왜 m - methyl 치환 살충제들은 강한 살충작용을 나타낼까 ? : Phenyl N - methylcarbamate 와 m - xylyl - N - methylcarbamate 유도체들에 관하여 On the Phenyl N - methylcarbamate and m - xylyl - N - methylcarbamate Derivatives

성낙도 한국농화학회 1989 Applied Biological Chemistry (Appl Biol Chem) Vol.32 No.2

In order to seek the molecular basis of higher insecticidal activity of the carbamates with two methyl groups, m-xylyl-N-methylcarbamate(MXNMC) than the corresponding unsubstituted phenyl N-methylcarbamate(PNMC), these two derivatives have been studied by molecular orbital(MO) theoretically using extended Hu◎ckel theory(EHT), and analysis of regression and linear free energy relationship(LFER). The most stable stereo structure(Z,Z) shows that the phenyl group occupies vertical(θ=90°) position on the plane of the N-methylcarbamyl group. Regression analysis shows that especially good correlation exists between the pI_(50) values and the calculated MO quantities when the hydrogen atomic charge of metaposition and of m-methyl groups, and LUMO energy are taken as variables. The LFER analysis on the carbamylation indicates that field(F) effect(60%) is slightly larger than resonance(R) effect(40%) in PNMC(F$gt;R), whereas, in case of MXNMC, R effect(98.6%) is much larger than F effect(1.4%)(R≫F). From the basis on the findings, the enhancement of insecticidal activity of MXNMC may be the result of hyperconjugation by m-methyl groups.

The Kinetics and Mechanism of Hydrolysis of Styrylphenylsulfone Derivatives

성낙도,권기성,김태린,Nack-Do Sung,Ki-Sung Kwon,Tae-Rin Kim Korean Chemical Society 1989 대한화학회지 Vol.33 No.1

pH 0.0∼14.00 범위에서 styrylphenylsulfone 유도체들의 가수분해반응에 대한 반응속도론적 연구가 25$^{\circ}$C의 50% 메탄올-물속에서 자외선 분광법으로 이루어졌다. 반응속도식과 치환기 효과(${\rho}$=1.85(pH 7.0), ${\rho}$=1(pH 13.0))로부터, pH 11.0이상에서는 전형적인 Michael형의 친핵성 첨가반응, pH 9.0이하에서는 물분자에 의한 일반 염기촉매반응, 그리고 pH 9.0∼11.0사이에서는 이들 두 반응이 경쟁적으로 일어남을 제안하였다. The Kinetics of hydrolysis of styrylphenylsulfone derivatives in 50% methanol-water at 25$^{\circ}$C and ionic strength of 0.10 was investigated by UV spectrophotometry in the pH range of 0.0-14.0. The rate equations, which can be applied over a wide pH range, were obtained. The Hammett rho constants for the hydrolysis are 1.85 at pH 7.0 and 1.54 at pH 13.0, respectively. On the basis of the evidence, it is proposed that the general base-catalysis occurs in the hydrolysis of styrylphenylsulfone derivatives; above pH 11.0, Michael type nucleophilic addition take place, while below pH 9.0, the reaction is initiated by addition of water and from pH 9.0 to pH 11.0 these two reactions occur com-petitively.

Phenyl N-phenylbenzthioimidate 誘導體 들의 酸-觸媒 加水分解 反應 메카니즘

성낙도,박천규,권기성,김태린,Nack-Do Sung,Cheon-Kyu Park,Ki-Sung Kwon,Tae-Rin Kim 대한화학회 1991 대한화학회지 Vol.35 No.2

산성용액 중에서 Phenyl N-(p-chlorobenzoyl)chloroformimidate 유도체의 가수분해 반응 메카니즘

성낙도,전용구,권기성,김태린,Nack-Do Sung,Young-Gu Cheun,Ki-Sung Kwon,Tae-Rin Kim 대한화학회 1987 대한화학회지 Vol.31 No.4

