Heme and heme proteins are ubiquitous in nature and play many
varied and important biological functions. The biological properties of
the heme proteins are dependent on the interaction between the metal and
the porphyrin where each is dependent on the other to carry out specific
functions.
This thesis describes the syntheses of affinity ligands and monoazaporphyrins.
The synthesis of the ligand was based on a protoporphyr
in-IX derivative substituted on either the 2- or 4-vinyl group. The two
isomeric affinity ligands, 73 and 74 (2- or 4- substituted) were
synthesized from protoporphyrin-IX di-tert-butyl ester 106b by conversion
of the vinyl groups to monoformyl derivatives 122b (or 123b) via the
intermediacy of photoprotoporphyrin-IX derivatives. The spacer chain [formula omitted] using a formyl group was extended by Knoevenagel condensation with
malonic acid to give monoacrylic acid derivatives 132 (or 133). This
chain was further extended by linking an aliphatic diamine (1,3-diaminopropane)
to the monoacrylic acid derivatives 132 (or 133) through an
acid chloride mediated amide linkage.
The Fe(III) and Co(II) complexes of the affinity ligand (73 + 74)
were prepared and the tertiary butyl groups were removed by treatment
with trifluoroacetic acid at room temperature to give 71 and 72. [formula omitted] An improved synthesis of monoazaporphyrins (5-aza) (see p.iv) is
described in this work (section 3.4). Our approach consists of
constructing 1,19-dibromo-l,19-dideoxybiladiene-ac dihydrobromides which
were subsequently cyclized, to give corresponding monoazaporphyrins in
high yields, using dibenzo-18-crown-6 as a phase transfer agent for the
transfer of an azide ion. [formula omitted] / Science, Faculty of / Chemistry, Department of / Graduate
| Identifer | oai:union.ndltd.org:UBC/oai:circle.library.ubc.ca:2429/41441 |
| Date | January 1987 |
| Creators | Singh, Jai Prakash |
| Publisher | University of British Columbia |
| Source Sets | University of British Columbia |
| Language | English |
| Detected Language | English |
| Type | Text, Thesis/Dissertation |
| Rights | For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use. |
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