Mercury iodide, reaction

Thus, not only should alkylmercuric iodides and dialkylmercurials have a more nucleophilic carbon compared with the others, but their respective -Hg-X functions should also be better leaving groups in electrophilic substitution reactions. This latter prophesy is supported in part by the results of Hughes et al. from their kinetic studies of mercury exchange reactions (20). 

Dilithio 8 reacts with mercury iodide to give tetramer 11, as a 1 1 complex, in 80% yield. Longer reaction times and additional mercury iodide produces the 2 1 complex 12. Synthesis of neutral tetramer 6 is achieved by using silver acetate to decomplex diiodide 12. 

This effect, in which the production of mercurous ions probably plays a role, occurs even with very small amounts of mercuric salts, so that the mercury can be detected by the formation of tin i salts, which are then identified by the color reaction with cacotheline (see page 483). The test succeeds even with a solution of mercury cyanide, or of complex alkali mercury iodide, which yield exceedingly low concentrations of mercuric ions. 

Mercurimetric Method This procedure is based on the determination of mercuiy quantitativeh precipitated by the action of alkaline potassium mercury iodide (Xessler s reagent) on formaldehyde. The mercury is normally measured by iodimetiy so that the net effect is similar to the iodimetric procedui-e previously described. The principal chemical reaction is as follows ... 

Ethyl phenylethylmalonate. In a dry 500 ml. round-bottomed flask, fitted with a reflux condenser and guard tube, prepare a solution of sodium ethoxide from 7 0 g. of clean sodium and 150 ml. of super dry ethyl alcohol in the usual manner add 1 5 ml. of pure ethyl acetate (dried over anhydrous calcium sulphate) to the solution at 60° and maintain this temperature for 30 minutes. Meanwhile equip a 1 litre threenecked flask with a dropping funnel, a mercury-sealed mechanical stirrer and a double surface reflux condenser the apparatus must be perfectly dry and guard tubes should be inserted in the funnel and condenser respectively. Place a mixture of 74 g. of ethyl phenylmalonate and 60 g. of ethyl iodide in the flask. Heat the apparatus in a bath at 80° and add the sodium ethoxide solution, with stirring, at such a rate that a drop of the reaction mixture when mixed with a drop of phenolphthalein indieator is never more than faintly pink. The addition occupies 2-2 -5 hoius continue the stirring for a fiuther 1 hour at 80°. Allow the flask to cool, equip it for distillation under reduced pressure (water pump) and distil off the alcohol. Add 100 ml. of water to the residue in the flask and extract the ester with three 100 ml. portions of benzene. Dry the combined extracts with anhydrous magnesium sulphate, distil off the benzene at atmospheric pressure and the residue under diminished pressure. C ollect the ethyl phenylethylmalonate at 159-160°/8 mm. The yield is 72 g. 

Titanium diiodide may be prepared by direct combination of the elements, the reaction mixture being heated to 440°C to remove the tri- and tetraiodides (145). It can also be made by either reaction of soHd potassium iodide with titanium tetrachloride or reduction of Til with silver or mercury. 

The iodide ion induced decomposition of trimethyl (trifluoromethyl) tin and of phenyl (trifluoromethyl) mercury represent additional interesting possibilities. The reaction of the tin reagent and iodide ion with (31, X = H) in refluxing glyme for 168 hr gives (32) and the corresponding 6jff,7j0-difluoromethylene adducts in 46% and 7% yields, respectively. ... 

The photochemical or thermal reaction between petfluoroalkyl iodides and mercury-cadmium amalgams has been used for the synthesis of perfluoro-alkylmercury compounds [150] Functionalized analogues have been prepared similarly via this route [151, 152] (equation 117), and the preparation of bis(tri-fluoromethyl)mercury has been described [153]... 

Complex [(CXI )Ir(/j,-pz)(/i,-SBu )(/j,-Ph2PCH2PPh2)Ir(CO)] reacts with iodine to form 202 (X = I) as the typical iridium(II)-iridium(II) symmetrical species [90ICA(178)179]. The terminal iodide ligands can be readily displaced in reactions with silversalts. Thus, 202 (X = I), upon reaction with silver nitrate, produces 202 (X = ONO2). Complex [(OC)Ir(/i,-pz )(/z-SBu )(/i-Ph2PCH2PPh2)Ir(CO)] reacts with mercury dichloride to form 203, traditionally interpreted as the product of oxidative addition to one iridium atom and simultaneous Lewis acid-base interaction with the other. The rhodium /i-pyrazolato derivative is prepared in a similar way. Unexpectedly, the iridium /z-pyrazolato analog in similar conditions produces mercury(I) chloride and forms the dinuclear complex 204. 

More useful for synthetic purposes, however, is the combination of the zinc-copper couple with methylene iodide to generate carbene-zinc iodide complex, which undergoes addition to double bonds exclusively to form cyclopropanes (7). The base-catalyzed generation of halocarbenes from haloforms (2) also provides a general route to 1,1-dihalocyclopropanes via carbene addition, as does the nonbasic generation of dihalocarbenes from phenyl(trihalomethyl)mercury compounds. Details of these reactions are given below. 

Table 1.1 summarizes the solubility patterns of common ionic compounds in water. Notice that all nitrates and all common compounds of the Group 1 metals are soluble so they make useful starting solutions for precipitation reactions. Any spectator ions can be used, provided that they remain in solution and do not otherwise react. For example, Table 1.1 shows that mercury(I) iodide, Hg2I2, is insoluble. It is formed as a precipitate when solutions containing Hg22+ ions and I ions are mixed ... 

The reactions of mercuric iodide, mercuric bromide, and mercuric chloride with the excited species produced in the hexafluoroethane plasma were examined first, as the expected products were known to be stable and had been well characterized 13). Thus, these reactions constituted a "calibration of the system. Bis(trifluoromethyl)mercury was obtained from the reaction of all of the mercuric halides, but the highest yield (95%, based on the amount of metal halide consumed) was obtained with mercuric iodide. The mole ratios of bis(trifluoro-methyDmercury to (trifluoromethyl)mercuric halides formed by the respective halides is presented in Table I, along with the weight in grams of the trifluoromethyl mercurials recovered from a typical, five-hour run. 

In our laboratory, we find that the plasma reaction of trifiuoro-methyl radicals with mercuric iodide is an excellent source of bis(tri-fluoromethyDmercury. For those laboratories that lack access to radiofrequency (rf) equipment (a 100-W, rf source can at present be purchased for less than 1,000), synthesis of bis(trifluoromethyl)mercury by the thermal decarboxylation of (CFgCOjlzHg is also a functional, and quite convenient, source of bis(trifiuoromethyl)mercury (23). 

This product can also be produced by the reaction of iodine with the mercury compound shown earlier, which yields the iodide. The iodide reacts with magnesium to produce a Grignard product,... 

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