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Thioacetone

thebean - 15-12-2014 at 14:34

I have no intention of preparing thioacetone, but I am very curious to see if anyone has ever had experience with it. Is it as horrible as I've heard?

Zyklon-A - 15-12-2014 at 14:45

Let me guess, you just watched this video:? https://www.youtube.com/watch?v=ckSoDW2-wrc
I've never made it and don't want LOL.

dermolotov - 15-12-2014 at 15:06

Quote: Originally posted by Zyklon-A

I've never made it and don't want LOL.

x2. I see no use in doing this...

I may do it one day if I finally get my farm I've always wanted. Mostly because I'm curious if the simple NIOSH OV filters would be powerful enough to block the odours

UnintentionalChaos - 15-12-2014 at 15:59

See also, http://pipeline.corante.com/archives/2009/06/11/things_i_won...

DeIonized Plasma - 15-12-2014 at 19:59

Quote: Originally posted by UnintentionalChaos

Wow... The fact that they needed to use nitrogen dioxide says something about how terrible thioacetone is! I was also wondering how one would go about making it, but I have absolutely no experience making anything like that so I don't think I'll be attempting that any time soon either. If at all.

Paddywhacker - 16-12-2014 at 02:05

It seems to be generated by pyrolysis of trithioacetone.

I tried a simple experiment, dissolving FeS in acetone+H2SO4 but nothing interesting formed. Pyrolysing it didn't yield anything either.

I guess I was lucky, but would rather have been super-stinky.

CuReUS - 16-12-2014 at 03:38

in the video ,he said thioacetone was a "thiol"
i think he meant "thione"

paddy ,why dont you try passing H₂S through MAPP gas

http://en.wikipedia.org/wiki/MAPP_gas

Zyklon-A - 16-12-2014 at 11:17

DeIonized Plasma, what's wong with using N₂O₄? I use it all the time. It's farily easy to work with, as it can easily be liquified and in industries they can minimize leaks way better than I ever could.

Praxichys - 16-12-2014 at 12:39

Proceed at your own risk.

Zyklon-A - 16-12-2014 at 14:22

...And the risk of your entire city...
I might give it a try at some time. I didn't know it was a solid at STP.

aga - 16-12-2014 at 14:22

Could the OP please give a next-of-kin the login details to SM so that the results can be posted.

So many come-and-go and we seldom know how it turned out.

Many thanks.

Metacelsus - 16-12-2014 at 15:52

Wow, I didn't know thioacetone was so easy to make: just hydrogen sulfide, acetone, and hydrochloric acid? I might try this sometime, just to say I did.

And Sigma sells it as a "food grade flavor ingredient"?

http://www.sigmaaldrich.com/catalog/product/aldrich/w347507

(Yes, I know that's the trimer. I thought it smelled the same as the monomer, but I guess not.)

[Edited on 17-12-2014 by Cheddite Cheese]

Paddywhacker - 16-12-2014 at 16:04

That is for trithioacetone. Reputedly a pleasant-smelling compound.

You still have to pyrolyse it, but that could be done at a remote location.

Zyklon-A - 16-12-2014 at 16:12

Yeah, see the video I linked in the first reply.

DeIonized Plasma - 16-12-2014 at 22:35

Quote: Originally posted by Zyklon-A

DeIonized Plasma, what's wong with using N₂O₄? I use it all the time. It's farily easy to work with, as it can easily be liquified and in industries they can minimize leaks way better than I ever could.

I didn't mean it as being outlandishly ridiculous, I think it's fine to use when cleaning up. I am fairly new to chemistry, so I haven't yet gotten a chance to use any nitrogen compounds (Other than some KNO₃, which I will make some nitric acid with once I get proper distillation equipment) but the idea of releasing a toxic gas/strong oxidizer to clean something up because it smells bad seems almost comical.

careysub - 24-12-2014 at 10:23

In 1998 I was working at a company located in Long Beach near Signal Hill where there is oil extraction under way.

