Synthesis and properties of water-soluble 2-aminomethylidene derivatives of 1,3-dicarbonyl compounds

Article abstract of DOI:10.1134/S1070363213070050

A series of [(2-dimethylamino)ethylamino]methylidene-1,3-dicarbonyl compounds was synthesized for the first time starting from the corresponding 2-ethoxymethylidene derivatives and N,N-dimethylethylenediamine. It was shown that further alkylation of aminomethylidene derivatives with methyl iodide occurs regioselectively at the tertiary nitrogen atom. Quaternization products obtained exhibit high corrosion inhibition of mild steel in hydrochloric acid medium.

Full text of DOI:10.1134/S1070363213070050

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 7, pp. 1330–1335. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © D.N. Bazhin, Yu.S. Kudyakova, T.I. Gorbunova, Ya.V. Burgart, A.Ya. Zapevalov, V.I. Saloutin, 2013, published in Zhurnal
Obshchei Khimii, 2013, Vol. 83, No. 7, pp. 1077–1082.
Synthesis and Properties of Water-Soluble
2-Aminomethylidene Derivatives
of 1,3-Dicarbonyl Compounds
D. N. Bazhin, Yu. S. Kudyakova, T. I. Gorbunova,
Ya. V. Burgart, A. Ya. Zapevalov, and V. I. Saloutin
Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences,
ul. S. Kovalevskoi 22, Moscow, 620990 Russia
e-mail: bazhin@ios.uran.ru
Received July 9, 2012
Abstract—A series of [(2-dimethylamino)ethylamino]methylidene-1,3-dicarbonyl compounds was synthesized
for the first time starting from the corresponding 2-ethoxymethylidene derivatives and N,N-dimethylethylene-
diamine. It was shown that further alkylation of aminomethylidene derivatives with methyl iodide occurs
regioselectively at the tertiary nitrogen atom. Quaternization products obtained exhibit high corrosion inhibition
of mild steel in hydrochloric acid medium.
DOI: 10.1134/S1070363213070050
Reaction of 2-ethoxymethylidene-1,3-dicarbonyl com-
pounds with various amines is a convenient method of
synthesis of 2-aminomethylidene derivatives of 1,3-di-
carbonyl compounds, which are multidentate ligands.
The latter can be used to prepare different complexes
[1–9] and heterocyclic compounds having a wide
spectrum of biological activity [10–12].
The aim of this work is the synthesis of new 2-
aminomethylidene derivatives of 1,3-dicarbonyl com-
pounds by modifying the aminoalkyl substituent and
studying of their practically useful properties in
aqueous media.
The initial 2-ethoxymethylidene-1,3-dicarbonyl com-
pounds Ia–Id were synthesized by reacting 1,3-di-
carbonyl compounds with triethyl orthoformate in the
presence of acetic anhydride according to [13–16]. The
reaction of compounds Ia–Id with N,N-dimethyl-
ethylenediamine proceeds under mild conditions to
give 2-aminomethylidene derivatives of 1,3-dicarbonyl
compounds IIa–IId according to addition-elimination
mechanism. The high reaction rate (5–10 min,
monitored by TLC) is due to the high nucleophilicity
of the starting amine. In the obtained products IIa–IId
the enamine moiety is a push-pull system, which leads
to the existence of an equilibrium of geometric isomers
Earlier aliphatic amines, as well as (het)aryl amines
have been brought introduced into the reaction with 2-
ethoxymethylidene-1,3-dicarbonyl compounds. 2-Amino-
methylidene derivatives of 1,3-dicarbonyl compounds
obtained were insoluble in water, but they were
selectively soluble only in organic media. The syn-
thesis of water-soluble 2-aminomethylidene deriva-
tives of 1,3-dicarbonyl compounds is a probable and
promising task: the synthetic potential of 2-amino-
methylidene derivatives of 1,3-dicarbonyl compounds
makes it possible to create new classes of compounds
with other physicochemical properties expanding the
areas of their practical application.
