Mercuric salt

Terminal alkyne anions are popular reagents for the acyl anion synthons (RCHjCO"). If this nucleophile is added to aldehydes or ketones, the triple bond remains. This can be con verted to an alkynemercury(II) complex with mercuric salts and is hydrated with water or acids to form ketones (M.M.T. Khan, 1974). The more substituted carbon atom of the al-kynes is converted preferentially into a carbonyl group. Highly substituted a-hydroxyketones are available by this method (J.A. Katzenellenbogen, 1973). Acetylene itself can react with two molecules of an aldehyde or a ketone (V. jager, 1977). Hydration then leads to 1,4-dihydroxy-2-butanones. The 1,4-diols tend to condense to tetrahydrofuran derivatives in the presence of acids. 

Hydrazinothiazoles form stable complexes with Mn ", Ni. Cd Cu ", Co ", Fe ", and Fe " this property was used to detect small amounts of these salts in mixtures by paper chromatography (547, 548). Some infrared features of the complexes formed with the silver salts and with the mercuric salts have been reported (1583). 

Many catalytic systems have been described acidic solutions of mercuric salts are the most generally used. This process has long been superseded by more economical routes involving oxidation of ethylene or other hydrocarbons. 

Vinyl Ghloride and Vinylidene Ghloride. In the presence of mercuric salts, hydrogen chloride adds to acetylene giving vinyl chloride... 

Hydrogenation gives aUyl alcohol [107-18-6] C H O, its isomer propanal [123-38-6] (20), or propanol, C H O [71-23-8] (21). With acidic mercuric salt catalysts, water adds to give acetol, hydroxyacetone, C2H 02 [116-09-6] (22). 

With mercuric salt catalysts, hydrogen chloride adds to give 2-chloroallyl alcohol, 2-chloroprop-2-en-l-ol [5976-47-6] (27). 

Heating butanediol with acetylene in the presence of an acidic mercuric salt gives the cycHc acetal expected from butanediol and acetaldehyde (128). A commercially important reaction is with diisocyanates to form polyurethanes (129) (see Urethane POLYMERS). 

With Lewis acids as catalysts, compounds containing more than one alkoxy group on a carbon atom add across vinyl ether double bonds. Acetals give 3-alkoxyacetals since the products are also acetals, they can react further with excess vinyl ether to give oligomers (228—230). Orthoformic esters give diacetals of malonaldehyde (231). With Lewis acids and mercuric salts as catalysts, vinyl ethers add in similar fashion to give acetals of 3-butenal (232,233). 

The iodination reaction can also be conducted with iodine monochloride in the presence of sodium acetate (240) or iodine in the presence of water or methanolic sodium acetate (241). Under these mild conditions functionalized alkenes can be transformed into the corresponding iodides. AppHcation of B-alkyl-9-BBN derivatives in the chlorination and dark bromination reactions allows better utilization of alkyl groups (235,242). An indirect stereoselective procedure for the conversion of alkynes into (H)-1-ha1o-1-alkenes is based on the mercuration reaction of boronic acids followed by in situ bromination or iodination of the intermediate mercuric salts (243). 

Complete iodination of organic compounds can be achieved by preventing the formation of free hydrogen iodide through the addition of an oxidizing agent, neutralization of the HI with a base, or combination using mercuric salts. 

At ordinary temperatures, mercury is stable and does not react with air, ammonia (qv), carbon dioxide (qv), nitrous oxide, or oxygen (qv). It combines readily with the halogens and sulfur, but is Htde affected by hydrochloric acid, and is attacked only by concentrated sulfuric acid. Both dilute and concentrated nitric acid dissolve mercury, forming mercurous salts when the mercury is in excess or no heat is used, and mercuric salts when excess acid is present or heat is used. Mercury reacts with hydrogen sulfide in the air and thus should always be covered. 

Another method of preparing mercuric acetate is the oxidation of mercury metal using peracetic acid dissolved in acetic acid. Careful control of the temperature is extremely important because the reaction is quite exothermic. A preferred procedure is the addition of approximately half to two-thirds of the required total of peracetic acid solution to a dispersion of mercury metal in acetic acid to obtain the mercurous salt, followed by addition of the remainder of the peracetic acid to form the mercuric salt. The exothermic reaction is carried to completion by heating slowly and cautiously to reflux. This also serves to decompose excess peracid. It is possible and perhaps more economical to use 50% hydrogen peroxide instead of peracetic acid, but the reaction does not go quite as smoothly. 

