• Title/Summary/Keyword: tetrahydrofuran

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Reaction of Potassium 9-sec-Amyl-9-boratabicylco[3.3.1]nonane with Selected Organic Compounds Containing Representative Functional Groups

  • Cha Jin Soon;Yoon Mal Sook;Lee Kwang Woo;Lee Jae Cheol
    • Bulletin of the Korean Chemical Society
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    • v.10 no.1
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    • pp.75-80
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    • 1989
  • The approximate rates and stoichiometry of the reaction of excess potassium 9-sec-amyl-9-boratabicylco[3.3.1]nonane (K 9-sec-Am-9-BBNH) with selected organic compounds containing representative functional goups under standardized conditions (tetrahydrofuran, $0^{\circ}C)$ were examined in order to explore the reducing characteristics of the reagent for selective reductions. The reagent readily reduces aldehydes, ketones, acid chlorides and epoxides to the corresponding alcohols. However, carboxylic acid, aliphatic nitriles, t-amides, and some sulfur compounds show very little reactivity or no reactivity to this reagent. The most interesting feature of the reagent is that aromatic nitriles are reduced moderately to the corresponding aldehyde stage, wheras aliphatic nitriles are inert. In addition, the reagent shows a high stereoselectivity toward cyclic ketones at $0^{\circ}C$ and - $25^{\circ}C.$ The selectivity exhibited at $0^{\circ}C$ is comparable to that by lithium trisiamylborohydride at that temperature.

Lipophilic Crown-4 Derivatives as Lithium Ionophores for Lithium Ion Selective Liquid Membrane Electrodes

  • Jae Sang Kim;Sung Ouk Jung;Shim Sung Lee;Si-Joong Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.1
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    • pp.123-127
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    • 1993
  • New lipophilic Crown-4 compounds of 16-membered rings containing furan (neutral carrier,I), tetrahydrofuran (neutral carrier,II) and lithium complex of the latter (neutral carrier,III) have been synthesized and tested as the active sensors for lithium ion in poly(vinyl chloride) (PVC) membrane electrode, in the presence and absence of an anion excluder, tetrakis(4-chloro-phenyl)borate (KTClPB), 2-nitrophenyl phenyl ether (NPPE), tris(2-ethylhexyl)phosphate (TEHP), o-nitrophenyl octyl ether (NPOE), dioctyl adipate (DOA), bis(2-ethylhexyl)adipate (BEHA), di-n-octylphenyl phosphonate (DOPP) were used as plasticizing solvent mediators. The electrode response function had a nearly Nernstian slope of 54-61 mV per decade (25$^{\circ}$C) within the concentration range of $10^{-1}-10^{-4}$ M LiCl and the detection limits for all electrodes were ca. $5{\times}10^{-4}$ M. The response time of the electrode was faster at the higher lithium concentration and the response of the electrode was stable for longer than 6 months. The sensor membranes exhibit improved response times and increased lifetimes as compared to the system described earlier.

Electronic Absorption and Raman Spectroscopic Studies of ${\alpha},{\omega}$-Diphenylpolyenyl Anions with Odd Number of Polyene Carbons

  • Kim, Jin Yeol;Kim, Eung Ryeol;Ju, Jae Beom
    • Bulletin of the Korean Chemical Society
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    • v.22 no.8
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    • pp.837-841
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    • 2001
  • The electronic absorption and Raman spectra of $\alpha\omega-diphenylpolyenyl$, anions Ph(CH)nPh- (DPn- , n = 3, 5, 7, 9, and 13), with odd number of carbons at the polyene part, have been studied in the tetrahydrofuran (THF) solutions and in their solid film states, respectively. In the case of Raman spectra for DPn- , the frequencies and relative intensities of some Raman peaks regularly change with the increase of polyene chain length. The spectral patterns of anions (DPn- ) are very similar with those of radical anion (DPn${\cdot}$- ). However, the C=C stretching peaks of DPn- anions are observed in the 25-35 cm-1 higher frequency region than those of DPn${\cdot}$- radical anions. In the case of long chain models such as DP9- and DP13- , the C=C stretching peaks are observed in even higher frequency region than those of the corresponding neutral polyenes such as DP8, DP10, and DP12. The Raman patterns of DPn- anions in the THF solutions are similar with those in their solid film states. On the other hand, their electronic absorption spectra show a considerable difference each other. The n- ${\pi}*$ electronic absorption bands of DPn- anions in the THF solutions have been observed in the 0.27-0.39 eV lower energy region than those in their solid film states due to the solvent effects on polyene anions.