1
in solution [15]. The H NMR spectra of compounds
IIa–IId contain the proton signals of NH- and -CH-
groups as the doublets (coutling constant ~14 Hz),
which are characteristic of enaminodiketone form. The
presence of the signals of NH-protons in the downfield
region (~δNH 9.3–11.03 ppm) suggests the existence of
compounds IIa–IId as enaminodiketone tautomers,
The modification of 2-aminomethylidene deriva-
tives of 1,3-dicarbonyl compounds can be carried out
both by transformation of functional groups in the
aminoalkyl or (het)aryl substituent, and by func-
tionalization of 1,3-dicarbonyl moiety.
1330

SYNTHESIS AND PROPERTIES OF WATER-SOLUBLE 2-AMINOMETHYLIDENE
1331
where
a
hydrogen atom of amino group is
dissolve in aqueous media. However, the compounds
IIa–IId contain two nitrogen atoms, secondary and
tertiary, which are potential quaternization centers.
intramolecularly associated with one of the carbonyl
groups. The presence in the molecule of the
intramolecular interactions of this kind is confirmed
also by IR spectroscopy data. The absorption band of
the stretching vibrations of NH and C=O groups are
shifted to lower frequencies compared to the free
groups.
Under mild conditions the addition of an excess
methyl iodide to compounds IIa–IId results in the
quaternization products IIIa–IIId as white pre-
cipitates. According to spectral data (IR, 1H NMR), the
regioselective methylation of compounds IIa–IId
occurs at the tertiary nitrogen atom. In this case, NH-
group of the enamine fragment does not react with
methyl iodide because of the participation of the lone
electron pair of this nitrogen atoms in the conjugation
with C=C bond.
We believe that one of the simplest methods of
converting compounds IIa–IId into water-soluble
derivatives is their quaternization at the nitrogen atom
by an alkyl halide. This interaction usually results in
quaternary ammonium salts, which are capable to
+
NMe3
I _
NMe2
NH
R2
OEt
NH
R2
R1
R2
R1
R1
o
b
O
O
Ia_Id
O
O
O
O
IIa_IId, 95_98%
IIIa_IIId, 96_98%
a: H2NCH2CH2NMe2, Et2O, 25°C; b: MeI, 25–30°C. R1 = R2 = Me (a); R1 = R2 = OЕt (b); R1 = OЕt, R2 = Me (c), C3H7 (d).
Note that compounds IIIa–IIId in solutions also
exist as enaminodiketone tautomers and exhibit the
same spectral characteristics as compounds IIa–IId.
positively charged nitrogen atom of ammonium group
and the negatively charged electrode [19]. In the case
of 1,3-dicarbonyl fragment the inhibition mechanism is
more complex: the unpaired electrons of oxygen atoms
can interact with the vacant d-orbitals of the metal;
stable chelates can be formed on the electrode surface
creating significant barriers to corrosion; π-electrons
(if any) can interact with the metal; and the
combination of all these types of interactions is
possible [20–22].
All synthesized compounds IIIa–IIId belong to the
class of quaternary ammonium salts and exhibit high
water solubility and stability in acidic media. They are
characterized by the same structure of the hydrocarbon
moiety adjacent to the ammonium group and various
substituents bonded directly to dicarbonyl moiety.
Both ammonium group and 1,3-dicarbonyl moiety may
potentially exhibit activity against corrosion of metals
in acidic media. The synergy of their action has not yet
been established.
The rate of the uniform corrosion (Kn) of low-
carbon steel and inhibitory activity of the quaternary
ammonium salts IIIa–IIId (c 1×10–3 М) were studied
in 1 M HCl solution at room temperature by the
polarization resistance method. For each value of Kn
(Fig. 1) four parallel measurements were performed;
the standard deviation is no more than 3%.
It is known that most organic compounds
containing ammonium groups, including those com-
mercially available, have a high solubility in water
even if the ammonium nitrogen contains four hydro-
phobic substituents. Furthermore, it was shown that
often quaternary ammonium salts containing iodide
anion as counter ion possess the greatest inhibitory
activity against acid corrosion of low carbon steels [17,
18].
Reducing the concentration of quaternary
ammonium salt IIIa–IIId to 1×10–4 M results in
approximately 2-fold increase in Kn (Fig. 2).
The analysis of the graphic and numeric data on Kn
show that the quaternary ammonium salts IIIa–IIId
exhibit similar characteristics: In relatively low
concentrations they inhibit corrosion processes of
Inhibitory activity of quaternary salts is mainly
based on the electrostatic interaction between the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

1332
BAZHIN et al.
