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

Printable Version  
 Pages:  1  2    4
Author: Subject: Oxalyl Chloride Challenge
Opylation
Hazard to Others
***




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


[*] 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 119 times

View user's profile View All Posts By User
clearly_not_atara
International Hazard
*****




Posts: 2176
Registered: 3-11-2013
Member Is Offline

Mood: Big

[*] 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.




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




Posts: 584
Registered: 26-11-2019
Location: under the sycamore tree
Member Is Offline

Mood: ambivalent

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


What if we tried chlorinating glyoxal???



Reflux condenser?? I barely know her!
View user's profile View All Posts By User
karlos³
International Hazard
*****




Posts: 1383
Registered: 10-1-2011
Location: yes!
Member Is Offline

Mood: aminoketonologisch 8)

[*] 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
View user's profile View All Posts By User
clearly_not_atara
International Hazard
*****




Posts: 2176
Registered: 3-11-2013
Member Is Offline

Mood: Big

[*] posted on 9-6-2021 at 11:43


njl was making a joke, I think :D



[Edited on 04-20-1969 by clearly_not_atara]
View user's profile View All Posts By User
karlos³
International Hazard
*****




Posts: 1383
Registered: 10-1-2011
Location: yes!
Member Is Offline

Mood: aminoketonologisch 8)

[*] 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
View user's profile View All Posts By User
Opylation
Hazard to Others
***




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


[*] posted on 9-6-2021 at 17:44


Off topic… removed for irrelevance

[Edited on 10-6-2021 by Opylation]
View user's profile View All Posts By User
Praxichys
International Hazard
*****




Posts: 1063
Registered: 31-7-2013
Location: Detroit, Michigan, USA
Member Is Offline

Mood: Coprecipitated

[*] 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.
View user's profile Visit user's homepage View All Posts By User
S.C. Wack
bibliomaster
*****




Posts: 2345
Registered: 7-5-2004
Location: Cornworld, Central USA
Member Is Online

Mood: Enhanced

[*] 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]




"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
Praxichys
International Hazard
*****




Posts: 1063
Registered: 31-7-2013
Location: Detroit, Michigan, USA
Member Is Offline

Mood: Coprecipitated

[*] 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
View user's profile Visit user's homepage View All Posts By User
Jenks
Hazard to Self
**




Posts: 75
Registered: 1-12-2019
Member Is Offline


[*] 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?
View user's profile View All Posts By User
S.C. Wack
bibliomaster
*****




Posts: 2345
Registered: 7-5-2004
Location: Cornworld, Central USA
Member Is Online

Mood: Enhanced

[*] 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]




"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
RustyShackleford
Hazard to Others
***




Posts: 148
Registered: 10-12-2020
Location: Northern Europe
Member Is Offline


[*] 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.
View user's profile View All Posts By User
Praxichys
International Hazard
*****




Posts: 1063
Registered: 31-7-2013
Location: Detroit, Michigan, USA
Member Is Offline

Mood: Coprecipitated

[*] posted on 13-7-2021 at 07:09


Well, beans. Back to the drawing board.
View user's profile Visit user's homepage View All Posts By User
Triflic Acid
National Hazard
****




Posts: 411
Registered: 27-9-2020
Member Is Offline

Mood: Sulfonated

[*] 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...




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 5-8-2021 at 14:40


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



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
Triflic Acid
National Hazard
****




Posts: 411
Registered: 27-9-2020
Member Is Offline

Mood: Sulfonated

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


cyanuric chloride reacts with oxalyl acid to form oxalyl chloride



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




Posts: 2176
Registered: 3-11-2013
Member Is Offline

Mood: Big

[*] 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.



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




Posts: 3440
Registered: 15-10-2015
Member Is Offline


[*] 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.
View user's profile View All Posts By User
Triflic Acid
National Hazard
****




Posts: 411
Registered: 27-9-2020
Member Is Offline

Mood: Sulfonated

[*] 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.



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




Posts: 3440
Registered: 15-10-2015
Member Is Offline


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


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

IMG_20210820_100917649.png - 154kB
View user's profile View All Posts By User
Triflic Acid
National Hazard
****




Posts: 411
Registered: 27-9-2020
Member Is Offline

Mood: Sulfonated

[*] posted on 23-8-2021 at 16:19


So?



Hope is not a reagent
View user's profile View All Posts By User
garphield
Hazard to Self
**




Posts: 55
Registered: 9-12-2019
Member Is Offline


[*] 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.
View user's profile View All Posts By User
 Pages:  1  2    4

  Go To Top