• Title/Summary/Keyword: 벤질

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Substituent Effects on the Leaving Groups in Benzyl Arenesulfonates (Benzyl Arenesulfonate의 離脫基의 置換基效果에 關한 硏究 (第 1 報))

  • Yoh Soo Dong
    • Journal of the Korean Chemical Society
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    • v.19 no.2
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    • pp.116-122
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    • 1975
  • Determination has been made of the kinetics of the reaction of benzyl arenesulfonates with pyridine in acetone. The substituent effects of the leaving groups in benzyl arenesulfonates are correlated by Hammett equations, with the exception of p-MeO and $p-NO_2$ groups, where the electron attracting substituents in the benzyl arenesulfonate increase the rate. The substituent effects of the leaving groups are as expected due to the nucleophilic attack of amine on the benzyl carbon atom. This can be understood in terms of changes in bond formation (C-N) and bond breaking (C-O) in the transition state with charges in electron-attracting ability of the substituents. The predicted substituent effects may indicate a small increase in bond formation and thus a tighter transition state, in benzyl p-bromobenzene sulfonate than in benzyl p-nitrobenzenesulfonate. Predicting made by Thornton concerning the substituent effects on $S_N2$ transition state structures agrees with the changes in bond formation and bond breaking.

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Manganese Dioxide-Based Chlorination of Alcohols Using Silicon Tetrachloride (이산화망간 존재하에서 사염화규소를 이용한 알코올의 염소화반응)

  • Ha, Dong Soo;Yoon, Myeong Jong
    • Journal of the Korean Chemical Society
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    • v.41 no.10
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    • pp.541-546
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    • 1997
  • Manganese dioxide may react with silicon tetrachloride to form manganese(Ⅳ) oxodichloride which reacts subsequently with another molecule of silicon tetrachloride leading to manganese tetrachloride eventually in chlorinated solvents. This in situ generated manganese(Ⅳ) oxodichloride or manganese tetrachloride were found to be very effective for the chlorination of a wide variety of alcohols to the corresponding chlorides. Primary, secondary and benzylic alcohols were converted into corresponding chlorides when treated with silicon tetrachloride in the presence of manganese dioxide at room temperature.

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A Study on the Radiolytic Synthesis of PVBC-grafted ETFE Films and Their Quaternarization with Diamines for the Preparation of Anion Exchange Membranes (음이온 교환막 제조를 위한 염화비닐벤질 고분자가 그라프트된 ETFE 필름의 방사선 합성과 디아민류와의 4차 아민화에 관한 연구)

  • Ko, Beom-Seok;Sohn, Joon-Yong;Nho, Young-Chang;Shin, Junhwa
    • Journal of Radiation Industry
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    • v.5 no.2
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    • pp.179-184
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    • 2011
  • In this study, several anion exchange membranes were successfully prepared by radiation grafting of vinylbenzyl chloride (VBC) monomer onto a polyethylene-co-tetrafluoroethylene (ETFE) film and subsequent quaternarization with diamins such as 1,4-diazbicyclo[2,2,2]octane, N,N,N',N'-tetramethyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,6-diaminohexane, and trimethylamine. The anion exchange capacities of the prepared membranes were determined by using acid-base titration method. The cross-sectional morphology of the membranes was studied by using SEM instrument. The cross-sectional distribution patterns of the grafted polymers with anion exchange functional groups were also studied by EDX analysis.

The Reaction of 4,4′-Dihydroxydiphenyl Methane with Glycidyl Methacrylate

  • Pyun, Hyung-Chick;Park, Wan-Bin;Sung, Ki-Woung;Choi, Kyu-Suck
    • Nuclear Engineering and Technology
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    • v.11 no.2
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    • pp.119-126
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    • 1979
  • The reaction of 4,4'-dihydroxydiphenl methane (4,4'-DPM) with glycidyl methacrylate (GMA) catalyzed by triethylbenzyl ammonium chloride (TEBAC) has been studied for the purpose of synthesis of electron beam curable prepolymer. The reaction was in good agreement with third-order kinetics. according to -d[GMA]/dt=k[TEBAC][DPM][GMA] and the apparent activation energy was about 33.4kca1/mole. However, the reaction rates were increased if tile reaction proceeded after the mixtures exposed to air for 24 hrs at room temperature. The effects of the catalyst and the difference in the reactivity between 2.2'-DPM to GMA were discussed. The plausible reaction mechanism was proposed on basis of experimental data obtained.