Uniform corrosion rate, μm/year
Uniform corrosion rate, μm/year
Time, min
Fig. 1. Uniform corrosion rate of Steel-3 in 1 М HCl
solution in the presence of 1×10–3 M of ammonium salts
IIIа–IIId. (1) in the absence of ammonium salt; (2) in the
presence of IIIа; (3) in the presence of IIIb; (4) in the
presence of IIIc; (5) in the presence of IIId.
Time, min
Fig. 2. Uniform corrosion rate of Steel-3 in 1 М HCl
solution (1) in the absence of ammonium salt and (2) in the
presence of 1×10–4 M of ammonium salts IIIc.
Steel-3 in hydrochloric acid medium more than 10
times. Protection degree (Z) calculated from the
equation for compound IIIa is 92%, IIIb 91% IIIc
90%, IIId 89%.
In an acidic medium the protonation of both the
dicarbonyl moiety and the nitrogen atom of amino-
methylidene fragment of compounds IIIa–IIId is
possible. Obviously, the double electric layer of the
electrode is formed by orientation of the positively
charged ammonium nitrogen atoms to negatively
charged metal surface due to electrostatic interaction.
The difference in the behavior of compounds IIIa–
IIId occurs due to varying the nature of the
substituents in the 1,3-dicarbonyl moiety. Con-
sequently, for IIIa both the formation of hydroxy
groups from the corresponding keto groups and the
participation of the NH-moiety in the coordination
with the metal electrode surface is presumable. It
should also be noted that the best results in the test
series were observed for the symmetric molecules,
suggesting the possible contribution of intermolecular
interactions leading to a more ordered structure of the
protective layer on the metal. [24]
Kn1 – Kn2
Z = –———– × 100%,
Kn1
where Kn1 and Kn2 are uniform corrosion rates without
inhibitor and with the addition of inhibitor,
respectively.
The quaternary ammonium salts IIIa, IIIb having a
symmetrical structure of 1,3-dicarbonyl fragment show
the greatest inhibitory effect. Anticorrosive properties
of IIId containing heptafluoropropyl substituent are
similar to those of the quaternary ammonium salts
IIIc, although there are examples of a more effective
corrosion inhibition in the presence of fluorine-
containing quaternary ammonium salts, as compared
with non-fluorinated [17, 23].
Unlike ammonium salts of diphilic structure [23],
the explanation of the effect of the structure of
functional derivatives of 1,3-dicarbonyl compounds on
their properties requires further study.
The mechanism of chelation of the metal surface, as
well as a significant effect of 1,3-dicarbonyl fragment
on the polarization properties of the terminal ammo-
nium nitrogen atom are questionable. Noteworthy is
the absence of the alkyl groups having strong hydro-
phobic properties in the structure of the synthesized
compounds.
Thus, we developed an efficient approach to the
synthesis of water-soluble 2-aminomethylidene deri-
vatives of 1,3-dicarbonyl compounds comprising
quaternization of the starting compounds with methyl
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

SYNTHESIS AND PROPERTIES OF WATER-SOLUBLE 2-AMINOMETHYLIDENE
1333
iodide. The reaction proceeds regioselectively at the
terminal tertiary nitrogen atom. A series of quaternary
ammonium salts was obtained in preparative yields.
The developed techniques allow wide variation of
functionalities in both dicarbonyl and aminoalkyl
fragments. The synthesized quaternary ammonium
salts IIIa–IIId show high anticorrosion activity for
steel in hydrochloric acid medium: The corrosion of
the metal is reduced 10-fold.
2.26 s (3Н, Me), 2.28 s (6Н, 2 Me), 2.49 s (3Н, Me),
2.52 t (2Н, CH2, J 6.1), 3.41 q (2Н, CH2, J 6.1), 7.80 d
(1Н, СН, J 13.4), 11.05 br.s (1Н, NН). Found, %: C
60.48; H 9.10; N 13.99. С10Н18N2O2. Calculated, %: С
60.58; H 9.15; N 14.13.
