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Author: Subject: Gamma-butyrolactone from GABA
kaymatt
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[*] posted on 20-7-2019 at 03:38
Gamma-butyrolactone from GABA


Now that Beijing has finally come to its senses and banned the sale and export of gamma-butyrolactone (Full disclosure: I live in a jurisdiction that doesn't restrict its sale or possession), the last industrial-scale source for this incredibly useful solvent has been closed off. Not to be denied, I have spent some hours researching and conducting experiments in an attempt to synthesise small quantities for laboratory use. Rhodium's archive has provided mixed results in this endeavour.

There appear to be two syntheses that are suitable for the small scale chemist. I have already attempted to replicate one of these; the dehydrogenation of 1,4 Butanediol, a solvent widely used in the production of certain plastics, elastic fibres and polyurethanes and one that I have a reliable and cheap 99.3% source for. The synthesis in question can be found here.

Despite repeated, valiant attempts, I was not able to duplicate its results. I would get to the final distillation under reduced pressure, collect roughly 175mls of a clear distillate from roughly 500ml of catalysed BDO before the temperature would drop and distillation would cease. The liquid would be bubbly away, but no condensate was observed. When I tried bumping up the temperature to get a flow going again, the distilling flask liquid would start to turn a deep rusty colour. No further distillate was collected and that which was didn't contain any GBL. It is possible that I did not get enough of a reflux going, but I doubt it. My thermometer was sitting on 190C throughout, liquid dripped from the condenser into the flask throughout and there were bubbles popping continuously on the surface of the liquid.

If anyone has any possible explanations for this catastrophic failure, I'd love to hear them as I'm at a complete loss.

So after having thrown my hands up in exasperation, I went searching through the old Hive archives to see what I could find among the chattering classes found therein. That's when I discovered this. The Sandmeyer reaction. This synthesis does not involve any red-flagged chemicals like 1,4 Butanediol which means it can be made in any half decently equipped home lab.

I've recently placed an order for a 500ml additive funnel as it was the only piece missing from my kit. I was about to go to checkout for my reactants when I thought I'd pop in here to see if anyone's tried the Sandmeyer reaction for themselves. If so, do you have any pearls of wisdom to share regarding your experiences? Maybe a boffin or two could cast an eye over the reaction and give their considered opinion on any potential potholes therein? I've been defeated once already and have no intention of tasting that bitter brew a second time if I can possibly help it.

In such endeavours, one has no option but to plan for the worst and hope for the best. With any luck, we can get by with a little help from our friends. :D
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Tsjerk
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[*] posted on 20-7-2019 at 05:41


How did you prepare the copper chromite catalyst? I prepared mine by baking the copper ammonium chromate in an oven, I couldn't get it to 350, and my catalyst wasn't very efficient. But it still did the job. I got 20/30% percent yield after the first distillation. Later I pulled out more from the same batch with the same catalyst. Even at 0-10 degrees the catalyst is active at a very slow pase.

I would look at the catalyst again and think about prolonged reaction times at for example 100 degrees orso before distillation.

[Edited on 20-7-2019 by Tsjerk]
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kaymatt
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[*] posted on 20-7-2019 at 08:42


Quote: Originally posted by Tsjerk  
How did you prepare the copper chromite catalyst? I prepared mine by baking the copper ammonium chromate in an oven, I couldn't get it to 350, and my catalyst wasn't very efficient. But it still did the job.


I have a heating mantle that hits 380C after only 15 minutes. I used a three-necked flask and even fashioned a Hershberg type stirrer albeit using 32 gauge nichrome wire instead of stainless steel.

I emersed the flask in the mantle preheated to 350C and turned on the stirrer. It took some time to heat up but once it was there it started shooting black fumes out of the two open necks like a volcanic eruption. It then settled down until all the fumes had stopped. Time of addition was 15 minutes with an additional 15 minutes of stirring at 350C. Exactly as directed.

Quote: Originally posted by Tsjerk  
I got 20/30% percent yield after the first distillation.


That doesn't sound very encouraging and a lot less than what the Hive users were claiming.

Quote: Originally posted by Tsjerk  
Later I pulled out more from the same batch with the same catalyst. Even at 0-10 degrees the catalyst is active at a very slow pase.

I would look at the catalyst again and think about prolonged reaction times at for example 100 degrees orso before distillation.

[Edited on 20-7-2019 by Tsjerk]


Thanks, I'll give that a try, see where I end up.
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AvBaeyer
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[*] posted on 20-7-2019 at 15:04


If you have access to THF it can be selectively oxidized to butyrolactone. Search "oxidation of tetrahydrofuran" on Google for many leads.

