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Triphosgene: an efficient chlorination reagent for synthesis of 5-chloro-2-pentanone from 3-acetyl-1-propanol

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Abstract

5-Chloro-2-pentanone (5C2P) and its derivatives are widely utilized in the pharmaceutical and agrochemical industry. A new catalytic approach was proposed to convert 3-acetyl-1-propanol to 5C2P using bis(trichloromethyl)carbonate (triphosgene, BTC) as the efficient chlorine source. Various qualitative and quantitative nuclear magnetic resonance techniques (1H, 13C NMR), especially 1D selective gradient total correlation spectroscopy (Sel-TOCSY) and 2D heteronuclear single quantum correlation (1H-13C HSQC) were used in the process. The reaction conditions, such as temperature, time, mole ratio, solvent as well as initiator were optimized. Experiment results showed that the yield of 5C2P reached a maximum of 97.93% in 1,2-dichloroethane at 80 °C after 2 h under the initiation of N,N-dimethylacetamide, and the optimal molar ratio of 3-acetyl-1-propanol to BTC was 1:0.4. The reaction mechanism was proposed and confirmed accordingly. Interestingly, an intermediate product of 1-(dimethylamino)ethyl carbonochloridate was observed, and its chemical structure was characterized by both Sel-TOCSY and 1H-13C HSQC. This study enriched the catalytic reaction ways for the preparation of 5C2P.

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The authors confirm that the data supporting the findings of this study are available within the article and its supplementary materials. The datasets used and analyzed in the current study are available from the corresponding authors on reasonable request.

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Acknowledgements

The authors thank for National Natural Science Foundation of China (22075308) and Natural Science Foundation of Shanxi Province (202103021224439) for financial support.

Funding

This work was supported by National Natural Science Foundation of China (22075308) and Natural Science Foundation of Shanxi Province (202103021224439).

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Authors and Affiliations

  1. Shanxi Engineering Research Center of Biorefinery, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan, 030001, China

    Qianqian Xing, Jiancheng Zhao, Xianglin Hou & Yingxiong Wang

  2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China

    Qianqian Xing, Jiancheng Zhao, Xianglin Hou & Yingxiong Wang

  3. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, People’s Republic of China

    Yulei Zhu

  4. Synfuels China Co. Ltd, Taiyuan, 030032, People’s Republic of China

    Yulei Zhu

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  1. Qianqian Xing
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  2. Jiancheng Zhao
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  5. Yingxiong Wang
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Contributions

QX was in charge of experiments, data analysis and wrote the main manuscript text. JZ was in charge of the experimental design. YZ and XH were in charge of critical review and revision. YW received funding support for this project and had oversight and leadership responsibility for the planning and execution of research activities. All authors who contributed to this article are listed. All authors reviewed the manuscript and agreed to submit this manuscript to “Research on Chemical Intermediates.”

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Correspondence to Yingxiong Wang.

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Xing, Q., Zhao, J., Zhu, Y. et al. Triphosgene: an efficient chlorination reagent for synthesis of 5-chloro-2-pentanone from 3-acetyl-1-propanol. Res Chem Intermed 49, 241–252 (2023). https://doi.org/10.1007/s11164-022-04886-4

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