Dehydrogenation of Butanediol to GBL

[Rhodium]

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.thevespiary.org/rhodium/Rhodium/chemistry/copperchromite.html

Related procedure:

http://www.orgsyn.org/orgsyn/prep.asp?prep=CV4P0677

Reference: JACS 1385 (1946)

[foxy2]

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]

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.

[placebo]

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]

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]

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

[foxy2]

Well that explains why the yeild totally sucked!

Do Your Part To Win The War

[Rhodium]

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]

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]

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]

> 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]

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]

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...

[flipper]

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]

> 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 (missing)

(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]

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]

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

[g_junkie]

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

[foxy2]

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

[Osmium]

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

[g_junkie]

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]

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??

[Rhodium]

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.thevespiary.org/rhodium/Rhodium/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]

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.thevespiary.org/rhodium/Rhodium/pdf/14-bd.dehydrogenative.cyclization.pdf)
DOI:

10.1016/j.molcata.2003.10.028

Abstract
Synthesis of ?-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.