armageddon (Hive Bee)
07-06-04 22:13
No 517795
      lactone purification     

I once read in a patent that GBL can be purified by forming a phenylhydrazone (think it was 2,4-dinitro-phenylhydrazone..) which can then conveniently be recrystallized... (think I remember reading that something like "yellow needles" was said, but not sure about it)

- and unfortunately I am unable to relocate this useful bit of info... crazy

But hey, can't lactones - like most ketones - be purified via the oxime (or maybe bisulf)? (just an idea)

Greetz A

"..ein Trank von unterschiedlicher Farbe, in ihm ist Heilung fr die Menschen."
 
 
 
 
    Rhodium
(Chief Bee)
07-06-04 23:53
No 517808
      How about some afterthought?     

I once read in a patent that GBL can be purified by forming a phenylhydrazone (think it was 2,4-dinitro-phenylhydrazone..) which can then conveniently be recrystallized...

But as the molecular weight of butyrolactone is 86 g/mol and that of 2,4-dinitrophenylhydrazine is 198, it means that you would  need to use ~2.75 kilos of the hydrazine to purify one liter of GBL. Rather absurd if you ask me, especially considering its cost.

But hey, can't lactones - like most ketones - be purified via the oxime (or maybe bisulf)? (just an idea)

But hey, lactones are esters, not ketones...

The Hive - Clandestine Chemists Without Borders
 
 
 
 
    armageddon
(Hive Bee)
07-07-04 00:28
No 517816
      Well, I didn't think that far...     

Well, I didn't think that far... (2,4-dinitrophenylhydrazine is priced at ~120 bucks / 500g (ACROS) - this way of purifying is probably more suited for preparing analytical samples than for preparative work on big scale laugh)

But hey, gamma-butyrolactone is also called tetrahydrofuranone - so the ending "-one" doesn't stand for ketones? (funny - and the C=O in esters behaves different from carbonyl groups in ketones due to extra oxygen atom present - did I get that right?)

(sorry for my lack of afterthought)

A

"..ein Trank von unterschiedlicher Farbe, in ihm ist Heilung fr die Menschen."
 
 
 
 
    Rhodium
(Chief Bee)
07-07-04 01:20
No 517832
      Nomenclature and carbonyl surroundings     

But hey, gamma-butyrolactone is also called tetrahydrofuranone - so the ending "-one" doesn't stand for ketones?

I'd say that the "-one" suffix is rather an indication of the carbonyl group "C=O" being present. By looking at it that way, all nomenclature is consistent, but you still have to evaluate the chemical structure to find out if you have a ketone (as in 2-propanone) an ester (as in tetrahydrofuranone) or an amide (as in pyrrolidinone).

(funny - and the C=O in esters behaves different from carbonyl groups in ketones due to extra oxygen atom present - did I get that right?)

Exactly. If a carbonyl group has two alkyl substituents it's a ketone, if it only has one it's an aldehyde, and if it has one alkyl group and an oxygen it is a carboxylic acid or a derivative thereof. One has to look at each functional group together with its immediate surroundings to be able to predict its behavior.

The Hive - Clandestine Chemists Without Borders
 
 
 
 
    Rhodium
(Chief Bee)
07-08-04 07:45
No 518109
      NMR Identification and Quantitation of GHB/GBL
(Rated as: good read)
    

Identification and quantitation of gamma-hydroxybutyrate (NaGHB) by nuclear magnetic resonance spectroscopy
Chew SL, Meyers JA
J Forensic Sci, Mar. 2003, Vol. 48, No. 2 (../rhodium/pdf /forensic/ghb-gbl.nmr.analysis.pdf)

Abstract
The most common means of identification of gamma-hydroxybutyrate (NaGHB) involves using Fourier transform infrared spectroscopy (FTIR) or gas chromatography-mass spectrometry (GC-MS) of a suitable derivative. However, these methods may be complicated by possible shifts in chemical equilibrium between gamma-hydroxybutyric acid (GHB), GHB salts and the precursor lactone, gamma-butyrolactone (GBL). This paper addresses the technique of proton and carbon nuclear magnetic resonance spectroscopy (1H and 13C NMR) for the direct and accurate identification of GHB and GBL. The application of 1H NMR for GHB quantitation is also discussed.

