• Title/Summary/Keyword: O-Methyl

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The Reaction of Superoxide with Carbohydrate Sulphonates

  • Shin, Young-Sook;Nam Shin, Jeong E.
    • Bulletin of the Korean Chemical Society
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    • v.14 no.2
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    • pp.188-191
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    • 1993
  • The reaction between methyl 2,3-di-O-benzyl-4,6-di-O-mesyl-${\alpha}$-D-glucopyranoside (1b) and potassium superoxide resulted in hydrolysis, and gave methyl 2,3-di-O-benzyl-${\alpha}$-D-glucopyranoside (1) as a sole product. When the reaction was performed with a vicinal dimesylate, methyl 4,6-O-benzylidene-2,3-di-O-mesyl-${\alpha}$-D-altropyranoside (4b), again the hydrolysis product, methyl 4,6-O-benzylidene-${\alpha}$-D-altropyranoside (4) was obtained. However, the reaction of potassium superoxide with another vicinal dimesylate, methyl 4,6-O-benzylidene-2,3-di-O-mesyl-${\alpha}$-D-glucopyranoside (3b), nucleophilic displacement took place to afford methyl 4,6-O-benzylidene-${\alpha}$-D-altropyranoside (4). Apparently different results from two trans vicinal dimesylates, 3b and 4b are explained by the transient formation of epoxides, methyl 2,3-anhydro-4,6-O-benzylidene-${\alpha}$-D-allopyranoside (8) and methyl 2,3-anhydro-4,6-O-benzylidene-${\alpha}$-D-mannopyranoside (9) by $KO_2$. The reaction between the allo epoxide 8 and $KO_2$ gave altro 4. The manno epoxide 9 also afforded altro 4 as the major product. Facile epoxide formation by the reaction of a vicinal dimesylate and superoxide was also observed with 3-O-benzyl-1,2-O-isopropylidene-5,6-di-O-mesyl-${\alpha}$-D-glucofuranose: 5,6-anhydro-3-O-benzyl-1,2-O-isopropylidene-${\beta}$-L-idofuranose was obtained.

Computational Investigation of Isomeric and Conformeric Structures of Methyl Fluoroperoxide and Fluoromethyl Fluoroperoxides (Methyl fluoroperoxide와 fuoromethyl fluoroperoxides의 conformers와 isomers 구조에 대한 이론연구)

  • Lee, Kyoung-Min;Sung, Eun-Mo
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.405-411
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    • 2011
  • The ab initio calculations for fluoromethyl fluoroperoxides have been carried out using MP2/6-311G(d,p) and B3LYP/6-311++G(d,p) method. The structural optimizations were performed for several isomers and conformers of methyl fluoroperoxide, $CH_3OOF$ and the vibrational frequencies were calculated. The most stable conformer of $CH_3OOF$ is skew form and has fairly short O-O bond distance. The trans and cis conformers have 8-12 kcal/mol higher energies than skew form and the other isomers are very unstable. The structures of $CH_2FOOF$, $CHF_2OOF$ and $CF_3OOF$ are also optimized and vibrational frequencies were calculated. These molecules also have skew forms as the lowest energy conformers. The O-O bond distances are longer and C-O bond distances are shorter than $CH_3OOF$, but the structural parameters are almost independent of the number of fluorine atoms in methyl group.

Production of Methyl Ester from Coconut Oil using Microwave: Kinetic of Transesterification Reaction using Heterogeneous CaO Catalyst

  • Mahfud, Mahfud;Suryanto, Andi;Qadariyah, Lailatul;Suprapto, Suprapto;Kusuma, Heri Septya
    • Korean Chemical Engineering Research
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    • v.56 no.2
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    • pp.275-280
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    • 2018
  • Methyl ester derived from coconut oil is very interesting to study since it contains free-fatty acid with chemical structure of medium carbon chain ($C_{12}-C_{14}$), so the methyl ester obtained from its part can be a biodiesel and another partially into biokerosene. The use of heterogeneous catalysts in the production of methyl ester requires severe conditions (high pressure and high temperature), while at low temperature and atmospheric conditions, yield of methyl ester is relatively very low. By using microwave irradiation trans-esterification reaction with heterogeneous catalysts, it is expected to be much faster and can give higher yields. Therefore, we studied the production of methyl ester from coconut oil using CaO catalyst assisted by microwave. Our aim was to find a kinetic model of methyl ester production through a transesterification process from coconut oil assisted by microwave using heterogeneous CaO catalyst. The experimental apparatus consisted of a batch reactor placed in a microwave oven equipped with a condenser, stirrer and temperature controllers. Batch process was conducted at atmospheric pressure with a variation of CaO catalyst concentration (0.5; 1.0; 1.5; 2.0, 2.5%) and microwave power (100, 264 and 400 W). In general, the production process of methyl esters by heterogeneous catalyst will obtain three layers, wherein the first layer is the product of methyl ester, the second layer is glycerol and the third layer is the catalyst. The experimental results show that the yield of methyl ester increases along with the increase of microwave power, catalyst concentration and reaction time. Kinetic model of methyl ester production can be represented by the following equation: $-r_{TG}=1.7{\cdot}10^6{_e}{\frac{-43.86}{RT}}C_{TG}$.

On the Electrochemical Reduction of O, O-Dimethyl-O-(3-Methyl-4-Nitrophenyl)-Phosphorthioate (Fenitrothion) Pesticide in Acetonitrile Solution (Acetonitrile 용액중에서 살충제 O, O-Dimethyl-O-(3-Methyl-4-Nitrophenyl)-Phosphorothioate (Fenitrothion)의 전기화학적 환원)

  • Il-Kwang Kim;Youn-Geun Kim;Hyun-Ja Chun
    • Journal of the Korean Chemical Society
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    • v.32 no.3
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    • pp.186-194
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    • 1988
  • The electrochemical reduction of O,O-dimethyl-O-(3-methyl-4-nitrophenyl)-phosphorothioate (Fenitrothion) has been studied in acetonitrile solution containing surfactant micelle by direct current (DC)-differential pulse (DP) polarography, cyclic voltammetry (CV) and controlled potential coulometry (CPC). The partially reversible electron transfer-chemical reaction(EC, EC mechanism) of fenitrothion reduction proceeded by four electron transfer to form O,O-dimethyl-O-(3-methyl-4-hydroxyaminophenyl)-phosphorothioate which undergoes single bond of the phosphorus atom and phenoxy group cleaves to give p-amino-m-cresol and dimethyl thiophosphinic acid as major product by two electron transfer-protonation at higher negative potential. The polarograpic reduction waves shown to suppressed due to inhibitory effect of sodium lauryl sulfate micelle solution and split up on selectivity of anionic micelle effect in two step at the first reduction peak.

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Extractives from the Needles of Torreya (벼자나무 잎의 추출성분)

  • Kim, Jin-Kyu;Bae, Young-Soo
    • Journal of the Korean Wood Science and Technology
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    • v.29 no.4
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    • pp.53-59
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    • 2001
  • The needles of torreya(Torreya nucifera S. et Z) were collected, extracted with acetone-$H_2O$(7:3, v/v), fractionated with hexane, chloroform and ethylacetate, and freeze dried to give some dark brown powder. The ethylacetate soluble mixture was chromatographed on a Sephadex LH-20 column using a series of aqueous methanol and ethanol-hexane mixture as eluents. Most of the needle extractives were flavan and its methyl ether compounds such as (+)-catechin, (-)-epicatechin, (+)-gallocatechin, (-)-epigallocatechin, 3'-O-methyl-(+)-catechin and 3'-O-methyl-(-)-epicatechin including protocatechuic acid, one of benzoic acids. $^1H$- and $^{13}C$-NMR, NOE and CI-MS analyses were performed to elucidate the structures of the isolated compounds.

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Studies on the Chemical Structure of the New Polysaccharide C - (The New Polysaccharides of Gum Tragacanth. II) - (Tragacanth gum 의 신다당류(新多糖類) C 의 화학구조(化學構造) - Tragacanth gum의 신다당류(新多糖類)에 관(關)한 연구(硏究) 제2보(第二報) -)

  • Lee, Sung-Hwan
    • Applied Biological Chemistry
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    • v.3
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    • pp.25-48
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    • 1962
  • The polysaccharide C prepared from gum tragacanth powder (U. S. P. grade) by the precipitation method with 85% ethanol was a neutral polysaccharide, $[{\alpha}]^{30}_D-72.2$. The polysaccharide C consisted of L-rhamnose, D-xylose, L-arabinose and D-galactose in the molar ratio 2:1:17:9 (Table 1, 2, 3, ). The polysaccharide C was methylated with dimethylsulphate and 40% NaOH, and Purdies regent. The hydrolyzate of fully methlated product ($[{\alpha}]^{22}_D-102$ in chloroform, the methoxy content 40.6%) was composed of 2, 3, 5-tri-O-methyl-L-arabofuranose (I), 3,4-di-O-methyl-L-rhamnopyranose (II), 2,3-di-O-methyl-D-xylose (III), 2,3,4-tri-O-methyl-D-galactopyranose (IV), 2,4-di-O-methyl-L-arabopyranose (?), 2,4-di-O-methyl-D-galactose(VI), 2-O-methyl-D-arabinose (VII), and L-arabopyranose(VIII) (Table 4, 5, and Fig. 4). The first partial hydrolysis (A) of the polysaccharide C with 0.05N-HCl for 4.5 hours at $80-85^{\circ}C$ released only L-arabinose: the second hydrolysis (B) with 0.1N-HCl for 5 hours at $80-85^{\circ}C$, L-arabinose and D-galactose; and the third hydrolysis (C) with 0.3N-HCl at $90-95^{\circ}C$ in sealed tube, L-rhamnose, D-xylose, L-arabinose and D-galactose. From the unhydrolyzate A' were found L-rhamnose, D-xylose, L-arabinose, and D-galactose; from B' L-rhamnose, d-xylose, L-arabinose and D-galactose; and from C' D-xylose and D-galactose respectively (Table 6). The periodate consumption and formic acid production of the polysaccharide C were measured at various time intervals. After 120 hours periodat was consumed by 1.23 mole per $C_5H_8O_4$ and formic acid was produced 0.78 mole per $C_5H_8O_4$ (Table 7). Although a definite chemical structure for this polysaccharide C may not be formulated, experimental data, especially, from methylation, partial hydrolysie and determination of its molar ratio, and periodate analysis showed that the polysaccharide C is a highly branched polysaccharide and would be constructed of galactoaraban as a main chain residue and L-arabofuranose, D-galactopyranosyl $(1{\rightarrow}1)$-L-arabofuranose, D-xylopyranosyl $(1{\rightarrow}2)$-L-rhamnopyranosyl $(1{\rightarrow}1)$-L-arabofuranose, and L-rhamnopyranosyl $(1{\rightarrow}1)$-arabofuranose, and D-galactopyranosyl-$(1{\rightarrow}2)$-L-arabopyranosyl-$(1{\rightarrow}1)$-I-arabofuranose as a branch chain or end group (page 21).

