lugh
(Hive Bee)
08-02-01 23:35
No 200865
      DEA Hype
(Rated as: good read)
    

Those that seek another route to methamphetamine should study Patent GB782887, it describes a process that Del Cason states that can't work, perhaps Adolph Opferman knew something that Mr. Cason didn't, example one states:

"44 grams of acetaldehyde are dropped slowly, with constant stirring, into 100 grams of benzylmagnesium chloride dissolved in 150 cc of absolute diethyl ether. The temperature rises slowly to 50 degrees C, which is kept constant for two hours. the magnesium alkoxide is treated with gaseous methylamine for three hours. The reaction product is cooled slowly, and then extracted with ether, the ethereal solution is dried over magnesium sulfate, the ether carefully removed and pervitin is obtained as a residue."

Undoubtedly this reaction requires rigrously anhydrous conditions. Since the yields aren't given, it's quite possible that they leave a lot to be desired. The lesson that can be learned from the existence of this patent is that one's enemies can't be trusted to tell the truth, or as it said on the streets, "Don't believe the hype!"smile
 
 
 
 
    Rhodium
(Chief Bee)
08-03-01 00:49
No 200877
      Re: DEA Hype     

How could a magnesium alkoxide react with an amine to form a secondary amine? In that case, ammonia and magnesium methylate (from refluxing Mg in MeOH) could produce methylamine...

../rhodium/chemistry
 
 
 
 
    moo
(Hive Bee)
06-25-04 05:54
No 515278
      The German equivalent     

In Patent DE1025876 also referenced in Hyperlab Post 404384 (fallen_Angel: "Одностадийный синтез первитина - ОТС.", Russian HyperLab) a yield of 75% is mentioned for this mysterious synthesis.

fear fear hate hate
 
 
 
 
    UncleFester
(Popular Author)
06-25-04 22:49
No 515403
      Dal kassen reference....     

I quit reading DEA lit about 10 years ago, but I believe he was referring to a Chewbacca Darth book recipe in which this same reaction, which dates to the 60's in an Italian lit reference, was wrongly transmitted in his book. I use that term because the subtitle of the book was "The Complete Transmittal"...in any case benzyl grignard reagent when scaled up is hell to work with, and I wonder about the side products, and separating them from the product...and that unreacted benzyl chloride...sounds like a horror show from my early college days.
 
 
 
 
    Organikum
(Wonderful Personality)
06-26-04 00:22
No 515426
      A question on the russian thread     

Might a russian speaking bee please tell if the by moo linked thread in the hyperlab actually mentions success with the Opfermann reaction?
I really dont want to rely on what I could interpret from the online translation I made, understandable I hope.

It was and is not understandable to me why publications of the enemy on drug synthesis are taken for valid information here at the HIVE. Forensic has its own - real clandestine - publication network for real information. What goes to public accessible journals will be "selected" information. And thats a most polite verbalisation of the facts. These forensic whores fool us. Thats the more explicite wording.

Anyways, Opfermann is well known in chemistry. Carson - who? Thats it. Articles written or payed for by certain agencies are no valid information. If you deny this you might think on the brain damage all this MDMA did to you already.....

Even if Carson was right here, what I doubt. This would change nothing what was told about the credibility of forensic or DEA et al financed publications.



But please - somebody answer my question, yes?
thanks
ORG

PS: The german patent names the yields: 75% It also names the results of the analysis of the product: 10,34% H theory, 11% H found in product after reaction without further purification. This is pretty pure, better than what comes out of a Al/Hg alkylation I bet. Far better.

Schnabufugl!
 
 
 
 
    UncleFester
(Popular Author)
06-30-04 04:17
No 516462
      back in the 70"s...     

I did the exact reaction shown in the first post...oh, what memories come back...such hell in a cell..meaning a little room...extract the product with ether??? there is already a massive ether solvent load...the problem is that adding methylamine,. even pretty dry methylamine...just makes a white mass in the flask...and none is extractable by ether, and none makes crystals when gassed...I think the original Italian lit said to add schiff's base of methylamine and actaldehyde to benzyl grignard reagent...That I may be tempted to try...the aldehyde addition to grignard is more likely to make aldol even before adding questionable methylamine...the torture still lives...
 
 
 
 
    UncleFester
(Popular Author)
06-30-04 04:40
No 516474
      your Uncle is a Dope...     

It's not an aldol that results as by-product from adding the acetaldehyde to benzyl grignard reagent...it is the diol centered upon the isopropyl side chain carbon. I made attempt to minimise this by bubbling acetaldehyde gas into the mix....still white solid upon addition of methylamine gas heated out of 40% aqueous methylamine...punish yourself at will...that benzyl grignard will chew you up when scaled.
 
