Higher mercury alkyls

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

The reaction has also been used to prepare 1,3-dilithiopropanes" and 1,1-dilithio-methylenecyclohexane" from the corresponding mercury compounds. In general, the equilibrium lies in the direction in which the more electropositive metal is bonded to that alkyl or aryl group that is the more stable carbanion (p. 228). The reaction proceeds with retention of configuration an Sgi mechanism is likely. Higher order cuprates (see Ref. 1277 in Chapter 10) have been produced by this reaction starting with a vinylic tin compound ... 

Apart from CH3 Hg+, other forms of R-Hg+ have been found in the natural environment, which originate from anthropogenic sources but are not known to be generated from inorganic mercury. These forms have been found in terrestrial and aquatic food chains. A major source has been fungicides, in which the R group is phenyl, alkoxy-alkyl, or higher alkyl (ethyl, propyl, etc.). These forms behave in a similar manner... 

The mean bond dissociation energies (E ) given in Table 12 are based on thermochemical data at 25 C19. Unless previously discussed, the heat of formation of the metal alkyl used is that given by Long60. The higher values of E and D2 for dimethyl mercury are obtained when Long s recommended value for the heat... 

The direct reduction of haloalkynes using either mercury or vitreous carbon as the cathode has been examined in considerable detail [80-84] one example is portrayed in Eq (77). The influence of reduction potential, current consumption, proton donor, electrode, and substrate concentration on the course of the process has been examined. Vitreous carbon electrodes are preferred, though mercury has been used in many instances. Unfortunately, these reactions suffer from the formation of diorganomercurials. While both alkyl iodides and bromides can be used, the former is generally preferred. Because of their higher reduction potential, alkyl chlorides react via a different mechanism, one involving isomerization to an allene followed by cyclization [83]. 

Isotopic enrichment has also been found by monoisotopic photosensitization for mixtures of natural mercury and alkyl chlorides and vinyl chloride by similar processes. Isotopic enrichment is dependent on such factors as lamp temperatures, flow rates, and substrate pressures. Enrichment increases with decreasing lamp temperature and increasing flow rate, since process (VIII-1) is more ellicient at low temperatures and Cl atoms react with natural mercury containing higher fractions of 202Hg in (VIII-3) at higher flow rates of HC1 or under intermittent illumination. The intermittent illumination results in higher enrichment than the steady illumination. 

Both its solubility and any potential side reaction with reductant dictate the choice of precursor metal salt or complex. In many cases the reductant is an aluminium alkyl or electropositive metal (Goups 1,2, 12 or 13, possibly amalgamated with mercury), requiring the use of anhydrous metal salts or complexes. Carbonyls of higher nuclearity are... 

Dithioacetals of aldehydes are sources of carbanions and hence may be used to form new C-C bonds in reactions in which the formerly electron-deficient character of the aldehydic carbon has been reversed. The 1,3-dithianes derived from formaldehyde or a higher aldehyde may be metallated and then alkylated (Scheme 2.27). Hydrolysis of the dithioac-etal is usually carried out in the presence of a thiophilic (sulfur seeking) metal salt such as a mercury salt. The insoluble sulfides cause the equilibrium to move in favour of the parent carbonyl compound. 

At a mercury cathode the propensity for cleavage from a phosphonium salt in methanol increases in the sequence methyl < ethyl < -butyl phenyl < tert-huiy < allyl < benzyl however, at a lead cathode the tendency for loss of an alkyl group from an alkyltriphenylphosphonium group is much higher than at a mercury cathode ethyltriphe-nylphosphonium chloride is thus reduced in methanol at a mercury cathode to a 5 3 mixture of ethyldiphenylphosphine and triphenylphosphine, whereas 91% triphenylphos-phine was isolated at a lead cathode [196]. 

Alkenyl groups are transferred in preference to s-alkyl groups. The yields of trans-alkenylmercurials from RC=CH are greater than 85% yields from internal alkynes are lower. Use of (I) rather than tris(alkenyl)boranes leads to higher yields of alkenyl-mercurials. 

Cyclopentyl radicals substituted in the /1-position relative to the radical center are formed during the solvomercuration/reductive alkylation reaction of cyclopentene34. The organomer-curial produced in the first solvomercuration step is reduced by sodium borohydride and yields free cyclopentyl radicals in a radical chain mechanism. Addition of alkenes can then occur tram or cis to the / -alkoxy substituent introduced during the solvomercuration step. The adduct radical is finally trapped by hydrogen transfer from mercury hydrides to yield the tram- and ris-addition products, The transicis ratio depends markedly on the alkene employed and it appears that the addition of less reactive alkenes occurs with higher trans selectivity. In reactions of highly substituted alkenes, this reactivity control is compensated for by steric effects. Therefore, only the fnms-addition product is observed in reactions of tetraethyl ethenetetracarboxylate. The choice of alcohol employed in the solvomercuration step has, however, only a small influence on the stereoselectivity. 

A different method of preparation is advisable if the pure, solvent-free organolithium compound is required. In a procedure due to Schlenk and Holtz50 the organolithium compound is prepared from metallic lithium and the organomercury compound in an indifferent solvent since most organolithium compounds, in particular the higher alkyl derivatives, are very readily soluble in hydrocarbons, they can be easily separated from the separating mercury and then obtained pure by evaporation of the solution. 

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