• Title/Summary/Keyword: C-O bond

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Ketene-Forming Elimination Reactions from Aryl Thienylacetates Promoted by R2NH in MeCN. Effects of Base-Solvent and β-Aryl Group

  • Pyun, Sang-Yong;Cho, Eun-Ju;Seok, Hyoun-Jung;Kim, Ju-Chang;Lee, Seok-Hee;Cho, Bong-Rae
    • Bulletin of the Korean Chemical Society
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    • v.28 no.6
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    • pp.917-920
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    • 2007
  • Ketene-forming eliminations from C4H3(S)CH2C(O)O-C6H3-2-X-4-NO2 (1) promoted by R2NH in MeCN have been studied kinetically. The reactions are second-order and exhibit Bronsted β =0.51-0.62 and |βlg|= 0.47-0.53. Hence, an E2 mechanism is evident. The Bronsted β increased from 0.33 to 0.53 and |βlg| remained nearly the same by the change of the base-solvent from Bz(i-Pr)NH/Bz(i-Pr)NH2+ in 70 mol% MeCN(aq) to Bz(i-Pr)NH-MeCN, indicating a change to a more symmetrical transition state with similar extents of Cβ -H and Cα -OAr bond cleavage. When the β-aryl group was changed from thienyl to phenyl in MeCN, the β value increased from 0.53 to 0.73 and |βlg| decreased from 0.53 to 0.43. This indicates that the transition state became skewed toward more Cβ -H bond breaking with less Cα-OAr bond cleavage. Noteworthy is the greater double bond stabilizing ability of the thienyl group in the ketene-forming transition state.

SHEAR BOND STRENGTH OF COMPOSITE RESIN CORE USED IN COMBINATION WITH VARIOUS RESIN CEMENTS AND DENTIN BONDING AGENTS (레진 시멘트와 상아질접착제를 사용한 콤포지트 레진 코아의 전단결합강도에 관한 연구)

  • Kim Hyun-O;Vang Mong-Sook
    • The Journal of Korean Academy of Prosthodontics
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    • v.42 no.1
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    • pp.30-40
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    • 2004
  • Purpose : The purpose of this study was aimed to compare the shear bond strength on dentin of three dentin bonding agents and two resin cements used in conjunction with self-cured composite resin core material. Material and method : Control group and six experimental groups were divided for this study. Control group was designated as specimens bonded with Tenure$ A&B^{(R)}$. Experimental groups were as follows : PB-BL group : specimens bonded with Prime&Bond $NT^{(R)}$, $BondLink^{(R)}$ SB-BL group : specimens bonded with $^{(R)}$, BondLink$SingleBond^{(R)}$ PB group : specimens bonded with Prime&Bond $NT^{(R)}$ SB group : specimens bonded with $SingleBond^{(R)}$ PF group : specimens bonded with $Panavia-F^{(R)}$ BI group specimens bonded with Bistite $II^{(R)}$ All specimens were stored in $37^{\circ}C$ distilled water for 24 hours, followed by the shear bond strength was tested by universal testing machine. The data was analysed statistically by Mann-Whitney test. Results : 1. For Prime&Bond $NT^{(R)}$ and $SingleBonde^{(R)}$, the shear bond strength was 0.24 MPa and 7.19 MPa each by each, while Tenure $A&B^{(R)}$ group control was measured at 13.93 MPa (p<0.05). Especially for Prime&Bond $NT^{(R)}$ it did not get conjunction with dentin. 2. For Prime&Bond $NT^{(R)}$ and $SingleBond^{(R)}$ using $BondLink^{(R)}$, there was no significant difference as a result of 11.73 MPa and 14.00 MPa each by each (p<0.05). 3. For $Panavia-F^{(R)}$ and Bistite $II^{(R)}$, they showed the highest shear bond strength as measured by 18.24 MPa and 16.09 MPa each (p<0.05).

The Crystal Structure of Thiourea of Derivatives(I) (Thiourea Deirvatives의 결정과 분자구조 (제1보))

  • Park Young Ja;Suh Chung Sun;Koo, Chung Hoe
    • Journal of the Korean Chemical Society
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    • v.21 no.5
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    • pp.307-319
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    • 1977
  • The crystal structure of $N-({\alpha}-dimethyl\;{\beta}-hydroxy)ethyl\;N'-cyclohexyl\;thiourea,\;C_{ll}H_{22}N_2OS)$, has been determined by X-ray diffraction method. The compound crystallizes in the orthorhombic space group Pbca with a = 10.33(3), b = 11.82(3), c = 22.57(4)${\AA}$ and Z = 8. A total of 1414 observed reflections collected by the Weissenberg photographs and was solved by heavy atom method and refined by block diagonal least-squares methods to the R value of 0.13. The cyclohexane ring has a normal chair conformation and the thiourea unit is planar. The primary alcoholic group O-H bonded to C(l) makes an intramolecular hydrogen bond with N(2), which leads to stablize the molecule. There are two independent hydrogen bonds in the structure. One of them is of the type N-H${\cdot}{\cdot}{\cdot}$O intramolecular hydrogen bond with the length 2.71${\AA}$, another is of the type O-H${\cdot}{\cdot}{\cdot}$S intermolecular hydrogen bond with the length 3.21${\AA}$ parallel to the b axis. Apart from the hydrogen bonding system the molecules are held together by van der Waals forces in the crystal.

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Mechanical and durability properties of marine concrete using fly ash and silpozz

  • Jena, T.;Panda, K.C.
    • Advances in concrete construction
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    • v.6 no.1
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    • pp.47-68
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    • 2018
  • This article reports the utilization of fly ash (FA) waste product from industry and silpozz which is an agro-waste from agriculture as an environmental friendly material in construction industry. The evaluation of strength and durability study was observed using FA and silpozz as a partial replacement of Ordinary Portland Cement (OPC). The studied parameters are compressive strength, flexural strength, split tensile strength and bond strength as well as the durability study involves the acid soluble chloride (ASC), water soluble chloride (WSC), water absorption and sorptivity. Scanning electron microscopy (SEM) and XRD of selected samples are also done. It reveals from the test results that the deterioration factor (DF) in compressive strength is 4% at 365 days. The DF of split tensile strength and flexural strength is 0.96% and 0.6% at 90 days respectively. The minimum slip is 1mm and 1.1mm after 28 days of testing bond strength for NWC and SWC sample respectively. The percentage decrease in bond strength is 10.35% for 28 days SWC samples. The pre-cast blended concrete samples performed better to chloride diffusion. Modulus of elasticity of SWC samples are also studied.The water absorption and sorptivity tests are conducted after 28 days of curing.

Kinetic Studies on the Reaction of Benzyl m-Nitrobenzenesulfonate with N,N-Dimethylanilines (벤질 m-술폰산니트로벤젠과 N,N-디메틸아닐린類와의 反應에 關한 反應速度論的 硏究)

  • Yoh Soo-Dong;Lee Mu-Sang
    • Journal of the Korean Chemical Society
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    • v.23 no.1
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    • pp.37-41
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    • 1979
  • The kinetics of the reaction of benzyl m-nitrobenzenesulfonate with m-and p-substituted N,N-dimethylanilines in acetone have been investigated by an electric conductivity method. The effects of substituents on the reactivity of N,N-dimethylaniline and the existence of linear free energy relationship were discussed. The rate constants k were in the range 2.55∼487 $10^{-4}l{\cdot}mol^{-l}{\cdot}sec^{-1} (35^{\circ}C)$ and increased with the electron donating ability of substituents. In the present reaction, the Hammett plot was correlated with ${\sigma}$ substituent constant, especially using the new ${\sigma}$ value of 0.35 in p-MeO and it's ${\rho}$ value was found to be -1.37. r value for the reaction was very large than the value obtained in the reaction of benzyl bromide. $Br{\"{o}}nsted$ linear relationship was shown between rate constant and basicites except for p-MeO resulted from solvent effect. From the Bronsted plot, this reaction was suggested that the cleavage of the C${\cdot}{\cdot}{\cdot}$O bond in the $S_N2$ transition state proceed the bond formation.

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Electrospun Nanofibrous Polyacrylonitrile(PAN)/ Fe2O3 Membrane as Co2Gas Sensor

  • Kim, Ye-Na;Park, Eun-Young;Lee, Deuk-Yong;Lee, Myung-Hyun;Lee, Se-Jong;Kim, Bae-Yeon;Cho, Nam-Ihn
    • Journal of the Korean Ceramic Society
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    • v.44 no.4 s.299
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    • pp.194-197
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    • 2007
  • Polyacrylonitrile (PAN)/$Fe_2O_3$ nanocomposite membranes with a thickness of 0.02 mm were electrospun by adding 0 to 5 wt% of $Fe_2O_3$ into PAN. The surface tension, density, kinematic viscosity and dynamic viscosity of the PAN solution were determined to be $33.8{\pm}1mN/m$, 0.9794 g/ml, $1548.6mm^2/sec$ and 1516.7 cP, respectively. The average diameters of PAN fibers containing 0, 1 2, 3, and 4 wt% $Fe_2O_3$ particles were 300, 260, 210, 130, and 90 nm, respectively. Fourier-transform infrared spectroscopy results showed that the addition of $Fe_2O_3$ nanoparticles to the PAN mat reduced the absorption peak intensity at $2242cm^{-1}$ ($C{\equiv}N$ bond) while it caused a sharp increase in the peak intensity at $2356cm^{-1}$(C=O bond). Thus, it appears that an appropriate amount of $Fe_2O_3$ nanoparticles in the PAN backbone leads to an improvement of the performance of the $CO_2$ gas sensor, most likely due to the change of functional groups in the membrane.

