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Author: Subject: Rhodiums loss of GABA to GHB
Darkfire
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[*] posted on 3-1-2005 at 20:44
Rhodiums loss of GABA to GHB


I found a rhodium mirror which described GHB from GABA. They wayback machine shows no such arctical existing.

Anyways, not that it matters but the GHB has no intent of misuse on any unwilling person.

From what i rember NaNO2 and HCl were used to take the amino to a hydroxy. If anyone has details on this, or any other method of GABA to GHB id be grateful. I cant seem to find the mirror that had the reaction im looking for.




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[*] posted on 4-1-2005 at 04:36


Here it is:


Sandmeyer Reaction of GABA to GBL/GHB
by Chromic


Quick introduction:
As other writeups that I have published, this method is 100% OTC. It is awesome for a chemist who wishes to prepare GHB in small quantities and high yields and to do so without directly obtaining any regulated chemicals such as gamma-butyrolactone (GBL) or 1,4-butanediol (BDO). It also avoids the typically low yields seen from the oxidation of tetrahydrofuran (THF). It uses an easy to obtain amino acid, gamma-aminobutyric acid (GABA), and sodium nitrite (NaNO2). It scales very nicely and runs without too much hassle. Not one suspect chemical is used.

The Sandmeyer reaction uses nitrous acid to turn amines into diazonium salts. This reaction, as it applies to turning GABA into GHB, is shown in the first reaction below. Aliphatic diazonium salts rapidly undergo hydrolysis in the presence of water giving off nitrogen gas and leaving a hydroxyl group behind. This is shown in the second step. As a result of these reactions, GABA can be turned into GHB in an easy to perform one-pot reaction.


Running the reaction:
Set up a 2L flask, sitting in ice-water on top of a magnetic stirrer. Now:

Add 3mol GABA (309.4g)
Add 3mol NaNO2 (207.0g)
Add 700ml water (total volume becomes about 1100ml)
Drop in a 1" stir bar and start stirring
Charge a 500ml pressure equalized addition funnel with 3.3mol HCl(aq) (385.0g 31.25%, 334.8ml 31.25%)
Fit the addition funnel with a gas outlet adapter and vent to theoutside
Begin slowly dripping the hydrochloric acid into the mixture. Drip it in at a constant rate of about 1 drop every 2-5 seconds. Speed it up as time progresses and replace the ice as necessary, but do not allow the evolution of the brown poisonous gas to become vigorous. After about one hour after the last drop of acid has been added, there is no need to replace the ice. Once the reaction is done, proceed to extract. (usually 24-36 hours later)


Extracting the goods:
There are many options for this. This is still a work in progress, but after about 20 runs, I came to use this work up. You can use ethyl acetate (EtOAc), chloroform or methylene chloride (dichloromethane aka DCM) to perform the solvent extractions. I have normally used DCM as it's nice since the organic layer drops to the bottom of the separatory funnel.

Setup for a simple distillation.
Distill, throwing out the first 5-10mls, or so, of distillate as it will contain a fair amount of nitric oxides. Distill off as much water as possible, basically until the sodium chloride starts to saturate the aqueous layer and precipitate out.
The remainder of the distillate (approximately 700ml) will contain approximately 1g GBL/10ml.
Treat the remainder of the distillate with NaHCO3 at reflux for 30 mins
Boil with about a 5% volume of activated charcoal (ie 35ml activated charcoal) (compared to the volume of the solution) for 5-10mins.
Allow it to cool and filter, wash the charcoal with distilled water. Save the NaGHB.
With the remainder of the aqueous, extract 5 times with 625ml portions of DCM.
Distill off the DCM (reuse that DCM!).
Distill the GBL (under vacuum if available).
React with NaHCO3 and distilled water and treat with activated charcoal as before.
Typically 375g of NaGHB is made from the solvent extracted GBL and 100g NaGHB from the aqueous distillate. Although conversion is nearly quantitative (as measured by GC/MS), the overall recovered yield is usually about 70%.

