• 한국응용과학기술학회지
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• 제14권1호
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• pp.27-32
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• 1997

Furfurylidene acetophenone derivatives were synthesis, it was measured that nucleophilic addition made use of UV at a wide pH 1.0${\sim}$13.0 range in 30% dioxane-$H_2O$ solution, 25$^{\circ}C$. On the basis of general base catalysis, substitutent effect, confirmation of nucleophilic addition products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It may be concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion: Above pH 10.0. sulfide anion adds to the double bond (Michael type addition), a part having no concern with pH, addition reaction to double bond is initiated by addition of neutral thiourea molecule. From the result of measurement the reaction rate, nucleophilic addition of furfurylidene acetophenone derivatives confirmed to the irreversible first order. Through measurement the substituent effect. It found that reaction rate was accelerated by electron attracting group. On the basis of these findings, nucleophilic addition of thiourea for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

• 한국응용과학기술학회지
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• 제8권2호
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• pp.175-181
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• 1991

The kinetics of the addition of 1-benzylindole-3-(p-substituted) acetophenone derivatives was investigated by ultraviolet spectrophotometery in 30% dioxane -$H_2O\;at\;25^{\circ}C$. A rate equation which can be applied over wide pH range was obtained. The Substituent effects on 1-benzylindole-3-(p-substituted) acetophenone derivatives were studied, and addition were facilitated by electron attracting groups. On the base of the rate equation, substituent effect, and general base effect the plausible addition mechanism was proposed : Below pH 3.0, only neutral thiourea molecule was added to the carbon-carbon double bond, and in the range of pH 0.0${\sim}$14.0, netural thiourea molecule and thiourea anion competitively attacted the double bond. By contrast, above pH 10.0, the reaction was dependent upon only the addition of thiourea anion.

• 농업과학연구
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• 제10권2호
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• pp.354-364
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• 1983

pH 7.0~14.0의 중성에서 강염기성 용액에 이르는 넓은 pH 범위에서 Cinnamonitrile의 알카리 가수분해 반응속도 상수를 $25^{\circ}C$의 50% methanol 물 혼합용매로 부터 측정하여 실험사실을 잘 설명할 수 있는 반응 속도식을 유도하여 가수분해 반응 메카니즘을 제안하고, 반응 속도론적으로 고찰 검토하였으며 (Z)형의 형태에 관하여 분자의 안정성과 반응성을 알아보기 위하여 cinnamonitrile의 분자궤도 함수를 EHT와 CNDO/2방법으로 계산하였다. (1) Cinnamonitrile의 전체 에너지 계산 결과로부터 ${\theta}_1$ 회전에 따르는 형태의 안정도는 (E)형을 포함하여 (E)-planar > (E)-gauche > (Z)-gauche > (Z)-planar이였고 (E)-gauche와 (Z)-gauche의 에너지 차는 1.94Kcal/mole이였다. 따라서 반응은 가장 안정한 (E)-planar의 $C_7({\alpha})$ 원자에 chydroxide 이온이나 물분자의 첨가로 ${\alpha}C-{\beta}C$ 결합이 분열하게 된다. (2) pH7.0~14.0 범위에서 측정한 반응속도상수로 부터 유도된 전체 반응속도식은 다음과 같다. $$k_t=k_o+k^{\prime}[OH^-]=({\frac{1.41{\times}10^{-14}+1.21{\times}10^{-7}/[H_3O^+]}{2.65{\times}10^{-7}+1.64/[H_3O^+]})+9.14{\times}10^9/[H_3O^+]$$ (3) 분자 궤도함수의 계산 결과와 반응 속도식을 토대로 하여 pH10.0~14.0에서는 hydroxide 이온의 첨가로 가수분해가 진행되는 Scheme(I)과 같은 Michael형의 친핵성 첨가반응 메카니즘을 그리고 pH7.0~10.0사이의 중성 용액중에서는 물분자의 첨가로 반응이 진행되는 Scheme(II)와 같은 가수분해 반응메카니즘을 제안하였다. (4) pH10.0~12.0사이의 약 알칼리성 용액중에서는 Scheme(I)과 Scheme(II)의 두 반응이 서로 경쟁적으로 일어나는 대단히 복잡한 일련의 가수분해 반응이 진행됨을 알았으며 분해 생성물은 공히 benzaldehyde와 methylnitrile 그리고 acetic acid 이였다. 앞으로의 과제는 cinnamonitrile 의 ${\alpha}{\cdot}{\beta}$ 탄소불포화 이중결합에 미치는 치환기에 의한 자유에너지 직선성의 상관관계와 물 L-cysteine 및 hydrogene cyanide 등의 서로 다른 친핵체들과의 반응으로 부터 이들의 친핵 첨가반응성을 검토하고자 한다.

• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.3973-3978
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• 2011

The reductive pinacol coupling reaction of aldehydes or ketones creating a new C-C bond has been a major tool to produce 1,2-diol compounds. The reaction mechanism is known to be composed of sequential three steps (activation, coupling, and dissociation). In this work, we studied the dissociation step of half-titanocene-based catalytic systems. Cp and $Cp^*$ derivatives of the pinacolato-bridged dinuclear complex were synthesized and evaluated as possible models for intermediates from the coupling step. We monitored $^1H$-NMR spectra of the reaction between the metalla-pinacol intermediates and $D_2O$. New reaction routes of the dissociation step including oxo- and pinacolato-dibridged dinuclear complexes and oxo-bridged multinuclear complexes have been suggested.

