sodium ethoxide vs orange VICTORY

loki · guinea pig

some pilz that a foaf was working with, recently started resulting in a nasty murky yellowish plastic gak after the final workup. swil had played with these pilz a few times and he decided that this foaf was not aware that the pilz have had a change of formulation and now, even pfed.sulphate based pilz have got nasty gakks in them. swil thought this gak must be what the bees had been calling 'orange'

swil tried something a bit different recently. he put his pilz into a flask, crushed, with ethanol and half a teaspoon of sodium hydroxide, and refluxed it for a bit. In the pilz swil uses, there is this ugly yellow plasticy stuff, and refluxing it in sodium ethoxide changed the stuff from icky yellow to dark orange. swil did two passes with ethanol over this material, yielding a murky yellow extract in the alcohol. After filtering, the alcohol/NaOH solution was evaporated in a beaker under an electric fan and to swil's delight, as it got to the bottom, pretty sparkles of what looked and smelled like pseudoephedrine freebase.

swil has adopted a new policy of doing very small scale experiments, was only a tiny little bit, because swil has been bamboozled by the nasty additives in modern pill formulations many many times and he is sick of it eating all his meagre welfare funds.

swil's plan, after the alcohol/NaOH solution completed its evaporation was to follow it with a rextallisation geezmeister style with dH2O and reflux, to keep the azeotrope of the pfed/water from escaping, and then cooling.

there was loratadine also in the pilz, so the next logical step was to separate the floaty pfed.fb/loratadine, and add HCl solution to it, which should then convert the pfed to HCl, evaporate it down again, and wash out the loratadine with toluene, and then naptha, and evaporate to yield nice crispy pfed HCl

...to be continued *spooky old synthesiser music plays*

loki · guinea pig

indeed, the alkaline ethanol idea seemed effective. having completed his total process, swil went and ingested the product, and the degree of conversion of precursor to product was clearly virtually complete.

A peculiar contaminant emerged in the final product, a yellow odd smelling material. It seemed to come free with a slosh of acetone, to a significant degree, but it's effects on the product were, while not insignificant, a little noticable.

The feed was combined with resublimed I2 and HCl and acetone washed mbrp. The particular mbrp that swil used was not very friendly to filtration, as swil learned in previous occasions, but it seemed to mostly settle out to the bottom when let to stand. acidic water seemed to hold up the settling process the most, but enough settled out that the minor loss was accepted as the cost of not needing to use filters.

After the rxn, the first step swil took was to add a small amount of sodium ethoxide and naptha on top, and theoretically, a dry kerplunk was run for about 20min, and then toluene was added to the top of the rxn solution and the process of extracting followed. alkalinised water was added, a small amount, but there was a very small amount of the rxn/aqueous phase compared to the toluene layer on top. The mixture was agitated with a battery powered swizzle thingy and 3 passes of 50ml was run thru it. One tap water wash was done on the extract, and then it was zapped (courtesy of the swizzler) into an excess of HCl solution, and swil concluded that because he over-acidified that it should all cross over in one go.

The crystal formations that appeared on the evaporating dish were visibly different from the crystals that appeared in the feed extraction, the feed tended to form more pinwheels whereas the product formed fragmented semi-laminar patterns that broke into new ones, which swil decided was the way that proper product should look. Swil was amazed when he scraped it all up, to discover that the amount of product resembled very closely in mass the amount of feed that went in. With one very significant difference - the feed had a pale yellow tint and slight stickiness, but overall was crunchy, whereas the product had a bright yellow colour, the yellow washed out in a quick acetone wash.

swil had never quite before experienced such a smooth and subtle effect from product before. He ended up dosing a lot higher than he originally planned, but almost 24 hours after the first administration, he was still feeling a noticable buzz. swil was impressed that he was able to come out with such a lot, and so good a product from such a small start, and accounting for losses due to a couple of mistakes and one nasty spill of the feed extract.

swil spent the evening with his old friend from yore and, although he over-indulged somewhat more than he planned, and ended up splitting it with his comrade. Thanks to the highly beneficial effects on swil's clarity of thought and improvement of his creativity, swill came forth from the session with a lot of clear insights on a topic that had been plaguing him for the better part of his whole life, and as a result, swil put together a relatively coherent and, for swil, well-written material which contained the answers he had been looking for.

swil now feels that he has crossed a threshold in his practise of honey making into a state of near competence. The process that was followed was somewhat haphazard, however, swil thinks that the alkaline ethanol freebase extraction concept which seemed to, compared to previous attempts on this pillstock, yield a much cleaner product. Crunchy even, with just a slight trace of the orange/yellow/brownish goop that had been seen previously in a much greater concentration, to the point that in swils and foafs previous recent efforts, had resulted in incomplete or completely unreacted product at the end, of a consistency that swil will simply term as 'gunk'.

gluecifer69 · Thu Mar 17, 2005 1:15 am

loki · guinea pig

ah yes i seem to recall the debate about KOH being used to deactivate it. I think that being a stronger base, sodium ethoxide may be more effective still. certainly, the degree of contamination was not such that there was a loss of yield, although only eyeballed, it seemed that the same amount came out as went in. subsequent observation of the application of the alkalineised ethanol sans heat, the colour change was not observed. swil thinks that this means that the use of heat may be required for success.

loki · guinea pig

ok, i went and fucked up and deleted what i was just posting because i clicked on a link a friend sent me...

so, i will be brief:

a particular pill which contains 120mg pseudoephedrine and 5mg loratadine (look up loratadine to get the first part of the name, and think 'nasal decongestion' together with it) is composed of a dual spaced release system. The compound which contains the second dose is a gacky yellow substance which vaguely resembles a crumbly sticky version of acrylic paint.

