• Journal of Photoscience
• /
• v.10 no.3
• /
• pp.241-243
• /
• 2003

Photoreactions of some carbonyl compounds with TiO$_2$ were investigated in methanol. Although 1,3-cyclohexanedione and phthalimide afforded 3-methoxy-2-cyclohexen-l-one and 3-methoxy-1-isoindolinone, respectively, acid anhydrides such as succinic, phthalic, and maleic anhydrides gave the monoesters of dicarboxylic acids in good to excellent yields, when they were irradiated on TiO$_2$ in methanol with 300 nm UV light.

• Journal of Photoscience
• /
• v.10 no.2
• /
• pp.181-184
• /
• 2003

Photochemical reactions of some organic molecules on titanium dioxide were investigated in methanol. A methanolic solution of trans-cinnamic acid and titanium dioxide was irradiated with 300 nm UV lamps for 24 h to afford methyl cinnamate. In the case of trans-cinnamamide, the major product was found to be 3-phenylpropionamide, i.e., a saturation product of ethylenic double bond. However, irradiation of urocanic acid, caffeic acid, ethyl cinnamate, trans-chalcone, trans-cinnamonitrile, trans-stilbene or trans, trans-1,4-diphenyl-1,3-butadiene on titanium dioxide under the same conditions did not give any noticeable products. Meanwhile, when irradiated some aromatic aldehydes, such as trans-cinnamaldehyde, l-naphthaldehyde, and 2-naphthaldehyde in methanol, vicinal diols and alcohols derived from the diols were produced. On the other hand, irradiation of 9-anthraldehyde and titanium dioxide in methanol afforded only alcohols, in which diol was not observed.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.5
• /
• pp.1018-1024
• /
• 2008

Photolysis of 2-(pentamethyldisilanyloxy)phenylpentamethyldisilane 1 in methanol provides five photoproducts 3, 4, 5, 6, and 7. Compounds 3 and 4 were probably formed from the methanol addition reactions of silene intermediate 2 and the formation of 5, 6, and 7 can best be explained by the nucleophilic attack of methanol to silicon atom in pentamethyldisilanyloxy or pentamethyldisilanyl group of the photoexcited state of 1. Irradiation of 1 in n-hexane gives a photoproduct 6 via silyl radical intermediate 8 and a novel intramolecular cyclization photoproduct 11 via silene 9 and silyl radical intermediate 10. Irradiation of 1 in deaerated methylene chloride in the presence of acetone affords a novel photoproduct 11 and phenol 7 but the expected photoproducts from the reaction of the silene intermediate with acetone were not obtained.

• The Journal of Natural Sciences
• /
• v.5 no.1
• /
• pp.59-65
• /
• 1992

In this study, new photosensitive polymers bearing acyloxyimino(AOI) group were prepared and the relationship between photochemical reactions of the polymers and changes of their physical properties was investigated. It was found that main reaction of these copolymers depended on the structure of polymer mainchain. From the view point of amino groups formation, acryl type polymers were superior to methacryl type polymers. On the other hand, in the case of mathacryl type polymers, mainchain scissions and formation of double bonds occurred very effectively. Applications of these copolymers to photofunctional polymers were also discussed.

• Macromolecular Research
• /
• v.9 no.6
• /
• pp.339-344
• /
• 2001

In order to investigate the photoalignment mechanism of nematic liquid crystals on a polymer film, a new photoreactive polymer having chalcone groups as side chains was synthesized. Linearly polarized UV light causes preferential photoreactions of the chalcone unit along the polarization direction and thus induces the anisotrpy in the polymer alignment layer resulting in homogeneous LC alignment perpendicular to the polarization direction. The sequential investigations of photoalignment generated by the preferential E/Z isomerization and (2+2) cycloaddition reactions show that either photoreaction can solely induce the LC alignment in the direction perpendicular to UV polarization.

• Journal of Photoscience
• /
• v.11 no.3
• /
• pp.129-132
• /
• 2004

Photochemically stable dibenzoylmethane and curcumin were cleaved dramatically when they were irradiated in the presence of N,N-dimethylaniline in methanol with 300 nm UV light. Several products such as benzil, secondary product derived from 1,4-diphenyl-1,4-butanedione, and unidentified compound were observed from the photoreactions of dibenzoylmethane with N,N-dimethylaniline. It was also found that one of the primary fragments produced by irradiation of curcumin in methanol were coupled with N,N-dimethylaniline to give a new enone compound, i.e., 1-(4-dimethylaminophenyl)-4-(4-hydroxy-3-methoxyphenyl)-but-3-en-2-one, as the major product.

