Log in

View Full Version : Nearly OTC Sarin Nerve Gas


megalomania
May 10th, 2003, 04:11 PM
I have been pouring through all my references because I am getting ready to do a write up for my website and I just wanted to collate my thoughts. While looking through everything I have finally settled on a route that appears to be damn near OTC. Without further ado I present a rough outline of the Sarin synthesis scheme.

In the beginning we start with good ol’ phosphorus. From my website I have the handy instructions on making phosphorus trichloride, from whence all toxic gasses seem to originate. Add a little chlorine to the P and we get PCl<sub>3</sub> hopefully (I know that rhymes).

Phosphorus trichloride is our ultimate precursor with which we can make a trialkyl phosphite, namely triisopropyl phosphite. How you say? Dissolve phosphorus trichloride in ether along with (presumably equimolar amounts) triethylamine and isopropyl alcohol, and you will get triisopropyl phosphite. You can even recover the waste triethylamine hydrochloride and make triethylamine again; I just discussed some of this recently.

Now comes the Arbusov rearrangement reaction; it’s pretty simple. Mix an excess of methyl iodide with triisopropyl phosphite and reflux on a steam bath for only a few minutes and you will get diisopropyl methylphosphonate. The good news is we can also use methyl bromide or chloride as our alkyl halide here to keep things OTC, although they require longer reaction times and higher temperatures being less reactive. Naturally using other alkyl halides (ethyl, propyl, butyl, etc.) will give us funky diisopropyl alkylphosphonates that will eventually make strange Sarin derivatives. Methyl is probably best for a reason… At this point you can see how close we are to Sarin; the molecules are quite similar.

If you are still following me, most of the work is done. We just need to get the right halogen. We first swap an isopropyl for a chlorine. To do this carbonyl chloride is passed into 20-30 degree diisopropyl methylphosphonate for 10 hours, with stirring mind you. Let this sit overnight and distill at over 30 degrees. We get isopropyl methylphosphonochloridate. At this point we have a chlorinated version of Sarin. I suppose this stuff must be deadly itself, but not deadly enough, not enough my friends.

What follows is the easiest part yet, our final product Sarin. Add the isopropyl methylphosphonochloridate to a minimum of methylene chloride along with an equimolar amount of sodium fluoride and reflux for 4 hours, with stirring mind you. Afterwards, filter the solution to remove any impurities, and wash the residue with a few portions of methylene chloride. What you will have left is Sarin dissolved in methylene chloride. The solvent can be removed by warming under reduced pressure. This is where a rotovap would come in handy.

Let us recap: phosphorus, chlorine, ether, triethylamine, isopropyl alcohol, methyl chloride (or Br, I), carbonyl chloride, methylene chloride, and sodium fluoride. None of these chemicals are forbidden as far as I know, and most if not all could be made OTC.

For bonus points the astute in the class will notice how one could substitute isopropyl alcohol with any alcohol, be it alkyl or aryl, and this is in fact how we get Soman nerve gas by using pinacolyl alcohol. To take this a step further, just to piss off the government types who probably have detectors specifically tuned to detect only isopropyl related components, one could use any manner of alcohols, alkyl halides, and carbonyl halides to make hundreds of different Sarin isomers.


http://www.roguesci.org/images/sarin.gif
http://www.roguesci.org/images/sarinesk.gif

nbk2000
May 11th, 2003, 12:26 AM
While nearly everything needed is OTC, the one key ingredient, Phosphorus, is not. Without the P, nothing else matters, so getting that is of prime importance.

Buying it is out of the question, since I'm sure any useable P chemical (like PCl3/POCl2/PCl5) is on a short list of "Terrorist" supplies for WMD's. To buy it would be the equivalent of waving a big flag over your in while screaming "ALLAH AKBAR! DEATH TO AMERICA!" at an NRA convention, with the same results. :p

So self-sufficency in being able to make P yourself would be the first step. This has already been discussed before, and attempted, but failed because of lack of a suitable furnace. But, with a suitable furnace, it shouldn't be at all difficult to crank out P yourself.

Once that's in hand, you can chlorinate it into either PCl3 for sarin, or PCl5 for conversion into POCl2 for making Tabun (GA). Personally, I'd go with Tabun instead.

It's easier to make, not requiring any fluorination like Sarin, so it's less destructive on the equipment and less sensitive to water presence in the precursors.

Assuming you've made the P yourself, then you've already got a furnace suitable for making cyanides, which are processed to make pure NaCN via HCN/NaOH.

Plus, Tabun is more persistant than Sarin, meaning longer contamination of the scene.

Most electronic CW detectors (that I'm aware of) are keyed to detect the presence of fluorine and sulfur atoms, which the majority of CW agents have...except Tabun. :)

Trying to substitute other alcohols is pointless, since they've been tried in every conceivable combination by the military, and the only ones they've bothered with is the pinacocyl/isopropyl/cyclo-hexanone (SP?) alcohols. So why bother with things that don't work?

Prior to any work on this, a person would be well advised to read "Some aspects of the chemistry and toxic action of organic compounds containing phosphorus and fluorine" by B.C. Saunders (on the FTP), as well as all mentioned journal and patent references. There's all sorts of little details that don't make it into a book that could make the difference between success and spectaculary lethal (to you) failure.

And I guess it's media fixation with "Nerve Gas" that gets all "terrorists" to thinking about it, but given the difficulty in obtaining the precursors in mass, why not use something that, while less toxic, in many times easier to obtain and make? Methyl Fluoracetate isn't nothing to sneeze at. And there's just gobs more of other nasties listed in the book that are almost piss easy to make.

