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Author: Subject: OTC Oxalyl Chloride Challenge
clearly_not_atara
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I think sulfur tetrachloride with liquid chlorine is already easier than using hella-nasty and explosive Cl2O. The downside of course is that SCl4 is unstable above -30 (need dry ice) and it's gonna be tough to solvate oxalic acid at that temperature.

http://en.wikipedia.org/wiki/Dichlorine_monoxide#Explosive_p...

[Edited on 12-7-2017 by clearly_not_atara]
JJay
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Making sulfur tetrachloride probably requires handling liquid chlorine, but how hard can it be to condense chlorine gas with dry ice?

Tellurium
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I once condensed chlorine using a bath of dry ice and acetone, it worked out quite well, but I was somewhat scared to accidentally drop the tube full of liquid chlorine
fumingjohnny
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Got it @woelen
give option no. 3,4,5 a try.
Cl2O is only explosive at higher concentrations. for lower yields of SOCl2 it may be used.
JJay
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I don't know what to think about #3, chlorination of diethyl oxalate. It's pretty easy to do a Fischer esterification of oxalic acid with ethanol, right? Then what?

#4 requires use of phosphorus compounds, which are not permitted. But it occurred to me today that you could conceivably ignite a calcium phosphate thermite and then chlorinate the slag in a 250 C oven to make phosphorus pentachloride and chlorinate the oxalyl chloride with it. It is even possible to do it purely OTC, although I imagine it could be hard to set off calcium phosphate thermite made by heating chicken bones in a crucible and grinding aluminum foil in a coffee grinder.

I'm not sure what to think about #5, but I remember seeing a writeup recently on an experiment that obtained sulfuryl chloride as a significant byproduct....

[Edited on 13-7-2017 by JJay]

plastics
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 Quote: Originally posted by JJay I don't know what to think about #3, chlorination of diethyl oxalate. It's pretty easy to do a Fischer esterification of oxalic acid with ethanol, right? Then what? #4 requires use of phosphorus compounds, which are not permitted. But it occurred to me today that you could conceivably ignite a calcium phosphate thermite and then chlorinate the slag in a 250 C oven to make phosphorus pentachloride and chlorinate the oxalyl chloride with it. It is even possible to do it purely OTC, although I imagine it could be hard to set off calcium phosphate thermite made by heating chicken bones in a crucible and grinding aluminum foil in a coffee grinder. I'm not sure what to think about #5, but I remember seeing a writeup recently on an experiment that obtained sulfuryl chloride as a significant byproduct.... [Edited on 13-7-2017 by JJay]

Only patents I know, curious nonetheless

Attachment: TetrachloroethyleneOxalate.pdf (204kB)
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Attachment: OxalylChloride.pdf (209kB)
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clearly_not_atara
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I suggest using iron phosphate with titanium metal since the corresponding phosphides are much less prone to hydrolysis and do not release phosphine.
JJay
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I think iron phosphide can be purchased also. I do assume that if you have measures in place to deal with chlorine fumes, you can also deal with a little phosphine, but it is worth mentioning that all traces of water should be kept away from calcium and aluminum phosphides, and people should only attempt to work with them if they understand what they're getting into.

[Edited on 13-7-2017 by JJay]

fumingjohnny
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Sulfuryl chloride SO2Cl2 is prepared by the reaction of sulphur dioxide and chlorine in the presence of activated charcoal or camphor catalyst. If small quantities can be prepared by anyone having a reasonably good lab then it may be tested against oxalic acid to confirm the formation of oxalyl chloride.
P.S If you never try youl'll never know.......My lab is not good enough to make these compounds.
somebody give it a go and spread the word on the results.
fumingjohnny
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sorry.....not oxalic acid but calcium oxalate +sulfuryl chloride
JJay
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Hello everyone. I think some great information has been compiled here. I know I've certainly learned a lot about chlorinating agents while researching possible routes to oxalyl chloride. But the challenge won't be a complete success unless someone actually synthesizes some oxalyl chloride. The challenge deadline is still September 1, midnight in your time zone (so you can spend all day on September 1 on your entry if you like) although I could extend it if anyone is close and needs more time.

Please post here or contact me by U2U for further instructions if you intend to submit an entry for the prize. Good luck!!

Melgar
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I may actually give it a shot. I'm only missing one chemical, and have large excesses of the others. If I can find the one for sale that I'm looking for, then sure. But I only can test one specific theoretical synthesis, and if it doesn't work, I've got nothing.

The first step in the process of learning something is admitting that you don't know it already.

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XeonTheMGPony
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 Quote: Originally posted by byko3y The reason why i don't even try to make videos is because text and few pictures are much more informative than watching a video. 5-20 seconds of video might be needed, but that's more than enough. Many of those making youtube videos actually fail to ascertain the quality of the product, and some even don't bother with idendification at all. That's the result of focus on making video and not on making a reaction product. For this reason it would be great if someone made some new-age picture- and video-assisted guides on preparatory methods while being guided by a hardcore autistic experimentalist.

That's what I plan to do some point, I'll be starting on core lab techniques as I notice not allot of use full treaties on say proper distillation methods where they get to all the 5 W's and on why you do what is don.

Then start on the making of use full lab solvents, Ethanol/Chloroform/Acetic Acid and GAA, so on.

