Tris(2-hydroxyethyl)ammonium salts: 2,8,9-Trihydroprotatranes

Article abstract of DOI:10.1134/S1070363209110097

New method of synthesis of tris(2-hydroxyethyl)ammonium salts, 2,8,9-trihydroprotatranes X-[HN(CH₂CH₂OH) ₃]⁺, based on the reaction of tris(2-hydroxyethyl)amine (triethanolamine) with ammonium salts NH₄X (X = F, Cl, Br, I, NO ₃, ClO₄) was developed. ¹H, ¹³C, ¹⁵N NMR and IR spectra of these protatranes were investigated, as well as those of their analogs with X = RCH₂COO (R = H; 2-MeC ₆H₄O; 2-Me-4ClC₆H₃O; 2-MeC ₆H₄S; 4-ClC₆H₄S; 4-ClC ₆H₄SO₂; 3-IndS; 3-(PhCH₂-IndS) prepared from the corresponding acids RCH₂COOH and triethanolamine. The parameters of IR and NMR spectra of the studied protatranes were governed by the nature of substituent X, which also determined the character of the intra and intermolecular hydrogen bonds NH...O and OH...O in the protatrane framework.

Full text of DOI:10.1134/S1070363209110097

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 11, pp. 2339–2346. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © M.G. Voronkov, A.I. Albanov, T.N. Aksamentova, S.N. Adamovich, N.N. Chipanina, R.G. Mirskov, T.A. Kochina, D.V. Vrazhnov,
M.Yu. Litvinov, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 11, pp. 1817–1824.
Tris(2-hydroxyethyl)ammonium Salts: 2,8,9-Trihydroprotatranes
a,b
b
b
b
M. G. Voronkov , A. I. Albanov , T. N. Aksamentova , S. N. Adamovich ,
b
b
a
a
a
N. N. Chipanina , R. G. Mirskov , T. A. Kochina , D. V. Vrazhnov , and M. Yu. Litvinov
a
Grebenshchikov Institute of Chemistry of Silicates of the Russian Academy of Sciences,
nab. Makarova 2, St. Petersburg, 199034 Russia
e-mail: voronkov@isc.nw.ru
b
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: mir@irioch.irk.ru
Received March 31, 2009
Abstract—New method of synthesis of tris(2-hydroxyethyl)ammonium salts, 2,8,9-trihydroprotatranes
–
+
X [HN(CH
salts NH X (X = F, Cl, Br, I, NO
were investigated, as well as those of their analogs with X = RCH
ClC O; 2-MeC S; 4-ClC S; 4-ClC SO ; 3-IndS; 3-(PhCH -IndS) prepared from the corresponding
acids RCH COOH and triethanolamine. The parameters of IR and NMR spectra of the studied protatranes were
2 2 3
CH OH) ] , based on the reaction of tris(2-hydroxyethyl)amine (triethanolamine) with ammonium
1
13
15
4
3
, ClO
4
) was developed. Н, С, N NMR and IR spectra of these protatranes
COO (R = H; 2-MeC O; 2-Me-
2
6 4
H
4
6
H
3
6
H
4
6
H
4
6
H
4
2
2
2
governed by the nature of substituent X, which also determined the character of the intra and intermolecular
hydrogen bonds NH···O and OH···O in the protatrane framework.
DOI: 10.1134/S1070363209110097
We developed a novel original method of synthesis
of tris(2-hydroxyethyl)ammonium salts of general
bonds. Following Verkade [15], we called them prota-
tranes (PA), more correctly, 2,8,9-trihydroprotatranes,
of the formula:
–
+
formula X [NH(CH CH OH) ] , where Х = F (I) Cl
2
2
3
(
II), Br (III), I (IV), NO (V), ClO (VI) based on the
3 4
H
reaction of triethanolamine (TEA) with the
corresponding ammonium salts NH X both in aqueous
or nonaqueous medium as well as in the absence of a
solvent:
H
O
O
H1
H
−
4
X
O
+
N
NH
NH
4
X + N(CH
2
CH
2
OH)
3
А
–
+
→
3
+ X [NH(CH
2
CH
2
3
OH) ] .
The earlier known method of synthesis of PA (for
example, compound VI) [10] was the reaction of TEA
with the corresponding acid. Using this method, we
have earlier first synthesized PA, which are tri-
ethanolammonium salts of carboxylic acids of general
Reaction of TEA with NH F [1] proceeded in an
4
unusual way: the product was a very viscous liquid
corresponding to the composition TEA·3HF. This is
not surprising since similar hydrofluorides are formed
in the reaction of tertiary amines (Me N, Et N,
-
+
3
3
formula RCH COO [NH(CH CH OH) ] , where R = H
2
2
2
3
pyridine) with HF. They have low (below 0°С) melting
(VII); 2-MeC H O (VIII); 2-Me-4ClC H O (IX); 2-
6 4 6 3
point and correspond to the composition R N·nHF (n =
MeC H S (X); 4-ClC H S (XI); 4-ClC H SO (XII); 3-
6 4 6 4 6 4 2
3
3
–6). The molecules of HF in these hydrofluorides are
IndS (XIII); 3-(PhCH -IndS) (XIV) [16–20].
2
linked by hydrogen bonds [2].
Compounds of this type are not only of theoretical
but also of practical interest since they have unique
biological activity substantially exceeding or different
from the action of the starting biologically active acids.
From the XRD analysis [3–14], the triethanol-
ammonium salts have tricyclic atrane structure A
closed by three intramolecular trifurcate hydrogen
2339

2
340
VORONKOV et al.
Such compounds include, first of all, triethanol-
ammonium salts of 2-methylphenoxyacetic acid VIII ,
trecrezan” preparation, which have already found
wide application in medicine [3, 16–33], and also 2-
methyl-4-chlorophenoxyacetic acid (IX), “chloro-
crezacin” [17, 31], etc. Under the name “crezacin,”
trecrezan is successfully used in agriculture (in plant-
growing, cattle-breeding, breeding of useful insects)
DMSO-d are broadened, and their fine structure
6
cannot be observed. Only at a low concentration of the
solutions (when the intensity of the signals are
comparable with those of the residual protons of
“
DMSO-d ) the signals appear as multiplets: triplet of
6
3
3
NCH ( JHH 4.7 Hz), doublet of triplets of ОСН ( J
2 2
5.0, 4.7 Hz), triplet of ОН. In all Н NMR spectra
1
separate signals are observed which belong to the
[
34–38]. It was also shown to be a stimulator of
traces of water in DMSO-d at 3.48–3.63 ppm, OH
6
microbiological synthesis [37].
groups at 4.4–5.3 ppm, and NH groups at 8.5–8.7 ppm.
The data of Table 1 suggest that the chemical shifts of
protons of the NCH and OCH groups are shifted
Crystal structure of PA was first established by the
XRD method during our studies of their biological
activity [3, 4]. Later on, the crystal structure of PA
with X = SH [5], Cl [5], Br [6–8], NO [9], ClO [10],
2
2
downfield relative to the initial TEA by 0.76 and
1
3
0
.34 ppm, respectively. С NMR chemical shifts of
3
4
the protatrane cation in the spectra of the studied PA
HSeO [11], BPh [12], 2-(2,3-Me C H )NHC H COO
3
4
2
6
3
6
4
are displaced upfield relative to TEA by 2 ppm for the
[
13], 2-HCOC H COO [14] was examined. Their
6 4
13
NCH and by 4 ppm for the OCH group. The
С
2
2
crystals are formed by layers of cations and anions
linked by hydrogen bonds. Inside each layer, the cation
and anion are linked by hydrogen bridges O–H···X . In
NMR chemical shifts of these groups in the spectra of
PA II–VI are very close.
–
PA containing the anion of functionally substituted
carboxylic acid, the bonding with the anion can be
accomplished by means of the functional group.
Protonation of nitrogen atom in tertiary amines is
known to be followed by a downfield shift of the N
resonance (4–16 ppm) [39]. The chemical shifts in the
N NMR spectra of PA II–VI are shifted downfield
relative to TEA by 20 ppm, which is indicative of the
positive charge on the nitrogen atom.
15
1
5
+
The protatrane cation [HN(CH CH OH) ] has
2
2
3
tricyclic structure with the N→H directed inward the
protatrane framework. The length of this bond depends
on the nature of the anion and varies from 0.88 Å (X =
Cl) [5] to 1.01 Å (X = 4-ClC H SCH COO) [4]. For
1
13
15
In the Н, С, N NMR spectra of PA VII–XIV ,
which are the derivatives of carboxylic acids (Table 2),
6
4
2
comparison, the N–H bond length in organic
chemical shifts of the NCH
no regular dependence on the nature of substituent
RCH . The internal chemical shift (the difference
2 2
and ОСН groups show
ammonium salts R NHX lies within 0.87–0.89Å [2].
3
Three oxygen atoms in the cations of PA form the
surrounding of the hydrogen atom of NH group
resulting in trifurcate hydrogen bond.
2
between the chemical shifts of these groups) is 0.5–
0.6 ppm. The signals of the carbon atoms of the
protatrane cation are shifted upfield by 2.2–2.4 ppm on
The effect of the anion’s nature on the protatrane
cation is first studied by us using the methods of NMR
and IR spectroscopy.
15
going from acetate VII to PA (IX). The N NMR
chemical shift in the spectra of PA VII–XIV is
displaced downfield relative to free TEA, on the
average, by 14 ppm (–354.5 ppm). Moreover, variation
of this chemical shift in the spectra of PA VII–XIV
The resonance signals of the NCH and OCH
groups in the Н NMR spectra of solutions of all PA in
2
2
1
1
13
15
+
–
2 2 3
Table 1. Parameters of Н, С, N NMR spectra of PA [HN(CH CH OH) ] X (II–VI) and triethanolamine (TEA) in
DMSO-d
6
δ
Н
, ppm
С
δ , ppm
Comp.
no.
а
рK of
–
Х
N
δ , ppm
НХ [21]
NCH
2
OCH
2
ОН
NH
NCH
2
OCH
2
II
III
IV
Cl
–
3.29
3.27
3.28
3.29
3.27
2.52
3.75
3.70
3.72
3.74
3.73
3.39
5.35
5.13
5.18
5.30
5.24
4.44
9.31
7.27
8.7
8.7
8.5
–
55.46
55.30
55.24
55.38
55.51
57.42
55.49
55.38
55.24
55.43
55.47
59.54
–330.07
–330.71
–331.57
–331.54
–332.17
–354.50
Br
I
–9
–11
–1.64
–8
V
NO
3
VI
ClO
–
4
TEA
–
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 11 2009

TRIS(2-HYDROXYETHYL)AMMONIUM SALTS
2341
1
13
15
о
Table 2. Н, С, N NMR spectra of PA VII–XIV (20% solutions in D
2
O, 25 С)
a
Н
δ , ppm
δ
С
, ppm
Comp.
no.
N
δ , ppm
СН
2
N
CH
2
O
CH
2
CO
Ar; CH
2
Ph
Me
Me
СН
2
N
CH
2
O
CH
2
CO
CO
b
VII
3.25
3.42
3.85
3.92
–
–
1.94
2.26
23.21
15.51
57.01
54.89
57.46
55.14
–
179
–341.4
–339.0
6
VIII
4.48
6.80(H )
66.94
177.00
4
6
7
7
.95(H )
5
.21(H )
3
.25(H )
6
IX
3.44
3.93
4.45
6.70(H )
2.21
15.33
54.77
55.03
66.98
176.51
–338.6
5
7
7
.11(H )
3
.18(H )
4
X
3.41
3.46
3.48
3.36
3.9
3.63
3.64
4.19
3.38
7.16(H )
2.34
19.23
54.91
54.93
54.94
54.86
55.16
55.19
55.21
55.11
37.13
38.15
62.90
41.43
176.88
176.71
167.63
178.16
–340.5
–338.9
–338.9
–339.1
3
2
,5,6
7
.24(H
)
,6
XI
3.94
3.95
3.88
7.30(H )
–
–
–
–
–
–
3
,5
7
.35(H )
2
,6
XII
XIII
7.66(H )
3
,5
7
.89(H )
6
,7
7.22–7.30 (H )
5
7
7
7
.52(H )
2
.51(H )
8
.79(H )
XIV
3.19
3.78
3.41
4.66(CH
2
,7
)
–
–
55.08
55.08
41.96
177.20
–340.1
6
6
6
6
6
7
7
.66(H )
5
,o
,74(H )
m
.78(H )
p
.89(H )
2
.20(H )
8
.64(H )
a
6
3
4
1
2
5
6
Chemical sifts of aromatic carbons: VIII: 111.39(С ); 130.90(С ); 121.05(С ); 156.02(С ); 126.78(С ); 127(С ). IX: 112.31 (С ); 124.64
5
2
4
3
1
4
5
6
3
2
1
(
1
С ); 126.09(С ); 128.66(С ); 130.08(С ); 154.61(С ). X: 125.72(С ); 126.31(С ); 126.76(С ); 130.05(С ); 135.26(С ); 136.63(С ). XI:
3
,5
2,6
1
4
3,5
2,6
1
4
3
28.97(С ); 129.33(С ); 131.25(С ); 134.68(С ). XII: 129.54(С ); 129.59(С ); 136.15(С ); 140.58(С ). XIII: 102.88(С ); 112.21
8 6 5 7 4 2 9 3 8 6 5
(
1
С ); 118.59(С ); 120.17(С ); 122.40(С ); 128.30(С ); 130.67(С ); 136.15(С ). XIV: 103.46(С ); 110.36(С ); 119.18(С ); 120.17(С );
7
о
4
m
р
2
9
i
b
3
22.17(С ); 126.61(С ); 127.28(С ); 128.40(С ); 129.41(С ); 133.44(С ); 136.13(С ); 137.09(С ). In CD OD.
