Ascorbic Acid와 2-Methoxyestradiol에 의한 내분비선 장애물질의 제거효율

성대동,이성식,최금찬,성낙창 동아대학교 환경문제연구소 2000 硏究報告 Vol.23 No.1

The removal efficiency of an environmental endocrine disrupter, 1,l-bis (4-chlorophenyl)-2,2,2-trichloroethane(CPT) has been studied using L-ascorbic acid(ACA) and 2-methoxyestradiol(MSD). l,l-Bis(4-chlorophenyI)-2,2,2-trichlorcethyl anion(CPT^( θ)) is formed by treatment of OH- ion to l,l-bis(4-chlorophenyl)-2,2,2-trichloroethane(CPT), l,l-Bis(4-chlorophenyl)-2,2,2-trichiorcethyl radical(CPT·) yields during the reaction of l,l-his(4-chlorophenyl)-2.2,2-trichloroethyl anion with iodine occurs. A high m v a l efficiency for l,l-bis(4-chlorophenyl-2,2,2-trichlorcethyl radical(CPT·) reveals in the case of L-ascorbic acid(ACA) used more than that of 2-methozyestradiol(MSD). This is in accord with the rate of yielding L-ascorbic acid radical(ACA·) is faster than the one of 2-methoxyestradiol radical(MSD·). The removal efficiency of 1,1-bis(4-chlorophen~l)-2,2,2-trichloroethyl radical(CPT·) is increased with increasing of solvent acidity and solvent hydrogen bonding degree.

Seyferth시약의 발암성과 반응메카니즘 연구

성대동,박유미 동아대학교 환경문제연구소 1993 硏究報告 Vol.16 No.1

The reaction mechanism and molecular carcinogenetic property for the reaction of Seyferth's reagents such as phenyl(bromodichloromethyl)mercury and phenyl(tribromomethyl) mercury with food additives as dehydroacetic acid and coumarin has been studied under the conditions fo UV/vis photolysis and laser flash photolysis. 1. The reaction reactivities of Seyferth's regents as phenyl(bromodichloromethy1)mercury and phenyl(tribromomethyl) mercury are compared in all reaction conditions. The reactivity of phenyl(bromodichloromethy1) mercury is higher than the reactivity of phenyl(tribomomethy1) mercury at any reaction conditions in this research. This means that the leaving effect of : CCl₂carbene is higher than that of CBr₂carbene from mercury atom in Seyferth's reagent. 2. The yield of a highly toxic carcinogenetic carbene intermediate in the condition of UV/vis photolysis is less than those of laser flash photolysis. It is explainable that the reactions of Seyferth's reagent with the food additives are inhibited compared with the dimerization reaction of dihalogen carbenes each other. 3. The reactions of Seyferth' s reagents with dehydroacetic acid and coumarin are accelerated increasing with the negative(-) values of the bond energy of HgCCX₂and σ MO energy.

질량분석법을 이용한 알칼리토중금속 검출시 용매 분자의 방해작용과 검출한계

성대동,강상수,정진희,성낙창,최금찬 동아대학교 환경문제연구소 2003 硏究報告 Vol.25 No.2

At the detection of heavy alkaline-earth metal in the solution using mass spectrometer, the identification of exact molecular ion is difficult due to be surrounded with solvent molecules around the metal ion and to make the solvated cluster. An exact identification method is developed using the method in compensation for the number of solvation on the mass spectrum when the heavy alkaline-earth metal analyze. The cluster surrounded with solvent molecules is interpreted as solvation number and the solvation number could be applied to the determination of exact molecular ions to be drawn out an exact quantitative molecular mass ion on the mass spectrometry.

