DDNP: Mega's procedure: Production of Picramic Acid? - Archive File

[megalomania]

Dhzugasvili
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posted 07-03-2001 06:40 PM
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I have made some DDNP, it detonated lovely when confined very well in a tube of notecard jammed at both ends with tissue paper and cellotape. otherwise, it would not detonate, only burn. This DDNP was produced by the masterj method where sulfur, lye, potassium nitRITE, Picric Acid, and sulfuric acid are used etc etc im sure some of you are familiar with it.
I was just wondering do any of you know how to PREPARE PICRAMIC ACID for use in Mega's procedure? he says he included it in synth section but it is not there.





10fingers
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posted 07-03-2001 07:05 PM
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In the first part of the procedure you used, where you mix picric acid with the sulfur/lye solution, that's making picramic acid.


Tony Montana
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posted 07-03-2001 07:13 PM
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The chemistry of powder and explosives "Picramic Acid, red needles, may be prepared by evaporating ammonium picrate in alcohol solution with ammonium sulfide."
[This message has been edited by Tony Montana (edited July 03, 2001).]



Mr Cool
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posted 07-04-2001 07:38 AM
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Yes, it is formed by the reduction of one of the nitro groups on TNP, to form C6H2(NO2)2NH2OH.
The most common substance used to reduce it is a sulphide of an alkali metal or ammonium.


Dhzugasvili
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posted 07-04-2001 07:23 PM
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Ah! So! then shit, PA has to be made first and sacrifice some of it to produce DDNP. I was looking for a way around to produce picramic acid with phenol, or otherwise without using sacrificial TNP, but I guess that was just a stupid querry.

[megalomania]

stanfield
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posted 07-21-2001 05:37 AM
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I did a search but I didn't found precis things ...
so, is there a way to make picramic acid (for DDNP) ? Megalomania forgot to post them on his site

tahnx !



cutefix
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posted 07-21-2001 06:38 AM
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Stanfield,there is an simpler way to make DDNP found in KIBC(by Tim Lewis).
MANUFACTURE:
In a pint glass jar place 90 ml warm water and 1.5 grams of lye
(sodium hydroxide). Mix these with a "teflon" stirrer until all the lye had
dissolved. Dissolve 9 grams of picric acid crystals in the lye-water
solution by stirring. Label this jar solution #1. In a 500 ml beaker 3 ml
of water is placed. Dissolve 7.5 grams of sulfur and 7.5 grams of lye (sodium
hydroxide) by stirring the solution. Boil this solution over a heat source.
When the solution turns dark red remove and allow the liquid to cool. Label
this solution #2. Add this cooled solution #2 in three portions, to
solution #1. Stir with a teflon rod while the liquid is being added. Again
allow the solution mixture cool. Filter this mixture through filter papers
(coffee filter, paper towels). Small red particles will gather on the
paper. Discard the liquid. Dissolve these red particle in 180 ml of boiling
water. Remove and filter this hot liquid through a filter paper (coffee
filter, paper towels). Discard the particles left on the paper and label
the liquid left #3. To Solution t#3 with an eyedropper slowly add sulfuric
acid (Janitor supply, boiled battery acid) to the filtered solution until
it turns orange brown. Add an additional 7.5 grams of acid to the liquid.
In a separate pintjar, dissolve 5.4 grams of potassium or sodium nitrite in
240 ml of water. Label this solution #4. In one portion solution #4 is
added with stirring to solution #3. Allow the solution to stand for 10
minutes. The mixture will turn light brown.
Filter the light brown solution through a filter paper (paper towel, coffee
filter). Wash the particles left on the paper with 60 ml of water. Allow to
completely dry for 24 hours. Drying time can be reduced to 2 hours if
crystals are placed in a shallow pyrex dish and this placed in a hot (not
boiling) water bath.
This powder should be stored in small quantities in stoppered glass
containers. More safety in storage leave 25% water in the powder and dry
immediately prior to use.
Good Luck to your experiments,and be careful,this is a sensitive primary explosive.




