РЕАКЦІЙНА ЗДАТНІСТЬ НУКЛЕОФІЛІВ І α-ЕФЕКТ У ПРОЦЕСАХ ЗАМІЩЕННЯ У ЕЛЕКТРОНОДЕФІЦІТНИХ ЦЕНТРІВ (частина 2)

The review analyzes issues related to the reactivity of nucleophiles and the manifestation of the α-effect in substitution processes at electron-deficient centers. The fundamental aspects of this phenomenon, as well as the possibilities and prospects of using α-nucleophiles in systems for the highly...

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Дата:	2020
Автори:	Popov, Anatolii, Kapitanov, Illia, Serdyuk, Anna, Sumeiko, Aleksandr
Формат:	Стаття
Мова:	Англійська
Опубліковано:	V.I.Vernadsky Institute of General and Inorganic Chemistry 2020
Онлайн доступ:	https://ucj.org.ua/index.php/journal/article/view/213
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Назва журналу:	Ukrainian Chemistry Journal
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Ukrainian Chemistry Journal

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author	Popov, Anatolii Kapitanov, Illia Serdyuk, Anna Sumeiko, Aleksandr
author_facet	Popov, Anatolii Kapitanov, Illia Serdyuk, Anna Sumeiko, Aleksandr
author_institution_txt_mv	[ { "author": "Anatolii Popov", "institution": "Институт физико-органической химии и углехимии им. Л.М.Литвиненко НАН Украины" }, { "author": "Illia Kapitanov", "institution": "Институт физико-органической химии и углехимии им. Л.М.Литвиненко НАН Украины " }, { "author": "Anna Serdyuk", "institution": "ganna.serdyuk@gmail.com" }, { "author": "Aleksandr Sumeiko", "institution": "Институт физико-органической химии и углехимии им. Л.М.Литвиненко НАН Украины ––––– Институт органической химии НАН Украины" } ]
author_sort	Popov, Anatolii
baseUrl_str	https://ucj.org.ua/index.php/journal/oai
collection	OJS
datestamp_date	2026-07-22T08:23:44Z
description	The review analyzes issues related to the reactivity of nucleophiles and the manifestation of the α-effect in substitution processes at electron-deficient centers. The fundamental aspects of this phenomenon, as well as the possibilities and prospects of using α-nucleophiles in systems for the highly efficient degradation of substrates - ecotoxicants of various natures, are discussed. In the first part of the review such aspects were observed: inorganic α-nucleophiles as the most effective class of reagents for the decomposition of organic phosphorus compounds, hydroxylamine, its N-alkyl derivatives, oximes, and hydroxamic acids, reactivity of the НОО– anion in the processes of acyl group transfer, reactivity of oximate ions, inorganic α-nucleophiles as the basis of formulations for the degradation of neurotoxins, vesicants, and organophosphorus pesticides, design of inhibited acetylcholinesterase reactivators based on hydroxylamine derivatives, ways of structural modification of α-nucleophiles and systems based on them. The data on the reactivity of typical inorganic α-nucleophiles in the cleavage of acyl-containing substrates, including phosphorus acid esters, which provide abnormally high reaction rates in comparison with other supernucleophiles, are analyzed. Various types of such α-nucleophiles, features of their structure and reactivity are considered. It was shown that an important feature of hydroxylamine, oximes, and hydroxamic acids is the presence of a fragment with adjacent O and N (–N – O – H) atoms containing one or more lone electron pairs, which determines their belonging to the class of α-nucleophiles. It has been shown that a many of factors can be responsible for the manifestation of the α-effect and its magnitude, the main of which is the destabilization of the ground state of the nucleophile due to repulsion of lone electron pairs, stabilization of the transition state, the unusual thermodynamic stability of reaction products, solvation effects of the solvent, type of hybridization of the electrophilic center, etc.
doi_str_mv	10.33609/2708-129X.86.8.2020.77-100
first_indexed	2025-09-24T17:43:33Z
format	Article
fulltext	77 UDC 541.124:541.183:547.288.4 doi: 10.33609/2708-129X.86.8.2020.77-100 REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS (Part 2) A. F. Popov1, I. V. Kapitanov1,3, A. A. Serdyuk1,3, A. E. Shumeiko1,2* 1Institute of Physical Organic Chemistry and Coal Chemistry, L. M. Litvinenko NAS of Ukraine; Kharkiv highway 50, Kyiv 02160, Ukraine. 2Institute of Organic Chemistry, NAS of Ukraine; st. Murmanskaya 5, Kyiv 02660, Ukraine 3Center for Excellence in Green Chemistry, European Research Area. Department of Chemistry and Biotechnology, Faculty of Science, Tallinn University of Technology, Academia 15, 12618 Tal- linn, Estonia * E-mail: ashumeiko@ukr.net The review analyzes issues related to the reactivity of nucleophiles and the manifestation of the α-effect in substitution processes at electron-deficient centers. The fundamental aspects of this phenomenon, as well as the possibilities and prospects of using α-nucleophiles in sys- tems for the highly efficient degradation of substrates - ecotoxicants of various natures, are discussed. Key words: functionalized surfactants, α-nucleophiles, micellar systems, hydroxylamine, oximes, amidoximes, hydroxamic acids, peroxides. 