Vapour phase reaction of m-cresol and ethyl acetate over MCM-41 molecular sieves: One-pot synthesis of coumarin derivatives

K. Shanmugapriya; M. Palanichamy; V. V. Balasubramanian; V. Murugesan

doi:10.1016/j.micromeso.2006.05.020

Vapour phase reaction of m-cresol and ethyl acetate over MCM-41 molecular sieves: One-pot synthesis of coumarin derivatives

K. Shanmugapriya, M. Palanichamy, V. V. Balasubramanian, V. Murugesan

Chemical Engineering and Materials Science

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

12 Scopus citations

Abstract

Mesoporous Al-MCM-41 (Si/Al = 55 and 104) and Al,Zn-MCM-41 (Si/(Al + Zn) = 102) were synthesized by the surfactant-templated route. The catalytic activity was evaluated in the vapour phase reaction of m-cresol with ethyl acetate in the temperature range 200-400 °C. The identified products were 4,7-dimethylcoumarin (4,7-DMC), 2-acetyl-5-methylphenol (2A-5MP), 3-methylphenyl acetate (3-MPA), 2-ethyl-5-methylphenol (2E-5MP) and 4-ethyl-3-methylphenol (4E-3MP). Reaction parameters such as temperature, feed ratio and WHSV were optimised to obtain high 4,7-DMC selectivity at maximum conversion of m-cresol. The time-on-stream study revealed slow deactivation of the catalyst under optimum conditions. Though alkylation of m-cresol was the reaction, acylation dominated over alkylation, suggesting that ethyl acetate is also an active acylating agent for m-cresol. Ring acylation followed by esterification, and subsequent intramolecular condensation observed in this study, suggest an interesting novel one-pot route for the synthesis of coumarin derivatives in the vapour phase.

Original language	English (US)
Pages (from-to)	272-278
Number of pages	7
Journal	Microporous and Mesoporous Materials
Volume	95
Issue number	1-3
DOIs	https://doi.org/10.1016/j.micromeso.2006.05.020
State	Published - Oct 18 2006

Bibliographical note

Funding Information:
The authors are grateful to the Department of Science and Technology (DST), New Delhi, India, for the financial support for carrying out this research work. The authors acknowledge deeply the financial support for creation of instrumental facilities in the Department of Chemistry under DST-FIST program and University Grants Commission (UGC) under special assistance DRS. One of the authors, K. Shanmugapriya, is thankful to CSIR for the award of SRF fellowship.

Keywords

4,7-Dimethylcoumarin
Acylation
Al-MCM-41
Ethyl acetate
m-cresol

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title = "Vapour phase reaction of m-cresol and ethyl acetate over MCM-41 molecular sieves: One-pot synthesis of coumarin derivatives",

abstract = "Mesoporous Al-MCM-41 (Si/Al = 55 and 104) and Al,Zn-MCM-41 (Si/(Al + Zn) = 102) were synthesized by the surfactant-templated route. The catalytic activity was evaluated in the vapour phase reaction of m-cresol with ethyl acetate in the temperature range 200-400 °C. The identified products were 4,7-dimethylcoumarin (4,7-DMC), 2-acetyl-5-methylphenol (2A-5MP), 3-methylphenyl acetate (3-MPA), 2-ethyl-5-methylphenol (2E-5MP) and 4-ethyl-3-methylphenol (4E-3MP). Reaction parameters such as temperature, feed ratio and WHSV were optimised to obtain high 4,7-DMC selectivity at maximum conversion of m-cresol. The time-on-stream study revealed slow deactivation of the catalyst under optimum conditions. Though alkylation of m-cresol was the reaction, acylation dominated over alkylation, suggesting that ethyl acetate is also an active acylating agent for m-cresol. Ring acylation followed by esterification, and subsequent intramolecular condensation observed in this study, suggest an interesting novel one-pot route for the synthesis of coumarin derivatives in the vapour phase.",

keywords = "4,7-Dimethylcoumarin, Acylation, Al-MCM-41, Ethyl acetate, m-cresol",

author = "K. Shanmugapriya and M. Palanichamy and Balasubramanian, {V. V.} and V. Murugesan",

note = "Funding Information: The authors are grateful to the Department of Science and Technology (DST), New Delhi, India, for the financial support for carrying out this research work. The authors acknowledge deeply the financial support for creation of instrumental facilities in the Department of Chemistry under DST-FIST program and University Grants Commission (UGC) under special assistance DRS. One of the authors, K. Shanmugapriya, is thankful to CSIR for the award of SRF fellowship.",

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doi = "10.1016/j.micromeso.2006.05.020",

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AU - Shanmugapriya, K.

