Mercury allyl iodide

Iodide,—Combination takes place between ethyl iodide and metallic mercury when exposed to diffused daylight, with formation of ethyl mercuric iodide.This may also be obtained by the addition of an alcoholic solution of iodine to ethyl mercuric hydroxide, or from mercury diethyl by boiling for one or two days with allyl iodide. iVnother preparation from mercury diethyl is to heat for several days at 120° C. with iodoform, when the iodide, ethyl iodide, ethylene, and acetylene are formed. ... 

AHyl mercuric iodide, CH2-CH CH2-HgI. o Anyi iodide containing a trace of dissolved iodine, readily reacts with mercury. If mercury be shaken with some iodine, then with allyl iodide, an evolution of heat takes place and the mass becomes solid. This may be avoided to some extent by mixing the aiiyl iodide Avith alcohol. The iodide crystallises from alcohol in silvery scales, w hich turn yellow on drying. It commences to volatilise at 100° C. and melts at 135° C.,... 

According to Bard and Merz [108], in MeCN containing TBAP, allyl bromide and allyl iodide interact chemically with a mercury electrode to form allylmercury halides. These allylmercury halides undergo reduction to yield diallylmercury, which is itself electroactive. Allyl bromide and allyl iodide are reduced at platinum in MeCN in a two-electron process to give the allyl anion, and the allyl radical is not involved as an intermediate. Reduction of allyl halides at platinum in DMF containing TEAOTs and in the presence of trimethylchlorosilane results in silylated compounds [100]. 

Mercury(I) iodide also catalyzes the reaction of Mel . For the more reactive allylic iodide and cinnamyl bromide, irradiation is not necessary . 

Berthelot and de Luca attempted to esterify glycerol with phosphorus iodide instead of hydriodic acid, but obtained instead propylene and propylene iodide (allyl iodide). The latter with mercury and fuming sulphuric acid gave propylene. Propylene had been discovered and named by Capt. J. W. Reynolds (a pupil of Hofmann), who made it by passing amyl alcohol vapour... 

Indirect electroreduction of allyl alcohols leading to the corresponding unsaturated hydrocarbons is attained using a mercury electrode in a strongly acidic medium containing an iodide salt [554]. The reaction involves transformation of the alcohol into the iodide, the reaction of the iodide with mercury, the protonation of the... 

One further reaction of this type studied by Kreevoy and his group [50] is the acid catalysed cleavage of unsaturated compounds containing a carbon—mercury bond, for example, allyl mercuric iodide (29). The important conclusion is that rate-determining proton transfer to unsaturated carbon occurs as a first step (A—SE2 mechanism) and as expected the reactions are catalysed by general acids. 

From allyl mercuric iodide and zinc diethyl in cold ether, the reaction yielding, in addition, diallyl and mercury. ... 

Indirect electrolysis of allyl alcohols can be performed at a mercury electrode at a rather positive potential [—0.2 V (SCE)], and high current densities may be used (10-20 A dm ). The first step is a transformation of the alcohol to an iodide the double bond is shifted to the terminal position, even if it means breaking a conjugation with a phenyl ring [56]. A 20 1 mixture of 1-butene and 2-butene was obtained from crotyl alcohol ... 

Ketene dithioacetals are deprotonated with LDA-HMPA and complexed with copper(l) iodide (Scheme 36). This reagent reacts with allylic halides exclusively at the y-position with allylic rearrangement (5n20. The reaction of the lithium reagent with simple alkylating reagents gives mostly a-attack. Ketene dithioacetals can be converted to esters by aqueous mercury(II) chloride. 

Reaction of 6-methoxy-l-tetralone (30) with methylmagnesium iodide gave the dihydronaphthalene (31) in high yield (Scheme 4). However, the transformation of 31 to the tetralone 33, via perbenzoic acid epoxidation followed by acid workup, was capricious and resulted in low yields. A better route was developed, involving hydroboration (hydrogen peroxide oxidation) to the alcohol 32, followed by Pfitzner-Moffatt oxidation to the tetralone 33 in an overall yield of 61%. Other oxidation methods were tried but with varied and poor results. Alkylation of the tetralone 33 with 3-bromopropyne yielded 34, which underwent hydration [mercury (II) acetate in acetic acid-formic acid] to the diketone (35). The enone (36) obtained by base catalyzed cyclization was ster-eospecifically reduced with lithium aluminum hydride to the allylic alcohol... 

Zinc and Mercury.—As in previous years, reports of new transformations and methodologies involving zinc have been at a low level. A useful high-yielding conversion has been published, however, of allylic thioethers such as (84) into homoallylic thioethers (85). The initial ylide formation with a homogeneous solution of diethylzinc and methylene (R = H) or ethylidene (R = Me) iodide is followed by a 2,3-sigmatropic rearran ment to the observed products, and the poor yields found in previous experiments can be avoided by quenching the reaction mixture with acetaldehyde. Conventional Simmons-Smith cyclo-propanation of these compounds fails, as does the cyclopropanation of cyclohexene in the presence of various thioethers. 

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