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	All 47 posts	Subject: Phenylacetone Synth

	Optimus Prime (Member) 06-30-98 16:26 No 172182		Phenylacetone Synth	Bookmark Reply
			This lovely little gem waited on me in my box today compliments of a hardworking Labrat, I just gotta share... EXPERIMENTAL "A mixture of phenylacetic acid (13.6 g, 0.10 mole), acetic anhydride (50 ml) and pyridine (50 ml) was refluxed six hours, during the first part of which time carbon dioxide evolution was vigorous. After removal of the solvent the residue was taken up in benzene and shaken out with 10% sodium hydroxide. Removal of the benzene left 12 g of non-acidic material which on fractional distillation was separated into 7.5 g (56% yield) phenylacetone, bp 30-64 C(0.1 mm)" Woo Woo.... Thanks partna OP
	Osmium (Moderator) 07-01-98 03:51 No 165300		Phenylacetone Synth	Bookmark Reply
			Yuck. Pyridine. 56% yield. Why doesn't anybody use the PAA/acetic anhydride/NaOAc method? Doesn't stink and higher yields!
	Optimus Prime (Member) 07-01-98 05:37 No 165301		Phenylacetone Synth	Bookmark Reply
			Probably since I havent looked into the NaOAc... the pyridine doesnt smell half as bad as the PAA OP
	Labrat (Member) 07-01-98 11:21 No 165302		Phenylacetone Synth	Bookmark Reply
			Osmium, which article states that using sodium acetate instead of pyridine gives a HIGHER yield? Using pyridine gives a 56% yield and using sodium acetate gives 50% yield, according to my refs. Lr/
	Osmium (Moderator) 07-02-98 10:02 No 165303		Phenylacetone Synth	Bookmark Reply
			It is in CA, between 1940-50, if I remember correctly. I can't search it, because my library doesn't have it. Fester mentioned it in some of his SOMM editions (third? dunno). He said it would not work, "typical for these lying commies" or something like that. Yield somewhere above 80%. When you have a good cheap source for acetic anhydride, yield will even be higher, because it greatly depends on the excess of this reagent. Trust me, it worked in my dreams.
	Osmium (Moderator) 07-02-98 10:03 No 165304		Phenylacetone Synth	Bookmark Reply
			It is in CA, between 1940-50, if I remember correctly. I can't search it, because my library doesn't have it. Fester mentioned it in some of his SOMM editions (third? dunno). He said it would not work, "typical for these lying commies" or something like that. Yield somewhere above 80%. When you have a good cheap source for acetic anhydride, yield will even be higher, because it greatly depends on the excess of this reagent. Trust me, it worked in my dreams.
	Labrat (Member) 07-02-98 10:38 No 165305		Phenylacetone Synth	Bookmark Reply
			Osmium, the articles I mean are JACS articles from around that period too (if I remember correct, one is from '46 and one from '50 or something), so I guess these refs are the ones referred to in the CA. I have read SOMM are long, long time ago so I can't remember what Fester said about this method. However, if you say employing an even greater excess of acetic anhydride will produce higher yields, I have to take your word on it. I've never tried the friggin process, simple because it uses very hot chemicals (PAA, acetic anhydride, pyridine) and the PAA and pyridine certainly smell like something you wouldn't waste your nostrils on. OP, if you're reading this, I think the man has a point. Give it a shot and let us know what the results are. Oh yes, we're all talking hypothetically here, ofcourse... Lr/
	drone 342 (Member) 07-02-98 16:44 No 165306		Phenylacetone Synth	Bookmark Reply
			For those daring enough to play with tube furnaces, PAA and actic acid, piped through a tube furnace with the approprate inorganic catalyst, will yield phenylacetone in high yields. You can get all the inorganic catalysts from Stem chemicals. They're on the web. -drone #342
	Optimus Prime (Member) 07-02-98 19:04 No 165307		Phenylacetone Synth	Bookmark Reply