One day a spill of of a couple of hundred grams or so of ethanethiol took place and businesses over a 1 square mile area closed down (including mine). The odor was disagreeable the next day, somewhat nauseating over the course of hours, and it lingered for a couple of more days afterward (I think it was not until the start of the next work-week that it was gone).

Accounts of this incident can no doubt be unearthed for local newspapers.

Concerning "thioacetone" according to Organic Chemistry
(ISBN 0199270295) by Jonathan Clayden, ‎Nick Greeves, ‎Stuart Warren (2012), pg. 4 the actual identity of this super-smelly compound has not been identified conclusively. It suggests that it is either propane dithiol or 4-methyl-4-sulfanylpentan-2-one rather than actual thioacetone.

Further Googling though indicates that 4-methyl-4-sulfanylpentan-2-one is a known compound in fragrance chemistry found in grapes with the odor of black currants. The reliability of the textbook account on this is thus suspect (of course no references cited in the text).

A good summary of historical accounts, with references and links is this one:
http://pipeline.corante.com/archives/2009/06/11/things_i_won...

The references are:
Chemistry and Industry, 1967, p. 1430
Chemische Berichte 1889, 2593
Chemical News and Journal of Industrial Science, Volume 61, 9 May 1890, Pg. 219.

What is especially interesting is that the overwhelming odor is only discernible at extremely low concentrations - apparently at some (still quite low) threshold it shuts down the receptors detecting it so that someone experimenting with this stuff cannot smell it (until they try to clean up the lab).

Seems like science would benefit from positive identification of the odorant here, and its actual threshold of detection.

Microscale techniques in a well-equipped air-sensitive laboratory set-up with a GC system would likely be required to do the work without creating another colorful incident.

ALSO NOTE: the Leeds epsiode occurred "While distilling the product of the reaction of sulphuretted hydrogen on about 20 grms. of acetone" without a pyrolysis step. Anyone working with H2S and acetone should be wary.

I remember running across a bottle of valeric acid in a chem lab with a bright red warning label "STENCH". But that has nothing on some of these thiols.

[Edited on 24-12-2014 by careysub]

DrMario - 24-12-2014 at 23:41

Quote: Originally posted by Zyklon-A

Let me guess, you just watched this video:? https://www.youtube.com/watch?v=ckSoDW2-wrc

Am I the only one that is immensely irritated by that guy's style? But nowhere as irritated as I am by the professor in Periodic Table of Videos. I would do unspeakably violent things to that man, if I could.

Zyklon-A - 25-12-2014 at 09:01

Why? I enjoy watching both of them, one talks too fast, the other too slow, but I like them.

Mailinmypocket - 25-12-2014 at 09:04

Quote: Originally posted by DrMario

Quote: Originally posted by Zyklon-A

Let me guess, you just watched this video:? https://www.youtube.com/watch?v=ckSoDW2-wrc

That was hilarious, he is unique for sure but to the point of doing violent things to him, why? Lol

HgDinis25 - 25-12-2014 at 11:02

Quote: Originally posted by DrMario

Quote: Originally posted by Zyklon-A

Let me guess, you just watched this video:? https://www.youtube.com/watch?v=ckSoDW2-wrc

I honestly hope you wrote that comment under the influence of psychedelic agents...

The promise of violence against someone because of someone's style is... I actualy lack the words to describe how pathetic and stupid that is...

Mailinmypocket - 25-12-2014 at 14:17

The reason it amused me for a moment is that I don't see what is so bad about his personality? He would be a fascinating person to have conversations with and seems like a very kind person. I really don't get it. Even if he was extremely annoying and stupid he still would not deserve to be hurt, I mean.. Wtf.

Hawkguy - 7-9-2015 at 19:34

Going to try to make it soon. Trying to judge if this would be a good grad prank. The trimer shouldn't be an issue, but for the monomer, I'll use a bent glass tube retort with the end pointed into a vial in a sealed box. The box will be separated from the atmosphere by a bath of Potassium Permanganate. It looks like I'll only need a drop or two, which can be aerosolized or volatized.

careysub - 7-9-2015 at 21:43

Might I suggest an apropos synonym for "prank" - "gag"?

