• Title/Summary/Keyword: Cyclization Reaction

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Syntheses and Characterization of PBO Precursors Containing Dimethylphenoxy and/or MPEG Pendant Groups (Dimethylphenoxy와 MPEG 팬던트 그룹을 갖는 폴리벤즈옥사졸 전구체의 합성 및 특성)

  • Yoon Doo-Soo;Choi Jae-Kon;Jo Byung-Wook
    • Polymer(Korea)
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    • v.29 no.5
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    • pp.493-500
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    • 2005
  • Polyhydroxyamides(PHAs) having poly(ethylene glycol)methyl ether (MPEG) and/or dimethylphenoxy pendant groups were synthesized by solution polycondensation at low temperature. The inherent viscosities of the PHAs measured at $35^{\circ}C$ in DMAC or DMAc/LiCl solution were in the range of $0.51\~2.31dL/g$. This precursor polymers were studied by FT-IR, $1H-NMR$, DSC, and TGA. Solubility of the precursors with higher MPEG unit was increased, especially the polymer having MPEG $(M_n=1100)$ was soluble or partially soluble in ethanol, methanol, and water as well as aprotic solvents, but the PBOs were nearly insoluble in a variety of solvents. PHAs were converted to polybenzoxazoles (PBOs) by thermal cyclization reaction with heat of endotherm. In case of the precursors having MPEG nit, the precursor polymers with a higher $M_n$ were fully cyclized at a lower temperature than one with a lower $M_n$.

Synthesis of Cyclohexene Derivatives from 1,5-Enynes via Gold-Catalysis and Iodocyclization: A Comparative Study and Applications in the Synthesis of 7/5- or 8/5-Fused Rings and Biaryls

  • Lee, Young-Un;Lim, Choong-Min;Kim, Sung-Hwan;Shin, Seung-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.31 no.3
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    • pp.670-677
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    • 2010
  • A comparative study on the Au(I)-catalyzed and IBr-promoted tandem cyclization of 1,5-enyne was reported. This study provides a meaningful mechanistic insight to the concerted nature of this tandem reaction and also provides interesting applications in the synthesis of 7/5- or 8/5-fused bicycles and biaryls.

Synthesis of Novel Pyrazolylquinoxalines (새로운 Pyrazolylquinoxaline류의 합성)

  • Kim, Ho Sik;Kwag, Sam Tag
    • Journal of the Korean Chemical Society
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    • v.44 no.3
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    • pp.229-236
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    • 2000
  • The reaction of 6-chloro-2-hydrazinoquinoxaline 4.oxide(10) with acetylacetone or dibenzoylmethane gave 6-chloro-2-(3,5-disubstituted pyrazol-1-yl)quinoxaline 4-oxides (11) through the intramolecular·cyclization.The chlorination of compound 11 with phosphoryl chloride afforded 3,6-dichloro-2-(3,5-disubstituted pyrazol-1-yl)quinoxalines (12), whose reaction with hydrazine hydrate provided 6-chloro-3-hydrazinodehydes, benzenesulfonyl chloride, substituted benzoyl chlohdes or acyl chlorides gave novel pyrazolylquinoxalines (14-17).

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A Synthetic Study on Trans-2,5-Disubstituted Tetrahydrofurans via Phenylselenoetheriflcation

  • Kang, Sung-Ho;Hwang, Tae-Seop;Lim, Joong-Ki;Kim, Wan-Joo
    • Bulletin of the Korean Chemical Society
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    • v.11 no.5
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    • pp.455-460
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    • 1990
  • 2,5-Disubstituted tetrahydrofurans 11-13 were prepared by phenylselenoetherification of 1-alkyl-4-phenyl-(3E)-butenols 8-10 under kinetic conditions. Their stereochemical outcome and reactivity were controlled by solvent, reaction temperature and the alkyl substituent. While the cyclization was stereorandom in dichloromethane, its stereoinduction was moderate to good in propionitrile and good to excellent in diethyl ether. The reaction went to completion in dichloromethane and propionitrile, but it did not in diethyl ether. The results can be rationalized by the degree of reversibility in the formation of episelenonium cation and 1,3-diaxial interactions in the transition state of the formation of tetrahydrofuranonium cation.

