• Title/Summary/Keyword: E/Z isomers

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Inclusion Selectivity of the Cyanocadmate Host Complex with Piperazine Ligand for Aromatic Guest Molecules; Benzene, Toluene, Ethylbenzene and Xylene Isomers (Piperazine 리간드를 가진 시아노카드뮴 호스트 착물의 방향족 게스트 분자에 대한 포접선택성)

  • Kim, Chong-Hyeak;Lee, Sueg-Geun
    • Analytical Science and Technology
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    • v.16 no.4
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    • pp.333-338
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    • 2003
  • Inclusion selectivity of a three-dimensional piperazine-ligated cyanocadmate host complex, $[Cd_x(CN)_{2x}\{HN(CH_2CH_2)_2NH\}_y]{\cdot}zG$, has been investigated for benzene (B), toluene (T), ethylbenzene (E), o- (O), m- (M), and p-xylene (P) isomers as the aromatic guest molecules. From the binary, ternary and quarternary guest mixtures of E and xylene isomer (X), the order of inclusion selectivity in the host complex is O>E>P>M. From the binary to quinary BTX mixtures, the order of preference in the complex is seen to be B>T>O${\gg}$P>M.

M.O. Studies of Configuration and Conformation (Part II) Configuration and Conformation of Ketimine isomers

  • Kim, Shi-Choon;Chun, Young-Gu;Lee, Ikchoon
    • Nuclear Engineering and Technology
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    • v.9 no.1
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    • pp.39-44
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    • 1977
  • The configuratior and conformation of N-methyl-C-phenylalkyl-ketimine isomers, Ph-CR=N$CH_3$ (R=H, $CH_3$, $CH_3$CH$_2$), have been studied from extended Huckel molecular orbital calculations. The result shows that the E-configuration of the C=N double bond is favored compared with that of the Z-configuration. The most preferable conformation of the phenyl ring rotamer in N-methyl-C-phenylaldimine and N-methyl-C-phenylmethylketimine are the coplanar forms with regard to the C=N plane, but the conformation of the $CH_3$CH$_2$-rotamer, in N-methyl-C-phenylethyl-ketimine, the gauche form (dihedral angle between C=N and $CH_3$CH$_2$- plane=90$^{\circ}$) is favored.

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Cerebrosides from Longan Arillus

  • Ryu, Ji-Young;Kim, Ju-Sun;Kang, Sam-Sik
    • Archives of Pharmacal Research
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    • v.26 no.2
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    • pp.138-142
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    • 2003
  • From the pulp of Euphoria longana (Longan Arillus), three cerebroside molecular species have been isolated. Six known cerebrosides, soyacerebrosides I and II, 1-Ο-$\beta$-D-glucopyranosyl-(2S,3R,4E,8E)-2-(2 -lignoceroylamino)-4,8-octadecadiene-1,3-diol (long an cerebroside I) and its 8Z isomer (Iongan cerebroside II), momor-cerebroside I, and phytolacca cerebroside, were identified as major components of these cerebroside molecular species. All the cerebrosides were shown to be a mixture of geometrical isomers (8E and 8Z) of sphingosine-type or phytosphingosine-type glucocerebrosides possessing 2-hydroxy fatty acids. The structures of these cerebrosides have been determined on the basis of chemical and spectroscopic evidence.

Phytochemical Studies on Paeoniae Radix (4);Cerebrosides and Other Constituents

  • Kim, Yoon-Jung;Yean, Min-Hye;Lee, Eun-Ju;Kim, Ju-Sun;Lee, Je-Hyun;Kang, Sam-Sik
    • Natural Product Sciences
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    • v.14 no.3
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    • pp.161-166
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    • 2008
  • A mixture of sixteen cerebrosides, which comprised four cerebroside molecular species (PL-1 ${\sim}$ PL-4) was separated from the roots of Paeonia lactiflora. The structures of cerebrosides were characterized as $1-O-{\beta}$-D-glucopyranosides of phytosphingosines, which comprised a common long-chain base, (2S,3S,4R,8E/Z)-2-amino-8-octadecene-1,3,4-triol with eight fatty acids or 2-hydroxy fatty acids of varying chain lengths ($C_{16}$, $C_{18}$, $C_{20-26}$) linked to the amino group. Aralia cerebroside and its 8Z isomer (PL-1), $1-O-{\beta}$-D-glucopyranosyl-(2S,3S, 4R,8E/Z)-2-[(2'R)-2'-hydroxytetracosanoylamino]-8-octadecene-1,3,4-triol (PL-2), $1-O-{\beta}$-D-glucopyranosyl-(2S,3S,4R, 8E/Z)-2-[(2'R)-2'-hydroxydocosanoylamino]-8-octadecene-1,3,4-triol (PL-3), and $1-O-{\beta}$-D-glucopyranosyl-(2S,3S,4R, 8E/Z)-2-[(2'R)-2'-hydroxytricosanoylamino]-8-octadecene-1,3,4-triol (PL-4) were identified as major components of these cerebroside molecular species. All the major cerebrosides were shown to be a mixture of geometrical isomers (8E and 8Z) of phytosphingosine-type glucocerebrosides possessing 2R-hydroxy fatty acids. In addition, three ${\beta}-sitosterol$ derivatives and adenosine were also separated. The structures of these isolates have been determined on the basis of chemical and spectroscopic evidence.

Photoreaction of 1,4-Disubstituted-1,3-Butadiyne with Alcohol

  • Lee, Tae-Suk;Shim, Sang-Chul;Kim, Sung-Sik
    • Bulletin of the Korean Chemical Society
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    • v.7 no.2
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    • pp.116-120
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    • 1986
  • Irradiation of 1,4-diphenyl-1,3-butadiyne and 5,5-dimethyl-1-phenyl-1,3-hexadiyne with methanol yields 1:1 polar addition products, [E]- and [Z]-1,4-diphenyl-1-methoxy-1-buten-3-yne and [E]- and [Z]-5,5-dimethyl-1-methoxy-1-phenyl-1-hexen-3-yne, respectively. These geometrical isomers were converted into each other reaching the photostationary state on irradiation with 300 nm UV light. The photoaddition reaction of 1,4-diphenyl-1,3-butadiyne and 5,5-dimethyl-1-phenyl-1,3-hexadiyne with methanol seems to proceed from the zwitterionic lowest excited state.

Deoxygenation of ${\beta}$-Aryl-${\alpha}$,${\beta}$-Epoxy Silanes to Vinylsilanes by Magnesium-Magnesium Halide

  • Kang, Kyung-Tae;Park, Chun-Yi;Kim, Joung-Sook
    • Bulletin of the Korean Chemical Society
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    • v.13 no.1
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    • pp.48-53
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    • 1992
  • The reactions of ${\beta}-aryl-{\alpha},{\beta}-epoxy$ silanes with magnesium bromide or magnesium iodide in the presence of excess magnesium in ether at room temperature afforded vinylsilanes in 18-100% yields. E-Vinylsilanes were predominant over Z-isomers (> 80%) regardless of the stereochemistry of ${\alpha},{\beta}-epoxy$ silanes.

Mechanism of the Hydrolysis of Phenyl N-(p-chlorobenzoyl)Chloroformimidate Derivatives in Acid Media (산성용액 중에서 Phenyl N-(p-chlorobenzoyl)chloroformimidate 유도체의 가수분해 반응 메카니즘)

  • Nack-Do Sung;Young-Gu Cheun;Ki-Sung Kwon;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.31 no.4
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    • pp.352-358
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    • 1987
  • 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.

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Synthesis and X-ray Structure Analysis of (Z)-1-(4-Bromophenyl)-1-phenyl-2-(4-tert-butylphenyl)ethene ((Z)-1-(4-브로모페닐)-1-페닐-2-(4-tert-부틸페닐)에텐의 합성 및 X-선 구조분석)

  • Kim, Chul-Bae;Cho, Hyun-Jong;Lee, Sung-Kyung;Park, Kwangyong
    • Applied Chemistry for Engineering
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    • v.20 no.3
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    • pp.335-338
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    • 2009
  • As important intermediates for blue emitting materials of organic light-emitting diodes, bromotriphenylethylene derivatives for distrylarylenes are prepared by reactions of bromobenzophenone with benzylphosphonates. The reaction produces a 60 : 40 mixture of (Z)- and (E)-geometric isomers that are difficult to be resolved. The (Z)-isomer is successfully isolated by a selective recrystallization process using 2-propanol as a solvent. The X-ray structure analysis of (Z)-isomer shows that dihedral angles between tert-butylphenyl ring and bromophenyl ring and between bromophenyl ring and phenyl ring are $56.5(4)^{\circ}$ and $74.1(4)^{\circ}$, respectively.

One-pot Four Component Reaction of Unsymmetrical 1-Methylbarbituric Acid with BrCN and Various Aldehydes in the Presence of Et3N and/or Pyridine

  • Jalilzadeh, Mohammad;Pesyan, Nader Noroozi
    • Journal of the Korean Chemical Society
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    • v.55 no.6
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    • pp.940-951
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    • 2011
  • Reaction of 1-methylpyrimidine-(1H,3H,5H)-2,4,6-trione (1-MBA 1) as an unsymmetrical barbituric acid with cyanogen bromide and various aldehydes in the presence of triethylamine and/or pyridine afforded diastereomeric mixtures of new class of heterocyclic stable 5-aryl-1,1'-dimethyl- and 5-aryl-3,1'-dimethyl-1H,1'H-spiro[furo[2,3-d]pyrimidine-6,5'-pyrimidine]2,2',4,4',6'(3H,3'H,5H)-pentaones which are dimeric forms of 1-methyl barbiturate at the range of $0^{\circ}C$ to room temperature. In the reaction of some aldehydes with 1-MBA and BrCN were afforded a mixture of diastereomers. Another two aldehydes such as 4-cyano- and 2-hydroxybenzaldehydes gave exclusively two diastereomers in which binded to the salt of triethylammonium hydrobromide by intermolecular H-bond in ratio of 1:1. 4-Hydroxybenzaldehyde and 2-pyridinecarbaldehyde gave exclusively one diastereomer under the same condition. Aldehydes possessing strong electron-donor were produced exclusively two geometric isomers of Knoevenagel adduct (E- and Z-isomers). The structures of compounds were deduced by $^1H$ NMR, $^{13}C$ NMR and FT-IR spectroscopy. Mechanism of the formation is discussed.