Sciencemadness Discussion Board - Tabun-think I got it

Tabun-think I got it

Iv4 - 5-8-2003 at 02:06

Dimethylphoprylcyanide/Tabun.I been thinking about this for a while no and I thnk I got it's synthesis down.This is the first time I've ever tried to come up with the synthesis and my chemistry skills are'nt too good,so be please be gentle

I'm thinking dimethylamine could be used as the starting point.With caclium phospahte I'm thinking/hoping for demethylphospate.Or would this require phophoric acid?After that I think cyanogen iodide could place the cyanide bit in.Maybe hcn on the calciumphosphate itself?

The other way (this I havent really thought over but just a thought).Hydrogen cyanide on calcium phosphate and then in methanol.I'm hoping to have calcium hydroxide and a cyanide/phospouros 'thing'(lack of better word-told you my chemistry is shit).Then if that could be added to methanol I'm thinking I might get methylphoprylcyanide(not the same but thinking that it could be similer).

[Edited on 5-8-2003 by Iv4]

DDTea - 7-8-2003 at 09:38

Well, we all have our firsts, and our firsts tend not to be our bests

First and foremost, you don't seem to have Tabun's structure right. Tabun is N,N-Dimethyl O-ethyl Phosphoryl Cyanide (I hope I got the nomenclature right, because I never quite got it down for Phosphates...). Dimethyl Phosphorylcyanide is another OP, which may or may not have high toxicity (I have never looked into it- but Organophosphates w/ a reactive leaving group such as -CN, -F, -Cl, etc. tend to have high toxicity).

The purpose of Dimethylamine is not to form Dimethyl Phosphate, but rather get the N,N-Dimethyl group attached directly to the Phosphorus. This is the tricky part, and I don't believe such a between Dimethylamine and Phosphoric Acid would give you what you want (if it reacts at all).

That is why in the Tabun synthesis, they prefer to use Phosphorus Oxychloride- because the Chlorine is attached directly to the Phosphorus atom, and does not like to be there

. As such, it is reactive and gives the desired results. So then you bring in the Dimethylamine, which reacts w/ the POCl3, and forms N,N-Dimethyl Phosphorus-Chlorine crap (as I said, I never quite got the nomenclature

) and HCl.

To get the O-Ethyl group onto the phosphorus, The N,N-Dimethyl Phosphorus crap is reacted with Ethanol is used- which forms more HCl as the side product.

Finally, Sodium Cyanide is reacted, and Sodium Chloride is the side product.

As far as the Calcium Phosphate goes, I think you'd be better off working with straight Phosphoric Acid...but still, don't expect wonderful results from that either.

Better choices may include Phosphorous Acid or Phosphine (some things which I am looking into, but haven't found much time to do serious research on).

Perhaps you could react N-chlorodimethylamine with Phosphorous Acid, thus attaching the Dimethylamine to the Phosphorus, then react the product with Ethanol to attach the Ethyl group. The trouble after that, though, is attaching the -CN group directly to the Phosphorus

.

But keep in mind- this is just random stuff I've thought up in a hurry; it probably won't work...just something to keep you thinking

DDTea - 8-8-2003 at 09:41

Now that I think about it... If you are still interested in Dimethyl Cyanophosphonate...

Perhaps you could react Cyanogen Iodide with the Phosphorous Acid, and then react the product with an excess of Dimethyl Sulfate?

Alternately, if you're looking to be nasty, perhaps a current of straight Chlorine might displace the non-acidic Hydrogen in Phosphorous Acid? From there, I imagine you could react that with HF, KF, or NaF to get the corresponding Flouride...

Does this sound like a different way to DFP? Or am I just spewing chemical-diarrhea again

BTW- Tabun's PROPER nomenclature is "O-Ethyl N,N-Dimethyl Phosphoroamidocyanidate."

Also, does anyone have much information related to Hexafluorophosphoric Acid? Such as, what is it used in, and any regulations?

