Sciencemadness Discussion Board - Chloroacetone tear gas: A Theory, A Mishap, and Questions

Chloroacetone tear gas: A Theory, A Mishap, and Questions

Ioxoi - 5-10-2008 at 16:27

Hi everyone,

Recently I read about chloroacetone as a tear gas agent, and decided to make my own, resulting in a mishap that is burning my eyes as of this typing.

What I theorized: (Mono)Chloroacetone can be made by bubbling chlorine through a mix of acetone and water with a tiny amount of dilute sulfuric acid.

(CH3)CO + Cl2 --> (CH3)(CH2Cl)CO + HCl

Unsymmetrical dichloroacetone supposedly can be made the same way with more chlorine, with the advantage that it is comparatively insoluble in water and separates as a dense oily layer and can be sep funneled out, whereas monochloroacetone needs distillation for purification.

Since I don't have an effective glassware setup for chlorine bubbling, I decided to go an alternate route, that of pool TCA and acetone with a small amount of HCl as catalyst:

TCA powder would be added to acetone with a small amount of HCl. The following ought to occur-
(CNOCl)3 + 3HCl --> (HCNO)3 + 3Cl2
3Cl2 + 3(CH3)2CO --> 3(CH3)(CH2Cl)CO + 3HCl
and thus the HCl would act as a catalyst. In practice it should be a problem of having 'just enough' HCl to have a SLOW decomposition of TCA to cyanuric acid. Too fast, and it seemed to just bubble out on small trials (with water added to prevent disastrously fast reaction).

What I did: It was kind of a disaster, but it could have been worse had it been done indoors. I took 30 grams of acetone and weighed out and powdered 39 grams of TCA, roughly stoichiometric amounts. I added a little sulfuric acid (maybe 0.25 grams) and about a mL of water to the acetone. Then I poured about 1/3 of the TCA into the acetone mix. (Noted that TCA is pretty soluble in acetone, about 30% or so). Nothing seemed to happen. No greenish tinge or anything, no smell (other than acetone, of course). I let it sit about an hour and nothing happened.

Eventually I decided I had to speed things up. I took a drop of 10% HCl and put it in the bottom of a test tube and dropped a couple mL of the acetone/TCA liquid (I'd be terrified to pour HCl directly into the ~70 grams of reaction mix!) in the test tube and swirled. A faint green color appeared after a while but nothing else. Deciding that it was not doing anything, I poured the liquid in the test tube back into the reaction vessel (a recycled glass honey jar).

I came in and ate dinner with my family. After dinner my mom started complaining that her eyes were burning. I immediately thought of the liquid I had outside, but decided that it was impossible because we were inside and it was outside. Eventually my eyes began to sting a little and I went outside to find the once clear liquid acetone/TCA solution having turned into what appeared to be a grey-white rock. Immediately my eyes, nose and throat began to burn, and though barely able to see I managed to screw the lid on the glass jar. (There ought to be a gas mask smiley). I am guessing that the reaction did nothing for a while and then suddenly decided it wanted to go runaway and spew out a hot cloud of acetone and chloroacetone vapors into my yard, which then somehow managed to wind its way into our house. Poor outdoor animals! Keep in mind that I only added 1/3 of the TCA. I am not sure exactly what the solid is in the sealed jar, as I've left it outside and will check it out tomorrow.

The questions for you guys: Essentially I am asking on some good ways to moderate the reaction, so that it doesn't go insane and blow forth poisonous gas clouds at inopportune moments, such as when I am ladeling TCA into the mix.

One thing I thought of was having 50% acetone and 50% water, instead of just straight acetone. Would this moderate the reaction? The problem is that I do not have a distillation rig, so separating the water afterwards could not be done, unless I could "salt out" the chloroacetone with CaCl2 or some similar high solubility salt, as was stated on an alternate chloroacetone synthesis I saw on the Net (using different reagents).

Another thing I could try is to have the acetone well acidified with HCl and H2SO4, and add the powdered TCA in SMALL quantities over a long period of time. Is this feasible? The one problem I see with it is a labor problem; it would necessitate adding TCA multiple times to a liquid that was continually fuming lacrimatory vapors at me.

I am searching for a slow, one-step (in terms of adding chemicals into the flask) reaction. Any ideas on moderating this beast?

[Edited on 5-10-2008 by Ioxoi]

kclo4 - 5-10-2008 at 17:27

When you say TCA do you mean TCCA, as in Trichlorocyuranic acid?

you probably had a run-away if it was with TCCA
When it reacts it produces HCl as a byproduct, correct? This will then react with the TCCA producing more chlorine, and then that will react producing more HCl and so on and so forth.

Since you had water in it, I'm going to assume instead of the HCl gas just leaving it dissolved in the water allowing it to react more with the TCCA then it would have with out the water.

You seem to have formed chloroacetone, or something very similar if you didn't.

The solid you speak of could maybe be some funky chlorinated condensation product of acetone. Acetone condensation is after all catalyzed by acid.

Perhaps you could try mixing smaller portions of the TCCA, to an excess of acetone while having some base (CaCO3?) in it to react with the HCl formed?

