Mercury trifluoroacetates ketones

Hydrolysis of vinyl chlorides. One step in the Wichterle annelation with l,3-dichloro-cw-2-butene (1,214-215 2, 111-112) involves hydrolysis of an intermediate vinyl chloride to a ketone. This reaction has been conducted with cone. H2SO4. A new method involves reaction with mercury(II) trifluoroacetate, which can result in either a methyl or an ethyl ketone depending on the solvent. For example, hydrolysis of 1 with the mercury salt in CH3NO2, CH2CI2, or HOAc gives only the 1,5-diketone 2 in 90-97% yield hydrolysis in CH3OH gives 3 as the major product in 83% yield. ... 

The homobullvalenone 39 was cleaved by mercury(II) bromide to give a good yield of tricyclo[4.3.2]undeca-2,4,8,10-tetraen-7-one (40)/ but rearranged to tricyclo[5.4.0.0 ]unde-ca-2,6,9-trien-8-one (42) on heating. The tricyclic ketone 42 was formed in better yield by silver(I) trifluoroacetate promoted cleavage of the dibromocarbene adduct 41 of bullvalene. Homobullvalenone was probably the initial product of this rearrangement too, but at the reaction temperature (100°C), this completely rearranged. ... 

Mercury(II) compounds are less effective as catalysts for Cope and oxy-Cope rearrangements777- 783, 84. Treatment of tertiary alcohol 14 with stoichiometric amounts of mereury(II) trilluoroacetate primarily leads to a mercurated ketone 15, from which the mercury is removed by sodium borohydride reduction, 85. The same overall result is obtained by using catalytic amounts of mercury(II) trifluoroacetate in the presence of an excess of lithium tri-fluoroacetate783. 

A one-carbon homologation of ketones (R R CO) to carboxylic acids (4) involves a Wittig reaction leading to difluoro-olefins (3) followed by hydrolysis to (4) using mercury(ii) acetate in trifluoroacetic acid the overall process seems to be very efficient. 

Lithium tetrafluoroborate in wet acetonitrile has been described as an effective combination for the hydrolysis of acetals under mild weakly acidic conditions. Dithians were unaffected. Methods for the hydrolysis of thioacetals continue to appear. Reagents that have been described include a polystyryl-mercury(n) trifluoroacetate combination, which retains the metal on the resin, lead(iv) dioxide and boron trifluoride etherate, aqueous hydrochloric acid in dioxan containing dimethyl sulphoxide, methyl-bis(methylthio)sulphonium hexa-chloroantimonate, and iodoxybenzene, catalysed by toluene-p-sulphonic acid. Dithioacetals derived from ethane-1,2-dithiol may be cleaved with dimethyl sulphoxide in combination with either t-butyl or trimethylsilyl bromides and iodides. Regeneration of ketones from ethanediyl-S S -acetals via the lithium-di-isopropylamide-promoted fragmentation to the thioketone and subsequent hydrolytic work-up only gives satisfactory yields for aryl methylketone derivatives. Dithioacetal SS-dioxides are rapidly cleaved in hot methanolic hydrochloric acid solution. ... 

A new type of catalyst, a cobalt carbonyl complex, has been found for low-temperature (viz. 50 °C) homogeneous hydroformylation of alkenes. Nafion-H (a superacidic perfluorinated resin sulphonic acid) impregnated with mercury is recommended as a catalyst for the hydration of alkynes R C=CR (R = H or aryl, R = H, alkyl, or aryl) to form ketones R CH2C0R. Two mild methods for the hydrolysis of vinyl halides to ketones have been described one utilizes Bp3,Et20 and mercury(ii) acetate in acetic acid and the second mercury(ii) acetate in trifluoroacetic acid/ ... 

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