Benzylmagnesium chloride 2-

By a similar procedure benzylmagnesium chloride and 2,3-dibromopropene give 4-phenyl-2-bromobutene-i in about 45 per cent yield, b.p. ii9°/20 mm. and heptylmagnesium bromide and 2,3-dibromopropene give 2-bromodecene-i in 60-65 per cent yields, b.p. 76-77°/3 mm. 

From benzylmagnesium chloride and ethyl />-toluenesulfon-ate. Gilman and Beaber, J. Am. Chem. Soc. 47, 518 (1925). 

Using the same procedure, stilbene may be prepared from benzaldehyde and benzylmagnesium chloride in 25-35 per cent yield. 

Baeyer-Villager oxidation, 10, 151, 433 Bamford-Stevens reaction, 402 Barton reaction, 253 Beckmann rearrangement, 140 Benzilic acid rearrangement, 418, 435 3 -Benzoyloxy-7-methylenecholest-5-ene, 60 Benzylmagnesium chloride, 64 3-Benzyloxycholesta-3,5-diene, 342... 

The reaction of benzylmagnesium chlorides wnth thiophenealde-hydes and thienyl ketones has been used for the preparation of styrylthiophenes and 1,2,2-triarylethylenes, which are of biological interest. In stilbene and 1,2,2-triphenylethylene the reactivity toward electrophilic reagents is transferred with deactivation to the double bond. However, styrylthiophene is formylated and acylated... 

Alkylation of 4-hydroxybenzophenone by means of base with 2-ihlorotriethylamine affords the so-called basic ether (29). In a lequence analogous to the preparation of 28, the ketone is first reacted with benzylmagnesium chloride (30). Dehydration (31) and rlilorination complete the synthesis of clomiphene (32). ° It is itf note that the commercial product is in fact a mixture of the... 

The intermediate 1-[p-((3-diethylaminoethoxy)phenyl]-1,2-diphenylethanol was obtained by treating 4-((3-diethylaminoethoxy)benzophenone with benzylmagnesium chloride. It melted at 95° to 96°C. 

The stereospecific conversion of menthyl arenesulphinates into chiral aryl methyl sulphoxides may also be achieved by means of methyllithium . The reaction of methyllithium with diastereoisomerically or enantiomerically pure arenesulph-inamides 283 was found to give optically active aryl methyl sulphoxides 284 (equation 156). The preparation of optically active sulphoxides 285 and 286, which are chiral by virtue of isotopic substitution (H - D and - respectively), involves the reaction of the appropriate non-labelled menthyl sulphinates with fully deuteriated methyl magnesium iodide (equation 157) and with benzylmagnesium chloride prepared from benzyl chloride labelled with carbon (equation 158). 

One mole of benzylmagnesium chloride is prepared in a 2-1. three-neck round-bottom flask from 24.3 g. (1 mole) of magnesium turnings, 126.5 S- C1 m°le) of benzyl chloride and 500 cc. of anhydrous ether, according to the directions given in Org. Syn. 4,59. Stirring should be commenced with the first addition of the benzyl chloride. The time of addition of the benzyl chloride in this preparation is about two hours. When all has been added, the mixture is gently boiled for about fifteen minutes (Note 1). 

N,N,o-trimethyl-, 34, 61 N-Benzylaniline, 36, 22 Benzyl chloride, 34, 65 Benzyl cyanide, 31, 53 32, 64, 65, 92 N-Benzylidenemethylamine, 34, 65 Benzyl isocyanide, 31, 54 Benzylmagnesium chloride, 34, 65 3-Benzyl-3-methylpentanenitkile, 35, 8 3-BENZYL-3-METHYLPENTANOIC ACID, 35, 6 /S-Benzyl-/ -methylvaleric acid, 35, 6 Benzylthiosulfuric acid, 32, 103 Benzyltrimethylammonium hydroxide,... 

The second synthesis involved preparation of the (—)-menthyloxystannane 33 and subsequent displacement of the menthyloxy grouping with benzylmagnesium chloride to afford stannane 34, a i) 4.6, of unknown configuration and enantiomeric purity (equation 6)18. 

Stereoselective synthesis of pseudo C2-symmetrical 1,3-dibenzyldiamino alcohol (S,S) (323) a core unit of HIV protease inhibitors, and the two meso-stereoisomers (323a) and (323b) was achieved by stereocontrolled addition of benzylmagnesium chloride to nitrones (63a) and (63b) (Scheme 2.137). The yield of (S,S)-(323), based on N-Boc-L-phenylalaninal, accounts for 23% (Scheme 2.137) (211). 

With good stirring, benzylmagnesium chloride (34.2 mL) was added dropwise using a syringe. When the addition was complete, the stirring was continued for 12 h whilst the mixture warmed slowly to room temperature. 

The trimethylsilyl radical produced either rapidly dimerizes or reacts with solvent so that very clean ESR spectra of the radical anion, with minimum interactions with the counterion, can be obtained (116). Further reduction to dianions is very slow, and exhaustive reduction to anion radicals minimizes problems associated with exchange between anion radicals and unreduced substrate (115). It now appears that the solvent HMPA greatly facilitates the one-electron reduction, not only for trimethylsilylsodium, but also for organolithium and magnesium reagents (110). It was found that 0.1F solutions of methyl-, n-butyl-, or f-butyllithium or benzylmagnesium chloride will quantitatively reduce biphenyl to its radical anion in less than 10 minutes (110). 

The related 6-trifluoromethyl-l,3-dioxin-4-ones underwent conjugate addition reactions with Gilman reagents, or with Grignards with copper(I) catalysis (Eq. 112). The 6-substituted compounds were also available, and were used to synthesise threonine and aZZo-threonine analogues [303]. Stark contrast between the behaviour of fluorinated and non-fluorinated compounds is revealed in Eq. (113). While benzylmagnesium chloride adds smoothly to the 6-methyl... 

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