• Bulletin of the Korean Chemical Society
• /
• 제20권4호
• /
• pp.422-426
• /
• 1999

The Grignard reactions of bis(chloromethyl)dimethylsilane (1) with trimethylchlorosilane (2) in THF give both the intermolecular C-Si coupling and intramolecular C-C coupling products. At beginning stage, 1 reacts with Mg to give the mono-Grignard reagent ClCH2Me2SiCH2MgCl (1) which undergoes the C-Si coupling reaction to give MC2Si(CH2SiMe3)2 3, or C-C coupling to a mixture of formula Me3SiCH2(SiMe2CH2CH2)nR1 (n = 1, 2, 3, ..; 4a, R1I = H: 4b, R1 = SiMe3). In the reaction, two reaction pathways are involved: a) Ⅰ reacts with 2 to give Me3SiCH2SiMe2CH2Cl 6 which further reacts with Mg to afford a Me2SiCH2Mel-SiCH2MgCl (Ⅱ) or b) I cyclizes intramolecularly to a silacyclopropane intermediate A, which undergoes a ring-opening polymerization by the nucleophilic attack of the intermediates I or Ⅱ, followed by the termination reaction with H2O and 2, to give 4a and 4b, respectively. As the mole ratio of 2/1 increased from 2 to 16 folds, the formation of product 3 increased from 16% to 47% while the formation of polymeric products 4 was reduced from 60% to 40%. The intermolecular C-Si coupling reaction of the pathway a becomes more favorable than the intramolecular C-C coupling reaction of the pathways b at the higher mole ratio of 2/1.

• 대한수학회지
• /
• 제43권3호
• /
• pp.659-676
• /
• 2006

In this paper, we consider three-component reaction-diffusion system. With an integral condition and a global coupling, this system gives us an interesting free boundary problem. We shall examine the occurrence of a Hopf bifurcation and the stability of solutions as the global coupling constant varies. The main result is that a Hopf bifurcation occurs for global coupling and this motion is transferred to the stable motion for strong global coupling.

• Bulletin of the Korean Chemical Society
• /
• 제24권11호
• /
• pp.1632-1636
• /
• 2003

Palladium-catalyzed cross-coupling reactions of neopentyloxysulfonylphenyl bromides with arylboronic acids provided a variety of neopentyl biphenylsulfonates in good yields. 2-Bromo- and 4-bromobenzenesulfonates underwent the coupling reaction more rapidly than 3-bromobenzenesulfonate, while chlorobenzenesulfonate did not produce the coupling product under the standard reaction conditions.

• 대한화학회지
• /
• 제21권3호
• /
• pp.180-186
• /
• 1977

1-chloro-2-iodoperfluorocycloalkenes를 종전에는 DMF 용매속에서 KI를 사용하여 Halogen 교환반응에 의하여 합성하였으나 alkyllithium으로 금속교환반응을 통하여 iodination함으로써 반응시간이 단축되던지 특히 1,2-dichloroperfluorocyclohexene의 경우에는 더 높은 수득률의 1-chloro-2-iodoperfluorocyclohexene을 얻을 수 있었다. 그리고 1,2-dihaloperfluorocycloalkenes의 coupling 반응도 fluorocycloolefins과 동분을 DMF와 혼합하여 slurry를 만들어 이것을 sublimer속에서 감압하에 반응시키므로서 반응시간과 온도를 낮출 수 있었으며 생성물의 수득률도 많이 증가시킬 수 있었다. 대표적인 예로서 1-chloro-2-iodotetrafluorocyclobutene의 coupling 반응에 있어서는 종전에 비해서 더 높은 수득률의 coupling product를 얻을 수 있었다. 한편 coupling반응이 가능한 기구를 검토하고 그 생성물의 물리적 성질을 측정하여 확인하였다.

• Bulletin of the Korean Chemical Society
• /
• 제20권4호
• /
• pp.427-430
• /
• 1999

The Grignard coupling reaction of bis(chloromethyl)diorganosilanes [(ClCH2)2SiR1R2: R1 = R2 = Me, la; R1 = Me, R2 = Ph, lb; R1 = R2 = Ph, lc] with diorganodichlorosilanes [(Cl2SiR3R4: R3 = R4 = Me, 2a; R3 = Me, R4 = Ph, 2b; R3 = R4 = Ph, 2c] at THE reflux temperature gave the intermolecular C-Si coupling product of 1,1,3,3-tetraorgano-1,3-disilacyclobutanes 3a-f in poor to moderate yields ranging from 7% to 50% along with polydiorganosilapropanes. The cyclization reaction of la-c with methyl-substituted dichlorosilanes 2a, b gave 1,3-disilacyclobutanes 3a-c, e, d in moderate yields (42-50%), while the same reaction with dichlorodiphenylsilane (2c) to 1,3-disilacyclobutanes 3d, f resulted in low yield (7-18%) probably due to the steric hindrance of two-phenyl groups on the silicon of 2c.

• 약학회지
• /
• 제57권5호
• /
• pp.357-361
• /
• 2013

A formal synthesis of Lespedezol $A_1$ has been accomplished. The key feature of this synthesis involves an efficient and powerful palladium-catalyzed cross coupling reaction of diazocarbonyl compound with bis(benzyloxy)phenylboronic acid for the key 3-aryl-chromen-4-one intermediate, which was difficult to be prepared by Suzuki coupling reaction in the previous study. The versatile and efficient synthetic procedure would facilitate synthesis of pterocarpenes and their derivatives.

• Elastomers and Composites
• /
• 제49권3호
• /
• pp.239-244
• /
• 2014

용매를 사용하지 않고 실리카와 실란커플링제의 반응을 투과 방식 휴리에 변환 적외선 분광법(FTIR)과 열중량 분석법(TGA)을 이용하여 조사하였다. 실란커플링제로 bis[3-(triethoxysilylpropyl) tetrasulfide] (TESPT)를 사용하였다. 미반응 TESPT를 제거한 후, FTIR로 화학 결합 형성을 분석하였고 TGA로 반응한 TESPT 함량을 결정하였다. 커플링제의 함량이 증가할수록 실리카에 결합한 커플링제의 양이 증가하였으나, 커플링제를 과량으로 첨가하면 커플링제 간의 축합반응에 의해 올리고머를 형성하였다. 실리카와 커플링제 그리고 고무의 결합을 확인하기 위하여 개질 실리카와 저분자량 액상 BR을 반응시켜 실리카-커플링제-BR 모델 복합체를 제조하여 화학 결합 형성을 조사하였다. 미반응 고무는 용매를 사용하여 제거하였고 FTIR과 TGA로 분석하였다. BR은 개질 실리카의 커플링제와 반응하여 화학 결합을 형성하였다. 실리카-커플링제-BR의 화학 결합 형성으로 인해 실리카 표면의 극성은 크게 낮아졌고 실리카 입자 크기는 커지는 효과를 보였다.

• Elastomers and Composites
• /
• 제12권1호
• /
• pp.27-32
• /
• 1977

The kinetics of azo-coupling reaction of N-acetyl-H-acid (1-acetamino-8-hydroxynaphthalene-3, 6-disulfonic acid) with several heterocyclic diasonium compounds such as diazotiged 3-aminopyridine, 3-aminoquinoline, 8-aminoauinoline and aniline was studied. It was found that reactions proceeded at remarkably different rate. Reaction rate was in increasing order; 3-aminopyridine, 3-aminoquinoline, 8-aminoauinoline and aniline. And the activation energies were 9.62, 10.10, 10.39, 10.70 Kcal/mole, respectively. Especially, the rate constant of 3-aminopyridine was 100 times larger than that of benzene diasonium compound even in strong acidity. Hammett plot was also made of the rate constants obtained against the heterocyclic substituent constants reported in the literature. A good linear relationship was obtained and the reaction constant of N-acetyl H-acid was calculated to be 3.14.

• Bulletin of the Korean Chemical Society
• /
• 제30권11호
• /
• pp.2697-2700
• /
• 2009

A $Pd(OAc)_2/(o-MeOPh)_3P$ system has been developed for the catalytic Suzuki coupling of aryl bromides with arylboronic acids. Our catalyst system covers a broad spectrum of commonly available arylboronic acids and aryl bromides to provide biaryls in very good yields. The catalyst system works very well in the synthesis of sterically hindered biaryls.

• Journal of Microbiology and Biotechnology
• /
• 제25권11호
• /
• pp.1810-1818
• /
• 2015

For the synthesis of various pharmaceuticals, chiral alcohols are useful intermediates. Among them, (R)-ethyl-4-chloro-3-hydroxybutanoate ((R)-ECHB) is an important building block for the synthesis of L-carnitine. (R)-ECHB is produced from ethyl-4-chloro-3-oxobutanoate (ECOB) by a reductase-mediated, enantioselective reduction reaction. The Saccharomyces cerevisiae YOL151W reductase that is expressed in Escherichia coli cells exhibited an enantioselective reduction reaction toward ECOB. By virtue of the C-terminal His-tag, the YOL151W reductase was purified from the cell-free extract using Ni²⁺-NTA column chromatography and immobilized onto Ni²⁺-magnetic microparticles. The physical properties of the immobilized reductase (Imm-Red) were measured using electron microscopy, a magnetic property measurement system, and a zeta potential system; the average size of the particles was approximately 1 μm and the saturated magnetic value was 31.76 emu/g. A neodymium magnet was used to recover the immobilized enzyme within 2 min. The Imm-Red showed an optimum temperature at 45℃ and an optimum pH at 6.0. In addition, Bacillus megaterium glucose dehydrogenase (GDH) was produced in the E. coli cells and was used in the coupling reaction to regenerate the NADPH cofactor. The reduction/oxidation coupling reaction composed of the Imm-Red and GDH converted 20 mM ECOB exclusively into (R)-ECHB with an e.e._p value of 98%.