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

<p>All fluorochemicals&mdash;including elemental fluorine and nucleophilic, electrophilic, and radical fluorinating reagents&mdash;are prepared from hydrogen fluoride (HF). This highly toxic and corrosive gas is produced by the reaction of acid-grade fluorspar (&gt;97% CaF<sub&g...

Full description

Bibliographic Details
Main Authors: Patel, C, André-Joyaux, E, Leitch, JA, de Irujo-Labalde, XM, Ibba, F, Struijs, J, Ellwanger, MA, Paton, R, Browne, DL, Pupo, G, Aldridge, S, Hayward, MA, Gouverneur, V
Format: Journal article
Language:English
Published: American Association for the Advancement of Science 2023
_version_ 1826310440479621120
author Patel, C
André-Joyaux, E
Leitch, JA
de Irujo-Labalde, XM
Ibba, F
Struijs, J
Ellwanger, MA
Paton, R
Browne, DL
Pupo, G
Aldridge, S
Hayward, MA
Gouverneur, V
author_facet Patel, C
André-Joyaux, E
Leitch, JA
de Irujo-Labalde, XM
Ibba, F
Struijs, J
Ellwanger, MA
Paton, R
Browne, DL
Pupo, G
Aldridge, S
Hayward, MA
Gouverneur, V
author_sort Patel, C
collection OXFORD
description <p>All fluorochemicals&mdash;including elemental fluorine and nucleophilic, electrophilic, and radical fluorinating reagents&mdash;are prepared from hydrogen fluoride (HF). This highly toxic and corrosive gas is produced by the reaction of acid-grade fluorspar (&gt;97% CaF<sub>2</sub>) 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<sub>2</sub>. Inspired by calcium phosphate biomineralization, we herein disclose a protocol of treating acid-grade fluorspar with dipotassium hydrogen phosphate (K<sub>2</sub>HPO<sub>4</sub>) under mechanochemical conditions. The process affords a solid composed of crystalline K<sub>3</sub>(HPO<sub>4</sub>)F and K<sub>2&minus;</sub><em><sub>x</sub></em>Ca<em><sub>y</sub></em>(PO<sub>3</sub>F)<em><sub>a</sub></em>(PO<sub>4</sub>)<em><sub>b</sub></em>, which is found suitable for forging sulfur-fluorine and carbon-fluorine bonds.</p>
first_indexed 2024-03-07T07:52:06Z
format Journal article
id oxford-uuid:c33d0be5-b6e7-4513-a5f8-002989384972
institution University of Oxford
language English
last_indexed 2024-03-07T07:52:06Z
publishDate 2023
publisher American Association for the Advancement of Science
record_format dspace
spelling oxford-uuid:c33d0be5-b6e7-4513-a5f8-0029893849722023-07-24T06:52:16ZFluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HFJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:c33d0be5-b6e7-4513-a5f8-002989384972EnglishSymplectic ElementsAmerican Association for the Advancement of Science2023Patel, CAndré-Joyaux, ELeitch, JAde Irujo-Labalde, XMIbba, FStruijs, JEllwanger, MAPaton, RBrowne, DLPupo, GAldridge, SHayward, MAGouverneur, V<p>All fluorochemicals&mdash;including elemental fluorine and nucleophilic, electrophilic, and radical fluorinating reagents&mdash;are prepared from hydrogen fluoride (HF). This highly toxic and corrosive gas is produced by the reaction of acid-grade fluorspar (&gt;97% CaF<sub>2</sub>) 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<sub>2</sub>. Inspired by calcium phosphate biomineralization, we herein disclose a protocol of treating acid-grade fluorspar with dipotassium hydrogen phosphate (K<sub>2</sub>HPO<sub>4</sub>) under mechanochemical conditions. The process affords a solid composed of crystalline K<sub>3</sub>(HPO<sub>4</sub>)F and K<sub>2&minus;</sub><em><sub>x</sub></em>Ca<em><sub>y</sub></em>(PO<sub>3</sub>F)<em><sub>a</sub></em>(PO<sub>4</sub>)<em><sub>b</sub></em>, which is found suitable for forging sulfur-fluorine and carbon-fluorine bonds.</p>
spellingShingle Patel, C
André-Joyaux, E
Leitch, JA
de Irujo-Labalde, XM
Ibba, F
Struijs, J
Ellwanger, MA
Paton, R
Browne, DL
Pupo, G
Aldridge, S
Hayward, MA
Gouverneur, V
Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF
title Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF
title_full Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF
title_fullStr Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF
title_full_unstemmed Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF
title_short Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF
title_sort fluorochemicals from fluorspar via a phosphate enabled mechanochemical process that bypasses hf
work_keys_str_mv AT patelc fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT andrejoyauxe fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT leitchja fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT deirujolabaldexm fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT ibbaf fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT struijsj fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT ellwangerma fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT patonr fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT brownedl fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT pupog fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT aldridges fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT haywardma fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf
AT gouverneurv fluorochemicalsfromfluorsparviaaphosphateenabledmechanochemicalprocessthatbypasseshf