The dose separating agent in this pill is particularly nasty for would-be extractors of it. The pill as a whole is compounded extremely hard, it does not submit easily to being pulverised. so cracking layers is not an option, once it cracks the thing really stays stuck together. The outer layer is a coating of some kind of plastic material, which does not come apart very easily in ethanol, it may be a part of the slow releasing system.

so. the thing is, if one does not deactivate or eliminate this plastic, possibly two different plastics, one ends up with a sticky greyish waxy goo, which is voracious for water, although it can be pursuaded to turn into a hard wax with heat and heavy ventilation... swil has seen it completely ruin a foaf's chemistry, to the point it seems to also prevent the reaction as well.

after resulting in a bluish waxy substance as described, swil indulged, and became much more lucid and competent at his work.

now, a minor diversion, possibly related to this duo of gakkage, but maybe not (methinks it may be relevant)

he had taken a shortcut of not filtering out the red phosphorous because filtering it, being so damn fine, resulted in a great deal of loss to the filter paper, as well as a hell of a lot of it getting through. Prior to it's use in the reaction with the aforementioned contaminant, he observed that acidic water seemed to make it form floaty cloddy lumpy clustery things.

but after basifying it properly, he discovered that the red phosphorous behaved differently, markedly, and in fact he thought it seemed to make a neat pH indicator for the right basification level. When the water was too acidic, it seemed to be repelled from the water and aggregated in the bottom layer of the toluene. When the pH was raised to what seemed (no pH measurement device was used, but instead, a super-sensitive nose and visual observations) to be the right pH for extracting, the RP seemed to settle quite nicely in the water layer, right out of the way. after looking back, swill is now not surprised his first attempt at post rxn workup did not work - not enough base.

Maybe this has already been said somewhere before, but regardless, swil wants me to repeat it: red phosphorous seems to settle out of water very rapidly when the pH is somewhere around 12-13 (sodium hydroxide). In acid, it tends to want to float and if there is a nonpolar layer, it will tend to sit above the water, at the bottom of the nonpolar.

Ok, back to the gak - the diversion was merely to incorporate something which is in part relevant, and may be more so relevant in the post reaction when one has not got this gak out first. (in other words, for those who seem to be suffering a bad result with similar materials, it's quite possible that the gaks firther interfere by coating the phosphorous and creating changes in solubility (and this may apply to the glue on the matchboxes but having not tested the initial material in base, swil cannot say for sure)

the gak most definitely seems to not like high alkalinity. it dissolves moderately well in toluene too, which really sucks, and worse, it dissolves quite well in mildly alkaline water as well as acidic water.

The initial discovery of the colour change and solubility effect talked about in the inital posts here, is the key clue to how to remedy this problem.

Using the strongly alkalinised ethanol helps a lot in reducing the amount that comes out of the pill mass itself, but this is not a total solution. it reduces, not kills, the problem.

what kills the problem is really simple. once the alkaloids have been extracted into toluene, this murky greyish gunk comes across too, it clouds up the toluene. It possibly is in fact a suspension created by the material, however, strong base makes it completely fall out of solution.

So in a nutshell, swil solved the problem of this nasty evil gak by taking the freebase extracted into toluene, adding a moderate excess of dry sodium hydroxide, and then refluxing for a little while (a cold finger condenser comes in very handy as a cheap ghetto condenser for reflux incidentally, as well as cleaning iodine). The previously cloudy toluene, which contains this nasty gak in some form or other, turns perfectly clear, and can then be filtered, yielding perfect clear freebase extract.

This is a tentative solution, only done once, but a trail of breadcrumbs lead to it. swil hopes that this information can be of some use to others.

he thinks that the gentle reflux with solid sodium hydroxide serves a twofold purpose. one: it completely dries the toluene, utterly. two: the gak, when it comes into contact with the raw sodium hydroxide, seems to become insoluble in the toluene, and thus gets the fuck out of one's face.

swil came to this solution, because having read umpteen pill cure teks, he has gotten rather sick of how fucking complicated they are. and he has now seen that a much simpler method can be applied which gets the job done and is not fiddly. The key thing that allows this method to be used in this way is that pseudoephedrine doesn't mind strong bases, unlike some alkaloids that turn to black tar very quickly in its presence (tryptamines).

loki · guinea pig

nope, BZZZT wrong, this is not an effective method of clearing the gak, in fact it changed it, but not much of an improvement is golden hygroscopic liquid than white waxy gak laden.

swil thinks that it is time for him to quit the business.