Sciencemadness Discussion Board

VX preparation

jimwig - 9-6-2008 at 14:25

follows: the patent description of preparaation of nerve (war) gas

Description of US391059

This invention relates to the manufacture of S-(2-dialkylaminoethyl) O-alkyl alkylphosphonothiolates. These compounds have the formula ##EQU6## wherein R, R@1 and R@2 are lower alkyl groups. R is preferably methyl or ethyl, R@1 is preferably methyl, ethyl, isopropyl, n-propyl or butyl, and R@2 is preferably methyl, ethyl or isopropyl. Of all the compounds, S-(2-diisopropylaminoethyl) O-ethyl methylphosphonothiolate is regarded as the most important. The compounds have extremely high percutaneous toxicity to mammals and are useful as chemical warfare agents.

Our method involves the addition of sulfur to a 2-dialkylaminoethyl alkyl alkylphosphonite of the formula ##EQU7## giving an O - (2-dialkylaminoethyl)-O - alkyl alkylphosphonothioate of the formula ##EQU8## which is isomerized by heating to give our desired compounds.

We have found that if certain precautions are taken it is possible to secure consistent yields, in the range 95-98% of the theoretical, in the sulfur isomerization steps and the product is of such purity that no subsequent purification step is required.

this is only the first few paragraphs. i am interested in not only this most dangerous gas from a preparational point of view but also a historical one. the federal of american scientists talks about this a bit on its site.

and also there is the "missing wma" from iraq and hussein's/bush's era of ?????

i have read but cannot find a description of the extreme conditions of saafety employed to manufacture this gas. that also included some words about onsite accidents aand their outcome.

any interest?

[Edited on 9-6-2008 by jimwig]

Klute - 9-6-2008 at 15:41

Why people want to prepare war gasses for the sake of preparing a chemical warfare is beyond me.

crazyboy - 9-6-2008 at 15:46

Indeed even explosives can be used to help people and save lives. But I can't say the same for nerve gas why would you want it?

Formatik - 9-6-2008 at 16:34

Wait a minute now, nerve gas has legitimate uses. Maybe he just wants a really, really, really effective pesticide?

octave - 9-6-2008 at 17:02

A human pesticide?

Sauron - 9-6-2008 at 19:05

First of all the US and UK patents relating to VX and other V-agents have been posted here before.

Secondly, anyone who tries to actually make this will be dead faster than you can say acetylcholinesterase.

Aum Shin Rikkyo spent $11 Million US on their lab to prepare GB and VX and still had a number of accidents.

The intermediates and precursors to V-agents are also quite toxic, more than enough to be lethal under ordinary conditions, and so a wannabe VX maker will be dead long before he gets to the end product.

There is nothing wrong with studying this technology. There are indeed insecticides closely related to VX, that have been useful to mankind. One such is actually mentioned in the CWC - that's how close it is.

A number of OPAs do find use in medical research.

So study, ywes, if one is interested. Understand, yes. Prepare, NO. Not unless you have a world class deathwish.

Klute - 10-6-2008 at 04:12

Secondly, anyone who tries to actually make this will be dead faster than you can say acetylcholinesterase.

Hilarious :D

len1 - 10-6-2008 at 04:23

I dont know whats the point of studying such things as you can never do them. If its a way of commiting suicide one is after VX is a very longwinded way to go and theres always the chance of failure - maybe its the not knowing that makes it interesting.

ScienceGeek - 10-6-2008 at 06:59

Now this is a darn- funny thread!

Jimwig: Download or rent this movie: The Rock (With Nicholas Cage and Sean Connery)

Ask yourself again if you really want to make this nerve- agent...

Sauron - 10-6-2008 at 07:02

All the G agents and V-agents were originally developed as insecticides. Sarin, Soman and tabun in the 30s by Schrader at Baeyer IIRC. The V-agents in the 1950s initially in the UK.

All are relatively simple OP molecules, and if one is at all interested in OP, it is well worth knowing in some details what NOT to build, or one can get in a lot of trouble, in more ways than one, quite by accident.

The Baeyer people simply found that certain strucures unexpectedly possessed very high mammalian toxicity and in the process learned how to turn that toxicity on and off, as it were. In other words, knowing how to make insecticides that are effective while possessing low mammalian toxicity is inseperable from knowing how to engineer high mammalian toxicity.

