• 제목/요약/키워드: Substituents

검색결과 567건 처리시간 0.017초

Asymmetric Inducing Effect of Substituents in Chiral Oxazaborolidines on Enantioselective Borane Reduction of Ketones

  • Cho Byung Tae;Ryu, Mi Hae
    • Bulletin of the Korean Chemical Society
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    • 제15권12호
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    • pp.1080-1084
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    • 1994
  • Asymmetric inducing effects of substituents attached at nitrogen, the 5-position and boron in oxazaborolidine rings on asymmetric borane reduction of ketones were investigated. Thus, the effect of N-substituents examined with the oxazaborolidines prepared from (lR,2S)-N-alkyl norephedrine derivatives showed the remarkable decrease of enantioselectivities of the product alcohols by the variation of the steric size of alkyl groups on nitrogen from Me${\leftrightarro}$n-Bu(${\simeq}$Bn)${\leftrightarro}$ neopentyl${\leftrightarro}$i-Pr, such as 83${\%}$ ee with 5b, 22${\%}$ ee with 5c, 23${\%}$ ee with 5f, 16${\%}$ ee with 5e, and 3${\%}$ ee with 5d for the reduction of acetophenone. The presence of diphenyl groups at the 5-position enhanced the enantioselectivities dramatically. The effect of B-alkyl substituents in the oxazaborolidines derived from (lR,2S)-ephedrine showed that the enantioselectivities of product alcohols decreased gradually when the substituents were changed from hydrogen to steric bulky groups such as methyl, n-butyl, thexyl and phenyl.

벤즈아닐리드에 있어서 치환기가 카르보닐 신축진동에 미치는 영향 (On the Correlation of the Carbonyl Stretching Frequency with Substituents in Benzanilides)

  • 홍순영;박용태;최원형
    • 대한화학회지
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    • 제17권3호
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    • pp.193-197
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    • 1973
  • Hammett형의 식${\nu}={\nu}_0 +{\rho}{\sigma}$을 적용하여 벤즈아닐리드에 있어서의 카르보닐 신축진동과 치환기의 상관관계를 조사하였다. 치환기가 C-페닐기에 있을때는 ${\sigma}$보다 ${\sigma}^{+}$ 와 더 좋은 상관관계를 나타내었고 한편 치환기가 N-페닐기에 있을때는 ${\sigma}$와 더 좋은 상관관계를 나타내었다. 치환기가 C- 및 N- 양페닐기에 동시에 있을때는 이들 치환기는 카르보닐 신축진동에 서로 독립적으로 적용하였다. 이와같은 결과를 벤즈아닐리드의 구조를 이용하여 고찰하였다.

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순수 폴리프로필렌 섬유용 안트라퀴논계 마젠타 염료의 합성과 응용 (Synthesis and Application of Anthraquinoid Magenta Dyes for Pure Polypropylene Fibers)

  • 김태경;채유리
    • 한국염색가공학회지
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    • 제25권2호
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    • pp.102-109
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    • 2013
  • A new series of anthraquinoid magenta dyes having alkylphenyl substituents was synthesized and applied toward pure polypropylene fibers. The affinity of the dyes toward polypropylene fibers was increased gradually with the increase of the length of alkyl substituents. The optimum length of alkyl group was determined as heptyl substituents from the practical point of view. The color values of the dyes on polypropylene fabrics displayed slight bluish red, namely magenta which is more practical than primary red in color matching. The good fastness ratings to washing, rubbing and light were obtained for the dyes having longer alkyl groups than hexyl substituents. Expecially they exhibited ratings 4 of light fastness, which is higher than primary red dyes previously reported.

N-(2-Fluoro-4-chloro-5-alkyloxyphenyl)-3,4-dimethyl-2-arylthio-5-oxo-2,5-dihydropyrrole 유도체 중 arylthio- 치환체들의 제초활성에 관한 구조-활성관계 (Structure-activity relationships on the herbicidal activity of the arylthio substituents in N-(2-fluoro-4-chloro-5-alkyloxyphenyl)-3,4-dimethyl-2-arylthio-5-oxo-2,5-dihydropyrrole derivatives)

  • 성낙도;임치환;윤기섭;송종환;김형래
    • 농약과학회지
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    • 제4권2호
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    • pp.32-36
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    • 2000
  • N-(2-fluoro-4-chloro-5-alkyloxyphenyl)-3,4-dimethyl-2-arylthio-5-oxo-2,5-dihydro-pyrrole, 유도체들은 0.1 g/ha 이하의 농도에서 발아 후(Post-emergence), 벼와 논피 (Echinochloa crus-galli)와 올챙이고랭이 (Scriptus juncoides)에 대하여 선택성을 나타내었으며 pyrrole 고리상의 $SR_{2}$-기가 변화함에 따른 구조와 제초활성과의 관계 (SAR)를 청량적으로 검토하였다. 전체적으로 $R_{1}$=propargyl-치환체 (IA), $1{\sim}12$$R_{1}$=2-chloro-2-propenyl-치환체 (IB), $13{\sim}16$보다 높은 제초 활성을 나타내었으며 phenyl 고리상의 위치별 제초활성은 meta > para > ortho의 순으로 meta-치환체가 양호하였다. IA의 논피에 대한 제초활성은 $SR_{2}$-기가 Es상수의 적정값 $(Es)_{opt.}=3.25$을 가질 때 가장 큰 제초활성을 보인 반면에 올챙이 고랭이의 경우에는 MR상수에 의존적이었다.

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Synthesis of Aniline-Based Azopolymers for Surface Relief Grating

  • Jung, Woo-Hyuk;Ha, Eun-Ju;Chung, Il-Doo;Lee, Jang-Oo
    • Macromolecular Research
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    • 제16권6호
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    • pp.532-538
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    • 2008
  • Epoxy-based azopolymers were synthesized by the reaction of the diglycidyl ether of bisphenol A (DGEBA) or N,N-diglycidyl aniline (DGA) with disperse orange 3 (DO3) to give poly(DGEBA-co-DO3) or poly(DGA-co-DO3), respectively. Aniline-based azopolymers prepared from poly(DGA-co-An) precursors, synthesized by the reaction of DGA with aniline, were produced by the post-azo coupling reaction with diazonium salts containing various substituents. Holographic gratings were carried out to measure the diffractive efficiencies (DE) for the interference patterns of the $Ar^+$ laser from 50 to $300\;mW/cm^2$ intensity. The shorter repeating unit with higher chromophore density induced deeper surface relief gratings (SRG). Large surface gratings were observed for the aniline-based azopolymers with -COOH substituents, as compared with those for epoxy-based azopolymers. The aniline-based azopolymers with dimerized chromophores and various substituents were also synthesized to observe the effect of chromophore substituents and dimerization on the holography. The dimerized chromophores were more sensitively photoisomerized by the $Ar^+$ laser beam, and demonstrated a larger grating than that with one azo bond.

Flavone 유도체들의 Tyrosinase 저해활성화 반응에서 Hydroxyl 치환기들의 역할 (The Roles of Hydroxyl Substituents in Tyrosinase Inhibitory Activation of Flavone Analogues)

  • 박준호;성낙도
    • Journal of Applied Biological Chemistry
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    • 제54권1호
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    • pp.56-62
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    • 2011
  • Tyrosinase 저해활성화 반응에 대한 polyhydroxy 치환된 flavone 유도체(1-25) 중, hydroxyl-치환기($R_1-R_9$)들의 역할을 이해하기 위하여 Free-Wilson 분석과 tyrosinase (PDB ID: Deoxyform (2ZMX) 및 Oxy-form; 1WX2)의 활성화 지점에 대한 분자도킹이 연구되었다. Free-Wilson 분석으로부터 $R_1-R_9$ 치환기중에서 $R_1$=hydroxyl 치환기가 tyrosinase 저해활성에 가장 큰 영향을 미치고 있음을 알았다. 기질분자의 hydroxyl 치환기들과 tyrosinase의 반응점 내 아미노산 잔기들 사이의 수소결합들은 안정한 기질-수용체 착 화합물을 형성하는데 기여하였다. 특히, 수소결합성에 기초한 비경쟁적 저해활성화 반응은 기질분자의 hydroxyl 치환기들과 tyrosinase의 반응점 내 peroxide 산소원자(Per404) 사이의 수소결합을 경유하여 일어날 것임을 제안하였다.