I'm interested in if it can be converted to Phosphorus Oxyfluoride .

Thanks

Iv4 - 9-8-2003 at 02:54

Thanks for the reply.Fraid I dont have anything to offer back.

Phosphine is used for rat killing in some remote places still so I'll see if I can get some and sneak it into the UK before my flight(and ofcourse there's the ugly kid to check potency).Is this my trip talking(really need to be more carefull from now on-not the most encouraging thought for anyone in london?)or is phospouros acid used as a rust remover?

PS
Come to think of it (from a warfare prespective)wouldnt VX pose itself better?

DDTea - 9-8-2003 at 08:35

All the different Nerve Agents have their specific uses on the battlefield; some do certain jobs far better than others. VX is an area-denial weapon, while Sarin is a quick-gas weapon (due to its fast action), and Tabun fits somewhere in between.

I don't know about Phosphine, however. I believe the Hypophosphoric and Metaphosphoric Acids would be much better options.

Now, in regards to how to purchase said acids... I have read that Metaphosphoric Acid (aka Phosphorous Acid) is used in some limescale removers in Pool Stores and such... However, it is mixed with a few other acids too

Iv4 - 10-8-2003 at 06:39

I supose that very true.What I meant is that with the effort to make 100mls of tabun you could get 40 mls of VX for example.

PS
I'll be looking for diferent acids.

DDTea - 1-10-2003 at 15:46

Looking at this thread makes me recall a discussion with Vulture a few weeks ago. We were discussing the synthesis of Phosphorus Oxychloride from Phosphoric Acid or Phosphorus Pentoxide.

Basically, Carbonyl Chloride reacts with them at high temperature (around 500*C) to produce Phosphorus Oxychloride. Carbonyl Chloride can be substituted by straight Carbon Monoxide and Chlorine gas. Similarly, Phosphoric Acid can be a substitute for Phosphorus Pentoxide, but the reaction seems so much cleaner using P2O5 and COCl2.

After getting Phosphorus Oxychloride, we all generally know what to with it

Iv4 - 12-10-2003 at 23:23

But since carbon monoxyde and phosphoric acid are cheaper it would be better right?Since that way you could make up for th ineficiancyby working in larger amounts.

I'm thinking something like a methbomb?

Oh please...!!!!

Wolfram - 13-10-2003 at 12:13

What normal person would be interested in manufacturing tabun in the garage for personal some needs.

It is not that he is trying to make home made firecrackers..

Obviously this person is´nt connected to any department since he writes: "my chemistry skills are'nt too good,so be please be gentle"

I hope I dont live near where you live.

[Edited on 13-10-2003 by Wolfram]

Haggis - 13-10-2003 at 13:05

Many home scientists produce such chemicals for just the pure satisfaction of doing it. I, for one, am a person to make something, write up in my little notebook about it, store it in a vial or similar on my shelf and forget about it. I keep it till I either get sick of it (sometimes literally) or need the container. Others like to have knowledge of such things, which is most likely the case. These 'knowledge junkies' enjoy knowing all sorts of 'bad' information just because they can. Just because one speaks of such things does not mean they have the intent to manufacture said chemical, or even use said chemical.
Edit: Take a look around, we aren't 'normal people'.

[Edited on 13-10-2003 by Haggis]

madscientist - 13-10-2003 at 18:57

Samosa: metaphosphoric acid is (HPO3

n.

DDTea - 14-10-2003 at 11:19

Madscientist- do you mean that Metaphosphoric Acid is a polymer (hence the n) ? If so, would it not be possible to depolymerize it and therefore use it in reactions? I have read that it is used in the pesticide industry, so I'm quite confident it could somehow be used for our purposes.

