Author Topic: msg -> ghb?  (Read 5484 times)

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Chromic

  • Guest
msg -> ghb?
« on: October 04, 2002, 04:35:00 AM »
In a recent message in alt.drugs.ghb the idea of turning MSG to GHB was discussed. Here is the reference:

http://groups.google.ca/groups?q=msg+ghb&hl=en&lr=&ie=UTF-8&oe=UTF-8&selm=e4omhu42qecao9095n29h2t8de203s0rij%404ax.com&rnum=1



The above reference refers to a message on Ceri, here:

http://www.ceri.com/alabama3.htm



Which states:

monosodium glutamate (MSG), the essential amino acid, dietary supplement and flavor enhancer which converts to GHB in one step using nitrous acid (HNO2, a deaminating agent)

Ok, so turning NH2-CH(CH2CH2COOH)-COO- Na+ into HOCH2CH2CH2COO- Na+ seems kinda far-fetched to me. Sure nitrous acid in the presence of sulfuric acid can nitrosate alkylamines, but you don't hear of many of these reactions since the N-nitroso compounds decompose to the diazonium salt... which is unstable and break down to yield a carbocation.

Would it be possible that the carbocation would react with water, eliminate the alpha-C (in the form of CO2) and form GHB?

If not, is it possible that this reaction would work if MSG were decarboxylated to GABA--can anyone suggest a way other than GAD (glutamate decarboxylase)? Then react GABA with nitrous acid? NaGlu is cheap and everywhere, it would be cool if this rxn worked.

... even if there was an easy way to get GABA from MSG it would be of interest to me.

Rhodium

  • Guest
Intuition says yes, must check the refs though
« Reply #1 on: October 04, 2002, 05:50:00 AM »
Would it be possible that the carbocation would react with water, eliminate the alpha-C (in the form of CO2) and form GHB?

That could happen, that could happen.

Chromic

  • Guest
Well, not too promising...
« Reply #2 on: October 04, 2002, 10:36:00 PM »
It looks like adding nitrous acid to NH2-CH(R)-COOH will make HO-CH(R)-COOH as in:



If the diagram is right, it appears that the result would be 2-hydroxyglutarate not gamma-hydroxybutryate. (ie HO-CH(CH2-CH2-COOH)-COOH not HO-CH2-CH2-CH2-COOH). It appears that reacting GABA with nitrous acid would make a mixture of crap (including GHB) as in:



Now, ok, 2-hydroxyglurate can be made... but is that good for anything? Not really, my bets are on it entering the Krebb's cycle and being turned into CO2 & H2O.

It also came to my attention when searching that heating monosodium glutamate will produce sodium pyroglutamate. (sodium salt of pyroglutamic acid). Heating GABA will also produce a lactam (cyclic amide). Damn, damn & damn.

I'd love for someone to tell me that I'm wrong!  8)

Rhodium

  • Guest
GABA -> GBL + GHB
« Reply #3 on: October 04, 2002, 10:59:00 PM »
Reactant: 4-amino-butyric acid
Products: dihydro-furan-2-one (70%), 4-hydroxy-butyric acid (30%)
Reagents: NaNO2, HCl
Solvent: H2O
Time: 24 hour(s)
Other Conditions: Ambient temperature
Reference: Bull.Soc.Chim.Fr.; 1; 88-94 (1989)

Reactant: butyric acid
Product: 4-hydroxy-butyric acid, dihydro-furan-2-one
Reagent: O2, K2PtCl4, K2PtCl6
Time: 144 hour(s)
Temperature: 80-90°C
Other Conditions: other aliphatic carboxylic acids; also without Pt(IV)-catalyst
Reference: J.Chem.Soc.Chem.Commun.; 18; 1991; 1242-1243.

Reactant: succinic acid monomethyl ester
Product: 4-hydroxy-butyric acid
Yield: 90 percent
Reagent   NaBH4
Solvent: H2O
Time: 12 hour(s)
Other Conditions: Ambient temperature
Reference: Synth.Commun.; 18; 15; 1988; 1765-1772.

Reactant: succinic acid anhydride
Product: 4-hydroxy-butyric acid
Reagent: hydrogen, nickel
Other Conditions: die Saeure bezw.ihr Lacton, das Butyrolacton entsteht
Ref: Chem.Zentralbl.; GE; 78; I; 1907; 1617.