See Tetrahedron 56, 1905-1910 (2000) for oxidation of THF

See Synth.Commun., 25, 719-724 (1995) for oxidation of 1,4-butanediol.

Assuming that you have a grasp of the chemistry you are doing it helps to do a bit of independent searching before seeking help. Also, if you searched the hive you should have found this: https://chemistry.mdma.ch/hiveboard/novel/000242315.html

AvB
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kaymatt
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[*] posted on 20-7-2019 at 22:14


Quote: Originally posted by AvBaeyer  
If you have access to THF it can be selectively oxidized to butyrolactone.

Search "oxidation of tetrahydrofuran" on Google for many leads.


I don't have access to THF, plus my independent searches revealed that the yields from oxidising THF are fairly poor when compared to BDO.

Quote: Originally posted by AvBaeyer  
See Tetrahedron 56, 1905-1910 (2000) for oxidation of THF

See Synth.Commun., 25, 719-724 (1995) for oxidation of 1,4-butanediol.


There's a lot of conflicting information out there. I was hoping to exchange ideas with those who've had experience with the reactions I have identified. But thanks, I guess.

Quote: Originally posted by AvBaeyer  
Assuming that you have a grasp of the chemistry you are doing


You're too kind...

Quote: Originally posted by AvBaeyer  
...it helps to do a bit of independent searching before seeking help. Also, if you searched the hive you should have found this: https://chemistry.mdma.ch/hiveboard/novel/000242315.html

AvB


I did find that Hive entry and the solvent-free permanganate oxidation of 1,4 BDO reply found therein did raise my interest. Since coming across this reaction I have acquired some copper sulphate pentahydrate and potassium permanganate is simple enough to order online so I can now add the reaction to my lab schedule.

Thanks for the reminder. Did you have to be so condescending though? Was it really necessary?
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kaymatt
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[*] posted on 20-7-2019 at 22:34


Quote: Originally posted by AvBaeyer  
If you have access to THF it can be selectively oxidized to butyrolactone. Search "oxidation of tetrahydrofuran" on Google for many leads.

See Tetrahedron 56, 1905-1910 (2000) for oxidation of THF

See Synth.Commun., 25, 719-724 (1995) for oxidation of 1,4-butanediol.

Assuming that you have a grasp of the chemistry you are doing it helps to do a bit of independent searching before seeking help. Also, if you searched the hive you should have found this: https://chemistry.mdma.ch/hiveboard/novel/000242315.html

AvB

I came across this old sciencemadness thread in case anyone was interested.

It appears that the handling of large quantities of solvent is the one big drawback in the practical application of this reaction.
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Metacelsus
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[*] posted on 20-7-2019 at 22:43


If you're planning to use the GBL as a drug, 1,4-butanediol will also work. They both get metabolized to GHB (although the kinetics and dosage will be different).



As below, so above.
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kaymatt
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[*] posted on 21-7-2019 at 00:41


Quote: Originally posted by Metacelsus  
If you're planning to use the GBL as a drug, 1,4-butanediol will also work. They both get metabolized to GHB (although the kinetics and dosage will be different).


That's true up to a point, but the effect is notably less euphoric and shorter in duration. GBL has a similar deficiency when compared to GHB, though not to the same extent as 1,4 BDO.

1,4 BDO could be used as a muscle relaxant or as a sedative in a pinch, but its potential use for recreational purposes is rather more limited. The long term effects of its use are also unknown so if you have the choice between 1,4 BDO and a bottle of pure Xyrem, I'd choose the latter, if I were so disposed...

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draculic acid69
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[*] posted on 21-7-2019 at 03:41


1,4bdo is being used for recreation here in Australia on a humongous scale:
https://www.google.com/amp/s/amp.smh.com.au/national/the-but... so it obviously has recreational appeal. Also upon reading the solventless kmno4/cuso4 process it requires 40g of oxidant to 1.5ml of thf which makes 1 kg of. oxidant to 35 ml of thf which when you work out price makes it unfeasible.
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[*] posted on 21-7-2019 at 03:48


Monochlorinate 1,3 propanediol to 3chloropropanol then react with nacn followed by hydrolysing the nitrile to GBL is another option correct?
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[*] posted on 21-7-2019 at 04:56


GHB as a recreational drug... never found the appeal.
Did some, tried some and... what's the hype all about ?

Sure, you get drunk fast.
I'll stick to alcohol if I want that feelin thanks. Kidneys dont sing the same song after a bottle of Jack also.

Then, the other intentional use when you give it to somewone who already had alcohol is just... despicable.

As a sleeping aid it might be interesting in minute quantities but there are many legitimate drugs that operate the same way as GHB that the doctor can prescribe.




