Phenylmagnesium bromide 2-

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). 

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. 

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. 

PhenyI-4-benzylidene-5(4H)-thiazolinone (206) reacts with benzene under Friedel-Crafts conditions or with phenylmagnesium bromide to... 

Use curved arrows to show the flow of electrons in the reaction of butyllithium with water and that of phenylmagnesium bromide with methanol J... 

Addition of phenylmagnesium bromide to 4 tert butylcyclohexanone gives two isomeric ter tiary alcohols as products Both alcohols yield the same alkene when subjected to acid catalyzed dehydration Suggest reasonable structures for these two alcohols... 

The addition of phenyllithium to 6-arylpyridazin-3(2Er)-one takes place at position 6 to give 6-aryl-3-oxo-6-phenyl-l,2,3,4-tetrahydropyridazine and the reaction of 6-aryl-2,4-diphenylpyridazin-3(2H)-one with phenyllithium or phenylmagnesium bromide affords 6-aryl-2,3,4,6-pentaphenyl-l,2,3,4-tetrahydropyridazine (80S457). 

The reaction of cinnoline 2-oxide with phenylmagnesium bromide gives phenanthrene, trans- and cfs-stilbene, 2,3-diphenyl-l,2-dihydrocinnoline and 2-styrylazobenzene in yields of 1-15%. Analogous results are also obtained from 4-methylcinnoline 2-oxide. 

Addition of phenylmagnesium bromide to phthalazin-l(2//)-one or derivatives like 4-phenylphthalazin-l(2/f)-one, 4-phenylphthalazine-l(2/f)-thione and 2-substituted phthalazin-l(2//)-ones results in the formation of 1,4-diphenylphthalazines, while addition of organolithium compounds to phthalazin-l(2/f)-one gives the 4-substituted derivative. 

Reaction of pyridazine 1-oxide with phenylmagnesium bromide gives 1,4-diphenyl-butadiene as the main product and l-phenylbut-l-en-3-yne and 3,6-diphenylpyridazine as by-products, while alkyl Grignard reagents lead to the corresponding 1,3-dienes exclusively (79JCS(P1)2136>. 

Aryl-2-phenyl-4,5-dihydropyridazin-3(2//)-ones react either with phenylmagnesium bromide or with phenyllithium to give 6-aryl-2,6-diphenyl-l,4,5,6-tetrahydropyridazin-3(2//)-ones (135) (products of 1,2-addition to the azomethine bond), while 2-methyl-6-phenyl-4,5-dihydropyridazine-3(2//)-one reacts with two equivalents of phenylmagnesium bromide at the carbonyl and azomethine group to produce 2-methyl-3,3,6,6-tetraphenyl-hexahydropyridazine (136) (Scheme 53) (80JPR617). 

Methyl-2-phenyl-5-oxazolinone (196) with phenylmagnesium bromide gives (197) (65AHC(4)75). 

Reaction of quaternized isoxazolin-5-ones with phenylmagnesium bromide produced a chalcone and dibenzoylethane. Those 5-ones with a 4,4-disubstituent undergo addition of the Grignard reagent to give a 5-ol (Scheme 63) (73BSF3079). 

Despite the strained nature of the azetidin-2-one system, a surprising number of transformations in which the /3-lactam is preserved can be carried out, and some of these will be dealt with in subsequent sections. The highly hindered /3-lactam l-benzyl-3,3,4-triphenyl-azetidin-2-one is claimed to be stable towards hydrochloric acid, sodium and potassium hydroxides, LAH and phenylmagnesium bromide (80IJC(B)702). 

The yield is decreased by about 10 per cent if only an equivalent molecular quantity of phenylmagnesium bromide is used. 

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. 

An extension ot this reaction provides a number of other perfluorovinylic halides [54] The type of reaction products from the thermal decomposition reaction and the type of hydrocarbon Grignard reagent used in the exchange reaction are solvent-dependent When an excess ot phenylmagnesium bromide is used, a variety of phenylated products are formed depending on the excess amount used [4S (equation 23)... 

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