I don't really know your probably better off reading a patent and see what you can do from there.

smuv - 5-10-2008 at 17:59

Use the search engine; you were lucky!

To see how lucky you were, grind up a ~500mg TCCA, and mix it with an excess acetone in a test tube, then add a drop or two of H2SO4 (outside mind you); VERY EXOTHERMIC! This is fun on a small scale, but on a larger scale

kclo4 - 5-10-2008 at 18:18

I believe I've done what smuv is talking about with a common alcohol of some sort and a dash of HCl. It was pretty freaky, I knew it was going to be pretty violent, but it was more impressive then I thought it would be.

smuv - 5-10-2008 at 18:58

Yeah, I have tried the same; I only wish I tried to isolate some products. I'm guessing these would be chlorinated acetic acids through chlorinated acetaldehyde species. IIRC this reaction was not as vigorous as that with acetone, with acetone a runaway occurs almost as soon as you add the acid.

The trick for the acetone reaction, is to get most of the TCCA to dissolve before adding the acid, then it is really vigorous.

Anyhow, loxoi, I would use caution in the future with TCCA, it is a strong oxidizer and prone to runaways. I would also recommend in the future to use the forum search before trying anything, as they say "stand on the shoulders of giants". Of course not everything has been tried here before, but when something has, seeing others' problems, mistakes and solutions always gives your experiments a higher chance of success.

Anyhow, I wish your future experiments luck.

[Edited on 10-5-2008 by smuv]

Nicodem - 5-10-2008 at 23:09

Quote:

Originally posted by Ioxoi
I am searching for a slow, one-step (in terms of adding chemicals into the flask) reaction. Any ideas on moderating this beast?

I find it unbelievable that after all the warnings and accidents reported here (UTFSE!) there are still people who, rather than following the original patent procedure of chloroacetone preparation using TCCA, they try to do their own immensely irresponsible and irrational modifications.
You are very lucky the whole thing just did not blow into your eyes! Not to mention the stupidity of using a stoichiometric ratio and on such a huge scale! And why the hell you did not just follow the experimental from the French patent which was checked and works perfectly even on a larger scale?

:mad:

I wonder how many times we will still have to read about accidents with chloroacetone? Use the fucking search engine! That's how a responsible person finds the information about "moderating this beast".

kmno4 - 5-10-2008 at 23:53

Right.
I have just wanted to write about one-pot preparation of chloroacetone (and also chloroacetophenone - scope of this method is propably very wide) from NaCl/H2SO4/KClO3 and acetone, but I am not going to wrtie this. Just because of such nincompoops.
ps. chloroacetone looses with chloroacetophenone in "lacrymatory power" discipline. At least my nose and eyes say so. Flood of tears...

[Edited on 6-10-2008 by kmno4]

Sauron - 6-10-2008 at 01:02

Haloacetones only briefly saw use as riot control agents almost a century ago, they quickly fell out of favor because they were way too toxic, for police use, and not toxic enough for military use as lethal agents. Better RCAs were found that were more effective and far less toxic. No need for me to recite them here, due to the nincompoop factor, as kmno4 has so aptly phrased the problem.

Chloroacetone remains an important industrial chemical commodity but its utility as a CW agent is nil.

ScienceSquirrel - 6-10-2008 at 05:12

Having some experience of chloroacetone I think you would have to be bonkers to try and make it on this scale in a honey jar.
It is a powerful irritant and lacrymator.
As for DIY tear gas manufacture, this could get you into really serious trouble!

panziandi - 6-10-2008 at 14:40

Indeed!

Haloacetones are awfully irritating!

We made 1-iodoacetone in A-level in a kinetics experiment. Even on a small scale I could detect the odour but it didnt cause discomfort per se. However I made these on a (semi)microscale years ago as perhaps one of the first organic reactions I did! Easy to make but not stable, you have to add (calcium carbonate? IIRC been a while).

Personally I wouldn't recommend anyone make anything lacrymatory at home unless you have a pretty decent hood and are not in a built up area!

Look at these chlorine and bromine "bombs" on youtube... that is quite a scary thing to have, especially if it went wrong in a glass container with flammables, corrosives and extreme irritants!

BE VERY CAREFULL

Ioxoi - 8-10-2008 at 07:54

Really sorry, guys, for acting kind of retarded and pretty unsafe/deadly in my procedure. Organikum, I did eventually find your modified French patent procedure (after an hour of searching though! Search engine on this site doesn't work well; if you type "(chloroacetone)" you get your procedure but if you type "chloroacetone" without parenthesis you don't) and performed it on 1/10 (!) the scale you recommended and got a couple tablespoons of dilute chloroacetone solution in acetone.

I could not, however, find the original French patent FR 2,633,614 on the internet, at least not on Google. The internet was littered with references to it, but could not find the original. Do you have to ask for it in paper form? Anyone have the original?