			I had a dream about Festers little synth... as it turned out Fester strikes again...(no pun) it is a shame too, since at one time I thought he was the best thing since sliced cheese... the dream I had showed no red tarry polymer that Fester said was present, although once the rxn had finished and solvents reduced under vac, the solution had a slight reddish tint(?)... might have been my subconcious just hopin... I awoke from the dream and I could have sweared a gang of cats broke into my place and pissed all over everything.... me thinks that the phen. a. molecule might have been just a tad hygroscopic Labrat: Pyridine and Acetic Anhydride are hot...?????? Os: Sodium acetate from acetic acid??? OP
	assholium (Member) 07-03-98 03:16 No 165308		Phenylacetone Synth	Bookmark Reply
			Hi,  gays, possibly I can add some words to you discussion :) Drone: >For those daring enough to play with tube furnaces, PAA and actic acid, >piped through a tube furnace with the approprate inorganic catalyst, will >yield phenylacetone in high yields. You can get all the inorganic catalysts Yes. I made it from 60-cm quartz tube, nichrome spiral and some asbestos cover on it. Best catalyst is zeolite, impregnated with thorium nitrate. For you information, Th(NO3)2 is radioactive, and radiation near my 1g sample is 130 mkR, it's ten times more then usual background natural radiation. Like it? Well, further. Yields of P2P no more then 50% - from real experiments. Osmium: >It is in CA, between 1940-50, if I remember correctly. I can't search it, >because my library doesn't have it. Fester mentioned it in some of his >SOMM editions (third? dunno). He said it would not work, "typical for >these lying commies" or something like that. Yield somewhere above 80%. Yes, this is work of Magidson and Garkusha, Zh. Obsh. Khimii, v.11, N4, p. 339. Typical procedure follows: Methyl benzyl ketone: 1000 g water-free phenylacetic acid, 6000 g Ac2O and 500 g fused AcONa loaded in flask with vertical reflux condenser with attached  CaCl2 tube.This mixture refluxed at 145-150C (bath temp) during 18 hrs. Then excess of solvent was distilled off, and after cooling added some water, and then dichloroethane. Dichloroethane layer  separated, and solvent removed. Residue distilled in vacuo, fraction 125-135C(30-32 mm) was collected. Twice redistilled fraction had bp 210-215 C (norm.) Yield 50-55% from theory. Really, this works. Prolonged reflux (up to 48 hrs) not improve yields - always notoriously 50-55%. Using AcOK instead of AcONa raises yields up to 60-65%...  Never try to use large excess of Ac2O. How much large, Osmium? Huh, one old idea: anybody try acylation of benzylcyanide in PTC conditions? f.e. with pentylacetate... I feel that this must work smoothly... and after ordinary hydrolysis with sulphyric acid we have P2P...
	Inorganic ( ) 07-06-98 03:49 No 165309		Phenylacetone Synth	Bookmark Reply
			This was posted the other day but seems to have been lost somewhere along the way, if you are seeing this again, sorry. A couple things, first the catalyst is not thorium nitrate but rather thorium oxide; which is produced by igniting the deposited thorium nitrate at red heat.  The original reference for this reaction (Phenylacetic + acetic = p2p) is the following ref: Organic Syntheses Vol 16; p47-50 or Organic Syntheses Collective Edition Vol 2 (essentially the same article) it details the catalyst preparation as well as the rest of the procedure in detail. As for the thorium, instead of buying it from your favorite chemical retailer, one could go for a walk and find chuck of the mineral Monazite and extract the thorium from it using only Sulfuric acid and water, according to the following reference: Inorganic Syntheses Vol 2; p38-43 Hint: Phenylacetone is refered to as "methyl benzyl ketone" in the organic syntheses references.  Nomanclature is a bitch eh?
	Osmium (Moderator) 07-06-98 04:07 No 165310		Phenylacetone Synth	Bookmark Reply
			Assholium: those names sound familiar. But in that CA ref. a higher yield was claimed. And I achieved a higher yield, too. I also remember some old german refs from around the turn of the century who did it. They too had better yields. I guess I'll have to search Beilstein again to find some of those refs.