Things like parathion and malathion are not very far away from either class of military agent.

The V-agents were "improvements" possessing extremely high percutaneous toxicity against mammals, including man.

Again, there are commercial insecticides that are in the same general class, they just don't have the specific molecular features that optimize certain effects for military purposes.

These are first and second generation OPAs we are talking about. There are at least four or five generations out there, the governments have simply gotten somewhat better at keeping a lid on most of that (but not all.)

Unless one knows the chemistry and SARs of these things, how can one even begin to think about decontamination, prophylaxix, therapy, design or detection equipment or protective apparel and equipment?

Pharmacologists and medicinal chemists are always intensely interested in anything possessing extremely potent biological effects. That's why the natural toxins like saxitoxin, from red-tide infected shellfish, or the fugu toxin (also employed in zombie dust) are interesting to those disciplines. (Tetradotoxin). See The Serpent and the Rainbow sometime.

Even the mustards, scourge of WWI, eventually produced pharmacological windfalls of great benefit to mankind. Cancer chemotherapy would not exist without them.

This is simply knowledge. How knowledge is used is entirely dependent on human beings. There's no such thing as evil knowledge, just evil applications of that knowledge. There is nothing mankind was not meant to know. Lines like that belong only in B-grade sci fi movies.

Anyway, everything I know about this subject came from the open literature and surely none of that is off limits here.

Sauron - 10-6-2008 at 07:05

BTW ScienceGeek, that film had almost NOTHING to do with reality as far as VX was concerned. Hollywood bullshit. A bad place to get one's chemistry.

VX is low volatility, kills almost exclusively by contact with the skin, so all that garbage about the marine dropping the little globe and then having his skin melt off, was horseshit.

Some Hollywood asshole decided that would be more impressive visually than just having him to the dance that we used to call "Deadbug" in the military, where you get on your back end emulate a cockroach sprayed with RAID.

That's what it does. It's an enzyme inhibitor,

The G-agents are volatile, but VX used to be worked with on the open desktop till the Edgewood people found out the hard way that there was a chronic low level exposure problem. Now it's in the hood, too. They used to trot out one of their scientists who had his nervous system profoundly affected by working with VX on the benchtop too long, to impress new personnel with the need for the containment procedures. He was not a pretty sight.

No I never worked there but I have friends who did. And I have been there.

[Edited on 10-6-2008 by Sauron]

jimwig - 10-6-2008 at 10:06

most infatically not interested in preparing --- just the preparation. process is my interest - not necesarily product......

thanks Sauron for the memory boost - as i mentioned i have forgotten the historical aspect of this whole topic. i for some reason just wanted to regain my recollections.

and of course the personal knowledge of the plants involved......!!!

the lecture i knew would be given so thanks anyway.....

many many procedures, protocols, etc are discussed here. i enjoy most all of them and sincerely apprreciaate the opportunity to learn even in a small manner.

having said that i aalso would argue that very few of those things presented here onl this board reach any sort of production stage -- despite what may be said. i could be wrong......

so it goes

Formatik - 10-6-2008 at 12:59

I've seen the Rock recently, and highly doubt the skin melts off. It's hollywood bunk. You can also read the MSDS on VX here. Though it would make sense to mix it with a dye, in case of a leak, the green color is also added for special effects, as VX is colorless to straw colored.

The volatility at 25ºC of the common nerve agents is here from Kirk-Othmer "Chemicals in war":

GA: 610 mg/m3
GB: 21,900 mg/m3
GD: 3,060 mg/m3
VX: 10.5 mg/m3

From this list I would say not VX is the most frightening, but GB. The volatility of water at the same temperature has been said to be 23,000 mg/m3. More on toxicological data from the Federation of American Scientists, estimates for 70 kg man:

...Route ....................................................Form........Effect.....Type ......GA .........GB........GD.........VX.........Dosage
Inhalation at RMV = 15 liters/•min/m3

The volume of a drop is something like 0.02 mL, so if 10 mg percutaneous is deadly for VX (70 kg man), then since v = m/d: 0.01g/1.0083g/cc = 0.01 mL, so about half of a drop is deadly 50% of the time. Though by a subcutaneous route, it will likley require much less, probably in the microgram range.

[Edited on 10-6-2008 by Schockwave]

Jor - 10-6-2008 at 15:42

So that means sarin spills are the most dangerous, followed by soman.
However, AFAIK, VX attacks will be done by creating a mist of VX in the battlefield (very small droplets). Not sure, though.

Formatik - 10-6-2008 at 17:01

Yeah, the deadliest common one per raw chemical handeling basis I would say is GB. It is much easier to avoid skin contact than inhalation. However, dispersed in specialized aerosols, specifically engineered bombs, etc. VX is the worst.

Sauron - 10-6-2008 at 17:32

Please note that while the chemistry of these comounds is fair game on this forum, my understanding is that the weapons engineering of them is definitely out of bounds.

Formatik - 10-6-2008 at 19:54

To weaponize them requires far more complex procedures than a simple discussion.

Sauron - 10-6-2008 at 22:23

True, but the forum proprietor demands no such discussions at all. Not chemical weapons (as opposed to the chemistry involved), not explosive devices (as opposed to the chemistry of energetic materials) and so on. I agree with him.

Just a cautionary reminder. I'd hate to see the thread get Detritused or locked because someone runs his mouth the wrong way.

MagicJigPipe - 12-6-2008 at 10:01


dont know whats the point of studying such things as you can never do them.

Why study drugs?
Why study nuclear weapon design?
Why study other galaxies?
Why study anything that you can't or probably won't "do"?


I'll probably never go to Siberia, never time travel, go to the moon, go to Egypt or synthesize F2, Me2Hg or cocaine but I still choose to study them. Why? Knowledge is power. Knowledge is fun. It's just the "beezneez".

Studying chemical weapon manufacture is no different than studying how fission is induced in plutonium. To each his own. I think people who study anything should be praised.

crazyboy - 12-6-2008 at 14:29

Originally posted by MagicJigPipe

dont know whats the point of studying such things as you can never do them.

Why study drugs?
Why study nuclear weapon design?
Why study other galaxies?
Why study anything that you can't or probably won't "do"?


I'll probably never go to Siberia, never time travel, go to the moon, go to Egypt or synthesize F2, Me2Hg or cocaine but I still choose to study them. Why? Knowledge is power. Knowledge is fun. It's just the "beezneez".

Studying chemical weapon manufacture is no different than studying how fission is induced in plutonium. To each his own. I think people who study anything should be praised.

Well I would like to go to Siberia and time travel or go to other galaxies but I don't want to make VX gas. Even with a top of the line lab and millions of safety precautions I don't want to make it. For starters the synthesis isn't interesting and the products only purpose is to kill.

Even studing radiation can benefit mankind with irradiating food, microwaves, atomic clocks and nuclear power plants. Cocaine in correct doses CAN be used to relive pain or aid other problems. VX gas has been studied extensively and has the sole purpose to kill.

Sauron - 12-6-2008 at 18:13

Who says this synthesis is not interesting? Whoever says that does not understand the synthesis or the precursors involved.

Who says the only purpose of chemical weapons is to kill? That's a sophomoric simplification. There have been many serendipitous discoveries that sprang out of CW research. I have stated many of them before so I do not feel called upon to state them again just to refute such a childish remark.

The_Davster - 12-6-2008 at 19:11

We have closed threads for ideological bickering before, but that need not happen to this thread, further posts not chemistry related will be removed. Chemistry discussion of CW agents are just fine.

Sauron - 12-6-2008 at 21:24

The starting material, methyldichlorophosphine, MePCl2, is not commercially available AFAIK, and is not easy to prepare. It is very air and moisture sensitive and is pyrophoric. It is also toxic. I have posted about its preparation previously. Making it would be rather technique-intensive.

The type and quality of sulfur employed is critical.

The esterification and transesyerification steps are equilibrium controlled. Isolation of the desired product by fractionation is necessary.

The nitrogenous side chain is recognizably a close derivatibe of Hunig's base, the famous non-nucleophilic strongly basic tertiary amine. The properties of this side chain, its steric hindrance, and the S-CH2-CH2-NR2 structure all point to the liphophilicity and persistance.

The thermal isomerization is the last step.

All of the precursors and intermediates are toxic. The final product is extremely so.

While I would not care to conduct this preparation, I certainly regard it as interesting organophosphorus chemistry.