It's not the chemical used, but the efficiency of the dispersion and targeting, that makes something a terror weapon. Imagine some terrorist setting up a beer stand at some resort during spring break, selling top-line beer at dirt-cheap prices. Every cup worth of beer has a few LD's of some slow poison that takes days (or weeks) to kill. How many people would that one beer stand kill? Hundreds? Thousands? Multiply that by several of them all over the country...

No "Terrorist Response Joint Task Force" in the world is going to stop some frat-boy and his slut from buying good beer at a too-good-to-be-true price in Cancun, mexico. :D

Or, conversely, targeting one specific room at the MIT computer technology lab could set back an industry worth billions by a decade, by wiping out the only three people in the world who know how to do (whatever). Now wipe out the whole campus of MIT, Harvard, etc...all at once...instant lobotomization of a nations brainpower, with financial impact in the trillions over the coming decades, and possible upset of the balance of world power.

Specific targeting of a key person can have an impact for outweighing the death of that person, as an individual. Imagine the impact on physics if Einstein was whacked before his General Relativity theory...no atom bombs, H-bombs, or anything that stemmed from them. Or Hawkings. See?

You could wipe out the entire superbowl stadium, and it'd have less real impact, than killing just a few selected individuals. After all, sheep get slaughtered everyday and it doesn't stop the world from turning, so what's the difference if it's sheeple? None.

Then again, Abdula Raghead is looking for publicity, and mass casualties, since that's the only thing that really garners attention in this age of a media-induced attention span that last only 30 seconds. :( Wiping out a few thousand people gets you a few days attention, killing one or two gets a 15 second blurb, even if those few are vastly more important and have a greater impact in the long term. Does anyone remember the name of a single person who died in the WTC? I don't.

'Course, just discussing this qualifies us for "special treatment" from some Alphabet Agency, being "Terrorist" training and all that...:rolleyes:

jfk
May 11th, 2003, 03:50 AM
ahh, but of course this is only for informational purposes :)

and if someone was to attempt this proceedure under an 'academic' study, what safety percausions[sp] would they have to observe? What kind of filters for a gas mask would they require to eliminate the chance of gassing themselves? Or would the entire process have to be carried out by a robot?

One more thing I was wondering, Is this one of the forums that can only be viewed by members of rougesci ?

Now for my real imput to this conversation, the phosphorus. Are strike anywhere matches not phosphorus coated in wax? (or something else). If so there is a convienient supply of phosphorus.

This is pure speculation on my part, as the new zealand government has never allowed these types of matches for sale, for safety reasons here.

megalomania
May 11th, 2003, 06:20 PM
What motivation someone has in actually making or using a nerve gas is none of my concern. I offer my material “for informational purposes only” or so the saying goes. One does not actually have to make the stuff to shock the public. Just by presenting this information the sheeple bleat in fear…

The book nbk mentioned is a good one. It covers some alternative older routes sarin syntheses that are not as efficient and give a lower purity product according to my information. The chemistry is very similar though.

I have mulled over the safety of this procedure and I conclude that it does not seem all that dangerous. Sure you will need a fume hood, but the final product ends up as sarin dissolved in a solvent, not some gaseous vapors. It would only be dangerous during any distillation operations.

Al Nobel
May 11th, 2003, 07:05 PM
I dont think it´s that suspicious if you order small amounts of red Phosphorus (a friend of mine ordered 50g without any trouble).

It should be possible to use red Phosphorus for the Tabun/Sarin synthesis.IIRC you can convert red Phoshorus into white Phosphorus by cooling down the vapors of red P.,so you have two of the three possible modifications of Phosphorus to work with.

nbk2000
May 11th, 2003, 09:54 PM
Indeed, just discussing this would send any soccer-mom into a self-rightous shit fit of condemnation of such "dangerous" knowledge.

I don't even think you'd actually have to make any significant quantity of a CW to still have the panic factor. Imagine a kilo of sarin dissolved into a 55 gallon drum of non-volatile solvent, then line sourced upwind of a monitored event like the superbowl. The CW detectors are going to start yowling and the piggies are going to start freaking.

And if abdula raghead chooses that precise moment to broadcasting his rant over the local TV/radio stations about his righteous purifying of the great satans unholy sports events with Sarin, the same stations that fans in the stadium would be watching/listening to, then what's the probability of starting a stampede for the exits that'll make the worst crush disaster in soccer history look like a church picnic in comparison? ;)

A fume hood would be inadequate. Saunders and Myers, both expert chemists with many years experience handling toxic chemicals, where constantly getting "intoxicatied" by DFP, which is several orders of magnitude less toxic than Sarin.

A negative pressure glove box would be required, for safe handling, I'd think. If a fume hood blower died on you, you could be the next thing to die, especially if your not paying attention to the manometer while focusing on a particularly tricky part of the synth.

RP is a DEA controlled substance, which would be just as bad as ordering PCl3 directly, so you'll either have to steal or make the needed phosphorus to avoid that hassle.

Synthesis processes are pretty much open source now, but the really important knowledge, keeping the product stable for storage and weaponization, isn't. The lack of stabilization is what fucked off the Aum Supremem cults attempt at gassing the Tokyo subway. Because their product wasn't stable enough to weaponize for transportation and use, they had to resort to the crude binary method that resulted in incomplete reaction/warning fumes/low dispersion.

Acid scanvengers and anti-oxidants would be needed to prevent trace acid residues from either reacting with the weapons casing, catalyzing decomposition, or oxidation into less toxic (or even inert) variants. The exact nature of these are beyond my understanding, but I do know they're needed, if you wish to be able to do anything more than mix it with hours of use.

megalomania
May 12th, 2003, 04:33 PM
I would assume such reactions would be done in all standard taper glassware, in the usual vacuum configuration, with an aspirator vacuum source and a fume hood. While the reaction is being conducted there are few vapors, but when it comes time to distill things and remove the solvents… that’s when you get in trouble. I would say just keep the stuff in the solvent.