	Optimus Prime (Member) 07-06-98 06:13 No 165311		Phenylacetone Synth	Bookmark Reply
			InO: "Organic Syntheses Vol 16; p47-50 ".... I have no access to this fine Journal...but if the application is "practical" could you possibly post the experimental... Os: Drone sent those refs from the ole' jackboots you refered to I have them if ya want em'... It seems that in a couple of the reactions one would want to use something other than pyridine, but what would one choose for the replacement or could one... OP
	Labrat (Member) 07-07-98 10:04 No 165312		Phenylacetone Synth	Bookmark Reply
			Labrat thinks he has the solution to get higher yields. I thought of it when reading the ref (JACS 73:4911('51). The reaction is actually a base-catalysed condensation reaction of acetic anhydride on a phenylacetic anhydride. The first step in the reaction is making phenylacetic anhydride 1)PhAcOH + Ac2O --> PhAcOAc + AcOH This anhydride condenses with acetic anhydride while splitting off CO2 to give phenylacetone 2)PhAcOAc + Ac2O -->PhCH2COCH3 + CO2 + Ac2O Even if you use a large excess of acetic anhydride you'll still end up with a mixture of anhydrides, including diphenylacetic anhydride. If this latter anhydride condenses with itself, it'll form dibenzylketone. So it's very important to keep the concentration diphenylacetic anhydride low to avoid formation of dibenzylketone. The solution to this is ofcourse dripping phenylacetic acid into a refluxing mixture of  acetic anhydride and pyridine (or Na-Ac), while maintaining a steady reflux and hopefully a steady evolution of CO2. I'd really like another chemist's opinion about this. I've a good feeling that this will work, but some comments (especially of the practical work) would be appreciated. Lr/
	Optimus Prime (Member) 07-07-98 10:55 No 165313		Phenylacetone Synth	Bookmark Reply
			I would have to agree on the drip method since the shit gets very hot, I seem to remember reading about how someone didnt add very slowly or in ice bath, and ended up with nada... although they seemed to have released the co2 which left quite quickly and rapidly... altogether I think that the stuff only boiled for 2-3 min on a hundred gram scale... OP
	Osmium (Moderator) 07-08-98 03:47 No 165314		Phenylacetone Synth	Bookmark Reply
			I know it works. In high yields. I dreamed about it repeatedly in my early chemistry days. Using big excess of acetic anhydride will favor formation of P2P, because the mixed anhydride will predominate. With plenty of Ac2O floating around, the mixed anhydride will react preferably with Ac2O. I don't exactly remember, but yields were around 80%.
	Labrat (Member) 07-08-98 10:21 No 165315		Phenylacetone Synth	Bookmark Reply
			Osmium - The usual way to perform this reaction is simply mixing phenylacetic acid, acetic anhydride and a base and start heating it. However, you can also promote the formation of the mixed anhydride by simply dripping in the phenylacetic acid into a refluxing mixture of acetic anhydride/base. That way you can avoid the large excesses of acetic anhydride. Isn't that a much better way (if it works)? Lr/
	Osmium (Moderator) 07-08-98 11:31 No 165316		Phenylacetone Synth	Bookmark Reply
			That way the acetic anhydride is always in excess, right. But I guess at reflux extensive exchange of the anhydrides takes place, so it probably makes no big difference. The equilibrium will always produce its share of unwanted side products. This means that big excess of acetic anhydride is really needed for best yields, to force the equilibrium in the right direction. I also remember that one time the decarboxylation (loss of CO2) took place mainly at the addition of water, resulting in a big cluster-fuck, meaning most product was not inside of the beaker, but mainly at the walls and ceiling.  Don't know right now if the formation of the carboxylic acid intermediate is reversible. If it is, then slow PAA addition is useless. But I guess it isn't. So this might really work.