• Bulletin of the Korean Chemical Society
• /
• v.5 no.1
• /
• pp.32-37
• /
• 1984

The photoreaction of 2, 3-benzo-1, 1-diphenyl (or dimethyl)-1-sila-2-cyclobutene (9 or 10) with an aldehyde or ketone results in 1:1 cycloadduct of [4 + 2] type. In the reactions of 2, 3-benzo-1, 1-dimethyl-1-sila-2-cyclobutene (10) with acetone and butanone, another 1:1 adducts (13) were also formed, respectively. The following facts indicate that the formation of adduct involves an attack of a triplet carbonyl compound on the silicon of the benzosilacyclobutene, an $S_H2$ process. (1) Even when the reaction of 9 with acetophenone was carried out under conditions such that more than 99% of incident light was absorbed only by acetophenone using the filter solution of aq. cupric sulfate, the same adduct was still formed. (2) When the reaction of 9 with acetone was carried out under oxygen atmosphere, only trace amount of adduct was formed.

• Bulletin of the Korean Chemical Society
• /
• v.17 no.6
• /
• pp.506-510
• /
• 1996

The syntheses and photoreactions of haloarenes, in which the aryl and haloaryl moieties are tethered by a simple alkyl group, were studied. For 2-benzyl-1-halobenzene, in which two aryl moieties were connected by methylene group, photoreduced product, diphenylmethane, was obtained along with the minor formation of the photocyclized product, fluorene, in acetonitrile solvent. For 1-halo-2-phenethylbenzene, in which two aryl moieties were connected by ethylene group, photocyclized products, 9,10-dihydrophenanthrene and phenanthrene, were obtained along with the minor formation of photoreduced product, bibenzyl, in acetonitrile solvent. The photoreaction selectivities in several solvent systems were studied: In cyclohexane, 2-benzyl-1-chlorobenzene was photoreduced more effective than 2-benzyl-1-bromobenzene; In the presence of NaOH, 1-halo-2-phenethylbenzenes gave 9,10-dihydrophenanthrene and, in the presence of toluene, they gave phenanthrene. A radical reaction mechanism is proposed for the explanation of the reactions. This study shows that the photoreaction of haloarene, in which haloaryl and aryl moieties are tethered by ethylene group, can be used for ring formation of 9,10-dihydrophenanthrene otherwise difficultly accessible.

• Journal of the Korean Chemical Society
• /
• v.41 no.12
• /
• pp.666-671
• /
• 1997

Photoreactions of pseudosaccharin pyridinemethyl ethers have been investigated. Pseudosaccharin 2-pyridinemethyl ether, pseudosaccharin 4-pyridinemethyl ether and pseudosaccharin 3-pyridinemethyl ether all undergo a facile photoreaction via reaction pathways involving homolysis of the bond between pseudosaccharyl oxygen and pyridinemethyl carbon, and excited nucleophilic substitution of pyridinemethoxy group by solvent, methanol which are not quenched by oxygen present in the reaction. Product yield demonstrates that the homolysis pathway predominates over the nucleophilic substitution.

• Bulletin of the Korean Chemical Society
• /
• v.23 no.1
• /
• pp.35-40
• /
• 2002

Photoreaction of guest organic anions in layered organic-inorganic hybrid materials was investigated. The layered hybrids were synthesized by an anion-exchange reaction of $[LiAl_2(OH)_6]Cl{\cdot}yH_2O$ layered double hydroxide with aqueous (Z,Z)- and (E,E)-muconates under inert atmospheric condition, to give new organicinorganic hybrids of $[LiAl_2(OH)_6]_2[(Z,Z)-C_6H_4O_4]{\cdot}zH_2O$ and $[LiAl_2(OH)_6]_2[(E,E)-C_6H_4O_4]{\cdot}H_2O$, respectively. The basal spacings calculated by XRPD of intercalates indicate that muconate anions have almost vertical arrangements against the host $[LiAl_2(OH)_6]^+$ lattices in the interlayer of organic-inorganic hybrid materials. When UV light was irradiated on the suspension of $[LiAl_2(OH)_6]_2[(Z,Z)-C_6H_4O_4]{\cdot}zH_2O$, the (Z,Z)-muconate anions of the gallery space of hybrids were polymerized in the aqueous media while it was isomerized into more stable (E,E)-muconate in the methanollic suspension in the presence of catalytic amount of molecular iodine. All the products were characterized using elemental analysis, TGA, XRPD, FT-IR, $^1H$ NMR and $^{13}C$ CP-MAS NMR.