할로겐화 카르벤의 반응성과 동력학적 성질

성대동,이종팔,엄태섭,이상훈 東亞大學校附設基礎科學硏究所 1995 基礎科學硏究論文集 Vol.12 No.1

할로겐화 디아조메탄 및 아릴할로겐화 카르벤의 전구물질을 레이저 섬광분해법으로 반응시키면서 이때의 카르벤중간체의 반응속도를 시분해 레이저 분광법으로 측정한 후 얻어진 속도상수로부터 카르벤의 전자스핀상태를 알아 보았다. 카르벤 탄소에 치환된 치환기에 따라 반응속도상수가 달라졌고 그 경향은 대체로 methylence의 수소원자 대신에 전기음성도가 큰 원자나 전자흡인기가 치환되어 있을 경우는 속도상수가 크게 나타났고 반대로 전기음성도가 작은 원자나 전자주게기가 치환되어 있을 경우는 속도상수가 작게 나타났다. 열반응이 배제된 저온 아르곤 매트릭스에서 디아조 화합물과 Seyferth시약을 광화학적으로 분해시켰더니 단일항 카르벤에 의한 반응은 ylid중간체가 생성되는 반응으로 진행하지 않고 단일항 카르벤은 빠른 시간에 계간건너기를 하여 삼중항카르벤과 평형을 이루었다. 그러나 카르벤 탄소에 전기음성도가 큰 원자나 전자흡인기가 치환되어 있을 경우는 단일항과 삼중항과의 스핀 평형이 깨어져 단일항 카르벤과 삼중항 카르벤과의 에너지 차이, ?? 크게 관측되었다. The study of photodecomposition reaction of various diazo compounds and their dynamics of carbene intermediates are investigated. The fluorescence decay rates of the carbenes which have two substituents on the carbonic carbon are determined by a time-resolved laser flash photolysis. The decay rate constants change depending on the substituent ; the carbene bearing high electronegative atom or the electron withdrawing substituent reveals higher decay rate constants than the carbene bearing the low electronegative atom or the electron donating substituents. The photodecomposition reactions of diazo compounds and Seyferth's reagent have been investigated in an argon matrix of low temperature. The singlet carbene reaction does not proceed by the mechanism of forming the ylid intermediate. The singlet carbene is equilibrated with the triplet carbene quickly by intersystem crossing. The carbene bearing the high electronegative atom or the electron withdrawing substituents, however, shows a high energy ?? between the singlet state carbene and the triplet state carbene.

多面體 硼素化合物의 反應性과 메카니즘

成大東,金奎喆,柳俊夏,徐敬賢,金良姬 東亞大學校附設基礎科學硏究所 1990 基礎科學硏究論文集 Vol.7 No.1

1,2-dicarba-closo-dodecaborane과 carbene들과의 icosahedral carborane반응에 대한 반응성과 cage borane반응에 대한 메카니즘을 icosahedral skeleton 의 구조적 관점에서 연구하였다. 반응 생성물은 주로 B-inserted-o-carborane이였으며, B-inserted methyl-??-carborane과 di-,tri-o-carborane은 상대적으로 적게 생성되었다. B-inserted chloro-o-carborne과 carbene반응으로부터 carbone의 전자배열은 cage carborane의 구조변화에 따라 open-shell, lowest triplet 그리고 lowest closed-shell 전자배열이 유리한 것으로 나타났다. Reactivity for the reaction of icosahedral carborane, 1,2-dicarba-closo-dodecaborane with various carbenes and the mechanism for the reaction of cage borane have been studied in view point of structure of icosahedral skeleton. From Friedel-Craft reaction, the reaction products were B-inserted-0-carborane mainly and B-inserted methyl-0-carborane and di-and tri-0-carborane were produced only a little. From the carbenic reaction with B-inserted chloro-0-carboranes the electronic configurations of carbenes were favored open-shell, lowest triplet, and lowest closed-shell electronic configurations along with the structure variation of cage carboranes.

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.

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.

1-Di-butylaminonaphthalene-5-Sulfonyl Chloride와 Pyridine 置換體와의 反應

成大東,李鍾八,朴現錫,金良姬 東亞大學校 大學院 1989 大學院論文集 Vol.14 No.-

Nucleophilic substitution reaction of bansyl chloride with mathyl substituted pyridines have been studied kinetically at 0℃ in methanol-acetonitrile binary solvent mixtures. The order of magnitude of reactivity is γ-picoline>β-picoline>pyridine to react with bansyl chloride. The Bronsted βand Hammett ??values indicated that the bond formation is advanced more than the bond breaking at the transition state. The reactivity of nucleophiles is in accord with charge controlled and the reactivity of substrate has shown an orbital controlled 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.

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.

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.

親核性 置換反應에서 最大速度現象과 Hammett 相關關係

성대동,이종팔,이미정,엄태섭 東亞大學校 大學院 1996 大學院論文集 Vol.21 No.-

The nucleophilic substitution reactions of p-substituted benyl bromide with p-substituted N,N-dimethyl anilines in methanol and acetonitrile binary solvent mixtures which are known as an isodielectric olvent system kinetically and the results are as follows. 1.The postive dharge 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 on the analogy of Hammett ?? values. 2.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 anlogy of Hammett ?? values. 3.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 interacton coefficient, ??.