	Labrat (Member) 07-09-98 09:51 No 165317		Phenylacetone Synth	Bookmark Reply
			You're right, Os, at reflux exchange of the anhydride will take place. But can you imagine one drop of phenylacetic acid swimming around in a swimmingpool filled with acetic anhydride/base forming much diphenylacetic anhydride? I can't. The mixed anhydride will predominate. Further, if the phenylacetic anhydride condenses with the acetic anhydride, an irreversible reaction takes place with release of CO2 (that's why it's irreversible) with formation of P2P. So the phenylacetic acid is irreversibly removed from the equilibrium. So what I'm trying to say here is, that if you add the phenylacetic acid drop by drop to the acetic anhydride/base mixture, the phenylacetic acid will react immediately with acid anhydride forming the mixed anhydride. Then, the base abstracts a benzylic proton and the formed intermediate condenses irreversibly with acetic anhydride with evolution of CO2. The concentration phenylacetic acid/mixed anhydride will be kept very low, because all the anhydride can react instantly. This promotes formation of P2P in favor of formation of dibenzylketone, making the overall yields higher. My guess is that you can get about 80-85% yield with this modification. And that's good, eh? Lr/
	Dusty ( ) 07-10-98 22:59 No 165318		Phenylacetone Synth	Bookmark Reply
			Topic of the week at http://asnmr4.la.asu.edu/wwwboard/pchem_forum.htm
	mindless (Member) 07-12-98 05:34 No 165319		Phenylacetone Synth	Bookmark Reply
			how about it being put this way:  i pound of pa, one-half pound sodium acetate, 600mls acetic anhydride, refluxed for 18 hours, then distilled, produces enough p2p to make one half pound of meth...minimum
	Optimus Prime (Member) 07-12-98 09:35 No 165320		Phenylacetone Synth	Bookmark Reply
			Os: What is the standing of Sodium Acetate...??  Is this as "hot" as the others listed... OP
	dreamer (Member) 07-12-98 19:26 No 165321		Phenylacetone Synth	Bookmark Reply
			is there a methode to separate dibenzylketone from P2P without vacuum distillation ? can you get 3,4 MD-P2P with 3,4 MD phenylacetic acid,sodium acetat and acetic anhydride too ?
	Osmium (Moderator) 07-13-98 05:10 No 165322		Phenylacetone Synth	Bookmark Reply
			The Na acetate needed here must be anhydrous. Standard Na acetate can easily dried at higher temps. Na acetate isn't hot at all.
	mindless (Member) 07-17-98 04:51 No 165323		Phenylacetone Synth	Bookmark Reply
			the sodium acetate, must be anhydrous. it dries very nicely at a low temp. in the oven
	Scooby Doo (Member) 09-25-98 08:30 No 165324		Phenylacetone Synth	Bookmark Reply
			Os I think the ref you were talking about is CA (1941) 5868 by the Russian dudes mentioned above. However in the abstract they use 60g of PAA and 100g Ac2O with the yield being 80%. This makes no sence to me, I thought abstracts were supposed to be shortend down ref's not different reactions.
	Osmium (Moderator) 09-25-98 16:31 No 165325		Phenylacetone Synth	Bookmark Reply
			Thanks for the confirmation (although it comes a little late  )
	Stimpy ( ) 09-26-98 20:27 No 165326		Phenylacetone Synth	Bookmark Reply
			test
	PolytheneSam (Master Searcher) 05-08-01 17:23 No 192779		Re: Phenylacetone Synth	Bookmark Reply
			Tube furnaces discussed back in 1998. http://www.privacy.org/article.php?sid=620&mode=thread&order=0&thold=0 http://www.privacy.org/
	CheshireHouse (Newbee) 05-08-01 18:50 No 192804		Re: Phenylacetone Synth	Bookmark Reply
			this being (seemingly) so easy, why isn't everybody doing this, and getting the phenylacetic through the Wilgerodt (sp?) reaction? jen gee, I sure am learnin' a lot
	Ritter (Master Whacker) 05-08-01 22:23 No 192839		Re: Phenylacetone Synth	Bookmark Reply
			The Willgerodt reaction works amazingly well, especially when morpholine is used as the amine substrate.  Yields can be expected to be at least 75% w/ morpholine.  The only problem with the synth is it produces serious quantities of sulfur dioxide which is hard to disguise from the neighbors noses.  The only effective way to supress the stench is to feed the vapors into a high capacity water aspirator down the drain.  If you want refs, I have a few good ones.  Just ask and I'll see what I can dig up.
	terbium (Hive Addict) 05-08-01 22:42 No 192847		Re: Phenylacetone Synth	Bookmark Reply
			this being (seemingly) so easy, why isn't everybody doing this, and getting the phenylacetic through the Wilgerodt (sp?) reaction? Years ago I made lots of P2P this way. 'Course, at the time I could acquire multi-gallon quantities of acetic anhydride without any problems so the tube furnace was unnecessary, quantities of benzyl cyanide were also easy to acquire at the time so there was not need of a Willgerodt.