Solvent-Induced Photoemissions of High-Energy Chromophores of Conjugated Polymer MEH-PPV: Role of Conformational Disorder

  • Traiphol, Rakchart;Charoenthai, Nipaphat
    • Macromolecular Research
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    • v.16 no.3
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    • pp.224-230
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    • 2008
  • This study examined the photoemission behaviors of isolated chains of poly[2-methoxy, 5-(2'-ethylhexyloxy)-1,4-phenylenevinylene](MEH-PPV) dispersed in various solvents including dichloromethane, chloroform and tetrahydrofuran(THF). A change in polymer-solvent interactions in these solutions caused the MEH-PPV chains to adopt different local conformations, which in turn affected their radiative de-excitation pathways. For the polymer in dichloromethane and chloroform, in which the conjugated chains are relatively extended, photoemission occurs mostly at the long chromophores with lowest HOMO-LUMO energy gap. Their emission spectra showed a main peak at ${\sim}560\;nm$. Dual photoemission of high- and low-energy chromophores was observed when the conjugated chains were forced to partially collapse in a poor solvent THF. Novel high-energy peaks and a typical low-energy peak were detected at ${\sim}414\;nm$ and ${\sim}554\;nm$, respectively. The observation of the high-energy peaks indicates significant suppression of the intrachain energy transfer process, which was attributed to the increase in conformational disorder in the partially collapsed coils. An analysis of the excitation spectra suggests that the high-energy peaks belong to short chromophores constituting of one or two repeat units. This study systematically investigated the effects of polymer concentration, temperature and single bond defects along the backbone on the photoemission of the high-energy chromophores.

Reduction of Representative Organic Functional Groups with Gallane-Trimethylamine

  • 최정훈;오영주;김민정;황북기;백대진
    • Bulletin of the Korean Chemical Society
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    • v.18 no.3
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    • pp.274-280
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    • 1997
  • The rates and stoichiometry of the reaction of gallane-trimethylamine with selected organic compounds containing representative functional groups were examined in tetrahydrofuran solution under standardized conditions (THF, 0 ℃). And its reducing characteristics were compared with those of aluminum hydride-triethylamine(AHTEA). The rate of hydrogen evolution from active hydrogen compounds varied considerably with the nature of the functional group and the structure of the hydrocarbon moiety. Alcohols, phenol, amines, thiols evolved hydrogen rapidly and quantitatively. Aldehydes and ketones were reduced moderately to the corresponding alcohols. Cinnamaldehyde was reduced to cinnamyl alcohol, which means that the conjugated double bond was not attacked by gallane-trimethylamine. Carboxylic acids, esters, and lactones were stable to the reagent under standard conditions. Acid chlorides also were rapidly reduced to the corresponding alcohols. Epoxides and halides were inert to the reagent. Caproamide and nitrile were stable to the reagent, whereas benzamide was rapidly reduced to benzylamine. Nitropropane, nitrobenzene and azoxybenzene were stable to the reagent, whereas azobenzene was reduced to 1,2-diphenylhydrazine. Oximes and pyridine N-oxide were reduced rapidly. Di-n-butyl disulfide and dimethyl sulfoxide were reduced only slowly, but diphenyl disulfide was reduced rapidly. Finally, sulfones and sulfonic acids were inert to the reagent under the reaction.

