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DOI: 10.1055/s-0040-1705948
Fine-Bubble–Slug-Flow Hydrogenation of Multiple Bonds and Phenols
This work was supported in part by JSPS KAKENHI Grant Numbers JP15H03844 and JP18H02012, and MEXT KAKENHI Grant Number JP18H04397.
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Abstract
We describe a promising method for the continuous hydrogenation of alkenes or alkynes by using a newly developed fine-bubble generator. The fine-bubble-containing slug-flow system was up to 1.4 times more efficient than a conventional slug-flow method. When applied in the hydrogenation of phenols to the corresponding cyclohexanones, the fine bubble–slug-flow method suppressed over-reduction. As this method does not require the use of excess gas, it is expected to be widely applicable in improving the efficiency of gas-mediated flow reactions.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1705948.
- Supporting Information
Publikationsverlauf
Eingereicht: 27. August 2020
Angenommen nach Revision: 16. September 2020
Artikel online veröffentlicht:
21. Oktober 2020
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8 Ultrafine bubbles (UFBs) are defined as bubbles with diameters of less than 1000 nm. Although the term nanobubbles (NBs) is also used to describe bubbles that have diameters of less than 1000 nm, we use the term UFBs in this communication, based on the appropriate standard: ; ISO 20480-1:2017: Fine Bubble Technology: General Principles for Usage and Measurement of Fine Bubbles: Part 1: Terminology; International Standards Organization: Geneva, 2017;
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9 Model: FBG-OS Type 1: liquid flowrate range: 0.01–99.99 mL/min; maximum gas-feed rate: 50% of liquid volume; maximum discharge pressure: 5 MPa. Distributor: Process Maximize Technologies (PMT) Corporation (2-13-18 Akanedai Aoba-ku, Yokohama 227-0066, Japan; Phone: +81-90-9104-3595; E-mail: odajima@dh.catv.ne.jp).
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15
Hydrogenation of Alkenes or Alkynes by the H2-FB-Slug-Flow Method: Typical Procedure
A 500 mL Duran bottle was charged with a solution of the appropriate substrate 1 (8.28 mmol) in MeOH (400 mL). The reactor was charged with 10% Pd/C (1.1 g, 0.47 mmol) and placed in a column oven (CTO-10AC; Shimadzu, Japan) at 60 °C. The solution of 1 was delivered at a flow rate of 2.0 mL/min (residence time in the reactor = 35 s), and H2 gas was delivered at a flow rate of 1.0 mL/min (1 equiv). The pressure in the front of the reactor was set to approximately 4 MPa to generate FBs. After 30 min of operation at 60 °C, the reaction mixture was collected every 10 min and analyzed by GC-FID, without purification.
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There are various recent approaches for flow gas–liquid reactions: for flow microreactors with a falling film, see:
For flow microreactors with a microfluidic ‘pipe’, see:
For flow microreactors with a microfluidic ‘bollard’, see:
For flow reactors with a tube-in-tube, see:
For recent reviews on fine bubbles, see:
In the NTA method, many particles are individually and simultaneously analyzed, and their hydrodynamic diameters are calculated based on the Stokes–Einstein equation, see:
For selected reviews on the selective hydrogenation of phenol, see:
For recent studies on the selective hydrogenation of phenol, see: