• Title/Summary/Keyword: 입체 화학

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Synthesis of Permethrin using Ester Enolate Claisen Rearrangement (에스테르엔올 음이온의 Claisen 자리옮김 반응에 의한 Permethrin의 합성)

  • In-Kyu Kim;Suk-Ku Kang;Jang-Hoo Hong
    • Journal of the Korean Chemical Society
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    • v.30 no.6
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    • pp.548-552
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    • 1986
  • A stereoselective synthesis of 3-phenoxybenzyl (${\pm}$)-cis and trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-1-cyclopropanecarboxylic acid starting from readily available 2-methyl-3-buten-2-ol($\underline{2}$) is described. Allylic rearrangement of 2-methyl-3-buten-2-ol, in the presence of acetic acid and acetic anhydride gave 3-methyl-2-butenyl acetate($\underline{3}$). The [3,3] sigmatropic rearrangement of the allyl acetate($\underline{3}$), as the silylketene acetal, produced the ${\gamma},\;{\delta}$-unsaturated acid($\underline{4}$). Treatment of 3,3-dimethyl-4-pentenoic acid($\underline{4}$) with SOCl2 followed by esterification with 3-phenoxybenzyl alcohol yielded 3, 3-dimethyl-4-pentenoic acid ester($\underline{5}$). Addition of carbon tetrachloride to the olefin ester($\underline{6}$) furnished 4,6,6,6-tetrachloro-3,3-dimethylhexanoic acid ester ($\underline{7}$). Cyclization with potassium t-butoxide and elimination of hydrogen chloride afforded 3-phenoxybenzyl (${\pm}$) cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-1-cyclopropanecarboxylic acid.

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Kinetics Studies on Nucleophilic Reactions of Methanesulfonyl Chloride with Substituted Aniline in Methanol (메탄올 속에서 치환아닐린과 염화메탄술포닐의 친핵성반응의 속도론적 연구)

  • Lee Suk-Kee
    • Journal of the Korean Chemical Society
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    • v.19 no.3
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    • pp.156-162
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    • 1975
  • Rates of reactions of methanesulfonyl chloride with various substituted anilines have been measured in methanol. Substituent effects in aniline are found to be linearly correlated with pKa(Bronsted relation with ${\beta}$ = 0.84) and ${\rho}$(Hammett equation with ${\rho}$ = -2.46) respectively. The results are interpreted in terms of degree of bond-formation at the transition state, which was found to have progressed relatively further. The rates for o-methylaniline deviated from the Bronsted plot established by meta and para substituted anilines because of a steric effect of ortho position in aniline. Activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ have also been determined. The enthalpy of activation showed a regular variation in that electron donating substituents in the p-substituted aniline decrease ${\Delta}H^{\neq}$ and increase the negative value of ${\Delta}S^{\neq}$.

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The Physicochemical Properties on the Charge Transfer Complexes under High Pressure (고압하의 전하이동착물에 대한 물성론적 연구-사염화탄소 용액내에서 헥사메틸벤젠과 여러 전자받게들간의 전하이동착물 생성에 대한 압력과 온도의 영향)

  • Kwun Oh Cheun;Kim Myong Ja;Kim Se Kyung
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.335-342
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    • 1991
  • The effect of pressure and temperature on the stabilities of the charge transfer complexes of 1,3,5-trinitrobenzene, tetrachloro-p-benzoquinone and tetracyanoethylene with hexamethylbenzene in carbon tetrachloride has been investigated by spectrophotometric measurements. The equilibrium constants for the formation of the complexes were obtained at various temperature and pressure, and thermodynamic parameters for the formation of the charge transfer complexes are calculated from these values. The relative stabilities of charge transfer complexes with hexamethylbenzene increase in the order; 1,3,5-trinitrobenzene < tetrachloro-p-benzoquinone < tetracyanoethylene. This may be regarded as an order of relative acidity of these compounds in complexation with hexamethylbenzene and is explained in terms of the negative inductive effect of the ${\pi}$ acceptors. The red-shift at higher pressure, the blue-shift at higher temperature and the relation between pressure and oscillator strength are discussed on the basis of thermodynamic functions.

