title: Single-step gas-phase polyperfluoroalkylation of naphthalene leads to thermodynamic products.
abstract: High-temperature gas-phase, solvent- and catalyst-free reaction of naphthalene with an excess of RF I reagent (RF CF3 , C2 F5 , n-C3 F7 , and n-C4 F9 ) was used for the first time to produce a series of highly perfluoroalkylated naphthalene products NAPH(RF )n with n=2-5. Four 95+ % pure 1,3,5,7-NAPH(RF )4 with RF CF3 , C2 F5 , n-C3 F7 , and n-C4 F9 were isolated using a simple chromatography-free procedure. These new compounds were fully characterized by (19) F and (1) H NMR spectroscopy, X-ray crystallography (for RF CF3 and C2 F5 ), atmospheric-pressure chemical ionization mass spectrometry, and cyclic and square-wave voltammetry. DFT calculations confirm that the proposed synthesis yields the most stable isomers that have not been accessed by alternative preparation techniques.
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, CO 80523 (USA).
authors.forename: Long K
authors.initials: LK
authors.lastname: San
authors.forename: Eric V
authors.initials: EV
authors.lastname: Bukovsky
authors.forename: Igor V
authors.initials: IV
authors.lastname: Kuvychko
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Popov
authors.forename: Steven H
authors.initials: SH
authors.lastname: Strauss
authors.forename: Olga V
authors.initials: OV
authors.lastname: Boltalina
mesh_terms: D000478:Alkylation; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D005461:Fluorine / Q000737:chemistry; D005740:Gases / Q000737:chemistry*; D008968:Molecular Conformation; D009281:Naphthalenes / Q000138:chemical synthesis / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013696:Temperature; D013816:Thermodynamics
chemical_list: D005740:Gases; D009281:Naphthalenes; D012997:Solvents; D005461:Fluorine
keywords: density functional calculations; electron acceptors; naphthalene; perfluoroalkyl iodides; perfluoroalkylation