If you choose, Phosphoric Acid could be subsituted for Phosphorous Pentoxide. However, by doing this, a lot of HCl is created and has to be removed from the final product. Also, since vulture and I were discussing means of procuring Phosphorous Pentoxide (by burning of Matchbook strikers in controlled conditions), we figured we could simply use that. Similarly, if you don't feel like having one "super" poison on hand, you could work with the two moderate poisons- Carbon Monoxide and Chlorine Gas. However, I figured that with little additional effort (3 more reaction vessels-1 for the actual reaction, 1 for drying, and 1 for neutralizing the Sulfuric Acid used in the drying process), the Chlorine and Carbon Monoxide could be combined to Phosgene and make the reaction a lot "cleaner."

EDIT: and yes, I do consider myself a "knowledge junky," as you put it

. I take an interest in dangerous chemicals because a) not many amateur chemists care to work with them, b) there is nothing much I can really contribute to amateur explosives, and c) it gives you a rush when you succeed in making one

.

[Edited on 10-14-03 by Samosa]

[Edited on 10-14-03 by Samosa]

Iv4 - 15-10-2003 at 22:24

No interest in actually making it(we right now)but just wanted to check my half ass theory.

DDTea - 16-10-2003 at 07:31

Now that I think about it some more, a much easier way of generating Phosgene is by heating Carbon Tetrachloride and Concentrated Sulfuric Acid together. Only problem is, I have no clue how to get CCl4 or how expensive it may be.

vulture - 16-10-2003 at 10:18

CCl4 is going to be very hard to get. Even professional chemists need a good reason to be working with it, since it has been labeled as one of the evil chlorinated carcinogens of death. I leave it to you if it is correct to treat/label it as such...

Polverone - 16-10-2003 at 11:55

J. Chem. Rev.
THE HALOFORM REACTION
REYNOLD C. FUSON AND BEETON A. BULL Department of Chemistry, University of Illinois, Urbana, Illinois
Received September 28, 1934

Quote:

The haloforms, when prepared by the haloform reaction, are contaminated to a greater or less degree by the corresponding tetrahalomethanes. This is due to the action of the hypohalites on the haloforms by which the latter are converted into the corresponding tetrahalogen compounds: CHX3 + NaOX = CX4 + NaOH. This is a general reaction (83, 73, 8, 38); it often becomes the principal reaction when dilute solutions are used. Thus, Wallach (198) found that in the formation of bromoform from hypobromite and acetone in very dilute solutions, the reaction was slow and that carbon tetrabromide was the chief product. This influence of the pH on the course of reactions involving hypohalites is frequently noticed (105, 119, 79).

(198) WALLACH: Ann. 276, 149 (1893).
(105) KOLTHOFF: Pharm. Weekbald 62, 652 (1925).
(119) VAN DER LEE: Chem. Weekblad 23, 444 (1926).
(79) HATCHER AND MEELLER: Trans. Roy. SOC. Can. [3] 23, Sect. 3, 35 (1929).

Perhaps it can be done stepwise too? Preparing CHCl3 from acetone and hypochlorite, then further chlorinating the CHCl3?

I also found a possibly interesting alternative chlorine/chlorination tool: according to the Journal of Applied Chemistry of the USSR (can't remember specific issue

), calcium hypochlorite + a cobalt salt yields copious oxygen when heated in aqueous solution. When heated dry, the cobalt + hypochlorite mixture instead yields chlorine. The catalytic effect is even stronger if a 3:2 mass ratio of cobalt and iron salts is used. I believe they used something like 1 gram of catalyst for 50 grams of calcium hypochlorite. I think this bears further investigation.

DDTea - 10-11-2003 at 07:35

On another note, sciencelab.com sells Phosphorus Oxychloride in lab size amounts for a rather high price ($180 for 500 ml-- still, for our work, I don't think we're looking to fill artillery shells or missiles). POCl3 lends itself well to making all sorts of dangerously reactive Organophosphates... But, after reading a few sections from that Phosphorus/Fluorine Toxic Action book, Phosphorus Oxydichloride Fluoride (whatever it's called) lends itself even better... The trick is to fluorinate POCl3.