Maya - 13-6-2008 at 20:52

I suppose from Di-isopropylamineethylchloride hydrochloride it wouldn't be too far a stretch to make the S substituted compound?

Sauron - 13-6-2008 at 21:41

You would not have to make the thiol.

You make the aminoethanol. transesterify that with the diethyl ester of the methylthiophosphonate, (itself made from the dichloride). Purify that to obtain the mixed ester that is desired, and then you are ready for the thermal isomerization.

The P=S sulfur exchanges with the O of the aminoethyl ester and voila. Read the patent posted by thread author and the related UK patents I posted last year. It's all there in the open lit.

Of course they don't tell you how to survive the synthesis. For that you have to more or less take a job at Edgewood, or Porton Down, or some similar facility of the sort, still allowed under CWC.

I first saw that patent about 27 years ago.

ANTICIPATE - 14-7-2008 at 03:43

PATENT NO. IS 3911059,NOT 391059

Sauron - 14-7-2008 at 04:17

That is the most important of many patents on this series of compounds because it describes the actual process by which VX, the only one of the series mass produced, was made at the polit plant. Eckhaus, first name on the patent, was director of that plant and codeveloper of the process.

It has been posted on the forum previously.

It would be well to note that the starting material is corrosive and pyrophoric as well as toxic and all the intermediates are potent AChE inhibitors (except for sulfur and ethanol). The only safe way to work with this compound is on paper or on a computer display.

ScienceSquirrel - 14-7-2008 at 04:33

All compounds can be handled safely if you have the right equipment and good technique.

This stuff is pretty nasty but an appropriately set up university lab can handle it with ease.

ScienceSquirrel - 14-7-2008 at 05:01

Oh, and phosphorous trifluoride is squitterlingly easy to make if you can get your mitts on some phosphorous trichloride and a suitable metal fluoride.

Mix and stir and it just bubbles off, make sure you have a nice cylinder to condense it in though as it is creeping death :D

Sauron - 14-7-2008 at 06:28

There was I time when I thought so as well. There was a time when the people at Edgewood thought so, too, till they found out the hard way to the contrary.

VX is primarily a contact hazard.

HOWEVER it turns out that, even though its vapor pressure at ordinary temperatures is trivial, its toxicity is such that it does present an inhalation hazard at such very low concentrations.

Gone are the days when the EA people worked with VX on open benchtops and in beakers.

We learned a LOT about the effects of low level exposures to these agents in the 80s and 90s and we are still learning and what the shakeout is, is frightening.

So now I must disagree and say: no, a good university lab is not adequate, special precautions are absolutely necessary if you value the integrity of your CNS and those of all others around. It would take a very unusual university lab to be properly equipped to work with this class of military OPA. This isn't Saunders and colleagues at Oxbridge in the 30s and 40s experimenting on each other with DFP. DFP is peppermint chnaaps compared to the V-series.

The Edgewood folks were caught totally off their guard, one of their scientists suddenly had his nervous system go haywire in the middle of the night, at home. Fortunately his wife knew who to call. The man survived but he was never neurologically intact again. Not a pretty sight, I hear. For many years they would trot him in to be shown to classes of new investigators/trainees. It was a very effective demonstration of why it is necessary to take their new protocols seriously, why SCBAs and MOPP gear are mandatory.

VX is persistent and difficult to decontaminate and when you do DC it, some of the degradation and hydrolysis products are still very toxic (though less than VX itself.) Something can be 25X less toxic than VX and still be as toxic as GB and 500 X as toxic as HCN. (OK I pulled those numbers out of my head but they are close enough for argument's sake.)

This why I am unconcerned about discusing this chemistry in the clear: because anyone stupid enough to try it outside of a REAL CW lab, is going to get a lesson in how evolution works. He'll take himself out of the gene pool, permanently. Faster than you can say acetylcholinesterase.

Sauron - 14-7-2008 at 06:38

And PS, I would not make the MePF2 from PF3 and methane. That may be a valid industrial process, but in a lab it would suck. MePCl2 is not hard to make, and no great precutions are required if your skills set includes airless operations.

Once you move to the next step, the diester, it's time for moon suits and SCBAs. After that things get steadily riskier.

