• Journal of Photoscience
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• v.11 no.32
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• pp.75-76
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• 2004

${\alpha}$,${\alpha}$-Dibromovalerophenone and ${\alpha}$,${\alpha}$-dichlorovalerophenone were prepared and their photochemical behaviors were investigated. The former gives C-Br cleavage products and the latter gives mainly the Yang photocyclization products upon irradiation. The reactivity of the chlorine substituted ketone turned out to be quite different from that of ${\alpha}$,${\alpha}$-difluorovalerophenone which gives both the cyclization and elimination products from the 1,4-biradical intermediate.

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.857-860
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• 1994

We have calculated the ${\pi}$-electron density, atom self-polarizability, and free valence on each atom of N-(2-chlorobenzyl)-pyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-2-chloropyridinium salts using a simple Huckel method in order to discuss their intramolecular photocyclization reaction in a qualitative method. Our calculation qualitatively predicts that photocyclization occurs through forming radicals as a reaction intermediate by breaking a C-Cl bond after photoexcitation into a triplet state via intersystem crossing from an initially excited singlet state. We noticed that this C-Cl bond breaking is aided by ${\pi}$-complex formation between a chlorine atom and the ${\pi}$ -electrons of the neighboring ring in the triplet state and a stronger ${\pi}$-complex bond makes C-Cl bond breaking, i.e., radical formation, much easier. A chlorine atom will form a stronger ${\pi}$ -complex bond to a benzyl ring of N-(benzyl)-2-chloropyridinium than a pyridinium ring of N-(2-chlorobenzyl)-pyridinium because the former can donate its ${\pi}$-electron more easily than the latter. The chlorine at position 15 of N-(2-chlorobenzyl)-2-chloropyridinium salt in the excited state also provides its ${\pi}$-electron to the benzyl ring. So this ${\pi}$-electron can increase the bond strength of the $\pi-complex.$ Therefore, the strength of ${\pi}$-complex follows the order of N-(2-chlorobenzyl)-2-chloropyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-pyridinium salts and thus the radical formation rate. This provides us with an intramolecular photocyclization reaction rate of the same order as given above.

• Bulletin of the Korean Chemical Society
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• v.18 no.2
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• pp.141-142
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• 1997

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.270-271
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• 1990

• Journal of Photoscience
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• v.1 no.1
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• pp.39-45
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• 1994

Haloarene in which the phenyl group and halophenyl group are connected by alkyl groups were synthesized to study the photochemical behavior. The photochemical reactions of 1-halo-2-(phenylalkyl)enzenes (1 and 2) were studied in several aerated or unaerated solvents. In the case of 2-benzyl-1-halobenzene photoreduced product (biphenyl) is major in acetonitrile or benzene. In cyclohexane or acetonitrile with triethylamine, photoreduced product is obtained exclusively, while in acetonitrile with toluene, xylene, or sodium hydroxide photocyclized product (fluorene) is mainly obtained. In the case of 1-halo-2-phenethylbenzenes (5 and 6), photocyclized product (9,10-dihydrophenanthrene and phenanthrene) are major in acetonitrile or benzene. While the haloarenes 1 or 2 connecting the two arene rings by methylene is photoreduced, the other haloarene 5 or 6 connecting by ethylene is photocyclized. In cyclohexane or acetonitrile with a small amount of triethylamine, photoreduced reactions of 5 or 6 mainly occur. In acetonitrile with sodium hydroxide, toluene, or xylene, photocyclization of 5, 6 occur exclusively. The triplet state is mainly involved in the photocyclization of 5 or 6, because of the inhibition of oxygen.

• Rapid Communication in Photoscience
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• v.3 no.4
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• pp.73-75
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• 2014

Novel diphenylphenanthrenes (DPPs) were prepared by a photocyclization method, and the substituent effects of the phenyl groups on the photophysical properties of the phenanthrene chromophore were investigated based on measurements of fluorescence yields, lifetimes, and transient absorption. Fluorescence activities in DPPs are increased by introducing phenyl rings that can enhance the transition moment along the short axis of the phenanthrene skeleton. Intersystem crossing from the fluorescent states to the triplet manifolds is shown to be operative through the triplet-triplet absorption spectra obtained by laser photolysis techniques.

• Journal of Photoscience
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• v.8 no.3_4
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• pp.99-104
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• 2001

Studies have been conducted to explore single electron transfer (SET) promoted photocyclization reactions of ($\omega$-phthalimidoalkylthio)acetic acids (alkyl=ethyl, n-propyl, n-butyl, n -hexyl and n-nonyl). Photocyclizations occur in methanol in modest yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the carboxylic group. The initially formed cyclized products undergo efficient water eliminations to produce enthiol ethers in secondary ground state reactions.

• Journal of the Korean Chemical Society
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• v.23 no.3
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• pp.119-124
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• 1979

The cyclization of o-terphenyl type compounds were interpreted by means of orbital symmetry theory and energy correlation diagram. Results show that the cyclization of o-terphenyl type compounds are photocyclization. This agrees with the experimental result and other theoretical ones.

• Bulletin of the Korean Chemical Society
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• v.32 no.2
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• pp.503-509
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• 2011

New types of lariat type crown ethers containing peptide sidearms were prepared by using a novel strategy employing single electron transfer (SET)-induced photocyclization reactions of $\alpha$-silylether terminated phthalimides. Reactions of chiral substrates in this series produced diastereomeric mixtures of crown ether products as a result of the formation of new stereogenic center generation in the photocyclization process.

• Bulletin of the Korean Chemical Society
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• v.20 no.5
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• pp.539-542
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• 1999

The diastereoselectivity in the photocyclization of α-(o-ethylphenyl)acetophenone(1) to 1-methyl-2-phenyl-2-indanol was studied in zeolites X and Y, and compared with that in isotropic solvents. The yields of E-diastereomer at the irradiation of 1 in protic solvents were higher than those in aprotic solvents. The ratios of E-diastereomer to Z-diastereomer in zeolites X and Y were much higher than those in isotropic solvents. The E/Z ratios at the irradiation of 1 in zeolites X were also found to be dependent on the cations present. As the cation size increased from Li+ to Cs+, the ratio decreased. However, any pattern in the E/Z ratios was not found in zeolites Y. The diastereoselectivity observed in the zeolites was interpreted by the conformational restriction imposed by the cavity size. An efficient oxidation of 1 in zeolites RbX and CsX was also observed.