Nitro derivatives of phenolic oxidation products.

[Mr Cool]

What a fancy sounding title this thread has :D.

Anyway, I remember reading that someone was trying to make TNP, but ended up with a dark yellow, very sensitive compound. I can't remember who it was, or even if it was on this Forum, which is annoying because now I don't know the method I used!!

Anyway, I tried their method, got a dark yellow product, and forgot about it for a while, only to remember what it was earlier today.

(If anyone knows the post/thread I'm talking about, please provide a link!)

So anyway, I've been playing around with this, and it is very sensitive! I recrystalised a small amount from dil. HCl (a few %) to rule out the possibility of it just being a picrate salt, and am drying a small amount out now to try some DDT tests. A grain on the end of a splint deflagrates like a picrate salt.

In a little while I'll be able to post a few pics, when my camera batteries have recharged.

Now, anyone who has read FEMFEP will recall lead nitranilate. I'm not really sure what this is - chloranil (tetrachloroparaquinone) is produced by oxidative chlorination of a phenol derivative, salicylic acid in that case, and then this is reacted with sodium nitrite to produce "sodium nitranilate." The thing that confuses me is, how does tetranitroparaquinone form a salt? Unless nitrite ions reduce tetranitroparaquinone into tetranitroparahydroxyquinone, which could form a salt... I don't know. And then sodium nitranilate is reacted with lead nitrate to give lead nitranilate.

I'm thinking that this violently flammable, dark yellow substance that I have here might be a nitro derivative of paraquinone.

What do you all think? Has anyone else come accross this product? Does anyone have any more info on nitranilates?

Please post anything and everything that you think might be relevant...

(Pics coming soon...)

Edit: IMHO, the paraquinone structure is supported by the fact that it is darker yellow and more sensitive than TNP. As illustrated in the attached diagram, picrate anions have three resonance forms, which increase in sensitivity and "yellowness" as they increase in similarity to the quinone structure.

[Mr Cool]

I can even post a little vid!!

Please remeber - my degree is not in film making, and it's hard to ignite something with a long stick if you're viewing it in 2D through a camera :). But it get's the point accross - this is NOT TNP!

Here's (http://www.boomspeed.com/mrcool/NotTNP.rar) the vid. You'll probably need WinRAR to view it.
Oh, and the attached diagram in the post above was drawn in MDL ISIS Draw 2.5, I'm not sure what you can view it with!

[Mr Cool]

Hmmm...

A small lump dropped into conc. sodium bicarbonate solution did not produce effervescence.
A column, 5mm by 3mm diameter (hand pressed), did not detonate when ignited by visco - it just looked like a little tiny rocket engine, and made a surprisingly loud "ROAR" kinda noise. It is VERY sooty - the little "rocket engine" was held in place on the ground, and the test left a large sooty area on the ground where the exhaust was. This would seem, to me, to contradict the tetranitroparaquinone idea, since this has lots of oxygen. Maybe it is a less-nitrated quinone.
Although it makes a strongly yellow-coloured solution in water, this solution does not dye things.
I have not been able to obtain it in the molten state - it seems to darken, almost to red, and go kinda mushy looking, then ignite.

I have run out of the dried-out stuff, but I have plenty more of it stored underwater - whatever it was, it was produced in quite a high yield!

Here (http://www.boomspeed.com/mrcool/Comparison.jpg) is a remarkably awful photo comparing its colour to that of TNP (on the left).

[Mr Cool]

No-one got anything to say?

Oh well, I thought it was interesting :(.

Come on, talk to me!

Edit: Sorry, I'm just bored, waiting for some things to dry...

[tom haggen]

Heres a pic of some mystery yellow crap I made, I behaves much like the way your dark yellow mystery crap does. I have posted threads about this stuff before, but I don't remember where. Heres some characteristics- when I put it on the end of a toothpick its ignites and burns sporadically almost like a crappy home fuse, and smells quite a bit like burning nitrocellulose.

[Mr Cool]

Yes, I had a feeling it was you who first posted it, I searched for ages without luck though.

I'm sure that is the same stuff - mine is exactly the same colour and physical apperance when wet like that.

Are you sure yours was dry? I've never had it burn sporadically!

[T_Pyro]

Could you please explain how you inadvertently ended up with this product? Maybe the synthesis of this compound itself could be as interesting, if not more than, that of TNP.

You should check to see whether the product dissolves in NaOH. If it does, then there's definitely a phenolic -OH group. Perhaps it isn't nitrated enough to be a stronger acid than carboxylic acid.

