• Journal of the Korean Chemical Society
• /
• v.18 no.2
• /
• pp.85-96
• /
• 1974

Extended H ckel Theory and CNDO/2 MO calculation methods have been applied to $C_6H_5YCH_2Cl$(Y = None, -$CH_2$-, -O-, -S-, -CO-, -$SO_2$-). It has been shown that charge distributions in molecules are mainly controlled by the migration of valence inactive electron, giving the order of ${\sigma}$-acceptor and ${\pi}$-donor effects -O- > -S- > -$CH_2$- > -$SO_2$-. The -CO- group exceptionally acts as ${\sigma}$-donor and ${\pi}$-acceptor. It was also predicted that, $S_N2$ reactivities of C$C_6H_5YCH_2Cl$ would be in the order of -O-${\thickapprox}$-CO- >>-S-${\thickapprox}$None > -$CH_2$-, neglecting solvent effect. From the results of our studies, we conclude that the structural factors influencing 의 $S_N$ reactivities will be: (1) positive charge developments on reaction center carbon atom (2) energy level of ${\sigma}$-antibonding unoccupied MO with respect to C-Cl bond. (3) ${\sigma}$-antibonding strength of C-Cl bond at that level.

• Journal of Korean Vacuum Science & Technology
• /
• v.3 no.1
• /
• pp.24-29
• /
• 1999

The characteristic behaviors of CH3Br were examined first for the dry etching of polysilicon in a Cl2/CH3Br/O2 plasma. CH3Br is revealed one of the excellent additive gases to control anisotropy of etching profile and to give no undercutting for various typed of polysilicons. CH3Br acts as a passivation precursor on the side wall in etch cavity by forming polymer-like films such as CHxBry(x+y=1,2). The decrease of etch selectivity due to the reaction if the C-containing species from CH3Br with the surface O atoms of SiO2 was overcome by the addition of O2 into plasma, resulting that the selectivity increased by 2~3 times. According to the results of optical emission signals, CH3Br should be dissociated into several fragments to give more hydrogen atoms than bromine atoms in our helical resonator system.

• Journal of the Korean Applied Science and Technology
• /
• v.15 no.2
• /
• pp.41-48
• /
• 1998

The catalytic oxidations of several cycloolefins in $CH_2Cl_2$ were been investigated using Mn(III)-, Fe(III)-porphyrin complexes as a catalyst and sodium hypochlorite as a terminal oxidant. Porphyrins were $(p-CH_3O)TTP,\;(p-CH_3)TTP,$ TPP, (p-F)TPP, (p-Cl)TPP and $(F_{20})TPP$ (TPP = tetraphenylporphyrin), and olefins were cyclopentene, cyclohexene and cycloheptene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin. The conversion yield of substrate by changing the substituent of TPP increased in the order of $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl, which was consistent with the sequence of $4{\sigma}$ values of TPP. The conversion of cycloalkene followed the order of $C_5\;<\;C_6\;<\;C_7$.

• Bulletin of the Korean Chemical Society
• /
• v.5 no.4
• /
• pp.167-169
• /
• 1984

Analyses of $_1$H-NMR, infrared and electronic spectral data for $[Ir(CH_2 = CHCN)(CO)(P(C_6H_5)_3)_2]ClO_4 (1)$prepared by the reaction of $Ir(OClO_3)(CO)(P(C_6H_5)_3)_2$ with $CH_2 = CHCN$, agree with the suggestion that 1 is a mixture of the nitrogen-bonded acrylonitrile complex, $[(CO)(P(C_6H_5)_3)_2Ir-NCCH = CH_2]ClO_4$ and other compound which may be the C = C ${\Pi}$ -system-bonded acrylonitrile complex, "[(CO)(P(C6H5)3)2Ir-CHCN = CH2]ClO4.

• Analytical Science and Technology
• /
• v.19 no.2
• /
• pp.131-141
• /
• 2006

Hydrobromic acid salt of a $N_2O_2$ tetradentate ligand, N,N'-bis(2-hydroxybenzyl)-ethylene-diamine ($H-BHE{\cdot}2HBr$) was synthesized. $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$ and $CH_3O-BHE{\cdot}2HBr$ having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of $H-BHE{\cdot}2HBr$ were also synthesized. $Nap-BHE{\cdot}2HBr$ having naphthalen-2-ol instead of the phenol group was also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and the order of the calculated overall proton dissociation constants (${\log}{\beta}_p$) of each ligand was Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE. The order showed a similar trend to that of Hammett substituent constants(${\sigma}_P$). The order of the stability constants (${\log}K_{ML}$) was CO(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order in their stability constants (${\log}K_{ML}$) of each transition metal complex agreed well with that of the overall proton dissociation constants (${\log}{\beta}_p$).

• Bulletin of the Korean Chemical Society
• /
• v.7 no.5
• /
• pp.391-395
• /
• 1986

MNDO calculations were carried out to determine reactant complexes and transition states of the $S_N2$ reactions of $CH_3X\;+\;Y^-\;{\to}\;CH_3Y\;+\;X^-$ where X = F, Cl, CN and Y = CN, OH, F, Cl. The leaving group ability was found to vary inversely with the activation barrier, which in turn was mainly ascribable to the deformation energies accompanied with bond stretching of C-X bond and inversion of $CH_3$ group. The nucleophilicity was shown to be in the order $Cl^->F^->OH^->CN^-$ but the effect on the activation barrier was relatively small compared with that of the leaving group. The bond breaking and bond formation indices and energy decomposition analysis showed that the TS for the reaction of $CH_3$Cl occurs in the early stage of the reaction coordinate relative to that of $CH_3$F. It has been shown that the potential energy surface (PES) diagrams approach can only accommodate thermodynamic effects but fails to correlate intrinsic kinetic effects on the TS structure.