8. Use of micellar systems to increase the ef- ficiency of reactions of ecotoxicants degradation by supernucleophilic reagents It is rather difficult to create a compound that, in an aqueous solution, would be superior to the hydroxylamine anion in its nucleophilic reactivity. Therefore, the way to increase the efficiency of systems for the splitting of ecotox- icants should be not so much trough the struc- tural modification of the splitting agent, but rather trough the use of alternative methods of influencing the reaction rate, for example, by changing the properties of the medium, in which it occurs [3, 4, 7, 8]. Microorganized media (micellar solutions, microemulsions, ionic liquids, concentrated aqueous solutions of quaternary ammonium salts, etc. [3, 4, 7, 8, 94–100]) have been in the center of attention of researchers for quite a long time. They are widely used to solve sev- eral applied and fundamental problems, such as modeling biological objects [38, 96, 100], implementing various technological processes [96, 98], preparing samples for chemical anal- ysis [97], etc. Carrying out chemical reactions in microorganized systems is of great practical interest since it opens up new possibilities for influencing the rates and products of reactions [94–100]. ORGANIC CHEMISTRY REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS (Part 2) 78 ISSN 2708-129X. Укр. хім. журн., 2020 The undoubted advantage of micellar sys- tems, in comparison with other organized mi- croheterogeneous media, lies in the fact that a radical change in the properties of the me- dium is achieved by introducing sufficiently small amounts of micelle-forming substances (in quantities higher than the critical concen- tration of micelle formation, which is about 10-6 – 10-2 mol∙l-1) [96, 97]. In this case, the main component of such systems in most cases is water, which makes them extremely attrac- tive for practical application from the stand- point of “green” chemistry [101]. Carrying out the process of cleavage of or- ganophosphorus ecotoxicants in the presence of surfactant micelles allows solving the prob- lem of solubilization of substrates (most OPCs are poorly soluble in water) [75–78], as well as increasing the observed reaction rate due to the implementation of the micellar catalysis ef- fects [3, 4, 7, 8, 96–99]. 8.1. Features of the course of chemical reac- tions in the presence of surfactant micelles. The presence of surfactant micelles can significantly affect the rates of chemical reac- tions due to the implementation of the micel- lar catalysis effects [96–99]. The essence of it is change in the local concentrations and reactiv- ity of substrates and reagents when the reaction is transferred to the micellar pseudophase, as well as the shift of protolytic equilibria in such solution. The nature of the effect (catalysis or inhibition) depends on surfactant type (cati- onic, anionic, nonionic) the reagent charge. In most cases, cationic detergents accelerate re- actions involving negatively charged particles, and anionic - positively charged ones. Non ionic surfactants, in the case of using charged or sufficiently polar reagents, practically do not change the reaction rate [98, 99]. To describe the kinetics of the processes oc- curring in the presence of surfactant micelles two main models are usually used - pseudo- phase distribution and ion-exchange [98, 113– 120]. The pseudophase distribution model pro- posed by Berezin et al. [98, 113–115], based on the fact that surfactant solutions above the CMC consist of two phases (aqueous phase and micellar pseudophase), between which there is an equilibrium distribution of reagents occurts that is not disturbed by the proceeding reaction. It is assumed that the reagents do not affect properties of micelles and do not change the CMC. In general, the kinetic scheme of the bimo- lecular reaction proceeding in such a system can be represented as follows (Fig. 14). Fig. 14. Scheme of a bimolecular reaction proceeding in the presence of surfactant micelles: where PS = [S]m/[S]w and PA = [A]m/[A]w are the distribution coefficients of the substrate (S) and the reagent (A); km и kw, l·mol–1·s–1 are the reaction rate constants in micellar pseudophase (m) and aqueous phase (w) respectively UCJ № 8 / Vol. 86A. F. Popov, I. V. Kapitanov, A. A. Serdyuk, A. E. Shumeiko 79https://ucj.org.ua The mathematical expression for the ob- served reaction rate constant ko, s –1, in this case will have the form: m A S m w m A m S m CV (1 CV ) (1 ( 1)CV )(1 ( 1)CV )o k P P kk P P + − = + − + − . (7) In equation (7), C, mol·l–1, is the total sur- factant concentration minus the CMC; Vm, l·mol–1, is the molar volume of the surfactant. Taking into account that, in the case of di- lute surfactant solutions, the volume fraction of the micellar pseudophase is small (CV << 1), and we assume that the binding of reagents oc- curs efficiently (PS, PA>>1), expression (7) can be simplified: m m A S w A S ( / V ) C (1 C)(1 C)o k K K kk K K + = + + . (8) where KS = (PS – 1) Vm and KA = (PA – 1) Vm are the binding constants of the reagent and sub- strate with the micellar pseudophase. The pseudophase distribution model de- scribes most of the processes occurring in the presence of surfactant micelles quite well [98, 114]. However, when studying reactions in- volving high concentrations of small hydro- philic ions, such as, for example, hydroxide ion, its use does not give an adequate picture, since in this case the processes of ion exchange in the Stern layer begin to play a decisive role [116, 117]. To describe the kinetics of such re- actions, it is advisable to use the ion-exchange model, which considers this feature and allows calculating the ion exchange constant charac- terizing the saturation of the Stern layer with reactive counterions. This model is described in detail in papers [116–120]. Unfortunately, the direct determination of the ion exchange constants is a rather complicated experimental problem [116, 117], which in many cases sig- nificantly limits the possibilities of its applica- tion. 8.2. Reactions of ecotoxicants cleavage by nucleophilic reagents in micellar systems The use of cationic surfactants solutions as a medium for carrying out the degradation of ecotoxicants by nucleophilic reagents makes it possible to effectively solubilize OPC, most of which, in the absence of detergents, are poorly soluble in water, as well as to ensure the wet- ting of hydrophobic and highly developed surfaces [4, 8, 77, 96]. In this case, the reali- zation of the effects of micellar catalysis leads to an additional increase in the rate of the process of electron-deficient substrates cleav- age by nucleophilic reagents (hydroxide ion, oxymate, hydroxamate ions, etc.) by a factor of 10–103 [85–88; 113–131]. In works [85–88; 113–131], it was repeatedly shown that at the background of minor changes in nucleophilic reactivity during the transfer of the reaction from water to the micellar pseudophase, an in- crease in the reaction rate is provided due to the concentration of reagents in surfactant mi- celles. As a rule, in reactions involving organic nucleophiles, the concentration effect is more pronounced than for inorganic ones. Thus, for example, in the reactions of alkaline hydroly- sis of the substrates indicated below, it is, on average, one order of magnitude, and for re- actions with 3-bromobenzaldoxime - from 60 (p-nitrophenyl acetate) to 2∙103 (p-nitrophenyl heptanoate) times [115]. A typical profile of a bimolecular reac- tion proceeding in the presence of cationic surfactant micelles is shown in Fig. 15. With an increase in the concentration of the de- ORGANIC CHEMISTRY REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS (Part 2) 80 ISSN 2708-129X. Укр. хім. журн., 2020 tergent, the reaction rate increases, reaches a maximum, and then decreases. This type of dependence is because with an increase in the surfactant concentration, the number of reagents bound by the micellar pseudophase increases. After the entire substrate and the agent that decomposes it are bound by mi- celles (maximum point), a further increase in the surfactant concentration will lead to a de- crease in the reaction rate due to an increase in the volume of the micellar pseudophase and, as a consequence, a decrease in the local concentrations of reagents [131]. Fig. 15. Micellar effects of cetyltrimethylammo- nium bromide (CTAB) for reactions of interaction of 4-nitrophenyl diphenylphosphate with 4-ni- trobenzaldoxymate (●) and 2-quinolin aldoxymate (O) ions [131]. 9. Functional surfactants containing an α-nu- cleophilic fragment are highly effective reagents in the transfer of acyl groups. Despite the fact that the presence of cat- ionic surfactant micelles makes possible to significantly increase the rates of the reactions of model substrates cleavage by nucleophilic reagents, the efficiency of such systems is still insufficient [4, 8]. First of all, this is due to the fact that the binding of nucleophiles by the micellar pseudophase is often character- ized by rather small distribution coefficients [85–88, 113–131]. One of the most promising ways to increase the efficiency of nucleophilic reagents binding to micelles is to create func- tional detergents - surfactants, containing in their structure reactive fragments. When this approach is implemented, the concentration of nucleophilic groups on the micelle surface will always be equal to the surfactant concen- tration [3, 4]. Since micellar systems were re- peatedly used as models of enzymes [38, 96, 100], initially groups and fragments of amino acids were introduced into the structure of sur- factant molecules, which are present in the ac- tive center of enzymes and are responsible for the catalysis. During the development of this direction, a large number of functional sur- factants of the most varied structure were syn- thesized and studied, containing as a reactive fragment an imidazole nucleus (XXX –XXXVI [132–140]), hydroxyl (XXXVIII –XLII [132, 136, 137, 139, 141–144]), thiol (XLIII–XLVI [138, 140, 145, 146]), amino group (XLVII– XLVIII [140, 145]), etc. However, an increase in the rate of model substrates splitting with these functional detergents, in comparison with alkaline hydrolysis in the presence of non-functional surfactants, was small (it was k 2 , l·m o l– 1 ·с – 1 [CTAB]·103, mol·l–1 UCJ № 8 / Vol. 86A. F. Popov, I. V. Kapitanov, A. A. Serdyuk, A. E. Shumeiko 81https://ucj.org.ua 1.5–6 times) and significantly lower than the rates of enzymatic reactions [132–146]. These data clearly demonstrated that the introduc- tion of fragments of “normal” nucleophiles into the structure of surfactants does not give the expected results. A much more productive direction in the design of the structure of highly reactive func- tional surfactants was the use of an α-nucleo- phile fragment as a functional group [3, 4, 7, 8, 10, 11]. Such detergents supports providing not only effective solubilization of sufficiently hydrophobic and, as a result, poorly water-sol- uble substrates (such as most organophospho- rus pesticides and neuroparalytic CWA) [75– 78], but also their abnormally fast degradation due to α-effect of a functional fragment [3, 4, 7, 8, 10, 11]. At the moment, the main types NC16H33 N H N Br- NC18H37 Cl- N HN N H N NH C7H15 O XXX XXXI XXXII XXXIII N H N NH C13H27 O O OH N H NC16H33 N H O N HN t-Boc Cl- NH N NH O C12H25 N O H3CO Cl- N OHC16H33 Br- XXXIV XXXV XXXVI XXXVII N OHC12H25 Br- N OHC16H33 Ph Br- N OHC12H25 Ph Br- N OHC12H25 OH Cl- XXXVIII XXXIX XL XLI N H OH C13H27 O O OH N SHC16H33 Cl- N H OH O SH C11H23 O HS H N O O N Br- NH C16H33 XLII XLIII XLIV XLV N H NC16H33 NH2 SH OCl- N NH2C16H33 Cl- N H NC16H33 NH2 OCl- XLVI XLVII XLVIII ORGANIC CHEMISTRY REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS (Part 2) 82 ISSN 2708-129X. Укр. хім. журн., 2020 of functional surfactants containing a super- nucleophilic fragment are detergents based on hydroxylamine derivatives [147–172], as well as detergents, which include peroxy [173] and iodosocarboxylate groups [11, 174–146]. 9.1. Reactivity of functional surfactants based on hydroxylamine derivatives. Between functional α-nucleophilic frag- ments to be introduced into the surfactant structure, the greatest and quite natural inter- est was aroused by hydroxylamine. It is the an- cestor of compounds of three different classes (oximes, amidoximes, hydroxamic acids) that are stable, easy to obtain and allow modifying the basic structure within a wide range [10], which is undoubtedly important in the search for surfactants with an optimal combination of properties. At the same time, effective work in this direction will be difficult without develop- ing a unified scientifically grounded approach to modifying the structure of functional sur- factants. Therefore, the main efforts should be directed at establishing the patterns of changes in the nucleophilicity of functional detergents and developing a method that allows its pre- diction [4]. 9.2 Reactivity of functional detergents con- taining a hydroxamate moiety. A significant advantage of hydroxamic ac- ids as cleaving agents over other derivatives of hydroxylamine is that their functional group transforms into a highly reactive anionic form (hydroxamate anion) even at rather low pH values. This allows carrying out the reactions of decomposition of acyl-containing substrates under “mild” conditions - when the acidity of the medium is close to neutral. In this regard, the creation of surfactants containing a hy- droxamate fragment seems to be very attrac- tive and promising [4]. The main directions for modifying the structure of these surfactants included: - changing the properties of the hydrophobic fragment and the place of its introduction; - introduction of catalytically active centers; - introduction of positively charged centers. By varying the length of the alkyl chain in hydroxamic acids XLIX (Alk = C5H11, C7H15, C9H19, C11H23, C15H31), and studying their re- activity in the processes of cleavage of a se- ries of 3-nitro-4-acyloxybenzoic acids, it was shown [147] that the transition from non-micelle-forming (Alk = C5H11, C7H15) to micelle-forming (Alk = C11H23, C15H31) com- pounds leads to an increase in the observed reaction rate constants, while an increase in the hydrophobicity of the substrate reduces the rate of the process. Results similar to those given above (cleav- age of 3-nitro-4-acyloxybenzoic acids) were ob- tained for the destruction of diphenyl phosphate (DPP) [148; 149]. In this case, micelle-forming hydroxamic acid (Alk = n-(C9H19) C6H4-O- (C2H4-O)8CH2–) provided an increase in the reaction rate by about 3 times compared to non-micelle-forming (Alk = C7H15). The intro- duction of a chlorine atom into the 2-position of hydroxamic acid led to the fact that even for non-micelle-forming compounds (Alk = C2H5 and C7H15), the rates of DPP cleavage became XLIX UCJ № 8 / Vol. 86A. F. Popov, I. V. Kapitanov, A. A. Serdyuk, A. E. Shumeiko 83https://ucj.org.ua comparable to the rates of cleavage in the pres- ence of micelle-forming surfactant [148, 149]. Replacement of an inert phenyl fragment in hydroxamic acid by an imidazole nucleus leads to an approximately twofold increase in the rate of NPA cleavage [155]. The observed ef- fect is explained by the implementation of in- tramolecular catalysis of the process of the hy- droxamate ion deacylation with an imidazole fragment. The -СН2–СН2- bridge between the carbonyl group and the imidazole nucleus re- duces the rate of NPA cleavage [155]. The introduction of tetraalkylammonium [148; 149], imidazolium [151, 157–160] or pyridinium [151] positively charged center in hydroxamic acid leads to an increase in its sol- ubility in water [151, 148, 158], and undoubt- edly, reduces the constants of acid ionization of the hydroxamate fragment. An increase in the distance between a functional group and a charged center neutralizes influence of the lat- ter [156]. Replacing methyl groups with reac- tive acethydroxamate fragments not only does not lead to an increase in the observed rate of DPP cleavage, but even decreases it by about a factor of 2 [148, 149]. Under the same experimental conditions, the observed rate constant of the cleavage re- action of NPA by a 2-methylimidazolium functional detergent practically does not differ from that for an unsubstituted imidazolium surfactant containing a pyridinium nucleus [151]. This indicates the absence of a marked influence of the heterocyclic nucleus nature on the reactivity of the hydroxamate fragment. 9.3 Reactivity of functional detergents con- taining an oximate fragment. Compared with other directions of modi- fication, the introduction of an oximate frag- ment into a surfactant molecule has several advantages: firstly, it allows obtaining a large number of compounds with basicity varying over wide ranges [4, 10, 158], and secondly, surfactants functionalized with an oximate fragment are superior in solubility in water to the derivatives of hydroxamic acids and ami- doximes [158]. It should also be noted that additional interest in this area is caused by the fact that it was on the basis of oximes that the most effective antidotes for OPC poisoning (pralidoxime (PAM), isonitrosine, dipiroxime, etc.) were created [77–79], the intensive study of analogs of which continues at the present time [53–61, 92, 93]. The studies carried out cover compounds with a rather diverse structure [148, 149, 154, 157–172], and in papers [148, 149, 161–167] much attention was paid to the study of the re- activity of surfactants, the head group of which is structurally similar to AChE pyridinium re- activators (2-PAM, 4-PAM, etc. [77–79]). The modification of detergents containing an oximate fragment was carried out in the fol- lowing directions: - varying the counterion structure; - varying the length of the alkyl chain; - varying the nature of the head group. Influence of the anion nature. Varying the structure of the anion (Cl–, Br–, I–, MsO–, TsO–), carried out for surfactants of different structures [162, 163, 170], made it possible to demonstrate that their reactivity is practically independent of the nature of counterion. Varying the length of the alkyl chain. The transition from non-micelle-forming com- pounds (Alk ≤ C7H15) to micelle-forming ones (Alk ≥ C8H17) is accompanied by a decrease in the half-transformation time of model sub- strates into reaction products [162, 163], which ORGANIC CHEMISTRY REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS (Part 2) 84 ISSN 2708-129X. Укр. хім. журн., 2020 is explained by the realization of the micellar catalysis. Information on the nature of the ef- fect of an increase in the length of alkyl chain on reactivity of micelle-forming substances (with Alk ≥ C8H17) is very contradictory. The data are given, from which it follows that with an increase in the length of the alkyl chain, for some cases the nucleophilicity of the function- al group increases, while in others the same dependence has the opposite character [148, 162, 167]. The differences in the data obtained can be caused by the fact that with an increase in the length of the alkyl chain, the solubility of the surfactant in water decreases and this leads to complete dissolution of detergent with Alk = C8H17 [148] at a concentration of 6.0·10–2 mol l–1, and partial dissolution of those with Alk = C12H25 and C16H33 [148]. A decrease in the amount of a dissolved substance leads to the observed effect of a decrease in the rate of DPP cleavage with an increase in the length of the alkyl chain. Varying the nature of the head group. The literature [148, 149, 154, 157–172] describes functional detergents containing imidazolium, pyridinium, tetraalkylammonium fragments and an oximate group in the head part of the molecule. The study of their reactivity in the processes of model substrates (NPA, DPP, NP- DPP, NPDEP, NPDEP, NPDETP, NPTS, NPB) cleavage showed that they are effective accep- tors of acyl groups. Unfortunately, it is rather difficult to carry out a full-fledged comparative analysis based on the available literature data [148, 149, 154, 157–172]. This is because the authors use substrates of different reactivity and hydrophobicity, and reaction conditions are significally different (surfactant concen- tration, degree of ionization of a functional fragment, degree of substrate binding, temper- ature, additives of co-detergents, organic sol- vents, etc.). 