• Title/Summary/Keyword: tetrahydrofuran

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Polymerization of Tetrahydrofuran with New Transition Metal Catalyst and Its Mechanism: (p- Methylbenzyl)- o -cyanopyridinium Hexafluoroantimonate

  • 강준원;한양규
    • Bulletin of the Korean Chemical Society
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    • v.18 no.4
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    • pp.433-438
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    • 1997
  • (p-Methylbenzyl)-o-cyanopyridinium hexafluoroantimonate, a new catalyst, was synthesized by the reaction of o-cyanopyridine with α-bromo-p-xylene followed by exchange of counteranion with SbF6θ. We examined the effect of the catalyst on the bulk polymerization of tetrahydrofuran under various conditions. The catalytic activity was best in the presence of 1 : 1 of epichlorohydrin used as cocatalyst versus catalyst concentration. The resulting polymers had relatively low conversions in 1.0-40%. Their number average molecular weights were in the range of 800 to 5300. Propagation rate increased with increase in temperature according to an Arrhenius expression giving an activation energy of 62 KJ/mol. We also found catalyst proceeds via a cationic mechanism.

Photochemistry of Conjugated Polyacetylenes. Photoreaction of 1,4-Diphenylbutadiyne with a Mixture of Olefins

  • Chang Beom Chung;Geon-Soo Kim;Jang Hyuk Kwon;Shim Sang Chul
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.506-510
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    • 1993
  • Irradiation of 1,4-diphenylbutadiyne (DPB) with a mixture of electron-deficient and electron-rich olefins in deaerated tetrahydrofuran yields a 1 : 1 primary photoadduct between DPB and electron-deficient olefins. Irradiation of the primary photoadduct of DPB and dimethyl fumarate (DMFu) with various olefins such as DMFu, acrylonitrile (AN), and 2,3-dimethyl-2-butene (DMB) in deaerated tetrahydrofuran yields regiospecific 1 : 1 photoadducts. The electron-deficient olefins are more reactive than electron-rich olefins in the photoreaction which proceeds through excited triplet state.

Thermally Crosslinkable Second-Order Nonlinear Optical Polymer Using Pentaerythritol tetrakis(2-mercaptoacetate) as Crosslinker

  • 한관수;심상연;이용석;장웅상;김낙중
    • Bulletin of the Korean Chemical Society
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    • v.19 no.11
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    • pp.1168-1171
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    • 1998
  • Two kinds of second-order nonlinear optical copolymers were prepared by the copolymerization of the vinyl monomers containing NLO chromophore, methacrylic acid, and methyl methacrylate or butyl methacrylate. Glass transition temperatures (Tg of copolymers were around 130 ℃. The copolymers were soluble in common organic solvents such as tetrahydrofuran (THF), cyclohexanone, and N,N-dimethylformamide (DMF). The crosslinked copolymer was obtained by thermal treatment using pentaerythritol tetrakis(2-mercaptoacetate) as a crosslinker and became insoluble in tetrahydrofuran (THF) and N,N-dimethylformamide (DMF). Poling was carried out at 120 ℃ for 20 min and identified with UV-Vis spectroscopy. Electro-optic coefficient (r33) measurement showed a value of 35 pm/V for polymer 2 at 633 nm. Temporal stability of copolymers was improved owing to the crosslinked network, which was successfully obtained at 170 ℃ for 30 min after poling.

Reaction of 2,2'-Biphenoxyborane in Tetrahydrofuran with Selected Organic Compounds Containing Representative Functional Groups

  • Cha, Jin-Soon;Kim, Jong-Mi;Lee, Ja-Cheol;Lee, Hyung-Soo
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.612-617
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    • 1991
  • The approximate rates and stoichiometry of the reaction of excess 1,3,2-biphenyldioxaborepin [2,2'-biphenoxyborane (BPB)] with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, hydride to compound being 4 : 1, room temperature) was examined in order to define the characteristics of the reagent for selective reductions and compare its reducing power with those of other substituted boranes. The results indicate that BPB is unique and the reducing power is much stronger than that of other dialkoxyboranes, such as catecholborane and di-s-butoxyborane. BPB reduces aldehydes, ketones, quinones, lactones, tertiary amides, and sulfoxides readily. Carboxylic acids, anhydrides, esters, and nitriles are also reduced slowly. However, the reactions of acid chlorides, epoxides, primary amides, nitro compounds, and disulfides with this reagent proceed only sluggishly.

Reaction of Dipyrrolidinoaluminum Hydride in Tetrahydrofuran with Selected Organic Compounds Containing Representative Functional Groups

  • Jin Soon Cha;Oh Oun Kwon;Jong Mi Kim;Jae Cheol Lee
    • Bulletin of the Korean Chemical Society
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    • v.15 no.8
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    • pp.644-649
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    • 1994
  • The approximate rates and stoichiometry of reaction of excess dipyrrolinoaluminum hydride (DPAH) with selected organic compounds containing representative functional groups under standardized conditions (tetrahydrofuran, 0, reagent : compound=4 : 1) were examined in order to define the characteristics of the reagent for selective reductions. The reducing ability of DPAH was also compared with that of bis(diethylamino)aluminum hydride (BEAH). The reagent appears to be stronger than BEAH, but weaker than the parent reagent in reducing strength. DPAH shows a unique reducing characteristics. Thus, the reagent reduces aldehydes, ketones, esters, acid chlorides, epoxides, and nitriles readily. In addition to that, ${\alpha},\;{\beta}$-unsaturated aldehyde is reduced to the saturated alcohol. Quinone are reduced cleanly to the corresponding 1,4-reduction products. The examination for possibility of achieving a partial reduction to aldehydes was also performed. Both primary and tertiary aromatic carboxamides are converted to aldehydes with a limiting amount of DPAH. Finally, disulfides and sulfoxides are readily reduced to thiols and sulfides, respectively.

