• Title/Summary/Keyword: Substitution reaction

검색결과 580건 처리시간 0.03초

Benzyl benzenesulfonate류의 구조-반응성 관계 (2보). 벤질 유도체의 친핵성 치환반응 (Structure-Reactivity Relationship of Benzyl benzenesulfonates (Part 2). Nucleophilic Substitution Reaction of Benzyl Derivatives)

  • 정덕영;김성홍;이명호;여수동;후지오 미즈에;츠노 유우호
    • 대한화학회지
    • /
    • 제39권8호
    • /
    • pp.643-649
    • /
    • 1995
  • 35$^{\circ}C$와 50$^{\circ}C$ 에서 치환(Z)-benzyl계와 치환(Y)-pyridine 그리고 N, N-dimethylaniline의 Menschutkin형 반응을 아세토니트릴에서 전기전도도법으로 측정하였다. 유사 1차 반응속도상수와 친핵체의 농도로부터 2차반응 속도상수를 계산하였다. $4-CH_3-$보다 전자 받게 치환기를 가진 benzyl bromide는 정상 $S_N2$ (직접 치환 2분자)반응속도만 관찰되었으나 3, $4-(CH_3/O)_2$-benzyl bromide와 $4-CH_3O$-benzyl bromide의 경우 밀착 이온쌍 중간체를 거치는 2분자 반응의 속도도 관측되었다.

  • PDF

Kinetics and Mechanism of the Pyridinolysis of Aryl Ethyl Chlorothiophosphates in Acetonitrile

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
    • /
    • 제32권11호
    • /
    • pp.3947-3951
    • /
    • 2011
  • The nucleophilic substitution reactions of Y-aryl ethyl chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Me. The substituents of X = 4-CN and 4-Ac show great positive deviations from both the Hammett and Bronsted plots. The Hammett plots for substituent Y variations in the substrates exhibit biphasic concave upwards with a minimum point at Y = H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are all in spite of the biphasic free energy correlations for both substituent X and Y variations, since the ${\rho}_X$values with both the strongly and weakly basic pyridines are almost constant. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed where the distance between X and Y does not vary from the intermediate to the second transition state. A frontside attack is proposed with the strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values and a backside attack is proposed with the weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$. The positive deviations of the two strong ${\pi}$-acceptor parasubstituents, X = 4-Ac and 4-CN, from both the Hammett and Bronsted plots are rationalized by the great extents of bond formation and breaking.

Pycnometric and Spectroscopic Studies of Red Phosphors Ca2+(1-1.5x)WO4:Eu3+x and Ca2+(1-2x)WO4:Eu3+x,Na+x

  • Cho, Seon-Woog
    • Bulletin of the Korean Chemical Society
    • /
    • 제34권9호
    • /
    • pp.2769-2773
    • /
    • 2013
  • Red phosphors $Ca_{(1-1.5x)}Eu_xWO_4$ and $Ca_{(1-2x)}Eu^_xNa_xWO_4$ were synthesized with various concentrations x of $Eu^{3+}$ ions by using a solid-state reaction method. The crystal structure of the red phosphors were found to be a tetragonal scheelite structure with space group $I4_1/a$. X-ray diffraction (XRD) results show the (112) main diffraction peak centered at $2{\theta}=28.71^{\circ}$, and indicate that there is no basic structural deformation caused by the vacancies ${V_{Ca}}^{{\prime}{\prime}}$ or the $Eu^{3+}$ (and $Na^+$) ions in the host crystals. Densities of $Ca_{(1-1.5x)}Eu_xWO_4$ were measured on a (helium) gas pycnometer. Comparative results between the experimental and theoretical densities reveal that $Eu^{3+}$ (and $Na^+$) ions replace the $Ca^{2+}$ ions in the host $CaWO_4$. Also, the photoluminescence (PL) emission and photoluminescence excitation (PLE) spectra show the optical properties of trivalent $Eu^{3+}$ ions, not of divalent $Eu^{2+}$. Raman spectra exhibit that, without showing any difference before and after the doping of activators to the host material $CaWO_4$, all the gerade normal modes occur at the identical frequencies with the same shapes and weaker intensities after the substitution. However, the FT-IR spectra show that some of the ungerade normal modes have shifted positions and different shapes, caused by different masses of $Eu^{3+}$ ions (or $Na^+$ ions, or ${V_{Ca}}^{{\prime}{\prime}}$ vacancies) from $Ca^{2+}$.

Effect of Ni dopant on the multiferroicity of BiFeO3 ceramic

  • Hwang, J.S.;Yoo, Y.J.;Kang, J.H.;Lee, K.H.;Lee, B.W.;Park, S.Y.;Lee, Y.P.
    • 한국진공학회:학술대회논문집
    • /
    • 한국진공학회 2016년도 제50회 동계 정기학술대회 초록집
    • /
    • pp.139.1-139.1
    • /
    • 2016
  • Multiferroic materials are of great interest because of its potential applications in the design of devices combining magnetic, electronic and optical functionalities. Among various multiferroic materials, $BiFeO_3$(BFO) is known to be one of the intensively focused mainly due to the possibility of multiferroism at device working temperature (> $200^{\circ}C$). However, leakage current and weak polarization resulting from oxygen deficiency and crystalline defect should be resolved. Furthermore the magnetic ordering of pure BFO mainly prefers to have antiferromagnetic coupling. Up to now many attempts have been performed to improve the ferromagnetic and the ferroelectric properties of BFO by doping. In this work, we investigated the effects of Ni substitution on the multiferroism of bulk BFO. Four BFO samples (a pure BFO and three Ni-doped BFO's; $BiFe_{0.99}Ni_{0.01}O_3$, $BiFe_{0.98}Ni_{0.02}O_3$ and $BiFe_{0.97}Ni_{0.03}O_3$) were synthesized by the standard solid-state reaction and rapid sintering technique. The XRD results reveal that Ni atoms are substituted into Fe-sites and give rise to phase transition of cubic to rhombohedal. By using vibrating sample magnetometer and standard ferroelectric tester, the multiferroic properties at room temperature were characterized. We found that the magnetic moment of Ni-doped BFO turned out to be maximized for 3% of Ni dopant.

  • PDF

Associations between an MDM2 gene polymorphism and ulcerative colitis by ARMS-PCR

  • Doulabi, Mahsa Sadat Hashemi;Moghaddam, Reza Goleyjani;Salehzadeh, Ali
    • Genomics & Informatics
    • /
    • 제18권1호
    • /
    • pp.9.1-9.5
    • /
    • 2020
  • Ulcerative colitis is a form of inflammatory bowel disease characterized by chronic inflammation of the colon and rectum. The abnormal lesions in the digestive system caused by ulcerative colitis and intermittent colitis are of major clinical importance. MDM2 is a phospho-protein that functions as a ubiquitin ligase for p53. Recently, a T>G substitution in the promoter of the MDM2 gene (rs309) has been identified. In this case-control study, 174 ulcerative colitis biopsy samples and 82 control samples were collected from colonoscopy centers, hospitals, and clinics in Mazandaran and Gilan Provinces in Iran from October 2014 to May 2015. This MDM2 polymorphism was investigated in DNA samples (extracted from biopsy samples) by amplification-refractory mutation system polymerase chain reaction. The mean age of patients with ulcerative colitis was 46.5 years (range, 28 to 69 years) and that of control individuals was 45.3 years (range, 26 to 71 years). Seventy-eight patients (44.82%) were men and 96 (55.18%) were women. The distribution of the TT, TG, and GG genotypes was 17.93%, 27.59%, and 34.48%, respectively, in the ulcerative colitis patients and 31.70%, 24.40%, and 43.90%, respectively, in the control individuals (odds ratio of GG for ulcerative colitis, 7.142; 95% confidence interval, 2.400 to 9.542; p = 0.001). It was found that a single-nucleotide polymorphism at rs309 in the MDM2 gene was associated with ulcerative colitis. A direct relationship was found between age and ulcerative colitis, while no relationship was found with sex. This finding is of note because the occurrence of intestinal inflammation and subsequent ulcers can precede the development of cancer.

카르본산계 고성능감수제의 제조 및 그들의 시멘트 흡착성(I) (Preparation of High Range Water Reducer Containing Carboxylic Acid and Their Cement Absorptivity(I))

  • 김화중;강인규;김성훈;김우성;권영도
    • 콘크리트학회지
    • /
    • 제7권2호
    • /
    • pp.175-182
    • /
    • 1995
  • 스티렌과 무수말레인산의 라디칼 공중합에 의해 스티렌-무수말레인산 공중합체(SMA)를 합성하고 SMA를 m-amino phenol과 치환반응하여 m-amino phenol 이 치환된 스티렌-무수말레인산 공중합체(mSMA)도 합성하였다. 합성한 SMA와 mSMA를 황산화하여 각각 황산화 SMA(SSMA) 및 황산화 mSMA(SmSMA)를 제조하였다. 공중합체의 합성은 적외분광스펙트럼의 특성피크로부터 확인할 수 있었다. 원소분석 결과 mSMA의 m-amino phenol의 치환율은 44%이었고 이것은 황산화 과정을 거치면서 35%로 감소하였다. 공중합체의 시멘트에 대한 흡착실험 결과 공중합체의 첨가량이 적을수록 흡착율이 높게 나타났고, 첨가량에 관계없이 SSMA의 흡착율이 SmSMA의 그것보다 크게 나타났다. 본 연구에서 합성한 공중합체 (SSMA, SmSMA)는 시멘트 분산제로서의 가능성이 기대되어진다.

서로 다른 친수성구조를 가지는 고분자전해질 연료전지용 멀티블록형 술폰산화 폴리아릴렌에테르술폰 전해질막의 합성 및 특성 분석 (Synthesis and Characterization of Multi-Block Sulfonated Poly (Arylene Ether Sulfone) Polymer Membrane with Different Hydrophilic Moieties for PEMFC)

  • 육진옥;이소정;양태현;배병찬
    • 전기화학회지
    • /
    • 제18권2호
    • /
    • pp.75-80
    • /
    • 2015
  • 방향족 친핵성 치환반응을 이용하여 멀티블록형 sulfonated poly(arylene ether sulfone)(SPAES) 공중합체를 합성하였다. 서로 다른 말단(F- 또는 OH-말단)을 가지는 친수성 및 소수성 올리고머를 합성한 후 이를 이용하여 고분자 전해질 막을 합성하였다. 각기 다른 말단이 블록공중합체의 분자량에 미치는 영향을 분석하였고, 서로 다른 친수성구조가 블록고분자의 특성에 어떠한 영향을 미치는지 분석하였다. 합성된 멀티블록고분자는 70%이상의 습도에서 나피온 막과 비슷하거나 우수한 이온전도도를 나타내었고, 특히 SPAES 9의 경우 전습도 영역에서 SPAES 10보다 높은 이온전도도를 보였는데, 이는 친수성 블록내의 술폰산기의 부분 농도가 높아짐에 따라 친수성-소수성 간의 상분리가 발달되어 이온전도도가 향상된 것으로 보인다.

Photoaddition Reactions of Silyl Ketene Acetals with Aromatic Carbonyl Compounds: A New Procedure for β-Hydroxyester Synthesis

