Phenylmagnesium bromide preparation

To a mixture of 100 ml of THF and 0.10 mol of the epoxide (note 1) was added 0.5 g Of copper(I) bromide. A solution of phenylmagnesium bromide (prepared from 0.18 mol of bromobenzene, see Chapter II, Exp. 5) in 130 ml of THF was added drop-wise in 20 min at 20-30°C. After an additional 30 min the black reaction mixture was hydrolysed with a solution of 2 g of NaCN or KCN and 20 g of ammonium chloride in 150 ml of water. The aqueous layer was extracted three times with diethyl ether. The combined organic solutions were washed with water and dried over magnesium sulfate. The residue obtained after concentration of the solution in a water-pump vacuum was distilled through a short column, giving the allenic alcohol, b.p. 100°C/0.2 mmHg, n. 1.5705, in 75% yield. 

A solution of 130 g. (1.08 moles) of allyl bromide in twice its volume of dry ether is added dropwise to an ethereal solution of p-bromo-phenylmagnesium bromide prepared from 1.0 mole (237 g.) of... 

Ethyl ethoxymethylenemalonale (EMME) allowed to react at -60 to -50 in ether with phenylmagnesium bromide prepared from bromobenzene and Mg diethyl benzylidenemalonate. Y 50.5%. - Whether simple or double conjugate addition (to a satd. product) occurs appears to depend on the structures of both the organometallic compd. as well as the conjugated enolether. F. e., also addition of 2 molecules, s. D. P. Nabar and S. V. Sunthankar, Bull. Chem. Soc. Japan 42, 2991 (1969). 

An ethereal soln. of dineopentyl ketone added during 2 hrs. to 2,4,6-trimethyl-phenylmagnesium bromide prepared from bromomesitylene and Mg in ether, refluxed 2 hrs., then acetic anhydride in ether added during 2 hrs. with icecooling, and stirring continued 1 hr. - 2,2,6,6-tetramethylhept-3-en-4-yl acetate. Y 90%. F. e. s. H. G. Hauthal, P. Kluge, and H. Schmidt, J. pr. 29, 296 (1965). 

A soln. of phenylmagnesium bromide prepared from bromobenzene and Mg in tetrahydrofuran added dropwise during 2 hrs. to N-(3-chlorobenzoyl) imidazole in the same solvent, and stirred 3 hrs. at room temp. 3-chlorobenzophenone. Y 94%.— This and other reactions (s. 441) are based on the great ease of nucleophilic substitution at the carbonyl group of the N-acylimidazoles. F. e. s. H. A. Staab and E. Jost, A. 655, 90 (1962). 

To a refluxing solution 0. phenylmagnesium bromide in 650 ml of diethyl ether, prepared from 1.15 mol of broraobenzene (see Chapter 11, Exp. 5) was added 1.00 mol of ally] bromide at a rate such that refluxing was maintained (about 30 min). 

Phenylmagnesium bromide (2.8 mol) was prepared in anhydrous ether (21) from bromobenzene (440 g, 2.9 mol) and magnesium turnings (68.0 g 2.8 g-atom). To this solution was added dropwise a solution of indole (328 g, 2.8 mol) in benzene (8(X)ml). The resulting solution was stirred for 10 min and then a solution of cyclopentanoyl chloride (322 g, 2.4 mol) in benzene (800 ml) was added dropwise. The solution was stirred for 1 h and then water (11) was added carefully. The precipitate which formed was collected by filtration and dried to give 169 g of crude product. Additional product (97 g) was obtained by evaporation of the organic layer of the filtrate. The combined products were recrystallized from toluene to give 250 g (49% yield) of pure product. 

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. ... 

The preparation of other 6-aIkylated steroids has also been accomplished with 5,6-epoxides. Thus treatment of 3,3-ethylenedioxy-5a,6a-epoxy steroids (6) with acetylenedimagnesium bromide,propargylmagnesium bromide " or phenylmagnesium bromide, gives the corresponding 6 -ethynyl-, 6j5-propargyl- and 6/ -phenyl-3,3-ethylenedioxy-5a-ols. 

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)... 

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... 

Benzophenone (Coll. Vol. x, 89) In 57 per cent yield from benzoyl chloride and diphenylcadmium or phenylcadmium halides, prepared by adding cadmium chloride to 2 moles of phenylmagnesium bromide. Gilman and Nelson, Rec. trav. chim. 55i Sig (1936). 

Strecker153 reported in 1910 that the reaction of thionyl chloride with two equivalents of phenylmagnesium bromide or benzylmagnesium bromide afforded diphenyl or dibenzyl sulphoxides, respectively (equation 49 Table 8). The corresponding sulphides are formed as by-products of this reaction. Recently, other sulphoxides were prepared by this procedure154,155. It should be pointed out that this rather simple approach to the synthesis of symmetrical sulphoxides has not yet found wider application. 

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. " ... 

When we prepared tetrafluorobenzobarrelene (24) from pentafluoro-phenylmagnesium bromide in the presence of benzene we isolated another compound which, from n.m.r., i.r., and u.v. evidence, was evidently closely related to the compound (24). 

A. 1-Phenyldialin. A solution of phenylmagnesium bromide is prepared in the usual manner 1 from 11 g. (0.45 gram atom) of... 

The preparation reported here is based on the method of Christie and Rapoport.4 9-Bromo-9-phenylfluorene has also been prepared by a light-initiated reaction of bromine and 9-phenylfluorene in carbon disulfide,2 by addition of phenylmagnesium bromide to fluorene36 followed by treatment with acetyl bromide,5 and by treatment of 9-phenylfluorene with N-bromosuccinimide.6... 

Tetraphenylcyclopentadienone has been prepared by the action of phenylmagnesium bromide on benzaldiphenylmaleide,1 and by reduction, dehydration, and oxidation of the methylene-desoxybenzoin obtained by condensing formaldehyde with desoxy-benzoin.2 The present procedure is essentially that of Dilthey.3... 

The described method of preparing 3-benzoylpyridine is a modifica-lion of that of Wolffenstein and Hartwich.2 Other methods of preparing this compound are by the addition of phenylmagnesium bromide to... 

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... 

Freshly opened commercial (Baker and Adamson) anhydrous ether is suitable. The checkers found it more convenient to use commercial phenylmagnesium bromide than to prepare it. They obtained 80 g. (88%) of the ketimine by charging the flask with 175 ml. (0.525 mole) of 3N phenylmagnesium bromide (Arapahoe Chemicals, Boulder, Colorado), then adding 51.5 g. of benzonitrile as described. 

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