Selective Reduction with Zinc Borohydride. Reaction of Zinc Borohydride with Selected Organic Compounds Containing Representative Functional Groups (수소화붕소아연에 의한 선택환원. 수소화붕소아연의 대표적 유기화합물과의 반응)

  • Yoon Nung Min;Ho Jun Lee;Hye Kyu Kim;Jahyo Kang
    • Journal of the Korean Chemical Society
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    • v.20 no.1
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    • pp.59-72
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    • 1976
  • The addition of one mole of zinc chloride to 2.33 moles of sodium borohydride in tetrahydrofuran at room temperature gave a clear chloride-free supernatant solution of zinc borohydride after stirring three days and standing at room temperature.The approximate rates and stoichiometry of the reaction of zinc borohydride with 54 selected organic compounds were determined in order to test the utility of the reagent as a selective reducing agent. Aldehydes and ketones were reduced rapidly, aromatic ketones being somewhat slowly, and the double bond of cinnamaldehyde was not attacked. Acyl halides were reduced rapidly within one hour, but acid anhydrides were reduced at a moderate rate. Carboxylic acids, both aliphatic and aromatic, were slowly reduced to alcoholic stage. Esters were inert to this reagent but a cyclic ester, γ-butyrolactone, was slowly attacked. Primary amides were reduced slowly with partial evolution of hydrogen, whereas tertiary amides underwent neither reduction nor hydrogen evolution. Epoxides and nitriles were all inert, as well as nitro, azo, and azoxy compounds. Cyclohexanone oxime and phenyl isocyanate were reduced slowly but pyridine was inert. Disulfide, sulfoxide, sulfone and sulfonic acids were stable to this reagent.

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Study on thermodynamic and kinetic properties of $CO_2/H_2$ hydrate with THF, TBAB addition (THF, TBAB 첨가에 의한 $CO_2/H_2$ 하이드레이트의 특성 연구)

  • Ha, Rin;Lee, Hyun Ju;Park, Young Bin;Shin, Jae Ho;Kim, Yang Do
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.11a
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    • pp.153.2-153.2
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    • 2010
  • 화력발전 분야에서 $CO_2$ 분리는 크게 연소전 탈탄소화(pre-combustion capture)와 연소후 포획(post-combustion capture)으로 나누어진다, 연소후 포획은 연료를 연소한 후 발생하는 $CO_2$$N_2$가스에서 $CO_2$를 분리하는 기술로 흡수나, 흡착, 막분리 등을 주로 이용한다, 연소전 탈탄소화는 연소 전에 $CO_2$가 발생되지 않도록 하는 기술로써, 부분 산화나 개질 및 수성가스 변위반응 등이 포함되며 생성된 $H_2$$CO_2$를 분리하여 수소를 생산하는 기술($CO_2/H_2$분리가 핵심)이다. 우리나라는 대부분 연소후 포획 위주로 많은 연구가 진행되어 왔다, 하지만 최근 고유가 시장이 형성되면서 석탄화력 발전 및 복합가스발전(IGCC)에 필요한 연소전 탈탄소화($H_2/CO_2$ 가스로부터 $CO_2$ 회수) 연구에 산업적 관심이 급상승되고 있다. 특히, 연소전 탈탄소화 과정에서는 높은 자체압력(약 2.5 - 5.0MPa)과 비교적 높은 농도의 $CO_2$(약 40%의)가 발생되기 때문에, 연소전 탈탄소화는 가스하이드레이트 형성/분해 원리가 가장 잘 적용될 수 있는 기술이라 할 수 있다. 본 연구에서는 가스 하이드레이트 형성원리를 이용하여 정온 정압 조건에서 $CO_2/H_2$ 하이드레이트를 제조하였으며 특히, 하이드레이트 형성 촉진제인 THF(Tetrahydrofuran)와 TBAB(Tetra-n-butyl ammonium bromide)를 첨가하여 각각 0.5, 1, 3mol% 농도에 따른 상평형 및 속도론 실험을 수행 하였다. 또한 라만 분석을 통하여 $CO_2$ 회수 분리에 대한 연구도 병행하였다. 이러한 연구는 연소전 탈탄소화 기술에서의 $CO_2$ 회수 분리에 대한 핵심 연구임과 동시에 탄소배출권 규제에 실질적인 기여를 할 수 있을 것으로 사료된다.

