Pyridine 존재여부에 따른 Trans-3-hexene의 오존 산화 반응

김철규; 홍원표

Journal of the Korean Industrial and Engineering Chemistry, Vol.3, No.4, 579-587, December, 1992

Export Citation

Pyridine 존재여부에 따른 Trans-3-hexene의 오존 산화 반응

Ozone Oxidation of Trans-3-hexene with/without Pyridine

김철규, 홍원표

초록

올레핀의 오존화 반응에서 보여지는 통상의 반응경로가 pyridine의 도움으로 modification될 수 있는지 여부가 검토되었다. 먼저, trans-3-hexene의 오존 산화 반응이 aprotic non-participating solvent인 n-pentane과 dichloromethane을 사용하여 시험되었다. 덧붙여, 올레핀의 오존 산화 반응에서 pyridine의 역할과 반응기구를 검토하기 위하여, monomeric과 Polymeric ozonides의 염기성 촉매 분해반응이 시험되었다. 본 연구에서 반응 과정의 고찰뿐만 아니라 생성물의 정량, 정성 분석을 위하여 현대적인 분석 기기들이 사용되었다. 본 연구의 결과로서, Pyridine 무존재하 aprotic solvent에서 올레핀과 오존의 반응으로 주로 과산화물인 monomeric이나 polymeric ozonides가 생성되었으며, pyridine 존재하에서는 과산화물의 생성없이 propionaldehyde와 Criegee zwitterion의 자리옮김 생성물인 propionic acid가 주생성물이었다. 또한, tans-3-hexene의 오존 산화 반응에서 Pyridine의 촉매작용에 의하여 trans-3-hexene의 Criegee zwitterion의 propionic acid로 이성화되는 것으로 사료된다.

It was explored, whether the usual course of the ozonolysis of olefins can be modified with the help of pyridine. In the First step, the ozone oxidation of trans-3-hexene was performed with and without pyridine in the inert solvents n-pentane and dichloromethane. In addition, base catalyzed decompositions of monomeric and polymeric ozonides were also examined to identify the reaction mechanism. The reaction products were identified by modern analytical tools. The results of this work showed that reactions of ozone with olefins in the absence of pyridine in aprotic solvents gave, one hand, dominantly peroxidic products, namely monomeric and polymeric ozonides. The other hand, they in the presence of pyridine gave only the non-peroxidic products, namely propionaldehyde and rearranged propionic acid without peroxidic products. It seems, also, that the pyridine-catalyzed isomerization of the Criegee zwitterion of trans-3-hexene to give propionic acid takes place in the ozone oxidation of trans-3-hexene.

[References]

Bailey PS, "Ozonation in Organic Chemistry," Vol. 1, Academic Press, New York (1978)
Griesbaum K, Chem. Commun., 920 (1966)
Griesbaum K, Burton GW, Preprints of Papers, A.C.S. Petroleum Chemistry Division, 13, 216 (1968)
Bailey PS, Chem. Rev., 58, 925 (1958)
Slomp G, Johnson JI, J. Am. Chem. Soc., 80, 915 (1958)
Slomp G, Johnson JI, Adv. Chem. Ser., 21, 162 (1959)
Pryde EH, Cowan JC, Top Lipid Chem., 2, 1 (1971)
Murry RW, Youssefyeh RD, Williams GJ, Story PR, Tetrahedron, 24, 4347 (1968)
Murry RW, Ramachandran V, J. Org. Chem., 48, 813 (1983)
Reinhardt C, "Solvents and Solvent Effects in Organic Chemistry," 2nd Ed., 69, VCH Verlagsgesellschaft mbH, Weinheim (1988)
Schroeder G, Chemische Berichte Jahrg, 95, 733 (1961)
Loan LD, Murray RW, Story PR, J. Am. Chem. Soc., 87, 737 (1965)
Ball V, Diplomarbeit, Universitaet Karlsruhe (1990)
Lorenz O, Parks CR, J. Org. Chem., 30, 1976 (1965)
Razumovskii SD, Niazashvili GA, Tutorskii IA, Yur'ev YN, Polym. Sci. USSR, 13, 217 (1971)
Corey FA, Sundbery RJ, "Advanced Organic Chemistry," Part A, 267, Plenum, New York and London (1984)
Kornblum N, DeLaMare HE, J. Am. Chem. Soc., 73, 880 (1951)
Ellam RM, Padbury JM, Chem. Commun., 1094 (1971)
Criegee R, Korber H, Adv. Chem. Ser., 112, 22 (1972)

[Referenced By]

[1] Bailey PS, "Ozonation in Organic Chemistry," Vol. 1, Academic Press, New York (1978)

[2] Griesbaum K, Chem. Commun., 920 (1966)

[3] Griesbaum K, Burton GW, Preprints of Papers, A.C.S. Petroleum Chemistry Division, 13, 216 (1968)

[4] Bailey PS, Chem. Rev., 58, 925 (1958)

[5] Slomp G, Johnson JI, J. Am. Chem. Soc., 80, 915 (1958)

[6] Slomp G, Johnson JI, Adv. Chem. Ser., 21, 162 (1959)

[7] Pryde EH, Cowan JC, Top Lipid Chem., 2, 1 (1971)

[8] Murry RW, Youssefyeh RD, Williams GJ, Story PR, Tetrahedron, 24, 4347 (1968)

[9] Murry RW, Ramachandran V, J. Org. Chem., 48, 813 (1983)

[10] Reinhardt C, "Solvents and Solvent Effects in Organic Chemistry," 2nd Ed., 69, VCH Verlagsgesellschaft mbH, Weinheim (1988)

[11] Schroeder G, Chemische Berichte Jahrg, 95, 733 (1961)

[12] Loan LD, Murray RW, Story PR, J. Am. Chem. Soc., 87, 737 (1965)

[13] Ball V, Diplomarbeit, Universitaet Karlsruhe (1990)

[14] Lorenz O, Parks CR, J. Org. Chem., 30, 1976 (1965)

[15] Razumovskii SD, Niazashvili GA, Tutorskii IA, Yur'ev YN, Polym. Sci. USSR, 13, 217 (1971)

[16] Corey FA, Sundbery RJ, "Advanced Organic Chemistry," Part A, 267, Plenum, New York and London (1984)

[17] Kornblum N, DeLaMare HE, J. Am. Chem. Soc., 73, 880 (1951)

[18] Ellam RM, Padbury JM, Chem. Commun., 1094 (1971)

[19] Criegee R, Korber H, Adv. Chem. Ser., 112, 22 (1972)