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JJay
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[*] posted on 3-5-2018 at 09:50
Oxalyl Chloride Challenge


After my proposed challenge, Total Synthesis of Lysergic Aldehyde, was rejected by the site moderators, I have decided to open up the Oxalyl Chloride Challenge!

The rules are a little bit different this time around:

1. You must synthesize oxalyl chloride without using any phosphorus compounds.
2. Your synthesis must be performed without using any chemicals that are available only from chemical suppliers. OTC materials and common industrial chemicals may be used, as can chemicals available from pottery suppliers, photo suppliers, cleaning suppliers, grocery stores, welding stores, garden stores, hardware stores, etc. Obviously, oxalic acid is an acceptable chemical to use in your synthesis, but anything as exotic as sodium borohydride is out. You can use chemicals successfully made by amateurs such as sodium, bromine, nitric acid, etc.
3. Your synthesis must not produce any phosgene as a byproduct.
4. If more than one submission is received, the submissions will be ranked according to how convenient they are and how easy it is to obtain the materials required, with the winning submission receiving the prize.
5. I reserve the right to close the competition before any submissions are received by producing oxalyl chloride in my own lab.
6. Once a documented synthesis of oxalyl chloride has been submitted, the contest will close within one one week if no further submission is made. If more than one submission is received, the contest will close exactly 7 days after the last submission.
7. Submissions will only be accepted if they document an actual synthesis of oxalyl chloride.

Possibly useful threads:
OTC Oxalyl Chloride Challenge
Modified Patent Route to Oxalyl Chloride

The prize will be some quartz labware. Oh and also bragging rights. Lots of them. All submissions should be attached to this thread. Questions can be asked here or via U2U.







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Magpie
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[*] posted on 3-5-2018 at 12:36


This is a worthy challenge. I will not submit my entry using homemade SOCl2.



The single most important condition for a successful synthesis is good mixing - Nicodem
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Tsjerk
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[*] posted on 3-5-2018 at 12:54


@Magpie; you would lose big time from my super OTC and easy method anyway ;)

I actually have an idea... I just have to get some anhydrous oxalic acid and something else. Should be easy to test on a gram scale whether it is worth pursuing.

I'm actually quite broke at the moment and in the foreseeable future... could anyone spare a couple grams of oxalic acid? I will post the photos here in case of failure, as I think the reaction is interesting anyway.
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JJay
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[*] posted on 3-5-2018 at 13:04


I have about 4500 grams of oxalic acid dihydrate and can easily send someone 10 grams or so if that would be helpful....

I've never made it, but the synthesis from sucrose looks pretty straightforward: https://www.youtube.com/watch?v=M5bAbvw6IQQ




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Tsjerk
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[*] posted on 3-5-2018 at 13:14


Ok, nevermind, I just found a 100 gram source for about 10 euros including shipping
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clearly_not_atara
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[*] posted on 3-5-2018 at 13:41


Maybe you can go via glyoxylic chloride, and chlorinate this to get the product? Glyoxylic acid is not the easiest target, but it is doable. You can form the anhydride by any of the standard procedures (S/Br2, S2Cl2, NO2, etc) and gas this with HCl, or you can try the unproven nitrile method: bubble HCl through a mixture of 2 parts benzonitrile to 1 part glyoxylic acid, giving glyoxylic acid (glyoxylyl?) chloride and N-benzoylbenzamidinium chloride.



[Edited on 04-20-1969 by clearly_not_atara]
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Magpie
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[*] posted on 3-5-2018 at 15:10


@Tsjerk: May we see the equation, please.



The single most important condition for a successful synthesis is good mixing - Nicodem
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[*] posted on 3-5-2018 at 18:10


One question, what's sort of 'proof of completion' is required, i.e. tests or quality criteria that need to be considered to say that oxalyl chloride has been produced?



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JJay
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[*] posted on 3-5-2018 at 18:30


One of the best ways to demonstrate that oxalyl chloride has been created would be to make TCPO and use it in a glowstick-type demonstration. Of course, other methods could be acceptable.... The synthesis should be repeatable and considered valid by a consensus (or at least an overwhelming majority) of amateur scientists.




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[*] posted on 4-5-2018 at 05:14


Oh wow, that sounds pretty cool, I think I have a way that would be pretty easy if it would work, and I don't see how it shouldn't work, so I'll give it a try!
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JJay
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[*] posted on 4-5-2018 at 18:45


I'm glad there is so much interest in this challenge. I'd appreciate it if a moderator would sticky this thread.



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4-5-2018 at 20:56
Tsjerk
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[*] posted on 5-5-2018 at 00:49


Yeah! This morning my oxalic acid dihydrate came in. I did a really quick and definitely dirty dehydration by putting between 5 and 10 grams in the microwave. This works, is fast, but please don't do it in your mothers kitchen and stay up-wind. Probably some carbon monoxide was formed.

There were a lot of fumes, the oxalic acid partly burned, but it only took two minutes to get a couple of grams of nicely sublimated acid.

