Synthetic approaches to and mass spectrometry of alkylpyrimidines

Bell, Dennis John (1987). Synthetic approaches to and mass spectrometry of alkylpyrimidines PhD Thesis, School of Molecular and Microbial Science, The University of Queensland. doi:10.14264/uql.2015.556

Attached Files (Some files may be inaccessible until you login with your UQ eSpace credentials)
Name Description MIMEType Size Downloads
THE6105.pdf Thesis (fulltext) application/pdf 4.76MB 2

Author Bell, Dennis John
Thesis Title Synthetic approaches to and mass spectrometry of alkylpyrimidines
School, Centre or Institute School of Molecular and Microbial Science
Institution The University of Queensland
DOI 10.14264/uql.2015.556
Publication date 1987
Thesis type PhD Thesis
Supervisor R. F. Evans
Total pages 231
Language eng
Subjects 03 Chemical Sciences
Formatted abstract
Two interrelated research topics are presented in this thesis.

Initially the preparation of a series of ring deuterium labeled alkylpyrimidines and side chain deuterium labeled methylpyrimidines has been described. Exchange of the hydrogen atoms for deuterium atoms on the methyl groups of the 2- and 4(6)-positions of the ring was readily achieved through the use of hydrochloric acid-d. In order to replace the hydrogen atoms by deuterium atoms directly on the 2- and 4(6)-positions of the ring a catalytic deuteriumolysis of a ring chlorinated alkyIpyrimidine was required, through use of deuterium gas with palladium on charcoal as the catalyst.

From a comparison of the low resolution spectra of the isotoplcally labeled and unmodified alkylpyrimidines together with accurate mass measurements and metastable defocusing results the decomposition pathways and intermediate ion structures, consistent with this data, have been proposed.

The second portion of this thesis investigated the nucleophilic displacement of a chloro substituent upon a pyrimidine ring, with or without alkyl substituents, using the anions of either ethyl isobutyrate, diethyl malonate or methyl diethyl malonate as the nucleophiles. It was intended that these substituents introduced could be used as precursors to deuterium labeled alkyl groups through a suitable synthetic sequence.

With a monochlorinated pyrimidine displacement of a chloro substituent could only be achieved at the 2-positlon of the ring. It was also found that either a 2,4- or 4,6-dichlorInated pyrimidine In addition to a 2,4,6- trichlorinated pyrimidine were more reactive than the monochlorinated species and gave displacement of the chloro substituent on the 4(6)-position of the ring. The thermal decomposition of a di(ethoxycarbonyl)all substituent on a pyrimfdine ring through deethoxycarbonylation was however an everpresent complication.

An account was also presented of the tautomeric forms detected in some di(ethoxycarbonyl)methyl substituted pyrimidines.
Keyword Alkyl pyrimidines
Mass spectrometry

Document type: Thesis
Collection: UQ Theses (RHD) - UQ staff and students only
Citation counts: Google Scholar Search Google Scholar
Created: Tue, 27 Jan 2015, 16:35:54 EST by Mary-Anne Marrington on behalf of Scholarly Communication and Digitisation Service