What well known nerve gas info?

[megalomania]

I have been reviewing my chemical weapons information as of late and I have been tinkering with my website preparing to add some wonderful new stuff. I have been reviewing other websites looking for minor details when it occurred to me that there is actually no chemical weapons information on the web about synthesis. What strikes me as odd are the many ‘upstanding’ websites out there that allude to the “well known procedure of preparing this nerve gas” or “all those other websites that give the synthesis” while at the same time saying they would never provide such info. They all say the other guy's site has it...

Well where the hell are those sites? Has anyone actually seen one? Are there thousands of websites teeming with chemical synthesis information for any chemical weapon, or even a reference to such data?

I found an article by Scientific American from last November about the great availability of chemicals just waiting to be used by terrorists. All they had to do was call up Aldrich and order the chemicals:

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> By following one of the well-known recipes for sarin—mixing dimethyl methylphosphonate, phosphorus trichloride, sodium fluoride and alcohol in the right amounts and sequence—he could have made 280 grams of the stuff or a comparable amount of soman or GF. (That’s more than 100 teaspoonfuls.) All this for $130.20 plus shipping and handling. </font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">Well gee, is that all? How naive of them to think everyone can just order what they want from Sigma and get it the next day. And what is this well known ‘recipe’ for Sarin? Well known to whom, organophosphate chemists, or the rest of us? I suspect that ‘recipe’ is one of the earlier methods by which sarin was first prepared.

The conclusion of the article is that tighter restrictions are needed on chemical precursors. I find that especially funny since they are rather easy to skirt. Oh my no, whatever will the terrorists do if they can’t order from Sigma? It would be horrible if they made their own phosphorus trichloride by exposing phosphorus to chlorine. Will they shut down KFC as a source of bones from which white P can be had? Perhaps they think dimethyl methylphosphonate is the only means by which sarin can be made. I would hate to think what would happen if they used the much more convenient refluxing of methylphosphonyldichloride with methylphosphonyldifluoride and evil isopropyl alcohol.

So, has anybody seen another website that actually has any synthesis info on any nerve agent? Does anybody know the ‘well known recipe’ for sarin that uses dimethyl methylphosphonate? If this is all so easy why haven’t a bunch of kewls already done it?

<small>[ August 16, 2002, 12:50 AM: Message edited by: megalomania ]</small>

[nbk2000]

You'd find the sarin "recipe" on the same site that has the polio virus "recipe". Along with convenient links to all the chemical suppliers to whip it up in your kitchen. :D

What they mean by "well known" is (well known) to any practiced researcher with access to a large university library, subscribed online access to JACS, Med-Line, etc.

Thank God that the k3wLs are too ignorant to figure this out or we'd have kiddiez gassing themselves with 43ArZo/\/\E N3RV gAZ. <img border="0" title="" alt="[Wink]" src="wink.gif" />

[MrSamosa]

The Dimethyl Methylphosphonate synthesis is the original way Sarin was prepared, I believe. Here's the general reaction (of course, excluding ratios, temperatures, and all the necessary information <img border="0" title="" alt="[Wink]" src="wink.gif" /> ):

Methanol is reacted with Phosphorus Trichloride to produce Dimethyl Methylphosphate (DMMP). The DMMP is heated, causing the transformation to Trimethyl Phosphate (TMP). Phosphorus Trichloride is reacted with TMP in the presence of Chlorine gas to yield Methyl PhosphonylDichloride. Methyl Phosphonyl Chloride is fluorinated using Hydrogen Fluoride, Sodium Fluoride, or Potassium Fluoride producing Methyl PhosphonylDifluoride (DF). In the final step, Methyl PhosphonylDifluoride is reacted with DiMethyl Phosphonylchloride and Isopropyl Alcohol to make Sarin.

Information relating to the synthesis of Nerve Agents is all over the place, the US Patent Office database is a great source. I just wrote a list of Nerve Agent-related patents in the Links and Literature section...relating to the precursor Monofluorophosphoric Acid. I think you will find more useful information on OP pesticides than you will on actual nerve agents...and the leap from a powerful pesticide to a nerve agent is not a big one.

I think that this would be the easiest synthesis thus far, requiring mostly OTC chemicals. Once again, the general reaction:

Phosphorus Pentoxide (produced by burning Phosphorus extracted from Matchbook strikers...atleast, that's what I understand from some older posts) is poured into Hydrofluoric Acid to make Difluorophosphoric Acid. By heating in a Sodium Hydroxide solution, one Fluoride ion is lost and forms a Monofluorophosphate salt. Heating the Silver salt (doh, expensive metals) with Methyl, Ethyl, or Isopropyl Iodide forms the corresponding Dialkyl ester.

More information on this method can be found in the patents. It's not Sarin, but you can get something quite close, and quite potent...Di-isopropyl Fluorophosphate (DFP) comes to mind.

What I want to know now though, is would it be possible to replace one of the Methyl groups in Dimethyl Fluorophosphate with an Isopropyl group; thus making Sarin?

I haven't gone over all of the patents yet; I just pulled this info. off a website about toothpaste, so I can't tell you anything about the equipment yet.

EDIT- Oh, and try the Organic Synthesis database for information on the synthesis of precursors, I've found it to be very useful...I'm sure you've already checked there though, but just making sure <img border="0" title="" alt="[Wink]" src="wink.gif" /> .