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Host-Guest Interactions of Cyclic and Acyclic Polyethers with Alkylammonium Ions (고리 및 비고리 폴리에테르와 알킬암모늄 이온과의 호스트-게스트 상호작용)

  • Jeong, Jong Hwa;Kim, Dae Yeon;Lee, Sim Seong
    • Journal of the Korean Chemical Society
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    • v.38 no.7
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    • pp.509-515
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    • 1994
  • The interactions of 11 kinds of primary and secondary alkylammonium ions with cyclic (12C4, 15C5, 18C6, DT18C6 and DA18C6) and acyclic$(Q_2O_5)$ polyethers were investigated by NMR titration and conductometry. All of the alkylammonium ions under investigation form the relatively stable 1 : 1 complexes with crown ethers and acyclic polyether by H-bond. The interactions of alkylammonium ions with analogeous hosts having different size were in the order of 18C6 > 15C5 > 12C4, and the strengthes of donor atoms toward the alkylammonium ions were in the order of N > O > S. 18C6 forms more favorable interactions with primary alkylammonium ions than secondary alkylammonium ions, otherwise DA18C6 shows the opposite behaviors. The stability constants for complexations of 18C6 with the alkylammonium ions were determined conductometrically in methanol at 25$^{\circ}C$. The major factors affecting the stability of complexes were the type of alkylammonium ions, the length of alkyl-chain and the steric hindrance due to the structure of alkyl groups on complexation.

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Characteristics of Zeolites (Zeolite의 특성)

  • Im, Goeng
    • The Journal of Natural Sciences
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    • v.6 no.1
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    • pp.103-108
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    • 1993
  • Zeolites were discovered as a natural mineral more than two hundred ago. In the beginning, the mineral was used as ion-exchange material and adsorbent. After the end of World War II , however, a variety of zeolites have become available in large amounts because of the establishment of low temperature synthesis and the discobery of natural zeolite deposits of sedimentary origin. Various uses of xeolite were developed utilizing the unique crystal strucrure and function of these minerals. In connection with this development remakable progress has also been made in basic stuides on the related geology and mineralogy, crystallization from sols and gels, structure, ion exchange, adsorption and cataiysis. As a result, zeolites, which had been known only as mineral specimens displayed in museums. established a firm position among the high-technology masterials with excellent functional capabilities.

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Surface Modification of Biomaterials for Hard Tissue Substitutes to Improve Biocompatibility and Osteoconductivity (생체적합성 및 골전도성 향상을 위한 경조직 대체용 생체재료의 표면개질)

  • Kim, Sung-Wook;Lee, Woo-Kul
    • Applied Chemistry for Engineering
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    • v.16 no.6
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    • pp.725-730
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    • 2005
  • In the development of biomaterials as a substitute of hard tissues, the biocompatibility and osteoconductivity of the biomaterial are considered to be one of the most significant considerations. These biological properties of a material can be greatly improved by the modification of the surface properties by the depositing calcium phosphate thin films on the material since calcium phosphate films possess similar chemical compositions to hard tissues. The success of a material as a biomaterial will be determined by the interaction of the surface of the material with the adhesion molecules which induce cellular adhesion and biological responses of the adherent cells. Depending on the adsorption mechanisms and adsorbed conformation of the adhesion molecules on the surface of the biomaterial, cellular responses, such as adhesion, proliferation and differentiation of osteoblast cells, can be promoted or restricted. It has been reported that materials of which surfaces were modified with thin films of calcium phosphate appeared to be more osteoconductive. Rapid formations of bone nodule in addition to higher differentiations of osteoblast have been observed on the calcium phosphate thin films.

