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All 36 posts Subject: Dehydrogenation of Butanediol to GBL Please login to post Down

Rhodium
(Chief Bee)
12-07-01 10:27
No 245251
User Picture       Dehydrogenation of Butanediol to GBL
(Rated as: excellent)

Dehydrogenation of 1,4-Butanediol to gamma-Butyrolactone with a copper chromite catalyst

A mixture of 90.1g (1 mole) 1,4-butanediol, 4g of copper chromite catalyst and 0.15g of powdered reagent grade sodium hydroxide (or better KOH) was stirred vigorously and heated under reflux. At about 200°C, a lively evolution of hydrogen occurred, and the temperature dropped about 10°C and the dehydrogenation proceeded smoothly. The evolution of gas (39L/2mol per mole 1,4-butanediol reacted) ceased in about 3h. The reaction mixture was cooled to room temperature, filtered from the catalyst and distilled under reduced pressure to give gamma-butyrolactone in about 80% yield and unreacted 1,4-butanediol in about 10% yield.

Preparation of Copper Chromite: https://www.rhodium.ws/chemistry/copperchromite.html
Related procedure: http://www.orgsyn.org/orgsyn/prep.asp?prep=CV4P0677

Reference: JACS 1385 (1946)

foxy2
(Distinctive Doe)
12-07-01 15:02
No 245302
      Re: Dehydrogenation of Butanediol to GBL

Note: The copper chromite used in the above procedure is the org. syn. copper chromite(there is a link on Rhodiums Copper Chromite page) and not the copper chromite synth on Rhod.

I think this 1,4-->GBL procedure might bee better, yeild is 95%.
Post 243620 (foxy2: "Re: Easy Oxidation of THF to GBL", Novel Discourse)

Do Your Part To Win The War

Rhodium
(Chief Bee)
12-07-01 15:05
No 245305
User Picture       Re: Dehydrogenation of Butanediol to GBL

Yeah, that's right Foxy. But finally, we have a Butanediol -> butyrolactone synth that is almost impossible to screw up, and it is suitable for large-scale operation (just watch out so you don't ignite the two moles of hydrogen which evolves in the reaction, it is enough to blow out all your windows.

Prdy2GO
(Hive Bee)
12-07-01 21:49
No 245390
User Picture       Re: Dehydrogenation of Butanediol to GBL
(Rated as: whining)

Have done this and in my oppinion this may be a waste.
Don't look at me I didn't do it!

Rhodium
(Chief Bee)
12-07-01 23:40
No 245435
User Picture       Re: Dehydrogenation of Butanediol to GBL

Why? What kind of problems did you encounter while performing the reaction? How did you prepare the copper chromite catalyst?

flipper
(Newbee)
12-08-01 13:19
No 245593
User Picture       Re: Dehydrogenation of Butanediol to GBL

It's bloody beautiful. I you Rhodium.

placebo
(irritable and cranky)
12-15-01 23:22
No 247965
      Re: Dehydrogenation of Butanediol to GBL

I rarely look in the serious or novel forums...
So it was quite funny when I stumbled upon this thread today.
You'll see why in a minute...

I disagree with all of you a little bit. This was first discussed years ago by some old cats on the old, old, old, old Hive. Then Prefix brought it up here, Post 30904 (Prefix: "1,4-butanediol to GBL - Will this work?", Methods Discourse) and a lively discussion ensued. Following this, SWIM did some research and aquisition.
In the other ref. the only difference is, it does not use any addition of NaOH or KoH and the catalyst is different.

Anyways, SWIM made the catalyst exactly as per synth on Rhodium's website. (The other one is a pain in the ass.) It proceeded as written and could be made by a 3 year old. SWIM made about 450gm. Then, following the ref. from Prefix he proceeded on a test run with 8L BDO, to see if all was as intended.

SWIM said it works like a charm and all went as written, including the 99% yeild. So one can only assume the NaOH is put in there to fuck up 20% of your GBL.
Foxy, this is much easier, faster and higher yeilding then the ref. you suggest.

The funny thing I elluded to, is the irony of stumbling on this thread as SWIM was taking a break to let the mantle cool, after a 12L batch finished!

Off to distill we go.....
Bored...

foxy2
(Distinctive Doe)
12-16-01 22:31
No 248225
      Re: Dehydrogenation of Butanediol to GBL

Might I ask how long you refluxed the bdo for?

