Continuous ruthenium-catalyzed methoxycarbonylation with supercritical carbon dioxide

Catal. Sci. Technol., 2016, Advance Article
DOI: 10.1039/C5CY01883H, Paper

Stefan Christiaan Stouten, Timothy Noel, Qi Wang, Matthias Beller, Volker Hessel
The methoxycarbonylation of cyclohexene with carbon dioxide over a ruthenium catalyst was realized in a micro flow system under supercritical conditions.

Continuous ruthenium-catalyzed methoxycarbonylation with supercritical carbon dioxide

http://pubs.rsc.org/en/Content/ArticleLanding/2016/CY/C5CY01883H?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2Fcy+%28RSC+-+Catalysis+Science+%26+Technology+latest+articles%29#!divAbstract

The methoxycarbonylation of cyclohexene with carbon dioxide over a ruthenium catalyst was realized in a micro flow system under supercritical conditions. Instead of the toxic and flammable carbon monoxide, this process utilizes carbon dioxide, thereby avoiding issues with bulk transportation of carbon monoxide as well as eliminating the need for safety precautions associated with the use of carbon monoxide. Obtained was a 77% yield of the ester product at 180 °C, 120 bar and with a 90 min residence time, which is over five times faster than for the same reaction performed under subcritical conditions in batch. An important factor for the performance of the system was to have a sufficiently polar supercritical mixture, allowing the catalyst to dissolve well. The optimal temperature for the reaction was 180 °C, as the activity of the system dropped considerably at higher temperatures, most likely due to catalyst deactivation.

Department of Chemical Engineering and Chemistry

ir. S.C. (Stefan) Stouten –

Address:

Technische Universiteit Eindhoven
P.O. Box 513
5600 MB EINDHOVEN

Department:

Department of Chemical Engineering and Chemistry

Section:

Micro Flow Chemistry and Process Technology

Positioncategory:

doctoral candidate (PhD) (PhD Stud.)

Position:

doctoral candidate

Room:

STW 0.

Email:

s.stouten@tue.nl

Volker Hessel

prof.dr. V. (Volker) Hessel

Address:

Technische Universiteit Eindhoven
P.O. Box 513
5600 MB EINDHOVEN

Chair:

Micro Flow Chemistry and Process Technology

Department:

Department of Chemical Engineering and Chemistry

Section:

Micro Flow Chemistry and Process Technology

Positioncategory:

Professor (HGL)

Position:

Full Professor

Room:

STW 1.45

Tel:

+31 40-247 2973

Tel (internal):

2973

Email:

v.hessel@tue.nl

////////Continuous,  ruthenium-catalyzed,  methoxycarbonylation, supercritical carbon dioxide, flow reactor