Author Topic: Gakinator?  (Read 13315 times)

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Prepuce

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Gakinator?
« on: June 12, 2004, 07:36:00 AM »
Swip heard about a bee who had tried another approach to the degakification of feedstock, that in his opinion looked promising. At first he was considering sharing only with a few who have been especially helful, but then he read a bit of Geez's "making me sick" thread and reallized that others are probably having similar problems. SWIP was. So he decided to share what is thus far an unperfected technique, in hopes that others may improve on it.

However  his decision to share didn't come before he had already contacted the fist bee on his list, and this was another reason he decided to tell me to post the information now. He heard nothing for several days after sending the PM. Finally it dawned on him how he might react if the situation had been reversed--especially considering the kind of questions he was asking. (Sorry, Shorty. SWIP was feeling enthusiastic and didn't think it through.)

As a final preface, SWIP wants to again emphasize that this procedure has not been perfected, it just seems better than the presently available alternatives, and has been working moderately well for SWIM for several weeks.

Here's what SWIM's acquaintance said to do:

Grind up some 120's as fine as possible and put them in a beaker or a glass that will hold them without being more than about 1/3 full. Run out to the grocery store and buy a bottle of ammonium hydroxide, or as it's usually labeled, household ammonia. (Don't get sudsy ammonia!) Also pick up a box of washing soda if you don't have any. Poor some [edit]ammonium hydroxide [/edit] into the glass with the GUPS--not too much, just enough to turn them into what looks like smooth marshmallow cream.

Pause a moment to laugh maniacally as the GUPS turn to slime--a pitiful attempt to thwart your intentions.

Next take your jar of washing soda and add a volume approximately equal to the marshmallow creme. The amount isn't critical but it's better to have too much than too little. Stir well, pressing the washing soda into the creme as thoroughly as possible. Now add xylene. Again, be generous, but not so much that you will have trouble getting the pfed back out of it. Stir this mixture and right away you may notice the volume decrease as the freebase disolves. Let it sit for at least fifteen minutes. Leave it overnight if you wish, or continue on immediately. Decant off the xylene into a funnel with a moderately compacted cotton ball in the barrel and a coffee filter. Gass the pfed to extract. Be patient during the gassing. SWIP says he was used to having the pfed fall right out, but that it took much longer than usual. (Maybe his HCl generator wasn't working well?)

After capturing the product in the coffee filter, rinse off the xylene with some acetone, and allow it to dry.

Now go back and do it again for better yeild, beginning by pouring the xylene back in with the GUPS. The second time through you might want to add a little dH2O*. No more than 5ml for two 20 count boxes of feedstock. Swim hasn't yet determined the optimum amount, just be conservative. When you finish, pull again and again until you're happy with your yeild. SWIP doesn't think heat helps at all, and in fact may cause you to pull some gak. If the last pull you made is sparse but you're nowhere near the theoretical yeild, add a bit more dH2O.

When this is all finished, combine the fruits of your labors in a beaker and add enough concentrated NaOH solution to thoroughly wet the product. Stir well until it's all been converted to free base. Add a little more NaOH if you aren't sure. Then add dH2O in about the same quantity as the liquid already in the beaker. Swirl and filter through two coffee filters. Rinse again 2-3 times with cold dH2O, and don't discard the rinse water. [When you have saved enough of the rinse water to make it worthwhile, add a layer of xylene to pull, separate then gas to recover more pfed.) Spread out on a plate to dry, but don't use heat. Remember, pfed freebase turns to vapor at a reletively low temperature, and even warming it will cost you yeild.

While you're waiting, take an ehrlenmeyer flask and match it up with a test tube with a diameter nearly the same as the mouth of the flask. If what you have is too small, cut rubber strips from an inner tube about 3/4 inch wide. Wrap this around the top of the test tube, stretching it snug as you go. Keep at this until it makes a nice snug fit with the mouth of the flask. Now cover all of the rubber with several layers of teflon tape pulled snug.