<small>[ August 17, 2002, 01:01 AM: Message edited by: MrSamosa ]</small>

[megalomania]

I have read a rather disparaging article recently that stated some of the chemical literature may actually be intentionally falsified to cause complications for the ‘uninformed’ attempting to make such substances. The article said the conditions are precisely altered to dissuade only capeable scientists, or the ‘alchemical art’ is left out so that only a trained scientist could determine the reaction conditions.
How rude of them. Now I will have to carefully examine each and every process to determine if the temperature is off, or if the amounts of reactants and solvents are askew. I doubt the older literature bothers with such deception, but modern sources may at that. Of course that article could itself be a means of deception. It is certainly true that the ‘alchemical art’ is frequently left out, as demonstrated by the above reaction given by MrSamosa.
The experts seem to be of the universal opinion that only a scientist with some graduate training could ever synthesize a nerve gas (and live). They also seem to think that anyone with the knowledge to make such stuff would not have the knowledge to use it, and vice versa.
There have even been calls to remove such information from publicly available sources, such as patent databases. Specifically such concerns have arisen in Great Britain. I suggest everyone save a copy of those patents now in preparation for the time when they do take it away.

From what I gather about nerve gas chemistry, one could substitute just about any alcohol to make a myriad of different compounds of similar lethality. For example, there is little difference between sarin, soman, cyclosarin, and cyclosoman except for the choice of alcohol used to make the ester. One is certainly not limited to the major published nerve gasses, indeed there are thousands of possible variants one could employ. This much was stated in the article I was reading, in fact I should post a link when I finish reading it. It gives a good foundation about what can and cannot be done with clandestine chemical weapons.

As an aside, I am looking for a British patent concerning the preparation of VM nerve gas. The chemical name is O-Ethyl-S-[2-(diethylamino)ethyl] methylphosphonothioate. This is quite similar to VX, O-Ethyl-S-[2(diisopropylamino)ethyl] methylphosphonothioate, but I would still like to see the patent. The reference I have mentions there is such a patent and it is a British patent. They were trying to be clever by not mentioning what the patent number is. I tried a search of espace but found no mention of VM nerve gas or several variations of that formula name. If anyone knows of this patent, please post the number. Thank you.

[Polverone]

If online journal censorship comes around (Rhodium thinks it's already here for certain high-potency drug analogs) then it will be time to go through paper at the library. Tedious, slow, but not unbearable. Electronic patents censorship is slightly harder to deal with, since they're not going to be at the local university and it's going to be pretty suspicious if you show up wanting to look at all the dangerous patents censored from the online database. Nevertheless, I'm sure this is an area where the Forum can shine.

The actual synthesis is probably going to be... very difficult. I can't estimate any better than that. Aum Shinrikyo failed to carry out an effective nerve agent attack and they had graduate-level chemists, billions of dollars in resources, and fanatical dedication.

I do always get a chuckle out of articles that suggest weapons of mass destruction can be whipped up in your kitchen. Sure, if your kitchen has a high performance fume hood, tens of thousands of dollars worth of equipment, and comes with a no-questions-asked account with JT Baker... Oh, and if you have a PhD chemist and/or microbiologist (depending on your path to destruction) who lives in your refrigerator.

What about other highly toxic chemicals? Fentanyls, synthetic opiates thousands of times stronger than morphine, are extremely potent depressants and can cause death in the milligram range. *And* they've already been clandestinely synthesized at least once, by some East Coast drug chemist in the 1980s who sold them, extremely diluted, for recreational use. He was eventually caught and jailed but it at least provides proof of concept. Plus, since they have been used as recreational drugs, the denizens of the Hive are inclined to locate and store information about them. And they're not going to be effectively detected/countered by standard methods designed for nerve agents.

None of these items are going to be easy to synthesize, but organophosphates aren't the only chemicals worth considering. And, if you're willing to accept a considerable drop in potency, there are some pretty easy to prepare poisons that would certainly give WW I chemical weapons a run for their money. Methyl isocyanate, the chemical that killed and sickened thousands of people in Bhopal, India, is only a hop, skip, and jump away for a moderately knowledgeable individual with a few household materials.

[Chaoslord]

Mega : have you tried earching for ALKYLPHOSPHONOTHIOLATES ?
it's the name of those kind of compounds, so it should be easier that way
I have the VX patent (US) an the only change to the VM prepatarion should be the amino-alcohol (2-Diethylamino-ethanol instead of 2-Diisopropylamino-ethanol) anyway, i think THAT should work, shound't it?

P.S. :any of u guru's can find the synthesis for the Dichloro Methyl Phosphine? Ch3PCl2

sample image :

<img src="http://pwp.netcabo.pt/0170647201/vx-s.gif" alt=" - " />

<small>[ August 18, 2002, 10:47 AM: Message edited by: Chaoslord ]</small>

[nbk2000]

Polverone, the clandestine drug you're referring to was known as "China White". Actually, it was MPPP (forgot the technical name). Problem with it was that, if heated too long/too hot/too much acid, some or most of it was converted to MPTP, a nuerotoxin that destroys brain cells and induces immediate (and severe) Parkinsons.

There were quite a few addicts who got "frozen". That gave such a bad rep to synthetics that nobody will buy them.

