- Photochemistry of the chlorine monofluoride, CIF. Thermal and photochemical reactions with sulfur tetrafluoride SF4
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The thermal and photochemical reactions of chlorine monofluoride have been studied with xenon, perfluoroethane C2F6, and sulfur tetrafluoride, SF4, which had been considered as possible scavengers for the excited or unstable species.No reaction has been observed with Xe and C2F6 either under thermal or photochemical activation.Photochemical reaction of CIF with SF4 has been studied at several wavelengths with a cw laser.From these studies, two reaction paths have been emphasized: (1) the molecular addition of ClF* to SF4 to give sulfur chloropentafluoride SF5Cland (2) a typical laser induced radical process yielding disulfur decafluoride S2F10 and chloride Cl2.This former effect has been shown to be hidden at low mean power irradiation by the thermal reaction which seems to be dramatically enhanced at low pressure by wall-catalyzed processes.
- Naulin, Christian,Bougon, Roland
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- Chemoselective Hydro(Chloro)pentafluorosulfanylation of Diazo Compounds with Pentafluorosulfanyl Chloride
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Pentafluorosulfanyl chloride (SF5Cl) is the most prevalent reagent for the incorporation of SF5 group into organic compounds. However, the preparation of SF5Cl often relies on hazardous reagents and specialized apparatus. Herein, we described a safe and practical synthesis of a bench-stable and easy-to-handle solution of SF5Cl in n-hexane under gas-reagent-free conditions. The synthetic application of SF5Cl was demonstrated through the unprecedented reaction with diazo compounds. The chemoselective hydro- and chloropentafluorosulfanylations of α-diazo carbonyl compounds were developed in the presence of K3PO4 or copper catalyst, respectively. These reactions provide a direct and efficient access to various α-pentafluorosulfanyl carbonyl compounds of high value for potential applications.
- Qing, Feng-Ling,Shou, Jia-Yi,Xu, Xiu-Hua
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supporting information
p. 15271 - 15275
(2021/06/08)
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- METHOD FOR PREPARING A POLYFLUORINATED COMPOUND
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The present invention relates to a process for preparing a polyfluorinated compound of formula Ar-Ri(l), wherein Ar-Ri(l) is an aromatic ring system wherein R1 is selected from the group consisting of SF4CI, SF3, SF2CF3, TeFS, TeF4CF3, SeF3, IF2, SeF2CF3, and IF4, X2 is N or CR2, X3 is N or CR 3, X 4 is N or CR 4, X 5 is N or CR 5, X 6 is N or CR 6, and the total number of nitrogen atoms in the aromatic ring system is between 0 and 3, and if X 5 is CR 5 and X 6 is CR 6 R 5 and R 6 may form together a saturated or unsaturated five or six membered ring system comprising one or more nitrogen, wherein said five or six membered ring system may be substituted with one or more residues R 7 said process involving the following reaction step reacting a starting material selected from the group consisting of Ar2S2, Ar2Te2, Ar2Se2, ArSCF3, Arl, ArTeCF3, ArSeCF3, ArSCF3, and ArSCI, wherein Ar has the same definition as above, with trichloroisocyanuric acid (TCICA) of the formula (III) in the presence of the alkali metal fluoride (MF).
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Page/Page column 50-51
(2019/12/25)
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- Some reactions of sulfonyl hypohalites with sulfur tetrafluoride
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The reactions of ClOSO2F, BrOSO2F, and ClOSO2CF3 with SF4 have been investigated. It has been found that the reactions proceed to form either trifluorosulfonium salts or covalent adducts. In the cases where the hypochlorites were used, the unusual cation SF4Cl+ can be postulated as a reactive intermediate. Characterizations of the new compounds SF3+FSO3-, SF3+CF3SO3-, cis-SF4(Cl)OSO2F, trans-SF4(Cl)OSO2F, and trans-SF4(Cl)OSO2CF3 are reported. The SF3+ salts are thermally unstable, decomposing to SF4, SOF2, and (XSO2)2O (X = F, CF3).
- O'Brien, Brian A.,DesMarteau, Darryl D.
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p. 644 - 648
(2008/10/08)
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- The Reaction of S2NAsF6 with Halogens: Preparation and X-Ray Crystal Structure of Bis(difluorothio)nitronium Hexafluoroarsenate(V), (SF2)2NAsF6; Preparation of (SBr)2NAsF6, and Vibrational Spectrum and Normal-co-ordinate Analysis of the (SX)2N+ (X=Cl or Br) Cations
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Solutions of S2NAsF6 in liquid SO2 react with elemental chlorine and bromine yielding (SX)2NAsF6 (X=Cl or Br), essentially quantitatively.No reaction was detected with iodine.The vibrational spectrum of (SBr)2N+ was similar to that of (SCl)2N+ of known structure, implying a similar structure for the bromine derivative.This conclusion was supported by a normal-co-ordinate analysis of (SX)2N+.The analysis was consistent with some positive interaction between the halogen atoms in (SX)2N+, possibly accounting for the cis planar geometry of these cations.Attempts to prepare (SF)2NAsF6 were unsuccessful.However, (SF2)2NAsF6 was synthesised by the reaction of S2NAsF6 and XeF2 in liquid SO2F2, essentially quantitatively.The structure of (SF2)2NAsF6 was determined by X-ray diffraction.The crystals are orthorhombic with a=14.909(1), b=9.843(4), c=12.113(1) Angstroem, and Z=8.The structure was refined in space group Pbca to a conventional R factor of 0.076 for 902 independent reflections with I>2?(I).It consists of discrete (SF2)2N+ and AsF6- with some cation-anion interactions.The (SF2)2N+ cation has approximate C2γ symmetry with essentially eclipsed fluorine-sulphur bonds as viewed along the sulphur-sulphur axis.The average S-N and S-F distances are 1.551(10) and 1.523(8) Angstroem, and the average FSF and FSN bond angles are 94.0(5) and 100.2(6) deg.The SNS bond angle is 121.1(6) deg.The vibrational spectrum of (SF2)2NAsF6 is reported.
- Brooks, Wendell V. F.,MacLean, Gregory K.,Passmore, Jack,White, Peter S.,Wong, Chi-Ming
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p. 1961 - 1968
(2007/10/02)
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