Benzyl chloride Grignard reagent from

Bis(phenyl acetyl)benzene was obtained from the reaction of 1,4-dicyanobenzene with Grignard reagent of benzyl chloride, mp. 175-177 C ( 54.4% yield ), and recrystallized from ethylQ acetate to yield white or light yellow crystals, mp. 178-180 C. 

In an extension of this work, Schnider and his colleagues condensed the salt (36) with the Grignard reagent from p-methoxy-benzyl chloride. The product (40), on reduction (41) and cyclizar-tion, affords the methoxylated morphinan (41). Removal of the methyl ether affords the narcotic analgesic racemorphan (43). ... 

The Grignard reagent derived from benzyl chloride undergoes ready alkylation with an alkyl toluene-p-sulphonate, a reaction which provides a further useful synthesis of an alkylbenzene (e.g. pentylbenzene, Expt 6.2). 

An acceptable method is to oxidize methyl benzyl carbinol (l-phenyl-2-propanol) to phenylacetone (methyl benzyl ketone) with chrome oxide (CrO3) in pyridine solvent. The problem with this is that methyl benzyl carbinol is not commercially available, and so must be made from benzyl chloride grignard reagent and acetaldehyde. This grignard works well, although there can be a problem getting unreacted benzyl chloride out of the product. Their boiling points are very close, so distillation does not separate them completely. But the real question is Why make the synthesis of phenylacetone a two-step process when it can be done with one reaction ... 

Grignard reagent from -amyl bromide, 16, 41 from benzyl chloride, 10, 4 17, 89 from bromomesitylene, 11, 66 from a-bromonaphthalene, 11, 80 from 2-bromopentane, 11,84 from -butyl bromide, 15,11 from ethyl bromide, 11, 98 17, 48 from iso propyl bromide, IS, 48... 

Another approach for the total synthesis of anisomycin derivatives from (+)-tartaric acid has been reported via the N -benzyl tartarimide (95) (Scheme 11) [89]. Thus, (+)-tartaric acid was refluxed with benzyl amine in a xylene solution to give 95, which was subjected to reaction with the Grignard reagent of anisyl chloride in THF to give the keto-amide 96 in 55% yield. 

The Grignard reagent obtained from benzyl chloride was reported to give high yields of benzyltrimethylsilane when reacted with TMClSi [108], [109] with some 1,2-diphenylethane the one-step procedure with benzyl bromide, magnesium and TMClSi in diethyl ether [110] also gave excellent yields of the... 

The ketone 15 was eventually prepared by Grignard addition to Weinreb amide 21, as shown in Scheme 5.5. The Weinreb amide 21 was prepared from p-iodobenzoic acid (20). The phenol of readily available 3-hydroxybenzaldehyde (22) was first protected with a benzyl group, then the aldehyde was converted to chloride 24 via alcohol 23 under standard conditions. Preparation of the Grignard reagent 25 from chloride 24 was initially problematic. A large proportion of the homo-coupling side product 26 was observed in THF. The use of a 3 1 mixture of toluene THF as the reaction solvent suppressed this side reaction [7]. The iodoketone 15 was isolated as a crystalline solid and this sequence was scaled up to pilot plant scale to make around 50 kg of 15. 

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