:52

If you find exact,step by step synthesis please PM me.
exotic catalists will be pretty much available for me in next few years.

Anders Hoveland - 26-6-2010 at 16:30

Nitro compounds are much more insensitive than organic nitrate ester compounds. About as stable as nitro are organic amine perchlorates. Your compound, though somewhat "oxygen defficient", would still be almost as powerful than if all the CO was oxidized to CO2. Yes, it is powerful, but something more powerful and stable could be made with nitro groups instead, theoretically.

[Edited on 27-6-2010 by Anders Hoveland]

mfilip62 - 27-6-2010 at 07:33

I bet this compound would be as powerful as HMX,at least, pretty dense and a little bit less stable than PETN.
Will it be solid or liquid!?

Only thing I am sure of is that OB is the least important thing to me, just add some AN and VIOLA!

Those prediction are solely based on my experience with similar stuff, and might be totally moronic
I don't have software to test theoretical crystal structure, density... nor did I ever attended higher organic chemistry.
(I left if to be my last class for few reasons, first after old kicks-off(he is VERY old and pain in the ass,so he probably met Franz Joseph in person)
and after I solve things I hate like math and physics,so I can give full attention to my favorite class

)

Anders Hoveland - 27-6-2010 at 15:14

I did some more research. Apparently, 1mole quinone reacts with only 1mole NH2OH to make 4-nitroso phenol. You can see a picture of this compound here: http://www.chemdrug.com/databases/dataimg/1/7729.png

This is still a way to get a nitroso on a benzene ring, so you can reduce it with HSO3- and get a --NHOH group that can be used to make energetic perchlorate salts. This is just more speculation, but tell me if it seems unreasonable;
4-hydroxylamino phenol. reacts with acetyl chloride CH3COCl to put a protective acetyl group on the hydroxylamine instead of the hydrogen atom. A nitration should first attack the ring. For example, nitration of TNT does not attack the methyl group first.
After the nitro groups are added, the acetyl is hydrolyzed off with NH4OH. This should leave, 2,5-dinitro, 4-hydroxylamino phenol, which could react either as an acid or base. Adding HClO4 to this should make an explosive salt. It could also form a salt with Ammonia. Any comments welcome.

mfilip62 - 27-6-2010 at 16:23

Ammonia salt tends to be to too stable,and this doesn't look powerful,so iiiik...Not use of something too stable,expensive to make and not as powerful.
Sounds like crack-head version of NH4NO3.

Perchlorates tend to be relatively stable without presence of fuel,and this phenyl(organic fuel) perchlorate(strong oxidans) combination might be one o the first useful phenyl derivatet primary explosives,who knows!? Lets do some experiments!

Only problem that might be present is corrosion due the perchlorate,so not pretty much useful in military unless it unleashes deadly gasses like phosgen(C+Cl+O quite likely!!!)
Imagine,High Explosive and chemical agent in one compund! That is what russians call GREAT SEXESS!!!

I am curently searching for p-benzoquinoe which is next to imposible to find here.
(Yes, I know I can make it easily from p-hydroquinone,but it is hard to find too!)

Anders Hoveland - 27-6-2010 at 18:00

Phloroglucinol on wikipedia also has some interesting chemistry.

Making Benzoquinone
From Aniline using Potassium Dichromate

A solution of 20g of aniline in a mixture of water (600 ml) and concentrated sulfuric acid (160g, 80ml) is placed in a stout beaker immersed in ice-cold water and continous stirring is begun. During the course of an hour 20g of finely powdered potassium dichromate are added in portions of about 1g at a time, care being taken that the temperature does not rise above 10°C. A better method is to add a solution of 20g of sodium dichromate in 100 ml of water from a dropping funnel. In either case the mixture is left in a cool spot overnight, and then a further quantity of potassium dichromate (33g), or a solution of sodium dichromate (40g in 200 ml of water), added under conditions similar to the above. After four or five hours the mass is extracted three times with ether, the ethereal solution dried with calcium chloride, and the ether removed by evaporation. The crude quinone is purified by distillation in steam, or by sublimation, and forms orange-yellow needles with a characteristic pungent odour. Melting-point, 116°. Yield: 19g