What I did was putting a glass bowl on top of another bowl with the two open sides onto each other. After 30 seconds the acid dissolved in its own water while starting to boil, after two minutes in the microwave there was no more oxalic in the bottom of the bottom bowl, except for a bit of completely carbonized acid, and a grayish ring where the acid started to condense (what is the correct term for this? From gas to solid?) Above this grey ring there were nice white crystals of presumable anhydrous acid. I scraped all white fluffy crystals off of the glass, the gray and black stuff were discarded.

The yield is probably below 50%, but I have enough anhydrous acid for the tests I want to do; hopefully this afternoon. Next time I will try if I can do it a little cleaner by halving the microwave power, do it in shorter burst while cooling the top bowl with some ice in between heating.

DSC_0017.jpg - 2MB
Bottom bowl, note that the bottom where the acid was is now completely clean (well, almost clean).

DSC_0015.jpg - 1.9MB
Two bowls like they were while microwaving

DSC_0016.jpg - 2.2MB
Top bowl after microwaving

DSC_0018.jpg - 2.3MB
Recovered fluffy white crystals
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[*] posted on 5-5-2018 at 06:05


Wow, that's really nice. A lot cleaner than when I dehydrated some in a toaster oven once. More reason for me to see about getting a lab microwave at Goodwill.



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Tsjerk
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[*] posted on 5-5-2018 at 10:04


The field was a bit lower than I thought, I only scraped out 0.6 grams. Maybe a microwave with a hole in the top with a non-cooled condensor would be an idea.

I think I might have made something condensable chlorinated, fuming in the air, turning into a white solid upon exposure to moist air, today.

What I did was dissolving TCCA in concentrated sulfuric acid, cooled it to 5 degrees, added my 0.6 grams of anhydrous oxalic acid, then let it warm (nothing exothermic) to RT, warmed it to 60-80 degrees.

What I saw was bubbling and fumes from 60 degrees and up. I put a round bottom flask with ice water on top of the beaker
There was definitly chlorine gas coming off, but also some condensate on the round bottom.

The condensate(quite viscous) left a white precipitate after fuming in the air (I swapped the ice water for hot water).

My guesses are that the fume cannot be oxalic acid, as chlorine would oxidize that quickly, it can also not be water, as it was coming of concentrated sulfuric. The fumes were definitly HCl, as those are unmistakable.

Now the question is, what was condensing? It was coming of from 60 degrees and up (I overdid the heating big time), it was turning solid upon exposure to air. Could there be some cyanuric something evaporation? I heated the sulfuric to 90 degrees to get the TCCA to dissolve before adding the oxalic acid, no fumes there.

I will post pictures in a bit.


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JJay
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[*] posted on 5-5-2018 at 10:17


Be careful.



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Tsjerk
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[*] posted on 5-5-2018 at 10:35


https://www.google.nl/amp/s/www.researchgate.net/publication...



[Edited on 5-5-2018 by Tsjerk]

DSC_0026.JPG - 2.1MBDSC_0024.JPG - 2.1MB
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[*] posted on 5-5-2018 at 11:17


Quote: Originally posted by Tsjerk  
The field was a bit lower than I thought, I only scraped out 0.6 grams. Maybe a microwave with a hole in the top with a non-cooled condensor would be an idea.

I think I might have made something condensable chlorinated, fuming in the air, turning into a white solid upon exposure to moist air, today.

What I did was dissolving TCCA in concentrated sulfuric acid, cooled it to 5 degrees, added my 0.6 grams of anhydrous oxalic acid, then let it warm (nothing exothermic) to RT, warmed it to 60-80 degrees.

What I saw was bubbling and fumes from 60 degrees and up. I put a round bottom flask with ice water on top of the beaker
There was definitly chlorine gas coming off, but also some condensate on the round bottom.

The condensate(quite viscous) left a white precipitate after fuming in the air (I swapped the ice water for hot water).

My guesses are that the fume cannot be oxalic acid, as chlorine would oxidize that quickly, it can also not be water, as it was coming of concentrated sulfuric. The fumes were definitly HCl, as those are unmistakable.

Now the question is, what was condensing? It was coming of from 60 degrees and up (I overdid the heating big time), it was turning solid upon exposure to air. Could there be some cyanuric something evaporation? I heated the sulfuric to 90 degrees to get the TCCA to dissolve before adding the oxalic acid, no fumes there.

I will post pictures in a bit.




Be a bit more careful, what you did sounds quite dangerous tbh, because the chlorine could oxidize the oxalic acid, making stuff like phosgene. You don't need chlorine for that, because you don't wanna oxidize the oxalic acid, you need chloride which replaces the OH groups on the oxalic acid, like PCl5, SOCl2, stuff like that. And don't confuse TCCA with cyanuric chloride, they are not the same, not at all.
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Tsjerk
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[*] posted on 5-5-2018 at 11:43


I know, I know, it was not my intention to generate chlorine. I was hoping it would not evolve. I do think there is something here as I got a condensate while there was chlorine. It is not a question if chlorine will oxidize oxalic, it will for sure, definitely at 60 degrees.

