Phenyl mercury acetate, reaction with

The role of siroheme in the reduction of nitrite is supported by the observation that nitrite perturbs the spectrum of the oxidized or reduced enzyme. Carbon monoxide reaction with the reduced siroheme can be followed spec-trophotometrically. The complex can be dissociated with oxygen. The kinetics of CO-complex formation and dissociation correspond with those for CO inhibition of nitrite reductase. The inhibition of nitrite reductase by p-chloromercuribenzoate, phenyl mercury acetate, and sodium mersalyl demonstrate the involvement of SH groups presumably associated with cysteine residues found in nitrite reductase. Epr studies and spectral data indicate the oxidation/reduction of iron sulfur centers and the formation of a NO-heme complex however, other intermediates have not been confirmed (Aparicio et al., 1975 Vega and Kamin, 1977 Hucklesby et al., 1979). 

Alkyl phenyl sulfones (piCj,27) are nearly as acidic as esters hence they are readily deprotonated by n-BuLi, LDA in THF, or EtMgBr in THF to give a-metalated sulfones. Their reaction with aldehydes gives a mixture of diastereomeric P-phenylsul-fone alkoxide adducts. Reductive elimination of the benzenesulfinate moiety from the adduct to produce the alkene is usually slow. To minimize side reactions, the hydroxyl group is first converted to an acetate, benzoate, mesylate, or /7-toluenesul-fonate and then treated with an excess of sodium amalgam [Na(Hg), prepared by adding small pieces of sodium to mercury] in methanol to furnish the trans-dlk n P... 

Using bromodichloromethyl(phenyl)mercury, vinyl acetate afforded 2-acetoxy-l,l-dichlo-rocyclopropane (1, 85%), dichlorocyclopropanation of other aldehyde enol esters would also be expected. The cyclopropane 1 ( 10%) together with 2-acetoxy-l,l,l-trichloropropane (2,10%) were formed when the dichlorocarbene was generated from sodium trichloroacetate, the chain product 2 results from the reaction of the trichloromethyl anion (for the mechanism, see ref 197). These reactions are described in Houben-Weyl, Vol. 4/3, pp 177-178. Under phase-transfer catalytic conditions (CHClj/base/PTC), with a typical catalyst such as benzyl-triethylammonium chloride, vinyl acetate gave 2 (65%) only (Houben-Weyl, Vol.E19b, ppl550-1551). 

Indeed, the reaction of an equimolar quantity of bromodichloromethyl(phenyl)mercury with alk-2-enoic acids affords the dichloromethyl esters. Dichlorocyclopropanation is only possible if a second mole of carbene source is used (see Houben-Weyl, Vol. 4/3, pp 178-179). Competition between acetic acid and cyclohexene for dichlorocarbene indicates that the acid is considerably more reactive.Furthermore, dichloromethyl 2,2-dichlorocyclopropane-carboxylates cannot be hydrolyzed to the corresponding acids. To avoid all of these difficulties, addition of dichlorocarbene, generated under nonhydrolytic conditions using dichloro-halomethyl(phenyl)mercury, to the bromides of alk-2-enoic acids is possible. 

Mercury salts have previously been shown to be capable of cleaving cyclopropyl bonds. Phenyl-substituted cyclopropanes react with mercury(II) acetate to give 3-mercurio-l-methoxy-l-phenylpropane derivatives, which can undergo further reactions such as reduction with sodium borohydride or addition to alkenes. For example, treatment of phenyl-cyclopropane (1) with mercury(II) acetate in methanol, followed by the addition of sodium chloride, produced 3-(chloromercurio)-l-methoxy-l-phenylpropane(2) in good yield.When the primary mercury adduct was reacted with alkenes without isolation, the yields were lower than those in the two-step transformation. ... 

An interesting application of the method was to the synthesis of the heterocyclic mctacyclophane (8), 3,5-[l0]-pyrazolophane.13 Cyclododecanone (4) was converted into the enol acetate (5) and this was refluxed with phenyl(trichloromethyl)mercury in benzene under nitrogen for 48hrs. to produce l-acetoxy-2,2-dichlorobicyclo-[10.1.0]tridecane (6). Reaction with hydrazine gave as the chief product (49% yield)... 

