• Title/Summary/Keyword: Michael-type addition

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Kinetics and Thermodynamic Studies on the Reaction of Cysteine with Cinnamaldehyde

  • Kim, Tae-Rin;Yun, Se-Joon;Park, Byung-Bin
    • Bulletin of the Korean Chemical Society
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    • v.7 no.1
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    • pp.25-29
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    • 1986
  • The reaction of cysteine with cinnamaldehyde have been studied kinetically and thermodynamically. It was found that the reaction proceeds in two steps; formation of the monoadduct by a Michael type addition followed by the nucleophilic attack of the second cysteine to the carbonyl carbon of the monoadduct to afford the thiazolidine derivative. A reaction profile for the reaction of cysteine with cinnamaldehyde was constructed based on the thermodynamic parameters analyzed for the forward and the reverse reactions. It was assumed that the second step of this reaction accompanies an intermediate, a Schiff base.

Kinetic Studies on the Mechanism of Hydrolysis of 2-Phenyl-4H,5H-3-methyl-3-thiazolinium Perchlorate Derivatives (2-Phenyl-4H,5H-3-methyl-3-thiazolinium Perchlorate 유도체의 가수분해 반응 메카니즘에 관한 반응속도론적 연구)

  • Kim, Tae-Rin;Lee, So-Young;Han, Man-So;Pyun, Sang-Yong;Lee, Seok-Hee
    • Journal of the Korean Chemical Society
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    • v.44 no.2
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    • pp.120-126
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    • 2000
  • The rate constants for the hydrolysis of 2-phenyl-4H,5H-3-methyl-3-thiazolinium perchlorate(PTP) derivatives were detemined by the use of ultraviolet visible spectrophotometer in water. The rate equations which could be applied over a wide pH ranges were obtained. On the basis of rate equation, hydrolysis product analysis, general base catalysis, and substituent effect, a plausible mechanism of the hydrolysis is proposed: Below pH 4.0, the reaction is initiated by addition of water, while above pH 9.0, Michael type nucleophilic addition takes place. In the pH range of $4.5{\sim}8.0$, these two reactions appear to occur competitively.

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The Kinetics and Mechanism of the Nucleophilic Addition of Thiourea for Furfurylidene Acetophenone derivatives (Furfurylidene acetophenone유도체에 대한 Thiourea의 친핵성 첨가반응 메카니즘과 그 반응속도론적 연구)

  • Lee, Ki-Chang;Mok, Gap-Young;Oh, Se-Young;Ryu, Jung-Wok
    • Journal of the Korean Applied Science and Technology
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    • v.14 no.1
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    • pp.27-32
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    • 1997
  • Furfurylidene acetophenone derivatives were synthesis, it was measured that nucleophilic addition made use of UV at a wide pH 1.0${\sim}$13.0 range in 30% dioxane-$H_2O$ solution, 25$^{\circ}C$. On the basis of general base catalysis, substitutent effect, confirmation of nucleophilic addition products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It may be concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion: Above pH 10.0. sulfide anion adds to the double bond (Michael type addition), a part having no concern with pH, addition reaction to double bond is initiated by addition of neutral thiourea molecule. From the result of measurement the reaction rate, nucleophilic addition of furfurylidene acetophenone derivatives confirmed to the irreversible first order. Through measurement the substituent effect. It found that reaction rate was accelerated by electron attracting group. On the basis of these findings, nucleophilic addition of thiourea for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

Curing and Coating Properties of Photo-Curable Self-Photoinitiating Acrylate (광경화형 자가광개시 아크릴레이트의 경화특성 및 도막물성)

  • Han, A-Ram;Hong, Jin-Who;Kim, Hyun-Kyoung
    • Journal of Adhesion and Interface
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    • v.15 no.1
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    • pp.22-30
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    • 2014
  • Self-photoinitiating acrylate (SPIA) which can undergo self-initiation under UV irradiation was synthesized by a Michael addition in the presence of a base catalyst. The SPIA polymerizations were investigated by photo-differential scanning calorimeter (photo-DSC) and surface physical properties such as pendulum hardness and pencil hardness. The results showed that the SPIA can cure upon UV irradiation by itself without a photoinitiator. But we found out that both the curing rate and the conversion were too low for the self-curing reaction of SPIA. In order to improve the SPIA curing properties, we introduced the SPIA/cationic hybrid system and observed the effects of the addition of commercial free radical type monomer and photoinitiator on the curing behaviors. SPIA/cationic hybrid system was the best suitable to improve the SPIA curing properties. The kinetic analysis indicated that the cationic monomer and photoinitiator apparently accelerated the cure reaction and rate of the hybrid SPIA system, mostly due to the synergistic effect of cationic monomer and photoinitiator increasing the mobility of active species and the generation of reactive species (free radical, cation) during the photopolymerization process. The physical properties showed that, unlike typical free radical system, the hybrid systems did not show oxygen inhibition effect because of cationic reaction on the coating surface.