	CheshireHouse (Newbee) 05-08-01 23:04 No 192850		Re: Phenylacetone Synth	Bookmark Reply
			The Willgerodt reaction works amazingly well, especially when morpholine is used as the amine substrate.  Yields can be expected to be at least 75% w/ morpholine.  The only problem with the synth is it produces serious quantities of sulfur dioxide which is hard to disguise from the neighbors noses.  The only effective way to supress the stench is to feed the vapors into a high capacity water aspirator down the drain.  If you want refs, I have a few good ones.  Just ask and I'll see what I can dig up. I'd love to have whatever info you can find.  SWIM's crazy 62-year-old Libertarian housemate just happens to have several gallons of acetic anhydride lying about, left over from 'the good old days' jen gee, I sure am learnin' a lot
	tecnetium (Hive Bee) 05-09-01 21:00 No 193153		Re: Phenylacetone Synth	Bookmark Reply
			Has anyone ever checked out the PAA-> P2P synth buried at Rhodiums page? It involves heating your PAA with Pb, Ca or Barium Acetate- distilling off the water and then further heating to distill off the P2P. Sounds fairly easy.
	CheshireHouse (Newbee) 05-09-01 21:44 No 193154		Re: Phenylacetone Synth	Bookmark Reply
			i thought the same thing... jen gee, I sure am learnin' a lot
	Osmium (Stoni's sexual toy) 05-10-01 02:57 No 193212		Re: Phenylacetone Synth	Bookmark Reply
			I tried that heating with Ba acetate once. Crappy yield of evil smelling wild ass mixture. Never again.
	CheshireHouse (Newbee) 05-10-01 03:08 No 193216		Re: Phenylacetone Synth	Bookmark Reply
			hmmm... so, then, what is your reccommendation?  do you think it possible that it was just the Ba at fault, & that Ca acetate or whichever else might have been less offensive? jen gee, I sure am learnin' a lot
	Osmium (Stoni's sexual toy) 05-10-01 04:00 No 193228		Re: Phenylacetone Synth	Bookmark Reply
			> so, then, what is your reccommendation? NaOAc/acetic anhydride worked pretty well for me. If you don't have a source for AA, you can make your own by pyrolysis of acetone on hot wires, which will produce ketene. There's a description in Vogels' book for an apparatus for continuous ketene production. Ketene can be considered the anhydride of the anhydride, if that makes sense CH3-CO-CH3 -------> CH2=C=O + CH4 CH2=C=O + CH3-COOH -------> (CH3-CO)2O
	Osmium (Stoni's sexual toy) 05-10-01 04:36 No 193232		Re: Phenylacetone Synth	Bookmark Reply
			Regarding the Willgerodt reaction, this probably is the best reaction for PAA synthesis. It works both with acetophenones and styrenes as starting material. Unfortunately morpholine is somewhat watched to my knowledge, due to its usability in PCP analogues syntheses. Maybe somebody cums up with a cheap, readily available and non-suspicious replacement for it, then the doors for widespread P2P production starting with cheap styrene will be wide open.
	CheshireHouse (Newbee) 05-10-01 08:28 No 193270		Re: Phenylacetone Synth	Bookmark Reply
			what exactly does 'somewhat watched' mean?  i mean, it seems like, if it's not a 'listed' chem, and not even on the 'suspicious purchaces' list, then what chem supplier is going to bother reporting such a purchase, unless you are acting suspiciously in some other way?  from the merck entry on morpholine, it seems like morpholine has a wide range of industrial uses, from rust-proofing boilers to making wax or something. jen gee, I sure am learnin' a lot
	xtaldoc (Mega Meth Man) 05-10-01 14:57 No 193343		RE: Has anyone tried the PAA + Pb acetate synth?	Bookmark Reply
			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. Sole proprietor of URANUS LABS,Inc. Remember..."If its from URANUS, you've already tried it".
