Hey vesp is a good idea , look the pdf

Hey vesp , there is a way to the thermolysis/pyrolysis of Clacium benzoate and Calcium propionate, look this pdf table 1 and 2

I also think it is a nice idea. It is strange, that i have never came accross it, and it seems a good option for propiophenone. Maybe the yield would not be too high, but the reagents are cheap

Tis a good idea albeit an old one. Posted a few times at the Hive and elsewhere...Nice one anyhow.

Search in the reference section at W.D and you will find a Ref posted by Java on thermal decarboxylation of said Iron salts to form the ketone.
Then of course the free acids themselves with a touch of catalytic help.

This step is the killer? Zn/hcl you reckon>?

Methcathinone (ephedrone) => Methamphetamine


If you have a copy of the HIve files,someone named either Pharmacist of FormerChemist IIRC posted a write up from methylone to MDMA.
Cant remember how he did it though...

Did you tried the method? By replacing calcium benzoate with the salt of piperonylic acid, one might easily get Methylone.

It may hold up to some degree but i can't imagine the yields being to high, and you'd likely get some nasty products forming from it decomposing making for an impure if not dangerous mixture at the end.

I've never tried it as I have neither benzoates, propionates, or a still that can handle the heat.

"I find it hard to believe it would stand up to a strong lewis acid such as AlCl3 at reflux"

As would I...
I suppose this is why he chose a weak Lewis acid in the form of elemental iodine.


NOVEL N-SUBSTITUTED-2-AMINO-3',4'-METHYLENE-DIOXYPROPIOPHENONES   

    

   JACOB PEYTON III; SHULGIN ALEXANDER T



EXAMPLE lB
Second (and Preferred) Route to the Intermediate Ketone
A stirred mixture of 39 g methylenedioxybenzene, 48 g propionic anhydride and 1.54 g elemental iodine was held at reflux temperature with a heating mantle for 3.5 h. The crude reaction mixture was freed of all volatiles that could be removed at 65"C, at the water pump, yielding 42 g of a heavy black oil. The distillate smelled strongly of propionic acid. (Attempts to purify or decolorize this thick crude product by acid, base, or bisulfite washing, were not successful.) The crude product was distilled at 0.1 mm/Hg. At 600C a sizable quantity of clear colorless liquid distilled over (the temperature was maintained until the distillation was complete and the distillate was flamed into the traps).

Between 100-125 C a pale brown fraction distilled over, weighing 28 g. This was dissolved in 200 mL methylene chloride and decolorized by washing with 2x600 mli water, each portion containing 1 g sodium bisulfite. Removal of the organic solvent under vacuum gave 27.1 g of a pale brown residue which was again distilled at 0.2 mm/Hg to give a fraction boiling at 90-1150C that was essentially white. This, on cooling, crystallized to give 3,4methylenedioxypropiophenone as a mass of off-white solids, weighing 24.46 g. Analysis by GC-MS showed a single sharp peak (about 97% purity) with a spectrum identical to the product from the Grignard reaction above. A reference sample without color was obtained by grinding a little of the distillate under a third its weight of cold methanol, followed by filtration.This sample had no detectable impurities by GC-MS.

http://v3.espacenet.com/publicationDetails/biblio?DB=EPODOC&adjacent=true&locale=en_gb&FT=D&date=19961212&CC=WO&NR=9639133A1&KC=A1

I may be wrong but I think the strength of the Lewis acid is substrate specific.

But here is an example showing the bridge standing up to AlCL3

Process for producing ?-chloro-?-(3,4-dihydroxyphenyl) propionitrile or an O-protected derivative thereof

http://www.freepatentsonline.com/3920701.html


To a mixture consisting of 12.2 g (0.1 mole) of 1,2-methylenedioxybenzene and 18.6 g (0.15 mole) of 2,3-dichloropropionitrile, 1.3 g of aluminum chloride anhydride was added and dissolved completely. 0.2 ml of 10% sulfuric acid was added thereto. The mixture was maintained at 100°C with stirring for 2 hours. And then a solution of 1.3 g of aluminum chloride anhydride and 3.1 g of 2,3-dichloropropionitrile and 0.1 ml of 10%-sulfuric acid was added thereto. A solution of aluminum chloride anhydride and 2,3-dichloropropionitrile, and 10%-sulfuric acid was added further three times at intervals of 30 minutes. The reaction mixture was reacted at the same temperature with stirring for the overall period of the above adding procedure. The mixture was stirred at 100°C for 30 minutes after the final addition, and was cooled. The resulting solution was treated by the similar manner as in Example 1 to obtain 13.4 g of ?-chloro-?-(3,4-methylenedioxyphenyl)-propionitrile as a fraction having a boiling point of 139° - 140°C/1.0 mmHg. The values of elemental analysis of this fraction agreed well with the calculated ones.



Sedit,out of curiousity,what did you have in mind? Chloroacetone,Acetic anhydride?

Vesp,sorry man,wasnt meaning to ignore your question,just caught it then for some reason.

Do you mean plain 1,Zn/Hcl or 2,Clemmenson? I dont understand why you suspect the amino ketone will reduce all the way to the amine with either. 1,to the alcohol and 2 ,no good on amino ketones(C-N cleavage I think)

Could be wrong.Cant remember,I havent looked at such things for quite a while.
What makes you think this would work?

I guess you could always turn the propiophenone into propylbenzene via clemmensen and do bromination, reduction, and all the other stuff from then on to get the compound.

This wouldn't work because bromination as described by the rhodium page only works with a carbonyl group as a synthetic handle. There are, however, electrochemical methods of reducing aromatic ketones. The birch reduction can also do this. Also, I don't see what you'd reduce once you're at the bromo propylbenzene.