• Title/Summary/Keyword: isomers

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A Novel Synthetic Route to Highly Cross-Linked Poly(vinyl ethers): Ⅲ. Synthesis and Free Radical Polymerization of Aryloxyethyl Vinyl Ethers Having an Electron Acceptor in ortho- or meta-Position

  • 이주연;김무용;안광덕
    • Bulletin of the Korean Chemical Society
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    • v.18 no.3
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    • pp.318-323
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    • 1997
  • ο-(2-Vinyloxyethoxy)benzylidenemalononitrile (3a) and methyl ο-(2-vinyloxyethoxy)-benzylidenecyanoacetate (3b), m-(2-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl m-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b) were prepared by the condensation of ο-(2-vinyloxyethoxy)benzaldehyde (1) and m-(2-vinyloxyethoxy)benzaldehyde (2) with malononitrile or methyl cyanoacetate, respectively. Bifunctional vinyl ether monomers 3a and 3b polymerized quantitatively with radical initiators in γ-butyrolactone solution at 65 ℃, while meta-isomers 4a and 4b gave lower yields of polymers under the same conditions. The polymers 5-6 obtained from the monomers 3-4 were insoluble in common solvents due to cross-linking. Under the same polymerization conditions ethyl vinyl ether polymerized well with model compounds ο-methoxybenzylidenemalononitrile 7a, methyl ο-methoxybenzylidenecyanoacetate 7b, m-methoxybenzylidenemalononitrile 8a, and methyl m-methoxybenzylidenecyanoacetate 8b, respectively, to give 1:1 alternating copolymers 9-10 in high yields. Cross-linked polymers 5-6 showed a thermal stability up to 300 ℃, and showed a double phase degradation pattern in their TGA thermograms. Polymers 5-6 showed broad endothermic bands around 75-110 ℃ without any characteristic Tg peaks in DSC thermograms. Alternating copolymers 9-10, except copolymer 9b were soluble in common organic solvents. The inherent viscosities of polymer 9-10 were in the range of 0.35-0.62 dL/g. Polymer films cast from acetone solution were cloudy and tough and Tg values obtained from DSC thermograms were in the range of 118-165 ℃.

Quality Characterization of Yanggaeng with Rice Germ Powder (쌀눈 분말을 첨가한 양갱의 품질 특성)

  • Eom, Hyun-Ju;Kang, Hye Jeong;Kwon, Nu Ri;Yoon, Hyang-Sik;Kim, In Jae;Kim, Youngho;Song, Yong-sup
    • The Korean Journal of Food And Nutrition
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    • v.34 no.3
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    • pp.302-309
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    • 2021
  • This study examined the quality characteristics of yanggaeng with rice germ; it was incorporated into yanggaeng at different levels (containing 5% rice germ, 10% rice germ, 15% rice germ, and 20% rice germ) based on the total weight of red bean extracts. For analyzing the quality characteristics of yanggaeng, moisture content, hardness, color, antioxidant activity, total polyphenol content, reducing sugar, and vitamin E were determined. There was no significant difference in the moisture content and hardness except in the control. For color, lightness and yellowness of yanggaeng increased as the concentration of the powder was increased, whereas there was no significant difference in redness. As the rice germ powder was increased, total polyphenol content and antioxidant activity increased significantly, whereas reducing sugar decreased. Especially, total vitamin E, including isomers, increased as the concentration of the powder increased from 0.41 mg/100 g to 4.03 mg/100 g. Therefore, it could be possible to develop processed products with functional snack for yanggaeng prepared by adding 10% rice germ.

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.