수종유말물 시용이 인삼생육에 미치는 영향 (Effect of the Application of Several Organic Materials on Ginseng Growth)

  • 이일호;박찬수
    • Journal of Ginseng Research
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    • 제14권3호
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    • pp.427-431
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    • 1990
  • To search for substituents of greens, several organic materials such as rice straw, barley straw, corn stem and manufactured compost were applied in a ginseng cultivating field. The yields of six year old ginseng harvested in the rice straw, barley strait and corn stem treated field were similar to or higher than that of the greens treated one. The varied amount of applied substituents resulted in a yield change, but statistical linearity was not found. The growth of ginseng aerial part and soil physicochemical property in the field fortified with these substituents showed similar results to those of the greens treated one. So, it is though that these organic materials can substitute for greens.

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The Structural distortion by a Substituent : Monosubstituted Benzene Derivative cases

  • 민병진
    • 자연과학논문집
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    • 제15권1호
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    • pp.47-56
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    • 2005
  • The substituent dependence of geometric distortion through the two independent electronic substituent effects is analyzed for mono-substituted benzene derivatives of $C_{2v}$. Based on resonance structures, quantitative relationships expressing the resonance and field/inductive contribution terms in bond distortions are derived. The calculated field-effect parts of $C_{ipso}$_$C_{ortho}$ ring bonds increase and decrease compared to benzene for electropositive and electronegative substituents respectively. The nonbonded axial distance, $C_{ipso}$....$C_{para'}$ decreases for electronegative substituents and increases for electropositive substituents. As the electronegativity increases, the distance $C_{ortho}$....$C_{ortho'}$ increases. With the $\pi$-donors, $C_{meta}$....$C_{meta'}$ nonbonded distances are shorter compared to the ones of benzene, and for $\pi$-acceptors, the are longer. Our model based on valence bond approach predicts that the average bond length determined the area of ring, and the sum of the angles <$C_{ortho}$_$C_{ispo}$_$C_{ortho}$ and <$C_{meta}$_$C_{para}$_$C_{meta}$ determines the axial distance.

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A Theoretical Study on the Reaction of Phosphadioxiranes and Thiadioxiranes;Disproportionation versus Epoxidation

  • Nahm, Keep-Yung
    • Bulletin of the Korean Chemical Society
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    • 제30권10호
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    • pp.2217-2222
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    • 2009
  • The transition structures for the epoxidations of ethylene and the disproportionations by the dioxiranes of phosphines, phosphites and sulfides were studied with density function theory methods using the Becke3LYP functional and 6-311+G(2d,p) basis set. When the dioxiranes have methyl substituents rather than hydrogen substituents, the reaction barriers ($E_{TS}$) become higher in their epoxidations of ethylene by the steric hindrance, but become lower in their disproportionations of phosphines, phosphites and sulfides, which indicates that the nature of the dioxiranes seems to be electrophilic and in their disproportionations the reaction barriers are effected both by the electrophilicity and the steric hindrance. The steric factors in the disproportionations were calculated and more bulky substituents at dioxiranes may be necessary to retard the disproportionation and to enhance the epoxidation.

2-Substituted Phenyl-5-phenyltetrazole 生成에 있어서의 置換基의 影響에 關하여 (Effect of Substituents on the Formation of 2-Substituted Phenyl-5-phenyltetrazole)

  • 홍순영
    • 대한화학회지
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    • 제11권4호
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    • pp.170-172
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    • 1967
  • 2-Phenyl-5-substituted phenyltetrazole and 2-substituted phenyl-5-phenyltetrazole were prepared from the corresponding hydrazone and phenyl azide with 2-methoxyethanol and metallic sodium as reaction medium at 110~115 $^{\circ}C$. At this reaction condition, however, the preparation of 2-substituted phenyl-5-phenyltetrazoles with substituents of relatively high Hammett substituent constant was unsuccessful. Surprisingly it was found that the solvent molecule was exchanged with substituent during the reaction when tried to obtain 2-m-fluorophenyl-5-phenyltetrazole using benzaldehyde m-fluorophenylhydrazone as starting material. Also disscussed the effect of electronic nature of substituents on the formation of 2,5-diphenyltetrazole derivatives.

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