카본전극을 이용한 9-Methyl-2,3,6,7-tetramethoxyfluorene의 합성

김덕현

Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.1, 39-48, February, 1997

Export Citation

카본전극을 이용한 9-Methyl-2,3,6,7-tetramethoxyfluorene의 합성

Electrolytic Synthesis of 9-Methyl-2,3,6,7-tetramethoxyfluorene with Carbon Electrodes

김덕현

초록

카본전극을 이용한 양극산화을 통해 1,1-Bis-(3,4-dimethoxyphenyl)ethane으로부터 CH₃CN이나 CH₂Cl₂/TFA-혼합용액계에서 Intramolecular cyclizatlon 반응이 일어났다. Intramolecular cyclization에 의한 생성물(9-methyl-2,3,6,7-tetramethoxyfluorene)은 출발물질보다 더 쉽게 산화되고, 그에 따른 산화생성물은 CH₃CN계에서 불안정하여 낮을 수율을 나타냈다. TFA가 존재하는 계에서는 Fluorene 유도체의 산화생성물인 radical cation이 안정하여 환원 후에 더 좋은 수율로 합성할 수 있었다.

The intramolecular cyclization of 1,1-bis-(3,4-dimethoxyphenyl)ethane was shown to take place upon anodic oxidation at carbon electrodes in acetonitrile or in a solvent-mixture containing dichloromethane, trifluoroacetic acid(TFA). Yields are low in the former solvent due to the fact that the cyclized product (9-methyl-2,3,6,7-tetramethoxyfluorene) is more easily oxidized than it's precursor and the oxidation product is not stable. In the presence of TFA, the cation radical derived from the oxidation of the cyclized product is stabilized thus, after reduction may be isolated with better yields.

[References]

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[1] Chang IF, Gilbert BL, Sun TI, J. Electrochem. Soc., 122, 955 (1975)

[2] Kim DH, Ph.D. Dissertation, Aachen Univ. of Technology, Aachen, Germany (1995)

[3] Furuta T, Shimomura T, Mada H, Kobayashi S, Jpn. J. Appl. Phys., 20, L768 (1981)

[4] Genies EM, Bidan G, Diaz AF, J. Electroanal. Chem., 149, 101 (1983)

[5] Yosino K, Kaneto K, Inuishi Y, Jpn. J. Appl. Phys., 22, L157 (1983)

[6] Kaneko M, Nokamura H, Makromol. Chem. Rapid Commun., 8, 179 (1987)

[7] Plamquist U, Ronlan A, Parker VD, Acta Chem. Scand., 2, 267 (1976)

[8] Ronlan A, Coleman J, Hammerich O, Parker VD, J. Am. Chem. Soc., 96, 845 (1974)

[9] Ronlan A, Hammerich O, Parker VD, J. Am. Chem. Soc., 95, 7132 (1973)

[10] Koton S, Obsc Z, Chim., 27, 2142 (1957)

[11] Arcoleo A, Natoli HC, Marino ML, Anmoli di Chimca., 69, 323 (1970)

[12] Russel GS, J. Chem. Soc., 81, 4834 (1959)

[13] Gramstad T, Haszeldine RN, J. Chem. Soc., 4096 (1957)

[14] Olah GA, Nishimura J, J. Am. Chem. Soc., 98, 2214 (1974)

[15] Yakobson GG, Furin GG, Synthesis, 345 (1980)

[16] Autorenkollektiv, Organikum, 18, Auflage, Berlin (1992)

[17] Gattermann, Wieland, Die Praxis des Organischen Chemikers, 43. Auflage (1982)

[18] Heinskill J, Ph.D. Dissertation, Aachen Univ. of Technology, Aachen, Germany (1989)