• 한국세라믹학회지
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• 제37권7호
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• pp.645-650
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• 2000

Effects of the chemical composition and sintering atmosphere on the formation of reaction phases and physical properties of reactive hot-pressed TiB2-AlN-BN composites were investigated. At N2 atmosphere, TiN was formed by the reaction between Ti and N2, which inhibited the densification and results in inferior mechanical-and electrical properties of the composites. However, at Ar atmosphere, enhanced densification and physical properties of composites were obtained due to that the TiN formation reaction was excluded. Densification of the composites was also hindered by BN, therefore, inferior mechanical-and electrical properties of composites were obtained with amount of BN in the starting materials. At Ar atmosphere, TiB2-AlN-BN composites having 318 MPa of flexural strength, 3.5 MPa.m1/2 of fracture toughness and 276$\mu$Ω.cm of electrical resistivity were fabricated from mole ratio 1:2:1.6 of Ti-Al-BN mixtures.

• Bulletin of the Korean Chemical Society
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• 제1권2호
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• pp.45-49
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• 1980

During the homolytic reactions of $CCl_4$ or $Cl_3CBr with ${\beta}-halo^1$-styrenes,$\beta$-haloradicals are key intermediates. They are to be stabilized via three pathways; $\beta$-cleavage, halogen transfer and telomerization. The three reaction paths are delicately controlled by the energetics of their formation and stabilization. When the formation of a $\beta$-haloradical is accompanied by considerable excess of energy from an exothermic reaction, $\beta$ -cleavage is often dominant over the halogen transfer. On the other hand, if the radical forms via a reversible reaction, two processes become competitive. $\beta$-Eliminated bromine atoms from ${\beta}$ -bromoradicals generate $Br_2$ via $Cl_3CBr + {\cdot}Br {\leftrightarrow} Br_2 + {CCl_3}{\cdot}{Br_2}$ may act as a better scavenger than Cl3CBr for the ${\beta}$-bromoradicals. Different reactivities of chlorine, bromine and trichloromethyl radicals towards olefinic pi-bond are clarified in terms of the beat content of the addition reactions.

• Bulletin of the Korean Chemical Society
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• 제8권5호
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• pp.376-380
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• 1987

The cyclobutane forming photocycloaddition reaction of 5(E)-styryl-1,3-dimethyluracil with some olefins occurs on the 5,6-double bond of uracil ring rather than the expected central double bond via an intermediate, probably the photochemical Diels-Alder type adduct. This intermediate formed on short term irradiation of 5(E)-styryl-1,3-dimethyluracil and 2,3-dimethyl-2-butene solution is converted into the $C_4$-cycloadduct on the prolonged irradiation. Quantum yield of the intermediate formation is not linear with the concentration of 2,3-dimethyl-2-butene probably due to the secondary reaction accompanied with the complex reaction kinetics. The intermediate is formed from the lowest excited singlet state.

• Bulletin of the Korean Chemical Society
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• 제20권12호
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• pp.1464-1468
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• 1999

Non-activated indolinobenzospiropyrans, 6-(p-substituted phenylazo)-1',3',3'-trimethylspiroindolinobenzopyrans(1-4) have been synthesized by the reaction of commercially available Fischer's base with 2-hydroxy-5-arylazobenzaldehyde (S1-S4). The arylazosalicylaldehydes were obtained from the diazocoupling reaction of substituted anilines with salicylaldehyde. The rate of spiro-ring formation from the open form of these nonactivated spiropyran derivatives at room temperature has been investigated utilizing the stopped-flow method de-veloped earlier. Half life times $(t_{1/2})$ of the ring-closure reaction in ethanol are about 0.3-14 seconds for the nonactivated spiropyrans examined. UV-Visible absorption spectral data of the open merocyanine form of nonactivated spiropyrans, which showed no chromotropism at room temperature, have also been obtained.

• Bulletin of the Korean Chemical Society
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• 제19권3호
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• pp.314-319
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• 1998

