Sodium sulfide nitro alcohols

Selective reduction (e.g., partial reduction of one of two nitro groups) is carried out with an alkali sulfide, such as sodium hydrogen sulfide NaHS ( sodium sulfhy-drate ) or sodium sulfide Na2S, in an aqueous or alcoholic solution. Azo groups are not affected by this method. The reaction converts sodium hydrogen sulfide or sodium sulfide mainly to sodium thiosulfate. 

Nitro alcohols were reduced to amino alcohols by catalytic hydrogenation over platinum [632] and with iron [JJ9], and nitrosophenols [255] and nitro-phenols [256] to aminophenols with sodium hydrosulfite, sodium sulfide [238] or tin [176]. Bromine atoms in 2,6-di-bromo-4-nitrophenol were not affected [176]. 

Partial reduction of aromatic polynitro compounds leads to nitro amines. The most successful reagents are the alkali metal or ammonium sulfides in aqueous alcoholIn some instances, sodium bicarbonate combined with sodium sulfide gives better results because of the formation of sodium hydrosulfide, which is believed to be the main reducing agent. Also, aqueous methanol is preferred to aqueous ethanol. Nitro compounds that are sparingly soluble in alcohol solutions may be reduced by hydrogen sulfide in pyridine solution. ... 

Thiols have also been prepared from alcohols. One method involves treatment with H2S and a catalyst, such as Al203, but this is limited to primary alcohols. Another method involves treatment with Lawesson s reagent (see 16-10). When epoxides are substrates, the products are (3-hydroxy thiols. Tertiary nitro compounds give thiols (RNO2 —> RSH) when treated with sulfur and sodium sulfide, followed by amalgamated aluminum. ... 

Orthanilic acid was first made by the reduction of nitro-benzenesulfonic acid by ammonium sulfide.2 This reduction has also been carried out electrolyticallv, and by the use of iron or zinc.3 The acid has also been made by the rearrangement of phenylsulfamic acid,4 by the action of sodium hypobromite upon potassium o-carbaminebenzenesulfonate,5 by the reduction of the mixed nitrobenzenesulfonic acids followed by separation of the isomers,6 by the action of methyl alcohol upon o-nitro-phenylsulfurchloride,7 by the action of acid upon diacetyl diphenylsulfamide,8 by the debromination of />-bromoaniline-e-sulfonic acid,9 by the reduction of 1,2,6-aminothiophenolsulfonic acid,10 and by the hydrolysis and reduction of e-nitrobenzene-sulfonyl chloride, which was obtained from di-o-nitrophenyl-disulfide.11... 

Applications The Karl Fischer reagent can be applied directly to the determination of water in a variety of organic compoimds, including saturated or unsaturated hydrocarbons, alcohols, halides, acids, acid anhydrides, esters, ethers, amines, amides, nitroso and nitro compounds, sulfides, hydroperoxides, and dialkyl peroxides. The use of sodium tartrate dihydrate for standardization of the response of the Karl Fischer reagent has been shown to lead to a small error because of occlusion of about 2% (relative) water in the crystal structure. 

Sodium perborate, NaBOa dlljO (mp 60 °C dec), is used for oxidations of primary aromatic amines to azo compounds [795] or nitro compounds [194] and of sulfides to sulfoxides and sulfones [794]. This reagent does not affect alcohols and only slightly affects alkenes [794]. 

In individual cases nitro compounds are reduced to azo compounds by glucose in aqueous or alcoholic alkali.337 Tin(n) chloride,338 alkali sulfides,339 and sodium amalgam386 have been used for the same reduction. 

Preparative Methods Different methods are reported for reagent preparation sulfonylation of methallyl chloride, oxidation of the corresponding sulfide, sequential bromination-sulfony-lation of methallyl alcohol, and palladium-catalyzed sulfonylation of the corresponding a-nitro olefin. Sulfonylation of methallyl chloride with sodium benzenesulfinate is the recommended preparation for this reagent. ... 

Ozone dimethyl sulfide-sodium alcohol Oxo from aliphatic nitro compds. 

Ozoneldimethy I sulfide-sodium/alcohol Oxo from aliphatic nitro compds. s. 29,199 s. a. Org. Synth. 56,36 (1977)... 

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