PrimoPyro (Sector G)
03-28-02 05:39
No 288978
      Propiophenones To Phenylacetones  Bookmark   

Here's an idea. Take a propiophenone, ArCOCH2Me, and halogenate it. As Rhodium showed me in a previous thread, it will halogenate next to the carbonyl. It can only halogenate at the methylene group, as the other group on the carbonyl is the aromatic ring, and will not undergo addition at that carbon.

So now you have ArCOCHXMe. Reduce the ketone to an alcohol, and then dehydrate the alcohol with a hydrogensulfate to the alkene: ArCH=CXMe.

Reaction of the halogen with a base such as hydroxide, or an amide, MOH or MNH2, would yield the enol ArC=C(OH)Me, which would tautomerize to the ketone ArCH2(CO)Me, which is of course a phenylacetone.

Alternatively, if a metallic amide was used, the enamine would tautomerize to the imine, which could easily be hydrolyzed to the ketone, or reduced if desired.

I got the idea as an extrapolation on the following text, so if my version will not work, then perhaps this is something to think about. smile

"Ketones, carboxylic esters (including lactones), and amides (including lactams) can be sulfenylated at the alpha position by conversion to the enolate ion with a base such as lithium N-isopropylcyclohexylamide and treatment of this with a disulphide. The reaction involves nucleophillic substitution at sulfur.

*   *   *

The alpha sulfenyl carbonyl compounds prepared by this reaction can be converted to alpha,beta-unsaturated carbonyl compounds (by reduction of the carbonyl to the alcohol, followed by dehydration, according to the picture scheme) The sulfenylation reaction has also been used as a key step in a sequence for moving the position of a carbonyl group to an adjacent carbon."

Then it shows the following, but as structural pictures, not text:

RCOCH2Me --> RCOCH(SPh)Me --> RCH(OH)CH(SPh)Me --> RCH=C(SPh)Me --> RCH2COMe

This effectively moves the carbonyl group one position in either direction that it is possible, determined by which side the sulfenyl group adds onto. In propiophenone, the only side it can add onto is the one and only alpha carbon, the middle methylene group of the aliphatic chain. This would of course reposition the carbonyl at this position, effectively transforming propiophenone into phenylacetone.

It cites OrgSyn VI, 23, 109; 688 for this specific concept, but I am unable to locate this entry on

I really think it is there, I am just being a retard and cannot find it with my queries. If someone could provide a link to that paper here, I'd be very thankful.

It sounds like this procedure is meant to be done in one pot, which would make for a cool P2P synthesis from propiophenone. This is better than synthing propenylbenzenes from propiophenones in my opinion. You are that much closer to the final product.


Vivent Longtemps La Ruche!
03-29-02 12:43
No 289562
      unnecessary work  Bookmark   

Nice idea, but think practical. Just react the alpha-bromopropiophenone with pyrrolidine and you have an active compound. Easy, clean and high yield synthesis with (in many countries) OTC precursors. Oh yes, the product is somewhat less potent than amphetamine but is this really a disadvantage? Use a somewhat higher dosage and everything is O.K.. Can you now imagine why this product was illegalized in germany in 1998 ?wink
(Sector G)
03-29-02 19:02
No 289684
      MDXA  Bookmark   

I was thinking about another angle for MDMA (and analogs) synthesis.

A catechol soup, a touch of propionic anhydride, and a dash of aluminum chloride. Extract, methylenate, voila: 3,4-methylenedioxy-propiophenone.

But of course your angle is viable as well. I assume this means that straight propiophenone is a watched chemical then?


Vivent Longtemps La Ruche!
(Her Majesty, Stoni's Kitty)
03-29-02 19:06
No 289685
      Yeah, but you'd have to go through ...  Bookmark   

Yeah, but you'd have to go through a-bromo-propiophenone and handle it several times.  Believe me, it's way too lacrymatory for this synthesis to be worthwhile.  YUCK!