Facile Regiocontrolled Three-Step Synthesis of Poly-Substituted Furans, Pyrroles, and Thiophenes: Consecutive Michael Addition of Methyl Cyanoacetate to α,β-Enone, CuI-Mediated Aerobic Oxidation, and Acid-Catalyzed Paal-Knorr Synthesis

  • Kim, Se-Hee;Lim, Jin-Woo;Lim, Cheol-Hee;Kim, Jae-Nyoung
    • Bulletin of the Korean Chemical Society
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    • v.33 no.2
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    • pp.620-624
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    • 2012
  • An efficient synthesis of poly-substituted furans, pyrroles, and thiophenes was carried out in a regiocontrolled manner via a three-step process; (i) conjugate addition of methyl cyanoacetate derivatives to ${\alpha}$,${\beta}$-enones, (ii) CuI-mediated aerobic oxidation, and (iii) Paal-Knorr type synthesis of five-membered heterocycles.

The Kinetics and Mechanism of Nucleophilic Addition of Thioglycolic Acid to ${\beta}$-Nitrostyrene Derivatives

  • Kim, Tae-Rin;Huh, Tae-Sung;Han, In-Sup
    • Bulletin of the Korean Chemical Society
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    • v.3 no.4
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    • pp.162-165
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    • 1982
  • The rate constants of the nucleophilic addition of thioglycolic acid to the derivatives $(H,\;p-CH_3,\;p-CH_3O,\;p-Cl,\;p-NO_2)$ of ${\beta}$-nitrostyrene were determined by ultraviolet spectrophotometry. The rate equations which can be applied over a wide pH range were obtained. Therefrom a reaction mechanism was proposed. Above pH 8.5 sulfide anion adds to the double bond (Michael type addtion). However, below pH 8.5, the neutral molecule and $HSCH_2COO^{\theta}$ add to the double bond.

Surface-modified Nanoparticle Additives for Wear Resistant Water-based Coatings for Galvanized Steel Plates

  • Becker-Willinger, Carsten;Heppe, Gisela;Opsoelder, Michael;Veith, H.C. Michael;Cho, Jae-Dong;Lee, Jae-Ryung
    • Corrosion Science and Technology
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    • v.9 no.4
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    • pp.147-152
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    • 2010
  • Conventional paints for conversion coating applications in steel production derived mainly from water-based polymer dispersions containing several additives actually show good general performance, but suffer from poor scratch and abrasion resistance during use. The reason for this is because the relatively soft organic binder matrix dominates the mechanical surface properties. In order to maintain the high quality and decorative function of coated steel sheets, the mechanical performance of the surface needs to be improved significantly. In fact the wear resistance should be enhanced without affecting the optical appearance of the coatings by using appropriate nanoparticulate additives. In this direction, nanocomposite coating compositions (Nanomer$^{(R)}$) have been derived from water-based polymer dispersions with an increasing amount of surface-modified nanoparticles in aqueous dispersion in order to monitor the effect of degree of filling with rigid nanoparticles. The surface of nanoparticles has been modified for optimum compatibility with the polymer matrix in order to achieve homogeneous nanoparticle dispersion over the matrix. This approach has been extended in such a way that a more expanded hybrid network has been condensed on the nanoparticle surface by a hydrolytic condensation reaction in addition to the quasi-monolayer type small molecular surface modification. It was expected that this additional modification will lead to more intensive cross-linking in coating systems resulting in further improved scratch-resistance compared to simple addition of nanoparticles with quasi-monolayer surface modification. The resulting compositions have been coated on zinc-galvanized steel and cured. The wear resistance and the corrosion protection of the modified coating systems have been tested in dependence on the compositional change, the type of surface modification as well as the mixing conditions with different shear forces. It has been found out that for loading levels up to 50 wt.-% nanoparticles, the mechanical wear resistance remains almost unaffected compared to the unmodified resin. In addition, the corrosion resistance remained unaffected even after $180^{\circ}$ bending test showing that the flexibility of coating was not decreased by nanoparticle addition. Electron microscopy showed that the inorganic nanoparticles do not penetrate into the organic resin droplets during the mixing process but rather formed agglomerates outside the polymer droplet phase resulting in quite moderate cross linking while curing, because of viscosity. The proposed mechanisms of composite formation and cross linking could explain the poor effect regarding improvement of mechanical wear resistance and help to set up new synthesis strategies for improved nanocomposite morphologies, which should provide increased wear resistance.