MPTP is fairly easy to make (compared to VX), induces the parkinsons with just a milligram or two (by any route), and is irreversable. I've thought it would make quite the terror weapon since it leaves its victims alive, but trapped in crippled or paralyzed bodies. <img src="http://www.roguesci.org/ubb/icons/icon23.gif" alt=" - " />

Blow a cloud of dusty MPTP through a building full of lawyers and judges and watch the roaches twitch. :D

Unfortunately, some asshole writer for the show "Law and Order" had to go and use it for a story line. :mad: Now there's the chance people would know what you were referring to by MPTP if they overheard you talking about it, and companies on the lookout for sales.

It be good for mixing in with poisons for bullets. Even if you don't kill them then, they'll be fucked up for life.

I've looked quite a bit over the years for CW info on the net. It's really not there to be found. Oh sure, you can find all kinds of crap about the enviromental effects, de-milling, arms control, precursors used (but not synths), etc. But an actual how to make it? No.

That's what the journals and books have over the net. Festers "Silent Death" (I upped to the FTP) has the basic procedures detailed adequately. It looks like it'll be up to us to be the site that everyone else is referring to. :D

Aum Shinriko screwed up, not in product quality, but in weaponization. They had two plastic bags of the DF and Iso that were mixed by simply poking with an umbrella tip?! <img border="0" title="" alt="[Eek!]" src="eek.gif" />

No wonder it didn't work. Well, I shouldn't say that since 12 people DID die, and thousands sickened...but compared to a unitary agent with proper aerosol dispersion? Weak. It was nothing more than a puddle on the floor.

[megalomania]

I was remiss in my previous post about VM as I did not check my VX patents first (*whine* it was clear up stairs). After making that post I went to get my patents, both the British and the US patent. Indeed they describe non-specific functional groups, not VX exclusively. I have reviewed the formula and have concluded that VM is merly a matter of using a different R group.

The patent database is actually my last resort. I was fortunate that a trip to the reference library yielded a considerable number of references for nerve gasses and explosives. I requested these articles be sent to me by the dozens this past spring. I had all of these articles coming from all over the US, with them having full knowledge of who I am, and they have to copy the article so they can see what it is.

Basically the task of dusting off my requested tomes, copying them, and sending them to my library is delegated to some lazy undergrad who I doubt is sharp enough to determine from the journal title exactly what it is he is copying. Journal titles do not say "How to synthesize SARIN nerve gas!" oh my no, they say "The Preparation and Physical Properties of Isopropyl Methylphosphonofluoridate.” As a matter of fact I had the collected edition of the Journal of the Chemical Society sent to me for that one, all 3 massive volumes from 1960, so no one knows which article I extracted from there.

My point being I have no trouble getting journals thus far. Furthermore, most of the real good stuff is not available in electronic format. Even my online journal database only extends back to 1996 for even venerable journals. In the future I expect this to change, but will they weed out the ‘good stuff’ by then? I will stick to the tried and true method. Of course I do have a stack of journals sitting right next to me that I have no idea what they are for… I forgot to write down what references led me to request them and reading them is not always obvious if they are for precursors, or general functional groups, and especially the ones that aren’t in English (what in the hell am I going to do with a Chinese journal?!?). Even so I have the info, and I will eventually make use of it.

Ironically the best sources for references to synthesis articles are journal articles themselves. This means you have to have a journal to begin with. I have the above mentioned article on sarin synthesis. That journal references what I believe to be the original method of synthesis (Saunders, “Phosphorus and Fluorine,” Cambridge Univ. Press, 1957, p. 93. also in Sartori, Chemical Review, 1957, 48). My journal disparages this information saying the method of synthesis is tedious and gives impure product, as good a reason as any not to bother. Even so I may get it one day. That ref is actually a book (somewhat harder to get), and I can’t quite remember if Chemical Review publishes full text articles, but that would be a better source. I could also check Quinchon, J. et al, Bulletin. Societe Chimique de France, 1961, 1084, 1086 and Boter, H.L. et al, Recueil des Travaux Chimiques des Pays-Bas, 1966, 85, 147, 919. I don’t suppose and French Forumites happen to have these lying around? I suppose the one I have is quite good enough.

In truth an intense literature search was sufficient for me to quite readily find many references to the synthesis for many chemical weapons. Once I stumbled on a starting point that is (the Dictionary of Organophosphorus Compounds). I also used those handy websites that refuse to divulge synthesis details, I used the names and molecular structures of the nerve gasses they provided to fine tune my literature search (and I came up with a jackpot). To recap, this was quite easy… if you happen to be an experienced searcher of chemical literature, with a reference library at your fingertips, access to expensive literature searching software, and can use a network of national libraries to access the world’s journals (all for free as well).

I have these things, do you? Muhahahaha!

[Polverone]

Mega: you say your chem journal databases only go back to 1996. Is this ACS or other journals too? Because for several months now all the ACS journals have been full-text online all the way back to 1870 or whenever it was that they started publishing. I have access to Tetrahedron Letters and a few other miscellaneous sources that I can't access online, but my #1 source is ACS online. Does anybody know about other English-language journals that have online versions? Preferrably online versions having archival material as well as recent articles?

[megalomania]

My journal collection is a system of about 3 thousand journals of all types (not just scientific) which only seems to extend back to 1996 so far. It is not affiliated with the actual journals in that they have a say in the content. It is created by a company who charges big bucks to grant access and they in turn buy the rights to display the articles.

This is different from the ACS system. However, I do have access to the actual journals themselves. This is probably why there is not (yet) access to their electronic system. There is something invigerating about clamboring about all those dusty tomes with the promise of such a vast wealth of knowledge just waiting to be revealed. It is an innefficient process though.

Somewhere out there is a university or library with access open to all... what do you think it would take to create a mirror of the entire ACS database? Perhaps all one needs is an external hard drive with spidering software and a little bit of time. Ahh, such a great treasure could then be disseminated to the masses :D

I forgot to mention my blurb on dichloromethylphosphine. Don't quote me on this, but it looks like a job for a Grignard reaction. A nice aldehyde, like formaldehyde, would add a methyl group in place of one of those chlorines. This reaction would also replace 1, 2, and all 3 chlorines to some degree, so purification is in order. Ether is out for most Grignards involving chlorine, use THF instead.

<small>[ August 20, 2002, 12:17 AM: Message edited by: megalomania ]</small>

[PrimoPyro]

If going to manufacture an anelgesic depressant of severe potency, to be used for lethal intoxication, here is the compound for you:

<img src="http://www.methinfo.com/boards/general/binaries/19/19257.gif" alt=" - " />

This is the t-BuOOPr- analog of fentanyl, and replaces the phenethyl function with the t-BuOOPr group. Fentanyl analogs are beyond being described as "potent." This adjective does them little justice.

For instance, a very weak analog of fentanyl, the open chain analog 2,3-seco-fentanyl, has an ED50 of 0.35mg/kg. Fentanyl itself has an approximate ED50 of 0.0011mg/kg. That is 1.1 micrograms per kilogram. That is not a lot of drug to kill someone. And there are fentanyl analogs far more powerful than this.

For synthetic opioids, the LD50 (which I dont have access to those figures so you'll make do with ED50's) is usually 3-4 times the ED50, as a rough estimate.

Carfentanil and cis-3-methylfentanyl have approximate/equal potencies, only varying slightly. Carfentanil oxalate salt has an ED50 of 0.0006mg/kg and cis-3-methylfentanyl has an ED50 of 0.00058mg/kg, and another source I have (The Designer Drugs Directory, ISBN:0-444-20525-X) states that 300 micrograms of cis-3-methylfentanyl is lethal.

And then we have this lovely compound here. Do you know what the ED50 of this beauty is, as if these compounds previously stated were not postent enough? 0.000028mg/kg 28 fucking nanograms per kilogram ED50. As was discussed at the Hive, it is quite possible you might suffer respiratory depression by merely LOOKING at this compound through a glass window. <img border="0" title="" alt="[Wink]" src="wink.gif" />

[EDIT:]NBK2000, MPTP is extremely easy to make, if you go by Grignard Reaction of phenylmagnesium bromide added to N-methylpiperidone, forming the tertiary alcohol which is very easily dehydrated to MPTP in assumedly decent yields at least. The amine should not inhibit Grignard action because it is tertiary and has no protons. I think the dehydration can occur with simple KHSO4 even. Easy.

[EDIT#2]Ha! Cool, I was right about that synthetic pathway, it is an improvement on the original synthesis procedure. The Grignard WILL react with N-methyl-4-piperidone to produce the alcohol, which is "undesireably unstable" in hot acid. So KHSO4 would make a great dehydrating agent to prepare MPTP. Just quench the grignard with KHSO4 and heat, and voila, MPTP in one reaction. :D

Source: The Chemistry of Mind Altering Drugs, pg.79; ISBN: 0-8412-3253-9

PrimoPyro

<small>[ August 20, 2002, 02:29 AM: Message edited by: PrimoPyro ]</small>

[nbk2000]

I've heard the Mossad hitsquads have snuffed a few arabs using a weapon that blows a cloud of a fentanyl analog into the targets face, causing almost immediate death.

What's the time for effect from these derivatives? Are we talking seconds, minutes, hours?

Certainly nanogram toxicities would make forensic analysis very difficult, if not impossible. Such things may be better suited to murders, rather than mass terror.

Also, isn't the pathways and precursors for these things rather complicated? In my research into analogs (pre-hive), it was a rather involved process with many restricted precursors, or complicated workarounds.

It'd seem to me that the analogs would be better off being sold, and the money being converted into more conventinal weaponary, for which the larger amounts per dollar, and known effects, would compensate for lower LD50s.

Though the MPTP was a much easier thing to make, it still needs the piperidene. Is there a ready source of that? I thought I remember reading about an electrolytic conversion of THF into it. Or maybe that was pyridine... :confused:

Phosgene wouldn't be as "sexy", but you could blow up a tanker car of it in the middle of a city and wipe out a few thousand people with only a couple pounds of cheap explosive.

Simplicity is the ultimate sophistication. :D

[PrimoPyro]

Piperidine is not needed, 4-piperidone is. Traditionally, in the USA at least, piperidone itself is heavily watched, but seek the northern cold for the N-methyl derivative and you shan't bee disappointed. Sad fact is not everyone will be able to make this in their time, and many will die trying. But this only means that the sources' not being available everywhere doesn't even matter, since not everyone can sue it anyway. Anyone with the skill to make fentanyl can acquire the needed precursors, either by sourcing them or by synthesizing them.

