Phenyl magnesium chloride

Some tumors are estrogen-dependent and the use of an antiestrogen has therapeutic value. One such antineoplastic agent appears to be patterned after clomiphene. Complex aryl ketone 204 is treated with phenyl magnesium chloride and the resulting tertiary... 

The starting bibenzyl was prepared from -methoxybenzyl chloride by a modified Wurtz reaction. The checkers found the procedure described by Buu-HoY and Lavit inadequate and used the copper(I) chloride-catalyzed coupling of -methoxy-phenyl magnesium chloride in its place. 

Starting with a copper catalyzed epoxide ring opening, using phenyl magnesium chloride, a secondary alcohol was generated, which in turn was transformed into an electrophile by tosylation (Scheme 29). The tosylate 117... 

This process was superceded by the Friedel-Crafts reaction of benzene and ethylene oxide which is now the most important commercial process (11). Cheap ethylene oxide brought about this shift. For a short time, commercial quantities of phenylethyl alcohol were made by the Grignard reaction of phenyl magnesium chloride on ethylene oxide but this process could not compete with the Friedel-Crafts process. 

As mentioned above, phenylethoxysilanes are synthesised by the Grig-nard technique with the ratio Mgi HsO Si of 1 1. First chlorobenzene interacts with metallic magnesium to form phenyl magnesium chloride Then, tetraethoxysilane is phenylated ... 

Flowever, the reaction between phenyl magnesium chloride and tetraethoxysilane is a complicated process, which forms not only phenyltrieth-oxysilane, but also diphenyldiethoxysilane and triphenylethoxysilane. 

Some reagents for thn Grignard synthesis can serve as their own solvents. In the previous chapter it was pointed out that ethyl silicate is such a solvent, and that alkyl- or arylethoxysilanes may be made by adding the appropriate organic halide to a stirred mixture of magnesium and ethyl silicate.10 In the same way excess chlorobenzene is a solvent for the preparation of phenyl magnesium chloride.11... 

Close the tap to the addition funnel, and add the solution of 3-(bis[trimethyl-silyl]amino)phenyl magnesium chloride (50 mL, 1 M in pentane) (Caution ). 

Grignard reaction. The reagent reacts with benzylmagnesium chloride, phenyl-magnesium chloride, phenyllithium, and 1-naphthylmagnesium bromide to give... 

Finally, an interesting organotin compound is the product obtained from the reaction of 3 equivalents of (2-[(diphenylphosphino)methyl] phenyl magnesium chloride with 2 equivalents of SnCl2 (84). For 11, the... 

Many studies of the addition of nucleophiles to palladium-allyl complexes have been conducted. Hayashi has shown that the additions of stabilized anions, such as malonate anions or amine nucleophiles, to chiral, non-racemic allyl complexes occur with inversion of configuration.Addition of excess phosphine and either diethyl malonate or dimethylamine to a chiral, non-racemic allyl complex results in nucleophilic attack with nearly complete inversion. The reaction with sodium dimethylmalonate is shown at the right of Equation 11.40. In contrast, nonstabilized carbanions such as allyl or phenyl magnesium chloride react with the same Ti -allylpalladium complex with retention of configuration as shown at the left of Equation 11.40. The stereochemistry from reaction of the Grignard reagents likely results from nucleophilic attack at the metal, followed by reductive elimination. 

Much of the work in this area has focussed on polymeric dyes which can participate in redox reactions. Early work by Manecke and Kossmehl on vinyl Malachite Green (VMG) is specially significant as it established a simple method of entry into the polymerizable triphenylmethane class of dyes. Thus the carbinol base form (ill) of VMG was synthesized by a Grignard reaction between vinyl-phenyl magnesium chloride (l) and Michler s ketone (ll). 

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