• 제목/요약/키워드: $S_N'$ Reactions

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Cross Interaction Constants As a Measure of the Transition State Structure (Part VI). Nucleophilic Substitution Reactions of Benzyl Chlorides with Anilines and Benzylamines

  • Lee, Ik-Choon;Huh, Chul;Koh, Han-Joong;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제9권6호
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    • pp.376-378
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    • 1988
  • Results of kinetic studies on the reactions of benzyl chlorides with anilines and benzylamines are reported. Analyses of the cross interaction constants relevant to the degree of bond formation, ${\rho}_{XY}$ and ${\lambda}_{XY}$, are carried out. The magnitudes of the two parameters indicated that the degree of bond formation in the transition state is the typical of that expected for an $S_N2$ reaction, but the reactions with benzylamines appear to have a slightly less degree of bond formation compared with the reactions with anilines.

메탄올-아세토니트릴 혼합용매에서 염화알칸술포닐과 아닐린의 친핵 치환반응에 대한 속도론적 연구 (Kinetic Studies on Nucleophilic Substitution Reactions of Alkane Sulfonylchlorides with Anilines in MeOH-MeCN Mixtures)

  • 이익춘;강한근;이해황
    • 대한화학회지
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    • 제29권5호
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    • pp.478-481
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    • 1985
  • 염화 알칸술포닐과 파라 치환된 아닐린간의 친핵성 치환반응을 메탄올-아세토니트릴 혼합용매하에서 연구하였다. 기질의 반응성, 친핵체의 치환기효과 및 용매효과로 부터 반응 메카니즘이 $S_N2$임을 알았다. i-PSC의 경우 메탄올 조성이 커짐에 따라 전이상태가 더 loose해 짐을 알았다.

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아동의 또래 인기도에 따른 거짓말에 대한 이해, 도덕적 판단 및 정서 반응 (Understanding, Moral Judgment, and Emotional Reactions about Different Types of Lies : Links to Children's Popularity)

  • 박영아
    • 아동학회지
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    • 제30권1호
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    • pp.89-107
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    • 2009
  • This study investigated how peer popularity is linked to children's understanding, moral judgment, and emotional reactions about three different types of lies. Participants were second (n=53) and fourth (n=54) grade children. Results showed that (1) popular children afforded better understanding of white lies than unpopular children; most children understood the definition of an antisocial lie, but not a trick lie. (2) Popular children rated lies more positively than unpopular children. Second graders did not differentiate between the morality of white and trick lies; fourth graders rated white lies as the least serious type of lie. (3) Second graders anticipated greater positive emotional reaction for antisocial lies and greater negative emotional reaction for white lies and trick lies, respectively, than fourth graders.

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Kinetic Studies on Halogen Exchange Reactions of Phenethyl Chloride in Acetone

  • Kim, Shi-Choon;Cheun, Young-Gu;Sakong Yul
    • Nuclear Engineering and Technology
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    • 제7권1호
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    • pp.25-29
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    • 1975
  • 1-Phenethyl Chloride와 2-Phenethyl Chloride의 할로겐 교환반응 속도를 아세톤 용매속에서 방사성 할라이드 이온을 사용하여 측정하였으며, 활성화 엔탈피와 활성화 엔트로피를 결정하였다. 이 반응은 S$_{N}$2 반응이며 할라이드 이온의 상대적 친핵성의 순서는 Cl->Br->I-이고 반응 속도는 Benzyl Chloride와 비교해 볼때 대체적으로 느리다. 이 결과를 할라이드 이온의 용매화 효과와 HSAB원리로 설명하였다.

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Synthesis and Cycloaddition Reactions of N-Aryl-2-furohydrazonyl Chlorides

  • S, Shawali-Ahmad;M, Hassaneen-Hamdi;A, Ibrahim-Hossin
    • Archives of Pharmacal Research
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    • 제13권2호
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    • pp.126-131
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    • 1990
  • The novel N-phenyl-2-furohydrazonyl chloride 4A and its p-nitro analog 4B have been prepared and identified. The cycloaddition reactions of nitrilimines 5A and 5B, derived by base catalyzed dehydrochlorination of 4A and 4B respectively, to a variety of dipolarophiles were investigated. The results showed that 4A and 4B are usuful precursors for synthesis of differently substituted 3-(2-furyl)-2-pyrazoline derivatives and their pyrazoles and analogs.

