Supernucleophilic systems based on functionalized surfactants in the decomposition of 4-nitrophenyl esters derived from phosphorus and sulfur acids. III. Reactivity of mixed micellar systems based on tetraalkylammonium and imidazolium surfactants

Article abstract of DOI:10.1134/S1070428015080047

Reactivity of mixed micellar systems based on the functionalized imidazolium and tetraalkylammonium surfactanats in the reaction of cleavage of 4-nitrophenyl ethyl ethylphosphonate was studied. Replacing of an imidazolium fragment in the detergent structure with a tetraalkylammonium one reveals decreasing the substrate solubilization efficiency. In the case of dimeric surfactants, the nucleophilicity of the oximate fragment is considerably (ca. 2 times) decreased thus additionally decreasing the rate of cleavage of the organophosphorus substarte. Therefore the nature of the cationic center in the head group may affect the extent of the observed micellar effects of functionalized surfactants.

Full text of DOI:10.1134/S1070428015080047

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 8, pp. 1083–1090. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © T.M. Prokop’eva, I.V. Kapitanov, I.A. Belousova, A.E. Shumeiko, M.L. Kostrikin, M.K. Turovskaya, N.G. Razumova, A.F. Popov,
2
015, published in Zhurnal Organicheskoi Khimii, 2015, Vol. 51, No. 8, pp. 1105–1112.
Supernucleophilic Systems Based on Functionalized Surfactants
in the Decomposition of 4-Nitrophenyl Esters
Derived from Phosphorus and Sulfur Acids.
*
III. Reactivity of Mixed Micellar Systems Based
on Tetraalkylammonium and Imidazolium Surfactants
a
a,b
a
a,b
T. M. Prokop’eva , I. V. Kapitanov , I. A. Belousova , A. E. Shumeiko ,
a
a
a
a
M. L. Kostrikin , M. K. Turovskaya , N. G. Razumova , and A. F. Popov
a
Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine,
Kharkov shosse 50, Kiev, 02160 Ukraine
e-mail: ivkapitanov@gmail.com
b
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
Received May 8, 2015
Abstract—Reactivity of mixed micellar systems based on the functionalized imidazolium and tetraalkyl-
ammonium surfactanats in the reaction of cleavage of 4-nitrophenyl ethyl ethylphosphonate was studied. Rep-
lacing of an imidazolium fragment in the detergent structure with a tetraalkylammonium one reveals decreasing
the substrate solubilization efficiency. In the case of dimeric surfactants, the nucleophilicity of the oximate
fragment is considerably (ca. 2 times) decreased thus additionally decreasing the rate of cleavage of the organo-
phosphorus substarte. Therefore the nature of the cationic center in the head group may affect the extent of the
observed micellar effects of functionalized surfactants.
DOI: 10.1134/S1070428015080047
Solutions of surfactants are among the most
its concentration is always maximal since the reactive
fragment is covalently linked to the surfactant
molecule [1, 2, 8, 9].
favorable reaction media, in particular, for the
nucleophilic cleavage of ester bonds [1–12]. They
possess a unique combination of being environ-
mentally friendly (since the main system component is
water) [1–5], the possibility to ensure high reaction
rates [1–9], and easily adjusting the properties by
preparing multicomponent supramolecular ensembles
In the course of the last decade we have carried out
a purposeful designing of monomeric and dimeric
surfactants functionalized with an oxime group [1, 8,
9
, 18–22]. A scientifically based designing of
detergents possessing desired properties should be
underlain by the establishment of the correlation
between the structure and the micellar effects. The
analysis of the correlation the structure of surfactant/
substrate–property made it possible to reveal the main
factors governing the reactivity and the micellar effects
of the functionalized surfactants. Thus, one of the key
factors proved to be the nature of the head group since
it to a large extent governs the structure, the surface
charge, the partial molar volume of the micelle, the
saturation of the micelle surface layer with water
molecules, etc. [6–9]. In the most cases the α-
nucleophilic functional moiety ensuring the nucleo-
(
mixed micelles [10, 11], metallomicelles [12],
surfactant–polymer aggregates [13–15], surfactant–
calixarene [16, 17], etc.).
In the nucleophilic cleavage of esters of phosphorus
and sulfur acids in micellar systems the best effect was
observed at the use as cleavage agents of surfactants
functionalized with the fragments of α-nucleophiles
[1–4, 8–10]. The obvious advantage of these
detergents over the other types of micellar systems
consists in the lack of the necessity to bind the reagent:
*
For communication II, see [1].
1
083

1
084
PROKOP’EVA et al.
philic cleavage of the acyl-containing substrates is also
a part of the head group of the surfactant [1, 2, 8, 9, 18–
The changes in the structure of the cationic center
of dimeric surfactants 2 and 5 may result in more
significant effect than in the case of monomeric
detergents 1 and 4. This is due to the fact that micelles
(and mixed micelles) of dimeric surfactants are
considerably more sensitive to the structural changes
in the surfactant [25].
2
2]. Its reactivity, similar to that of the non-micelle-
forming structural analogs [8, 9, 19, 23, 24], is directly
connected with its acid-base properties, and the
Brønsted dependence has a break in the same рKа
range [1, 8, 9]. Beside the structure of the head group
the micellar effects of the surfactant depend on the
hydrophobic properties of substrate as well as of
detergent [1, 8, 9, 18, 20–22]: with the growing length
of the alkyl substituent in the surfactant and with the
constant of the substrate binding the observed reaction
rates increase.
Kinetic regularities of ester 3 cleavage with
mixed micellar systems based on surfactant (1 and
2
) and (4 and 5). Since the solubility of functionalized
tetraalkylammonium detergents 1 and 2 turned out to
be low, the quantitative estimation of the micellar
effects and comparative analysis were performed using
mixed micellar system functionalized surfactant–
cetyltrimethylammonium bromide 6. In this approach
the analysis of factors governing the observed
acceleration may be properly performed considering
the special features of the experimental conditions
(fraction of functionalized detergent in the mixed
micelles, ionization degree of the oxime fragment, etc.)
Whereas the effect of the properties of the
functional fragment, hydrophobicity of surfactant and
substrate on the reactivity of the surfactant may be
regarded as sufficiently clearly established [1, 8, 9,
1
8], the effect of the nature of the cationic center of the
head group requires more detailed investigation.
In this study a method was developed of the
synthesis of new functionalized tetraalkylammonium
surfactants 1 and 2 and their micellar effect in the
cleavage of 4-nitrophenyl ethyl ethylphosphonate 3
was estimated. The influence of detergents 1 and 2 on
the rate of cleavage of ester 3 was compared with the
micellar effects of their structural analogs, imidazole-
containing surfactants 4 and 5, thus allowing the
analysis of the influence on the reactivity of the nature
of the cationic center.
[
2, 7–10, 20].
The character of the influence of mixed micellar
systems functionalized surfactant–6 on the rate of
cleavage of substrate 3 is analogous to the laws
previously established for micellar and mixed micellar
systems based on surfactants containing in their
structure of an oximate moiety [1, 8, 9, 18, 20–22].
Firstly, at the constant surfactant concentration the
–1
apparent reaction rate constant (k , s ) grows with
obs
increasing рН of the medium tending to a limit (Fig. 1).
Consequently, the zwitter-ion forms of detergents 1
and 2 act as reactive forms, and the zwitter-ion is
_
_
_
NOH
NOH
Cl
Cl
Br
N
N
N
involved in a nucleophilic attack of the oximate-ion
+
C
H
12
+
+
C H
12 25
C12H25
25
–
(
Ох ) on the electron-deficient phosphorus atom
1
2
leading to the formation of the corresponding О-acyl
derivatives [2, 8, 26, 27]. Secondly, the dependences
of kobs on the summary concentration of the surfactant
_
Et
O
Cl
NOH
–
1
P
(
с , mol L ) at рН = const have the pattern typical of
N
+
N
0
EtO
O
NO2
C12H25
the ester cleavage in the presence of functionalized
detergents [1, 8, 9, 18, 20 – 22]: till the critical micelle
3
4
–
1
concentration (CMC, mol L ) only
a
slight
_
_
acceleration is observed , and then with the growing
Cl
NOH
Cl
concentration of micellized surfactant (с = с – CMC,
0
–
1
N
+
N
N
+
N
mol L ) the k values significantly increase due to
obs
C12H25
C12H25
the growing binding of the substrate with micelles
5
(
mixed micelles) of the surfactant (Figs. 2, 3).
_
The analysis of kinetic data (like those of
Br
N +
previously studied functionalized detergents and mixed
micellar systems based thereon) was performed in the
C16H33
6
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

SUPERNUCLEOPHILIC SYSTEMS BASED ON FUNCTIONALIZED SURFACTANTS
1085
frame of the pseudophase distribution model [1, 2, 7,
, 20, 28]. Therewith it is assumed that the cleavage of
ester 3 in the presence of mixed micelles proceeds
4
3
2
1
0
9
1
along two parallel routes:
K
a,app
_H+
m
2
_
_
k2
OxH
Ox
+
(S)m
Reaction products
Reaction products
+
H+
PS
w
OH
_
k
OH
+
(S)w
–
In the scheme the designations ОхН, Ох
correspond to the functionalized detergents with the
non-ionized and ionized functional groups, P = [S] /
0
1
2–1
3
S
m
2
[
S] is the distribution coefficient of the substrate (S)
с
0
× 10 , mol L
w
between two phases, micellar pseudophase (m) and
Fig. 2. Concentration dependences for substrate 3 cleavage
in mixed micellar systems 1/6, χ 0.25 (1) and 2/6, χ 0.25
m
w
–1 –1
water (w); k 2 and k ОН, L mol s , are the second
order rate constants characterizing the nucleophilicity
of the oximate group in the micelles of the surfactant
–1
(2); рН 10.5, borate buffer solution 0.01 mol L , 25°C.
4
–
and ОН ion in water. The apparent rate constant of the
pseudofirst order is described by the Eq. (1):
3
m
w
χ ⋅k K C + k
⋅аOH
−
S
−
−
K а, app
OH
1
kapp.
=
⋅
=
1
+ K C
K а, app + аH
+
S
2
1
0
2
m
w
χ (k 2 / Vm ) K с + k
⋅ а
S
−
K а, app
OH
OH
=
⋅
, (1)
1
+ K с
K а, app + аH +
S
where χ is the molar fraction of the functionalized
m
–1
detergent in the mixed micelle; k , s , is the reduced
nucleophilic reactivity of the functional fragment in
the micellar pseudophase; K = (P – 1)V ≈ P V ,
0
1
2–1
3
2
с × 10 , mol L
0
S
S
m
S
m
Fig. 3. Concentration dependences for substrate 3 cleavage
in mixed micellar system 1/6: χ 0.25 (1), χ 0.125 (2); рН
0.5, borate buffer solution 0.01 mol L , 25°C.
–
1
L mol , is the constant of the equilibrium binding of
–
1
1
3
–
1
the substrate; V , L mol , is the partial molar volume
m
–
1
of the surfactant; с, mol L , is the concentration of the
micellized detergent; Ka,app is the apparent constant of
acid ionization of the oxime group.
2
1
0
When estimating the kinetic parameters from Eq. (1)
the contributions from the alkaline hydrolysis in the
micellar pseudophase and the cleavage of substrate 3
by the functional group of non-micellized part of the
surfactant in the water phase were not taken into
account since under the chosen experimental
conditions their rates are low and did not essentially
contribute to the kobs value.
8
9
10
11 рН
Fig. 1. Dependence of the rate of substrate 3 cleavage in a
mixed micellar system 2/6 on рН of environment; χ 0.25, с
All concentration and рН-dependences are
adequately described in the framework of the above
0
–
1
–1
0
.0158 mol L , borate buffer solution 0.01 mol L , 25°C.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

1
086
PROKOP’EVA et al.
Table 1. Physicochemical properties and nucleophilic reactivity of detergents 1, 2, 4, and 5 in the cleavage of ester 3; borate
–1
a
buffer solution 0.01 mol L , 25°С
b
a
c
d
m
2
–1
m
2
–1 –1e
–1
–1f
Compound no.
pK
χ
pH
α
k
/V
m
, s
k
, L mol s
S
K , L mol CMC, mol L
0
.25
0.25
0.23 (sp, χ 0.125) 0.125
11.30
10.45
10.48
~ 0.9
~ 0.5
~ 0.5
0.33
0.33
0.33
0.13
0.13
0.13
70
70
60
0.001
0.002
0.0006
1
1
0.15 (sp, χ 1.0)
1
0
0
0
0
.5
.25
10.45
10.46 g ~ 0.9 g
~ 0.9
0.19
0.20g
0.076
0.080g
0.080
0.076
72
74
74
93
0.0004
0.0003
0.0003
0.0003
9
.44 (sp, χ 1.0)
g
2
9.21 (kin, χ 0.25)
9
.25 8.4–11.0 0.1–1.0
.125
0.20
0.19
.49 (sp, χ 0.125)
10.46
~ 0.9
1
1
0
0
0
0
.0
.0
.5
.5
.125
.125
11.40
10.32
11.50
10.43
11.43
10.53
~ 0.9
~ 0.5
~ 0.9
~ 0.5
~ 0.9
~ 0.5
0.21
0.28
0.30
0.30
0.33
0.28
0.11
0.14
0.12
0.12
0.13
0.11
70
76
95
91
162
155
0.003
0.0035
0.0006
0.0006
0.0004
0.0006
1
0.50 (sp, χ 1.0)
4
5
10.10 (kin, χ 1.0)
1
0.29 (sp, χ 0.125)
8
.8 (kin, χ 1.0)
1
0
.0
.125
10.00
10.51
~0.9
>0.9
0.40
0.43
0.20
0.17
155
160
0.00005
0.0001
8.9 (sp, χ 1.0)
.9 (sp, χ 0.125)
8
а
m
2
The determination error of values k
/V
m
from kinetic data did not exceed ±10%, of K
S
and CMC was no larger than ±15%. Data for
surfactants 4 and 5 at χ 1.0 are taken from [1, 18].
Values of рK were determined from kinetic (kin) or spectrophotometric (sp) data.
а
Molar fraction of functionalized detergent in mixed micelles with compound 6.
b
c
d
e
Fraction of anionic form of the oxime fragment of surfactant.
m
2
–1
In calculation of k
values at χ 1.0 the partial molar volume was assumed at 0.5 01 mol L [1, 9, 12, 21], and that of mixed micelles
–
1
(
χ 0.125–0.5) was assumed as equal to the partial molar volume of detergent 6, ~0.4 01 mol L [6, 7].
f
CMC values were calculated from kinetic data.
Parameters were obtained by processing the dependence kobs–рН.
g
m
model [Eq. (1)]. In Table 1 the values of рKа,app, k 2
and the other parameters of the systems based on
surfactants 1, 2 and 4, 5 are compiled, characterizing
the cleavage of ester 3 with these compounds in the
micellar pseudophase. The CMC values were
estimated from kinetic data (Fig. 4).
рKа,app of compound 2 relative рKа,app 1 decreases by
~0.8 log unit, and рKа,app of compound 5 relative to 4
diminishes by ~1.5 log unit. The variation of the
2
Acid-base properties and the nucleophilicity of
surfactants (1 and 2) and (4 and 5). The apparent
constants of acid ionization of the oxime group in
detergents 1, 2, 4, and 5 and in mixed micellar systems
functionalized surfactant–6 were determined by
spectrophotometry and/or by kinetic method (Table 1).
The character of changes in рKа,app of the oxime group
is of the same type in the surfactants with a different
nature of the cationic center: Regardless of its structure
in going from of monomeric to dimeric surfactants the
acidity of the oxime fragment increases in agreement
with the influence of the second electron-acceptor
substituent (cf. рKа,app of detergents 1 and 2, 4, and 5 in
Table 1). Yet the values of these changes are different:
1
CMC
0
0
2
4
6
8
4
–1
с × 10 , mol L
0
Fig. 4. Determination of CMC by the kinetic method for
the mixed micellar system 2/6; substrate 3, χ 0.5, рН 10.5,
borate buffer solution 0.01 mol L , 25°C.
–
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

SUPERNUCLEOPHILIC SYSTEMS BASED ON FUNCTIONALIZED SURFACTANTS
1087
0
atom of the oximate group and the positively charged
nitrogen atom of the tetraalkylammonium fragment
resulting in the reduction of the nucleophilic reactivity.
Micellar effects of systems based on
functionalized surfactants (1 and 2) and (4 and 5) in
the cleavage of ester 3. The values of apparent
micellar effects for the system based on functionalized
surfactants in the cleavage of ester 3 may be
characterized by the ratio of the apparent rate constants
at the constant рН, initial concentration and the value
of χ. At the detergent concentration in micelles
exceeding ~10-fold the CMC and at similar experi-
mental conditions the maximum increase in kobs is
observed for the mixed micelles of detergent 5: appro-
ximately 3–4-fold compared with monomeric (1 and 4)
–
0.5
5
1
4
–
1
2
–
1.5
7
8
9
рK
10
11
а
Fig. 5. Brønsted dependence for substrate 3 cleavage with
functionalized surfactants containing an oxime group
points for surfactants 1, 2, 4, and 5, all others are taken
from [1, 9, 19, 20]).
m
m
and dimeric (2) surfactants [Table 2, k obs(5)/k obs(sur-
factant)]. Even more significant differences are obser-
ved at the comparison of the apparent rate constants in
(
*
the micellar pseudophase and in water. In this case the
fraction of the functionalized detergent does not
considerably affect the values of рKа,app, although it
was presumed that the increasing content of the catio-
nic detergent 6 in the mixed micelles with 1, 2 and 4, 5
should favor the ionization of the oxime group due to
the growing contribution of the field effect [6, 22].
reaction rate grows 200–500 times (Table 2).
With the growing fraction of the functionalized
detergent in the mixed micelles with surfactant 6 the
values of kobs regularly grow (Fig. 3) and consequently
the half-time of substrate conversion into the reaction
products considerably decreases. For instance, for the
–
1
The analysis of the kinetic behavior of surfactants
mixed micelles 2/6 at рН 10.5, с 0.0029 mol L , χ
0
1
, 2 and 4, 5 in the frame of the pseudophase
0.125, τ1/2 attains about 180 s, and at χ 0.5 τ , ~50 s.
1/2
distribution model allows the establishment of the
following laws in the changes of the nucleophilicity of
the oximate group. Firstly, according to the level of the
nucleophilicity the studied surfactants form the follow-
Influence of structural factors on micellar effects
of monomeric (1 and 4) and dimeric (2 and 5)
surfactants in the cleavage of ester (3). Micellar
effects of monomeric and dimeric detergents in the
cleavage of acyl-containing substrates depend on quite
a number of factors: concentrating reagents in micelles
(mixed micelles), changes in the reactivity of the
functional group, ester orientation in the micellar
pseudophase, the shift in the apparent constants of acid
ionization, etc. [1, 2, 8, 9, 18, 20–22]. The importance
of each factor depends significantly on noncovalent
interactions, first of all, hydrophobic ones, which are
directly connected with the hydrophobicity of the
substrate and the surfactant [1, 9, 18, 21, 22]. The
analysis of kinetic data allows establishing the
following. Firstly, at рН = const the micellar effects
depend on the acidity of the oxime group of the
detergent: The lower its value, the higher is the
m
m
m
m
ing series: k (5) > k (4) ≈ k (1) > k (2) (Table 1).
2
2
2
2
Secondly, the reactivity of the oximate fragment is
independent of the fraction of the functionalized
m
2
detergent in the mixed micelles (k , Table 1). Since
the character of microsurrounding is one of the main
m
2
factors affecting the k value at the variation of the
composition of mixed micelles [1, 6, 7, 22] the
constancy of this value shows the relatively constant
properties of the surface layer and its close properties
to those of the micelles 6. Thirdly, whereas for the
monomeric (1 and 4) and dimeric surfactant 5 the
nucleophilicity of the oximate group corresponds to
the Brønsted dependence for the functionalized
detergent, the point of dimeric surfactant 2 shows a
significant negative deviation (Fig. 5). It is apparently
due to the higher conformational mobility of the head
group in detergent 2 than in surfactant 5 [25, 29]. This
provides a possibility for an efficient electrostatic
interaction between the negatively charged oxygen
*
The kobs in water were estimated from the second order rate
constants of the non-micelle-forming oximes possessing pK
a
,
comparable with the basicity of the functional group of
detergents 1, 2, 4, and 5 [1, 9, 19, 20].
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088
PROKOP’EVA et al.
Table 2. Micellar effects of mixed micellar systems based on imidazolium and tetraalkylammonium functionalized
–1
surfactants in the cleavage of ester 3; χ 0.125, рН 10.5, borate buffer solution 0.01 mol L , 25°C
4
–1
а
3
–1b
3
-1
m
m
c
m
w d
Surfactant CMC·10 , mol L
α
с
0
·10 , mol L
k
obs·10 , s
k
obs(5)/k obs(surfactant)
k
obs/k obs
~ 230
~ 180
~ 330
~ 500
1
2
4
5
6.0
3.0
4.0
1.0
~0.5
1.0
2.7
2.7
2.3
2.4
2.5
3.9
~ 4.4
~ 2.8
~ 3.0
1.0
~0.5
1.0
3.6
10.9
а
b
c
d
Ionization degree of the functional fragment.
Summary concentration of the surfactant.
Ratio of apparent rate constants of surfactant 5 to kobs(1), kobs(2), kobs(4).
m
w
Ratio of values k obs to the apparent rate constants of substrate 3 cleavage with anions of non-micelle-forming oximes in water (kobs). The
data on non-micelle-forming oximes are taken from [1, 9, 19, 20].
concentration of the nucleophilic fragment. Near рН
10.5 monomeric detergents 1 and 4, as also the
is ~1.5–2 times smaller than for the other surfactants
(Table 1). This fact in its turn affects the value of the
micellar effects.
~
dimeric surfactant 2, react with substrate 3 with
approximately equal rates, and the maximum values of
kobs are found for compound 5 (Figs. 6, 2). However
the fractions of ionized nucleophilic group of the
surfactant in these conditions are different: α(1) ≈ α(4)
Finally, just the effects of reagents concentrating
govern the increase in the reaction rate at the transition
of the process in the micellar pseudophase [1, 6, 7, 9,
18, 20, 21]. The efficiency of substrate solubilization is
characterized by the corresponding binding constants
≈
0.5, α(2) ≈ α(5) ≈ 1.0. With accounting for the
fraction of the ionized functional fragment [α = Kа,app
Kа,app + α +)] the sequence of the variation of the
/
(
(K , Table 1). Under the identical experimental
Н
S
apparent rate constants of the reaction is another
Fig. 7): at с = const k /α 5 > 4 > 1 > 2. Secondly, the
condition (at the fraction of functionalized detergent χ
0.125 in the mixed micelles with compound 6 and рН
10.5) K (5) ≈ K (4) > K (2) > K (1). Considering the
(
0
obs
character of variation in kobs and k /α reflects not only
obs
S
S
S
S
the difference in the concentration of the oximate
fragment (because of different ionization degree of the
surfactant), but also the existing distinctions in the
character of the change in the nucleophilicity of the
m
m
functionsl fragment of the surfactant [k (5) > k (4) ≈
2
2
m
2
m
2
k (1) > k (2)] and the efficiency of the substrate
m
reactivity (Figs. 6, 7). The value k /V for detergent 2
binding [K (5) ≈ K (4) > K (2) > K (1)] the decrease in
2
m
S
S
S
S
3
2
1
4
3
4
1
5
4
1
5
2
1
2
2
0
0
0
1
2 –1
3
2
0
1
2–1
3
с
0
× 10 , mol L
2
с
0
× 10 , mol L
–
1
Fig. 6. Dependences of apparent rate constants (kobs, s ) of
substrate 3 cleavage on the concentration of functionalized
surfactants 1, 2, 4, and 5; χ 0.125, рН 10.5, borate buffer
Fig. 7. Dependences of kobs/α values on the concentration
of functionalized surfactants 1, 2, 4, and 5 for the substrate 3
cleavage; χ 0.125, рН 10.5, borate buffer solution 0.01 mol L ,
25°C (α is the degree of ionization of the functional group).
–1
–1
solution 0.01 mol L , 25°C.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

SUPERNUCLEOPHILIC SYSTEMS BASED ON FUNCTIONALIZED SURFACTANTS
1089
1
the micellar effects in the series 5 > 4 > 1 > 2 (Fig. 7)
Н NMR spectra were registered on a spectrometer
is expectable.
Bruker Avance II-400 (400 МHz) in DMSO-d ,
6
internal reference TMS.
Relatively low K values for mixed micellar system
S
based on tetraalkylammonium surfactants 1 and 2
appear as unexpected and require more detailed
investigation since under given conditions (at χ 0.125)
the properties of mixed micelles 1/6 and 2/6 should be
materially identical to the properties of individual
1-Chloroacetoxime was synthesized by procedure
[30]. Yield 52%, bp 52–54°С (0.75 mmHg). Н NMR
1
spectrum, δ, ppm: 1.83 s (3Н, CH
11.07 s (1H, NOH). Found, %: С 33.02; Н 5.67; Cl
33.10; N 13.50. C ClNO. Calculated, %: C 33.51;
H5.62; Cl 32.97; N 13.03.
), 4.22 s (2Н, CH ),
3
2
H
6
3
micelles 6, where K of ester 3 lies in the range 160–
S
–
1
2
50 L mol (as is observed for the mixed micelles
[
2-(Hydroxyimino)propyl]dimethylamine.
A
based on imidazolium surfactants 4 and 5 [9, 20] and
the other similar systems [22]).
mixture of solutions of 10 g (0.09 mol) of 1-
chloroacetoxime in 20 mL of ethanol and 50 mL of
4
0% aqueous dimethylamine was heated for 24 h in a
Therefore the results obtained show that in
designing supernucleophilic systems the changes in the
structure of the cationic center of the head group of the
functionalized surfactant also may affect its properties,
and the strongest effect would be observed in dimeric
detergents. The replacement of the imidazolium core
for the tetraalkylammonium fragment results in
decrease in the observed micellar effects therefore in
designing new supernucleophilic systems it is more
feasible to use the functionalized imidazolium
surfactants.
hermetically sealed vessel at 60°С. On cooling the
reaction mixture was tice extracted with ethyl ether.
Combined ether extracts were dried with sodium
sulfate, evaporated, the residue was crystallized from
methanol. Yield 6.2 g (57%), mp 98–99°С. Н NMR
spectrum, δ, ppm: 1.74 s (3Н, CH ), 2.09 s (6Н,
2
%
%
1
3
CH ), 2.83 s (2Н, CH ), 10.50 s (1H, NOH). Found,
3 2
: С 52.07; Н 10.87; N 23.94. C H N O. Calculated,
5 12 2
: С.70; Н 10.41; N 24.12.
[
2-(Hydroxyimino)propyl]dimethyldodecylam-
monium bromide (1). To a solution of 1 g (9 mmol)
of [2-(hydroxyimino)propyl]dimethylamine in 20 mL
of ethanol at room temperature was added by portions
an emulsion of 2.14 g (9 mmol) of dodecyl bromide in
EXPERIMENTAL
Synthesis of functionalized imidazolium surfactants
and 5 was described in [1, 18]. 4-Nitrophenyl ethyl
ethylphosphonate 3 was obtained and purified by
4
2
0 mL of ethanol. The mixture was heated for 48 h in a
hermetically sealed vessel at 65°С, then it was
evaporated on a rotary evaporator. The residue was
procedure [20].
crystallized from acetone. Yield 0.75 g (24%), mp
Cetyltrimethylammonium bromide 6 purchased
from Sigma Aldrich (BioUltra, ≥ 99.0%) and inorganic
reagents of grades “pure for analysis” and “extrapure”
were used without additional purification. The
solutions were prepared in bidistilled water.
1
1
04–106°С. Н NMR spectrum, δ, ppm: 0.85 t (3Н,
CH , J 6.7 Hz), 1.19–1.33 m [18Н, (CH ) ], 1.65–1.75
3
2 9
m (2Н, CH ), 1.96 s (3Н, CH ), 3.03 s (6Н, 2CH ),
2
3
3
+
+
3
.24–3.30 m (2Н, CH N ), 4.07 s (2Н, CH N ), 11.77
2 2
s (1H, NOH). Found, %: С 56.10; Н 10.77; Br 21.51;
All solutions were prepared just before the kinetic
measurements. The required pH values were obtained
adjusting at 25°С by adding small portions of conc.
KOH. The рН was measured with рН-meter Metrohm
N 7.39. C H BrN O. Calculated, %: C 55.88; H
17
37
2
1
0.21; Br 21.87; N 7.67.
