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Author: Subject: Oxalyl Chloride Challenge
Opylation
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[*] posted on 8-6-2021 at 16:29


I would like to post one more paper, a parent actually, that describes the preparation on oxalyl chloride via tetrachloroethylene oxalate. I feel like this could be the holy grail in oxalyl chloride preparation from OTC resources. Unless someone else has a better method.

Attachment: Tetchloret oxalate to Oxalyl Chloride.pdf (442kB)
This file has been downloaded 556 times

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clearly_not_atara
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[*] posted on 9-6-2021 at 04:50


That patent was already posted here:
https://www.sciencemadness.org/whisper/viewthread.php?tid=82...

Did you read the thread? Please, read the threads. We don't need more repetition, either.




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[*] posted on 9-6-2021 at 08:10


What if we tried chlorinating glyoxal???



Reflux condenser?? I barely know her!
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karlos³
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[*] posted on 9-6-2021 at 10:45


Quote: Originally posted by njl  
What if we tried chlorinating glyoxal???

Tried to search for that term in this thread?
Because atara said this:
Quote:

Did you read the thread? Please, read the threads. We don't need more repetition, either.

I would second that, but I rather suggest to, maybe, just read the thread instead? :P
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clearly_not_atara
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[*] posted on 9-6-2021 at 11:43


njl was making a joke, I think :D



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[*] posted on 9-6-2021 at 11:47


Damn... I guess I am "angloautistic" then, because I failed to grasp that, and often do so with obvious jokes when they're in english :o
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[*] posted on 9-6-2021 at 17:44


Off topic… removed for irrelevance

[Edited on 10-6-2021 by Opylation]
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[*] posted on 7-7-2021 at 07:42


My lab is being moved but there is a lot of promise in (trihalomethyl)arenes like benzotrichloride and 1,3 and 1,4 bis(trichloromethyl)benzene. I did some research on this years ago during my SOCl2 and acetic anyhdride preps.

Each is easily produced through exhaustive uv photochlorination of toluene or xylene and does not have the side products involved with radical chlorination of carbonates or esters like methyl formate. A germicidal lamp, quartz flask, and chlorine generator make this pretty trivial albeit tedious.

These react with carboxylic acids (US 1,921,767 etc) to form acid chlorides and benzoyl chloride.

Where M is the arene:

RCOOH + M(MeCl3) --> RCOCl + M(COCl) + HCl

This happens at 80-140°C with a variety of available catalysts and the oxalyl chloride should continuously distill out.

I saw JJay had this as cursory suggestion further up but nobody followed up on it. I am not able to use my lab right now but I'd venture to guess this works as long as you're okay with 6+ moles of chlorine for every 1 of oxalyl chloride and a side product of 2 moles of benzoyl chloride. The waste economy goes up to 1:2 if you can hexachlorinate xylenes but the chlorine usage is the same.
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[*] posted on 7-7-2021 at 19:02


My guess is that it would not be unwise to use an inexpensive, disposable reactor when heating anhydrous oxalic acid with Ar(CCl3)x, (when x is >1) and to expect 0.0000% yield of oxalyl chloride.

[Edited on 8-7-2021 by S.C. Wack]




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[*] posted on 12-7-2021 at 06:43


Quote: Originally posted by S.C. Wack  
My guess is that it would not be unwise to use an inexpensive, disposable reactor when heating anhydrous oxalic acid with Ar(CCl3)x, (when x is >1) and to expect 0.0000% yield of oxalyl chloride.


Any particular reason for that assessment?

AcidChloride.jpg - 70kB
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[*] posted on 12-7-2021 at 07:20


Am I right in thinking that the difficulty with making oxalyl chloride is that when one end of oxalic acid is made into the acid chloride, the other half decarboxylates?
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[*] posted on 12-7-2021 at 14:57


Quote: Originally posted by Praxichys  
Any particular reason for that assessment?


Quote: Originally posted by S.C. Wack  
Some benzoic anhydride seems likely, as it's a general method for anhydrides. Same for benzotrichloride


C6H5CCl3 + C2O4H2 = C6H5COCl + 2HCl + CO2 + CO
2C6H5COCl + C2O4H2 = (C6H5CO)2O + 2HCl + CO2 + CO
dates to no later than 1884.

Those able to remember 17 years of history may recall my referring to Roscoe and Schorlemmer...what do they say about oxalyl chloride asks no one..."From these decompositions it is clear that neither the anhydride nor the chloride of oxalyl can be prepared by the reactions which are employed for the preparation of the corresponding derivatives of other organic acids." This includes your patent.

BTW acetyl chloride and benzoyl chloride from benzotrichloride was patented in Germany 50 years earlier than that. They too left oxalyl chloride for others, but did also claim benzyl acetate, acetyl chloride, and ethyl chloride from ethyl acetate. With benzal chloride: ethyl chloride and benzaldehyde with ethanol, or benzaldehyde, acetyl chloride, and ethyl chloride with ethyl acetate, or benzaldehyde, acetyl chloride, and HCl with acetic acid. They did claim formic or anhydrous oxalic acid plus benzotrichloride and zinc acetate/chloride...to make benzoic acid. That was figured out by 1879.

