Clean‐Chemistry Sulfonation of Aromatics.

Abstract

Sulfonic acids and esters Sulfonic acids and esters Q 0550Clean-Chemistry Sulfonation of Aromatics. -A solution of trifluoroacetic anhydride in conc. H 2 SO 4 is an efficient system for the rapid sulfonation of aromatic compounds. H 2 SO 4 is consumed stoichiometrically and the spent trifluoroacetic anhydride is readily recovered as trifluoroacetic acid which can be recycled to trifluoroacetic anhydride. -(CORBY, B. W.; GRAY, A. D.; MEANEY, P. J.; FALVEY, M. J.; LAWRENCE, G. P.; SMYTH*, T. P.; J. Chem. Res., Synop. 2002, 7, 326-327; Dep. Chem. Environ. Sci., Univ. Limerick, Plassey Technol. Park, Limerick, Ire.; Eng.) -M. Bohle 01-088

Blocky Ionomers via Sulfonation of Poly(ether ether ketone) in the Semicrystalline Gel State

“…Trifluoroacetyl sulfate was prepared according to previously published procedures. 39,40 Trifluoroacetic anhydride (3.8 mL, 0.027 mol) was added to a nitrogen-purged round-bottom flask. The flask was cooled in an ice bath for 15 min, and then concentrated sulfuric acid (1 mL, 0.018 mol) was added.…”

Novel methane activation by sulfur dioxide and molecular oxygen via trifluoroacetylsulfuric acid

“…Scheme 2 Facile preparation of trifluoroacetyl sulfuric acid (1). The formation of TFAOSO 3 H was confirmed comparatively by 19 F NMR spectral analysis between the previously reported methods 18,19 and our new technique using sulfur dioxide and molecular oxygen.…”

“…Trifluoroacetic anhydride (TFAA), aqueous hydrogen peroxide (30% solution), sulfur dioxide, molecular oxygen, and 13 Clabeled methane ( 13 CH 4 ) were purchased from commercial providers, and oven-dried reactors and glassware were employed for the reactions. 1 H, 13 C, and 19 F NMR spectra were recorded on a Varian Mercury 400 two-channel NMR spectrometer or a Varian VNMRS-500 two-channel NMR spectrometer. The chemical shifts were reported in δ ( ppm) values with the coupling constants ( J) in hertz (Hz).…”

“…By mixing TFAA and aqueous H 2 O 2 , we generated a catalyst solution of trifluoroperacetic acid (TFAO-OH), to which SO 2 and O 2 gases were charged in a high-pressure bomb. This reaction solution was heated at 50 °C for 16 hours to smoothly afford TFAOSO 3 H (1), and its structure was elucidated by comparative NMR spectral analysis with the same product generated by exploiting two different known methods: (1) mixing H 2 SO 4 and TFAA [17][18][19] and (2) using TFAOH and SO 3 . 20 The main peak and pattern of the 19 F NMR spectrum of the crude sample from our new protocol with SO 2 overlapped with that of each sample from the known methods 1 and 2, verifying the successful synthesis of TFAOSO 3 H (1).…”

“…This reaction solution was heated at 50 °C for 16 hours to smoothly afford TFAOSO 3 H (1), and its structure was elucidated by comparative NMR spectral analysis with the same product generated by exploiting two different known methods: (1) mixing H 2 SO 4 and TFAA [17][18][19] and (2) using TFAOH and SO 3 . 20 The main peak and pattern of the 19 F NMR spectrum of the crude sample from our new protocol with SO 2 overlapped with that of each sample from the known methods 1 and 2, verifying the successful synthesis of TFAOSO 3 H (1). With the preparation of the reactive intermediate confirmed, we subjected the crude product to the sulfonation of methane and obtained MSA successfully (vide infra).…”