1
,3-Dichloroacetoxime was synthesized by pro-
cedure [31]. Yield 54%, bp 100–105°С (0.75 mmHg).
7
44. The reaction progress was monitored by spectro-
1
Н NMR spectrum, δ, ppm: 4.35 s (2Н, CH ), 4.38 s
2
photometry following the accumulation of 4-nitrophe-
nolate ion (water, 25°С, 400–410 nm; spectrophoto-
meter Genesys 10 S UV-VIS, Thermo Electron Corp).
The method of calculation of the apparent rate constants
(
2Н, CH ), 12.00 s (1H, NOH). Found, %: С 25.25; Н
2
3
2
.37; Cl 49.21; N 9.74. C H Cl NO. Calculated, %: C
3 5 2
5.38; H 3.55; Cl 49.94; N 9.86.
–1
1
3
1
1
3
3
of the pseudofirst order (k , s ), the detailed description
N ,N -Didodecyl-2-(hydroxyimino)-N ,N ,N ,N -
obs
of the procedure of the kinetic experiment, and the
method of the spectrophotometric determination of рKа
values are given in [1, 9, 20, 32–34].
tetramethylpropane-1,3-diammonium chloride (2).
A mixture of 0.27 g (1.9 mmol) of 1,3-dichloro-
acetoxime, 0.8 g (3.8 mmol) of N,N-dimethyldodecyl-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

1
090
PROKOP’EVA et al.
amine (Sigma Aldrich, 97%), and 10 mL of anhydrous
ethanol was heated for 48 h in a hermetically sealed
vessel at 90°С. On cooling the precipitated crystals
were filtered off and washed with a minimal quantity
16. Pashirova, T.N., Ziganshina, А.Yu., Sultanova, E.D.,
Lukashenko, S.S., Kudryashova, Yu.R., Zhiltsova, E.P.,
Zakharova, L.Ya., and Konovalov, A.I., Coll. Surf. A,
2
014, vol. 448, p. 67.
1
7. Mirgorodskaya, A.B., Yackevich, E.I., Kudryasho-
va, Yu.R., Kashapov, R.R., Solovieva, S.E.,
Gubaidullin, A.T., Antipin, I.S., Zakharova, L.Ya., and
Konovalov, A.I., Coll. Surf. B, 2014, vol. 117, p. 497.
8. Belousova, I.A., Kapitanov, I.V., Shumeiko, A.E.,
Anikeev, A.V., Turovskaya, M.K., Zubareva, T.M.,
Panchenko, B.V., Prokop’eva, T.M., and Popov, A.F.,
Theor. Exp. Chem., 2010, vol. 46, p. 225.
of anhydrous ethanol. Yield 0.75 g (70%), mp 142–
1
1
6
2
2
1
1
44°С. Н NMR spectrum, δ, ppm: 0.85 t (6H, 2CH , J
3
.7 Hz), 1.25 m [36Н, 2(CH ) ], 1.67–1.77 m (4Н,
2
9
CH ), 3.09 s (12Н, 4CH ), 3.31–3.40 m (4Н,
2
3
1
+
+
+
CH N ), 4.29 s (2Н, CH N ), 4.35 s (2Н, CH N ),
2
2
2
3.52 s (1H, NOH). Found, %: С.35; Н 11.68; Cl
2.58; N 7.45. C H Cl N O. Calculated, %: C 65.46;
3
1
67
2
3
H11.87; Cl 12.46; N7.39.
1
2
2
9. Prokop’eva, T.M., Simanenko, Yu.S., Suprun, I.P.,
Savelova, V.A., Zubareva, T.M., and Karpichev, E.A.,
Russ. J. Org. Chem., 2001, vol. 37, p. 655.
0. Simanenko, Yu.S., Karpichev, E.A., Prokop’eva, T.M.,
Lattes, A., Popov, A.F., Savelova, V.A., and Belouso-
va, I.A., Russ. J. Org. Chem., 2004, vol. 40, p. 206.
1. Kapitanov, I.V., Belousova, I.A., Shumeiko, A.E.,
Kostrikin, M.L., Prokop’eva, T.M., and Popov, A.F.,
Russ. J. Org. Chem., 2013, vol. 49, p. 1291.
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