Phenylmagnesium bromide, and

Although phenylmagnesium bromide and zinc chloride do form an equilibrium mixture of diphenylzinc and magnesium halide, diphenylzinc is not thought to be the actual organometal-lic reagent in this addition reaction. In fact, even at room temperature, the addition reaction of pure diphenylzinc to 2-naphthaldehyde in the presence of 21 is very slow, affording little of the addition product. 

The method described here is a modification of that of Schoeller.1 Diphenyl selenide has also been prepared from diazotized aniline and alkali monoselenides 2 by the Friedel-Crafts reaction with benzene and selenium tetrachloride3 or selenium dioxide 4 from diphenyl sulfone and selenium 5 from phenylmagnesium bromide and selenium,6 selenium dichloride,7... 

Diphenyl diselenide has been prepared by disproportionation of phenyl selenocyanate in the presence of potassium hydroxide" or ammonia/ and by air oxidation of benzeneselenol. The preparation of benzeneselenol is described in an earlier volume in this series/ In the present procedure phenylselenomagnesium bromide formed from phenylmagnesium bromide and selenium is oxidized directly to diphenyl diselenide with bromine/ Thus the liberation of the malodorous and toxic hydrogen selenide and benzeneselenol is avoided. Benzeneselenenyl chloride has been prepared by thermal elimination of ethyl chloride from ethyl phenyl selenide di-chloride/ by thermal elimination of chlorine from phenylselenium trichloride," and by chlorinolysis of diphenyl diselenide with either sulfuryl chloride " or chlorine. " ... 

Triphenylcarbinol has been obtained by the reaction between phenylmagnesium bromide and benzophenone,1 methyl benzoate, or phosgene 8 by action of phenylsodium upon benzophenone, benzoyl chloride, ethyl chlorocarbonate, or ethyl benzoate 4 by hydrolysis of triphenylchloromethane 5 and by oxidation of tri-phenylmethane.6... 

The procedure for the preparation of 1-phenyl-2,2,2-trichloro-ethanol is based on the work of Bergmann, Ginsburg, and Lavie.3 l-Phenvl-2,2,2-trichloroethanol has also been prepared from phenylmagnesium bromide and chloral.4... 

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-... 

Triphenylborane prepared from phenylmagnesium bromide and boron trifluoride ether-ate also reacted with HOSA, but gave a low yield of aniline (equation 12). ... 

Theuseof DMPU (l,3-dimethyl-3,4,5,6-tetrahydro-2(l//)-pyrimidmone) as acosolvent in THF has been reported to increase the amination yield of arylzinc chlorides with Erdik and Omiir also reported competitive kinetic studies for the amination of substituted phenylmagnesium bromides and CuCN-catalyzed phenylzinc chlorides with acetone 0-(mesitylenesulfonyl)oxime 6f in THF and analyzed the rate data via the Hammett... 

Treatment of l-methyl-2-piperidone with phenylmagnesium bromide and subsequent reaction with acetic anhydride and then water gave the acetate 21 in small yield.139 This indicates that the salt of the carbinolamine form is an intermediate which, on liberation, affords the cyclic enamine in the five- and six-membered series, for steric reasons. 

Grignard reagents were said to give low yields of products with the A-oxides themselves. For example, phenylmagnesium bromide and pyridine A-oxide yielded a small amount of 2-phenylpyridine.335-337 Poor yields were also reported with sec-butyl and -butylmagnesium bromides.338 It has recently been reported, however, that pyridine... 

An 81 per cent yield is reported from phenylmagnesium bromide and mercuric bromide. Bachmann, J. Am. Chem. Soc. 55, 2830 (1933). 

Allylbenzene can be prepared from phenylmagnesium bromide and allyl bromide.2 The maleic anhydride used was Eastman Kodak Company white label grade. Slightly higher yields are obtained if it is freshly distilled at 25 mm. Commercial o-dichlorobenzene should be distilled before use. 

On a laboratory scale, 1,1-diphenylethylene may be prepared using the Grignard reaction between phenylmagnesium bromide and acetophenone [6]. 

B-Benzoylpropionic Acid (13, 13) From phenylmagnesium bromide and succinic anhydride. Koiippa and ROERUAisr, Ann. 509, 259 (1934). 

Thiobenzoylthioglycolic acid has been prepared by the interaction of potassium dithlobenzoate and alkali chloroacetate. " The required intermediate, dithiobenzoic acid, has been obtained from phenylmagnesium bromide and carbon disulfide, -or by the condensation of benzaldehyde and hydrogen polysulfides, or most conveniently by treatment of benzotrichloride with potassium hydrogen sulfide. - The last procedure has been adapted here to afford improved yields. 

---