2-Nitrobenzenesulfonyl chlorid chloride

The resulting acetyl compound is usually hydrolyzed with aqueous alkaU to give the free amine. Other A/-acyl derivatives may be used, particularly for the less soluble succinyl and phthaloyl products. The use of -nitrobenzenesulfonyl chloride, followed by reduction of the nitro to an amino function, is much more expensive and is rarely used. A/-Acetylsulfanilyl chloride [121 -60-8] is obtained by the chlorosulfonation of acetanilide [103-84-4] which is the basic material for most of the sulfonamides. 

The much-used sulfonylation by aromatic sulfonyl chlorides is illustrated by the conversion of quinazolin-4-amine into the sulfonamide (247) using p- nitrobenzenesulfonyl chloride at 60 °C (56JCS3509). 

The procedure given is applicable to many other aulfonyl chlorides as well (see Table I). Solid sulfonyl chlorides are added as such. When heavy frothing occurs in the reduction (e.g., with p-nitrobenzenesulfonyl chloride), addition of 50 ml. of chloroform to the reaction mixture will eliminate the foam without reducing the final yield. When the sulfonyl chlorides were prepared according to Meerwein and co-workers, it was found advantageous to use the crude, damp sulfonyl chlorides, since these are more easily reduced than the dried or recrystallized materials. 

In the alternate approach, the amide formation is performed on para-nitrobenzenesulfonyl chloride (91). Reduction by either chemical or catalytic methods affords directly the desired product (90). ... 

Nitriles from aromatic aldehydes, diammonium hydrogen phosphate, and 1-nitropropane, 43, 59 w-Nitrobenzenesulfonyl chloride, reduction to m-nitrophenyl disulfide by hydriodic acid, 40, 80 2 Nitro-2,3-dimethylbutane, 43, 89... 

The classic syntheses of the antibacterial sulfonamides involve reaction of the appropriate arylamine with an acid addition salt of p-amino-benzenesulfonyl chloride, or p-nitrobenzenesulfonyl chloride followed by reduction. Chemical interest largely resides in preparation of the corresponding arylamines. For the synthesis of sulfacytine (134), N-ethyl uracil (131) was converted to its thioamide (132) by reaction with phosphorous pentasulfide. The newly introduced sulfur is then displaced with ammonia in methanol to give 133. Standard reactions complete... 

R)-Cyanohydrins react with toluenesulfonyl chloride, methanesulfonyl chloride or 4-nitrobenzenesulfonyl chloride without loss of stereochemical purity, and the 2-sulfonyloxy-nitrile reacts with a variety of Sn2 reactions to give a variety of products, such as 2-fluoro nitrile [64], 2-azidonitrile [65] and /V- p h t h a I o yl - p rot e c te d 2-aminonitrile [66], 2-acetoxy nitrile [66], and 2-mercapto nitrile [67]. Hydrogenation of 2-sulfonyloxynitriles with LiAIH4 in good chemical yields and high ee afforded 2-monosubstituted (S)-aziridines [68]. 

Chlorosulfuric acid, Hydrocarbons, 3997 4-Hydroxy-3-nitrobenzenesulfonyl chloride, 2146... 

Complete reduction of sulfonyl chlorides to thiols can be achieved by lithium aluminum hydride [680,693], with zinc [696] and with hydriodic acid generated in situ from iodine and red phosphorus [230]. m-Nitrobenzenesulfonyl chloride, however, was reduced not to the thiol but to bis(m-nitrophenyl)disulfide by hydriodic acid in 86-91% yield [697]. 

Sulfamethizole Sulfamethizole, AfL(5 niethyl-l,3,4-thiadiazole-2-yl)sulfanilamide (33.1.15), is synthesized in two ways. According to the first, 5-amino-2-methyl-l,3,4-thiadiazole is reacted with 4-nitrobenzenesulfonyl chloride to make a nitro derivative (33.1.14), which is then reduced using iron filings in acetic acid to give the desired sulfamethizole. 

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). 

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