Chemical Properties
yellow crystalline powder
Uses
Sulfonyl fluoride motif can be used as a connector for the assembly of -SO
2- linked small molecules with proteins or nucleic acids. This new click chemistry approach through sulfates is a complimentary approach to using amides and phosphate groups as linkers.
Uses
4-Nitrobenzenesulfonyl Fluoride is a protein modifying agent shown to be specific for tyrosine.
reaction suitability
reaction type: click chemistry
Synthesis
The general procedure for the synthesis of p-nitrobenzene methanesulfonyl fluoride from 4-nitrobenzene-1-sulfonyl chloride was as follows: potassium fluoride (KF, 26.0 g, 451 mmol) and 18-crown-6 (1.2 g, 4.5 mmol) were added to a 500 mL solution of 4-nitrobenzene-1-sulfonyl chloride (20.0 g, 90.2 mmol) in acetonitrile (CH3CN). The reaction mixture was stirred at room temperature for 24 h before the solvent was evaporated to dryness by rotary evaporator. Subsequently, ethyl acetate (EtOAc, 600 mL) was added to the residue for dissolution. The resulting solution was washed sequentially with deionized water (H2O, 300 mL × 3) and saturated brine (300 mL). The organic layer was dried over anhydrous sodium sulfate (Na2SO4), filtered and concentrated in vacuum to give p-nitrobenzene methanesulfonyl fluoride (17.4 g, 94% yield) as a yellow solid with a melting point of 76-77 °C. Thin layer chromatography (TLC) showed an Rf value of 0.63 (Expanding agent: hexane/ethyl acetate = 6/4). Nuclear magnetic resonance hydrogen spectrum (1H NMR, 400MHz, CDCl3): δ8.47 (d, J=8.7Hz, 2H, aromatic-H), 8.25 (d, J=8.7Hz, 2H, aromatic-H); nuclear magnetic resonance carbon spectrum (13C NMR, 100MHz, CDCl3): δ151.8 (C), 138.2 (d, J=26.7Hz (C), 130.0 (CH), 124.9 (CH); nuclear magnetic resonance fluorine spectrum (19F NMR, 376MHz, CDCl3): δ65.1. infrared spectrum (IR, KBr): 3105,2872,1951,1818,1613,1540,1420,1354,1314,1215 cm-1. high resolution mass spectrometry (HRMS) calculated values C (HRMS) calculated value of C6H5FNO4S ([M+H]+) was 205.9923 and measured value was 205.9918.
References
[1] Tetrahedron, 2016, vol. 72, # 1, p. 58 - 68
[2] ACS Combinatorial Science, 2018, vol. 20, # 11, p. 672 - 680
[3] Journal of Fluorine Chemistry, 2013, vol. 145, p. 35 - 40
[4] Organic and Biomolecular Chemistry, 2017, vol. 15, # 45, p. 9685 - 9695
[5] Journal of Organic Chemistry, 2013, vol. 78, # 22, p. 11262 - 11270
