Micellar effect of ionic surfactants in the reaction ofo-dimethylaminomethylphenol withp-nitrophenyl diphenyl phosphate

Рыжкина, И. С.; Shagidullina, R. A.; Kudryavtseva, L. A.; Исмаев, И. Э.; Ivanov, B. E.

doi:10.1007/bf00695814

Cited by 2 publications

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“…10 -4 s -I) and 20-fold more rapidly than that for phosphorylated aggregate 9 (kob s = 2-10 -4 s-I), i.e., the intramolecular catalysis of the hydrolysis of the phosphorylated macrocycles is much more efficient than the hydrolysis of their structural units. 25 Thus, the study of the reactivity of AMC in reactions with EPA in a water--DMF mixture (30 vol.% DMF) showed that AMC that form aggregates of the micellar and nonmicellar types more efficiently catalyze EPA hydrolysis than their structural units AMP. The catalytic activity of the AMC aggregates depends on their structure, pH of the medium, and solvent nature.…”

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confidence: 99%

Catalytic activity of aminomethylated calix[4]resorsinolarene aggregates in hydrolysis of esters of phosphorus acids

et al. 2000

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The reaction kinetics of aminomethytated calix [4]resorcinolarenes {AMC) with p-nitrophenyl esters of phosphorus acids (EPA) in a water--DMF solution (30 vol.% DMF) was studied by spectrophotometry, and 3~ p NMR spectroscopy in the presence and absence of the nonionic surfactant Triton X-100. The AMC form aggregates of micellar and nonmicellar types and are the catalysts for EPA ttydrolysis. The catalytic activity of the aggregates depends on their structure, pH of the medium, and the nature of the solvent.Key words: kinetics, micetles, aggregates, surfactants, aminomethylated calix[4]resorcinolarenes, esters of phosphorus acids, hydrolysis.Calix[nlarenes (n = 4--8) 12 containing various functional groups at the "bottom" and "upper" rims of the cavity formed by aromatic rings are "endo-receptors" 3 and models of enzymes. 4-8 At the same time, amphiphilic water-soluble calix[nlarenes possess the properties of surfactants. They are self-organized to form, depending on the conformation, aggregates of micellar and lamellar types 9 and, similarly to natural detergents, are readily incorporated in micelles and bilayers formed by other amphiphilic substances, l~ However, the catalytic activity of aggregates of calix[nlarenes and, in particular, calixl4] resorcinolarenes is poorly studied, t l--H The purpose of this work is to study the reactivity of the aggregates of aminomethylated calix[41resorci-nolarenes (AMC, 1--4) in the reaction with 4-nitrophenyl bis(chloromethyl)phosphinate (5), 4-nitrophenyl chloromethylethylphosphonate (6), and 4-nitrophenyl diphenylphosphate (7) in aqueous DMF (30 vol.% DMF) in the absence and presence of the nonionic surfactant Triton X-100.We have previously shown that in water--alcohol solutions the reactions of AMC t3 and 2-aminomethylphenols (AMP), 14 which are the structural units of AMC, with esters of phosphorus acids (EPA) proceed in two stages: the first stage produces phosphorylated AMP or AMC, which then are hydrolyzed to the corresponding acids, i.e., AMP and AMC are the catalysts for EPA hydrolysis and model the action of esterases. According to the data of spectrophotometry and 31p NMR spectroscopy, the reactions of AMC with EPA in aqueous DMF studied in this work also proceed in two stages by Scheme 1.

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Catalytic activity of aminomethylated calix[4]resorsinolarene aggregates in hydrolysis of esters of phosphorus acids

et al. 2000

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“…[n the first stage, 4-nitrophenolate is formed by transesterification to give phospho~'lated AMP (PAMP). The second stage is the hydrolysis of the latter due to the intramolecular catalysis of the aminomethyl group, t. 3 In these media, CAMP is more reactive towards EPA than AM P. The reactivity depends, to a great extent, on the structure and stability (log[3) of complexes that are closely related to the presence of substituents at the nitrogen atom. t,z.5 It has also been found that the biological activity of AMP, their quaternary, ammonium salts, and CAMP are mainly determined by the hydrophobicity of the substituents in the benzene ring and at the nitrogen atom.…”

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“…"r Substrates 1--3 were prepared by known procedures. 3,8 The other reagents were reagent grade. The acid-base properties of AMP and its complexation with copper(H) were studied by pH-metric titration and spec[rophotometry (T = 25+0.05 ~ according to the published procedure.…”

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The reaction of 2-aminomethylphenols and their copper(II) complexes with esters of phosphorus acids

et al. 2000

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ul. Kremlevskaya, 420008 Kazan, Russian Federation. Fax: +7 (843 2) 38 0122 2-Alkyl-and 2-dialkylaminomethylphenols (AMP) with different hydrophobic substituents at the nitrogen atom and their copper(t)) complexes (CAMP) react with the esters of phosphorus acids in aqueous solutions of ethanol in two stages: phosphorylated AMP (PAMP) are formed at the first stage and then hydrolyzed to the corresponding acids. The reactivity of AMP and PAMP significantly decreases when the hydrophobicity and steric hindrances of substituents at the nitrogen atom increase. An inverse dependence was found for CAM P.Key words: 2-aminomethylphenols, copper00, esters of phosphorus acids; hydrolysis, reactivity, acid-base properties, complex formation.We have previously shown that 2-dimethyl-and 2-diethylaminomethylphenols (AMP+ HI.) and their copper(H) complexes (CAM P, Cul_ 2) are catalysts of the hydrolysis of 4-nitropheny[ esters of phosphorus acids (EPA) in aqueous-ethanol I,z and micellar solutions of surfactants. 3-5 The reactions between AMP and EPA proceed in two stages. [n the first stage, 4-nitrophenolate is formed by transesterification to give phospho~'lated AMP (PAMP). The second stage is the hydrolysis of the latter due to the intramolecular catalysis of the aminomethyl group, t.3In these media, CAMP is more reactive towards EPA than AM P. The reactivity depends, to a great extent, on the structure and stability (log[3) of complexes that are closely related to the presence of substituents at the nitrogen atom. t,z.5 It has also been found that the biological activity of AMP, their quaternary, ammonium salts, and CAMP are mainly determined by the hydrophobicity of the substituents in the benzene ring and at the nitrogen atom. 6In this work, we studied the influence of the hydrophobicity and steric effects of the substituents at the nitrogen atom of AMP (HI" ~-4) on the reactivity of these compounds towards EPA (1--3) in the absence and presence ofcopper(ll) (Scheme I) and on the acidbase properties of HL I-4 and their complexation with copper(H) in aqueous ethanol containing 70 vol.% EtOH. the previously described procedure. "r Substrates 1--3 were prepared by known procedures. 3,8 The other reagents were reagent grade. The acid-base properties of AMP and its complexation with copper(H) were studied by pH-metric titration and spec[rophotometry (T = 25+0.05 ~ according to the published procedure. 9 An EV-74 ionomer was used. An ESL-43-07 glass electrode was calibrated in water--ethanol solutions, i~ The ionic strength of the solutions was maintained at a level of g = 0.1 tool L -I (KNO3). The electronic absorption spectra of the solutions were recorded on a Specord UV--Vis spectrophotometer. In the study of complex tbrmation between Cu H and HL 1-4, we examined the following dependences of absorption (A): (1) on the pH of the solutions (the concentrations were unchanged, CQ2+ = 5. 10 -4 tool L -t, CHL = 1 -l0 -2, ExperimentalCompounds HL ~-4 were synthesized by the reaction of phenol, paraform, and the corresponding ami...

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Micellar effect of ionic surfactants in the reaction ofo-dimethylaminomethylphenol withp-nitrophenyl diphenyl phosphate

Cited by 2 publications

References 3 publications

Catalytic activity of aminomethylated calix[4]resorsinolarene aggregates in hydrolysis of esters of phosphorus acids

Catalytic activity of aminomethylated calix[4]resorsinolarene aggregates in hydrolysis of esters of phosphorus acids

The reaction of 2-aminomethylphenols and their copper(II) complexes with esters of phosphorus acids

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