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Studies toward the chemistry of N-confused porphyrins Xiao, Ziwei
Abstract
The objectives of this work were to study the chemistry of N-confused porphyrins, which is a porphyrin isomer with an inverted pyrrole ring, and to develop new photosensitizers based on N-confused porphyrins for photodynamic therapy (PDT). Alkylation reactions of N-confused porphyrins were studied. N-confused tetraarylporphyrins reacted with CH₃ I in the presence of Na₂C0₃ to yield N,N'-dimethylated N - confused porphyrin salts 103 - 107, which are mixtures of structural isomers. The structures of the major isomers (III) were determined by X-ray diffraction and NMR spectroscopic analyses. These N,N'-dimethylated N-confused tetraarylporphyrin salts can generate singlet oxygen when irradiated with light of the appropriate wavelengths and are potential photosensitizers for PDT. The peripheral carbon-nitrogen double bonds of Ni(II) N-confused porphyrins are partially isolated from the 18 π conjugated aromatic system and reacted as dienophiles in Diels- Alder reactions with o-benzoquinodimethane yielding novel Ni(II) N-confused isoquinoporphyrins 133 (a-c). Ni(II) N-confused tetraphenylisoquinoporphyrin, 133a, was structurally characterized by X-ray diffraction analysis. Reaction of Ni(II) N-confused tetrakis(p-tolyl)porphyrin with NaOCH₃ and DDQ resulted in the inner C(21) cyanide addition product 146. Minor product 145 was presumably formed by subsequent nucleophilic addition of CH₃O⁻ to 146 at C(3) followed by oxidation with DDQ. Structures of both complexes 145 and 146 were determined by X-ray diffraction analyses. The Ni(III) complex of N-confused porphyrin inner C-oxide 153 was synthesized from oxidation of the precursor Ni(II) N-confused porphyrin using OSO₄. This Ni(III) complex has been structurally characterized.
Item Metadata
Title |
Studies toward the chemistry of N-confused porphyrins
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Creator | |
Publisher |
University of British Columbia
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Date Issued |
2003
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Description |
The objectives of this work were to study the chemistry of N-confused porphyrins, which
is a porphyrin isomer with an inverted pyrrole ring, and to develop new photosensitizers based
on N-confused porphyrins for photodynamic therapy (PDT).
Alkylation reactions of N-confused porphyrins were studied. N-confused
tetraarylporphyrins reacted with CH₃ I in the presence of Na₂C0₃ to yield N,N'-dimethylated N -
confused porphyrin salts 103 - 107, which are mixtures of structural isomers. The structures of
the major isomers (III) were determined by X-ray diffraction and NMR spectroscopic analyses.
These N,N'-dimethylated N-confused tetraarylporphyrin salts can generate singlet oxygen when
irradiated with light of the appropriate wavelengths and are potential photosensitizers for PDT.
The peripheral carbon-nitrogen double bonds of Ni(II) N-confused porphyrins are
partially isolated from the 18 π conjugated aromatic system and reacted as dienophiles in Diels-
Alder reactions with o-benzoquinodimethane yielding novel Ni(II) N-confused
isoquinoporphyrins 133 (a-c). Ni(II) N-confused tetraphenylisoquinoporphyrin, 133a, was
structurally characterized by X-ray diffraction analysis.
Reaction of Ni(II) N-confused tetrakis(p-tolyl)porphyrin with NaOCH₃ and DDQ
resulted in the inner C(21) cyanide addition product 146. Minor product 145 was presumably
formed by subsequent nucleophilic addition of CH₃O⁻ to 146 at C(3) followed by oxidation with
DDQ. Structures of both complexes 145 and 146 were determined by X-ray diffraction analyses.
The Ni(III) complex of N-confused porphyrin inner C-oxide 153 was synthesized from
oxidation of the precursor Ni(II) N-confused porphyrin using OSO₄. This Ni(III) complex has
been structurally characterized.
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Extent |
7900407 bytes
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Genre | |
Type | |
File Format |
application/pdf
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Language |
eng
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Date Available |
2009-11-12
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Provider |
Vancouver : University of British Columbia Library
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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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DOI |
10.14288/1.0061223
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URI | |
Degree | |
Program | |
Affiliation | |
Degree Grantor |
University of British Columbia
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Graduation Date |
2003-05
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Campus | |
Scholarly Level |
Graduate
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Aggregated Source Repository |
DSpace
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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.