Phenylmagnesium halide

This small class of compounds is characterized by an N-alkyl moiety, and they are synthesized from isoxazolium salts by isomerization or by the dehydration of 2-alkyl-isoxazolidin-3-ols (Scheme 128) (74BSF1025). The reaction of isoxazolium salts that are unsubstituted in the 5-position with phenylmagnesium halides was reported to give 3-isoxazolines by 1,4-conjugate addition, and this reaction is also shown in Scheme 128 (74CPB70). 

Asymmetrical triarylstibines had been prepared (1,9, 60) by Campbell from the reaction of phenylmagnesium halides with diarylchlorostibines RR SbCl, which were obtained by the diazonium reaction. However, the alkyl-substituted analogs were not identified. 

Benzophenone (Coll. Vol. i, 89) By the rapid addition of phenylmagnesium halides to one equivalent of benzoyl chloride. In one-tenth mole experiments using phenylmagnesium iodide, bromide, and chloride, the yields reported are 68, 55, and 48 per cent, respectively. Giluan and Mayhde, Rec. trav. chim. gi, 47 (1932). 

By-products of the decomposition of Grignard reagents are an additional concern. As with flammable organic halides, there is a potential for the release of hazardous hydrogen halide vapors (HCl, HBr). If the fire involves certain Grignard reagents (notable phenylmagnesium halide), the hazardous hydrocarbon, benzene, may be released. 

The methoxy ethers of the amino alcohols obtained from the addition of methyl-, ethyl-, or phenylmagnesium halide to 7V-benzylproline methyl esters can be converted to the corresponding, /V-amino derivatives by exactly the same procedures as described for SAMP10. The products [e.g., SADP, (S)-27, the a,a-dimethyl product] form azaenolates with carbonyl compounds which are used in enantioselective a-oxidations (Section D.4.I.). 

Mongin F, Mojovic L, Guillamet B, Trecourt F, QueguinerG (2002) Cross-coupUng reactions of phenylmagnesium halides with fluoroazines and fluorodiazines. J Org Chem 67 8991-8994... 

The intermediate dehydration in the Barbier-Wieland degradation is facilitated if phenylmagnesium halide is replaced by the p-dimethylaminophenyl or anisyl analog . ... 

The intermediate dehydration in the Barbier-Wieland degradation is facilitated if phenylmagnesium halide is replaced by the p-dimethylaminophenyl or anisyl analog.—E Methyl norcamphanecarboxylate allowed to react with the Mg-derivative of p-bromo-N-dimethylaniline prepared in tetrahydrofuran, hydrolyzed with satd. NH4Cl-soln., and steam-distilled bis-(p-dimethylaminophenyl) methylene compound. Y 95%. F. e. s. M. Fetizon, M. Golfier, and A. Rassat, C.r. 252, 139 (1961). 

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