THE SYNTHESIS OF NOVEL AROMATIC COMPOUNDS

[摘要] 2-Chloro-1,3-didehydronaphthalene was generated as a reactive intermediate in both the open (diradical) and closed (bicyclo{3.1.0}-hexatriene) forms by treating either 1-bromo-3,4-benzo-6,6-dichlorobicyclo{3.1.0}hexane or 3,4-benzo-1,6,6-trichlorobicyclo{3.1.0}hexane with potassium tert-butoxide in tetrahydrofuran at 0(DEGREES)C. The open form reacts with solvent to produce 2-chloronaphthalene, 2-chloro-1-(2;;-tetrahydrofurfuranyl)naphthalene, and 2-chloro-3-(2;;-tetrahydro-furfuranyl)naphthalene. The closed form reacts with nucleophiles to produce 2,3-dichloronaphthalene, 2-bromo-3-chloronaphthalene, 1,2-dichloronaphthalene, 1-bromo-2-chloronaphthalene, 1,3-di(tert-butoxy)naphthalene, 1-tert-butoxy-2-chloronaphthalene, and 2-tert-butoxy-3-chloronaphthalene. Naphtho{a}cyclopropene was generated in low yield by treating 1-bromo-2-(p-boluenesulfonatomethyl)naphthalene with n-butyl lithium in tetrahydrofuran at -15(DEGREES)C. This compound was characterized by both low temperature nuclear magnetic resonance spectroscopy and by its reaction with tert-butyl alcohol in the presence of silver tetrafluoroborate to produce a mixture of 1 and 2-(tert-butoxymethyl)-naphthalene. The reactions of 2,2-dichloro-1-methylenecyclopropane with potassium tert-butoxide were studied. The products of this reaction were cis and trans-1-tert-butoxybut-1-ene-3-yne. 2-Chloro-1-methylene-cyclopropene is proposed as a reactive intermediate in these reactions.

[发布机构] Rice University