Does anyone know how the Cyanide ion compares to the Fluoride ion in terms of reactivity of Organophosphates?? I hear all sorts of things comparing Sarin to Tabun- "Tabun is more irritating than Sarin," "Both Tabun and Sarin have poor detection qualities," (i.e.: both are odorless, both are have no irritating properties) "Tabun is more toxic than Sarin," "Sarin is more toxic than Tabun." I wish people would get their facts and nomenclature straight- it would make research so much easier

[Edited on 11-10-03 by Samosa]

madscientist - 10-11-2003 at 08:12

Remember that purchases of POCl3 could be considered highly suspicious due to its use in LSD synthesis.

[Edited on 10-11-2003 by madscientist]

Iv4 - 22-11-2003 at 10:02

Here's emedecines bit about nerve agents.I think I have some actual tables here somewhere.I'll post them when I find them.

Al Koholic - 9-12-2003 at 15:50

One can produce phosgene very easily from chloroform, sulfuric acid, and heat. No need to bother making CCl4 when CHCl3 is so easily obtained.

Also, something that you might want to consider for phosgene is a gas stream of CO and Cl2. This reacts and I believe can be used directly after mixing because the reaction is quick. Just lead the gases together into a tube which leads to your main purpose, ie: bubbling it through something...

vulture - 10-12-2003 at 08:10

Phosgene will decompose above 300C, so that would suggest the formation is exothermic. So leading it through a second reactor with a cold trap might grealty improve yield.

And of course higher pressure, 2molecules of gas --> 1 molecule, le chatelier.

Al Koholic - 11-12-2003 at 14:16

Indeed indeed! Also, the boiling point of phosgene is a modest 8C so there should be no trouble at all cooling it to the point of condensation. Hell, if you do the prep in a garage in the dead of winter, ie: -25C, you should be able to collect the liquid with no problem from a distillation. This is probably much easier to deal with than the gas in some apps, more difficult in others....the point is you have an easy choice.

fritz - 13-12-2003 at 08:52

I want to add that the for reacting CO with Cl2 the apparatus shuold be exposed to sunlight(UV-light) or you let the mixed gases stream in a tube over activated carbon(cooling(!) the tube to 250°C) Phosgene could be made free of Cl2 by streaming over Sb.

Other methods are:
-Soda+PCl5
-heating Chloro-formic acid trichloro-methylester at 340-340 degree C
-CO+SbCl5(hot)

for storage the use of Chloro-formic acid trichloro-methylester might be preferable, since it´s a liquid (b.p. 127,5°C) this stuff is also called diphosgene. I have unfortunatelly only spare information about synthesizing:
-reacting HCOOH and MeOH
-photocatalysated chlorination

but I could tell you where to find this substance in the Beilstein-enceclopedia:
EIV3, 33 I hope this could help!

DDTea - 13-12-2003 at 11:15

Chloroformic Acid, Trichloromethyl Ester is more popularly known as Trichloromethyl Chloroformate

. It is prepared by bubbling Chlorine through Methyl Formate; however, there are impurities by this route (mono- and dichloromethyl Chloroformate). The temperature is at first maintained at 30*C by a slow current of Chlorine, and then the stream increased and the temperature is gradually increased to 90*C. Also, UV light is very important in this reaction. To separate the impurities, the product should be distilled. The yield is 70% of the theoretical. This is according to The War Gases.

To me, this sounds like a candidate for Electrolysis. I imagine we'd want an excess of Chlorine gas too, so as to completely chlorinate the Methyl Formate.

I also remember a crude method to generate Phosgene on E&W-- by adding Methylene Chloride (CH2Cl2) to Gasoline and then burning it. However, since CCl4 and CHCl3 like to form Phosgene on reaction with Sulfuric Acid, could the same apply to Methylene Chloride, which is readily sold OTC?