I tried this except using CuCl2 instead of Copper(II)Nitrate. Refluxed for a couple hours and shot some in the GC. Only about 20% of the bdo had converted to something(I had no gbl standard) and due to the low conversion I didn't bother distilling.

Do Your Part To Win The War

Osmium
(Stoni's sexual toy)
12-16-01 22:37
No 248228
      Re: Dehydrogenation of Butanediol to GBL

Chlorides are catalyst poisons for copper chromites as far as I remember.

foxy2
(Distinctive Doe)
12-16-01 22:40
No 248230
      Re: Dehydrogenation of Butanediol to GBL

Well that explains why the yeild totally sucked!
frown
Do Your Part To Win The War

Rhodium
(Chief Bee)
12-16-01 23:56
No 248256
User Picture       Re: Dehydrogenation of Butanediol to GBL

Placebo: So you say you made the catalyst according to the procedure at my page, used the procedcure above minus the sodium hydroxide, and then got 99% yield? Great. Could we have a more detailed description of your experience with this, so others doesn't have to repeat the possible problems you've had with this method?

placebo
(irritable and cranky)
12-17-01 07:06
No 248336
User Picture       Re: Dehydrogenation of Butanediol to GBL

SWIM had no problems really, SWIM doesn't think anyone could stuff it up really. SWIM was concerned whether he would be able to reach the temps necessary to finish the catalyst. So SWIM did it on a stove top, a little at a time, and then all together in an oven for 2 hours at max temp.

The only probs SWIM had with the rxn was getting it to the temp of 200c as his mag st/hotplate at max temp just wouldn't get there, even though it is capable of 450c. Temp would creep up a couple of degrees every 3 hours. Took 5 days!
$4k later he has a lovely mantle and temp is acheived in 1 hour. Then as Rhod said above, just watch the bubbles of hydrogen, and you'll know when your done.

SWIM got about 95% on first attempt, (99% is in the ref.) this is only a guess, worked out from the amount of NaOH required to convert to GBL. SWIM distilled after the rxn to get a mix of GBL/BDO, then converted it to GHB.
SWIM would love to do a write-up for your site Rhod, BUT, SWIM was meaning to keep this one a secret for a little while, and only replied here coz' being in the novel section SWIM hoped not many would see it, because SWIM fears that BDO will become controlled very shortly. SWIM would like some time to stock up. Just don't say SWIM is a selfish prick, always taking and never giving, as you already have one of his write-ups on your site. SWIM will have a write-up on the catalyst and rxn soon.

Funny how nobody would help SWIM when SWIM was interested in this rxn.
Bored...

Rhodium
(Chief Bee)
12-17-01 14:52
No 248440
User Picture       Re: Dehydrogenation of Butanediol to GBL

They will never be able to control butanediol. It is a precursor to butadiene, which in turn is the precursor of all synthetic rubber that is manufactured in the whole world. It is a too large industrial product as it is.

Osmium
(Stoni's sexual toy)
12-17-01 15:26
No 248447
      Re: Dehydrogenation of Butanediol to GBL

> They will never be able to control butanediol. It is a
> precursor to butadiene, which in turn is the precursor of
> all synthetic rubber that is manufactured in the whole
> world.

They could still make it unavailable to the general public, just like acetic anhydride or many other chemicals.
I know that there is a company using shitloads of acetic anhydride close to where I live, I'm talking several tons arriving by rail daily, yet it's not like I can buy that stuff OTC easily.

placebo
(irritable and cranky)
12-17-01 15:44
No 248449
User Picture       Re: Dehydrogenation of Butanediol to GBL

BTW, SWIM used Copper Nitrate and sodium chromate for the catalyst, and due to lack of supply, SWIM also tried Pottasium chromate with positive results. (No thanks to Os, who must have had his PM's turned off when I wanted to run it by him!) Bastage!
Bored...

Rhodium
(Chief Bee)
12-17-01 15:49
No 248451
User Picture       Re: Dehydrogenation of Butanediol to GBL

Os: I was thinking of diversion (buying through a company front etc) - noone will ever notice that a ton of butanediol is missing, considering the amount used annually...

Osmium
(Stoni's sexual toy)
12-17-01 15:52
No 248452
User Picture       Re: Dehydrogenation of Butanediol to GBL

Placebo: Bullshit. You probably were too high to type my name.

placebo
(irritable and cranky)
12-18-01 07:06
No 248642
      Re: Dehydrogenation of Butanediol to GBL

Very possibly so, in fact most probably, but I never typed it, I clicked on your name and then "send a PM". It's just the lazy type of guy I am. It was about 2 months ago. You weren't around for a while, so I put it down to absense.