	CheshireHouse (Hive Bee) 05-10-01 15:51 No 193359		Re: RE: Has anyone tried the PAA + Pb acetate synth?	Bookmark Reply
			wow, thank you, that was a great post.  i like posts like that, that detail the practical difficulties bees have faced, and how they were overcome.  SWIM will definitely look into this one further.  sounds easily enough scalable, too, which i like :-D jen gee, I sure am learnin' a lot
	xtaldoc (Mega Meth Man) 05-13-01 09:44 No 194054		Re: Substitute for Morpholine?	Bookmark Reply
			As folks here are probably aware, the Kindler modification using Morpholine has been extended to Pyridine and co-solvents have been added, as well.  Organic Reactions covers some basic mods in a treatise on the subject.  For a variation that would employ a more readily available potential substitute for morpholine, how about trying it out with piperazine derived from veterinary de-wormer that uses piperazine?  It seems, to Swix's recollection, that lots of higher boiling secondary amines facilitate the reaction, with greater or lesser efficiency.  It also looks like the playing field can be opened up to include other, lower boiling, amines by the use of a co-solvent.  Yeild when employing styrene seems lower, but Swix did not experiment enough to form a solid opinion on that issue, by itself.  Instead, he looked into the original reaction and ran it using acetophenone and styrene, at different times, in a newly purchased gas cylinder of about 5 liter capacity that was simply placed in his oven and baked.  Yeilds were only so-so this way.  Work-up was a stinky mess and once the safety valve popped about 3/4 through the reaction, IN SWIX'S FUCKING OVEN and created major havoc for awhile; not to mention it nearly murdered his 33 plants nearing harvest in the basement.....  Well, live and learn: always check for and BLOCK any pressure relief safety valve on a cylinder that you have reason to believe may exceed its pre-set release point.  Anyway, further experiments, at that time, were terminated under threat of divorce. Swix would love to read any accounts of Willgerodt reaction experiments done sealed of modified as in Kindler; especially interested in any co-solvent atempts and attempts using other 2nd degree amines.  Maybe Swix will personally look into piperazine or pyrrole or (lesser idea) pyrrollidine/pyrroline/collidine, etc.  Anyone have any further suggestions???? URANUS LABS: The company with Your mind in mind.... -Xtaldoc Sole proprietor of URANUS LABS,Inc. Remember..."If its from URANUS, you've already tried it".
	foxy2 (Hive Addict) 05-13-01 21:46 No 194214		Re: Substitute for Morpholine?	Bookmark Reply
			"Well, live and learn: always check for and BLOCK any pressure relief safety valve on a cylinder that you have reason to believe may exceed its pre-set release point." That sounds dangerous, but maybee i'm just a wuss? Do Your Part To Win The War
	xtaldoc (Mega Meth Man) 05-14-01 01:03 No 194234		Re: Substitute for Morpholine?	Bookmark Reply
			Hey Foxy2- Yeah, Swix admits that when the cylinder went off in the oven- his heart rate immediately red lined.  He was in the living room at he time and it was in the wee hours before dawn.  Could not tell exactly, from the sound, whether the tank had literally 'blown', suffered a lesser 'rupture' or  tossed the valve.   It was also far too hot to simply pick up and run with it.... The dreaded part was having to open the oven door (while it was still spewing crap of the nastiest sort) to get a visual so a snap decision could bee made as to immediate course of action... You know, "SHIT!- How freaking bad is this emergency???"  The hell of it is; it was a fluke.  One of those unpredictable inevitabilities that once every now and then reminds us there's a Joker in every deck.  When the cylinder was bought from a local gas company, Swix told the folks at the company that it was to replace a cylinder that he had accidentally damaged while using the forklift of another business, and so he just needed to purchase a clean, empty cylinder in this rather odd size.  Swix was not aware that there was this peculiar regulation that intruded in on his intended transaction and required the gas company to only sell the cylinder 'empty' with the tank valve disabled, thereby insuring that 'the customer' will not be able to fill the tank himself, one supposes, and the gas company cannot later be said to have been in colusion.  I mean, who could forsee this bureaucratic psycho-babble and its illogical result?  In Swix's mind at the time, it was no big deal, just another regulatory paradox to file away, and so, when the man came out and informed Swix that, "Yes we have the size cylinder you're requesting, but we'll have to disable the valve before selling it empty to a private party, will that be a problem?" Swix just laughed and said, "Hell no- as long as the cylinder is not harmed". The man replied, "No prob- I'm just gonna bang the outlet threads with this here hammer(not the tank side).  