Amalgam sulfur compounds

A different approach to the stereospecific synthesis of sulfinamides described by Johnson (117,118) is based on the conversion of suitable chiral tetracoordinate sulfur compounds into sulfinamides. It was shown (117) that optically active methyl phenyl sulfoximide undergoes a clean and stereospecific reduction to the corresponding sulfinamide by means of aluminum amalgam. On the other hand,... 

Mercury diphenyl has been prepared in a number of ways. The most important methods are by the action of sodium on a mixture of bromobcnzene and mercuric chloride 1 from sodium amalgam and phenyl mercuric iodide 2 by the interaction of phenyl mercuric bromide and potassium sulfide2 or phenyl mercuric acetate and sodium stannite 3 from phenyl magnesium bromide and mercuric chloride 4 by the action of phenyl hydrazine on mercury compounds 5 from mercuric chloride and phenyl arsenious oxide 6 and from diphenyl mercuric ammonium acetate and sulfur compounds.7... 

Aluminum amalgam (Al/Hg) is also a useful reagent that is most commonly employed for hydrogenolysis of sulfur compounds.533 Reduction of sulfoxides is an important application,534 as is reduction of sulfones. Aluminum amalgam reduces the a-phenylsulfonyl moiety in 554 to give lactone 555 in 68% yield.535 Aluminum amalgam has also been used for reduction of nitro compounds to the amine,536 and reduction of azides to the amine.532... 

Caustic soda by reaction of sodium amalgam and water Nitration of organic compounds with aqueous nitric acid Formation of soaps by action of aqueous alkahes on fats or fatty acids Sulfur removal from petroleum fractious by aqueous ethauolamiues Treating of petroleum products with sulfuric acid... 

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. 

Inorganic solid wastes, particularly those containing toxic metals and toxic metal compounds, used Raney nickel, manganese dioxide, etc. should be placed in glass bottles or lined fiber drums, sealed, properly labeled, and arrangements made for disposal in a secure landfill. Used mercury is particularly pernicious and small amounts should first be amalgamated with zinc or combined with excess sulfur to solidify the material. 

Boron substituents in the [l,3,2]diazaborolo[l,5- ]pyridine derivative 109 were studied. This compound was obtained via reduction of its precursor 108 with sodium amalgam (Scheme 27). The bromide attached to the boron atom was further displaced with various halide, hydride, sulfur, and carbon nucleophiles <2001JCD378>. [l,2,5]thiadiazolo[2,3- ]pyridine derivative 110 was deprotected (R = Cbz to R=H) by classical hydrogenolysis <2002AGE3866>. 

Let us now consider the conversion of nitro compounds into mercaptanes. Nitro compounds were treated with a mixture of sodium sulfide with sulfur and after that, they were reduced with aluminum amalgam (Kornblum and Widmer 1978) (Scheme 5.8). 

Perfluoroalkylmercury compounds have been prepared by reaction of perfluoroalkyl halides with cadmium amalgam or by reaction of fluoroalkenes with mercury(II) fluoride. Due to the high thermal stability of perfluoroalkylmercury compounds, they can be sublimed from concentrated sulfuric acid without decomposition and are of limited synthetic utility. These reagents have found use as difluorocarbene sources and do react with elemental sulfur at elevated temperatures to afford thioacid fluorides, di- and polysulfides, and thioketones. ... 

A few examples of the reduction of aliphatic diazo compounds to hydrazines exist," but this is not a generally applicable method for the synthesis of alkylhydrazines. On the other hand, arylhydrazines can be prepared by reduction of aromatic diazonium salts.The most commonly used reagents for this conversion are sulfur dioxide (or sodium sulfite) and tin(II) chloride, these being used to reduce arenediazo-nium chlorides in aqueous solution. Several other reagents, including sodium amalgam and triphenylphosphine, have been used for specific reductions of this type. Arenediazonium tetrafluoro-borates have been reduced to the correspwnding hydrazinium salts (3) by benzeneselenol in dichloro-... 

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