Sciencemadness Discussion Board
Not logged in [Login ]
Go To Bottom

Printable Version  
 Pages:  1    3  
Author: Subject: Oxalyl Chloride Challenge
Triflic Acid
National Hazard
****




Posts: 407
Registered: 27-9-2020
Member Is Offline

Mood: Sulfonated

[*] posted on 25-3-2021 at 06:30


And, how are you going to deal with that nice chlorinated decomposition product COCl2, commonly called phosgene? One member is believed to have died from phosgene poisonings a few years back. Do you even have a citation to prove what you said? I seriously doubt that this will give oxalyl chloride in anything above dismal yields. You should also give more information regarding what you mean by chlorinated products, just saying that they are derived from ethylene oxalate does not tell us anything.



Hope is not a reagent
View user's profile View All Posts By User
Sigmatropic
National Hazard
****




Posts: 301
Registered: 29-1-2017
Member Is Offline

Mood: No Mood

[*] posted on 25-3-2021 at 11:06


Quote: Originally posted by Sigmatropic  
I just had another idea, what if you make ethylene oxalate from dimethyl/diethyl oxalate and ethylene glycol. Then chlorinate it to the tetrachloroethylene oxalate. That with either activated carbon or a tertiary amine catalyst should rearrange to two molecules of oxalyl chloride.
https://patents.google.com/patent/US2816287
https://patents.google.com/patent/US2816140A/en

I don't have a reason to make oxalyl chloride or a fume hood so I'm not about to start this :(.


Triflic Acid, I found some patents while ago, right before getting flamed by Eldritch. Patents are arguably not te best source of information but there is atleast some literature to support this dubious proposition.
View user's profile View All Posts By User
mackolol
National Hazard
****




Posts: 437
Registered: 26-10-2017
Location: Poland
Member Is Offline

Mood: Psychedelic

[*] posted on 25-3-2021 at 11:07


Quote: Originally posted by Triflic Acid  
And, how are you going to deal with that nice chlorinated decomposition product COCl2, commonly called phosgene? One member is believed to have died from phosgene poisonings a few years back.

Go outside and wear a gasmask. Am I missing something?
View user's profile View All Posts By User
Triflic Acid
National Hazard
****




Posts: 407
Registered: 27-9-2020
Member Is Offline

Mood: Sulfonated

[*] posted on 25-3-2021 at 12:20


Oh, when he said decomposition, I immediately thought that he was doing something around pyrolysis. A hot bubbling phosgene gyser is not the best thing to deal with. If he's doing it with a tertairy amine its safer.



Hope is not a reagent
View user's profile View All Posts By User
njl
International Hazard
*****




Posts: 583
Registered: 26-11-2019
Location: under the sycamore tree
Member Is Offline

Mood: ambivalent

[*] posted on 25-3-2021 at 13:25


@mack indeed you are missing something, namely the fact that a supplied air respirator is necessary according to the CDC (but that's just the man trying to keep us amateur chemists down). So a surplus Israeli gas mask that has a 40 year old filter might not cut it. And the rules say no phosgene. And no source is provided.

Right now I can't imagine a decomposition of "chlorinated ethylene carbonate" that doesn't involve carbonate itself, which would form water in its own decomposition thus destroying some product. But I could be totally off.




Reflux condenser?? I barely know her!
View user's profile View All Posts By User
mackolol
National Hazard
****




Posts: 437
Registered: 26-10-2017
Location: Poland
Member Is Offline

Mood: Psychedelic

[*] posted on 25-3-2021 at 13:48


Probably if you work with it all the time under the fan you would need the supplied air respirator.
But to be honest, when you're outside and in your gasmask, you could even hold the breath when you get close to it to make sure you don't expose yourself too much.
Of course any accident would be really dangerous, but it's probably not that bad
View user's profile View All Posts By User
MaeBorowski
Harmless
*




Posts: 5
Registered: 8-3-2021
Member Is Offline


smile.gif posted on 27-3-2021 at 18:09


Quote: Originally posted by Triflic Acid  
And, how are you going to deal with that nice chlorinated decomposition product COCl2, commonly called phosgene?

