• 제목/요약/키워드: C-N bond formation

검색결과 89건 처리시간 0.036초

Chemistry of the 3a,7a-Dihydro-1H-indole Esters. Aromatization by Bromine$^\dag$

  • Lee, Chang-Kiu;Ahn, Yu-Mi;Han Lee, In-Sook
    • Bulletin of the Korean Chemical Society
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    • 제7권4호
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    • pp.311-314
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    • 1986
  • A series of tetramethyl 1-substituted benzyl-3a,7a-dihydro-1H-indole-2,3,3a,4-tetracarboxylates were prepared and their reactions with bromine were examined. The initial reaction seemed to be the formation of the intermediate N-bromo quaternary ammonium bromide. This intermediate underwent aromatization with loss of the 3a-methoxycarbonyl group. Bromine replaced the N-substituent of the p-methoxybenzyl compound and addition of bromine occurred across the $C_6-C_7$ double bond of the indole ring. Bromination of the benzyl ring and aromatization occurred for the m-methoxybenzyl compound.

The Versatile Conversion of Acyclic Amides to a-Alkylated Amines

  • Suh, Young-Ger;Lee, Do-Sang;Shin, Dong-Yun;Jung, Jae-Kyung;Kim, Seok-Ho
    • 대한약학회:학술대회논문집
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    • 대한약학회 2002년도 Proceedings of the Convention of the Pharmaceutical Society of Korea Vol.2
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    • pp.350.2-350.2
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    • 2002
  • The reaction of N-acyliminium ion with a variety of nucleophiles is one of the powerful method to introduce various substituents at the a-carbon of an amine. Particularly this type of inter and intramolecular C-C bond formation can be effectively applied to the synthesis of the bioactive natural or unnatural compounds as well as many bioactive peptidomimetics. Accordingly. much attention has been devoted to the practical and efficient methods for the generation of acyliminium ion precursors though there are many important aspects in the reaction involving N-acyliminium ions. (omitted)

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N-아실 아미노산계 계면활성제에 관한 연구(제9보) -Sodium N-Lauroyl-N-methyl-taurate의 미셀형성에 대한 온도 및 전해질의 영향- (Studies on the Surfactants of the N-Acyl Amino Acid(part 9) -The Effect of Temperature and Electrolytes on the Micellization of Sodium N-Lauroyl-N-Methyl-Taurate-)

  • 김진현;김태영;주명종;남기대
    • 공업화학
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    • 제7권3호
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    • pp.401-409
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    • 1996
  • Sodium N-lauroyl-N-methyl taurate의 cmc에 대한 온도효과를 검토하였다. cmc값들은 처음 $20^{\circ}C{\sim}40^{\circ}C$의 온도 범위에서는 감소하다가 더욱 온도가 증가되면 다시 증가하는 경향이었다. cmc에 대한 온도의 의존성으로부터 여러가지 열역학적 파라미터들(${\Delta}H_m$, ${\Delta}G_m$, ${\Delta}S_m$)을 산출하였다. Sodium N-lauroyl-N-methyl taurate의 cmc에 대한 여러 전해질들의 첨가효과를 또한 검토하였고, 소수성결합 형성에너지 및 미셀의 해리도를 log cmc와 log conc.의 곡선으로부터 산출하였다. ${\Delta}H_m$값들은 온도가 증가함에 따라 감소하였고, $40^{\circ}C{\sim}50^{\circ}C$의 온도범위에서 부호가 양에서 음으로 변하였다. ${\Delta}G_m$값들은 전해질 농도 및 온도가 증가할수록 감소하였다.

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50 nm 이상의 CMOS 기술에 이용되는 Spin-on Dielectric 박막 형성과 그 특성에 미치는 전구체의 영향 (The Effects of Precursor on the Formation and Their Properties of Spin-on Dielectric Films Used for Sub-50 nm Technology and Beyond)

