ATEG 잔기를 갖는 가용성 또는 불용성 Polystyrene의 상이동촉매 활성

정광보; Kohno Y; Tomoi M

Journal of the Korean Industrial and Engineering Chemistry, Vol.6, No.2, 260-266, April, 1995

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ATEG 잔기를 갖는 가용성 또는 불용성 Polystyrene의 상이동촉매 활성

Phase-transfer Catalytic Activity of Soluble or Insoluble Polystyrenes with ATEG Residue

정광보, Kohno Y, Tomoi M

초록

big(2-(2-hydroxyethoxy)ethyl)azine(ATEG) 구조를 갖는 가용성 또는 불용성 polystyrene의 상이동촉매 활성을 검토하였다. ATEG 구조를 갖는 가용성 polystyrene은 2상계에서 수용성 NaOH와 KOH와의 반응에 의해 alkoxides를 생성하였다. polymer 골격과 ATEG사이의 산소를 갖는 측쇄의 도입으로 상대 양이온이 ATEG와 측쇄의 산소 donor의 헙동작용에 의해 결합되는 유사 cryptand alkoxides가 형성되었다. ATEG기를 갖는 가용성, 불용성 Polymer는 각각 2상계, 3상계 조건하에서 2-bromoethylbenzene의 수용성 NaOH와 KOH와의 브롬화수소이탈 반응에서 고활성을 나타내었다. 측쇄잉여 산소 donors의 협동작용으로 촉매의 활성은 증가하였다.

The phase-transfer catalytic activity of soluble or insoluble polystyrenes with bis(2- (2-hydroxyethoxy)ethyl)amine(ATEG) residue has been studied. The soluble polystyrenes with ATEG residue afforded polymeric alkoxides by the reaction with aqueous NaOH or KOH under two-phase conditions. The introduction of oxygen-containing spacer chains between ATEG residue and the polymer backbone resulted in the formation of cryptand-like alkoxides, in which the counter cations were bound by cooperative coordination of the oxygen donors in the ATEG residue and in the spacers. The soluble and insoluble polystyrenes with ATEG residue exhibited high catalytic activity for the dehydrobromination of 2-bromoethylbenzene with aqueous NaOH or KOH under two- and three-phase conditions, respectively. The extra coordination of the oxygen donors in the spacers resulted in increased catalytic activity.

[References]

Regen SL, Angew. Chem.-Int. Edit., 18, 421 (1979)
Montanari F, Landini D, Rolla F, Top. Curr. Chem., 101, 147 (1982)
Ford WT, Tomoi M, Adv. Polym. Sci., 55, 49 (1984)
Smid J, Sinta R, Top. Curr. Chem., 121, 105 (1984)
Tomoi M, Ford WT, Syntheses and Separations Using Functional Polymer, D.C. Sherrington and P. Hodge, Eds., Wiley, Chichester (1988)
VanZon A, DeJong F, Onwezen Y, REcl. Trav. Chim. Pays-Bas., 100, 429 (1981)
Manecke G, Kramer A, Makromol. Chem., 182, 3017 (1981)
Tomoi M, Yanai N, Shiki S, Kakiuchi H, J. Polym. Sci. A: Polym. Chem., 22, 911 (1984)
Anelli PL, Czech B, Montanari F, Quici S, J. Am. Chem. Soc., 106, 861 (1984)
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Kimura Y, Regen SL, J. Org. Chem., 48, 195 (1983)
Tomoi M, Suzuki T, Kakiuchi H, React. Polym., 10, 27 (1989)
Chung KB, Kohno Y, Tomoi M, in proceeding
Pedersen CJ, Frensdroff HK, Angew. Chem.-Int. Edit., 11, 16 (1972)
Stark CM, Liotta C, "Phase Transfer Catalysis," Chap. 3, Academic Press, New York (1987)
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Chung KB, Tomoi M, J. Polym. Sci. A: Polym. Chem., 30, 1089 (1992)
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[1] Regen SL, Angew. Chem.-Int. Edit., 18, 421 (1979)

[2] Montanari F, Landini D, Rolla F, Top. Curr. Chem., 101, 147 (1982)

[3] Ford WT, Tomoi M, Adv. Polym. Sci., 55, 49 (1984)

[4] Smid J, Sinta R, Top. Curr. Chem., 121, 105 (1984)

[5] Tomoi M, Ford WT, Syntheses and Separations Using Functional Polymer, D.C. Sherrington and P. Hodge, Eds., Wiley, Chichester (1988)

[6] VanZon A, DeJong F, Onwezen Y, REcl. Trav. Chim. Pays-Bas., 100, 429 (1981)

[7] Manecke G, Kramer A, Makromol. Chem., 182, 3017 (1981)

[8] Tomoi M, Yanai N, Shiki S, Kakiuchi H, J. Polym. Sci. A: Polym. Chem., 22, 911 (1984)

[9] Anelli PL, Czech B, Montanari F, Quici S, J. Am. Chem. Soc., 106, 861 (1984)

[10] Montanari F, Quici S, Anelli PL, Br. Polym. J., 16, 212 (1984)

[11] Pugia MG, Czech A, Czech BP, Bartsch RA, J. Org. Chem., 51, 2945 (1986)

[12] Kimura Y, Regen SL, J. Org. Chem., 48, 195 (1983)

[13] Tomoi M, Suzuki T, Kakiuchi H, React. Polym., 10, 27 (1989)

[14] Chung KB, Kohno Y, Tomoi M, in proceeding

[15] Pedersen CJ, Frensdroff HK, Angew. Chem.-Int. Edit., 11, 16 (1972)

[16] Stark CM, Liotta C, "Phase Transfer Catalysis," Chap. 3, Academic Press, New York (1987)

[17] Soula G, J. Org. Chem., 50, 3717 (1985)

[18] Jordan PC, "Chemical Kinetics and Transport," chap. 3, Plenum Press, New York (1979)

[19] Chung KB, Tomoi M, J. Polym. Sci. A: Polym. Chem., 30, 1089 (1992)

[20] Reichardt C, "Solvents and Solvent Effects in Organic Chemistry," 27-35, 2nd ed., VCH, Weinheim (1988)