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Topic: Use of sulfonyl fluorides to produce sulfonyl Phosphonates  (Read 5465 times)

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Offline rolnor

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #15 on: July 13, 2022, 05:40:31 PM »
Yes, the double bond would be nice if possible, cleave to aldehyde, then wittig. Or metathesis reaction. The acidic proton in the sulphone-phosphonate makes som limitation, you easily get polymer if you have an electrophile present in the other end of the molecule and use basic conditions. Or ringclosure.
You could make the first step with sodium sulfide, to get the phosphonate-sulfide, then you can put on different alkyl groups, sulfur being a powerfull nucleophile, then oxidize with oxone. But it will be a smelly business. You can also use LDA+the methyl phosphonate , then add elemental sulfur, then one-pot add the alkyl halide to the formed lithium sulfide to form the sulfide of your choice. Then oxidize  with oxone, three one-pot steps.

Offline Babcock_Hall

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #16 on: July 19, 2022, 06:43:17 PM »
I tried the reaction of diethyl methylphosphonate, LiHMDS, and PhSO2F twice.  The first time did not go well, and there were several things that might have contributed.  Yet the second time gave me a crude yield of 72% and what looks like almost a pure compound by P-31 and H-1 NMR. 

Offline rolnor

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #17 on: July 20, 2022, 06:27:58 AM »
Fantastic! Nice! You really need some success after so much hard work.

Offline Babcock_Hall

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #18 on: March 27, 2023, 10:46:17 AM »
Using sulfonyl fluorides is an attractive route to sulfonyl phosphonates, yet at least one of the sulfonyl fluorides that we would like to use is on backorder.  Another one is expensive and is also on backorder.  It has been suggested to me that potassium bifluoride could be used to convert a sulfonyl chloride into a sulfonyl fluoride.  Does such a reaction require special glassware or present any unique problems of execution?
« Last Edit: March 27, 2023, 11:17:31 AM by Babcock_Hall »

Offline wildfyr

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #19 on: March 28, 2023, 09:49:35 PM »
Ive done this dozens of times! Literally my area of grad school expertise, to make SuFEx substrates.

Works like a charm. Do it in polypropylene bisphaic with MeCN/water. Treat it with the respect of aqueous HF.

Use my supplementary information

https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201506253

« Last Edit: March 28, 2023, 10:05:43 PM by wildfyr »

Offline rolnor

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #20 on: March 29, 2023, 10:17:49 PM »
Nice wildfyr! Its supplied as a hydrate, or? Yes, hydrogen fluoride is nasty, causes neuropathy?

Offline wildfyr

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #21 on: April 04, 2023, 12:06:24 AM »
KFHF is just a white salt, but you use a large excess and its in water/MeCN anyways so hydrate hardly matters.

Offline Babcock_Hall

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #22 on: April 07, 2023, 11:06:40 AM »
Thank you.  We will purchase a sulfamyl fluoride which can be the precursor to one of our targets.  The 1998 article (upon which I based a test reaction) used a sulfonyl fluoride, and I cannot find an example of the same chemistry with a sulfamyl fluoride in the literature yet.  I imagine that the reaction will be slower, but I don't see a problem.  There are other targets on our to-do list that will need fluoride exchange, and we will pursue them as we move forward.

Offline wildfyr

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #23 on: April 10, 2023, 08:16:20 PM »
Look up Barry Sharpless' recent work, he has pursued a lot of things around SOx-F cores lately and their corresponding reactivity.

Offline Babcock_Hall

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #24 on: April 12, 2023, 07:33:58 PM »
https://doi.org/10.1021/acssuschemeng.8b00489
This paper has a synthesis of 2-propanesulfonyl fluoride from the corresponding chloride in the presence of Bu4NCl and potassium bifluoride in water.  This sounds similar.  I am not familiar with "bisphaic."

Offline Babcock_Hall

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #25 on: April 12, 2023, 08:58:48 PM »
Zhang L et al., Chinese Journal of Chemistry (2022), 40(14), 1687-1692.  https://doi.org/10.1002/cjoc.202200112.
"The Et3N-3HF complex is a liquid HF with improve safety. In this work, we report electrochemical synthesis of a series of sulfonyl fluoride with Et3N-3HF as fluoride source."  The method is electrochemical.  One of the sulfonyl fluorides that they make is cyclopropanesulfonylfluoride, in 18% isolated yield.

Offline Babcock_Hall

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #26 on: April 13, 2023, 07:54:24 AM »
"2-propanesulfonyl fluoride (9.58 g; 75.9 mmol; 76%) collected at 48–52 °C/35 mbar as a colorless liquid".  Should I be worried about losing a little product in the prior rotary evaporation of DCM.  I am interested in both 2-propyl and cyclopropy, and I am looking for the boiling point of cyclopropanesulfonyl fluoride.  Wildfyr, should I have read bisphaic as biphasic?
EDT
My last few comments were either written late at night or very early in the morning, before the coffee kicked in.  I apologize for any lack of clarity.
« Last Edit: April 13, 2023, 11:08:49 AM by Babcock_Hall »

Offline wildfyr

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Re: Use of sulfonyl fluorides to produce sulfonyl Phosphonates
« Reply #27 on: April 14, 2023, 10:09:58 PM »
Yes, its bisphasic. Also known as "on water." You just stir the organic and aqueous phases very aggressively with a magnetic stir bar in a plastic bottle for a few hours or overnight. Never failed.

 I think the Et3N-3HF probably acts like a bit of a phase transfer agent, but I never found that to be necessary. Just MeCN and water with KFHF. Dilute in ether or DCM and take the organic phase. Don't overthink it. The swap of chloride for fluoride is just much more favored than hydrolysis. You can flash the material through a plug of silica or do a weakly basic wash to remove any sulfonic acid from hydrolysis of sulfonyl chloride.

Something that low boiling maybe you could lose some. I would be more concerned with not inhaling it than the yield for the 2-propyl, since starting material 2-propyl sulfonyl chloride is pretty cheap.

https://www.sigmaaldrich.com/US/en/product/aldrich/242705

The cyclopropyl is a whole different can of worms, sigma selling cyclopropane sulfonyl chloride for $300/500mg. Maybe sulfonic acid/sulfonate salt is cheaper and you can make it with thionyl chloride. Couldn't find it quickly.

FYI it is pretty difficult to tell the SO2-F from the SO2Cl by NMR, so pay close attention if you suspect there is leftover SO2Cl.

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