• Bulletin of the Korean Chemical Society
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• 제34권2호
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• pp.615-621
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• 2013

Solvolyses of isobutyl chloroformate (4) in 43 binary solvent mixtures including highly aqueous media, water, $D_2O$, $CH_3OD$, 2,2,2-trifluoroethanol (TFE) as well as aqueous 1,1,1,3,3,3-hexafluoro-isopropanol (HFIP) solvents were performed at $45^{\circ}C$, in order to further investigate the recent results of D'Souza, M. $J^1$. et al.; solvolyses of 4 are found to be consistent with the proposed mechanism ($Ad_E$). The variety of solvent systems was extended to comprise highly ionizing power solvent media ($Y_{Cl}$ > 2.7 excepted for aqueous fluorinated solvents and pure TFE solvent) to investigate whether a mechanistic change occurs as solvent compositions are varied. However, in case of 18-solvent ranges having aqueous fluorinated solvent systems (TFE-$H_2O$ and HFIP-$H_2O$) and/or having $Y_{Cl}$ > 2.7 solvent systems, the solvent effect on reactivity for those of 4 are evaluated by the multiple regression analysis as competition with $S_N2$ - type mechanism. And in pure TFE and 97 w/w % HFIP solvents with high $Y_{Cl}$ and weak $N_T$, these solvolyses are understood as reactions which proceed through an ionization ($S_N1$) pathway.

• Bulletin of the Korean Chemical Society
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• 제24권8호
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• pp.1207-1210
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• 2003

The effect of solvent structure on the slope in the plot of ln K vs. solute carbon number was examined. It was found that the free energy of methylene group transfer from the gas phase into a solvent was always negative and that the absolute magnitude of interaction free energy between the methylene group and the solvent was always larger than the absolute magnitude of cavity formation free energy of the methylene group in the solvent. Thus, the slope in the plot of ln K vs. solute carbon number was always positive and its value decreases with increase of solvent polarity since the cavity formation energy of the CH₂ unit increases with increase of solvent polarity while the dispersive interaction energy of the CH₂ unit is virtually invariant. We also examined the effect of sequential addition of CH₂ unit to a solvent molecule upon ln K for three homologous series of solvents: n-alkanes, n-alcohols, and n-nitriles. Characteristic trends in the plots of ln K vs. solvent carbon number were observed for individual solvent groups. A decrease of ln K with solvent carbon number was observed for n-alkanes. An abrupt increase in ln K followed by levelling off was observed for n-alcohols while a final slight decrease in ln K after an abrupt increase followed by rapid levelling off was noted for n-nitriles. All of theses phenomena were found related to variation in cavity formation energy. It was clearly shown that a structural change of a polar solvent by sequential addition of CH₂ units causes an abrupt polarity decrease initially, then gradual levelling off, and finally, conversion to a virtually nonpolar solvent if enough CH₂ units are added.

• Bulletin of the Korean Chemical Society
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• 제28권11호
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• pp.2051-2055
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• 2007

The solvent effect on sulfur ylide mediated epoxidation reaction was studied systematically. While higher trans/cis ratio of the epoxide was obtained in the more polar solvent, protic solvent produced the lower trans/ cis ratio than any aprotic solvent.

• 폴리머
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• 제24권1호
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• pp.23-28
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• 2000

Solvent 용접에 따른 무정형 고분자 폴리스티렌/폴리스티렌 계면의 접착강도의 변화를 butt joint실험을 통하여 살펴보았다. 폴리스티렌과 용해도 상수가 유사한 용매를 계면에 코팅함으로써 계면 분자쇄의 유동성 증가와 계면의 거침정도의 변화에 따른 접촉표면의 증가로 인하여 접착 강도가 증가함을 확인하였다. 사용용매의 비등점이 접착온도보다 높은 경우, 접착강도의 증가는 용매에 의한 분자쇄의 유동성 증가에 기인되는 반면 용매의 비등점이 접착온도에 비해 낮을 경우 접착강도의 증가는 용매에 의한 접촉표면의 증가에 의존함을 알 수 있었다. 접착온도가 높을수록, 접착시간이 길어질수록 접착강도는 증가되며, 사용용매가 접착강도에 미치는 영향은 감소함을 알 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제13권6호
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• pp.642-647
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• 1992

Second-order rate constants have been measured spectrophotometrically for the reactions of substituted phenyl acetates with butane-2,3-dione monoximate and p-chlorophenoxide anions in MeCN-H$_2$O mixtures of varying compositions. The reaction rate, unexpectedly, decreased remarkably upon initial additions of MeCN to H$_2$O up to 30-40 mole ${\%}$ MeCN, and followed by a gradual increase upon further additions of MeCN. The change in solvent composition also influenced the magnitude of the ${\alpha}$-effect, i.e., the ${\alpha}$-effect increased as the mole ${\%}$ MeCN increased. The solvent dependent ${\alpha}$-effect for the present system appears to indicate that the differential solvation between the ${\alpha}$-effect nucleophile and the corresponding normal nucleophile is not solely responsible but the difference in the transition-state stabilization is also responsible for the ${\alpha}$ -effect in organic solvent-rich region.

