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Olah’s Reagent Fluorination for Preparing Alkyl Fluorides

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Fluorination

Part of the book series: Synthetic Organofluorine Chemistry ((SYOC))

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Introduction

Pyridinium poly(hydrogen fluoride), also known as Olah’s reagent, is a versatile fluorine source for various nucleophilic carbon−fluorine bond forming reactions [1,2,3]. The reagent is typically prepared by condensing hydrogen fluorine (HF) to pyridine (pyr) at −78 °C under anhydrous conditions [1, 4]. Commercial Olah’s reagent is usually available as a solution of 30 wt% pyridine and 70 wt% HF, which corresponds to an empirical formula of pyr·(HF)9. Under atmospheric pressure, such a mixture does not exhibit the dissociation of HF at temperatures up to 55 °C. The low volatile nature of pyr·(HF)9, compared to that of anhydrous HF, makes it a convenient reagent for fluorination reactions.

Structural Properties

In the solid state, hydrogen fluoride forms zigzag (H−F···H−F···)n chains [5, 6]. Liquid HF, although containing some branched HF oligomers, is mainly composed of short, winding, unbranched hydrogen-bonded chains [7]. In contrast, as revealed by an X-ray...

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References

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Authors and Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Fang Wang

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  1. Fang Wang
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Correspondence to Fang Wang .

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Editors and Affiliations

  1. Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China

    Jinbo Hu

  2. R&D Center, Zhejiang Jiuzhou Pharmaceutical Co., Ltd, Taizhou, Zhejiang, China

    Teruo Umemoto

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Wang, F. (2018). Olah’s Reagent Fluorination for Preparing Alkyl Fluorides. In: Hu, J., Umemoto, T. (eds) Fluorination. Synthetic Organofluorine Chemistry. Springer, Singapore. https://doi.org/10.1007/978-981-10-1855-8_36-1

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  • DOI: https://doi.org/10.1007/978-981-10-1855-8_36-1

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  • Publisher Name: Springer, Singapore

  • Print ISBN: 978-981-10-1855-8

  • Online ISBN: 978-981-10-1855-8

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