Dehydration of Amides to Nitriles over Heterogeneous Silica-Supported Molybdenum Oxide Catalyst

Yo hei Nagasaki; Masazumi Tamura; Mizuho Yabushita; Yoshinao Nakagawa; Keiichi Tomishige

doi:10.1002/cctc.202101846

Dehydration of Amides to Nitriles over Heterogeneous Silica-Supported Molybdenum Oxide Catalyst

Yo hei Nagasaki, Masazumi Tamura, Mizuho Yabushita, Yoshinao Nakagawa, Keiichi Tomishige

ENG - Applied Chemistry

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

Silica-supported molybdenum oxide (MoO_x/SiO₂) with 4.8 wt% Mo (0.5 mmol g⁻¹) was an effective and reusable heterogeneous catalyst for dehydration of 2-furamide to 2-furonitrile (96 % yield). The catalyst was applicable to the dehydration of various amides including heteroaromatic, aromatic and alkyl amides, providing the corresponding nitriles in high yields (87-97 %). Based on the results of catalyst characterizations (XRD, TEM, UV-vis, Raman) and activity tests, MoO_x species are highly dispersed over SiO₂, and heptamolybdate anion ([Mo₇O₂₄]⁶⁻) and isolated dioxo ((O=)₂MoO₂) were mainly formed on the SiO₂ support of the optimal MoO_x/SiO₂ catalyst. The strong Brønsted acid sites (Mo-OH−Si site) can be formed from the MoO_x species and the adjacent silanol group, and the acid-base pair site (Mo(=O)−OH−Si site) of the strong Brønsted acid site (Mo−OH−Si site) and base site (Mo=O) over MoO_x/SiO₂ catalyst could be the main active site for the dehydration of amides.

Original language	English
Article number	e202101846
Journal	ChemCatChem
Volume	14
Issue number	9
DOIs	https://doi.org/10.1002/cctc.202101846
Publication status	Published - 2022 May 6

Keywords

Amides
Dehydration
Heterogeneous catalysis
Molybdenum oxide
Nitriles

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1002/cctc.202101846

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title = "Dehydration of Amides to Nitriles over Heterogeneous Silica-Supported Molybdenum Oxide Catalyst",

abstract = "Silica-supported molybdenum oxide (MoOx/SiO2) with 4.8 wt% Mo (0.5 mmol g−1) was an effective and reusable heterogeneous catalyst for dehydration of 2-furamide to 2-furonitrile (96 % yield). The catalyst was applicable to the dehydration of various amides including heteroaromatic, aromatic and alkyl amides, providing the corresponding nitriles in high yields (87-97 %). Based on the results of catalyst characterizations (XRD, TEM, UV-vis, Raman) and activity tests, MoOx species are highly dispersed over SiO2, and heptamolybdate anion ([Mo7O24]6−) and isolated dioxo ((O=)2MoO2) were mainly formed on the SiO2 support of the optimal MoOx/SiO2 catalyst. The strong Br{\o}nsted acid sites (Mo-OH−Si site) can be formed from the MoOx species and the adjacent silanol group, and the acid-base pair site (Mo(=O)−OH−Si site) of the strong Br{\o}nsted acid site (Mo−OH−Si site) and base site (Mo=O) over MoOx/SiO2 catalyst could be the main active site for the dehydration of amides.",

keywords = "Amides, Dehydration, Heterogeneous catalysis, Molybdenum oxide, Nitriles",

author = "Nagasaki, {Yo hei} and Masazumi Tamura and Mizuho Yabushita and Yoshinao Nakagawa and Keiichi Tomishige",

note = "Funding Information: A part of this work was supported by JSPS KAKENHI 18H05247 and NEDO. We appreciate Mr. Yuichiro Hayasaka (The Electron Microscopy Center, Tohoku University) for his support with STEM analysis. Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

year = "2022",

month = may,

day = "6",

doi = "10.1002/cctc.202101846",

language = "English",

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T1 - Dehydration of Amides to Nitriles over Heterogeneous Silica-Supported Molybdenum Oxide Catalyst

AU - Nagasaki, Yo hei

AU - Tamura, Masazumi

AU - Yabushita, Mizuho

AU - Nakagawa, Yoshinao

AU - Tomishige, Keiichi

N1 - Funding Information: A part of this work was supported by JSPS KAKENHI 18H05247 and NEDO. We appreciate Mr. Yuichiro Hayasaka (The Electron Microscopy Center, Tohoku University) for his support with STEM analysis. Publisher Copyright: © 2022 Wiley-VCH GmbH.

PY - 2022/5/6

Y1 - 2022/5/6

N2 - Silica-supported molybdenum oxide (MoOx/SiO2) with 4.8 wt% Mo (0.5 mmol g−1) was an effective and reusable heterogeneous catalyst for dehydration of 2-furamide to 2-furonitrile (96 % yield). The catalyst was applicable to the dehydration of various amides including heteroaromatic, aromatic and alkyl amides, providing the corresponding nitriles in high yields (87-97 %). Based on the results of catalyst characterizations (XRD, TEM, UV-vis, Raman) and activity tests, MoOx species are highly dispersed over SiO2, and heptamolybdate anion ([Mo7O24]6−) and isolated dioxo ((O=)2MoO2) were mainly formed on the SiO2 support of the optimal MoOx/SiO2 catalyst. The strong Brønsted acid sites (Mo-OH−Si site) can be formed from the MoOx species and the adjacent silanol group, and the acid-base pair site (Mo(=O)−OH−Si site) of the strong Brønsted acid site (Mo−OH−Si site) and base site (Mo=O) over MoOx/SiO2 catalyst could be the main active site for the dehydration of amides.

AB - Silica-supported molybdenum oxide (MoOx/SiO2) with 4.8 wt% Mo (0.5 mmol g−1) was an effective and reusable heterogeneous catalyst for dehydration of 2-furamide to 2-furonitrile (96 % yield). The catalyst was applicable to the dehydration of various amides including heteroaromatic, aromatic and alkyl amides, providing the corresponding nitriles in high yields (87-97 %). Based on the results of catalyst characterizations (XRD, TEM, UV-vis, Raman) and activity tests, MoOx species are highly dispersed over SiO2, and heptamolybdate anion ([Mo7O24]6−) and isolated dioxo ((O=)2MoO2) were mainly formed on the SiO2 support of the optimal MoOx/SiO2 catalyst. The strong Brønsted acid sites (Mo-OH−Si site) can be formed from the MoOx species and the adjacent silanol group, and the acid-base pair site (Mo(=O)−OH−Si site) of the strong Brønsted acid site (Mo−OH−Si site) and base site (Mo=O) over MoOx/SiO2 catalyst could be the main active site for the dehydration of amides.

KW - Amides

KW - Dehydration

KW - Heterogeneous catalysis

KW - Molybdenum oxide

KW - Nitriles

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ER -

Dehydration of Amides to Nitriles over Heterogeneous Silica-Supported Molybdenum Oxide Catalyst

Abstract

Keywords

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