Phenylmagnesium chloride, reaction with

Derivation By Grignard reaction of silicon tetrachloride and phenylmagnesium chloride, reaction of benzene with trichlorosilane. 

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 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]. 

Copper(I) chloride is not recommended for the preparation of some copper compounds in ether. Examples are the preparation of the supposed magnesium diphenylcuprate from phenylmagnesium bromide 193), and in reactions with pentafluorophenyllithium 146) and trichloro-2-thienyllithium 264). Instead, the copper compounds can be obtained by using copper(I) iodide, or by employing a more basic solvent such as dimethoxyethane or THE 146, 264). 

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. ... 

One year later, in 1934, Vavon and co-workers [5] determined the relative reactivities of Grignard reagents with a different type of substrates benzoic acid esters. Steric requirements played a role when the alcohol component of the ester was changed from primary, to secondary, to tertiary the relative rates of reactions of ethylmagnesium bromide were 400 40 1, respectively. The relative rates of reaction of ethyl-, isopropyl-, n-butyl-, and phenylmagnesium bromide with ethyl benzoate decreased in this order. The reaction with rert-butylmagnesium chloride was reported to be extremely slow."... 

Derivation (1) Reaction of powdered silicon and chlorobenzene in the presence of copper powder as catalyst (2) reaction of phenylmagnesium chloride with silicon tetrachloride. 

Lactones have been converted to (hydroxyalkyljcyclopropyl phenyl ketones on reaction with phenylmagnesium bromide and phenyllithium. Reductive dimerization of ethyl cyclo-propanecarboxylate with sodium gave l,2-dicyclopropylethane-l,2-dione in 69% yield when thionyl chloride treatment was carried out prior to hydrolytic workup, and to dicyclopropyl ketone in 74% yield, when workup included sodium bromate treatment. A related reaction occurred during thermolysis of 6,6-dimethyl-5,7-dioxaspiro[2.5]octane-4,8-dione to give dispiro[2.1.2.1. ]octane-4,8-dione. ... 

An efficient conversion of 5-chloro-)V-methylisatoic anhydride and glycine into 7-chloro-l-methyl-3,4-dihydro-lJT-l,4-benzodiazepine-2,5-dione has been described. Further reaction of its (V-acetyl derivative with phenylmagnesium chloride followed by treatment with hydroxylamine and then sodium bisulphite provides another new synthesis of Diazepam in ca. 50% overall yield. The 1,4,5-benzotriazocinium salts (103), prepared by the cyclization of (2-chloro-acetamido)benzophenone ATV-dimethylhydrazones (102), reacted with sodium methoxide in a Stevens-type reaction to give 3-amino-l,4-benzodiazepin-2-ones (104) in good yield. The same products were also obtained by direct treatment of (102) with base. 

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