As far as I know, (not much) it's only made by one kraut company.
Bored...

flipper
(Hive Bee)
12-19-01 21:26
No 249014
      Re: Dehydrogenation of Butanediol to GBL
(Rated as: good read)

And here is a useful patent I think (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=US5955620&ID=US+++5955620A1+I+)

One for 1,4-butanediol from maleic acid (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=US5473086&ID=US+++5473086A1+I+)

An improved way (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=EP0919530&ID=EP+++0919530A1+I+)

An improved catalyst (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=EP0848991&ID=EP+++0848991A1+I+)

And yet another method for 1,4-butanediol (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=US5945571&ID=US+++5945571A1+I+)

GBL again (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=US6239292&ID=US+++6239292B1+I+)

This is from this year. Another GBL prep patent (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=US6297389&ID=US+++6297389B1+I+)

And again GBL and THF (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=WO0027834&ID=WO+++0027834A1+I+)

GBL again. Those people really liked this stuff (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=WO0027834&ID=WO+++0027834A1+I+)

Peace cool

Osmium
(Stoni's sexual toy)
12-20-01 14:31
No 249267
      Re: Dehydrogenation of Butanediol to GBL

> I was thinking of diversion (buying through a company
> front etc) - noone will ever notice that a ton of
> butanediol is missing, considering the amount used
> annually...

No diversion anymore. At least not for NZ bees:

http://www.nzdf.org.nz/update/messages/1672.htm
Post 249265 (Osmium: "NZ and UK illegalize GHB", Law and Order)

* Dealing in the dance drug Fantasy could result in a 14-year prison sentence.

* The Fantasy range of drugs, which included gamma hydroxybutyrate (GHB), 1,4 butanediol (One4b) and GBL, should be classified as Class B under the Misuse of Drugs Act 1975.

* Under the planned law change, anyone caught importing, manufacturing or supplying the drug would face up to 14 years' imprisonment. Possession could result in up to three months' imprisonment, a $500 fine, or both.

* those wanting to bring the substances - One4b contains the same chemical as an industrial solvent - into New Zealand for legitimate purposes would require an import licence.

* The quantity being imported and who it was being sold to would be contained in the licence. If the substance was being bought for drug use from the importer, both importer and user would be prosecuted.

Are they fucking nuts?!? Up to 14 years for GHB!!! Who elects these assholes into office? And why aren't intelligence tests mandatory for government officials?

g_junkie
(Stranger)
01-10-02 06:02
No 254680
      Re: Dehydrogenation of Butanediol to GBL

when making the catalyst as described on Rhod's site, did SWIM do the acetic acid washes that are used in the org synth catalyst doc??

the org synth doc also mentions a sodium bicarbonate wash... did SWIM also do this or just follow the recipe from the post???

one more question... what was the pH of the BDO/GBL after it was distilled, as SWIM's came out neutral. frown

Rhodium
(Chief Bee)
01-10-02 09:54
No 254732
User Picture       Re: Dehydrogenation of Butanediol to GBL

Distilled Butanediol/Butyrolactone should definitely be pH neutral - why shouldn't it?

g_junkie
(Stranger)
01-11-02 07:58
No 255131
      Re: Dehydrogenation of Butanediol to GBL

i was assuming that since it had to be reacted with NaOH (basic) to create GHB, then it would need to be acidic???

foxy2
(Distinctive Doe)
01-11-02 09:19
No 255151
      Re: Dehydrogenation of Butanediol to GBL

Not reversable?
If you add a strong acid it reverses.
I hate my government, does this mean I'm a terrorist??

Osmium
(Stoni's sexual toy)
01-11-02 11:32
No 255190
User Picture       Re: Dehydrogenation of Butanediol to GBL

Smartass! Trying to confuse newbees foxy?
He didn't mention adding a strong acid.
[strong acid =! LSD!!!) wink

g_junkie
(Stranger)
01-12-02 08:25
No 255563
      Re: Dehydrogenation of Butanediol to GBL

thanks... i kinda figured that out after i posted, i forgot that there was also water in the equation.

another newbie question...

whats the difference between the two types of copper chromite catalyts?? (rhod's and org synth's)

i realise that they use different chemicals/methods, but the end product is still copper chromite, right? (wrong, obviously, but why????)

foxy2
(Distinctive Doe)
01-14-02 17:16
No 256276
      Re: Dehydrogenation of Butanediol to GBL

They will have different activities.