For those who don't know how to make NaGHB from GBL using NaHCO3 please read the section on preparation of Sodium GHB using Sodium Bicarbonate (Baking Soda, NaHCO3) found in the GHB faq. Never use unknown grades of NaOH--they may contain toxic heavy metal contaminants.


Notes on procedure:
1M NaNO2/GABA, as the French ref states is far, far too much water. You don't need it. I don't use that much.

It's possible to reduce the water further, down to the minimum necessary to dissolve the NaCl formed, thus avoiding the distillation of the aqueous layer. The trouble with this is that it's not fully practical. All of the GABA/NaNO2 will not dissolve, and you'll see more of an evolution of nitric oxides. The amount of water used is just barely enough to dissolve all of the NaNO2 and GABA to begin with.

If you want to skip the simple distillation (steps 1a-e) and go straight to step 2 (the extraction with the organic solvent) make sure to increase your organic solvent amounts by about 20%. Your yields will go down slightly.

It's possible to used sulfuric acid, however Na2SO4 is not as soluble as NaCl is, mole for mole. You'll need to use more water.

It's possible to use just a little bit less HCl, but hey, a slight excess is always a good idea.

It's possible to dump in a fair amount more HCl to try and push the GBL into the organic layer. It doesn't really work that well though. Yields don't go up.

It's possible to use chloroform or ethyl acetate instead of dcm. Diethyl ether will work as well. Do not try to use anything more nonpolar such as toluene, hexanes or the like. They won't extract much GBL.


Figuring out where the other 30%+ of the yield is going has been frustrating. Perhaps it is staying in the aqueous as free GHB. But do not consume the post-reaction aqueous layer!

The GBL produced from distillation has an putrid sour smell. This is likely trace quantities of butyric acid (the molecule responsible for the smell of rancid butter). It is not toxic in trace quantities and the off-smell and off-taste is cleared by treatment with activated charcoal.

The dose/response curve for NaGHB is exponential. 2g may be a nice buzz, 2.5g an amazing high, and at 3g a novice user could be violently ill, passed out and completely unresponsive. These doses are guidelines. Every person's response will vary. Chronic use of GHB will result in tolerance and physical addiction. Never mix with any other CNS depressants (especially alcohol).

References
Bull. Soc. Chim. Fr.; 1; 88-94 (1989)
GHB Letter to the Alabama Senate Committee on the Judiciary
Acknowledgements
Last, but surely not least, come the thank yous!

First, thank you to the girl who will always have a special place in my heart (and your determination in helping me with my struggles, especially my addiction to GHB and alcohol).

Thank you Rhodium for your hard-work and dedication to your site and the Hive in general. Thank you for pushing me to publish this document. A big round of applause for Steven Fowkes (even though you got your info wrong on MSG -> GBL in one step rxn), Fierceness, Moo, StraightEdge, hCiLdOdUeDn, Roundbottom, Osmium, Bright Star, Methyl Man, Dr_Sister, AB2, Aztec, Hypo, Ueruma, Ezekill, Terbium, Antoncho, Eleusis and Sasha Shulgin for raising my knowledge, awareness and inspiration. :)

Also thank you to the chemists who performed and published Bull. Soc. Chim. Fr.; 1989; 1; 88-94.



Thats what you were looking for right?Have fun.

-rlr
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Darkfire
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biggrin.gif posted on 4-1-2005 at 14:00
Thank you!


:D:D:D



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[*] posted on 1-2-2005 at 08:24
writeup/experience


Thaks runlabrun!

Does anybody have any experience they would like to share regarding this synth?

Perhaps a writeup?
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[*] posted on 1-2-2005 at 08:25


would like some comments b/c all refs for sandmeyer I have encountered refer to converting aromatics
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tom haggen
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[*] posted on 1-2-2005 at 09:46


Sounds pretty shady to me. I don't really understand how you can say that this synthesis obtains high yields. You start out will 1100 mL of reactants in the beginning of the synthesis, and you end up obtaining only 10mL of GBL? Though I don't doubt this is a good method, the information given here must be taken at face value. For one, you say that this synthesis is 100% OTC. NO2 salts are hardly over the counter, and if they were everyone including myself would be having a field day with preparing DDNP at our own leisure. I have actually gained some new interest in the synthesis of GHB considering that I’m a recovering alcoholic. I have yet to run across this particular route of obtaining GBL. I must say it seems quite promising. I just have a few questions and then I will quit ranting. Where exactly do you find a good source of GABA? Also, what exactly happened to all of those great rhodium sites that were all over the internet a few months ago? Right when I started getting interested in that kind of chemistry those sites disappeared:(
I tried browsing the rhodium thread on this forum to see what happened, but didn't have the patience to pick out the info I was looking for in such a crappy written thread.