Conversion into 6-methyl-2-(4-methylphenyl)hepta- 1,5-diene. 2- 4-methyl-phenyl)prop-2-enyl vinyl ether. A mixture of the foregoing allylic alcohol (2.5 g), ethyl vinyl ether (75 ml) and freshly crystallised mercury(n) acetate (600 mg) is refluxed continuously for 12 hours on a water bath. The reaction mixture is chilled in ice and mixed with 10 per cent aqueous sodium carbonate solution (25 g) and stirred well for 30 minutes at 0 °C. The organic layer is... 

Benzaldehyde dimethylacetal (200 pi, 1.33 mmol) and a catalytic amount of p-toluenesulfonic acid (37 mg) are added to methyl (2R,3S)-3-(4-nitrobenzenesulfonamido)-3-phenyl-2-hydroxypropionate (315 mg, 0.83 mmol) in toluene 5 ml. The mixture is heated at 100°C under reduced pressure (15 mm mercury) with no condenser. After 1 h the crude reaction mixture is diluted with ethyl acetate and washed with water (2 times). After drying the organic layer over magnesium sulfate the crude material is purified by column chormatography (silica gel eluting with ethyl acetate/cyclohexane, 35/65) to give the (2S,4S,5R)-2,4-diphenyl-3-(4-nitrobenzenesulfonamido)-5-methoxycarbonyl-l,3-oxazolidine, melting point 118°-120°C. 

The reaction between aryl (phenyl, substituted phenyl, naphthyl) tellurium trichlorides and aryl mercury chlorides or acetates are best carried out with dioxane as the solvent. The mercury(II) salts precipitate as their dioxane adducts. The symmetrical or unsymmetrical... 

The first stereochemical study of the cleavage of a cyclopropane derivative by a mercuric salt was reported by DeBoer and DePuy 22). By the series of reactions given (Eq. (30)), they showed that 1-phenyl-cts, fyaws-2,3-dimethylcyclopropanol 33) and l-phenyl- ra s, methyl ethers, react with mercuric acetate in acetic acid exclusively with inversion of configuration at the carbon to which the mercury becomes attached. More recently... 

Along this same line the reaction of the 3-acetoxy irfo-5-norticyclyl bis(p3rridine) palladium with diphenylmercury gave the e (/o-3-phenyl-5-mercury derivative. This was postulated to proceed via attack of coordinated phenyl on the carbon-acetate bond (278) ... 

The chloro[exo-5-acetoxytricyclo[2.2.1.0 ]hept-enifo-3-yl]dipyridinepalladium complex 17 [prepared from norbornadiene and palladium(II) chloride bisbenzonitrile complex with subsequent substitution and ligand exchange ] underwent exchange with acetoxy(phenyl)mer-cury, analogous to the known exchange reactions between palladium(II) chloride or acetate and phenylmercury salts, to afford a mixture of products, including biphenyl (54%), exo,exo-3,5-diacetoxytricyclo[2.2.1.0 ]heptane (19,20%) and chloro[exo-5-acetoxytricyclo[2.2.1.0 ]-hept-e Jo-3-yl]mercury (18, 57%). 

Cyclopropane bonds are susceptible to oxidative cleavage (see Section 2.1.1.2.). Most of the oxidation reactions of activated cyclopropanes involve phenyl-substituted derivatives. When phenylcyclopropane was treated with lead(IV) acetate, 1,3-diacetoxy-l-phenylpropane (63%) and the elimination product cinnamyl acetate (32%) were obtained. The occurrence of traces of l,3-diacetoxy-2-phenylpropane could not be confirmed in later studies. The kinetics of the oxidation of various arylcyclopropanes with lead(IV) acetate, thallium(III) acetate and mercury(II) acetate have been studied. 4-Methoxyphenyl, 4-tolyl, and 4-chlorophenyl derivatives and their meta analogs were treated with these reagents and the rates of reaction and product distributions analyzed. Using lead(IV) acetate, diacetates 1 and cinnamyl acetates 2 were obtained in ratios of about 4 1, whereas thalhum(III) acetate gave the diacetates almost exclusively (see following table). ... 

On irradiation in the presence of alkynes the stable zwitterion (49) yields 5,7-dinitrobenzofuran (Equation (51)) <86JOC3453>. In an intramolecular alkoxymercuration reaction phenyl ethers of type (50) are cyclized with mercury(II) acetate to give mercurated benzofurans (Equation (52)) <84JA4218, 86JOC3453>. 

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