Abstract
dc:description.abstractThe synthesis of <i>ortho</i>-halogenated pyridine derivatives (A-D; R = CN, CO<sub>2</sub>Et; R<sub>1</sub> = CN, CO<sub>2</sub>Me, CO<sub>2</sub>Et) containing methylene groups activated by the nitrile or ester functionality is described. Derivatives (A-D) are reacted with carbon disulfide in the presence of base, followed by alkylation with iodomethane, to afford novel thienopyridines (E-H; R = CN, CO<sub>2</sub>Et; R<sub>1</sub> = CN, CO<sub>2</sub>Me, CO<sub>2</sub>Et; X = SMe).<br/><br/>Pyridine derivative (B; R = CN) also reacts with phenyl isothiocyanate to form thienopyridine (F; R = CN; X = NHPh). Reaction of the nitriles (A, C and D; R, R<sub>1</sub> = CN) under identical conditions, however, does not give the bicyclic compounds but ketene dithioacetals (I, J and K). Increasing the reaction temperature allows formation of thienopyridines (E, G and H; R, R<sub>1</sub> = CN; X = NHPh). Thienopyridines R = CO<sub>2</sub>Et; R<sub>1</sub> = CO<sub>2</sub>Me, CO<sub>2</sub>Et; X = NHPh) are also synthesised from the ruction of the derivatives (A-D; R = CO<sub>2</sub>Et; = CO<sub>2</sub>Me; CO<sub>2</sub>Et) with phenyl isothiocyanate.<br/><br/>Reaction of nitrile (A; R<sub>1</sub> = CN) with carbon disulfide in the presence of base, followed by quenching with ethyl chloroacetate affords thienopyridine (E; R1 = CN; X = SCH<sub>2</sub>CO<sub>2</sub>Et) which in turn cyclises with base to give tricyclic compound (L).<br/><br/>Thienopyridines (E; R<sub>1</sub> = NH<sub>2</sub>; X = CN, Ph, CO<sub>2</sub>Et, COMe, COPh, COCH<sub>2</sub>CO<sub>2</sub>Et) are synthesised from reactions of 3-cyanopyridine-2(lH)-thione with compounds containing a halogen atom adjacent to an active methylene group.<br/><br/>Nucleophilic reactions of thienopyridines (E; R<sub>1</sub> = CN; X = SMe, SOMe, SO<sub>2</sub>Me) are investigated, in an attempt to prepare tricyclic compounds.
Degree
thesis:*- Name dc:type.qualificationname
- PhD
- Level dc:type.qualificationlevel
- Doctoral Thesis
- Year dc:date.issued
- 1992
Author and committee
dc:creator, dc:contributor.*- Author dc:creator
-
- Wilson, Kenneth
- Advisor dc:contributor.advisor
-
- Bremner, David
Rights
- Language dc:language
- eng
Identifiers
dc:identifier.*- Identifier
- oai:rke.abertay.ac.uk:studenttheses/a399e9f6-e2c3-4dc4-81a8-85aa2e0614e6
- OAI identifier oai:identifier
- oai:rke.abertay.ac.uk:studenttheses/a399e9f6-e2c3-4dc4-81a8-85aa2e0614e6