Lagen
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posted 07-21-2001 07:01 AM
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I believe there should be 300ml, not 3ml of water in the preparation of soln. #2.

quote:
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... Add this cooled solution #2 in three portions, to solution #1. Stir with a teflon rod while the liquid is being added. Again allow the solution mixture cool. Filter this mixture through filter papers (coffee filter, paper towels). Small red particles will gather on the paper. Discard the liquid. ...
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They then use these "red particles" to proceed to DDNP. This is picramic acid. You can plug it into Mega's recipe. Picramic acid is soluble in benzene and acetic acid, but not in other organic solvents. It's not explosive, yet more dangerous than PA, this is the stuff that forms in small amounts in your body from picric acid and accounts for most of its toxicity. Also have a look at "DDNP: Mega's procedure: Production of Picramic Acid?" in this section.
[This message has been edited by Lagen (edited July 21, 2001).]



stanfield
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From: FRANCE
Registered: MAY 2001
posted 07-21-2001 12:27 PM
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"I believe there should be 300ml, not 3ml of water in the preparation of soln. #2"
so, is there 300 or 3 mL ??
thanx !



stanfield
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From: FRANCE
Registered: MAY 2001
posted 07-21-2001 01:38 PM
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another question :
"Add an additional 7.5 grams of acid to the liquid"
ok but what's the concentration ?
thanx



Lagen
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posted 07-21-2001 02:31 PM
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Obviously, the author meant 300ml. Dirk Goldmann in his Improvised Primary Explosives noticed that typo, so in IPE you'll find a similar procedure, but with 300ml. Why would they put 3ml and a few grams of other stuff into a 500ml beaker? And how on earth could the sodium sulfide that's produced dissolve in 3ml solvent? Only a fraction of a gram would dissolve.
Anyways, you could just as well get away with as little as 100ml water, and as much as 10gr sulfur and NaOH each.

Tonight (maybe in 1-2 hours) I will try the experiment with 3ml, 100ml and 300ml and will post the results here immediately.

The acid is just a catalyst, the amount is not that important, but if yours is real dilute increase the amount accordingly. They probably meant concentrated. HCl can be used also. When I post the results of the sulfide experiment I will give the exact procedure for HCl as well. Please excuse me I'm in a hurry now...



stanfield
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From: FRANCE
Registered: MAY 2001
posted 07-21-2001 04:32 PM
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yeah, post your exact recipe plz !
it will be very nice
see ya !



Lagen
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posted 07-21-2001 04:43 PM
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Ok guys I'm back, I just had to get a few explosives precursors from the local grocery before they closed up shop at 9pm. Will append the results to this post...
OK I wiped the beaker completely dry... At first with an ordinary towel, then with a soft paper towel. Then I placed it in the oven for 10 minutes to drive off the remaining moisture, the usual procedure in every recipe Then 3ml of water were carefully measured out into the beaker... I added 7.5g sulphur and 7.5g NaOH. There was no reaction. I put it on the hotplate. Soon I realised that there is no way this is gonna work. All of the NaOH dissolved, and some sulphur too, the solution indeed turned yellow-red (which I assume to be Na2S and Na2S4), some yellow-green oily liquid formed on the top of the mixture, which I assume to be molten sulphur. But, on cooling (which they suggest) the sulphur solidifies, so it's neither dissolved nor reacted. Some S remains unreacted. The red solution started boiling and smelling like hell, I fear it's decomposing. OK so tell me (with a straight face) how many of you guys have actually attempted DDNP according to the Tim Lewis' recipe...

Now adding 297ml H2O. At first solution turned yellow-green. After a while the red stuff started dissolving. I stirred it, solution turned orange. Small bubbles formed on the sulphur. Now I am cracking up the solidified sulphur, it still takes ages to dissolve it... After some time solution is about the color of tea. Now there are huge bubbles on the sulphur pieces, and I can't crack them up, because they're flying around, funny... The volume of the solution was reduced to 270ml by boiling! Reduced the heat, now it's at lowest heat. The 3ml experiment was a fuckup in that it turned the sulphur to big pieces, which don't dissolve. So when you do this, start with a fine sulphur powder. Solution is brown, 250ml. After some more ages it starts turning red. Refilled to 320ml. Finally, it all dissolved, by the time it was boiled down to 120ml. Solution is reddish brown, but stains paper in yellow-green. Some fine insoluble residue appears in the liquid, but I assume this to be an impurity from the sulphur.