There is no way to know exactly how your catalyst will perform until you test it. There are many many variables that can affect how your catalyst performs.
I hate my government, does this mean I'm a terrorist??

g_junkie
(Stranger)
01-21-02 04:29
No 258850
User Picture       Re: Dehydrogenation of Butanediol to GBL

but is that to say that Rhod's cat wont work at all?? coz if it will, it will save me a 5hr trip to buy more chems wink

Antoncho
(Official Hive Translator)
01-21-02 06:26
No 258880
User Picture       Re: Dehydrogenation of Butanediol to GBL

Read the thread, mister.

Antoncho

coglib
(Stranger)
03-22-02 20:11
No 286517
      h2o in bdo

does 1,4 butanediol form an azeotrope with water?
if these two chemicals are mixed, will a simple atmospheric distillation be sufficient to separate them or is all hope lost?
(swim is interested in dreaming this rxn)

Rhodium
(Chief Bee)
03-22-02 21:42
No 286541
User Picture       Distillation

I don't think they would form an azeotrope.

311311311
(Hive Bee)
03-27-02 19:17
No 288607
      crockpot

This has not been posted for too long, but is there a reason why baking soda and a crockpot(as talked about in another thread) would work for this reaction(the only reason I would think no is if the reagent reacts with the crockpot)? What are the imputities left over, and is distillation necessary? If u must distill, is OTC naoh good enough for the reaction?

terbium
(Old P2P Cook)
03-27-02 19:46
No 288622
User Picture       Wrong reaction

This has not been posted for too long, but is there a reason why baking soda and a crockpot(as talked about in another thread) would work for this reaction
I think you are confusing reactions. This thread is about dehydrogenating butanediol to make GBL. You seem to be asking about the procedure for converting GBL to GHB.

311311311
(Hive Bee)
03-28-02 00:27
No 288752
User Picture       Confused

Very correct. I actually realized this while thinking and walking. I'll respectfully just watch from the sidelines when I'm stoned. wink

Rhodium
(Chief Bee)
11-18-03 19:33
No 471608
User Picture       Maleic Anhydride + BDO -Zn/Cu-> 2 GBL
(Rated as: good read)

A novel route for synthesis of -butyrolactone through the coupling of hydrogenation and dehydrogenation
Yu-Lei Zhu, Hong-Wei Xiang, Gui-Sheng Wu, Liang Bai and Yong-Wang Li
J. Chem. Soc. Chem. Commun. (3), 254-255 (2002) (https://www.rhodium.ws/pdf/ma-bdo2gbl.pdf)
DOI:10.1039/b109658n

Abstract

A coupling process of the hydrogenation of maleic anhydride and the dehydrogenation of 1,4-butanediol has been invented for the synthesis of -butyrolactone over a Cu–Zn catalyst, realizing optimal hydrogen utilization and better energy efficiency.

Rhodium
(Chief Bee)
05-19-04 23:52
No 508294
User Picture       Dehydrogenative cyclization of 1,4-butanediol
(Rated as: good read)

Dehydrogenative cyclization of 1,4-butanediol over copper-based catalyst
Naoki Ichikawa, Satoshi Sato, Ryoji Takahashi, Toshiaki Sodesawa and Kanichiro Inui
Journal of Molecular Catalysis A: Chemical, 212(1-2) 197-203 (2004) (https://www.rhodium.ws/pdf/14-bd.dehydrogenative.cyclization.pdf)
DOI:10.1016/j.molcata.2003.10.028

Abstract
Synthesis of γ-butyrolactone (GBL) from 1,4-butanediol (BDO) over copper-based catalysts with ZnO, Al₂O₃ and ZrO₂ was investigated. Catalytic activity of copper was greatly affected by the additive oxides. The highest activity was obtained at a catalyst molar ratio of CuO:ZnO:ZrO₂:Al₂O₃=6:1:2:2. ZrO₂ showed the highest additive effect for the GBL synthesis with enhancing dehydrogenation ability of metallic Cu and enlarging Cu surface area. Al₂O₃ enlarged Cu surface area, whereas a large amount of tetrahydrofuran (THF) was formed over the acid sites of Al₂O₃ surface, and ZnO reduced the THF yield. The reaction pathway from BDO to GBL was also clarified: BDO was initially dehydrogenated to 4-hydroxybutanal, which was immediately hemiacetalized to 2-hydroxytetrahydrofuran, followed by the dehydrogenation to GBL over metallic Cu.

