• Title/Summary/Keyword: Addition reactions

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A Mechanistic Study on the Nucleophilic Addition Reactions of Benzylamines to the Activated Olefins

  • Oh, Hyuck-Keun
    • Bulletin of the Korean Chemical Society
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    • v.29 no.6
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    • pp.1195-1198
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    • 2008
  • Kinetic studies of the additions of benzylamines to a noncyclic dicarbonyl group activated olefin, methyl $\alpha$-acetyl-$\beta$ -phenylacrylates (MAP), in acetonitrile at 30.0 ${^{\circ}C}$ are reported. The rates are lower than those for the cyclic dicarbonyl group activated olefins. The addition occurs in a single step with concurrent formation of the $C_\alpha$ -N and $C_\beta$ -H bonds through a four-center hydrogen bonded transition state. The kinetic isotope effects ($k_H/k_D$ > 1.0) measured with deuterated benzylamines ($XC_6H_4CH_2ND_2$) increase with a stronger electron acceptor substituent ($\delta\sigma$ X > 0) which is the same trend as those found for other dicarbonyl group activated series (1-4). The sign and magnitude of the cross-interaction constant, ρXY, is comparable to those for the normal bond formation processes in the $S_N2$ and addition reactions. The relatively low ${\Delta}H^\neq$ and large negative ${\Delta}S^\neq$ values are also consistent with the mechanism proposed.

A Study on the Variation of Vitamin C Content in Cooked Spinach by the Cookery Method. (시금치나물의 조리방법에 따른 Vitamin C 함량변화에 관한 연구)

  • 김양희
    • Journal of the Korean Home Economics Association
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    • v.11 no.1
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    • pp.44-56
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    • 1973
  • The effect of the temperature and the time of scalding, and the addition of various seasoning on the remaining % of total Vitamin C contained in Spinach (Spinacia oleracea) was studied and discussed by means of chemical kinetics. The quantitative measurements of total Vitamin C were made by 2,4-dinitrophenyl hydrazine (DNPH) method with Clinical Electrophotometer (Fisher). The sample spinach contains 39.88mg. % of total vitamin C on the average, and the ratio of oxidized and reduced forms of Vitamin C is 1 : 4.7. When the sample spinach was scalded, the kinetics of the decrease of the remaining total vitamin C. % was observed to follow the first order reactions regardless of the temperatures applied (i,e. 70$^{o}$ , 80$^{o}$ , 90$^{o}$ and 100$^{o}$ ) with half-life range of 2.10 - 1.47 minutes. In the case of the addition of various seasonings, the addition of various seasonings, the kinetics remaining Vitamin C % showed to be the zero order reactions regardless of the kinds of seasonings and storage temperatures. With the addition of seasonings, the stability of Vitamin C was found to be increased in the order table salt+sesame oil+vinegar+soybean sauce, without seasoning, table salt+sesame oil, table salt+sesame oil+soybean sauce.

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Addition and Subtraction of Emotion Codons Igniting by Sijo

  • Park, In-kwa
    • International Journal of Advanced Culture Technology
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    • v.6 no.3
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    • pp.117-128
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    • 2018
  • This study attempts to derive the possibility of literary therapy through addition and subtraction of emotional codons. It is presumed that the remnants of the emotions formed by the addition and subtraction of emotions will remain in the human body and cause chemical reactions. When this research is activated, cluster of emotional codons will be created by a combination of literary emotions. This is expected to accelerate therapeutic action of sentences by encoding certain emotional codons in AI.

