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Author: Subject: Production of carbon disulfide + acyl chlorides via the reaction of sulfur monochloride with methyl ketones
garphield
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[*] posted on 9-9-2021 at 22:51
Production of carbon disulfide + acyl chlorides via the reaction of sulfur monochloride with methyl ketones


I was reading a paper and came across something very interesting:

"Analysis of the volatile components formed during the
reaction of methyl ketones with S2Cl2 revealed that large
amounts of carbon disulfide (CS2) were being formed as C1-
byproduct."

The paper focused only on aryl methyl ketones i.e. acetophenone, but I have seen multiple SDS's mention that sulfur chlorides react with acetone without any further explanation. It's possible that the reaction might be similar in that case, although I am not the most knowledgeable person about chemistry. I'm at uni right now and won't be able to do any experiments until around Christmas but someone should definitely look into this, as it's a possible way to carbon disulfide that would require only acetone, sulfur, and a source of chlorine.

The paper was focusing on this as a pathway to acid chlorides, so if this does work with acetone you'd get acetyl chloride as a byproduct as well, possibly with some chloroacetyl chloride as well.

[Edited on 10-9-2021 by garphield]
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clearly_not_atara
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[*] posted on 10-9-2021 at 07:35


It's plausible that AcCl and CS2 are both produced in this rxn, but I imagine that a lot of volatile thiols and intractible polymers are also byproducts.



[Edited on 04-20-1969 by clearly_not_atara]
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macckone
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[*] posted on 10-9-2021 at 08:54


83% alkyl chloride and corresponding carbon disulfide is quite good.

And yes, the reaction flask is going to be bad to clean and the thiols are going to be quite smelly.

The potential for thioacetone formation is enough to make anyone trying to avoid angry mobs think twice. I doubt it is significant but the potential is there.
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garphield
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[*] posted on 10-9-2021 at 10:57


Another potential idea would be to use MEK instead of acetone. Looking at the reaction mechanism in the paper you might get phosgene from acetone but this would not be possible for MEK. You also couldn't get any thioacetone, although I doubt butane-2-thione smells amazing either. If there is any way to get (substituted)acetophenone(s) over the counter that would definitely work but I don't know of any sources. MEK would give propanoyl chloride, which while not regulated in and of itself in the USA is very similar to propionic anhydride (a DEA list 1 precursor bc it's used to make fentanyl) so you might not want to keep it around for too long after making it, although the carbon disulfide produced would still be fine.

If anyone knows of any fairly cheap OTC ketones besides acetone and MEK, that would be pretty nice. Methyl isobutyl ketone is apparently used as a solvent, although I don't know where specifically you would get it. There is an ebay seller I found selling diacetyl (butane-2,3-dione) for $50/liter but that's somewhat expensive and may not work, although if it does work it would give oxalyl chloride which would be very nice.

It may be possible to make diacetone alcohol and then protect the alcohol group somehow, but this might be a lot of work. If there are no other methyl ketones available for a price comparable to that of acetone or MEK, it might be worth it for someone to try it on a very small scale to see if anything prohibitively nasty is formed. I will try it if no one else can but I won't be back home until late December so it would be quite a bit of time.
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[*] posted on 11-9-2021 at 02:44


Given the reservation rightly expressed by the people above, I'd recommend conducting a pilot experiment at a *very low* scale. Like, few mL at most.

For carbon disulphide, I was exploring the pathway of cracking thiourea at around 300 °C under inert atmosphere. This reaction apparently produces a lot of CS₂. My first crack at it was a fiasco, but I suspect probably all the CS₂ dissolved in the Drechsel bottle full of mineral oil I used as a seal.

I got a lot of ammonia, on the other hand, which is supposed to be the other product of the pyrolysis.
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garphield
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[*] posted on 14-9-2021 at 22:12


https://link.springer.com/article/10.1007/s42452-021-04777-0

Apparently acetate esters undergo the haloform reaction as well. If this also works for this reaction, you'd get ethyl chloroformate with no risk of phosgene/thioacetone/butane-2-thione formation.
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[*] posted on 27-9-2021 at 05:35


can someone link the entire paper please referred to in the opening post please
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[*] posted on 27-9-2021 at 05:51


Just punch the DOI into SciHub



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[*] posted on 17-12-2021 at 13:06


I found this and remembered that there are people wanting to synthesize CS2 at home lab conditions.
Symmetrical dichloromethyl sulfide is formed when trithioformaldehyde
is reacted with sulfur chlorides. When sulfur dichloride is employed,
symmetrical dichloromethyl sulfide is obtained in practically quantitative
yield according to the following equation:
(CH2S)3 + 2SCl2 -> (CH2Cl)2S + CS2 + 2HCl + 2S

page 130 here
https://library.sciencemadness.org/library/books/formaldehyd...

synth of tritiane here:
https://www.sciencemadness.org/whisper/viewthread.php?tid=11...




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