There is an option to dump it on the absorption column, but it would be better to use it to produce new ethylene carbonate or put it in some solvent like toluene or other useful purposes for the chemist. This is quite dangerous, however, I have some experience with highly toxic gases (in my case carbon monoxide, but phosgene is much, much angrier) outside the fume hood. Don't do this yourself.
Quote: Originally posted by Triflic Acid  
saying that they are derived from ethylene oxalate does not tell us anything.

It can be concluded that the product of the exhaustive chlorination of ethylene oxalate will be tetrachloroethylene oxalate :)
Quote: Originally posted by njl  
And the rules say no phosgene.

I apologize for not mentioning the release of phosgene in the ethylene carbonate method. I tried to find a rational method through one's lens and completely forgot about the rules. Thank you for pointing out my mistake.
Quote: Originally posted by njl  
And no source is provided.

To be honest, I have no sources for the direct reaction of oxalic acid with ethylene glycol. In my opinion, there are no theoretical obstacles in this synthesis: water is distilled with carbon tetrachloride, which shifts the equilibrium, and oxalic acid is strong enough to carry out the reaction without a catalyst. It should be remembered that the difference between theory and practice is much greater in practice than in theory :)




The chemists are a strange class of mortals, impelled by an almost insane impulse to seek their pleasures amid smoke and vapour, soot and flame, poisons and poverty; yet among all these evils I seem to live so sweetly that may I die if I were to change places with the Persian king. -- Johann Joachim Becher
View user's profile View All Posts By User
clearly_not_atara
International Hazard
*****




Posts: 2167
Registered: 3-11-2013
Member Is Offline

Mood: Big

[*] posted on 28-3-2021 at 07:45


Quote:
It can be concluded that the product of the exhaustive chlorination of ethylene oxalate will be tetrachloroethylene oxalate :)

This is a pretty stark example of textbook chemistry with no consideration of the real world. Free-radical chlorinations like you refer to run slowly at low concentration and low temperature with a strong UV light. Running that can be pretty annoying.

Could it work? Yeah. Is it practical? Probably not. Could it fail? Yes: HCl byproduct might cleave the ester before chlorination completes. Is it basically the same thing as free-radical chlorination of glyoxal, which was suggested almost immediately? Yes. Does it satisfy the conditions of the bet? No: phosgene production is pretty likely when Cl* radicals interact with oxalate...

EDIT: third idea: rxn of 1,2-dibromoethane with two equivalents of phenol under Ullmann condensation conditions to 1,2-diphenoxyethylene, then Br2, DBU, NaNH2, 2xCl2. Same as the previous with a different way of forming the vinylene-1,2-diether.

[Edited on 28-3-2021 by clearly_not_atara]




[Edited on 04-20-1969 by clearly_not_atara]
View user's profile View All Posts By User
MaeBorowski
Harmless
*




Posts: 5
Registered: 8-3-2021
Member Is Offline


[*] posted on 29-3-2021 at 07:32


Quote: Originally posted by clearly_not_atara  
This is a pretty stark example of textbook chemistry with no consideration of the real world.

You're goddamn right. But only partially: the product of chlorination isn't a tetrachloroethylene oxalate. In reality, chlorination requires 6.76 mol of chlorine versus the theoretical 4 (carbonate 4.93 mol vs the same 4), which indicates that there are changes in the oxalic acid residue. It is strange that in the production of oxalyl chloride, phosgene is released from tetrachloroethylene bis-chloroformate, which, in theory, should be obtained by breaking the carbon-carbon bond in the oxalic acid residue, but phosgene isn't obtained from the "tetrachloroethylene oxalate" itself, according to the data. Now I am even more interested in this idea.
Quote: Originally posted by clearly_not_atara  
low temperature with a strong UV light

The synthesis took place under a reflux. UV, I think, can be replaced by direct sunlight. This was used in some older manuals.
Quote: Originally posted by clearly_not_atara  
HCl byproduct might cleave the ester before chlorination complete

By hydrolysis? :P Most esters are perfectly resistant to hydrogen chloride.
Quote: Originally posted by clearly_not_atara  
free-radical chlorination of glyoxal

Something in me says that we will get hydrogen chloride and carbon monoxide instead of the coveted oxalyl chloride.
Quote: Originally posted by clearly_not_atara  
phosgene

In the process of decomposition — possibly, in the process of chlorination — excluded. If there is phosgene, it will be in such concentrations that hydrogen chloride is a bigger problem.
Quote: Originally posted by clearly_not_atara  
third idea: rxn of 1,2-dibromoethane with two equivalents of phenol under Ullmann condensation conditions to 1,2-diphenoxyethylene, then Br2, DBU, NaNH2, 2xCl2. Same as the previous with a different way of forming the vinylene-1,2-diether.

In Russian, to describe such syntheses, there is a stable expression "to hammer nails with a microscope". This is a possible way, I agree, but everyone who can repeat it has a) a fume hood b) several kgs of oxalyl chloride :)

[Edited on 29-3-2021 by MaeBorowski]




The chemists are a strange class of mortals, impelled by an almost insane impulse to seek their pleasures amid smoke and vapour, soot and flame, poisons and poverty; yet among all these evils I seem to live so sweetly that may I die if I were to change places with the Persian king. -- Johann Joachim Becher
View user's profile View All Posts By User
clearly_not_atara
International Hazard
*****




Posts: 2167
Registered: 3-11-2013
Member Is Offline

Mood: Big

[*] posted on 29-3-2021 at 14:35


Okay, your chemistry isn't wrong, you just don't seem to understand what JJay wanted. As to why, I don't know, he left the forum in a huff some months ago. Phosgene simply isn't allowed. It might be contained by someone sufficiently dedicated, but its generation is strongly discouraged here due to the sneaky lethality and common use of improvised safety equipment, which are a bad combination.

That kinetically stable chloroformates appear, rather than phosgene being released, does make sense to me. That is an interesting process.

When I said "free radical chlorination of glyoxal", I undersold the problems with this route, I agree. Homolytic cleavage of the radical intermediate is an issue I didn't consider. I'm not convinced it will happen, but polymerization is another problem.

How about free-radical chlorination of phenoxyacetyl chloride? Now that's three steps:

phenol + chloroacetic acid >> phenoxyacetic acid + SOCl2 >> phenoxyacetyl chloride etc.

EDIT: free-radical chlorination is not required, ordinary enol chlorination will do

[Edited on 29-3-2021 by clearly_not_atara]




[Edited on 04-20-1969 by clearly_not_atara]
View user's profile View All Posts By User
mr_bovinejony
Hazard to Others
***




Posts: 106
Registered: 20-4-2018
Member Is Offline

Mood: ASS

[*] posted on 29-3-2021 at 19:07


Is there a way from oxalyl bromide to oxalyl chloride? Or is it only possible from chloride to bromide? Bromine is much easier to handle than chlorine I think
View user's profile View All Posts By User
Triflic Acid
National Hazard
****




Posts: 407
Registered: 27-9-2020
Member Is Offline

Mood: Sulfonated

[*] posted on 30-3-2021 at 05:48


I just saw something on prepchem: https://prepchem.com/oxalyl-chloride/. It is the ethyl carbonate synth, but sure enough, it makes phosgene. Also, I think that it is only a one way thing going from bromide to chlorine, https://www.prepchem.com/synthesis-oxalyl-bromide/.



Hope is not a reagent
View user's profile View All Posts By User
MaeBorowski
Harmless
*




Posts: 5
Registered: 8-3-2021
Member Is Offline


[*] posted on 2-4-2021 at 17:53


Quote: Originally posted by mr_bovinejony  
Bromine is much easier to handle than chlorine I think

I've worked with both chlorine and bromine. The second one is much more smelly and corrosive, and, moreover, not cheap.
The problem with bromine is the need to dry it. This requires additional synthesis steps, whereas to produce dry chlorine, you only need a chlorine generator and a flask of concentrated sulfuric acid. Due to the gaseous state, you can not worry about contamination and assemble the glasswares on paraffinized rubber plugs.