Yes, it was pyridine reduction that yielded the piperidine, and it is quite easy too, with CTH. But piperidine is worthless unless you like PCP.

And there ARE workarounds that involve ingenious reaction mechanisms, but they lengthen the synthesis pathway much too far to be desirable. As for the reaction time, minutes at the longest, seconds are much more likely for the more potent compounds (fentanyl and above) if introduced via either IV or inhalation. Opioids react very quickly.

Personally, I'd rather whip up a batch of carfentanil over tabun or sarin anyday. I dont like phosphorus halides. Icky.

PrimoPyro

[pyromaniac_guy]

from mega:
</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> Somewhere out there is a university or library with access open to all... what do you think it would take to create a mirror of the entire ACS database? Perhaps all one needs is an external hard drive with spidering software and a little bit of time. Ahh, such a great treasure could then be disseminated to the masses

</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">A friend of mine mused over what it would take to produce an offline copy of the IEEE database... Aparently they use software to detect systematic downloads, and have their database set up in such a way as to preclude the easy use of a spider type program... ie their main search engine may be at ieee.org, but when you display a journal article you are actually pulling data from a redirect that goes from abc.com to xyz.com, so unless you know ahead of time where all the 'good stuff' is, you arent going to snag the whole thing....

If anyone can come up with a way to snag such databases, I'll dedicate a high speed connection, and storage space up to a tb or so of hd space for it... a good buddy of mine works for a cable isp, and has acess to ungodly amounts of bandwidth, if a dedicated 24/7 highspeed dsl doesnt cut it, then i can go to a much aftter pipe if need be...

[MrSamosa]

Hmmm...not much love for nerve agents, is there?

Many highly toxic organophosphates CAN be made in your kitchen...but not efficiently. Putting commong OP pesticides through a few additional reactions can either give you a nerve agent, a crude nerve agent, or a precursor to a stronger nerve agent. Tetraethyl Pyrophosphate is a good example, just breakdown Diazinon using an oxidizer. Wait about a day or two, and distill the TEPP from the other products (due to TEPP's high volatility, I don't think much heat will be necessary for this). Diazinon can still be bought off certain gardening websites, and if you're lucky, in the local hardware store. TEPP (LD50= 1.13 mg/kg orl rat) is almost as toxic as Sarin (LD50 = 1 mg/kg orl rat). The only problem I can think of with TEPP is difficult storage: reacts with metals, highly flammable, highly toxic, and causes skin damage. But that is the same with many OP's, and I guess that's what probably turns a lot of you off towards them; particularly the Fluorinated ones.

I on the other hand, do not really make anything... I just research and figure out how different things are made; but never actually make them. So for me, Nerve Agents are exciting :) .

Maybe, for the sake of ease of production, Chlorine could be substituted for Fluorine? Chloro-Sarin comes to mind. I'm not sure about how big the difference in toxicity would be, but I doubt that it would make a dramatic difference (it is still very acutely toxic). All that is needed in the leaving group is something particularly reactive, so the core Phosphorus can quickly bond to the active site on the Cholinesterase. That problem solved, a lot of the other processes involved in Nerve Agent synthesis are not as difficult as one would think, not minding the costs of personal protection and warning equipment. If you aren't planning to use Fluorine as the leaving group, that cuts costs for a Nerve Agent-producing lab.

Nevertheless, in terms of Flourinated Organophosphates...I think that DFP would be an excellent choice due to the relatively non-suspicious chemicals involved in its synthesis as well as its prompt knock-out action, similar to that of Hydrogen Cyanide. It is also colorless, odorless, and otherwise undetectable; aside from its typical nerve-agent symptoms.

If we're going to get into other fun poisons though, I'd have to say my favorite would be Sodium Fluoroacetate dissolved in a Nitrogen Mustard... If you don't die, you suffer from fluid-filled blisters and bone marrow damage :D .

<small>[ December 28, 2002, 02:51 AM: Message edited by: MrSamosa ]</small>

[James]

I read on a website (no, I never take notes) that the new nerve gas detectors all use the photo ressonance of the P-F bond. I suppose theoretically a chlorinated (as opposed to fluoridated) nerve gas might be undetectable by it.

[MrSamosa]

I read about that too, James. It seems a little strange to me though that the detectors are based off the P-F bond. Tabun is a well-known Nerve Agent, can be easily synthesized by decently supplied chemist, yet it does NOT contain the P-F group...it doesn't even contain a Halogen attatched to the core P. Instead, it contains a P-CN group. There has to be something more to these detectors, otherwise there is a big security hole that could easily be exploited.

On another note, if you are in search of Hydrofluoric Acid, I found some as a limescale remover in a local Pool-Spa shop. It was a mixture of Hydrofluoric Acid and Hydrochloric Acid. These two can probably be separated with little effort. I'm sure most of you have known about this for some time, but I just felt like bringing it up since we were talking about Fluorine.

[zeocrash]

OK well, i recently aquired a copy of a the reinhold condensed cheical dictionary sixth edition, This is an 8" thick red book containing information on most substances you can imagine
while the entry for sarin provides little information as to how to make sarin :( , the entry for tabun is far more helpful
</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica">Tabun...

use, proposed as a military nerve gas and experimental choline sterase inhibitor. toxic effects similar to parathion</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">so i looked at the entry for parathion.

this says

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> Parathion...

derivation: from sodium ethylate, thiophosphoryl chloride and sodium para nitrophenate.
uses: insecticide... </font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">from what i have seen, parathion is still on sale as an industrial insecticide

according to the dictionary/ bible it makes a suitable substitute for tabun nerve gas, and it is fairly unknown.

