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

• 成果类型: Article
• 署名作者: Patel, Calum; Andre-Joyaux, Emy; Leitch, Jamie A.; de Irujo-Labalde, Xabier Martinez; Ibba, Francesco; Struijs, Job; Ellwanger, Mathias A.; Paton, Robert; Browne, Duncan L.; Pupo, Gabriele; Aldridge, Simon; Hayward, Michael A.; Gouverneur, Veronique
• 署名单位: University of Oxford; University of London; University College London; University of Oxford; Colorado State University System; Colorado State University Fort Collins
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-12727
• DOI: 10.1126/science.adi1557
• 发表日期: 2023-07-21
• 页码: 302-306
• 关键词: nucleophilic fluorination; sulfonyl fluorides; phase; derivatives; nmr; deoxyfluorination; crystallography; inhibitors; ketones; alkenes

摘要

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% CaF2) 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 CaF2. Inspired by calcium phosphate biomineralization, we herein disclose a protocol of treating acid-grade fluorspar with dipotassium hydrogen phosphate (K2HPO4) under mechanochemical conditions. The process affords a solid composed of crystalline K-3(HPO4)F and K2-xCay(PO3F)(a)(PO4)(b), which is found suitable for forging sulfur-fluorine and carbon-fluorine bonds.