고분자 물질로 지지된 크라운 에테르류: 6. Lariat Azacrown Ether의 상간이동촉매 활성

심재우; 정광보; Tomoi M

Polymer(Korea), Vol.16, No.3, 291-297, May, 1992

Export Citation

고분자 물질로 지지된 크라운 에테르류: 6. Lariat Azacrown Ether의 상간이동촉매 활성

Polymer-Supported Crown Ethers: 6. Activities of Lariat Azacrown Ethers

심재우, 정광보, Tomoi M

초록

삼상계 조건하에서 halogen 교환반응에 대한 고정화 lariat azacrown ether의 상간이동 촉매활성을 환치환율, 기질의 구조, 시약의 종류, 용매, 촉매구조를 중심으로 평가하였다. 측쇄에 여분의 산소 donor를 갖는 lariat촉매는 donor를 갖지않는 대응하는 고정화 촉매에 비해 고활성을 나타내었다. 1-bromooctane과 KI와의 반응에 대한 monoaza-15-crown-5 unit와 두개의 여분 donor를 갖는 촉매의 활성 증대는 crown unit donor와 측쇄 donor와의 협동작용에 의해 K⁺이온과의 착체 형성의 촉진에 의한 것으로 결론되었다. 회수한 촉매는 활성의 감소없이 재사용이 가능하였다.

The phase-transfer catalytic activity of the immobilized lariat azacrowns for halogen exchange reactions under tri-phase conditions has been studied as a function of loading, substrate structure, reagent structure, solvent, and catalyst structure. The lariat catalysts with extra oxygen donors in the spacer chain exhibited higher activity than the corresponding immobilized catalysts without the donors in the spacer. The increased activity of the catalyst containing monoaza-15-crown-5 unit and two txtra donors fot the reaction of 1-bromooctane with KI was concluded to result from the enhanced complexation with the K⁺ ion, induced by the cooperative coordination of the crown unit donors and the donors in the spacer chain. The recovered catalysts could be re-used without decrease in activity.

[References]

Chiellini E, Solaro R, Antone SD, Makromol. Chem., 5, 82 (1981)
Ford WT, Tomoi M, Adv. Polym. Sci., 55, 49 (1984)
Tomoi M, Hosokawa Y, Kakiuchi H, J. Polym. Sci. A: Polym. Chem., 22, 1234 (1984)
Regen SL, Besse J, J. Am. Chem. Soc., 101, 4059 (1979)
Regen SL, Bolikal D, Barcelon C, J. Org. Chem., 46, 2511 (1981)
Polym.(Korea), to submitted
Valter B, Janout V, Hrudkova H, Cefelin P, Lukyanenko NG, Basok SS, Kurigina EY, Polym. Bull., 22, 261 (1989)
Tomoi M, Yanai N, Shiiki S, Kakiuchi H, J. Polym. Sci. A: Polym. Chem., 22, 911 (1984)
Tomoi M, Ford WT, J. Am. Chem. Soc., 103, 3821 (1981)
Tomoi M, Ogawa E, Hosokawa Y, Kakiuchi H, J. Polym. Sci. A: Polym. Chem., 20, 3421 (1982)
Tomoi M, Nakamura E, Hosokawa Y, Kakiuchi H, J. Polym. Sci. A: Polym. Chem., 23, 49 (1985)
Tomoi M, Kori N, Kakiuchi H, Makromol. Chem., 187, 2753 (1986)
Gokel GW, Phase-Transfer Catalysis: New Chemistry, Catalysis, and Application, C.M. Starks, ed., ACS Symp. Ser., 326, Am. Chem. Soc., Washington, D.C. (1987)
Weber E, Crown Ethers and Analogs, S. Patai, Z. Rappoport, Eds., Wiley, New York (1984)
Gokel GW, Trafton JE, Cation Binding by Macrocycles, Y. Inoue, G.W. Gokel, Eds., Marcel Dekker, New York (1990)
Schultz RA, White BD, Dishong DM, Arnold KA, Gokel GW, J. Am. Chem. Soc., 107, 6659 (1985)
Tomoi M, Suzuki T, Kakiuchi H, React. Polym., 10, 27 (1989)
Anelli PL, Czech B, Montanari F, Quici S, J. Am. Chem. Soc., 106, 861 (1984)
Montanari F, Quici S, Anelli PL, Br. Polym. J., 16, 212 (1984)
Pedersen CJ, Frensdorff HK, Angew. Chem.-Int. Edit., 11, 16 (1972)

[1] Chiellini E, Solaro R, Antone SD, Makromol. Chem., 5, 82 (1981)

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

[3] Tomoi M, Hosokawa Y, Kakiuchi H, J. Polym. Sci. A: Polym. Chem., 22, 1234 (1984)

[4] Regen SL, Besse J, J. Am. Chem. Soc., 101, 4059 (1979)

[5] Regen SL, Bolikal D, Barcelon C, J. Org. Chem., 46, 2511 (1981)

[6] Polym.(Korea), to submitted

[7] Valter B, Janout V, Hrudkova H, Cefelin P, Lukyanenko NG, Basok SS, Kurigina EY, Polym. Bull., 22, 261 (1989)

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

[9] Tomoi M, Ford WT, J. Am. Chem. Soc., 103, 3821 (1981)

[10] Tomoi M, Ogawa E, Hosokawa Y, Kakiuchi H, J. Polym. Sci. A: Polym. Chem., 20, 3421 (1982)

[11] Tomoi M, Nakamura E, Hosokawa Y, Kakiuchi H, J. Polym. Sci. A: Polym. Chem., 23, 49 (1985)

[12] Tomoi M, Kori N, Kakiuchi H, Makromol. Chem., 187, 2753 (1986)

[13] Gokel GW, Phase-Transfer Catalysis: New Chemistry, Catalysis, and Application, C.M. Starks, ed., ACS Symp. Ser., 326, Am. Chem. Soc., Washington, D.C. (1987)

[14] Weber E, Crown Ethers and Analogs, S. Patai, Z. Rappoport, Eds., Wiley, New York (1984)

[15] Gokel GW, Trafton JE, Cation Binding by Macrocycles, Y. Inoue, G.W. Gokel, Eds., Marcel Dekker, New York (1990)

[16] Schultz RA, White BD, Dishong DM, Arnold KA, Gokel GW, J. Am. Chem. Soc., 107, 6659 (1985)

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

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

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

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