Chemistry and Chemical Biology ETDs

Publication Date

2-20-1976

Abstract

With the goal of synthesizing 1-deaza-1-thialysergic acid (31), a series of substituted 2-stilbazole precursors of 31 was prepared.

313, R1=SCH3, R2=H

314, R1=SOCH3, R2=H

315, R1=SO2CH3, R2=H

173, R1=H, R2=COOC2H5

152, R1 =SCH3, R2=COOC2H5

162, R1=SOCH3, R2=COOC2H5

153, R1=SO2CH3, R2=COOC2H5

In connection with the synthesis of the 2-stilbazoles, a new synthesis was developed for the preparation of o-(methylthio)benzaldehyde (150) by the active manganese dioxide oxidation of o-methylthiobenzyl alcohol (320). 2-Stilbazoles 173, 313 and 152 were prepared by the condensation of benzaldehyde or 150 with either 2-picoline (249) or ethyl 6-methylnicotinate (151). Reaction of 152 and 313 with 1.05 equivalents of sodium metaperiodate at room temperature gave sulfoxides 162 and 314, whereas reaction of 152 and 313 with excess sodium metaperiodate in refluxing methanol-water gave sulfones 153 and 315, respectively. A scheme for the total synthesis of 31 was suggested and a key intermediate in this scheme, 2-ethoxycarbonyl-7-methylsulfonylbenzo[f]quinoline (154), was prepared by the photocyclization of 153. Similarly, model compounds 160 and 204 were prepared by the photocyclization of 173 and 315, respectively. The structure of photoproduct 160 was proved by an independent, non-photochemical synthesis.

154, R1=SO2CH3, R2=COOC2H5

160, R1=H, R2=COOC2H5

204, R1=SO2CH3, R2=H

Finally, initial investigations of the feasibility of a proposed intramolecular Michael reaction of 154 to give 155 were carried out with the methiodide derivative 389 of 2-stilbazole 315. Dimsyl sodium appeared to react with 389 in an SN2 manner at the pyridinium methyl carbon atom to give 315 as a leaving group instead of the expected reaction, formation of a carbanion at the methylsulfonyl group of 389.

Project Sponsors

The Petroleum Research Fund administered by the American Chemical Society, the National Science Foundation

Language

English

Document Type

Dissertation

Degree Name

Chemistry

Level of Degree

Doctoral

Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

Eleftherios Paul Papadopoulos

Second Committee Member

Douglas C. Neckers

Third Committee Member

Guido Herman Daub

Fourth Committee Member

Ulrich Hollstein

Fifth Committee Member

Richard Willis Holder

Sixth Committee Member

Thomas W. Whaley

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