• Bulletin of the Korean Chemical Society
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• v.23 no.9
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• pp.1229-1258
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• 2002

This paper reports the photochemical reduction of benzil 1 to benzoin 2 and the reduction of 2 to hydrobenzoin 4 in deoxygenated solvents in the presence of triethylamine (TEA) and/or TiO2. Without TEA or TiO2, the photolysis of 1 resulted in very low yield of 2. The presence of TEA or TiO2 increased the rate of disappearance of 1 and the yield of 2, which were further increased considerably by the presence of water. The photoreduction of 1 to 2 proceeds through an electron transfer to 1 from TEA or hole-scavenged excited TiO2 followed by protonation. In the reaction medium of 88 : 7 : 2 : 3 CH3CN/CH3OH/H2O/TEA with 2.5 $㎎/m{\ell}$ of TiO2, the yield of 2 was as high as 85 % at 50 % conversion of 1. The photolysis of 2 in homogeneous media resulted in photo-cleavage to benzoyl and hydroxybenzyl radicals, which are mostly converted to benzaldehyde. The reduction product 4 is formed in low yield through the dimerization of hydroxybenzyl radicals. The addition of TEA increased the conversion rate of 2 and the yield of 4 significantly. This was attributed to the scavenging effect of TEA for benzoyl radical to produce N,N-diethylbenzamide and the photoreduction of benzaldehyde in the presence of TEA. The ratio of $(\pm)$ and meso isomers of 4 obtained from the photochemical reaction is about 1.1. This ratio is the same as that from the photochemical reduction of benzaldehyde in the presence of TEA. In the TiO2-sensitized photochemical reduction of 2, meso-4 was obtained in moderate yield. The reduction of 2 to 4 proceeds through two consecutive electron/proton transfer processes on the surface of the photocatalyst without involvement of ${\alpha}-cleavage$. The radical 11 initially formed from 2 by one electron/proton process can also combine with hydroxy methyl radical, which is generated after hole trapping of excited TiO2 by methanol, to produce 1,2-diphenylpropenone after dehydration reaction.

• Korean Chemical Engineering Research
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• v.58 no.4
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• pp.618-623
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• 2020

Spherical phenolic resin beads were synthesized by suspension polymerization at 98 ℃ from phenol, ortho-cresol, formaldehyde, with triethylamine as a basic catalyst, and spherical phenol-cresol copolymer resin beads with relatively low crosslinking density as well. Phenol reacts with formaldehyde at two ortho- and one para- positions to form a crosslinked structure, but ortho-cresol instead of phenol reduces the crosslinking density during copolymerization due to the methyl group at a ortho- position. As a result, spherical phenol-cresol copolymer beads showed more shrinkage with decreasing apparent density compared to the spherical phenol beads when carbonized at 700 ℃ under nitrogen. As the molecular weight of the cresol oligomer increases, the pore radius of the carbonized copolymer beads decreases, which is consistent with the density and shrinkage results. It was confirmed that the characteristics such as density decrease, shrinkage, yield and so on during carbonization can be controlled by controlling the degree of crosslinking of the spherical phenolic resin particles with cresol.

• Journal of Adhesion and Interface
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• v.8 no.1
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• pp.8-14
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• 2007

Poly(urethane-methyl methacrylate) hybrid emulsions can be controlled with their thermal, mechanical and anti-chemical properties as plastic coating materials. In this study, water dispersed poly(urethane-methyl methacrylate) hybrid emulsions were prepared by prepolymer synthesis and soap free emulsion polymerization. For imparting hydrophilicity on polyurethane prepolymer, 2,2-bis (hydroxymethyl) propionic acid was added to the polyurethane prepolymer with methyl methacrylate monomer and was neutralizated by triethylamine (TEA). After neutralization, the prepolymer mixture was dispersed in the water phase with stable droplets. The synthesis was carried out with chain extension from the ethylene diamine and initiation of methyl methacrylate by soap free emulsion polymerization. Stable poly(urethane-methyl methacrylate) hybrid emulsion was successfully obtained with different synthetic conditions and acrylic monomer contents. Poly(urethane-methyl methacrylate) hybrid emulsion were characterized and compared with tensile strength, viscosity, and adhesion properties.