9.4 Reactivity of functional detergents con- taining amidoximate fragment. Functional surfactants based on pyridine [161] and imidazole [157–160], containing amidoximate group as a reactive fragment, are close to functional detergents containing oxi- mate ion in terms of the cleavage efficiency of model acyl-containing substrates. However, since amidoximate group has higher basicity, the cleavage reactions have to be carried out in strongly alkaline media, which is less pref- erable from a practical point of view [4]. Their rather low solubility in water should also be noted, which creates additional experimental difficulties. Even when using additives of or- ganic solvents (ethyl alcohol, acetonitrile) and co-detergents (CTAB), it is extremely difficult to obtain stable solutions of these substances with a concentration sufficient for effective binding of model substrates [157–161]. 9.5. Reactivity of functional surfactants con- taining a peroxy group. Hydroperoxide anion is one of the most effective α-nucleophiles in substitution reac- tions at unsaturated electron-deficient centers [4]. Along with that, only one work [173] is devoted to its introduction into the detergent molecule and the study of the properties of the obtained functional surfactants. N OOHC16H33 CF3SO3- L I O O O RO LI R: C8H17 C16H33(CH3)2NCH2CH2 CH2(CH3)2NCH2CH2 CHOOCC15H31 CH2OOCC15H31 (а) (б) (в) N I O O O R' LII R’: C8H17 C12H25 C16H33 (а) (б) (в) UCJ № 8 / Vol. 86A. F. Popov, I. V. Kapitanov, A. A. Serdyuk, A. E. Shumeiko 85https://ucj.org.ua Detergent L, described in [173], was iso- lated in the form of a mixture with functional surfactant XXXVII, which served as a start- ing material for the synthesis of L (the content of the target product L was 60–70%). When studying the kinetics of NPA cleavage by a XXXVII / L mixture, cetyltrimethylammoni- um chloride (CTAC) additives were used as a co-detergent (molar ratio of the components of co-micelles L:XXXVII:CTAC = 6:5:4). The observed rate constant of the NPA splitting in the presence of the L / XXXVII / CTAC co-mi- celles was 0.4 s-1 (1.42 / 1.30 / CTAC = 0.045 M, pH = 8), which is ~ 500 times higher than the observed rate constant for the NPA splitting by arylate ion, which has the same basicity, but in the absence of surfactants. Another rather attractive direction in the design of systems for the degradation of organ- ophosphorus ecotoxicants is the creation and study of surfactants containing an iodosocar- boxylate group [11, 174–176]. N OOHC16H33 CF3SO3- L I O O O RO LI R: C8H17 C16H33(CH3)2NCH2CH2 CH2(CH3)2NCH2CH2 CHOOCC15H31 CH2OOCC15H31 (а) (б) (в) N I O O O R' LII R’: C8H17 C12H25 C16H33 (а) (б) (в) An undoubted advantage of these com- pounds is that their functional group can be converted into an ionized form at pH values close to neutral (see table). Thus, compound LI (b), being one of the most effective nucleophilic reagents of this type, in co-micelles with CTAC, provides ex- tremely high rate of NPDPP cleavage in a weakly alkaline medium (pH = 8.0) [174], and LII (c) allows carrying out decomposition re- actions of organophosphorus substrates al- ready at pH ≥ 6.0 [176]. Table Reactivity of functional surfactants containing iodosocarboxylate group in the process of NPDPP cleavage; pH 8.0, [PD] = 1.0·10-4 mol∙l-1, 25 0С. № Compound рКа [CTAC], mol∙l-1 ko s -1 τ1/2, s Ref. 1 LI (а) 7.20 2.0·10-4 1.04 0.7 [174] 2 LI (б) 6.45 2.0·10-4 1.14 0.6 [174] 3 LI (в) 7.20 2.0·10-4 * 0.014 50 [175] 4 LII (а) < 5.0 1.0·10-4 0.0038 182 [176] 5 LII (б) < 5.0 1.0·10-4 0.071 10 [176] 6 LII (в) 4.85 1.0·10-4 0.18 4 [176] Remark. CTAB was used as co-detergent. ORGANIC CHEMISTRY REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS (Part 2) 86 ISSN 2708-129X. Укр. хім. журн., 2020 The disadvantage of such functional deter- gents containing iodosocarboxylate group is low solubility in water, which significantly nar- rows the possibilities of their use [4, 11]. CONCLUSIONS. Thus, the presented ma- terials show the following: 1) The phenomenon of the α-effect plays an important role in understanding the nature of the nucleophilic reactivity and the mecha- nisms of nucleophilic reactions involving both “ordinary” organic and inorganic nucleophiles and α-nucleophilic particles. 2) The use of α-nucleophilic reagents as the basis of formulations for the cleavage of eco- toxicants makes it possible to provide abnor- mally high rates of degradation of acyl-con- taining substrates. 3) The use of nucleophilic oxidation sys- tems hypohalogenic acid / hypohalogenite ion, hydrogen peroxide / hydroperoxide ion allows splitting substrates of various chemical nature with high efficiency. 