Interesting. Any propositions on what one might do with it?

That butyl chain is going to be a problem, for much the same reason that the piperonal from piperic acid discussion has been beaten to death for years with no real progress. Oxidizing it down to piperonylic acid leaves us with the same problem as before concerning the difficulty and trouble of getting it back to (iso)safrole or piperonal.

"Piperonylic acid can just be decarboxylated to benzodioxole"

Interesting. How would one go about doing this?
 Ive know of people who tried the old caustic distillation method(tried formates for the aldehyde also) but no joy was to be had. Not that they expected much.
 
This looks a little nicer than I first thought.

"Piperonylic acid can just be decarboxylated to benzodioxole"

Interesting. How would one go about doing this?
 Ive know of people who tried the old caustic distillation method(tried formates for the aldehyde also) but no joy was to be had. Not that they expected much.

I don't know if acylative decarboxylations work with formates. I'm sure it'd be a documented reduction method since selectively reducing a carboxylic acid to an aldehyde has been a target of both clandestine and licit chemistry for aeons. I wouldn't expect the formate method to succeed with anything at all, even a highly labile acid like acetoacetate.

I'm also very surprised to hear that the distillation of sodium piperonylate with NaOH failed. I'd have to try it myself to believe it. It's probably worth pointing out that distillation of the calcium salt would be expected to give the benzophenone.

If I was trying to decarboxylate something where distillation had failed, I'd probably go for one of the Hunsdiecker variants, which are milder and more reliable:

http://www.4shared.com/dir/5526855/424dc959/Decarboxylation.html

(there are many many more in the literature; one of the interesting ones uses lead (IV) acetate and lithium chloride, another uses thallium, a third uses manganese (II) acetate, and so forth)

many of which depend on lithium, lead, or mercury salts and so avoid expensive and fulminate-forming Ag+. The resulting 5-bromo-1,3-benzodioxole can then undergo an easy reduction to benzodioxole or a conversion to the grignard or organolithium.

The organolithium/grignard would normally be unamenable to acetonylation via chloroacetone/bromoacetone since the carbonyl will react faster than the chlorine, however, there's a cool bit of organocopper chemistry I just learned today that avoids this:

http://en.wikipedia.org/wiki/Gilman_reagent

I personally would forgo the Gilman in favor of reducing to benzodioxole, though.

An additional possibility is the reaction of the bromobenzodioxole with ethyl acetoacetate and subsequent decarboxylation, again producing MDP2P. This nucleophilic aromatic substitution is also catalysed by copper (I) salts. Ethyl acetoacetate itself can be produced rather easily by the Claisen condensation of ethyl acetate, which isn't bad at all. Aaaaand... it's 4 AM here so I'm not going to even attempt to reference this. Caveat emptor!

We're discussing ways this butylated thing can be turned into MDMA, and the only route I see involves piperonylic acid. Piperonylic acid, therefore, is the topic, to some extent.

Now, MBDB, that's a different story, and could probably be done using a suitable dehydrogenating agent to dehydrate the alkane alpha-beta to the phenyl ring, then glycol -> ketone -> amine. But MBDB is boring.

I concede on the formate. My guess would have been the formate pyrolyses to carbon monoxide but apparently this is wrong.

Piperonylic acid can just be decarboxylated to benzodioxole, and then alkylated with acetol / ZnCl2 or allyl alcohol / ZnCl2 or Mn(OAc)3 or something. Both acetol and allyl alcohol may be obtained from glycerol. Acetol is additionally obtained by the distillation of sugars (like sucrose) with strong bases.

While that's true on a theoretical level, I don't know that a multistep from an impure natural product to benzodioxole through piperonylic acid does us any good, considering that catechol is OTC and can be methylenated with DCM in DMSO with 90% yields.

The trouble is putting something in that 5 position, so stripping everything completely off is somewhat counterproductive. We could brominate it and make the Grignard, but there are better ways of not putting oneself in that position.

I always saw the relative obscurity of piperic acid as a result of the relatively tiny quantities found in pepper, and the difficulty of purifying piperine relative to the volatile essential oils (e.g. eugenol / vanillin / safrole).

Well, fresh black and white peppercorns (Piper nigrum) are loaded with piperine, with the usual peppercorns of commerce being somewhere in the 5-7% range. P. nigrum oleoresin / essential oil usually is around 40% piperine. If a bee knows where to look, he can find commercially-oriented natural pepper flavoring extract, containing a whopping 90% piperine.

The piperine can be hydrolyzed to piperic acid and piperidine (don't get any crazy ideas, folks) with great yields.

The KMnO4 and dichromate oxidations of piperic acid give a terrible yield of the desired piperonal. Too much of our desired product is instead overoxidized to the troublesome piperonylic acid. Ozonolysis was suggested years back, although I don't think anything ever came of it.

If we had something to do with the piperonylic acid that would certainly change things quite a bit, because we can produce this in fantastic yields with the KMnO4 from a wide variety of sources.


On second thought, I don't mean to hijack this thread, but I didn't know if yet another theoretical pepper precursor thread would be welcome.