[Edited on 1-2-2005 by tom haggen]




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runlabrun
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[*] posted on 1-2-2005 at 21:47


i have never tried this synth, this was just a copy/paste from rhodium mirror.

NaNO2 is not OTC... correct however its not suspect at all to order, with an appropriate reason as per normal for any order, so OTC in a more liberal sense, just a different counter....

"Typically 375g of NaGHB is made from the solvent extracted GBL and 100g NaGHB from the aqueous distillate. Although conversion is nearly quantitative (as measured by GC/MS), the overall recovered yield is usually about 70%. "
Whats wrong with the yields?

Tom, the 1100mL of reactants includes 700mL of solvent.... ie cannot be used to judge yield?

Tom if you want any rhodium stuff i have several mirrors on my hard drive so just pm me and i can get you what ever you want...

GABA is just as restricted as GBL and 1,4-BD and other associated precursors for GHB, best idea now is oxidation of THF to GBL i belive... in the spirit of the hive... for info UTFSE... lol

-rlr

[Edited on 2-2-2005 by runlabrun]
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[*] posted on 1-2-2005 at 21:52


Found this also....
http://www.chemguide.co.uk/organicprops/amines/nitrousacid.h...
Reaction of primary amines with nitrous acid, formation of alcohols.
The only refs for sandmeyer i found were indeed only aromatics, however at this ref it uses primary alkyl amines...

-rlr
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[*] posted on 1-2-2005 at 22:12


GABA is not restricted in the US. Just look on Google or in the nearest health food store. It's more expensive than THH, but more readily available in reasonable purity too.



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tom haggen
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[*] posted on 1-2-2005 at 23:08


What exactly is it used for in health food stores? I might go down to the local GNC and have a looksy.



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[*] posted on 2-2-2005 at 14:12


Quote:
Originally posted by runlabrun

GABA is just as restricted as GBL and 1,4-BD and other associated precursors for GHB, best idea now is oxidation of THF to GBL i belive... in the spirit of the hive... for info UTFSE... lol

-rlr

[Edited on 2-2-2005 by runlabrun]


GABA is not restricted and is avilible at health stores, not GNC, at least i havent seen it there. You will have better luck at those stores where old lady shop for "organic" foods.




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[*] posted on 2-2-2005 at 17:36


quote from a site selling it:


Quote:

GABA, or Gamma-Aminobutyric Acid, is a powerful amino acid that was first discovered in 1883 in Berlin. It is actually classified as a neurotransmitter, which means it helps nerve impulses cross the synapses (gaps) and communicate better. GABA has a great number of positive effects on the nervous system.

In addition, GABA has some startling effects on promoting fat loss. How does this work? GABA stimulates the production of Human Growth Hormone (HGH). It is HGH that has been found in studies to facilitate the metabolism of fats in the body. HGH is also known for its powerful muscle-building effects. Increasing HGH can definitely be a good thing, especially for bodybuilders. HGH tends to decrease naturally with age, so the older you get, the harder it is to lose fat. That's one reason GABA has become so popular.

Other studies have shown that GABA increases the body's sleeping cycle and patients reported much more vivid dreams. Getting a good night?s sleep and obtaining more rest can lead to more energy throughout the day. Not to mention, decreasing fat loss and promoting muscle growth also leads to an increase in energy.


It looks fairly cheap. 100g for about $15-$17.
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runlabrun
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[*] posted on 2-2-2005 at 21:26


ok my mistake.... i was refering to an old pacia document and subsequent amendment that stated gaba was to be listed as catagory 1....
i now have the new version which i was unaware of.... and it seems they have not put it on there.... strange....

ghb precursor from the local health food store.... hmmmm

-rlr
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Darkfire
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[*] posted on 2-2-2005 at 21:44


Man in the old days it was the GHB itself in the healthfood stores.