As for the "tear gas" part, I must make clear I was not planning on launching some kind of terror strike or something ridiculous like that. My interests were simple chemical curiosity; having a tiny vial of liquid that makes you feel like you're cutting onions when you unstopper it. I would never try and do a prank or something because that would at the very least be illegal and at the most a serious felony. I referred to it as "tear gas" because it was once used as a tear gas and have no destructive plans, only for curiosity and perhaps as a cool thing to show to my friends.

Seeing as I've now gotten Organikum's procedure and there probably is little novel academic merit left in this topic, if you guys would like it can be detritused because it probably won't serve you guys much use anymore (other than another example of how NOT to make chloroacetone for other people!

smuv - 8-10-2008 at 08:18

European patents can be obtained from the European Patent office. You can do a number search, do not include commas though.
FR2633614

Also, you can use google to search within websites for example to look for chloroacetone you could type into the google search bar "site:www.sciencemadness.org chloroacetone."

Additionally, I want to emphasize that good research skills come in very handy for any chemist (pro or amateur) so it is something worth putting effort into.

chemrox - 8-10-2008 at 22:48

Invest in some glassware. Look on ebay and get one of those organic chem kits. If you do get one in the 19/22 size. 24/40 is more costly and commits you to larger batches. Main use of chloroacteone is for Friedel-Krafts reax. Whatever you do, don't react it with benzene!

Nicodem - 9-10-2008 at 23:20

Quote:

Originally posted by chemrox
Main use of chloroacteone is for Friedel-Krafts reax. Whatever you do, don't react it with benzene!

What? There are nearly no Friedel-Crafts reactions with chloroacetone described in the literature. Just a couple maybe. It is of very low reactivity compared to other alkyl chlorides in this reaction (due to the electron withdrawing effect of the neigbouring carbonyl and the tendency to become crap in presence of acids like AlCl3).
Chloroacetone is nearly exclusively used in heterocyclic chemistry and even there only rarely. It is commercially available but it is not particularly common outside heterocyclic chemistry labs.

Ephoton - 10-10-2008 at 04:21

finklstien (damb my spelling sucks).

not the titled compound but an ample solution.

isn't chloroacetone carcenogenic.

TheMadMen - 28-5-2009 at 12:18

Chloroacetone is nifty. A Definite chemical weapon in every sense of the word however. How many of you blokes have actually made it? You'd be stupid to make it without a gas mask on, infact, it's the one chemical which has caused me the most strife in terms of worry, i remember when i made it, i just pumped pure molecular chlorine gas into a 500ml flask filled with acetone, and watched as the acetone turned grey as the chlorine went in, once all of the chlorine was gone, i, outside, with a gask mask on, and heavy gloves, quickly transferred the chloroacetone into an amber container, with a strong glass lid, with which it sits to this day. With a toxic skull symbol on it.

But before that i also made it, once, and i kept it in a clear 250ml flask with a rubber stopper, it turned the most evil looking dark color after a few days, and drops of it use to suspend on the rubber stopper, i sealed it in a air-tight container, and buried it deep far away from civilization. As for it's riot control status, it is apparently the most effective riot control agent of all, according to the book "A Laboratory History of Chemical Warfare Agents", not nessecerily causing death at all, unless you where unluckly, but serving the goal of complete incapacitation towards enemy militants/rioting civilians. I'm glad that i have it to protect my family to be honest.

[Edited on 28-5-2009 by TheMadMen]

hissingnoise - 28-5-2009 at 13:44

Quote: Originally posted by TheMadMen

Chloroacetone is nifty. I'm glad that i have it to protect my family to be honest.

Nice to see you have an irreverent sense of humour, guys. . .

DJF90 - 29-5-2009 at 07:14

The reaction of halogen with acetone is acid catalysed, and, IIRC (I did the same kinetics experiment as panziandi) the rate equation is:
rate = k[H+][acetone]

As you can see the concentration of the halogen does not appear! So I suggest making iodo- or bromoacetone, purely because you can mix the halogen and acetone, then a small quantity of acid catalyst. If you still persist on making chloroacetone, then make it in a gas generator and bubble it through acidified acetone - making the chlorine in situ as you have seen is dangerous and should not be attempted.

Sauron - 30-5-2009 at 02:10

Vh;oroacetone is an industrial chemical, period.

It is an OBSOLETE lachrymatory agent and LESS effective as such than chloroacetophenone (CN) or o-chlorobenzalmalononitrile (CS) which are what eclipsed it almost a century ago.

No one stockpiles haloacetones as CW agents. They are of historical interest only as such.

-TheMadMen- - 31-5-2009 at 07:16

Chloroacetone presents itself as a useful, powerful, incapacitating agent, and ..... is also a useful industrial chemical in it's own right.

Quote:

As you can see the concentration of the halogen does not appear! So I suggest making iodo- or bromoacetone, purely because you can mix the halogen and acetone, then a small quantity of acid catalyst. If you still persist on making chloroacetone, then make it in a gas generator and bubble it through acidified acetone - making the chlorine in situ as you have seen is dangerous and should not be attempted.

I Might just do that next time to be honest. Sounds alot easier. Bubbling chlorine gas through acidified acetone you mean?