An alternative method of verifying whether it indeed is nitrated p-benzoquinone, would be to nitrate quinone itself, and compare properties. I'm not sure about this method, but it seems logical.

The sooty residue would indicate two things: that the product has a low oxygen content, and/or that the product is highly unsaturated.

Regarding nitranilates, I think March would be a good place to look. Sorry, I'm not priveleged enough to own a copy.

[tom haggen]

Mr. Cool- I think that your mystery yellow precipitate must contain more of whatever makes it flame sensitive than my product. I have no doubt that we have both manufactured the same product. However, I'm willing to bet that yours is slighty more pure than mine for some reason. Below is a link to a few posts of me talking about this topic. I wrote about my methods. At this point I have no desire to try and recreate this synthesis, or synthesize picric acid. The stuff is just too damm messy! I did finally manage to obtain some picric acid via rosco explaining a recrystallization towel trick.

http://www.roguesci.org/theforum/showthread.php?t=2492&page=1

[Mr Cool]

T_Pyro, I do intend to come up with a method that will reliably produce this product. Unfortunately I don't have time to do any serious experimenting until mid June :( :mad:. University sucks. And I hate my course. And it sucks. They make me do maths for god's sake!! MATHS!!! Grrrrrr... university sucks... kill them all...

The product does dissolve in NaOH soln., but it also dissolves in water... I'll recrystalise some from NaOH, and see if the product is any different.

I have no quinone :(.

"must contain more of whatever makes it flame sensitive"

I am certain that it is not TNP contaminated with something flame sensitive, since it behaves just the same after recrystalisation.

[tom haggen]

I should add that although my product burns sporadically, it does so quite violently. mr. cool, I wasn't really implying that your product is TNP contaminated with flame sensitive components. Anyway good luck determining what this substance is, I will be very interested to see what kind of uses can be applied with this chemical. Hope you mods get your avatars back someday, I miss those things.

[T_Pyro]

That the product should dissolve in NaOH but not in sodium bicarbonate solution is a little worrying. It indicates the presence of a phenolic -OH, but it isn't picric acid, either. It could be a lesser nitrated phenol, but in that case, it shouldn't be so violently flammable. The only other compound that I can think of that is weakly acidic is a β keto ester, but there's no way you could end up with such a product here... On the other hand, perhaps the actual product is quite different, but it undergoes alkaline hydrolysis.

If you have access to some aniline, you could try this: Convert aniline to quinone by oxidising it using acidified K2Cr2O7. The quinone thus obtained could be nitrated using the nitrating mixture. Quinone itself is supposed to be quite yellow, BTW. For more on quinone, see this (http://www.worldwideschool.org/library/books/sci/chemistry/OrganicSynthesis/chap22.html) page.

[Mr Cool]

"That the product should dissolve in NaOH but not in sodium bicarbonate"

It dissolves in solns. both; I merely said that there was no effervescence when it was dissolved in sodium bicarbonate soln. But I don't know if the fact that the alkali is there makes any difference, since it dissolves in water anyway.

[FUTI]

As far as remember (H-W is my source -chemist will knew what I talk about) if you nitrate quinone/hydroquinone you can end up with 2,5-dinitro-3-hydroxy-paraquinone (don't be angry at me if I mess up the exact position of groups it was long time ago and reaction wasn't what I was looking for). This is (from the same source) sensitive explosive substance. Maybe your product contain this.

[tom haggen]

I've been think about something regarding this subject for a few weeks now. I noticed that on the powerlabs website they add all of the nitric acid at once into the hot Phenol. This creates a violent reaction creating plooms of nitrogen dioxide. I can't remember off the top of my head if mega's synthesis creates large amounts of nitrogen dioxide. Either way when I made that yellow crap I used the KNO3 method and added it very slowly and never really created any nitrogen dioxide. If I'm not mistaken I think that in order for TNP to synthesize NO2 must be released.

[Bugger]

How about nitrating phenol or hydroqunine (para-diphenol), and THEN oxidizing the product to a quinone derivative e.g. with dichromate? I very much doubt that quinone, as an alkene, would nitrate in the same way as (aromatic) hydroquinine, if at all. (Under sufficiently rigorous conditions, the C=C double bonds would be oxidatively cleaved).

Bugger.

[FUTI]

to Bugger: what you said is true for alkene, but do some research and you will understand why did I put that / mark between hydroquinone and quinone:) Let me know if you solve the mistery of that substance.