Diphenyl mercury

In a i-l. round-bottom flask fitted with a reflux condenser are placed goo g. of 3 per cent sodium amalgam (Note 1), 180 g. (1.15 moles) of bromobenzene, 200 cc. of dry toluene or dry xylene, and 10 cc. of ethyl acetate. The mixture is refluxed with frequent shaking for twelve hours in an oil balh at 130°. 

The mixture is transferred (Hood) (Note 5) while still hot to a a fluted filter paper in a 20-cm. glass funnel, leaving behind as much mercury as possible (Note 2). The funnel is made part of a special extraction apparatus as described in Org. Syn. 2, 49. The mercury diphenyl is extracted with 600 cc. of boiling benzene for about ten hours (Note 3). 

The solution is distilled under reduced pressure on an oil bath, the temperature of which is raised to iio° near the end of the distillation. The solid residue left in the flask after removal of the solvent is taken out and washed until nearly white with 95 per cent alcohol which has been cooled in an ice bath. This requires about four washings of 50 cc. of alcohol each (Note 4). The yield is 65-75 g. (32-37 per cent of the theoretical amount). The melting point is 121-1230. 

Care must be taken to remove ail the mercury diphenyl  

In some cases the extraction may not be complete in this length of time. 

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Mercury Diphenyl Dimethylpyrone 1 5-Dibromopentane Diphenylnitrio Oxide Thioindigotin Thioindigo Scarlet Isatin (Sandmeyer s method)... 

Tolylmercuric chloride has been prepared from />-toluene-sulfinic acid and mercuric chloride,1 from /)-toluenesulfochloride and mercury diphenyl at 1200,2 by treating />-tolueneboric acid with mercuric chloride,3 by the direct mercuration of toluene with mercuric acetate,4 from -tolylmercuric nitrate and hydrochloric acid,5 from hydrochloric acid and / -tolylmercuric hydroxide formed by the oxidation of mercury di-/>-tolyl,6 and from mercury di-/>-tolyl by heating with mercuric chloride in alcohol.7... 

Similar results are obtained with other aromatic amines such as aniline and />-iodoaniline yielding mercury diphenyl and mercury di-/>-iodopheny]. 

Triphenylmethane has hitherto usually been prepared by the interaction of benzene and chloroform in the presence of aluminium chloride 5 or ferric chloride,2 but the yields are considerably lower. Other methods consist in the action of benzal chloride upon benzene and aluminium chloride,6 in heating benzal chloride and mercury diphenyl,7 and in heating a mixture of benzaldehyde, benzene, and zinc chloride.8... 

Mercury diphenyl and powdered selenium react at 220° to 230° C. to form the diphenyl selenide.6... 

Although these liquid-phase and vapor-phase alkylations serve well to attach aliphatic groups to silicon, they are not so satisfactory for the substitution of aromatic groups. Very early in the history of organosilicon chemistry, Ladenburg found that the aryl compounds of mercury were more effective reagents than those of zinc. For example, mercury diphenyl reacted with silicon tetrachloride in a sealed tube at 300° to form phenyltrichlorosilane ... 

Metal alkyl. A compound of a metal with directly linked aliphatic or aromatic hydrocarbon radicals, as in zinc dimethyl, Zn(CHs)2, or mercury diphenyl, Hg(C6H5)2. A normal alkyl has sufficient organic groups to satisfy the normal valence of the metal and therefore contains no halogen or other substituent in place of organic radicals. 

Some mercury diphenyl may be recovered by combining the washings from several runs. 

Mercury diphenyl is very poisonous. The vapors of the benzene solution must not be breathed. 

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... 

Phenyl dichloroarsine was prepared in 1878 by La Coste and Michaelis by passing the vapours of benzene and arsenic trichloride through a heated tube. The product obtained was impure with the diphenyl compound and could be purified by distillation or crystallisation only with some difficulty. The same workers later studied another method for its preparation. This is more convenient and consists in heating mercury diphenyl to 250° C. with an excess of arsenic trichloride. 

Diphenyl chloroarsine was prepared in 1880 by La Coste and Michaehs by heating mercury diphenyl with phenyl dichloroarsine ... 

By working up the residues in the preparation of diphenyl-chloroansine from mercury diphenyl and phenyldichloroarsine. ... 

Diphenylchloroarsine, (CeH6)s sCl.—This compound, which jfiaycd an ini])ortant part as a material for chemical warfare, has been the subject of several detailed researches. It was initially obtained by the interaction of mercury dijfiicnyl and arsenious chloride in the following way 50 grams of mercury diphenyl and 230 grams of arsenious chloride arc heated under rellux for several hours at 270° C. The... 

Lithium phenyl, Li.GgHg or LiPh, may be prepared from mercury diphenyl and metallic lithium or lithium ethyl and mercury diphenyl. In the dry state it is a pure white, microcrystalline powder, w hich burns in air with a yellow flame, not a red lithium flame. 

Sodium phenyl, NaCgHg, formed from mercury diphenyl, exhibits tlie same properties as the alkyls. 

Only one aryl compound is knowm, namely, magnesium diphenyl, formed by heating magnesium powder and mercury diphenyl at 200° C. in an atmosphere of nitrogen. Like the alkyl compounds, it is readily oxidisable in air and decomposed by water. 

Be(CgH4.CH3)2, may be readily prepared by heating beryllium with equivalent quantities of mercury diphenyl and mercury di-p-tolyl and a trace of mercuric chloride in sealed tubes at 225° C. for six hours. 

Cadmium diphenyl, CdPhgA niay be obtained by heating metallic cadmium and mercury diphenyl in an atmosphere of hydrogen. It is stable in the dry state, but becomes discoloured w hen kept in a vacuum desiccator for an hour. When air is passed through its benzene solution several colour changes take place, and a reddish-brown body is finally precipitated. With water the brown solution is decolorised and cadmium hydroxide preci]>itated. Cadmium diphenyl quickly decolorises iodine solution, and the cadmium may be replaced by mercury or zinc with formation of mercury and zinc diphenyl. 

Mercury diphenyl, PhaHg, may be prepared in several ways, as follows —... 

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