Reactant: succinic acid anhydride
Product: 4-hydroxy-butyric acid
Reagent: sodium amalgam, diethyl ether, hydrochloric acid
Other Conditions: die Saeure bezw.ihr Lacton, das Butyrolacton entsteht
Reference: Chem.Ber.; 29; 1896; 1193.

Chromic

  • Guest
Good to be wrong
« Reply #4 on: October 04, 2002, 11:47:00 PM »
It's good to be wrong! GBL and GHB in 100% yields from NaNO2/HCl and GABA, excellent!

Now please, someone show me how to turn Na-Glu into Na-GABA.  :)

But, luckily even GABA is available in 100ct bottles of 750mg capsules for moderately reasonable prices. I should check to see if the local nutrition store carries it...

If so, then it's definitely time to polish up on my French and check out the Bulletin de la Société chimique de France to find out the details on the rxn.

I was definitely discouraged to check out the refs from Oxidations in Organic Chemistry by Hudlicky on the oxidation of cyclic ethers, because the references for CrO3 and KMnO4 did not apply to cyclic ethers (which I find really odd!). This has brought my hopes up again!

Thanks Rhodium.

Chromic

  • Guest
Reference
« Reply #5 on: October 05, 2002, 01:04:00 AM »
My nutrition store came up short! Where is the GABA?  :)  Anyways, I wasn't discouraged to go to the library. I had my hopes up.

I found out that's an awesome reference. I confirmed the 30% GHB & 70% GBL from GABA (80% and 20% from GABA-OMe), and read that you get 100% of 2-hydroxyglutarate lactone from Glu.

The experimental reads:

Des solutions aqueuses equimoleculaires en nitrite de sodium et acide amine sont realisees a une concentration de 0,5 M ou 1 M suivant la solubilite des acides amines. Le pH de la solution est ajuste a la valeur desiree (pH = 4-5) avec HCl 2N. Le melange est agite a temperature ambiante pendant 24 heures afin que le degagement gazeux soit termine. Puis la solution resultante est analysee par RMN 13C.

Which I think roughly means:

Aqueous equimolar solutions of sodium nitrite and amino acid are made up at 0.5 M or 1 M depending on the solubility of the amino acid. The solution is adjusted to pH = 4-5 with 2N HCl. The mixture is stirred at room temperature for 24 hours (until the nitrogen emission is done). Then the solution is analyzed by carbon-13 NMR.

How do I remove that carboxy group? Anyone? Please!  :)

Chromic

  • Guest
Experimental in mass qtys
« Reply #6 on: October 05, 2002, 01:27:00 AM »
Suggested experimental:

103.1g GABA and 69.0g NaNO2 is added to 1L of water. Stirring is started. 116.7g of 31.25% HCl is slowly added. pH is checked to make sure it's around 4-5 (if not add more HCl). Reaction is run 24hrs with no heating.

The expected yield is 86.1g of GBL. The whole mixture can be distilled to dryness, then 84.0g of NaHCO3 is added to the distillate, refluxed for 30 minutes and boiled down to a reasonable volume and enjoyed responsibly.

In the case of MSG, 2 mol of 31.25% HCl is added (233.3g) and 1 mol of MSG (169.1g). This unfortunately won't make GHB.

Now, who's gonna try this out?!?  :)

El_Zorro

  • Guest
So GAMA is just gamma amino butyric acid, or 4 ...
« Reply #7 on: October 05, 2002, 04:54:00 AM »
So GAMA is just gamma amino butyric acid, or 4 amino butyric acid?  And it can be found at the local drug store?  is there a special name they call it?  PM me, Chromic, immediately. 8)

Who is that masked man?

Chromic

  • Guest
A run with this reaction
« Reply #8 on: October 05, 2002, 05:00:00 AM »
This reaction appears to be quite exothermic. I'm doing it on a 0.1 mole scale with MSG. I'd highly recommend anyone attempting this to slowly drop in the hydrochloric acid. I can see bubbles of what I hope are N2. Very nice, very easy!

