2-Nitrobenzenesulfonyl chlorid

Methoxybenzylamine, triethylamine, and 2-nitrobenzenesulfonyl chloride were purchased by the submitters from Tokyo Kasei Kogyo Co. The checkers obtained 4-methoxybenzylamine and 2-nitrobenzenesulfonyl chloride from Alfa Aesar and triethylamine from Mallinckrodt Inc.. 

Nitrobenzenesulfonylperoxy intermediate 51 had shown a larger oxidizing ability towards olefins compared with the 4-nitrobenzenesulfonylperoxy intermediate. When 2-nitrobenzenesulfonyl chloride reacts with 02" at low temperature (—20 to —35°C) in CH3CN, the corresponding sulfonylperoxy radical 51 or anion 52 is generated. The radical character of the sulfonylperoxy intermediate 51 was further confirmed by the electrophilic oxidizing nature of a 2-nitrobenzenesulfonyl chloride/KOi mixture. 

Various mono- or di-olefins were oxidized regioselectively to their epoxides in high yield with the 2-nitrobenzenesulfonylperoxy intermediate 51 generated in situ from 2-nitrobenzenesulfonyl chloride and KO2 at —35°C in CH3CN (equation Thus /3-... 

Spectroscopic evidence for peroxy radical 51 was obtained from ESR. Spin trapping studies monitored by ESR have demonstrated that 02 reacts efficiently with 2-nitrobenzenesulfonyl chloride and results in the formation of the peroxy radical intermediate 51 (equation 88). The 5,5-dimethyl-l-pyrroline-l-oxide (DMPO) spin adduct of 51 shows the hyperfine coupling constants, aN = 1.8 G and aH = 10.1 G. 

The 1,2,5-benzothiadiazepine 1,1-dioxide (545) and its 3,4-dihydro analogue have been prepared by the reaction of 2-nitrobenzenesulfonyl chloride with w-aminoacetophenone to give (544) followed by reductive cyclization (79JHC835). 

The reaction of methyl ester of D-alanine 185 with 4-methoxy-2-nitrobenzenesulfonyl chloride 186 in presence of ethyl diisopropylamine gave the sulfonamide 187, which was alkylated with allyl bromide 188 to afford 189 (Scheme 41). Ozonolysis of 189 resulted in the formation of aldehyde 190, and the subsequent reductive cyclization with zinc and AcOH led to the benzothiadiazepine 120 through intramolecular reductive alkylation. Using similar reaction sequence, the 1,2,5-thiadiazepines 191 and 192 were also synthesized <2003JME1811>. 

The sulfonamide 364 was obtained from the reaction of 2-nitrobenzenesulfonyl chloride 362 and the substituted anilines 363, which were then converted to the 1,2,5-thiadiazepines 365 by refluxing 364 with copper, followed by hydrolysis of the amide (Scheme 75) <2004H(63)2457>. 

The condensation of 2-nitrobenzenesulfonyl chlorides with 3-amino-2-chloropyridine in the presence of pyridine at 60 °C gave the corresponding sulfonamides, which were reacted with sodium hydride and iodomethane to give the N-methylated products. Catalytic hydrogenation of the N-methylated compounds followed by acetylation, treatment with sodium hydride in DMF, and reaction with arylalkyl chlorides or methanesulfonates resulted in the formation of novel benzo[/]pyrido[]3,2-r-][l,2,5]thiadiazepines <2005JME7363>. 

Arene oxides.1 K02 converts 2-nitrobenzenesulfonyl chloride into a peroxy-sulfur radical that effects epoxidation of polyarenes to give arene oxides in aprotic solvents at -30°. Anthracene is converted into the 9,10-quinone (70% yield). 

Solutions of KO2 and l8-crown-6 in DMSO cause oxidation of the solvent to die sulfone. The phosphorus-containing peroxy anion (EtO)2P03" obtained on reaction of KO2 widi diefiiyl chlorophosphate [(EtO)2POCl] in acetonitrile has been used to prepare sulfones from sulfoxides at 20 C. Similarly, various sulfoxides are readily oxidized chemoselectively to the sulfones in high yields by 2-nitrobenzene peroxysulfur intermediate (26) generated in situ from 2-nitrobenzenesulfonyl chloride and KO2 (Scheme 8 Ar = 2-N02C6H4). ... 

Treatment of 5-aminotetrazole with 2-nitrobenzenesulfonyl chloride (179) does not yield the... 

Methyl-2-nitrobenzenesulfonyl chloride 621 Bis-(2-nitrotolyl) disulfide (2 g) is dissolved in glacial acetic acid (10 ml), water (2 ml) is added, and the solution is saturated with chlorine whilst being allowed to become warm. On cooling, part of the sulfonyl chloride separates as colorless crystals and the remainder is obtained by evaporation for purification it is recrystallized from benzene-light petroleum, then having m.p. 98-99°. 

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