EDIT by Davster: the bulk of this message was personal attacks which has been removed.

[Edited on 31-5-09 by The_Davster]

The_Davster - 31-5-2009 at 08:46

Ok, back to the chemistry NOW :mad:

Any more personal attacks and I will purge this thread...

That said, chloroacetone is amusing stuff. Organikum posted a procedure years ago using TCCA as the chlorination agent, which can be done without a gas mask easily. In acetone solution the stuff is manageable.

That said, themanmen, you do not have pure chloroacetone, to convert 500ml of acetone to chloroacetone you would have needed to add 482g of chlorine gas, which would have left your chloroacetone very acidic after the reaction. Acidic chloroacetone is known to not be stable on storage. You likely had a dilute solution of it, and now because of residual acid, you likely have nothing.

-TheMadMen- - 31-5-2009 at 09:01

Thankyou for the informative information The_Davster, you may well be right, it is stored in an amber glass bottle though, would that help?

Maybe i'll just have to make another batch oneday soon. Your calculations make sense, and i will definitely make use of them next time if i do.

DJF90 - 31-5-2009 at 11:44

How would storing it in an amber bottle help if its too acidic INSIDE the bottle. Especially when The_Davster states explicitly

Quote:

Acidic chloroacetone is known to not be stable on storage.

panziandi - 31-5-2009 at 11:54

monochloroacetone is stablised with calcium carbonate powder in amber bottles stored in the cool.

The_Davster - 31-5-2009 at 12:59

I found that MgCO3 worked as well. Must be that any carbonate destroys any acid that happens to be around.

http://www.sciencemadness.org/talk/viewthread.php?tid=2713

panziandi - 31-5-2009 at 16:36

Yes I suspect that MgCO3 and CaCO3 are probably functioning as weak bases to destroy the HCl that can form and thus stabilise the remaining material. I'd even suspect MgO to be ok too, but I doubt CaO would be suited. Not sure about ZnO/CO3, I suppose that maybe ok too. Nice to link loxoi to proper procedure, hopefully safer too

-TheMadMen- - 11-6-2009 at 00:44

Hmm, if i may be excused for a moment. Chloroacetone definitely seems to be a popular chemical amongst the readers of this board. And as The_Davster said, it is amusing, not sure what he meant by it exactly, but it is definitely amusing in it's own right as a chemical which presents itself with such unwelcoming properties, if not handled correctly.

It is also highly useful in many regards. As we all know. But it seems, as far as i am aware, that i am the only one so far, at least in this topic, who has made it by directly bubbling chlorine gas into acetone, i admit that it was a bold move, it is never nice to be around chlorine gas, even when everything is well-fitted, some of it still leaks, it is repugnant material, to say the least. I Had a gas mask on however, and i am pretty sure that i achieved the goal of converting the acetone into chloroacetone, or polychloroacetone/monochloracetone whatever, needless to say, the chlorine definitely reacted with the acetone, as i have said before, it turned grey, it was a visible reaction, the acetone absorbed all of the chlorine that i fed it. If memory serves me right however, it did not seem to give off that much heat, interestingly enough. But from previous experiments doing the same thing, in which i still dread when thinking about, i bubbled some chlorine gas, a smaller amount than i did in my previous mentioned experiment, into some acetone, and left it in a sealed vacuum-filter flask for a couple of weeks, it turned an evil looking black color very quickly, as it was exposed to light, and it would form droplets of itself on the rubber stopper above, from the vapor formation, indicating to me what would happen should i open the stopper, i ended up burying it deep underground in my backyard. Stupid move, but what can ya do, it was a while ago anyway hehe.

Paddywhacker - 11-6-2009 at 12:50

I tried bubbling Cl2 through acetone several years ago, but there was a very low rate of reaction and most of the chlorine was wasted.

Yeah, I did it in the back yard.

From the only slight lacramatory properties of the acetone I figured that the reaction was a failure, and wanted to try bromine, where the reactants would be together in higher concentration.

I was planning on stablizing the chloroacetone as the bisulfite adduct, where it should be nonvolatile and easy to handle, but never got that far.

Iodoacetone is another amusing compound.

Nicodem - 11-6-2009 at 14:31

The chlorination of acetone with Cl2 is autocatalytic, which means some HCl must first form at a sufficient concentration to promote enolization. If the temperature is too low, the acetone too dry, or whatever other reason, the reaction will not even start in any decent amount of time.
In alpha-halogenations of ketones with elemental halogens, a tiny amount of a strong acid is commonly added at the beginning to prevent this problem as well as to avoid reaction runaways. The acid used is almost always AlCl3 (1 mol% is enough), but any strong enough acid will do. Alternatively a protic solvent that does not react with the halogen is used to promote enolization and the polarization of the halogen. Acetic acid is most suitable as it does not react with halogens at the reaction conditions.

