Nick F
Hazard to Others
Posts: 439
Registered: 7-9-2002
Member Is Offline
Mood: No Mood
|
|
DATB (and beyond) from C6H5OONa...
I have been thinking, and I think this is one of the rare times that I have an idea that would actually work in practice!
But I wanted to see what people thought before I try.
You see, I have several pounds of sodium benzoate here, not doing much except for an occaisional whistle or other LE mix.
But, what if...
1) Form benzoic acid by reacting a solution of it with conc. HCl;
2) Nitrating benzoic acid with mixed acid to make 3,5-dinitrobenzoic acid (or 3-nitrobenzoic acid, see below...);
3) Reducing the -NO2's to -NH2's with Zn/HCl;
4) Nitrating the product to 3,5-diamino-2,4,6-trinitrobenzoic acid (should be very easy, even with the -COOH, because of the -NH2's);
5) Boiling it in water under reflux for several hours to decarboxylate (which should be easy since the -COOH is adjacent to two -NO2's).
There! DATB!
And this can be reacted with NaOCl and KOH in EtOH at 0*C to make nitrobenzodifuroxan, a dense, powerful IHE.
I'm not sure if you'll get the dinitro- compound at step 2), but you'll certainly be able to get mononitro-, in which case you'll end up with
sym-TNAniline, which could be made into dinitrobenzofuroxan.
Even if it doesn't decarboxylate, it could still make some primary compounds, for example the lead salt.
Do you think it's worth trying, or will it waste my chemicals? I can't see any flaws, but it's possible that I've overlooked something...
|
|
|
Nick F
Hazard to Others
Posts: 439
Registered: 7-9-2002
Member Is Offline
Mood: No Mood
|
|
Yes, I know it should be "C6H5COONa" in the title...
Anyone know the mp of either DATB or sym-TNAniline? I haven't been able to find out yet.
|
|
|
Nick F
Hazard to Others
Posts: 439
Registered: 7-9-2002
Member Is Offline
Mood: No Mood
|
|
No comments? OK, I'll go and try it.
Just thought, the nitrobenzoic acid would probably have to be reduced as its sodium salt, to make it more soluble.
|
|
|
Nick F
Hazard to Others
Posts: 439
Registered: 7-9-2002
Member Is Offline
Mood: No Mood
|
|
... but obviously if you reduce it as the sodium salt, you'll have to use Na2Sx instead of Zn/HCl.
|
|
|
Polverone
Now celebrating 21 years of madness
Posts: 3186
Registered: 19-5-2002
Location: The Sunny Pacific Northwest
Member Is Offline
Mood: Waiting for spring
|
|
Sorry, I've nothing to contribute other than to say "go for it." If you have several pounds of benzoates I don't think you really have anything to
lose (excepting body parts in case of accident, of course).
|
|
|
Marvin
National Hazard
Posts: 995
Registered: 13-10-2002
Member Is Offline
Mood: No Mood
|
|
I'm not clear on something.......
How are you going to nitrate without destroying the NH2 groups?
|
|
|
Nick F
Hazard to Others
Posts: 439
Registered: 7-9-2002
Member Is Offline
Mood: No Mood
|
|
Very gently!
It depends on what you mean by "destroying", they will make the compound more susceptible to oxidation during nitration (so it must be done as gently
as possible), but I don't think that they will themselves be nitrated or otherwise made into non-NH2's (except by protonation to form -NH3+).
For example, tetranitroaniline is prepared by nitrating m-nitroaniline with mixed acid, and trinitroaniline is formed by nitrating aniline in AcOH, or
with HNO3/H2SO4 with only a very slight excess of H2SO4. If a large excess of H2SO4 is used, tetranitroaniline is the end product.
But the -NH2's remain intact during nitration.
(info taken from COPAE)
|
|
|
Marvin
National Hazard
Posts: 995
Registered: 13-10-2002
Member Is Offline
Mood: No Mood
|
|
I'm not convinced. I'll explain why.
Knowing you cant nitrate a primary amine on a benzene ring is basic chemistry here but the reasons are less commonly explained...
In mixed acid the NH2 being a base will indeed fully protonate, nitric and sulphuric being strong acids. Being protonated, its nolonger electron
donating, its withdrawing. So this is now a deactivating group, and a meta director.
The amine group is very easily oxidised, as I recall, aniline will oxidise in air by itself, albeiit slowly. In the conditions of the nitration this
might be hard to avoid.
Any trace amounts of nitrous acid, always present in the nitrating mixture will diazotise the amine, and since the temperature isnt low, it will
decompoise probably ending up as an OH group, which will be strongly ring activating, and in normal nitration will produce a lot of oxidation products
itself.
Nitrating in acetic acid might work, formation of an amide is a common method of protection but requires different methods, and I dont know how well
it would work here. Doing nitrations in acetic acid is nolonger considered safe practice for obvios reasons.
I'm not saying it *cant* be done. Just that this is not well vouched for chemistry. I have some references to the nitration of aniline to
metanitroaniline, which is what would be expected from above.
Nitration of secondary amines is fine, but you can form N-nitro and N-nitroso compounds in the process which must be broken down.
I am somewhat concerned the information in Davis doesnt entirly follow modern teachings in this area.
I am rather uncertain why a larger amount of concentrated sulphuric acid would make a difference in the nitration of aniline, it should be fully
protonated in either reaction mixture.
In the same circumstances I would probably base my synth around sym trinitrotrichlorobenzene which is much better understood allthough requires rather
less subtle conditions.
|
|
|
pentathlon
Harmless
Posts: 1
Registered: 30-10-2002
Location: on toxic-waste-dump
Member Is Offline
Mood: No Mood
|
|
DATB
Is it possible reduce DATB from TATB or by a
double-substituting- reducing- synthesis from
1,2,3-tribromo-2,4,6-trinitro-benzene ?
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
