• 제목/요약/키워드: tertiary amines

검색결과 38건 처리시간 0.018초

친핵성 첨가반응에 대한 용매효과 (I) Phenylvinylketone에 대한 아민의 첨가반응속도에 미치는 용매의 극성효과 (Solvent Effects on the Nucleophilc Addition (I) Effect of Solvent Polarity on the Nucleophilic Addition of Amine to Phenylvinylketone)

  • 신갑철;김태린
    • 대한화학회지
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    • 제36권2호
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    • pp.287-292
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    • 1992
  • 여러 가지 용매에서 phenylvinylketone에 대한 아민(piperidine 및 diethyl-amine)의 친핵성 첨가반응 속도 상수를 $25^{\circ}C$에서 분광광도법으로 측정한 결과 그의 첨가반응 속도상수는 용매의 극성에 비례함을 알았고 이것을 Kirkwood식으로 잘 설명할 수 있었다. 즉, 이 반응은 고리형 구조의 zwitter ion 중간체를 거쳐 일어남을 알 수 있었다. 또 phenylvinylketone에 대한 아민의 첨가반응에서 3차 아민은 1차 및 2차 아민에서 보다 반응이 훨씬 느리게 진행되었으며 이것은 1차 및 2차 아민에서는 고리형 구조의 zwitter ion 중간체를 형성할 수 있고 또한 음전하의 비편재화 및 엔올형의 구조까지 가능하지만 3차 아민에서는 위의 구조들이 불가능하기 때문에 1차 및 2차 아민에서 보다 느리게 진행된다고 생각된다.

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Silicate 上에서의 아민의 吸着. Protonic 酸 자리와 Aprotonic 酸 자리의 區別 (The Adsorption of Amines on Silicates. Distinction Protonic and Aprotonic Acids Sites)

  • 김종택;손종락
    • 대한화학회지
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    • 제20권6호
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    • pp.441-447
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    • 1976
  • 여러가지 양이온이 교환된 silicate 상에 pyridine, tertiary butylamine, ethylenediamine을 흡착시켜 IR spectra를 4000 ∼ 1200 $cm^{-1}$의 범위에서 그리고 여러 다른 탈기온도에서 얻었다. 이 결과 protonic 산 자리와 aprotonic 산 자리를 구별할 수 있었으며 양이온이 교환된 모든 silicate는 Bronsted 산과 Lewis 산을 모두 나타내었다. 그리고$ Na^+$이온이 교환된 silicate가 adsorbate와의 반응성이 가장 적게 나타났다. Tertiary butylamine의 band intensity의 상대적인 비는 교환된 양이온의 polarizing power와 비례하고 두개의 amino group을 가지고 있는 ethylenediamine은 tertiary butylamine에 비해서 silicate 표면으로부터 쉽게 탈착되지 않았으며 또한 Lewis 산 자리와 coordination bond를 이루는 경우와 Bronsted 산 자리와 $NH3^+$ 종을 만드는 경우외에 migrating proton을 떼어 냄으로 말미암아 표면산소와의 수소결합을 이루는 경우가 조사되었다.

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지방족 아민 추출제에 의한 초산의 추출 (Extraction of Acetic Acid by Aliphatic Amino Extractants)

  • 이한섭
    • 공업화학
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    • 제5권1호
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    • pp.121-126
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    • 1994
  • 초산의 반응추출에 미치는 영향을 규명하기 위하여 추출제로 2급과 3급 아민 및 용매화 추출제, 용매로 n-butylacetate, modifier로 4-nonylphenol, TBP 및 isodecanol을 이용하였다. 그외에 수용액상의 pH와 온도의 영향을 연구하였다. 실험결과 초산의 추출에서 3급 아민인 tril-n-octyl과 tri-n-decylamine의 50% 혼합 추출제인 MODA가 추출도 및 선택도에서 가장 좋았다. Modifier로서는 4-nonylphenol이 우수하였다. 이외에도 수용액의 pH와 추출계의 온도가 낮을수록 추출도가 높았다.

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Studies on Benzofuran-7-carboxamides as Poly(ADP-ribose) Polymerase-1 (PARP-1) Inhibitors

  • Lee, Sun-Kyung;Yi, Kyu-Yang;Lee, Byung-Ho;Oh, Kwang-Seok
    • Bulletin of the Korean Chemical Society
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    • 제33권4호
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    • pp.1147-1153
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    • 2012
  • Benzofuran-7-carboxamide was identified as a novel scaffold of poly(ADP-ribose) polymerase-1 (PARP-1) inhibitor. A series of compounds with various 2-substituents including (tertiary amino)methyl moieties substituted with aryl ring and aryl groups containing tertiary amines, were synthesized and biologically evaluated to elucidate the structure-activity relationships and optimize the potency. 2-[4-(Pyrrolidin-1-ylmethyl)phenyl]-benzofuran-7-carboxamide (42) was the most potent as an IC50 value of 40 nM among those.

