Ethyl acetate-TiCL

In U.S. Patent 4,174,429 [54], Montedison characterized a large number of Mg/Ti/Cl/electron donor complexes based on a wide variety of ligands such as ethyl acetate, ethanol, ethyl benzoate, benzonitrile, ethylene carbonate, n-butyl acetate and diethyl ether, using TiClj prepared from hydrogen reduction of TiCl. ... 

Many dialkyl and diaryl cadmium compounds have found use as polymerization catalysts. For example, the diethyl compound catalyzes polymerization of vinyl chloride, vinyl acetate, and methyl methacrylate (45), and when mixed with TiCl can be used to produce polyethylene and crystalline polypropylene for filaments, textiles, glues, and coatings (45). With >50% TiCl diethyl cadmium polymerizes dienes. Diethyl cadmium maybe used as an intermediate ethylating agent in the production of tetraethyllead. The diaryl compounds such as diphenylcadmium [2674-04-6]> (C H Cd, (mp 174°C) are also polymerization catalysts. These compounds are also prepared using Grignard or arylUthium reagents in tetrahydrofiiran (THF) solvent but may be prepared by direct metal substitution reactions such as ... 

Michael additions of ketene alkyl silylacetals. In the presence of TiCl, (1 equiv.) these acetals undergo Michael addition to ethyl propiolate via a titanate intermediate. 

A. change of the reactivity order in Figure 11 takes place if conditions of addition rate control are employed. Hosomi, Endo and Sakurai studied the reaction of triethyl orthoformate with allyltrimethyl-silane in presence of equimolar amounts of TiCl. As expected for conditions of addition rate control, the homoallylic acetal was found to be more reactive than ethyl orthoformate, and only a 2 1 product was isolated. When we repeated this reaction with catalytic amounts of SnCl, the homoallylic acetal was obtained in 51 yield. In a similar way the other 3 > "V-unsaturated acetals shown in Figure 12 were synthesized under conditions of concentration control. 

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