The chemists are a strange class of mortals, impelled by an almost insane impulse to seek their pleasures amid smoke and vapour, soot and flame, poisons and poverty; yet among all these evils I seem to live so sweetly that may I die if I were to change places with the Persian king. -- Johann Joachim Becher
View user's profile View All Posts By User
Opylation
Hazard to Others
***




Posts: 131
Registered: 30-8-2019
Member Is Offline


[*] posted on 21-5-2021 at 17:47


Has someone already mentioned the benzyl alcohol to benzoyl chloride reaction? Then Benzoyl chloride + oxalic acid -> Benzoic acid + oxalyl chloride reaction. This seems like the most OTC reaction to me. The oxalyl chloride boils out pushing the equilibrium to the right-hand side

[Edited on 22-5-2021 by Opylation]
View user's profile View All Posts By User
clearly_not_atara
International Hazard
*****




Posts: 2167
Registered: 3-11-2013
Member Is Offline

Mood: Big

[*] posted on 22-5-2021 at 08:26


BzCl + H2C2O4 >> BzOH + CO2 + CO + HCl

Next!




[Edited on 04-20-1969 by clearly_not_atara]
View user's profile View All Posts By User
S.C. Wack
bibliomaster
*****




Posts: 2315
Registered: 7-5-2004
Location: Cornworld, Central USA
Member Is Offline

Mood: Enhanced

[*] posted on 22-5-2021 at 10:43


Some benzoic anhydride seems likely, as it's a general method for anhydrides. Same for benzotrichloride...I wonder what the yield of benzaldehyde from benzal chloride and oxalic acid is.



"You're going to be all right, kid...Everything's under control." Yossarian, to Snowden
View user's profile Visit user's homepage View All Posts By User
Opylation
Hazard to Others
***




Posts: 131
Registered: 30-8-2019
Member Is Offline


[*] posted on 22-5-2021 at 19:57


Quote: Originally posted by clearly_not_atara  
BzCl + H2C2O4 >> BzOH + CO2 + CO + HCl

Next!


Ouch! hahah oh well, I guess using BzCl for acyl chloride preparation can't be used for everything. There is a neat Thionyl Chloride preparation from, I think, phthalic anhydride and SO2. Let me see if I can find it

EDIT: Curiously, would using alkyl oxalate esters stabilize the reaction?

EDIT2: Found it! I also had a screen grab of a post from this forum, but didn't include the poster. I apologize in advance for not giving credit to that person but they pointed me to this paper. It actually uses phthalyl chloride which reacts to form phthalic anhydride in a reversible reaction

EDIT3: I also found another paper regarding the use of tetrachloroethylene carbonate as a precursor, which can be prepared from ethylene carbonate and chlorine. The issue with this method is that it also produces phosgene, which isn't the nicest of chemicals to work with. Since it's produced in-situ however, maybe using a double wash bottle; the first you're preferred absolute carboxylic acid (double product fun!), and the second being either sodium hydroxide solution or ammonium hydroxide solution to scrub the remaining phosgene. I'm sure if you use concentrated sulfuric acid as grease and perform this entirely outside with the proper precautions it could be done responsibly.

EDIT4: I'm sorry, I guess I'm beating the dead horse on that last mention. That method has been mentioned plenty in this thread

Attachment: kyrides1937.pdf (318kB)
This file has been downloaded 70 times

Attachment: Process for the Production of Oxalyl Chloride (US Patent 2816140) (1).pdf (293kB)
This file has been downloaded 66 times

[Edited on 23-5-2021 by Opylation]
View user's profile View All Posts By User
Opylation
Hazard to Others
***




