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I. Synthesis of substituted naphthalenes utilizing active nickel. II. Synthesis of substituted naphthoquinones and formation of a charge transfer complex. III. Synthesis of substituted 1,4-diphenyl-2-butenes from (eta(6):eta(6)-1,4-diphenyl-1,3-butadiene)-bis(tricarbonylchromium)
Abstract
Active nickel-mediated cycloaddition of fumaronitrile, diethyl fumarate, or maleic anhydride with 5,6-disubstituted-$\alpha,\alpha\sp\prime$-dibromo-3,6-dimethoxy-o-xylene gave substituted tetrahydronaphthalenes in good yields. Substitution on the 5,6 positions of the o-xylene were bromo, cyano, and hydro. Conversion of the substituted tetrahydronaphthalenes to the fully aromatic naphthalenes was accomplished in very good to excellent yields. Oxidation of 2,3-dicyano-5,8-dimethoxynaphthalene gave 6,7-dicyano-1,4-naphthoquinone in good yield. Bromination gave 2,3-dibromo-6,7-dicyano-1,4-naphthoquinone which had a stable reduction potential close to TCNQ. A charge transfer complex of 2,3-dibromo-6,7-dicyano-1,4-naphthoquinone and tetrathiofulvalene was formed in acetonitrile. Reduction of ($\eta\sp6$:$\eta\sp6$-1,4-diphenyl-1,3-butadiene)bis-(tricarbonylchromium) with two moles of lithium naphthalide produced a stable dianion. Treatment of the dianion with electrophiles, followed by oxidative cleavage of the two tricarbonylchromium groups, yielded 1,4-disubstituted-1,4-diphenyl-2-butenes. Yields were from fair to very good, with increased yields from use of HMPA as a co-solvent. Electrophiles included primary and secondary alkyl halides, alkyl halides with remote cyano and carboethoxy functionality, and benzaldehyde.
Subject Area
Organic chemistry
Recommended Citation
Forkner, Matthew W, "I. Synthesis of substituted naphthalenes utilizing active nickel. II. Synthesis of substituted naphthoquinones and formation of a charge transfer complex. III. Synthesis of substituted 1,4-diphenyl-2-butenes from (eta(6):eta(6)-1,4-diphenyl-1,3-butadiene)-bis(tricarbonylchromium)" (1988). ETD collection for University of Nebraska-Lincoln. AAI8818619.
https://digitalcommons.unl.edu/dissertations/AAI8818619