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Topic: Synthesis of trichloromethanesulfinyl chloride  (Read 17448 times)

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Offline Babcock_Hall

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Synthesis of trichloromethanesulfinyl chloride
« on: January 23, 2016, 10:36:10 AM »
There is a starting material that I would like to have that is no longer commercially available (trichloromethanesulfinyl chloride).  The only published route I have found involves the use of hydrogen sulfide gas, which is quite toxic.  I have standard glassware available to me.  How difficult would it be to use hydrogen sulfide in a reaction?  The earliest I would perform this reaction is a couple of months from now, and I have a little NaSH in the lab at the moment, which I could potentially use to generate H2S if that would be safer.
« Last Edit: March 09, 2016, 10:26:44 PM by Arkcon »

Offline kriggy

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Re: hydrogen sulfide as a reactant
« Reply #1 on: January 23, 2016, 11:04:24 AM »
I think generating it in situ would be the safest method because you could control the amount of H2S generated. Could you generate the H2S in situ from the NaSH or Na2S and acid?
Or you could generate in buchner flask by having the sulfide placed in and slowly adding from addition funnel and lead the gas through the tubing into the reaction. Im not sure how to get rid of the excess gas after the reaction is over, maybe add something like NaOH to convert it back to NaSH?
Not sure if I answered your question

Offline discodermolide

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Re: hydrogen sulfide as a reactant
« Reply #2 on: January 23, 2016, 11:55:39 AM »
You can probably buy lecture bottles of H2S. If not use a Kipps generator. https://en.wikipedia.org/wiki/Kipp%27s_apparatus
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Offline opsomath

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Re: hydrogen sulfide as a reactant
« Reply #3 on: January 23, 2016, 01:57:44 PM »
What're you trying to do with it?

Offline Babcock_Hall

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Re: hydrogen sulfide as a reactant
« Reply #4 on: January 23, 2016, 03:58:42 PM »
I would like to reduce trichloromethanesulfonyl chloride to trichoromethanesufinic acid with H2S then chlorinate it to the sulfinyl chloride.  Of course if there were another route to the sulfinyl chloride, that would be great.

Offline kriggy

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Re: hydrogen sulfide as a reactant
« Reply #5 on: January 23, 2016, 04:17:02 PM »
maybe oxidation of sulfenyl chloride? or rather thiol to sulfenic acid?

Offline Babcock_Hall

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Re: hydrogen sulfide as a reactant
« Reply #6 on: January 23, 2016, 05:52:05 PM »
Trichloromethanesulfenyl chloride is commercially available, but I would need a method of oxidizing it but not over oxidizing it.

Offline kriggy

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Re: hydrogen sulfide as a reactant
« Reply #7 on: January 24, 2016, 03:18:37 PM »
I looked into a clever book and found something you might want to look at:
http://www.orgsyn.org/Content/pdfs/procedures/CV5P0709.pdf
http://www.sciencedirect.com/science/article/pii/S0040403900842938
It could work on the substrate you want to make what you desire.
Im not sure if the needed disulfide is available or can be easy made (maybe from trifluorobromomethane and Na2S2?)


Offline Babcock_Hall

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Re: hydrogen sulfide as a reactant
« Reply #9 on: February 02, 2016, 09:06:52 AM »
I have contacted a few of the firms that come up in searches.  One company wanted over $10,000.  Some companies did not even respond.

Offline zarhym

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Re: hydrogen sulfide as a reactant
« Reply #10 on: February 03, 2016, 01:18:54 AM »
There is an easy way to synthesis this chemical. According to the literature I found (attached below), trichloromethanesulfinyl sulfenyl chloride(95.4kg), H2O2 (150kg, 98%) and KF(89kg) are refluxed at 150 degree C to synthesis trichloromethanesulfinyl chloride and used in situ. The sulfinyl chloride is pumped into another container as a gas. The container you need should tolerant HF (No glass).

Here is the reference. It's written in Chinese.
CN102633722 page 10&11

Offline phth

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Re: hydrogen sulfide as a reactant
« Reply #11 on: February 03, 2016, 03:16:59 AM »
Funny, hydrogen sulfide is not toxic in small quantities is actually beneficial to cells.  The experiemtn was to take a mouse/rat and remove its kidney.  Next they sewed it back in.  The animal exposed to the H2S livedwith 20% death versus control 70% death.  H2S is apart of the natural digestion, garlic, horseradish (isothiocanates).    It's prolly worse because its stinky than toxic at small levels.  Cysteine, homocysteine are natural releasing agents of H2S.

This guy does some good work on detection and ways to measure it: http://chemistry.uoregon.edu/profile/pluth/
  In addition, photo labile dithianes are possible sources from within my department:
http://pubs.acs.org/doi/abs/10.1021/ol401118k
I can ask questions.  All they study is sulfur chemistry.  Us too..

Offline Borek

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Re: hydrogen sulfide as a reactant
« Reply #12 on: February 03, 2016, 04:54:54 AM »
Funny, hydrogen sulfide is not toxic in small quantities is actually beneficial to cells

It is a dose that makes a poison, nothing new here. Still, it is quite dangerous.
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Offline zarhym

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Re: hydrogen sulfide as a reactant
« Reply #13 on: February 03, 2016, 07:56:42 PM »
Funny, hydrogen sulfide is not toxic in small quantities is actually beneficial to cells.  The experiemtn was to take a mouse/rat and remove its kidney.  Next they sewed it back in.  The animal exposed to the H2S livedwith 20% death versus control 70% death.  H2S is apart of the natural digestion, garlic, horseradish (isothiocanates).    It's prolly worse because its stinky than toxic at small levels.  Cysteine, homocysteine are natural releasing agents of H2S.

This guy does some good work on detection and ways to measure it: http://chemistry.uoregon.edu/profile/pluth/
  In addition, photo labile dithianes are possible sources from within my department:
http://pubs.acs.org/doi/abs/10.1021/ol401118k
I can ask questions.  All they study is sulfur chemistry.  Us too..

It's beneficial in small quantities. However, in real synthesis it's always VERY LARGE quantities. We are not talking about ppm level in biology. In chemistry, most likely the chemical are used in mmol to kmol level.

Offline Enthalpy

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Re: hydrogen sulfide as a reactant
« Reply #14 on: February 06, 2016, 06:20:54 PM »
How dangerous is 150kg of 98% H2O2 refluxed at 150°C considered to be?

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For my information: would SOCl2 be a possible reactant for the desired product?

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