Edit: Oxalyl cloride should be stable though in hot sulfuric and or chlorine


[Edited on 5-5-2018 by Tsjerk]
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[*] posted on 5-5-2018 at 13:10


Quote: Originally posted by Tsjerk  
I know, I know, it was not my intention to generate chlorine. I was hoping it would not evolve. I do think there is something here as I got a condensate while there was chlorine. It is not a question if chlorine will oxidize oxalic, it will for sure, definitely at 60 degrees.

Edit: Oxalyl cloride should be stable though in hot sulfuric and or chlorine


[Edited on 5-5-2018 by Tsjerk]


Still tho, the problem is that you used chlorine in the +1 oxidation state, but you need chlorine in the -1 oxidation state. For your reaction to work, it would have to generate trihydroxyisocyanuric acid, and I don't think that exists. I think treating carbon compounds where the carbon is in a higher oxidation state like +2, +3 with chlorine is always risky, because it could generate phosgene.
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[*] posted on 14-5-2018 at 10:01


Hi, today i tried synthesis of oxalyl chloride by chlorination of ethylene glycol. I have read an article about that and says that yield is nearly 100% if used solvent. They used o-dichlorobenzene. I have chosen tetrachloroethylene as it dissolves chlorine well and boils at 120C. So i attempted synthesis with my fresh obtained TCE. At the beginning everything was ok mixture turned green because of dissolved chlorine and heated. But as it was going it became cloudy and eventually it formed big crystal that blocked my magnetic stirrer. I found that it was hexachloroethane as it smelled the same and it was only option. So my question is how it was chlorinated to HCE if doug was attempting this with catalyst and under reflux and it almost didnt work and every patent says that it requires very strong light and other shit like that. I can also say that this was performed outside under daylight. Can anybody explain this and help what to do with this solvent?
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[*] posted on 14-5-2018 at 11:14


Did you simply chlorinate the solvent TCE to add Cl across the double bond? Not sure how easy that is, but seems quite likely. That may be why they use o-dichlorobenzene as the solvent, as it is less likely to chlorinate in those conditions.
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[*] posted on 14-5-2018 at 12:43


Quote: Originally posted by theAngryLittleBunny  
Quote: Originally posted by Tsjerk  
I know, I know, it was not my intention to generate chlorine. I was hoping it would not evolve. I do think there is something here as I got a condensate while there was chlorine. It is not a question if chlorine will oxidize oxalic, it will for sure, definitely at 60 degrees.

Edit: Oxalyl cloride should be stable though in hot sulfuric and or chlorine


[Edited on 5-5-2018 by Tsjerk]


Still tho, the problem is that you used chlorine in the +1 oxidation state, but you need chlorine in the -1 oxidation state. For your reaction to work, it would have to generate trihydroxyisocyanuric acid, and I don't think that exists. I think treating carbon compounds where the carbon is in a higher oxidation state like +2, +3 with chlorine is always risky, because it could generate phosgene.


1,3,5-trihydroxyisocyanuric acid can be prepared, but it looks like it's not a simple procedure from quick searching. See here.

Edit: Aaaand here's the paper.

[Edited on 14-5-2018 by weilawei]

Attachment: THICA.pdf (261kB)
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[*] posted on 4-8-2018 at 10:42


Quote:
I think I might have made something condensable chlorinated, fuming in the air, turning into a white solid upon exposure to moist air, today.

What I did was dissolving TCCA in concentrated sulfuric acid, cooled it to 5 degrees, added my 0.6 grams of anhydrous oxalic acid, then let it warm (nothing exothermic) to RT, warmed it to 60-80 degrees.

What I saw was bubbling and fumes from 60 degrees and up. I put a round bottom flask with ice water on top of the beaker
There was definitly chlorine gas coming off, but also some condensate on the round bottom.

The condensate(quite viscous) left a white precipitate after fuming in the air (I swapped the ice water for hot water).

My guesses are that the fume cannot be oxalic acid, as chlorine would oxidize that quickly, it can also not be water, as it was coming of concentrated sulfuric. The fumes were definitly HCl, as those are unmistakable.

Now the question is, what was condensing? It was coming of from 60 degrees and up (I overdid the heating big time), it was turning solid upon exposure to air. Could there be some cyanuric something evaporation? I heated the sulfuric to 90 degrees to get the TCCA to dissolve before adding the oxalic acid, no fumes there.


Two thoughts:

- TCCA is not TCT. TCT converts acids to acyl halides. TCCA is an oxidizer.

- Anyone attempting oxalyl chloride by deoxychlorination of oxalic acid needs a fume hood because dehydration of oxalic acid can quickly generate a lot of carbon monoxide. At the very least, you should have a carbon monoxide detector installed and good ventilation. There is no smell warning; you just get a headache, pass out, and die. CO will probably not be formed with TCCA and oxalic acid, though, thankfully.




[Edited on 04-20-1969 by clearly_not_atara]
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[*] posted on 15-12-2018 at 01:14


I will be actively working to synthesize oxalyl chloride next week. I'll check back, and if someone has actually beaten me to the punch then I'll award the prize, but I have an advantage: under the rules, as the contest sponsor, I am permitted to use phosphorus compounds. So if you have a winning entry, now is the time to submit it.



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[*] posted on 15-12-2018 at 11:28


Somedays I drink and may post when I should be sleeping but here it is.
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