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	All 36 posts		Subject: Dehydrogenation of Butanediol to GBL		Please login to post		Down


		Rhodium (Chief Bee) 12-07-01 10:27 No 245251				Dehydrogenation of Butanediol to GBL (Rated as: excellent)
						*Dehydrogenation of 1,4-Butanediol to gamma-Butyrolactone with a copper chromite catalyst* A mixture of 90.1g (1 mole) 1,4-butanediol, 4g of copper chromite catalyst and 0.15g of powdered reagent grade sodium hydroxide (or better KOH) was stirred vigorously and heated under reflux. At about 200°C, a lively evolution of hydrogen occurred, and the temperature dropped about 10°C and the dehydrogenation proceeded smoothly. The evolution of gas (39L/2mol per mole 1,4-butanediol reacted) ceased in about 3h. The reaction mixture was cooled to room temperature, filtered from the catalyst and distilled under reduced pressure to give gamma-butyrolactone in about 80% yield and unreacted 1,4-butanediol in about 10% yield. Preparation of Copper Chromite: https://www.rhodium.ws/chemistry/copperchromite.html Related procedure: http://www.orgsyn.org/orgsyn/prep.asp?prep=CV4P0677 Reference: JACS 1385 (1946)



		foxy2 (Distinctive Doe) 12-07-01 15:02 No 245302				Re: Dehydrogenation of Butanediol to GBL
						Note: The copper chromite used in the above procedure is the org. syn. copper chromite(there is a link on Rhodiums Copper Chromite page) and not the copper chromite synth on Rhod. I think this 1,4-->GBL procedure might bee better, yeild is 95%. Post 243620 (foxy2: "Re: Easy Oxidation of THF to GBL", Novel Discourse) Do Your Part To Win The War



		Rhodium (Chief Bee) 12-07-01 15:05 No 245305				Re: Dehydrogenation of Butanediol to GBL
						Yeah, that's right Foxy. But finally, we have a Butanediol -> butyrolactone synth that is almost impossible to screw up, and it is suitable for large-scale operation (just watch out so you don't ignite the two moles of hydrogen which evolves in the reaction, it is enough to blow out all your windows.



		Prdy2GO (Hive Bee) 12-07-01 21:49 No 245390				Re: Dehydrogenation of Butanediol to GBL (Rated as: whining)
						Have done this and in my oppinion this may be a waste. Don't look at me I didn't do it!



		Rhodium (Chief Bee) 12-07-01 23:40 No 245435				Re: Dehydrogenation of Butanediol to GBL
						Why? What kind of problems did you encounter while performing the reaction? How did you prepare the copper chromite catalyst?



		flipper (Newbee) 12-08-01 13:19 No 245593				Re: Dehydrogenation of Butanediol to GBL
						It's bloody beautiful. I you Rhodium.



		placebo (irritable and cranky) 12-15-01 23:22 No 247965				Re: Dehydrogenation of Butanediol to GBL
						I rarely look in the serious or novel forums... So it was quite funny when I stumbled upon this thread today. You'll see why in a minute... I disagree with all of you a little bit. This was first discussed years ago by some old cats on the old, old, old, old Hive. Then Prefix brought it up here, Post 30904 (Prefix: "1,4-butanediol to GBL - Will this work?", Methods Discourse) and a lively discussion ensued. Following this, SWIM did some research and aquisition. In the other ref. the only difference is, it does not use any addition of NaOH or KoH and the catalyst is different. Anyways, SWIM made the catalyst exactly as per synth on Rhodium's website. (The other one is a pain in the ass.) It proceeded as written and could be made by a 3 year old. SWIM made about 450gm. Then, following the ref. from Prefix he proceeded on a test run with 8L BDO, to see if all was as intended. SWIM said it works like a charm and all went as written, including the 99% yeild. So one can only assume the NaOH is put in there to fuck up 20% of your GBL. Foxy, this is much easier, faster and higher yeilding then the ref. you suggest. The funny thing I elluded to, is the irony of stumbling on this thread as SWIM was taking a break to let the mantle cool, after a 12L batch finished! Off to distill we go..... Bored...



