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Synthetic and mechanistic investigation of piperonyl butoxide from dihydrosafrole

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Abstract

Piperonyl butoxide (PBO) 1 was prepared via the successive chloromethylation and etherification of dihydrosafrole 3. In this work, during the chloromethylation of 3, several by-products such as 5 (the isomer of chloromethyldihydrosafrole 4), 6-propylpiperonyl alcohol 6, bis(chloromethyl)-dihydrosafrole 7 and 8, bis(2-propyl-4,5-methylenedioxyphenyl)methane 9 and di(2-propyl-4,5-methy lene-dioxybenzyl)ether 10 were found. However, it was found that 5, 6, 7, and 8 could undergo a further reaction to the final product (PBO), rather than its derivatives, though the by-products 9 and 10 still existed. Based on these results, the plausible mechanism of the chloromethylation and etherification of 3 was proposed. Furthermore, the reliability of the plausible mechanism was verified by quantum chemical calculations using DFT. In addition, the final product (PBO) was produced with a high selectivity and yield by reducing the by-products 9 and 10.

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Scheme 1
Fig. 1
Fig. 2
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Scheme 3

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Acknowledgments

The authors gratefully acknowledge the funding support by a grant from the National Natural Science Foundation of China and the Natural Science Foundation of the Zhejiang Province (Y4090045 and R4090358).

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Authors and Affiliations

  1. Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China

    Shuai Wang, Jinqiang Liu, Chao Qian & Xinzhi Chen

  2. College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, 471022, China

    Jinqiang Liu

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  1. Shuai Wang
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  2. Jinqiang Liu
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  3. Chao Qian
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  4. Xinzhi Chen
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Correspondence to Xinzhi Chen.

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Wang, S., Liu, J., Qian, C. et al. Synthetic and mechanistic investigation of piperonyl butoxide from dihydrosafrole. Res Chem Intermed 38, 147–160 (2012). https://doi.org/10.1007/s11164-011-0333-8

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