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Chemical Characteristics and Immuno-stimulating Properties of Biopolymers Extracted from Acanthopanax sessiliflorus

  • Jeong, Sang-Chul;Jeong, Young-Tae;Yang, Byung-Keun;Song, Chi-Hyun
    • BMB Reports
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    • v.39 no.1
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    • pp.84-90
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    • 2006
  • During our search for macrophage stimulating compounds from medicinal plants, we isolated biopolymers from Acanthopanax sessiliflorus. Isolated fraction AS-5 showed maximum potential, and stimulated lysosonal enzymatic activity by 230% at $300\;{\mu}g/ml$. The nitric oxide (NO) producing ability of AS-5 $100\;{\mu}g/ml$ was $58\;{\mu}M$ when treated with interferon-$\gamma$ and lipopolysaccharide $20\;{\mu}g/ml$. The lymphocyte proliferating effects of isolated biopolymer fractions were also investigated. Highest lymphoproliferative activity (a 2.8-fold enhancement compared to saline treated group was exhibited by AS-3 at $200\;{\mu}g/ml$ followed by AS-5 and AS-6. The AS-3 fraction stimulated only T-lymphocytes and had little or no effect on B-lymphocyte proliferation. Partially methylated alditol acetates were prepared to elucidate the glycosyl linkage-compositions of the AS-3 and AS-5 biopolymers, and were analyzed by GC-MS. The AS-3 and AS-5 biopolymer fractions were found to contain 2,3,4-tri-O-methyl-D-glucitol, 2,3,4-tri-O-methyl-D-galacitol 3,4,6-tri-O-methyl-galacitol, 2-O-methyl-arabinitol and 2,4,6-tri-O-methyl-D-glucitol, 2,3,6-tri-O-methyl-D-galacitol linkages, respectively.

Inactivation of the Preservative in Cosmetic by the Addition of Inorganic Powder (화장품에서 무기분말에 의한 방부제의 효능저하)

  • 정광수
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.11 no.1
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    • pp.13-20
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    • 1985
  • The decreased preservative effect by tale and $TiO_2$ for emulsions obtained with polyoxyethylene surfactant was studied by various analytical methods and biological test. The preservative effect of methyl p-hydroxybenzoate was decreased by the addition of talc and $TiO_2$ and this result was attributed to the adsorption of methyl p-hydroxybenzoate on them. Talc exhibited more decreased preservative effect than that of $TiO_2$. The amount of the adsorption of methyl p-phydroxybenzoate by talc at $20^{\circ}C$ could be represented by the following equation; $a=11.511C^{0.747}$.

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Photocatalytic Degradation Mechanism of Methyl Mercaptan using $TiO_2$ (TiO$_2$를 이용한 메틸메르캅탄의 광촉매 분해메커니즘)

  • Lee, Byung-Dae;Lee, Jin-Shik;Kim, Yeoung-Chan
    • Journal of the Korean Applied Science and Technology
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    • v.24 no.3
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    • pp.296-300
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    • 2007
  • This paper presents applicability of photocatalytic decomposition of methyl mercaptan using $TiO_2$. A quartz reactor was used in order to elucidate reaction pathway in photocatalytic decomposition of methyl mercaptan. Experimental results showed that more than 99.9% of methyl mercaptan was decomposed within 30 minutes. It was found that the photocatalytic decomposition of methyl mercaptan followed pseudo first order and its reaction coefficient was $0.05min^{-1}$ During 30 minutes in the photocatalytic reaction, the concentration of methyl mercaptan, dimethyl disulfide, $SO_2$, $H_2SO_4$, COS, $H_2S$ were determined. These results showed that 64% of methyl mercaptan were compensated for the increase in sulfur after 30 minutes through the mineralization. The proposed main photocatalytic decomposition pathway of methyl mercaptan was methyl $mercaptan{\rightarrow}dimethyl$ $disulfide{\rightarrow}SO_2{\rightarrow}H_2SO_4$.