• Title/Summary/Keyword: Substituents

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Solvolysis of 2-Phenylethyl Benzenesulfonates in Methanol-Water Mixtures

  • Han, Goang-Lae;Park, Jin-Ha;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.8 no.5
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    • pp.393-398
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    • 1987
  • Solvolyses of 2-phenylethyl benzenesulfonates have been studied in methanol-water mixtures. Cross interaction constants, $\rho_{YZ}$, between substituents Y in the substrate and Z in the leaving group indicated somewhat closer distance between the two substituents than expected for the reaction system, which supported the involvment of phenyl group assisted pathway in the solvolysis. A smaller magnitude of $\rho_{YZ}$for MeOH was interpreted as the enhencement of solvent assisted pathway since MeOH is more nucleophilic than $H_2O$. Other selectivity parameters, Winstein coefficient m, Hammett's $\rho_Y^{+_Y}$ and $\rho_Z$, as well as activation parameters supported the participation of aryl assisted and aryl unassisted pathways in the $S_{N^2}$ process of the solvolysis reaction.

Enantioseparation on HPLC Chiral Stationary Phases

  • Hyun Myung-Ho;Ryoo Jae-Jeong;Min Chung-Sik;William H. Pirkle
    • Bulletin of the Korean Chemical Society
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    • v.13 no.4
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    • pp.407-413
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    • 1992
  • The chromatographic separation of the stereoisomers of the N-(3,5-dinitrobenzoyl) derivatives of fifteen dipeptide methyl esters and nine dipeptide alkyl esters was investigated on three different chiral stationary phases derived from N-acylated ${\alpha}-arylalkylamines$. Two of these CSPs contain second stereogenic centers. These secondary stereogenic centers of CSPs were proposed to provide secondary effects in terms of chiral recognition. From the elution orders of the four dipeptide stereoisomers and the separation factors of the enantiomeric pairs of the N-(3,5-dinitrobenzoyl) derivatives of the dipeptide alkyl esters having different alkoxy substituents, it was proposed that the intercalation of the alkoxy substituents of dipeptide derivatives between the connecting arm of CSPs may control the magnitude of chiral separations of dipeptide derivatives.

X-ray Structure and Electrochemical Properties of Ferrocene-Substituted Metalloporphyrins

  • Kim, Jin Won;Lee, Seok U;Na, Yong Hwan;Lee, Gi Pyeong;Do, Yeong Gyu;Jeong, Se Chae
    • Bulletin of the Korean Chemical Society
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    • v.22 no.12
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    • pp.1316-1322
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    • 2001
  • Transition metal complexes of novel mono- and di-ferrocene-substituted porphyrins have been synthesized and characterized by structural and electrochemical methods. The X-ray structures of Mn(FPTTP)Cl and Mn(DFTTP)Cl showed the distorted square pyramidal coordination geometry with syn configuration of chloride and ferrocenyl substituents. The electrochemistry of ferrocene-substituted porphyrins and their metal complexes has been determined to elucidate the ${\pi}-conjugation$ effect of the porphyrin ring. The ferrocenyl group of H2FPTTP underwent a reversible one-electron transfer process at 0.30 V, indicating the good electron donating effect of the phorphyrin ring to the ferrocene substituent. The redox potential of the ferrocenyl subunit and porphyrin ring was affected by the central metal ions of the metalloporphyrins, that is, Zn(II) and Ni(II) made the oxidation of ferrocene much easier and Mn(III) made it harder. The ferrocene subunits of H2DFTTP interacted electrochemically with each other with peak splitting of 0.21 V. The strength of the electrochemical interactions between the two ferrocenyl substituents can be controlled by central metal ions of metalloporphyrins.

Effects of N-and C-Substituents on Protonation of 14-Membered Tetraaza Macrocycles and Formation of their Copper(II) and Nickel(II) Complexes

  • Shin-Geol Kang;Mi-Seon Kim;Jang-Sik Choi;Moon Hwan Cho
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.594-598
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    • 1993
  • The protonation constants of the 14-membered tetraaza macrocycles A(3,14-dimethyl-2,6,13,17-tetraazatricyclo$[l6.4.0^{1,18}.0^{7,12}]$docosane) and B(2,3,6,13,14,17-hexamethyl-2,6,13,17-tetraazatric yclo-[l6.4.$0^{1,18}.0^{7,12}$]docosane) were measured by potentiometry. The formation constants of each of these ligands with copper(II) and nickel(II) were determined by an out-of-cell spectrophotometric method. The results indicate that the per-N-methylated macrocycle B exhibits much higher selectivity for complex formation with copper(II) over nickel(II) ion than A and other related 14-membered tetraaza macrocycles. The effects of the N-and C-substituents on the basicity and the metal ion selectivity of the ligands are discussed. The synthesis and properties of copper(II) and nickel(II) complexes of B are also described.

Theoretical Studies of Substituent Effects on S$_N$2 Transition States$^\dag$

  • Lee, Ik-Choon;Song, Chang-Hyun
    • Bulletin of the Korean Chemical Society
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    • v.7 no.3
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    • pp.186-190
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    • 1986
  • Effects of substituents in the nucleophile(X), the substrate(Y) and the leaving group(Z) on the structure of $S_N2$ transition states have been analyzed by considering effects of four components, electrostatic($E_{es}$), exchange repulsion ($E_{ex}$), polarization($E)_{pl}$) and charge transfer($E_{ct}$) terms, of interaction between the reactants on the degree of bond making and bond breaking. Prediction of net effects of all substituents(X, Y and Z) on the degree of bond making were found to be clearcut whereas the effect of an electron withdrawing group on the substrate (Y = EWG) on the degree of bond breaking was complex; the substituent(Y = EWG) is normally carbon-leaving group($C^{\ast}$-L) bond tightening($E_{pl}$ dominance) but becomes $C^{\ast}$-L bond loosening when the bond is strongly antibonding ($E_{ct}$ dominance). Our model calculations on the reaction of $CH_2XNH_2$ with $YCH_2COOCH_2Z$ using energy decomposition scheme have confirmed that predictions based on our analysis are correct.

Synthesis and Liquid Crystalline Properties of Dimesogenic Compounds Containing Trifluoromethyl Substituents at Terminal Phenylene Rings and Central Decamethylene Spacer

  • Jo, Byung-Wook;Choi, Jae-Kon;Jin, Jung-Il;Chung, Bong-Yong
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.333-339
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    • 1990
  • A series of new dimesogenic compounds whose mesogens are of aromatic ester or amide type having a trifluoromethyl $(CF_3)$ substituent at the para-position of each terminal phenolic rings were prepared and their liquid crystalline properties were studied by differential scanning calorimetry (DSC) and on a cross-polarizing microscope. The compounds have two identical mesogenic units bracketing a central decamethylene spacer. Trifluoromethyl group appears to favor the formation of smectic phases when it is attached to a phenoxy or anilide terminal. Its group efficiency for mesophase formation seems to be inferior to other common substituents. A thermodynamic analysis of the phase transitions was made and the results were explained in relation to the structures of the compounds.