폴리에틸렌글리콜 상이동 촉매를 이용한 디페닐메탄의 산화반응

이화수; 문정열; 박대원; 박상욱; 신정호

Journal of the Korean Industrial and Engineering Chemistry, Vol.4, No.4, 715-720, December, 1993

Export Citation

폴리에틸렌글리콜 상이동 촉매를 이용한 디페닐메탄의 산화반응

Oxidation of Diphenylmethane Using Polyethylene g1yco1s as Phase Transfer Catalysts

이화수, 문정열, 박대원, 박상욱, 신정호

초록

보통의 산화조건에서는 산화되기 어려운 diphenylmethane (pKa=33.4)을 상이동 촉매와 고체인 potassium tert-butoxide를 염기로 사용하여 상온과 상압에서 산화시켜 benzophenone을 합성하였다. 4급염인 benzylytriethylammonium chloride, tetrabutyl ammonium bisulphate, tetrabutylphosponium chloride 등은 이 반응에 활성이 없었으나 18-crown-6와 폴리에틸렌글리콜은 촉매활성을 나타내었다. 같은 무게나 같은 몰수의 폴리에틸렌글리콜을 상이동 촉매로 사용한 경우 모두에서 diphenylmethane의 전화율은 폴리에틸렌글리콜의 사슬길이가 길수록 증가하였다. Diphenylmethane의 반응속도는 교반속도가 클수록 증가하였고, 비양성자성 용매인 DMF를 사용한 경우가 벤젠을 용매로 사용한 경우보다 높은 반응속도를 나타내었다.

Diphenylmethane (pKa=33.4), which is difficult to be oxidized in normal oxidation conditions, was oxidized to produce benzophenone at ambient temperature and atmospheric pressure by using phase transfer catalysts and solid potassium tert-butoxide as base. Quaternary salt such as benzyltriethylammonium chloride, tetrabutyl ammonium bisulfate, tetrabutylphosponium chloride, are ineffective catalysts for this reaction, but 18-crown-6 and polyethylene glycols showed catalytic activity. The conversion of diphenylmethane was increased with increasing chain length of PEG molecules when they are used as phase transfer catalysts both in equal molar and equal weight basis. The conversion of diphenylmethane was increased with the agitation speed, and aprotic solvent like DMF showed higher reaction rate compared with benzene.

[References]

Starks CM, Liotta C, "Phase Transfer Catalysis," Academic Press, New York (1978)
Makosza M, Pure Appl. Chem., 43, 439 (1975)
Rabinovitz M, Cohen Y, Halpern M, Angew. Chem.-Int. Edit., 25, 960 (1986)
Dietrich B, Lehn J, Tetrahedron Lett., 15, 1225 (1973)
Bartok W, Rosenfeld DD, Schriesheim A, J. Org. Chem., 28, 410 (1963)
Russell GA, Janzen EG, Becker HD, Smentowsky FJ, J. Am. Chem., 84, 2652 (1962)
Hofmann JE, Rosenfeld DD, Schriesheim A, Prepr. Pap. Am. Chem. Soc. Div. Fuel Chem., 10, 183 (1965)
Neumann R, Sasson Y, J. Org. Chem., 49, 1282 (1984)
Clack JH, Kybett AP, Landon P, Macquarrie DJ, Martin K, J. Chem. Soc.-Chem. Commun., 85, 1355 (1989)
Frensdorff HK, J. Am. Chem. Soc., 93, 600 (1971)
Harris JM, Hundley NH, Shannon TG, Struck EC, J. Org. Chem., 47, 4789 (1981)
Oh SY, Chun SW, Park DW, Park SW, Shin JH, J. Korean Ind. Eng. Chem., 3(4), 620 (1992)
Gokel GW, Goli DM, Schultz RA, J. Org. Chem., 48, 2837 (1983)
Wallace TJ, Schrieshein A, Jacobson N, J. Org. Chem., 29, 2907 (1964)

[1] Starks CM, Liotta C, "Phase Transfer Catalysis," Academic Press, New York (1978)

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

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

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

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

[9] Clack JH, Kybett AP, Landon P, Macquarrie DJ, Martin K, J. Chem. Soc.-Chem. Commun., 85, 1355 (1989)

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

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

[12] Oh SY, Chun SW, Park DW, Park SW, Shin JH, J. Korean Ind. Eng. Chem., 3(4), 620 (1992)

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

[14] Wallace TJ, Schrieshein A, Jacobson N, J. Org. Chem., 29, 2907 (1964)