The spirit of adventure was upon me. Having nitric acid and copper, I had only to learn what the words 'act upon' meant. - Ira Remsen
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Tsjerk
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[*] posted on 21-7-2019 at 05:17


Quote: Originally posted by kaymatt  
Quote: Originally posted by Tsjerk  
How did you prepare the copper chromite catalyst? I prepared mine by baking the copper ammonium chromate in an oven, I couldn't get it to 350, and my catalyst wasn't very efficient. But it still did the job.


I emersed the flask in the mantle preheated to 350C and turned on the stirrer. It took some time to heat up but once it was there it started shooting black fumes out of the two open necks like a volcanic eruption. It then settled down until all the fumes had stopped. Time of addition was 15 minutes with an additional 15 minutes of stirring at 350C. Exactly as directed.

Quote: Originally posted by Tsjerk  
I got 20/30% percent yield after the first distillation.


That doesn't sound very encouraging and a lot less than what the Hive users were claiming.

Quote: Originally posted by Tsjerk  
Later I pulled out more from the same batch with the same catalyst. Even at 0-10 degrees the catalyst is active at a very slow pase.

I would look at the catalyst again and think about prolonged reaction times at for example 100 degrees orso before distillation.

[Edited on 20-7-2019 by Tsjerk]


Thanks, I'll give that a try, see where I end up.


Did you stirr the catalyst as a solid? I'm just making sure it was dry when you did the heating.

I remember some literature that adviced to do the heating by slowly going up to the 350. I might have found it in one of the articles Erowid.org cites. There was some data about how the catalyst forms, with graphs on endothermic and exothermic phases during the formation. I have the feeling the catalyst is more active if you give it time to go through all the steps.

I never noticed much smoke, only ammonia coming off.

Never trust what is written on erowid.org/the Hive, always try to find the articles were they got their information from, usually they just summarize and screw up things along the way.

[Edited on 21-7-2019 by Tsjerk]
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kaymatt
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[*] posted on 21-7-2019 at 07:30


Quote: Originally posted by Tsjerk  


Did you stirr the catalyst as a solid? I'm just making sure it was dry when you did the heating.


I used an overhead stirrer equipped with a Herschberg type wire propeller that scraped along the surface of the flask up to the half way point. The precipitate had been dried at 90C overnight. No liquid was observed condensing on the flask when it was immersed in the 350C mantle.

Quote: Originally posted by Tsjerk  
I remember some literature that advised to do the heating by slowly going up to the 350. I might have found it in one of the articles Erowid.org cites. There was some data about how the catalyst forms, with graphs on endothermic and exothermic phases during the formation. I have the feeling the catalyst is more active if you give it time to go through all the steps.

I never noticed much smoke, only ammonia coming off.

Never trust what is written on erowid.org/the Hive, always try to find the articles were they got their information from, usually they just summarize and screw up things along the way.

[Edited on 21-7-2019 by Tsjerk]


I hadn't considered that possibility. I've made three separate batches of the copper chromite and each time a lot of black fumes have evolved. I have placed 500ml BDO on reflux for 12 hours at 190C today and will reduce temp to 100C overnight and see if that makes any difference. If not, I have to assume its the catalyst that I'm screwing up.
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[*] posted on 21-7-2019 at 07:33


Quote: Originally posted by draculic acid69  
1,4bdo is being used for recreation here in Australia on a humongous scale:
https://www.google.com/amp/s/amp.smh.com.au/national/the-but... so it obviously has recreational appeal. Also upon reading the solventless kmno4/cuso4 process it requires 40g of oxidant to 1.5ml of thf which makes 1 kg of. oxidant to 35 ml of thf which when you work out price makes it unfeasible.


Beggars can't be choosers. Australia has few points of entry and its customs Gestapo are pretty ruthless... Comes from being founded as a convict colony.

No offence intended. I have some roots there.
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[*] posted on 21-7-2019 at 07:36


Quote: Originally posted by Herr Haber  
GHB as a recreational drug... never found the appeal.
Did some, tried some and... what's the hype all about ?

Sure, you get drunk fast.
I'll stick to alcohol if I want that feelin thanks. Kidneys dont sing the same song after a bottle of Jack also.

Then, the other intentional use when you give it to somewone who already had alcohol is just... despicable.

As a sleeping aid it might be interesting in minute quantities but there are many legitimate drugs that operate the same way as GHB that the doctor can prescribe.


It's like alcohol, but without any of the health risks or hangovers. It's also probably one of the only known aphrodisiacs which is why the fear mongers called it a date-rape drug.

Damn those fear mongers. Why won't they leave us alone!?!
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[*] posted on 21-7-2019 at 07:51


Quote: Originally posted by kaymatt  


I hadn't considered that possibility. I've made three separate batches of the copper chromite and each time a lot of black fumes have evolved. I have placed 500ml BDO on reflux for 12 hours at 190C today and will reduce temp to 100C overnight and see if that makes any difference. If not, I have to assume its the catalyst that I'm screwing up.