The 100ml batch took a lot of time too, I haven't crushed it properly, but finally it dissolved, some residue appears - the amount is negligible, but it's a bit coarser than in the previous batch. After cooling nothing precipitates, so 100ml should be OK.

10fingers suggested the Lewis formula is correct so I tried the controversial stuff again... Trying with 1ml, 2x 2.5g. Upon addition of the NaOH to the 1ml water there is a violent reaction and heating, some of the NaOH cakes. Put it on the hotplate. The 1ml water is quickly boiled away, it's difficult to keep replacing it so that the volume is constant. When heated, the mixture is brick red. Then it starts to fizzle, decompose and gives off some irritant gas (feels kinda like tear gas). After cooling it forms the sulphur lumps same as before, color is reddish brown. I cycled through this 3 times, and allowed to cool. It definitely doesn't form a solution, but rather a thick mass. So my conclusion is: This way it is difficult to moderate the reaction, it gives off nasty fumes, cannot be poured out the reaction vessel, and does not behave the way it's described in the books (I cannot imagine how this could be poured in three portions). I can't help it but I keep thinking the 3ml or 1ml formulas, must be wrong. And why would they use a 500ml beaker? (The next day I inspected the "solution", it was a tough cake, difficult to remove from the beaker even with a wire, smelled like rotten eggs...)

The recipe: Crush 10g of sulphur to a fine powder. Into a 250ml beaker or jar place 100ml distilled water. Dissolve 10g NaOH in the water, stir to prevent caking. Pour in the sulphur powder and heat the mixture so that it gently boils. Stir occasionally and keep replacing what is being boiled away, until everything had dissolved. Solution should be a reddish brown color. This is a mixture of sodium sulfides in water. Let it cool down. If an insoluble residue remains in the solution, do not filter, it will be removed later in the process. Into another 500ml beaker or jar put 90ml distilled water and 1.5g NaOH and stir until the lye had dissolved. Dissolve 12g of PA in the solution with stirring. Add the cooled sodium sulfide solution in five portions, to the PA solution. Stir with a teflon rod while the liquid is being added. Again allow the solution mixture cool. Filter this mixture through filter papers (coffee filter, paper towels). Small red particles will gather on the paper. Discard the liquid. Dissolve these red particles in 180 ml of boiling water. Remove and filter this hot liquid through a filter paper (coffee filter, paper towels). Discard the particles left on the paper and save the liquid.

Now if you just wanted to make %SUBJ% (why??? Silly idea! It's toxic!) just evaporate the liquid to dryness (do not overheat, dry in an oven with precise regulation at 150°C, or on an oil bath, do NOT exceed this temperature) and you should get red crystals of pure picramic acid. You should evaporate this and weigh it out anyway, at least for the first time, to ascertain the yield of picramic acid. Theoretical yield is 11,26g.

10g of picramic acid is dissolved with strong stirring (or magnetic stirrer) in 120ml of 5% HCl in a 250ml beaker placed in an ice bath. 3.6g of NaNO2 is dissolved separately in 10ml water and added in one portion to the picramic acid solution, with stirring. Let the mixture stand for 20 minutes. The mixture will turn a brown color. Filter the brown solution through a filter paper (paper towel, coffee filter). Wash the particles left on the paper with 60 ml of ice cold water. The DDNP is then purified by dissolving in the smallest amount of acetone possible. The acetone should be preheated to 40-45°C. With stirring this solution is slowly dumped into ice cold water, the precipitate is filtered and allowed to dry. Leave a small amount of water for safety.

I will keep updating this recipe and will write a note here if anything changes. Recently I adjusted amounts so that amount of picramic acid matches second step. Now I found out that the "second step" is virtually identical to Megalomania's procedure. Any input is welcome.