Crush some ice and fill the test tube, dump your dry freebase into the flask and insert the test tube. It should fit snuggly enough that you have to push with moderate pressure to seat it in the flask. Not so much you rusk breaking it, but enough that you don't have to worry that it might fall inside. If it's too loose add more rubber and teflon. If it's too tight, take some off.

Now place the (borosilicate) flask on a hotplate or a burner covered with a flat metal plate. Don't try to substitute anything else. Cups and jars can't take it and may break explosively. (Also, don't ever put your glassware directly on heating coils!)

It's a little tedious the first time through this because you've got to find just the right setting for your hotplate. Turn it on but keep the heat very low. Wait five minutes and if the freebase isn't melting, turn up the heat just a little. Keep at this until you find the setting that will just cause the freebase to melt and subsequently vaporize. If you mark the spot on the hotplate you won't have to go through this again. Having found the right temperature you might want to watch it for a few minutes to make sure it isn't going to get lots hotter as soon as you turn your back, and once you're satisfied set up a fan to blow on the outside of the beaker and go do something else for 1/2 hour. If you think of it, come back after fifteen minutes and suck out the now melted ice from the test tube with an eyedropper, and replace it with fresh. Try not to distrube the beaker though, because the crystals will fall back to the bottom and melt again. Not a big deal, just another few minutes wait.

After 1/2 hour take a look, and you should see the sides of the beaker are now coated with freebase crystals, and there will likely be some gak at the bottom that hasn't done much of anything. Remove the flask from heat and set aside to cool, being as gentle as you can so as not to disturb the fragile crystals. When completely coooled turn off the fan, and carefully pull out the test tube. Holding it over a container, scrape the crystlas from it's sides. Invert the beaker over teh container and shake out the loose crystals. Finally, reach a scraper into the beaker and scrape the remaining crystals off of the sides and into the container. The clean crystals will be found on the side down to just above the bottom of the flask, and it will be easy to see where you want to stop scraping. Be careful not to scrape loose any of the gak at the bottom.

*On dH2O, listen to what everyone has been saying lately. If you don't believe it makes a difference, the next time you need to mix up some NaOH, mix two batches. In one use dH2O and in the other use tap water. It may not be immediately obvious, but after  a few days the batch made with tap water will have particles floating around in it--a really visible contamination. SWIP used to think it was because his drain cleaner NaOH was poor quality but he was wrong!

Looking forward to hearing of improvements and other comments.

PP

ning

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Petri dish? Baking pan?
« Reply #1 on: June 12, 2004, 06:18:00 PM »
Since you're sublimating the freebase (or could this bee called a short-path distillation?), why not use something flat with a wide top, to collect the crystals better?

For example, a round, shallow pyrex baking pan or bowl with a glass plate or bowl sitting on top of it with cold or ice water in it might do quite nicely, and would surely make cleaning easier.

A very interesting approach....


Prepuce

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Strictly speaking it's not sublimation, since...
« Reply #2 on: June 12, 2004, 06:47:00 PM »
Strictly speaking it's not sublimation, since the freebase melts before becoming a gas, so SPD is a good term.

In SWIPs experience a beaker is easier to deal with. A pyrex pie plate with ice in the top has been suggested by others, but if it doesn't seal well around the sides it will leak during the process. The ice or water must be removed when the process is finished or you risk dumping it into the collection container, all the while workign with crystals that are so light and fragile that the slightest breeze makes them fall away.

The psuedo-cold finger that SWIP suggests is the easiest and most efficient method he's come across. Other than the test tube, which could probably be eliminated in a pinch, your end product is nicely contained until you're ready to deal with it.

PP

Shane_Warne

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Is this right?
« Reply #3 on: June 12, 2004, 07:46:00 PM »
Base with carbonate, extract with NP, Gas out as pe.HCl, collect, base (again) with NaOH, vaporise?


I can't see where the ammonia water is used.