But that thing called life eats allot of my time!
XeonTheMGPony
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 Quote: Originally posted by fumingjohnny Sulfuryl chloride SO2Cl2 is prepared by the reaction of sulphur dioxide and chlorine in the presence of activated charcoal or camphor catalyst. If small quantities can be prepared by anyone having a reasonably good lab then it may be tested against oxalic acid to confirm the formation of oxalyl chloride. P.S If you never try youl'll never know.......My lab is not good enough to make these compounds. somebody give it a go and spread the word on the results.

Can you provide names for these reactions or the reaction conditions, as I am adept at doing gas phase reactions!, mind you still rebuilding/building my lab.
clearly_not_atara
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Sulfuryl chloride will not work for this reaction, so it doesn't matter.

Melgar: What route? Benzotrichloride?

JJay: bit silly to end the contest with no entries don't you think?

[Edited on 31-8-2017 by clearly_not_atara]
JJay
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Well, I can't extend the deadline forever, but I can push it back 1-2 weeks if someone is working on an entry and needs more time.

Geocachmaster
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I made a good plan that started with 100% hardware store chemicals, I'm 60-70% sure that it would work. Only a few steps too. Unfortunately I would probably need at least a full week (all day everyday) of experimenting to get it working and I am very short on time. Maybe if I devoted all of my free time from now on I could do it by October but I've got a bunch of other projects to do too. I won't be able to enter the competition, but maybe sometime later (IDK December?) I'll post about it. Sorry for being cryptic but I think it's a very good idea and I don't want to give it away or embarrass myself if it doesn't work.

Melgar
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 Quote: Originally posted by clearly_not_atara Melgar: What route? Benzotrichloride?

Yes. Toluene hasn't been easy to find, although I'm pretty sure there are auto body shops nearby that would sell it. I called up a Sherwin-Williams in Manhattan, but apparently the closest one to me that carries any is on the far side of the Bronx. I guess I'll have to call up auto body shops again today.

If I'm going to be gassing all the way to benzotrichloride, I'd need to do a much better job than usual of drying the chlorine going into it, as well as scrubbing the off-gases. Sodium sulfite solution (NaOH + metabisulfite) should get HCl and Cl2, right? I'd probably use like 90% NaOH and 10% metabisulfite.

By the way, how hard is it usually to get dry ice? There's one place in Manhattan that sells it for sure, but I feel like it has to be more common. I don't think I've ever seen it advertised though.

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Crowfjord
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Dry ice accessibility is kind of touch and go. It's not usually advertised but some grocery stores will sell it, they will have a cooler in the open under lock and key. Sometimes hardware stores will sell it in areas where hunting and fishing are popular. Barring those, you might try an ice cream place like Baskin Robins, or ask a vendor that sells that super-cold "future" ice cream, Dippin Dots.
zed
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Here in Portland, the local supermarkets carry dry ice. Fred Meyer has it. About $1.50 per pound. As for Toluene, our local auto-parts stores (Shucks/O'Reilly) sell it for about$25.00 per gallon.

Kinda spendy if you ask me, but alas, I didn't make the world as it is....and I can't make it cheaper.
TheNerdyFarmer
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So, I have seen that this challenge has been postponed. What is the new ending date of this now?
JJay
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I'm pretty sure the prize is off the table at this point. If someone feels this is unfair to him/her personally, we can talk about it, but I'm not convinced that postponing even two weeks would generate any oxalyl chloride, and I'd like to try to make some. So let's say that if you make some oxalyl chloride before I do, feel free to hit me up.

boilingstone
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Ozonolysis of acetylenes can give the diketone, among other products. As awful an idea attempting an ozonolysis of dichloroacetylene is, could something like that work? How does dibromoacetylene compare to dichloroacetylene, and would oxalyl bromide be just as useful?

This prepchem page describes a simple synthesis of dibromoacetylene from 1,1,2-tribromoethylene at least.
http://www.prepchem.com/synthesis-of-dibromoacetylene/

Edit:
Here's my brainstorm,

1. Pass acetylene through dry bromine to yield tetrabromoethane
2. React with a base to yield 1,1,2-tribromoethylene

3. Follow Prepchem procedure linked above to yield dibromoacetylene

4. Ozonolysis(?) to yield oxalyl bromide

The War Gases Chemistry and Analysis, by M. Sartory, 51, 1939 has a good section on acetylene halides (pg. 57) and oxalyl halides (pg. 66), but doesn't mention synthesizing one from the other. Interestingly, the acetylene halides are ranked in stability from I>Br>Cl, where as the oxalyl halides are ranked in stability from Cl>Br>I. Working with the bromides might be a happy medium, in a very loose sense of the word "happy".

Attachment: The War Gases Chemistry and Analysis.pdf (4.1MB)
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[Edited on 25-8-2018 by boilingstone]
JJay
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boilingstone:

I have no idea if your proposed route would work. Ozone would not be the first oxidizer I would think of for that oxidation... why ozone?

clearly_not_atara
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If chloroacetyl chloride is available, this might be converted to a thioglycolic thioester by rxn with eg thiophenol. That can become an oxalic dithioester by rxn with SeO2 if the Riley oxidation works on such a substrate. Sulfuryl chloride can convert some thioesters to the acyl chlorides as illustrated by the conversion of monothiocarbonates to chloroformates: