jimwig (Hive Bee)
05-31-03 13:52
No 436844
      some old info on propionic acid  Bookmark   

this information was found by searching volume by volume in the journal of the chemical society. if interest warrants i will type relevant details - for now just the titles. Unfortunately none of the years were included in retrosight.
But they are all from the early volumes - about 2 through 20.

NOTE: these articles do not appear in any CA that I have searched.

Production of propionic acid by means of carbon oxide-  Berthelot page 614

Propionic acid- Pierre and Puchot page 615

Formation of propionic acid from carbon oxide and potassium or sodium ethylate - Hagemann - page 143

Synthesis of n-propyl alcohol - Linnemann - page 234

A new synthesis of propionic acid - van't Hoffman - page 141

On barium ethylate and the formation of propionic acid from carbon monoxide - Berthelot - page 246

Synthesis of n-propyl alcohol from ethyl alcohol - Rossi - page 1030

Prepatation of propionic acid from lactic acid - Freund - page 54

Propionic acid - Renard - page 275 (from ACS) no date
(Hive Bee)
05-31-03 15:09
No 436857
      Yes, I 'm most certainly interested.  Bookmark   

Yes, I 'm most certainly interested.  Please elaborate.
(Hive Addict)
05-31-03 15:57
No 436864
      what about sodium propionate  Bookmark   

it's used as a preservative in the breadmaking industry, can't you just react that with H2SO4? and distill?
05-31-03 18:17
No 436882
      sorry... excuse my ignorance...  Bookmark   

sorry... excuse my ignorance... but for what purpose you you require propionic acid?  just as a substitute for GAA?
05-31-03 18:45
No 436886
      propionic acid.  Bookmark   

Bones, i think (s)he's working on new pickling techniqueslaugh

A new synthesis of propionic acid - van't Hoffman - page 141

is that a proc for hypohalite oxidation of MEK? - that would be very useful since MEK is everywhere. Whats the volume No.?,
(Hive Bee)
06-01-03 04:11
No 436956
      sorry... excuse my ignorance...  Bookmark   

sorry... excuse my ignorance... but for what purpose you you require propionic acid?  just as a substitute for GAA?

Propionic acid is used to pickle several analgesic precursors (to obtain for example the reversed ester of phenoperidine
http://webhome.idirect.com/~schapman/g616.gif  <-- phenoperidine
In the reversed ester, the -CO-O-Et group is replaced by a -O-CO-Et group, which increases analgesic activity exceedingly).  Phenoperidine itself is 25 - 50 x morphine.

A haloform reaction on MEK would indeed bee nice.  However, a possible side reaction is the alpha halogenation of the R group in R-CO-CH3.  Sometimes, these groups are even cleaved (JACS (1950) vol 72 p 1642).

Hence, an accurate procedure would bee wellcome.
(Hive Bee)
06-03-03 11:39
No 437587
      some details
(Rated as: excellent)

I typed all this in and then lost it all because this damn compooter system doesn't allow using the back key. Or some such bullshit. Pissed, I was.

In Org Syn Coll. (page541) there is procedure for Propionaldehyde. In that are a number of refs. All of them in English - NOT.

So if some teutonic speaking bee could get these and post them I think a major hurdle could be dealt with.

After reading the above referenced abstracts (Post No 436844) several stand out.

Propionic Acid - Pierre and Puchot (Ann Chim Phys [4] xxviii, 71-86)
Abst says "when powdered potassium dichromate is added gradually to a mixture of water, sulphuric acid and propyl alcohol, the principal product is propylic propionate, this being decomposed by caustic potash into propyl alcohol and propionic acid."
Formation of propionic acid from Carbon Oxide and Potassium or Sodium Ethylate -Hagemann (Deut.Chem.Ges. Ber. iv, 877)
says "A current of dry carbon dioxide was passed through a solution of 20 grams potassium or sodium in absolute alcohol for about about 20 hours. The acid was finally isolated in the form of silver salt, which analysis proved to have the composition of silver propianate." etc.
A New synthesis of propionic acid - van't Hoff (Deut.Chem.Ges. Ber. iv, 1107) says "On distillation of a dry mixture of potassium oxalate and sodium ehtylate, oily products pass over--------"
Preparation of Propionic Acid from Lactic Acid - Freudn (J.pr.Chem.[2],v,446-452) says "The formation of propionic acid by the action of hydriodic acid on lactic acid, orignally observed by Lauteman, has been confirmed by the author, who finds, moreover that this reaction affords a convenient mehtod for the preparation of propinoic acid."
"670grams of iodine are suspended in 140 grams of water, converted in hydriodic acid by means of hydrosulphuric acid, and the hydriodic acid thus obtained is placed in a retort with 60 grams of lactic acid, after which the mixture is distilled until about 100 grams of liquid have passed over. A condensing tube being now adapted to the apparatus, the contents of the retort are digested for about four hours, when the iodine, which is by this time has crystalised in the condensing tube, is washed back into the retort with the 100 grams distillate previously drawn off, and hydrosulphuric acid is passed through the mixture in order to rehydrogenise the free iodine. The deposed sulphur being removed, 100 grams are again distilled off, the contents of the retort are diges during another period of four hours, and this series of operation repeated six or seven times, the whol of the lactive acid being converted into propionic acid, almost the whole of which is contained the 100 grams drawn off after the last digestion. This distillate is now mixed with 50 grams of water, adn distilled as long as the contents of the receiver contain only traces of hydriodic acid; tyhe distillate is then neutralized  with sodium carbonate, and sufficient liquid propionate is added to convert the sodium iodide into sodium propionate, The solution is then evaporated, and the dry sodium propionate is decomposed with hydrochloric acid gas, as directed by Linneman. (Ann.Chim.Pharm.,cix,197)

Lactic acid when treated in this way yields about 62 per cent pure sodium propinate."
Priopinoc Acid - A.Renard (Compt.Rend.,103,157)
says "This acid is yielded in considerable quantity by the destructive distillation of colophony (gum rosin)."
Synthesis of normal alcohol from ethyl alcohol--Rossi (Gazetta chimica Italiana,i,230-239)
says "Propionic acid, prepared by heating ethyl cyanide (propionitrile) with pulverised potash in an appartus with reversed condenser, as long as almmonia is given, off and deomcosing the resulting potassium salt with dilute sulpuric acid, is converted into a calcium salt; and an intimate mixture of this salt with an equial weight of calcium formate, dried at 100 degrees, is subjected to  distillaiton by small portions at a time (10 to 12 grams) in a retort uniformly heated over a charcoal fire, and connected with a receiver cooled by a freezing mixture. " etc. goes on to talk about propyl alcohol and propyl compounds.

The synth from rosin and the one from lactic acid are very interesting. I will attempt to find more info in CA.