Mercurous Nitrate. Mercurous nitrate [10415-75-5] Hg2N20 or Hg2(N02)2, is a white monoclinic crystalline compound that is not very soluble in water but hydrolyzes to form a basic, yellow hydrate. This material is, however, soluble in cold, dilute nitric acid, and a solution is used as starting material for other water-insoluble mercurous salts. Mercurous nitrate is difficult to obtain in the pure state directly because some mercuric nitrate formation is almost unavoidable. When mercury is dissolved in hot dilute nitric acid, technical mercurous nitrate crystallizes on cooling. The use of excess mercury is helpful in reducing mercuric content, but an additional separation step is necessary. More concentrated nitric acid solutions should be avoided because these oxidize the mercurous to mercuric salt. Reagent-grade material is obtained by recrystaUization from dilute nitric acid in the presence of excess mercury. 

Yellow mercuric oxide may be obtained by precipitation from solutions of practically any water-soluble mercuric salt through the addition of alkah. The most economical are mercuric chloride or nitrate. Although yellow HgO has some medicinal value in ointments and other such preparations, the primary use is as a raw material for other mercury compounds, eg, Millon s ha.se[12529-66-7], Hg2NOH, which is formed by the reaction of aqueous ammonia and yellow mercuric oxide. 

Mercuric Sulfide. Mercuric s A ide[1344 8-5] HgS, exists ia two stable forms. The black cubic tetrahedral form is obtaiaed when soluble mercuric salts and sulfides are mixed the red hexagonal form is found ia nature as cinnabar (vermilion pigment). Both forms are very insoluble in water (see Pigments, inorganic). Red mercuric sulfide is made by heating the black sulfide in a concentrated solution of alkah polysulfide. The exact shade of the pigment varies with concentration, temperature, and time of reaction. 

After inorganic mercuric salts are absorbed and dissociated into the body fluids and in the blood, they are distributed between the plasma and erythrocytes. Aryl mercuric compounds and alkoxy mercuric compounds are decomposed to mercuric ions, which behave similarly. 

This latter reaction is reversible. Sulfuryl chloride can be fractionally distilled from boiling chlorosulfonic acid ia the presence of a catalyst, eg, a mercuric salt. 

Since 17a-ethynyl-17 -hydroxy steroids are so readily prepared, they represent attractive starting materials for conversion to 20-ketopregnanes. Standard methods for the hydration of aliphatic acetylenes (e.g, mercuric salts alone, with aniline, or with BF3) give variable results, and sometimes no product at all, due to D-homo rearrangement. 233,235,265-7 mercury... 

The sodium or potassium salt of 6-azauracil in aqueous ethanol, anhydrous ethanol, or ethylene glycol reacted with methyl iodide practically exclusively to give the 3-methyl derivative (63). In toluene the sodium, potassium, and mercuric salts produced no methylated derivatives whereas the silver salt also yielded the 3-methyl derivative, Similarly, the 3-methyl derivative was prepared from the mercuric salt of 6-azathymine, and its structure was established by hydrolysis to pyruvic acid 4-methylthiosemicarbazone. ... 

The first chemical synthesis of these substances, using a procedure which yields 1-ribofuranosyl derivatives by pyrimidine bases, was described by Hall. By using the mercuric salt of 6-azathymine and tribenzoate of D-ribofuranosyl chloride, he obtained a mixture of two monoribosyl derivatives and a diribosyl derivative. He determined the structure of the 3-substituted derivative by the similarity of spectra and other properties to those of 3-methyl-6-razauracil. The structure of the 1-ribosyl derivative was then determined from the similarity of the spectra with 6-azathymine deoxyriboside obtained enzymatically. 

Handschumacher applied a similar procedure to 6-azauracil and obtained a mixture of two monoribosyl derivatives from the mercuric salt of 6-azauracil, with the 3-substituted derivative predominating. 

Angier and Marsico followed the course of alkylation first. The 7-dimethylamino-5-methylmercapto derivative reacted with dimethyl sulfate in an alkaline medium to yield a mixture of the 2- and 3-methyl derivatives. The reaction of the 7-diraethylamino derivative with ethyl iodide in an alkaline medium led to a mixture of all three possible monoethyl derivatives. The position of the alkyl group in all these substances was defined by comparing the UV spectra with derivatives prepared by a straightforward synthesis. After reacting the mercuric salts with tri-0-benzoylribofuranosyl chloride, they demonstrated the ribose residue to be bound in position 2. The same structure was shown to be valid for the derivative prepared by Andrews and Barber. ... 

Vinylbutoxyethyl ether can also be used for the cyclization in presence of mercuric salts ... 

Recently, Kochetkov and Khomutova have reported on the mercuration of isoxazoles with mercuric acetate. The reaction occurs quite smoothly, more readily than for benzene derivatives and results in a 90-100% yield of 4-acetoxymercury derivatives (74) whose structure was proved by converting them to known 4-bromoisoxazoles (75). Under these reaction conditions isoxazole itself is oxidized by mercuric acetate, mercurous salts being thereby produced. 

