• Title/Summary/Keyword: Secondary Amines

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Synthesis of Quinolinones for Novel Flavonoid Derivatives

  • Park, Myung-Sook;Park, Hae-Sun;Yoon, Myung-Sun;Kim, Nan-Young;Lee, Jae-In
    • Proceedings of the PSK Conference
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    • 2003.04a
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    • pp.241.2-241.2
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    • 2003
  • We report the synthesis of key intermediates for the development novel flavonoid derivatives with potential antiinflammatory activity and propose a mechanism of the one-pot reaction. The various amines (1) for this work were commercially available. Secondary amines (2) were formed by nucleophilic attraction using ethyl benzoylacetate. The C-N bond formation proceeded at refluxing in toluene with catalytic amount of p-toluenesulfonic acid and a removal of water was important in this reaction. (omitted)

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Selective Oxidation of Amines to Imines or Nitriles by Manganese Dioxide in Air (공기 중에서 망간 다이옥사이드에 의한 아민에서 이민 또는 나이트릴로의 선택적 산화 반응)

  • Kim, Yo Han;Hwang, Seung Kyu;Lee, Yoon Sik;Kim, Jung Won
    • Applied Chemistry for Engineering
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    • v.25 no.2
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    • pp.215-221
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    • 2014
  • A simple heterogeneous system has been developed by using base treated manganese dioxide (B-$MnO_2$) for the aerobic oxidation of amines under mild reaction conditions of 1 atm of air and $50^{\circ}C$ in hexane. This system was highly efficient to oxidize various kinds of primary or secondary amines including aliphatic, aromatic, and hetero-atomic ones under the applied reaction conditions. Amines were oxidized to nitriles or diimines by the self-condensation or oxidative dehydrogenation through imine intermediate. The B-$MnO_2$ was reused for at least 5 times without any loss of its catalytic performance and showed its cost effectiveness, easy workup, and easy separation of the products for achieving the protocol of green chemistry.

Changes of Secondary, Tertiary Amines and Quarternary Amminium Compounds, and Formation of N-Nitrosamine during Fermentation of Kimchi with Anchovy Sauce (멸치젓 첨가 김치 숙성중 제 2급, 제 3급 아민 및 제 4급 암모늄 화합물의 함량 변화와 N-Nitrosamine의 생성)

  • 김수현;현재석;오창경;오명철;박제석;강순배
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.23 no.4
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    • pp.704-710
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    • 1994
  • The changes of secondary and teriary amines, and quanternary ammonium compounds, and the formation of N-nitrosamine during fermentation of Kimchi with anchovy was investigated. Nitrate-N decreased gradually during fermentation, while nitrite-N was in the lower level of detection limit. Secondary amine increased continuously during fermentation, and then increased sharply after 60 days of fermentation. TMA-N show tiny change during fermentation, while TMAO-N slightly decreased. Betaine-N increased remarkably at the beginning of fermentation, and then decreased after 60 days. However, choline-N decreased at the beginning, and then increased after middle stage of fermentation. Creatinine-N show a tiny change during fermentation. N-nitrosamine was detected from a few at the beginning to 45 ug/kg at the end of fermentation.

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A Study on Characteristics of pH Control with Amines in the Secondary Side of Nuclear Power Plants (원전 2차 계통에서 아민의 pH 제어 특성 연구)

  • Rhee, In-H.;Ahn, Hyun-Kyoung;Park, Byung-Gi;Jun, Gwon-Hyuk;Ho, Song-Chan
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.11 no.8
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    • pp.3112-3118
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    • 2010
  • The pH control agent in PWRs, to insure the integrity of steam generator, was changed from ammonia to ethanolamine(ETA) which decreased pH at condensate system and low pressure feedwater heater drain system, so that several amines were investigated for the selection of the optimum amine. There was no single alternative amine to meet the optimum condition. The more volatile ammonia provides the higher pH in condensate, while the less volatile ETA increases the pH in wet steam area. Thus, the combined amine of ammonia and ETA is able to equally raise the pH in both region so that the flow accelerated corrosion be reduced in the every system of the secondary side and the integrity of steam generator be also improved in pressurized water reactors (PWRs).

Analysis of Pipe Wall-thinning Caused by Water Chemistry Change in Secondary System of Nuclear Power Plant (원전 2차계통의 수화학 변화가 배관감육에 미치는 영향 분석)

  • Yun, Hun;Hwang, Kyeongmo;Moon, Seung-Jae
    • Corrosion Science and Technology
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    • v.14 no.6
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    • pp.325-330
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    • 2015
  • Pipe wall-thinning by flow-accelerated corrosion (FAC) is a significant and costly damage of secondary system piping in nuclear power plants (NPPs). All NPPs have their management programs to ensure pipe integrity from wall-thinning. This study analyzed the pipe wall-thinning caused by changing the amine, which is used for adjusting the water chemistry in the secondary system of NPPs. The pH change was analyzed according to the addition of amine. Then, the wear rate calculated in two different amines was compared at the steam cycle in NPPs. As a result, increasing the pH at operating temperature (Hot pH) can reduce the rate of FAC damage significantly. Wall-thinning is affected by amine characteristics depending on temperature and quality of water.

Kinetic Study on Nucleophilic Displacement Reactions of Y-Substituted-Phenyl 2-Methylbenzoates with Cyclic Secondary Amines in Acetonitrile: Effects of Modification of 2-MeO in Benzoyl Moiety by 2-Me on Reactivity and Reaction Mechanism

  • Lee, Ji-Youn;Kim, Mi-Yeon;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3795-3799
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    • 2013
  • The second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted-phenyl 2-methylbenzoates (6a-e) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. Comparison of the $k_N$ values for the reactions of 4-nitrophenyl 2-methylbenzoate (6d) with those reported previously for the corresponding reactions of 4-nitrophenyl 2-methoxybenzoate (5) reveals that 6d is significantly less reactive than 5, indicating that modification of 2-MeO in the benzoyl moiety of 5 by 2-Me (i.e., $5{\rightarrow}6d$) causes a significant decrease in reactivity. This supports our previous report that aminolysis of 5 proceeds through a six-membered cyclic intermediate, which is highly stabilized through intramolecular H-bonding interactions. The Br${\o}$nsted-type plot for the reactions of 6d with a series of cyclic secondary amines is linear with ${\beta}_{nuc}=0.71$, which appears to be a lower limit of ${\beta}_{nuc}$ for a stepwise mechanism with breakdown of an intermediate ($T^{\pm}$) being rate-determining step (RDS). The Br${\o}$nsted-type plot for the reactions of 6a-e with piperidine is curved, i.e., the slope of Br${\o}$nsted-type plot (${\beta}_{lg}$) decreases from -1.05 to -0.41 as the leaving-group basicity decreases. The nonlinear Br${\o}$nsted-type plot has been taken as evidence for a stepwise mechanism with a change in RDS (e.g., from the $k_2$ step to the $k_1$ process as the leaving-group basicity decreases). Dissection of $k_N$ into the microscopic rate constants associated with the reactions of 6a-e with piperidine (e.g., $k_1$ and $k_2/k_{-1}$ ratio) also supports the proposed mechanism.

Ruthenium Complex Catalyzed Reaction of Diols or Triol with Amines (루테늄 착물 촉매를 이용한 디올 및 트리올과 아민과의 반응)

  • Sang Chul Shim;Young Zoo Youn;Jae Wook Lee;Dong Yeob Lee;Jae Goo Shim;Ju Hee Kim;Keun Tae Huh
    • Journal of the Korean Chemical Society
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    • v.37 no.11
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    • pp.967-973
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    • 1993
  • ${\alpha},{\omega}$-Diols such as 1,6-hexanediol and 1,7-heptanediol react with secondary amines in the presence of catalytic amount of ruthenium complex at 180$^{\circ}$C for 24 hrs to give the corresponding diamino compounds in good yields. The yield of diamino compound was affected by the molar ratio of ${\alpha},{\omega}$-diol to secondary amine. The reaction was also affected by the nature of the phosphorus ligands employed. On the other hand, aromatic primary amines react with 1,2,6-hexanetriol in the presence of RuCl_3{\cdot}H_2O-3PPh_3$ at 180$^{\circ}$C for 3 hours under argon atmosphere to give selectively 1-substituted aryl-3-hydroxyperhydroazepines in good yields. Selective synthesis of these products show that two primary hydroxy groups (1,6-positions) oxidize predominantly than secondary hydroxy group (2-position) by ruthenium-phosphorus complex. The yields were decreased according to the order of para-, meta- and ortho-substituent.

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N-Alkylatin of Secondary Amines in Nickel(II) Complexes of Polyaza Macrotricyclic Ligands

  • Suh, Paik-Myunghyun;Kim, Myung-Jin;Kim, Hyun-Kyung;Oh, Kye-Young
    • Bulletin of the Korean Chemical Society
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    • v.13 no.1
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    • pp.80-83
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    • 1992
  • The secondary nitrogen donors of the Ni(II) complexes of macrotricyclic ligands 8-methyl-1,3,6,8,10,13,15-heptaazatricyclo $[13.1.1.1^{13,15}]$octadecane (A) and 1,3,6,9,11,14-hexaazatricyclo $[12.2.1.1^{6,9}]$octadecane (B) are N-alkylated and the Ni(II) complexes of $N-Me_2A,\;N-Et_2A,\;and\;N-Me_2B$ are obtained. The Ni(II) complexes of $N-Me_2A\;and\;N-Et_2A$ are stable in acidic aqueous solutions while that of $N-Me_2B$ decomposes relatively rapidly. The N-alkylation leads to the decrease in the ligand field strength as well as an anodic shift in both of the oxidation and the reduction potentials of the Ni(II) complexes.

A Study on Reactive Extraction of Citric Acid in Citric-acetic-lactic Acid System (구연산-초산-유산계에서 구연산의 반응추출에 관한 연구)

  • Lee, Han-Seob;Kang, An-Soo
    • Applied Chemistry for Engineering
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    • v.5 no.1
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    • pp.90-98
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    • 1994
  • For elucidation of various parameters' effects on the reactive extraction of citric acids, citric-acetic-lactic acid system with various carriers, diluents, and modifiers were investigated. Carries used were secondary amines, tertiary amines, and solvation extract. Dileunts were n-butylacetate, methoisobutylketon(MIBK), kerosine, and xylene. Modifiers were TBP and isodecanol. The effects of temperature and pH in aquous phase were studied, and equilibrium constants for the reactive extraction were obtained. The re-extraction was performed by alkali solutions such as NaOH, $Na_2CO_3$, and $K_2HPO_4$. Based on the experiment Di-isotridecylamine(secondary amine ) gave higher degree of extraction and more selective than other extractants tested for the extraction of citric acid. N-butylacetate and TBP showed heigher performance for a diluent and modifier, repetitively. The degree of extraction was getting better with decreasing the pH in the aquous phase and the temperature of extraction system. The degree of re-extraction was getting higher with decreasing basicity in the stripping phase and the system temperature, and with increasing the concentration of alkali solution.

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CHANGES OE DIMETHYLAMINE (DMA) CONTENT IN FISH MUSCLE DURING HEAT PROCESSING (어육 열처리 가공중의 dimethylamine(DMA)의 변화)

  • Ryu Byeong-Ho;LEE Jong-Chul;LEE Eung-Ho
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.7 no.3
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    • pp.115-120
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    • 1974
  • Secondary amines are known as one of the precursors of nitrosamines which are potent carcinogenic compounds of man and animals. Nitrosamines are formed when both secondary amines and nitrite are present. The nitrites are occurred naturally in vegetables, fruits and many others, and frequently used in fish product as a color fixative or a preservative. In this paper, to know the formation of nitrosamines in fish meat, the changes of dimethylamine (DMA) content during the heat treatment such as drying, roasting and fish cake processing are discussed. The results showed that generally DMA increased considerably during heat processing. During drying, DMA in cuttle fish increased 16 times higher, while in Alaska pollack doubled than the fresh. In the roasted mackerel, the DMA content appeared 6 times higher than the fresh, while 9 times higher in canning. In fish cake from yellow corvenia, DMA increased 4 times higher than the fresh. On the contrary diethylamine and diphenylamine were not found in this experiment.

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