[vir sapit qui pauca loquitur]

Not sure that this will help, but a chemistry professor introduced me to a book "assorted book of nasties" and he gave me a guided tour of the items that he made, and it was quite a large and scary list. mostly nerve gasses (soman/vx) unfortunatly he passed away before I could ask him some questions (he was a mad but brilliant professor) and i was wondering, if I should post up a few recipies? I dont have access to a scanner at the momment but I can type in entire syntheses to post, the subject is most interesting. but the only tests conducted by myself would be using DMSO and various organo-phosphate based insecticides on evil mutts that inhabit the local area.

[MrSamosa]

You should see the thread "Pesticides and Harmful Breakdown Products"...it deals mostly with OP pesticides, their dangerous -oxon breakdown products, and their conversion to more lethal Nerve Agents.

Anyhow, Parathion is certainly a potential chemical weapon. If I remember correctly, it has a median lethal dose of 30 - 50 mg/kg. Although that is not at the level of other Organophosphate-type Nerve Agents, Parathion is extremely toxic and should not be overlooked. There have been numerous accidents involving this pesticide, and keep in mind: 30-50 mg/kg is still a very small amount. Even more toxic is the oxidation product of Parathion, Paraoxon. Nevertheless, this will be extremely difficult to find; definately not something found in the local hardware store. Furthermore, the EPA is considering banning Parathion; as it has done to a lot of effective and legitimate OP pesticides: Diazinon, Chlorpyrifos, etc.

If you can still find Diazinon, you can break it down to TEPP and Sulfo-TEPP by means of oxidation. TEPP has a considerably low median lethal dose of 1.13 mg/kg. However, it is very easily hydrolyzed and therefore not persistent at all. S-TEPP would be a better choice as a chemical warfare agent due to higher persistency, at a small cost in toxicity. That considered, S-TEPP is still far more toxic than Parathion.

What you want to keep in mind though is that to have a truly effective Organophosphate Pesticide, it needs to have a good leaving group. Perhaps understanding how OP's bond with Cholinesterase will help:

(Nerve Agent)-X + HO-(Cholinesterase) --&gt; (Nerve Agent)-O-(Cholinesterase) + HX.

X is the leaving group. Usually, Fluorine is used because it is highly reactive. However, any Halogen may be substitued, as well as a -CN group. If it were my choice, I would prefer to use -CN. Why? Because Nerve Agent detectors depend on the P-F bond :D . Also, the HCN formed by the reaction with Cholinesterase aids in the poisoning.

Pesticides do not use reactive leaving groups and are therefore, inherently less toxic than Nerve Agents. If you are modifying a pesticide, the first thing you will want to consider is replacing those worthless Alkyl- groups or Aromatic structures with a decent leaving group. Mega posted a way of doing this in "Pesticides and Harmful Breakdown Products."

Aside from the leaving group, other things affect a G-Agent's toxicity. I have read that longer Carbon chains will yield increasingly higher toxicity until 6 Carbons are reached, at which point toxicity decreases. What I am interested in is the influence of different Alkyl groups to the products. That is to say: why does the Pinacolyl group allow the agent to penetrate the skin more readily than the Isopropyl group? Why is the Ethyl group less persistent in the body than the Methyl group?

On another note, I have heard of Alkyl-Halides other than Alkyl Iodides being used in Nerve Agent syntheses, including the common Methyl Chloride. Can anybody confirm this? If this is accurate, then this could be yet another way to cut costs in said syntheses.

<small>[ December 28, 2002, 03:05 AM: Message edited by: MrSamosa ]</small>

[NoltaiR]

We're not interested in something any grade schooler can find in the 3rd grade classroom library.

:rolleyes:

Details not found in "common" sources, or silence. One or the other.

NBK

<small>[ October 14, 2002, 02:17 PM: Message edited by: nbk2000 ]</small>

[nbk2000]

While perusing the USPTO site, I ran across this tidbit in a patent about using foam to nuetralize improvised chemical weapons (hey, got to keep up with the "enemies" counters, right? <img border="0" title="" alt="[Wink]" src="wink.gif" /> )

A mixture of diethyl malonate (DEM)(propanedioic acid, diethyl ester) and water (50/50 v/v) registers as a G-type CW agent to certain chemical weapon detectors such as the Graseby Ionics Chemical Agent Monitor (or CAM) and Chemical Agent Detection Systems Mark II (CADS II) stations. :D

What possible use might this info have you ask? Well...what if you included said mix in with an otherwise everyday bomb, like the finland bombing? With a little acrolein or chloropicrin added in to let the piggies know there's something chemical about the explosion, when they whip out their newly aquired post-9/11 detectors, they'll go nuts when the thing screams out "NERVE GAS!". <img border="0" title="" alt="[Eek!]" src="eek.gif" />

Well, here comes the entire national task force with their billion dollar state-of-the-fuckin'-art mobile hazmat lab flown in on a C-5 galaxy to the scene. After careful analysis, it's discovered to be $30 worth of harmless chemicals.