Preparation of Polyesters Containing Enaryloxynitrile Moiety and Their Thermal Properties

  • Moon Sung-Hee;Lee Seung-Jae;Kim Jin-Bong;Gong Myoung-Seon
    • Bulletin of the Korean Chemical Society
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    • v.15 no.12
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    • pp.1089-1093
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    • 1994
  • Polyesters containing enaryloxynitriles moiety have been newly prepared from p-bis[1-[4-(3-hydroxypropyl)phenoxy]-2,2-dicyano vinyl]benzene (3) and common diols with terephthaloyl chloride. The copolyesters have a good solubility in common organic solvents as well as polar aprotic solvents. They undergo a curing reaction at around 350 $^{circ}C$ and show a 50-60${\%}$ of residual weight at 500 $^{circ}C$. The enhanced thermal stabilities were due to the intramolecular cyclization or intermolecular cross-linking reaction of the dicyanovinyl group incorporated into polyester by copolymerization.

A New Synthesis of Hydantoin derivatives by the Reaction of Unnatural Amino acids with Potassium Isocyanate

  • Park, Hae-Sun;Choi, Hee-Jeon;Kwon, Soon-Kyoung;Park, Myoung-Sook
    • Proceedings of the PSK Conference
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    • 2002.10a
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    • pp.339.1-339.1
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    • 2002
  • Since two selective COX-2 inhibitors. celecoxib and rofecoxib, showed good biological activity as antiinflammatory agents. many medicinal chemists are interested in specific COX-2 inhibitors. The distinguished feature of these drugs is that the 5-membered heterocycle ring is substituted with two aryl groups. Therefore, in this study, we designed a new hydantoin derivatives via the reaction of unnatural amino acids as selective COX-2 inhibitors, In systematically steps. 5-phenyl-1 (or substituted) hydantoin derivatives were prepared through esterification. bromination, C-N bond formation, cyclization from phenyl acetic acid. Particularly. a novel hydantoin ring was converted from unnatural amino acids with potassium isoyanate. In last step. the final analogs were synthesized the substitution at 3-position with alkyl reagents.

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Synthesis of New Heterocycles Derived from 3-(3-Methyl-1H-indol-2-yl)-3-oxopropanenitrile as Potent Antifungal Agents

  • Gomha, Sobhi M.;Abdel-Aziz, Hatem A.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.9
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    • pp.2985-2990
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    • 2012
  • New thiazoline derivatives 7a-c, and thiophenes 9a-c linked to indole moiety were easily prepared via the reaction of the acrylamide derivative 3 with phenacyl bromides 4a-c, depending on the reaction conditions. In addition, the reaction of compound 3 with hydrazonoyl chlorides 11a-f afforded a series of 1,3,4-thiadiazole derivatives 13a-f. Moreover, coupling of 3-(3-methyl-1H-indol-2-yl)-3-oxopropanenitrile (2) with the diazonium salts of 3-phenyl-5-aminopyrazole 16 or 3-amino-1,2,4-triazole 17 gave the corresponding hydrazones 18 and 19, respectively. Cyclization of the latter hydrazones yielded the corresponding pyrazolo[5,1-c]-1,2,4-triazine and 1,2,4-triazolo[5,1-c]-1,2,4-triazine derivatives 20 and 21, respectively. The structures of the synthesized compounds were assigned on the basis of elemental analysis, IR, $^1H$ NMR and mass spectral data. All the synthesized compounds were tested for in vitro activities against certain strains of fungi such as Aspergillus niger, Aspergillus nodulans, Alternaria alternate. Compounds showed marked inhibition of fungal growth nearly equal to the standards.

Synthesis and properties of PBO precursors having bulky groups and ether linkages in the main chain (주사슬에 벌키그룹과 에테르 연결고리를 갖는 PBO 전구체의 합성 및 특성)

  • Yoon, Doo-Soo;Kim, Hee-Sun;Choi, Jae-Kon;Hong, Wan-Hae
    • Elastomers and Composites
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    • v.43 no.4
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    • pp.271-280
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    • 2008
  • Aromatic polyhydroxyamides (PHAs) having bulky groups and ether linkages in the polymer main chain were synthesized by the low temperature solution polycondensation reaction. FT-IR, $^{1}H-NMR$, DSC, and TGA were used to study the properties of these polymers. The PHAs were converted into polybenzoxazoles (PBOs) by a thermal cyclization reaction, and endothermic peaks were observed in the range of $220{\sim}400^{\circ}C$. The introduction of the ether and bulky groups in the main chain improved the solubility of the PHAs in aprotic solvents such as DMSO and DMF, but the PBOs were nearly insoluble in common solvents. All the PBOs, except for PBO 5 with 2,6-dimethylphenoxy pendant and 2,3-dihydroxyquinoxaline ring, and PBO 6 with 2,6-dimethylphenoxy pendant and 2,3-dihydroxyquinoxaline ring, exhibited $T_g's$ in the range from 149 to $217^{\circ}C$ by DSC. The thermogravimetric analyses indicated that most of the PBOs were thermally stable up to $400^{\circ}C$ in nitrogen. Maximum weight loss temperatures of PHA 5 and PBO 5 with 2,6-dimethylphenoxy pendant and 2,3-dihydroxyquinoxaline ring were $707^{\circ}C$ and $683^{\circ}C$, respectively, which were the hightest temperatures among the corresponding copolymers. The PBOs in nitrogen exhibited relatively high char yields in the range of $63{\sim}70%$ at $900^{\circ}C$.

Studies on the Synthesis of Etodolac Derivatives as Potential Anti-inflammatory Agents (항염증제인 Etodolac 유도체의 합성에 관한 연구)

  • Cho, Hoon;Chung, Yong Seog;Jang, Hang Dong;Ryu, Seong Ryual
    • Applied Chemistry for Engineering
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    • v.10 no.1
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    • pp.135-137
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    • 1999
  • For the synthesis of new anti-inflammatory agents as indol derivatives, we have synthesized ${\alpha}$-benzoyl-1-ethyl-1,3,4,9-tetrahydro-8-ethyl-9-(N-benzoyl)pyrano[3,4-b]indole-1-acetic acid methyl ester. It was a new method for ${\alpha}$-substituted etodolac carboxylic acid. The synthetic process was composed of four steps, and 7-ethylindole and oxalyl chloride were used as starting materials. The third step, cyclization was carried out by addition of borontrifluoride diethyl etherate in 66% yield. The step of reduction and cyclization were simplified successfully. The final product, ${\alpha}$-benzoyl-1-ethyl-1,3,4,9-tetrahydro-8-ethyl-9-(N-benzoyl)pyrano[3,4-b]indole-1-acetic acid methyl ester was obtained in 66% yield by the reaction of methyl 1,8-dimethyl-1,3,4,9-tetrahydropyrano[3,4-b]indole-1-acetate (etodollic acid methyl ester) and benzoyl chloride.

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Optical Properties of Proton-irradiated Polyacrylonitrile Film (양성자 조사된 폴리아크릴로니트릴 필름의 광학적 특성)

  • Lee, Hwa-Su;Baek, Ga-Young;Jung, Jin-Mook;Hwang, In-Tae;Jung, Chan-Hee;Shin, Junhwa;Choi, Jae-Hak
    • Journal of Radiation Industry
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    • v.10 no.1
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    • pp.1-5
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    • 2016
  • In this study, the effect of high-energy proton irradiation on the optical properties of polyacrylonitrile (PAN) films was investigated. PAN thin films spin-coated on a substrate were irradiated 150 keV proton ions at various fluences. The changes in the chemical structure and optical properties were investigated by FT-IR and UV-vis spectroscopy. The results of the FT-IR analysis revealed that the cyclization reaction took place by proton irradiation and the degree of cyclization increased with an increasing fluence. Based on the UV-vis analysis, the optical band gap of PAN decreased from 2.84 to 2.52 eV with an increasing fluence due to the formation of carbon clusters by proton irradiation. In addition, the number of carbon atoms per carbon cluster and the number of carbon atoms per conjugation length were found to be increased with an increasing fluence.