Righto - thanks in a massive part to Psychokitty (a large part of this is built directly upon her research, such as for example this) and in no small part to others (Java and Psycho Chemistfor instance), this was worked out:

(1) Propiophenone¹ can be brominated with Cupric Bromide(CuCl₂), but what to do with the a-bromopropiophenone?²  (per attached - Bromination.Cupric.Bromide) quite readily (separation of Cuprous Bromide is via filtration - see the first paper - "Bromination.Cupric.Bromide.pdf")

From the third paper ("iodide.catalysis.of.dmso.oxidation" - attached - page 2)

2-Bromocyclododecanone

Cyclododecanone (9.1 g, 0.050 mol), chloroform (50 ml), and ethyl acetate (50 ml) were placed in a 250-ml three-necked flask equipped with magnetic stirrer, nitrogen inlet tube, and reflux condenser. Powdered cupric bromide (22.3 g, 0.10 mol) was added in small portions over a 2-hr period, with the reaction mixture maintained at 75-80' while a constant
stream of nitrogen gas was bubbled through the reaction solution. The green color from each portion was allowed to disappear before the next portion was added. After the addition was completed, the solution was heated for 1.5 hr until the green color and dark cupric bromide disappeared, cooled, and filtered, and the colorless solid cuprous bromide was washed with 25 ml of chloroform. The combined filtrate and washings were rotary evaporated and the oily residue was redissolved in 200 ml of diethyl ether, washed with water (50 ml), 5% sodium bicarbonate (2 X 50 ml), and brine
(50 ml), then dried over sodium sulfate. After filtration, rotary evaporation of solvent, and cooling (-lo'), the resulting oil solidified to give cream-colored crystals (11.8 g, 90%) of 2-bromocyclododecanone, mp 52-53' (lit.I7 mp 53-54']. The product could also be recrystallized from pentane at -78'.

...

[NOTE - the result below was presumably gained using the above procedure]

a-Bromopropiophenone was prepared on the 100-mmol scale (addition 1.5 hr, stirring 1.5 hr): yield 95%; bp 64-66' (1 mmHg) [lit.22 bp 110-111' (3 mmHg)].

(2) 2-Bromopropiophenone (aka a-bromopropiophenone) is used to alkylate Methylamine (per Hyde, et al - see attached) to give Methcathinone in FUCKING good yield:

From page 4 (ie 2290) of the attached paper - "Synthetic.Homologs.of.Ephedrine.Hyde.etal":

Reaction of the Bromo Ketones with Methylamine.

One-tenth of a mole of the bromo ketone was added drop-wise with vigorous stirring to 0.25 mole of methylamine (in the form of a 30% solution in absolute alcohol) over the required period of time (one hour for bromopropiophenone, seventeen to eighteen hours for a-bromobutyrophenone, twenty-four hours for a-bromovalerophenone). The reaction flask was immersed in ice water during the reaction and stirring was continued for one-half to three-quarters of an hour after the addition of the bromo compound. Cold, coned. hydrochloric acid was then added very slowly along with some finely cracked ice until the mixture was acidic. If it became warm the product turned very dark in color and a larger proportion of tar was produced. At this point the reaction mixture was orange or red due to the presence of some bromo ketone that had not reacted and to the formation of certain tarry by-products. These were extracted with ether from the water layer and the bromo ketone recovered. The water layer was evaporated to dryness in vacuo, treated
with a little chloroform and evaporated to dryness again to assist in removing the moisture from the rather hard mass.

After standing in a vacuum desiccator for a day, the residue was extracted several times with fresh portions of chloroform and each time the insoluble crystals of methylamine hydrochloride^a were filtered. The chloroform solution was then evaporated until it was very concentrated, and acetone was added to cause the crystallization of the amino ketone hydrochloride. Recrystallization was carried out by dissolving in a small amount of alcohol, filtering, and adding about
twice the volume of acetone in small portions.

^a The following note is at pages 2-3 (ie. 2288-2289): the method of purification of the a-methylaminopropiophenone is worthy of mention, since the purity is important for the success of the subsequent reduction. The reaction mixture containing a-methylaminopropiophenone hydrochloride and excess methylamine hydrochloride was evaporated to dryness in a vacuum. The crude mixture obtained was extracted several times with
chloroform, which left methylamine hydrochloride insoluble and dissolved the amino ketone hydrochloride. The latter was recrystallized and reduced by means of hydrogen and platinum-oxide platinum black to the amino alcohol.