Prepuce

  • Guest
You've almost got the steps in the correct order,
« Reply #4 on: June 12, 2004, 10:41:00 PM »
but not quite. First the GUPS are mixed with ammonium hydroxide, a base. Then the washing soda added, followed by the non polar to extract. After extraction the non-polar is gassed, then the freebase is vaporized and condensed back into a solid.

SWIP is not a chemist and doesn't understand exactly what happens, but here's his speculation. The ammonia kills the detergent's hold on the pfed HCl. The xylene is now able to pull the pfed freebase without the polysorbate fighting to keep it in solution and countering everything you try to do with it. The gassing precipitates the pfed from the xylene, and the alternative would be to let it evaporate. Unfortunately we need it in freebase form to do the vaporization step, so it's based again.

SWIP isn't happy with the last step but hasn't found a way around it. He tried hot VM&P but oddly, the freebase wouldn't come back out of it just by letting it cooled. It had to be gassed or titrated. The only conclusion he can draw from that is that either pfed freebase is soluble in naptha unless it's mated with PEG or relative, or there's another gak that follows in xylene that causes the pfed freebase to become soluble. Regardless, the best solution seems to be a double A/B in spite of the associated losses.

The good news is that the product is very clean, there's no boiling of solvents, and it's a comparatively quick procedure to perform.

PP

Shane_Warne

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I like it myself
« Reply #5 on: June 13, 2004, 02:58:00 AM »
I like it Prepuce, well done mate!

Basing two times does seem tedious though. What was the yield like from the ammonia/carbonate step?

White 60s?

hehe, the ammonia water is what I really like the most, because it cuts out a lot of sodium that they've probably been working around for years.
I wonder how the hydrogels and cellulose binders react to the presence of the ammonium hydroxide instead of sodium compounds, because I know that sodium chloride makes some of them contract.

Do you think you would get a complete basification with ammonia water if you just added more?

Prepuce

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Basing with ammonia
« Reply #6 on: June 13, 2004, 09:34:00 AM »
SW, it actually takes a lot longer to explain it than it does to do it. SWIM says he can get through the first part of the procedure in about five minutes, then it's a matter of waiting for some acetone to dry. Even if you stand there and wait it doesn't take long for that. The second basing is even quicker than the first, and why bother with the vaporization until you're completely finished with all else. In other words, that part only needs to be done once.

I believe SWIM said he's done this on generic and brand name 120s, generic and brend name white 60s, and recently on something he found for the first time--white 30s with no antihistamines. He usually does three pulls on the GUPs. Yeilds have varied because he was working through the mechanics of the procedure, but he checked after working some white 60s and the yeild was about 60 percent. That might not sound very good, but before he came up with this his average must have been somewhere around 10 percent and it was still full of nasty gak.

Vaporization is a good way to see how clean you're getting your pfed, if nothing else. You might be reallly surprised what you find left over. SWIM has convinced himself that the detergent gaks don't actually inhibit the reaction very much, as many have speculated. The pfed is never finding it's way into the reaction. Even though it looks sparkling clean, SWIM has over and over found it to be loaded with crap--especially piss yellow oil--after vaporization.

As SWIM keeps telling me, the procedure needs fine tuning. Aommonia is a fairly strong base and should be capable of basing the pfed on it's own. He has thought about doing so, but so far hasn't thought of an advantage to doing so. (One disadvantage would be dealing with all the water.) He thinks the contribution of ammonia is primarily in breaking down the detergent gaks. In fact, he's been meaning to try adding a little NaOH to the first basing to see how yeilds are effected.

PP

geezmeister

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gassing for freebase?
« Reply #7 on: June 13, 2004, 08:04:00 PM »
Gassing for the freebase form of pseudo? I don't think so.
You gas for the salt form. You convert freebase pseudo to pseudo HCl by gassing with HCl gas. You could evaporate the solvent for the freebase, or you could freeze the freebase out of naptha. If you are having problems with the freebase not precipitating from naptha... you are using too much naptha. Pseudo freebase is soluble in naptha, it just isn't anywhere near as soluble in room temp naptha as it is in hot naptha. In VE's striaght to bee, there was always some pseudo left in the naptha, which could be had by titrating. But titrating carried gakk with it.

If you have freebase after gassing, you are carrying the Eudragit polymers with you and they are preventing the conversion to the salt form. Scottydog noted this in an earlier thread about 120's.

I like the approach with ammonia, though. You may be correct in your assumptions that it breaks a lot of inerts down that we aren't breaking down by solvents. I also applaud your purification step, and look forward to your honing it down even more. Thanks for the writeup. If I can gather enough pills to mess with, I'll try this out.


Prepuce

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re: gassing for freebase?
« Reply #8 on: June 14, 2004, 12:34:00 AM »
Geezmeister-sama,

SWIM has been going over his posts to see what might have given you the idea that he thought he could gas for freebase. The only thing he could find, and for which he is unable to post an edit, it the statement,

"He tried hot VM&P but oddly, the freebase wouldn't come back out of it just by letting it cooled. It had to be gassed or titrated."

He should have completed that sentence by stating that gassing or titrating caused the hcl salt to precipitate. What he had intended was chilling it out of the hot solvent, ala Straight to B. When SWIP used that process there was always freebase crystals that would fall out as soon as the solution even began to cool. Not so in the incident he describes in this thread. The only way he could get the pfed out of the solution at all, short of evaporation, was to gas for the hcl which did precipitate.

SWIM is famous for leaving too much between the lines, however, so if there's something else please point it out specifically so he can correct it. The technnique is all about getting past the gassing/titrating gremlins, which coincidentally are also the reaction thwarting demons.

As for trying the procedure, SWIM did most of his testing on 3-5 pills at a time in a test tube. Two or three is enough for 120s, and should be sufficient to decide if the technique is workable or not.

The purification step--vaporization, is working well for SWIM the way it is. (Although he would heartily welcome any suggestions for improvements!) When he first started with it he found it messy and prone to waste, but with a little practice he has come to regard it as quite workable. The keys are to not disturb the beaker, keep cooking until there is no liquid remaining at the bottom, then gently remove from heat and let it cool before further disturbing it.

PP

ning

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someone seems to like their anime
« Reply #9 on: June 14, 2004, 02:19:00 AM »
my uneducated guess is that if there's gaks designed to hold onto freebase amines, the ammonia overwhelms them and takes the place of the pseudo.

I like the idea of ghetto short-path distillation much better than chromatography (yes, no fun, I know)


geezmeister

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here's the passage..
« Reply #10 on: June 14, 2004, 02:51:00 AM »

After extraction the non-polar is gassed, then the freebase is vaporized and condensed back into a solid.




That comment will mislead six thousand newbees into disaster. How about filling in the missing between-the-lines comments so you don't confuse the new ones, or the old geezers like me, who have nothing to do with their hands these days but bitch at the keyboard... ;D  Damn pill laws! I have to drive a couple of hours just to get enough pills to make it worth my time to try any new method. (Get ready folks, its headed your way before you know it.)




Prepuce

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Missing phrase
« Reply #11 on: June 14, 2004, 06:01:00 AM »
Thanks, Geez. Guess SWIPs ADHD is kicking up worse than he thought. (Good thing he has a supply of the temporary cure.)

For some reason the option to edit that post is not offerred by the board, but the sentence should read:

=============================
"After extraction the non-polar is gassed, the hcl salt is collected and based with NaOH to turn it back into the freebase. The mixture of NaOH, dH2O and freebase is filtered, then dried. Finally the freebase is vaporized and condensed back into a solid."
====================================

Gee, it sounded so much easier before. It really is harder to write about it than to do it, though.

You have to drive 2 hours to get enough pfed to react? SWIM didn't realize it had gotten that bad. He assumes it's because of ID checks in SWIGs locale, but not in the other. That's exactly the kind of thing SWIP had in mind when his intention was to not make this method public. Whatever people may think of the WOD, however, neither I nor SWIM can imagine that anyone could see making people sick as the right thing to do.