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Fabrication of Polymer Thin Films on Solid Substrates (고체 기판에 고분자 박막의 고정화)

  • Kim, Min Sung;Jeong, Yeon Tae
    • Applied Chemistry for Engineering
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    • v.21 no.2
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    • pp.200-204
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    • 2010
  • Surface properties are important for determining the functions and uses of materials. So modification of materials with polymer thin films has emerged as an important method to control the physical and chemical properties of the surface layer. We report a simple and effective method to photochemically attach thin polymeric layers to solid surface without chemical derivatization of the substrate and/or the polymer. The system is based on a photoreactive poly(4-vinylpyridine) (P4VP) thin film which is formed on the $SiO_{2}$ surface via spin coating. This substrate is then covered with another polymer film that is reacted with the benzyl radical moieties by UV irradiation. As a result of photochemical reaction, a thin layer of the later polymer is covalently bound to the surface of P4VP. Unbounded polymer is removed by sonication. The thickness of the attached film is a function of the irradiation time and the molecular weight of the polymer. Spatially defined polymer thin films can be fabricated by way of photolithography.

Synthesis and X-ray Structure Analysis of (Z)-1-(4-Bromophenyl)-1-phenyl-2-(4-tert-butylphenyl)ethene ((Z)-1-(4-브로모페닐)-1-페닐-2-(4-tert-부틸페닐)에텐의 합성 및 X-선 구조분석)

  • Kim, Chul-Bae;Cho, Hyun-Jong;Lee, Sung-Kyung;Park, Kwangyong
    • Applied Chemistry for Engineering
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    • v.20 no.3
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    • pp.335-338
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    • 2009
  • As important intermediates for blue emitting materials of organic light-emitting diodes, bromotriphenylethylene derivatives for distrylarylenes are prepared by reactions of bromobenzophenone with benzylphosphonates. The reaction produces a 60 : 40 mixture of (Z)- and (E)-geometric isomers that are difficult to be resolved. The (Z)-isomer is successfully isolated by a selective recrystallization process using 2-propanol as a solvent. The X-ray structure analysis of (Z)-isomer shows that dihedral angles between tert-butylphenyl ring and bromophenyl ring and between bromophenyl ring and phenyl ring are $56.5(4)^{\circ}$ and $74.1(4)^{\circ}$, respectively.

Enhancement of Bt-Plus Toxicity by Unidentified Biological Response Modifiers Derived from the Bacterial Culture Broth of Xenornabdus nematiphila (Xenorhabuds nematophila 세균 배양액 유래 미확인 생리활성 물질의 비티플러스 살충력 상승효과)

  • Park, Youngjin;Kim, Minwoo;Kim, Kunwoo;Kim, Yonggyun
    • Korean journal of applied entomology
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    • v.54 no.2
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    • pp.55-62
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    • 2015
  • 'Bt-Plus' has been developed by mixing spores of Bacillus thuringiensis (Bt) and culture broth of Xenorhabdus nematophila (Xn). Despite its high toxicity, it has some imitation to broaden its efficacy against diverse insect pest spectrum. This study focuses on enhancement of Bt-Plus toxicity against semi-susceptible insect, Spodoptera exitgua, by addition of Xn metabolites. Two main Xn metabolites, oxindole (OI) and benzylideneacetone (BZA), are known to enhance the Bt insecticidal activities. The addition of OI or BZA significantly increased Bt-Plus pathogenicity. However, when the freeze-dried Xn culture broth was added to Bt-Plus, much less amount was enough to enhance the toxicity compared to the amount of OI or BZA. An HPLC analysis indicated that there were more than 12 unidentifed bacterial metabolites in Xn culture broth. These suggest that there are potent biological response modifiers in Xn metabolites other than OI and BZA.

