Mercury 1- cyclohexanol

Reaction of cyclohexene with mercury(II) acetate in CH3OH rather than H20, followed by treatment with NaBH4, yields cyclohexy) methyl ether rather than cyclohexanol. Suggest a mechanism. 

The mechanism of this defunctionalization was discussed in connection with Figure 1.14. It took place via approximately planar radical intermediates. This is why in the reduction of alkyl mercury(II) acetates, the C—Hg bond converts to a C—H bond without stereocontrol. The stereochemical integrity of the mercury-bearing stereocenter is thus lost. When the mer-curated alcohol in Figure 3.48 is reduced with NaBD4 rather than NaBH4, the deuterated cyclohexanol is therefore produced as a mixture of diastereomers. 

DVB were valid in this system as well. These concern the dependence of surface area and pore volume on the amount of diluent and cross-linker. The surface area increases with the amount of EDMA and goes through a maximum with increasing amount of diluent. Using cyclohexanol-dodecanol as a solvent-non-solvent pair, the factors of importance for the structure and morphology of the polymers were studied by experimental design [34]. In these experiments the concentration of the diluent mixture was varied between 20 and 77% (volume/total volume), the concentration of EDMA between 25 and 100% (volume/monomer volume), the concentration of initiator (AIBN) between 0.2 and 4% (w/w), the concentration of non-solvent (dodecanol), between 0 and 15% (v/v) and the polymerisation temperature between 70° and 90°C. The surface area (determined by nitrogen sorption), pore volume (determined by mercury porosimetry) (see Section 2.11.6.) and the mechanical properties were chosen as responses. 

Wallace, J. E., Schroeder, L. R. Koenigs-Knorr reactions. Part II. A mechanistic study of mercury(ll) cyanide-promoted reactions of 2,3,4,6-tetra-O-methyl-a-D-glucopyranosyl bromide with cyclohexanol in benzene-nitromethane. J. Chem. See., Perkin Trans. 2 1976,1632-1636. 

Photolysis of alkanes in air gives rise to the formation of oxygenated products in very low yields. Thus irradiated with high-pressure mercury arc, cyclohexane saturated with air ([0 1 = 1.9 x 10 mot dm ) yields cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide (ratio 1.0 0.6 0.9) [37a], Under analogous conditions, toluene is transformed into the mixture of benzaldehyde and benzyl alcohol (after 24 h the total yield 0.15 %, ratio aldehyde/alcohol is 3 1) [37b]. Benzyl hydroperoxide is the initial product of this reaction which decomposes further to yield more stable oxygenates [37c]. 

When a solution of the complex [(f-BuOO)Pd(OCOCHj)]4 and cyclohexane in methylene chloride was exposed to the tight of a high-pressure mercury lamp in a glass vessel (A. > 310 nm), cyclohexanol and cyclohexanone were detected in the reaction mixture [88], The oxidation of alkanes by the complex [(f-BuOO)-Pd(OCOCp3)]4 occurs in a benzene solution both in the dark and under tight irradiation. It is interesting that in the dark reaction a significant amount of cyclohexyl hydroperoxide is formed in addition to cyclohexanol and cyclohexanone [88]. 

Caprylic/capric acid Cetoleth-19 Cyclohexanol Deodorized kerosene N-(p-Ethoxycarbonylphenyl)-N -ethyl-N-phenylformamidine Ethylene/acrylic acid copolymer Hydroxystearic acid Isobutyl stearate Mercury oxide (ic), red Nonoxynol-55 PEG-4 PEG-6 PEG-8 PEG-9 PEG-12 PEG-14 PEG-16 PEG-20 PEG-32 PEG-40 PEG-75 PEG-100 PEG-150 PEG-200 PEG-350 Pentaerythrityl tetrastearate Polyethylene glycol Propyl alcohol Soy acid Stearamide MEA-stearate... 

Details of the careful purification used for the a-CD, 3-CD,3 5) distilled water, and mercury ) have been described elsewhere. All solutions were prepared by mass and corrected for the water content of the cyclohexanol. 

The reaction of 2-0-acetyl-3,4,6-tri-0-methyl-a-D-glucopyranosyl bromide and cyclohexanol in benzene-nitromethane in the presence of mercury(ii) cyanide displayed a first-order dependence on the concentrations of the glycosyl bromide and mercury(ii) cyanide, and the rate of the reaction was independent of the concentration of cyclohexanol. The proportion of P-glycoside in the initial products increased as the concentration of cyclohexanol was increased and the p-glycoside appears to be formed directly from carboxonium ion intermediates and by selective... 

Fig. 38. Influence of the adsorption of cyclohexanol on the reduction of zinc on mercury.

---