Reactions of N-(2- and 4-methylsulfonylphenyl)hydroxylamines and 2-methylsulfonylnitrosobenzene in dilute aqueous sodium hydroxide solution

1970 ◽  
Vol 48 (9) ◽  
pp. 1404-1413 ◽  
Author(s):  
K. B. Shaw ◽  
R. M. Heggie ◽  
R. K. Miller
Keyword(s):  
Sodium Hydroxide ◽  
Room Temperature ◽  
Sodium Hydroxide Solution ◽  
Aqueous Sodium Hydroxide ◽  
Major Product ◽  
Quantitative Yield ◽  
Aqueous Sodium Hydroxide Solution ◽  
Aqueous Sodium ◽  
Hydroxide Solution ◽  
Dilute Sodium Hydroxide

When N-(2-methylsulfonylphenyl)hydroxylamine (4) was treated with dilute sodium hydroxide solution the major product was always 2,2′-di(methylsulfonyl)azoxybenzene (5). At room temperature other significant products were 2-hydroxy-2′-methylsulfonylazoxybenzene (6a) and 2-methylsulfonylnitrobenzene (2), while 6a was also formed at reflux together with small amounts of 2-hydroxy-2′-methylsulfonylazobenzene (8), 2-methylsulfonylaniline (7), 3-methylsulfonyl-3′-nitro-4-amino-4′-hydroxybiphenyl (3), and 2. The compounds 5, 6a, and 7 were also obtained when 2-methylsulfonylnitrosobenzene (9) was boiled with alkali. The decomposition of N-(4-methylsulfonylphenyl)hydroxylamine (16) in dilute alkali at room temperature gave a quantitative yield of 4,4′-di(methylsulfonyl)azoxybenzene (17) and at reflux, mixtures of 17 and 4,4′-di(methylsulfonyl)azobenzene (18) were obtained. The modes of formation of the various products from the two hydroxylamines are discussed.

Reactions of some 2-aminophenyl- and 2- and 4-nitrophenyl sulfones in aqueous sodium hydroxide solution

1970 ◽  
Vol 48 (9) ◽  
pp. 1394-1403 ◽  
Author(s):  
K. B. Shaw ◽  
R. K. Miller
Keyword(s):  
Sodium Hydroxide ◽  
Alkaline Solution ◽  
Sodium Hydroxide Solution ◽  
Aqueous Sodium Hydroxide ◽  
Major Product ◽  
Aqueous Sodium Hydroxide Solution ◽  
Aqueous Sodium ◽  
Hydroxide Solution ◽  
Orthanilic Acid ◽  
Dilute Sodium Hydroxide

When 2-aminophenylsulfonylacetic acid (3) was heated under reflux in an excess of dilute sodium hydroxide solution, the only product identified was 2-methylsulfonylaniline (6). When 2-nitrophenyl-sulfonylacetic acid was treated under the same conditions, the major products identified were 2-methyl-sulfonylnitrobenzene (7), 2-nitrophenol (8), and orthanilic acid (13); minor products of this reaction were 6 and 3-methylsulfonyl-3′-nitro-4-amino-4′-hydroxybiphenyl (12). The same products were obtained although the yields were different when 7 was boiled with alkali, but the reaction of 4-methylsulfonyl-nitrobenzene (15) with alkali was less complex and 4-nitrophenol (16) was the only major product. The biphenyl 12 was also formed in small yield when N-(2-methylsulfonylphenyl)hydroxylamine (19) was treated with alkali and its formation in these reactions was investigated in detail. It was concluded that 12 arises from 7 and 19, but it could also be prepared from 19 and 2-chloro- or better, 2-fluoronitrobenzene, in alkaline solution, and based on all these observations, a mechanism for its formation is suggested. The genesis of the various other products is also discussed. Reference is made to the infrared spectra of sulfones.

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