[Sudborough & Campbell, Practical Organic Chemistry]

I am unsure if nitronium ions will spare the acetyl by attacking the benzene ring first.
"SO3" from H2S2O7 could also be used as the protecting group on the hydroxylamine.
C6H5N(OH)SO2(OH)

mfilip62 - 28-6-2010 at 07:09

Thanks!
Anyone tried this synthesis,an tips!?

Well,aniline is hard to find too,but I will try...

Anders Hoveland - 28-6-2010 at 19:09

Analine can be made by doing a nitration on benzene. The nitration bath must be 70C, just below benzene's boiling point. from wikipedia: "Nitrobenzene is prepared by nitration of benzene with a mixture of concentrated sulfuric acid, water, and nitric acid, called "mixed acid." Its production is one of the most dangerous processes conducted in the chemical industry because of the exothermicity of the reaction (ΔH = −117 kJ/mol)."
Then zinc metal is added to nitrobenzene, and HCl solution is added. This reduces the nitro to an amine.
I think there is a more direct route to make benzoquinone from benzene or phenol, or benzoic acid, but it has a low yield and is messy. It involved a severe oxidation, but I cannot remember the details.
There must be a way to buy quinone, perhaps an online photography store? A craft or big art store, in the photographic developer section?

[Edited on 29-6-2010 by Anders Hoveland]

JohnWW - 28-6-2010 at 21:19

Quote: Originally posted by Anders Hoveland

Aniline can be made by doing a nitration on benzene. The nitration bath must be 70C, just below benzene's boiling point. from wikipedia: "Nitrobenzene is prepared by nitration of benzene with a mixture of concentrated sulfuric acid, water, and nitric acid, called "mixed acid." Its production is one of the most dangerous processes conducted in the chemical industry because of the exothermicity of the reaction (ΔH = −117 kJ/mol)."

I am very surprised that it should be so dangerous, because the nitration of benzene to C6H5NO2 was one of the class laboratory experiments that students, including myself, were given to do in second-year Organic Chemistry at Victoria University Of Wellington, New Zealand, in 1967. I still remember the strong, sickly smell of the product, like oil of bitter almonds. Another experiment that we later did on the product, in Physical Chemistry, was to measure its dielectric constant.

mnick12 - 28-6-2010 at 22:19

Nitrobenzene is pretty easy to make here is a prep from the chemistry of powder and explosives,

"Preparation of Nitrobenzene. One hundred and fifty grams of concentrated
sulfuric acid (d. 1.84) and 100 grams of nitric acid (d. 1.42)
are mixed in a 500-cc. flask and cooled to room temperature, and 51
grams of benzene is added in small portions at a time with frequent
shaking. Shaking at this point is especially necessary lest the reaction
suddenly become violent. If the temperature of the mixture rises above
50-60°, the addition of the benzene is interrupted and the mixture is
cooled at the tap. After all the benzene has been added, an air condenser
is attached to the flask and the material is heated in the water
bath for an hour at 60° (thermometer in the water). After cooling, the
nitrobenzene (upper layer) is separated from the spent acid, washed
once with water (the nitrobenzene is now the lower layer), then several
times with dilute sodium carbonate solution until it is free from acid,
then once more with water, dried with calcium chloride, and distilled
(not quite to dryness). The portion boiling at 206-208° is taken as
nitrobenzene."

Benzene is pretty hard to nitrate, but can still be done pretty easily.

Also anders if you plan on making benzoquinone from benzene that will be a pain in the ass. The way I make benzoquinone is from the oxidation of hydroquinone. I followed this procedure but modified it to use potassium chlorate instead of sodium chlorate, since I have a lot of potassium chlorate from my electrolyis expiriments. It works very well and my yield is often around 90%, here is the page http://www.lycaeum.org/rhodium/chemistry/benzoquinone.html , there a whole lot on there. the chlorate method is high yielding and cheap.

Taoiseach - 28-6-2010 at 22:43

p-benzoquinone can be made from OTC precursors:

https://www.sciencemadness.org/whisper/viewthread.php?tid=82...

mfilip62 - 29-6-2010 at 11:10

Seems simple enough...
Anyone know how pure it is!?
Chlorinated byproduct might be a problem, how to remove it!?

This question might be better fitting into "techniques" but does anyone know how to purify it totally!?
Any method of simultaneous drying and resublimiation!?

[Edited on 30-6-2010 by mfilip62]

Anders Hoveland - 1-7-2010 at 16:58

Bromine mixed with benzene and a little sunlight will quickly make bromobenzene, because of the radical cascade, discussed elsewhere on this forum. Bromobenzene will react with AgNO3 dissolved in benzene to make benzene nitrate, which is unstable. This would be an interesting way to make nitrophenol.

Here is an easy synthesis: Start with 2-nitro phenol. This should condense with hydroxylamine through the tautomeric ketone!
Whereas phenol would not condense with NH2OH; it would only form a salt. 1-hydroxylamino, 2-nitro benzene would form an explosive salt with HClO4.
Of course picric acid could be used instead, making compound #5.

Or you could start with dinitro phenol (the nitration generates almost entirely 2,4-dintro). Then do a nitrosation by adding to conc. H2SO4 and slowly adding NaNO2. This will add an "NO" group in position 6. Use bisulfite to reduce the NO to a NHOH group. Then make the OH group in position 1, condense with NH2OH, as previously described in this post. You will end up with 1,6-di[hydroxylamino], 2,4- dinitro benzene. This will of course form a very powerful explosive salt with HClO4. The decomposition products from a molecule of this salt are:
3H2O, 2HCl, 5CO2, 1CO, 2N2. excellent oxygen balance.
The use of hydroxylamino groups, rather than plain amino, helps make this compound more powerful.

picric.bmp - 1.4MB

497 - 1-7-2010 at 20:21

I wonder if you might have a hard time forming the perchlorate salt of trinitrophenylhydroxylamine because the electron withdrawing effect of the nitro groups should reduce the basicity.. Picramide isn't basic from what I remember, and IIRC hydroxylamines tend to be even less basic than amines..

Anders Hoveland - 1-7-2010 at 20:40

Yes, it is not basic, but it should still be able to act as a base with a strong acid. Furthermore, even if the nitro groups do strongly pull electrons away, an extra H+ ion should be able to stick on the nitro group.
I mean, if there is a positive charge on the NHOH group, then it will be double bonded to the ring, meaning one of the NO2 groups will also be double bonded to the ring, each of its oxygen atoms having their own electron.
thus you would get a ==N(+)(O-)(OH) on the ring, and of course the ==N(+)H(OH) from the NHOH group.
The net effect still uses the NHOH as a base, except the hydrogen would go on a nitro, not the hydroxylamino.
Hope this makes sense, just do not feel like making another picture.
Of course, a perchlorate salt of trinitro-analine would be quite acidic and deliquescent (it would have to be kept from absorbing moisture from the air), and it probably would not crystallize out of solution easily. Mono-nitro-Analine could be dried much more easily; and probably could be handled with bare hands without chemical burns.
Also just to clarify:
Obviously nitro-phenol does not condense with NH4OH, it only forms the ammonium salt.
Obviously phenol would not condense with hydroxylamine, it would only form the carbolate salt.
It is mono or di-nitro phenol that should condense with NH2OH, since hydroxylamines are known to condense with ketones to make oximes.

This is a synthesis most members here can do easily, and it would be an interesting reaction.

[Edited on 2-7-2010 by Anders Hoveland]

Anders Hoveland - 5-7-2010 at 22:28

[Edited on 6-7-2010 by Anders Hoveland]

CL-14 from Rosorcinol

AndersHoveland - 5-12-2011 at 18:21

I did a search and could not find anything about the explosive Cl-14 in this forum. Not wanting to start a new thread, I will just put a post here, since the proposed chemistry is similar.

