• 제목/요약/키워드: ring opening

검색결과 329건 처리시간 0.029초

초음파 조사에 의한 에폭사이드 비대칭 고리열림 반응의 속도 증진 효과 (Accelerating Effects of Ultrasonic Irradiation on Reaction Rates for the Asymmetric Ring Opening Reaction of Epoxides)

  • 이예원;박근우;김건중
    • 공업화학
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    • 제30권3호
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    • pp.365-370
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    • 2019
  • 본 연구에서는 키랄 코발트 살렌 촉매 존재 하에서 에폭사이드 화합물의 비대칭 고리 열림 반응(EKR)에 미치는 초음파 조사 효과를 기존의 기계적 교반법과 비교하여 고찰하였다. 촉매의 활성을 비교하기 위하여 $AlCl_3,\;BF_3$ 및 니트로벤젠술폰산(NBSA)이 결합된 키랄 코발트 살렌을 합성 사용하였으며, 반응물로는 에피클로로히드린(ECH), 에폭시페녹시프로판(EPP) 및 프로필렌 옥사이드(PO)를 친핵체로는 물과 메탄올을 각각 사용하여 EKR 반응을 수행하였다. 이 반응에서 반응물을 혼합시키는 조작의 일환으로써 초음파를 반응계에 적용한 경우가 통상의 기계적인 교반보다 반응속도를 현저히 증가시키는 결과를 나타내었다. 최고의 거울상 이성체 과잉도 값인 99 ee%를 얻는데 요하는 반응시간은 초음파를 적용하였을 때가 격렬한 물리적 교반을 행한 경우보다 60% 이상 단축되었으며, 이는 용액 중에서 발생하는 초음파의 공동화 현상에 의해 형성된 강한 전단력에 의한 결과로 해석된다.

From L-Ascorbic Acid to Protease Inhibitors: Practical Synthesis of Key Chiral Epoxide Intermediates for Aspartyl Proteases

  • Chang, Sun-Ki;So, Soon-Mog;Lee, Sang-Min;Kim, Min-Kyu;Seol, Kyoung-Mee;Kim, Sung-Min;Kang, Jae-Sung;Choo, Dong-Joon;Lee, Jae-Yeol;Kim, B.-Moon
    • Bulletin of the Korean Chemical Society
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    • 제33권7호
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    • pp.2213-2218
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    • 2012
  • Efficient synthetic routes were developed to prepare a sizable amount (4-15 grams) of the chiral epoxides 4-6 as versatile intermediates for the synthesis of aspartyl protease inhibitors of therapeutic interest such as HIV protease and ${\beta}$-secretase. Oxidative cleavage of the C(2)-C(3) double bond of L-ascorbic acid followed by functional group manipulation led to the preparation of the epoxide 10, which was opened with an azide to yield a common aziridine intermediate 12. Through opening of the aziridine ring of 12 with either a carbon or a sulfur nucleophile, chiral epoxide precursors 4-6 could be prepared for various HIV protease inhibitors. Except for the final low melting epoxides 5 and 6, all intermediates were obtained as crystalline solids, thus the synthetic pathway can be easily applied to a large-scale synthesis of the chiral epoxides.

Glycidyltrimethylammonium Chloride(GTAC)를 이용한 양모 섬유 표면의 Silver Nanoparticle 부착 (Attachment of Silver Nanoparticles to the Wool Fiber Using Glycidyltrimethylammonium Chloride(GTAC))

  • 이승영;설인환;이재웅
    • 한국염색가공학회지
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    • 제28권2호
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    • pp.70-76
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    • 2016
  • Silver nanoparticles(AgNPs) were attached to wool fibers using glycidyltrimethylammonium chloride(GTAC), which is a type of quaternary ammonium salt. GTAC, which contains an epoxy functional group that, under high temperatures, generates a ring-opening reaction with wool fibers, which contain the amine group. Then, the AgNPs are attached to the surface of the GTAC-treated wool fibers by treatment with a silver colloidal solution. The process involves the following procedures: (1) The wool fibers are immersed in the GTAC solution, followed by pre-drying at $80^{\circ}C$ and curing at $180^{\circ}C$ to induce an alteration in the chemical structure; and (2) The wool fibers treated with GTAC are immersed in the silver colloid at $40^{\circ}C$ for 120 min to chemically induce a strong attachment of the AgNPs to the wool fibers. Scanning electron microscopy was used to analyze the influence of the concentrations of GTAC and the silver colloid, as well as the influence of the applied temperature of the silver colloid on the wool fibers, and the influence of the morphological changes in the wool fiber surfaces. As a result, the enhanced concentrations of GTAC and the silver colloid together with an elevated applied temperature of silver colloid have a tendency to increase in Ag atomic%.

면섬유염색폐수의 공정별 폐수성상과 이온화가스에 의한 처리특성 (Composition of Cotton Textile Dyeing Process Wastewater and its Treatment Characteristics by Ionized Gas)

  • 임경은;정팔진;권지영;이은주
    • 한국물환경학회지
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    • 제23권3호
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    • pp.303-308
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    • 2007
  • Three types dyeing wastewater (dark, medium, light color) discharged from cotton textile dyeing with reactive dye was collected at each step of process. Each process dying wastewater was analyzed and treated by ionized gas. The analysis focused on $COD_{Cr}$, SS and color. Bleaching & scouring process wastewater has the highest $COD_{Cr}$ value in the three type dyeing wastewater. SS shows the highest value at dyeing process wastewater in dark and medium color but light color has at finishing process wastewater. The result of process wastewater treatment by ionized gas was that the ionized gas was effective in $COD_{Cr}$ removing of bleaching & scouring process and finishing process wastewater but was not good at dyeing process wastewater. From that result it is estimated that the ionized gas could not work in opening the aromatic ring and react only in aliphatic component of the molecule. Because the surfactants contained in bleaching & scouring process and finishing process wastewater have only one aromatic ring in its molecular structure, in contrast with the reactive dye compounds consist of aromatic rings great part of its molecular structure. The color almost removed in 1.5 hrs reaction time but $COD_{Cr}$ removal effiency was only 30.7% through 3hrs in 1500 mL of total dyeing wastewater treated by 10 L/min ionized gas.

Molecular Cloning and Enzymatic Characterization of Cyclomaltodextrinase from Hyperthermophilic Archaeon Thermococcus sp. CL1

  • Lee, Jae-Eun;Kim, In-Hwan;Jung, Jong-Hyun;Seo, Dong-Ho;Kang, Sung-Gyun;Holden, James F.;Cha, Jaeho;Park, Cheon-Seok
    • Journal of Microbiology and Biotechnology
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    • 제23권8호
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    • pp.1060-1069
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    • 2013
  • Genome organization near cyclomaltodextrinases (CDases) was analyzed and compared for four different hyperthermophilic archaea: Thermococcus, Pyrococcus, Staphylothermus, and Thermofilum. A gene (CL1_0884) encoding a putative CDase from Thermococcus sp. CL1 (tccd) was cloned and expressed in Escherichia coli. TcCD was confirmed to be highly thermostable, with optimal activity at $85^{\circ}C$. The melting temperature of TcCD was determined to be $93^{\circ}C$ by both differential scanning calorimetry and differential scanning fluorimetry. A size-exclusion chromatography experiment showed that TcCD exists as a monomer. TcCD preferentially hydrolyzed ${\alpha}$-cyclodextrin (${\alpha}$-CD), and at the initial stage catalyzed a ring-opening reaction by cleaving one ${\alpha}$-1,4-glycosidic linkage of the CD ring to produce the corresponding single maltooligosaccharide. Furthermore, TcCD could hydrolyze branched CDs (G1-${\alpha}$-CD, G1-${\beta}$-CD, and G2-${\beta}$-CD) to yield significant amounts (45%, 40%, and 46%) of isomaltooligosaccharides (panose and $6^2$-${\alpha}$-maltosylmaltose) in addition to glucose and maltose. This enzyme is one of the most thermostable maltogenic amylases reported, and might be of potential value in the production of isomaltooligosaccharides in the food industry.

링타입 고무막을 이용한 식품 포장용 가스배출 밸브(Degassing Valve) 개발 (Development of Degassing Valves for Food Packaging using Ring Type Rubber Disk)

  • 유하경;이경호;오재영
    • 한국포장학회지
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    • 제20권2호
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    • pp.35-39
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    • 2014
  • 최근 커피시장의 고속 성장과 더불어 커피 포장용 가스배출 밸브(Degassing valve)의 수요도 급격히 증가하고 있다. 가스배출 밸브 주요 제조사(Big maker)로 Goglio사(이탈리아), Bosch사(독일) 및 Wipf사(스위스)가 있는데, 이들이 전세계 가스배출 밸브 포장재 소비량의 80%이상을 공급하고 있다. 국내시장 역시 대부분 수입에 의존하고 있어 수입 대체와 국내 포장산업 활성화를 위해 기술적 차별화와 동시에 선진기업 수준의 품질 성능을 갖춘 가스배출 밸브의 개발이 필요하였다. 따라서, 본 연구에서는 링타입 고무막을 적용하여 중앙 개폐형 가스배출 밸브(SP 밸브)를 개발하였으며, 실험을 통해 열림압력 820~1200 Pa, 닫힘압력 10~50 Pa, 가스 유동율 1.2~1.6 L/min로 Goglio 밸브와 대등한 수준의 품질 성능을 확인할 수 있었다. 또한, 식품용 기구 및 용기 포장 공전에 따른 밸브의 식품용기 품질 적합성을 확인하였으며, 향후 커피 포장용 밸브의 국내외 시장 점유율 확대와 함께 국내 발효식품 포장에 적용함으로써 한식 세계화에 기여할 것으로 기대된다.

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아세톡시 1,3-옥사티올란의 입체화학의 결정 (Determination of Stereochemistry of Acetoxy 1,3-Oxathiolane)

  • 한호규;장기혁;이화석;마혜덕
    • 대한화학회지
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    • 제40권5호
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    • pp.357-364
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    • 1996
  • 아세톡시 1,3-옥사티올란 1의 이성체들의 입체화학을 두 가지 방법에 의해 결정하였다. 첫째, 산촉매하에서 디히드로옥사티인 2로의 전환되는 반응속도 차이에 의해 알파이성체 7과 베타이성체 9의 구조를 결정하였다. 이탈기인 아세톡시기가 황원자와 트랜스 위치에 있을 때 1,3-옥사티올란 고리에 대한 입체장애가 적은 이성체가 알파이성체 7이며 반응속도가 느린 이성체가 베타이성체 9이었다. 둘째, 술폭시드의 각각의 diastereomer들의 중수소 치환반응에서, methine 수소가 중수소로 치환된 화합물은 시스이성체 15, 17, 그리고 메틸기의 수소가 중수소로 치환된 화합물은 트랜스이성체 16, 18이었다. Methine 또는 메틸기의 수소의 중수소로의 치환은 [2,3] 시그마트로픽 전위에 의한 입체특이적 개환 및 폐환의 결과였다.

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Crystal Structure of Fully Dehydrated Partially Cs+-Exchanged Zeolite X, Cs52Na40-X (The Highest Cs+-Exchanged Level Achieved by Conventional Method and Confirmation of Special Site Selectivity)

  • Bae, Myung-Nam
    • Bulletin of the Korean Chemical Society
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    • 제28권2호
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    • pp.251-256
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    • 2007
  • The crystal structure of fully dehydrated partially Cs+-exchanged zeolite X, [Cs52Na40Si100Al92O384], a = 24.9765(10) A, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at 21 °C. The crystal was prepared by flow method for 5 days using exchange solution in which mole ratio of CsOH and CsNO3 was 1 : 1 with total concentration of 0.05 M. The crystal was then dehydrated at 400 °C and 2 × 10-6 Torr for 2 days. The structure was refined to the final error indices, R1 = 0.051 and wR2 (based on F2) = 0.094 with 247 reflections for which Fo > 4σ (Fo). In this structure, about fifty-two Cs+ ions per unit cell are located at six different crystallographic sites with special selectivity; about one Cs+ ion is located at site I, at the centers of double oxygen-rings (D6Rs), two Cs+ ions are located at site I', and six Cs+ ions are found at site II'. This is contrary to common view that Cs+ ions cannot pass sodalite cavities nor D6Rs because six-ring entrances are too small. Ring-opening by the formation of ?OH groups and ring-flexing make Cs+ ions at sites I, I', and II' enter six-oxygen rings. The defects of zeolite frameworks also give enough mobility to Cs+ ions to enter sodalite cavities and D6Rs. Another six Cs+ ions are found at site II, thirty-six are located at site III, and one is located at site III' in the supercage, respectively. Forty Na+ ions per unit cell are located at two different crystallographic sites; about fourteen are located at site I, the centers of D6Rs and twenty-six are also located at site II in the supercage. Cs+ ions and Na+ ions at site II are recessed ca. 0.34(1) A and 1.91(1) A into the supercage, respectively. In this work, the highest exchange level of Cs+ ions per unit cell was achieved in zeolite X by conventional aqueous solution methods and it was also shown that Cs+ ion could pass through the sixoxygen rings.

Preparation and Characterization of Water-Dispersible Silver Nanoparticles Stabilized by PEO-Conjugated Pro-Drugs

  • Kim, Tae-Hwan;Kim, Keun-Suk;Park, Geon-Hee;Choi, Jin-Hee;Lee, Sang-Mi;Kang, Ho-Jung;Lee, Jae-Yeol;Kim, Jung-Ahn
    • Macromolecular Research
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    • 제17권10호
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    • pp.770-775
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    • 2009
  • $\omega$-Anhydride-functionalized poly(ethylene oxide) (PEO) obtained from chain-end functionalization and anionic ring-opening polymerization of ethylene oxide using n-butyllithium with potassium t-butoxide in the presence of dimethylsulfoxide (DMSO) was found to be an efficient material for the preparation of water-soluble, polymeric pro-drugs. The reaction of $\omega$-anhydride-functionalized PEO with sulfonamide or with vancomycin provided an efficient method to produce corresponding, water-soluble, PEO-conjugated sulfonamide or PEO-conjugated, vancomycin pro-drugs. These were used successfully to prepare water-dispersible, silver nanoparticles. In this study, the particle sizes were in the range of $5{\sim}40$ nm. The resulting products were characterized by $^1H$ NMR spectroscopy, transmission electron microscopy, electron and X-ray diffraction, size exclusion chromatography, and UV/Visible spectroscopy.

Preparation and Properties of Novel Biodegradable Hydrogel based on Cationic Polyaspartamide Derivative

  • Moon, Jong-Rok;Kim, Bong-Seop;Kim, Ji-Heung
    • Bulletin of the Korean Chemical Society
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    • 제27권7호
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    • pp.981-985
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    • 2006
  • Novel copolymers consisting of poly(2-hydroxyethyl aspartamide-co-N,N'-dimethyl-1,3-propane aspartamide) (PHEA-DPA) were prepared from polysuccinimide (PSI), which is the thermal polycondensation product of aspartic acid, via a ring-opening reaction with N,N'-dimethyl-1,3-propane diamine (DPA) and ethanolamine. The prepared water-soluble copolymer was then crosslinked by reacting it with hexamethylene diisocyanate to provide the corresponding gel. The swelling behavior and morphology of the crosslinked hydrogels were investigated. The degree of swelling decreased with increasing crosslinking reagent due to the higher crosslinking density. It was also confirmed that the swelling property is affected by pH. At low pH (< pH 4), swelling is increased due to the ionization of DPA with a tertiary amine moiety. In addition, a reversible swelling and de-swelling behavior was demonstrated by adjusting the pH of the solution. The prepared hydrogels showed a well-interconnected microporous structure with regular 5-20 $\mu$m sized pores.