CTABr 미셀 용액속에서 2-Alkylbenzimidazole 음이온에 의해 추진되는 Isopropyl phenyl-4-nitrophenyl phosphinate(IPNPIN)의 탈인산화반응 = Dephosphorylation of Isopropyl phenyl-4-nitrophenylphosphinate, IPNPIN, onto 2-Alkylbenzimidazolide Anion in CTABr Micellar Solution

다국어 초록 (Multilingual Abstract)

This study is mainly focused on micellar effect of cetyltrimethyl ammonium bromide(CTABr) solution including alkylbenzimidazole(R-BI) on dephosphorylation of isopropyl-4-nitrophenylphosphinate(IPNPIN) in carbonate buffer(pH 10.7). The reactions of IPNPIN with R-BIe are strongly catalyzed by the micelles of CTABr. Dephosphorylation of IPNPIN is accelerated by BIe ion in 10-2 M carbonate buffer(pH 10.7) of 4×10-3 M CTABr solution up to 89 times as compared with the reaction in carbonate buffer by no benzimidazole(BI) solution of 4×10-3 M CTABr. The value of pseudo first order rate constant(kψ) of the reaction in CTABr solution reached a maximum rate constant increasing micelle concentration. Such rate maxima are typical of micellar catalyzed bimolecular reactions. The reaction mediated by R-BIe in micellar solutions are obviously slower than those by BIe, and the reaction rate were decreased with increase of lengths of alkyl groups. It seems due to steric effect of alkyl groups of R-BIe in Stern layer of micellar solution. The surfactant reagent, CTABr, strongly catalyzes the reaction of IPNPIN with R-BI and its anion(R-BIe) in carbonate buffer(pH 10.7). For example, 4×10-3 M CTABr in 1×10-4 M BI solution increase the rate constant(kψ=98.5×10-3 sec-1) of the dephosphorylation by a factor ca.25, when compared with reaction(kψ=3.9×10-4 sec-1) in 1×10-4 M BI solution(without CTABr). And no CTABr solution, in 1×10-4 M BI solution increase the rate constant(kψ=3.9×10-4 sec-1) of the dephosphorylation by a factor ca.39, when compared with reaction (kψ=1.0×10-5 sec-1) in water solution(without BI). This predicts that the reactivities of R-BIe in the micellar pseudophase are much smaller than that of BIe. Due to the hydrophobicity and steric effect of alkyl group substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long alkyl groups of CTABr.

참고문헌 (Reference)

1 김정배, "음이온 및 양이온 미셀 용액에서 친핵체에 의한유기 포스피네이트의 탈인산화반응" 한국환경과학회 15 (15): 485-491, 2006

2 Romsted, I. R., "Secondary valence force catalysis.Ⅶ. Catalysis of hydrolysis of p-nitrophenyl hexanoate by micelle-forming cationic detergents" 90 : 4404-4409, 1968

3 Bunton, C. A., "Reactivity in aqueous association colloids. Descriptive utility of the pseudophase model" 72 : 231-249, 1997

4 Fendler, E. J., "Reaction mechanism in phosphate ester hydrolysis" John Wiley 65-89, 1966

5 Blatt, A. H., "Organic Synthesis" 2 : 65-, 1943

6 Bunton, C. A., "Nucleophilic reactions in zwitterionic micelles of amine oxide or betaine sulfonate surfactants" 93 (93): 854-858, 1989

7 Bunton, C. A., "Micellar reactions of hydrophilic ions; A coulombic model" 89 (89): 4166-4169, 1985

8 McBain, J. W., "Micellar formation of aqueous solution" 9 : 99-112, 1913

9 Al-Lohedan, H, "Micellar effects upon spontaneous hydrolyses and their relation to mechanism" 104 : 6654-6660, 1982

10 Bunton, C. A., "Micellar catalysis and reactant incorporationin dephosphorylation and nucleophilic substitution" 101 : 2429-2435, 1979

11 Cook, R. D., "Mechanism of nucleophilic displacement at phosphorus in the alkaline hydrolysis of phosphinate esters" 95 : 8088-8096, 1973

12 Quina, F. H., "Ion exchange in micellar solutions 1; Conceptual framework for ion exchange in micellar solutions" 83 (83): 1844-1850, 1979

13 Santiago, J. Y., "Examination of the pseudophase model of monomer-micelle interconversion in cetylpyridinium chloride" 281 : 482-487, 2004

14 Dekeijzer, A. H., "Enhancement of nucleophilic substitution reactions in phosphate esters; Influence of conformational transmission on the rate of solvolysis in alkyl diphenylphosphinates" 54 : 1453-1456, 1988

15 Foroudian, H. J., "Effects of nonionic micelles on dephosphorylation and aromatic nucleophilic substitution" 250 : 230-237, 2002

16 Bunton, C. A., "Dephosphorylation in cationic micelles and microemulsions; Effects of added alcohols" 48 : 2457-2461, 1983

17 Maximiano, F. A, "Decarboxylation of 6-nitrobenzisoxazole-3-carboxylate in mixed micelles of zwitterionicand positively charged surfactants" 22 : 8050-8055, 2006

18 Hong, Y. S., "Chemical reactions in surfactant solution(Ⅰ). Substituent effects of 2-alkylbenzimidazolide ion on dephosphorylation in CTABr solution" 29 (29): 522-532, 1984

19 Fendler, J. H, "Catalysis in micellar and macromolecular system" Academic press 30-47, 1975

20 Bunton, C. A., "Catalysis by hydrophobic tetraalkyl ammonium ions; Dephosphorylation of p-nitrophenyl diphenyl phosphate" 103 : 5788-5794, 1981

21 김정배, "CTAX 미셀 용액속에서 유기인 에스테르 화합물의 탈인산화 반응에 대한 OH？ 및 o-Iodosobenzoate 이온의 영향" 한국환경과학회 14 (14): 241-249, 2005

22 Perrin, D. D, "Buffers for pH and metal ion control" Champman and Hall 5-, 1974

23 Hartly, G. S, "Aqueous solution of paraffin chain salt" Herman Paris. press 125-258, 1936

24 Bunton, C. A., "Abnormal micellar effects on reactions of azide and N-alkyl-2- bromopyridinium ions" 52 (52): 901-907, 1987