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MO 理論에 依한 反應性의 決定 (第14報). Diels-Alder 反應의 配向性에 미치는 酸觸媒의 效果
이익춘,류근배,전용구,Ikchoon Lee,Keun Bae Rhyu,Jeon, Yong Gu 대한화학회 1979 대한화학회지 Vol.23 No.5
非對稱으로 置環된 diene과 dienophile 間의 反應에서 配向性에 미치는 산촉매의 효과를 豫期하기 위해서 루이스酸과 錯物을 形成한 dienophile의 理論的모델에 FMO 理論을 적용하여CNDO/2 방법으로 고찰하였다. 電子的性質이 類似한 치환기로 치환된 diene, dienophile의 반응(즉, 電子不足 diene과 電子不足 dienophile의 반응)에서 일어나는 半極性 고리化반응을 제외한 주어진 대부분의 반응에 대해서, CNDO/2방법이 실험적인 配向性과 一致하는 좋은 결과를 주었다. 또한 二次軌道相互作用이 非對稱으로 치환된 diene과 dienophile의 Diels-Alder 반응의 배향성에 중요한 역할을 했다는 사실을 보여주었다. Anh의 방법이 다른 방법보다 수식적으로 간단할지라도, 非對稱전이상태를 강조한 Anh의 방법이 配向性 결정에 좋은 결과를 주었다. In order to predict the effect of Lewis acid catalysis on the regioselectivity of the Diels-Alder reactions between unsymmetrically substituted dienes and dienophiles, the frontier orbital theory applied to the theoretical model of the Lewis acid complexed dienophile was studied by means of CNDO/2 MO. In the majority of reactions, CNDO/2 calculations gave good results in accordance with experimental orientation. Also, it was shown that the secondary orbital interaction played an important role in the regioselectivity of the Diels-Alder reaction between unsymmetrically substituted dienes and dienophiles. Although ANH's treatment is mathematically simpler than other methods, ANH's method which laid emphasis on dissymmetrical transition state gave good results on decision of regioselectivity.
R_(2)NNSO화합물의 N-N회전에 대한 활성화에너지에 관한 AM1연구
류근배 청주대학교 산업과학연구소 2000 産業科學硏究 Vol.18 No.1
AM1 semi-empirical MO calculations were performed to investigate the activation free energy for the rotation of N-N in R₂NNSO where R=H, methy, ethyl, iso-propyl, phenyl. It was found that theoretical activation free energy, which was determined in this study, was increased in the order of phenyl <methyl<ethyl<iso-propyl and thus was in accord with experimental trend. The extraordinary small activation free energy of phenyl substituent was due to formation of6the effective conjugation between phenyl and NNSO fragment. This activation free energy was predominantly determined activation enthalpy and thus was the enthalpy controlled rotational barrier.
Tropone과 Diene의 (6+4)고리화 반응의 배향선택성에 관한 AM1연구
류근배 청주대학교 산업과학연구소 2001 産業科學硏究 Vol.18 No.2
AM1 semi-empirical MO calculations were performed to investigate theoretical method for determining the regioselectivities in the (6+4) cycloaddition reactions between substituted-tropones and simple dienes. It was found that theoretical activation enthalpy calculations gave a good regioselectivities in accordance with the experiments and thus could be a useful tool for determining the regioselectivities in the (6+4) cycloaddition reactions.
단일 치환 술피닐 히드라진의 형태 안정성에 대한 이론적 연구
류근배 청주대학교 산업과학연구소 1998 産業科學硏究 Vol.15 No.3
AM1 semi-empirical MO calculations were performed to investigate the main factors determining the geometrical stability of N-sulphinylhydrazines; RHNNSO where R= H, methyl, C1, vinyl. It was found that though through-space π-nonbonded interactions contributed to one-electron factor for methyl- and vinyl-substituted N-sulphinylhydrazines, steric factor preferentially played an important role in determining its conformational stabilities. But for C1-substituted N-sulphinylhydrazine through-bond interctions contributed to one-electron factor and thus predominantly plyed an important role in determining the conformational stability.
