Vinyl phenyl carbinol

The reaction of crotonaldehyde and methyl vinyl ketone with thiophenol in the presence of anhydrous hydrogen chloride effects conjugate addition of thiophenol as well as acetal formation. The resulting j3-phenylthio thioacetals are converted to 1-phenylthio-and 2-phenylthio-1,3-butadiene, respectively, upon reaction with 2 equivalents of copper(I) trifluoromethanesulfonate (Table I). The copper(I)-induced heterolysis of carbon-sulfur bonds has also been used to effect pinacol-type rearrangements of bis(phenyl-thio)methyl carbinols. Thus the addition of bis(phenyl-thio)methyllithium to ketones and aldehydes followed by copper(I)-induced rearrangement results in a one-carbon ring expansion or chain-insertion transformation which gives a-phenylthio ketones. Monothioketals of 1,4-diketones are cyclized to 2,5-disubstituted furans by the action of copper(I) trifluoromethanesulfonate. ... 

A more recent synthesis for (14-9) takes quite a different course. The first step comprises the displacement of one of the halogens in 1,4-dibromobenzene by the alkoxide from A-2-hydroxyethylpyrrolidine (15-2) in the presence of 18-crown ether to afford (15-3). Condensation of the lithium salt from (15-3) with 6-methoxy-tetralone (15-4) followed by dehydration of the initially formed carbinol give the intermediate (15-5), which incorporates the important basic ether. Reaction of that compound with pridinium bromide perbromide leads to the displacement of the vinylic proton by halogen and the formation of bromide (15-6). Condensation of that product with phenylboronic acid in the presence of a tetrakistriphenyl-phosphine palladium catalyst leads to the coupling of the phenyl group by the formal displacement of bromine. The product (14-9) is then taken on to lasoxifene (14-11) as above [16]. 

The current product range of developmental samples covers monofunctional fluids of aminoalkyl, chloroalkyl, vinyl, and (meth)acryloyl types. Molecular mass is 1700 and 4000 Da, and product viscosities reach from 15 to about 80 mPas. The appearance of the fluids is optically clear and colorless to slightly amber. Technologically accessible future fiuictionalities include carbinol, epoxide, substituted phenyl, hydrosilyl, carboxy, sulfhydryl, polyglycol, and other groups (see literature attached). In Fig. 2, currently available products are sketched. 

This reaction was initially studied by Anschutz between 1879 and 1886. It is the synthesis of anthracene from vinyl bromide and benzene in the presence of aluminum chloride. In addition, methyl phenyl carbinol or 1,1-diphenyl ethane can also be converted into anthracene derivative in the presence of aluminum chloride. 

Much of the work in this area has focussed on polymeric dyes which can participate in redox reactions. Early work by Manecke and Kossmehl on vinyl Malachite Green (VMG) is specially significant as it established a simple method of entry into the polymerizable triphenylmethane class of dyes. Thus the carbinol base form (ill) of VMG was synthesized by a Grignard reaction between vinyl-phenyl magnesium chloride (l) and Michler s ketone (ll). 

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