• Title/Summary/Keyword: 알릴 치환반응

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An Efficient Synthesis of Alkoxyallylthiopyridazine Derivatives from Maleic Anhydrides (Maleic Anhydrides로부터 Alkoxyallylthiopyridazines 유도체의 효과적 합성)

  • Lee, Jae-In;Yun, Young-Sook
    • Journal of the Korean Chemical Society
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    • v.48 no.6
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    • pp.609-615
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    • 2004
  • Alkoxyallylthiopyridazine derivatives which exhibit superior effect for the treatment of hepatic diseases were synthesized from maleic anhydrides. The reaction of maleic anhydrides with hydrazine monohydrate in aq HCl at reflux afforded dihydroxypyridazines, which were transformed to dichloropyridazines with phosphorus oxychloride. The substitution of the first chlorine atom in dichloropyridazines proceeded selectively with alcoholic sodium alkoxides in THF to afford alkoxychloropyridazines, which were converted to alkoxyallylthiopyridazines with lithium 2-propene-1-thiolate in high yields.

Nickel Complexes Having (N-C-N) Tridentate Ligands ((N-C-N) 세자리 리간드를 가지는 니켈 착물)

  • Lee, Dong-Hwan;Park, Soon-Heum
    • Journal of the Korean Chemical Society
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    • v.51 no.6
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    • pp.499-505
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    • 2007
  • Monomeric complexes of nickel(II) having terdentate bis(imino)aryl ligands (N,C,N-pincer) are reported. New complexes (2,6-(ArN=CH)2C6H3)NiBr (Ar=2,6-dimethylphenyl (1), 2,6-diisopropylphenyl (2)) have been synthesized through oxidative addition of 1,3-(ArN=CH)2C6H3Br (bis(N-Ar)-2-bromoisophthalaldimine: Ar=Ph-2,6-Me2, Ph-2,6-iPr2) to Ni(COD)2 (COD=1,5-cyclooctadiene), in high yields. The development of a synthetic route to ligands and nickel complexes is outlined. The complexes were characterized by IR, 1H-NMR and elemental analysis. Full characterization of complexes 1 and 2 is discussed. An investigation into the catalytic activity of the complexes in ethylene polymerization was performed, resulting in no formation of polyethylenes but producing a small amount of oily oligomers. Preliminary results indicate that the pincer complexes were found to be inactive as catalysts in ethylene polymerization.

The Study on the Reactivity of Dioxygen Bridged Palladium Complexes Having ${\pi}$-Allyl Ligands (${\pi}$-알릴리간드를 갖는 산소가교 팔라듐착화합물의 반응성에 관한 연구)

  • Pyeong Jin Chung
    • Journal of the Korean Chemical Society
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    • v.30 no.6
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    • pp.516-520
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    • 1986
  • This study is related to reactivity of dioxygen bridged palladium complexes having ${\pi}$-allyl ligands. In this case, new dioxygen bridged palladium complexes were prepared using superoxide ion$(O_2^-)$ as an oxygen source. Reactions of the dioxygen palladium complexes prepared in the study were examined in order to clarify the nature of the coordinated dioxygen. Treatments of a solution of the dioxygen bridged palladium complexes in benzene by water, methanol and acetic acid gave hydrogen peroxide $(H_2O_2)$ as hydroxy-, methoxy-, and acetoxybridged palladium complexes, respectively. The dioxygen bridged palladium complexes reacted also with substitution phenols of salicylaldehyde, 8-hydroxyquinoline and active methylenes of acetylacetone, dimethyl malonate to afford mononuclear complexes of palladium and hydrogen peroxide. The results suggest that dioxygen is coordinated as peroxo $(O_2^{2-})$ in the complexes and behaves as a strong base.

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Preparation of Dioxygen Bridged Palladium Complexes by Superoxide Ion $(O_2^-)$ (초과산화이온 $(O_2^-)$ 에 의한 산소가교팔라듐착화합물의 합성)

  • Pyeong Jin Chung
    • Journal of the Korean Chemical Society
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    • v.28 no.2
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    • pp.135-142
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    • 1984
  • New type dioxygen bridged complexes of palladium were prepared by using $KO_2$ as a source of superoxide ion $(O_2^-)$. The method is completely different from the traditional one which has adopted the oxidative addition of molecular oxygen to transition metal complexes in low valency. It was suggested that the reaction to prepare the dioxygen complexes proceeded via nucleophilic displacement followed by electron transfer reaction. Five new type dioxygen complexes having ${\pi}$-allyl ligand were prepared and characterized by the application of the reaction of $O_2^-$.