  • Yoon, Ung-Chan;Kim, Moon-Jung;Moon, Jae-Joon;Oh, Sun-Wha;Kim, Hyun-Jin;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
    • /
    • 제23권9호
    • /
    • pp.1218-1242
    • /
    • 2002
  • Photochemical reactions of aromatic carbonyl compounds with silyl ketene acetals have been explored. Irradiation of acetonitrile or benzene solutions containing aryl aldehydes or ketones in the presence of silyl ketene acetals is observed to promo te formation of ${\beta}-hydroxyester$, 2,2-dioxyoxetane and 3,3-dioxyoxetane products. The ratios of these photoproducts, which arise by competitive single electron transfer (SET) and classical Paterno-Buchi mechanistic pathways, is found to be dependent on the degree of methyl-substitution on the vinyl moieties of the ketene acetals in a manner which reflects expected alkyl substituent effects on the oxidation potentials of these electron rich donors. An analysis of the product distribution arising by irradiation of a solution containing butyrophenone (6) and the silyl ketene acetal 9, derived from methyl isobutyrate, provides an estimate of the rate constants for the competitive Norrish type Ⅱ, SET and Paterno-Buchi processes occuring. Finally, sequences involving silyl ketene acetal-aryl aldehyde or ketone photoaddition followed by 2,2-dioxyoxetane hydrolysis represent useful procedures for Claisen-condensation type, ${\beta}-hydroxyester$ synthesis.

질소-주게 합성수지를 이용한 U(VI), Ca(II) 및 Lu(III) 금속 이온들에 관한 연구 (A Study on the U(VI), Ca(II) and Lu(III) Metal Ions Utilizing Nitrogen-Donator Synthetic Resin)

  • 정만태
    • 환경위생공학
    • /
    • 제15권1호
    • /
    • pp.25-33
    • /
    • 2000
  • 1%, 2%, 10%, 및 20%의 가교도를 갖는 클로로메틸화된 1,4-divinyl benzene에 1-aza-15-crown-5 거대고리 ligand를 치환반응으로 결합시키고, 이들 수지로부터 흡착에 미치는 pH, 시간, 수지의 가교도 그리고 용매의 유전상수 크기에 따른 흡착특성을 조사하였다. 금속이온들은 pH 4 이상에서 우라늄과 칼슘 이온들은 루테튬 이온보다 큰 흡착률을 보였으며, 금속이온들의 흡착 평형시간은 약 2 시간이었다. 한편, ethanol 매질에서의 흡착선택성은 $UO_2^{2+}>Ca^{2}>Lu^{3+}$ 이었고, 흡착력은 1%, 2%, 10%, 20%의 가교도 순 이었으며, 용매의 유전상수(물 : 78.54, 메탄올 : 32.63, 에탄올 : 24.30) 크기에 반비례하였다. 컬럼에서 1%의 가교도를 가진 수지와 금속이온들을 흡착시킨 후 용리액으로 pH2.5 $HNO_3$을 사용하여 각각 분리할 수 있었다.

  • PDF

Eu2+/Dy3+ 이온이 도핑된 Sr2MgSi2O7 분말 합성 및 발광 특성 (Synthesis and Luminescent Characterization of Eu2+/Dy3+-Doped Sr2MgSi2O7 Powders)

  • 박재한;김영진
    • 한국재료학회지
    • /
    • 제24권12호
    • /
    • pp.658-662
    • /
    • 2014
  • $Eu^{2+}/Dy^{3+}$-doped $Sr_2MgSi_2O_7$ powders were synthesized using a solid-state reaction method with flux ($NH_4Cl$). The broad photoluminescence (PL) excitation spectra of $Sr_2MgSi_2O_7:Eu^{2+}$ were assigned to the $4f^7-4f^65d$ transition of the $Eu^{2+}$ ions, showing strong intensities in the range of 375 to 425 nm. A single emission band was observed at 470 nm, which was the result of two overlapping subbands at 468 and 507 nm owing to Eu(I) and Eu(II) sites. The strongest emission intensity of $Sr_2MgSi_2O_7:Eu^{2+}$ was obtained at the Eu concentration of 3 mol%. This concentration quenching mechanism was attributable to dipole-dipole interaction. The $Ba^{2+}$ substitution for $Sr^{2+}$ caused a blue-shift of the emission band; this behavior was discussed by considering the differences in ionic size and covalence between $Ba^{2+}$ and $Sr^{2+}$. The effects of the Eu/Dy ratios on the phosphorescence of $Sr_2MgSi_2O_7:Eu^{2+}/Dy^{3+}$ were investigated by measuring the decay time; the longest afterglow was obtained for $0.01Eu^{2+}/0.03Dy^{3+}$.