Hawkguy - 22-1-2016 at 18:17

Hmm didn't end up making TA before (We found better pranks), but certain circumstances have given me reason to prepare the stuff tomorrow. I'll be doing it on very small scale (from >0.5g Trithioacetone), and if it works I'll post results.

Velzee - 22-1-2016 at 18:32

Quote: Originally posted by Hawkguy

Hmm didn't end up making TA before (We found better pranks), but certain circumstances have given me reason to prepare the stuff tomorrow. I'll be doing it on very small scale (from >0.5g Trithioacetone), and if it works I'll post results.

I'm excited to hear your results!

Hawkguy - 23-1-2016 at 09:00

Got the setup ready to go, everything prepared. If you don't hear from me, it's because I'm being hunted down by Mr.Clean, his Lysol henchmen, and their Febreeze goons.

Hawkguy - 23-1-2016 at 12:16

Okay so I put 5ml Sulfuric Acid in a 25ml Erlenmeyer flask, stoppered, with a bent glass pipet protruding from the stopper( I just heated it to bend it, nothing funky) the pipet went into a scintillation vial with 10ml acetone and 5ml hydrochloric acid. The scintillation vial was in an ice bath. I added 0.8g of FeS to the Sulfuric Acid, and heated until it started bubbling. It turned cloudy (the flask was cloudy, the vial stayed clear), and bubbled for 5m. I took the vial and added it to 20ml ice water. Put that in the freezer. My lab smells shitty, and although this wouldn't have made Thioacetone monomer, it still smells like a weird butyl pyrolysis product or something. It smells like the black polymer gunk from an iodoacetone preparation awhile ago, but I think theres just a side reaction and no smelly thiones have been formed yet.

[Edited on 23-1-2016 by Hawkguy]

[Edited on 23-1-2016 by Hawkguy]

[Edited on 23-1-2016 by Hawkguy]

[Edited on 23-1-2016 by Hawkguy]

In the photo, everything had finished and I took a bad photo of the vial and flask

[Edited on 23-1-2016 by Hawkguy]

Hawkguy - 23-1-2016 at 12:33

Okay so its been a few minutes and it really shouldn't smell bad but the garage smells aweful. I think its because suckback during the bubbling heated tiny amounts of TA trimer and cracked it. Like it doesn't small bad in the conventional sense, it smells bad in a stranger way. It makes you want to throw up. The smell also goes away after about 2min which is strange too.
It makes you feel pretty sick I'm lying down right now.
I know I sound like a fear mongerer, but it is honestly dreadful.
[Edited on 23-1-2016 by Hawkguy]

[Edited on 23-1-2016 by Hawkguy]

Hawkguy - 23-1-2016 at 16:14

Hmm its gone away, but no precipitate has formed. I'll cool it down more and do a larger scale tomorrow

careysub - 24-1-2016 at 10:26

Quote: Originally posted by Hawkguy

The smell also goes away after about 2min which is strange too.

You are aware that one of the notable characteristics of thioacetone is that it can be smelled only in extremely low concentrations are you not? It rapidly shuts down the ability to smell it, so that you cannot tell if you gassing the entire neighborhood.

Hawkguy - 24-1-2016 at 12:04

Quote: Originally posted by careysub

Quote: Originally posted by Hawkguy

The smell also goes away after about 2min which is strange too.

Im pretty sure only tiny amounts of the monomer were actually produced. I went out for a few hours and when I came back I couldn't smell it much at all. Although a few other people remarked on the smell, it definitely didnt gas anyone. I also feel like it might not be completely stable in air, because of how it faded somewhat fast over what must have been a few hours.

Another note; even when I couldn't smell it, like half an hour after making it, I really felt like throwing up. Its kinda involuntary, a weird property for a smell IMO, as I usually have a strong stomach and can ignore bad odors.