If a run doesn't work you can add new catalyst and try again, with or without filtration of the old catalyst.
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unionised
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[*] posted on 21-7-2019 at 07:53


Quote: Originally posted by kaymatt  
It's also probably one of the only known aphrodisiacs ...


https://xkcd.com/285/
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Tsjerk
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[*] posted on 21-7-2019 at 11:06


GHB usage is correlated with severe physical dependency, even after relevantly short times of usage. GHB is one of the few compounds with a possible lethal outcome after abstinence, even after short periods of useage as 3-6 months.
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[*] posted on 21-7-2019 at 19:26


Quote: Originally posted by unionised  
Quote: Originally posted by kaymatt  
It's also probably one of the only known aphrodisiacs ...


https://xkcd.com/285/


"Sexual enhancing effects of GHB

GHB is “aphrodisiac” in man. It has four sexual-enhancing effects; disinhibition (e.g. relaxation), a heightened sense of touch, enhancement of male erectile capacity and increased power of orgasm."

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3853692/

"The influence of GHB on sex was a popular theme throughout the focus group discussions. Both male and female participants recalled increased feelings, sometimes quite intense, connected to many aspects of sexuality, such as sexual desire, arousal, and activity. Reports of these effects did not differ by sexual orientation"

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2257870/
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[*] posted on 21-7-2019 at 19:30


Quote: Originally posted by Tsjerk  
GHB usage is correlated with severe physical dependency, even after relevantly short times of usage. GHB is one of the few compounds with a possible lethal outcome after abstinence, even after short periods of useage as 3-6 months.


Now this claim really does need a citation
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Metacelsus
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[*] posted on 21-7-2019 at 22:53


About withdrawal being lethal: yes, it's definitely possible. GHB is a GABA receptor agonist, meaning delirium tremens can result from withdrawal. See: https://en.wikipedia.org/wiki/Delirium_tremens#Causes https://en.wikipedia.org/wiki/Gamma-Hydroxybutyric_acid#With...

See also this paper: https://onlinelibrary.wiley.com/doi/abs/10.1111/j.1360-0443....

although it's 20 years outdated it does mention a few cases of fatal withdrawal.

[Edited on 2019-7-22 by Metacelsus]




As below, so above.
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draculic acid69
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[*] posted on 22-7-2019 at 03:50


Even if withdrawal can cause death how many addicts and chronic addicts get through withdrawal with no major or minor issues? I think it's only the most extreme chronic addicts that are drinking large amounts that have a bad enough habit to die from withdrawal.think about a dose being 3ml that lasts a few hours it's hard to imagine taking more than 25ml a day in an extreme case of continuos intoxication.
I take a medication called lyrica and according to people who were on it for 3months and then stopped taking it the withdrawals were apparently; horrible, painful and the worst feeling theyd ever had. I took it for two years then stopped with nothing more than a slight mild annoyance that was barely noticeable for maybe a week.its also a
gabaergic thing.ppl say phenibut has a horrible painful withdrawal and I took it once and never took it again.also a gaba drug.alcohol can cause all of the above symptoms same as GBL or benzos but how often do ppl die from alcohol withdrawal in real life.
Even chronic alcos will tell you that it's rare.how many ppl are addicted to alcohol and don't get anything more than a craving for booze when they don't have it.

[Edited on 22-7-2019 by draculic acid69]
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[*] posted on 22-7-2019 at 03:59


Quote: Originally posted by draculic acid69  
Even if withdrawal can cause death how many addicts and chronic addicts get through withdrawal with no major issues? I think it's only the most extreme chronic addicts that are drinking large amounts that have a bad enough habit to die from withdrawal.think about a dose being 3ml that lasts a few hours it's hard to imagine taking more than 25ml a day in an extreme case of continuos intoxication.


It's hard to imagine wanting to be G'ed out of your skull all day every day for months on end. I mean, yeah, there are people out there who slip into this habit, but I would suggest that you would need impressive amounts of will power to even get close.

As usual, the fun police only need one excuse to slam the regulatory door shut (and that excuse doesn't even need to be substantiated in truth) to throw otherwise responsible people into jail cells. Fuckwits, all.
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[*] posted on 22-7-2019 at 04:03


Your right
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[*] posted on 22-7-2019 at 04:13


Anyway back to the chemistry, does anyone think the method I posted with cyanide and chloropropanol seem like it would be a good route to this compound. the grignard can't be used to make it so this seemed logical. 1,2,dichloroethane could be used for 1,4,BDO if formaldehyde can be piped in gaseous form.
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