• Title/Summary/Keyword: Carbonyl

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MPV-Reduction of C=O bond with Al-substituted-dialkylalan; A Theoretical Study on Relative Reactivity of Various Carbonyl Substrates

  • Nahm, Keepyung
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.546-550
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    • 2014
  • Relative reactivity of various carbonyl and acid derivatives in MPV-type (Meerwein-Ponndorf-Verley) reduction with an DIBAL(F) model has been studied via DFT and MP2 methods. Free energies of initial adduct formation (-Gadd) of DIBAL(F) model and carbonyls are in the order of amide < ester < aldehyde < ketone < acid chloride; in the alan-amide adduct, the developed positive charge at carbonyl carbon is expected to be stabilized by amide resonance, but in the acid chloride adduct it is destabilized by inductive effect of chloride. However the TS barrier energies (${\Delta}G_{TS}$) for the MPV-type hydride reduction of the carbonyl adducts are in the order of aldehyde < ketone < acid chloride << ester < amide; presumably decreasing order of electrophilicity of carbonyl carbon at adducts, which is well correlated with experimental data. It is noted that the relative reactivity of carbonyl derivatives in MPV-type reduction with DIBAL(X) is not governed by the alan-adduct formation energies, but follows the order of electrophilicity of carbonyl carbon of transition states.

Separation and Quantitative Determination of Carbonyl Compounds in the Filtrated Myulchichuts by HPLC (HPLC에 의한 멸치액젓의 Carbonyl 화합물 분석)

  • Chang, Pack-Kyung;Rhee, Hei-Soo
    • Journal of Nutrition and Health
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    • v.18 no.3
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    • pp.189-193
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    • 1985
  • Qualitative and quantitative analysis for carbonyl compounds contained in the five kinds of filtrated myulchichuts have been made using HPLC. Carbonyl compounds were separated by converting them into 2,4-dinitrophenylhydrazine derivatives which, in turn extracting with hexane. The extract was dehydrated, filtered and examined on HPLC with $C_{18}column$. The quantitative determination of carbonyl species was achieved using standard calibration technique. Highly reproduceable results were obtained by this methods and the amounts of 2,4-dinitrophenylhydrazine derivatives were highly correlative to peak heights. As the results, we find that the seven kinds of carbonyl compounds are contained in each of myulchichuts examined in this study. Five of which are identified as pyruvic acid, formaldehyde, acetaldehyde, acetone and butanone. But the amounts of carbonyl compounds vary widely with the kinds of the filtrated myulchichuts.

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Measurement of Carbonyl Compounds in Ambient Air using a DNPH Cartridge coupled with HPLC Method (DNPH 카트리지와 HPLC를 이용한 대기 중 카르보닐화합물의 농도측정)

  • 황윤정;박상곤;백성옥
    • Journal of Korean Society for Atmospheric Environment
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    • v.12 no.2
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    • pp.199-209
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    • 1996
  • The purpose of this study is to evaluate analytical method for the measurement of carbonyl compounds and to apply method to the measurement of indoor and outdoor concentrations of these compounds at public facilities. For sampling, 2.4-dinitrophenylhydrazine (DNPH) coated DNPH-Silica cartridges were uwed in this study. DNPH reacts with carbonyl compounds and forms carbonyl hydrazone, The carbonyl hydarzone was eluted from the cartridge with acetonitrile and analyzed by reverse-phase HPLC with UV detection. Possible interference caused by ozone during sampling was eliminated by using KI trap commected in series with the DNPH-Silica cartridge. A number of experimental studies were undertaken to evaluate and validate the analytical method, including collection efficiency, recovery, repeatability, lower limits of detection, and effect of ozone. Indoor and outdoor measurements of carbonyl compounds were simultaneously carried out at 14 public facilities located in Taegu city and Kyungsan city from June to July, 1995. Except for one or two sites, the indoor concentrations were found to be higher than the outdoor concentrations for carbonyl compounds. And the concentrations of carbonyl compounds measured in the morning and afternoon were showed higher than the concentrations measured in the evening.

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Kinetic Studies on Nucleophilic Substitution Reaction for Naphthalene Carbonyl Chloride (염화나프탈렌카르보닐의 친핵성 치환반응에 관한 연구)

  • Sang Kee Yoon;Tae Sup Uhm;Dae Dong Sung
    • Journal of the Korean Chemical Society
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    • v.24 no.5
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    • pp.347-355
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    • 1980
  • The rate constants for the reaction of ${\alpha}$-naphthalene carbonyl chloride and ${\beta}$-naphthalene carbonyl chloride have been determined in methanol-acetonitrile and methanol-acetone. The rate constant of ${\alpha}$-naphtalene carbonyl chloride is higher than that of ${\beta}$-naphthalene carbonyl chloride. This behavior is consistent with Dewar's number, Nr and also Streitwieser's value ${\sigma}^+$. Since in the transition state carbonyl carbon is transformed to$sp^3$, no peri-hydrogen effect was observed.

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Contribution of Primary and Secondary Sources to the Atmospheric Concentrations of Carbonayl Compounds in Seoul (서울지역에서 대기 중 카르보닐 화합물 농도에 대한 1,2차 발생원의 기여율 산정)

  • 여현구
    • Journal of Korean Society for Atmospheric Environment
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    • v.16 no.4
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    • pp.317-326
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    • 2000
  • Carbonyl compounds have been measured in downtown Seoul for September 1998 using 2-series impinger method. Average concentration (ppbv) of carbonyl compounds were 12.66$\pm$5.77 HCHO, 12.05$\pm$4.86 CH3CHO and 7.92$\pm$2.63 CH3CHCH3 These compounds were the most abundant carbonyl,. They showed maximum concentration during the daytime when photochemical activity was very strong minimum concentration were usually showed during the night and early morning. Comparison of diurnal variation of carbonyl compounds with the concentration of O3, NMHC, CO and meteorological data indicated that primary and secondary sources contributed the observed carbonyl compounds. Photochemical Formation Rate(PFR) of carbonyl compounds dur-ing the sampling periods were 61% HCHO, 85% CH3CHO, 85% CH3CHO, 71% CH3COCH3.

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The Effect of Solvent Trap Apparatus on the Analysis of Carbonyl Compounds in Cigarette Smoke (용매 포집장치가 연기 중 Carbonyl 화합물의 분석에 미치는 영향)

  • 김효근;이존태;윤오섭;이문수
    • Journal of the Korean Society of Tobacco Science
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    • v.25 no.2
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    • pp.137-143
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    • 2003
  • Among the most popular means of mainstream smoke collection for specific analysis are solvent traps. Determination of the carbonyl compounds as their 2,4-dinitrophenylhydrazones(DNPHs) by HPLC offers increased sensitivity and reproducibility in the analysis of mainstream cigarette smoke. In this work, the mainstream smoke of a reference cigarette(lR4F) was collected in four kinds of gas washing bottles and their effects on the analysis of carbonyl compounds were investigated. The results show that the porosity of fritted glass filter in gas washing bottles exerted profound effect on the composition of the carbonyl compounds in mainstream smoke.

Investigation of Adsorption Mechanism and Selective Adsorption of Carbonyl Compounds of Mainstream Tobacco Smoke by Ion Exchangers (이온교환체에 의한 담배 주류연 중 카보닐 화합물의 선택적 흡착 특성 및 흡착 메카니즘 구명)

  • Lee John-Tae;Kim Hyo-Keun;Ji Sang-Un;Hwang Keon-Joong;Rhee Moon-Soo;Park Jin-Won
    • Journal of the Korean Society of Tobacco Science
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    • v.26 no.2 s.52
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    • pp.159-167
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    • 2004
  • This work has been conducted to select appropriate filter materials for removing carbonyl compounds in mainstream tobacco smoke. To investigate of the usability of this filter materials, two types of bead ion exchangers were synthesized and their adsorption characteristics for carbonyl compounds were investigated. Sulfonic acid group-containing cation exchanger and ammonium group-containing anion exchanger were synthesized by the suspension polymerization of glycidylmethacrylate(GMA) and divinylbenzene(DVB) followed by the subsequent functionalization, respectively. The removal efficiency of carbonyl compounds by these two ion exchangers increased in the presence of moisture. However, the amount of carbonyl compounds adsorbed on the anion exchanger was larger than that on the cation exchanger under two levels of water contents tested. This phenomenon seems to arise from the electron delocalization in carbonyl group of the anion exchangers. There was not any significant relationship between the amount of carbonyl compounds adsorbed on ion exchangers and the length of adsorption column. From the large ion exchange capacity and rapid ion exchange reaction rate of the anion exchanger, it is suggested that the anion exchanger may be a good filter material for removing carbonyl compounds in the mainstream tobacco smoke.

Rapid Determination of Carbonyl Compounds in Mainstream Cigarette Smoke Using by RRLC (RRLC를 이용한 담배 연기 중 카보닐 화합물의 신속 분석)

  • Lee, Hyoung-Seok;Kim, Ick-Joong;Kim, Hyo-Keun;Hwang, Keon-Joong
    • Journal of the Korean Society of Tobacco Science
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    • v.31 no.1
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    • pp.45-50
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    • 2009
  • In this study, a simple gradient RRLC method for rapid determination of carbonyl compounds of cigarette smoke was developed. Within 10 min, 8 carbonyl compounds have been separated and identified on ZORBAX Eclipse XDB-C18 column ($4.6{\times}50\;mm$, $1.8\;{\mu}m$) with gradient elution using water and acetonitrile as a mobile phase. RRLC was used for the quantification of carbonyl compounds in mainstream smoke of 3R4F reference cigarette, and evaluated those efficiencies in the recovery, repeatability and reproducibility. The correlation coefficients ($r^2$) for calibration curves of carbonyl compounds were over 0.9998. The developed RRLC method was successfully applied to the analysis of smoke samples and the recoveries of carbonyl compounds were in the range of 97.5~102.1% with RSD<3.1%.

Chemical Changes and Volatile Carbonyl Formation Occurred in Rice during Cooking Process (취반(炊飯)중 쌀성분(成分)의 화학적(化學的) 변화(變化) 및 휘발성(揮發性) Carbonyl 성분(成分)의 생성(生成))

  • Cheigh, Hong-Sik
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.14 no.1
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    • pp.61-66
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    • 1985
  • Cooked rice was prepared by the conventional cooking method being used among Korean families. The bottom layer (very slightly roasted and charred) and upper layer of the cooked rice in a cooking vessel were collected separately in order to determine the chemical changes and volatile carbonyl formation occurring in rice during the cooking process. Amino acids, especially free amino acid contents were reduced with the decrease of reducing sugar in rice after cooking. A little change was shown in the fatty acid composition of lipid fractions, however, decreased iodine values and increased fatty acid values were observed after cooking process. Volatile carbonyl compounds from cooked rice were isolated and 8 carbonyls of them were identified. A significant difference of relative composition of the identified carbonyls was found between the upper layer and bottom layer of cooked rice. Generally, the cooked rice obtained from the bottom layer had shown a little more changes in chemical composition and a stronger browning flavour than those of the upper layer of cooked rice.

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Spatial and Temporal Variations of Atmospheric Concentrations of Carbonyl Compounds in Seoul Metropolitan Area (수도권 지역 대기 중 카보닐화합물의 시.공간적 농도 분포 특성)

  • Seo, Young-Kyo;Jeong, Eun-Hui;Seo, Seok-Jun;Hwang, Yun-Jeong;Han, Jin-Seok;Bae, Sung-Ok
    • Journal of Korean Society for Atmospheric Environment
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    • v.24 no.2
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    • pp.206-219
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    • 2008
  • The purpose of this study is to evaluate concentrations of carbonyl compounds during summer season in Seoul metropolitan area. The air samples were collected at 7 sites in this area from June 2001 to June 2003. The carbonyl compounds were analyzed by DNPH/HPLC method. The analytical method applied in this study showed good repeatability, linearity, and sensitivity. The most abundant carbonyl was formaldehyde (average 4.48 ppb), and followed by acetone, acetaldehyde, methyl ethyl ketone, butyraldehyde, propionaldehyde and benzaldehyde, respectively. Concentrations of carbonyl compounds in June were higher than those in August. There was not only higher solar radiation but also higher ozone concentration in June than in August. As a result o photochemical reactions, carbonyl compounds from both primary and secondary sources are likely to contribute to the formation of ozone. The contributions to photochemical ozone creation of two carbonyl compounds such as formaldehyde and acetaldehyde were estimated to be about 70%. Ratios of formaldehyde to acetaldehyde in this study ranged from 1.13 to 4.26, which are generally equivalent levels to those of other urban areas in domestic and foreign countries.