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Author: Subject: Is producing 4,4'-dichlorodiphenyl sulfone with H2SO4 possible?
Gryn
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[*] posted on 28-4-2019 at 09:24
Is producing 4,4'-dichlorodiphenyl sulfone with H2SO4 possible?


Title says it all, is there a way to use just regular conc. H2SO4 to make DDS via the sulfonation of chlorobenzene? If so, does anyone have a source that gives a procedure?

[Edited on 4-28-2019 by Gryn]




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clearly_not_atara
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[*] posted on 28-4-2019 at 11:25


There’s an autoclave method in DE 2252571:

https://depatisnet.dpma.de/DepatisNet/depatisnet?action=pdf&...

Actually, I was considering the 4,4’-difluoro version of this compound particularly when I posted about “fluorodefluorosulfonation”. The idea there was to p,p’-difluorosulfonate diphenyl sulfide, then oxidize it to 4,4’-bisfluorosulfonyldiphenyl sulfone, then SNAr with F-. But this is complicated.

https://www.sciencemadness.org/whisper/viewthread.php?tid=14...

[Edited on 28-4-2019 by clearly_not_atara]




[Edited on 04-20-1969 by clearly_not_atara]
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CuReUS
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[*] posted on 2-5-2019 at 09:54


You can make dichloro-DDS from chlorobenzene using thionyl chloride -https://www.thieme-connect.com/products/ejournals/abstract/1... , followed by oxidation - https://www.ias.ac.in/article/fulltext/jcsc/128/08/1321-1325

Do you have the reference to replace Cl with NH2 to make dapsone ?

I don't understand why you selected this route when a more simple and common route exists ;)

1.Nitrobenzene to nitrobenzene sulphide - http://www.rsc.org/suppdata/cc/c3/c3cc37795d/c3cc37795d.pdf (pg 6 of pdf)

2.Oxidation of sulphide to sulphone-https://www.organic-chemistry.org/abstracts/literature/433.s...
UHP - https://en.wikipedia.org/wiki/Hydrogen_peroxide_-_urea#Produ...

3.reduction of nitro to amine to get dapsone :)

[Edited on 2-5-2019 by CuReUS]
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Gryn
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[*] posted on 3-5-2019 at 06:34


Quote: Originally posted by CuReUS  
You can make dichloro-DDS from chlorobenzene using thionyl chloride -https://www.thieme-connect.com/products/ejournals/abstract/1... , followed by oxidation - https://www.ias.ac.in/article/fulltext/jcsc/128/08/1321-1325

Do you have the reference to replace Cl with NH2 to make dapsone ?

I don't understand why you selected this route when a more simple and common route exists ;)

1.Nitrobenzene to nitrobenzene sulphide - http://www.rsc.org/suppdata/cc/c3/c3cc37795d/c3cc37795d.pdf (pg 6 of pdf)

2.Oxidation of sulphide to sulphone-https://www.organic-chemistry.org/abstracts/literature/433.s...
UHP - https://en.wikipedia.org/wiki/Hydrogen_peroxide_-_urea#Produ...

3.reduction of nitro to amine to get dapsone :)

[Edited on 2-5-2019 by CuReUS]


We had several limitations. One of them was that, we could only use lab available materials and equipment.

For equipment, we had a hotplate (the cooking kind! We couldn't use the stirring hotplate cuz we couldnt move it from the other room to move it under a better fume hood. Wouldn't want to expose everyone so we made do.), distillation equipment (lack of temp control meant we couldn't do fractional distillation for azeotropic stuff though), a rotavap (only option for vacuum distillation. We avoid it cuz if anything breaks we're absolutely dead), and oven, and UV for TLC. We also have an HPLC, but were not allowed to use that (we havent trained for it yet, and the thesis people are using it)

Also, we only have a few weeks to do it. We can't do overnight refluxes, cuz we also have to be under supervision. Your suggested sulphide route was so close to being possible though!

As for the chemicals, we dont have SOCl2 for some reason. So that route is also impossible :(

As for the source, we based our synthesis on this patent:
https://patents.google.com/patent/CN106518735A/en

But it really didn't go how it described. Something formed, but we think it's just chlorobenzenesulfonic acid. We dropped this project cuz we really didn't have the time to deliberate errors.

The amination procedure described in that patent uses ammonium chloride. We also considered this metal catalyzed aryl halide amination method:
https://pubs.rsc.org/en/content/articlelanding/2010/cs/c0036...




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CuReUS
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[*] posted on 3-5-2019 at 10:30


Quote: Originally posted by Gryn  
Your suggested sulphide route was so close to being possible though!
what stopped it
Quote:
But it really didn't go how it described. Something formed, but we think it's just chlorobenzenesulfonic acid.
You need oleum for that reaction to work,which isn't mentioned,which in turn is very typical of patents

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[*] posted on 3-5-2019 at 12:14


From your description of what you're working with, it doesn't sound like you have the equipment necessary to do what you want. If the method using an autoclave with online water removal could be done in simpler equipment, it would be. Professional chemists don't use expensive machines just because they think it's fun. Well, usually.

In the attached paper, Pilyugin describes a number of methods that have been used to convert 4-nitrochlorobenzene and sodium sulfide into an aryl disulfide. He gives a one-pot two-phase method for converting 4-chloronitrobenzene into 4-amino-4'-nitro-diphenyl sulfide, which should be good enough for dapsone production. Pilyugin does this successfully without a nitrogen atmosphere or an overnight reaction.

The reagents used are chlorobenzene (solvent), 4-nitrochlorobenzene, sodium sulfide, and PEG-400, which is a phase-transfer catalyst, and happens to be relatively safe and cheap. 4-nitrochlorobenzene is made by nitration of chlorobenzene. The only special equipment required is a "hydroacoustic device", but you may be able to improvise using e.g. a speaker, or some commercial ultrasound-producing equipment.

Attachment: pilyugin2003.pdf (2MB)
This file has been downloaded 39 times





[Edited on 04-20-1969 by clearly_not_atara]
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Gryn
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[*] posted on 4-5-2019 at 04:38


Quote: Originally posted by clearly_not_atara  

In the attached paper, Pilyugin describes a number of methods that have been used to convert 4-nitrochlorobenzene and sodium sulfide into an aryl disulfide. He gives a one-pot two-phase method for converting 4-chloronitrobenzene into 4-amino-4'-nitro-diphenyl sulfide, which should be good enough for dapsone production. Pilyugin does this successfully without a nitrogen atmosphere or an overnight reaction.

The reagents used are chlorobenzene (solvent), 4-nitrochlorobenzene, sodium sulfide, and PEG-400, which is a phase-transfer catalyst, and happens to be relatively safe and cheap. 4-nitrochlorobenzene is made by nitration of chlorobenzene. The only special equipment required is a "hydroacoustic device", but you may be able to improvise using e.g. a speaker, or some commercial ultrasound-producing equipment.


Aw shucks I missed this one. This one could have totally worked, and we do have an autoclave and the reagents. But now the research group unanimously chose to go with our backup synthesis. I'll make sure to remember this for the future though.

Another restriction that i didn't mention is that we have 3 weeks. We're on the third now, and its not like we're free to just do stuff. We need to be on the prof's free time, as well as our own. Thats about a spotty 20+ hrs week, with next to no room for failure or experimentation (good thing we were somewhat ready).

Wish I could go back to this one, this would finish quite quickly. Too bad the decision's not on me

And to answer this:
Quote:
what stopped it

the overnight reaction part. The above would have solved it though

[Edited on 5-4-2019 by Gryn]




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