I should say all nerve gasses prepared in the lab, especially on an improvised scale, should be used very shortly after synthesis. The synthesis info is out there, but what is still classified are stabilizers to store the stuff and material resistance data (like material incompatibilities, breakthrough times) for industrial manufacture. Fluorine compounds play havoc with most materials, only lab scale stuff could have a chance. One can not scale these reactions up with any degree of safety, or hope of purity. The Germans never worked out a good industrial scale synthesis of sarin, and it took the US a couple of decades. Even then they shut the plant down because it was unsatisfactory.

One would have to experiment themselves to find methods of stabilizing nerve gasses. It would be a good idea to check through available organophosphorus texts and journals to see what chemicals are used to stabilize the various pesticides and herbicides as it is logical to assume what works there should at least be a place to start for nerve gasses.

I was reading some forensic journals yesterday about trace detection methods. It is reasonable to assume a reasonably equipped forensics lab will pick up as little as pico gram amounts of chemical weapons. Imagine if they did detect just a tiny wisp… they would have no way of knowing how much there was to begin with, just that there was “some” in the sample. One could drip a few drops of sarin + solvent on a letter, mail it to congress (Dear Senator Feinstein, congratulations, you have just touched nerve gas…) and the techs would know you aren’t bluffing. They won’t know all you can make is a few mL of the stuff, but they will know you can.

One should definitely not buy phosphorus trichloride. It is a scheduled chemical of the chemical weapons convention and has very few uses nowadays. All companies that may have used it in the past have been encouraged to find alternate chemicals. It is not as bad as most other chemical weapons precursors, but it is watched. I wonder what Aldrich would say if I ordered up a Kg of the stuff? (only $39.30)

MrSamosa
May 27th, 2003, 12:55 PM
Very interesting topic, and I'm sorry that I have not been here in a while...but now, I have quite a bit to add :) .

1- Could Trialkyl Phosphites possibly be prepared from Phoshorous Acid and an Alkyl Halide? I'm thinking of the reaction that produces TEPP, where Ethyl Iodide is reacted with Silver Pyrophosphate to produce TEPP and Silver Iodide...

So, could one use the Ag3(PO3) and Methyl Iodide to produce the Trimethyl Phosphite, which in turn is heated, and the rest of the reaction follows the "Traditional" Sarin synthesis that we all know of. If this way is feasible, it would eliminate the need of the nasty reaction to produce PCl3 or PCl5, and it would eliminate the need to acquire straight P.

Unless I'm mistaken, Phosphorus Acid is not a banned chemical?

2- I brought up a topic on another web forum a few days ago, without a response... It was concerning Fluorination of Pyrophosphates. The logic was that since Fluorine is more reactive than Alkyl Pyrophosphates, I was thinking it would displace the Dialkyl Phosphate, and attach an F directly to the Phosphate Molecule. The side product would be a Dialkyl Phosphoric Acid.

3- The first reaction to produce Triisopropyl Phosphite is very interesting. If you have this, why stop at Sarin? It would be possible to produce VX from this chemical, would it not? I don't remember the pathway off the back of my head (I need to review the patent), but I do recall that one of the main precursors for VX is Triisopropyl Phosphite.

4- The solvents most commonly used in Organophosphorus Pesticides are Aromatic compounds. I just checked the label on Malathion yesterday, and it stated something along the lines of, "Contains solvents in the Xylene range." However, one must keep in mind that Pesticide Organophosphates are of a very different class than weapons Organophosphates.

Arthis
May 29th, 2003, 05:34 AM
Just a question about getting phosphorus: isn't it possible to make it from P2O5 , as it's common chemical ? I can't find any info about that.

zaibatsu
May 30th, 2003, 08:36 AM
http://news.bbc.co.uk/1/hi/uk/2948900.stm

The media storm starting already?

MrSamosa
May 30th, 2003, 12:16 PM
A recipe describing how to manufacture the nerve agent was found on the internet.

3 scare words in one sentence! "Recipe," "Nerve Agent," and "Internet." But, on to something more related to the Sarin synth.

As you all know, the trouble with Nerve Agents is obtaining the Phosphorus precursors. That is why I hope to find some way to eliminate the need for Phosphorus altogether, even if it means a significant reduction in yields. Phosphorus is expensive, and by having a synthesis that does not use it, lower yields will be more than made up in lower costs (does that make sense?).

As such, since Phosphorus is needed to catalyze the reaction between Iodine and Methanol to make Methyl Iodide, let's abandon MeI eh? A suitable substitute would be Dimethyl Sulfate, which is easily made by the reaction between fuming Sulfuric Acid and Methanol.

However, if we are going to be following the "Traditional" route. Diisopropyl Methyl Phosphite needs to be reacted with Phosphorus Pentachloride, or Phosphorus Trichloride with a current of Chlorine Gas. This is the tricky part.

To bypass this, could we not use Isopropyl Iodide to react with the Silver Phosphite? Therefore, we could follow Mega's synth (which he has many references on, thus being more well established than my conjecture) except for the first step involving the formation of Phosphorus Trichloride.

But if you insist on the Phosphorus Trichloride route... I believe the reaction to form Triisopropyl Phosphite is done between PCl3 and Isopropanol in Carbon Tetrachloride instead of ether; I believe this was part of the "One-Stage" process which gave very high yields for this reaction (about 86% of the theoretical). I don't have my references on hand, so I'm just relying on my memory for this.

