Fine-Bubble–Slug-Flow Hydrogenation of Multiple Bonds and Phenols

Takuya Iio; Kohei Nagai; Tomoki Kozuka; Akhtar Mst Sammi; Kohei Sato; Tetsuo Narumi; Nobuyuki Mase

doi:10.1055/s-0040-1705948

Synlett, Inhaltsverzeichnis

Synlett 2020; 31(19): 1919-1924
DOI: 10.1055/s-0040-1705948

cluster

Integrated Synthesis Using Continuous-Flow Technologies

Fine-Bubble–Slug-Flow Hydrogenation of Multiple Bonds and Phenols

Takuya Iio

^aDepartment of Engineering, Graduate School of Integrated Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

,

Kohei Nagai

^aDepartment of Engineering, Graduate School of Integrated Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

,

Tomoki Kozuka

^bDepartment of Applied Chemistry and Biochemical Engineering, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

,

Akhtar Mst Sammi

^aDepartment of Engineering, Graduate School of Integrated Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

,

Kohei Sato

^aDepartment of Engineering, Graduate School of Integrated Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

^bDepartment of Applied Chemistry and Biochemical Engineering, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

^cGraduate School of Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

,

Tetsuo Narumi

^aDepartment of Engineering, Graduate School of Integrated Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

^bDepartment of Applied Chemistry and Biochemical Engineering, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

^cGraduate School of Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

^dResearch Institute of Green Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan eMail: mase.nobuyuki@shizuoka.ac.jp

,

Nobuyuki Mase∗

^aDepartment of Engineering, Graduate School of Integrated Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

^bDepartment of Applied Chemistry and Biochemical Engineering, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

^cGraduate School of Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan

^dResearch Institute of Green Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8561, Japan eMail: mase.nobuyuki@shizuoka.ac.jp

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Abstract

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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.

Key words

flow reaction - gas–liquid reaction - hydrogenation - alkynes - alkenes - phenols

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References and Notes

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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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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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