Spontaneous Formation of Revival Waves in the 1,4-Cyclohexanedione-Bromate-Ferroin Reaction

  • Huh, Do-Sung;Kim, Young-Joon;Kim, Hye-Sook;Kang, Jong-Kon;Choe, Sang-Joon
    • Bulletin of the Korean Chemical Society
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    • v.25 no.2
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    • pp.267-270
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    • 2004
  • The bromate-1,4-cyclohexanedione-ferroin oscillating reactions are uncovered to support two types of wave activities, in which spontaneous formation of circular waves has been achieved after the disappearance of initial waves. The induction period of the revival wave is typically above 10 hours and its dependence on the initial concentrations of reactants is qualitatively different from that of initial waves. In addition to their differences in propagating speed and wavelength, the initial waves and the revival patterns have different colors, suggesting that different reaction mechanisms are involved in the formation of these spatiotemporal behaviors. Our experiments further show that the addition of hydroquinone to the reacting system can significantly shorten the induction time of the revival wave, which implicates that hydroquinone is not only a product in the bromate-1,4-cyclohexanedione-ferroin oscillating reaction but also plays a critical role in the following reactions.

Acrolein, the toxic endogenous aldehyde, induces neurofilament-L aggregation

  • Jeong, Moon-Sik;Kang, Jung-Hoon
    • BMB Reports
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    • v.41 no.9
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    • pp.635-639
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    • 2008
  • Acrolein is a highly reactive by product of lipid peroxidation and individuals with neurodegenerative disorders have been shown to contain elevated concentrations of this molecule in the brain. In the present study, we examined the pattern of neurofilament-L (NF-L) modification elicited by acrolein. When NF-L was incubated with acrolein, protein aggregation occurred in a acrolein concentration-dependent manner. Exposure of NF-L to acrolein also led to the generation of protein carbonyl compounds. Through the addition of free radical scavengers we observed a significant decrease in acrolein-mediated NF-L aggregation. These results indicate that free radicals may be involved in the modification of NF-L by acrolein. In addition, dityrosine crosslink formation was observed in acrolein-mediated NF-L aggregates and these aggregates displayed thioflavin T reactivity, reminiscent of amyloid. This study suggests that acrolein-mediated NF-L aggregation might be closely related to oxidative reactions, thus these reactions may play a critical role in neuro-degenerative diseases.

Synthesis and Reactions of Benzimidazoline-2-thione Derivatives

  • Lee Tae Ryong;Kim Kyongtae
    • Bulletin of the Korean Chemical Society
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    • v.10 no.1
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    • pp.80-84
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    • 1989
  • Two properties of sodium naphthalenide (2), i.e. a strong base and a good electron donor were utilized for one pot synthesis: 2-alkylthiobenzimidazoles were synthesized in excellent yields from the reactions of benzimidazoline-2-thione (1) with an equimolar amount of alkyl halides in the presence of 2. Continuous addition of a different alkyl halide without the isolation of 2-alkylthiobenzimidazoles afforded 1-alkyl-2-alkylthiobenzimidazoles having different alkyl groups at N and S atoms in excellent yields. Further addition of 2 to 1-alkyl-2-alkylthiobenzimidazoles gave excellent yields of 1-alkylbenzimidazoline-2-thiones. When 2 in THF was added to a suspension of 1-alkyl-2-alkylthiobenzimidazoles in THF, a bond cleavage between N and C of alkyl group as well as S and C of alkyl group occurred. This is in contrast to the observation in which only cleavage between S and C of alkyl group takes place in the homogeneous solution.

Mechanism and Products During the Homolytic Addition of CCl$_4$ and Cl$_3$CBr to $\beta$-Halostyrenes

  • Kim Sung-Soo
    • Bulletin of the Korean Chemical Society
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    • v.1 no.2
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    • pp.45-49
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    • 1980
  • During the homolytic reactions of $CCl_4$ or $Cl_3CBr with ${\beta}-halo^1$-styrenes,$\beta$-haloradicals are key intermediates. They are to be stabilized via three pathways; $\beta$-cleavage, halogen transfer and telomerization. The three reaction paths are delicately controlled by the energetics of their formation and stabilization. When the formation of a $\beta$-haloradical is accompanied by considerable excess of energy from an exothermic reaction, $\beta$ -cleavage is often dominant over the halogen transfer. On the other hand, if the radical forms via a reversible reaction, two processes become competitive. $\beta$-Eliminated bromine atoms from ${\beta}$ -bromoradicals generate $Br_2$ via $Cl_3CBr + {\cdot}Br {\leftrightarrow} Br_2 + {CCl_3}{\cdot}{Br_2}$ may act as a better scavenger than Cl3CBr for the ${\beta}$-bromoradicals. Different reactivities of chlorine, bromine and trichloromethyl radicals towards olefinic pi-bond are clarified in terms of the beat content of the addition reactions.

