• Title/Summary/Keyword: 1,2-Ketone

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Stereoselective Reduction of Methyl Vinyl Ketone Dimer

  • Jun, Jong-Gab;Shin, Dong-Gyun;Lee, Chang-Kiu;Sin, Kwan-Seog
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.307-309
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    • 1990
  • The stereoselectivity of the reaction between methyl vinyl ketone dimer, which contains two possible sites of chelation, and zinc borohydride or diisobutylaluminum hydride has been studied in order to illuminate the factors involved in the high levels of asymmetric induction obtained in the bicyclic system. The conditions for the formation of the exo-5,7-dimethyl-6,8-dioxabicyclo[3.2.1]octane are DIBAH reduction of MVK dimer in ether at reflux followed by acidic cyclizatioan, and for the endo isomer are $Zn(BH_4)_2$ reduction with $ZnCl_2$ at $0^{\circ}C.$.

Anionic Synthesis of Dipyridine Chain End-Functionalized Polystyrene and Polybutadiene (리빙 음이온 중합에 의한 Dipyridine 말단 관능화 폴리스티렌 및 폴리부타디엔의 합성)

  • Ji, Sang-Chul;Lee, Jong-Seop;Kim, Doo-Hwan;Kang, Cheol-Han;Park, Jong-Hyuk;Lee, Bum-Jae
    • Polymer(Korea)
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    • v.34 no.2
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    • pp.159-165
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    • 2010
  • Dipyridine-terminated polystyrenes and polybutadienes were synthesized by the chain endfunctionalization reaction of polystyryllithium (PSLi) and polybutadienyllithium (PBDLi) with di(2-pyridyl) ketone(DPK) using a living anionic polymerization method in the Ar-glove box. Living polymeric lithiums with low molecular weights (Mw=1000~2000 g/mol) were used to investigate the chain end-functionalization yield with DPK and the degree of coupling reaction by the attack of organolithium to the pyridine ring in the presence of TMEDA using GPC, $^1H$-NMR, $^{13}C$ analysis. DPK-terminated PBD exhibited much higher functionalization yield and less amount of coupling reaction compared with DPK-terminated PS. 86% functionalization yield with 9% degree of coupling was obtained when the PBDLi was added dropwise to DPK solution at room temperature. The functionalization yield was increased as the reaction temperature decreased, however, no LiCl effect was observed in this chain end-functionalization reaction with DPK.

Synthesis and Substituent Effects in Substituted Styryl 4-Methoxy-1-Naphthyl Ketones (다양한 치환기가 붙은 Styryl 4-Methoxy-1-Naphthyl Ketone의 합성과 치환기 효과에 관한 연구)

  • Thirunarayanan, G.;Ananthakrishna Nadar, P.
    • Journal of the Korean Chemical Society
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    • v.50 no.3
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    • pp.183-189
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    • 2006
  • A series of substituted styryl 4-methoxy-1-naphthyl ketones [(2E)-1-(4-methoxy-1-naphthyl)-3-phenyl-2-propen-1-ones] were synthesized using facile method of microwave assisted condensation reaction. The yield of chalcones is more than 90%. They are characterized by their physical constants, micro analysis, infrared (KBr, 4000-400 cm?1) and NMR both 1H and 13C spectral data. From infrared spectra, the s-cis and s-trans stretching vibrations of carbonyl group, from NMR spectra the ethylenic proton and carbon chemical shifts (ppm) are assigned. These spectral data are correlated with various Hammett substituent constants. From the results of statistical analysis the effect of substituents on CO, ? and ? proton and carbons are explained.

Effect of Trialkylborane on the Stereochemistry of Ketone Reduction with Lithium Borohydride

  • Nung-Min Yoon;Jin-Soon Cha;Won-Suh Park
    • Bulletin of the Korean Chemical Society
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    • v.4 no.1
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    • pp.14-17
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    • 1983
  • The effects of trialkylborane on the stereochemistry of ketone reduction with lithium borohydride were studied for the four representative ketones, namely 4-t-butylcyclohexanone, 2-methylcyclohexanone, norcamphor, and camphor. The presence of trialkylborane increased the yields of the less stable alcohols. For example, in the presence of tri-s-butylborane, 42 % yield of cis-4-t-butylcyclohexanol was observed whereas only 8 % yield with lithium borohydride alone in the reduction of 4-t-butylcyclohexanone. The in situ formation of lithium trialkylborohydride, by the hydride transfer from lithium trialkoxyborohydride to trialkylborane, was demonstrated as a possible mechanism for the catalytic effect of trialkylborane.