The Hive - Clandestine Chemists Without Borders
 
 
 
 
    Raver71
(Stranger)
07-31-04 02:57
No 522804
      i tried gbl a bunch of times but it doesnt...     

i tried gbl a bunch of times but it doesnt give you that happy mood like ghb does..its more euphoric but without the happyness...
 
 
 
 
    armageddon
(Hive Bee)
07-31-04 04:58
No 522839
      really?!     

Did you know that you can convert GBL to GHB by adding 10% w/w of d.H2O to it, heating to >100C and then adding an equimolar amount of aequous lye (NaOH, KOH etc.) dropwise?

Besides, I don't understand what you mean when making difference between euphoria and happiness - aren't you happy when u get euphoric??? tongue

(I would rather say that GBL has sedative properties, whereas GHB is euphoric...)

Greetz, A

Pleased to meet you hope you get my name.
But whats puzzlin you is the nature of my game!
 
 
 
 
    ApprenticeCook
(Hive Bee)
07-31-04 07:25
No 522874
      ive seen this question many times.....     

ive seen this question many times..... why do people eat the precursor when the drug is so easily made from it and much much better???

i dont know.... weird....
-AC

Its just my opinion, but no-one listens to me anyway, and rightly so...
 
 
 
 
    raybeez
(Newbee)
08-09-04 17:09
No 524439
      Worked, but with low yields     

Swim finally gave this reaction a try following chromic's writeup on rhodium.ws and had some success but seemingly low yields. Swim ran a 1mol rxn and finished with just under 70g of NaGHB(s).

Swim used ACS grade NaNO2, OTC GABA (that had been tested against a small quantity of ACS grade GABA and was found to have identical solubilities in hot/cold dH2O and EtOH) and OTC muriatic acid.

Reagents where dissolved w/ mag stirring in 300mL dH2O and chilled to below 0C in an ice-water batch. Acid was added via an addition funnel (was worried a pressure-eq funnel would be needed, but vacuum never seemed to build up) and fumes were vented far away from SWIM using tubing.

Acid was added over the course of two hours.. went very slowly at first, keeping the buildup of yellow-brown gas under control in the rxn flask. Near the end, gas evolution diminshed, and the last 1/3rd of acid was added pretty quickly (over 15-20min). After acid addition, flask sat and stirred and bubbled at 0C for an hour. At this point, stirring was turned off, and the rxn flask was allowed to sit overnight for 14hrs.

Upon returning, the temp was around 20C and no bubbling was observed. Swim proceeded to setup flask for simple distillation and began steam distilling off GBL/water, but noticed as the temp increased and stirring was turned back on small gas bubbles formed in the flask (perhaps hadn't finished reacting yet?) Steam distillation continued into NaCl precip. was observed. Distillate was refluxed with ACS NaOH, boiled with 5% activated charcol, filtered, heated to 140-150degC to boil off H2O/excess lactone, and poured into pyrex dish...giving 20g or so of NaGHB. Product was hard, pure white in colour, looked identical to the product of a NaOH/99.9% GBL rxn (yay!). Had a slight tangy aftertaste however (butryic acid maybe?)

Remainder of aqueous was extracted with 5x230mL washes of ethyl acetate. Solvent was removed under vacuum, then swim was planning on distilling off the GBL, but when the temp hit around 50C in the distillation flask, swim's vacuum failed (one of the joints in the apparatus was the wrong size, and was being held together with parafilm which seemed to melt off ruining the seal).

Distillation was continued until 92C at 1 atm, then the 48mL of resulting yellowish/brown liquid was reacted with NaOH, boiled with activated carbon, filtered, re-heated to 140-150 C then poured into a pyrex dish and allowed to harden into NaGHB. Yield was 48g of slightly brownish NaGHB. Swim was worried about product purity, but it tasted and smelled _fine_ (even better then the white NaGHB recovered earlier). Of course was bioassayed and +ve results (no difference in required dosing noted to 0.1 of a gram).