이산화탄소 흡수제의 화학구조별 반응열량 특성 연구 (Analysis of the Heat of Absorption Based on the Chemical Structures of Carbon Dioxide Absorbents)

  • 곽노상;이지현;엄용석;김준한;이인영;장경룡;심재구
    • Korean Chemical Engineering Research
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    • 제50권1호
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    • pp.135-140
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    • 2012
  • 반응열량계를 사용하여 1, 2, 3차 아민 수용액과 이산화탄소의 반응열을 각각 측정하였다. 이를 통해 MEA(monoethanolamine, 1차 아민), EAE(2-(ethylamino) ethanol, 2차 아민), MDEA (N-methyldiethanolamine, 3차 아민) 30 wt% 수용액이 $40^{\circ}C$에서 이산화탄소와 반응시 발생하는 반응열을 측정하고 이를 $CO_2$의 loading ratio에 따라 어떻게 변화하는지 평가하였다. 또한, 입체장애 구조를 가지는 AMP(2-amino-2-methyl-1-propanol, 1차 아민), DEA(diethanolamine, 2차 아민), TEA(triethanolamine, 3차 아민) 30 wt% 수용액의 반응열을 각각 측정하여 입체장애 구조가 반응열에 미치는 영향을 살펴보았다. 그 결과, 흡수제의 입체장애 유무와 관계없이 1차 > 2차 > 3차 아민 순으로 반응열이 증가함을 확인하였다. 그리고 입체장애 아민이 동일 차수의 비 입체장애 아민보다 상대적으로 반응열이 낮지만 그 차이는 크지 않음을 확인하였다.

Selective Reduction by Lithium Bis- or Tris(dialkylamino)aluminum Hydrides. VIII. Reaction of Lithium Tripiperidinoaluminum Hydride in Tetrahydrofuran with Selected Organic Compounds Containing Representative Functional Groups

  • 차진순;이재철;주영철
    • Bulletin of the Korean Chemical Society
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    • 제18권8호
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    • pp.890-895
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    • 1997
  • The approximate rates and stoichiometry of the reaction of excess lithium tripiperidinoaluminum hydride (LTPDA), an alicyclic aminoaluminum hydride, with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, 25°) were examined in order to define the reducing characteristics of the reagent for selective reductions. The reducing ability of LTPDA was also compared with those of the parent lithium aluminum hydride (LAH) and lithium tris(diethylamino)aluminum hydride (LTDEA), a representative aliphatic aminoaluminum hydride. In general, the reactivity of LTPDA toward organic functionalities is weaker than LTDEA and much weaker than LAH. LTPDA shows a unique reducing characteristics. Thus, benzyl alcohol, phenol and thiols evolve a quantitative amount of hydrogen rapidly. The rate of hydrogen evolution of primary, secondary and tertiary alcohols is distinctive. LTPDA reduces aldehydes, ketones, esters, acid chlorides and epoxides readily to the corresponding alcohols. Quinones, such as p-benzoquinone and anthraquinone, are reduced to the corresponding diols without hydrogen evolution. Tertiary amides and nitriles are also reduced readily to the corresponding amines. The reagent reduces nitro compounds and azobenzene to the amine stages. Disulfides are reduced to thiols, and sulfoxides and sulfones are converted to sulfides. Additionally, the reagent appears to be a good partial reducing agent to convert primary carboxamides into the corresponding aldehydes.

Reaction of Sodium Tris(diethylamino)aluminum Hydride with Selected Organic Compounds Containing Representative Functional Groups