Infernus
June 4th, 2003, 02:16 AM
Hey all.

Well, here in portugal all P compounds are easy to get (except for CH2PCl2, used in VX synthesis, cause it's WAY to expensive). we still dont worry much about nerve gases, and even
KCN is kinda easy to buy here, from merck itself.

Well, anyway just my two cents

Cheers

Chaos

MrSamosa
June 5th, 2003, 12:14 PM
How easily obtainable are such P products in Portugal, specifically PCl3, PCl5, and POCl3?? If they are so easy to get, then perhaps it would be worthwhile to have a group of people go to Portugal and buy the chemical, then smuggle it onto the plane to get back to where they will be using it... Does this sound too unreasonable to obtain precursors? Especially considering that in most other countries, you would probably be arrested for even trying to purchase them...

Is Portugal part of the Chemical Weapons Convention though?

nbk2000
June 5th, 2003, 05:18 PM
If he was still a member here, I'm sure he'd answer. ;) :D

Portugal is a signatory of the CWC.

80r15
June 10th, 2003, 09:15 AM
Originally posted by VoD
IIRC phosphorus is used in methamphetamine synthesis as well, so while they may not think you are making a CW with something as small as 50g of red phosphorus, the gestappo may come knocking on your door looking for your meth lab....

Yes Red Phosphorus is used in methamphetamine production, that is why I know how you can get some. Now this method is not economical(relative to buying it, I think), but it works really well nonetheless and you can get lab-grade, or weapons-grade in this case, red P. The procedure from getting it off matchbox covers can be found at http://www.rhodium.ws/chemistry/rpbible.html
:)...

Also I would like to apolagize for my K3w|_ name and some posts "I" when "I" first got registered. When you are in a foreign country, never leave it up to your brother to register you at explosives sites. He is a moron. Apparantly, he posted something about having VX in a glass ball or some shit like that. Don't worry though, I have cut off all his fingers so that he may never type again.........:)

Oh yeah, I forgot to tell you what the recipe requires
_______________________
Materials:

5 Gallon Bucket
Drill (1/2" chuck)
Mud/Paint/Concrete Mixer
Coffee Filters
Strainer (big enough to fit over pot and bucket opening)
2 gallon Cooking Pot
Tin Snips or Scissors

200 Matchbook Boxes
2 Gallons Acetone
Sulfuric Acid
Hydrochloric Acid
Water
Iodine
________________________
The only "hard" thing to get is the Iodine, but that can be ordered from www.unitednuclear.com, I know from making....stuff... ;)

And Megalomania, if you are having trouble or want alternate synthesis methods for various nerve agents, I have a couple sites which may be able to help you out.

croc
September 17th, 2004, 10:11 AM
A better way to make red phosphorus is to scrape the powder off with a sharp knife. The two main chemicals in match pads are red phosphorus and antimony sulfide, the next most occurring is powdered glass.
The antimony sulfide could be neutralized with an acid to make hydrogen sulfide and another antimony compound hopefully easier to remove.
Hydrochloric acid cannot be used because it will react with the red phosphorus to form phosphorus chloride. I don’t know what sulfuric acid or hydrogen peroxide would do.

teshilo
September 18th, 2004, 02:13 PM
Phosphorus trichloride may be produced from red P and chlorine.Final product this mix from PCL3 and POCL3.I seen process for made dialkilphosphites from alkile sodium hypophosphite and CuCl2.Icannt search patent where this process described... :confused:

FUTI
September 18th, 2004, 05:14 PM
to zaibatsu: Thanks for the link that makes few good laughs out of me. That part with chemical ban or control was hilarious. I still remember the time after some dumb ***** try to sell diluted industrial grade ethanol as some kind of brandy, the government here set the law by which ethanol became hardest to find substance in the country...that makes lot of chemist here to curse as well. Next to it was some decision I heard of in American Senat that PI-number is highly impractical and that for now on they should ignore the decimal point and count it as 4. I don't know is it a hoax or not but it is good laugh too:)

EDIT : I almost forgot since whole thing come out of insecticide production...I can put some money on it that we could make a route from comercial insecticidal solution and isolate the binary compound that can be set to react in explosive device producing the hell on earth. I would like to see them try to check every farmer to see does he have a legitimate purpose for those pesticide.

croc
September 21st, 2004, 09:20 PM
Phosphorus trichloride may be produced from red P and chlorine.Final product this mix from PCL3 and POCL3.

then where does the iodine in the red P go?

Chris The Great
December 15th, 2004, 12:01 AM
Since I started doing some research into this area with the intention of making a few mL of VX (much lower evaporation rate of sarin makes it much easier and safer to handle, despite the much higher toxicity). Since I started looking for info on sarin first, I got a basic (though undetailed) synthesis which was different from Mega's synthesis, although I didn't actually look on the forum for any synthesis info while doing this, (http://s-a-t.org/images/sarin/siryo/hyoka/seto-zu-2.jpg), and used by a terrorist organization, so I know it works. I then decided VX would be better to make, but the only information I found was a synthesis that was reportably very difficult (it didn't go into details). So, I simply decided to use the sarin synthesis with a modified ending to end up with VX, and figure out the rest based on what I already knew.

Of course, this is still in the research phase, and I don't yet have ftp access, although I did get a hold of the book by a link posted in this thread http://www.roguesci.org/theforum/showthread.php?t=1537 on page two. Another goal of this is to use ONLY chemicals that are extremely easy to get. Right now, there some parts I'm not 100% sure about, and so have marked with a (?) after that part.

