• Title/Summary/Keyword: Tertiary Amide

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Syntheses of Amide Bonds and Activations of N-C(sp3) Bonds

  • Hong, Jang-Hwan
    • Journal of Integrative Natural Science
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    • v.10 no.4
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    • pp.175-191
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    • 2017
  • In organic chemistry amide synthesis is performed through condensation of a carboxylic acid and an amine with releasing one equivalent of water via the corresponding ammonium carboxylate salt. This method is suffering from tedious processes and poor atom-economy due to the adverse thermodynamics of the equilibrium and the high activation barrier for direct coupling of a carboxylic acid and an amine. Most of the chemical approaches to amides formations have been therefore being developed, they are mainly focused on secondary amides. Direct carbonylations of tertiary amines to amides have been an exotic field unresolved, in particular direct carbonylation of trimethylamine in lack of commercial need has been attracted much interests due to the versatile product of N,N-dimethylacetamide in chemical industries and the activation of robust N-C($sp^3$) bond in tertiary amine academically. This review is focused mainly on carbonylation of trimethylamine as one of the typical tertiary amines by transition metals of cobalt, rhodium, platinum, and palladium including the role of methyl iodide as a promoter, the intermediate formation of acyl iodide, the coordination ability of trimethylamine to transition metal catalysts, and any possibility of CO insertion into the bond of Me-N in trimethylamine. In addition reactions of acyl halides as an activated form of acetic acid with amines are reviewed in brief since acyl iodide is suggested as a critical intermediate in those carbonylations of trimethylamine.

Preparation of Amine-Containing Poly(amide-sulfone)s Using Vinylsulfone Reactive Monomers and Their Properties

  • Jeon, Young-Min;Lim, Tai-Ho;Kim, Soo-Han;Kim, Jong-Gyu;Gong, Myoung-Seon
    • Macromolecular Research
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    • v.15 no.1
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    • pp.17-21
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    • 2007
  • A series of new, vinyl sulfone-containing monomers was prepared by p-aminophenyl vinyl sulfone (1) with various acid chlorides such as adipoly chloride, terephthaloyl chloride and isophthaloyl chloride. Finally, tertiary amine-containing poly(amide-sulfone)s were prepared by the Michael-type addition polymerization using N,N-dimethylethylenediamine (DMEDA), p-phenylenediamine and piperazin. To evaluate the relevant properties for permselective membranes and enzyme substrate, various physical properties such as molecular weight, solubility, quaternization behavior and thermal properties were examined.

Structural Dynamics of Myoglobin Probed by Femtosecond Infrared Spectroscopy of the Amide Band

  • Kim, Seong-Heun;Jin, Geun-Young;Lim, Man-Ho
    • Bulletin of the Korean Chemical Society
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    • v.24 no.10
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    • pp.1470-1474
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    • 2003
  • The dynamics of the tertiary conformation of myoglobin (Mb) after photolysis of carbon monoxide was investigated at 283 K solution by probing amide I and II bands using femtosecond IR absorption spectroscopy. Time-resolved spectra in the amide region evolve with 6-12 ps time scale without noticeable subpicosecond dynamics. The spectra measured at 100 ps delay after photolysis is similar to the difference FTIR spectrum at equilibrium. Time-resolved spectra of photoexcited Mb evolve modestly and their amplitudes are less than 8% of those of photolyzed MbCO, indicating that thermal contribution to the spectral evolution in the amide region is negligible. These observations suggest that the conformational relaxation ensuing photolysis of MbCO be complex and the final deoxy protein conformation have been substantially formed by 100 ps, probably with 6- 12 ps time constant.

Highly CO2-soluble 5-Amido-8-hydroxyquinoline Chelating Agents for Extraction of Metals in Sc-CO2

  • Chang, Fei;Park, Seo-Hun;Kim, Hakwon
    • Bulletin of the Korean Chemical Society
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    • v.29 no.7
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    • pp.1327-1331
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    • 2008
  • Novel $CO_2$-soluble 8-hydroxyquinoline (8-HQ) chelating agents were synthesized and evaluated for solubility and metal ion extraction ability in supercritical $CO_2\;(Sc-CO_2)$. Among them, secondary amide-containing 8- HQ derivatives cannot be dispersed well into Sc-$CO_2$, but tertiary amide-containing derivatives can dissolve completely in Sc-$CO_2$ even at low CO2 pressures, perhaps owing to the predominant intermolecular interaction between the chelating agent and the $CO_2$ molecule. Based on 8-HQ chelating agent solubility data, we investigated the extraction of metal ions ($Co^{2+}$, $Cu^{2+}$, $Sr^{2+}$, $Cd^{2+}$, and $Zn^{2+}$) using two highly $CO_2$-soluble 8-HQ derivatives (4d, 4e) in Sc-$CO_2$. The extraction efficiency of tertiary amide-containing 8-HQ ligands, both fluorinated and non-fluorinated forms, was dramatically increased in the presence of diethyl amine (organic base). We suggest that diethyl amine could play an important synergistic role in the stronger metal binding ability of 8-HQ through an in situ deprotonation reaction in Sc-$CO_2$ medium.

Preparation of Poly(hydroxypropyl methacrylate) Membraney by Sintering Method and Its Permeation Characteristics (소결공정에 의한 Poly(hydroxypropyl methacrylate) Membrane 제조와 그의 투과특성에 관한 연구)

  • Shim, Jyong-Sup;Lee, Dong-Kweon;Hong, Jae-Min
    • Applied Chemistry for Engineering
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    • v.1 no.2
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    • pp.147-153
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    • 1990
  • Poly(hydroxypropyl methacrylate) membranes and matrix devices having tertiary amine moiety were prepared by sintering method, and their permeation characteristics were investigated. The water content of this membrane was increased with decreasing the pH of the medium. The permeability of this membrane was increased with decreasing the sintering pressure. Using sintered matrix device 'burst effect' was found at the early stage, and initial insulin release of glucose oxidase immobilized matrix device could be controlled by glucose concentration of the solution.

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