ortho-DIRECTED LITHIATION OF ω-PHENOXYALKANETHIOLS AND N, N-DIMETHYL-ω-PHENOXYALKYLAMINES. CRYSTAL STRUCTURE OF BIS[O-[(2-DIMETHYLAMINO) ETHOXY]PHENYL]-MERCURY

摘要

ω-Phenoxyalkanethiols, PhO(CH2)n SH(n=2-6)were prepared and ortho-metallated with two equivalents of n-butyllithium in tetrahydrofuran/methylcyclohexane.Carboxylation and subsequent acidic hydrolysis of the resultingdilithiated species yielded the corresponding o-(ω-mercaptoalkoxy) benzoic acids in yields ranging from 30 to 78%.The previously reported methodology for the ortho-lithiation of(2-dimethylamino) ethoxy-benzene by n-butyllithium in ether wasextended to higher members of this class, PhO(CH2)n Nme2 withn-2-4. The resulting organolithiums react normally withelectrophilic reagents, benzaldehyde (n=2-4), benzophenone(n=2-4) and dichlorodiphenylsilane (n=2) in yields of 63-77%; inaddition, reaction with 0.5 molar equiv of mercuric dichloride(n=20 afforded the bis[o-(2-dimethylamino) ethoxy]phenyl)mercury in a 78% yield, the crystal structure of which hasbeen determined.