[Edited on 12-13-03 by Samosa]

guaguanco - 13-12-2003 at 13:01

Quote:

Originally posted by vulture

CCl4 is going to be very hard to get. Even professional chemists need a good reason to be working with it, since it has been labeled as one of the evil chlorinated carcinogens of death. I leave it to you if it is correct to treat/label it as such...

Well, it's by far one of the more toxic halocarbons; it reaks havoc on the liver. It's not as bad as sarin, but it's bad news.

guaguanco - 13-12-2003 at 13:11

In the real world, intermediates like O,ethyl dichloro phosphonate are prepared from POCl3 via fractional distallation. Lacking than it's well nigh impossible to prepare a pure ester like that.

It's not hard to replace the chorine atoms with fluorine atoms in a suitable aprotic solvent. Again, this reation is pretty much out of reach of the home experimenter working with beakers in the garage. The resulting fluoro-esters get so toxic so fast that you just can't risk *any* exposure to them.

DDTea - 13-12-2003 at 14:54

Oh, you present too much reason/fear of the unknown for us mad scientists, guaguanco. We're all about doing the impossible, or the next to impossible, or just what is crazy and wild and immediately harmful to life and limb

.

You are right on the question of Fluorinating POCl3. The reaction requires Antimony Trifluoride and Hydrofluoric Acid, and some mildly complicated apparatus. But it's not impossible by any means. There are always alternative methods (ahh, the mad scientist optimism).

Why would you need O,Ethyl Dichlorophosphate in the production of Tabun? It is much easier to add the Ethyl and -CN groups in the last stage of the synthesis. N,N-Dimethyl Dichlorophosphate is reacted with NaCN in Ethanol, and the product is Tabun. Details such as temperatures and pressures can be worked out later; but at the moment we're hoping to get the groundworks-- notably, POCl3.

DDTea - 13-12-2003 at 15:20

Here's something interesting, from the Federation of American Scientists (www.fas.org)... I grabbed the excerpt from http://www.panix.com/~hncl/HectorsJournal/archives/000109.ht... :

Quote:

Tabun synthesis does not require the use of corrosive starting materials and does not produce highly reactive intermediates. The two-step process involves mixing the ingredients and a carrier solvent in a reaction vessel equipped with a sodium-hydroxide scrubbing system to neutralize the gaseous hydrochloric acid (HCl) byproduct. A relatively simple air-tight enclosure is also needed to prevent the escape of toxic vapors. The ingredients must be added in the correct order, without heating, and the vessel cooled to keep the reaction from building up too much heat. Little or no distillation equipment is required, although the purity of tabun can be increased to more than 80 percent by removing the carrier solvent and the off-gasses by vacuum distillation. In sum, tabun production is relatively easy because it does not include the difficult alkylation reaction needed to make the other nerve agents. The major technical hurdle in tabun synthesis is the cyanation reaction (in which a cyanide group is added to the central phosphorus), because of the difficulty of containing the toxic hydrogen cyanide HCN gas used as the reagent..

Why would HCN be needed? Most synthesis sources I've seen say that NaCN is fine. Then again, some Sarin sources say HF can be used in fluorination, while others recommend NaF. I suppose either way can work...naturally, the amateur would choose NaCN to address the issue of handling.

guaguanco - 13-12-2003 at 18:13

Quote:

Originally posted by Samosa

Oh, you present too much reason/fear of the unknown for us mad scientists, guaguanco.

You are right on the question of Fluorinating POCl3. The reaction requires Antimony Trifluoride and Hydrofluoric Acid, and some mildly complicated apparatus. But it's not impossible by any means. There are always alternative methods (ahh, the mad scientist optimism).

Why would you need O,Ethyl Dichlorophosphate in the production of Tabun? It is much easier to add the Ethyl and -CN groups in the last stage of the synthesis. N,N-Dimethyl Dichlorophosphate is reacted with NaCN in Ethanol, and the product is Tabun. Details such as temperatures and pressures can be worked out later; but at the moment we're hoping to get the groundworks-- notably, POCl3.