• Journal of the Korean Chemical Society
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• v.26 no.1
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• pp.43-48
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• 1982

Four 2, 2, 2-trichloroethyl esters possessing a phthalimido group, 2,2,2-trichloroethyl phthalimidoacetate (1a), 2,2,2-trichloroethyl 6-phthalimidohexanoate (2a), 2,2,2-trichloroethyl 2-phthalimidopropanoate (3a) and 2,2,2-trichloroethyl N-phthaloylcarbamate (4a) were prepared and treated with zinc dust in aqueous acetic acid(Method A), in aqueous THF(Method B), and in aqueous THF containing triethylamine (Method C). By Methods A and B, 2,2,2-trichloroethyl ester linkage of the compounds 1a, 2a and 3a was reductively cleaved with concurrent reduction of phthalimido group to a 3-hydroxyphthalimidino group. By employing Method C, however, 2,2,2-trichloroethyl ester linkage of all the four compounds was selectively cleaved while the phthalimido group was preserved.

• Applied Chemistry for Engineering
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• v.1 no.2
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• pp.232-239
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• 1990

${\gamma}$-Glycidoxy propyl trimethoxy slilane, CTBN rubber(carboxyl terminated butadiene acrylonitrile rubber) and GMA(glycidyl methacrylate) were reacted with the surface of silica one by one in existence of TEA(triethylamine) or BPO(benzoyl peroxide). The amount of reactant was 2.5~5.8% of treated silica weight. The treated silica was mixed with epoxy resin and MTHPA(methyltetrahydrophthalic anhydride) in the range of 0~60% (wt. %) of total component. The flexural and thermal properties were tested for cured products. In filler content 35~55%, the using of silica treated with silane/rubber or silane/rubber/vinyl represented 25% higher flexural strength, 5% lower flexural modulus and 13% higher than mixing liquid rubber 3% with epoxy resin containing untreated silica.

• Bulletin of the Korean Chemical Society
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• v.29 no.4
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• pp.790-794
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• 2008

Nucleophilic addition reaction of benzenethiols (PhSH) to 1-(2-nitrovinyl) benzenes ($\beta$ NS) in the presence of triethylamine (TEA) has been studied in acetonitrile at 25 ${^{\circ}C}$. The rate is first order with respect to [PhSH], [TEA] and [$\beta$ NS]. The reaction is found to proceed with the formation of ion-pair between benzenethiol and TEA. A suitable mechanism with the formation of an adduct between ion-pair and substrate in a slow step followed by its rearrangement to 1,2-addition product in a fast step has been proposed and corresponding rate law derived. From the rate law, the rate constants for the interaction between ion-pair and $\beta$NS have been evaluated. Interestingly, in both para-substituted substrates and benzenethiols the rate increases with the electron-withdrawing power of the substituents. The positive sign of $\rho_x$ in benzenethiols has been explained. The magnitude of cross-interaction constant, $\rho_{xy}$ is small (0.08). The magnitude of the Hammett $\rho_x$ values is higher than that of the Bronsted, $\beta_x$ values for benzenethiols. The kinetic isotope effect, $k_H/k_D$, is found to be greater than unity. A suitable transition state with simultaneous formation of $C_\beta$ -H and $B_\alpha$ -S bonds involving the ion-pair and $\beta$NS in a single concerted step has been proposed to account for these observations.