Diethyl 2-[(2-dimethylamino)ethylamino]methyl-
idenemalonate (IIb). Yield 5.04 g (97.5%). IR spec-
trum, ν, cm–1: 3290 br.s (N–H); 2978, 2946, 2902,
2863, 2822 (C–H); 1684, 1660 (C=O); 1609 (C=C);
1
1518 (N–H). Н NMR spectrum (CDCl3), δ, ppm (J,
EXPERIMENTAL
Hz): 1.29 t and 1.34 t (6H, Me, J 7.1), 2.24 sand 2.27 s
(6H, Me), 2.49 t (2H, CH2, J 6.1), 3.41 q (2H, CH2, J
6.1), 4.19 q and 4.24 q (4H, CH2, J 7.1), 8.02 d (1Н,
СН, J 14.4), 9.21 br.s (1Н, NН). Found, %: C 55.76; H
8.52; N 10.79. С12Н22N2O4. Calculated, %: С 55.80; H
8.58; N 10.84.
The IR spectra were recorded on a Perkin-Elmer
Spectrum One B spectrophotometer. The NMR spectra
were obtained on a Bruker DRX-400 instrument (1H,
400 MHz, internal reference Me4Si; 19F, 376 MHz,
internal reference С6F6). Elemental analysis was
carried out on a Perkin Elmer PE 2400 elemental
analyzer of series 2 CHNS-O EA 1108.4. Melting
points were measured in open capillaries on a Stuart
SMP3 instrument. The reaction progress was
monitored by thin-layer chromatography using
Alugram Sil G/UV254 plates.
Ethyl 2-[(2-dimethylamino)ethylamino]methyl-
idene-3-oxobutanoate (IIc). Yield 5.04 g (98.5%). IR
spectrum, ν, cm–1: 3182 br.s (N–H); 2977, 2947, 2904,
2856, 2822 (C–H); 1695, 1638 (C=O); 1581 (C=C). 1Н
NMR spectrum (CDCl3), δ, ppm (J, Hz): E,Z, 2.26 s
and 2.27 s (6H, Me), 2.50 t (2H, CH2, J 6.2), 3.41 q
(2H, CH2, J 6.2); E (12%), 1.35 t (3H, Me, J 7.1), 2.43
s (3H, Me), 4.25 q (2H, CH2, J 7.1), 8.16 d (1Н, СН, J
14.9), 9.27 br.s (1Н, NН); Z (88%), 1.30 t (3H, Me, J
7.1), 2.47 s (3H, Me), 4.19 q (2H, CH2, J 7.1), 8.00 d
(1Н, СН, J 13.8), 11.03 br.s (1Н, NН). Found, %: C
57.90; H 8.78; N 12.21. С11Н20N2O3. Calculated, %: С
57.87; H 8.83; N 12.27.
The rate of uniform corrosion of low-carbon steel
was studied in a 1 M HCl solution using the universal
automatic corrosion gage Expert-004 and a two-
electrode sensor (LLC “Ekoniks–Expert,” Moscow).
The electrode material is Steel-3 (composition, %: Si
0.05–0.15, Mn 0.40–0.65, P ≤ 0.04, Cr ≤ 0.30,
S ≤ 0.05); the area of each electrode is 0.00078 m2.
Ethyl
2-[(2-diethylamino)ethylamino]methyl-
2-Ethoxymethylidene-1,3-dicarbonyl compounds
were prepared by methods [13–16].
idene-4,4,5,5,6,6,6-heptafluoro-3-oxohexanoate (IId).
Yield 5.04 d (98.5%). IR spectrum, ν, cm–1: 3245 br.s
(N–H); 2981, 2907 (C–H); 1700, 1650 (C=O); 1630
(C=C), 1230–1119 (C–F). 1Н NMR spectrum (CDCl3),
δ, ppm (J, Hz): E,Z, 2.27 br.s (6H, 2Me), 2.53 m (2H,
CH2), 3.48 m (2H, CH2); E (63%), 1.29 t (3H, Me, J
7.2), 4.23 q (2H, CH2, J 7.2), 8.09 d (1Н, СН, J 14.7),
10.52 br.s (1Н, NН); Z (37%), 1.31 t (3H, Me, J 7.2),
4.26 q (2H, CH2, J 7.2), 7.96 d (1Н, СН, J 14.7), 9.65
br.s (1Н, NН). 19F NMR spectrum (CDCl3), δF, ppm
(J, Гц): E (63%), 38.35 m (2F, β-CF2), 48.67 m (2F, α-
CF2), 81.52 t (3F, γ-CF3, J 9.8); Z (37%), 37.66 m (2F,
β-CF2), 49.33 m (2F, α-CF2), 81.69 t (3F, γ-CF3, J 9.8).