 
 
 
    UncleFester
(Popular Author)
06-30-04 05:03
No 516478
      and the yield is...     

about zero....The grignard was good as was the acetaldehyde add...the methylamine may have been less than 100% water free, but it wasn't bad for 70's standards...back then we thought up stuff ourselves...and the reaction sucked.
 
 
 
 
    Rhodium
(Chief Bee)
06-30-04 05:06
No 516479
      P2Pol by benzyl grignard addition to acetaldehyde
(Rated as: excellent)
    

It's not an aldol that results as by-product from adding the acetaldehyde to benzyl grignard reagent...it is the diol centered upon the isopropyl side chain carbon.

Benzylmagnesium chloride and acetaldehyde results in a mixture of 1-phenyl-2-propanol and 1-(o-tolyl)-1-ethanol (the latter by rearrangement).
Arriving at a diol by reacting the two is impossible - there is only a single oxygen in the acetaldehyde molecule.

Reference:

The Reaction of Benzylmagnesium Chloride with Aliphatic Aldehydes
Samuel Siegel, William M. Boyer, Raymond R. Jay
J. Am. Chem. Soc. 73, 3237-3240 (1951) (../rhodium/pdf /p2pol.ch3cho-phch2mgcl.pdf)

The Hive - Clandestine Chemists Without Borders
 
 
 
 
    UncleFester
(Popular Author)
07-01-04 23:47
No 516794
      I am corrected...     

Back in the 70's, I was using as my source guide the book Grignard Reactions of Nonmetallic Sunstances, and it said a by-product would be the diol if the aldehyde was dripped in too fast, resulting in two aldehydes reacting with the grignard. I think that book predated this paper. In any case, half abnormal product even if the aldehyde is led in as gas...that reaction sucked, and I'll never do it again.
 
 
 
 
    UncleFester
(Popular Author)
07-02-04 01:07
No 516804
      that old dead goat Lewis...     

wasn't that far off, as the by-product is a diol, and the result of adding two aldehydes to the grignard reagent. His book was published in the late 1930's, and that may seem ancient, but it is for someone in the 70's looking at a 1960's paper now the same time span. I'm sure he had crude instrumentation, and the book covered thousands of reactions.
 
 
 
 
    azole
(A Truly Remarkable HyperLab Bee)
07-20-04 17:39
No 520426
      other anomalous reactions of PhCH2MgCl
(Rated as: excellent)
    

Ref. 5 from the above article (Post 516479 (Rhodium: "P2Pol by benzyl grignard addition to acetaldehyde", Stimulants)).

Some Rearrangement Reactions of Benzylmagnesium Chloride
H. Gilman and J. E. Kirby
J. Amer. Chem. Soc.
, 54, 345-355 (1932).


   Benzylmagnesium chloride undergoes rearrangement reactions with a variety of electrophiles. The rearrangement may be exclusively ortho, exclusively para or mixtures of ortho and para in varying proportions depending on the reactants and on experimental conditions. Carbon dioxide and some other reagents behave normally.

Electrophile PhCH2X, % o-TolX, % p-TolX, %
CO2 100 0 0
Br2 100 0 0
PhCN 100 0 0
PhCOCH2Cl 100 0 0
Ph2NCOCl 100 0 0
AcCl <100 traces 0
(CH2)2O 58 0 42
EtOCH2Cl 53 16 31
EtOCOCl ~80 ~20 0
HCO2Et ~94 ~6 traces
PhCH2Cl 100 0 0


   What is the selectivity of the reaction of PhCH2MgCl with MeCN? I don't know.

   To Organikum:

Might a russian speaking bee please tell if the by moo linked thread in the hyperlab actually mentions success with the Opfermann reaction?

   No, fallen_Angel has failed to reproduce the procedure from the patent (Patent DE1025876).
 
 
 
 
    acx01b
(Newbee)
10-25-04 18:34
No 537713
      hi mfs, Ph-CH2-MgX + CH3COCH3 ----(reflux then     

hi mfs,

Ph-CH2-MgCl + CH3COCH3 ----(reflux then h2o)----> 1,1-dimethyl-2-Phenylethanol
then this tertiary alcohol is reacted with 90% H2SO4 and urea, to yield after hydrolysis a-methyl-amphetamine

or:
Ph-CH2-MgCl + (CH3)2-C=N-CH2-CH3 (acetone-ethylamine imine) --> a-methyl-amphetamine

cause of the rearrangement of Ph-CH2 cation the yield would be around 40% ?
(Note by Rhodium: Another synthesis of methamphetamine by the Grignard addition to an imine has been reported by the italian researcher V. Emdokimoff3. The reaction of 2 eq. of benzylmagnesium chloride with acetaldehyde methylimine in diethyl ether followed by reflux and aqueous hydrolysis gave the desired amine in 40% yield (calculated on the imine). ../rhodium/chemistry /meth.phenylacetaldehyde.html