상이동 촉매를 이용한 B-피콜린의 산화반응

문정열; 양정규; 박대원

Journal of the Korean Industrial and Engineering Chemistry, Vol.6, No.5, 904-909, October, 1995

Export Citation

상이동 촉매를 이용한 B-피콜린의 산화반응

Oxidation of β-Picoline Using Phase Transfer Catalysts

문정열, 양정규, 박대원

초록

본 연구는 보통의 조건에서는 산화되기 어려운 β-피콜린(pKa=30)을 상이동 촉매와 고체인 potassium tertbutoxide(PTB)를 염기로 사용하여 상온과 상압에서 산화시켜 니코틴산을 합성하는데 관한 것이다. 4급 암모늄염과 18-crowns-6 그리고 폴리에틸렌글리콜이 상이동 촉매활성을 나타내었다. 동일 무게나 동일 몰수의 폴리에틸렌글리콜을 상이동 촉매로 사용한 경우 모두에서 β-피콜린의 전화율은 PEG의 사슬길이가 길수록 증가하였다. 4급 암모늄염 촉매의 경우 알킬기의 구조가 클수록, 음이온의 친수성이 강할수록 높은 β-피콜린 전화율을 나타내었다. β-피콜린과 PTB의 농도, tertbutyl alcohol의 농도, 산소의 분압등이 반응에 미치는 영향을 고찰하여 상이동 촉매의 역할이 포함된 반응 메카니즘을 제시하였다.

β-Picoline (pKa= 30), which is difficult to be oxidized in normal conditions, was oxidized to produce nicotinic acid at ambient temperature and atmospheric pressure by using phase transfer catalysts and solid potassium tertbutoxide as base. Quaternary ammonium salts, 18-crown-6 and polyethylene glycols showed phase transfer catalytic activity. The conversion of β-picoline was increased with increasing chain length of PEG molecules when they are used both in equal molar and equal weight basis. Among the quaternary ammonium salt catalysts, the ones with a larger alkyl group and more hydrophilic counter anions, exhibited a high β-picoline conversion. A reaction mechanism, involving the role of phase transfer catalyst, was proposed after kinetic studies on the effect of the concentration of β-picoline, PTB, tert- butyl alcohol and partial pressure of oxygen.

[References]

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[1] Starks CM, Liotta CL, Halpern M, "Phase Transfer Catalysis," Chapman & Hall, New York (1994)

[2] Makosza M, Pure Appl. Chem., 43, 439 (1975)

[3] Rabinovitz M, Cohen Y, Halpern M, Angew. Chem.-Int. Edit., 25, 960 (1986)

[4] Dietrich B, Lehn J, Tetrahedron Lett., 15, 1225 (1973)

[5] Russell GA, Janzen EG, Becker HD, Smentowsky FJ, J. Am. Chem. Soc., 84, 2652 (1962)

[6] Hofmann JE, Rosenfeld DD, Schriesheim A, Prepr. Pap. Am. Chem. Soc. Div. Fuel Chem., 10, 183 (1965)

[7] Bartok W, Rosenfeld DD, Schriesheim A, J. Org. Chem., 28, 410 (1963)

[8] Neumann R, Sasson Y, J. Org. Chem., 49, 1282 (1984)

[9] Frensdorff HK, J. Am. Chem. Soc., 93, 600 (1971)

[10] Harris JM, Hundley NH, Shannon TG, Struck EC, J. Org. Chem., 47, 4789 (1981)

[11] Gokel GW, Goli DM, Schultz RA, J. Org. Chem., 48, 2837 (1983)

[12] Heriott AW, Picker D, J. Am. Chem. Soc., 97, 2345 (1975)

[13] Dehmlow EV, Lissel M, Tetrahedron Lett., 1783 (1983)

[14] Moon JY, Chun SW, Park DW, Park SW, J. Korean Ind. Eng. Chem., 6(2), 331 (1995)

[15] Lee HS, Moon JY, Na SE, Park DW, J. Korean Ind. Eng. Chem., 5(2), 373 (1994)