Cost to respond to this "incident"...$50,000,000+. :D

Multiply many times over..."boy crying wolf" syndrome kicks in. THEN whap them with the real deal. Because of previous false alarms, responders are lax in their protective posturing and are taken out by your (now real) CW agent.

Methyl salicylate (oil of wintergreen at the pharmacy) registers as mustard gas too. <img border="0" title="" alt="[Wink]" src="wink.gif" />

<small>[ October 19, 2002, 06:55 AM: Message edited by: nbk2000 ]</small>

[Machiavelli]

This would also be very useful when you're up against cops or soldiers equipped with detectors and protection suits, since they have to change into their lovely bunny suits when the detector gets off while you at the same time can operate with your normal equipment. Once they get the trick it's probably too late. Same goes for EOD people who'll have to disarm bombs under hazmat conditions.
And for something similar, in "Guerillas in the Mist" Bob Newman suggest a cheap alternative to mines for area denial: NATO NBC warning signs.

[MrSamosa]

I see some alternate use for this, besides mere hoaxing. Yes, use the mix of said harmless chemicals and a lachrymator to alert people of its presence.

Now, imagine this "agent" used in battle. Soldiers/Police force feel burning on the eyes and throat, they throw on all their protective gear. You, knowing that it is nothing dangerous, do NOT don protective gear. Therefore, the enemy force is now hindered by heavy chemical-proof equipment, their breathing slightly impaired by the gas mask. Try fighting in THAT, especially on a hot, humid day. <img border="0" title="" alt="[Wink]" src="wink.gif" />

NBK- you mentioned Chemical Detection stations...doesn't the military use the little strips that change colors according to what agent is present? I don't know the name of these strips, and you may very well have mentioned them. Anyhow, do you know if it would register as a G-Agent on those? I like this use of Chemical Weapons. Who ever said Chemicals had to be used to kill or incapacitate; why not just hinder fighting performance?

On another note, I remember a story a few months ago where the Pentagon was evacuated because the Nerve Gas detectors went off. It turns out, all that was present was a pesticide mixture. Perhaps that could be used too?

[Machiavelli]

Hmm, Mr.Samosa, that's exactly the same thing I suggested, apart from the lachrymator, which you shouldn't use if you're planning on operating unprotected yourself.
A better method to suggest that you're using a chemical agent would be lightly colored smoke (if it's too thick it might look fake) and maybe something with a strong "chemical" smell like pyridine.

I'm afraid this might not work with detection paper, since the paper works with a chemical reaction opposed to the normal detectors whích use physical properties. Here however your suggestion with the pesticide might work, since organophosphate pesticides are so similar in structure to organophosphate anthropocides.

[nbk2000]

You wouldn't want to use ANY kind of pesticide since they're all toxic to some degree. All you'd need would be some NON-toxic chemical that has the P=F bonding so it'll set off the detectors. Thusly the enemy is all suited up in their easter costumes (bunny suits), while you're unencumbered by suit or masks.

Tin or titanium tetrachloride could be mixed in to give a suitably "evil" appearance of gasous white vapors to an explosions residue to freak out survivors and give the responders the creeps. <img border="0" title="" alt="[Wink]" src="wink.gif" />

I don't know if the contact papers would respond to the simulant in the same manner as the CAM, but if it didn't, I don't think that'd be a big deal anyways, since they're much more likely to put their faith in the $10,000 machine screaming "NERVE GAS!", as compared to the 10 cent paper slip that says "There's nothing here.". :)

[MrSamosa]

Here's an article on how the Nerve Agent detectors work: <a href="http://www.photonics.com/Spectra/Tech/Dec00/techNerve.html" target="_blank">http://www.photonics.com/Spectra/Tech/Dec00/techNerve.html</a> . Here's the relevant portion of it:
</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica">The new device, developed at the University of California by postdoctoral researcher Jun Gao and a team led by Michael J. Sailor, is composed of a red laser pointer, a beamsplitter, two photodiodes and a porous silicon chip coated with a catalyst that reacts to phosphorous-fluorine bonds. The catalyst hydrolyzes P-F bonds to yield hydrogen fluoride, which etches the oxidized chip, said Sonia Létant, a postdoctoral researcher at the university and member of the team. The reflected laser beam generates interference fringes from the chip, and the chemical reaction changes its refractive index, producing a nonreversible shift in the fringes.</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">As such, you will need something that produces HF on Hydrolysis...or at least something else that will etch that chip. The problem is, many Fluorides have a tendency to be toxic :( . As for the P-F bond that is what makes nerve agents so toxic, isn't it? :confused: Anyhow, it mentions a "Catalyst" that reacts to PF bonds. I know that Sodium and Potassium Hydroxide are regularly used to decontaminate Nerve Agents...do you think this is what they use in the detectors?

This is addressing the cheap nerve agent detectors that they have installed in the Washington DC Subway system. I'm not sure how widely they are used though.

<small>[ October 20, 2002, 01:07 AM: Message edited by: MrSamosa ]</small>

[nbk2000]

Sulfur is chemically similar to phosphorus, so you could possibly use a chemical with a S=F bond instead of P=F.

There's many organophosphates that are virtually non-toxic, their just not well known because they're useless as pesticides or CW. But they'll still react in alarms.

Though, if you have to make a harmless organophosphate, you might as well use the chemicals to make the real deal and dilute it to harmless concentrations that'll still set off the alarms, saving the remainder for the later, actual, attack.

