• Title/Summary/Keyword: 치환반응

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Synthesis of Various Siloxylcellulose Derivatives (Siloxylcellulose 유도체의 합성)

  • Hong, Jae-Jin;Yang, Jae-Kun
    • Applied Chemistry for Engineering
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    • v.10 no.2
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    • pp.275-280
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    • 1999
  • Cellulose has three hydroxyl groups with different reactivity. By substitution reaction, trimethylsiloxyl-, vinyldimethylsiloxyl-, allyldimethylsiloxyl-, phenyldimethylsiloxyl-, 3,3,3-trifluoropropyldimethylsiloxyl- and tris(trimethylsiloxy)siloxylcellulose were synthesized IR, NMR, and elemental analysis were used for confirming their structures, degree of substitution (D.S.) and the reactivity of siloxylation agent, respectively. The D.S. values were 2.5, 2.2, 2.1, 2.2, 2.6, 0.7 for the corresponding siloxylcellulose.

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Determination of Reactivities by Molecular Orbital Theory (Ⅹ). $S_N2$ Retention Mechanism at a Carbonyl Carbon (화학반응성의 분자궤도론적 연구 (제10보). 카르보닐 탄소에서의 $S_N2-$보존형 메카니즘)

  • Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.21 no.1
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    • pp.16-22
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    • 1977
  • Bimolecular substitution of $Cl^-$ at carbonyl carbon of $CH_3COCl$ has been investigated MO theoretically by calculating energy profiles (EHT) and electronic distribution (CNDO/2) for frontside and backside attacks at several distances of approach. Considerations of other experimental and MO data together with these calculations support the $S_N2-$retention mechanism for the substitution at carbonyl carbon.

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Reactions of Iron Alkynyl(Ethoxy)Carbene Complexes with Amines (철 알킨일(에톡시)카르벤 착물 유도체와 아민의 반응)

  • Park, Jaiwook;Kim, Jinkyung;Jung, Hyunmin
    • Journal of the Korean Chemical Society
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    • v.40 no.8
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    • pp.571-578
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    • 1996
  • Iron alkynyl(amino)carbene complexes, (${\beta}$-aminovinyl)carbene complexes, ${\eta}^3$-(2-(alkylcarbonyl)vinyl)carbene complexes, and a 3-aminoallenylidene complex were formed in the reactions of iron alkynyl(ethoxy)carbene complexes with amines. The ratio of the products, which were formed by substitution reaction, the Michael addition of amines, rearrangements after the addition reaction, and the addition followed by the elimination of the ethoxy group, respectively, was dependent on reaction temperature, the substituent of the alkynyl moiety, and employed amines.

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Thermal Rearrangement of 1,1-Disubstituted 2-Vinylcyclopropanes to 4,4-Disubstituted Cyclopentenes (두 치환체를 가진 비닐시클로프로판의 시클로펜텐으로의 열적자리 옮김반응)

  • Iwhan Cho;Kwang-Duk Ahn
    • Journal of the Korean Chemical Society
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    • v.22 no.3
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    • pp.158-163
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    • 1978
  • The four 1,1-disubstituted 2-vinylcyclopropanes, 1,1-diphenyl-2-vinylcyclopropane (1a), 1,1-dicyano-2-vinylcyclopropane(1b), ethyl 1-cyano-2-vinylcyclopropanecarboxylate(1c), and diethyl 2-vinylcyclopropane-1,1-dicarboxylate(1d) rearranged below $300{\circ}C$ to the corresponding 4,4-disubstituted cyclopentenes, 4,4-diphenylcyclopentene(2a), 3-cyclopentene-1,1-dicarboxylate(2d). Diphenpyl derivative 1a rearranged almost quantitatively to 4,4-diphenylcyclopentene(2a) at the temperature of $250{\circ}C$. Although dicyano derivative 1b in solution underwent the thermal rearrangement at rather low temperature of $170{\circ}C$, the other vinylcyclopropanes, 1c and 1d, in solution rearranged thermally above $220{\circ}C$. In the thermal reaction of 1b, 1c, and 1d considerable amounts of polymers 3 were also produced. Also detected product was the ring-opened diene, ethyl 2-cyano-2,4-hexadienoate(4), in case of the pyrolysis of 1c. The observed facile rearrangement of disubstituted vinylcyclopropanes was explained by the radical stabilization effect of substituents on the diradical intermediates 5.

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Solvolysis of Substituted Benzyl Benzenesulfonates in MeOH-MeCN Mixtures (MeOH-MeCN 혼합용매계에서 치환된 벤젠술폰산벤질의 가용매 분해반응)

  • Ikchoon Lee;Won Hee Lee;Chul Hyun Kang;Se Chul Sohn;Choong Shik Kim
    • Journal of the Korean Chemical Society
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    • v.28 no.6
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    • pp.366-373
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    • 1984
  • Methanolysis rates of benzylbenzenesulfonates, substituted both on the substrate (Y) and on the leaving group (Z), were determined in MeOH-MeCN mixtures. The results showed that the reaction proceeds via the dissociative $S_N2$ mechanism, in which bond breaking proceeds in greater degree compared to bond formation at the transition state(TS). Multiple Hammett correlation analysis showed that the cross term, ${\rho}_{YZ}$, is very small and hence the cross interaction of two substituents, Y and Z, at the TS is not important, supporting the dissociative $S_N2 $ type mechanism. While transition state variations predicted by the quantum mechanical model is shown to agree in general with the experimental results, those predicted by the potential energy surface model failed to account for the leaving group effect properly.

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Kinetics of Reactions of Phenacyl Bromides with Imidazoles (치환 브롬화페나실과 이미다졸류의 반응에 대한 반응속도론적 연구)

  • Im, Dong Sun;Gwon, Jong U;Kim, Chang Seok;Hong, Soon Yung
    • Journal of the Korean Chemical Society
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    • v.34 no.2
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    • pp.184-188
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    • 1990
  • Rates for reactions of substituted phenacyl bromides with imidazole and those of substituted imidazoles with phenacyl bromide were measured by an electric conductivity method. The rates were accelerated by electron-withdrawing substituents of phenacyl bromide and these reactions obeyed well both the linear free energy relationship and the isokinetic relationship. The relation between pKa's of substituted imidazoles and reaction constants fit the Bronsted rule. However, the case of 2-methylimidazole deviated far from this rule exerting steric hindrance. The reaction proceeded much faster in acetonitrile than in methanol and the observed ratio, k2 (acetonitrile)/k2 (methanol), was considerably larger than the value calculated from the Kirkwood equation.

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Nucleophilic Substitution at a Carbonyl Atom (III). Solvolysis of Benzoyl Chlorides in Acetone-Water Mixtures (카르보닐 탄소 원자의 친핵성 치환반응 (제3보) 아세톤-물 혼합용액에서의 염화벤조일의 가용매반응)

  • Wang Gi Kim;Ik Choon Lee
    • Journal of the Korean Chemical Society
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    • v.17 no.4
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    • pp.235-239
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    • 1973
  • Kinetic studies of benzoyl chlorides solvolysis have been carried out in acetone-water mixtures. Results show that bimolecular process predominates in the low water content region but SN1 process becomes increasingly important in the high water content solvent composition.

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수소 발생 반응 촉매 개발: 원소 치환을 통한 MoS2 표면 최적화

  • Lee, Gyeong-Pung;Yu, Dong-Seon
    • Proceeding of EDISON Challenge
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    • 2016.03a
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    • pp.330-332
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    • 2016
  • 수소 발생 반응 촉매는 주로 백금(Pt)족 물질로 만들어져왔으나, 그 높은 가격과 희귀성으로 인해 이를 대체할 촉매의 개발이 요구되고 있다. 그중에서 주목받는 물질이 판상 $MoS_2$인데, 순물질로써의 $MoS_2$는 오직 모서리 부분만이 촉매로 기능하며 표면은 안정하여 촉매로써 기능을 하지 못한다는 한계가 있었다. 따라서 $MoS_2$의 표면도 촉매로 기능하여 보다 효율적인 촉매가 될 수 있도록, 자연계에 비교적 풍부한 원소들로 Mo원자를 치환해 보고 평면 스트레인을 줌으로써 표면이 촉매로 기능할 수 있는 조건을 밀도 범함수 이론에 근거해 계산해 보았다. 그 결과, Ge로 치환되고 -10% 스트레인이 걸린 $MoS_2$의 표면이 촉매로 기능할 수 있는 조건을 만족시켰다. 한편 Ge로 치환된 샘플에 수소를 흡착시켰을 때, 치환된 원자와 수소 원자가 반발력을 나타내는 듯한 현상이 관찰되었다.

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The Nucleophilic Crown Ether Ring Cleavage of Nitro Derivatives of Dibenzo-18-crown-6-(I) (친핵성 치환 반응에 의한 Dibenzo-18-crown-6 의 Nitro 유도체 화합물의 Crown Ether 고리 끊어짐 (제 1 보))

  • Sae Hee Chang;Sung Ah Cho
    • Journal of the Korean Chemical Society
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    • v.32 no.1
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    • pp.71-78
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    • 1988
  • The crown ether ring of 20, 21, 24, 25-tetranitrodibenzo-18-crown-6(TNDB-18-C-6) was cleaved by various alcoholic bases to give 2,4,5-trialkoxynitrobenzene derivatives and 4,5-dialkoxy-1,2-dinitrobenzene derivatives as the major products, and bis[(alkoxynitrophenoxy)ethyl]ether derivatives from partially cleaved crown ether ring as the minor products. The ring cleavage reaction of TNDB-18-C-6 with ethylene glycolic base resulted ring contraction through intramolecular nucleophilic cyclization of the initially formed ring cleavage product to give nitro derivatives of DB-14-C-4.

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