Found, %: C 40.77; H 4.45; N 7.29; F 34.70.
С13Н17F7N2O3. Calculated, %: С 40.84; H 4.48; N
7.33; F 34.79.
Synthesis of compounds IIa-IId. To a solution of
2-ethoxymethylidene-1,3-dicarbonyl compound Ia–Id
(0.02 mol) in 30 ml of diethyl ether at room
temperature was added dropwise N,N-dimethylethyl-
enediamine (0.024 mol). The reaction mixture was
stirred for 10 min and then washed with water. The
organic layer was separated and dried over CaCl2.
Thereafter, the solvent was evaporated and the
precipitate formed was recrystallized from hexane.
Compound IIa was obtained as pale yellow crystals.
The products IIb–IId were obtained as yellow oily
substances after the solvent removal.
3-[(2-Dimethylamino)ethylamino]methylidenepen-
tane-2,4-dione (IIа). Yield 3.80 g (96%), mp 57–58°С.
IR spectrum, ν, cm–1: 3180 br.s (N–H); 2966, 2943,
2861, 2822 (C–H); 1615 (C=O); 1586 (C=C); 1567
Synthesis of ammonium salts IIIа–IIId. To amine
IIa–IId (0.01 mol) was added MeI (0.03 mol). The
mixture was stirred for 15 min. Then an excess of MeI
1
(N–H). Н NMR spectrum (CDCl3), δ, ppm (J, Hz):
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

1334
BAZHIN et al.
was removed. The products IIIа–IIId were obtained as
spectrum (DMSO-d6), δF, ppm (J, Hz): E (65%), 38.61
br.s (2F, β-CF2), 49.83 m (2F, α-CF2), 83.13 t (3F, γ-
CF3, J 9.5); Z (35%), 39.31 br.s (2F, β-CF2), 50.20 m
(2F, α-CF2), 83.15 t (3F, γ-CF3, J 9.5). Found, %: C
32.07; H 3.79; N 5.29; F 25.44. С14Н20N2F7O3I.
Calculated, %: С 32.08; H 3.85; N 5.34; F 25.37.
white powders.
2-[(2-Acetyl-3-oxobuten-1-yl)amino]-N,N,N-tri-
methylethaneammonium iodide (IIIa). Yield 3.37 g
(99%), mp 202–203°С. IR spectrum, ν, cm–1: 3178 br.s
(N–H); 2996, 2982, 2901 (C–H); 1621 br.s (C=O);
1586 (C=C); 1570 (N+–CH3). 1Н NMR spectrum
(DMSO-d6), δ, ppm (J, Hz): 2.22 s and 2.31 s (6H,
Me), 3.11 s (9H, 3 Me), 3.57 t (2Н, CH2, J 6.5), 3.86 q
(2Н, CH2, J 6.5), 8.12 d (1Н, СН, J 13.4), 10.65 m
(1Н, NН). Found, %: C 38.77; H 6.18; N 8.27.
С11Н21N2O2I. Calculated, %: С 38.84; H 6.22; N 8.23.
ACKNOWLEDGMENTS
This work was financially supported by the Ural
Branch of the Russian Academy of Sciences (project
no. 12-M-123-2045) and the Russian Foundation for
Basic Research (project no. 10-03-96017, 12-03-
31135).
2-[{2,2-(Diethoxycarbonyl)propen-1-yl}amino]-
N,N,N-trimethylethaneammonium iodide (IIIb).
Yield 3.92 g (98%), mp 192–193°С. IR spectrum, ν,
cm–1: 3191 br.s (N–H); 3000, 2901 (C–H); 1709, 1698
REFERENCES
1. Gottschaldt, M., Wegner, R., Gorls, H., Klufers, P.,
Jager, E.-G., and Klemm, D., Carbohydrate Res., 2004,
vol. 339, p. 1941.
2. Wegner, R., Gottschaldt, M., Gorls, H., Klufers, P.,
Jager, E.-G., and Klemm, D., Chem. Eur. J., 2001, vol. 7,
p. 2143.
1
(C=O); 1652, 1620 (C=C); 1598 (N+–CH3). Н NMR
spectrum (DMSO-d6), δ, ppm (J, Hz): 1.20 t and 1.21 t
(6H, Me, J 7.1), 3.10 s (9H, 3 Me), 3.52 t (2H, CH2, J
6.6), 3.83 q (2H, CH2, J 6.6), 4.06 q and 4.12 q (2H,
CH2, J 7.1), 8.07 d (1Н, СН, J 14.4), 9.14 m (1Н, NН).
Found, %: C 39.06; H 6.25; N 6.97. С13Н25N2O4I.
Calculated, %: С 39.01; H 6.30; N 7.00.
3. Uzu, T. and Sasaki, S., Org. Lett., 2007, vol. 9, p. 4383.
4. Zhang, X., Zhou, H., Ding, C., and Zhang, S., Chem.
Commun., 2009, p. 5624.
2-[2-(Ethoxycarbonyl)-3-oxobuten-1-yl)amino]-
N,N,N-trimethylethaneammonium iodide (IIIc).
Yield 3.67 g (99%), mp 149–150°С. IR spectrum, ν,
cm–1: 3159, 3126 (N–H); 3002, 2984, 2936 (C–H);
5. Kudyakova, Yu.S., Goryaeva, M.V., Burgart, Ya.V.,
Saloutin, V.I., and Slepukhin, P.A., Russ. Chem. Bull.,
2009, p. 1241.
6. Kudyakova, Yu.S., Goryaeva, M.V., Burgart, Ya.V.,
Slepukhin, P.A., and Saloutin, V.I., Russ. Chem. Bull.,
2010, p. 1582.
1
1687 (C=O); 1633 (C=C); 1574 (N+–CH3). Н NMR
spectrum (DMSO-d6), δ, ppm (J, Hz): E,Z, 3.12 s
(9H, 3Me), 3.55 t (2H, CH2, J 6.6), 3.87 q (2H, CH2, J
6.6); E (13%), 1.27 t (3H, Me, J 7.1), 2.29 s (3H, Me),
4.19 q (2H, CH2, J 7.1), 8.15 d (1Н, СН, J 14.6), 9.18
m (1Н, NН); Z (87%), 1.24 t (3H, Me, J 7.1), 2.33 s
(3H, Me), 4.12 q (2H, CH2, J 7.1), 8.12 d (1Н, СН, J
13.8), 10.72 m (1Н, NН). Found, %: C 38.90; H 6.18;
N 7.61. С12Н23N2O3I. Calculated, %: С 38.93; H 6.26;
N 7.57.
7. Kudyakova, Yu.S., Goryaeva, M.V., Burgart, Ya.V.,
and Saloutin, V.I., Russ. Chem. Bull., 2010, p. 1753.
8. Kudyakova, Yu.S., Goryaeva, M.V., Burgart, Ya.V.,
and Saloutin, V.I., Russ. J. Org. Chem., 2011, vol. 47,
no. 3, p. 331.
9. Kudyakova, Yu.S., Burgart, Ya.V., and Saloutin, V.I.,
Chem. Heterocycl. Compd., 2011, vol. 47, p. 558.
10. Altenbach, R.J., Liu, H., Banfor, P.N., Browman, K.E.,
Fox, G.B., Fryer, R.M., Komater, V.A., Krueger, K.M.,
Marsh, K., Miller, T.R., Pan, J.B., Pan, L., Sun, M.,
Thiffault, C., Wetter, J., Zhao, C., Zhou, D.,
Esbenshade, T.A., Hancock, A.A., and Cowart, M.D.,
J. Med. Chem., 2007, vol. 50, p. 5439.
2-[2-(Ethoxycarbonyl)-4,4,5,5,6,6,6-heptafluoro-
3-oxohexen-1-yl)amino]-N,N,N-trimethylethane-
ammonium iodide (IIId). Yield 5.24 g (100 %), mp
209–210°С. IR spectrum, ν, cm–1: 3165, 3140 (N–H);
3010, 2979, 2945 (C–H); 1737, 1680 (C=O); 1630
11. Pochat, F., Tetrahedron, 1986, vol. 42, p. 3537.
1
(C=C); 1582 (N+–CH3); 1269–1118 (C–F). Н NMR
12. Nosova, E.V., Lipunova, G.N., Charushin, V.N., and
Chupakhin, O.N., J. Fluor. Chem., 2010, vol. 131,
p. 1267.
13. Palanki, M.S.S., Erdman, P.E., Gayo-Fung, L.M., Shev-
lin, G.I., Sullivan, R.W., Suto, M.J., Goldman, M.E.,
Ransone, L.J., Bennett, B.L., and Manning, A.M.,
J. Med. Chem., 2000, vol. 43, p. 3995.
spectrum (DMSO-d6), δ, ppm (J, Hz): E,Z, 3.11 br.s
(9H, 3Me), 3.57 m (2H, CH2), 3.95 m (2H, CH2); E
(65%), 1.22 t (3H, Me, J 7.2), 4.15 q (2H, CH2, J 7.2),
8.30 d (1Н, СН, J 14.7), 10.49 m (1Н, NН); Z (35%),
1.21 t (3H, Me, J 7.2), 4.19 q (2H, CH2, J 7.2), 8.18 d
(1Н, СН, J 14.7), 9.59 m (1Н, NН). 19F NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013

SYNTHESIS AND PROPERTIES OF WATER-SOLUBLE 2-AMINOMETHYLIDENE
14. Sanfilippo, P.J., Urbanski, M.J., Beers, K.N., Eckardt, A.,
1335
Appl. Surf. Sci., 2005, vol. 252, p. 1634.
Falotico, R.,Ginsberg, M.H., Offord, S., Press, J.B.,
Tighe, J., Tomko, K., and Andrade-Gordon, P., J. Med.
Chem., 1995, vol. 38, p. 34.
19. Mairanovskii, S.G., Dvoinoi sloi i yego effekty v
polyarografii (Double Layer and Its Effects in
Polarography), Moscow: Nauka, 1971.
15. Pryadeina, M.V., Burgart, Ya.V., Saloutin, V.I.,
Slepukhin, P.A., Kazheva, O.N., Shilov, G.V., D’ya-
chenko, O.A., and Chupakhin, Russ. J. Org. Chem.,
2007, vol. 43, no. 7, p. 945.
20. Lebrini, M., Traisnel, M., Lagrenŭe, M., Mernari, B.,
and Bentiss, F., Corros. Sci., 2008, vol. 50, p. 473.
21. Singh, A.K. and Quraishi, M.A., Corros. Sci., 2010,
vol. 52, p. 1373.
16. Wang, J.-H., Shen, Y.-Q., Yu, C.-X., and Si, J.-H.,
22. Flores, E.A., Olivares, O., Likhanova, N.V., Domin-
guez-Aguilar, M.A., Nava, N., Guzman-Lucero, D., and
Corrales, M., Corros. Sci., 2011, vol. 53, p. 3899.
23. Gorbunova, T.I., Bazhin, D.N., Zapevalov, A.Ya., and
Saloutin, V.I., Russ. J. Appl. Chem., 2011, vol. 84,
no. 6, p. 972.
24. Herrag, L., Hammouti, B., Elkadiri, S., Aouniti, A.,
Jama, C., Vezin, H., and Bentiss, F., Corros. Sci., 2010,
vol. 52, p. 3042.
J. Chem. Soc., Perkin Trans. 1, 2000, p. 1455.
17. Zotikov, V.S., Ryabinin, N.A., Gankin, E.A., Novo-
zhilov, E.N., Kasaeva, D.Ya., and Shal’man, B.Ya.,
Book of Abstracts, IV Vsesoyuznaya konferentsiya po
khimii ftororganicheskikh soedinenii (Union Conference
on the Chemistry of Organofluorine Compounds),
Tashkent, 1982, p. 5.
18. Niu, L., Zhang, H., Wei, F., Wu, S., Cao, X., and Liu, P.,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013