Anyway, here's what I've come up with. I assume we've already got white phosphorus from extracting it from whatever is on hand containing phosphorus. Calcium triphosphate apparently works very well for this. I suppose most common fertilizers (30% P2O5) could also work, though I've never seen anything about this except in this thread. It appears nearly all fertilizers are extremely phosphorus rich, some above 50% by weight, so this is definatly something for me to look into.

The first step is to create phosphorus trichloride. This is simple, chlorine is run into a reactor where the white phosphorus is. The entire reactor vessel must be purged of oxygen before the reaction begins, to avoid phosphorus oxide impurities. CO2 from a paintball gun canister is probably fine for this application, as it's going to be distilled anyway. Dry chlorine gas is slowly released into the chamber, which immediately reacts with the phosphorus much like burning in the air, but controlled by the amount of chlorine being let into the reactor. The phosphorus trichloride is distilled out as it will be in vapour form after the reaction. The chlorine flow needs to be regulated to avoid overheating the reactor or reacting too fast or causing other unpleasant problems.
The phosphorus trichloride is then distilled at 75 C to remove any impurities. It will be a clear liquid when pure.

The phosphorus trichloride is then slowly poured into methanol (sold as methyl hydrate in large amounts in your local hardware store), with the evolution of hydrogen chloride gas and heat. The temperature should remain below 45 C to prevent the methanol from evaporating (?). Distill out any remaining methanol and other impurities at about 80 C.

Iodine crystals are then added to the methylphosphate. This catalyses the reaction of methylphosphate to dimethyl methylphosphonate when the mixture is heated. No idea of the temperature required yet, either I'll find out or experiment. The I2 crystals are then filtered out (if they don't dissolve (?) ).

The dimethyl methyl phosphonate is then reacted with thionyl chloride (see thionyl chloride synthesis, briefed at the end of the VX and sarin synthesis) to form methylphosphonate dichloride. The dimethyl sulfite is distilled out at 130 C to leave behind the methylphosphonate dichloride crystals.

Up to this point it is basically the procedure for making any nerve agent. For sarin, one would replace the chlorine with fluorine and react with isopropyl. I chose to use this synthesis up to this point as it was the one I have the most information on. Apparently, it is also possible to only replace one chlorine atom in the phosphorus trichloride with a methyl group, which is then reacted straight to methylphosphonate dichloride. The source that gave me this info was not very detailed at all, and simply said that this was a very hard
procedure. Apparently it's the method the US used to produce VX nerve agent.

This is then reacted with a 50/50 molar mix of ethylene glycol (distilled antifreeze, see end) and ethanol, with the evolution of hydrogen chloride gas. This is very similar to the reaction of phosphorus trichloride with methanol.

This is then reacted with diisopropylamine to form the immediate precurser to VX and water. Interestingly enough, this molecule cannot inhibit acetylcholinesterase, and can actually stimulate the production of antibodies against VX (http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=8452483&dopt=Abstract). I never knew you could develop antibodies against a nerve agent.

Finally, this is reacted with sulfur powder to form VX (?). Apparently elemental sulfur will work for this step, although I'm not sure as none of the sources I've found plainly state that.

If one where to make sarin instead of VX, then it the procedure would be as follows, taking up after the creation of methylphosphonate dichloride. The problem here is the need for flourine, which is fairly hard to find in your average pharmacy I would think, and of course sarin evaporates 1500 times faster than VX.

Sodium floruide or hydroflouric acid is added to the methylphosphonate dichloride, giving up salt and methylphosphonate diflouride. Half of the methylphosphonate dichloride remains unreacted. Isopropyl alcohol is added, and it reacts with the flourine on the methylphosphonate diflouride. The HF released puts F onto the methylphosphonate so it is reacted into sarin as well.

Thionyl chloride: This is highly reactive with water, breaking down immediately to form hydrogen chloride and sulfur dioxide gas upon contact with any moisture, so I will probably use a different chlorinating agent if another is available that it is made from such easily available chemicals. Again, more research is needed.

Monosulfurdichloride is formed by reacted sulfur with chlorine to form disulfurdichloride, which is then further reacted with chlorine with a small amount of iron powder added to give monosulfurdichloride. This is then distilled.

Sulfur trioxide, in the form of 65% oleum, is heated to drive the SO3 into the much cooler monosulfurdichloride. SO2 gas is given off, and the mixture will eventually come to a dark red liquid. This is distilled several times at 76 C until it is only a light yellow color, which will be very pure thionyl chloride. It is essential to keep all moisture out of this setup.

Diisopropylamine: This is formed by reacting isopropyl alcohol with dry ammonia gas in the correct molar ratios. Ammonia gas can be made by driving it out of ammonium hydroxide solutions by applying heat, dried, and then bubbled through the anhydrous isopropyl.

Antifreeze can be heated to 140 C to drive out all the moisture, then the ethylene glycol is distilled out at 200 C, leaving behind the rest of it (mainly diethylene glycol, boiling point >285 C and dissolved solids). This should yield near pure ethylene glycol.

So, that's my still being developed procedure for making VX from chemicals that are easily picked up at your local hardware and garden store and supermarket pharmacy. There are still a lot of the parts of the actual synthesis that needed to be worked out, but I'd say that's a pretty good yeild from just googling around. And they're all worried about proliferation amoung terrorists.
A few more weeks and the procedure should be complete, and I can attempt it except for the last step of adding sulfur. I'll want a gas mask and some atropine injectors before I try that. Safety doesn't mean not doing dangerous things, it's being prepared for the dangers brought about by doing those dangerous things. Maybe I can pick up the atropine injectors at a military surplus store or something.

VX can be easily destroyed using household bleach with the evolution of chlorine gas, making removal very easy if you don't plan on using it immediately, or not at all in my case. It also makes spills (hopefully not!) easy to clean, as well as glassware safe to use again.

