• Title/Summary/Keyword: Primary amines

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Ruthenium Catalyzed Synthesis of N-Substituted Perhydroazepine Derivatives (루테늄 촉매를 이용한 N-치환 과수소아제핀 유도체의 합성)

  • Sim, Sang Cheol;Do, Chil Hun;Lee, Seung Yeop;Jo, Wan Ho;Heo, Geun Tae
    • Journal of the Korean Chemical Society
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    • v.34 no.6
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    • pp.652-657
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    • 1990
  • Primary amines react with 1,6-hexanediol at 180$^{\circ}C$ for 5 h under argon atmosphere in the presence of both $RuCl_3{\cdot}3H_2$O and $PR_3$ to give N-substituted perhydroazepine derivatives in good yields. For aromatic amines such as anilines, $RuCl_3{\cdot}3H_2$O combined with $PPh_3$ showed the highest catalytic activity. On the other hand, in the reaction of aliphatic amines, $RuCl_3{\cdot}3H_2$O combined with $PBu_3$ showed the highest catalytic activity. These differences may be attributed to the difference in the basicity of these amines. Less basic aromatic amines may require less basic phosphines, while more basic aliphatic amines may require more basic phosphines as the ligands.

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Analytical examples of volatile amines in ambient airs (공기 중 저급아민류의 분석과 측정 사례)

  • Yu, Mee-Seon;Yang, Sung-Bong
    • Analytical Science and Technology
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    • v.18 no.3
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    • pp.216-223
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    • 2005
  • In this study, several kinds of volatile amines in ambiant air were collected and their concentrations were expected from the calibration curves prepared by standard solutions of 7 amines by the official measuring method prescribed in Japanese Offensive Odor Law. The obtained calibration curves showed a good linearity and the detection limit of trimethyl amine was found to be about 0.033 ppb (0.040 ng) in case of 50 liters air. It means that trimethyl amine could be detected with the concentration of lower than its permitting level at the border line of companies. As typical examples of measuring amines in air, results of investigation of two sewage works and one rendering plant around the capital area indicated that 4 kinds of amines, i.e. methyl amine, dimethyl amine, trimethyl amine and isopropyl amine were detectable and concentrations of trimethyl amine at the primary sedimentation pond and sludge dewatering building of the sewage plant A showed 9.07 ppb and 7.79 ppb respectively, being over the concentration of odor strength 2.5, And the aeration tank, excrement input facility and indoor of maintenance room of excrement process building in the sewage plant B showed 70.0 ppb of dimethyl amine and 2.44 ppb of trimethyl amine.

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

  • Gap-Cheol Shin;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.287-292
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    • 1992
  • The rate constants of the nucleophilic addition reaction of amines (piperidine and diethylamine) to phenylvinylketone in various solvents have been determined by UV spectrophotometry at $25^{\circ}C$. On the basis of the high sensitivity of the rate to the polarity of the medium, it may be concluded that the reaction intermediate has zwitterionic character. The effect of the solvents on the rate of the bimolecular nucleophilic addition reaction is described well by the Kirkwood equation: The transition state of the reaction has a cyclic structure formed through an intramolecular hydrogen bond. The addition reaction of primary and secondary amines to phenylvinylketone in all solvents take place considerably faster than that of tertiary amine and this results also can be explained by the intermediate products in the reaction have a cyclic structure formed through an intramolecular hydrogen bond for the primary and secondary amines but not for the tertiary amine.

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Synthesis of 2-n-Butyl-3-fluoropyrrole Derivatives

  • Kim, Bo-Mi;San, Quan-Ze;Bhatt, Lok Ranjan;Jung, Dong-Woon;Lee, Young-Hang;Chai, Kyu-Yun
    • Bulletin of the Korean Chemical Society
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    • v.30 no.6
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    • pp.1293-1296
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    • 2009
  • A new series of N-substituted 2-n-butyl-3-fluoropyrroles were prepared by a simple one-pot reaction designed of retrosynthesis. $\alpha,\alpha-Difluoro-\gamma-iodo-\gamma$-(trimethylsilyl)propyl n-butyl ketone, a component precursor molecule to 2-n-butyl-3-fluoropyrroles, was prepared with Cu(0) catalyst. It reacted with various primary amines to yield N-substituted 2-n-butyl-3-fluoropyrroles. The products were synthesized via a one-pot reaction scheme between $\alpha,\alpha-Difluoro-\gamma-iodo-\gamma$-(trimethylsilyl) propyl n-butyl ketone and primary amines in excess ( $\geq$ 5 molar equivalence), which eliminate the need of KF required in obtaining n-butyl-1H-3-fluoropyrrole. The yield of products depended reversely on spatial bulkness around N-binding carbon.

