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A Direct Comparison Study of Asymmetric Borane Reduction of C=N Double Bond Mediated by Chiral Oxazaborolidines

  • Cho Byung Tae;Ryu, Mi Hae;Chun Yu Sung;Dauelsberg Ch.;Wallbaum Sabine;Martens Jurgen
    • Bulletin of the Korean Chemical Society
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    • v.15 no.1
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    • pp.53-57
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    • 1994
  • A comparison study on asymmetric borane reduction of ketoxime ethers and N-substituted ketimines possesing C = N double bond mediated by the selected chiral oxazaborolidines (1-6) was investigated. Thus, an aromatic ketoxime O-alkyl ether acetophenone oxime O-methyl ether was reduced to the corresponding amine (1-phenylethylamine 8a) with optical yields, such as 58% ee with 1, 86% ee with 2, 3% ee with 3, 99% ee with 4, 60% ee with 5, and 73% ee with 6. However, the reduction of an aliphatic ketoxime derivative 2-heptanone oxime O-methyl ether provided low optical inductions (7-13% ee). For ketoxime O-trimethylsilyl ethers, the reduction of acetophenone O-trimethylsilyl ether afforded 8a with optical yields which were 90% ee with 1, 40% ee with 2, 2% ee with 3, 62% ee with 4, 5% ee with 5, and 60% ee with 6. The reduction of 2-heptanone O-trimethylsilyl ether also gave the product amine with low optical yields (10-40% ee). In the case of N-substituted ketimines, the reduction of acetophenone N-phenylimine afforded the corresponding amine with 79% ee, 78% ee, 9% ee, 73% ee, 78% ee and 67% ee using 1, 2, 3, 4, 5, and 6, respectively, whereas low optical inductions (5-18% ee) for 2-heptanone N-phenylimine were achieved.

Asymmetric Reduction of Prochiral Ketones with Potassium 9-O-isopinocampheyloxy-9 boratabicyclo[3.3.1]nonane$^+$

  • Park, Won-Suh;Cho, Byung-Tae;Cha, Jin-Soon
    • Bulletin of the Korean Chemical Society
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    • v.8 no.3
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    • pp.211-214
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    • 1987
  • Asymmetric reduction of a series of aliphatic ketones and representative other classes of ketones with potassium 9-O-isopinocampheyloxy-9-boratabicyclo[3.3.1]non ane (K 9-O-Ipc-9-BBNH) was studied. All the ketones examined were reduced smoothly to the corresponding alcohols in THF at -$78^{\circ}C$. Thus, the reduction of 2-butanone, 3-methyl-2-butanone, 3,3-dimethyl-2-butanone, 2-octanone, and 4-phenyl-2-butanone provides 51% ee, 61% ee, 44% ee, 35% ee, and 33% ee of optical inductions, respectively. The reduction of other classes of ketones gave 52% ee for 2,2-dimethylcyclopentanone, 47% ee for acetophenone, 23% ee for 3-acetylpyridine, 50% ee for methyl benzoylformate, 4.8% ee for 2-chloroacetophenone, 30% ee for trans-4-phenyl-3-butene-2-one, and 2% ee for 4-phenyl-3-butyn-2-one. Thus, the reagent was found to be most useful in the asymmetric reduction of acyclic and cyclic aliphatic series of ketones.

A coverage driven test method for J2EE Applications through flow analysis (J2EE 애플리케이션의 흐름분석을 통한 커버리지 기반 테스트 방법)

  • Junggyw Lee;Seunghak Kuk;Hyeonsoo Kim
    • Proceedings of the Korea Information Processing Society Conference
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    • 2008.11a
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    • pp.516-519
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    • 2008
  • 최근 엔터프라이즈 애플리케이션은 J2EE 컴포넌트로 개발된다. J2EE 플랫폼은 애플리케이션을 개발하는데 편리한 기능을 제공한다. 하지만 J2EE 애플리케이션의 테스트는 J2EE 서버 내부에서 자원을 관리하는 컨테이너의 접근 통제 때문에 기존의 테스트 방법으로 수행하기 어렵다. 본 논문에서는 J2EE 환경에 맞는 J2EE 애플리케이션의 테스트 방법을 제안한다. 이 방법은 애플리케이션을 구성하는 EJB 컴포넌트를 정적 및 동적 분석하여 획득한 정보로 애플리케이션의 메소드 커버리지를 분석하고, 메소드 커버리지를 향상시키기 위한 테스트 데이터를 생성하여 J2EE 애플리케이션을 테스트한다.

Enantioselective Synthesis of 1-Substituted 1,2,3,4-Tetrahydroisoquinoline Alkaloids via Asymmetric Reduction

  • Byung Tae Cho;Cheol Kyu Han
    • Bulletin of the Korean Chemical Society
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    • v.12 no.5
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    • pp.565-569
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    • 1991
  • Enantioselective synthesis of 1-substituted tetrahydroisoquinoline alkaloids (1) via asymmetric reduction of 1-substituted 3,4-dihydroisoquinolines (2) and the corresponding iminium salts (3) with the selected chiral hydride reagents, such as K glucoride (5), Itsuno's reagent (6), and Mosher's reagent (7) were examined. In these reactions, dihydroisoquinolines were not reduced by the hydride reagents, whereas the iminium salts were easily reduced under the same reaction conditions found in successful reduction of ketones. Thus, the reduction of 6,7-dimethoxy-3,4-dihydroisoquinolium iodide(3a) with 5, 6 and 7 provided the product 1a with 52.3 % ee, 18 % ee, and 66.4 % ee, respectively. For 1-benzyl derivatives (3b-3d), syntheses of 1b-1d with 0.7-6.2 % ee, 5.9-21 % ee, and 1.4-2.7 % ee were achieved with chiral reducing agents 5, 6 and 7, respectively. For 1-aryl derivatives, use of 5, 6 and 7 resulted in optical inductions in the range of 25.2-43 % ee, 13-21.1 % ee, and 6.3-16 % ee, respectively.

Expression Patterns of the chgH:rfp Transgene in Response to 17α-Ethinylestradiol (EE2) Exposure in Marine Medaka Oryzias dancena

  • Nam, Yoon Kwon;Cho, Young Sun;Kim, Dong Soo
    • Fisheries and Aquatic Sciences
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    • v.18 no.1
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    • pp.65-71
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    • 2015
  • The functional utility of a transgenic marine medaka Oryzias dancena strain carrying the red fluorescent protein (RFP) gene driven by an endogenous choriogenin H (chgH) promoter was evaluated for its ability to detect waterborne $17{\alpha}$-ethinylestradiol (EE2), a synthetic estrogen derivative. The chgH:rfp transgenic marine medaka larvae showed an age-dependent tendency in the efficiency of EE2-mediated transgene expression, in which transgenic larvae older than 6 days post-hatching displayed a more effective response in their transgene expression to EE2 than did younger hatchlings. During experimental exposures to high concentrations of EE2 (200 to 1,000 ng/L), the transgenic responses in the hatchlings were broadly dose- and duration-dependent. With exposures using lower doses of EE2 (25, 50 and 100 ng/L), EE2-induced transgenic RFP was also observed in the transgenic larvae, although the lower doses required exposure of longer duration. Under the EE2 exposure and microscope assay conditions used in our study, transgenic marine medaka larvae exhibited a similar degree of EE2-mediated RFP phenotype expression at various salinity levels (0, 15 and 30 ppt).

Asymmetric Reduction of Prochiral $\alpha,\beta$-Acetylenic Ketones With Potassium 9-0-(1,2 : 5,6-Di-O-isopropylidene-$\alpha$-D-glucofuranosyl)-9-bortabicylco[3.3.1]nonane$^\dag$

  • Cho, Byung-Tae;Park, Won-Suh
    • Bulletin of the Korean Chemical Society
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    • v.8 no.4
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    • pp.257-260
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    • 1987
  • The asymmetric reduction of representative prochiral ${\alpha},{\beta}$-acetylenic ketones with a new chiral borohydride reducing agent, potassium 9-0-(1,2: 5,6-Di-O-isopropylidene-${\alpha}$ -D-glucofuranosyl)-9-boratabicyclo[3.3.1]nonane, 1, in THF at $-78^{\circ}C$ was studied. Structurally different acetylenic ketones such as internal ${\alpha},{\beta}$-acetylenic ketones $RC {\equiv} CCOCH_3$ and terminal ${\alpha},{\beta}$-acetylenic ketones $HC {\equiv} CCOR$ were chosen. Thus, the reduction of internal ${\alpha},{\beta}$-acetylenic ketones yields the corresponding propargyl alcohols, such as 67% ee for 3-hexyn-2-one, 75% ee for 5-methyl-3-hexyn-2-one, 86% ee for 5,5-dimethyl-3-hexyn-2-one, 74% ee for 3-nonyn-2-one and 61% ee for 4-phenyl-3-butyn-2-one. Terminal ${\alpha},{\beta}$-acetylenic ketones, such as 3-butyn-2-one, 1-pentyn-3-one, 4-methyl-1-pentyn-3-one and 1-octyn-3-one, are reduced to the corresponding alcohols with 59% ee, 17% ee, 44% ee and 12% ee of optical induction respectively. With one exception (4-methyl-1-pentyn-3-one), all propargyl alcohols obtained are enriched in R-enantiomers.

