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A photochemical study of dibenzobarrelene amides and ester-amides: solution and solid state rearrangements Rattray, Alistair Graham McLeod
Abstract
The photochemical reactions of various dibenzobarrelene acyl derivatives has been investigated in solution and in the solid state. These derivatives consisted of monoamides, symmetrical diamides, mixed ester-amides, and mixed ester-thioesters. The two types of reactions found in the irradiation of these systems were the di-π-methane rearrangement and/or hydrogen abstraction. Photolysis of dibenzobarrelene monoamides in solution and in the solid state gave a symmetrical dibenzosemibullvalene photoproduct. Two monoamides (R,R = Bz and R,R = iPr) gave ring-fused spiro β-lactam analogues of the starting materials in addition to the semibullvalene product. These two amides also gave an ethano-bridged monosubstituted amide photoproduct as did a third monoamide (R,R = Et). Photolysis of all monoamides in the solid state resulted in the formation of semibullvalenes only. X-ray crystallographic analysis of the diethyl and the di-iso-propyl starting materials were performed in order to correlate the lack of hydrogen abstraction in solid state irradiations with the geometric constraints of the crystalline starting material. An X-ray crystallographic analysis of the dibenzyl amide-derived β lactam was also performed in order to establish the relationships between the various stereochemical centres in the molecule. A series of symmetrical diamides was prepared and photolyzed in solution and in the solid state. All diamides gave a single semibullvalene photoproduct upon irradiation in solution. Two of the starting materials (N,N-dimethyl and N,N-diethyl) also reacted rapidly and efficiently in the solid state to give the semibullvalene product, whereas two others (N-methyl and N-ethyl) were found to be very unreactive in the solid state. [more abstract]
Item Metadata
Title |
A photochemical study of dibenzobarrelene amides and ester-amides: solution and solid state rearrangements
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Creator | |
Publisher |
University of British Columbia
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Date Issued |
1991
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Description |
The photochemical reactions of various dibenzobarrelene acyl derivatives has
been investigated in solution and in the solid state. These derivatives consisted of monoamides, symmetrical diamides, mixed ester-amides, and mixed ester-thioesters. The
two types of reactions found in the irradiation of these systems were the di-π-methane
rearrangement and/or hydrogen abstraction.
Photolysis of dibenzobarrelene monoamides in solution and in the solid state gave
a symmetrical dibenzosemibullvalene photoproduct. Two monoamides (R,R = Bz and
R,R = iPr) gave ring-fused spiro β-lactam analogues of the starting materials in addition
to the semibullvalene product. These two amides also gave an ethano-bridged
monosubstituted amide photoproduct as did a third monoamide (R,R = Et). Photolysis of
all monoamides in the solid state resulted in the formation of semibullvalenes only. X-ray
crystallographic analysis of the diethyl and the di-iso-propyl starting materials were
performed in order to correlate the lack of hydrogen abstraction in solid state irradiations
with the geometric constraints of the crystalline starting material. An X-ray
crystallographic analysis of the dibenzyl amide-derived β lactam was also performed in
order to establish the relationships between the various stereochemical centres in the
molecule.
A series of symmetrical diamides was prepared and photolyzed in solution and in
the solid state. All diamides gave a single semibullvalene photoproduct upon irradiation
in solution. Two of the starting materials (N,N-dimethyl and N,N-diethyl) also reacted
rapidly and efficiently in the solid state to give the semibullvalene product, whereas two
others (N-methyl and N-ethyl) were found to be very unreactive in the solid state. [more abstract]
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Extent |
9077801 bytes
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Genre | |
Type | |
File Format |
application/pdf
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Language |
eng
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Date Available |
2008-12-17
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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 |
10.14288/1.0061742
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URI | |
Degree | |
Program | |
Affiliation | |
Degree Grantor |
University of British Columbia
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Graduation Date |
1992-05
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Campus | |
Scholarly Level |
Graduate
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Aggregated Source Repository |
DSpace
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Item Media
Item Citations and Data
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.