• Title/Summary/Keyword: Pyrrole

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N-Acyliminium에의 친핵성 부가에 의한 Octahydro-2,3-dioxo-cyclopenta[b]pyrrole-3a-carboxylates의 합성 (Synthesis of Octahydro-2,3-dioxo-cyclopenta[b]pyrrole-3a-carboxylates by Nucleophilic Addition to N-Acyliminium)

  • 서원준;정창희;최승주;박영규;김태흥;이상규
    • 대한화학회지
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    • 제38권12호
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    • pp.908-914
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    • 1994
  • 5원자 고리형 ${\beta}$-keto ester와 phenylalkylamine의 탈수축합으로 얻은 enamine A의 oxalyl화 및 물이나 메탄올 부가에 의하여 octahydro-2,3-dioxo-cyclopenta[b]-pyrrole-3a-carboxylate의 6a-hydroxy- 및 6a-methoxy-유도체(1~6)를 합성하였다. 헤테로 고리의 형성은 불안정한 N-acyliminium(B)체를 경유하여 일어나며, 안정한 부가체 C (1∼6)는 endo-ene형 pyrrolinium B에 친핵체를 부가하여 얻을 수 있었다.

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전도성 고분자 복합체 제조를 위한 신합성 연구(II) : 중합변수에 따른 전도성 고분자 복합체의 전도도 변화 (Process for the Preparation of Conducting Polymer Composites (II) : The Effect of Polymerization Parameters on Conductivity)

  • 손석희;박영준;김중현
    • 공업화학
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    • 제7권6호
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    • pp.1061-1068
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    • 1996
  • 본 연구는 다공성 입자에 전도성 단량체를 침투시켜서 전도성 고분자 복합체를 제조하는 연구로 다단계 seed 중합법을 이용하여 입자를 제조하고, 용매추출법으로 선형 고분자를 제거하는 방법으로 specific pore volume 및 specific surface area가 각기 다른 다공성 입자를 제조하였고, 이 다공성 입자를 모체 고분자로 하여 도핑제를 산화용액에 녹여 흡수시키고 건조한 뒤 전도성 단량체를 유기용매에 녹여 다공성 입자에 침투시킨 후 중합하여 전도성 복합체를 제조하였다. 이때, 모체 고분자에 침투되는 전도성 단량체의 농도 및 유기용매와 산화제의 산화용매 등을 중합 변수로하여 이 변수들과 전도도와의 상관 관계를 살펴보았다.

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Versatilities of Calix[4]pyrrole Based Anion Receptors

  • Lee, Chang-Hee
    • Bulletin of the Korean Chemical Society
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    • 제32권3호
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    • pp.768-778
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    • 2011
  • Calixpyrroles and related macrocycles are non-planer synthetic anion receptors that have attracted considerable attentions in recent years. Although the synthesis of calix[4]pyrrole (known as meso-octamethylporphyrinogen) was reported more than 100 years ago, the anion binding properties were first discovered in 1996. The simple calix[4]pyrroles can be synthesized in single step in high yield by condensation of pyrrole with acetone. The compounds showed preferential binding for halide anions including fluoride, phosphate, carboxylate, and chloride in organic media. Efforts to improve the anion affinity of calix[4]pyrrole and to enhance its selectivity have led to the synthesis of a variety of new calixpyrrole derivatives. Among the various modifications, introduction of straps on one side of the calix[4]pyrroles are the most effective. Incorporation of aromatic rings other than pyrroles also exhibited interesting binding behaviour. Introduction of signalling units as part of the strapping element enable to detect the anions on chromogenic or fluorogenic fashion. Finding of the anion transport properties across the membrane and cytotoxic effects of the calix[4]pyrroles open new window for calixpyrrole-related research. The polymer-incorporated systems have also been employed as anion complexants in solvent-solvent extraction. These old, yet easy-to-make macrocycles have well advanced more recently with the discovery of the ion-pair complexation properties. In this review, the synthetic developments and anion binding properties of calixpyrroles for the last decades will be discussed and will cover the advances in calixpyrrole chemistry.

