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Author: Subject: Preparation of Diethyl Sulfate
Magpie
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[*] posted on 29-12-2018 at 12:54


I recently attempted to make diethyl sulfate (DES) by sparging ethene into con H2SO4 held at 97°C. The gas was sparging profusely into the acid using a fritted tube. Sparging continued until the ethene was gone, about 4 hrs. Much char was produced and no hint of DES.

An article in the Canadian Journal of Chemical Engineering, 1991) indicates that the pressure in the vessel must be between 20-30 bar. My sparging was done at ~6" of acid hydrostatic pressure.

Since I can make ethene efficiently I wanted to make this method work. But I would have to buy a pump capable of 20-30 bar plus make a pressure vessel, etc, so I will abandon this approach for now.

I have great hopes for a method that first makes ethyl hydrogen sulfate. I will try this next.





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kmno4
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[*] posted on 5-1-2019 at 18:14


The simplest method for making DES seems reaction of EtOH and H2SO4, without any additives. It must work, but (from available literature) reaction has to meet some important conditions.
The yield sholud be somewhere between 20% and 40%, at least I think so. I am going to try this, but currently I have no time for experiments, even such simple ones :(




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[*] posted on 6-1-2019 at 09:30


Magpie,

I came across the following article a few minutes ago:

On the production of the sulphates of the alcohol-radicals from the nitrites by the action of sulphurous acid
Ernest T. Chapman, J. Chem. Soc., 1870, 23, 415
DOI: 10.1039/JS8702300415

It suggests that ethylnitrite and SO2 or its concentrated solution in water yield DES.
The article is an ancient one, a bit confusing with its old nomenclature and such but seems interesting.

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Magpie
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[*] posted on 6-1-2019 at 11:30


kmno4: I have use this method with yields of 0-14.4%.

Pumulki: Thanks for the procedure. I may try it eventually. My next try will be using the procedure in patent GB 581,115. It is extremely simple and promises good yields.

[Edited on 7-1-2019 by Magpie]




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kmno4
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[*] posted on 6-1-2019 at 14:40


Quote:
kmno4: I have use this method with yields of 0-8%.

"This method" means nothing. Your method may not be my method.Besides, cited patent exploits reaction of H2SO4 and EtOH without any additional substance (but stream of air and heating). So, you did not try every method :P




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Magpie
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[*] posted on 6-1-2019 at 16:49


The method I am referring to is in the first post of this thread.



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[*] posted on 6-1-2019 at 17:36


Impressive as always



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[*] posted on 7-1-2019 at 12:31


Magpie, I fished out this one:

"Solution of Ethylen in Sulphuric Acid
By Buttlerow and Gorgainow (Deut. Chem. Ges. Ber., VI, 196).
Strong sulphuric acid at 160-170 C perfectly absorbs ethylene. In Berthelot's well known experiment the absorbtion may be due to the heat developed by friction."

Source: Organic chemistry
J. Chem. Soc., 1873, 26, 743
DOI: 10.1039/JS8732600743

It is just the abstract, but that Berichte article may be worth a look up. Also, the once well-known Berthelot method may be referenced in that article, who knows?

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[*] posted on 7-1-2019 at 15:39


I tried sparging ethylene into con sulfuric acid but at 100°C. The patent I listed above said the reactor pressure must be 20-30 bar. My pressure was atmospheric.

I will look for that reference the next time I am at the library.

I don't think that making diethyl sulfate can be all that easy. Usually if it is easy it is given in Vogel.




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[*] posted on 7-1-2019 at 22:46


I tried to save you a journey to the library and downloaded that Berichte article - because all issuses of this journal can be searched online. :-)

Unfortunately the referenced article is just a "correspondence from St. Petersburg" - which is just an abstract in German. As I can tell it does not say a word more than the cited English version, except that "strong sulphuric acid" is "concentrated".

No reference to the original (russian) article nor to the mentioned Berthelot's method of absorbtion. :-(

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[*] posted on 4-3-2019 at 07:27


Still no time for experiments .... but not for some little literature.
Here is very interesting article, with many important things for interested in Et2SO4 preparations.

Attachment: estr.pdf (99kB)
This file has been downloaded 27 times





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[*] posted on 14-3-2019 at 11:05


My preliminary experiment with 98% EtOH and 96% H2SO4 gave 0% of Et2SO4. It seems that H2O is very harmful for this esterification and must be removed. Added Na2SO4 extracts practically H2SO4 only, added heptane as extractant, it extracts nothing.
I have just ordered some "H2O remover" to test some concept, we will see.....




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[*] posted on 14-3-2019 at 13:09


Preparation of Neutral Ethyl Sulphate. By A. Villiers (Compt. rend., 90, 1291—1292).—This ether can be prepared by distilling in a vacuum a mixture of sulphuric acid and alcohol. 200 grams of absolute alcohol distilled very slowly in this manner with twice their volume of concentrated sulphuric acid, yielded from 25 to 30 grams of the neutral ether; the end of the operation is indicated by the frothing of the contents of the retort, and by an increase of the internal pressure. The distillate separates into two layers, the lower of which consists of the pure ether. There is no advantage in using fuming sulphuric acid, or in substituting ordinary ether for alcohol. The boiling point of ethyl sulphate under a pressure of 45 mm. is 120.5°, which falls regularly 2.5° as the pressure diminishes 5 mm. It solidifies at about —24.5°, and when treated with warm baryta-water it gives the theoretical quantity of barium ethyl sulphate and alcohol.

JCS 38, 797 (1880)

[Edited on 15-3-2019 by S.C. Wack]




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[*] posted on 15-3-2019 at 11:36


Yes, I have seen the article from Comptes Rendus, I think I have seen most of articles about preparation of Et2SO4 :P
My goal is not to use vacuum and/or oleum, the ethyl precursor must be EtOH, the yiel must be better than 50% counting on EtOH. I thought about Na2S2O7 (prepared from Na2S2O8, checked), but after calculations I decided not to do this (expected problems with work-up).
Unfortunately Et2SO4 is sensitive to water or H2SO4, they both cause its decomposition....
As I said, I am waiting for "H2O remover" which is able to remove water even in fair acidic conditions (up to 80% H2SO4) and not consuming too much H2SO4 by the way. However, I have never seen this substance to be reported for this purpose, maybe it simply does not work :D
But it is cheap and worth trying.




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[*] posted on 16-3-2019 at 08:01


Boron trioxide?



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[*] posted on 18-3-2019 at 15:02


No, it is not B2O3. Firstly, I would expect borate esters formation in the mixture. Secondly, glassy B2O3 is terribly hard. Not so long time ago, I prepared some B2O3 (from H3BO3) for another project (triphenyl borate).
To my surprise, I was not able to powder it in my porcelain mortar, ha. It scratches glass, so it would damage my equipment, especially under magnetic stirring. Fortunately, for this purpose partly dehydrated H3BO3 (~HBO2) was equally good.




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