Merkuri-jodid, n. mer curic iodide, mercury (II) iodide, -nitrat, n. mercuric nitrate, mercury-(II) nitrate. -oxyd, n. mercuric oxide, mercury (II) oxide, -rhodanid, n. mercuric thiocyanate, mercury(II) thiocyanate, -salz, n. mercuric salt, mercury (II) salt, -sulfati n. mercuric sulfate, mercury (II) sulfate, -sulfidt ti. mercuric sulfide, mercury (II) sulfide. -sulfozyamd, n. mercuric thiocyanate. 

Merkuro-. mercurous, mercury (I), -azetat, n. mercurous acetate. mercury(I) acetate, -chlorld, n. mercurous chloride, mercury(I) choride. -chrom, n. (Pharm.) mercuro chrome, -jodid, n. n ercurous iodide, mer-cury(I) iodide. -nitrat, n. mercurous nitrate, mercury(I) nitrste. -oxyd, n. mercurous oxide, mercury(I) oxide, -salz, n. mercurous salt, mercury (I) salt, -sulfat, n. mercurouasulfate, mercury(I) sulfate, -sulfid, n. mercurous sulfide, mercury(I) sulfide, -verbindung, /. mercurous compound, mercury (I) compound. 

Quick-erz, n. mercury ore. -gold, n. gold amalgam. -metall, n, amalgamated metal. -mUhle, /. amalgamating mill, -wasser, n. Plating) quickening liquid (solution of a mercuric salt). 

The conditions adopted in this procedure favor the production of a-monosulfonate in a state of high purity at the expense of a high conversion of anthraquinone. A better conversion can be achieved by conducting the sulfonation at a higher temperature, or by using more oleum, but in either case there is a considerable increase in the amount of disulfonic acids formed. The extent of /3-sulfonation is not influenced greatly by the temperature, but is dependent chiefly on the amount of mercuric salt present in the solution. The amount specified corresponds approximately to the limit of solubility of the salt in the acid employed, and very little of the /3-acid is formed. As the potassium /S-sulfonate is more soluble than the a-salt, traces of this isomer are easily eliminated by crystallization. 

The only practical method for the preparation of anthra-quinone-a-sulfonates is that based upon the discovery 1 that in the presence of a small amount of mercuric salt anthraquinone is sulfonated chiefly in the a- rather than in the /3-position. Detailed procedures are described by Fierz-David,2 by Lauer,3 and by Groggins 4 the above directions are based largely upon the observations of Lauer.3... 

Alkyl mercuric hydrides are generated in situ by reduction of an alkyl mercuric salt with sodium borohydridc (Scheme 3.91). Their use as radical traps was first reported by Hill and Whitesides491 and developed for the study of radical-olefin reactions by Giese,489490 Tirrell492 and coworkers. Careful choice of reagents and conditions provides excellent yields of adducts of nucleophilic radicals (e.g. -hexyl, cyclohexyl, /-butyl, alkoxyalkyl) to electron-deficient monomers (e.g. acrylics). 

Mercury as Masking Agent. Mercuric salts such as HgCl2 were frequently added to wet NC to... 

Mercurous Oxalate. Hg2C 2O4, mw 489.22, wh cryst powd. Prepd by Souchay Lenfsen (Ref 2) by treating sol mercurous salts, such as the nitrate, with oxalic acid. Insol in cold w, ale eth decompd by hot w insol in dil sulfuric acid sol in dil hydrochloric and nitric acids... 

The reaction was first-order in benzene, and approximately first-order in mercuric salt. 

The variation in the second-order rate coefficients with time and with change in initial concentration of mercuric salt can also be explained on the basis of equilibria (213) and (214). At low acidities, conversion of mercuric acetate to acetoxymercury perchlorate is incomplete, and, therefore, decreasing the concentration of the acetate increases the concentration of free perchloric acid which thus increases the conversion of the acetate into the more reactive perchlorate, hence the second-order rate coefficients increase. Decreasing the concentration of mercuric perchlorate will, however, decrease the concentration of free perchloric acid and this effect will be particularly marked since solvation of the perchlorate produces two equivalents of perchloric acid the second-order rate coefficients will, therefore, decrease. In both cases, substitution changes the concentration... 

Mercuration of aromatic compounds can be accomplished with mercuric salts, most often Hg(OAc)2 ° to give ArHgOAc. This is ordinary electrophilic aromatic substitution and takes place by the arenium ion mechanism (p. 675). ° Aromatic compounds can also be converted to arylthallium bis(trifluoroacetates), ArTl(OOCCF3)2, by treatment with thallium(III) trifluoroacetate in trifluoroace-tic acid. ° These arylthallium compounds can be converted to phenols, aryl iodides or fluorides (12-28), aryl cyanides (12-31), aryl nitro compounds, or aryl esters (12-30). The mechanism of thallation appears to be complex, with electrophilic and electron-transfer mechanisms both taking place. 

In base-catalyzed addition to triple bonds, the rate falls in going from a primary to a tertiary alcohol, and phenols require more severe conditions. Other catalysts, namely, BF3 and mercuric salts, have also been used in addition of ROH to triple bonds. 

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