FriendlyFinger (Hive Bee)
07-15-03 19:33
No 447654
      Propiophenone via carboxylic acid & tosic ??  Bookmark   

Antoncho posted this a while ago; Post 400120 (Antoncho: "A _possibly_ ABSOLUTELY BEST way of F-C'ing", Chemistry Discourse)

"Looks like all we need to make aceto- and propiophenones from all sorts of stuff is:

a) Tosic acid (make some yourself from toluene and H2SO4)
b) Dean-Stark trap"

Patent US5041616

"I have discovered that aryl ketones may be obtained by heating a carboxylic acid with certain aromatic compounds in the presence of (1) a volatile, organic compound which forms an azeotrope, i.e., a constant boiling mixture, with water and (2) a catalytic amount of an organic sulfonic acid, whereby the water of reaction is removed as an azeotrope from the reaction mixture. "

"The carboxylic acid employed is not critical and may be selected from a wide variety of unsubstituted and substituted, aliphatic, cycloaliphatic and aromatic carboxylic acids containing from 2 to 20 carbon atoms."

"...Phenols and benzenediols, as well as ethers and esters thereof, may be acylated using methanesulfonic and toluenesulfonic acids. In the case of less reactive aromatic compounds such as alkylaromatic compounds, e.g., toluene and xylene, a more acidic sulfonic acid such as a perhaloalkylsulfonic acid, e.g., trifluoromethanesulfonic acid normally is required to achieve satisfactory reaction rates."

Hydroquinone (11.0 g, 0.1 mole), octanoic acid (30.2 g, 0.21 mole), heptane (110 mL), and methanesulfonic acid (10 mL, 0.14 mole) were heated at reflux ( C.) for 5 hours in a 300 mL flask equipped with a Dean-Stark trap. During this time, 3 mL of water was collected. The sulfonic acid layer was separated, and the heptane layer was washed once with 50 mL of water and twice with 50 mL portions of saturated, aqueous sodium bicarbonate solution. The mixture was filtered to remove 5 g of product, octanoylhydroquinone octanoate ester, while evaporation of the organic layer gave 17.3 g. The total yield of octanoylhydroquinone was 22.3 g, 94% of theory.

In layman's terms, does mean that all I need to make plain old propiophenone is benzene, propanoic acid and tosic acid?

(Active Asperger Archivist)
07-15-03 20:25
No 447673
      Ummm...  Bookmark   

...Yes.   If you have hydrogenation facilities, this fits well with:

Post 447186 (Aurelius: "Ephedrine by reductive amination [GB302940]", Stimulants)

Act quickly or not at all.
(Hive Bee)
07-16-03 17:03
No 447874
      That's slightly depressing news.  Bookmark   

That's slightly depressing news. Because  I don't understand how to do it. You mention in your link that there are several easy way to make the phenone with OTC chemicals except for benzene. The only methods I'm aware of is;

Propanoyl Chloride + AlCl3 + Benzene or
Polyphosphoric acid + propanoic acid + benzene.

Polyphosphoric is expensive and from what I've read, hard to make, not OTC. None of the others are OTC, unless I'm totally wrong.


Be joyful, though you've concided the facts!
(Active Asperger Archivist)
07-16-03 22:06
No 447933
      methods  Bookmark   

Those methods aren't as un-OTC as you think.  Nor are they as hard as you think.

the acid chlorides can be made from the acid and trichloroisocyanuric acid (cheap and OTC).

The anhydrides can be made from the chlorides.

Polyphosporic only requires phosphoric acid, a heating source and a vacuum.

Propanoic acid (propionic acid) can be made by haloform reaction of MEK, acidification, extraction, removal of solvent, distillation.

Not to mention the method you just posted.  Other than the benzene, you should be set to go.

Act quickly or not at all.
(Hive Bee)
07-17-03 03:51
No 447999
      Well ok, that makes feel a little better.  Bookmark   

Well ok, that makes feel a little better. Let's see if I understand this. I can make Propinoyl Chloride from Propionic acid and Pool pills.

This is all I found here;

"Propionyl chloride was prepared not only by the usual methods with phosphorus bichloride or phosphorus pentachloride, but also by the chlorination of propionic acid in the cold with sulfur monochloride present.

To 540 g of propionic acid, 245 g of sulfur monochloride was added and chlorine was passed through the mixture while it was stirred for 15 hours. The chlorination proved to be incomplete at this point, since 150 g of unchanged propionic acid was recovered. There  was also considerable sulfur monochloride, which was removed from the propionyl chloride by treatment with hydrogen sulfide. The  propionyl chloride obtained amounted to 250 g. This product functioned as satisfactorily in the subsequent preparation of propiophenone as that prepared by the phosphorus halide methods
[1] JACS 44, 1751-1752 (1922)"

Can someone point me to a reference or a proceedure and I'll take it from there.

Thanks for the reply,

Be joyful, though you've concided the facts!
(Active Asperger Archivist)
07-17-03 07:12
No 448029
      Correction  Bookmark   

I apologize, I was wrong on the name of the reagent, not trichloroisocyanuric acid, but cyanuric acid.

Post 382242 (Rhodium: "trichloroisocyanuric acid - cyanuric chloride", Novel Discourse)
Post 383271 (Aurelius: "Cyanuric chloride: -COOH to -COCl/COOR/CONR2", Novel Discourse)
Post 383284 (Aurelius: "Mechanism", Novel Discourse)

Act quickly or not at all.
07-17-03 07:34
No 448034
      Take a look at the newbie forum  Bookmark   

I posted some stuff on propiophenone.
I dont want to repost it again here for no reason.

Industrially, propiophenone is synthesized two way:

Propiophenone is produced by Friedel Crafts acylation of benzene with propionic acid chloride in the presence of an equivalent amount of aluminum chloride [99]. Another industrial method is the catalytic ketonization of benzoic acid with propionic acid over a calcium acetate aluminum oxide catalyst at 440 520 C Post 100 (not existing).

[99]  A. I. Vogel, J. Chem. Soc. 1948, 614.

Taken from Ullman's encyclopedia of industrial chemistry

Edit: its good you corrected me, i posted in the chemical and equipement forum
Post 448028 (not existing)
(Active Asperger Archivist)
07-17-03 09:27
No 448055
      Linking  Bookmark   

So why didn't you just create a link to the other post?  you already took the time and effort to create your last post mentioning it.  Why not include the link?

Act quickly or not at all.
(Active Asperger Archivist)
07-23-03 20:33
No 449395
      Propionic acid  Bookmark   


Example of chloroform (and acetic acid) with the haloform reaction:
../rhodium/chemistry /chloroform.html

MEK reacted with the hypohalite ion, OXl- ,from M+n(OXl-)n, effects the haloform reaction.  (halogination, oxidation, cleavage) This cleavage will give you the salt of propionic acid containing a metal cation, M+n, as the counter ion.  Also a haloform (thus the name of the reaction) will form.  The haloform will be that of the halide, X, such as chloroform formed by the use of a hypochlorite, OCl- ion.  (This is also a method for the production of chloroform, iodoform and bromoform for the clandestine chemist.) The haloform is removed and distilled to purify and then placed in a amber, tightly-capped bottle.  The aqueous phase is separated, evaporated to give the appropriate salt of propionic acid.  This is again acidified with concentrated sulfuric acid:
Post 445659 (Aurelius: "Preparing Weak Acids from Salts and Strong Acids", Chemistry Discourse)
and distilled:
Post 445906 (Aurelius: "Acid Reagents Physical Properties", Chemistry Discourse)
to obtain the propionic acid.  This acid is redistilled for better purity.

Act quickly or not at all.