(Main) Sources:

http://s-a-t.org/images/sarin/siryo/hyoka/seto-zu-2.jpg taken from
http://s-a-t.org/sat/sarin/siryo_syoukai/seto.html
which shows the reactions for the sarin synthesis this is based on.

http://www.mitretek.org/home.nsf/homelandsecurity/VX good info on the actual agent and how to get rid of it with bleach.

http://www.cbwinfo.com/Chemical/CWList.shtml
and
http://www.cbwinfo.com/Chemical/Nerve/VX.html
had good info on the precursors for the weapons, as well as some info on the actual chemicals themselves.


Croc: There is no iodine in red phsophorus. Red phosphorus is merely a different crystal form of phosphorus which makes it much more stable. The same goes for black phosphorus.

Wow, that was a long post....

Criticisms on the ideas appreciated.

Mendeleev
December 15th, 2004, 02:37 AM
Originally Posted by MrSamosa
As such, since Phosphorus is needed to catalyze the reaction between Iodine and Methanol to make Methyl Iodide, let's abandon MeI eh? A suitable substitute would be Dimethyl Sulfate, which is easily made by the reaction between fuming Sulfuric Acid and Methanol.

Umm, this is very untrue. Methyl iodide is easy to make, it involves mixing an iodide salt with methanol in phosphoric acid, the last two ingredients are OTC. Furthermore methyl bromide can be used which is even easier to make, sodium bromide which can be bought in multi-kg quanitities at any hardware or pool store as brominating tablets for pools, is mixed with methanol and H2SO4. Totally OTC. If you want to go messing around with oleum, which is difficult to find and expensive as hell, that's your choice. You could make it but this involves heating various metal sulfate to over 400 C, and generating SO3, also not fun.

akinrog
December 15th, 2004, 06:36 AM
Di methyl sulfate is a nasty substance too. It is very poisonous and acts something like a nerve agent.

According to some claims, it is also mutagenous (however I failed to find toxicity data of dimethylsulfate).

So I would really be careful handling this dangerous (and quite volatile) substance.

Chris The Great
December 15th, 2004, 08:12 PM
Can't oleum be made by dehydrating H2SO4 with P2O5 creating phosphoric acid and sulfur trioxide, then distill out the phosphoric acid at 160 C? I figured that would be how one would get the 65% oleum for making the thionyl chloride, although there is probably an easier way to make the stuff.

nbk2000
December 16th, 2004, 08:46 PM
VX is hydrolyzed only slowly, and the hydrolysis products include EA2192, which is nearly as toxic as VX itself and longer lived....

EA2192 is very long-lived; under comparable conditions (22°C, pH 13-14) EA2192 undergoes hydrolysis over 1,000 times more slowly than VX.


Sounds interesting.

Kind of like how you can make hydrate salts out of mustard gas that'll last for decades, impervious to further decomposition. :)

I also doubt you'd be able to find atropine injectors, as the atropine is a lethal poison if you're not suffering from OP poisoning, and thus not likely to be permitted for purchase in a ready-to-use injector for assassination-type murders.

Though it may be available for the taking if you live in the right area, in the form of plant extracts.

redbull
December 22nd, 2004, 05:10 AM
A local cat bought two atropine auto injectors from an army surplus stand about 3 years back.. $5. They eventually got confisgated by police when looking for something else... Atropine is a prescription drug but yes it can be removed from plants like deadly
nightshade I think. An Isralei company sells it anyway.. if you really look in secondary markets you can get it... goto the doctor and say you work with pesticides and need it just in case... then you can order straight from the company.. pick up a cyanide explosure kit while the doc has his prescription pad out...

teshilo
December 23rd, 2004, 03:03 PM
OTC Sarin... On my look best way for production methylphosphoryldichloride
this his preparation from PCL3+ALCL3+methyl chloride and after mixing hydrolise with water...Details in english patent posted Sarevok in thread Patents section Links and literature.
PCL3 may be from red phosphorus and chlorine heat..... :rolleyes:
ALCL3 also from chlorine and aluminium dust with heat.... :rolleyes:
Methanol+HCL=methyl chloride... :rolleyes:
Next step fluorination with NaF(produced from sodium fluorsilicate used for preservating wood and sodium bicarbonate or calcium fluoride+sulfuric acid and water solution sodium bicarbonate) and you make methylphosphoryldifluoride or DF
and mixe DF with Isopropanol(anhydrous) you get pain in the ass -GB.
Simple as can see? - NOT :mad: ,very danger step on this method -fluorination, use NaF against HF make process more secure for you.And main problem this not making precursors -this is his refinery and refinery final product..
Added reading: Assorted Nasties by David Harber and Silent Death By Uncle Fester (on ftp) also threads Patents :D :D .
P.S Who have any info about chlorosarin..etc?

nbk2000
January 29th, 2005, 08:10 PM
Found a picture of a 'hot' lab setup for the production of sarin. The reason why the people are behind glass walls is because it's a training session for 'Homeland' defense at dugway, and they're actually making it. :)

The original picture was 2MB in size, so you could zoom in and read the names of the chemicals off the bottles. All are sarin precursors. At what point in the production the photo was taken, I don't know for sure, but it's set up for vacuum distillation, so I'd say it was ready for preliminary distillation of the sarin from the reaction vessel, and not the final purification.

TreverSlyFox
February 2nd, 2005, 09:07 AM
This may be a stupid question, but I don't know the answer so I'm going to ask it. With all the pesticides used in Farming and just the OTC wasp, hornet killers they must have some rather nasty stuff in them. Wouldn't it be easier to isolate and concentrate the nasty part and use it.

I remember getting a very little "Back Blast" from a wasp/hornet killer on a windy day and my lips went numb in seconds, along with sweating and got the shakes for several minutes. The label says to administer Atropine if things get bad. It contains .25% Chlorpyrifos [0,0-diethyl 0-(3,5,6-trichloro-2-pyridinyl) phosphor-othioate] which is a Cholinesterase Inhibitor, so it's a Central Nervous System chemical agent.

At .25% it was interesting but only annoying, but what if it had been a hell of a lot higher concentration mix with somthing like DMSO?

nbk2000
February 2nd, 2005, 10:20 PM
That might work for a tete'-a-tete' murder, but not for mass cleansing.

DMSO greatly increases the toxicity of OPA's, up to two orders of magnitude! :o

Variables, of course, can dimish this greatly.

Man Down Under
January 8th, 2008, 07:43 PM
Found some videos on Youtube! of a military training tape where they show live fire testing of GB artillery rounds against emplacements with pigeons and goats in them.

From the videos (in my FTP folder) the reason given is that it takes 2.5x the LD for man to kill a goat, and 0.5x LD for the pigeon. Thus, if the pigeon is dead, but the goat is alive, the concentration was an incapacitating dose for a man. If the goat is dead too, you assuredly would have killed the man.

It took 80 seconds to kill the pigeon, and 2.5 minutes for the goat.

So it would be good to acquire some goats and pigeons when doing any testing of weaponized SARIN. :)

aliced25
March 4th, 2008, 09:35 AM
I have the following article: Reactions of Trialkylphosphites with Methanol: http://tinyurl.com/2shukm

[CONTRIBUTION FROM THE CHEMICAL LABORATORY OF THE UNIVERSITY OF CALIFORNIA]

Reaction of Trialkyl Phosphites with Methanol'

JAMES CASON AND WARREN N. BAXTER

Received March 3, 1968

At 210-215' in a sealed glass tube, n-butyl alcohol reacts with triethyl phosphite to give only transesterification; ethyl alcohol reacts slou-ly to give phosphonates; and methyl alcohol reacts more rapidly to give phosphonates. Under the most favorable conditions found, there was obtained an 85% yield of a phosphonate mixture which consisted of about 60% diethyl methylphosphonate, 25% diethyl phosphonate, and 15% triethyl phosphate. Evidence is presented that the latter two compounds do not arise by simple hydrolysis and oxidation of a part of the triethyl phosphite by moisture and air. Significant amounts of ethylphosphonates or mixed esters such as methyl ethyl methylphosphonate mere shown to be absent. Transesterification is the most rapid reaction between methyl alcohol and triethyl phosphite; subsequent rearrangement may proceed in a manner analogous to the Arbuzov reaction. Reaction of trimethyl phosphite with less than 0.1 mole equivalent of methyl alcohol gave a 92% yield of pure dimethyl methylphosphonate. In pentavalent phosphorus compounds, such as dialkyl methylphosphonates, absorption in the infrared for the CHI-P structure was found to occur at 7.65 +/- 0.02um in contrast with the trivalent phosphorus compounds where absorption for this structure was observed at about 7.75um, as has been previously reported.

As interesting as this article is, this one is perhaps even more intriguing: Efficient Synthesis of Dialkyl or diaryl phosphonates using SiO2-Cl (2006) 47 Tet Let 3107: http://tinyurl.com/2qdg5p (although this is from the now ultra unreliable Tetrahedron Letters - ie. take it with a grain of salt).

An efficient method for the esterification of phosphonic and phosphoric acids using silica chloride

Manisha Sathe, Arvind K. Gupta and M. P. Kaushik*

Process Technology Development Division, Defence R&D Establishment, Jhansi Road, Gwalior 474002, MP, India

Received 19 December 2005; revised 16 February 2006; accepted 27 February 2006

Available online 20 March 2006

Abstract—Silica chloride is used as an effective heterogeneous catalyst for the rapid esterification of alkyl/aryl phosphonic/phosphoric acids to their corresponding alkyl/aryl phosphonates/phosphates under mild conditions with quantitative yields.

Finally, for those who are interested in more 'normal' routes to the methylphosphonic acids, here is a route to Phosphorous Trichloride and Phosphoryl Chloride (amongst others): Tarbutton, et al, 'Phosphorus Halogen Compounds from P2O5 & Halides...' (1941) 63(7) JACS 1782; http://tinyurl.com/2wyghj.

[CONTRIBUTION FROM THE DEPARTMENT OF CHEMICAL ENGINEERING, TENNESSEE VALLEY AUTHORITY]

Phosphorus-Halogen Compounds from Phosphorus Pentoxide and Halides.
Properties of Phosphorus Trifluoride and Phosphorus Oxyfluoride*

BY GRADY TARBUTTON, E.P. EGAN Jr AND S.G. FRARY

The reaction of non-volatile halides with phosphorus pentoxide has been mentioned in the literature, but the conditions of the experiments and the properties of the products formed have not been thoroughly investigated. Schultze prepared phosphoryl trifluoride by the action of phosphorus pentoxide on a fluoride, and Thorpe and Hambly obtained the same compound from phosphorus pentoxide and cryolite. Lucas and Ewing however, reported that phosphorus pentafluoride, not phosphoryl trifluoride, was obtained by heating a mixture of phosphorus pentoxide and calcium fluoride. Curtis, Copson and Abrams stated that the reaction between phosphorus pentoxide and sodium chloride yielded volatile phosphorus chlorides and that this type of reaction should be a general one. They also pointed out that most of the fluorine in rock phosphate is liberated in the process of making crude calcium metaphosphate (metaphos) by treating rock phosphate with phosphorus pentoxide at a high temperature.

