Organikum
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Thermal Decarboxylation - Alkyl Phenyl Ketones
The attached articles refer to the production of ketones by thermal decarboxylation. The second one in special refers to the production of
acetophenone and propiophenone from iron acetetate or propionate and benzoate.
The method for sure applies also to the production of phenyl-2-propanone from PAA and iron acetate.
The iron salts can also be prepared from iron oxides - black iron oxide as used as cement-pigment comes to mind here and acetic acid of less than 65%
strength.
The practical method is similar to the making of benzene from sodium benzoate and NaOH as described by me in the "benzene" thread.
Articels courtesy lugh.
Attachment: davis_ferric.djvu (92kB)
This file has been downloaded 1699 times
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frogfot
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Thanks for this good info!! I didn't know one could use usual glass equipement for this.. gonna try this out once I get some heavy carboxylic
acids.
Maby it's worth to try this with fatty acids.. They don't mentions any yelds with really long acids, like say stearic acid..
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FriendlyFinger
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I can't download this file, It doesn't seem to be there. Does anyone have another link?
Thanks,
FF
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solo
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I reloaded the file again........solo
Attachment: davis_ferric.djvu (92kB)
This file has been downloaded 1234 times
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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leu
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You have to right click, select save as and rename the file extension to djvu to download and open it, or you can download the same two articles in
the Wet Dreams thread for literature requests from this and other forums 
Chemistry is our Covalent Bond
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FriendlyFinger
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Sorry, can't find them at wetdreams and definately can't rename after right clicking. The computer automatically tries to download then says it can't
find it. Fuck I wish I had a brick right now!
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FriendlyFinger
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Could someone please post another link or at least the name of these two articles so I can look for them somewhere else because I simply can't
download it! I have tried for hours and hours. I really have.
See where it says " this file has been downloaded 81 times" well that's me, trying 80 times!
please, thanks.
[Edited on 30-4-2006 by FriendlyFinger]
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solo
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Here you go.....................solo
http://rapidshare.de/files/19241162/thermal_decarboxylation_...
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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Nicodem
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| Quote: | Originally posted by FriendlyFinger
See where it says " this file has been downloaded 81 times" well that's me, trying 80 times! |
The next time this hapens to you either use normal HTTP (not HTTPS) access or simply copy the URL link to another window and delete the S from
HTTPS. That should do.
It is due to a bug in Internet explorer. 
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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FriendlyFinger
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Well blow me down. Solo, please mail me your shoes, I keep them under my bed!
Thank you very much
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FriendlyFinger
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What's the chance of this reaction working with ordinary non reduced iron powder?
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bio2
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Iron can be reduced in a few minutes by
being the Cathode in an electrolytic cell.
Turnings in a net or something.
Precipitated Fe should work and scrap iron
is used in industry and works somewhat
less vigorously.
Main thing is relatively oxide free and clean!
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FriendlyFinger
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Oh! How do you do that? I know nothing about electrolytic cells. How much current? what medium do you use? Is there a book you can mention that I can
read?
Also can iron propionate be made using iron oxide or is Organikum refering to iron acetate?
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solo
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Principles of Electrochemistry
Jiri Koryta Jiri Dvorak Ladislav Kavan
Publisher: John Wiley & Sons Inc
Publication Date: 1993-05
Number Of Pages: 502
http://www.uploading.com/?get=BJPZU620
Review
Presents electron transfer and double-layer theories in an understandable manner while keeping mathematics to a minimum. Revised and expanded, this
edition features a number of new sections which deal with electrochemical materials science, photoelectrochemistry, stochastic processes, novel
aspects of ion transfer across biological membranes, biosensors and more.
.........source,
http://anuvinu.blogspot.com/
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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Organikum
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| Quote: | Originally posted by bio2
Iron can be reduced in a few minutes by
being the Cathode in an electrolytic cell.
Turnings in a net or something.
Precipitated Fe should work and scrap iron
is used in industry and works somewhat
less vigorously.
Main thing is relatively oxide free and clean! |
IIRC then the problem of using oxides was solved by somebody at the HIVE, he used lead though, not iron. But the basic principle stays the same I
suppose - the formation of the iron salt in the needed oxidation state depends on the concentration of the acid as mentioned in the first post of
mine. Using foir example acetic acid of more then 65% strength in the salt formation will give lousy yields (for lead salts and I think the same for
iron salts).
Davis mentiones that magnetic black iron oxide as used as cement pigment gives poor yields (at least in one example - 4%). But when the preparation is
tweaked then....
[Edited on 16-2-2007 by Organikum]
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manimal
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See here: instead of risking oxidative degradation by recovering iron acetate from solution, it can be made in situ from ferrous sulfate and sodium
carboxylate; this would form ferrous carboxylate and sodium sulfate. The NaSO4 would stick around, but may act as a bulking agent and not interfere
with the decarboxylation.
[Edited on 23-11-2009 by manimal]
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bbartlog
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And then you have ferrous carboxylate (I would say carbonate), which (I can only assume) you will further treat with acetic acid (or propionic acid)?
But why not just use sodium acetate (and benzoate or w/e) in that case and do things in one step? Also, while the carbonate will react so long as
benzoic acid and/or propionic acid are used, some other carboxylic acids are weaker and would not be able to displace the CO2.
As for the general procedure, it looks like a variety of metals other than iron would work. The paper mentions the original work done by Friedel using
calcium, and I see someone else above mentions using lead. From what I recall about pyrolysis of calcium salts of carboxylic acids (to produce
ketones), the temperatures needed are higher than those used for the iron salts in the paper. I don't know whether this is the only reason they used
iron.
Too bad about the ortho- effects. Can't do anything neat with salicylates this way.
[Edited on 24-11-2009 by bbartlog]
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