A quick question on nitronapthalenes:

[Mr Cool]

Well, making the mononitro compound is easy. When I do this I get a roughly 90% yield of deep yellow/orange MNN.
The second step I see in every procedure did not change this product! So I thought, "Fuck that step, I'll do the last one twice." I figured it should work, and I *think* it has. I got a light yellow, grainy product the first time, but it didn't change the second time! When I added the MNN to the nitrating solution (40mL of H2SO4, 45g of KNO3 for the MNN from 5g of napthalene, so quite a large excess of acids I believe) in small amounts at about 35*C, it melted due to the extra heat from the reaction. I was stirring vigorously, and the orangy blobs of MNN quickly changed to yellow grains. During the addition the temperature was not allowed to go above 40*C, it was at about 35*C for most of the time. When it had all been added (sorry, I wasn't timing how long it took), I left it for a further 15 minutes and then dumped it into 200mL of cold water. The yellow grains sank in the murky greenish yellow liquid.
When I used these grains in the last step, they did not appear to change.

So what I'd like to know is: what colour are DNN and TeNN, what are their melting points etc etc. Anything that will help me to determine what I have here.

Thanks for any help you can give!

[Lagen]

I don't know the colors, sorry http://theforum.virtualave.net/ubb/smilies/frown.gif All I found is this:

1,3-DNN: m.p.:148°C, b.p.:sublimes, ins. H2O, sol. EtOH, ace
1,5-DNN: m.p.:219°C, b.p.:sublimes, density:1.586[20°C], ins. H2O, slight.sol. EtOH,ace, very sol. ether
1,8-DNN: m.p.:173°C, b.p.:445°C [decomposes], ins. H2O, slight.sol. EtOH,bz, sol. ace
1,3,6,8-TeNN: m.p.:207°C, b.p.:explodes, density:1.64[0°C], very sol. bz,HOAc

Obviously the various DNN isomers make things a bit complicated...

[wantsomfet]

alpha-nitronaphtalene: bright-yellow needles, soluble in most organic solvents. Melting point: 60 - 61 °C.
Dinitronaphtalenes: tiny grey-yellow crystals, could be slightly red if NOx is present, soluble in acetone, toluene, acetic acid, terpentine, benzene, not very good in ethanol & ethylether. Melting point between 140 and 160 °C, depending on mixture of isomeres.
1,3-dinitronaphtalene: 114 °C
1,5-dinitronaphtalene: 215 - 216 °C
1,8-dinitronaphtalene: 170 -172 °C
Trinotronaphtalenes: tiny, bright grey-brown crystals. Not very soluble in organic solvents. Melting point between 115 and 160 °C, depending on mixture of isomeres.
1,3,5-trinitronaphtalene: 123 °C
1,3,8-trinitronaphtalene: 218 °C
1,4,8-trinitronaphtalene: 147 °C
1,2,5-trinitronaphtalene: 112 - 113 °C
Tetranitronaphtalenes: tiny sand colored crytals, not very soluble in organic solvents, but some isomeres (1,3,5,8-) are readily soluble in acetone.
alpha-tetranitronaphtalene: 259 °C
beta-tetranitronaphtalene: 203 °C (1,3,6,8-)
gamma-tetranitronaphtalene: 194 - 195 °C (1,3,5,8- & 1,4,5,7-)
delta-tetranitronaphtalene: decomposition at 270 °C (1,2,5,8- & 1,4,5,6- & 1,3,5,7-))

quick & dirty, too much work to write it all down now. Perhaps some other member who has the Urbanski books could post some more info.

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[Lagen]

wantsomfet: I have looked in the Urbanski books, and there is nothing more, than what you have written (as far as colours and temperatures go). There is a major discrepancy between our posts in the m.p. of 1,3-DNN, and I think Mr.Urbanski was wrong here. The CRC book states 148°C for the pure substance, and my Sigma-Aldrich catalogue states 146-148°C for the 97% pure product. I respect and value Mr.Urbanski's work, but in his times a lot of the things he writes about was not completely explored. Note the "uncertain location" of two nitrogroups in one of the TeNN isomers.
Mr Cool: After going through the few pages of Urbanski on nitronaphthalenes, I must say this is really mindboggling stuff. Nothing to envy, so I wish you good luck!

[Mr Cool]

Thanks for all your help.
Now I have to decide if it's grey-yellow or sand coloured! It doesn't look like either to me.
The closest colour match that I can think of are the wrappers from Mars ice-creams! The wrapper is probably the same colour everywhere in the world.
I would have thought that there was enough acid mixture to nitrate it to the tetranitrocompound, but I want something a bit more solid than guess work. I'll see how it behaves in acetone, and try to find its m.p.

[wantsomfet]

Lagen: I think you are right about the 1,3-DNN, but since the product mostly consists of the 1,5- & 1,8-DNN isomeres, it shouldn't be the biggest problem.

Here's a pic that could help a bit with nitronaphtalenes (concentrations of HNO3/H2SO4/H2O & obtained product):
http://internettrash.com/users/altreal/frame/U1-210.gif

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[Mr Cool]

So if the number is twice as close to H2SO4 as HNO3, then you'll need twice as much H2SO4 as HNO3, right? In other words, the ratios of HNO3:H2SO4:H2O are 1/(the distance from the number to the chemical formula)?
That's the best way I can think to describe it, hopefully you'll understand what I'm trying to say. This theoretical example might help:

e.g. imagine that number 5 is 3cm away from "H2O", 2cm away from "HNO3" and 1cm away from "H2SO4" on the diagram. Therefore the ratio of H2O:HNO3:H2SO4 is 1/3:1/2:1/1, which means 18.2% H2O, 27.3% HNO3 and 54.5% H2SO4 in this example. Is that right?

Anyway, thanks for the diagrams!

[Dave Angel]

wantsomfet, (or for that matter anyone who understands the diagrams better than I do), when it is said that the "concentrations" of the reactants is shown, does this literally mean moles of reactant per dm^3 of reagent mix?

If not, I'm guessing the units of reactant, used to draw the diagrams were either: moles, grams or mL. Each of which used in a hypothetical calculation of 20mL H2O / 50mL H2SO4 / 39mL HNO3, gives different ratios of reactant depending on which unit the amounts of reactants used were converted into.

If anyone can shed any light on this it would be very useful in designing a new synthesis for TeNN, I'm sure you will agree.

Alternatively you could point out if I've made a blindingly obvious mistake and tell me that the units don't matter, but I just can't see that they don't at the moment.

[Microtek]

The diagrams very likely show the constituents of the mixed acids in % (w/w) so the point in the exact middle of the triangle means 33 g HNO3, 33g H2SO4 and 33 g H2O per 99 g nitration mix ( in total, so remember the water content of your nitric and sulfuric acids ). Similarly the point on the middle of the lower edge of the triangle means 50 g H2SO4 and 50 g HNO3 per 100 g nitration mix. What it doesn't tell you, is how much substrate ( naphthalene or dinitronaphthalene ) to use.

[Rosco Bodine]

There is a Swiss nitration method which uses nitration catalysts
to achieve the tetra and even the penta nitrated naphthaline
under less extreme conditions of acid concentration than usual .

See GB501034

Another patent which describes higher nitrations of aromatics
using milder concentrations of acids while azeotroping water
from the nitration mixture is interesting also . Even TNT from
ordinary concentrated nitric is reportedly produced in high yield .

See US2435314