  • 이완규
    • 한국진공학회지
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    • 제20권3호
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    • pp.182-188
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    • 2011
  • 탄소가 없는 폴리실라잔 계와 탄소가 함유된 폴리메틸 실라잔 계 전구체를 실리콘 기판에 스핀코팅하고 $150^{\circ}C$, $400^{\circ}C$, $850^{\circ}C$에서 열처리하여 형성된 박막의 물리적 화학적 특성을 평가하였다. 프리에 변환 적외선 분광, 수축 율, 갭-충진, 식각속도 등을 평가하여 박막형성과 형성된 박막의 물리화학적 특성에 미치는 탄소의 영향을 고찰하였다. 탄소함유 전구체는 (탄소가 없는 전구체보다) $400^{\circ}C$에서 질소, 수소, 탄소의 휘발량이 더 적고 산소 흡수량이 더 적어서 (15.6%)보다 낮은 14.5% 두께 수축을 나타내었으나, $800^{\circ}C$에서는 휘발 량이 더 많고 산소 흡수량도 더 많아져 (19.4%)보다 높은 37.4% 두께 수축을 나타냈다. 프리에 변환 적외선 분광분석결과, 전구체내의 탄소는 Spin-on dielectric (SOD) 박막으로 하여금 Si-O 결합형성을 적게, 박막특성을 불균일하게, 그리고 화학 용액에 더 빨리 식각되도록 만들었다.

Kinetics and Mechanism of Anilinolysis of Phenyl N-Phenyl Phosphoramidochloridate in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제33권10호
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    • pp.3274-3278
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    • 2012
  • The kinetic studies on the reactions of phenyl N-phenyl phosphoramidochloridate (8) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $60.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are huge secondary inverse ($k_H/k_D$ = 0.52-0.69). A concerted mechanism is proposed with a backside attack transition state (TS) on the basis of the secondary inverse DKIEs and the variation trends of the $k_H/k_D$ values with X. The degree of bond formation in the TS is really extensive taking into account the very small values of the DKIEs. The steric effects of the two ligands on the rates are extensively discussed for the aminolyses of the chlorophosphate-type substrates on the basis of the Taft equation.

Bond and fracture strength of metal-ceramic restorations formed by selective laser sintering

  • Bae, Eun-Jeong;Kim, Ji-Hwan;Kim, Woong-Chul;Kim, Hae-Young
    • The Journal of Advanced Prosthodontics
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    • 제6권4호
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    • pp.266-271
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    • 2014
  • PURPOSE. The purpose of this study was to compare the fracture strength of the metal and the bond strength in metal-ceramic restorations produced by selective laser sintering (SLS) and by conventional casting (CAST). MATERIALS AND METHODS. Non-precious alloy (StarLoy C, DeguDent, Hanau, Germany) was used in CAST group and metal powder (SP2, EOS GmbH, Munich, Germany) in SLS group. Metal specimens in the form of sheets ($25.0{\times}3.0{\times}0.5mm$) were produced in accordance with ISO 9693:1999 standards (n=30). To measure the bond strength, ceramic was fired on a metal specimen and then three-point bending test was performed. In addition, the metal fracture strength was measured by continuing the application of the load. The values were statistically analyzed by performing independent t-tests (${\alpha}=.05$). RESULTS. The mean bond strength of the SLS group (50.60 MPa) was higher than that of the CAST group (46.29 MPa), but there was no statistically significant difference. The metal fracture strength of the SLS group (1087.2 MPa) was lower than that of the CAST group (2399.1 MPa), and this difference was statistically significant. CONCLUSION. In conclusion the balling phenomenon and the gap formation of the SLS process may increase the metal-ceramic bond strength.

질화규소에 의한 SiC 소결체의 제조에 관한 연구 (Febrication of $Si_3-N_4$ Bonded SiC Ceramics)

  • 정주희;김종희
    • 한국세라믹학회지
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    • 제20권1호
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    • pp.63-69
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    • 1983
  • It is know that $Si_3-N_4$ bonded SiC has almost all the valuable properties needed for the high temperature material and thus has bery wide range of applicability. Si powder and two different sized SiC powder were used as the raw mateials. Specimens were prepared by heating the green compact mode of the raw materials with polyvinyl alcohol binder in the nitrogen atmosphere. The bond-ing of SiC particles is brought about with the formation of reaction bonded silicon nitride phase between the particles he influences of the variation of the relative amounts of the raw materials and the amount of the organic binder on the density and the bend strength of the specimens were investigated. It was shown that the calculation of the amount of the nitridation of Si is somewhat complicated matter since some portion of the organic binder reacts with the Si during the firing process. Fixing the Si amount to 20w/o the distributions of the size of the SiC particles that gives the maximum density and the maximum strnegth were obtained through experiments. It was observed that the two distributions were not equal to each other. As the amount of Si increased the amount of Si reacted with nitrogen and the strength increased. The fracture mode was intergranular for the most part and the transgranular fracture was scarcely observed.