		foxy2 (Distinctive Doe) 12-16-01 22:31 No 248225				Re: Dehydrogenation of Butanediol to GBL
						Might I ask how long you refluxed the bdo for? I tried this except using CuCl2 instead of Copper(II)Nitrate. Refluxed for a couple hours and shot some in the GC. Only about 20% of the bdo had converted to something(I had no gbl standard) and due to the low conversion I didn't bother distilling. Do Your Part To Win The War



		Osmium (Stoni's sexual toy) 12-16-01 22:37 No 248228				Re: Dehydrogenation of Butanediol to GBL
						Chlorides are catalyst poisons for copper chromites as far as I remember.



		foxy2 (Distinctive Doe) 12-16-01 22:40 No 248230				Re: Dehydrogenation of Butanediol to GBL
						Well that explains why the yeild totally sucked! Do Your Part To Win The War



		Rhodium (Chief Bee) 12-16-01 23:56 No 248256				Re: Dehydrogenation of Butanediol to GBL
						Placebo: So you say you made the catalyst according to the procedure at my page, used the procedcure above minus the sodium hydroxide, and then got 99% yield? Great. Could we have a more detailed description of your experience with this, so others doesn't have to repeat the possible problems you've had with this method?



		placebo (irritable and cranky) 12-17-01 07:06 No 248336				Re: Dehydrogenation of Butanediol to GBL
						SWIM had no problems really, SWIM doesn't think anyone could stuff it up really. SWIM was concerned whether he would be able to reach the temps necessary to finish the catalyst. So SWIM did it on a stove top, a little at a time, and then all together in an oven for 2 hours at max temp. The only probs SWIM had with the rxn was getting it to the temp of 200c as his mag st/hotplate at max temp just wouldn't get there, even though it is capable of 450c. Temp would creep up a couple of degrees every 3 hours. Took 5 days! $4k later he has a lovely mantle and temp is acheived in 1 hour. Then as Rhod said above, just watch the bubbles of hydrogen, and you'll know when your done. SWIM got about 95% on first attempt, (99% is in the ref.) this is only a guess, worked out from the amount of NaOH required to convert to GBL. SWIM distilled after the rxn to get a mix of GBL/BDO, then converted it to GHB. SWIM would love to do a write-up for your site Rhod, BUT, SWIM was meaning to keep this one a secret for a little while, and only replied here coz' being in the novel section SWIM hoped not many would see it, because SWIM fears that BDO will become controlled very shortly. SWIM would like some time to stock up. Just don't say SWIM is a selfish prick, always taking and never giving, as you already have one of his write-ups on your site. SWIM will have a write-up on the catalyst and rxn soon. Funny how nobody would help SWIM when SWIM was interested in this rxn. Bored...



		Rhodium (Chief Bee) 12-17-01 14:52 No 248440				Re: Dehydrogenation of Butanediol to GBL
						They will never be able to control butanediol. It is a precursor to butadiene, which in turn is the precursor of all synthetic rubber that is manufactured in the whole world. It is a too large industrial product as it is.



		Osmium (Stoni's sexual toy) 12-17-01 15:26 No 248447				Re: Dehydrogenation of Butanediol to GBL
						> They will never be able to control butanediol. It is a > precursor to butadiene, which in turn is the precursor of > all synthetic rubber that is manufactured in the whole > world. They could still make it unavailable to the general public, just like acetic anhydride or many other chemicals. I know that there is a company using shitloads of acetic anhydride close to where I live, I'm talking several tons arriving by rail daily, yet it's not like I can buy that stuff OTC easily.



		placebo (irritable and cranky) 12-17-01 15:44 No 248449				Re: Dehydrogenation of Butanediol to GBL
						BTW, SWIM used Copper Nitrate and sodium chromate for the catalyst, and due to lack of supply, SWIM also tried Pottasium chromate with positive results. (No thanks to Os, who must have had his PM's turned off when I wanted to run it by him!) Bastage! Bored...



		Rhodium (Chief Bee) 12-17-01 15:49 No 248451				Re: Dehydrogenation of Butanediol to GBL
						Os: I was thinking of diversion (buying through a company front etc) - noone will ever notice that a ton of butanediol is missing, considering the amount used annually...