친핵성 치환반응에서 최대속도현상과 Hammett 상관관계

성대동,임귀택,김양희,김민식 한국식품영양학회 1995 韓國食品營養學會誌 Vol.8 No.3

등유전성 용매로 알려진 methanol과 acetonitrile의 이성분 혼합용매에서 p-치환 benzyl bromide와 p-치환 N, N-dimethylaniline과의 친핵성 치환반응을 반응속도론적으로 연구하여 다음과 같은 결론을 얻었다. 1. Hammett ρ_X값으로부터 전이상태에서 반응기질의 반응 중심 원자에 양(+)하전이 증가하고 결합 형성보다는 결합파괴가 진전됨을 알 수 있었다. 그러나 친핵체에 -NO_2기가 치환된 Y-p-NO_2인 경우 반응 중심 원자에 음(-)하선이 증가하여 결합파괴와 동시에 결합형성도 크게 진전되었음을 알 수 있었다. 2. Hammett ρ_Y값으로부터 기질의 치환기가 전자주게기일수록 결합형성이 작게 되고 기질의 치환기가 전자 받게기일수록 결합형성이 크대 되었음을 알 수 있었다. 3. 교차 상호작용 상수, ρ_XY값으로부터 80%(v/v)의 methanol조성에서 친핵체가 반응 기질을 공격하는 능력이 가장 크게 나타나고 동시에 결합형성이 잘 진전됨을 보여 주었다. 4. 퍼텐셜 에너지 표면 모델에 적용했을 때 반응은 각 반응지수로부터 구한 반응물의 전이상태의 구조와 잘 일치하였다. 5. 분광용매화 피라미터식에 적용하였더니 본 반응은 용매의 편극-극성 효과에 크게 지배됨을 알 수 있었다. The nucleophilic substitution reactions of p-substituted benzyl bromide with p-substituted N.N-dimethylanilines in methanol and acetonitnle binary solvent mixture which is known to an isodielectric solvent system kinetically and the results are as follows. The positive charge is developed on the reaction center of the substrate and it means that the bond cleavage is preceded more than bond formation in the transition state on the analogy of Hammett ρX values. The bond formation is not progressed in the case of electron donating substituent of substrate. However, the bond formation is much developed in the case of electron withdrawing substituent of substrate on the analogy of Hammett ρY values. The nucleophilic attacking ability is shown a highest at 80%(V/V) methanol content and the bond formation is well progressed at the same methanol composition on the result of a cross interaction coefficient, ρXY. The result of transition state structure that is applicated to the potential energy surface model is in accord with the result that is applicated to the reaction susceptibilities. The reaction is subject to the polarity-polarizability term more than the hydrogen bond donor acidity term by application to the solvatochromic parameter equation.

수처리 부산물로 생성되는 염소산화물의 효율적 제거에 관한 연구

성대동,이성식 동아대학교 환경문제연구소 1999 硏究報告 Vol.22 No.1

The photodegradation efficiency of chlorine oxides in the drinking water has been studied by means of laser flash photolysis. The results are summarized as follows ; A high amount of ClO is produced just at the irradiation of laser flash. The absorption spectrum of ClO shows strong on the spectrophotometric measurement. The efficiency of removal of ClxOy reveals about 60~70% within 2㎲ after laser flash irradiation. The removal efficiency is decreased with the increase of the water thickness from 40㎝ to 80㎝ and also the efficiency is decreased about 4~6%. The removal rate of Cl₂O_(7) shows 3 times higher than one of Cl₂O_(6).