allows to rank them in the following sequence, which
Apparently, for strong acids this dependence is
leveled out due to the presence of H-bonds between
their anions and the protatrane cation.
corresponds to the strength of acids RCH COOH
2
(
Table 2): VII < X < XIV < XIII < VIII < XI =
XII < IX.
In the IR spectroscopic study of crystalline PA II–
VI in comparison with TEA we have investigated their
spectra of absorption and FTIR (see the figure) in
order to exclude the effect of pressing of compounds in
KBr pellets. In the absorption IR spectra (KBr pellets)
15
The N NMR chemical shift of PA II–VI , which
are derivatives of inorganic acids, is more displaced
downfield than that of their organic analogs VII–XIV.
This is due to stronger protonating ability of inorganic
acids HX, precursors of PA II–VI . Unlike the
+
of these PA a wide ammonium band ν(N H) is
observed for PA VII–XIV dependence of δ on the
strength of the carboxylic acid, the N NMR chemical
shift of PA derived from inorganic acids (330–
observed with a number of separate maxima in the
range of 2500–3000 cm . In the FTIR spectra of PA
II–VI the intensity of this band is substantially lower
N
1
5
–1
3
32 ppm) is practically independent on the strength of
relative to the absorption spectra. In the spectrum of
liquid TEA the strong band at 3311 cm of half-width
–
1
acid HX [40] (Table 1).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 11 2009

2
342
VORONKOV et al.
–
1
∆
ν1/2 ~400 cm corresponds to the stretching vibra-
the molecules of these salts. The decrease in the
frequency in its maximum in the spectra of protatranes
from 3380 (IV) to 3346 (III) and further to 3306 cm
tions of the OH groups involved in intramolecular
hydrogen bonds. In the spectra of chloro- (II), bromo-
–1
(
III) and iodoprotatranes (IV) the strong ν(ОH) band
(I) is due to an increase in the strength of the formed
O–H X bonds with the electronegativity of the
halogen atom (I < Br < Cl). In the spectrum of PA V
–
1
…
is much narrower than in TEA itself (∆ν1/2 ~25 cm ).
This band is due to vibrations of the three hydroxy
groups of the cation whose oxygen atoms form
intramolecular hydrogen bonds with the endocyclic
(X = NO ), three ν(ОH) bands are present (3440, 3400,
3
–
1
and 3255 cm ) corresponding to its structure with
different in strength hydrogen bonds between the OH
+
hydrogen atom of the N H group whereas their
hydrogen atoms form hydrogen bonds with anions X.
The form of this band is defined by high symmetry of
groups and the oxygen atoms of the NO anion. Three
bands at 3480, 3350 and 3276 cm in the spectrum of
3
–
1
PA VI are also due to vibrations of the OH groups
(
a)
involved in the formation of hydrogen bonds with
–
ClO anion.