Since I'm on my soapbox anyway, consider this: The war on drugs makes no sense to any reasoning individual if you look at the results. Who benefits? Follow the money.

Even honest politicians alert enough to think it through wouldn't dare to suggest decriminalization because it's political suicide. (What became of the mayor of Baltimore, anyway?) Those in favor of continuation are driven by emotion, and could be made to see reason if reason were presented. So who is making the money as a result of the WOD anyway? Who benefits? There's a lot of money being spent. Someone likes it very much.

So much for the soapbox.

PP

Prepuce

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Well, short path distillation
« Reply #12 on: June 14, 2004, 06:09:00 AM »
is certainly easier than chromatography! Faster too!

"I like the idea of ghetto short-path distillation much better than chromatography (yes, no fun, I know)"

PP

Shane_Warne

  • Guest
What are the gaks the like to hold on to ...
« Reply #13 on: June 14, 2004, 07:10:00 AM »
What are the gaks the like to hold on to amines? I could name orange, and that's it.
I've ignored polysorbate too, either rightly or wrongly.

Prepuce, what detergents are you refering to, mate?

Prepuce, so have you had any issues with condensation of water with the freebase, due to the ice-filled coldfinger?

swisw would expect that and would add CaCl2 to the fb before heating.

I didn't know fb vaporised so rapidly by the way. Warming will cost yield? Didn't know that.

ning

  • Guest
I wonder
« Reply #14 on: June 14, 2004, 05:52:00 PM »
do you think the pfed-salt could be sublimed as well?

After all, people smoke meth HCl...


Prepuce

  • Guest
Gaks that hold amines
« Reply #15 on: June 15, 2004, 06:29:00 AM »
SW, ning:

The two that SWIM is most familiar with are PEG and poloysorbate 80. Both are non-ionic surfactants. Detergents. Polysorbate in particular has been difficult to deal with, but PEG has also been a big problem in the past. For more information on the subject than you probably want, see the thread  "Know the enemy: More data on polysorbate 80." Never have figured out how to post hyperlinks here, so you'll have to UTFSE to find it. Sorry.

SWIM has had some issues with water when vaporizing fb and it makes it really messy. Tends to drip off the end of the test tube and recycle itself. Fortunately it's not difficult to let it dry out well first. You don't need to do anything special since it doesn't tend to absorb moisture. SWIP puts it in a box with an exhaust fan, and that's all. No heat, no fan blowing on it for obvious reasons.

The test tube with ice in it usually has only water by the time it's removed from the beaker, so condensation is not a problem. Removing it early complicates things anyway, since you'll shake loose some crystals that will fall back onto a hot spot, melt, the vapor will escape since the test tube is out, etc. The test tube isn't such a big deal anyway, since most of the crystals cling to the sides of the beaker. Just cook it until there's no liquid in the bottom that wants to vaporize, and don't be tempted to turn up the heat if all of it doesn't turn to a gas. That's a sure way to start vaporizing gak. It might break your heart to leave it there, but if it doesn't vaporize it's not what you want.

When you find the temperature where vaporization occurs, most all of your freebase will vaporize just by letting it cook. After you harvest the results, scrape everything remaining into a pile on the bottom of the flask and heat it again. SWIM doesn't clean out the beaker until it gets pretty nasty, because there's always a little more fb mixed with the gak, and the gak doesn't hurt anything as long as it doesn't get too hot.

Adding CaCl2 will probably get you wet freebase and dry CaCl2. There's no reason to do that anyway. Just let the fb dry before you start. If it's wet and you chop it into small peices it won't take that long.

It does vaporize easily. Really easily. The melting point is only 118°C, and the vaporization temperature is not much higher. The HCl salt, on the other hand, melts at around 180°C, and it seems to prefer burning to vaporizing. If you're careful enough to get it to vaporize, at 180+ you're going to probably be vaporizing a lot of gak as well. So you see, this really only works on the freebase.