A Study on the Flash Point Determination of Toluene-o-Xylene and Toluene-Methyl Ethyl Ketone Mixtures by Air-Blowing Method (유통법을 사용한 톨루엔과 o-크실렌 및 톨루엔과 메틸에틸케톤 혼합용제의 인화점 측정에 관한 연구)

  • 신열우;목연수;최일곤
    • Journal of the Korean Society of Safety
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    • v.10 no.2
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    • pp.92-96
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    • 1995
  • The flash point is generally used as a hazardous index of fire or explosion of a flammable liquid. In this study, the lower flash points and the upper flash points according to the composition of Toluene-o-Xylene and Toluene-Methyl Ethyl Ketone mixtures are determined by air-blowing method. As results, relations between the flash points and the compositions of mixtures ; (1) for Toluene-o-Xylene mixtures $T_{fL}$=25.23 $\alpha$ +5.34 $T_{fu}$=27.36 $\alpha$ +40.50 (2) for Toluene-Methyl Ethyl Keton mixtures $T_{fL}$=10.00 $\beta$-5.00 $T_{fu}$=16.91 $\beta$+20.45.

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A Study on Desorption Efficiency for Polar Solvents Collected on Charcoal Tube (활성탄관에 포집된 극성유기용제의 탈착효율에 관한 연구)

  • Kim, Kyeong-Ran;Paik, Nam-Won
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.5 no.1
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    • pp.104-118
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    • 1995
  • This study was performed to evaluate factors affecting desorption of organic solvents collected on charcoal tube and to find out the optimum condition. Desorption efficiency for polar analytes was improved when several polar desorption solvents such as methanol, dimethylformamide(DMF), 2-(2-butoxyethoxy)ethanol were added to carbon disulfide($CS_2$). The best improvement was achieved when 10% dimethylformamide(DMF) in $CS_2$ was used as desorption solvent. During storage of polar analytes, recovery was greatly reduced. Especially, the recovery of cyclohexanone was decreased to 18.1 % after a month storage at $34^{\circ}C$. After two weeks storage, recovery of polar analytes was sharply decreased. Water adsorbed on charcoal interfered the recovery of polar analytes but didn't interfere that one of nonpolar solvent, toluene. When 10% DMF in $CS_2$ was used as desorption solvent, the effect of water on recovery was decreased, comparing with Desorption efficiency increased when analyte loading increased, and usage of 10% DMF in $CS_2$ decreased the loading effect. Increasing volume of desorption solvent was not effective to improve desorption efficiency of analytes when 10% DMF was used. Continuous shaking and sonication is not helpful to increase the desorption efficiency of analytes except cyclohexanone using 10% DMF. When silica gel used as adsorbent, methanol was better desorbent than dimethylsulfoxide. Analytes adsorbed on silica gel showed high recovery in low concentration and less affected by humidity. On the basis of this study, the following conclusions have been drawn. To improve the recovery of polar organic materials in air samples, it is necessary to analyze samples as soon as possible after they were collected. Otherwise, samples must be stored at low temperature. Using two components of desorption solvents, such as 10% DMF in $CS_2$, the effects of loading and humidity decreased for polar analytes such as methyl ethyl ketone and methyl isobutyl ketone. When work place has high humidity with low concentration of polar organic solvents, silica gel can be used as adsorbent, because it produces quantitative recovery for polar analytes at this condition. But it should be noted that high humidity makes breakthrough easy in silica gel samples.

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Reaction of Lithium Gallium Hydride with Selected Organic Compounds Containing Representative Functional Groups

  • Choe, Jeong Hun;Yun, Mun Yeong;Yun, Jong Hun;Jeong, Dong Won
    • Bulletin of the Korean Chemical Society
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    • v.16 no.5
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    • pp.416-421
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    • 1995
  • The approximate rates and stoichiometry of the reaction of excess lithium gallium hydride with selected organic compounds containing representative functional groups were examined under the standard conditions (diethyl ether, 0 $^{\circ}C)$ in order to compare its reducing characteristics with lithium aluminum hydride and lithium borohydride previously reported, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, and amines evolve hydrogen rapidly and quantitatively. However lithium gallium hydride reacts with only one active hydrogen of primary amine. Aldehydes and ketones of diverse structure are rapidly reduced to the corresponding alcohols. Conjugated aldehyde and ketone such as cinnamaldehyde and methyl vinyl ketone are rapidly reduced to the corresponding saturated alcohols. p-Benzoquinone is mainly reduces to hydroquinone. Caproic acid and benzoic acid liberate hydrogen rapidly and quantitatively, but reduction proceeds slowly. The acid chlorides and esters tested are all rapidly reduced to the corresponding alcohols. Alkyl halides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced slowly. Benzonitrile consumes 2.0 equiv of hydride rapidly, whereas capronitrile is reduced slowly. Nitro compounds consumed 2.9 equiv of hydride, of which 1.9 equiv is for reduction, whereas azobenzene, and azoxybenzene are inert toward this reagent. Cyclohexanone oxime is reduced consuming 2.0 equiv of hydride for reduction at a moderate rate. Pyridine is inert toward this reagent. Disulfides and sulfoxides are reduced slowly, whereas sulfide, sulfone, and sulfonate are inert under these reaction conditions. Sulfonic acid evolves 1 equiv of hydrogen instantly, but reduction is not proceeded.