Spring-back Evaluation of Automotive Sheets Based on Combined Isotropic-Kinematic Hardening Rule (Combined Isotropic-Kinematic 경화규칙에 기초한 자동차용 알루미늄합금-및 Dual-Phase 강 판재의 스프링백 예측)

  • ;;;Chongmin Kim;Michael L. Wenner
    • Proceedings of the Korean Society for Technology of Plasticity Conference
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    • 2003.10a
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    • pp.144-147
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    • 2003
  • In order to evaluate spring-back behavior in automotive sheet forming processes, a panel shape idealized as a SS-rail has been investigated. After spring-back kas been predicted fer SS-rails using the finite element analysis, results has been compared with experimental measurements for three automotive sheets. To account for hardening behavior such as the Bauschinger and transient effects in addition to anisotropic behavior, the combined isotropic-kinematic hardening law based on the Chaboche type single-surface model and a recently developed non-quadratic anisotropic yield function have been utilized, respectively.

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The Role of Thymic Stromal Lymphopoietin (TSLP) in Glomerulonephritis

  • Lee, Keum Hwa;Yang, Jae Won;Cho, Jin Young;Lee, Joo Yup;Lim, Eun Kyung;Eisenhut, Michael;Jeong, Dong Yeon;Steingroever, Johanna;Shin, Jae Il
    • Childhood Kidney Diseases
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    • v.22 no.1
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    • pp.17-21
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    • 2018
  • Thymic stromal lymphopoietin (TSLP) is an interleukin-7-like cytokine that is an important trigger and initiator of many allergic diseases. TSLP promotes a T-helper type 2 (Th2) cytokine response that can be pathological. A relationship is formed both at the induction phase of the Th2 response through polarization of dendritic cells to drive Th2 cell differentiation and at the effector phase of the response, by promoting the expansion of activated T cells and their secretion of Th2 cytokines and TSLP. In transgenic mice with TSLP overexpression, it has been reported that TSLP leads to the development of mixed cryoglobulinemic membranoproliferative glomerulonephritis. In addition, TSLP can play an important role in the pathogenesis of IgA nephropathy and systemic lupus erythematosus-related nephritis. From our knowledge of the role of TSLP in the kidney, further studies including the discovery of new therapies need to be considered based on the relationship between TSLP and glomerulonephritis.

New Hyperbranched Polyimides and Polyamides: Synthesis, Chain-End Functionalizations, Curing Studies, and Some Physical Properties (새로운 Hyperbranchedpolyimidesandpolyamides: 합성, 말단기 변형, 경화 연구, 그리고 물리적 성질)

  • Baek, Jong-Beom;Chris B. Lyon;Tan, Loon-Seng
    • Proceedings of the Korean Society For Composite Materials Conference
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    • 2003.10a
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    • pp.1-2
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    • 2003
  • While aromatic polyimides and polyamides have found widespread use as high performance polymers, the present work addressed the need for organosoluble materials through the use of a hyperbranching scheme. The $AB_2$ monomers were prepared. The $AB_2$ monomers were then polymerized via aromatic fluoride-displacement and Yamazaki reactions to afford the corresponding hydroxyl-terminated hyperbranched polyimides (HT-PAEKI) and amine-terminated hyperbranched polyamides, respectively. HT-FAEKI was then functionalized with allyl and propargyl bromides as well as epichlorohydrin to afford allyl-terminated AT-PAEKI, propargyl-terminated PT-PAEKI, and epoxy (glycidyl)-terminated ET-PAEKI, in that order. All hyperbranched poly(ether-ketone-imide)s were soluble in common organic solvents. AT-PAEKI was blended with a bisphenol-A-based bismaleimide (BFA-BMI) in various weight ratios. Thermal, rheological, and mechanical properties of these blend systems were evaluated. Two characteristic hyperbranched polyamides, which the one has para-electron donating groups to the surface amine groups and the other has para-electron withdrawing groups to the surface amine groups, were selected to compare BMI curing behaviors. The electron rich polymer displayed ordinary Michael addition type exothermic reaction, while electron deficient polymer did display unusual curing behaviors. Based on analytical data, the later system provided the strong evidences to support room temperature curing of BMI by reactive intermediates instead of reactive primary amine groups on the macromolecule surface.

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