Acetals reactions with organometallic compounds

A thermographic material with only one heat-sensitive component is prepared by reaction of an organometallic compound such as phenylmercury(II) nitrate with a thiourea derivative.230 The product is ball milled and coated in a binder such as poly(vinyl acetate). Other organometallic compounds disclosed are those of bismuth, tin, gallium and germanium combined with a variety of sulfur-containing compounds such as thioamides and xanthates. 

Manufacture and Uses. Acetoacetic esters are generally made from diketene and the corresponding alcohol as a solvent in the presence of a catalyst. In the case of liquid alcohols, manufacturing is carried out by continuous reaction in a tubular reactor with carefully adjusted feeds of diketene, alcohol, and catalyst, or alcohol—catalyst blend followed by continuous purification (Fig. 3). For solid alcohols, an inert solvent is used. Catalysts used include strong acids, tertiary amines, salts such as sodium acetate [127-09-3], oiganophosphorus compounds, and organometallic compounds (5). 

Figure 12.13 shows that the iso-A enols of the /3-diketones A react with an a,/3-unsaturated carboxonium ion C that acts as a C electrophile. This oxocarbenium ion is formed by reversible protonation of the oc,/3-unsaturated methyl vinyl ketone in acetic acid. However, the oxocarbenium ion C in this figure does not react with the iso-A enols at its carbonyl carbon atom—as the protonated acetone in Figure 12.12 does with the enol of acetone—but at the center C-/3 of the conjugated C=C double bond. Accordingly, an addition reaction takes place whose regioselectivity resembles that of a 1,4-addition of an organometallic compound to an 0C,/3-unsaturated carbonyl compound (see Section 10.6). 1,4-additions of enols (like in this case) or enolates (as in Section 13.6) to a,/3-unsaturated carbonyl and carboxyl compounds are referred to as Michael additions. 

Organometallic compounds are used widely as homogeneous catalysts in the chemical industry. For example, if the alkene insertion reaction continues with further alkene inserting into the M C bond, it can form the basis for catalytic alkene polymerisation. Other catalytic cycles may include oxidative addition and reductive elimination steps. Figure above shows the steps involved in the Monsanto acetic acid process, which performs the conversion... 

Scheme 9 demonstrates the further synthetic application of the thus obtained N,0-acetals. Substitution of the alkoxy or acyloxy group by nucleophiles like enol ethers, enol esters, enamines, other electron-rich olefins, CH-acidic compounds, electron-rich aromatics, isocyanides, trimethylsilyl cyanide, organometallics, vinyl and allyl silanes, hydroxy functions, or trialkylphosphites either catalyzed by Lewis acids or proton acids leads to the product of the amidoalkylation reaction (path a). In the presence of stereocenters as control elements, diasteroselective amidoalkylation reactions can be performed as shown in a large number of examples. On the other side, as Nyberg showed for the first time [196], elimination with formation of enecarbamates [208] and enamides [196,208,209] followed by reaction with electrophiles or nucleophiles (path b) also is possible. 

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