• 한국세라믹학회지
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• 제15권2호
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• pp.89-97
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• 1978

The basic mechanism of adherence in sintered high purity alumina ceramic-to-metal bonding was studied. Emphasis was placed on flux composition, porosity of the fired ceramics, and metallizing mixtures. The study was conducted on 95 and 99.5% alumina, using molydbenum-manganese, molybdenum-manganese-silicon dioxide metallizing compositions. Metallizing was performed in wet hydrogen (dew point, ＋17$^{\circ}C$) at 145$0^{\circ}C$ for 45min. This experiment indicated that adhernece mechanism of ultra high purity alumina ceramic was attributed to formation of $MnAl_2O_$4, and in the case of 95% alumina containing glass, the migration of glass from the interface into the void of the metal coating was the main role to the adhrence. It showed also that greater the bond-strength was resulted as porosity was increased.

• 한국세라믹학회지
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• 제27권6호
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• pp.755-762
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• 1990

The tungsten paste was printed on the surface of 92% alumina sheet which was made by type casting process. The printed tungsten was bonded on the Al2O3 by co-firing in reducing atmosphere. During the co-firing, the binder burn-out was easier in wet H2 atmosphere than in dry H2, which affected sintered density. In practically, the use of wet H2 above 100$0^{\circ}C$ was beneficial for density of alumina and bond strength. This phenomena occured more distinctly when atmosphere varied from dry H2 to wet H2 than varied dew point in wet H2. In wet H2, the improvement in bonding strength can be attributed to good glass migration into the metal layer due to inhibition of the tungsten particle growth, with increase of alumina density, at the temperatrue higher than 100$0^{\circ}C$.

• Bulletin of the Korean Chemical Society
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• 제3권1호
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• pp.9-13
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• 1982

Sulfametrole, $C_9H_{10}N_4O_3S_2$, crystallizes in the monoclinic system, space group $P2_1/n$ , with a = 8.145(2), b = 16.505(4), c = 9.637(1)${\AA},{\beta}=103.72(1)^{\circ},D_m=1.52gcm^{-3}$,Z=4.Intensities for 3594(2143 observed) unique reflections were measured on a four-circle diffractometer with Mo $K{\alpha}$ radiation $({\lambda}=0.71069{\AA})$. The structure was solved by direct method and refined by full-matrix least squares to a final R of 0.070. The geometrical features of the thiadiazole ring indicate some ${pi}$-electron delocalization inside the ring. The least squares planes defined by the benzene and thiadiazole rings are nearly perpendicular to each other(dihedral angle; $93.9^{\circ}$ ). All the potential hydrogen-bond donor atoms in the molecule, N(1) and N(2), are included in the hydrogen bonding. The molecules through hydrogen bonding form three dimensional network.

• Bulletin of the Korean Chemical Society
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• 제4권3호
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• pp.123-127
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• 1983

The crystal structure of metoclopramide, $C_14H_22ClN_3O_2$, has been determined by X-ray diffraction techniques using diffractometer data obtained by the ${\omega}-2{\theta}$ scan technique with Mo $K\alpha$ radiation from a crystal with space group symmetry $P{\overline{1}}$ and unit cell parameters a = 7.500(1), b = 8.707(2), c = 13.292(2) ${\AA}$; ${\alpha}$ = 101.70(2), ${\beta}$ = 81.20(2), and ${\gamma}$ = $114.90(l)^{\circ}$. The sructure was solved by direct methods and refined by full-matrix least-squares to a final R = 0.055 for the 1524 observed reflections. The bent overall-conformation of the molecule seems to be determined mainly by the bifurcated intramolecular hydrogen bond from the amide nitrogen atom to the methoxy oxygen and the amine nitrogen atoms. The crystal packing consists of the hydrogen bonds, ${\pi}-{\pi}$ interaction and hydrophobic interaction.

• 약학회지
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• 제24권2호
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• pp.135-141
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• 1980

The crystal and molecular structure of 2-methyl-3-(N-trimethyl ammonium)phenol iodide, $C_{10}H_{16}NOI, was determined by X-ray diffraction method. The compound crystallizes in the orthorhombic space group $P_{na2}_{1}$ with a=13.327(3), b=12.496(3), C=7.227(2)A and Z=4. A total of 489 independent observed reflections were collected by the automated Four-circle diffractometer and was solved by heavy atom method and refined by anisotropic block-diagonal least-squares method to the R value of 0.04. The benzene ring is slightly distorted from regular hexagon. The I atom and 2-methyl-3-(N-trimethyl ammonium)phenol group is held together by van der Waals forces in the crystal. Intermolecular hydrogen bond is of the type O-H....I with the length 3.35.angs.. Apart from the hydrogen bonding system the molecules are held together by van der Waals forces in the crystal.

• Bulletin of the Korean Chemical Society
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• 제5권4호
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• pp.158-162
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• 1984

The crystal structure of chloramphenicol base, $C_9H_{l2}N_2O_4$, the deacylated base of antibiotic chloramphenicol, has been determined by X-ray diffraction techniques using diffractometer data obtained by the ${\omega}-2{\theta}$ scan technique with CuK${\alpha}$ radiation from a crystal with space group symmetry $P2_12_12_1$ and unit cell parameters a = 22.322(6), b = 7.535(6), c = 5.781(5) ${\AA}$. The structure was solved by direct methods and refined by full-matrix least-squares to a final R = 0.051 for the 573 observed reflections. The overall conformation of the base is quite different from those of the chloramphenicol congeners which are similar despite the presence of many rotatable single bonds. The propane chain in the base is bent with respect to the phenyl ring, while it is extended in the chloramphenicol congeners. There is no intramolecular hydrogen bond between the hydroxyl groups of the propanediol moiety. All of the molecules in the crystal lattice are connected by a three-dimensional hydrogen bonding network.