[This message has been edited by Lagen (edited July 22, 2001).]



10fingers
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Registered: SEP 2000
posted 07-21-2001 07:28 PM
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In the Improvised Munitions Handbook the formula says, "place 1 milliter water in a glass container, add 2.5 gms. sulfur and 2.5 gms. sodium hydroxide. Boil over heat source until solution turns dark red".
The ratios of chemicals in this book are all 1/3 of the formula in the Tim Lewis formula.
so if this formula is correct then the correct amount would be 3 milliters.


Lagen
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posted 07-21-2001 11:27 PM
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There is an issue regarding DDNP which any of the *IPE books don't tell you. The crystal density of DDNP seems to be high, but when made with the usual process above, the density of the material is only 0.27 g/cm3... When pressed mildly, this can be pushed to 0.86, resulting in a VOD of only 4400... The crystals are also long and thin, difficult to load in the detonator, and very sensitive. These disadvantages can be overcome by modifying the reaction conditions, which results in a smaller, grainlike material of somewhat higher density (0.82 unpressed). Similar results are obtained when using a different process, you start from the sodium salt of picramic acid.
I will post the details sometime, now it's morning here and I'm exhausted...



Lagen
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posted 07-22-2001 12:02 PM
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I found out about three possible ways of increasing the density of DDNP. When using these methods, the DDNP purification step must be omitted, as that would change the crystal shape and size.

Carrying out the diazotization step (the second part of the process) at a higher temperature (25-45°C). This way a higher density (0.82) should be obtained, but it looks kinda dangerous.
Adding a small amount (perhaps 0.5-1%) of a triphenylmethane dye to the diazotization mixture. An example of such a compound would be 2-amino-5-[(4-amino-3-sulfophenyl)(4-imino-3-sulfo-2,5-cyclohexadien-1-ylidene)methyl]-3-methyl-benzenesulfonic acid, disodium salt, otherwise known under the following trade names: Acid Magenta, Acid Violet 19, Acid Fuchsin-sodium salt, CI 42685. Don't let the name fool you, it is a quite common organic dye. The molecular formula is C20H17N3Na2O9S3, CAS# 3244-88-0, Aldrich cat.# 33,270-4. Edit: The formula from the CRC book was wrong!
The best method IMO: starting from the sodium salt of picramic acid. I have found no info on its synthesis, but I assume one could prepare a solution of picramic acid in absolute alcohol, and neutralize by stirring in some NaOH (in the ratio 1.9g NaOH to 10g picramic acid). The salt would then be precipitated in the form of a very fine powder by adding a large excess of cold water, filtered out and dried. 10 grams of this powder would be stirred into 80ml water (20°C). To this suspension a solution of 3.6g NaNO2 in 20ml water is added slowly. Then 60ml of a 5% HCl solution is added dropwise over a period of two hours (with stirring, eg. a magnetic stirrer). The temperature rises from 20°C to 25°C, if necessary, moderate the temperature. The DDNP is then filtered out, washed with cold water and dried at 35-40°C. Yield approx. 84% theory, or 7.44g.

[tom haggen]

I read about the synthesis of picramic acid in The Chemistry of Powder and Explosives. It says to evaporate ammonium picrate in an alcohol solution with ammonium sulfide.
Anyone have any ideas on what ratios should be used for this? When it says evaporate ammonium picrate in an alcohol solution, I assume they mean mix ammonium picrate in with a solution of ammonium sulfide and ethonal, and let the ethonal evaporate. I noticed that the chemlab is under construction. Hopefully this synthesis will be covered along with many others. I'm ripe with anticipation, It's like Christmas in August. Ya I have rep power, I guess all that studying and kissing ass is paying off.

[bobo]

I think the molar ratio should be like 120% of sulfide. I think i will try this one out soon, my old procedure (sulfur to sulfide in water) works somewhat well but the downside is birds drop dead over the roof from the godawful stench that is produced.

EDIT: found some info on ammonium sulfide. Somehow, I think this compound has more hooks than sodium sulfide or others. Why would the ammonium compound be preferred (since it is the sulfide or rather HS- ion that seems to act).

Also, the ammonium sulfide that seems mostly available is in aquous solution, should you purchase it. I think that using ethanol is a bit roundabout however, the ammonium picramate would crystallize out

http://www.fact-index.com/a/am/ammonia.html

Ammonium sulfide, (NH4)2S, is obtained, in the form of micaceous crystals, by passing sulfuretted hydrogen mixed with a slight excess of ammonia through a well-cooled vessel; the hydrosulfide NH4.HS is formed at the same time. It dissolves readily in water, but is probably partially dissociated in solution. The hydrosulfide NH4.HS can be obtained as a white solid, by mixing well-cooled ammonia with a slight excess of sulfuretted hydrogen. According to W. P. Bloxam (Jour. of Chem. Soc., 1895, lxvii. p. 283), if sulfuretted hydrogen is passed into strong aqueous ammonia at ordinary temperature, the compound (NH4)2S.2NH4HS is obtained, which, on cooling to 0°C and passing more sulfuretted hydrogen, forms the compound (NH4)2S.12NH4HS. An ice-cold solution of this substance kept at 0°C and having sulfuretted hydrogen continually passed through it gives the hydrosulfide. Several complex polysulfides of ammonium have been isolated, for details of which see Bloxam's paper quoted above. Compounds are known which may be looked upon as derived from ammonia by the replacement of its hydrogen by the sulfo-group (HSO3); thus potassium ammon-trisulfonate, N(SO3K)3.2H2O, is obtained as a crystalline precipitate on the addition of excess of potassium sulfite to a solution of potassium nitrite, KNO2 + 3K2SO3 + 2H2O = N(SO3K)3 + 4KHO. It can be recrystallized by solution in alkalies. On boiling with water, it is converted, first into the disulfonate NH(SO3K)2 thus, N(SO3K)3 + H2O = NH(SO3K)2 + KHSO4, and ultimately into the monosulfonate NH2.SO3K. The disulfonate is more readily obtained by moistening the nitrilosulfonate with dilute sulfuric acid and letting it stand for twenty-four hours, after which it is recrystallized from dilute ammonia. It forms monosymmetric crystals which by boiling with water yield amidosulfonic acid. (See also E. Divers, Jour. of Chem. Soc., 1892, lxi. p. 943.) Amidosulfonic acid crystallizes in prisms, slightly soluble in water, and is a stable compound.

[K9]

Well I went with the procedure of dissolving NaOH and S in water and then boiling to make a mixture of sulfides and polysulfides. When I mixed that with sodium picrate I got a reddish powder (I'm assuming picramic acid) which was then reacted with KNO2. Seemed to work for me.

[bobo]

I suppose you mean you mix sodium picrate with the sulfide bath, then toss that mixture in the vessel for diazotization with nitrite.

The problem with this is that the intermediate contains sulfur compounds and in general is just a mess. Try burning your product just to smell sulfur oxides, and of course, if it shows primary properties.

[K9]

Well what I did was mix the the sodium picrate and sulfides together and then filtered the reddish precipitate. That filter paper was later burned and definitely gave off a strong smell of sulfur oxides. That precipitate was then dissolved in water and filtered getting rid of something - I assume impurities. The solution was then acidified with H2SO4 and KNO2 was added. The yield wasn't great, but I suppose the experiment could have gone more smoothly at some points. The product was burned in the open but didn't det - and apparently it's not supposed to det in open air except for larger amounts. Is there anyway to be certain of the product?

EDIT:

At this point, I think something was screwed up in the synth. Apparently others have had the same problem as what seems to have happened in my synth. I guess all that's left is trying again.

Ok here's the new question - was that picramic acid that was created from the addition of the sulfides to the sodium picrate? It was a reddish coloured solid that precipitated and was filtered. If up to that point is right, then I can deal with the next step as a new point.

But everyone seems to have a different idea about this synthesis.