-TheMadMen- - 11-6-2009 at 17:39

Would it help catalyze the reaction rate if maybe the acetone was heated(bold move i know, considering it's minuscule boiling point) and then the chlorine passed through? Heat always seems to act in favour of increase in the reaction rate in any chemical reaction doesn't it??? As a matter of fact, i remember reading in a classic chloroacetone prep patent from the 1940s that if you combine acetone vapour with chlorine vapour in separate chambers or something, you get an extremely efficient reaction taking place. But that could have been because the acetone vapours themselves where hot or super-heated?? I Do not recall this procedure requiring anything but raw chlorine gas and acetone, no special or fancy catalysts etc.....

And not to be rude, Nicodem, because what you said did sound interesting, and i took it to heart, so what your basically saying is, is that if i add a little bit of Aluminium Chloride or even Sodium Bisulphate to the acetone before i start bubbling a large stream of chlorine gas through, then the chloroacetone will start forming at quicker, greater, and more efficient rates??

[Edited on 12-6-2009 by -TheMadMen-]

sparkgap - 11-6-2009 at 17:42

That's not bold, that's Darwin Award material. You're exposing the vapors of an inflammable starting material to heat, so...

sparky (~_~)

-TheMadMen- - 11-6-2009 at 17:46

Yah, well maybe i would have learned the hard way hey!! :-) But i realize that though, it's why i spoke with caution..... :-)

Thankyou for reminding me though :p

[Edited on 12-6-2009 by -TheMadMen-]

Nicodem - 11-6-2009 at 22:54

Quote: Originally posted by -TheMadMen-

And not to be rude, Nicodem, because what you said did sound interesting, and i took it to heart, so what your basically saying is, is that if i add a little bit of Aluminium Chloride or even Sodium Bisulphate to the acetone before i start bubbling a large stream of chlorine gas through, then the chloroacetone will start forming at quicker, greater, and more efficient rates??

The acid added is not to increase the rate of the reaction. The reaction itself needs no speeding up or any external catalysis, because it is fast enough as it is. Like I said, it is autocatalytic (http://en.wikipedia.org/wiki/Autocatalysis) so to catalyse it any further would make little sense. The tiny amount of AlCl3 is only added to prevent delaying of the reaction initiation. Therefore you don't run the risk of a runaway reaction. When using Br2, runaways are seriously dangerous, particularly for those chemists, like a lab technician or a clumsy amateur, that do not or do not want to know the theory of the reaction. Seeing the bromine does not react (discolour) they would automatically add more and more until all of a sudden the autocatalytic cycle kicks in giving them an exquisite personal experience of a reaction runaway in their face. This problem in ketone alpha-halogenations is described in details in some classical lab manuals like Organicum, probably also in Vogel's. A serious chemist always takes great care to prevent such accidents.

Nevertheless, this is irrelevant when introducing gaseous Cl2 to acetone on a small scale since you can not build up dangerous amounts of Cl2 in the reaction mixture due to solubility issues. However even the reaction of acetone and chlorine can have troubles initiating sometimes. In such case just stop the introduction of Cl2 for some time to allow some HCl to build up and then continue. Heating is unnecessary and inadvisable due to product selectivity issues, but do not cool it bellow room temperature before the reaction initiates. But anyway, using Cl2 to prepare chloroacetone is pretty much impractical. Chlorination with trichloroisocyanuric acid is way simpler if done following the patent instructions. But for some reasons some adventurous members here have this (suicidal) tendency to do this by making some truly idiotic modifications. When one does not understanding what goes on during his chemical experiment and is doing it on a small scale, he is just being irresponsible. Fine enough. But when such a lazy person, who never bothers to venture in a library, decides to do it on a large scale, then he is behaving like an imbecile.

-TheMadMen- - 12-6-2009 at 00:29

Hehe, yeah, as amateurs, our art is not exactly fool-proof, and prone to destructive issues, i've been doing it for years though. Most crazy thing i did, and will never do again, is, by way of a mini-blow-torch held in place by a set of metallic helper hooks, melting sodium hydroxide pellets on an inverted softdrink can, with two electrodes and a 12 volt current embedded inside. I Watched as the sodium formed, but was rapidly oxidized to some green shit, with an incredibly foul, toxic, smell. God i was stupid then!!

And yet, i still have all 10 fingers, and 2 eyes, thank god!! :-) Hopefully i speak for us all hehe. :-)

I'm going to investigate the trichloroisocyanuric acid procedure for producing chloroacetone, but somehow, deep in the back of my mind, i still believe that the patent i mentioned above, and the procedure contained therein, is the best method for makin ' it.

We shall wait and see.

- TheMadMen.

Formatik - 12-6-2009 at 11:53

I've read some of the old literature which state HCl is formed in the Cl2-chlorination. This apparently interferes with yield by undergoing condensation reactions. No need to add or increase HCl prior or during addition. In one of those preparations, CaCO3 was added prior chlorination to get the chloroacetones (Fritsch, Ber. 26, 597).

Concerning it's lacrimator properties. Chloroacetone isn't such a big shot, considering stronger irritants like acrolein (which is also much more lethal though as well as mutagenic). Bromoacetone is considerably stronger than chloroacetone and less lethal, but more instable. Xylyl bromide and Bromo-MEK both around as strong as the latter. CN stronger lacrimator than all of those. Though judging by lacrimation alone (0.3 mg/m3 vs. 0.5 mg/m3), bromobenzyl cyanide is slightly stronger eye irritant than CN, and maybe a bit less lethal.

Attachment: Ber. 26, 597.pdf (117kB)
This file has been downloaded 803 times

-TheMadMen- - 18-6-2009 at 21:05

Thanks Formatik, the only problem is, chloroacetone is easily the most simple to prepare out of all of those tear gas irritants that you mentioned. No????

Sauron - 18-6-2009 at 21:47

Every one of those except for CN and BBC has been obsolete for 80-90 years for police use and since WWI for military use.

And both CN and BBC have been utterly eclipsed by CS, which is far more effective, and is easily prepared by the Knoevenagel reaction. I posted prep of CS with full text some time ago so UTFSE.

Chloroacetone is a JOKE. Calling it a CW agent is a century out of step with reality and thus little better than a lie. This thread is a waste of time by an obvious troll wannabe. Check out sll the old dope cook threads he has revived. He is a shit-stirrer. Do not assist him.

Formatik - 18-6-2009 at 22:48

Quote: Originally posted by -TheMadMen-

Thanks Formatik, the only problem is, chloroacetone is easily the most simple to prepare out of all of those tear gas irritants that you mentioned. No????

I would say a tie between chloroacetone and acrolein. Acrolein is quite a common molecule (responsible for stench and irritation by the burning of fats). The simplest lacrimator though is maybe thiopropanal S-oxide, the gaseous irritating principal from fresh cut onions.

The most potent lacrimator I've read of is CR (dibenz[b,f]-1,4-oxazepine). CR is a more potent lacrimator than CS (5 to 10 times more potent). Eye irritation occurs with 2mcg/m3.

-TheMadMen- - 19-6-2009 at 00:33

Shitposts will be deleted

[Edited on 19-6-2009 by Ramiel]

-TheMadMen- - 19-6-2009 at 00:36

Thanks for that info Formatik, i appreciate it bud. Yes you are right about Acrolein, it does indeed have a very foul odour to it i must agree!!!! :-) Albeit a simple one. :-)

[Edited on 19-6-2009 by -TheMadMen-]

Sauron - 19-6-2009 at 04:05

There are any number of research and industrial chemicals that are lachrymatory, but that does not make them "tear gases" much less "chemical warfare agents"

In WWI both sides as a matter of urgency pressed into use a nuber of such compounds, most of which proved to be highly unsatisfactory. Now almost a century later you will still see these on historically based lists of agents but that is just brainless bureaucracy in action not science.

Between the wars the criteria for ideal military and civilian (lae enforcement) lachrymators were established, most of the WWI agents were abandoned and newer agents such as CN were developed. CS came along and we used it against NVA and VC during the Indochina wars as well as ubiquitously as a police riot control agent.

In the 70s and 80s some newer agents were developed such as CR but AFAIK have not seen widespread use.

Anyone interested in the chemistry and technology of such agents can access a wealth of accurate information in the open lit but not in this benighted thread.

Sartori documents in details why chloroacetone and acrolein FAILED snd his book is in the forum library,

Formatik, please don't feed the animals.

SunlightLover - 21-6-2009 at 09:11

i didnt mean that btw, ok, sorry.

Chloroacetone - making it

Retired_Oz - 10-6-2010 at 19:05

I have produced chloro-acetone more times than i care to remember - whilst having an understanding of what's going on in literature - there are a few things to note from experience. - firstly adding cl2 to acetone - never in my considerable experience has it failed to initiate (with marble chips in it) when the cl2 is bubble in.

From time to time stir the marble chips - bubbles come up when they are stirred indicating reaction with the acid build-up . Cl2 s easiest to produce by dripping Hcl (32% hardware store is great) in calcium hyperchlorite (pool shop) - reacts vigorously to start with - then as water build up from the Hcl more slowly.

Some Hcl vapor can come across so a water bubble is inserted then the potential to carry water vapor - a sulfuric acid bubbler then inserted to remove water. 98% H2so4 will double its volume then cease to take out anymore water so be liberal with the acid in the bubbler.

So bubbling then into the acetone is dry cl2. The reaction is mildly exothermic. Bubble at a rate that keeps the temp under 5 degrees C whilst the acetone container is immersed in an ice bath. Stir every thirty min or more often. Literature states that the reaction should proceed until 10% chloroAc saturation - Then filter and distill- vacuum is good and at 5 tor comes over at around 70 degrees. My pump gets to 0.0004 of a tor so i have to chill the receiver bowl.

Runaways occur with no caco3 present - they dont explode just run away in a second and usually do blow apart the container.

20 liters of Hcl (about 7 liters of avail chlorine (the cl2 comes from the Hcl not the pool chlorine)) into 10kg of pool chlorine gives 3.5 kg of Hcl build up and 3.5 kg attaches to 5.7 kg of acetone to produce 9 or so kg of mono product minus the dichloro product which as long as the solution at the point of entry of the cl2 does not get above 5 degrees.

The Hcl neutralized by the caco3 gives calcium chloride plus c02 plus water. The cacl2 then removes the water (its hygroscopic and all settle on the bottom some what shielding the marble from the solution above - hence the need to stir. A mechanical stirrer is not good as even on slow a lot of cl2 is released into the room.

Using salt and water cooled to -12 or more getting the acetone down to -3 or 4 the blasting in the cl2 and cooling to holding it about 3 degrees gets you all the chlorine in in around 30 hrs. Not to shabby. The reaction becomes too sluggish at more than -3 degrees to be worthwhile.
I proceed from experience and saturate to 30 - 35 % without a large dichloro build up. At 35% saturation expect 10% di's - the effect it has does little in most reactions.

Allow to come to room temp when finished and a lot of acid vapor will be present above the acetone if u havent stirred well - bubbles come up from the marble and the production of mesityl oxide can can continue for hrs. Filter at the pump and u wind up with a dark red solution.

I find a distillation with packed column in a water bath keeping the temp at the top of the column at 56-57 degrees best - its lengthy - distill out of marble chips - then still through the column vacuum distill - you may get water if the cacl2 didnt remove it all or you filtered thru water when filtering. Chloroacetone form an aziatrope (common boiling point) when distilled with water.

I have used the trichloro process in the latter years but its harder to distill without disintergration due to impurities present in the commercial pool stabilizer products.

The WiZard is In - 11-6-2010 at 07:09

Quote: Originally posted by Nicodem

Amen.

Complete lab prep instructions can be found in the obvious
book in the SciMadOrg library.

And by the by you forgot an essential chemical in its synthesis —
calcium carbonate, in order to neutralise the hydrochloric
acid liberated in the reaction.

Did you say you added HCl.....!

djh
---
The Chymists are a strange Class of Mortals, impelled
by an incomprehensible Impulse to take their Pleasure
amid Smoke and Vapour, Fume and Flame, Poison and
Poverty - Yet among all these Evils, I seem to live so
sweetly that may I die if I would change places with the
Persian King!

Johann Beccher
Physica Subterranea, 1703

entropy51 - 11-6-2010 at 07:35

Quote: Originally posted by The WiZard is In

And by the by you forgot an essential chemical in its synthesis —
calcium carbonate, in order to neutralise the hydrochloric
acid liberated in the reaction.

And you think marble chips are composed of what, exactly?

The WiZard is In - 11-6-2010 at 07:58

Quote: Originally posted by entropy51

Quote: Originally posted by The WiZard is In

And by the by you forgot an essential chemical in its synthesis —
calcium carbonate, in order to neutralise the hydrochloric
acid liberated in the reaction.

And you think marble chips are composed of what, exactly?

-----------
The original poster does not mention marble chips. First mention
is by Retired_oz. I was not replying directly to his/her post.

Admittedly — I did not notice their mention of marble chips.

The WiZard is In - 11-6-2010 at 09:17

Quote: Originally posted by Sauron

Vh;oroacetone is an industrial chemical, period.

It is an OBSOLETE lachrymatory agent and LESS effective as such than chloroacetophenone (CN) or o-chlorobenzalmalononitrile (CS) which are what eclipsed it almost a century ago.

No one stockpiles haloacetones as CW agents. They are of historical interest only as such.

-----
I would expand on the historical aspects.

Amos A Fries and Clarence J West
Chemical Warfare
McGraw-Hill 1921

"The first lachrymator used was a mixture of chlorides and
bromides of toluene... Chloroacetone and bromoacetone
are also well know lachrymaotrs, though they are expensive
to manufacture and are none too stable.. Because of this
the French modified their preparation and obtained mixtures
to which they gave the name "martonite." This is a mixture
of 80 per cent bromoacetone and 20 percent chloroacetone,
and can be made with nearly complete utilization of the halogen."

Curt Wachtel
Chemical Warfare
Chemical Publishing 1941

Chloroacetone. French "Tonite"

The early gas mask gave, however, full protection against
choroactone. It was therefore discarded the follow year, 1915.

Technical Properties : It polymerizes on storage and is
transformed into less irritant forms.

Augustin M Prentiss
Chemicals In War
McGraw-Hill 1937

Because charcoal readily absorbs chloreacetone and therefore
even the early gas masks afforded adequate protection against
it and because bromoacetone proved to be a better tear gas,
chloreacetone was displaced in 1915 by bromoacetone and
other more powerful lacrimators then introduced. A relatively
small amount of chloroacetone was used in the war, and it
played but a minor role in the early stages of gas warfare.

