알킬암모늄 IBA의 가수분해 촉매반응

양일우; 김정수; 정영진; Il Woo Yang; Jeong Soo Kim; Yeong Jin Chung

Journal of the Korean Industrial and Engineering Chemistry, Vol.13, No.5, 407-410, August, 2002

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알킬암모늄 IBA의 가수분해 촉매반응

Catalitic Hydrolysis Reactions of Alkylammonium IBA

양일우^†, 김정수, 정영진 ¹

육군사관학교 화학과, 서울 139-799
¹삼척대학교 화학과, 강원 245-711

Il Woo Yang^†, Jeong Soo Kim, and Yeong Jin Chung¹

Department of Chemistry, Korea Military Academy, Seoul 139-799, Korea
¹Division of Chemistry, Samchok National University, Kagnwon 245-711, Korea

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초록

5-[N-(n-hexadecyl)-N,N-dimethyl-N-(β-ethyloxy)ammonium]-2-IBA를 사용하여 p-nitrophenyldiphenylphosphate (PNPDPP), sarin (GB), 그리고 soman (GD)의 가수분해 반응에 대한 촉매효과를 시험하였다. 25±0.2 ℃, pH 8.0의 cetyltrimethylammonium chloride (CTACl) 미셀 용액에서 PNPDPP의 가수분해 반응속도를 측정한 결과 최대 1차 반응속도 상수가 각각 0.7965 sec(-1)로서 iodosobenzoate (kφ(max) = 0.0645 sec(-1)) 혹은 iodoxybenzoate (kφ(max) = 0.0178 sec(-1))에 비해 12 및 45배 증가된 값이다. 같은 조건에서 GB와 GD에 대한 가수분해 반응성 측정에서도 알킬암모늄 IBA 촉매에서 반응성의 현저한 증가를 확인하였으며, 이는 5-hydroxy-2-IBA에 비해 GB일 경우 7.8배, GD일 경우에는 5.6배 증가된 값이다. 분자내에 친수성 및 친유성을 지니는 알킬암모늄 IBA는 PNPDPP, GB, 그리고 GD의 가수분해 촉매반응에서 단순한 iodosobenzoic acid 및 iodosobenzoate보다 우수하였다.

Catalytic effects of 5-[N-(n-hexadecyl)-N,N-dimethyl-N-(β-ethyloxy)ammonium]-2-IBA on hydrolysis reactions of p-nitrophenyldiphenylphosphate (PNPDPP), sarin (GB) and soman (GD) were surveyed. It was shown that PNPDPP was cleaved with cleaved with kφ(max) = 0.7965 sec(-1) which is 12 and 45 times more reactive respectively than iodosobenzoate (kφ(max) = 0.0645 sec(-1)) or iodoxybenzoate (kφ(max)=0.0178 sec(-1)) in aqueous cetyltrimethylammonium chloride (CTACl) micellar solution at 25±0.2 ℃ and pH 8.0. And 5-[N-(n-hexadecyl)-N,N-dimethyl-N-(β-ethyloxy)ammonium]-2-IBA also catalyzed hydrolytic cleavage of GB and GD. The catalyst showed enhanced reactivity by 7.8 (GB) and 5.6 (GD) times compared to 5-hydroxy-2-IBA in aqueous CTACl micellar solution at 25±0.2 ℃ and pH 8.0. Having both hydrophilic and lipophilic characters in the molecules, the alkylammonium IBA appeared to be superior to the simple iodosobenzoic acid, iodosobenzoate and iodoxybenzoate in catalitic hydrolysis of PNPDPP, GB and GD.

Keywords:catalitic hydrolysis;p-nitrophenyldiphenylphosphate (PNPDPP);sarin (GB);soman (GD);5-[N-(n-hexadecyl)-N,N-dimethyl-N-(β-ethyloxy)ammonium]-2-IBA

[References]

Moss RA, Alwis KW, Bizzigotti GO, J. Am. Chem. Soc., 105, 681 (1983)
Moss RA, Alwis KW, Shin JS, J. Am. Chem. Soc., 106, 2651 (1984)
양일우, 김을산, 정영진, 육사논문집, 49, 655 (1995)
양일우, 정우영, 허유봉, 육사논문집, 53, 677 (1997)
양일우, 강덕구, 군사과학기술학회지, 2(1), 73 (1999)
Furniss BS, Hannaford AJ, Smith PWG, Tatchell AR, Textbook of Practical Org. Chem., 400, Longman Scientific & Technical, London (1989)
Gulick WM, Gseke DH, J. Am. Chem. Soc., 88, 2928 (1966)
Moss RA, Kim KY, Swarup S, J. Am. Chem. Soc., 108, 788 (1986)
Moss RA, Chatterjee S, Wilk B, J. Org. Chem., 51, 4303 (1986)

[Related Articles]

[1] Moss RA, Alwis KW, Bizzigotti GO, J. Am. Chem. Soc., 105, 681 (1983)

[2] Moss RA, Alwis KW, Shin JS, J. Am. Chem. Soc., 106, 2651 (1984)

[3] 양일우, 김을산, 정영진, 육사논문집, 49, 655 (1995)

[4] 양일우, 정우영, 허유봉, 육사논문집, 53, 677 (1997)

[5] 양일우, 강덕구, 군사과학기술학회지, 2(1), 73 (1999)

[6] Furniss BS, Hannaford AJ, Smith PWG, Tatchell AR, Textbook of Practical Org. Chem., 400, Longman Scientific & Technical, London (1989)

[7] Gulick WM, Gseke DH, J. Am. Chem. Soc., 88, 2928 (1966)

[8] Moss RA, Kim KY, Swarup S, J. Am. Chem. Soc., 108, 788 (1986)

[9] Moss RA, Chatterjee S, Wilk B, J. Org. Chem., 51, 4303 (1986)