Chainhit222
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Diethyl ether peroxide synthesis?
Would it be possible to synthesize a small quantity of Diethyl ether peroxide in the laboratory?
The wikipedia page says it is formed by oxidation of ether due to oxygen, uv light and in the presence of certain metals.
My experiment idea is to put a small amount of ether (50ml or so) in a small two necked flask. I would bubble in oxygen through a bubbler and then
setup a reflux condenser on top of the flask, in order to prevent evaporation due to sparging. UV light could be shined on the flask too, perhaps
from a germicidal lamp or a black light.
I am not sure on what kind of metal should be used to promote faster formation, any ideas?
Additionally, would bubbling ozone through the mixture be a better idea then bubbling oxygen?
Then I would apply a vacuum to get rid of the diethyl ether, and hopefully be left with a small quantity of diethyl ether peroxide.
I understand it is a dangerous explosive, but I hope that with thick gloves/face shield and small quantities I could test a few milliliters of it in a
detonation safely.
Any input is appreciated.
[Edited on 27-5-2010 by Chainhit222]
The practice of storing bottles of milk or beer in laboratory refrigerators is to be strongly condemned encouraged
-Vogels Textbook of Practical Organic Chemistry
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Formatik
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Those are some of the most dangerous molecules out there. A few milliliters easily can cost a hand. The polymeric peroxide is an oil described as
extremely sensitive. The cause of ether explosions as it's distilled. Likely because on distillation or warming it dimerizes, which is a process that
usually results in detonation. Dimeric ethylidene peroxide is a very volatile and equally risky solid. They are highly sensitive, the power also
triumphs TNT. The diethyl ether peroxides have been discussed:
http://www.sciencemadness.org/talk/viewthread.php?tid=10380
http://www.sciencemadness.org/talk/viewthread.php?tid=6342
etc.
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The WiZard is In
International Hazard
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A footnote from —
Alwyn G Davis
Organic Peroxides
Butterworths : London 1961
p. 197
"... the 5 grams of acetyl peroxide in the bottle exploded with
sufficient force to tear off both the man's hands...." [80]
[80] N.B.F.U. Research Report 1956, No. 11, p. 37
[Fire and explosion hazards of organic peroxides.]
{Not found online. /djh/}
By da d-i methy and ethyl peroxide (gases) are easy to make.
Original references in -
GE Hawkins
Organic Peroxides : Their Formation and Reactions
D. Van Nostrand Co. 1961
djh
----
Experimentalism doesn't
have to be a dying art.
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12AX7
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What about the crystalline solid sometimes claimed to be present in ether? Is that a higher-mer peroxide, or an isomer?
Tim
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Chainhit222
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Well, a safer method in this case then would be instead of using like 50ml in a flask, why not use like 3ml of ether on a test tube fitted with a tiny
reflux condenser made out of twisted tubing (as per the articles on this website)?
I could bubble the oxygen/oxone through a capillary tube. Turn it into a micro scale experiment that would produce less then 1 gram, for safety
reasons.
The practice of storing bottles of milk or beer in laboratory refrigerators is to be strongly condemned encouraged
-Vogels Textbook of Practical Organic Chemistry
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Formatik
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I doubt preparation from commercial ether, since as the ether evaporates, the anti-peroxide forming compounds that are added (like BHT, hydroquinone,
which are solids), get more concentrated. Bayer has a method for the polymer starting from acetaldehyde.
Ouch! It's good to reiterate the point sometimes.
Quote: Originally posted by 12AX7  | | What about the crystalline solid sometimes claimed to be present in ether? Is that a higher-mer peroxide, or an isomer? |
The polymer is easily soluble in ether as noted in Federoff, E305. I have doubts that it's the solid dimer, since in Ber. Vol. 72, 1939, p. 1933-38
Rieche and Meister solubilize the dimer in ether and then evaporate it. I think that could leave the oxyethyl hydroperoxide or dioxyethyl peroxide,
one of those would maybe be less soluble, or reach a saturation and then crystallize out. The Beilstein references (4th ed.) for the:
Methyl-oxymethyl-peroxide is in Bd. 1, Sup. II, 641. Bis-[a-oxy-ethyl]-peroxide is in Bd. 1, Sup. II, 674.
Federoff also states the polymer oil is not very sensitive to friction. But if let stand in a closed container a few hours (even faster in air) the
oil changes into a tary mass which is extremely sensitive to shock and friction.
[Edited on 29-5-2010 by Formatik]
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