Well, just call me the little BlueBird of pessimism...

I was referring in general the the mono-substitution of things onto POCl3. It's very hard to just stick on one (CH3)2N- group and get a pure product. But knock yourself out!

(Actually, if you really did these reactions in your garage you'd probably end up doing a lot more than knocking yourself out.

)

POCl3

chloric1 - 26-2-2004 at 14:39

I remember reading that P2O5 could be heated with anhydrous FeCl3 for POCl3. Would not know a what temperature.

Wanting to try.

Sarevok - 18-6-2004 at 16:43

Tabun is made by reacting dimethylamidophosphoryl chloride with sodium/potassium cyanide, and ethanol. Details can be found at DE767511 and DE767830* (search for it on esp@cenet).

Dimethylamidophosphoryl chloride is made from dimethylamine and phosphoryl chloride. Details can be found at GB744484.

Dimethylamine can be made by neutralizing dimethylamine hydrochloride with alkali hydroxide, followed by the separation of the amine by distillation.

Dimethylamine hydrochloride can be made from ammonium chloride and formaldehyde - see Vogel's A Textbook of Practical Organic Chemistry, including qualitative organic analysis, pages 415-6.

Phosphoryl chloride can be made from any phosphoric acid, activated carbon, and chloride (or chlorine and carbon monoxide), or from any phosphoric acid and phosgene (which can be made by oxidizing chlorform (made from acetone and bleach)), etc. See details at GB416084, GB336065, US2622965, US2712494, US1381783, GB727950, US1462732, GB617990, US2002277, US1921370, US2712494, and GB617990.

Sodium or potassium cyanide were made from urea, carbon, and alkali hydrogen carbonate, by Mr Cool (of rogue science) and Polverone.

*: This patent was found by teshilo, of the rogue science forum. The other patents were found by myself.

Mendeleev - 12-7-2004 at 15:22

This is interesting that most of these G-agents are synthesized from phosphorus oxychloride as opposed to phosphorus tri and penta chlorides. Could anyone detail a procedure from the tri or penta chloride? These would be easier for me to synthesize than the oxychloride.

Edit: Oops, should've searched google more carefully. Megalomania has an awesome synthesis for damn near OTC sarin. Here's the link http://www.roguesci.org/archive/1043_6-27.html However I missed the part where he went from phosphite to phosphonate, was it when the methyl iodide adds the methyl group and one of the isopropyls falls off? Does the oxygen that was on that isopropyl become double bonded? Seriously though that is so damn near OTC it's scary. In a good way of course

.

Edit2: I am not sure how to convert this to tabun synthesis. I suppose in the place of all the isopropyl groups, you would ethanolize the hell out of it, but then you need to attach the dimethylamine, which poses a problem in that the methyl group in the sarin synthesis was added because it was methyl iodine, but I have never heard of halide amines. (Edit3)Well there is nitrogen triodide, but I would not put this stuff in a flask with G agents. This step would be even more important because I think it is the part where the oxygen becomes double bonded creating the phosphonate. But I guess the nitrile group could be added in the same manner as the fluorine atom in sarin, by using carbonyl chloride and then refluxing in ether with sodium cyanide.

[Edited on 13-7-2004 by Mendeleev]

[Edited on 13-7-2004 by Mendeleev]

[Edited on 13-7-2004 by Mendeleev]

DDTea - 13-7-2004 at 18:08

One way of attaching a Cyanide group on Organic Phosphate compounds is through Cyanogen Iodide... I just know the reaction, but not the method to do it. From Phosphorus Pentachloride, Phosphorus Oxychloride can easily be made by simply adding water.

Trying to produce Tabun via megalomania's route, or something similar, would be a very round-about and difficult way... I say stick with the Dimethylaminoethylphosphoryl chloride route.