schrodingers_hat
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propiophenone from calcium propionate and calcium benzoate
Hi all. In the attached excerpt, they discuss a synthesis of propiophenone from benzoic and propionic acid.
If one were to start from the calcium salts of these two compounds, would it be required that they be converted to their acid forms prior to the final
reaction?
As the reaction takes place at 250 C, I do not think there is a suitable solvent that could dissolve them in their salt forms and reach said
temperature, but reducing propionic acid seems like it would be somewhat difficult. I say this because it is soluble in water and therefore would be
dissolved by the the water in the HCL (or other acid) solution.
Would my only option be to add HCL (or other acid) to the calcium propionate then distill off the water, or is there a more elegant solution?
I should add that the article makes no mention to a solvent (because the propionic acid is used as the solvent?)
Attachment: 000512508-davis (2).djvu (92kB)
This file has been downloaded 1158 times
[Edited on 23-6-2014 by schrodingers_hat]
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leu
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Using:
http://www.sciencemadness.org/talk/search.php?fid=10
should have found:
http://www.sciencemadness.org/talk/viewthread.php?tid=6347&a...
There's other threads on this subject on this web site and elsewhere that would provide more information  The end really does result from the effort applied 
Chemistry is our Covalent Bond
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solo
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.....this might be of some help,
http://chemistry.mdma.ch/hiveboard/newbee/000512508.html
...here´s the article quoted,
Decarboxylation Studies. II. Preparation of Alkyl Phenyl Ketones
Charles Granito , Harry P. Schultz
J. Org. Chem.
1963, 28 (3), pp 879–881
DOI: 10.1021/jo01038a521
[Edited on 23-6-2014 by solo]
Attachment: Decarboxylation Studies. II.Preparation of Alkyl Phenyl Ketones.pdf (425kB)
This file has been downloaded 1610 times
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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Mildronate
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Anbody have some results with this method? I actually doesnt like steam destilation is it possible to use extraction insead of steam destilation?
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leu
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The reaction mechanism is discussed in:
The Mechanism of the Ketonic Pyrolysis of Calcium Carboxylates C. C. Lee , J. W. T. Spinks J. Org. Chem., 1953, 18 (9), pp
1079–1086 DOI: 10.1021/jo50015a003
which is attached Clearly more study is needed very badly since the article has
already been downloaded hundreds of times in the previous thread  The end
really does result from the effort applied
Attachment: jo50015a003.pdf (227kB)
This file has been downloaded 2920 times
[Edited on 24-6-2014 by leu]
Chemistry is our Covalent Bond
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schrodingers_hat
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Thank you Leu. That article cleared everything up. As for the other articles,
Decarboxylation Studies. II.Preparation of Alkyl Phenyl Ketones.pdf
http://www.sciencemadness.org/talk/viewthread.php?tid=6347&a...
are the exact article i attached which makes no reference to solvent used.
That being said, I am still grateful for all of the input. Thank you
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Paddywhacker
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No solvent is used, but maybe the yield would improve if a suitable one was. Maybe a eutectic salt mixture.
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Mildronate
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Maybe its posble to put benzoic acid, Fe powder and propionic acid in steal pipe and heat, actualy why need solvent propionic acid is liquid? I am
interested is its posible to extract propiophenone after heatingwith some solvent , because i dont like steam destilation.
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ChemPlayer_
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I recently tried this using calcium benzoate and calcium propionate. These were both separately prepared then oven dried and mixed in a 2:1 molar
ratio of benzoate:propionate, then oven-dried again before being dry distilled in a 500ml flask (110g of mixed salts used).
It took a lot of direct heat on the flask to get the distillate over, but quite a lot was obtained. The resulting liquid was distilled again but even
though the high fraction was coming over in a relatively short temperature range, it was seemed a bit impure (bright yellow in colour, too low in bp
to be pure propiophenone, and slightly wrong scent).
My conclusion was that if there's a good way to separate a really pure product (precise fractional distillation perhaps) from this then it's a
relatively easy and OTC method, but at the cost of risking damaging glassware.
Video of the entire process: https://www.youtube.com/watch?v=WrM7MGMI2uw
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hyfalcon
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Chromatography column. I have no idea which solvent to use for this though. Let some of the other more knowledgeable chime in here.
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Pumukli
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I'm not more knowledgeable but accidentally came across this article. It does use an inert solvent and a Fe-based catalist, treating both as trade
secrets though. :-)
LINK
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byko3y
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Pumukli, catalyst is Fe3O4, solvent is Downtherm A.
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Pumukli
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Thanks, byko3y.
May I ask how do you know that? Are you one of the authors? :-)
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clearly_not_atara
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He knows Google-fu.
http://onlinelibrary.wiley.com/doi/10.1002/adsc.201000429/ab...
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vannylaholic
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Would dry distillation calcium glycolate and calcium benzoate yeild mandellic acid?
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Chemi Pharma
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No, you will get major quantities of a keto-alcohol: 1-phenyl, 1-oxo, ethanol-2, and minor quantities of 1,3 dihidroxyacetone, a keto-diol, and
diphenyl ketone.
You'd better read again the article Leu had posted above in this thread as an attachment in PDF format: The Mechanism of the Ketonic Pyrolysis of
Calcium Carboxylates C. C. Lee , J. W. T. Spinks J. Org. Chem., 1953, 18 (9), pp 1079–1086 DOI: 10.1021/jo50015a003
[Edited on 17-10-2017 by Chemi Pharma]
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draculic acid69
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I think these rxn's are better run in steel vessels or modified paint/solvent tins.
glass is no good for the temps needed (450'c ish for calcium salts) and the residue can fuse to the glass causing cracking as it cools.look at the
NaOH/benzoate to benzene method.maybe the fe salts can be done in glass ( article says 180'c ish) but what kind of residue is left after the
distillation.ppl who have successfully done these rxn's w/lead found steel vessels and a slight vacuum increased yields by helping pull the product
over From the lava like conditions,I imagine it would help when doing calcium or iron variations as well.no need to use expensive fragile glass for
these rxn's.
[Edited on 15-8-2018 by draculic acid69]
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