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Kinetic Study on the Oxidation Reaction of Alcohols by Cr(VI)-Quinoline Compound (크롬(VI)-퀴놀린 화합물에 의한 알코올류의 산화반응에 대한 반응속도론적 연구)

  • Park, Young-Cho;Kim, Soo-Jong
    • Journal of Convergence for Information Technology
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    • v.11 no.9
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    • pp.109-114
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    • 2021
  • Cr(VI)-quinoline compound[(C9H7NH)2Cr2O7] was synthesized by the reaction between of quinoline and chromium(VI) trioxide, and structure was FT-IR, elemental analysis. The oxidation ability of benzyl alcohol greatly depends upon the dielectric constant of the used organic solvent, where carbon tetrachloride was worst and N,N'-dimethylformamide was best solvent. Noticeably, in N,N'-dimethylformamide solvent, Cr(VI)-quinoline compound oxidized substituted benzyl alcohols. The Hammett reaction constant(ρ)=-0.69(303K). As a resuit, Cr(VI)-quinoline compound was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones. Cr(VI)-quinoline compound was selective oxidizing agent of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary alcohol ones.

Preparation of Polysiloxane Composite Films with Microphase-Separated Silicone Oiol by Photocrosslinking (광가교 반응에 의한 미세 상 분리된 실리콘 오일을 함유하는 폴리실록산 복합체 필름의 제조)

  • 이정분;김정수;강영구;김동욱;이창진
    • Polymer(Korea)
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    • v.27 no.1
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    • pp.3-8
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    • 2003
  • Polysiloxanes with methacrylate groups at both terminals were synthesized by a hydrosilylation reaction between allyl methacrylate and hydride-terminated polysiloxanes. The polysiloxane methacrylates with high molecular weights could be prepared through the reaction of polysiloxane methacrylates and octamethylcyclotetrasiloxane with an acid catalyst. The structures of the prepared polysiloxane methacrylates were verified by $^1$H- and $^{29}Si-NMR.$ The polysiloxane methacrylates were freely miscible with silicone oils. Polysiloxane films with microphase-separated liquid silicone oil were prepared by photo-crosslinking the mixture of polysiloxane methacrylates and silicone oil. Scanning electron microscopy (SEM) of the films showed that the size of silicone oil droplets became smaller with a lower loading of silicone oil, lower molecular weight of polysiloxane methacrylate, and lower molecular weight of silicone oil.

Kinetics and Mechanism of the Oxidation of Alcohols by C9H7NHCrO3Cl (C9H7NHCrO3Cl에 의한 알코올류의 산화반응에서 속도론과 메카니즘)

  • Park, Young-Cho;Kim, Young-Sik;Kim, Soo-Jong
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.19 no.8
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    • pp.378-384
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    • 2018
  • $C_9H_7NHCrO_3Cl$ was synthesized by reacting $C_9H_7NH$ with chromium (VI) trioxide. The structure of the product was characterized by FT-IR (Fourier transform infrared) spectroscopy and elemental analysis. The oxidation of benzyl alcohol by $C_9H_7NHCrO_3Cl$ in various solvents showed that the reactivity increased with increasing dielectric constant(${\varepsilon}$) in the following order: DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. The oxidation of alcohols was examined by $C_9H_7NHCrO_3Cl$ in DMF. As a result, $C_9H_7NHCrO_3Cl$ was found to be an efficient oxidizing agent that converts benzyl alcohol, allyl alcohol, primary alcohols, and secondary alcohols to the corresponding aldehydes or ketones (75%-95%). The selective oxidation of alcohols was also examined by $C_9H_7NHCrO_3Cl$ in DMF. $C_9H_7NHCrO_3Cl$ was the selective oxidizing agent of benzyl, allyl and primary alcohol in the presence of secondary ones. In the presence of DMF with an acidic catalyst, such as $H_2SO_4$, $C_9H_7NHCrO_3Cl$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, and $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308K). The observed experimental data were used to rationalize hydride ion transfer in the rate-determining step.