Posts: 131
Registered: 30-8-2019
Member Is Offline


[*] posted on 3-6-2021 at 18:48


I was just thinking back to the ethylene carbonate -> chlorination -> oxalyl chloride + phosgene reaction and got to thinking would the transesterification of dialkyl oxalate to ethylene oxalate work? This forms 1,4-dioxane-2,3-dione. Theres a similar compound, Dioxalin, that is formed with oxalic acid and glycerol but the branching carbon group may stabilize it. I couldn't find any information on the formation of the 2,3-dione of dioxane which leads me to believe it's too unstable. But, if it were possible to form this compound, than the tetrachlorination followed by heating would liberate 2 moles of oxalyl chloride?
View user's profile View All Posts By User
Jenks
Hazard to Self
**




Posts: 66
Registered: 1-12-2019
Member Is Offline


[*] posted on 4-6-2021 at 09:29


That's a really brilliant idea. Happily, 1,4-dioxane-2,3-dione is known, CAS# 3524-70-7. The link shows that it is normally made from ethylene glycol and ... oxalyl chloride.
View user's profile View All Posts By User
Opylation
Hazard to Others
***




Posts: 131
Registered: 30-8-2019
Member Is Offline


[*] posted on 4-6-2021 at 09:49


I found a paper on cyclic oxalate ester formation and properties. It looks like ethylene oxalate has a high propensity to hydrolyze and polymerize/demolymerize. However, the paper does mention a preparation, so if used immediately it might be possible to prepare the tetrachloro derivative.

P.S. it uses transesterification for the prep :)

Attachment: carothers1930.pdf (2.5MB)
This file has been downloaded 58 times


[Edited on 4-6-2021 by Opylation]
View user's profile View All Posts By User
Opylation
Hazard to Others
***




Posts: 131
Registered: 30-8-2019
Member Is Offline


[*] posted on 8-6-2021 at 01:12


Just would like to provide an update that I have found a patent on the preparation of tetrachloroethylene oxalate via the transesterification of dialkyl oxalate and ethylene glycol followed by UV radical chlorination in carbon tetrachloride. Seems like a decent procedure to bump/update the thread for anyone who is curious :)

Attachment: Tetrachloroethylene oxalate.pdf (435kB)
This file has been downloaded 57 times

[Edited on 8-6-2021 by Opylation]
View user's profile View All Posts By User
BauArf56
Hazard to Self
**




Posts: 66
Registered: 22-8-2019
Location: between the moon and the sun
Member Is Offline

Mood: energetic

[*] posted on 8-6-2021 at 01:39


if this reaction is reversible, first oxalic acid could be treated with bromine (which can be made from pool sanitizer sodium bromide), getting oxalyl bromide. Then it could be treated with hydrogen chloride gas, yielding oxalyl chloride.





[Edited on 8-6-2021 by BauArf56]

cocm.png - 35kB
View user's profile View All Posts By User
Opylation
Hazard to Others
***




Posts: 131
Registered: 30-8-2019
Member Is Offline


[*] posted on 8-6-2021 at 01:58


Liquid bromine and Oxalic acid react to form hypobromic acid, carbon monoxide and carbon dioxide. Hypobromic acid reacts with oxalic acid to form hydrogen bromide, water, and CO2
View user's profile View All Posts By User
BauArf56
Hazard to Self
**




Posts: 66
Registered: 22-8-2019
Location: between the moon and the sun
Member Is Offline

Mood: energetic

[*] posted on 8-6-2021 at 02:32


forgot that bromine is an oxidiser! How about using hydrogen bromide instead of bromine? HBr could be made in situ with sulfuric acid and sodium bromide
View user's profile View All Posts By User
clearly_not_atara
International Hazard
*****




Posts: 2167
Registered: 3-11-2013
Member Is Offline

Mood: Big

[*] posted on 8-6-2021 at 09:00


This thread doesn't need more random guesses from people who didn't bother to study the problem at all. HBr will not brominate any carboxylic acid, much less oxalic.



[Edited on 04-20-1969 by clearly_not_atara]
View user's profile View All Posts By User
 Pages:  1    3  

  Go To Top