----------
Donald Richter
Chemical Soldiers: British Gas Warfare in World War I
U of Kansas Press 1992

Foulkes [Charles Howard b. 1875] considered that the rank of pioneer,
equivalent in the Engineers to the rank of private in the infantry, and the
corresponding daily base pay of one shilling nine pence would hardly
attract the class of men desired for his purposes. French, too, had urged a
higher rank and rate of pay on the grounds that many chemists already
serving in skilled positions in the army, especially those in the electrical
units, would already be receiving higher rates of pay than pioneers. [9]
Accordingly, the Army Council stipulated a rate of pay of three shillings a
day and an entering rank of corporal. " [10]

In late May, Foulkes drew up a poster advertising for volunteers: "Men
with training in Chemistry are required for service in the Royal Engineers
overseas. " The poster promised immediate promotion to corporal,
beginning pay of three shillings a day, and a term of service not to exceed
the duration of the war. Usual standards of height and chest measurement
were to be waived as long as the volunteer was "organically sound and fit
for service in the field." Furthermore, the eyesight examination might be
passed with the aid of eyeglasses." Foulkes suggested that recruiters also
disregard the upper age limit of forty-five, on the assumption that the
chemists would not be called upon to do anything physically more
strenuous than turn gas valves on and off. One would-be recruit, rejected
out of hand by all other units because of a severe foot deformity and
short-sightedness, found an easy entrance to the Special Companies."
Martin Sidney Fox, one of the early recruits, described the initial selection
as "almost willy-nilly. [13] Nor was there a single Regular Army officer in
the entire unit except Foulkes. Until the formation of the enlarged Special
Brigade in 1916, all the officers were carried on the army's General List, a
miscellaneous category of officers not permanently assigned to a
particular unit.

Foulkes continued the recruitment drive initiated earlier by the War Office
among the universities and colleges to identify graduates and advanced
students with chemical knowledge. One such volunteer later jocularly
maintained that he had been "taken in, in more senses than one, "-that he
had been asked about chemistry but not about ability to perform heavy
porterage. [11] "They wanted chemists," a youngster later recalled, "so I
looked up the formula for water and told them it was H2O, and I was in." "
Another soldier remembers being asked only one question at the
recruiting office: "What does H2SO, stand for?"" The Chatham
"examination," as many later came to realize, was the utmost farce, and
the examining officer was primed to admit as many acceptable and
marginally acceptable applicants and transfers as possible.

Foulkes also circulated notices seeking qualified chemists among the
ranks already in service in France, characteristically assuming that his
needs would be accorded high priority and that his requests for transfers
to the Special Companies would be made expeditiously. L. Hague, a
gunner with the Royal Field Artillery, remembers being sent by his ad-
jutant in August 1915 to Chatham where a Royal Engineers recruiter in-
terviewed him: "He reminded me that the Germans had used gas at
Ypres. They might use a new type of gas in the future. If so, could I take a
motorcycle and a vacuum flask to the front, take a sample of the new gas,
return to base and analyze it?" Hague was given a four-day leave and told
to visit his chemistry professor and learn what he could about gas
analysis. "So, almost overnight, I changed from Gunner to Corporal R. E.
(pay 3/- per day) almost unbelievable wealth. " [17]

Foulkes's transfer requests, however urgent, did not always meet with
such swift accommodation. Actually the notices elicited considerable
resistance from commanders asked to release their men. When a Lt.
James Pratt saw the notice, he immediately sought out his commanding
officer: "'As regards chemists,' I said, 'I'm a trained chemist myself and I've
got at least half a dozen more in the company. Do you want me to submit
their names?' He said 'I don't want my men to go into these God-damned
cushy jobs. You'll render a nil return.’ " [18] Foulkes sought support from
the War Office in overcoming such resistance. Occasionally the War
Office simply ordered such transfers despite objections from commanding
officers and not always with the consent of the individual soldier. Lt. Jack
Sewell, a bicyclist with the 28th Division, was repairing telephone
connections in the Ypres area when in mid-1915 "a mysterious wire"
arrived at divisional headquarters ordering him to report for special duty.
Sewell's wording suggests the transfer came as a total surprise. "For
some obscure reason the Staff had insisted on the use of trained or
half-trained chemists with a leavening of chemical labourers combed from
the P.B.I. [poor bloody infantry], to let off gas in the front line. Little Tin
Gods move in a mysterious way their wonders to perform." Sewell
thereupon joined the Company 186. [19] A pharmacist maintained he was
plucked out of the infantry because his recruiting officer had not been able
to spell pharmacist, and so had written chemist instead. Since the Guards
unit to which he had belonged suffered severe losses shortly afterward,
he considered he owed his life to his fluke transfer to the Special
Companies." [20]

Anders Hoveland - 24-6-2010 at 23:08

I made a bromoacetone tear gas by mixing bromide, H2O2, bisulfate and isopropyl alcohal. After putting in the freezer for a few hours, long thin Na2SO4 crystals appeared and dark brown oily droplet appeared at the bottom; I think these were brominated oil of some sort. The Br2 formed would have oxidized the alcohal to acetone and then to various bromoacetones. Some of the heavier of these would hydrolyze to make bromoform.
I had also read that an isopropyl ether of acetone can form under these conditions. The vapors that came out when the reaction container where opened brought tears to my eyes, whereas bromine, as irritating and corrosive smelling as it was, did not.

As a bit of side interest: chlorine reacts with methanol to form methyl hypochlorite. It reacts with ethyl alcohal in the presence of a base to form chloroform and CO2.