Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF

Author:

Patel Calum1ORCID,André-Joyaux Emy1ORCID,Leitch Jamie A.23ORCID,de Irujo-Labalde Xabier Martínez4ORCID,Ibba Francesco13ORCID,Struijs Job1ORCID,Ellwanger Mathias A.1ORCID,Paton Robert5ORCID,Browne Duncan L.2ORCID,Pupo Gabriele13ORCID,Aldridge Simon1ORCID,Hayward Michael A.4ORCID,Gouverneur Véronique1ORCID

Affiliation:

1. Chemistry Research Laboratory, University of Oxford, Oxford OX1 3TA, UK.

2. Department of Pharmaceutical and Biological Chemistry, University College London School of Pharmacy, London W1CN 1AX, UK.

3. FluoRok Ltd., Begbroke Science Park, Begbroke Hill, Woodstock Road, Begbroke OX5 1PF, UK.

4. Inorganic Chemistry Laboratory, University of Oxford, Oxford OX1 3QR, UK.

5. Department of Chemistry, Colorado State University, Fort Collins, CO 80528, USA.

Abstract

All fluorochemicals—including elemental fluorine and nucleophilic, electrophilic, and radical fluorinating reagents—are prepared from hydrogen fluoride (HF). This highly toxic and corrosive gas is produced by the reaction of acid-grade fluorspar (>97% CaF 2 ) with sulfuric acid under harsh conditions. The use of fluorspar to produce fluorochemicals via a process that bypasses HF is highly desirable but remains an unsolved problem because of the prohibitive insolubility of CaF 2 . Inspired by calcium phosphate biomineralization, we herein disclose a protocol of treating acid-grade fluorspar with dipotassium hydrogen phosphate (K 2 HPO 4 ) under mechanochemical conditions. The process affords a solid composed of crystalline K 3 (HPO 4 )F and K 2− x Ca y (PO 3 F) a (PO 4 ) b , which is found suitable for forging sulfur-fluorine and carbon-fluorine bonds.

Publisher

American Association for the Advancement of Science (AAAS)

Subject

Multidisciplinary

Reference99 articles.

1. H. Groult F. Leroux A. Tressaud Eds. Modern Synthesis Processes and Reactivity of Fluorinated Compounds: Progress in Fluorine Science (Elsevier 2016).

2. Contemporary synthetic strategies in organofluorine chemistry

3. Organofluorine chemistry: applications, sources and sustainability

4. G. Siegemund W. Schwertfeger A. Feiring B. Smart F. Behr H. Vogel B. McKusick P. Kirsch “Fluorine compounds organic” in Ullmann’s Encyclopedia of Industrial Chemistry (Wiley 2016) pp. 1–56.

5. C. W. Scheele “Undersŏkning om fluss-spat och dess syra (Investigation of fluoride and its acid)” in Kongl. Vetenskaps Akademiens Handlingar (Transactions of the Royal Swedish Academy of Sciences) (Royal Swedish Academy of Sciences 1771) pp. 120–138.

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