• 한국산업융합학회 논문집
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• 제7권3호
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• pp.299-303
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• 2004

A systematic investigation for the reactivity and solvent effect was studied on the reaction of optical resolving agents with the optically active assistant compounds. The reaction rate constants of the nucleophillic substitution reactions were determined by means of conductometric method The linear solvent energy relationship based on the solvent parameters and the thermodynamic parameters was discussed on the reactions of various physiological active compounds and optical resolving agents The reaction mechanism was discussed from the kinetic results compared with the optical purity.

• 한국패션뷰티학회지
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• 제3권3호
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• pp.56-63
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• 2005

In the study of permanent waving method after mixing ample and permanent wave solvent in permanent wave the dyed humans hair are as follows; First, Permanent waving method after mixing ample and permanent wave solvent is that the better effective way in permanent wave the dyed humans hair because permanent waving cycle is constant and hair cuticle is glossy. Second, This study is not interpret in permanent wave dyed humans hair that tensile strength is effect of permanent waving method after mixing ample and permanent wave solvent. A extension degree is effect of permanent waving method after mixing ample and permanent wave solvent use indifferent ample treatment method. Third, Hair cuticle damages are a little permanent waving method after mixing ample and permanent wave solvent in permanent wave dyed humans hair.

• 한국전기전자재료학회논문지
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• 제21권3호
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• pp.236-241
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• 2008

The effect of organic solvent mixture ratio on the rheology property of slurry and thickness control of ceramic green sheet was investigated. For selecting a suitable dispersant multiple light scattering method was used to evaluate the particle migration velocity and variation of clarification layer thickness. Using the selected dispersant the dispersion property of solution according to solvent mixture ratio was investigated. Binder and plasticizers were added to formulate slurries and their viscosity was evaluated according to solvent mixture ratio. Ceramic green sheets with average thickness of 30, 50 urn were fabricated via tape casting and their thickness tolerances measured. As a result according to solvent mixture ratio the solution and slurry properties varied and for the mixture ratio of ethanol/toluene of 80/20 the ceramic green sheet with the lowest thickness tolerance was obtained.

• 대한화학회지
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• 제28권4호
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• pp.210-216
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• 1984

MeOH-MeCN 혼합용매의 Taft용매 파라미터인 ${\pi}^{\ast}$(용매의 polarity-polarizability), ${\alpha}$(용매의 수소결합 주게 산도) 그리고 ${\beta}$(용매의 수소결합 받게 염기도)를 여러 지시약을 사용하여 분광용매화 비교법으로 구하였다. 또한 Swain의 용매 파라미터인 A(음이온을 용매화 시키는 척도)와 B(양이온을 용매화 시키는 척도)를 반응속도 자료를 이용하여 최소 자승법으로 구하였다. 용매 상수 ${\beta}$는 용매의 염기도에 의존하며 혼합용매의 MeOH 함량이 증가할 수록 $(MeOH)_n$의 기여에 의해 증가하는 것을 알 수 있었다. ${\pi}^*$는 용매의 쌍극자 모멘트에 의존하며 혼합용매의 MeCN 함량이 증가할 수록 ${\pi}^{\ast}$값도 커지며 ${\alpha}$는 MeOH의 수소결합주게 효과에 의해 혼합용매의 MeOH함량이 증가할 수록 크게 증가하는 것을 나타냈다. 앞서 보고된 반응들에 용매 파라미터를 적용하여 반응상수를 구하였으며 Taft의 반응상수 a, s와 Swain의 반응상수 a, b사이에는 용매 척도의 차이 때문에 서로 연관성이 없었다. 그러나 그들의 비인 a/s와 a/b는 서로 좋은 직선관계를 보여 주었으며 이들 반응상수 비를 이용하여 반응 메카니즘이나 치환기 변화 및 이탈기 변화에 미치는 용매효과를 논의 하였다.

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.2093-2096
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• 2011