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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.





The single most important condition for a successful synthesis is good mixing - Nicodem
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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



wanna be chemist who has no idea what he is doing and is provably a threat to himself and others.
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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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Magpie
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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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