[zeocrash]

i'm not sure that you could easily make an s=f bond fit into the chemical, as sulfur has a different amount of outer shell electrons than phosphorous. an N=F bond might work though or an as=f /sb=f/bi=f bond, all of which are in the same group as phosphorous

[Marvin]

Number of valence electrons in an atom does make a difference, but its by no means the be and end all of chemistry.

P and S are in seperate groups, but they are chemically similar, the oxides are both good acid formers, they are both octet expenders and this is important, PCl3 and SCl2 are both used for similar purposes in organic chemistry as chlorinating agents, the hydrides are both weak acids, gasses and flammable. NH3 isnt flamable in air, and its basic in water, NCl3 is a so so chlrinating agent but if you had to put them in the periodic table on the basis of the bonds they form, youd be very hard pressed without looking at the total number of bonds they form with other atoms.

Covalent and ionic radei are important, as are the ionisation energies. On balence these are more important than the total number of valence electrons which simply determine the total number of bonds an atom can form, rather than the quality (ie characteristics) of each bond. The number of valence electrons 'seem' to determine the property of each atom, but the more QM/spectroscopy you do the more you see its the ionisation energies of each electron (from which the orbitals and shells are derived) that determine the official number of 'electrons free for bonding' and not the other way around.

[akinrog]

Greetings,

from what I read from the post, I prepared a theoretical syntehsis for M//P//T//P (I am intermingling the name so it might escape the attention of indexing spiders, since I saw on google messages of this forum is indexed!! I know this forum is restricted part, but I cannot take any risks.)


I would like to learn your opinions about it.

Regards

(EDIT : I included a proposed synthesis.zip file but I cannot see it for a reason, although it is seen in the attachment list. If you cannot see it too, please let me know.)

[Rhadon]

Your attachment didn't show up immediately because attached files have to be approved first.

[vulture]

why does the Pinacolyl group allow the agent to penetrate the skin more readily than the Isopropyl group?

Longer carbon chains make the agent more soluble in fatty acids, thus allowing skin penetration.
However, if you pass a certain critical value, the solubility in bodily fluids will decrease, decreasing toxicity.

[akinrog]

Hi,
I found the following links on the net regarding meperidine synthesis (which is closely related to M//P//T//P

Does any body know what is "bn" in the first link I posted?
The second link shows how the synthesis diverts to either meperidine (synonym : demerol) or M//P//T//P
1. http://www2.umt.edu/medchem/teaching/medchem/mclect9.htm
2. http://holivo.pharmacy.uiowa.edu/morphine/chsix/mepersynth.html

Hope this bit of info helps.
P.S. Should I post this to NBK's memory killer thread?

[nbk2000]

MPTP isn't a memory killer, since the victims are still fully aware of their past and have full recall, but they are trapped in bodies crippled by parkinsons, as the motor nuerons that control voluntary movement are killed by the metabolization product MPT+ (I believe it's called).

This is what Tonya Harding should have used against Nancy Kerrigan. Not the blunt instrument of a thug with a pipe to a knee. :rolleyes: No subtlety. Though she'd have to have hired me to get such quality service. :)

Leave the MPTP info here, as it's a lot closer to a nerve agent (as a terror agent) than a memory killer.

PS: MPTP has been mentioned numerous times here on The Forum, so Google already "knows" about us. ;)

[Piglet]

The LD50 of fentanyl is similar to that of morphine, about 71. The thienyl analogue of fentanyl (thiofentanyl) is about 800 x morphine. Add a 4-ethyl group for 6 times the potency. More powerful (and easier to make) than carfentanil.
I think that the opiates and organophosphates are not the only class of highly toxic material. I hear that some modifications of the benzodiazipine system results in the destruction of GABA receptors. May I suggest modifying meclonazepam (strongest benzo known) replacing the 7 nitro with a 7 isocyano grouping. A similar change on PCP molecules results in highly toxic compounds destroying NMDA receptors.

[nbk2000]

Is this speculation of active groups just something you've pulled out of your ass? Or do you have some citations to provide? I hate people who speak techno-babble to try and sound impressive, but who can't cite any documentation.

I am impressed when someone can provide such citations, as it shows that they're not posers wasting bandwidth, and actually know something about what they speak of.

[Piglet]

The 4-isocyanate of PCP is sold specifically to destroy NMDA receptors for animal experiments (like MPTP & 6 hydroxy tryptamine are sold to cause parkinsons symptoms). I'm trying hard to remember the seller. I'm pretty sure it's part of the Fisher group. The thought behind meclonazepam (like clonazepam but with a 4 methyl group is that it's activity is about 1000 times that of clonazepam & the isocyanate at the 7 position from the receptor shape (i.e. binding configuration). I'm not about to write a large essay on benzo binding, go look for youself.

[nbk2000]

And what does destroying NMDA receptors do to a person?

[Piglet]

NMDA is a vital metabolic inhibitor. That's why attaching things like PCP or ketamine knock you out. Imagine the opposite. I know that 'nerve agent' research is supposed to be stopped. but many 'research chemicals' are ideal for mass poisioing. MPTP was tested as an insectaside & fucked up some of the staff involved in making it.
The benzodiazepines (especially meclonazepam) have, IMHO, the ability to be altered into rather vicious poisons.