Here is some information about Cl-14,
http://www.digitalprecursor.org/roguesci/chemlab/energetics/...
detonation velocity 8050 m/sec.

Rosorcinol (1,3-dihydroxy-benzene) can be converted to phloroglucinol (1,3,5-trihydroxy-bezene) by fusion with solid sodium hydroxide. the reaction also releases hydrogen gas.
"THE LIBERATION OF HYDROGEN FROM CARBON COMPOUNDS", Shipley Fry, Else L. Schulze, Helen Weitkamp
J. Am. Chem. Soc., 1924, 46 (10), pp 2268–2275

This preparation of phloroglucinol is of interest since the substance can tautomerize into the tri-ketone of cyclohexane http://en.wikipedia.org/wiki/Phloroglucinol , and thus condensation of phloroglucinol with NH3 would result in 1,2,3-triamino-benzene. This could then potentially be nitrated [see comments at bottom of this post] into TATB, http://en.wikipedia.org/wiki/TATB

The TATB would finally be treated with aqueous chlorine for conversion, in moderate yield, into the "advanced" explosive CL-14 (5,7-diamino-4,6-dinitrobenzofuroxan);

For example, the reaction of 2-nitroaniline with hypochlorite solution produces "benzofurazan oxide" (more commonly named benzofuroxan).
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv4...

Quote:

The literature extensively describes the preparation of phloroglucinol by hydrolysis of 1,3,5-triaminobenzene in the presence of concentrated hydrochloric acid.

hydrolysis of 1,3,5-triaminobenzene to give phloroglucinol, mention may be made of U.S. Pat. No. 4,115,451. That patent recommends hydrolysis of 1,3,5-triaminobenzene in an excess of concentrated hydrochloric acid at a temperature of 100 to 200° C., to end up with phloroglucinol. This hydrolysis step is followed by a step of extraction with an acetic ester. The extracted phase containing the phloroglucinol crystallizes after cooling.

My guess is that the reaction is reversible, but that such a reaction would not be mentioned in patents because phloroglucinol is industrially much more expensive than triaminobenzene.

As for the nitration, I also found this

Quote:

The triethyl tricarbamate of 1,3,5‐triaminobenzene was prepared... The tricarbamate underwent nitration to give the mono‐, di‐, or trinitro analogs in excellent yield

suggesting that direct nitration of unprotected 1,3,5‐triaminobenzene may be problematic. Probably best to react with acetyl chloride first. After the nitration, the acetyl (or carbamate groups resulting from oxidation) can be hydrolysed off by simple treatment with 20% solution of NH4OH.

[Edited on 6-12-2011 by AndersHoveland]

Rosco Bodine - 5-12-2011 at 22:26

Quote: Originally posted by AndersHoveland

thus condensation of phloroglucinol with NH3 would result in 1,2,3-triamino-benzene.

References ?

AndersHoveland - 6-12-2011 at 14:33

Quote:

From the foregoing results, it appears that phloroglucinol, a trihydric phenol, reacts more energetically with aromatic amines than the dihydric phenols [such as 1,3-dihydroxybenzene], which in turn are more reactive than the monhydric compounds [example, phenol].

In view of the complete analogy between the action of ammonia and the substituted amines, it seems probable that phloramine, the product of the action of ammonia on phloroglucinol, is also a derivative of trihydroxybenzene, and not of the secondary phloroglucinol, as indicated by Baeyer (Abstr. 1886, 350).

Journal of the Chemical Society, Volume 60
(Great Britain), p191

Quote:

Phloramine- A compound produced by the action of ammonia on phloroglucin.
C5H6O3 + NH3 --> C6H7NO2 + H2O

A dictionary of chemistry and the allied branches of other sciences, Volume 4, p488

It would appear that whereas phloroglucin[ol] is the tautomer of 1,2,3-trihydroxy-benzene, phloroglucin, which is a partial imine of a tri-ketone, is the tautomer of 3,5-dihydroxy-aniline.