Synthesis of Dynorphin B Analogues by Solid-Phase Method (고상법에 의한 Dynorphin B 유도체의 합성)

  • Kook, Soon Uoong;Son, Ki Nam
    • Journal of the Korean Chemical Society
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    • v.42 no.2
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    • pp.214-219
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    • 1998
  • Dynorphin B analogues, $[Arg^{11}, D-Ala^{12}]$dynorphin B, $[D-Ala^2, Ala^6, Arg^{11}, D-Ala^{12}]$dynorphin B, and dynorphin B (1-11) were synthesized by solid-phase method. A chloromethylated polystyrene resin cross-linked with 2% divinylbenzene was substituted with Thr in ethanol to contain 1.20 mmol Thr/g of resin. All amino groups of amino acids were protected with t-Boc group and 2,6-dichlorobenzyl and nitro groups were used to protect the side chains of Tyr and Arg, respectively. Stepwise synthetic method was applied for synthesis of the products. Dicyclohexylcarbodiimide (DCC) and 1-hydroxybenzotriazole (HOBT) were used as the coupling reagents. The crude peptides were purified by gel filteration on Sephadex LH-20 column $(2 \times 50 cm)$ using MeOH/MeCN (3/1) and then characterized with HPLC, amino acid analyzer.

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Structure-Reactivity Relationship of Benzyl benzenesulfonates (Part 2). Nucleophilic Substitution Reaction of Benzyl Derivatives (Benzyl benzenesulfonate류의 구조-반응성 관계 (2보). 벤질 유도체의 친핵성 치환반응)

  • Cheong, Duk-Young;Kim, Sung-Hong;Lee, Myung-Ho;Yoh, Soo-Dong;Fujio, Mizue;Tsuno, Yuho
    • Journal of the Korean Chemical Society
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    • v.39 no.8
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    • pp.643-649
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    • 1995
  • The Menschutkin type reactions of substituted(Z)-benzyl systems with substituted(Y)-pyridines and N,N-dimethyl aniline have been studied by the electro-conductometric method in acetonitrile at 35$^{\circ}C$ and 50$^{\circ}C$. On the plot of $k_{obs}$ versus concentrations of nucleophile under pseudo-first order conditions, 3,$4-(CH_3/O)_2$-benzyl bromide and $4-CH_3O$-benzyl bromide were a positive intercept at zero concentration of nucleophile. The $k_1$ value for each compound was invariant with the different nucleoephile. However, $4-CH_3-$ and other electron withdrawing substituents of benzyl bromides did not show the positive intercept. These results are suggested that the reactions have been proceeding simultaneously and independently for the activated benzyl bromides via direct bimolecular and intimate ion pair intermediate.

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Synthesis and Determination of Optical Purity of C2-Symmetric Pyrrolidine Amides as Chiral Auxiliaries (키랄 보조제로서의 C2-대칭성 피롤리딘 아미드의 합성과 광학 순도 결정)

  • Moon, Hong-sik;Koh, Dongsoo
    • Applied Chemistry for Engineering
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    • v.9 no.6
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    • pp.914-919
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    • 1998
  • Optically pure $C_2-Symmetric$ pyrrolidine amides (8) were synthesized from readily available 1,2:5,6-di-O-isopropylidene-D-mannitol (1). Cyclization of dimesylated hexitol (4) with benzyl amine gave an inseparable mixture of $C_2-Symmetric$ pyrrolidine amine derivative (5) as a major product, concurring with its cis isomer (6) as a minor product. The pyrrolidine amines (5,6) were converted to separable pyrrolidine amides (8,9) via free amine (7). Optical purity of desired $C_2-Symmetric$ pyrrolidine amide (8a) was determined with its Mosher derivatives (13,14) by their $^1H$ and $^{19}F$ NMR spectra.

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