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Chloromethylation of Aromatic Compounds Catalyzed by Surfactant Micelles in Oil–Water Biphasic System

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Abstract

In this work, the chloromethylation reaction of aromatic compounds was performed successfully by micellar catalysis in oil/water biphasic system at high reactant loadings that exceeded the solubilization capacity of micellar solutions. The effects of cationic, nonionic and anionic surfactants on the reaction were compared. The mechanism of chloromethylation reaction and the mechanism of micellar catalysis were investigated. The results show that the micellar catalysis is an effective way to realize the chloromethylation. The chloromethylation reaction consists of electrophilic substitution reaction and nucleophilic substitution reaction. Cationic surfactants, especially those containing longer hydrophobic carbon chain, are more effective. Selectivity for mono-chloromethylation was remarkably improved and regioselectivity was found to be dependent on the nature of the surfactant. Under the optimal reaction conditions, chloromethylation of isopropylbenzene could obtain 97.5% selectivity in mono-chloromethylation and 8.28 para/ortho selectivity ratio at 89.8% conversion.

Graphical Abstract

In oil/water biphasic system, surfactant micelles can catalyze the chloromethylation reaction of aromatic compounds effectively and different types of surfactants have different catalytic abilities. Good conversion and high selectivity in mono-chloromethylation were obtained.

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Authors and Affiliations

  1. Chemical Engineering College, Nanjing University of Science and Technology, Nanjing, 210094, People’s Republic of China

    Qifa Liu, Wei Wei, Ming Lu & Jiang Li

  2. Nanjing Cosmos Chemical Co., Ltd, Nanjing, 211162, People’s Republic of China

    Feng Sun & Yuchao Zhang

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  1. Qifa Liu
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  2. Wei Wei
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  3. Ming Lu
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  4. Feng Sun
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  5. Jiang Li
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  6. Yuchao Zhang
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Correspondence to Ming Lu.

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Liu, Q., Wei, W., Lu, M. et al. Chloromethylation of Aromatic Compounds Catalyzed by Surfactant Micelles in Oil–Water Biphasic System. Catal Lett 131, 485–493 (2009). https://doi.org/10.1007/s10562-009-9926-x

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  • DOI: https://doi.org/10.1007/s10562-009-9926-x

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