Active Material Crossover through Sulfonated Poly (Ether Ether Ketone) Membrane in Iron-Chrome Redox Flow Battery (철-크롬 산화환원흐름전지에서 Sulfonated Poly (Ether Ether Ketone)막의 활물질 Crossover)

  • Kim, Young-Sook;Oh, So-Hyeong;Kim, You-Jeong;Kim, Seong-ji;Chu, Cheun-Ho;Park, Kwonpil
    • Korean Chemical Engineering Research
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    • v.57 no.1
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    • pp.17-21
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    • 2019
  • The redox flow battery (RFB) is a large-capacity energy storage equipment, and the vanadium redox flow cell is a typical RFB, but VRFB is expensive. Iron-chrome RFBs are economical because they use low-cost active materials, but their low performance is an urgent problem. One of the reasons for the low performance is the crossover of the active materials. In this study, the sulfonated Poly (ether ether ketone) (sPEEK) membrane, which is a hydrocarbon membrane, was used instead of the fluorine membrane to reduce the crossover of the active materials. The chromium ion permeability of the sPEEK membrane was $1.8{\times}10^{-6}cm^2/min$, which was about 1/33 of that of the Nafion membrane. Thus, it was shown that the use of the sPEEK membrane instead of the fluorine membrane could solve the high active material crossover problem. The activation energy of iron diffusion through the sPEEK membrane was 24.9 kJ/mol, which was about 66% of Nafion membrane. And that the e-PTFE support in the polymer membrane reduces the active material crossover through Iron-Chrome Redox Flow Battery (ICRFB).

Effects of Methyl Ethyl Ketone and Methanol on the Survival and Reproduction of Paronychiurus kimi (Collembola: Onychiuridae) (메틸에틸케톤과 메탄올이 김어리톡토기의 사망 및 번식에 미치는 영향)

  • Wee, June;Lee, Yun-Sik;Son, Jino;Kim, Yongeun;Mo, Hyoung-ho;Cho, Kijong
    • Korean Journal of Environmental Biology
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    • v.35 no.2
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    • pp.169-174
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    • 2017
  • Acute and chronic toxicities of methyl ethyl ketone and methanol were investigated on Paronychiurus kimi (Collembola), for evaluating the potential effects of accidental exposures of these chemical substances on the terrestrial environments. This study was undertaken to establish a toxicity database for these chemical substances, which was required for the preparation of the response compensation and liability act for agricultural production and environmental damage. The 7-d acute toxicity and 28-d chronic toxicity were conducted using the OECD artificial soil spiked with varying, serially diluted concentrations of methyl ethyl ketone and methanol. Mortality was recorded after 7-d and 28-d of exposures, and the number of juveniles were determined after 28-d of exposure in the chronic toxicity test. In both assessments, methanol was more toxic than methyl ethyl ketone in terms of mortality ($LC_{50}$) and reproduction ($EC_{50}$). The 7-d $LC_{50}$ of methyl ethyl ketone and methanol were 762 and $2378mg\;kg^{-1}$ soil dry wt., respectively, and the 28-d $LC_{50}s$ were 6063 and $1857mg\;kg^{-1}$ soil dry wt., respectively. The 28-d $EC_{50}$ of methyl ethyl ketone and methanol were 265 and $602mg\;kg^{-1}$ soil dry wt., respectively. Comparison of results obtained in this study with literature data revealed that P. kimi was more sensitive to methanol than other soil invertebrates. However, given the high volatility of the chemicals tested in this study, further studies are necessary to improve the current test guideline, or to develop new test guidelines for an accurate assessment of chemicals that require toxicity databases for chemical accidents.

Poly(arylene ether ketone) block copolymer prepared through sulfonation process for polymer electrolyte membrane fuel cell (술폰화 공정을 통해 제조한 고분자 전해질형 연료전지용 폴리(아릴렌 이서 케톤) 블록 코폴리머)

  • Jang, Hyeri;Nahm, Keesuk;Yoo, Dongjin
    • Journal of Energy Engineering
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    • v.25 no.3
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    • pp.66-72
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    • 2016
  • In this study, a sulfonated poly(arylene ether ketone) block copolymer was prepared from hydrophilic oligomer and hydrophobic oligomer. The structure of the prepared membrane was characterized by $^1H$-NMR, FT-IR and GPC. The $M_w$(weight-average molecular weights) of the polymer was $209,700g\;mol^{-1}$ and the molecular weight distribution($M_w/M_n$) of 1.25 was obtained. The prepared membrane showed excellent thermal stability with gradual weight loss up to $200^{\circ}C$. The proton conductivity of SPAEK block copolymer reached the maximum of $9.0mS\;cm^{-1}$ at $90^{\circ}C$ under 100% relative humidity (RH). From the observed results, it is necessary to do more aggressive attempt to study the possibility of application as an ion-conductive composite electrolyte.