• The Microorganisms and Industry
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• v.20 no.1
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• pp.18-22
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• 1994

효소는 반응을 효율적으로 촉진시킬 뿐만 아니라 기질 및 입체특이성을 갖고 있어 광학활성 화합물을 합성하는데 매우 유용한 촉매이다. 효소 반응은 일반적으로 수용액에서 진해오디지만, 유기 용매를 포함하는 용액에서도 가능하다. 대부분의 유기 화학 반응이 유기 용매에서 진행된다는 점을 생각할 때, 유기 용매에서 효소 반응을 이용한 유기합성이 갈수록 중요해지고 있다. 본 글에서는 유기 용매에서 사용가능한 대표적인 효소인 지질 가수분해 효소(lipase)를 이용한 유기합성에 대해서 간략히 기술하고자 한다.

• Journal of the Korean Chemical Society
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• v.28 no.4
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• pp.210-216
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• 1984

Solvatochromic comparison methods were applied to determine Taft's solvent parameters, ${\pi}^{\ast}$(solvent polarity-polarizability), ${\alpha}$(solvent hydrogen bond donor acidity) and ${\beta}$ (solvent hydrogen bond acceptor basicity) for MeOH-MeCN solvent mixtures. Swain's solvent parameters A(anion solvation scale) and B(cation solvation scale) were also determined by least square fitting of kinetic data in the same binary solvent mixtures. It was found that: (i)${\beta}$ depends on the basicity of the solvent and increases with the MeOH content owing to the increase in polymeric structure of methanol; (ii) ${\pi}^{\ast}$depends on the dipole moment of the solvent and increases with the MeCN content of the solvent; (iii) ${\alpha}$ increases rapidly with the MeOH content as the hydrogen bond donor acidity of the solvent mixtures increases. Taft's reaction constants a and s and Swain's reaction constants a and b were determined for the reactions reported from our laboratory previously using solvent parameters determined in this work. No meaningful inter-relationship was found between the two set of reaction parameters, but a good linear correlation was found between the ratios a/s and a/b. Solvent effect on the reaction mechanism, substituent effect and leaving group ability were examined in the light of these reaction constants ratios.

• Journal of the Korean Chemical Society
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• v.27 no.1
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• pp.1-8
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• 1983

Solvent effects on nucleophilic substitution reaction of naphthalene sulfonyl chlorides with pyridine in protic and aprotic solvent have been studied by means of conductometry. Results showed that the rate constants increased with dielectric constants for protic solvents, while they decreased with dielectric constants for aprotic solvents, except for acetonitrile which has a higher dielectric constant but had also greater rate constant. The rate constants were shown to be more susceptible to polarity-polarizability parameter, , than to hydrogen bond donor acidity parameter, ${\alpha}$, indicating that the pulling effect of hydrogen bonding solvent.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.175.2-175.2
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• 2011

바이오디젤의 국가별 의무 사용 정책 확대로 인해 원료유 가격이 상승하고 있으며 원료유가 부족한 상황으로 다양한 원료를 찾는 연구가 진행되고 있다. 육상 유지 작물보다 단위면적당 생산성이 매우 높은 미세조류는 제3세대 바이오매스로 주목받고 있으며 산업체 배출 이산화탄소를 이용해 작은 면적에서 배양할 수 있는 장점이 있다. 미세조류로부터 바이오디젤 생산은 먼저 오일 함량이 높은 미세조류 종의 선정과 배양 및 수확 후 효율적인 방법으로 바이오디젤 원료유를 추출하는 과정이 중요하다. 본 연구는 Microwave로 전처리된 미세조류로 부터 원료유를 추출하여, 인지질, 단백질, 엽록소 등의 반응저해 물질을 일부 감소시키고 추출수율을 높였지만, 산가가 80이상으로 높게 추출되고 추출된 오일이 높은 점성을 가지는 문제가 있다. 이로 인해 전이에스테르화 반응의 진행이 불가하였으며 이러한 문제를 해결하기 위해, 에스테르화 반응에 용매를 혼합하여 반응성을 개선하고자 하였다. 추가된 보조 용매는 오일과 쉽게 혼합되어 반응물의 점성을 낮추고, 반응 완료후, 물에 쉽게 용해되는 불순물, 미 반응물, 촉매 등의 분리 및 제거를 용이하게 하는 장점이 있다. 또한 오일과 비교하여 낮은 끓는점을 갖는 용매는 증류를 통해 쉽게 제거가 가능하다. 반응이 완료된 오일은 초기산가 80에서 10이하의 감소를 나타내 용매 혼합 에스테르화의 효율적인 부분을 확인하였다.

