4-BROMOBENZYLSULFONYL CHLORIDE

To a solution of HC1 (2M, 1.547 mL) in MeCN (30 mL) was added NCS (3.3 g, 24.6 mmol) at 0 °C in portions. The resulting mixture was stirred for 5 mm at 0 °C. Then to this mixture was added a solution of (4-bromo-phenyl)-methanesulfonyl chloride (1.5 g, 6.15 mmol) in MeCN (3 mL) dropwise at 0°C during 1 mm. The reaction mixture was stirred for 10 mi Na2SO4 (about 5 g) was added and the mixture was filtered. The filtrate was concentrated. The residue was purified by silica gel column chromatography (PE/EA = 10/1) to give (4-bromo-phenyl)- methanesulfonyl chloride (1.2 g, yield 73percent) as a white solid. ‘H NIVIR (300 IVIHz, CDC13): ö = 7.62 (d, J 8.4 Hz, 2H), 7.37 (d, J= 8.4 Hz, 2H), 4.83 (s, 2H).To a solution of N-chlorosuccinimide (3.95 g, 29.6 mmol) in acetonitrile (11.6 mL) and 1 M HCl (2.31 mL) at 0° C. was slowly added a solution of thioacetic acid S-(4-bromo-benzyl)ester (1.81 g, 7.39 mmol) in acetonitrile (6.3 mL) over 60 minutes whilst allowing the reaction to warm to 15° C. The remaining solution was added and reaction left to warm to room temperature for 10 minutes. The mixture was cooled to 0° C. and stirred for 1 hour. Water was added and the product was extracted with EtOAc, washed with brine, dried with NaStep 2: To a solution of N-chlorosuccinimide (3.95 g, 29.6 mmol) in acetonitrile (11.6 mL) and 1 M HC1 (2.31 mL) at 0 °C was slowly added a solution of thioacetic acid S-(4-bromo-benzyl) ester (1.81 g, 7.39 mmol) in acetonitrile (6.3 mL) over 60 minutes whilst allowing the reaction to warm to 15 °C. The remaining solution was added and reaction left to warm to room temperature for 10 minutes. The mixture was cooled to 0 °C and stirred for 1 hour. Water was added and the product was extracted with EtOAc, washed with brine, dried with Na2504, concentrated to give (4-bromo-phenyl)-methanesulfonyl chloride (2.6 g, 9.6 mmol). ‘H NMR (300 MHz, CDC13): ö 7.60 (d, 2 H), 7.36 (d, 2 H), 4.81 (s, 2 H).General procedure: Step 1. An alkyl halide or mesylate (5 mmol) and thiourea (0.381 g, 5 mmol) wererefluxed in 5 mL of ethanol for 1 h. After removal of the solvent in vacuum thecorresponding S-alkyl isothiourea salt was obtained as white solid or sticky oil.Step 2. A 50 mL three-necked flask equipped with a thermometer and asolid-addition funnel was immersed in an ice-bath. To the flask was sequentiallyadded NaClO2 solid (for isothiouronium chlorides or sulfonate, 1.61 g, 15 mmol; forisothiouronium bromides, 2.14 g, 20 mmol, 85percent purity), MeCN (10 mL), and thenconc. HCl (for isothiouronium chlorides or sulfonate, 3 mL; for isothiouroniumbromides, 4 mL) during 1 min at such a rate that the inner temperature was maintainedless than 10 °C. Then S-alkyl isothiourea salt was slowly added througth the solidaddition-funnel to keep the inner temperature less than 20 °C. After the addtion, theresulting mixture was stirred for another 30 min. Then 25 mL of water was added, and the resultant mixture was evaporated in vacuum at 15 °C to remove acetonitrile. Afteraddition of 100 mL of water, the solid products were obtained by filtration on aBuchner funnel and dried under an infrared lamp, while the liquid products wereobtained by extraction with 15 mL of ethyl acetate, drying with Na2SO4, andconcentration in vacuum.For 1, 4-dibromobutane, the amounts of thiourea, NaClO2 solid, MeCN, and conc.HCl were doubled.

Molecular Weight:269.54
XLogP3:2.6
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:2
Exact Mass:267.89604
Monoisotopic Mass:267.89604
Topological Polar Surface Area:42.5
Heavy Atom Count:12
Complexity:226
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes