
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
Recommended Citation
Beller, Nicholas Richards. "Syntheses Directed Toward the Construction of 1-Deaza-1-Thialysergic Acid." (1976). https://digitalrepository.unm.edu/chem_etds/221