El_Zorro (Hive Addict)
11-20-02 23:57
No 381677
      Zincorganic MDP2P from piperonyl chloride  Bookmark   

Alright, I'll admit it.  I can find no comfortale source of sassy.  It's just too fuckin' scary for me now.  So what am I gonna do?  I'm gonna find another way of making MDMA.  I have seen several ways to do it, and I haven't seen too many appealing ones.  There's the neverending eugenol-->safrole synths, but frankly, I just don't give a fuck anymore.  It seems to me like it's just one more step that will have to be done, and as of yet, no one has come up with anything but low yeilding steps.

The only thing I can think of is synthing MDP2P from catechol, after methylation to 1,3 benzodioxole.  I don't want to synth safrole, because that's just added steps.  I'm looking for a synth that doesn't go through safrole, and has the least amount of steps as possible.

The one that keeps sticking in my head is the grignard reaction on benzyl chloride using acetonitrile, resulting in P2P after hydrolysis.
../rhodium/chemistry /phenylacetone.html#ephedrine
../rhodium/chemistry /grignardnitrile.html

I think that if the reaction works as advertised, it means just three steps from catechol to MDP2P, with methylation and then chloromethylation.
[url=../rhodium/chemistry /methylenation.html[/url]
Post 321291 (Antoncho: "An interesting chloromethylation procedure", Chemistry Discourse)

I didn't think that this could be a viable production synth, though, because of the grignard angle.  I don't think that grignards are a real option for most clandestine labs, given the fact that everything has to be very anhydrous, or the whole thing fails.  It might not be that bad for a small batch, but think of the risk of trying to put out a batch of over 500g.  IMHO, there's just too much risk of a failed reaction.  I just wouldn't take the risk.

But after I read Post 346231 (Antoncho: "Zealot: a new zincorganic synthesis of P2P's", Novel Discourse), I thought that this might be a very viable option.  Now, what are everyone's opinions on this reaction?  I remember someone mentioning that other reagents besides acetonitrile can be used to get the P2P, is that correct?  Does this reaction actually work?  Has anyone actually tried it?

It is seductive, way too seductive.             -Eleusis
 
 
 
 
    moo
(Hive Bee)
11-21-02 01:35
No 381707
      For the zincorganic synthesis you need ...  Bookmark   

For the zincorganic synthesis you need 3,4-methylenedioxyphenyl iodide, piperonyl chloride has one carbon too much. This of course is no obstacle given that both preparations needed benzodioxole. I doubt Zealot would claim yields and go on telling the reaction works well if it hadn't been tried. Even though some people have worked with bromoacetone without dying, is that really a risk worth taking at all, not to mention 500g batches?
 
 
 
 
    El_Zorro
(Hive Addict)
11-21-02 22:16
No 381940
      No, you misunderstood the reaction I was talking ...  Bookmark   

No, you misunderstood the reaction I was talking about.  I wasn't talking about using a substituted iodobenzene and bromoacetone, I was talking about using piperonyl chloride and reacting it with acetonitrile, which gives the P2P after hydrolysis.

It is seductive, way too seductive.             -Eleusis
 
 
 
 
    moo
(Hive Bee)
11-22-02 17:12
No 382256
      I see  Bookmark   

I got the urge to go to the library to have a look at how well do organozinc reagents react with nitriles and it doesn't look too good. The only successful example of such reaction in the literature seems to be the reaction between diallyl zinc, which is extremely reactive for a organozinc reagent, and acetonitrile.

In my opinion reacting piperonyl magnesium chloride with acetonitrile in the presence of 2 molar % of CuCl or CuBr as referenced in Post 308361 (PrimoPyro: "Grignard P2P Synthesis: Catalysts", Chemistry Discourse) looks good. The cupric salt makes the reaction much faster.
 
 
 
 
    El_Zorro
(Hive Addict)
11-22-02 22:09
No 382351
      Hmm... How can you add a Cu(I) salt to an ...  Bookmark   

Hmm...  How can you add a Cu(I) salt to an ether/toluene solution?  Is it only suspended, or what?


But I'm far more interested in the zincorganic reaction than the grignard, namely because of the greatly increased ease of drying the solvents.  This means two things to me: less risk of a failed reaction, and greater ease in scaling up.  Not to mention the rise in degree of OTCness once the anhydrous ether is cut from the equation.

But what I want to know is, does anyone know if the zincorganic reaction will work or not?  If not, I guess it'll come down to raw experimentation.  But if it's at all possible, I'd like to get some thoughts from you bees.

It is seductive, way too seductive.             -Eleusis
 
 
 
 
    Rhodium
(Chief Bee)
11-22-02 22:47
No 382359
      copper(I) addition to organometallic compound  Bookmark   

You grind the copper salt in a mortar to a fine dust, and drop it into a well stirred solution of the organometallic compound, preferably chilled to around 0C to minimize side-reactions. After 10 minutes of further stirring, the metathesis is completed.
 
 
 
 
    moo
(Hive Bee)
11-23-02 07:39
No 382504
      Zincorganic reaction  Bookmark   

The reaction of diallyl zinc with acetonitrile gave 47% if I remember correctly. It would be hard to imagine getting better yields with dibenzyl zinc given the fact that it has poorer reactivity, but there is only one way to find out. The poor reactivity of nitriles even towards grignard reagents was the problem those reseachers wanted to solve and found the cuprous salt catalyst. Acetic anhydride should be fine though, I guess that reaction could be done with toluene as solvent.
 
 
 
 
    El_Zorro
(Hive Addict)
11-23-02 22:29
No 382646
      Rhodium, I thought I saw a post of yours not too ...  Bookmark   

Rhodium, I thought I saw a post of yours not too long ago where you said that there were other reagents that could be used besides acetonitrile.  I think they were along the lines of acetaldehyde, acetic anhydride, etc.  I can't seem to find the post now, though.  Am I confused?

It is seductive, way too seductive.             -Eleusis
 
 
 
 
    Rhodium
(Chief Bee)
11-23-02 22:39
No 382650
      Esters, carboxylic acids, nitriles, acid ...  Bookmark   

Esters, carboxylic acids, nitriles, acid chlorides and anhydrides can form ketones with organometallics, aldehydes forms secondary alcohols (acetaldehyde gives P2Pol with benzylmagnesium halides).
 
 
 
 
    El_Zorro
(Hive Addict)
11-23-02 22:44
No 382652
      So you're saying that the infanitely more OTC ...  Bookmark   

So you're saying that the infanitely more OTC glacial acetic acid can be used instead of acetonitrile, and it might even be more reactive towards the zincorganics?

Well, I guess you didn't say anything about how reactive it would be, but still, I'm just getting kind of excited.cool

It is seductive, way too seductive.             -Eleusis
 
 
 
 
    Rhodium
(Chief Bee)
11-24-02 10:53
No 382777
      Carboxylic acids do not react with grignards ...  Bookmark   

Carboxylic acids do not react with grignards favorably (you mostly end up with a tertiary alcohol), but they do with methyllithium.

So, starting with phenylacetic acid, you can easily synthesize P2P:

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p0775