물 또는 Propylene Glycol 용매계에서 D-Glucose와 DL-Alanine 또는 DL-$\alpha$- Aminoutyric acid와의 마이야르 반응에 의한 휘발성 화합물의 생성 (Formation of Volatile Compounds from Maillard Reaction of D-Glucose and DL-Aranine or DL-?? -Aminobutyric acid in Water or Propylene Glycol Solution)

  • 김영회;김옥찬;이정일;양광규
    • 한국연초학회지
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    • 제10권2호
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    • pp.123-130
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    • 1988
  • The volitile compounds Produced from the Maillard reaction of D-glucose and DL-alanine or DL-$\alpha$-aminobutyric acid using water or propylene glycol as a reaction amdeum were analysed by gas chromatofiraphy and mass spectrometry. From two kinds of reaction products in water 18 compounds were identified. The major compounds in a reaction product of glucose with alanine were 5-hydroxy methyl-2-furfural, 2-acetyl pyrrole and 2-formyl-5-methyl pyrrole, and those in a reaction product of glucose with $\alpha$-aminobutyric acid were 2-ethyl crotonaldehyde and 2-methyl-3, 5-dihydroxy-4H-pyran-4-one including the above 3 compounds. From two kinds of reaction products in propylene glycol solution, 35 compounds were identified. The major compounds in a reaction product of glucose with alanine were alkyl pyraainef, 2-methyl furfuryl alcohol and 2-acetyl pyrrole, and those in a reaction product of glucose with $\alpha$-aminobutyric acid were propionaldehyde PGA, 2-ehtyl crotonaldehyde, 2-acetyl pyrrole and 2-acetyl-5-ethyl furan.

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Morecular Orbital Caculations for the Reactions of 2,5-dimethyl Pyrrole with Phenylsulfonyl Chloride

  • 서미경;김진범;성시열;심영기
    • Bulletin of the Korean Chemical Society
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    • 제20권8호
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    • pp.948-952
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    • 1999
  • Electrophilic substitutions on β-position of 2,5-dimethyl pyrrole have been investigated theoretically. The electron donating methyl groups enrich electron densities on C-3, C-4 positions and π* interactions with methyl groups substituted on C-2 and C-5 positions pushed up the HOMO level of the pyrroles consequently induce rapid substitutions on C-3, C-4 sites. Substitution of phenylsulfonyl group on nitrogen stabilized LUMO levels through weak π bonding interactions. Unexpected deoxidation reaction underwent on the sulfonyl group substituted at C-3 position. The structures were solved by X-ray crystallography. Meanwhile, gas phase HF/6-31G* and density functional method (B3LYP/6-31G*) calculations gave favorable energies for 1-phenylsulfinyl pyrrole (6) over 3-phenylsulfinyl pyrrole (5) by 3.6-4.7 kcal/mol which is contrary to the experimental result. However the methods involve the effects of molecular polarizability and solvent, molecular dynamics (MD) and ab-initio self consistent reaction field (SCRF) calculations showed same trend as experiments. According to MD calculations, compound 5 is more stable than compound 6 by 4.15 kcal/mol and the SCRF, HF/6-31G* calculations gave more stable energy value for structure 5 than 6 by 0.03 kcal/mol.

Bezoin in Heterocyle Synthesis: Synthesis and Reactions of 2, 3-Diphenyl-4-cyanopyrrole-5-thione

  • Khalifa, Fathy A.;Zohdi, Hussein F.;Ibrahim, M.K.A.;Ismail, N.A.
    • Archives of Pharmacal Research
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    • 제13권4호
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    • pp.351-354
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    • 1990
  • 2, 3-diphenyl-4-cyano-pyrrole-5-thione (4) was either by the reaction of benzoin (1) and cyanothioacetamide (3) followed by cyclization using AcOH/sodium acetate or by refluxing a mixture of benzoin (1) and cyanothioacethamide in pyridine to afford directly 4. Several new pyrrole and pyrazole derivatives were synthesised using 4 as synthon. The structure of the newly synthesised derivatives were based on celemental and spectral data studies. Methylation of the SH group in 4 afforded 5. Reaction of 4 with ethyl bromo acetate afforded (6). Treatment of (5) and (6) with hydrazine hydrate afforded the same pyrazole derivative (10) through the intermediate (9). Treatment of 6 with aniline and phenylhydrazine afforded the pyrrole derivatives 8a, b respectively. Treatment of 6 while dill HCI gave 2, 3-diphenyl-4-cyano-pyrrole-5-one (7). Treatment of 6 with $NH_3$/EtOH afforded the amidic derivatives (11) with treatment of 6 $NH_3$/ heat then acidification it gave the carboxylic derivatives (12).