AU - Palanichamy, M.

AU - Balasubramanian, V. V.

AU - Murugesan, V.

N1 - Funding Information: The authors are grateful to the Department of Science and Technology (DST), New Delhi, India, for the financial support for carrying out this research work. The authors acknowledge deeply the financial support for creation of instrumental facilities in the Department of Chemistry under DST-FIST program and University Grants Commission (UGC) under special assistance DRS. One of the authors, K. Shanmugapriya, is thankful to CSIR for the award of SRF fellowship.

PY - 2006/10/18

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N2 - Mesoporous Al-MCM-41 (Si/Al = 55 and 104) and Al,Zn-MCM-41 (Si/(Al + Zn) = 102) were synthesized by the surfactant-templated route. The catalytic activity was evaluated in the vapour phase reaction of m-cresol with ethyl acetate in the temperature range 200-400 °C. The identified products were 4,7-dimethylcoumarin (4,7-DMC), 2-acetyl-5-methylphenol (2A-5MP), 3-methylphenyl acetate (3-MPA), 2-ethyl-5-methylphenol (2E-5MP) and 4-ethyl-3-methylphenol (4E-3MP). Reaction parameters such as temperature, feed ratio and WHSV were optimised to obtain high 4,7-DMC selectivity at maximum conversion of m-cresol. The time-on-stream study revealed slow deactivation of the catalyst under optimum conditions. Though alkylation of m-cresol was the reaction, acylation dominated over alkylation, suggesting that ethyl acetate is also an active acylating agent for m-cresol. Ring acylation followed by esterification, and subsequent intramolecular condensation observed in this study, suggest an interesting novel one-pot route for the synthesis of coumarin derivatives in the vapour phase.

AB - Mesoporous Al-MCM-41 (Si/Al = 55 and 104) and Al,Zn-MCM-41 (Si/(Al + Zn) = 102) were synthesized by the surfactant-templated route. The catalytic activity was evaluated in the vapour phase reaction of m-cresol with ethyl acetate in the temperature range 200-400 °C. The identified products were 4,7-dimethylcoumarin (4,7-DMC), 2-acetyl-5-methylphenol (2A-5MP), 3-methylphenyl acetate (3-MPA), 2-ethyl-5-methylphenol (2E-5MP) and 4-ethyl-3-methylphenol (4E-3MP). Reaction parameters such as temperature, feed ratio and WHSV were optimised to obtain high 4,7-DMC selectivity at maximum conversion of m-cresol. The time-on-stream study revealed slow deactivation of the catalyst under optimum conditions. Though alkylation of m-cresol was the reaction, acylation dominated over alkylation, suggesting that ethyl acetate is also an active acylating agent for m-cresol. Ring acylation followed by esterification, and subsequent intramolecular condensation observed in this study, suggest an interesting novel one-pot route for the synthesis of coumarin derivatives in the vapour phase.

KW - 4,7-Dimethylcoumarin

KW - Acylation

KW - Al-MCM-41

KW - Ethyl acetate

KW - m-cresol

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U2 - 10.1016/j.micromeso.2006.05.020

DO - 10.1016/j.micromeso.2006.05.020

M3 - Article

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SN - 1387-1811

VL - 95

SP - 272

EP - 278

JO - Microporous and Mesoporous Materials

JF - Microporous and Mesoporous Materials

IS - 1-3

ER -

Vapour phase reaction of m-cresol and ethyl acetate over MCM-41 molecular sieves: One-pot synthesis of coumarin derivatives

Abstract

Bibliographical note

Keywords

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