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[*] posted on 3-2-2005 at 00:36


It was sold at the counter a the gym I worked out at in like 90 or 91 . I remeber the fucking cops have him yank it off the self which sucked and the cops that I worked out with thought that it was shit cause they was homicide cops and it helped them sleep
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[*] posted on 16-3-2005 at 17:33


Well I went down to the hippie store and had a look around for this fabled precursor. I asked one of the desk clerks if they had any supplements for burning fat by increasing metabolism, and no luck. I will continue on my quest for this precursor because the more I study chemistry the more opportunities I will have to obtain some NaNO2. Anyway if anyone knows a brand name that might help in my quest, I'm open to suggestions. :P

EDIT: I just called my local GNC and it seems they have some in stock. I guess I just wasn't looking hard enough;)

Has Anyone on the forum had first hand experience with this method of GBL synthesis? If so could you tell how your results were.

[Edited on 17-3-2005 by tom haggen]




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[*] posted on 16-3-2005 at 18:28


I tryed it with a complete failure. There was no observeable reaction, i think it was poor kno2,. i dont thiunk there was much nitrous acid formed. Also the gaba made a gooey mess, so i just dumped it in an angry tired pissed off way, and went to sleep.



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[*] posted on 17-3-2005 at 03:09


The method works as advertised. The product is effectively formed. Usage of the Sodium Nitrite gave good results. The problem with this proceedure lies in the tedious workup, the syntheis is easy enough for anyone to do. (keep in mind that the NO produced needs to be vented OUTSIDE!!!). The large amount of organic solvent needed makes the proceedure frustrating. But 2-3 distillations of the GBL followed by an active charcol treatment usually yields a fairly clean product.
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[*] posted on 26-4-2005 at 18:03


I noticed that the MSDS on GBL stated that GBL has a flashpoint of 98C so wouldn't this make it dangerous to distill? Not to mention, GBL has a boiling point of about 206C, so, how would you be able to distill this liquid anyway? Your reaction flask would be bone dry when you were done distilling, and I was under the impression that you’re not supposed to distill chemicals like that. Would you have to add the GBL to a solvent with a higher boiling point and then distill?

[Edited on 27-4-2005 by tom haggen]




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[*] posted on 28-4-2005 at 19:43


Flashpoints are the lowest temperatures the substance CAN be ignited with a source of ignition, such as a flame or spark. At temps lower than the flashpoint the substance wont ignite.
The auto-ignition temperature is the one you have to watch out for. Some MSDS list these under or near the flashpoint temp.

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[*] posted on 30-4-2005 at 13:32


I thought flash point was the lowest temperature that a material could self sustain combustion.
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[*] posted on 3-5-2005 at 07:47


I mixed up flash point with the auto ignitoin temp. If you are trying to distill something that has the highest boiling point in the solution, what do you do? Add it to a solution with a component that has a higher boiling point. What i'm getting at here is that I don't want a dry reaction flask.



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[*] posted on 31-7-2006 at 03:58


Any updates to this? Pure GABA can be sourced very cheaply from China by now. Sodium Nitrate is available and cheap as well from your one stop internet auction site. Al-Chymist has cheap DCM & Chloroform.

Come on, let's see some results! What of this distilling issue? Problematic?

[Edited on 31-7-2006 by Misanthropy]

[Edited on 31-7-2006 by Misanthropy]




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[*] posted on 31-7-2006 at 08:49


I always thought that GBL is best steamdistilled. At 100°C and ph 5-5,5 the equlibrium GBL/GHB is to 80% on the GBL side - the removal of GBL by the steam should push the equilibrium further into the right direction.
IIRC the Ullmann names this procedure as one way to produce GBL.

This should make the workup easy and solvents obsolete.

/ORG

[Edited on 31-7-2006 by Organikum]




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[*] posted on 31-7-2006 at 11:28


Thank you. Dealing with all that DCM was not so attractive. :)



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