柳根培,金英植 청주대학교 산업과학연구소 1985 産業科學硏究 Vol.3 No.-
Measurement were taken of the bulk rheological properties of concentrated suspensions of CaCO₃ Particulates in PVA and HEC solutions using a rotational viscometer (HAAKEROTOVISCO). The variation of apparent viscosity with concentration and temperature is illustrated. PVA suspension of calcium carbonate showed Newtonian behavior and HEC suspenion of calcium carbonate showed shear thinning behavior.
1-Vinyl cycloalkene과 Methyl propiolate 간의 반응에서 배향성에 대한 고리형치환기의 크기효과
柳根培 청주대학교 산업과학연구소 1984 産業科學硏究 Vol.2 No.2
The regioselectivity was studied by FMO theory in reactions of 1-vinyl cycloalkene with methyl propiolate. For elucidating satisfactorily its regioselectivity, not only primary orbital interaction and 1st secondary orbital interaction of butadiene moiety, but also 2nd secondary orbital interaction of ring substituent had to be considered. Especially, 2nd secondary orbital interaction played an important role in deciding its regioselectivity. As ring size n increases, ratio of ortho regioisomer to meta one also increases. This increment is due to the contribution of 2nd secondary orbital interaction. As n increases attractive 2nd secondary orbital interaction increases by (n-1). The (-CH_(2)-)_(n) group of ring substituent forms π-isocon/ugate system and acts as π-electron sink. In consequence, as n increases, electron-donating ability of (-CH_(2)-)_(n) decreases.
실리콘 함유 화합물과 니트로 올레핀 반응의 배향화학과 반응성
柳根培 청주대학교 산업과학연구소 1985 産業科學硏究 Vol.3 No.-
The regiochemistry was studied by FMO theory in reactions of silyloxy-dienes with nitro-olefins. For elucidating satisfactorily its regioselectirity, primary orbital interaction played more important role than secondary orbital interaction. Especially, HERNCON and ANH methods, in which energy gap is predominantly considered, produced a good regioselectivity in accord with experimental results. The Inversion of its regioselectivity by NO₂ substituent was due to its lowering effect of orbital energy and alteration of polarization of LUMO coefficient.
(E)-hydroximoyl chloride의 산 촉매 이성질화반응 메커니즘에 관한 이론적인 연구
류근배 청주대학교 산업과학연구소 2001 産業科學硏究 Vol.18 No.2
AM1 Semi-empincal MO Calculations were performed to investigate the acid-catalyzed isomerization of (E)-hydroximoyl chloride. It was found that the immonium ion rotation mechanism had the large rotational barrier(18.64 ㎉/㏖) in the process (_(11)) but the nucleophilic catalysis mechanism had no activational barrier in the process (_(1)) and thus the latter was energetically more advantageous than the former Especially in the process (_(1)), the nucleophilic attack of Cl^(-) to E-immonium ion(Ⅱ) could be easily occurred due to the large atomic charge of carbon atom, and also the elimination of Cl^(-) could easily be occurred because of (n-σ^(*)) anti interaction between lone pair of N atom and antibond of C-Cl bond in the TS.
케텐과 규소함유 아세틸렌간의 반응에서 반응성과 배향성에 대한 치환기 효과
柳根培 청주대학교 산업과학연구소 1987 産業科學硏究 Vol.5 No.-
The substituent effect on the reactivity and regiochemistry was studied by FMO theory in reactions of substituted ketene with vinylsilane and alkynylsilanes. It was found that: (1) The reactivity is determined by HOMO energy level of nucleophilic ketengphile. (2) 2-FMO interaction, ketene (LUMO)-ketenophile (HOMO), plays more important role than 4-FMO interaction for elucidating satisfactorily its regioselectivitv. Especially Anh's method, in which small energy gap and large AO coefficient are predo minantly considered, produces a good regioselectivity in accord with experimental results. (3) The TMS substituent controls its regioselectivity in ketenophile substituted with both TMS and H. The other hand in such a case that TMS group is substituted to acetylene moiety with a different group, Me, OEt and Ph, respectively, the relative order of regio-directing power is Ph>OEt>Me>TMS. Thus the other substituent groups, for example Ph, OEt and Me except TMS, are important regio-directing groups in deciding its regioselectivity.