Patent GB-955806-A (GB)
Title: Preparation and use of organomagnesium materials
Inventor: BRYCE-SMITH DEREK
IPC: C08F10/00
Filed: 1959-04-29
Abstract: A halogen-containing organo-magnesium material is prepared by contacting an aryl-, alkaryl-, aralkyl- or primary or secondary alkyl-saturated hydrocarbon monohalide or a saturated alkoxyaryl monohalide and metallic magnesium at elevated temperature in the presence of a dissolved magnesium or other metal derivative of an organic compound containing a hydroxy group or enolisable keto group which catalyses the reaction between the monohalide and the magnesium to yield a halo-magnesium derivative of the halide which is stable in the reaction mixture, the magnesium being present in a molar excess compared to the halide where a n-alkyl halide is used. The product contains less halogen than is required for the conventional Grignard reagent RMgHal.  The reaction may be carried out using the organic halide as reaction medium or in the presence of an inert diluent preferably a hydrocarbon e.g. a paraffin fraction, isopropyl benzene, tetrahydronaphthalene, xylene, benzene or toluene. The metal derivative should be used in amounts to provide from 0.5 to 10 equivalents per cent of metal-oxygen bonds per mol of halide, it being preferred to avoid the range below 5.0 equivalents per cent when using an aromatic solvent. Reaction is usually conducted between 30 DEG C. and 200 DEG C. The metal derivative may be added to the reaction vessel or prepared preliminary to the addition of or in the presence of the halide. An initiator e.g. iodine may be used. Alcohols and phenols specified include isopropyl and other secondary alcohols, primary alcohols such as methanol, ethanol, n-lauryl alcohol and benzylalcohol, tertiary alcohols such as tert. butyl alcohol, diols such as ethylene glycol, cyclic alcohols such as tetrahydrofurfuryl alcohol and unsaturated alcohols such as allyl and propargyl alcohols, 2-methoxy and 2-ethoxy-ethanol yield magnesium derivatives without the use of an initiator. Other compounds which may be used include diacetone alcohol, triethanolamine, dimethylaminoethanol, ethyl acetate, ethyl acetoacetate, diethyl malonate, diethylcarbonate, ketones such as acetone and aldehydes such as acetaldehyde.  Metal derivatives other than magnesium derivatives which may be used include lithium, sodium, potassium, beryllium, zinc and aluminium isopropoxides. Aluminium chloride, copper or small proportions of an ether such as diethylether, 1,2-dimethoxyethane, tetrahydrofuran, N-methylmorpholine or of dimethylaniline may be used as additional catalysts. The products may be used as polymerization catalysts (see Division C3) or in reactions similar to those of conventional Grignard compounds. Reaction of the product of magnesium, chlorobenzene and isopropyl alcohol (Example 1) with CO2 gives benzoic acid.  In example 2 the product of magnesium, chlorobenzene and aluminium isopropoxide is reacted with stannic chloride to give tetraphenyl tin and with aluminium chloride to give triphenyl aluminium.ALSO:Vinyl monomers may be polymerized in the presence of an organo magnesium compound containing less halogen than is required for the conventional Grignard RMgHal (see Division C2). Specified monomers include ethylene, propylene, styrene, isoprene, butadiene, vinyl ethyl ether, vinyl acetate methyl methacrylate, and acrylonitrile.  Styrene may also be copolymerized with acrylonitrile. Titanium tetrachloride, titanium trichloride and other heavy metal compounds of the Ziegler type catalysts may be used with the organo magnesium compounds. Example 8 describes the polymerization of ethylene or propylene and Example 9 the polymerization of methyl methacrylate.