Quote:

The conversion of phenol into aniline proceeds under very drastic conditions (350-450°C, 50-60 bar) and the substitution of one hydroxyl group in resorcinol by an amino group
occurs quite readily at 200°C, whereas phloroglucinol gives 3,5-dihydroxyaniline and 3,5-diaminophenol in almost quantitative yield under very mild conditions (long storage at room temperature with ethanolic solution of ammonia).

It was [calculated] that the enolic form, 1,3,5-benezenetriol, is by far more stable than the keto form, 1,3,5-cyclohexanetrione. On the other hand, the latter is more abundant in the phloroglucinol system than is the keto form of phenol (2,4-cyclohexadien-1-one)

The picture (on page 718, figures 15 and 16) clearly shows that hydroxylamine condenses with phloroglucinol to form the tri-oxime of cylcohexane.

Chemistry of Phenols, Part 2
Zvi Rappoport, p717-718

http://books.google.com/books?id=0pVQgwt5ODoC&pg=PA718&a...

I cannot find any references about further condensing 3,5-diaminophenol with ammonia to form 1,3,5-triaminobenzene, although I did find a reference to the reverse reaction,

Quote:

The most convenient method of preparation is the hydrolysis of the hydrochloride of 1:3:5-triamino- benzene by prolonged boiling with water.

Chemistry of carbon compounds: a modern comprehensive treatise, edited by E. H. Rodd, p483; specific reference made to H. Weidel and J. Pollak, Monatsh., 1900, 21, 20

Quote:

hydrolyse 1:3:5-triaminobenzene with 5% HCl and obtain 3:5-diaminophenol.

Reports on the progress of applied chemistry, Volume 33, p74

It may be possible that a third amino group cannot be added. But the fact that hydroxylamine can fully condense with 1,3,5-trihydroxybenzene suggests that ammonia may also be able to react likewise.

Summary of this Post
The above post is essentially providing references about the replacement of hydroxyl groups by amine groups. Ammonia can easily condense with certain specific types of hydroxybenzene derivitives through the formation of a transient imine, =NH, on the ketone, =O, tautomers. This is normally the type of information found in the organic chemistry section, but I think this type of basic organic chemistry is important in the energetics section also.

[Edited on 6-12-2011 by AndersHoveland]

AndersHoveland - 6-12-2011 at 15:20

Limited oxidation of para-quinone-di-oxime, HON=C6H4=NOH, produces para-di-nitroso-benzene,
O=N-C6H4-N=O

Quote:

...ortho-dinitroso-benzene, a para-isomere of which had already been made known by Nietzki. It was produced by the oxidation of para-quinone-dioxime.

Report of the annual meeting, Volume 64, Part 1894, p620
British Association for the Advancement of Science, year 1894

Rosco Bodine - 6-12-2011 at 16:01

I remain unpersuaded

AndersHoveland - 6-12-2011 at 17:10

Quote: Originally posted by Rosco Bodine

I remain unpersuaded

I have proved that at least two of the hydroxy -OH groups can be replaced with amine -NH2 groups. Just have to find information proving that third hydroxyl group can likewise substitute off also.

But you must admit it is remarkable that simple condensation with ammonia can effect such a substitution.

Rosco Bodine - 6-12-2011 at 17:28

I can see a halogen being exchanged or a nitro being reduced to get the amino,
a lot easier than I can see the ammonium salt of a phenolic acid being thermally dehydrated to the amino. That was a new one on me and I strongly suspected it would be a less than convenient method, probably not occurring easily and possibly not occurring at all.

C-14 from mothballs

AndersHoveland - 6-12-2011 at 17:40

I also have another similar idea that Cl-14 could be made from paradichlorobenzene. When I recently went to the store, I was surprised to see that relatively pure paradichlorobenzene is still used in some brands of mothballs.

Nitration of paradichlorobenzene
http://books.google.com/books?id=NUo2AQAAIAAJ&pg=PA2260&...

Here is a graph which show that the paradichlorobenzene is mostly consumed after 15 minutes using 12M (molar concentration) HNO3, at only 10 degC.
http://www.chem.uiuc.edu/weborganic/arenes/Nitration/diClben...
http://www.chem.uiuc.edu/weborganic/arenes/Nitration/diClben...
Obviously it would take longer to add the second nitro group.

"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)

Essentially 1,4-dinitro-2,5-diaminobenzene will be obtained, which could then be reacted with hypochlorite to form the di-furoxan of benzene. From here you might be wondering how this will ever get to Cl-14, but it is actually quite easy. Just do a nitration again.

Nitrobenzofuroxans can tautomerize in very remarkable ways, see "scheme 17" on page 16
4-methyl,3-nitro-benzofuroxan is thus the same compound as 6-methyl,3-nitro-benzofuroxan.
http://www.ark.chem.ufl.edu/Published_Papers/PDF/256.pdf

So once there are adjacent nitro groups, those furoxans can essentially move around on the molecule.

Finally, just reduce one of the nitro groups to an amine group using a ferrous salt (FeCl2), similar to reducing picric acid to picramic.

Quote:

When solutions of picric acid and Ferrous Sulfate are mixed, no obvious reaction happens, but when the Iron is precipated by addition of a strong base, the liquid takes on a deep red color, and Ferric Hydroxide precipitates. Ammonia may be used as the base, in which case, addition of acetic acid to the filtered solution (the insoluble Ferric Hydroxide being previously completely filtered out) causes thin red needle crystals of picramic acid to precipitate out. This way is much better than using sulfides and will give a much superior product to the previous one. (researcher Aime Girard)

The final product should be Cl-14 (5,7-diamino-4,6-dinitrobenzofuroxan)

......................................................................................
A note for terminology: In the benzofuroxan molecule, the furoxan ring is attached to the 1- and 2- positions of the benzene ring. The mention to "di-furoxan of benzene" in htis post referred to the two furoxan groups attached in the 1,2- and 4,5- positions.

I will post more information, more supporting references, and diagrams of this idea later. If someone else wants to make a diagram of this idea, showing the molecular structures, please feel free to save me the trouble.

[Edited on 7-12-2011 by AndersHoveland]

Third Idea for Route to Cl-14

AndersHoveland - 7-12-2011 at 14:48

Here is a third idea for a new synthesis route to Cl-14,
see the attachments at the bottom of the page on this site:
http://sites.google.com/site/energeticchemical/furoxan-witho...

(I made a mistake in the picture- nitration of aniline produces mostly 3-nitroaniline, best to start with chlorobenzene instead, partially nitrate it, then react with NH3 in anhydrous alcohol)

Quote:

Synthesis for Nitrating Chlorobenzene
90 mL of chlorobenzene is added dropwise with a dropper pipet or buret to a previously prepared, and cooled to room temperature, mixture of 110 mL of 99% nitric acid and 185 mL of 99% sulfuric acid, in a 1000-mL beaker, while the mixture is stirred mechanically with a magnetic stirrer. A stirrer is essential for the length of time required, you may try this by hand with a stirring rod at your own risk. The temperature will rise because of the heat of the reaction, but should not be allowed to go above 50-55 °C. After all the chlorobenzene has been added, the temperature is slowly raised to 95 °C and is kept there for 2 hours longer while the stirring is continued. An upper layer of light yellow liquid solidifies when cold. The layer is removed, broken up under water, and rinsed. The spent acid, on dilution with water, will precipitate an additional quantity of dinitrochlorobenzene. All the product is brought together, washed with cold water, then several times with hot water while it is melted, and once more with cold water under which it is crushed. Finally, it is drained and allowed to dry at room temperature. The product, melting at about 50 °C, consists largely of 2,4-dinitrochlorobenzene, along with a small quantity of the 2,6-dinitro compound, m.p. 87-88 °C. The two substances are equally suitable for manufacture of other explosives or alone as an explosive. You will need a graduated cylinder for measuring liquids, and a thermometer to monitor the temperature.

Warning: Dinitrochloro benzene is extremely poisonous. Inhaling the vapors can be deadly, as the compound oxidizes hemogoblin in the blood to a form that cannot bind with oxygen, leading to ischemia. Skin contact causes severe rash, itchy burning sensation, and blistering, analogous poison ivy.

2,4-dinitroanaline undergoes an unexpectedly complex reaction when treated in alkaline methanol solution at 50degC with aqueous sodium hypochlorite. The product is a “chloromethoxybenzofurazan oxide”, namely 1-chloro-3,4-furoxan-4-methoxy-benzene.
Green and Rowe (1912). and
“Furazan Oxides. An Unusual Type of Aromatic Substitution Reaction", Frank B. Mallory, Suzanne P. Varimbi (1963)

As can be seen in the second attachment (in the site), the chlorine and methoxy groups could potentially be substituted by amine groups by react with NH3.

Here is another reference to an adjacent amino and nitro group on a benzene ring being converted to an adjoining furoxan ring by treatment with NaOCl,
Green and Rowe, J. Chem. Soc., 101, 2452 (1912).

A fourth idea for a route to Cl-14
Not related to the previous idea, I also found a source that states that aniline reacts with bromine water, without a catalyst, to form 2,4,6-tribromo-aniline.
"Nitrations of Aromatic Compounds"
(Microsoft Powerpoint)

This type of reaction could potentially be very useful, because bromine substitutes off far more easily than chlorine atoms. Reacting the product with anhydrous NH3 would no doubt produce 1,2,4,6-tetraminobenzene. Protect the amine groups by reacting with acetic anhydride, then perform a nitration. React with NH4OH to hydrolyse off the acetyl groups. The resulting 3,5-dinitro-1,2,4,6-tetraminobenzene might be a useful precursor to make Cl-14.

Quote:

Azobenzene is also produced when KMnO, acts on aniline, or when aniline is oxidized in alkaline solution by hypochlorite.

Proceedings of the American Pharmaceutical Association ,Volume 58, p288

So reaction of the 3,5-dinitro-1,2,4,6-tetraminobenzene with sodium hypochlorite solution could potentially result in
azo-bis[nitrobenzo-di-furoxan], which is essentially two molecules of Cl-14 that are joined together by the former amino groups, the new molecule no longer containing any hydrogen atoms.
(N2O4)2(NO2)C6-N=N-C6(N2O4)2(NO2)

Azo linkages are easily reduced to hydrazo linkages, -NH-NH-
So I suppose this compound could be regarded as the "di-Cl-14"!

Bromine water also similarly reacts with phenol to give tribromophenol.
Journal of the Chemical Society, Volumes 31-32, p361

Quote:

Chloro and bromobenzene reacted with the very strong base sodium amide (NaNH2 at low temperature (-33 ºC in liquid ammonia) to give good yields of aniline (aminobenzene). However, ortho-chloroanisole gave exclusively meta-methoxyaniline under the same conditions.

source: http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/benz...

Anisole is the same thing as methoxybenzene, CH3-O-C6H5

[Edited on 8-12-2011 by AndersHoveland]

AndersHoveland - 7-12-2011 at 15:53

I found some more interesting information that may possibly relate to the condensation products of NH2OH on quinone:

Quote:

β-Phenylhydroxylamine forms colourless needles, m.p. 81°-82° ; soluble in 10 parts hot and 50 of cold water, readily soluble in alcohol, ether, carbon disulphide, and chloroform, sparingly in petroleum. It dissolves in sulphuric acid with a deep blue colour. By heating at 100° azobenzene together with aniline, azoxybenzene, and other products are formed. Oxidation with potassium permanganate gives first nitrosobenzene, then nitrogen and azoxybenzene (Bamberger and Tschirnmer, Ber. 1899, 32, 342); in dilute neutral solution hydrogen peroxide yields azoxybenzene, in alklaline solution azoxybenzene and nitrobenzene (Bamburger, Ber. 1900, 33, 119). In the presence of hydroxylamine and air it is partly oxidized to azoxybenzene and partly reduced to aniline, phenylazoimide, and benzeneazohydroxyanilide also being formed… Mineral acids yield p-aminophenol and azoxybenzene; alcoholic sulphuric acid gives azoxybenzene, o- and p-phenetidine, o—and p-aminophenols, aniline, and other compounds.

"A dictionary of applied chemistry", Sir Thomas Edward Thorpe, p88

Terminology and Structures
Just to save you the trouble of having to look up all the structures, I made a glossary of terminology below:

"beta-phenylhydroxylamine" refers to a benzene ring connected to the nitrogen atom of hydroxylamine.
C6H4-NHOH
as can be seen in the picture below,
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv1...

the structure for "phenetidine" is NH2-C6H4-O-CH2CH3
(obviously ethanol was used as the alcohol in the reaction)

"phenylazoimide" is the same thing as phenyl azide,
C6H5-N=N=N

azoxybenzene is C6H5-N=N(O)-C6H5, with the oxygen atom bonded to one of the nitrogen atoms.

azobenzene C6H5-N=N-C6H5

I think "benzeneazohydroxyanilide" might be
C6H5-N=N-C6H4-OH

[Edited on 8-12-2011 by AndersHoveland]

AndersHoveland - 7-12-2011 at 22:51

Here is a diagram, starting with paradichlorobenzene.
The final product is essentially Cl-14 but without the amino group.

I am not entirely sure what the result of treating NaOCl with 1,4-dinitro-2,5-diaminobenzene would be. I suspect two furoxan rings cannot both form in these positions. If only one furoxan ring forms, it might be possible that the other amino group could be oxidized, although it would be more resistant to oxidation because it is in an electron-donating position. Perhaps best to use only a limited proportion of hypochlorite solution to avoid potential oxidation of that second amino group.

[Edited on 8-12-2011 by AndersHoveland]

PHILOU Zrealone - 23-1-2012 at 15:22

There is a big chance your paradiamino-2,5-dinitrobenzene will be oxydised into a 2,5-dinitroparaquinon...
H2N-C6H2(NO2)2-NH2 -ox-> HN=C6H2(NO2)2=NH --> O=C6H2(NO2)2=O + 2NH3

On the other hand amino groups in ortho position of a nitro group on an aromatic ring often undergoes thermal oxydoreduction...into furoxan without need for NaOCl.
It is the very case for 1,3,5-Triamino-2,4,6-trinitrobenzene what turns upon heating into a mono, di or trifuroxan derivative...what explains the very high stability of related compounds and use in LOVA HE.

AndersHoveland - 23-1-2012 at 21:36

Quote: Originally posted by PHILOU Zrealone

There is a big chance your paradiamino-2,5-dinitrobenzene will be oxydised into a 2,5-dinitroparaquinon...

That could in fact be the case. Thanks for this insight.
Paradiaminobenzene, for example, hydrolyses to hydroquinone under mildly acidic conditions.

On the other hand, the two electron-withdrawing nitro groups, which are in the ortho- position relative to an amino, would be expected lend stability towards the configuration. Apparently 1,4-diamino-2-nitrobenzene is also used in hair products (where it hydrolyses to the quinone), which is not encouraging. An acetyl protecting group on one of the amines might prevent hydrolysis/oxidation so that the other amino group could be oxidized to a furoxan. Indeed, the industrial production of 1,4-diamino-2-nitrobenzene involves acetylation (with Ac2O) of both the amino groups before nitration.

2,5-dinitroparaquinone is described in the literature as not being very chemically stable.

[Edited on 24-1-2012 by AndersHoveland]