• Title/Summary/Keyword: Free Amine

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$^1H$ NMR Study of 4-Aminopyrimidine Coordinated to the Paramagnetic Undecatung-stocobalto(Ⅱ)silicate Anion: Rates of Internal Rotation of the Amine Group

  • 김병안;소현수
    • Bulletin of the Korean Chemical Society
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    • v.20 no.10
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    • pp.1149-1152
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    • 1999
  • 1H NMR spectrum of a DMF-d7 solution containing 4-aminopyrimidine and [SiW11CoIIO39]6- (SiW11Co) shows separate peaks from two linkage isomers, a and b, in which N(1) and N(3) of the pyrimidine ring are coordinated to SiW11Co, respectively. The signal from the amine group in the isomer a exhibits temperature dependence that is characteristic of a two-site exchange problem. Rates of internal rotation of the amine group were determined by simulating the NMR spectra at 5-35℃. The amine group of free 4-aminopyrimidine also shows temperature-dependent spectra at lower temperatures; rates of internal rotation at (-25)-25℃ were determined. The internal rotation of the amine group in the complex is much slower than that for free 4-aminopyrimidine, indicating that π-character of the C-N bond increases on coordination to SiW11Co. The amine group in the isomer b does not show such behavior. It is probable that hydrogen bonding between N-H and a bridging oxygen atom of SiW11Co prevents it from rotating at low temperatures.

Chemical synthesis of processable conducting polyaniline derivative with free amine functional groups

  • Kar, Pradip
    • Advances in materials Research
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    • v.3 no.2
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    • pp.117-128
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    • 2014
  • Processable conducting polyaniline derivative with free amine functional groups was successfully synthesized from the monomer o-phenylenediamine in aqueous hydrochloric acid medium using ammonium persulfate as an oxidative initiator. The synthesized poly(o-phenylenediamine) (PoPD) in critical condition was found to be completely soluble in common organic solvents like dimethyl sulfoxide, N,N-dimethyl formamide etc. From the intrinsic viscosity measurement, the optimum condition for the polymerization was established. The polymer was characterized by ultraviolet visible spectroscopy, Fourier transform infrared spectroscopy, proton magnetic resonance spectroscopy ($^1HNMR$) and thermogravimetric (TGA) analyses. The weight average molecular weights of the synthesized polymers were determined by the dynamic light scattering (DLS) method. From the spectroscopic analysis the structure was found to resemble that of polyaniline derivative with free amine functional groups attached to ortho/meta position in the phenyl ring. However, very little ladder unit was also present with in the polymer chain. The moderate thermal stability of the synthesized polymer could be found from the TGA analysis. The average DC conductivity of $2.8{\times}10^{-4}S/cm$ was observed for the synthesized polymer pellet after doping with hydrochloric acid.

Strontium Metabolism in Higher Plants: Effect of Strontium of the Polyamine Biosynthesis during Germination of Wheat(Triticum aestivum L.) (식물체 내에서 Strontium의 대사 : 밀(Triticum aestivum L.)의 발아과정중 Polyamine 생합성에 미치는 Strontium의 영향)

  • Kim, Tae-Wan;Heinrich, Georg.
    • Korean Journal of Environmental Agriculture
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    • v.14 no.1
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    • pp.55-71
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    • 1995
  • Wheat (Triticum aestivum L.) seeds were used to study a possible relationship between strontium and polyamines (PAs) in the coleoptile, root, and endosperm during germination. When $Sr^{2+}$ (0.001 mM + 10 mM) was applied to the incubation medium with $10\;{\mu}M$ $GA_3$, great increases in putrescine (Put) were observed in root and spermidine (Spd) in the coleoptile, depending on the concentration. In germinating seeds, putrescine accumulation was induced even at a low concentration (0.01 mM Sr), whereas spermidine accumulation was stimulated considerably at a high concentration (10 mM Sr). The putrescine levels, on a gram fresh weight (g-fr-wt) basis, in the roots which were growth-inhibited by 1 and 10 mM $Sr^{2+}$ were 22.4 and 15.3 fold higher respectively than at the same concentrations of $Ca^{2+}$. The accumulation of total polyamine (TA), in particular Put and Spd, induced by Sr seemed to be an important physiological response not only on a g fr wt basis but also on an RNA basis. In contrast, the levels of agmatine (Agm) and cadaverine (Cad) were notably enhanced by 10 mM $Ca^{2+}$ in the coleoptile and root. Cadaverine was detected only in $Ca^{2+}-treated$ seedlings. However, $Ca^{2+}-treatment$ in the range of 0.001 mM to 1.0 mM resulted in reduction of TA content. The distinction of accumulated polyamines and the change in diamine (DA) / TA and tri- and tertiary (tPA) / TA ratios were likely to be a physiological difference between $Sr^{2+}$ and $Ca^{2+}$ during germination in wheat.

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Solvent-Free Michael Addition Between EMME and Secondary Amine under Focused Microwave Irradiation

  • Kim, Ki-Won;Lee, Hee-Jung;Jo, Jeong-Im;Kwon, Tae-Woo
    • Bulletin of the Korean Chemical Society
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    • v.31 no.5
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    • pp.1155-1158
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    • 2010
  • Microwave-assisted Michael reaction between EMME and various amines such as diphenylamine, 4-methyl-N-phenylbenzenamine, N-phenylnaphthalen-1-amine, dihexylamine, diisopropylamine, and 4-nitrobenzenamine were described. Solvent-free conditions on alumina as solid support in the presence of $K_2CO_3$ catalysts gave moderate to good yields (55 - 93%) of diethylmalonate analogues having enamine moieties under focused microwave irradiation.

