• Title/Summary/Keyword: Pyridines

Search Result 114, Processing Time 0.022 seconds

Kinetic and Theoretical Studies on Pyridinolysis of 2,4-Dinitrophenyl X-Substituted Benzoates: Effect of Substituent X on Reactivity and Mechanism

  • Um, Ik-Hwan;Kim, Eun-Hee;Im, Li-Ra;Mishima, Masaaki
    • Bulletin of the Korean Chemical Society
    • /
    • v.31 no.9
    • /
    • pp.2593-2597
    • /
    • 2010
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for reactions of 2,4-dinitrophenyl X-substituted benzoates (X = 4-MeO, H and 4-$NO_2$) with a series of Z-substituted pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plots exhibit downward curvature (e.g., $\beta_2$ = 0.89 ~ 0.96 when $pK_a$ < 9.5 while $\beta_1$ = 0.38 ~ 0.46 when $pK_a$ > 9.5), indicating that the reaction proceeds through a stepwise mechanism with a change in rate-determining step (RDS). The ${pK_a}^o$, defined as the $pK_a$ at the center of Br${\o}$nsted curvature, has been analyzed to be 9.5 regardless of the electronic nature of the substituent X in the benzoyl moiety. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio has revealed that $k_1$ is governed by the electronic nature of the substituent X but the $k_2/k_{-1}$ ratio is not. Theoretical calculations also support the argument that the electronic nature of the substituent X in the benzoyl moiety does not influence the $k_2/k_{-1}$ ratio.

Flavor Characteristics of Volatile Compounds from Shrimp by GC Olfactometry (GCO) (GC Olfactometry를 이용한 새우의 휘발성성분 특성평가)

  • 이미정;이신조;조지은;정은주;김명찬;김경환;이양봉
    • Journal of the Korean Society of Food Science and Nutrition
    • /
    • v.31 no.6
    • /
    • pp.953-957
    • /
    • 2002
  • Volatile compounds from shrimp whole body (SWB) and shrimp shell waste (SSW) were isolated, and identified by the combination of SDE (simultaneous steam distillation and solvent extraction), GC (gas chromatography, HP-5890 plus)and MSD (mass selective detecter) or olfactometry. The peak numbers isolated from SWB and SSW were 20 and 46, respectively. The amounts of the volatile compounds isolated from SSW were higher than those of SWB. SWB produced more low-boiling compounds below 7$0^{\circ}C$ and SSW did more high boiling compounds over 10$0^{\circ}C$. The volatile compounds identified from SSW were 9 pyrazines,5 acids,4 aldehydes, and 4 alcohols. These volatile compounds were evaluated by aroma extraction dilution analysis and gas chromatography olfactometry (GCO). Some compounds which were not detected by GC-FID and GC-MSD were found to be a strong shrimp flavor of log$_3$ FD 3 value by GCO. Strong shrimp odors were detected in low temperature while nutty aromatic odors and unpleasant oily smells were found in high temperature.

Temperature Dependence on the Binding of the Homologs of Methyl Orange by Crosslinked Poly(4-vinylpyridine). 6. Effect of Crosslinking Agent (가교폴리 (4-비닐피리딘) 과 메틸오렌지동족체와의 결합에 대한 온도의 존성. 6. 가교제의 영향)

  • Lee, Suck-Kee;Park, Nam-Kyu;Kim, Woo-Sik
    • Applied Chemistry for Engineering
    • /
    • v.1 no.2
    • /
    • pp.182-189
    • /
    • 1990
  • Various crosslinked poly(4-vinylpyridines) having different degrees of crosslinking were prepared by radical copolymerizations of 4-vinylpyridine with N, N'-2, 6-pyridinebisacrylamide as a crosslinker. The abilities of these crosslinked polymers to bind methyl orange and butyl orange were investigated at various temperatures in a buffer solution of pH 7. The first binding constants were evaluated from the equilibrium binding amounts. The first binding constants against the temperatures showed bell-shaped curves. Also, the first binding constants against the degree of crosslinking showed bell-shaped curves. When the temperature and the degree of crosslinking of maximum binding in the curves of these binding systems were compared with those of previous systems containing crosslinked poly(4-vinylpyridines) prepared by using N, N'-methylenebisacrylamide, N, N'-tetramethy-lenebisacryamide and divinylbenzene as crosslinkers, respectively, they were varied with the crosslinked poly(4-vinyl pyridines) containing different crosslinkers. These results were discussed in terms of the properties of the crosslinkers.

  • PDF

The Effect of Aging on Flavor Precursors and Volatile Compounds of Top Round from Hanwoo (숙성에 따른 한우 우둔의 풍미 전구물질 및 향기성분 변화)

  • Lee, Juri;Kim, Sun Hyo;Lee, Hyun Jung;Yong, Hae In;Nam, Ki Chang;Jo, Cheorun;Jung, Samooel
    • The Korean Journal of Food And Nutrition
    • /
    • v.28 no.6
    • /
    • pp.1019-1025
    • /
    • 2015
  • The influence of aging on the flavor precursors and volatile compounds of top round beef was studied. The concentrations of free amino acids, nucleotides, creatine, dipeptides, and volatile compounds were measured after top round from Hanwoo was aged at $4^{\circ}C$ for 21 days. The amount of free amino acids in top round significantly increased with the increase of aging period. There was no effect of aging on the concentrations of adenosine monophosphate or inosine in top round. The inosine monophosphate content of top round significantly decreased with age, while the hypoxanthine content increased. The concentrations of creatine, carnosine, and anserine in top round were not influenced by aging. In total, 24 volatile compound were identified in aged, cooked top round. Of these, the quantities of aldehydes (propanal, pentanal, hexanal, heptanal, octanal, and nonanal), hydrocarbons (pentane and octane), 2-butanone, ethyl acetate, and pyridines (4-ethynyl-pyridine and 4-acetyl-pyridine) significantly increased after aging. We conclude that the flavor of top round can be improved by aging.

Volatile Constituents of Processed Squid Product (오징어 가공품의 냄새성분에 관한 연구)

  • Chiaki Koiiumi;Toshiaki Ohshima;Lee, Eung-Ho
    • Journal of the Korean Society of Food Science and Nutrition
    • /
    • v.19 no.6
    • /
    • pp.547-554
    • /
    • 1990
  • The precursor substance and volatile components of cooked flavor of squid meat were studied. Volatile components were trapped by simultaneous distillation-extraction method, and these were fractionated into the neutral, basic, phenolic and acidic fraction. Volatile flavor components in these frations were analyzed by GC and GC-MS. 80% methanol solution was the most effective solvent for extraction of the precursor substance for cooked flavor. The neutral and basic fraction, by organoleptic test, seem to have a major effect on squid-like flavor. Forty-four compounds, including 2 hydorcarbons, 10 alcohols, 5 aldehydes, 1 ketone, 1 furan, 3 sulfide compounds, 7 pyrazines, 2 pyridines, 1 amino, 2 phenols and 10 acids, identified as cooked flavor compounds of squid meat.

  • PDF

Synthesis of Novel Benzofuran and Related Benzimidazole Derivatives for Evaluation of In Vitro Anti-HIV-1, Anticancer and Antimicrobial Activities

  • Rida, Samia M.;El-Hawash, Soad A.M.;Fahmy, Hesham T.Y.;Hazzaa, Aly A.;El-Meligy, Mostafa M.M.
    • Archives of Pharmacal Research
    • /
    • v.29 no.10
    • /
    • pp.826-833
    • /
    • 2006
  • Previously, we synthesized and evaluated several benzofuran derivatives containing heterocyclic ring substituents linked to the benzofuran nucleus at C-2 by a two- to four-atom spacer as potential anti-HIV-1, anticancer and antimicrobial agents. Among these derivatives, NSC 725612 and NSC 725716 exhibited interesting anti-HIV-1 activity. To further investigate the structure-activity relationship, we synthesized several new benzofuran derivatives derived from 2-acetylbenzofuran (2, 3a-c) and 2-bromoacetylbenzofuran (6; 7a,b; 8a,b). The compounds were designed to comprise the heterocyclic substituents directly linked to the benzofuran nucleus at C-2. Moreover, various related benzimidazoles derived from 2-acetylbenzimidazole and from 2-cyanomethylbenzimidazole (12a,b; 13a,b; 15; 16a,b) were also prepared as isosteres. The synthesized compounds were preliminarily evaluated for their in vitro anti-HIV-1, anticancer and antimicrobial activity. Compounds 2, 3a, 3b, and 12b showed weak anti-HIV-1 activity. Compound 6 exhibited mild activity against S. aureus, while compound 15 had mild activity towards S. aureus and C. albicans. However, no significant anticancer activity was observed with any of the tested compounds. From these results, we conclude that the presence of the spacer between the heterocyclic substituent and the benzofuran nucleus may be essential for the biological activity.

Kinetic Studies for the Nucleopilic Substitution Reactions under High Pressure (친핵성 치환반응에 관한 고압에서의 속도론적 연구)

  • Kim Young Cheul;Kim Se Kyong
    • Journal of the Korean Chemical Society
    • /
    • v.37 no.6
    • /
    • pp.577-584
    • /
    • 1993
  • The reaction rates of para-substituted benzoyl chlorides with substituted pyridines have been measured employing the conductometry method in acetonitrile, and pseudo-first order and second order rate constants are determined at various pressures and temperatures. The activation parameters (${\Delta}V^\neq, {\Delta}{\beta}^{\neq}, {\Delta}H^{\neq}, {\Delta}S^{\neq} {\Delta}G^{\neq}$) and the Hammett ρ-values are determined from the values of rate constants. The values of △${\Delta}V^\neq, {\Delta}{\beta}^{\neq}and {\Delta}S^{\neq}$ are all negative. The Hammett ρ-values are negative for the nucleophile (ρ$_X$), and positive for the substrate (ρ$_Y$) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed in typical S$_N$2 reaction mechanism and in bond formation favored with elevating pressure.

  • PDF

Oxidative Stability and Flavor Compounds of Sesame Oils Blended with Vegetable Oils (식물성유를 첨가한 참기름 혼합유의 산화 안정성과 향기 성분)

  • Joo, Kwang-Jee;Kim, Jin-Ju
    • Korean Journal of Food Science and Technology
    • /
    • v.34 no.6
    • /
    • pp.984-991
    • /
    • 2002
  • Oxidative stability and flavor of sesame oil blended with canola oil (Ca), corn oil (Co), and soybean oil (Sb) at ratios of 90 : 10, 70 : 30, and 50 : 50 (w/w), respectively, were evaluated. Oxidative stability of sesame oil increased with the addition of vegetable oils (10, 30, and 50% of Ca and Co, and 10% of Sb). Pyrazines, pyrroles, pyridines, and thiazoles, good contributors to the characteristic flavor of sesame oil, were also found in sesame oil blended with vegetable oil. The sensory evaluation showed that no difference was observed between sesame oil and sesame oil blended with 10% of Ca, Co or Sb, which showed higher oxidative stability.

Effects of Added Corn Oil on the Formation of Volatile Flavor Compounds in Dry Shrimp During Roasting Process (볶음 과정중 첨가한 옥수수 기름이 마른 새우 향기성분 형성에 미치는 영향)

  • Joo, Kwang-Jee;Kang, Mi-Young
    • Journal of the Korean Society of Food Science and Nutrition
    • /
    • v.32 no.5
    • /
    • pp.655-660
    • /
    • 2003
  • Flavor components of dry shrimp, roasted-dry shrimp and roasted-dry shrimp with corn oil (w/w: 10%, 25%) were investigated to evaluate the effects of added corn oil on the formation of volatile components in dry shrimp during roasting process. The identified volatile included 20 nitrogen-containing compounds (7 pyrazines, 7 pyridines 3 pyrroles, others) 14 aldehydes, 5 alcohols, 4 ketones and 11 others. The largest quantities of lipid-derived products hexanal, nonanal, 2-pentylfuran, 1-octen-3-ol, trans-2-decenal, trans, cis-2,4-decadienal, trans, trans-2,4-decadienal were detected in the roasted-dry shrimp samples with corn oil. The lipid-derived aldehydes might be involved in the formation of 3- ethyl-2,5-dimethylpyrazine, 2,3,5-trimethyl-6- ethylpyrazine, 2-ethyl-5,6-dimethylpyrazine, 2,3,5- trimethylpyrazine, 3- ethyl-2,6-dimethylpyridine, 2-propylpyridine, ben-zopyrrole and the others. The nitrogen-containing compounds seem to be a major flavor component and responsible for characteristic flavor in roasted-dry shrimp with corn oil.

The Thermodynamics of the Formation of Pyridines-Iodine Charge Transfer Complexes (피리딘류와 요오드사이의 전하이동착물생성에 관한 열역학적 연구)

  • Oh Cheun Kwun;Jin Burm Kyong;Myong Kyun Kim
    • Journal of the Korean Chemical Society
    • /
    • v.25 no.4
    • /
    • pp.228-235
    • /
    • 1981
  • Ultraviolet spectrophotometric investigation were carried out on the systems of pyridine, ${\beta}$-picoline and 3,5-lutidine with iodine in carbon tetrachloride. The results reveal the formation of one to one molecular complexes of the type, $C_5H_5N{\cdot}I_2$, ${\beta}-C_5H_4(CH_3)N{\cdot}I_2$ and 3,5-$C_5H_3(CH_3)_2N{\cdot}I_2$. The equrilibrium constants of complexes were obtained in consideration of that absorption maxima have the blue shift with the increasing temperatures according to the formation of the charge transfer complexes. The thermodynamic parameters, ${\Delta}H$, ${\Delta}G$ and ${\Delta}S$ for the formation of the charge transfer complexes were calculated from these values. These results indicated that the relative stabilities of the pyridine, ${\beta}$-picoline and 3,5-lutidine complexes with iodine increase in the order, pyridine < ${\beta}$-picoline < 3,5-lutidine. These results were supposed to be the influence resulted from increase of electron density by the positive inductive effect and the dipole moment of the steric hindrance effect. And this results were compared and discussed with polymethylbenzene-iodine CT-complexes.

  • PDF