[Edited on 13-7-2021 by S.C. Wack]




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[*] posted on 13-7-2021 at 05:11


Quote: Originally posted by Praxichys  
My lab is being moved but there is a lot of promise in (trihalomethyl)arenes like benzotrichloride and 1,3 and 1,4 bis(trichloromethyl)benzene. I did some research on this years ago during my SOCl2 and acetic anyhdride preps.

Each is easily produced through exhaustive uv photochlorination of toluene or xylene and does not have the side products involved with radical chlorination of carbonates or esters like methyl formate. A germicidal lamp, quartz flask, and chlorine generator make this pretty trivial albeit tedious.

These react with carboxylic acids (US 1,921,767 etc) to form acid chlorides and benzoyl chloride.

Where M is the arene:

RCOOH + M(MeCl3) --> RCOCl + M(COCl) + HCl

This happens at 80-140°C with a variety of available catalysts and the oxalyl chloride should continuously distill out.

I saw JJay had this as cursory suggestion further up but nobody followed up on it. I am not able to use my lab right now but I'd venture to guess this works as long as you're okay with 6+ moles of chlorine for every 1 of oxalyl chloride and a side product of 2 moles of benzoyl chloride. The waste economy goes up to 1:2 if you can hexachlorinate xylenes but the chlorine usage is the same.


This apparently does not work with oxalic acid. Relevant sentence from patent US1963749A :
When a side chain polychlorinated product, such as benzotrichloride, is caused to react with dicarboxylic acid such as oxalic acid, benzoyl chloride and benzoic acid anhydride are formed without the formation of dicarboxylic acid ch10 rides such as oxalyl chloride.
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[*] posted on 13-7-2021 at 07:09


Well, beans. Back to the drawing board.
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[*] posted on 13-7-2021 at 15:01


Wait. Maybe this is too good to be true, but doesn't Atrazine, the pesticide, contain one of the chlorines of the cyanuric chloride?

https://en.wikipedia.org/wiki/Atrazine

Its also easily buyable:
https://www.ebay.com/itm/324527296326?epid=2256058930&ha...
https://www.ebay.com/itm/373597029173?epid=2254546174&ha...




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[*] posted on 5-8-2021 at 14:40


And how will this help in the synthesis of oxalyl chloride?



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[*] posted on 5-8-2021 at 15:44


cyanuric chloride reacts with oxalyl acid to form oxalyl chloride



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[*] posted on 5-8-2021 at 17:30


Unfortunately atrazine is nowhere near as reactive as cyanuric chloride due to the electron density donated to the ring by the amino groups. Compare trichlorobenzene with 3,5-diaminochlorobenzene, for example.



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[*] posted on 6-8-2021 at 00:30


Quote: Originally posted by Triflic Acid  
cyanuric chloride reacts with oxalyl acid to form oxalyl chloride


Does it?

https://chemistry.mdma.ch/hiveboard/rhodium/cyanuric.chlorid...

The product here is oxalyl dianilide. If oxalyl chloride is an intermediate, it should be possible to isolate it. I would question whether oxalyl chloride is ever actually formed or if the reaction proceeds through monochlorinated oxalic acid derivatives.
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[*] posted on 6-8-2021 at 07:07


So the oxalyl chloride produced reacts with the free amine on the atrazine. Maybe making the dihydrochloride salt would work, ammonium salts are generally much less reactive.



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[*] posted on 20-8-2021 at 12:04


I haven't had this flask out in a while.

IMG_20210820_100917649.png - 154kB
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[*] posted on 23-8-2021 at 16:19


So?



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[*] posted on 13-9-2021 at 12:09


https://pubs.acs.org/doi/pdf/10.1021/acs.joc.5b01707

If this works for diacetyl, you'd be able to get oxalyl chloride from just diacetyl + sulfur + chlorine. It may not work, but it could be worth trying.
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[*] posted on 27-6-2022 at 04:07


EDIT: I read garphield's paper about the reaction of S2Cl2 with methyl ketones. The reaction was demonstrated exclusively for aromatic ketones.

Related to the above, the transesterification of dimethyl oxalate with phenol is well-described elsewhere. The next step is a transesterification of phenyl esters to thioesters:
https://pubs.rsc.org/en/content/getauthorversionpdf/D1OB0018...

The oxalyl-bis-thioester can then be oxidized to the diacyl chloride with SO2Cl2 analogous to the same reaction with other thioesters. For example:
https://www.sciencedirect.com/science/article/pii/S004040200...

[Edited on 27-6-2022 by clearly_not_atara]




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[*] posted on 8-7-2022 at 15:14


Quote: Originally posted by Opylation  
I would like to post one more paper, a parent actually, that describes the preparation on oxalyl chloride via tetrachloroethylene oxalate. I feel like this could be the holy grail in oxalyl chloride preparation from OTC resources. Unless someone else has a better method.

Having to use oxalic acid ester, or the carbonate which produces phosgene, is not ideal. But other esters work too, acetate is mentioned in the patent, and I expect the sulfite/sulfate would work too. If SO2Cl2 is used to make the latter, it can also be used as the chlorine source for photochlorination which avoids using Cl2 gas.
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