Wont even really hurt the valve, its just that nothing will screw onto it after that".  Well, Swix didn't need to mate a hose or anything to the tank valve, so this was fine by him.  Now, most all these CGA cylinder valves have a presure relief safety valve built into the tank valve body itself. This relief valve is set to pop off at a pressure specific to the tank rating or the gas being contained, in certained cases.  Swix figures that the valve that was originally on the tank he bought was a costlier one than the one that the company guy had laying in a box nearby, and so it got switched for one generally used on a CO2 tank (as Swix recalls), which has a pretty low triggering PRV in the valve body.  Since the tank, itself, was overkill for the rxn temps & pressures- He did the dumb thing and decided that he didn't have time to waste on useless tests...Like his I.Q. test, I guess.  The mess was unpredictable but not unavoidable if proper technique was applied and safety factors given the respect deserved. All that Ca-Ca having been said; if you check your valve (or use a solid plug with a small needle valve set into it to bleed pressure at finish)integrity and buy a good, high pressure tank that hasn't been abused- it will handle all the reaction can dish out and much more. There's also  not the big expected outrushing of gasses upon cracking the tank valve after cooling.  But it do stink!  Swix advises that any experiments bee conducted 1st on a small scale, using a 1" to 2" dia heavy wall stainless Tube with one end plugged and the other end sealed with a threaded plug.  Experiments are then faster to run, since heat-up time is greatly lessened. Unforseen difficulties with sudden problem odors, or when the reaction decides its gonna launch its contents upon openning the cylinder, are always dealt with easier on a smaller scale.  Plus, if one can get several of these tubes, of course-  multiple experiments can be conducted at once in the same oven.  Yeah Foxy, the reaction itself was deserving of respect, but not at all unsafe with proper care.  As ever, it was the operator that was unsafe. Swix is much more patient and cautious anymore, but still does not shy away from reactions that function under extreme conditions: these are some of the richest areas of chemical knowledge & experience, IMHO. Sole proprietor of URANUS LABS,Inc. Remember..."If its from URANUS, you've already tried it".
	CheshireHouse (Hive Bee) 05-14-01 03:27 No 194252		Re: Phenylacetone Synth	Bookmark Reply
			. Unfortunately morpholine is somewhat watched to my knowledge, due to its usability in PCP analogues syntheses. what exactly does 'somewhat watched' mean?  i mean, it seems like, if it's not a 'listed' chem, and not even on the 'suspicious purchaces' list, then what chem supplier is going to bother reporting such a purchase, unless you are acting suspiciously in some other way?  never got an answer on this one, but is something i've wondered about in other instances as well.  i mean, the only way something is 'watched' is by having the chem suppliers report transactions, right?  and if the chems under discussion aren't on the list of things that the chem suppliers are required to report, or at least the list of things that they have been officially 'warned' might be suspicious, both of which lists are a matter of easily accessible public record, then in what way can they be 'watched' or 'somewhat hot'?  if the chem isn't one that requires a signature to get, that is a listed chem, then it's the same as any other unlisted chem, right?? jen Ever wonder why your dad has 'CheshireHouse' tattooed on his left butt cheek?
	xtaldoc (Hive Bee) 05-17-01 12:07 No 195176		RE: Morpholine somewhat watched?	Bookmark Reply
			In the real world of retail chemical sales there is a 'relationship' of some sort between the DEA compliance agent and the company that must be at least superficially friendly, to avoid the risk of serious harrassment by the Feds or indirectly, through any of the 'so called' regulatory agencies that work with them.  As a result, there is a list of watched items and there is also a less formal 'list' of whatever items that agent or his bosses feel are indicative of illegal activity, in view of what their sources currently tell them is going on locally, etc.  Sometimes this can result in a substance being hot, but only if the purchase happens within circumstances that fit whatever scenario the agent layed out.  Usually, it is triggered when the customer is other than a 'regular customer' as defined in the United States Code of Federal Regulations, Title 21, under "definitions" in the Controlled Substances Act P rovisions. Sole proprietor of URANUS LABS,Inc. Remember..."If its from URANUS, you've already tried it".

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