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아세토니트릴-메탄올 혼합용매계에서 질산벤질과 아닐린의 친핵성 치환반응 (Kinetic Studies on the Nucleophilic Reactions of Substituted Benzylnitrates with Anilines in $CH_3CN-CH_3OH$)

  • 손창국;김왕기;이수정;양기열
    • 대한화학회지
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    • 제34권3호
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    • pp.227-231
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    • 1990
  • 50-100% $CH_3CN-CH_3OH$ 혼합용매계에서 파라-치환된 질산벤질과 아닐린과의 친핵성 치환반응에 대한 2차 속도상수를 전기전도도법으로 구하였다. 속도자료를 이용하여 Hammett ${\rho}_N$${\rho}_C$값, Bronsted $\beta$값 및 용매화 파라미터 계수들을 구하였으며 이들을 PES및 양자역학 모형에 적용하여 구조 변화를 논의하였다. 연구 결과 결합형성보다 결합절단이 비교적 많이 진행된 상태에서 치환기 변화에 따라 결합절단의 진척이 결합형성을 촉진하는 동시적 $S_N2$ 반응메카니즘으로 진행됨을 알았다.

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Alanine and S-Methylcysteine Cobalt (III) Complexes of Ethylenediamine-N,N'-di-${\alpha}$-butyric Acid

  • Moo-Jin Jin;Jio Woo Cheon;Sung Rack Choi
    • Bulletin of the Korean Chemical Society
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    • 제11권3호
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    • pp.251-253
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    • 1990
  • L-Alanine(L-ala) and S-methyl-L-cysteine(L-mcy) cobalt(III) complexes of a flexible $N_2O_2$-type tetradentate ligand ethylenediamine-N,N'-di- -butyric acid(eddb), s-cis-[Co(eddb)(L-ala)] and s-cis-[Co(eddb)(L-mcy), have been prepared via the substitution reactions of the s-cis-$[Co(eddb)Cl_2]$-complex with, respectively, L-alanine and S-methyl-L-cysteine. Both L-alanine and S-methyl-L-cysteine are found to coordinate to the cobalt(III) ion via the nitrogen and oxygen donor atoms to give the meridional s-cis isomer. Electronic absorption, ir and pmr spectra are used to characterize the complexes obtained in this work along with elemental analysis data.

MeOH-MeCN 혼합용매계에서 브롬화벤질 및 요오드화벤질과 아닐린 사이의 친핵성 치환반응 (Nucleophilic Substitution Reactions of Benzyl Bromides and Benzyl Iodide with Anilines in MeOH-MeCN Mixtures)

  • 이익춘;손세철;송호봉;이병춘
    • 대한화학회지
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    • 제28권3호
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    • pp.155-162
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    • 1984
  • 메탄올-아세토니트릴 혼합용매계에서 파라치환된 브롬화 벤질 및 요오드화 벤질과 아닐린 치환체 사이의 친핵성 치환반응을 35.0$^{\circ}$C에서 연구하였다. Hammett관계식, Bronsted 관계식을 이용하여 반응 선택성 파라미터인$ {\rho}_N,\;{\rho}_C$${\beta}$값을 구했으며 분광용매화 관계식의 계수 a, s 등을 구했다. 분광용매화 관계식의 계수 a, s 및 a/s값으로부터 혼합용매의 ${\pi}^{sat}$효과가 본 반응에 크게 작용함을 알았다. PES 모형을 적용하여 본 반응이 dissociative $S_N$2메카니즘으로 진행됨을 알 수 있었으며 이탈기 효과의 논의에는 PES모형이 실험결과와 잘 일치하지 않음을 알 수 있었다. 양자역학적 해석방법을 이용하여 본 반응의 전이상태 변화를 논의했으며 실험결과와 잘 일치함을 알 수 있었다.

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Dichloro, Alanine and S-Methylcysteine Cobalt (III) Complexes of Ethylenediamine-N,N$^\prime$-di-$\alpha$-isobutyric Acid

  • Jun, Moo-Jim;Park, Chang-Woo;Park, Youn-Bong;Cheon, Jin-Woo;Choi, Sung-Rack
    • Bulletin of the Korean Chemical Society
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    • 제11권4호
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    • pp.354-357
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    • 1990
  • Synthesis of dichloro cobalt (Ⅲ) complexes of a flexible $N_2O_2-type$ tetradentate ligand, ethylenediamene-N,N'-di-${\alpha}$-isobutyric acid (eddib), has yielded two geometrical isomers, s-cis-$(Co(eddib)Cl_2)- and uns-cis-(Co(eddib)Cl_2)-.$ A series of substitution reactions, $(Co(eddib)Cl_2)^- {\to} (CO(eddib)Cl H_2O) {\to} (Co(eddib)CO_3)^- {\to} (Co(eddib(H_2O)_2)^+$ have been run for each of the two geometrical isomers. The reaction between the s-cis-(Co(eddib)Cl_2)^-$ complex and L-alanine (L-als) or S-methyl-L-cysteine (L-mcy) gave the meridional s-cis-[Co(eddib)(aa)) (aa = L-ala or L-mcy) complex. The S-methyl-L-cysteine was found to coordinate to cobalt (Ⅲ) ion via the nitrogen and oxygen donor atoms.