In a world devoid of a sassafras oil source, eugenol is the answer my fellow bees. No, I have never attempted a demethylation of it, but I believe that it is possible. There are many potential ether-cleavage reactions out there. But, I have to admit that so far, the SIBX oxidative demethylation is probably the best one so far developed. Why? Because it is simple, the reaction scheme is straight-forward, and most importantly, it seems that allylpyrocatechol is the only product that you get out of the reaction. No byproducts, in other words. Also, THF can't be the only solvent that can be used. If one were to read the relevant articles on IBX chemistry, as I have, one would discover that virtually all solvents are suitable for these reactions. That leaves acetone, MEK, toluene, xylene, 1,1,1,-trichloroethylene, and numerous others, available for potential application in the demethylation process.
Another important point is that SIBX is the stabilized form of IBX. IBX was unstable in a few reported instances, and this made it unsuitable for expanded commercial use. However, since the recent stabilization of IBX, and since, as an oxidant, SIBX is very specific to particular functional groups, SIBX is likely to soon to find wide use everywhere, just as trichloroisocyanuric acid and oxone have. That, or SIBX will at least find use by virtually all researchers and industrialists who are looking for a specific and gentle oxidant to replace the current oxidants used in their industrial processes.
Another thing about SIBX is that it should be easy to get ahold of. It's simply too new. It's also not illegal and has so many potential uses as a general oxidant that it should present few obstacles for those who might be asked to present an intended use. "I'm going to see if it will work in place of the potassium dichromate oxidant that I regularly use in a patent pending photographic process that I've been developing, sir" or "None of your fucking business. I'm not inclined to share my multi-million dollar secrets with a sales clerk". A variation of either one should do. But if it's of any help, only once have I ever been asked for a notice of intended use. Stating a simple and generic reaction scheme was good enough in that instance.
As for using the SIBX reaction scheme to demethylate eugenol, I think it's most important for someone to actually be exposed to allylpyrocatechol to log its properties. Does it really smell like smoke? Is it stable under standard atmospheric conditions? I suspect that it is much more stable that some have led us to believe. For one, there is no need for a nitrogen atmosphere to distill it. And contrary to popular belief, I do not believe that it will freeze in the condensor under vacuum distillation. Why? Simply because it's freezing point is somewhere around 48 degrees C at atmospheric pressure. Notice how oils distill at a reduced temperature while under vacuum pressure? Well solids melt at lower temperatures while under vacuum pressure too. What will likely happen is what I have witnessed many times before when conducting similar distillations of oils that are solids at room temperature. They will distill under vacuum as oils, drip over as oils, and then, when the vacuum is released, after about thirty minutes, they will freeze. Then, to determine if one has the correct substance, apart from smell and/or taste, one could insert a thermometer into the crystal matrix, heat the fucker a bit, and when the mass of solids melts, record the temperature. This has worked every time for me for the identification of like substances.
As for the methylenation, go with the DMSO/DCM/NaOH reaction. The reason I say this is because it is so damned easy. It's, in my opinion, idiotproof. Granted, you need a decent magnetic stirrer to stir that fucker and you need a pretty good condenser to keep all of the vapor inside the reaction flask, but aside from the smell, which is just merely unpleasant (as opposed to horrid), it really is a fast, efficient, and facile process; furthermore, it's really not all that vigorous as stated in the write-up. Isolation of your product is also easy as the steam distillation is pretty straight-forward. You just add water to the mixture, simple distill as per usual, and the desired product -- and only the desired product (along with just a bit of DMSO, but this is no problem as it mixes cleanly with the water) -- comes over forming an oil that lingers below the surface of the water layer. The one time I tried this was when I synthesized benzodioxole. Thinking that it was maybe still impure, I distilled it afterwards, but the only fraction that came over was the benzodioxole, which indicates that the end product is very VERY pure. The process is detailed in TS II. The only difference that I could point out was that I noticed a slightly different color scheme than that reported in the holy book. But no big deal. Also, I felt I had to use more water for the steam distillation than was suggested in the write-up. While the application of this reaction to other methylenations MAY end in lower yields, it WOULD at least prove that the end product of the SIBX reaction is indeed the desired allylpyrocatechol.
For those that have so far been discouraged, don't give up hope. The eugenol demethylation IS the HOLY GRAIL of, well, you know what. (Heh, heh) Look what Methyl Man did with Ritter's variation of nitromethane/Al-Hg reductive amination (not to mention his use of methanol as the solvent in the benzo-wacker). And what about Chromic? I may have first reported the potential use of oxone in the epoxidation reaction of propenyl benzenes, but he worked out the experimental details. So too did he develop the homemade peracetic acid/glycolization reaction. These are just two examples of hard-core newbees that made major contributions here. Of course, there are many MANY other great members -- shit, too MANY to name here -- that have made great strides and gone against conventional thinking and wisdom to develop novel approaches to chemistry. And so too can you, newbees . . .
Any questions?
PK