Phenylmagnesium chloride

Fig. 2. Preparation of 1,1-diphenylethanol from methylmagnesium chloride and ben2ophenone, phenylmagnesium chloride and acetophenone, or...

Dimesitylimidazolium chloride with chromocene gives the carbene 32 (R = C1) (990M529). With phenylmagnesium chloride, 32 (R = C1) gives 32 (R = Ph), the product of substitution of the chloride ligand by phenyl radical. In chloroform, 32 (R = C1) gives the chromium(III) species 33. In contrast,... 

The weak chemiluminescence of Grignard compounds in air has been known since 1906. A radical chain mechanism similar to that of hydrocarbon autoxidation appears to provide the excitation energy of the emitting product. Until recently the relations between constitution and chemiluminescence in Grignard compounds were rather obscure j>-chloro-phenylmagnesium chloride was found to be the most efficient compound. 

A/-[ F]Fluoro-A/-alkylsulphonamides react with a variety of carbanions and organometallic compounds [84]. For example, A/-[ F]fluoro-A/-enc/o-norbornyl-paratoluenesulphonamide has been successfully used for the preparation of [ F]fluorobenzene (40 and 61% radiochemical yields from phenylmagnesium chloride and phenyllithium, respectively), 1-f F]fluoronaphthalene (53%, from 1-naphthylmagnesium chloride) and [ F]fluorocyc/ohexane (29%, from cyclo-hexylmagnesium chloride) (Scheme 24). 

Treatment of diphenylmercury with nitrosyl chloride produced some nitro-sobenzene [64]. The reaction of phenylmagnesium chloride with nitrosyl chloride also produced this compound [65], However, cyclohexylmagnesium... 

In the third step an ethereal solution of the step 2 product was added to a solution of either 2.3 ml methyllithium (1.4 M in diethyl ether), 1.75 ml phenylmagnesium chloride (2 M in THF), or 7 ml of pentafluorophenylmagnesium chloride (0.5 M in diethyl ether). The reaction mixture was then slowly warmed to ambient temperature and stirred for 4 hours. The salt that formed was filtered and the filtrate concentrated. The residue was recrystallized from ether/pentane and the catalyst isolated from between 60 and 70% yield. 

Metalation. Benzene reacts with alkali metal derivatives such as methyl or ethyUithium in hydrocarbon solvents to produce phenyllithium [591-51-5], C6H5Li, and methane or ethane. Chloro-, bromo-, or iodobenzene will react with magnesium metal in ethereal solvents to produce phenylmagnesium chloride [100-59-4], C6H5MgCl, bromide, or iodide (Grignard reagents) (32). 

Present Day Methods. In the Grignard Synthesis (82,83), chlorobenzene [108-90-7] is converted to phenylmagnesium chloride which reacts with ethylene oxide [75-21-8] at 100°C to give (3-phenylethoxy magnesium chloride which is then decomposed with sulfuric acid to give PEA. 

One of the largest commercially used Grignard reagents is phenylmagnesium chloride. Millions of kg per year of this Grignard react captively with inorganic halides. Some examples of these products are triphenylphosphine, triphenyltin hydroxide, sodium tetraphenylborate, and triphenyl an tim ony. 

Methylcyclohexenone 281 upon oxidation with Mn(OAc)3 in benzene under reflux gave 282, which reacted with phenylmagnesium chloride and CuBr-Me2S to form two isomeric ketones 283 and 284. Further, 283 has been transformed to vinylsilane 285 followed by its hydrolysis to form the free alcohol 286, which in turn was alkylated with methoxyallyl bromide to give 287. Oxalic acid-mediated deprotection of 287 led to the formation of the ketone 288. Ozonolysis of 288 in methanol afforded the fused 1,2,5-trioxepine 289 in low yields (Scheme 66) <1997BML2357>. 

In this reaction a mixture of cis and trans isomers always occurs irrespective of the starting material (cis, trans, or a mixture). Separation into isomers may also be effected by gas chromatography. The different forms were identified from the phenyl derivatives obtained by reaction with phenylmagnesium chloride. 

The use of a functionalized silica-supported salen-nickel complex has allowed Kumada cross-couplings to be performed in flow the corresponding polystyrene supported complex was shown to be inferior for a number of reasons. Catalyst 33 (Figure 4.7) with the longer tether was found to be more active than the benzyl ether tether used for catalyst 34. This was postulated to be due to the fact that catalyst 33 resided further away from the silica surface and hence was more available for reaction. Under the conditions used a maximum conversion of 65% was found for the 1 1 reaction of 4-bromoanisole and phenylmagnesium chloride, which was found to be comparable to that obtained in batch mode. However, during the reaction catalyst degradation was observed and the conversion reduced from 60% in the first hour to 30% in the fifth hour of the reaction [155,156]. 

Phenylmagnesium chloride (2.0 M in tetrahydrofuran) was obtained from Aldrich Chemical Company, Inc. The vessel must be dry and flushed with nitrogen prior to the addition of the phenylmagnesium chloride. 

During concentration, a precipitate of diphenylprolinol sulfate and triphenylmethanol is formed. Caution Benzene (43 g), formed during the quench of the excess phenylmagnesium chloride, is removed during the concentration. 

Addition of phenylmagnesium chloride to methyl pyroglutamate followed by reduction with borane to give racemic a,a-diphenyl-2-pyrrolidinemelhanol (3 steps, 51% yield from pyrroglutamic acid) that was then resolved as its O-acetylmandelate salt 10 give (R)- or (S)-a,a-diphenyl-2-pyrrolidinemethanol (2 steps, 3 recrystallizations, 30% yield from racemic a,a-diphenyl-2-pyrrolidinemethanol ref. 5f). 

Addition of (S)-proline ethyl ester to phenylmagnesium chloride to give (S)-a,a-diaryl-2-pyrrolidinemethanol (2 steps, 21% yield from (S)-proline) (a) Roussel-UCLAF French Patent FR M3638, 1965 Chem. Abstr. 1969, 70, 106375m An earlier report (26% yield) did not indicate the enantiomeric purity of the product (b) Kapfhammer, J. Matthes, A. Z physiol. Chem. 1933, 223, 43-52. In the submitters hands, addition of (S)-proline methyl ester hydrochloride to phenylmagnesium chloride, afforded (S)-a,a-diphenyl-2-pyrrolidinemethanol in 20% yield and 80% e.e. See also ref. 5d. 

Addition of N-benzyl-(S)-proline ethyl ester to phenylmagnesium chloride followed by catalytic hydrogenolysis affords (S)-a,a-diphenyl-2-... 

Other authors have also described copper catalysis in the Grignard reaction. In the presence of copper salt, cyclohexene oxide reacts with phenylmagnesium chloride under mild conditions to give tra s-2-phenylcyclohexanol in good yield in the absence of the catalyst, the conversion is low. At the same time, benzylmagnesium chloride led to a yield of 90% even without the catalyst. The reactions between epoxynitriles and Grignard reagents have likewise been studied in detail. ... 

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