Solvent Effects upon Carbonyl Stretching Freguency Shifts of Raman Spectra : Ketones (라만 스펙트럼의 카보닐 신축진동 이동에 대한 용매효과 : 케톤)

  • In Ju Lee;Sung Hun Seo;Mu Sang Lee
    • Journal of the Korean Chemical Society
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    • v.37 no.12
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    • pp.987-994
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    • 1993
  • Inductive and resonance effects play an important role in determining carbony) stretching frequencies of ketones. Hydrogen bonding, dielectric effects, and steric effects are all factors which determine the carbonyl stretching frequency, νC=O of ketones in solution. The $ν_{C=O}$ frequencies were shifted by approximately 27$cm^{-1}$ each by substituting to a phenyl group for a methyl group in acetone. The $ν_{C=O}$ frequency for ketones shifted differently in various solvents and increased with increasing the volume ratio of the ketones in water solutions. The $ν_{C=O}$ frequency for ketones shifts continously at constant concentration of ketone in solutions of $(CH_3)_2SO/CCl_4$and$CHCl_3/CCl_4$ with changing of the mole ratio of two solvents. The $ν_{C=O}$ frequency was also affected by changing concentration in either $CCl_4$ or $(CH_3)_2SO$ solution and in either $CCl_4$or $CHCl_3$ solution.

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A three-dimensional patent evaluation model that considers the factors for calculating the internal and external value of a patent: Arrhenius chemical reaction kinetics-based patent lifespan prediction (특허의 내적.외적 가치산정요인을 고려한 입체적 특허평가모델: 아레니우스 화학반응속도론 기반의 특허수명예측)

  • Choi, Yong Muk;LEE, JAEWON;Cho, Daemyeong
    • Journal of Digital Convergence
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    • v.19 no.6
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    • pp.113-132
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    • 2021
  • This study is a new evaluation using the Arrhenius equation, which is known as the chemical reaction rate estimation equation, to evaluate the intrinsic and extrinsic value elements of patents as a model. The performance of the evaluation model was superior to the SVM, Logistic reg. and ANN models that were used as patent evaluation models in prior studies. In addition, there was a strong correlation between the predicted lifespan of the patent and the actual lifespan of the patent. These evaluation models may be used for evaluation purposes only, or if an evaluation is required, including a commercialization entity or technical characteristics.

Study on Degradation Rates of Biodegradable Polymers by Stereochemistry (입체화학을 이용한 생분해성 고분자의 분해속도에 관한 연구)

  • Park, Chan-Young;Choi, Yong-Hae;Lee, Won-Ki
    • Journal of Environmental Science International
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    • v.18 no.7
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    • pp.797-802
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    • 2009
  • To control degradation rate of biodegradable poly(lactide)s (PLA), the stereochemical PLAs with different ratios of d-lactide and l-lactide units were synthesized by the ring open polymerization and the their degradation kinetics were measured by a Langmuir film balance. The alkaline (pH=11) degradation of poly(l-lactide) (l-PLA) monolayer showed the faster rate at a surface pressure of 4 mN/m in the ranges from to 0 to 7 mN/m. However, the enzymatic degradation of l-PLA with Proteinase K did not occur until 4 mN/m. Above a constant surface pressure of 4 mN/m, the degradation rate was increased with a constant surface pressure. These behaviors might be attributed to the difference in the contacted area with degradation medium: alkaline ions need small contact area with l-PLA while enzymes require much bigger one to be activated due to different medium sizes. The stereochmical PLA monolayers showed that the alkaline degradation was increased with their optical impurities while the enzymatic one was inversed. These results could be explained by the decrease of crystallinity with the optical impurity and the inactivity of enzyme to d-LA unit.

UV Spectrometric Assay of Epoxide Hydrolase Activity of Microbial Cell Biocatalysts (자외선분광기를 이용한 미생물 세포 생촉매의 에폭사이드 가수분해효소 활성평가)

  • Kim, Hee Sook;Lee, Eun Yeol
    • Applied Chemistry for Engineering
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    • v.16 no.3
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    • pp.456-459
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    • 2005
  • UV spectrometric assay for measurement of epoxide hydrolase activity was tested for efficient screening of whole cell activity of epoxide hydrolase. Epoxide hydrolase activities were determined by measuring the amount of p-nitrostyrene diol (pNSD), which was the hydrolysis product of p-nitrostyrene oxide (pNSO). Enantioselective hydrolysis of racemic pNSO using epoxide hydrolase activity of Rhodosporidium toruloides was monitored by UV spectrometric assay, and the relevant $K_m$ and $V_m$ for R. toruloides were determined as $2.457nmol/min{\cdot}mg$ and 1.078 mM, respectively.