Influences of Liquid Rubber on the Surfacial and Mechanical Properties of Epoxy Composites (에폭시 복합체의 표면 및 기계적 특성에 미치는 액상고무의 효과)

  • Choi, Sei-Young;Chu, Jeoung-Min;Lee, Eun-Kyoung
    • Elastomers and Composites
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    • v.43 no.2
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    • pp.113-123
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    • 2008
  • Epoxy resins are thermoset polymers that exhibit good adhesion, creep resistance, heat resistance, and chemical resistance. These polymers, however, give poor resistance to crack propagation and low impact strength. In this study, epoxy/carboxyl-terminated butadiene acrylonitrile (CTBN) and epoxy/amine-terminated butadiene acrylonitrile (ATBN) composites were prepared with different ratio of CTBN and ATBN to improve low impact strength of epoxy resin. The impact strength of epoxy/elastomeric composites shows high values with increasting nonpolar surface free energy while the tensile strength and the glass transition are decreased. The highest surface free energy, impact strength observed when 15 phr CTBN and 15 phr ATBN added, respectively. It can be concluded that as liquid rubber to improve impact strength of epoxy resin, ATBN is more preferable to CTBN.

Analysis of the Heat of Absorption Based on the Chemical Structures of Carbon Dioxide Absorbents (이산화탄소 흡수제의 화학구조별 반응열량 특성 연구)

  • Kwak, No Sang;Lee, Ji Hyun;Eom, Yong Seok;Kim, Jun Han;Lee, In Young;Jang, Kyung Ryoung;Shim, Jae-Goo
    • Korean Chemical Engineering Research
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    • v.50 no.1
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    • pp.135-140
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    • 2012
  • In this study, the heats of absorption of $CO_2$ with aqueous solutions of primary, secondary and tertiary amine aqueous solutions were measured in the commercial reaction calorimeter SIMULAR (HEL, UK). The heats of absorption of 30 wt% amine aqueous solutions of MEA (monoethanolamine, primary amine), EAE(2-(ethylamino)ethanol, secondary amine), and MDEA (methyldiethanolamine, tertiary amine) were measured as function of the $CO_2$ loading ratio at $40^{\circ}C$, in each case. In addition, the heats of absorption of sterically-hindered amine aqueous solutions of AMP(2-amino-2-methyl-1-propanol, primary amine), DEA(diethanolamine, secondary amine) and TEA(triethanolamine, tertiary amine) were measured to observe the steric hindrance effect. The heat of absorption is high in the following order regardless of the steric hindrance: primary amine > secondary amine > tertiary amine. The heats of absorption of amines having sterically-hindered substituents surrounding nitrogen atoms are relatively low compare to that of sterically-free amines, although the difference is very small.

Solvent Free N-Heterocyclization of Primary Amines to N-Substituted Azacyclopentanes Using Hydrotalcite as Solid Base Catalyst

  • Dixit, Manish;Mishra, Manish;Joshi, P.A.;Shah, D.O.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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    • pp.1457-1464
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    • 2012
  • An ecofriendly catalytic route for selective synthesis of $N$-substituted azacyclopentanes, nitrogen-containing heterocyclic intermediates for many bioactive compounds, was established by carrying out $N$-heterocyclization (di $N$-alkylation) of primary amines with 1,4-dichloro butane (as dialkylating agent) using catalytic amount of hydrotalcite as solid base catalyst. The hydrotalcite was found to be efficient solid base catalyst for di $N$-alkylation of different primary amines (aniline, benzyl amine, cyclohexyl amine and n-butyl amine) giving 82 to 96% conversion (at optimized reaction condition) of 1,4-dichloro butane and > 99% selectivity of respective $N$-substituted azacyclopentanes within 30 min. under solvent free condition. The reaction parameters significantly influence the conversion of 1,4-dichloro butane to $N$-substituted azacyclopentanes. The nature of substituent present on amino group affects the reactivity of amine substrates for di $N$-alkylation reaction with 1,4-dichloro butane. The 1,4-dichloro butane was found to be highly reactive alkylating agent for di $N$-alkylation of amines as compared to 1,4-dihydroxy butane. The reusability of the catalyst and its chemical stability in the reaction was demonstrated.

Kinetics and Mechanism of the Aminolysis of Aryl N-Benzyl Thiocarbamates in Acetonitrile

  • Oh, Hyuck-Keun
    • Bulletin of the Korean Chemical Society
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    • v.32 no.1
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    • pp.137-140
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    • 2011
  • The aminolysis reactions of phenyl N-benzyl thiocarbamate with benzylamines in acetonitrile at $50.0^{\circ}C$ are investigated. The reactions are first order in both the amine and the substrate. Under amine excess, pseudo-first coefficient ($k_{obs}$) are obtained, plot of $k_{obs}$ vs free amine concentration are linear. The signs of ${\rho}_{XZ}$ (< 0) are consistent with concerted mechanism. Moreover, the variations of $\rho_X$ and $\rho_Z$ with respect to the sustituent in the substrate and large ${\rho}_{XZ}$ value indicate that the reactions proceed concerted mechanism. The normal kinetic isotope effects ($k_H/k_D$ = 1.3 ~ 1.5) involving deuterated benzylamine nucleophiles suggest a hydrogen-bonded, four-centered-type transition state. The activation parameters, ${\Delta}H^\ddagger$ and ${\Delta}S^\ddagger$, are consistent with this transition state structure.