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X-ray Crystal Structure and Luminescence Properties of Pd(II) and Pt(II) Complexes with Dithiopyrrole

  • Kang, Jun-Gill;Cho, Dong-Hee;Park, Changmoon;Kang, Sung Kwon;Kim, In Tae;Lee, Sang-Woo;Lee, Ha-Hyeong;Lee, Young-Nam;Lim, Dae-Won;Lee, Sung-Jae;Kim, Sung-Ho;Bae, Young-Ju
    • Bulletin of the Korean Chemical Society
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    • 제29권3호
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    • pp.599-603
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    • 2008
  • The complexes Pd(nbmtp)Cl2 and Pt(nbmtp)Cl2 (nbmptp = 1-nonyl-3,4-bis(methylthio)pyrrole) were prepared and their x-ray structures were determined at room temperature. The four-coordinated metal unit and the pyrrole ring formed a nearly planar geometry. The free ligand dissolved in CH2Cl2 produced two luminescence bands associated with the lone-pair electron of S (l max = 525 nm) and the pyrrole p electron (l max = 388 nm). When the two complexes were dissolved in CH2Cl2, these two luminescence bands were also observed, although the low-energy band was blueshifted. For the crystalline Pt(II) complex, only the strong charge transfer band (l max = 618 nm) from the d* orbital of Pt resulted from excitation of the lone-pair electron of S.

초음파 중합에 의한 polypyrrole 나노입자를 함유하는 메조포러스 TiO2 박막의 합성 (Synthesis of Mesoporous TiO2 Thin Films with Polypyrrole Nanoparticles by Ultrasonic-induced Polymerization)

  • 정광석;조성호;송명근;김종득
    • Korean Chemical Engineering Research
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    • 제46권4호
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    • pp.777-782
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    • 2008
  • 초음파 중합법을 이용하여 pyrrole을 중합시킴으로써 polypyrrole 나노입자를 합유하는 메조포러스 $TiO_2$ 박막을 합성하였다. 메조포러스 $TiO_2$ 박막을 만들기 위한 $TiCl_4$-계면활성제 용액에 pyrrole을 넣어주고 초음파 중합시킴으로써 용액 내에 polypyrrole 나노입자들이 잘 분산된 형태로 만들어졌다. 이 용액을 이용하여 spin-coating과 열처리를 함으로써 polypyrrole 나노입자를 합유하는 메조포러스 $TiO_2$ 박막을 제조하였다. 열처리 후에도 기공 구조는 잘 유지되었으며, polypyrrole 나노입자들이 박막 내에 잘 분산되었다. 주형물질인 계면활성제의 종류와 pyrrole의 양을 조절함으로써, 합성된 박막의 기공 크기와 빛의 흡광도를 조절하였다.

Ion and solvent transport during the redox reaction of Polypyrrole and poly(N-substituted pyrrole) films in aprotic solutions

  • Lee Hochun;Kwak Juhyoun
    • 전기화학회지
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    • 제1권1호
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    • pp.52-54
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    • 1998
  • Polypyrrole (PPy), Poly(N-methyl Pyrrole) (PMPy) and Poly(N-phenyl Pyrrole) (PPhPy) films in acetonitrile (Af and propylene carbonate (PC) have been compared focusing on their different ion and solvent transport behaviors. During the redox reaction of PPy films, cation, anion, and solvent take part in mass transport. Whereas during the redox reaction of PMPy and PPhPy films, anion and solvent transport are dominant but cation transport is negligible. In addition, solvent transport occurs in the same direction with cation transport for PPy films. On the other hand, solvent transport occurs in the opposite direction to anion transport for PMPy films, and it changes its amount and direction with the kind of the dopant anion and the solvent used at electropolymerization for PPhPy films.