• 약학회지
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• 제57권5호
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• pp.316-322
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• 2013

The new pyridazinone analogs were synthesized for development of candidates to retain anticancer activity. Various 6-substituted pyridazin-3(2H)-ones were prepared from the pyridazinyl chloride 3a~d via endothermic nucleophilic substitution with hydroxide ion as nucleophile for 2~48 h. Pyridazinyl chloride 3a~d could be converted to hydroxypyridazines (or pyridazin-3(2H)ones) using 1~5 equivalents of water (or 1 equivalent of sodium hydroxide) at reflux in DMF. The tautomerism of lactim form to lactam form was also accomplished in pyridazine derivatives. Formation of pyridazinones 10 was undertaken with stirring using sodium hydroxide at reflux in DMF for 2 h. Synthetic compounds were identified using NMR spectrum.

• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1117-1124
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• 2011

We present a brief review for theoretical/computational studies of proton transfer processes of some simple biomolecules promoted by microsolvating water molecules. Focus is given on the relative stability of the canonical vs. zwitterionic forms of amino acids, tautomeric forms of the DNA base adenine, and the biologically active vs. inactive forms of nicotine. The biochemical implications of these findings are also discussed.

• 대한화학회지
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• 제30권2호
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• pp.195-200
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• 1986

${\beta}$-diketones, ${\beta}$-thioxoketones and ${\beta}$-dithioketones류의 tautomeric forms (6${\pi}$ 전자계)의 1,5-H shift에 관해서 MNDO 방법으로 전이상태 구조를 결정하고, 활성화 에너지 장벽에 미치는 구조적 안정성을 분석하였다. 그 결과 1전자항 ${\Delta}( 2\sum\limits^{occ}{\varepsilon}_i)^{\neq}$ 이 증가할수록 활성화 장벽이 큼을 알았다. 또한 말단 헤테로원자의 하전분리가 클수록 바닥상태 분자의 안정성이 크며, 활성화 에너지 장벽$({\Delta}E^{\neq})$이 크다.

• Bulletin of the Korean Chemical Society
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• 제20권3호
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• pp.276-280
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• 1999

The different core-modified porphyrins 21-thia-23-carba-12-aza-5,10-dimesityl-15,20-diphenylporphyrin (6), and their N(12)-methyl derivatives (8) were synthesized by acid-catalyzed [3+1] condensation of the corresponding 16-thia-5,10-dimesityltripyrromethanes and 2,4-bis[(α-hydroxy-α-phenyl)methyl]pyrrole. Spectroscopic evidence indicates the existence of two different tautomeric forms at room temperature in porphyrin (6). A third form of tautomer was observed when the temperature was lowered to 223 K. The most stable tautomer is one in which the nitrogenic proton resides outside the core of the macrocycle. The ratio of the three different tautomers (outer N-H/ two inner N-H, i.e. 6/12/13) was 1/l/0.5 in the case of (6) while the ratio of 1/l/0.3 was observed in the case of (10). In the case of 21-oxa-23-carba-12-aza-5,10,15,20-tetraphenylporphyrin (7), the only stable tautomeric form observed by 1H NMR was the one that nitrogenic proton resides inside the core on

• Bulletin of the Korean Chemical Society
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• 제20권6호
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• pp.648-652
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• 1999

Studies have been carried out on the unusual molecular nonrigidity of CoⅢ(PymS)3 and Cp* RhⅢ(PymS)2(PymS:2-mercaptopyrimidine). The crystal structure of CoⅢ(PymS)3 approximates to an octahedral mer isomer with 4-membered N-Schelating fashion. For Cp*RhⅢ(PymS)2, one PymS ligand bonds to the rhodium ion in an S-monodentate mode (Rh-S(2) = 2.366(1)Å) while the other ligand chelates to the metal ion in an N,S-bidentae mode (Rh-S(1)=2.414(1);Rh-N(1)=2.103(3)Å). Even though the conformations and configurations of both complexes are still retained in solution, an unusual nonrigidity for the protons of the PymS region is obsered in the solution. The broad proton signals of CoⅢ(PymS)3 exhibit a temperature-dependence in the range of -40∼40℃ with a free energy of activation ΔG=64.49kJ/mol(40℃). For Cp*RhⅢ(PymS)₂,such a fluxionality has been markedly observed in solution. This fluxional behavior can be explained in terms of "ligand tautomerism" in metal complexes containing potential tautomeric forms.

• 대한화학회지
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• 제36권5호
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• pp.738-743
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• 1992

${\circo}-페닐렌디아민(3)을 출발물질로 하여 4단계를 거쳐 {\alpha}-arylhydrazonoacylazide(7)를 합성하였다. 얻어진 {\alpha}-arylhydrazonoacylazide(7)는 디메틸슬폭시드 용액에서 hydrazone imine형과 diazenyl enamine형으로 존재하는데 이들 사이의 토오토메리 현상을 ^1H-NMR 스펙트럼 데이타에 의하여 측정된 토오토머 비로서 고찰하였다. {\alpha}-arylhydrazonoacylazide(7)를 벤젠용매에서 환류시켜 1-aryl-3-quinoxalinyl-1,2,4-triazol(8)을 합성하였다.$