Transmission of Substituent Effects through Five-Membered Heteroaromatic Rings. III. Addition Equilibria of Hydroxide Anion to Benzaldehyde Analogues

손창국,전영아,이순기,김창건,김찬경,이익춘,Son, Chang Guk,Jeon, Yeong A,Lee, Sun Gi,Kim, Chang Geon,Kim, Chan Gyeong,Lee, Ik Chun Korean Chemical Society 2000 Bulletin of the Korean Chemical Society Vol.21 No.12

Transmission of substituent effects through 5-membered heteroaromatic rings is investigated theoretically at the RHF/6-31+G and B3LYP/6-31+G levels using the equilibria for the $OH^- addition to five-membered heteroaromatic aldehydes (5MHA). The transmission efficiency (S) in 5MHA(A) increases in the order NH>O>S>PH but the order exactly reverses in 5MHA($T^-$). This is originated by the delocalizability of the ${\pi}$ lonepair on Y, $$n_\pi$(Y)$. A better correlation is obtained with ${\sigma}_p^-$ in the Hammett plots with positive slope, $p_z$ > 0, indicating that the substituent (Z) effects are not transmitted by a direct conjugation. The magnitude of $p_z$ for Y=NH is the largest among the heteroaromatic systems, which is consistent with the largest transmission efficiency change $({\Delta}S)$. The equilibria for the addition processes are favorable in the gas phase $({\Delta}G^o<0)$, which reverses to unfavorable in aqueous solution $({\Delta}G^o>0)$ due to the relatively large salvation energy of $OH^-$ in the initial state in aqueous solution. The orders of ${\Delta}G^o$ and $p_z$ in the gas phase are almost maintained in solution.

Transmission Substituent Effects through Five-Membered Heteroaromatic Rigns, Ⅱ. Deprotonation Equilibra of Phenol Analogues

손창국,임선희,리순기,김창곤,김찬경,이익훈,Son, Chang Guk,Im, Seon Hui,Ri, Sun Gi,Kim, Chang Gon,Kim, Chan Gyeong,Lee, Ik Hun Korean Chemical Society 2000 Bulletin of the Korean Chemical Society Vol.21 No.9

Transmission of substituent effects through 5-membered heteroaromaticrings isinvestigated theoretically at the RHF/6-31+G* and B3LYP/6-31+G* levelsusing the deprotonation equilibria of phenol analogues with heteroatoms Y = NH, O, PHand S. The incr ease in the resonance delocalization of the $\pilone-pair$ on the phe-nolic oxygen atom, $n\pi(O)$, accompanied with the deprotonation depends on the heteroatom Y,in the order NH < O < PH < S. This represents the $\pielectron$ accepting ability, or conversely reverse order of the $\pielectron$ donating ability of the $\pilone-pair$ on Y, $n\pi(Y).$ The transmission efficiency of substituenteffects is, however,in the reverse order NH > O > S, which represents the order of delocalizability of $n\pi(Y).$ A better correlation is obtained with ${\sigma}p$ - than with ${\sigma}p$ for the Hammett type plots with the positive slope, $\rho-$ > 0, of the magnitude in the same order as that for the delocalizability of $n\pi(Y).$ Thedeprotonation energy, ΔG = [G(PA) + G(H+)] -G(P), decreases with the increasein the extence delocalization in the order NH > O > PH > S.

아세토니트릴-메탄올 혼합용매계에서 질산벤질과 아닐린의 친핵성 치환반응

손창국,김왕기,이수정,양기열,Son, Chang Guk,Kim, Wang Gi,Lee, Su Jeong,Yang, Gi Yeol 대한화학회 1990 대한화학회지 Vol.34 No.3

50-100% $CH_3CN-CH_3OH$ 혼합용매계에서 파라-치환된 질산벤질과 아닐린과의 친핵성 치환반응에 대한 2차 속도상수를 전기전도도법으로 구하였다. 속도자료를 이용하여 Hammett ${\rho}_N$과 ${\rho}_C$값, Bronsted $\beta$값 및 용매화 파라미터 계수들을 구하였으며 이들을 PES및 양자역학 모형에 적용하여 구조 변화를 논의하였다. 연구 결과 결합형성보다 결합절단이 비교적 많이 진행된 상태에서 치환기 변화에 따라 결합절단의 진척이 결합형성을 촉진하는 동시적 $S_N2$ 반응메카니즘으로 진행됨을 알았다. Kinetic studies on the nucleophilic reactions of p-substituted benzylnitrates with substituted anilines have been conductometically carried out in 50-100% $CH_3CN-CH_3OH$ mixtures. From the kinetic data, Hammett ${\rho}_C$ and ${\rho}_N$ values, Bronsted $\beta$ values, and solvatochromic coefficients were determined in order to examine the transition state variations caused by changes in substituents and solvent properties. It is concluded that the reaction proceeds via a synchronous $S_N2$ mechanism in which bond formation is more advanced than bond cleavage.

질산기의 친핵성 치환반응. 아세토니트릴용매에서 질산치환벤질류와 아닐린류와의 반응속도론

김왕기,손창국,Wang Ki Kim,Chang Kook Sohn 대한화학회 1989 대한화학회지 Vol.33 No.1

순수한 아세토니트릴용매에서 질산파라-치환 벤질과 파라-치환 아닐린간의 친핵성 치환반응에 대한 2차반응속도상수를 전기전도도법으로 구하여 Hammett ${\rho}$x와 ${\rho}$y값 및 Bronsted ${\beta}$값을 계산하였다. 이때 아닐린의 치환기 변화에 따르는 ${\rho}$x는 음의 값으로 주어졌으며 기질의 치환기에 따라서는 U자 모양의 비직선성 Hammett 도시가 얻어졌다. 포텐셜에너지표면 및 양자역학적 모형을 적용하여 치환기 변화에 따른 천이상태 구조의 변화를 고찰하여 본 결과 본 반응은 기질의 치환기의 성질에 따라 결합형성의 정도가 크게 변화하는 $S_{N}2$ 반응 메카니즘으로 진행함을 알 수 있었다. The second-order rate constants for the nucleophilic substitution reactions of para-substituted benzyl nitrates with para-substituted anilines in acetonitrile were conductometrically determined. Hammett ${\rho}$x and ${\rho}$y values and Bronsted ${\beta}$ values were obtained from these kinetic data. The reactions of Benzyl nitrates with the series of anilines showed linear Hammett plots with negative slopes. For the change of substituents in the benzyl nitrates, nonlinear Hammett plots with a concave upwards curve were obtained. We applied the potential energy surface and the quantum mechanical models in order to examine the transition state variations caused by changes in substituents on the nucleophile and the substrate. The results showed that the reaction was proceeded via the $S_{N}2$-type reaction mechanism in which the extent of bond-formation was greatly changed depending on the property of the substituents in substrate.

궤도간 상호작용의 섭동분자궤도 이론 (제4보). 헤테로 원자계에서의 n-n 궤도간 상호작용

이익춘,손창국,김왕기,Ikchoon Lee,Chang Kook Sohn,Wang Ki Kim 대한화학회 1983 대한화학회지 Vol.27 No.5

N개의 $\sigma$결합으로 분리되어 있는 분자내 두 비결합 궤도함수(nonbonding orbital)간의 상호작용을 PMO론적으로 고찰하기 위하여 질소, 산소 및 황화합물에 대하여 반경험적인 CNDO/2 및 ab initio(STO-3G 수준) 계산을 수행하였다. 각 사슬형 및 고리형 화합물에 대한 기저준위의 에너지, orbital 상호작용에 의한 에너지준위 분리 및 상호작용 에너지 변화에 대한 계산 결과는 섭동론적 에너지항으로 만족스럽게 설명될 수 있었다. 질소 및 산소화합물에서는 through-space 상호작용 에너지항으로서 계산결과가 만족스럽게 설명될 수 있었다. 이 경우 N이 홀수인 계에서는 n-준위가 n+준위보다 안정화되었고 N이 짝수인 계에서는 n+준위가 n-준위보다 안정화되었다. 이 때의 에너지 분리는 홀수계에서 더 큰 결과를 보였다. 그러나 cis-ethylene diamine과 o-phenylene diamine(Table 4의 구조 VI)에서는 through-space 상호작용의 기여가 무시될 수 없었고 그 결과 홀수계에서 에너지 준위의 순서가 뒤바뀌게 되었으며 에너지분리도 짝수계에서 더 큰 결과를 보였다. 끝으로 황화합물에서는 항상 through-space 상호작용의 기여가 무시될 수 없었다. 이 결과는 3주기 원소인 황의 크기가 2주기 원소인 질소 및 산소보다 크다는 사실과 일치하고 있다. The CNDO/2 and STO-3G calculations were performed on nitrogen, oxygen, and sulfur compounds in order to examine the effect of interactions between two nonbonding (n) orbitals in the same molecule separated by N intervening $\sigma$ bonds based on the PMO approach. Calculated basis level energies, energy splittings, and interaction energy changes for both chain and cyclic model compounds were qualitatively compared with the corresponding predictions derived from perturbational formalism for n-n orbital interactions and successfully explained in terms of the derived energy expressions. In general, through-space interaction term could be neglected in the N and O systems. And the calculated results were explained simply by through-bond interaction term. As a result, through-bond interaction placed n- below n+ for odd systems and n+ below n- for even systems. Also energy splittings in odd systems were larger than those in even systems. However, in the cases of cis-ethylene diamine and o-phenylene diamine(conformer VI in Table 4), through-space interaction term was found to be substantial and the opposing effects of through-space and through-bonds interactions were observed. Finally it was found that the interactions between two n orbitals on S atoms always had some contribution of the destabilizing through-space interaction term. This result was consistent with the fact that the lone pair lobes of third elements were larger in size than those of the second period elements.