In the present paper are reported studies of the reaction of phosphorus pentoxide with the following substances: (1) calcium fluoride, (2) rock phosphate, (3) fluorapatite, (4) calcium chloride, ( 5 ) sodium chloride. The reaction of phosphorus pentoxide with mixtures of sodium chloride and calcium fluoride also was studied, to determine whether mixed fluorochlorine compounds of phosphorus can be prepared in this way.

I'd imagine that based upon the series of reaction culminating in the excellent article by Tarbutton et al, it should be possible to work out a fairly simple route to at least the phosphorus/phosphoryl chlorides from metaphosphoric acid and calcium chloride. These can be converted rather easily to the trialkyl and thus the dialkyl alkylphophonic acids you seek.

W4RGASM
May 6th, 2008, 12:00 AM
If one where to make sarin instead of VX, then it the procedure would be as follows, taking up after the creation of methylphosphonate dichloride. The problem here is the need for flourine, which is fairly hard to find in your average pharmacy I would think, and of course sarin evaporates 1500 times faster than VX.

Sodium floruide or hydroflouric acid is added to the methylphosphonate dichloride, giving up salt and methylphosphonate diflouride. Half of the methylphosphonate dichloride remains unreacted. Isopropyl alcohol is added, and it reacts with the flourine on the methylphosphonate diflouride. The HF released puts F onto the methylphosphonate so it is reacted into sarin as well.

Calcium fluroride can be obtained extremely cheaply, say a buck for a bound, albeit in a relatively crude form which will require purification.

Head down you your local geology shop and ask if they sell large crystal samples. Pick up fluorite. I've got a 2kg chunk sitting in a box somewhere I got only a few months ago that way.

megalomania
May 6th, 2008, 06:30 PM
I think you can get calcium fluoride from pottery suppliers too. Hydrofluoric acid in dilute form is available in deck or siding wash; it can be neutralized and purified if one wanted to bother. The HCFC's in refrigerant refills are also commonly available at many stores that sell autoparts; these would require a chemical transformation to extract the fluorine. Combustion might do it actually

Telkor
May 15th, 2008, 04:26 PM
There's a different way which was used by Aum Shinrikyo to obtain Sarin for their terror attacks.

First of all, greater amounts of phosphor were produced by the reduction of phosphates with carbon.

Then they produced PCl3, which was reacted with methanol, forming trimethylphosphite.

Trimethylphosphite was converted to DMMP through application of heat and pressure.

The hot DMMP + phosphorous pentachloride will form methylphosphonyl dichloride.

Adding sodium fluoride of HF (use CaF2 and H2SO4 to produce HF) gives methylphosphonyl difluoride.


Mixed with isopropanol, you'll get Sarin, with cyclohexanol, the even more lethal Cyclosarin.

It's too dangerous, though. There are quite easier ways to produce very toxic stuff. For example, pure Ricin can be otained from castor beans quite easy.

Jacks Complete
May 17th, 2008, 12:14 PM
Um Shrinko were idiots. How many people actually died from their gas attacks? A dozen? Should tell you something about the procedure they used for making it.

megalomania
May 18th, 2008, 11:47 PM
Actually this entire incident should tell you a lot about the effectiveness of chemical weapons in general. We have an organization with hundreds of millions of dollars (I have posted before what their actual net worth was at the time of the attacks), staffed with knowledgeable scientists, access to professional laboratories, and yet they utterly failed in their delivery.

Making and using chemical weapons are two completely different aspects. This also applies to explosives, drugs, poisons, tools, food, etc.

They failed to develop a suitable delivery system that would not only maximize casualties, but that would also not implicate the cult. They lacked the practical military or security minded intelligence to use their weapon beyond what I consider amateurish considering the cult's essentially unlimited resources.

The synthesis is what is at issue in this thread. I was unaware there was a published (media, not scientific) source of the method Aum Shinrikyo used to produce their Sarin. I don't suppose you happen to know the source of that information, Telkor?

Again I must disabuse anyone with the notion that attempting a synthesis of a chemical warfare agent as toxic as a nerve gas is easy. Such a synthesis requires a level of skill many professional chemists do not have. The skill in question is not the synthesis itself, but the skill required to protect yourself from the final product. I am not saying it can't be done, I am saying it requires a type of laboratory technique few ever get the chance, or have the need, to do in the lab.

Look at that picture above, in post 27. Performing the synthesis in a sealed, isolated, sterile room, wearing a full hazmat suit with SCBA breathing apparatus, and having a wash station at the exit would be the improvised way of doing this. Then you have to ask yourself the question, how much do I trust my suit?

Ask yourself that question every minute you are in the room with a nerve gas.

FUTI
May 19th, 2008, 09:02 AM
http://www.globalsecurity.org/wmd/facility/blue_grass.htm

Link posted above is to support Mega's words. Look at the scale and painful work just to destroy the CW and you can get the picture how hard is to produce them from safety side of production.

Anyway I have read some article on the net about USA Army stored some barrels of CWs for several years outside in some yard in the open I guess in an attempt to make rain corrode barrels enough to start leaking the stuff, or maybe they wanted that lightning strike spew the stuff more explosively in the air for a most realistic NBC drill ever in the history of Army anywhere and ever (if you don't count the USSR small anthrax cloud escape from BW factory). They changed that and kept them later in some warehouse and latter in earth igloo's I guess. I can't find that article anymore.

Sometimes I wonder do we need an enemy when we have guys in the Army that make such fuck-ups. In my country not so long ago conventional ammo depot went sky high due to similar fuck-up.