Ethyl reaction with phenylmagnesium bromide

The ring-contracted analog of alphaprodine is prepared by a variation of the scheme above. Alkylation of 109 with ethyl bromoacetate affords the lower homolog diester (115). Dieckmann cyclization followed by saponification-decarboxylation yields the pyrrolidine (116). Reaction with phenylmagnesium bromide leads to the condensation product (117) acylation with propionic anhydride gives the analgesic agent prolidine (118)... 

Reaction of ethyl chlorofluoroacetate with phenylmagnesium bromide at -50° affords U, a ketone, chlorofluoromethyl phenyl ketone. Treatment... 

Triphenylmethanol can also be prepared from the reaction of ethyl benzoate with phenylmagnesium bromide and by the reaction of diethylcarbonate... 

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. ... 

Kagan has developed a useful asymmetric synthesis of chiral sulfoxides based on the derivatization of diol (31) with thionyl chloride (Scheme 2.25). Diol (31) is obtained in one step by reaction of readily available (S)-ethyl lactate with phenylmagnesium bromide. 

Triphenylethylene has been prepared by the reaction of phenylmagnesium bromide with benzyl benzoate, with desoxy-benzoin, or with ethyl pheaniylacetate, and by the reaction of diphenylketene-quinoline with benzaldehyde. The above procedure is an adaptation of that described by Hell and Wiegandt. ... 

Another important advance in organotransition metal chemistry was reported in 1957 by Zeiss and Herwig 26S). These workers found that reaction of phenylmagnesium bromide with chromium trichloride in tetrahydrofuran (THF), rather than in ethyl ether, yielded a red, crystalline compound, triphenylchromium-tris-tetrahydrofuranate (XXVI). 

Phenyltrichloromethylmercury has also been prepared by the reaction of phenylmercuric bromide with sodium methoxide and ethyl trichloroacetate (62-71% yield) of phenylmercuric chloride with potassium <-butoxide and chloroform (52% yield) of phenylmagnesium bromide with trichloromethylmercuric bromide (24% yield) of trichloromethylmercuric bromide with diphenyldichlorotin (49%) and of trichloromethylmercuric bromide with phenylmagnesium bromide (no yield given). 

Preparation by demethylation of 2,3-dimethyl-4-methoxy-benzophenone (SM) with pyridin-ium chloride at 180° for 2 h. SM was prepared by reaction of phenylmagnesium bromide with 2,3-dimethyl-4-methoxybenzal-dehyde in ethyl ether at 0° for 30 min [477],... 

In a dry 3-1. three-necked, round-bottomed flask fitted with an efficient reflux condenser, a stirrer, a Y-tube holding a 1-1. and a 250-ml. addition funnel, and protected from moisture by calcium chloride tubes is placed 5.76 g. (0.237 mole) of magnesium turnings barely covered by anhydrous ether, p -Bromotoluene (40 drops) and ethyl bromide (20 drops) are added, and the reaction starts immediately. />-Bromotoluene (35.0 g., 0.205 mole) in 200 ml. of anhydrous ether is added at such a rate that reflux is maintained. To the resultant solution of />-methyl-phenylmagnesium bromide is added, over a 1-hour period, a solution of 25.4 g. (0.200 mole) of dichloroacetone in 200 ml. of anhydrous ether. 

More conclusive evidence for the intermediacy of benzocyclopropenyl cations was obtained upon chloride/fluoride exchange of 22 with AgF in acetonitrile, which led to the chloro-fluoro derivative 278 and, ultimately, to the difluoro compound 279 in almost quantitative yield. Reaction of 22 with LiAlH AlClj afforded 2,5-diphenylbenzocyclopropene (264), while that with ethyl magnesium bromide lead to the diethyl derivative 280. Phenylmagnesium bromide and methylmagne-... 

Esters react with 2 mol of Grignard reagent to give the salt of an alcohol. For example, reaction of ethyl benzoate with 2 mol of phenylmagnesium bromide gives a salt of triphenylmethanol. The first addition gives an intermediate, 3-7, which is unstable under the reaction conditions. 

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."... 

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