The Facile Synthesis of N-Substituted 2,5-Dimethylpyrrolidine Derivatives from 2,5-Hexanedione and a Variety of Primary Amines using Tetracarbonylhydridoferrate(O) as a Selective Reducing Agent (II) (선택적 환원시약인 사카르보닐 철산염(O)을 이용한 N-치환-2,5-디메틸 피로리딘 유도체의 용이한 합성)

  • Sang Chul Shim;Keun Tai Huh;Kee Doo Kim;Woo Sik Kim
    • Journal of the Korean Chemical Society
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    • v.30 no.4
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    • pp.389-393
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    • 1986
  • The reaction of 2,5-hexanedione with a variety of primary amines using tetracarbonylhydridoferrate(O) as a selective reducing agent at room temperature or 60${\circ}C$ under an atmosphere of carbon monoxide gave the corresponding N-substituted 2,5-dimethylpyrrolidine derivatives. The reaction of synthesized 5-nitro-2-hexanone with benzaldehyde in the presence of tetracarbonylhydridoferrate(O) at 150${\circ}C$ under an atmosphere of carbon monoxide in an autoclave also gave N-benzyl-2,5-dimethylpyrrolidine in moderate yield. The mechanism of these reactions was investigated.

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Determination of Amine Compounds Using 1-(N,N-Dimethylamino) pyrene-6-sulfonyl chloride as a New Fluorescent Derivatizing Reagent for HPLC (새로운 HPLC용 형광유도체화제인 1-(N,N-dimethylamino) pyrene-6-sulfonyl chloride를 이용한 아민화합물의 분석)

  • 이윤중;김용희;조정길
    • YAKHAK HOEJI
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    • v.35 no.4
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    • pp.288-294
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    • 1991
  • A new fluorescent derivatizing reagent was developed to be used in HPLC for the trace determination of primary and secondary amines. This new reagent, 1-(N,N-dimethylamino)pyrene-6-sulfonyl chloride, was synthesized by the chlorination of sodium 1-(N,N-dimethylamino)pyrene-6-sulfonate which was obtained from 1-(N,N-dimethylamino)pyrene after sulfonation. Ephedrine and norephedrine were derivatized quantitatively by this reagent. The optimum conditions for the derivatization such as pH, reagent concentration, reaction time and reaction temperature ware examined. The structures of derivatives were identified by IR, $^{1}$H-NMR and MS methods. The fluorescence properties and the stability of the derivatives were examined. The derivatives were separated on silica column with an isocratic elution using the mixture of n-hexane and ethylacetate and monitored by fluorescene detector. Linear calibration curves were obtained and detection limits in a 10 $\mu$l injection volume were 5 picomole for ephedrine and norephedrine.

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Selective Synthesis of N-(Cyclohexylmethyl)-N-alkylamines from Primary Amines and Pimelaldehyde using Tetracarbonylhydridoferrate, $HFe(CO)_4^\;-$, as a Reducing Agent

  • Sang Chul Shim;Young Gil Kwon;Chil Hoon Doh;Byung Won Woo;Jin Ook Baeg;Hong Seok Kim;Tae Jeong Kim;Dong Ho Lee;Young Woo Kwak;Jin Soon Cha;Hyung Soo Lee;Jae Kook Uhm;Young Bae Park
    • Bulletin of the Korean Chemical Society
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    • v.11 no.2
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    • pp.140-143
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    • 1990
  • Ethanolic tetra carbonylhydridoferrate solution combined with dialdehyde (no of carbon; 4,5,6) is very efficient for the selective transformation of amino group into N-heterocyclic compound. However, a large variety of both aliphatic and aromatic amines react with the ferrate-pimelaldehyde at room temperature under an atmospheric pressure of carbon monoxide to give the corresponding N-(cyclohexylmethyl)-N-alkyiamine derivatives in moderate yields instead of the corresponding N-substituted perhydroazocine derivatives.

Ruthenium Complex Catalyzed Syntehesis of Diamino Compounds from ${\alpha},{\omega}$-Diols and Secondary Amines

  • Keun-Tae Huh;Sang Chul Shim;Chll Hoon Doh
    • Bulletin of the Korean Chemical Society
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    • v.11 no.1
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    • pp.45-49
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    • 1990
  • ${\alpha},{\omega}$-Diols react with secondary amines in the presence of a catalytic amount of ruthenium catalyst at $180^{\circ}C$ to give diamino compounds in good to excellent yields. The yield of diamino compound was affected by the molar ratio of ${\alpha},{\omega}$-diol to secondary amine. The reaction is affected by the nature of the phosphorus ligands employed and the effectiveness of the added ligand is completely different depending on the chain length of the ${\alpha},{\omega}$-diol. The reaction between ethylene glycol and primary amine in the presence of a catalytic amount of ruthenium catalyst gave 1,4-disubstituted piperazine.

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.

Four-Component Preparation of Disubstituted 1,3,4-Oxadiazoles from (N-isocyanimino)triphenylphosphorane, Phenylacetylenecarboxylic Acid, Biacetyl and Primary Amines

  • Ramazani, Ali;Abdian, Behnaz;Nasrabadi, Fatemeh Zeinali;Shajari, Nahid;Ranjdoost, Zahra
    • Bulletin of the Korean Chemical Society
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    • v.33 no.11
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    • pp.3701-3705
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    • 2012
  • A simple method has been developed for four-component synthesis of disubstituted 1,3,4-oxadiazoles using (N-isocyanimino)triphenylphosphorane, a primary amine, a carboxylic acid and biacetyl in $CH_2Cl_2$ by the Ugi-4CR/aza-Wittig sequence at room temperature in excellent yields.