Di-tert-butyl peroxide initiated free radical addition of THF to various fluorinated alkenes (CF(2)=CH(2), CF(2)=CFH, CH(2)=CHCF(3), CF(2)=CFCF(3), CF(2)=CFC(5)F(11), CF(2)=CFOCF(2)CF(CF(3))OCF(2)CF(2)SO(2)F) gives either bidirectional addition products [CH(2)CH(2)CH(2)OCH(CF(2)CH(3)) (1), CH(2)CH(2)CH(2)OCH(CH(2)CHF(2)) (2), CH(2)CH(2)CH(2)OCH(CF(2)CH(2)F) (3), and CH(2)CH(2)CH(2)OCH(CFHCHF(2)) (4)] or unidirectional products [CH(2)CH(2)CH(2)OCH(CH(2)CH(2)CF(3)) (5), CH(2)CH(2)CH(2)OCH(CF(2)CHFCF(3)) (6), CH(2)CH(2)CH(2)OCH(CF(2)CHFC(5)F(11)) (7), and CH(2)CH(2)CH(2)OCH(CF(2)CHFOCF(2)CF(CF(3))OCF(2)CF(2)SO(2)F) (8)] depending on the structure of the alkene. Reaction of dioxane with CF(2)=CFOCF(2)CF(CF(3))OCF(2)CF(2)SO(2)F gives a single product, CH(2)OCH(2)CH(2)OCH(CF(2)CHFOCF(2)CF(CF(3))OCF(2)CF(2)SO(2)F) (9). In the case of hexafluoropropene or perfluoroallylbenzene, reaction with an excess of tetrahydrofuran gives only the monosubstituted products CH(2)CH(2)CH(2)OCH(CF(2)CHFCF(3)) (6) and CH(2)CH(2)CH(2)OCH(CF(2)CFHCF(2)C(6)F(5)) (11) respectively. When tetrahydrofuran is reacted with a 3:1 molar excess of the same two perfluoroalkenes, the disubstituted products CH(2)CH(2)CH(CF(2)CHFCF(3))OCH(CF(2)CHFCF(3)) (10) and CH(2)CH(2)CH(CF(2)CFHCF(2)C(6)F(5))OCH(CF(2)CFHCF(2)C(6)F(5)) (12) are formed respectively. When 18-crown-6 is reacted in the same way with fluoroalkenes in a 1:1 molar ratio, the monosubstituted products 18-crown-6-CH(2)CH(2)CF(3) (13), 18-crown-6-CF(2)CHFCF(3) (14), 18-crown-6-CF(2)CFHCF(2)C(6)F(5) (15), and 18-crown-6-CF(2)CHFOCF(2)CF(CF(3))OCF(2)CF(2)SO(2)F (16) are obtained. Polyfluorinated 18-crown-6 products containing three and two polyfluroalkyl/aryl groups are prepared when 18-crown-6 is reacted with a 3:1 molar excess of perfluoropropene and perfluoroallylbenzene to give 18-crown-6-(CF(2)CHFCF(3))(3) (17) and 18-crown-6-(CF(2)CFHCF(2)C(6)F(5))(2) (18), respectively. (Pentafluorophenoxy)trimethylsilane reacts with 11 in the presence of a catalytic amount of cesium fluoride to give compound 19, CH(2)CH(2)CH(2)OCH(CF(2)CFHCF(2)C(6)F(4)OC(6)F(5)). Two molecules of 11 are bridged by reaction with Me(3)SiOCH(2)CF(2)CF(2)CF(2)CH(2)OSiMe(3) to give CH(2)CH(2)CH(2)OCHCF(2)CFHCF(2)C(6)F(4)OCH(2)CF(2)CF(2)CF(2)CH(2)OC(6)F(4)CF(2)CHFCF(2)CHOCH(2)CH(2)CH(2) (20), while 12 forms the macroheterocycle OCHCH(2)CH(2)CHCF(2)CFHCF(2)C(6)F(4)OCH(2)CF(2)CF(2)CF(2)CH(2)OC(6)F(4)CF(2)CFHCF(2) (21) under similar reaction conditions. The lanthanum triflate complexes of 18-crown-6 (22) and 18-crown-6(CF(2)CFHCF(3)) (23) were prepared and the structures were obtained via single-crystal X-ray analysis. Although crystals suitable for single-crystal X-ray analysis could not be formed, lanthanum triflate complexes were formed with polyfluorinated ethers 15 and 16 to give the fluorinated complexes La(OSO(2)CF(3))(3)(18-crown-6-CF(2)CFHCF(2)C(6)F(5))(H(2)O) (24) and [La(OCH(2)CH(2))(5)OCH(2)CHCF(2)CFHOCF(2)C(CF(3))FOCF(2)CF(2)SO(2)F](3+)[CF(3)SO(3)(-)](3) (25) respectively. The acid salt La[N(SO(2)CF(3))(2)](3) (26) was also prepared and characterized, and reacted with dibenzo-18-crown-6 to give the complex dibenzo-18-crown-6-La[N(SO(2)CF(3))(2)](3) (27).