Effects of Dietary Supplementation of Conjugated Linoleic Acid (CLA) on Piglets' Growth and Reproductive Performance in Sows

  • Park, J.C.;Kim, Y.H.;Jung, H.J.;Moon, H.K.;Kwon, O.S.;Lee, B.D.
    • Asian-Australasian Journal of Animal Sciences
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    • v.18 no.2
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    • pp.249-254
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    • 2005
  • The objective of this study was to investigate effects of dietary level of CLA and the duration of feeding CLAcontaining diets on reproductive performance in sows and piglet growth rate. Tallow (3% in gestation diet and 5% in lactation diet, respectively) was incorporated as a fat source in control diet, and each 50% (dietary CLA level of 0.75% in gestation diet, and 1.50% in lactation diet, respectively) or 100% (dietary CLA level of 1.50% in gestation diet, and 2.50% in lactation diet, respectively) of tallow was replaced by a commercial CLA preparation containing 50% CLA isomers. Diets containing CLA were fed either from d 15 premating to weaning or d 74 post-mating to weaning. The level of dietary CLA and feeding duration did not affect litter size. High dietary level of CLA, however, decreased piglet weights at birth (p<0.01) and tended to decrease backfat thickness of sows at weaning. Longterm feeding of CLA-containing diets decreased piglet weights at weaning (p<0.05) and backfat thickness of sows at weaning (p<0.05). CLA supplemented in sow diet was transferred to fetus and piglets during pregnancy and nursing period, respectively. CLA contents of femoral muscle of piglets were 2.08 to 2.57 mg per g of fat at birth, and 2.36 to 4.47 mg at 10 days of age in CLA groups, while CLA was not detected in the control group. In conclusion, dietary supplementation of CLA tended to lower backfat thickness of sow and piglets' weight at birth or weaning, but did not affect total litter size. Dietary CLA was transferred efficiently during prenatal and postnatal periods of time through the placenta and milk, respectively.

Dechlorination of Individual Congeners in Aroclor 1248 as Enhanced by Chlorobenzoates, Chlorophenols, and Chlorobenzenes

  • Kim, Jong-Seol;Cho, Young-Cheol;Frohnhoefer, Robert C.;Rhee, G-Yull
    • Journal of Microbiology and Biotechnology
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    • v.18 no.10
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    • pp.1701-1708
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    • 2008
  • Previous investigations showed that three classes of haloaromatic compounds (HACs; chlorobenzoates, chlorophenols, and chlorobenzenes) enhanced the reductive dechlorination of Aroclor 1248, judging from the overall extent of reduction in CI atoms on the biphenyl. In the present study, we further investigated the kind of polychlorinated biphenyl (PCB) congeners involved in the enhanced dechlorination by four isomers belonging to each class (2,3-, 2,5-, 2,3,5-, and 2,4,6-chlorobenzoates; 2,3-, 3,4-, 2,5-, and 2,3,6-chlorophenols; and 1,2-, 1,2,3-, 1,2,4-, and penta-chlorobenzenes). Although the PCB congeners involved in the enhanced dechlorination varied with the HACs, the enhancement primarily involved para-dechlorination of the same congeners (2,3,4'-, 2,3,4,2'-plus 2,3,6,4'-, 2,5,3',4'- plus 2,4,5,2',6'-, and 2,3,6,2',4'-chlorobiphenyls), regardless of the HACs. These congeners are known to have low threshold concentrations for dechlorination. To a lesser extent, the enhancement also involved meta dechlorination of certain congeners with high threshold concentrations. There was no or less accumulation of 2,4,4'- and 2,5,4'-chlorobiphenyls as final products under HAC amendment. Although the dechlorination products varied, the accumulation of ortho-substituted congeners, 2-, 2,2'-, and 2,6-chlorobiphenyls, was significantly higher with the HACs, indicating a more complete dechlorination of the highly chlorinated congeners. Therefore, the present results suggest that the enhanced dechlorination under HAC enrichment is carried out through multiple pathways, some of which may be universal, regardless of the kind of HACs, whereas others may be HAC-specific.