Numerical Studies on Combustion Characteristics of a Hybrid Catalytic Combustor (하이브리드 촉매 연소기의 연소특성에 관한 수치적 연구)

  • Hwang, Chul-Hong;Jeong, Young-Sik;Lee, Chang-Eon
    • Proceedings of the KSME Conference
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    • 2000.11b
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    • pp.328-334
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    • 2000
  • The hybrid catalytic(catalytic+thermal) combustor of a lean methane-air mixture on platinum catalyst was investigated numerically using a 2-D boundary layer model with detailed homogeneous and heterogeneous chemistries. For the more accurate calculations, the actual surface site density of monolith coated with platinum was decided by the comparison with experimental data. It was found that the homogeneous reactions in the monolith had little effect on the change of temperature profile, methane conversion rate and light off location. However, the radicals such as OH and CO were produced rapidly at exit by homogeneous reactions. Thus the homogeneous reactions were important to predict the productions of CO and NOx exactly. In thermal combustor, the production of $N_2O$ was more dominant than that of NO due to the relative important of the reaction $N_2+O(+M){\to}N_2O(+M)$. Finally the production of CO and NOx by amount of methane addition were studied.

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Combustion Modeling for Stratified Charge (성층화 혼합기의 연소 모델링)

  • 김용태;배상수;민경덕
    • Transactions of the Korean Society of Automotive Engineers
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    • v.9 no.4
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    • pp.50-55
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    • 2001
  • To simulate the combustion process under stratified charged conditions, like GDI engines, the new combustion model is proposed, which is based on Welter's FAE model and Peters' PDF model for considering primary reactions. In addition to these models, the new laminar burning velocity correlation and diffusion flame model are also included in the proposed model. The former can be applicable to much wider range of equivalence ratio, pressure and temperature than the others, such as Keck's and Guilder's models, and the latter has been derived from water-gas shift reaction and hydrogen oxidation, by which the secondary reactions can be considered after primary reactions. 3-D computation has been performed by using STAR-CD v3.05 in the simple cylindrical geometry under stratified charged condition. Judging from the calculated results, the present model proves to be reasonable to simulate the characteristics of flame propagation and concentrations of products in burned regions.

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Antigenicity Studies of the Aqueous Extract of Fresh Ginseng in Guinea Pigs

  • Lee, Jong-Wha;Rhee, Man-Hee;Park, Jong-Il;Han, Sang-Seop
    • Korean Journal of Pharmacognosy
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    • v.25 no.1
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    • pp.35-40
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    • 1994
  • Aqueous extreact of fresh ginseng (AFG) was examined for the antigenicity in Hartley guinea pigs in comparision with ovalbumin (OVA). When guinea pigs were sensitized with AFG emulsified with complete Freund's adjuvant (CFA), these animals showed negative reactions in active systemic anaphylaxis (ASA), active cutaneous anaphylaxis (ACA) and passive cutaneous anaphylaxis (PCA) tests and passive hemagglutination (PHA) reaction. On the contrary, when guinea pigs were sensitized with OVA emulsified with CFA as positive controls, these animals disclosed positive reactions in ASA, ACA and PCA tests and PHA reaction. From these results, AFG was considered not to possess antigenic properties in guinea pigs. In addition, the dose levels of AFG empolyed in the present experiment were confirmed not to suppress immune reactions.

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