Of note is the rather simplified separation of the product from the reagents.



¹ Doesn'tmattermuch / organikum repeatedly stressed that the best route to propiophenone was via the iron salts of benzoic & propionic acids (much as I did not & do not like the fuck - he did know his shit), but provided no ref's or details (that I know of at least). Nicodem has also suggested that the 3,4-methylenedioxybenzoic acid might be useful - (but whether that ether ring would survive thermal routes is far from clear).

² how to do this without having to isolate (or even come fucking close to) the lachrymatory 2-Bromopropiophenone (think tear gas apparently)?

(I don't think refluxing MeAm in ethyl acetate solution would be all that long-lived (strong-ish base with an ester? ), so what could be done)

PS With a decent route to propionic anhydride however, all routes to pretty much all propiophenones open up (thanks jon)

hey swin1u look for this book experimental organic chemistry?  by  H. Dupont Durst, George W. Gokel , ther is a chapter about bromination in ketones. when swin1u got the alfabromo ketone , look for the strike book page 152 to 158. to see the synthesis of cathinones

Other way is got pseudo  with sodium hipoclorite like in  the same  book experimental organic chemistry?  by  H. Dupont Durst, George W. Gokel , in the oxidations chapter they do a similar synthesis with other benzyl alcohol , and a ptc catalist.(swip like to try Benzalkonium chloride like ptc agent, http://en.wikipedia.org/wiki/Benzalkonium_chloride)

 ps : sorry about my bad english

Similar - but the use of the cupric bromide avoids having to handle bromine.  Also, if you have a look over @ WD you'll see where Java (who else) provided an article on the use of Cupric Chloride (it also uses Lithium Chloride - anyone able to work out why?) to form 2-chloropropiophenone which presumably could be used the same way.

As to the reduction - have a good look at the use of refluxing EtOH to affect transfer hydrogenation of ephedrine-type molecules with excess Ra/Ni - if we could only use the precipitated Nickel catalysts (Urushibara-type) then this could be a major route.

i've never heard of nickel catalysts and primary alcohols in transfer type reduction scheme there is however the meerwin ponddorf scheme as illustrated here.

http://en.wikipedia.org/wiki/Meerwein-Ponndorf-Verley_reduction

The MPV tends to fuck up with Ephedrines according to at least one report...(see attached - the aluminium isopropylate paper of course)

I also attached the paper on the CTH of mandelates and phenylpropionic derivatives by RaNi in refluxing EtOH (solvent & H donor)...

PS I seem to recall the yield was lower with methylamine... they cite 33% from the bromohydrin with a fucking old-school workup (ie. leave it for 28 days in the dark then work it up) to get dl-pseudoephedrine...

Still seems like something of a fuck around, especially given that the Ni/EtOH route might well reduce the Cathinone directly to the desoxyephedrine (according to the article given)

Righto - thanks in a massive part to Psychokitty (a large part of this is built directly upon her research, such as for example this) and in no small part to others (Java and Psycho Chemistfor instance), this was worked out:

(1) Propiophenone¹ can be brominated with Cupric Bromide(CuCl₂), but what to do with the a-bromopropiophenone?²  (per attached - Bromination.Cupric.Bromide) quite readily (separation of Cuprous Bromide is via filtration - see the first paper - "Bromination.Cupric.Bromide.pdf")

From the third paper ("iodide.catalysis.of.dmso.oxidation" - attached - page 2)

