10-16-01 23:25
No 225635
I though I would bring up this little document written by xtaldoc again. Has anyone else tried this method out, or do someone know a reference for it?
Swix has done that synth. Some time ago he came into alot of PAA on condition that he develope a workable synth that didnt involve AA and could scale up well, as well as be fairly low tech (able to be done by non-chem). For Swim's own set-up, the PAA and Methyl Lithium sounded like a good one, but not for the inexperienced; too hazardous. Considered lots of ideas, but decided to look into the old time stuff because the technology would be off the shelf now. Also, this was one of those orphaned reactions that sort of died out when more modern methods with reported higher yeilds became popular. Revisiting these oldies can sometimes bring unexpected rewards when something new is applied to something old. As the reaction sits, its a bitch. Reaction temp for the calcium variation is real high, even compared to the lead version(dunno about Barium), which is fairly toxic due to its water solubility and there's the expense of Lead Acetate to contend with at 3 to 4 Kg per Kg of PAA used....... The yeilds are low, for the most part. Even when lead acetate is increased to 4:1 with PAA the yeilds dont get over 40%, to my knowledge. The 'aftermath' of the reaction is a big 'clunker' of moon rock looking crap that fills half of the reaction flask and sets up almost like cement. That hard to get out, too. Most 'lead cooks' Swim talked to said they just bought lots of glass and smashed them up when done. Shit, that's like child abuse, IMO. However, after much experimentation, brain crunching thought and some lengthy research, Swix managed to address most all these issues and, in fact, employed little innovations here and there until finally this reaction was brought into the 20th Century as a player. Firstly, the reaction is better ran in Stainless Steel (Aluminum works fine also) so that the damn clinker can be easily removed. Its improved by also using a large cap. propane burner with the steel reactor. The reactor can be quite easily fabricated from a suitable sized pressure cooker that uses a metal to metal seal or the synth rubber seal provided can be replaced with a hand cut hi-temp silicone gasket (good for 6-10 runs). It is essentially a distillation process, so a condenser is made using a hand bent inner ss tube with opposing compression fittings forming the end pieces that also butt and seal the outer jacket, etc. Nipples were easy, as well. The distillation head is a goodly sized 90 ° steel pipe fitting with (you guessed it) another compression fitting sized to accept the slightly bent inner tube (for 15° slope). Since one cannot see in the steel reactor, a compression fitting seals a thermocouple probe that extends just into the headspace (or through the top of the dist head) to monitor vapor temp. Another similar probe extends well into the reaction mass. Since airborn lead fumes can be pretty toxic, the system should be closed. So, a receiver adapter is fabricated between the condenser output and a good sized separatory funnel. the fume take-off could be lead to a suitable fume trap, but this reaction apparantly suffers most of its yeild losses due to the brutal conditions in the reaction environment. Thermal decomposition seems the culprit. Swim reasoned that the desired ketone was, in large part, getting destroyed because it couldn't get out of the reaction fast enough. The molten lava conditions in the pot have the product trapped in a super dense muck that boils like a tar pit. At the end, it can only more or less 'sweat' the remaining product off of the solidifying post reaction mess. Preliminary experiments showed that the reaction itself initiated at a lower temp than that which was sustained during the roast. So, the first modification was to run it under a partial vacuum (5" Hg suction on a standard gauge). This did wonders for the reaction. Rapid heating to approx 185°C, then turn the gas down (vac from the start) so the initiation point is smooth(otherwise it'll puke into receiver) at about 195°C or so. A special gauge is placed in the vac. line: a tall water column type U-tube manometer made with clear vac tubing and filled with colored water for ease of viewing. A mark is placed next to the water level corresponding to 5"Hg vac on the gauge. This was a big help because when the rxn kicks, two thing immediately happen: CO2 is evolved in rapidly increasing amounts (built in speed-o-meter), which causes the system pressure to rise when it tries to over-run the vac pump. At the same time, pot temp will rapidly rise (aided by the pressure increase). However, if the operator is prepared, he simply adjusts the vac. orifice valve to compensate (could use automatic control; never did) and hold the vacuum set-point. Heat can be backed off a bit, but the vacuum helps cool the pot contents enough to bring the pot temp down to a bit over 215 -225°C, where it runs smoothly, at a vacuum, to actually provide very high yeilds in the 70% range for a practiced operator using a 4 fold excess of lead acetate. Onset of reaction is also accompanied by the appearance of a moderate to thick, white smoke, which shows up in the receiver (sep funnel) and is rich in lead compounds. Therefore, best to use one of those solid teflon vac pumps like KNF makes, or similar. Swix used a large chiller/circulator for antifreeze/water condenser coolant, set at about 10°C. The only problem left to solve was the lead acetate toxicity and $75.00/Kg price (plus limited avail in bulk, etc.). This was addressed by innovating the reaction. The lead acetate toxicity was partially solved by not using it (sorta). Instead, the PAA was mixed with an amount of glacial acetic acid calculated to yeild 4Kg of Lead acetate when mixed with the proper amount of litharge (PbO 2) right in the reaction vessel, just around 30 minutes prior to the run. Litharge is hardly water sol and its toxicity is therefore less an issue. It is also cheap as dog shit and available from any mining supply Co. where it sees extensive use. The cheapest grade works as well as the best grade but only costs about $2.00/lb in 50 or 100 lb bags.. This reaction, properly operated is no joke. Using a 20 liter ss pressure cooker about a gallon of phenylacetone will come pissing out into a lye/water solution thats placed in the separatory funnel within the course of about 1 1/2 hrs! Considering another 2 or 3 hrs involved in set-up and supplying the heat necessary to kick the rxn, then getting the last little cup or so of the 'squeeze' before the ketone becomes rather red in color and is mostly high boilers and dibenzyl ketone, its no slouch. The ketone can be used without a second distillation, only washing it with base, etc, especially if the reaction was a particularly smooth one, but Swix doesn't advise such. It's not a tricky distillation, especially if you dry it well before distillation and use a good, extra-fine capillary tube to avoid bumping. Then, a column isn't even really necessary, since the fore-run boils quite low and the cut-off between the phenylacetone and the poly-phenyl compounds is pronounced. This system does a much more honest pre-distillation than the method available to the public. Swix loved this reaction like his only child and it was good to him. BTW; if you're still interested in the PAA + AA & Sod. acetate reaction, but dislike the yeilds gotten, you might look for some experimental details that reference the reaction being run with cont. addition of ketene during the rxn in small amounts. It was told to me by a trusted and skilled operator that it largely increased yeilds and wasn't all that hard to set up, once you dialed it in. Hope you enjoyed reading this as much as I enjoyed the memory of that dream.
(Hive Bee)
10-17-01 07:10
No 225782
I'v heard that the product from paa -> p2p (with acetic anhydride) is contaminatet with a lot of diphenylacetone (up to 40%) so destilation might bee a god ide.
(Stoni's sexual toy)
10-17-01 07:51
No 225795
> I'v heard that the product from paa -> p2p (with acetic
> anhydride) is contaminatet with a lot of diphenylacetone
> (up to 40%)
Not when you do it right.
(Old P2P Cook)
10-17-01 19:04
No 226039
It doesn't look real workable to me at the moment.
What didn't you like about the lead technique? I thought it looked pretty good.
What other PAA-->P2P synths not using AA or similarly difficult to obtain chems are there? Any actually yield decent?
Vogel (and perhaps also Organic Syntheses) give a tube furnace/thoria catalyst technique using phenylacetic acid and glacial acetic acid. The yield is still only about 50% based on the PAA. Vogel states that satisfactory results can be obtained by replacing the thoria catalyst with manganous oxide.
The post that Rhodium used to start this thread is originally Post 193343 (xtaldoc: "RE: Has anyone tried the PAA + Pb acetate synth?", Chemistry Discourse) and is part of a long thread starting with Post 172182 (Optimus Prime: "Phenylacetone Synth", Chemistry Discourse) which contains a lot of discussion about PAA and P2P from PAA.
(Wizard Master)
10-19-01 19:47
No 227004
A ratio of 1 mole PA : 2 AA will give you some diphenylacetone. Increasing the ratio of AA will minimize the diphenylacetone.