• Fisheries and Aquatic Sciences
• /
• v.2 no.1
• /
• pp.1-7
• /
• 1999

Antioxidant activity of a methanol extract of Symphyocladia latiuscula was evaluated by the thiocyanate method in the linoleic acid system. The methanol extract inhibited the peroxidation of linoleic acid in a dose-dependent manner. The MeOH extract was then sequentially partitioned with n-hexane, $CH_2Cl_2$, EtOAc, n-BuOH and H20. The antioxidant activity of the fractions increased in order of $CH_2Cl_2$, n-hexane, EtOAc, and n-BuOH. There was no activity found in $H_2O$ partitoned fraction by the thiocyanate method. Especially, the activities of the fractions of n-hexane and $CH_2Cl_2$ were comparable to that of 2,6-di-tert­butylhydroxytoluene (BHT). Column chromatography of the $CH_2Cl_2$ fraction over silica gel yielded cholesterol (1) and 2,3,6-tribromo 4,5-dihydroxybenzyl methyl ether (2) which were identified by instrumental analysis of MS and $^1H-$ and $^{13}C-NMR$. The latter (2) demonstrated significant antioxidant activity.

• Fisheries and Aquatic Sciences
• /
• v.4 no.1
• /
• pp.47-49
• /
• 2001

Nitrite scavenging activity of a methanol extract of Symphyocladia latiuscula was studied. The methanol extract scavenged the nitrite in a dose-dependent manner. The MeOH extract was then sequentially partitioned with n-hexane, $CH_2Cl_2$, EtOAc, n-BuOH and $H_2O$. The scavenging activity of the fractions increased in order of $CH_2Cl_2$, n-hexane, EtOAc, n-BuOH, and $H_2O$. Especially, the activity of the $CH_2Cl_2$ fraction was comparable to that of L-ascorbic acid. Column chromatography of the most active $CH_2Cl_2$ fraction over silica gel yielded three active bromophenol congeners (1-3) which were identified as (2R)-2-(2,3,6-tribromo 4,5-dihydro­xybenzyl) cyclohexanone (1), 2,3,6-tribromo 4,5-dihydroxybenzyl methyl ether (2), and 2,3,6­tribromo 4,5-dihydroxybenzyl alcohol (3) respectively.

• Bulletin of the Korean Chemical Society
• /
• v.18 no.11
• /
• pp.1162-1166
• /
• 1997

Nature of palladium(Ⅱ) complexes with 7-membered chelates was studied by experimental and theoretical methods on a Pd(L)Cl2 system, where L is Ph2PNHCH2CH2NHPPh2(L1), Ph2PNHC6H4NHPPh2(L2). The palladium(Ⅱ) complexes were prepared and characterized by elemental analysis, IR, UV, 1H, and 31P NMR spectroscopy. Ab initio calculations with geometry optimizations were also performed for related model systems, Pd(L)Cl2; L=R2PNH(CH2)2NHPR2(L3), R2PNHC6H4NHPR2(L4), R2P(CH2)4PR2(L5), R2PCH2(C6H4)CH2PR2(L6); R=H, CH3.

• Journal of the Korean earth science society
• /
• v.22 no.4
• /
• pp.278-291
• /
• 2001

Mesothermal gold vein minerals of the Seolhwa mine were deposited in a single stage of massive quartz veins which filled the mainly NE-trending fault shear zones exclusively in the granitoid of the Gyeonggi Massif. The Seolhwa mesothermal gold mineralization is spatially associated with the Jurassic granitoid of 161 Ma. The vein quartz contains three main types of fluid inclusions at 25$^{\circ}$C: 1) low-salinity (< 5 wt.% NaCl), liquid CO$_{2}$-bearing, type IV inclusion; 2) gas-rich (> 70 vol.%), aqueous type II inclusions; 3) aqueous type I inclusions (0${\sim}$15 wt.% NaCl) containing small amounts of CO$_{2}$. The H$_{2}$O-CO$_{2}-CH$_{4}$-N$_{2}$-NaCl inclusions represent immiscible fluids trapped earlier along the solvurs curve at temperatures from 430$^{\circ}$ to 250$^{\circ}$C and pressures of 1 kbars. Detailed fluid inclusion chronologies may suggest a progressive decrease in pressure during the auriferous mineralization. The aqueous inclusion fluids represent either later fluids evelved through extensive fluid unmixing (CO$_{2}-CH$_{4}$ effervescence) from a homogeneous H$_{2}$O-CO$_{2}-CH$_{4}$-N$_{2}$-NaCl fluid due to decreases in temperature and pressure, or the influence of deep circulated meteoric waters possibly related to uplift and unloading of the mineralizing suites. The initial fluids were homogeneous containing H$_{2}$O-CO$_{2}-CH$_{4}$-N$_{2}$-NaCl components and the following properties: the initital temperature of >250$^{\circ}$ to 430$^{\circ}$C, X$_{CO}\;_{2}$ of 0.16 to 0.62, 5 to 14 mole% CH$_{4}$, 0.06 to 0.3 mole% N$_{2}$ and salinities of 0.4 to 4.9 wt.% NaCl. The T-X data for the Seolhwa gold mine may suggest that the Seolhwa auriferous hydrothermal system has been probably originated from adjacent granitic melt which facilitated the CH$_{4}$ formation and resulted in a reduced fluid state evidenced by the predominance of pyrrhotite. The dominance of negative ${\delta}\;^{34}$S values of sulfides (-0.6 to 1.4$%_o$o) are consistent with their deep igneous source.