PP

ning

  • Guest
So, then
« Reply #16 on: June 15, 2004, 05:51:00 PM »
First, to post a link to a post, put it's number in brackets. Your post number is 513459, put that in square brackets to obtain

Post 513459

(Prepuce: "Gaks that hold amines", Stimulants)
.

Now, those annoying detergents are of the polyoxoethylene type, eh? It would be ideal to perform an acid hydrolysis to crack those ether groups, but I don't know the conditions required or whether it would harm the pfed.

So let's imagine that they boil really high, and leave them as-is. Say we follow the following imaginary procedure:

pills are ground up with ammonia water and sodium carbonate until it is a pasty, chalky sludge. Then, the mixture is gently evaporated to yield a hard greasy cake which is crushed up and distilled as prepuce describes. Hopefully good yield of pfed.

Something worth trying, I guess.

Best luck  8)


Prepuce

  • Guest
Many details
« Reply #17 on: June 16, 2004, 06:28:00 AM »
ning: SWIM has been continually amazed at what he has neglected to mention with respect to this thread. What was presented is a procedure that evolved over the course of several weeks, so there have been many less than successful tests. What makes it difficult is that SWIP has been less than conscientious about recording all of his findings.

Having said that, he may be mistaken, but believes that the xylene plays an active but, at least for SWIM, unknown role in the process. In his tests he never allowed the GUPS/ammonia mixture to dry, however, so it's surely worth a try. In a similar vein, SWIM has tried other non polar solvents, but everything tried pulled gak along with the desired product.

When ammonia is mixed with GUPS, depending on what kind they are they usually melt into a smooth gooey paste. The transition when xylene is added can be somewhat striking to watch, as the gak withers and dies before your delighted eyes, a fate similar to that of the wicked witch when doused with water. If only it could scream!

Ahem. Sorry.

SWIP has a feeling that the next major improvement of the process will come with the addition of another as yet unidentified substance to the mix.

SWIP dreamt that he recentlly completed the first reaction using only the product of the gakinator process. He want's to double check the results before saying too much, but can't resist mentioning that he was astounded! by the yeild. Especially since he doesn't think he has ever achieved better than about 45% by weight of pfed, with some portion of that gak. . . This looks to be by far the best yeild he's ever produced by means of an rp/i reaction.

(Speaking of which and the associated difficulties, has anyone succeeded in extracting useable H3PO3 from pool antiscale additive? It boils down to a waxy solid when cooled, but has a pink tint, and SWIP has no idea what the contaminant may be.)

Thanks for explaining the link markup, btw.

PP

Shane_Warne

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SWIP dreamt that he recentlly completed the...
« Reply #18 on: June 16, 2004, 07:42:00 AM »
SWIP dreamt that he recentlly completed the first reaction using only the product of the gakinator process. He want's to double check the results before saying too much, but can't resist mentioning that he was astounded! by the yeild. Especially since he doesn't think he has ever achieved better than about 45% by weight of pfed, with some portion of that gak. . . This looks to be by far the best yeild he's ever produced by means of an rp/i reaction.

You'd want a good yield from the RPI, to make up for all the losses from 2 A/B's and a vaporization.  ;D

ning's shortened version is more to my taste, except you'd have to wait a long time to evap, and heating wouldn't be possible, because it would steam distill off.

How about just vaporizing after extracting with a NP? Worth a try?

Have you ever weighed the yield after the gassing?

barkingburro

  • Guest
funny you mention descaleant
« Reply #19 on: June 16, 2004, 12:17:00 PM »
swibb is at this very moment working on this. first step was to dry using dessicant rather than boiling it down. heat causes h3po3 to degrade when it is aqueous. the secondary chemical in swibbs descaleant is polymaeic acid.

thoughts on why the ammonia may work... ok the gaaks are designed to be activated and released in the body. is ammonia not pretty similar to chemicals in the body produced as waste? i suppose that would be more urea than anything.... hmm, just a thought