So... 70g yield. swim was expecting close to double that from this reaction.. what went wrong? Rxn not go to completion at the beginning? Solvent washes done incorrectly? Toss some ideas at swim as he is planning on doing the 3mol version of the run soon.
 
 
 
 
    fierceness
(Hive Addict)
08-10-04 22:55
No 524672
      It really sounds like you did everything ...     

It really sounds like you did everything right, even better than when I did it.  The only thing I can see that may have caused it is that you should really not want to see ANY yellow/brown gas because seeing that gas means that there will not be enough nitric acid in solution deaminating the GABA.  If you have a problem controlling the gas, maybe you could add a slight excess of sodium nitrite and HCl.  Other than that, I can't see anything wrong!
 
 
 
 
    Bwiti
08-16-04 03:55
      Lets Fucking Face It..
(Rated as: no sources!)
    
 
 
 
    fierceness
(Hive Addict)
08-17-04 20:33
No 525931
      Pills     

You dont want the kind in pills or even in capsules.  There exists some GABA in powdered form that you're supposed to mix in water or a protein shake or whatever.  This kind of GABA works for this synth.
 
 
 
 
    18294
(Hive Bee)
08-18-04 19:10
No 526092
      SWIM's slight modification     

SWIM may attempt to make some GBL in the near future. Here is a rough outline of his plans:

Using Sandmeyer rxn to turn GABA into GBL (well hopefully, anyway)

1. SWIM will add 1 part powdered Gamma Amino Butyric Acid,  0.68 parts Sodium Nitrite, and he will also add the appropriate amount of water.

2. Next He will titrate his acid

3. He will wait 2 or 3 days for the rxn to complette.

4.He will then add dichloromethane

5. He will titrate his Base (50% NaOH)

6. SWIM will then seperate the water layer and run it through an Activated Charcoal column

7. He will acidify it until it reaches a pH of 6.5

Does anyone have any comments or anything to add to this? SWIM has done quite a bit of reading on the subject, and believes his A/B extraction of the product in combination with an AC clean would be a good substitute for the recomended distillation.
 
 
 
 
    merbst
(Hive Bee)
08-18-04 21:56
No 526100
      Re: believes his A/B extraction of the product     


believes his A/B extraction of the product in combination with an AC clean would be a good substitute for the recomended distillation



As stated in this thread, there is no good substitute for the recommended distillation.  Although of course you are welcome to try! If you have success (or failure even), The Hive is happy to read what you have to say about it!  Beware of the brown gas!  Perform under a fume hood if possible, but don't put your life in the hands of your local electricity provider.

 
 
 
 
    bbeeasheets
(Newbee)
08-28-04 02:42
No 527852
      sodium methoxide     

well after  making about 400g of GBL i took a portion aside to experiment with. One portion I added %50 NaOH (to the dcm extraction) and decanted the aqeouus. At this point I forgot to neutralize with vinegar and just boiled off the water. I took about 40g and and disloved it in boiling meoh (just enuff to disolve it all while stiring). Well the solution gradually became purple! I thought this was weird so I went back over my notes, and saw that I didn't neutralize. So I did some googling and found out that methanol and excess NaOH makes Na-methoxide... but nothing about it going purple. Is this sample salvageable? (without reconverting to gbl and distilling). I hate to toss it.
 
 
 
 
    wimpy
(Hive Bee)
09-29-04 11:25
No 533772
      I'm sorry, but isn't there any alternative to...     

I'm sorry, but isn't there any alternative to sodium nitrite? Sodium Nitrite seems controlled here ... (- after searching a long time now for lots of different chemicals i have to state that the "responsible department" is doing a really good job in barring one's way ... especially annoying as GABA is so easy to obtain mad)
Nothing known? or even thinkable?
thanks

one could start feeling like shooting someone might be at least a little satisfaction :(( ...
 
 
 
 
    Rhodium
(Chief Bee)
09-29-04 20:22
No 533833
      NaNO2 Preparation     

Post 458114 (gruns: "Preparation of Sodium Nitrite: Discussion", Chemicals & Equipment)

The Hive - Clandestine Chemists Without Borders
 
 
 
 
    wimpy
09-30-04 12:24
      Thanks Rhodium, sounds promising!
(Rated as: UTF PM Function)
    
 
 
 
    wimpy
(Hive Bee)
10-03-04 11:59
No 534297
      There's probably no way to separate NaNO2 from     

There's probably no way to separate NaNO2 from NaCL out of a mixture of both (1-0.5% NaNO2 in NaCL)? All swim was able to find out was that both are soluble in H2O but not so good in alcohol ...