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Mechanism of workfunction modification on HAT-CN/Cu(111) interface: ab initio study

  • Kim, Ji-Hoon;Park, Yong-Sup;Kwon, Young-Kyun
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2009년도 제38회 동계학술대회 초록집
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    • pp.357-357
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    • 2010
  • Using ab initio density functional theory, we study the structural and electronic properties of interface between Cu surface and highly electron withdrawing hexaazatriphenylene-hexanitrile (HAT-CN) known as an efficient hole injection layer for organic light emitting diodes (OLEDs). We calculate the equilibrium geometries of the interface with different HAT-CN coverages. Usually, some of C-N bonds located at the edge of the HAT-CN molecule are deformed toward Cu atoms resulting in the reconstruction of Cu surface. By analyzing the electron charge and the potential distributions over the interface, we observe the formation of surface dipoles, which modify the work function at the interface. Such dipole formation is attributed to two origins, one of which is a geometrical nature and the other is a bond dipole. The former is related to structural deformation mentioned above, whereas the latter is due to charge transfer between organic and metal surface.

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3차 아민의 4차화반응에 관한 연구 (제2보). 치환 브롬화페나실류와 치환 피리딘류와의 반응에 관한 반응속도론적 연구 (Studies on the Quaternization of Tertiary Amines (Ⅱ). Kinetics and Mechanism for the Reaction of Substituted Phenacyl Bromides with Substituted Pyridines)

  • 여수동;심광택;이경아
    • 대한화학회지
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    • 제25권2호
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    • pp.110-118
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    • 1981
  • 치환 브롬화페나실과 치환 피리딘과의 반응속도를 메탄올과 DMF 용매중, 25∼$45^{\circ}C$의 온도범위에서 전기전도도법으로 측정하였다. 그 결과 두 용매 다 같이 치환 피리딘에서는 전자를 주는 기가 치환되었을 경우 반응속도 상수는 컸으며, 반대로 전자를 끄는 치환기일 경우는 반응속도 상수가 작았다. 기질에서의 치환기 효과는 핵에 전자를 끄는기가 치환되었을 경우 반응속도는 증가하였다. 이 사실들은 탄소원자에 아민이 친핵적으로 공격한다는 것을 알 수 있다. 브롬화페나실과 피리딘의 반응에서 보여준 등속온도는 메탄올과 DMF에서 각각 614와 $202^{\circ}K$였고 $Br{\phi}nsted {\beta}$값은 0.29와 0.36이었다. 치환 브롬화페나실과 피리딘과의 반응의 경우는 등속온도는 전자를 끄는 치환기일 수록 감소하였으며, ${\beta}$값은 그 반대였다. 위의 결과로부터 p-Cl에서 p-MeO 브롬화페니실로 감에 따라 N…C 결합형성이 점차적으로 줄어들고 있으며 결합 형성은 DMF가 메탄올보다 우세하게 진전함을 추측할 수 있다. 치환 피리딘의 경우 Hammett식의 ${\rho}$값은 양 용매에서 모두 부(-)의 값을 가졌다. 핵 치환 브롬화페나실에서의 ${\rho}$값은 0.3의 적은 값이었으며 이는 메틸렌탄소에 피리딘의 질소 원자가 직접적으로 $S_N2$공격을 한다고 생각된다.

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Reactions of 4-Nitrophenyl 2-Thiophenecarboxylates with R2NH/R2NH2+ in 20 mol % DMSO (aq). Effects of 5-Thienyl Substituent and Base Strength

  • Pyun, Sang Yong;Cho, Bong Rae
    • Bulletin of the Korean Chemical Society
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    • 제34권7호
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    • pp.2036-2040
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    • 2013
  • Reactions of 4-nitrophenyl 2-thiophenecarboxylate (1a-e) with $R_2NH/R_2NH{_2}^+$ in 20 mol % DMSO (aq) have been studied kinetically. The $2^{nd}$ order kinetics, ${\beta}_{nuc}$ = 0.88-0.98, and linear Hammett and Yukawa-Tsuno plots observed for these reactions indicate an addition-elimination mechanism in which the $2^{nd}$ step is rate limiting. The ${\beta}_{nuc}$ value increased with a stronger electron-withdrawing 5-thienyl substituent, the Hammett plots are linear except for X = MeO, and Yukawa-Tsuno plots are linear with ${\rho}$ = 0.79-1.32 and r = 0.28-0.93, respectively. The ${\rho}$ value increased and r value decreased with a stronger nucleophile, indicating an increase in the electron density at the C=O bond and a decrease in the resonance demand. These results have been interpreted with enhanced N-C bond formation in the transition state with the reactivity increase.