Effect of Cation Substitution on the Lattice Vibration and Crystal Structure of Magnetic RuSr1.9A0.1GdCu2O8 (A = Ca, Sr, and Ba) Superconductors

  • Kim, Tae-Woo;Yang, In-Sang;Hwang, Seong-Ju
    • Bulletin of the Korean Chemical Society
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    • v.30 no.11
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    • pp.2559-2562
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    • 2009
  • The lattice vibration and crystal structure of alkaline earth metal-substituted $RuSr_{1.9}A_{0.1}GdCu_{2}O_{8}$ (A = Ca, Sr, and Ba) have been investigated with micro-Raman spectroscopy. The present $RuSr_{1.9}A_{0.1}GdCu_{2}O_{8}$ materials show not only several weak Raman peaks corresponding to the vibrations of $O_{Cu}$ and $O_{Ru}$ but also strong characteristic phonon lines related to $O_{Sr}$ vibration mode. A comparison between the frequency of $O_{Sr}$ vibration and the bond distances of (Ru$O_{Sr}$) and (Cu‒$O_{Sr}$) in the present ruthenocuprates reveals that the vibration energy of $O_{Sr}$ is mainly dependent on the bond distance of (Ru‒$O_{Sr}$). The peak splitting of the $O_{Sr}$ phonon lines was observed for the unsubstituted $RuSr_{1.9}A_{0.1}GdCu_{2}O_{8}$, suggesting the existence of two different (Ru‒$O_{Sr}$) bond distances. Such a peak splitting caused by the appearance of low-energy shoulder reflects the presence of internal charge transfer pathway from the $RuO_2$ plane to the superconductive $CuO_2$ one. After the substitution of Sr with Ca or Ba, the low-energy shoulder peak of $O_{Sr}$ vibration becomes suppressed, underscoring the depression of internal charge transfer between the $RuO_2$ and $CuO_2$ planes. The weakened role of $RuO_2$ layer as charge reservoir in the $RuSr_{1.9}A_{0.1}GdCu_{2}O_{8}$8 (A = Ca, Ba) would be responsible for the depression of $T_c$ upon the Ca/Ba substitution.

Effect of surface treatments and universal adhesive application on the microshear bond strength of CAD/CAM materials

  • Sismanoglu, Soner;Gurcan, Aliye Tugce;Yildirim-Bilmez, Zuhal;Turunc-Oguzman, Rana;Gumustas, Burak
    • The Journal of Advanced Prosthodontics
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    • v.12 no.1
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    • pp.22-32
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    • 2020
  • PURPOSE. The aim of this study was to evaluate the microshear bond strength (µSBS) of four computer-aided design/computer-aided manufacturing (CAD/CAM) blocks repaired with composite resin using three different surface treatment protocols. MATERIALS AND METHODS. Four different CAD/CAM blocks were used in this study: (1) flexible hybrid ceramic (FHC), (2) resin nanoceramic (RNC), (c) polymer infiltrated ceramic network (PICN) and (4) feldspar ceramic (FC). All groups were further divided into four subgroups according to surface treatment: control, hydrofluoric acid etching (HF), air-borne particle abrasion with aluminum oxide (AlO), and tribochemical silica coating (TSC). After surface treatments, silane was applied to half of the specimens. Then, a silane-containing universal adhesive was applied, and specimens were repaired with a composite, Next, µSBS test was performed. Additional specimens were examined with a contact profilometer and scanning electron microscopy. The data were analyzed with ANOVA and Tukey tests. RESULTS. The findings revealed that silane application yielded higher µSBS values (P<.05). All surface treatments were showed a significant increase in µSBS values compared to the control (P<.05). For FHC and RNC, the most influential treatments were AlO and TSC (P<.05). CONCLUSION. Surface treatment is mandatory when the silane is not preferred, but the best bond strength values were obtained with the combination of surface treatment and silane application. HF provides improved bond strength when the ceramic content of material increases, whereas AlO and TSC gives improved bond strength when the composite content of material increases.

Studies on the Crystal Structure of Magnesite (마그네사이트 (MgCO$_3$)의 결정구조에 관한 연구)

  • 오기동
    • Journal of the Korean Ceramic Society
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    • v.12 no.3
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    • pp.8-12
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    • 1975
  • The crystal structure of synthetic magnesite has been studied by X-ray method. Magnesite is trigonal R3c, with a=4.637$\AA$, c=15.023$\AA$ and Z=6. Intensity data were collected with a Rigaku automated four-circle diffractometer and Mo-K$\alpha$ radiation. The structure was refined by the full-matrix least squares method using anisotropic thermal parameters. The final R index for 234 reflections is 0.037. The C-O and Mg-O bond lengths were 1.283 and 2.105$\AA$, respectively. The interatomic angles of three kinds of O-Mg-O were 88.25, 91.75 and 180.00$^{\circ}$, respectively. It is clarified that the distortion of the Mg-O6 octahedron in magnesite is smaller than that of Ca-O6 in calcite.

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