Final note; I'm pointlessly trying to defend myself, and even though I might officially be an asshole neighbor now, at least one SM member did it and can tell other people not to do the same.

Tsjerk - 24-1-2016 at 14:54

Is there anything know about toxicity of this compound? And about smell/toxicity/volatility of the trimer?

Maybe you didn't make any monomer and was what you smelled the trimer. It could be that the guys describing the trimer didn't mention this smell because if you work under a hood, the smell is not that bad (compared to other sulfur organics). OR you just made some random other acetone/sulfur compound, which I could perfectly imaging to be smelly/toxic.

Feeling like have to trow up sounds like something toxic to me.

One more thing: Did you ever smell H2S? As a comparison? What you did sounds like a nice way to produce H2S.

[Edited on 24-1-2016 by Tsjerk]

Hawkguy - 24-1-2016 at 18:03

Quote: Originally posted by Tsjerk

Is there anything know about toxicity of this compound? And about smell/toxicity/volatility of the trimer?

Maybe you didn't make any monomer and was what you smelled the trimer. It could be that the guys describing the trimer didn't mention this smell because if you work under a hood, the smell is not that bad (compared to other sulfur organics). OR you just made some random other acetone/sulfur compound, which I could perfectly imaging to be smelly/toxic.

Feeling like have to trow up sounds like something toxic to me.

One more thing: Did you ever smell H2S? As a comparison? What you did sounds like a nice way to produce H2S.

[Edited on 24-1-2016 by Tsjerk]

I smelled the FAINTEST traces of H2S while doing the reactions, but I'm pretty sure most dissolved, so it was really a minor thing. The bad smell wasn't anything like H2S, it was wierder, like a sulfurousy rubbery plastiky smell.

Tsjerk - 25-1-2016 at 02:06

Ok, I'm really interested in reports about real monomeric thioacetone. But do you have a place to experiment with better equipment in a way more desolated place? Then I would like you to encourage you in keeping your experiments going.

But until then, especially if people in your surroundings already noticed/mentioned the smell, please consider the possibility you didn't make anything but carbon-sulfur crap or that you only got to the trimer state.

careysub - 25-1-2016 at 05:09

Experiments with this stuff should ideally be done in an "air-sensitive" compound set-up. But then there is the problem with eventual decontamination of the set-up.

Praxichys - 25-1-2016 at 05:46

@Hawkguy - It's not very stinky because your experiment is only halfway there.

Bubbling H2S into acetone gives the trimer, trithioacetone. You need to isolate that (presumably via distillation) and heat it to thermally crack it to the linear polymeric state. This is what the researchers were doing when they contaminated a city - they were trying to isolate the monomer. Trithioacetone itself is moderately stinky but easily available commercially and is used as a food and fragrance additive to enhance earthy notes.

You will have to fractionally distill the trithioacetone from your mixture, or perhaps try a water extraction to get rid of the acetone. You will then need to pass trithioacetone over a hot wire or something similar to depolymerize it. Maybe try heating a nail red-hot and touching a drop of trithioacetone with it.

EDIT: If I could read, I would realize that you already know this. Whoops.

[Edited on 25-1-2016 by Praxichys]

Neuro- - 25-1-2016 at 11:19

I was having horrible ideas of making that. Since acetone is readily available all you would need to do is convert that oxygen into a sulfur. I found this little piece under thioketones on wikipedia to be quite useful "Thiones are usually prepared from ketones using reagents that exchange S and O atoms. A common reagent is phosphorus pentasulfide[2] and the related reagent Lawesson's reagent. Other methods uses a mixture of hydrogen chloride combined with hydrogen sulfide. Bis(trimethylsilyl)sulfide has also been employed." Best of luck, RIP to your nose

Blunotte - 30-1-2016 at 15:59

Excuse me, but at this point it would also work if I put a small piece of Na2S in a solution of acetone and hydrochloric acid, it's right?

I could make the experiment using small amounts in a open country, far away from the houses, these days