• Journal of the Korean Chemical Society
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• v.38 no.9
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• pp.676-681
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• 1994

Diels-Alder adducts, carbacephems were obtained when 4-acetoxyazetidine-2-one or (3R,4R)-4-acetoxy-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]azetidin-2-one was reacted with 2-(tert-butyldimethylsilyloxy)-1,3-butadiene or with 3-(tert-butyldimethylsilyloxy)-1,3-pentadiene. When tert-butyldiemethylsilyl acrylate was used as the diene, products in which was acetoxy group of 4-acetoxyazetidin-2-one derivatives was substituted by an acryloyloxy group were isolated. When the same reaction was carried out with 4-phenylsulfonylazetidin-2-one as a dienophile with 2-(tert-butyldimethylsilyloxy)-1,3-butadiene, 4-phenylsulfoyl-2-butanone was obtained instead of the expected carbacephem. When dimeric form of thiochalcone was reacted with 4-acetoxyazetidin-2-one in the presence of zinc chloride, the $\beta-lactam$ ring of the azetidin-2-one was destructed and no product was isolated. Also, the reaction of 2-trimethylsilyloxy-1-aza-1,3-butadiene, which was obtained from N-methylacrylamide by treatment of trimethylsilyl trifluoromethanesulfonate in the presence of triethylamine, with 4-acetoxyazetidin-2-one did not give any products.

• Applied Chemistry for Engineering
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• v.27 no.2
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• pp.190-194
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• 2016

Tricyclopentadiene (TCPD) is one of the important precursors for making tetrahydrotricyclopentadiene, which is well known as a next-generation fuel with high energy density. In this study, TCPD was obtained by polymerization reaction of dicyclopentadiene (DCPD) using an ionic liquid (IL) supported mesoporous silica catalysts. ILs were supported to two kinds of mesoporous silica catalysts with different pore sizes such as MCM-41 and SBA-15. Four different ILs were supported to mesoporous silicas using anionic precursors such as CuCl or $FeCl_3$ and cationic precursors such as triethylamine hydrochloride or 1-butyl-3-methylimidazolium chloride. We proved that IL supported mesoporous silicas showed better catalytic performance than those of using non-supported prestine IL in the aspect of TCPD yield and DCPD conversion. Among four kinds of IL supported mesoporous silica catalysts, CuCl-based IL supported MCM-41 system showed the highest TCPD yield.

• YAKHAK HOEJI
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• v.46 no.6
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• pp.392-397
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• 2002

A simple and sensitive high performance liquid chromatographic method to quantitate ursodeoxycholic acid in crude drug pharmaceuticals was investigated. Ursodeoxycholic acid react with 2-bromoacetyl-6-methoxynaphthalene (Br-AMN) in the presence of triethylamine to form highly fluorescent derivative. The derivatization procedure was performed at 7$0^{\circ}C$ and completed within 30 min. The optimal wavelength of the fluorescence detector are λ$_{ex}$=300 nm and λ$_{em}$ = 460 nm. The LOD of the ursodeoxycholic acid was 25 ng/mι based on the S/N =3, and the LOQ was 80 ng/mι based on S/N = 10. Crude drug pharmaceuticals pretreated by solid phase extraction (Sep-pak $C_{18}$ cartridge) which were shown very good separation and recovery values for the compound.d.

• Journal of Environmental Health Sciences
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• v.22 no.1
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• pp.21-27
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• 1996

5.7-Dibromo-8-hydroxyquinolinyl-N-ethylcarbamate, one of the carbamate derivative which are generally used as insecticide, was newly synthesized. Its physical properities were determined and chemical structure was identified by means of I.R., nmr in addition to elemental analysis. The yield of addition, using triethylamine as catalyst, 5.7-dibromo-8-hydroxyquinoline and isocyanate was better than that of condensation of 5.7-dibromo-8-hydroxyquinoline with carbamoylchloride. The present organic synthesized compound showed the bacteriostatic action on salmonella typhi, escherichia coli and pseudomonas aeruginosa, but no otherwise effect of contraction of rabbit's ileum in the concentration of $100 \mu g/ml$.