Newsgroups: alt.drugs.chemistry From: [an 216208] at [anon.penet.fi] Date: Wed, 14 Feb 1996 10:11:36 UTC Subject: *ZWITTERION* - MDP-2-Pol from Safrole via H2SO4 Oxidation Just when you scurvy ridden freaks thought it was safe to surf A.D.C, ZWITTERION has returned, burned but not beaten! Actually, ZWIT is in PRETTY FUCKING GOOD SHAPE, especially after testing this new trick, courtesy of a mystery contributor in anon land. Thanks go to [AN 418658] at [anon.penet.fi] for sending the experimental details on a process long suspected of being a viable way to produce the alcohol precursor to that ever-loved ketone, MDP-2-P. ZWIT ain't gonna go into any heavy-hitting theory crap here, but a quick OverView of what we's gonna do will be given. Alright, so you have some leftover Instant Power (tm) drain opener sitting around, and you're considering maybe tossing some on the local cat that always shits in your yard. WAIT! Before you make a nasty stinking mess, try making some MDP-2-Propanol! Yes! Yummmmm! Doesn't that sound TASTY?!?!?! Whaddya gonna do with that, you may ask in your blissful ignorance? Well hold onto your Depends (tm) undergarments, because you can do a LOT with it. For one thing, it's EASY to make alcohols from alkenes, this document will prove it, and for another, it's EASY to make alcohols into ketones! While some around here whine and moan about Markovnikov this and Markovnikov that (we won't name any names, but you know who you are), AN418658 delivers the GOODS. The pseudo-theory behind this process: Make the alkyl-hydrogen sulfate from the alkene using semi-concentrated, cooled sulfuric acid, then hydrolyse by heating in a near-boiling water bath. Here's what ZWIT did in a half-mole (based on amount of safrole) run... A 600mL beaker was situated in a ice/water bath on a mag stirrer and with a long stirrer bar (2") spinning happily away. 31g of distilled water was added and allowed to cool for 5 minutes, followed SLOWLY by 83g of concentrated sulfuric drain er... I mean, uh, acid. The acid heated the beaker up vigorously, so approximately 15 minutes were required to cool the contents back down. To what temperature? I dunno, it just felt cold to the touch (not the acid, idiot, the beaker). Next, 81g (.5mole) of distilled safrole (from sassafras oil) was added in a thin stream to the beaker. immediately, a light yellow color was apparent which slowly turned red, then brown (yuck - brown is never a good color in my book). This mixture was allowed to stir for 15 minutes. Next, a hot water bath was prepared, and the ritual bath salts thrown in for good measure and to keep the beaker Calgon smooth (it's a joke, you idiot). The beaker was transferred from the cold bath to the hot bath, and then 213mL of distilled water was added. In the scheme of things presented to me by the anon contributor, I should have dumped the 213mL of water into the beaker while still on the cold bath, then stirred for an additional 10 minutes, THEN placed on the hot water bath, but being a paragon of efficiency (or just plain half-assedness) ZWIT decided that the thermal inertia of the beaker contents would give the requisite 10 to 15 minutes of low-temp stir time and so skipped that tedium. Anyway, the beaker was allowed to stir in the hot water bath (heat provided by two beverage heater coils in a teflon-coated bread baking tin) for a total of 45 minutes, assuming that the contents were only actually at 90C or so for 30 minutes. The beaker was then removed from the heat and placed on a stirrer in free air to cool down until just warm. The contents are quite interesting looking, composed of a creme colored aqueous phase and a light-yellow organic phase (looks just like MDP-2-P, actually). Whoooooo-booooyyyeeeee, smells tasty, too. Hmmmm... well, it smells just like safrole, actually, with perhaps a hint of that alcohol quality to it. At any rate, now is when the solution must be neutralized with alkali. .15 molar equivalents of 5% sodium hydroxide is called for, which in this case works out to a total of 3g of anhydrous sodium hydroxide dissolved in the corresponding amount of water. ZWIT sucks at doing this sort of mindlessly-simple calculation, so 5g of NaOH (Red Devil Lye - nothing but the best for my drug precursors) was dissolved in 95g of water on the premise it wouldn't take that much to neutralize it??? Or are we really neutralizing it here? Who cares... 60mL of the solution was added to the beaker, delivering the required 3g of NaOH at the requisite dilution level of 5%. The pH meter said 170, which means the H+ ion concentration was still very high (or, in other words... what the fuck did I add the NaOH for?). ZWIT fairly expected this, but what the fuck, I'll just be a monkey on this one and follow directions. Now the slop is transferred to a sep funnel and allowed to sit. Even after 2 hours, it is apparent that this stuff is going to stay somewhat emulsified, and now ZWIT is shaking his old noggin' wondering why he even added the NaOH in the first place, as the stuff was clearly in two laters prior to that. Ugh... in fact, ZWIT surmises that it would probably be smartest to separate the alcohol from the aqueous acid layer THEN shake with base if necessary. Awww hell, it's not ZWIT's place to theorize, I leave that to the Brain Trust of A.D.C. Faced with the inexplicable, ZWIT dumps the sep funnel contents onto the ole vacuum buchner funnel and filters away. Lo and behold if that didn't straighten that nasty old emulsion mess up right straight! Funny, since that's what my anon friend TOLD me to do.. haha... well, such is life. ZWIT finally separates the two layers, properly, and extracts the aqueous side with 1x25mL of methylene chloride (yes, I chintzed out and only used *1* extraction). The organic only layer weighed in at 71g (without the extracts) so yield looks pretty good if the shit doesn't go to hell in distilling it. So of course it's time to distill, and distill ZWIT did! The extract was combined with the organic layer, dumped into a 24/40 ground glass simple distillation setup with vacuum receiver nipple, set stirring magnetically and heated with an electric Glas-Col (tm) heating mantle. The methylene chloride was stripped off, the last few drops flashed with vacuum, and the emulsified water stripped off under vacuum as well. The final reading on my manometer was 10mm Hg, and the temp climbed quickly to 120C where the MDP-2-Pol started coming over. The bp is supposed to be 113-116C at 3mm Hg, so I would expect the bp to be closer to 130 at 10mm Hg, but my thermometer adapter for my 24/40 stuff is notorious cantankerous and consistently reads about 8C too low. At any rate, it looked good! No, it looked FUCKING GREAT. The alcohol is fairly mobile, moreso than the ketone, and is nearly colorless but with the slightest tinge of perhaps lime green. The smell is not so pleasant as the ketone - very much like a heavy molecular weight alcohol with a tad of that isosafrole smell to it. Actually, it's hard to characterise the smell, as it doesn't have all that much scent to it. Anyway, the total yield of product, 3,4-methylenedioxyphenyl-2-propanol, was 72.0g, which comes out to a percent yield of 81%. Not bad for being intentionally sloppy, huh? Yes kids, I just converted plain old safrole to the secondary alcohol in under 4 hours total time with a percent yield of 81%, and I can only expect it to get better with more careful attention to detail next time and a more thorough extraction of the aqueous reaction matrix. Going from here to the ketone is a breeze, but at least one person (DrH) is a proponent of direct reductive amination starting from the alcohol. Hah! [END OF TRANSMISSION] --****ATTENTION****--****ATTENTION****--****ATTENTION****--***ATTENTION*** Your e-mail reply to this message WILL be *automatically* ANONYMIZED. Please, report inappropriate use to [a--u--e] at [anon.penet.fi] For information (incl. non-anon reply) write to [h--p] at [anon.penet.fi] If you have any problems, address them to [a--m--n] at [anon.penet.fi]