4) Introduction of an α-nucleophilic frag- ment into the structure of surfactant mole- cules leads to the creation of supernucleophilic functional detergents, which are one of the most effective reagents in the processes of de- composition of acyl-containing ecotoxicants. РЕАКЦІЙНА ЗДАТНІСТЬ НУКЛЕОФІЛІВ І α-ЕФЕКТ У ПРОЦЕСАХ ЗАМІЩЕННЯ У ЕЛЕКТРОНОДЕФІЦІТНИХ ЦЕНТРІВ (частина 2) А. Ф. Попов1, I. В. Капiтанов1,3, Г. О. Сер дюк1,3, О. Є. Шумейко1,2 1Інститут фізико-органічної хімії і вугле- хімії імені Л. М. Литвиненка НАН України; вул. Харківське шосе 50, Київ 02160, Україна 2Інститут органічної хімії НАН Украї- ни; вул. Мурманська 5, Київ 02660, Україна 3Центр передового досвіду в галузі зеле- ної хімії Європейського дослідницького про- стору, відділення хімії та біотехнології, факультет наук, Талліннський технічний університет, Академія, 15, Таллінн, 12618, Естонія * E-mail: ashumeiko@ukr.net Проведено аналіз даних із реакційної здатності типових неорганічних α-нуклео- філів у процесах розщеплення ацилвмісних субстратів, у тому числі ефірів кислот фос- фору, які забезпечують аномально високі швидкості реакцій порівняно з іншими су- пернуклеофілами. Розглянуто різні види таких α-нуклеофілів, особливості їхньої структури і реакційної здатності. Показано, що важливою особливістю гідроксиламі- ну, оксимів і гідроксамових кислот є наяв- ність фрагменту із суміжними атомами O і N (-N-O-H), що містять одну або більше неподілених пар електронів, що й визначає їхню приналежність до класу α-нуклеофілів. Показано, що за прояв α-ефекту і його величину можуть бути відповідальними ціла низка факторів, основними з яких є дестабілізація основного стану нуклеофі- лу внаслідок відштовхування неподілених електронних пар, стабілізація перехідно- го стану, незвичайна термодинамічна ста- більність продуктів реакції, сольватаці- йні ефекти розчинника, тип гібридизації електрофільного центру та ін. Особливий інтерес викликає вивчення нуклеофільної реакційної здатності окси- UCJ № 8 / Vol. 86A. F. Popov, I. V. Kapitanov, A. A. Serdyuk, A. E. Shumeiko 87https://ucj.org.ua мат-іонів, який зумовлений, перш за все, тією обставиною, що саме в ряду цього кла- су α-нуклеофілів було знайдено ефективні антидоти – реактиватори ацетилхолінесте- рази. Показано аномально високу реакцій- ну здатність неорганічних α-нуклеофілів – НОО- і ClO- іонів, які використовують для конструювання рецептур із метою знищен- ня екотоксикантів і бойових отруйних речо- вин. Важливе значення має використання міцелярних систем для підвищення ефек- тивності реакцій розщеплення екотокси- кантів супернуклеофільними реагентами, суть дії яких полягає в зміні локальних концентрацій і реакційної здатності суб- стратів і реагентів при перенесенні реакції в міцелярну псевдофазу, а також зміщення протолітичних рівноваг у такому розчині. Тут слід зазначити, що найбільш перспек- тивним шляхом підвищення ефективності зв›язування нуклеофільних реагентів міце- лами є створення функціональних детер- гентів – ПАР, що містять у своїй структурі реакційноздатні фрагменти. За реалізації такого підходу концентрація нуклеофіль- них груп на поверхні міцел завжди буде до- рівнювати концентрації ПАР. Наведені нами дані свідчать про пер- спективність шляху структурної модифі- кації ПАР, що призводить до створення супернуклеофільних функціоналізованих детергентів, які є одними з найбільш ефек- тивних реагентів у процесах розщеплення ацилвмісних екотоксикантів. Ключові слова: функціоналізовані ПАР, α-нуклеофіли, міцелярні системи, гідрокси- ламін, оксими, амідоксими, гідроксамові кислоти, пероксиди. РЕАКЦИОННАЯ СПОСОБНОСТЬ НУКЛЕОФИЛОВ И α-ЭФФЕКТ В ПРОЦЕССАХ ЗАМЕЩЕНИЯ У ЭЛЕКТРОНОДЕФИЦИТНЫХ ЦЕНТРОВ (часть 2) А. Ф. Попов1, И. В. Капитанов1,3, А. А. Сер дюк1,3, А. Е. Шумейко1,2 * 1 Институт физико-органической хи- мии и углехимии им. Л.М. Литвиненко НАН Украины; ул. Харьковское шоссе 50, Киев 02160, Украина 2 Институт органической химии НАН Украины; ул. Мурманская 5, Киев 02660, Украина 3 Центр передового опыта в области зе- леной химии Европейского исследователь- ского пространства, отделение химии и биотехнологии, факультет наук, Таллинн- ский технический университет, Академия, 15, Таллинн, 12618, Эстония * e-mail: ashumeiko@ukr.net В обзоре проанализированы вопросы, связанные с реакционной способностью нуклеофилов и проявлением α-эффекта в процессах замещения у электронодефи- цитных центров. Обсуждены фундамен- тальные аспекты этого явления, а также возможности и перспективы использова- ния α-нуклеофилов в системах для высоко- эффективного расщепления субстратов – экотоксикантов различной природы. Ключевые слова: функционализиро- ванные ПАВ, α-нуклеофилы, мицеллярные системы, гидроксиламин, оксимы, амидок- симы, гидроксамовые кислоты, пероксиды. ORGANIC CHEMISTRY REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS (Part 2) 88 ISSN 2708-129X. Укр. хім. журн., 2020 ЛИТЕРАТУРА 94. 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spelling	oai:ojs2.1444248.nisspano.web.hosting-test.net:article-2132026-07-22T08:23:44Z REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS (Part 2) РЕАКЦИОННАЯ СПОСОБНОСТЬ НУКЛЕОФИЛОВ И α-ЭФФЕКТ В ПРОЦЕССАХ ЗАМЕЩЕНИЯ У ЭЛЕКТРОНОДЕФИЦИТНЫХ ЦЕНТРОВ (часть 2) РЕАКЦІЙНА ЗДАТНІСТЬ НУКЛЕОФІЛІВ І α-ЕФЕКТ У ПРОЦЕСАХ ЗАМІЩЕННЯ У ЕЛЕКТРОНОДЕФІЦІТНИХ ЦЕНТРІВ (частина 2) Popov, Anatolii Kapitanov, Illia Serdyuk, Anna Sumeiko, Aleksandr functionalized surfactants, α-nucleophiles, micellar systems, hydroxylamine, oximes, amidoximes, hydroxamic acids, peroxides The review analyzes issues related to the reactivity of nucleophiles and the manifestation of the α-effect in substitution processes at electron-deficient centers. The fundamental aspects of this phenomenon, as well as the possibilities and prospects of using α-nucleophiles in systems for the highly efficient degradation of