EDIT: external cooling is definitely necessary! Sit your flask in some cold water otherwise you'll be breathing in NO2!

poix

  • Guest
NMP as a possible precursor?
« Reply #9 on: October 06, 2002, 06:44:00 PM »
I wonder if a monomethylamine can be utilized in such a reaction, if it is the case we can use the open form of 1-Methyl-2-pyrrolidinone (NMP) for the replacement of ol' GBL

carboxyl

  • Guest
Zoro: GABA = gamma amino butyric acid.
« Reply #10 on: October 07, 2002, 12:03:00 AM »
Zoro: GABA = gamma amino butyric acid. It is available at every health store and supermarket that I have encountered in my area.

This is a very exciting thread!! Thanks Chromic, Rodium and everyone else who has participated!!

The above post is purely fictional. Any resemblance to "real-life" is purely coincidental.

Chromic

  • Guest
NMP?
« Reply #11 on: October 07, 2002, 05:37:00 AM »
I think you mean pyrrolidone as a precursor for GHB (ie GABA lactam)--not NMP.

I gotta find me some GABA. This reaction is a breeze, the test with MSG went splendidly!

Precursor2112

  • Guest
As Neo Said in the Matrix...
« Reply #12 on: October 08, 2002, 01:38:00 AM »

El_Zorro

  • Guest
Does GBL steam distill?
« Reply #13 on: October 08, 2002, 03:54:00 AM »
Does GBL steam distill? Because if it does, then distillation should be a breeze, but you'll be left with some impure GBL.  If not, then it should be easy to distill it to reasonable purity, since it's BP is so much higher than anything else in the reaction mix.

Who is that masked man?

Chromic

  • Guest
Sure does.
« Reply #14 on: October 08, 2002, 04:51:00 AM »
>Does GBL steam distill?

Yes, 1 part GBL and 9 parts water seems to do it alright... which is EXACTLY what's called for in the reaction. Distill off the water/GBL and react the distillate with a base (eg sodium bicarbonate).

It's a very efficient way of purifying everything...

moo

  • Guest
NMP
« Reply #15 on: October 08, 2002, 06:39:00 PM »
Poix: A secondary nitrogen like the one in decyclised NMP, won't diazotise, so it won't be of any help.

Chromic

  • Guest
Glu decarboxylation
« Reply #16 on: October 21, 2002, 09:27:00 PM »
I wish decarboxylation could only be as simple as adding a dash of MSG to flavor up some immobilized Escherichia coli to produce the desired gamma-aminobutyric acid... (ie that you didn't need an ion exchange resin to work up the product)

So, I gather we're all pretty sure that there's no easy way to decarboxylate MSG?

thethethe

  • Guest
Free translator
« Reply #17 on: October 23, 2002, 09:54:00 PM »

Des solutions aqueuses equimoleculaires en nitrite de sodium et acide amine sont realisees a une concentration de 0,5 M ou 1 M suivant la solubilite des acides amines. Le pH de la solution est ajuste a la valeur desiree (pH = 4-5) avec HCl 2N. Le melange est agite a temperature ambiante pendant 24 heures afin que le degagement gazeux soit termine. Puis la solution resultante est analysee par RMN 13C.






This is what I get, from

http://www.freetranslation.com

:


Aqueous solutions equimoleculaires in sodium nitrite and acid amine are realisees has a concentration of 0,5 M or 1 following M the solubilite of the acids amines.  The pH of the solution is adjusts has the value desiree (pH = 4-5) with HCl 2N.  The mix is shakes has ambient temperature during 24 hours so that the gaseous degagement be finishes.  Then the solution resultante is analysee by RMN 13C. 




TTT


Chromic

  • Guest
Uhuh
« Reply #18 on: October 23, 2002, 10:16:00 PM »
Thethethe, I think what I wrote:

Aqueous equimolar solutions of sodium nitrite and amino acid are made up at 0.5 M or 1 M depending on the solubility of the amino acid. The solution is adjusted to pH = 4-5 with 2N HCl. The mixture is stirred at room temperature for 24 hours (until the nitrogen emission is done). Then the solution is analyzed by carbon-13 NMR.

Should make a lot more sense to anyone who speaks English.  :)

thethethe

  • Guest
I thinketh you're correct in your thinking
« Reply #19 on: October 24, 2002, 03:41:00 AM »
I think that translation is more akin to a dyslexic, ebonic-speaking, french-ghetto, monk-chemist; still, perhaps the freetranslation site can help some get a basic understanding of some foreign synths...

:)

TTT