On Deployment of Resource Adapter in J2EE Connector Architecture (J2EE 커넥터 아키텍처에서의 리소스 어댑터 배치방법)

  • 채정화;김송주;유철중;장옥배
    • Proceedings of the Korean Information Science Society Conference
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    • 2000.10a
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    • pp.466-468
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    • 2000
  • J2EE(JavaTM 2 Platform, Enterprise Edition)의 클라이언트 애플리케이션, 웹 컴포넌트, Enterprise JavaBeans 컴포넌트와 같은 앤터프라이즈 애플리케이션은 개발된 후 컨테이너에 배치되어 실행된다. 이러한 앤터프라이즈 애플리케이션(enterprise application)은 다양한 EIS(Enterprise Information System)에 접근하여 관련된 기능과 데이터를 사용할 필요가 있다. J2EE 커넥터 아키텍처(Connector Architecture)는 J2EE 플랫폼을 다양한 EIS와 연결하기 위한 표준을 정의하는 API 이며, 각 EIS 벤더는 이러한 커넥터 아키텍처의 설계서를 따르는 EISF의 시스템 레벨 소프트웨어 드라이버인 표준 리소스 어댑터(Resource Adaptor)를 제공한다. 커넥터 아키텍처를 구현한 리소스 어댑터를 사용함으로써 특정 벤더의 J2EE 플랫폼에 종속되지 않도록 EIS를 통합할 수 있다. 본 논문에서는 이러한 J2EE 커넥터 아키텍처를 구현한 리소스 어댑터를 애플리케이션 서버를 배치하기 위하여 배치기가 수행해야 하는 배치 단계를 크게 네 단계로 구분하고, 배치구성 활동을 다섯 가지로 분류 및 정의한다,

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New Chiral Borohydrides. 2. Preparation of Potassium B-Methoxydiisopinocampheylborohydride and Its Asymmetric Reducing Properties

  • Cho, Byung-Tae
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.662-665
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    • 1991
  • In order to prepare new chiral borohydrides (4) possessing chirality on dialkyl moieties, a series of B-alkoxydiisopinocampheylborinates (3) were synthesized by treatment of diisopinocampheylborane ($Ipc_2BH$) with alcohols (R in ROH: Me, Et, i-Pr, t-Bu) and reacted with excess of potassium hydride. Of these chiral borinic esters, only B-methoxydiisopinocampheyl borinate (3a) was converted into the corresponding dialkylmonoalkoxyborohydride (4a). For the other borinic esters, hydride uptake reactions were very slow at room temperature, accompanying disproportionation products at $65^{\circ}C$. The hydride (4a) formed is stable at $0^{\circ}C$ and can be stored over potassium hydride for few months. In the asymmetric reduction of the selected ketones, 4a provided the corresponding alcohols, such as 21% ee for 3-methyl-2-butanone, 11% ee for 2,2-dimethylcyclopentanone, 24% ee for acetophenone, 32% ee for 3-acetylpyridine, 30% for methyl benzoylformate, 31% ee for 4-phenyl-3-butyn-2-one, 39% ee for 3-butyn-2-one, and 34% ee for 3-hexyn-2-one.

Study of Performance deterioration Factor for Enterprise Application based on J2EE (J2EE 기반의 엔터프라이즈 애플리케이션 성능 저하 요인에 대한 연구)

  • Kim, Min-Kyu;Choi, Sung-Woon
    • Proceedings of the Korea Information Processing Society Conference
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    • 2005.11a
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    • pp.787-790
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    • 2005
  • 최근 엔터프라이즈 애플리케이션을 개발하는데 있어서 J2EE 이 중심 기술로 부각되었다. J2EE의 핵심 기술이라고 할 수 있는 EJB 는 컴포넌트 기반 분산 객체 시스템을 개발하는데 있어서 생산성 향상 및 유지 보수성 등에 있어서 장점이 있지만, 성능 등에 문제점이 발견되었다. J2EE 기반으로 개발된 엔터프라이즈 애플리케이션의 성능 저하 부분을 측정하여 그 요인을 알아낸다.

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Photodegradation of 17α-ethynylestradiol in nitrate aqueous solutions

  • Ren, Dong;Bi, Tingting;Gao, Shumei;Li, Xukun;Huang, Bin;Pan, Xuejun
    • Environmental Engineering Research
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    • v.21 no.2
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    • pp.188-195
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    • 2016
  • $17{\alpha}$-Ethynylestradiol (EE2) has gotten growing concerns due to its widely detected in the environment and high estrogenic potency. However, the knowledge on the photochemical behaviors of EE2 in natural waters is still limited. Herein, the photodegradation and estrogenic potency variation of EE2 induced by nitrate were studied using a sunlight simulator consisted by a 300 W medium pressure mercury lamp and 290 nm cut-off filters. It was found that EE2 could be photodegraded at a rate of $0.0193h^{-1}$ in pure aqueous solutions, and the photodegradation of EE2 could be significantly promoted by nitrate. The photodegradation removal rate of EE2 was increased from 9% in Milli-Q water to 85% in 2.0 mM nitrate solutions. Reactive species scavenging experiments demonstrated that the photogenerated $HO{\bullet}$ contributed about 55% to EE2 degradation. Fe(III), Cl- and dissolved humic acid (DHA) could inhibit the photodegradation of EE2 by competing the incident light and photogenerated $HO{\bullet}$, while $HCO_3{^-}$ had no influence on EE2 photodegradation. EE2 was determined to be phototransformed into organic chemicals without estrogenic potency by GC-MS and MCF-7 cell proliferation toxicity tests. These findings could extend our knowledge on the photochemical behaviors of steroid estrogens and provide information for ecological risk assessment.