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ic9509645 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Monofluorinated acetal electrolyte for high-performance lithium metal batteries.
Proc Natl Acad Sci U S A
January 2025
Department of Chemical Engineering, Stanford University, Stanford, CA 94305.
High degree of fluorination for ether electrolytes has resulted in improved cycling stability of lithium metal batteries due to stable solid electrolyte interphase (SEI) formation and good oxidative stability. However, the sluggish ion transport and environmental concerns of high fluorination degree drive the need to develop less fluorinated structures. Here, we depart from the traditional ether backbone and introduce bis(2-fluoroethoxy)methane (F2DEM), featuring monofluorination of the acetal backbone.
View Article and Find Full Text PDFDeriving Membrane-Water and Protein-Water Partition Coefficients from In Vitro Experiments for Per- and Polyfluoroalkyl Substances (PFAS).
Environ Sci Technol
January 2025
Department of Civil & Environmental Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States.
The phospholipid membrane-water partition coefficients () and equilibrium binding affinities for human serum albumin (HSA) of 60 structurally diverse perfluoroalkyl and polyfluoroalkyl substances (PFAS) were evaluated through laboratory measurements and modeling to enhance our understanding of PFAS distribution in organisms. Per- and polyfluoroalkyl carboxylic acids exhibited a 0.36 ± 0.
View Article and Find Full Text PDFOccurrence and distribution of brominated and fluorinated persistent organic pollutants in surface sediments focusing on industrially affected rivers.
Chemosphere
January 2025
Department of Civil and Environmental Engineering, Pusan National University, Busan 46241, Republic of Korea; Institute for Environment and Energy, Pusan National University, Busan, 46241, Republic of Korea. Electronic address:
Article Synopsis
- The study focused on legacy persistent organic pollutants like PBDEs, HBCDs, and PFAS found in sediments from five major rivers, revealing higher contamination levels in areas with industrial activity.
- The predominant compounds detected were decaBDE for PBDEs, γ-HBCD for HBCDs, and PFOS for PFAS, with alternative substances appearing less frequently.
- Overall, while most ecological risk assessment values were low, PBDEs and PFOS posed significant risks at certain sites, indicating a need for ongoing monitoring to protect aquatic ecosystems.
Base-catalyzed thiol-epoxy reactions: Energetic and kinetic evaluations.
J Mol Graph Model
March 2025
Chemical Engineering Department, Ondokuz Mayıs University, 55139, Samsun, Turkey. Electronic address:
The mechanism of the base-catalyzed thiol-epoxide stage of the thiol-ene/thiol-epoxide curing process was investigated using quantum chemical tools. This study searched for conventional tertiary amines with low to medium basicity as initiators to control reaction rates and tailor industrial applications. Challenges arise from the stronger basicity of initiators, leading to an uncontrollable and short curing application period.
View Article and Find Full Text PDFFON: An Innovative Fluorinated Group via Hydroetherification-Type Reactivity.
Org Lett
January 2025
Department of Chemistry, Brock University, St. Catharines, Ontario L2S 3A1, Canada.
An efficient strategy for preparing the novel -difluoroalkylhydroxylamine fluorinated functional group, coined FON, is reported. This analogue of medicinally important β-phenethyl ether scaffolds in uniting -difluoro and N-O moieties is synthesized in one step via chemo- and regioselectivity metal-free hydroetherification-type additions. As shown, this unique mode of reactivity is realized for a diverse substrate scope and applied to gram-scale synthesis and site-selective deuterium incorporation.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!