		Osmium (Stoni's sexual toy) 12-17-01 15:52 No 248452				Re: Dehydrogenation of Butanediol to GBL
						Placebo: Bullshit. You probably were too high to type my name.



		placebo (irritable and cranky) 12-18-01 07:06 No 248642				Re: Dehydrogenation of Butanediol to GBL
						Very possibly so, in fact most probably, but I never typed it, I clicked on your name and then "send a PM". It's just the lazy type of guy I am. It was about 2 months ago. You weren't around for a while, so I put it down to absense. As far as I know, (not much) it's only made by one kraut company. Bored...



		flipper (Hive Bee) 12-19-01 21:26 No 249014				Re: Dehydrogenation of Butanediol to GBL (Rated as: good read)
						And here is a useful patent I think (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=US5955620&ID=US+++5955620A1+I+) One for 1,4-butanediol from maleic acid (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=US5473086&ID=US+++5473086A1+I+) An improved way (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=EP0919530&ID=EP+++0919530A1+I+) An improved catalyst (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=EP0848991&ID=EP+++0848991A1+I+) And yet another method for 1,4-butanediol (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=US5945571&ID=US+++5945571A1+I+) GBL again (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=US6239292&ID=US+++6239292B1+I+) This is from this year. Another GBL prep patent (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=US6297389&ID=US+++6297389B1+I+) And again GBL and THF (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=WO0027834&ID=WO+++0027834A1+I+) GBL again. Those people really liked this stuff (http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=WO0027834&ID=WO+++0027834A1+I+) Peace



		Osmium (Stoni's sexual toy) 12-20-01 14:31 No 249267				Re: Dehydrogenation of Butanediol to GBL
						> I was thinking of diversion (buying through a company > front etc) - noone will ever notice that a ton of > butanediol is missing, considering the amount used > annually... No diversion anymore. At least not for NZ bees: http://www.nzdf.org.nz/update/messages/1672.htm Post 249265 (Osmium: "NZ and UK illegalize GHB", Law and Order) * Dealing in the dance drug Fantasy could result in a 14-year prison sentence. * The Fantasy range of drugs, which included gamma hydroxybutyrate (GHB), 1,4 butanediol (One4b) and GBL, should be classified as Class B under the Misuse of Drugs Act 1975. * Under the planned law change, anyone caught importing, manufacturing or supplying the drug would face up to 14 years' imprisonment. Possession could result in up to three months' imprisonment, a $500 fine, or both. * those wanting to bring the substances - One4b contains the same chemical as an industrial solvent - into New Zealand for legitimate purposes would require an import licence. * The quantity being imported and who it was being sold to would be contained in the licence. If the substance was being bought for drug use from the importer, both importer and user would be prosecuted. Are they fucking nuts?!? Up to 14 years for GHB!!! Who elects these assholes into office? And why aren't intelligence tests mandatory for government officials?



		g_junkie (Stranger) 01-10-02 06:02 No 254680				Re: Dehydrogenation of Butanediol to GBL
						when making the catalyst as described on Rhod's site, did SWIM do the acetic acid washes that are used in the org synth catalyst doc?? the org synth doc also mentions a sodium bicarbonate wash... did SWIM also do this or just follow the recipe from the post??? one more question... what was the pH of the BDO/GBL after it was distilled, as SWIM's came out neutral.



		Rhodium (Chief Bee) 01-10-02 09:54 No 254732				Re: Dehydrogenation of Butanediol to GBL
						Distilled Butanediol/Butyrolactone should definitely be pH neutral - why shouldn't it?



		g_junkie (Stranger) 01-11-02 07:58 No 255131				Re: Dehydrogenation of Butanediol to GBL
						i was assuming that since it had to be reacted with NaOH (basic) to create GHB, then it would need to be acidic???



		foxy2 (Distinctive Doe) 01-11-02 09:19 No 255151				Re: Dehydrogenation of Butanediol to GBL
						Not reversable? If you add a strong acid it reverses. I hate my government, does this mean I'm a terrorist??



		Osmium (Stoni's sexual toy) 01-11-02 11:32 No 255190				Re: Dehydrogenation of Butanediol to GBL
						Smartass! Trying to confuse newbees foxy? He didn't mention adding a strong acid. [strong acid =! LSD!!!)



		g_junkie (Stranger) 01-12-02 08:25 No 255563				Re: Dehydrogenation of Butanediol to GBL
						thanks... i kinda figured that out after i posted, i forgot that there was also water in the equation. another newbie question... whats the difference between the two types of copper chromite catalyts?? (rhod's and org synth's) i realise that they use different chemicals/methods, but the end product is still copper chromite, right? (wrong, obviously, but why????)



