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 (https://www.thevespiary.org/rhodium/Rhodium/chemistry/copperchromite.html)
Related procedure: http://www.orgsyn.org/orgsyn/prep.asp?prep=CV4P0677 (http://www.orgsyn.org/orgsyn/prep.asp?prep=CV4P0677)
Reference: JACS 1385 (1946)
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 (https://www.thevespiary.org/talk/index.php?topic=11867.msg24362000#msg24362000)
(foxy2: "Re: Easy Oxidation of THF to GBL", Novel Discourse)
Do Your Part To Win The War
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 (https://www.thevespiary.org/talk/index.php?topic=9945.msg3090400#msg3090400)
(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...
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+)
(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+)
(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+)
(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+)
(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+)
(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+)
(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+)
(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+)
(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+)
(http://l2.espacenet.com/dips/bnsviewer?CY=gb&LG=en&DB=EPD&PN=WO0027834&ID=WO+++0027834A1+I+)
Peace 8)
> 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 (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?
A novel route for synthesis of (https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000245251-file_xegs.gif)-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)
(https://www.thevespiary.org/rhodium/Rhodium/pdf/ma-bdo2gbl.pdf)
DOI:10.1039/b109658n (http://dx.doi.org/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 (https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000245251-file_xegs.gif)-butyrolactone over a Cu–Zn catalyst, realizing optimal hydrogen utilization and better energy efficiency.
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)
(https://www.thevespiary.org/rhodium/Rhodium/pdf/14-bd.dehydrogenative.cyclization.pdf)
DOI:10.1016/j.molcata.2003.10.028 (http://dx.doi.org/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.