- Beware of the Morphail Effect! -
 
 
 
 
    Rhodium
(Chief Bee)
10-03-04 13:34
No 534311
      Solubility of NaNO2 & NaCl at different temps     



I'd disagree. Check the tables above for a correlation of aqueous solubility of salts at different temperatures. The left shows NaCl and the one on the right shows NaNO2. As anyone can see, the solubility of NaCl does not differ much with temperature (it is always at 35-40g in 100mL water) while the solubility for NaNO2 more than doubles from 75g/100mL at 0C to 165g/100mL at 100C.

Thus extract the NaCl/NaNO2 mixture with boiling water (sodium nitrite being over four times more soluble than the chloride), then concentrate the extract to precipitate sodium chloride preferentially and filter hot (at room temp the solubility difference is much less).

The Hive - Clandestine Chemists Without Borders
 
 
 
 
    wimpy
(Hive Bee)
10-04-04 11:32
No 534406
      Hey! Really thanks a lot - that's kind of...     

Hey! Really thanks a lot - that's kind of light at the end of the tunnel :)
But do i get this right? As far as i understand one would not be able to get pure Nitrite out of this, or ... ?
So this leads to the question: would a smaller amount of NaCL affect the reaction?
Anyway, thanks a lot, swim will try as soon as possible!

- Beware of the Morphail Effect! -
 
 
 
 
    Rhodium
(Chief Bee)
10-04-04 13:51
No 534421
      Nitrite enrichment by fractional crystallization     

But do i get this right? As far as i understand one would not be able to get pure Nitrite out of this, or ...?

You have very good prospects for purifying the nitrite - for each iteration of a fractional crystallization procedure using the bare minimum of water needed to dissolve the nitrite (but not more than that as to avoid dissolving too much NaCl) you will remove 75%+ of whatever amount of NaCl you still have left in your salt mixture. If I have calculated it all correctly you will have enriched the nitrite content by three orders of magnitude in five recrystallizations (or less!). If you start out with a NaCl:NaNO2 ratio of 100:1 you will soon have changed that to 1:10...
100:1 → 25:1 → 6:1 → 3:2 → 4:10 → 1:10


The Hive - Clandestine Chemists Without Borders
 
 
 
 
    wimpy
(Hive Bee)
10-04-04 20:32
No 534406
      Hey! Really thanks a lot - that's kind of...     

Hey! Really thanks a lot - that's kind of light at the end of the tunnel :)
But do i get this right? As far as i understand one would not be able to get pure Nitrite out of this, or ... ?
So this leads to the question: would a smaller amount of NaCL affect the reaction?
Anyway, thanks a lot, swim will try as soon as possible!

- Beware of the Morphail Effect! -
 
 
 
 
    Rhodium
(Chief Bee)
10-04-04 22:51
No 534421
      Nitrite enrichment by fractional crystallization     

But do i get this right? As far as i understand one would not be able to get pure Nitrite out of this, or ...?

You have very good prospects for purifying the nitrite - for each iteration of a fractional crystallization procedure using the bare minimum of water needed to dissolve the nitrite (but not more than that as to avoid dissolving too much NaCl) you will remove 75%+ of whatever amount of NaCl you still have left in your salt mixture. If I have calculated it all correctly you will have enriched the nitrite content by three orders of magnitude in five recrystallizations (or less!). If you start out with a NaCl:NaNO2 ratio of 100:1 you will soon have changed that to 1:10...
100:1 → 25:1 → 6:1 → 3:2 → 4:10 → 1:10


The Hive - Clandestine Chemists Without Borders
 
 
 
 
    Agni
(Stranger)
10-25-04 06:14
No 537613
      using a retort     

i really want to try this synth but i dont have a disstilation unit or the money to buy one. Could i use a retort instead of the "normal" flask/condenser method? they are a good deal cheaper.