$25^{\circ}C$의 1 : 4 dioxane-물의 혼합용액속에서 파라-치환된 phenyl N-(p-chlorobenzoyl)chloroformimidate (I) 유도체들의 가수분해 반응속도 상수를 측정하고 반응속도식, 치환기 효과$(\rho\>{\rho}^+)$, 생성물 분석 및 분자궤도 함수의 계산 결과로부터 pH3.0 이하에서는 azocarbonium 이온(II)이 생성되는 $S_N1$반응 메카니즘으로 무촉매 반응이 일어나며, pH 4.0이상에서는 전이상태(III)를 지나는 $S_N2$반응 메카니즘을 통하여 염기 촉매반응이 일어남을 제안 할 수 있었다. 4가지 peri planar형태 이성질체들의 상대적인 안정도는 각각 (E-ap) > (Z-ap) > (E-sp) > 및 (Z-ap)이었고, (E-ap)형태의 가장 안정한 입체구조는 benzimidochloroformyl group면에 대하여 Y-치환 phenyl group이 수직$(90^{\circ})$을 이루었으며 (I)의 활성화된 azomethine탄소 원자에 대하여 물분자는 시그마 공격에 의하여 친핵성 반응이 일어난다. Rate constants for the hydrolysis of para-substituted phenyl N-(p-chlorobenzoyl)chloroformimidate (I) derivatives in 1 : 4 dioxane-water at $25^{\circ}C$ have been determined. Rate data, substituent effect $(\rho\>{\rho}^+)$, product analysis and MO calculation indicate that the uncatalyzed reaction proceeds through an $S_N1$ mechanism involving the formation of azocarbonium ion (II) below pH 3.0, and the base-catalyzed reaction proceeds through an $S_N2$ mechanism via transition state (III) above pH 4.0. The relative stability of four peri planar conformational isomers were (E-ap) > (Z-ap) > (E-sp) > (Z-ap), respectively, and the most stable stereo structures shows that the Y-substituted phenyl group $(C_6H_4-Y)$ occupy vertical $(90^{\circ})$ position on the plane of the benzimidochloroformyl group in (E-ap) conformer. The nucleophilic substitution of water molecule occurs by sigma attack to the activatived azomethine carbon atom of (I) derivatives.

생물학적 자극 통제 수단으로 활용하기 위한 돼지 페로몬성 냄새 물질의 탐색 3 : 2-(Cyclohexyloxy) Tetrahydrofurane 유도체와 Porcine Odorant Binding Protein 사이의 결합 친화력에 관한 비교 분자장 분석

성낙도,박창식,정훈성,성민규 한국동물번식학회 2006 Reproductive & developmental biology Vol.30 No.1

생물학적 자극통제 수단으로 활용하기 위한 돼지 웅성 페르몬성 분자를 탐색하고자 일련의 냄새 분자로서 2-(cyclo-hexyloxy) tetrahydrofurane 유도체들의 정량적인 구조와 수용체인 porcine odorant binding protein (pOBP)간의 결합 친화력 상수(p(Od)50)에 대한 비교 분자장 분석(CoMFA)을 실행하였다. 가장 양호한 CoMFA 모델 AIV (r2 cv.(q2)=0.886 및 r2 ncv.=0.984)은 기질 분자 내 입체 중심(chiral center)의 절대 배열이 C1(R),C2(S)인 분자를 atom based fit 방법으로 배열하였을 경우의 standard field와 indicator field가 조합된 CoMFA장의 조건에서 유도되었다. 이 CoMFA 모델은 입체장 40.8% 정전기장 14.6%및 소수성장 44.6%가 결합 친화력 상수에 영향을 미치는 요소임을 나타내었다. 등고도의 분석 결과로부터 효과적인 결합 친화력 냄새 분자를 수식하는 데 몇 가지 가치 있는 정보를 얻을 수 있었다. To search of new porcine pheromonal odorants for biostimulation control system technologies to improve reproductive efficiency in livestock species, the comparative molecular field analysis (CoMFA) for binding affinity constant (p(Od)50) between porcine odorant binding protein (pOBP) and ligands of odorant 2-(cyclohexyloxy) tetrahydrofurane derivatives as substrate molecule was conducted and discussed. In the optimized CoMFA model AIV with chirality (C1'(R), C2(S)) in substrate molecule and atom based fit alignment (A) of odorants, the statistical results showed the best predictability of the binding affinities (p(Od)50) based on the LOO cross-validated value r2 cv.(q2=0.886) and non-cross-validated conventional coefficient (r2 ncv.=0.984). the binding affinity constants exhibited a good correlation with steric (40.8%), electrostatic (14.6%) and hydrophobic (44.6%) factors of the substrate molecules. from the analytical results of the contour maps, which may give us some valuable informations to the modification of odorants for effective binding affinity.

N-[1-(benzotriazol-1-yl)aryl]arylamine 유도체의 항균성과 정량적 구조활성 관계(QSAR)

성낙도,김경훈,최우영,김홍기,Sung, Nack-Do,Kim, Kyoung-Hoon,Choi, Woo-Young,Kim, Hong-Ki 한국응용생명화학회 1992 Applied Biological Chemistry (Appl Biol Chem) Vol.35 No.1

일련의 새로운 N-[1-(benzotriazol-1-yl)-X-치환-aryl]-Y-치환-arylamine 유도체를 합성하고 Pyricularia oryzae, Fusarium oxysporum f. sp. sesami, Valsa ceratosperma 및 Botrytis cinerea에 대한 항균활성$(pI_{50})$을 한천 희석법으로 측정하여 정량적인 구조-활성 관계$(QSAR_S)$를 분석한 바, X 및 Y-치환기들의 ${\pi}$와 ${\sigma}$ 및 $M_R$ 파라미터가 항균 활성을 결정하는 중요한 요소이었다. 4-bromo 치환체(1d 및 2b)가 항균활성이 제일 큰 화합물이었으며, 중성 pH에서 1의 가수분해 반응에 대한 반감기$(T_{1/2})$는 약 1.5일 이었다. 기질 화합물의 분자궤도(MO) 함수와 항균 반응에 대한 자유에너지 관계$(LFER_S)$ 그리고 분자 설계의 결과들이 검토되었다. A series of new N-[1-(benzotriazol-1-yl)aryl]arylamine derivatives were synthesized and their antifungal activities $(pI_{50})$ in vitro against Pyricularia oryzae, Fusarium oxysporum f. sp. sesami, Valsa ceratosperma and Botrytis cinerea were dertermined by the agar medium dilution method. From the results of the quantitative structure-activity relationships $(QSAR_S)$ analysis, $hydrophobicity({\pi})$, $electronic({\Sigma\sigma})$ and molar $refractivity({\Sigma}M_R)$ parameter of X & Y-substituents on the phenyl group were also shown to be important factor in determining the variation in the antifungal activity. 4-Bromo group substituents (1d & 2b) were the most effective compounds and the $half-life(T_{1/2})$ on the hydrolysis of X(1) at netural pH was about 1.5 day. Molecular orbital(MO) functions of substrate compound, linear free energy relationships$(LFER_S)$ on the antifungal reactivity arid the results of molecular design were also discussed.

새로운 5,6-dihydro-2-trifluoromethyl-1,4-oxathiincarboxanilide 유도체의 항균활성에 미치는 치환-phenylcarbamoyl group의 영향

성낙도,유성재,남기달,장기혁,한호규 충남대학교 생물공학연구소 1999 생물공학연구지 Vol.7 No.-

기질(S) 화합물로 30종의 5,6-dihydro-2-trifluoromethyl-1,4-oxathiin carboxanilide 유도체들을 합성하고 벼 잎집무늬 마름병균(Rhizoctonia solani)과 밀 붉은 녹병균(Puccinia recondita)에 대한 항균활성(in vivo) 값(pI_50)을 측정하였다. (S)는 잘록병균보다 밀 붉은녹병균에 대하여 보다 큰 항균활성을 나타내었으며 두 종의 균에 대하여 3-methoxy, 11, 3-iso-propyloxy, 13 및 3-iso-propyl 치환체, 25가 제일 큰 활성을 보였다. 그리고 치환(X)-phenylcarbamoyl group의 변화에 따른 물리-화학 파라미터와 항균활성(pI_50)으로부터 구조-활성관계(SAR)를 검토 한 결과, 벼 잎집무늬 마름병균에 대하여는 공명효과에 따른 전자밀게(R<0)의 소수성이 큰(π>0) m-alkyl 치환기(X)가, 그리고 밀 붉은녹병균에 대하여는 분자 분극율(Sp.Po1.)과 분자의 음하전(ABSQ<0)을 위시하여 HOMO에너지(e.v.)가 클수록(HOMO<0) 높은 항균활성을 나타내었다. 또한, 전하-조절 반응에 의한 수용체-(S)간의 상호작용과 높은 활성발현 조건들이 검토되었다.(1998년 2월 3일 접수, 1998년 12월 1일 수리) New thirty derivatives of 5,6-dihydro-2-trifluoromethyl-1,4-oxathiin carboxanilide as substrate(S) were synthesized and their fungicidal activities in vivo against rice sheath blight(Rhizoctonia solani) and wheat leaf rust(Puccinia recondita) were examined. The structure activity relationships(SAR) between the activities(pI_50) and a physicochemical parameters of substituents(X) at the phenylcarbamoyl group were analyzed using the adaptive regression analysis method. The 3-methoxy, 11, 3-isopropyloxy, 13 and 3-isopropyl substituent, 25 as X on the phenylcarbamoyl group exhibited the most highest fungicidal activity against the two fungi. The fungicidal potency of the (S) against Puccinia recondita was higher than Rhizoctonia solani. In case of Rhizoctonia solani, the molecular hydrophobicity(π>0) and resonance effect(R<0) by meta-alkyl substitutents with electron donating were important factors in determining fungicidal activity. And the HOMO energy(HOMO>0), ABSQ, sum of absolute values of the atomic charges on each atom and specific polarizability(Sp.Pol<0) of (S) were significantly influential towards fungicidal activity against Puccinia recondita. The interaction between (S) and receptor against from the based on SAR studies proceeds through charge-control reaction, and conditions to show higher activity has been also discussed.