Besides, something in my gut tells me that the carbonyl reduction--at least by way of aluminum isopropoxide; sodium borohydride might work--will result in low yields.  Also, I have yet to see any published information regarding the dehydration of the halohydrin. 

March 5th edition perhaps?
(Chief Bee)
03-30-02 09:18
No 289897
      Pharmacology?  Bookmark   

Are there any published reports on the pharmacology of alpha-pyrrolidinopropiophenone?
03-30-02 12:58
No 289977
      lacrymatory/pharmacolgy  Bookmark   

Oh yes, alpha-bromopropiophenone is lacrymatory. I handle this precursor always "open air" with rubber gloves and i dont have problems. The pharmacology of alpha-pyrrolidinopropiophenone can best be described as a "hybride" between (unsubstituted) amphetamine and diethylpropion/amfepramone. Not psychedelic at normal, moderate dosages, duration somewhat shorter than amphetamine.
(Her Majesty, Stoni's Kitty)
03-31-02 19:13
No 290619
      "Are there any published reports on the ...  Bookmark   

"Are there any published reports on the pharmacology of alpha-pyrrolidinopropiophenone?"

Uh, not that I know of but I have information as to the quality of the experience of the following compounds:

1.)  a-dimethylamino-propiophenone
2.)  a-pyrrolidino-propiophenone
3.)  a-pyrrolidino-MDpropiophenone

The last one was taken from a brittish patent detailing the pharmacology and synthesis of many methylenedioxy substituted a-pyrrolidino-ketones (all psychostimulants; safe); the butyrl- and valeryl-analogues seem the most promising.  There was one lone compound, g-3,4-methylenedioxyacetophenone, that seemed oddly out of place.

As for the synthesis of the above compounds, you'll have to talk to SWIM.

PM me.
(Her Majesty, Stoni's Kitty)
03-31-02 19:16
No 290621
      Sorry. That's supposed to be ...  Bookmark   

Sorry.  That's supposed to be g-morpholino-3,4-methylenedioxyacetophenone.
(Her Majesty, Stoni's Kitty)
03-31-02 19:32
No 290628
      Propiophenone is not a watched compound.  Bookmark   

Propiophenone is not a watched compound.

As for the synthesis of 3,4-methylenedioxy-propiophenone, methyleneate the catechol first (simple, according to SWIM) and THEN go on to acylating it with propionyl chloride (good and not too smelly, according to SWIM).  (SWIM used anhydrous ferric chloride as the lewis acid; it SUCKED balls as far as yield goes).  According to SWIM a dark syrupy liquid resulted which was distilled under reduced pressure to yield a light yellow liquid that solidified in the receiving flask.  Smelled good, according to SWIM.

Then go on to brominating the a- position with either straight-up bromine or CuBr2 ethyl acetate/chloroform solvent (preferred) which will yield a product that isn't even 1/4 as lacrymatory as the unsubstituted bromoketone. 

(Untested by SWIM) Drip the solution at 5 C into a 10% MeNH2 toluene solution.  Stir for an hour at that temperature and then let stand--yes, STAND--in the freezer for about 12-49 hours (depends on amount of MeNH2 and solvent dilution). . . .

The above description was taken from a CA reference that I can get if anybee is interested.

. . . Remove from freezer and then wash with water several times and then dry solvent, gas, filter crystals, and recrystallize.  Yield is about 48%.

SWIM has never tried going past the formation of the MD-bromo-propiophenone to MDMC.  Instead, in the one trial, the MD-bromo-ketone was used towards synthesizing the pyrrolidino analogue.

PM me.
(PVC-Analog Taste-Tester)
03-31-02 21:52
No 290691
      I think Nemo has provided us with some useful ...  Bookmark   

  I think Nemo has provided us with some useful information. Sooner or later, bees with enough cash to support their habit and experiment will check these synths

Love my country, fear my government.