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

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.

Topics

No keywords indexed for this article. Browse by subject →

References

99

[1]

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

[2]

10.1038/s43586-021-00042-1

[3]

10.1039/c4gc02166e

[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. 10.1002/14356007.a11_349.pub2

[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.

[6]

J. Aigueperse P. Mollard D. Devilliers M. Chemla R. Faron R. Romano J. P. Cuer “Fluorine compounds inorganic” in Ullmann’s Encyclopedia of Industrial Chemistry (Wiley 2000) pp. 11–307. 10.1002/14356007.a11_307

[7]

D. Horowitz “This chemical kills. Why aren’t regulators banning it?” The New York Times 8 June 2019.

[8]

W. M. Haynes CRC Handbook of Chemistry and Physics (CRC Press ed. 95 2014). 10.1201/b17118

[9]

A. Haupt Organic and Inorganic Fluorine Chemistry: Methods and Applications (De Gruyter 2021). 10.1515/9783110659337

[10]

10.1021/ja01852a002

[11]

R. K. Jordan “Carbonyl fluorination process ” US Patent US4087475 (1975).

[12]

10.1021/acs.iecr.9b04958

[13]

10.1016/s0022-1139(02)00073-8

[14]

10.1002/anie.200604447

[15]

10.1002/anie.200701945

[16]

10.1126/science.aar7941

[17]

10.1021/jacs.2c00190

[18]

10.1021/ic030255o

[19]

10.1002/1521-3773(20020902)41:17<3130::aid-anie3130>3.0.co;2-1

[20]

10.1039/c1cs15171a

[21]

10.1021/acscatal.0c00142

[22]

10.1039/c7cs00813a

[23]

10.3389/fchem.2021.685789

[24]

10.1002/cssc.202200362

[25]

10.1021/acsami.8b04108

[26]

10.1002/anie.201309399

[27]

10.1038/s41570-021-00352-8

[28]

10.1039/c5sc00408j

[29]

10.1021/jacs.5b06307

[30]

10.1002/chem.201901176

[31]

10.1016/s0022-1139(00)85178-7

[32]

10.1039/dt9960002497

[33]

10.1021/ic50004a056

[34]

10.1021/acs.joc.2c02630

[35]

10.1002/ejoc.202000022

[36]

10.1002/ejoc.201801270

[37]

10.1021/acs.joc.7b00051

[38]

10.1002/anie.202009699

[39]

10.1021/jacs.9b06126

[40]

10.1021/acs.orglett.0c00484

[41]

10.1002/adsc.202000515

[42]

10.1038/s41467-019-11805-6

[43]

10.1021/acs.orglett.2c01604

[44]

10.1002/anie.202012229

[45]

10.1016/j.tet.2022.132657

[46]

10.1021/acs.joc.6b01423

[47]

10.2174/156800911796191015

[48]

10.1021/jo00431a054

[49]

10.1021/acs.orglett.2c03546

[50]

10.1002/anie.201406964

Showing 50 of 99 references

Cited By

111

Experimental and computational insights into efficiently synthesizing trimethyl orthoformate from calcium methoxide and chloroform

Hui Xu, Zhengrun Chen · 2026

Journal of Industrial and Engineeri...

Mechanochemical upcycling technologies for sustainable circular fluorine economy

Asuka Matsunami, Takashi Okazoe · 2025

Nature Chemistry

Mechanochemical pathway for converting fluoropolymers to fluorochemicals

Masashi Hattori, Debarshi Saha · 2025

Nature Chemistry

Lewis-acid induced mechanochemical degradation of polyvinylidene fluoride: transformation into valuable products

Minh Bui, Christian Heinekamp · 2025

Chemical Science

One-Step HF-Free Synthesis of Alkali Metal Fluorides from Fluorspar

Thomas Schlatzer, Christopher A. Goult · 2025

Journal of the American Chemical So...

Phosphate-enabled mechanochemical PFAS destruction for fluoride reuse

Long Yang, Zijun Chen · 2025

Nature

Review and Theoretical Analysis of Fluorinated Radicals in Direct C Ar −H Functionalization of (Hetero)arenes

Anthony J. Fernandes, Rahul Giri · 2024

Angewandte Chemie International Edi...

Metrics

111

Citations

99

References

Details

Published: Jul 21, 2023
Vol/Issue: 381(6655)
Pages: 302-306

Authors

C

Calum Patel

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

E

Emy André-Joyaux

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

J

Jamie A. Leitch

Department of Pharmaceutical and Biological Chemistry, University College London School of Pharmacy, London W1CN 1AX, UK.; FluoRok Ltd., Begbroke Science Park, Begbroke Hill, Woodstock Road, Begbroke OX5 1PF, UK.

X

Xabier Martínez de Irujo-Labalde

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

F

Francesco Ibba

Chemistry Research Laboratory, University of Oxford, Oxford OX1 3TA, UK.; FluoRok Ltd., Begbroke Science Park, Begbroke Hill, Woodstock Road, Begbroke OX5 1PF, UK.

J

Job Struijs

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

M

Mathias A. Ellwanger

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

R

Robert Paton

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

D

Duncan L. Browne

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

G

Gabriele Pupo

Chemistry Research Laboratory, University of Oxford, Oxford OX1 3TA, UK.; FluoRok Ltd., Begbroke Science Park, Begbroke Hill, Woodstock Road, Begbroke OX5 1PF, UK.

S

Simon Aldridge

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

M

Michael A. Hayward

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

V

Véronique Gouverneur

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

Cite This Article

Calum Patel, Emy André-Joyaux, Jamie A. Leitch, et al. (2023). Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF. Science, 381(6655), 302-306. https://doi.org/10.1126/science.adi1557

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

You May Also Like