Amide류에서 형태안정화와 C-N결합의 회전장벽에 관한 분자궤도론적 연구

김왕기,손창국,이익춘,Wang Ki Kim,Chang Kook Sohn,Ikchoon Lee 대한화학회 1988 대한화학회지 Vol.32 No.3

The MNDO calculations were performed on the various rotamers of N-methyl formamide, N,N-dimethyl formamide, N-methyl acetamide, and N,N-dimethylacetamide in order to investigate the contribution of the one-electron and the steric effect on their rotational barriers about the C-N bond. Results show that while the conformational stabilities of formamides depend mainly on the one-electron factor, those of acetamides depend mainly on the steric factor. According to results obtained by calculations on the rotational barriers about C-N bond, for N-monosubstituted amides the steric effect is larger in the rotational ground state than in the transition state and for N,N-disubstituted amides the steric effect is larger in the rotational transition state. N-methyl formamide, N,N-dimethyl formamide, N-methyl acetamide, 및 N,N-dimethyl acetamide의 여러 형태에 대한 상대에너지를 MNDO법으로 구하여 C-N결합 및 메틸기 회전에 대한 회전장벽에 미치는 1-전자 및 입체 반발에너지의 영향을 논의하였다. 그 결과 formamide의 형태안정화는 주로 1-전자 에너지항에 의하여 결정되고, acetamide의 형태안정화는 주로 입체인자항에 의하여 결정됨을 알았다. C-N 결합에 대한 회전장벽을 구한 결과 N-methyl formamide와 N-methyl acetamide에서 입체 장애 효과는 바닥상태에서 보다 전이상태에서 크게 작용하지만 N,N-dimethyl formamide와 N,N-dimethyl acetamide에서 입체장애 효과는 전이상태에서 보다 바닥상태에서 더 크게 작용함을 알았다.

MeOH-MeCN 혼합용매계에서 염화메틸아릴과 치환피리딘의 친핵성치환반응에 관한 연구

류왕선,손창국,김왕기 全南大學校 師範大學 科學敎育硏究所 1998 科學敎育硏究誌 Vol.22 No.1

Kinetic . studies on the nucleophilic substitution reactions of arylmethyl chlorides(9-chloromethyl anthracene, 1-chloromethyl naphthalene, 2-chloromethyl the nucleophilic substitution and benzyl chloride)with substituted pyridines. (p-aminopyridine, r -picoline,pyridine, and m-bromopyridine havebeen carried out in MeOH-MeCN mixtures. Rate constants were measured by conductivity method and· the pseudo-first-order rate constants were determined using Guggenheim method. Second-order rate constants were evaluated through plot of k obs a.gainst nucleophile concentrations . . It was concluded that increasing number of aromatic ring, the rate constants in order of phenyl<2-naphthyl <1-naphthyl<9-anthracyl were enhanced and the terms of Hammett p x value, Brc/Jnsted (3 N value, solvent effect, and aryl effect etc, as a result it can be predicted SNI-dissociative SN2. Kinetical results were compared between potential energy surface model and quantum mechanical model. The quantum mechanica lapproach showed to be consistent with kinetic results.

배치와 형태에 관한 분자궤도론적 연구 (제15보). 에틸렌 디아민의 Through-Space 및 Through-Bond 상호작용

이익춘,손창국,송창현,Ikchoon Lee,Chang Kook Sohn,Chang Hyun Song 대한화학회 1982 대한화학회지 Vol.26 No.2