ScienceSquirrel - 14-7-2008 at 06:44

I am not suggesting handling VX in a university lab.

I am pointing out that PF3 and other such goodies can be handled in a university lab.

I should think that the boys and girls down at Porton Down are set up quite nicely to handle this stuff.

Besides anyone who wants a Darwin Award can always have a go at nickel tetracarbonyl. Contrary to popular belief there are ways of making it apart from the Mond process and one of them starts with stuff you can buy down Walmart :cool:

ScienceSquirrel - 14-7-2008 at 06:48

Originally posted by Sauron
And PS, I would not make the MePF2 from PF3 and methane. That may be a valid industrial process, but in a lab it would suck. MePCl2 is not hard to make, and no great precutions are required if your skills set includes airless operations.

Once you move to the next step, the diester, it's time for moon suits and SCBAs. After that things get steadily riskier.

We made PF3 to make metal complexes of the stuff, we had no intention of making MePF2 that way.
We made our MePF2 from MePCl2
Transition metal phosphine chemistry is pretty hot in academic circles.

Sauron - 14-7-2008 at 06:55

No problem. We were talking about two different things.

ScienceSquirrel - 14-7-2008 at 07:14


This was back in the early eighties and there were a few middle Eastern gentlemen working quietly towards their PhD's.

Looking back now with 20 20 hindsight it is quite possible that they were more interested in the phosphine ligands than the metal complexes....

Sauron - 14-7-2008 at 08:54

Maybe. Maybe not. The Middle East is a big place, the Islamic world even bigger, and not everyone is motivated in the same way.

ScienceSquirrel - 14-7-2008 at 09:48

Very true and indubitably the case that they would have trained elsewhere if we had not taken them.

But I reckon there are a good few weapons programs around the world that would never have got going without a good technology injection from outside.

chloric1 - 14-7-2008 at 15:40

Serpent and the Rainbow, A kickass movie. I have not seen it in 14 years. Sauron you got me wanting to see it again, especially since I was fairly young last time I saw it and I did not understand everything going on.

Engager - 14-7-2008 at 17:48

This stuff is extremely nasty, good thing is that all this CW crap now beeing destroyed in US as well as here in Russia.

[Edited on 15-7-2008 by Engager]

Sauron - 14-7-2008 at 21:24

In the second to last step, the P=O bond of the "trans-ester" which you drew correctly, is thiated and that compound is then thermally isomerized. The final product however has P=O bond and thioester side chain. You show it with a P=S bond ands thioester side chain.

If you took VX and thiated it you would have the structure you show as final product but that is not VX.

Engager - 15-7-2008 at 00:02

Yes, i just mistyped =) Picture is now corrected.

[Edited on 15-7-2008 by Engager]

Sauron - 15-7-2008 at 01:51

There is considerable confusion in what passes for the literature as to the Russian (Soviet era) equivalent of VX also known as Substance 33, which is supposed to be different than the US VX but very similar.

Various books on the subject in the West also talk about VX-x, which may or may not be same as "Russian VX"

Obviously, the confusion is because neither the Russian government nor the US government is willing to state exactly what is what, so information tends to come from anonymous or pseudonymous sources, Cold War era defectors and dissidents, disaffected scientists inside and outside of Russia, and is difficult or impossible to verify. One alleged Soviet V-agent turned out to be a thickened version of GD (soman) and not a V-agent at all.

The situation is even worse as regards the so called novichoks, or nontraditional agents as the West refers to them obliquely.

How much of this could be disinformation is an open question.

I will understand if it would not be convenient for you to comment further.

Thanks for your input above.

Skrinkle - 18-7-2008 at 08:48

Do you think that very low dose atropine ingestion while working with the chemical would immunize him from some of it's nastier effects? Just speculating.

Also, shouldest disposal be a problem due to it being a powerful nerve destroying toxin and all? :o

[Edited on 18-7-2008 by Skrinkle]

Sauron - 18-7-2008 at 15:44

The short answer is "No". Atropine is useful with some OPAs but not with VX and never as a prophylaxis.

Disposal? No one here is proposing to make any VX only discussing how in fact it was done by a supposedly sane and responsible government. They are the ones with the disposal problem.

There is an excellent book in References on the chemistry, toxicology, therapeutics and pharmacology of chemical warfare agents. I recommend it.agents.