• Journal of the Korean Chemical Society
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• v.18 no.4
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• pp.251-258
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• 1974

The rate constants for the nucleophilic substitution reactions of substituted benzoyl chlorides with p-nitroaniline in such solvents as acetone, acetonitrile, methanol, ethanol, etc. were conductometrically determined, and the activation thermodynamic parameters were also evaluated. In result, the reaction rates were faster in protic solvents than in aprotic solvent; in the solvents of similar property, the reaction rate in the solvent of the large dielectric constant was faster than that in the solvent of the small dielectric constant. Hammett plots in individual solvents showed the straight lines with positive slope; and we concluded that the reaction occurred via the addition-elimination mechanism.

• Resources Recycling
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• v.23 no.1
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• pp.48-57
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• 2014

In this study, we have investigated the influence of the nature of solvent on the grafting reaction of maleic anhydride onto polyethylene wax obtained as a by-product in a high density polyethylene plant. The results show that the grafting ratio in xylene as a solvent was higher than toluene. This is because xylene has excellent monomer solubility, swelling property and miscibility. It has been also observed that grafting degree shows an initial jump in percentage of grafting with increasing amount of solvent, from 0% v/w to 200% v/w giving maximum grafting in 200% v/w and then slightly decreases on further increase in the amount of solvent and becomes almost constant. It can be also seen that gel content was not formed under the use of solvent. It means that solvent prevented cross-linking reaction due to chain transfer reactions to solvent molecules. Studies of melt viscosity at $140^{\circ}C$ showed that viscosity increased after grafting of maleic anhydride onto polyethylene wax.

• Journal of the Korean Chemical Society
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• v.22 no.1
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• pp.7-11
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• 1978

The reactions of 2,4-dinitroiodobenzene with para subtituted anilines in acetonitrile-methanol binary solvent mixtures have been studied. Rate constants for reactions in methanol rich solvents are greater than for reactions in acetonitrile rich solvents. Kinetic results show that the bond formation step is rate determining in the solvent system studied. The solvent effect can be explained by stabilization of the transition state by formation of hydrogen bond between oxygen atom of methanol and hydrogen atom of aniline.

• Journal of the Korean Chemical Society
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• v.31 no.3
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• pp.280-286
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• 1987

The effect of substituent inleaving group on the rates of reactions of phenacyl substituted-benzenesulfonates with pyridine was determined conductometrically in acetonitrile and in methanol at 35, 45, and $55^{\circ}C$, respectively. The reaction rate became faster in proportion to electron-attracting ability of substituent, which indicates that the substituent in leaving group can directly control reaction rate. It was shown that the specific to the carbonyl carbon as the rate-determining step.

• Journal of the Korean Chemical Society
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• v.29 no.5
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• pp.465-471
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• 1985

The rate constants for the solvolysis of anthraquinone-2-carbonyl chloride in binary solvent mixtures, methanol-acetonitrile, methanol-acetone, ethanol-acetonitrile and ethanol-acetone, have been studied by means of conductometry. Maximum rate phenomena were observed at the methanol mole fraction, $X_{MeOH}$ = 0.73~0.81 for methanol-acetonitrile and at $X_{MeOH}$ = 0.83 for methanol-acetone mixtures. The Kivinen and Grunwald-Winstein plots indicated that the reaction proceeds via $S_N2$ type mechanism. Application of Taft's solvatochromic correlation on the solvolysis rate revealed that both $\alpha$ and ${\pi}^*$ are important for reactions in methanol-acetonitrile and methanol-acetone mixtures, while only ${\alpha}$ influences significantly on the rate in ethanol-acetonitrile and ethanol-acetone mixtures.

• Journal of the Korean Chemical Society
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• v.23 no.6
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• pp.339-348
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• 1979

The kinetics of the solvolysis of 2-furoyl chloride and 2-thenoyl chloride in $MeOH-H_2O,\;EtOH-H_2O,\;(Me)_2CO-H_2O,\;MeCN-H_2O$ and MeCN-MeOH has been investigated. The rates were faster in protic solvents than in aprotic solvents. This was caused by the bond breaking of leaving group through hydrogen-bonding solvation of protic solvents. In MeCN-M$\'{e}$OH the rate in MeOH rich solvents was faster than in MeCN rich solvents by the specific solvation of alcoholic hydrogen and there was a maximum rate of reaction at MeOH mole fraction of 0.8. The reaction rates of solvolysis were considerably slower than those of benzoyl chloride owing to the electron withdrawing effect of thienyl and furyl groups. It was concluded that solvolytic reaction proceeds via a dissociative $S_N2$ mechanism in which bond-breaking precedes bond-formation at the transition state.