여러 형태의(n${\pi}$/m) 및 (n-${\sigma}^*$) 구조가 에너지에 미치는 구조적인 기여를 살펴보기 위하여 n-프로필아민, n-프로필아민 라디칼, trans-및 cis-에틸렌 디아민에 대한 STO-3G 수준의 계산을 수행하였다. 그 결과 (5${\pi}$/5)구조가 (4${\pi}$/4)구조는 각각 인력 및 반발의 비결합 상호작용을 나타내었으며 서로 부가관계를 가짐을 알았다. anti(n-${\sigma}^*$) 구조는 syn(n-${\sigma}^*$)구조보다 강한 hyperconjugation효과를 보이지만 anti(n-${\sigma}^*$)구조에서 강한 핵간 반발력을 가지기 때문에 결과적으로 불안정한 겉보기 효과를 나타내었다. 더우기 안정화${\pi}$ -비결합 (5${\pi}$/5)구조는 anti(${\pi}$-${\sigma}^*$)구조를, 불안정화 ${\pi}$-비결합(4${\pi}$/4)구조는 syn(n-${\sigma}^*$)구조를 수반하며 상호 보강적으로 작용함을 알았다. 또한 이러한 상호 보강성이 일반적인 성질임을 알았다. 끝으로 말단의 고립 전자쌍에 의한 through-bond 상호작용을 논의하였으며 이러한 상호작용으로 에너지 준위가 $n_+ = \frac{1}{\sqrt{2}}(n_1\;+\;n_2)$와 $n_-\;=\;\frac{1}{\sqrt{2}}(n_1\;-\;n_2)$로 갈라지는데 이때 고립 전자쌍의 간단한 overlap pattern으로 n_준위가 안정한 준위임을 알았다. STO-3G level computations were performed on n-propylamine, n-propylamine radical and cis-and trans-ethylene diamines in order to investigate structural contributions of (n${\pi}$/m) and (n-${\sigma}^*$) structures to the energy variations accompanying the conformational changes. It was found that (5${\pi}$/5) and (4${\pi}$/4) structures had attractive and repulsive nonbonded interactions, respectively, which were approximately additive. anti(n-${\sigma}^*$) structures had more stabilzing hyperconjugative interactions than syn(n-${\sigma}^*$) structures, but due to the large internuclear repulsion the net effect was destabilizing inthe former in contrast with the net stabilizing contribution in the latter. Moreover it was found that the stabilizing ${\pi}$-nonbond structure, (5${\pi}$/5) was always cooperatively reinforced by the more stabilizing anti(n-${\sigma}^*$) interaction, whereas the destabilizing (4${\pi}$/4) structure was accompanied by the less stabilizing syn(n-${\sigma}^*$) interaction. This type of cooperativity was found general through-bond interaction of the terminal lone pair lobes split the energy levels into two, $n_+ = \frac{1}{\sqrt{2}}(n_1 + n_2)$ and $n_- = \frac{1}{\sqrt{2}}(n_1 - n_2)$, the latter being the lower level, which can be shown using simple overlap patterns of the two lobes with a common vicinal ${\sigma}^*$ orbital.

염화아릴메틸의 親核性 置換反應

金旺起,孫昌國,曺泳奉 全南大學校 師範大學 科學敎育硏究所 1984 科學敎育硏究誌 Vol.9 No.1

The rate constants for the nucleophilic substitution reactions of l-and 2-Chloromethylnaphthalene with various substituted anilines in methanol were conducto-metrically determined at three temperatures(45℃, 50℃ and 55℃) and the activation thermodynamic parameters were caculated. As the electrondonating ability of substituted anilines increased, the rate constants increased. AIso It was found that substituent effects of anilines were linearly correlated with the σ values in the Hammett plot and the values in the Bronsted plot respectively. That the bond-breaking is bigger than bond-formation at the transition state could be expected from the negative slopes of values (-1.06~-1.25) and the positive slopes of ß values (0.36~0.45). Therefore the reaction should be followed dissociative SN2 mechanism and the rate constants of 1-Chloromethylnaphthalene were larger than those of 2-Chloromethylnaphthalene.This fact was also consisted with the result from PMO theory.

Carbon Dianion의 안정성과 전자구조에 대한 분자궤도함수론적 연구

이본수,이익춘,손창국,Bon Su Lee,Ik Choon Lee,Chang Kuk Sohn 대한화학회 1981 대한화학회지 Vol.25 No.2

Biindenyl dianion의 존재를 논의하기 위하여 모델 화합물로서 2, 3-dimethyl butadiene 을 취하여 이의 mono 및 dianion에 대하여 CNDO/2 계산을 수행하였다. 또한 부분적으로 기하학적 구조를 최적화함으로써 이들의 전자구조의 변화를 조사하여 보았다. 이 결과 dianion에 미치는 안정화 효과는 mono-anion에 미치는 안정화 효과와 현저하게 다르다는 사실을 알았다. In order to discuss the existence of the biindenyl dianion, we chose the 2, 3-dimethyl butadiene as a model compound and attempted the CNDO/2 calculations for its monoanino and dianion. We investigated the changes in the electronic structures by means of the partial geometry optimization. We found the stability effects on dianion were markedly different from those on monodianion.