		foxy2 (Distinctive Doe) 01-14-02 17:16 No 256276				Re: Dehydrogenation of Butanediol to GBL
						They will have different activities. There is no way to know exactly how your catalyst will perform until you test it. There are many many variables that can affect how your catalyst performs. I hate my government, does this mean I'm a terrorist??



		g_junkie (Stranger) 01-21-02 04:29 No 258850				Re: Dehydrogenation of Butanediol to GBL
						but is that to say that Rhod's cat wont work at all?? coz if it will, it will save me a 5hr trip to buy more chems



		Antoncho (Official Hive Translator) 01-21-02 06:26 No 258880				Re: Dehydrogenation of Butanediol to GBL
						Read the thread, mister. Antoncho



		coglib (Stranger) 03-22-02 20:11 No 286517				h2o in bdo
						does 1,4 butanediol form an azeotrope with water? if these two chemicals are mixed, will a simple atmospheric distillation be sufficient to separate them or is all hope lost? (swim is interested in dreaming this rxn)



		Rhodium (Chief Bee) 03-22-02 21:42 No 286541				Distillation
						I don't think they would form an azeotrope.



		311311311 (Hive Bee) 03-27-02 19:17 No 288607				crockpot
						This has not been posted for too long, but is there a reason why baking soda and a crockpot(as talked about in another thread) would work for this reaction(the only reason I would think no is if the reagent reacts with the crockpot)? What are the imputities left over, and is distillation necessary? If u must distill, is OTC naoh good enough for the reaction?



		terbium (Old P2P Cook) 03-27-02 19:46 No 288622				Wrong reaction
						This has not been posted for too long, but is there a reason why baking soda and a crockpot(as talked about in another thread) would work for this reaction I think you are confusing reactions. This thread is about dehydrogenating butanediol to make GBL. You seem to be asking about the procedure for converting GBL to GHB.



		311311311 (Hive Bee) 03-28-02 00:27 No 288752				Confused
						Very correct. I actually realized this while thinking and walking. I'll respectfully just watch from the sidelines when I'm stoned.



		Rhodium (Chief Bee) 11-18-03 19:33 No 471608				Maleic Anhydride + BDO -Zn/Cu-> 2 GBL (Rated as: good read)
						A novel route for synthesis of -butyrolactone through the coupling of hydrogenation and dehydrogenation Yu-Lei Zhu, Hong-Wei Xiang, Gui-Sheng Wu, Liang Bai and Yong-Wang Li J. Chem. Soc. Chem. Commun. (3), 254-255 (2002) (https://www.rhodium.ws/pdf/ma-bdo2gbl.pdf) DOI:10.1039/b109658n Abstract A coupling process of the hydrogenation of maleic anhydride and the dehydrogenation of 1,4-butanediol has been invented for the synthesis of -butyrolactone over a Cu–Zn catalyst, realizing optimal hydrogen utilization and better energy efficiency.



		Rhodium (Chief Bee) 05-19-04 23:52 No 508294				Dehydrogenative cyclization of 1,4-butanediol (Rated as: good read)
						Dehydrogenative cyclization of 1,4-butanediol over copper-based catalyst Naoki Ichikawa, Satoshi Sato, Ryoji Takahashi, Toshiaki Sodesawa and Kanichiro Inui Journal of Molecular Catalysis A: Chemical, 212(1-2) 197-203 (2004) (https://www.rhodium.ws/pdf/14-bd.dehydrogenative.cyclization.pdf) DOI:10.1016/j.molcata.2003.10.028 Abstract Synthesis of γ-butyrolactone (GBL) from 1,4-butanediol (BDO) over copper-based catalysts with ZnO, Al₂O₃ and ZrO₂ was investigated. Catalytic activity of copper was greatly affected by the additive oxides. The highest activity was obtained at a catalyst molar ratio of CuO:ZnO:ZrO₂:Al₂O₃=6:1:2:2. ZrO₂ showed the highest additive effect for the GBL synthesis with enhancing dehydrogenation ability of metallic Cu and enlarging Cu surface area. Al₂O₃ enlarged Cu surface area, whereas a large amount of tetrahydrofuran (THF) was formed over the acid sites of Al₂O₃ surface, and ZnO reduced the THF yield. The reaction pathway from BDO to GBL was also clarified: BDO was initially dehydrogenated to 4-hydroxybutanal, which was immediately hemiacetalized to 2-hydroxytetrahydrofuran, followed by the dehydrogenation to GBL over metallic Cu. ^{The Hive - Clandestine Chemists Without Borders}

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