substrates - ecotoxicants of various natures, are discussed. In the first part of the review such aspects were observed: inorganic α-nucleophiles as the most effective class of reagents for the decomposition of organic phosphorus compounds, hydroxylamine, its N-alkyl derivatives, oximes, and hydroxamic acids, reactivity of the НОО– anion in the processes of acyl group transfer, reactivity of oximate ions, inorganic α-nucleophiles as the basis of formulations for the degradation of neurotoxins, vesicants, and organophosphorus pesticides, design of inhibited acetylcholinesterase reactivators based on hydroxylamine derivatives, ways of structural modification of α-nucleophiles and systems based on them. The data on the reactivity of typical inorganic α-nucleophiles in the cleavage of acyl-containing substrates, including phosphorus acid esters, which provide abnormally high reaction rates in comparison with other supernucleophiles, are analyzed. Various types of such α-nucleophiles, features of their structure and reactivity are considered. It was shown that an important feature of hydroxylamine, oximes, and hydroxamic acids is the presence of a fragment with adjacent O and N (–N – O – H) atoms containing one or more lone electron pairs, which determines their belonging to the class of α-nucleophiles. It has been shown that a many of factors can be responsible for the manifestation of the α-effect and its magnitude, the main of which is the destabilization of the ground state of the nucleophile due to repulsion of lone electron pairs, stabilization of the transition state, the unusual thermodynamic stability of reaction products, solvation effects of the solvent, type of hybridization of the electrophilic center, etc. V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-09-15 Article Article Organic chemistry Органическая xимия Органічна xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/213 10.33609/2708-129X.86.8.2020.77-100 Ukrainian Chemistry Journal; Vol. 86 No. 8 (2020): Ukrainian Chemistry Journal; 77-100 Украинский химический журнал; ##issue.vol## 86 ##issue.no## 8 (2020): Украинский химический журнал; 77-100 Український хімічний журнал; Том 86 № 8 (2020): Український хімічний журнал; 77-100 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/213/119 Copyright (c) 2020 Anatolii Popov, Illia Kapitanov, Anna Serdyuk, Aleksandr Sumeiko https://creativecommons.org/licenses/by-nc/4.0
spellingShingle	Popov, Anatolii Kapitanov, Illia Serdyuk, Anna Sumeiko, Aleksandr РЕАКЦІЙНА ЗДАТНІСТЬ НУКЛЕОФІЛІВ І α-ЕФЕКТ У ПРОЦЕСАХ ЗАМІЩЕННЯ У ЕЛЕКТРОНОДЕФІЦІТНИХ ЦЕНТРІВ (частина 2)
title	РЕАКЦІЙНА ЗДАТНІСТЬ НУКЛЕОФІЛІВ І α-ЕФЕКТ У ПРОЦЕСАХ ЗАМІЩЕННЯ У ЕЛЕКТРОНОДЕФІЦІТНИХ ЦЕНТРІВ (частина 2)
title_alt	REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS (Part 2) РЕАКЦИОННАЯ СПОСОБНОСТЬ НУКЛЕОФИЛОВ И α-ЭФФЕКТ В ПРОЦЕССАХ ЗАМЕЩЕНИЯ У ЭЛЕКТРОНОДЕФИЦИТНЫХ ЦЕНТРОВ (часть 2)
title_full	РЕАКЦІЙНА ЗДАТНІСТЬ НУКЛЕОФІЛІВ І α-ЕФЕКТ У ПРОЦЕСАХ ЗАМІЩЕННЯ У ЕЛЕКТРОНОДЕФІЦІТНИХ ЦЕНТРІВ (частина 2)
title_fullStr	РЕАКЦІЙНА ЗДАТНІСТЬ НУКЛЕОФІЛІВ І α-ЕФЕКТ У ПРОЦЕСАХ ЗАМІЩЕННЯ У ЕЛЕКТРОНОДЕФІЦІТНИХ ЦЕНТРІВ (частина 2)
title_full_unstemmed	РЕАКЦІЙНА ЗДАТНІСТЬ НУКЛЕОФІЛІВ І α-ЕФЕКТ У ПРОЦЕСАХ ЗАМІЩЕННЯ У ЕЛЕКТРОНОДЕФІЦІТНИХ ЦЕНТРІВ (частина 2)
title_short	РЕАКЦІЙНА ЗДАТНІСТЬ НУКЛЕОФІЛІВ І α-ЕФЕКТ У ПРОЦЕСАХ ЗАМІЩЕННЯ У ЕЛЕКТРОНОДЕФІЦІТНИХ ЦЕНТРІВ (частина 2)
title_sort	реакційна здатність нуклеофілів і α-ефект у процесах заміщення у електронодефіцітних центрів (частина 2)
topic_facet	functionalized surfactants α-nucleophiles micellar systems hydroxylamine oximes amidoximes hydroxamic acids peroxides
url	https://ucj.org.ua/index.php/journal/article/view/213
work_keys_str_mv	AT popovanatolii reactivityofnucleophilesandaeffectinsubstitutionprocessesatelectrondeficiencycenterspart2 AT kapitanovillia reactivityofnucleophilesandaeffectinsubstitutionprocessesatelectrondeficiencycenterspart2 AT serdyukanna reactivityofnucleophilesandaeffectinsubstitutionprocessesatelectrondeficiencycenterspart2 AT sumeikoaleksandr reactivityofnucleophilesandaeffectinsubstitutionprocessesatelectrondeficiencycenterspart2 AT popovanatolii reakcionnaâsposobnostʹnukleofiloviaéffektvprocessahzameŝeniâuélektronodeficitnyhcentrovčastʹ2 AT kapitanovillia reakcionnaâsposobnostʹnukleofiloviaéffektvprocessahzameŝeniâuélektronodeficitnyhcentrovčastʹ2 AT serdyukanna reakcionnaâsposobnostʹnukleofiloviaéffektvprocessahzameŝeniâuélektronodeficitnyhcentrovčastʹ2 AT sumeikoaleksandr reakcionnaâsposobnostʹnukleofiloviaéffektvprocessahzameŝeniâuélektronodeficitnyhcentrovčastʹ2 AT popovanatolii reakcíjnazdatnístʹnukleofílívíaefektuprocesahzamíŝennâuelektronodefícítnihcentrívčastina2 AT kapitanovillia reakcíjnazdatnístʹnukleofílívíaefektuprocesahzamíŝennâuelektronodefícítnihcentrívčastina2 AT serdyukanna reakcíjnazdatnístʹnukleofílívíaefektuprocesahzamíŝennâuelektronodefícítnihcentrívčastina2 AT sumeikoaleksandr reakcíjnazdatnístʹnukleofílívíaefektuprocesahzamíŝennâuelektronodefícítnihcentrívčastina2

РЕАКЦІЙНА ЗДАТНІСТЬ НУКЛЕОФІЛІВ І α-ЕФЕКТ У ПРОЦЕСАХ ЗАМІЩЕННЯ У ЕЛЕКТРОНОДЕФІЦІТНИХ ЦЕНТРІВ (частина 2)

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