Oxametallaborane 및 Metallacarborane과 Phenyl Carbene 반응에 대한 반응성과 반응메카니즘

성대동,이용희,심경옥 동아대학교 기초과학연구소 2000 基礎科學硏究論文集 Vol.17 No.1

거대고리 뭉치 붕소화합물 중 산소원자를 포함하는 oxametallaborane과 탄소원자를 포함하는 metallacaborane을 이용하여 새로운 metallacarborane을 합성할 수 있는 방법을 알아보고 [9,9-(PMe2Ph)2-arachno-9,6-PtOB8H10]과 [9,9-(PMe2Ph)2-arachno-9,6-PtOB8H12]를 합성한 후 이들에 phenyl diazomethane을 반응시켰다. [9,9-(PMe2Ph)2-arachno-9,6-PtOB8H10]과 phenyl diazomethane의 반응생성물은 예상과는 달리 cis-및 trans-stilbene과 trans, trans-benzaldehyde azine이었다. 카르벤의 이량화 반응은 [9,9-(PMe2Ph)2-arachno-9,6-PtOB8H10]의 촉매 작용에 의해 촉진 되었다. Oxametallaborane의 Pt-원자에 있는 d-오비탈이 카르벤의 삼중항 상태의 T1과 T2전자상태를 안정화 시켰다. [9,9-(PMe2Ph)2-arachno-9,6-PtOB8H12]와 phenyl diazomethane의 반응생성 oxametallaborane의 결과와 유사하였고 동시에 미량의 C-카르벤 삽입 반응생성물이 생성되었다. Metallacaborane의 탄소 원자궤도함수인 SOMO와 phenyl diazomethane의 LUMO가 반응하여 분자궤도함수 에너지를 낮추는데 기여하였다. The reaction mechanism and a new synthetic method using oxametallaborane and metallacarborane compounds are investigated. [9,9-(PMe2Ph)2-arachno-9,6-PtOB8H10] and [9,9-(PMe2Ph)2-arachno-9,6-PtCB8H12] are synthesized then, reacted with phenyl diazomethane to find out a new synthetic method corresponding to the metallacarborane cage compound. Unexpectedly cis- and trans-stilbene and trans, trans-benzaldehyde azine are produced from the reaction of [9,9-(PMe2Ph)2-arachno-9,6-PtOB8H10] with phenyl diazomethane. [9,9-(PMe2Ph)2-arachno-9,6-PtOB8H10] is operated as a kind of catalyst to yield dimerization product of carbene. The d-orbital in Pt-atom of oxametallaborane stabilizes the two triplet states of carbene, T1 and T2. A similar reaction products are produced from the reaction of [9,9-(PMe2Ph)2-arachno-9,6-PtOB8H12] with phenyl diazomethane and a trace amount of a new product is also produced such as C-carbene insertion reaction product simultaneously. The molecular orbital energy is lowered by the SOMO energy of metallacarborane and the LUMO energy of phenyl carbene.

조춘 - 정인보

성대동 고요아침 2015 시조시학 Vol.54 No.-

Photodecomposition Mechanism of 2-Methoxy-1,2-diphenyl Diazoethane

성대동,임귀택,김민식,박동규,Seong, Dae Dong,Im, Gwi Taek,Kim, Min Sik,Park, Dong Gyu Korean Chemical Society 1995 Bulletin of the Korean Chemical Society Vol.16 No.1

The mechanism of the photodecomposition of 2-methoxy-1,2-diphenyl diazoethane has been investigated in methanol and isoprene using time-resolved laser flash photolysis techniques. The reaction of triplet carbene which is generated from 2-methoxy-1,2-diphenyl diazoethane with methanol is believed to proceed via thermal excitation to the singlet state. The activation energy and enthalpy are consistent with a mechanism involving thermal equilibrium between the triplet and singlet state followed by the reaction of the singlet with methanol to give ether.

염화나프토일의 親核性置換反應에 미치는 溶媒效果

成大東 東亞大學校 1980 東亞論叢 Vol.17 No.2

1-염화나프토일과 2-염화나프토일의 가매분해반응을 에탄올-아세토니트릴, 2-프로판올-아세토니트릴, 에탄올-아세톤, 2-프로판올-아세톤, 에탄올-물, 2-프로판올-물, 3차 부탄올-물 혼합용매 속에서 전기전도도법으로 측정하였다. 혼합용매의 조성에 관계없이 1-염화나프토일이 2-염화나프토일보다 속도가 크게 나타났다. 이것은 Dewar지수 Nr과 Streiwiesr의 σ+값과도 일치하였다. 1-염화나프토일은 Sn2전이상태에서 반응중심탄소가 sp²에서 sp³로 변하므로 peri-hydrogen effect가 relieve 됨을 알 수 있었으며 또한 모든 반응이 대체로 Sn2 반응메카니즘으로 진행됨을 알 수 있었다. 동일한 반응기질이 에탄올과 2-프로판올 및 공용매인 아세토니트릴의 혼합용매속에서도 메탄올-아세토니트릴 혼합용매에서와 같은 최대속도 현상이 나타났다. 즉 메탄올-아세토니트릴 혼합용매게에서는 메탄올의 물분율 0.85에서 최대치가 나타나는데 비해 등유전성이 아닌 에탄올-아세토니트릴 혼합용매게에서는 에탄올의 물분율 0.78에서 2-프로판올-아세토니트릴 혼합용매계에서는 2-프로판올도의 물분율 0.62에서 각각 최대속도상수를 갖는다. 이것으로 미루어 볼 때 에탄올과 2-프로판올도 메탄올과 같이 수소결합을 형성하여 다량체를 만들고, 가용매분해반응에서 아세토니트릴이 첨가될 때 이들 알코올의 다량체 구조가 파괴됨을 알 수 있었다. 또한 섭동분자이론(PMO)에서 구한 비결합분자궤도함수(NBMO)의 계수와 반응속도의 대수가 거의 직선적으로 비례함을 알 수 있었다. The kinetics for solvolysis of 1-naphthoyl and 2-naphthoyl chlorides have been measured in solvent mixtures, EtOH-Me추, 2-PrOH-MeCN, EtOH-(Me)₂CO, 2-PrOH-Me)₂CO, EtOH-H₂O, 2-PrOH-H₂O and t-BuOH-H₂O. The rate constants of 1-naphthoyl chloride were faster than 2-naphthoyl chloride in all solvent mixtures. This agrees with Dewar number, Nr and Streitwieser's σ+ value. It was concluded that the valence state of carbonyl carbon changed from sp² to sp³ in transition state and peri-hydrogen effect was relieved; the solvolytic reactions proceeded by Sn2 mechanism in all solvent mixtures system. There were maxima in rate of reaction for EtOH-MeCN, 2-PrOH-MeCN mixtures in the same way as for MeOH-MeCN mixture. The maximum rate in EtOH-MeCN mixture was observed at mole fraction of EtOH, 0.85 and in 2-PrOH-MeCN mixture was observed at mole fraction of 2-PrOH, 0.62. This behavior is interpreted as the structure of alcohols also has hydrogen bonding structure, and the polymer structure of alcohols is destroyed by adding aprotic solvent, MeCN. Comparing the perturbation molecular orbital theory in the transition state, the logarithms of solvolytic rate constants have been found to be proportional to the AO coefficient of nonbonding molecular orbital, 2a? in this solvolytic reaction.

Dabsyl Chlorides의 親核性 置換反應

成大東,朴現錫,柳俊夏,金良姬,李鍾八,嚴泰燮 東亞大學校 1990 東亞論叢 Vol.27 No.1

Kinetic studies of nuclsophilic substitution reaction of dabsyl chloride with pyridines have been investigated at 30℃ in a range of methanol-acetonitrile bianary solvent mixtures. The order of magnitude fo reactivity is β-picoline > pyridine > 1.5-N D A > α-picoline to react with dabsyl chloride, especially in case of α-picoline, the reactivity revealed lower than others, it is suggestd that nitrogen atom of pyfidine ring has a steric hinderance by the neightboring methyl group. The value of ρ(-0.96∼4.59) and β(0.36∼0.67) associated with a change of substituent in the nucleophile are large and indicate a realtively advanced bond formation in the transition state. Solvatochraomic correlations were predicted the importance of bond formation transition state, showing a greater contribution of polaritypolarizability (π*) lone paired to hydro-gen bond donar acidity (α). We conclude that the reaction of dabsyl chloride with pyridine proceed via S2 type reaction mechanism, as well as the reaction of dansyl chloride pyridine.