  • Cha, Jin-Soon;Jeoung, Min-Kyoo;Kim, Jong-Mi;Kwon, Oh-Oun;Lee, Keung-Dong;Kim, Eun-Ju
    • Bulletin of the Korean Chemical Society
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    • 제15권10호
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    • pp.881-888
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    • 1994
  • The approximate rates and stoichiometry of the reaction of excess sodium tris(diethylamino)aluminum hydride (ST-DEA) with selected organic compounds containing representative functional groups under standardized conditions(tetrahydrofuran, $0{\circ}$) were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The reducing ability of STDEA was also compared with those of the parent sodium aluminum hydride (SAH) and lithium tris(diethylamino)aluminum hydride (LTDEA). The reagent appears to be milder than LTDEA. Nevertheless, the reducing action of STDEA is very similar to that observed previously for LTDEA, as is the case of the corresponding parent sodium and lithium aluminum hydrides. STDEA shows a unique reducing characteristics. Thus, benzyl alcohol, phenol and 1-hexanol evolved hydrogen slowly, whereas 3-hexanol and 3-ethyl-3-pentanol, secondary and tertiary alcohols, were essentially inert to STDEA. Primary amine, such as n-hexylamine, evolved only 1 equivalent of hydrogen slowly. On the other hand, thiols examined were absolutely stable. STDEA reduced aidehydes and ketones rapidly to the corresponding alcohols. The stereoselectivity in the reduction of cyclic ketones by STDEA was similar to that by LTDEA. Quinones, such as p-benzoquinone and anthraquinone, were reduced to the corresponding 1,4-dihydroxycyclohexadienes without evolution of hydrogen. Carboxylic acids and anhydrides were reduced very slowly, whereas acid chlorides were reduced to the corresponding alcohols readily. Esters and epoxides were also reduced readily. Primary carboxamides consumed hydrides for reduction slowly with concurrent hydrogen evolution, but tertiary amides were readily reduced to the corresponding tertiary amines. The rate of reduction of aromatic nitriles was much faster than that of aliphatic nitriles. Nitrogen compounds examined were also reduced slowly. Finally, disulfide, sulfoxide, sulfone, and cyclohexyl tosylate were readily reduced without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent: like LTDEA, STDEA converted ester and primary carboxamides to the corresponding aldehydes in good yields. Furthermore, the reagent reduced aromatic nitriles to the corresponding aldehydes chemoselectively in the presence of aliphatic nitriles. Consequently, STDEA can replace LTDEA effectively, with a higher selectivity, in most organic reductions.

무염 원자흡광도법과 흡광광도법에 의한 제제중의 Metoclopramide의 정량 (Determination of Metoclopramide by Flameless Atomic Absorption and Spectrophotometry)

  • 박만기;임병연;유경수;용군호
    • 약학회지
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    • 제22권1호
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    • pp.27-32
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    • 1978
  • Metoclopramide reacts with ammonium cobaltothiocyanate to form a stable ion pair which has an absorption maximum of 625mm. The reaction product was insoluble in water but soluble in most organic solvents. 1,2-Dichlorethane was the best extracting solvent among the several organic solvents tested. Metoclopramide can be determinded not only by visible light spectrophotometry but also indirectly by estimation of cobalt in the organic phase by flameless atomic absorption spectrophotometry. Linear relationship was found between absorbance and concentration in the range of 10$^{-4/}$-10$^{-3}$M by spectrophotometry and 10$^{-5}$-10$^{-4}$M by flameless atomic absorption spectrophotometry. The coefficient of variation by spectrophotometry was 0.9% and that of flameless atomic absorption was 1.8%. There was no interference with excipients, pH, temperature and reaction time. With this method, it is possible to determine accurately metoclopramide and tertiary amines in pharmaceutical preparations.

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Studies on the Quaternization of Tertiary Amines (Ⅳ). Kinetics and Mechanism for the Reaction of Substituted Phenacyl Tosylates with Substituted Pyridines

  • Lee, Oh-Seuk;Yoh, Soo-Dong
    • Bulletin of the Korean Chemical Society
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    • 제6권2호
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    • pp.99-102
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    • 1985
  • Substituent effects of substrate and nucleophile for the reaction of substituted phenacyl tosylates with pyridines were determined conductometrically in acetonitrile. Activation parameters for these reactions were also calculated. The substituent effects in nucleophile were increased with electron-donating power of pyridines and Br${\o}$nsted linear relationship was shown. Rate constant was increased by both electron-donating and electron-attracting groups in the substrate. It seems that dissociative S$_{N}$2 ("loose" transition state) mechanism is operating in the case of electron-donating substituents while associative S$_{N}$2 ("tight" transition state) mechanism is operative in the case of electron-attracting substituents.

방사선그라프팅 음이온교환막의 기계적 물성에 대한 4차 암모늄 음이온교환기의 영향 (Influence of Quaternary Ammonium Anion Exchange Moieties onto Mechanical Properties of Radiation-grafting Anion Exchange Membranes)

  • 고범석;손준용;신준화
    • 방사선산업학회지
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    • 제6권1호
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    • pp.49-54
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    • 2012
  • Various anion exchange membranes were prepared by radiation graft copolymerization of vinylbenzyl chloride onto fluorinated films and subsequent quaternization with various tertiary amines such as trimethylamine, N,N-dimethylbuthylamine, N,N-dimethylaniline, and N-methylpiperidine. The quaternizations of the anion exchange membranes were confirmed by measuring of the ion exchange capacities of the membranes. The mechanical properties and the water uptakes were also measured. The elongation at break was found to be largely dependent on the fluorinated film, the quateranry ammonium, and the degree of grafting. The results indicate that the poly (ethylene-alt-tetrafluoroethylene) with quaternized trimethylamine moiety exhibits higher flexible property compared to the other prepared anion exchange membranes.