Mechanism of the Hydrolysis of Phenyl N-(p-chlorobenzoyl)Chloroformimidate Derivatives in Acid Media (산성용액 중에서 Phenyl N-(p-chlorobenzoyl)chloroformimidate 유도체의 가수분해 반응 메카니즘)

  • Nack-Do Sung;Young-Gu Cheun;Ki-Sung Kwon;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.31 no.4
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    • pp.352-358
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    • 1987
  • Rate constants for the hydrolysis of para-substituted phenyl N-(p-chlorobenzoyl)chloroformimidate (I) derivatives in 1 : 4 dioxane-water at $25^{\circ}C$ have been determined. Rate data, substituent effect $(\rho\>{\rho}^+)$, product analysis and MO calculation indicate that the uncatalyzed reaction proceeds through an $S_N1$ mechanism involving the formation of azocarbonium ion (II) below pH 3.0, and the base-catalyzed reaction proceeds through an $S_N2$ mechanism via transition state (III) above pH 4.0. The relative stability of four peri planar conformational isomers were (E-ap) > (Z-ap) > (E-sp) > (Z-ap), respectively, and the most stable stereo structures shows that the Y-substituted phenyl group $(C_6H_4-Y)$ occupy vertical $(90^{\circ})$ position on the plane of the benzimidochloroformyl group in (E-ap) conformer. The nucleophilic substitution of water molecule occurs by sigma attack to the activatived azomethine carbon atom of (I) derivatives.

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Liquid Membrane Permeation of Nitrogen Heterocyclic Compounds Contained in Model Coal Tar Fraction

  • Kim, Su-Jin;Kang, Ho-Cheol;Kim, Yong-Shik;Jeong, Hwa-Jin
    • Bulletin of the Korean Chemical Society
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    • v.31 no.5
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    • pp.1143-1148
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    • 2010
  • We investigated the separation of nitrogen heterocyclic compound (NHC) contained in a model coal tar fraction comprising four kinds of NHC [indole (In), quinoline (Q), iso-quinoline (iQ), quinaldine (Qu)], three kinds of bicyclic aromatic compound (BAC) [1-methylnaphthalene (1MN), 2-methylnaphthalene (2MN), dimethylnaphthalene (DMN) mixture with ten structural isomers (DMNs; regarded as one component)], biphenyl (Bp) and phenyl ether (Pe) by liquid membrane permeation (LMP). A batch-stirred tank was used as the permeation unit. An aqueous solution of saponin and n-hexane were used as the liquid membrane and the outer oil phase, respectively. Yield and selectivity of individual NHC was much larger than that of BAC, Bp and Pe. Increasing the initial mass fraction of the saponin to the membrane solution ($C_{sap,0}$) and the initial volume fraction of O/W emulsion to total liquid in a stirred tank (${\phi}_{OW,0}$) resulted in deteriorating the yield of individual NHC, but increasing the stirring speed (N) resulted in improving the yield of each NHC. With increasing $C_{sap,0}$, the selectivity of each NHC based on DMNs increased. Increasing ${\phi}_{OW,0}$ and N resulted in decreasing the selectivity of individual NHC based on DMNs. At an experimental condition fixed, the sequence of the yield and selectivity in reference to DMNs for each NHC was Q > Qu = iQ > In. Furthermore, we compared LPM method with methanol extraction method in view of the separation efficiency (yield, selectivity) of NHC.

A Comparative Study on the Effect of Commercialized Immobilized Lipases on the Selective Synthesis of 1,3-Diglyceride (1,3-디글리세리드의 선택적 합성에 있어서 상용 고정화 효소의 영향에 관한 비교 연구)

  • Chung, Dae-Won;Cho, Mi-Hye
    • Applied Chemistry for Engineering
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    • v.21 no.4
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    • pp.452-456
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    • 2010
  • It is known that 1,3-diglyceride (1,3-DG) hardly accumulates inside human body because the metabolism of 1,3-DG is entirely different from that of general fats such as triglycerides (TG). This research focuses on the selective synthesis of 1,3-DG by the esterification reaction using an immobilized lipase. For a reaction between glycerin and oleic acid (OA) with a mole ratio of 1 : 2 under vacuum, changes in the compositions of monoglyceride (MG), TG and DG and the contents of 1,3-isomers in DG were investigated, as a function of reaction temperature and the amount of lipase. The reactivities determined by the rate of the consumption of OA became higher with the increase in temperature and the amount of lipase. When the results were compared with those obtained in the earlier study where Novozym was applied as an immobilized lipase, the reactivity was higher for Novozym, on the other hand, selectivity to 1,3-DG was much higher for Lipozyme. Especially, it is remarkable that 1,3-DG content in total DG reached to 98% in the reaction carried out at $50^{\circ}C$ using Lipozyme.

Biosynthesis of Conjugated Linoleic Acid and Its Incorporation into Ruminant's Products

  • Song, Man K.;Kennelly, John J.
    • Asian-Australasian Journal of Animal Sciences
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    • v.16 no.2
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    • pp.306-314
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    • 2003
  • Bio-hydrogenation of $C_{18}$-unsaturated fatty acids released from the hydrolysis of dietary lipids in the rumen, in general, occurs rapidly but the range of hydrogenation is quite large, depending on the degree of unsaturation of fatty acids, the configuration of unsaturated fatty acids, microbial type and the experimental condition. Conjugated linoleic acid (CLA) is incompletely hydrogenated products by rumen microorganisms in ruminant animals. It has been shown to have numerous potential benefits for human health and the richest dietary sources of CLA are bovine milk and milk products. The cis-9, trans-11 is the predominant CLA isomer in bovine products and other isomers can be formed with double bonds in positions 8/10, 10/12, or 11/13. The term CLA refers to this whole group of 18 carbon conjugated fatty acids. Alpha-linolenic acid goes through a similar bio-hydrogenation process producing trans-11 $C_{18:1}$ and $C_{18:0}$, but may not appear to produce CLA as an intermediate. Although the CLA has been mostly derived from the dietary $C_{18:2}$ alternative pathway may be existed due to the extreme microbial diversity in the reticulo-rumen. Regardless of the origin of CLA, manipulation of the bio-hydrogenation process remains the key to increasing CLA in milk and beef by dietary means, by increasing rumen production of CLA. Although the effect of oil supplementation on changes in fatty acid composition in milk seems to be clear its effect on beef is still controversial. Thus further studies are required to enrich the CLA in beef under various dietary and feeding conditions.

Conformations, Chemical Reactivities and Spectroscopic Characteristics of Some Di-substituted Ketenes: An ab initio Study

  • Gupta, V.P.;Sharma, Archna;Agrawal, S.G.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1297-1304
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    • 2006
  • A systematic study of the structure, energetics and spectral characteristics of substituted aminoketenes $R(NH_2)$C=C=O (R = H, $CH_3$, $NH_2$, OH, $OCH_3$, CH=$CH_2$, C$\equiv$CH, CN, CHO, NO, $NO_2$) which are highly reactive and transient intermediates in synthesis has been conducted by ab initio calculations at the MP2/6- 31G*//MP2/6-31G* level. Twenty four stable isomers of the eleven substituted aminoketenes having dihedral angles $\phi NH_2\sim120{^{\circ}}$ and $60^{\circ}$ have been identified and their optimized geometries and energies obtained. Electrostatic and steric effects on the molecular geometries have been analyzed. While the $\pi$-acceptor groups lead to planar conformations, the electron-donor groups give rise to non-planar conformations. Isodesmic substituent stabilization energies relative to alkenes have been calculated and correlation with group electronegativities established. Role of induction effect by the substituent groups and resonance effects in charge distribution in the molecules has been analyzed. An analysis of the asymmetric stretching frequencies and intensities of the C=C=O group shows that affect of non-$\pi$ acceptor substituents on the frequency is determined by the field effect (F) and resonance effect (R) parameters, the calculated intensities I (km/mol.) are correlated to group electronegativities $x$ of the substituents by the relationship I = 640.2–100.1 $x$ (r = 0.92). The $\pi$-acceptor substituents increase the intensity which may be explained in terms of their delocalizing effect on the negative charge at the $C_{\beta}$ atom.