Quote

2-Bromocyclododecanone

Cyclododecanone (9.1 g, 0.050 mol), chloroform (50 ml), and ethyl acetate (50 ml) were placed in a 250-ml three-necked flask equipped with magnetic stirrer, nitrogen inlet tube, and reflux condenser. Powdered cupric bromide (22.3 g, 0.10 mol) was added in small portions over a 2-hr period, with the reaction mixture maintained at 75-80' while a constant
stream of nitrogen gas was bubbled through the reaction solution. The green color from each portion was allowed to disappear before the next portion was added. After the addition was completed, the solution was heated for 1.5 hr until the green color and dark cupric bromide disappeared, cooled, and filtered, and the colorless solid cuprous bromide was washed with 25 ml of chloroform. The combined filtrate and washings were rotary evaporated and the oily residue was redissolved in 200 ml of diethyl ether, washed with water (50 ml), 5% sodium bicarbonate (2 X 50 ml), and brine
(50 ml), then dried over sodium sulfate. After filtration, rotary evaporation of solvent, and cooling (-lo'), the resulting oil solidified to give cream-colored crystals (11.8 g, 90%) of 2-bromocyclododecanone, mp 52-53' (lit.I7 mp 53-54']. The product could also be recrystallized from pentane at -78'.

...

[NOTE - the result below was presumably gained using the above procedure]

a-Bromopropiophenone was prepared on the 100-mmol scale (addition 1.5 hr, stirring 1.5 hr): yield 95%; bp 64-66' (1 mmHg) [lit.22 bp 110-111' (3 mmHg)].

(2) 2-Bromopropiophenone (aka a-bromopropiophenone) is used to alkylate Methylamine (per Hyde, et al - see attached) to give Methcathinone in FUCKING good yield:

Quote

From page 4 (ie 2290) of the attached paper - "Synthetic.Homologs.of.Ephedrine.Hyde.etal":

Reaction of the Bromo Ketones with Methylamine.

One-tenth of a mole of the bromo ketone was added drop-wise with vigorous stirring to 0.25 mole of methylamine (in the form of a 30% solution in absolute alcohol) over the required period of time (one hour for bromopropiophenone, seventeen to eighteen hours for a-bromobutyrophenone, twenty-four hours for a-bromovalerophenone). The reaction flask was immersed in ice water during the reaction and stirring was continued for one-half to three-quarters of an hour after the addition of the bromo compound. Cold, coned. hydrochloric acid was then added very slowly along with some finely cracked ice until the mixture was acidic. If it became warm the product turned very dark in color and a larger proportion of tar was produced. At this point the reaction mixture was orange or red due to the presence of some bromo ketone that had not reacted and to the formation of certain tarry by-products. These were extracted with ether from the water layer and the bromo ketone recovered. The water layer was evaporated to dryness in vacuo, treated
with a little chloroform and evaporated to dryness again to assist in removing the moisture from the rather hard mass.

After standing in a vacuum desiccator for a day, the residue was extracted several times with fresh portions of chloroform and each time the insoluble crystals of methylamine hydrochloride^a were filtered. The chloroform solution was then evaporated until it was very concentrated, and acetone was added to cause the crystallization of the amino ketone hydrochloride. Recrystallization was carried out by dissolving in a small amount of alcohol, filtering, and adding about
twice the volume of acetone in small portions.

^a The following note is at pages 2-3 (ie. 2288-2289): the method of purification of the a-methylaminopropiophenone is worthy of mention, since the purity is important for the success of the subsequent reduction. The reaction mixture containing a-methylaminopropiophenone hydrochloride and excess methylamine hydrochloride was evaporated to dryness in a vacuum. The crude mixture obtained was extracted several times with
chloroform, which left methylamine hydrochloride insoluble and dissolved the amino ketone hydrochloride. The latter was recrystallized and reduced by means of hydrogen and platinum-oxide platinum black to the amino alcohol.

Of note is the rather simplified separation of the product from the reagents.



¹ Doesn'tmattermuch / organikum repeatedly stressed that the best route to propiophenone was via the iron salts of benzoic & propionic acids (much as I did not & do not like the fuck - he did know his shit), but provided no ref's or details (that I know of at least). Nicodem has also suggested that the 3,4-methylenedioxybenzoic acid might be useful - (but whether that ether ring would survive thermal routes is far from clear).

² how to do this without having to isolate (or even come fucking close to) the lachrymatory 2-Bromopropiophenone (think tear gas apparently)?

(I don't think refluxing MeAm in ethyl acetate solution would be all that long-lived (strong-ish base with an ester? ), so what could be done)

PS With a decent route to propionic anhydride however, all routes to pretty much all propiophenones open up (thanks jon)

Here is the first post - with suitable mods to the url's/hyperlinks - I'm unable to modify the original post - maybe one of the mods could sub this for it?