Synthesizing Diphenyl Oxalate: Esterification of Phenol and Oxalic Acid

[the_m-theorist]

How do I esterify phenol and oxalic acid to make diphenyl oxalate.
P.S. My initial researches using google have yielded no results.

 

[Borek]

I would start with Vogel's Textbook of Practical Organic Chemistry.

 

[DrDu]

Once I prepared the dinitrophenyloxalic esters used in lightsticks, but I started from oxalylchloride. Usually Beilstein is a good starting point to find syntheses of standard organic compounds.

 

[the_m-theorist]

I would start with Vogel's Textbook of Practical Organic Chemistry.

I downloaded the fifth edition yesterday and it seems like a great general reference but I haven't found diphenyl oxalate anywhere. Perhaps you could tell me some other more focused references.

 

[the_m-theorist]

Once I prepared the dinitrophenyloxalic esters used in lightsticks, but I started from oxalylchloride. Usually Beilstein is a good starting point to find syntheses of standard organic compounds.

The Beilstein database, right?
P.S. I'm going to use it for glow-science too!

 

[Borek]

I haven't found diphenyl oxalate anywhere

Vogel is more about finding general ideas and then trying by yourself.

Unless you can find a specific synthesis described in literature - but using google is not a good approach, as DrDu suggested you will get better results using specialized databases (typically behind a paywall, but your school may have access).

 

[the_m-theorist]

Vogel is more about finding general ideas and then trying by yourself.

Unless you can find a specific synthesis described in literature - but using google is not a good approach, as DrDu suggested you will get better results using specialized databases (typically behind a paywall, but your school may have access).

Well sadly I know that the school does not have access to any databases, but tell me do you have any other references, there is very little about esters in Vogel. Also is Beilstein not free?

 

[Borek]

I am afraid you will not find a free and reasonably complete database.

 

[the_m-theorist]

I am afraid you will not find a free and reasonably complete database.

any other refrences?

 

[DrDu]

Beilstein is not only a database but exists also as a shelf full of books, maybe at your local library.
I think I followed the following article:
http://pubs.acs.org/doi/pdf/10.1021/ed051p528
Maybe you can locate it in some library as it is not free.

 

[the_m-theorist]

I think I followed the following article:
http://pubs.acs.org/doi/pdf/10.1021/ed051p528
Maybe you can locate it in some library as it is not free.

Thanks for the link, but unfortunately I've just checked at the local library and they don't have Beilstein.
Still I'll keep searching in other libraries, in the meanwhile do you have any other references which might have the reaction.

 

[DrDu]

I always thought that the young generation was smarter than I being an old guy in localizing everything on internet.
Have a look at the Homepage of Turro, one of the authors I was citing. He has the article for download.
http://turroserver.chem.columbia.edu/LabSite/labsite.php?task=publications_range&range=101-150
I think I replaced benzene by toluene for obvious reasons.

 

[the_m-theorist]

I always thought thyat the young generation was smarter than I being an old guy in localizing everything on internet.

Yes, I found basically the same thing (the trichlorophenol variant though) here only in much better video form. It seems he also has a video where he prepares the TCPO. (he too uses toulene). Also I've been going through some books. (Including Morrison and Boyd.) I found some standard esterification methods and stuff but everywhere I looked I couldn't find anything which had two phenyl groups and 2 C double bonds. Still searching!

 

[DrDu]

Watching NurdRage is always fun. Probably the hardest step is getting the oxalylchloride. To show the fluorescence, you can also use Rhodamin B, which is way cheaper and easier to obtain than Bis phenylethinylantracene, although the fluorescence is not as strong.

 

[the_m-theorist]

Probably the hardest step is getting the oxalylchloride.

UPDATE:- I was talking with a lot of chemical dealers today. One was promising (I still had to spell out oxalyl chloride for him though), he said he'll tell me tomorrow if he could get me the chemicals. (hope for the best.)

To show the fluorescence, you can also use Rhodamin B

Do you think sodium fluorescein (is usually used in highlighters I believe) will work ? The article you quoted said that almost all fluorescent dyes work and this says that it is slightly soluble in ethanol, though I'm not sure it'll work in ethyl acetate or diethyl pthalate.

 

[DrDu]

Just take care in handling the oxalyl chloride. It is very toxic and volatile, comparable to phosgene. However, I was doing this as a high school project, too.

 

[epenguin]

I would start with Vogel's Textbook of Practical Organic Chemistry.

OMG I read it is still the best but that must go back a long way.

 

[the_m-theorist]

Just take care in handling the oxalyl chloride. It is very toxic and volatile, comparable to phosgene.

I admit that I had no idea oxalyl chloride was so toxic, I had intended to go through the MSDS of each chemical after the dealer told me that the chemicals were available, but I ended up downloading the MSDS of each one just after reading this comment! But the dealers here are ridiculous, he has no idea what oxalyl chloride (maybe I'll buy that from sigma aldrich or something) is and tells me that I need a permit for buying toluene from him!

However, I was doing this as a high school project, too.

Ahhh! so you have read my other posts! Funny how the number of people who read your other posts while conversating on one increases drastically on academic forums!

 

[David Carroll]

Reduce phenyl-chloroformate with phenyl formate?

 

[David Carroll]

Although I'm not sure if you can grignardize phenyl formate.

 

[michiel]

Once I prepared the dinitrophenyloxalic esters used in lightsticks, but I started from oxalylchloride. Usually Beilstein is a good starting point to find syntheses of standard organic compounds.

oxalylchloriden is to toxic and I am not allowed to work with this compound, does normal oxalic acid word to? (without chlorine)

 

[DrDu]

You could try the first method described here in Houben Weyl:
https://books.google.de/books?id=4B...=onepage&q=oxalic acid esterification&f=false

I have no idea whether this will work with phenols. I don't know whether you could consider simply buying these esters for your project?

 

[cpman]

I've seen a paper that suggests that transesterfication of dimethyl oxalate over an SnO₂ catalyst can be used to produce this compound with a ~22% conversion. I couldn't find the PDF of that paper, but I did find one on the production of SnO₂ catalysts for transesterification here.

Presumably you could produce dimethyl oxalate with a Fischer Esterification of methanol and oxalic acid. This should make a mix of the mono-, di-, and tri-esters of oxalic acid. I'm unsure how you could separate these esters off the top of my head. Or you could just but dimethyl oxalate somewhere and use that to perform the transesterification.

 

[DrDu]

I did some reading: Apparently, the toxicity of Oxalylchloride had been overestimated. It is no longer classified as T but only as Xn. So if you have a fumehood in your school, it should be safe to operate with it. I don't see any reasonable alternative synthesis of TCPO or the like via other routes.

 

[michiel]

thank you for your help , I tried the reaction with a Fischer Esterification but the result wasn't very clear. After a week at 50 degrees Celsius there were no visual changes
however the pH did change so mabey something did happen.

if I have a clear result I'll post the awnser so if more people have problems they can use it