Light Scattering Study on Polymer Chain Conformation: Polystyrene in Good Solvents

  • Park, Sang-Wook;Chang, Tai-Hyun;Lee, Jo-Woong;Pak, Hyung-Suk
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.682-685
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    • 1991
  • Solvent dependence of the static solution properties of a polymer chain was studied by static light scattering technique for polystyrene in three good solvents, toluene, tetrahydrofuran and $CCl_4$. The molecular parameters such as radius of gyration and second virial coefficients of polystyrene are found to be clearly larger in THF than the other two solvents and they are in the order of tetrahydrofuran > toluene > $CCl_4$. The radius of gyration shows the same order while the difference is smaller. Nontheless, the penetration functions are found to have a comparable value about 0.2, which confirms the universality of the penetration function in high expansion regime over different nature of solvents.

Reduction of Selected Carbonyl Compounds with 8-Oxyquinoline Dihydroboronite. Selective Reduction of Aldehydes in the Presence of Ketones

  • Kim, Sung-Gak;Yang, Sung-Bong;Kang, Ho-Jung
    • Bulletin of the Korean Chemical Society
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    • v.5 no.6
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    • pp.240-244
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    • 1984
  • 8-Oxyquinoline dihydroboronite is prepared by mixing equimolar amounts of 8-hydroxyquinoline and borane-dimethyl sulfide complex in tetrahydrofuran at room temperature and its structure is determined by spectroscopic methods. The reagent is shown to be an extremely mild reducing agent and reduces aldehydes, cyclohexanones, and acid chlorides to some extent. The reagent in the presence of 0.1 equiv of boron trifluoride etherate in tetrahydrofuran at room temperature reduces selectively aldehydes in the presence of ketones, while the reagent in the presence of 1 equiv of boron trifluoride etherate rapidly reduces simple aldehydes and ketones but does not reduce carboxylic acids, esters, and amides.

Reaction of Di-s-butoxyborane in Tetrahydrofuran with Selected Organic Compounds containing Representative Functional Groups. Catalytic Effect of Tetraalkoxyborate on the Reaction of Dialkoxyborane$^\dag$

  • Cha, Jin-Soon;Lee, Jae-Cheol;Kim, Jin-Euog;Lee, Kwang-Woo;Yoon, Mal-Sook
    • Bulletin of the Korean Chemical Society
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    • v.8 no.4
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    • pp.304-310
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    • 1987
  • The approximate rate and stoichiometry of the reaction of excess di-s-butoxyborane with selected organic compounds containing representative functional groups under standardized conditions (tetrahydrofuran, $25^{\circ}C)$ were examined in order to define the characteristics of the reagent for selective reductions. And the catalytic effect of lithium tetra-s-butoxyborate on the reaction of di-s-butoxyborane was also studied in order to increase the utility of this reducing system. Di-s-butoxyborane reacts only with simple aldehydes. However the addition of 2.5 mole % of lithium tetra-s-butoxyborate shows the tremendous rate enhancement of reaction for aldehydes, ketones, anhydrides, acid chlorides, lactones, and epoxides. This catalytic effect is assumed to in situ formation of lithium trialkoxyborohydride.

Acclimation of magnetic activated sludge with 1,4-dioxane and analysis of bacterial flora in the sludge

  • Toshiyuki Nikata;Hayato Ogihara;Yasuzo Sakai
    • Progress in Superconductivity and Cryogenics
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    • v.25 no.3
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    • pp.7-12
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    • 2023
  • Isolation of pollutant-degrading bacteria is important in bioaugmentation, one of the methods for biological degradation of environmental contaminants. We focused on the magnetic activated sludge (MAS) process as a culture method that efficiently concentrates degrading bacteria, and cultured activated sludge with 1,4-dioxane as a model pollutant. After 860 days of operation, MLVSS, which indicates the amount of sludge, increased from 390 mg/L to 10,000 mg/L, and the removal rate of organic matter including 1,4-dioxane, tetrahydrofuran, and glucose in the artificial wastewater reached up to 97%. Based on these results, the MAS process was successfully used to acclimate activated sludge with 1,4-dioxane. Bacterial flora analysis in the MAS showed that bacteria of the genus Pseudonocardia, already reported as 1,4-dioxane degrading bacteria, play an important role in the degradation of this pollutant. The MAS process is a suitable culture method for acclimation of environmental pollutants, and the findings indicate that it can be used as an enrichment unit for pollutant-degrading bacteria.