M-Nitrobenzenesulfonyl chloride

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]. 

Nitrobenzenediazonium fluoroborate, 166 p-Nitrobenzenesulfonoxyurethane, 736 m-Nitrobenzenesulfonyl chloride, 449 p-Nitrobenzenesulfonyl chloride, 736 p-Nitrobenzoic acid, 286,317,666, 866,901, 1060... 

Derivation Reduction of m-nitrobenzenesulfonyl chloride with hydriodic acid. 

The reagent has been prepared in 30% yield from m-nitrobenzenesulfonyl chloride and hydrogen peroxide.1 It is relatively safe to handle and is suggested for use in the synthesis of phenols, for example ... 

In the aryl nitro compounds, the powerful electron-withdrawing (—1, -M) effect of the nitro group results in the sulfonation of nitrobenzene being more difficult than that of benzene. Early work claimed that heating nitrobenzene with excess chlorosulfonic acid (two equivalents) afforded m-nitrobenzenesulfonyl chloride, but under drastic conditions (150 °C, 20 hours) the only product was reported to be tetrachloro-/>-benzoquinone (chloranil). 

However, other substituted reagents were also proposed, especially for the identification of those amines which give low-melting derivatives with benzene- and / -toluenesulfonyl chloride p-bromobenzenesulfonyl chloride (83) and m-nitrobenzenesulfonyl chloride (84),... 

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... 

A stirred solution of 5.0 gm (0.077 mole) of sodium azide in 75 ml of acetone is cooled to —10°C while 15 gm (0.66 mole) of o-nitrobenzenesulfonyl chloride dissolved in 75 ml of acetone is added dropwise. The reaction mixture is stirred for 1 hr at —10°C and for 1 hr at room temperature. The solution is filtered and diluted with 500 ml of ice water. The yellow product is removed by filtration, washed with water and dried. The product is dissolved in 150 ml of warm ethanol and freed from any insoluble material by filtration. The clear filtrate is cooled to afford 12.0 gm (80%), m.p. 71°-73°C. 

Tetrahydrofuran (3.2 ml) and S-(+)-3-chloro-l,2-propanediol (0.299 ml, 3.58 mmol, 1.19 eq) are mixed. The mixture of THF (3.2 ml) and S-(+)-3-chloro-1,2-propanediol (0.299 ml, 3.58 mmol, 1.19 eq) is cooled to -16°C and potassium t-butoxide (3.2 ml, 1.0 M) in THF (3.2 mmol, 1.07 eq) is added at less than -10°C. The resulting slurry is stirred at -14-0°C for 1 hour. Then added to the lithium anion mixture while maintaining both mixtures at 0°C, then rinsed in with THF (2 ml). The resultant slurry is stirred at 20-23°C for 2 hour and then cooled to 6°C and a mixture of citric acid monohydrate (0.4459 g, 2.122 mmol, 0.705 eq) in water (10 ml) is added. The resultant liquid phases are separated and the lower aqueous phase is washed with ethyl acetate (12 ml). The organic layers are combined and solvent is removed under reduced pressure until a net weight of 9.73 g remains. Heptane (10 ml) and water (5 ml) are added and solvent is removed 4-nitrobenzenesulfonyl chloride y reduced pressure until a total volume of 5 ml remains. The precipitated product is collected by vacuum filtration and washed with water (7 ml). The solids are dried in a stream of nitrogen to give (R)-[N-3-(3-fluoro-4-(4-morpholinylphenyl)-2-oxo-5-oxazolidinyl]methanol. 

A suspension of 4-nitro-l-(o-nitrobenzenesulfonyl)imidazole (made from 4-nitroimidazole, o-nitrobenzenesulfonyl chloride, and triethylamine) (0.745 g, 2.5mmol) and aniline (l.Og, 11 mmol) in aqueous methanol (1 1 20ml) is stirred and heated at 70°C (2h). The mixture is then steam distilled, and the hot undistilled residue is filtered to give the above product (0.41 g, 87%), m.p. 185-187°C. Cooling of the filtrate results in separation of... 

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°. 

A solution of 67.0 g o-nitrobenzenesulfonyl chloride (0.3 mol) in 400 mL anhydrous ether was added gradually with stirring to a cooled solution of 80.0 g 1,2,3,4-tetrahydroquinoline (0.6 mol) in 120 mL anhydrous ether. After the addition was complete, the cooling bath was removed, and the mixture was refluxed for 1 h. The cooled reaction mixture was filtered, and the precipitate was washed with hot water to remove the amine hydrochloride. The residue was combined with the ether filtrate, and the solvent was stripped to give " 50 g crude product. The product was dissolved in ethanol, decolorized, and recrystallized to give 43 g l-(phenylsulfonyl)-1,2,3,4-tetrahydroquinoline as a pale yellow solid, in a yield of 47%, m.p. 131-132 C. 

Benzenesulfonhydroxamic acid allowed to react with p-nitrobenzenesulfonyl chloride and 3-4 moles triethylamine N-p-nitrobenzenesulfonyloxybenzene-sulfonamide. Y 93%. F, e. s. M. Okahara and D. Swern, Tetrah. Let. 1969, 3301. 

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