살충성 O,O-Dimethyl-O-(3-Metyl-4-Nitrophenyl)-phosphorothioate (Sumithion^�)의 전기화학적 환원반응에 미치는 Micell의 영향

成洛道,明平根,朴勝熙,金日光 圓光大學校 基礎自然科學硏究所 1988 基礎科學硏究誌 Vol.7 No.3

The electrochemical reduction of sumithion in various surfactants, NaLS, CTABr, Triton X-100 and in acetonitrile solution has been examined by DC, DP polarography and cyclic voltammetry (CV). Especially, in anionic surfactant, NaLS solution, the height of reduction wave is dramatic eliminated and half-wave potentials are shifted to strong negative potential (-2.7 volt vs. Ag-AgCl) by repulsion of nitro group in sumithion and anionic micell surfaces. The processes of reduction of sumithion were irreversibly electrochemical mechanism and the result of the reaction at high cathodic potential (-2.7v. vs. Ag-AgCl), O,O-dimethyl-O-(3-methylhydoxyaminophenyl) phosphorothioate is formed as major product via O,O-dimethyl-O-(3-methylnitrosophenyl) phospho-rothioate in NaLS micell solution.

錦江 流域의 水質 汚染度(1981)

成洛道,鄭憲俊,吳仁敎 圓光大學校 基礎自然科學硏究所 1982 基礎科學硏究誌 Vol.1 No.1

The authors has made an investigation on the water pollution of Kum River in chungnam province area from January to December 1981 and discusses the results of the water quality for the water samples were taken from 5 stations along the Kum River basin that is, Caechung dam (Ⅰ), Meapo(Ⅱ), Yeungi(Ⅲ), Gongju(ⅳ) Bueyeu(ⅴ). It is confirmed, by the analysis of B.O.D., C.O.D., S.S. and coliform that the Kum rever water was relatively less polluted than the other. Therefore it may be suitable still as source of water system. The relationships between pollutants in the Kum River Basin are as follow; B.O.D.(㎎/ℓ)=1.30C.O.D.-0.05(㎎/ℓ)

殺蟲性 Phosphonate系 農藥의 加水分解

成洛道 忠南大學校 環境問題硏究所 1983 環境硏究 Vol.1 No.1

5가지 유기 인계 노업용 약제 중에서 p원자에 4개의 산소 원자가 결합된 phosphonate계 화합물에 대한 CNDO/2의 MO함수 계산 방법을 이용하여 반응성을 검토한 바, 알짜 전하는 P≫C₂이였으며 vinylphosphates와 phenylphosphates화합물 모두 O₃-C₂에는 π*-반결합성, P-O₃에는 π-결합성 궤도가 있음을 알았다. 반응중심인 vinylphosphates의 αC₂(sp²)와 phenylphosphates의 p원자는 sp³이므로 입체장애는 sp³>sp²이다. Vinylphosphate는 ASE₂반응이나 Michael형의 반응으로 αC₂(sp²)에 친핵체가 첨가되어 π*-반결합성인 O₃-C₂결합이 용이하게 분열되며, phenylphosphates는 p원자(sp³+(pπ-dπ))에 대한 친핵성 첨가-제거반응으로 trigonal bi-pyramidal(sp³d) 중간체를 경유하여 π-결합성인 P-O₃결합이 분열되기 때문에 반응성은 vinylphosphates≫phenylphosphates이다. Nodal properties, formal net charges and bond population of phosphoryl group of phosphonate derivatives have been studied in order to investigate structure-reactivity relationship using such as CNDO/2 MO calculation method. It was also found that MO show relatively strong π*-antibonding nature between αC2 atom and O3 atom, on the contrary, MO show strong π-bonding nature between P atom and O3 atom. The nucleophilic addition-elimination reactivity of phenylphosphates and Micheal type reaction or ASE₂reactivities of vinylphosphates may largely be more controlled by steric hinderance (sp³+(pπ-dπ)>sp²) than formal net charges of reaction site(P≫αC₂). Therefore, the order of hydrolysis rates studied was vinylphosphates≫phenylphosphates.