One flask synthesis of dithienylmethane and difurylmethane is reported. The reaction of aldehydes with excess furan or thiophene affords the meso-phenyldithienylmethane (DTM) and meso-phenyldifurylmethane (DFM), respectively. The reaction is catalyzed with trifluoroacetic acid or with BF3·O(Et)2. An acyl group is selectively introduced in 1 and 9 position of difurylmethane and dithienylmethane by use of an acid chloride and tin (IV) chloride. The reduction of resulting 1,9-bisacyldifurylmethane or 1,9-bisacyldithienylmethane affords the corresponding 1,9-bis-diol. An acid catalyzed condensation of diol with meso-phenyldipyrromethane followed by oxidation with DDQ gives the porphyrins. The reaction resulted meso-5,10,15,20-tetraphenyl-21,22-dithiaporphyrin (SSNN) or 15-mesityl-5,10,20-triphenyl-21,22-dioxaporphyrin (OONN), respectively. The formation of small amount of meso-tetraphenylporphyrin (TPPH2) is also observed. The formation of TPP indicates that meso-phenyldipyrromethane is reversibly cleaved and form pyrrole and pyrrylbenzylcarbocation during the condensation. The proton nmr and electronic spectrum of the SSNN and OONN porphyrins are somewhat different from the previously synthesized meso-5,10,15,20-tetraphenyl-21,23-dithiaporphyrin (SNSN) or meso-5,10,15,20-tetraphenyl-21,23-dioxaporphyrin (ONON).

• 대한화학회지
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• 제56권1호
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• pp.14-19
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• 2012

We investigate the doublet and quartet potential energy surfaces associated with the gas-phase reaction between $Ti^+$ and $CF_3COCH_3$ for two plausible reaction pathways, $TiF_2^+$ and $TiO^+$ formation pathways by using the density functional theory (DFT) method. The molecular structures of intermediates and transition states involved in these reaction pathways are optimized at the DFT level by using the PBE0 functional. All transition states are identified by using the intrinsic reaction coordinate (IRC) method, and the resulting reaction coordinates describe how $Ti^+$ activates $CF_3COCH_3$ and produces $TiF_2^+$ and $TiO^+$ as products. On the basis of presented results, we propose the most favorable reaction pathway in the reaction between $Ti^+$ and $CF_3COCH_3$.

• Bulletin of the Korean Chemical Society
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• 제26권10호
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• pp.1481-1490
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• 2005

Carbon-carbon single bond-forming reaction is the most useful and fundamental reaction in organic synthesis. Most of the basic carbon-carbon single bond-forming reactions, thus, developed in the past. In these respects, conceptually new C-C bond formation reaction can be highlighted. The Baylis-Hillman reaction was found at the early 1970’s. However, extensive studies on this highly potential reaction were started only before 15 years. This review has been written to shed more lights to the importance of Baylis-Hillman reaction. We have focused mainly on the reaction mechanism, conceptually related reactions, and chemical transformations of the Baylis-Hillman adducts.

• 한국세라믹학회지
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• 제30권6호
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• pp.433-440
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• 1993

The bioactivity of glasses in the CaO-SiO2 system and CaO-P2O5-SiO2 system with less than 10mol% of P2O5 was investigated by in vitro test in simulated body flood(SBF). The formation of Ca.P film and hydroxyapatite on the surface of glasses after in vitro test was analysed by X-ray photoelectron spectoscopy (XPS), fourier transform infrared reflection spectroscopy (FT-IRRS), energy dispersive X-ray spectroscopy (EDS), and scanning electron microscopy (SEM) observation. In the early stage of Ca.P film formation after in vitro test for CaO-SiO2 and CaO-P2O5-SiO2 glasses, the rate of Ca.P film formation on the surface of the glasses was dependent of structural parameter (Y) evaluated from the glass composition. First, in the case of the glasses having Y value below 2, Ca.P film and SiO2-rich layer were formed simultaneously, and there were no differences of the rate of Ca.P film formation in terms of the Y values. Second, in the case of the glasses having Y value above 2, the SiO2-rich layer was formed, and then Ca.P.Si mixed layer was formed in the silica gel structure of the SiO2-rich layer, and finally the Ca.P film on the surface of SiO2-rich layer. The rate of Ca.P film formation delayed as the Y values increased. The rate of hydroxyapatite formation of glasses (the rate of transformation from Ca.P film to hydroxyapatite) seems to be propotional to the rate of Ca.P film formation and Y value. The rate of hydroxyapatite formation of glasses belonging to the second group was delayed as structural parameter increased, and the hydroxyapatite crystal showed spherical growth in the early reaction stage, and then showed silkworm-like linear growth as the reaction time increased.

• 대한치과의사협회지
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• 제12권5호
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• pp.347-349
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• 1974

The demonstrations of collagenous fiber in mandibul ar bone formation were analized histochemically, using Carson's Mallary-Heidenhein stain, McManus' PAS reaction and H-E stain The stain ablity of osteoid increased with formation of bone tissue. In the surrounding areas of osteoblast and osteocyte were showed slight activity.

• Bulletin of the Korean Chemical Society
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• 제13권1호
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• pp.9-10
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• 1992