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Process Development for Recovery of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine from Compressible Polymer-Bonded Explosives Through the Pretreatment of Polymer Binders (폴리머 바인더의 선처리를 통한 압축형 복합화약으로부터 octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine의 회수 공정 개발)

  • Kim, Hyejoo;Kim, DongWoo;Huh, Eugene;Park, Sewon;Lee, Chang-Ha;Ahn, Ik-Sung;Lee, Keun Deuk
    • Journal of the Korea Institute of Military Science and Technology
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    • v.23 no.5
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    • pp.523-531
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    • 2020
  • Extraction and anti-solvent crystallization were proposed to recover octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from pressed polymer bonded explosives(PBXs). DXC-57 and DXC-59, whose polymeric binders are Estane and HyTemp with dioctyl adipate plasticizer, respectively, were used as pressed PBX models. Estane of DXC-57 was removed by washing with tetrahydrofuran prior to extraction, which enabled the crystallization of HMX at a low degree of supersaturation, sufficient to obtain β-form HMX. Using dimethyl sulfoxide and ethanol as the extraction solvent and the anti-solvent for crystallization, respectively, HyTemp and dioctyl adipate in DXC-59 were separated from HMX. The purity of recovered β-form HMX was higher than 99 %.

The Solvent Effect on the Chemical Changes in Binary Mixture : i.e. THF-H2O System (Ⅰ) (이성분 혼합용매에서 화학변화에 미치는 용매의 영향 : THF-$H_2O$ (제1보). 용매화된 전자의 흡수스펙트럼)

  • Yu-Chul Park;Sang Oh;P. Krebs;U. Schindewolf
    • Journal of the Korean Chemical Society
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    • v.24 no.5
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    • pp.371-379
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    • 1980
  • The spectral properties of the solvated electrons in tetrahydrofuran(THF)-water binary system have been investigated. In this study, the solvated electrons have been produced by applying nsec Q-switch Nd(YAG) laser photolysis technique. The experimental method photolysis were schematically described. The solvent and the temperature effects on the absorption spectrum of solvated electrons have also been studied. The observation of the spectrum with increasing THF content and temperatue showed a trend that the former shifted to longer wavelength and the other showed broadening effect. The half-life of solvated electrons were also increased with THF content. The absorption maxima of the mixtures were always observed in the middle of that of pure water and THF. The correlation between the volume and the absorption energy of solvated electrons were discussed from the results.

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Effect of the Addition of Propanol to PVC Solution on the Structure of Thin Film and its Surface Property (프로판올 첨가에 따른 PVC 용액의 박막 형성과 표면 특성에 미치는 영향)

  • Park, Jae Nam;Shin, Young Sik;Lee, Won Gyu
    • Applied Chemistry for Engineering
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    • v.26 no.1
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    • pp.35-39
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    • 2015
  • Polyvinylchloride (PVC) thin films having a microporous structure could be prepared by using the solubility difference in solvents. PVC thin film with a water contact angle of $150^{\circ}$ or more was obtained from the PVC solution consisting of the mixture of tetrahydrofuran as a solvent and propanol as a non-solvent. In the drying process of dip-coated PVC film, the increase of drying temperature reduced the tendency of roughened surface, which led the decrease of surface hydrophobicity. As the addition of propanol in the solution with 1 wt% PVC increased, the uniformity of surface roughness was improved. In the case of oxygen plasma treatments, even though the surface structure of PVC thin film was not notably changed, the surface property of the film was changed from the super-hydrophobicity to hydrophilicity as a function of the plasma exposing time.