3-Chlorophenylmagnesium bromide

The couplings are usually exothermic, and care must be taken not to add the phosphine-nickel catalyst to a mixture of a Grignard reagent and an organic halide, particularly in a large-scale preparation. For example the addition of a small amount of [Ni(dppp)Cl2] to a mixture of vinyl chloride and 4-chlorophenylmagnesium bromide in ethyl ether at 0° led, after a few minutes induction period, to an uncontrollable, violent reaction. 

Chlorophenylmagnesium bromide Magnesium, bromo(p-chloro-phenyl)- (8) Magnesium, bromo(4-chlorophenyl)- (9) (873-77-8) Ni(dmpe)Cl2 Nickel, dichloro[ethylenebis[dimethylphosphine]]-... 

Such couplings are generally exothermic, for example, the addition of this nickel catalyst to a mixture of vinylchloride, and 4-chlorophenylmagnesium bromide in ether at 0°C leads after a short induction period to a violent uncontrollable reaction. The scale and conditions used here, however, are sufficient to moderate the reaction. 

Terao and Kambe reported a rather unconventional use of 1,3-butadiene as an additive, which affects palladium- and nickel-catalyzed cross-couplings of alkyl bromides and tosylates [14]. In the presence of 50mol% of 1,3-butadiene and a catalytic amount of [Pd(acac)2], the cross-coupling of heptyl tosylate with 4-chlorophenylmagnesium bromide was achieved to give the corresponding arylation product in excellent yield (Equation 5.12). 

To a solution of/t-chlorophenylmagnesium bromide prepared from 0.29 gm (0.012 gm-atom) of magnesium and 2.1 gm (0.011 mole) of 4-chlorobromo-benzene in 30 ml of anhydrous ether is added 1.1 gm (0.011 mole) of freshly fused anhydrous zinc chloride in 50 ml of anhydrous ether. The resulting solu-... 

Lui et al. [8] prepared buclizine by reducing p-chlorophenyl phenyl ketone 1 with potassium borohydride to p-chlorobenzhydryl alcohol 2, which was converted into p-chlorobenzhydryl bromide 3. The latter compound 3 was prepared by reaction of p-chlorophenylmagnesium bromide 4 with benzaldehyde 5. p-ferf-Butylbenzyl chloride 6 was condensed directly with piperazine 7 to give p-ferf-butylbenzylpiperazine 8. Treatment of p-chlorobenzhydryl bromide 3 with p-ferf-butylbenzylpiperazine 8 in the presence of anhydrous sodium carbonate gave buclizine 9 hydrochloride. 

The A7, N -methenyltetrahydrofolate model (423) can transfer a formyl equivalent to nucleophiles p-chlorophenylmagnesium bromide, for example, is... 

Chlorophenylmagnesium bromide attacked only the ketonic carbonyl group of isatin (426) to give the oxindole (427). Michael addition to acrylonitrile followed by reduction gave the saturated primary amine (428) which in refluxing xylene containing 4-toluene sulphonic acid cyclized to ciclazindol (429) Scheme 5.101.). The intermediate (428) can also be... 

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