4
The bands of TEA observed in the range of 1500–
–
1
7
00 cm of the IR spectrum are due to the stretching
vibrations of the C–C, C–O, and C–N bonds and the
bending vibrations of the C–H and O–H bonds [41]. IR
spectra of isostructural PA II–IV in this range are
–1
similar and differ only in the range 1100–900 cm by
the ratio of intensities of separate bands having the
same frequencies in their maxima. They differ from
the spectrum of TEA mainly by the presence of an
(
b)
–
1
intense band at 1402 cm caused by mixed bending
+
vibrations of the CH, OH and N H groups in the
molecules. In the spectra of these salts the bands of
bending vibrations of the methylene groups are shifted
–
1
to high-frequencies up to 1490–1400 cm relative to
–
1
TEA (1450–1360 cm ). The band of stretching
vibrations of the C–N bonds which in the spectrum of
(
c)
–
1
TEA appears at 1152 cm is shifted in the spectra of
–
1
PA II–IV to 1090 cm , and the band of C–C
–
1
stretching vibrations at 1067 cm is split in two
components. The most intensive band ν(С–О) in the
–
1
spectrum of TEA at 1030 cm is also split in two
–1
components with maxima at ~1030 and ~1000 cm .
The spectra of PA V and VI contain strong bands at
–
1
(
d)
1390 and 1060 cm , respectively, corresponding to
–
–
vibrations of anions NO and ClO [41]. Changes of
3
4
the bands in these spectra as compared with TEA are
identical to those observed in the spectra of PA II–IV .
This is indicative of similarity of their structure in spite
of different strength of hydrogen bonds.
In the FTIR spectra of protatranes VII–XIV
containing organic anions, as well as in those of PA
+
II–VI , the vibration band ν(N H) is weaker than in the
–1
3
600 3200 2800 2400 2000 1600 1200 800 ν, cm
absorption spectra (see the figure). The interaction
between the cations and anions in these molecules
affects the frequencies of the symmetrical and
+
–
FTIR spectra: (а) TEA, (b) TEАH Cl (II) (absorption
+
–
+
spectrum in KBr), (c) TEАH Cl (II), and (d) TEАН О·
О)ССН ОС СН (VII).
–
asymmetrical vibrations ν(СОО) , as well as ν(ОН)
(
2
6
Н
4
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 11 2009

TRIS(2-HYDROXYETHYL)AMMONIUM SALTS
2343
vibrations (Table 3). This was demonstrated earlier on
spectrum the bands of stretching vibrations of the
the example of PA VIII and О-hydrometalloatranes
carboxylate ion of molecule VII appear at 1590 and
–
1
–1
[
42], for which the difference between the correspond-
1404 cm , and the value of ∆ν 186 cm corresponds
to structure B, where each cation, judged from the
XRD data [3], is connected with two oppositely
ing frequencies of the negatively charged carboxylic
group ∆ν = ν(C=O) – ν(C–O) was used to study
structural features of the molecules and their com-
plexes [43]. Thus, in the spectrum of 2-methylphen-
oxyacetic acid the doublet band of the С=О group
…
charged carboxylate groups by hydrogen bond ОН О.
–
1
1
stretching vibrations with maxima at 1737, 1702 cm
O
H O'
–
and a wide band ν(ОН) in the range 3000–2500 cm
O
O
C
H
C
are due to participation of the corresponding groups in
O
H
O
…
O
the hydrogen bonds ОН О=С forming its chain and
H1
H
cyclic self-associates. The distances between the
–
O
carbon and oxygen atoms of the acetate group СОО
N
of this acid in the molecule of PA VIII are very similar
(
1.265 and 1.238 Å). This suggests uniform charge
distribution between the oxygen atoms [3]. In the IR
B
Table 3. Stretching vibration frequencies of the carboxylic and hydroxy groups in the FTIR spectra of PA VII–XIV
+
–
[
HN(CH
2
2
CH OH)
3
] X and values of ∆ν = ν(C=O) – ν(C–O)
–
–
–1
–1
–1
Comp. no.
VII
X
ν(COO ), cm
∆ν, cm
ν(ОН), cm
MeCOO
1574
1590
1400
1404
174
3133
−
VIII
COO
186
3182
O
−
IX
X
COO
1606
1589
1588
1397
1368
1362
209
221
226
3156
3177
3150
Cl
O
−
COO
S
−
XI
COO
Cl
Cl
S
−
XII
1620
1588
1380
1367
240
221
3190
3181
COO
SO2
XIII
SCH COO
2
N
H
XIV
1589
1364
225
3173
SCH COO
2
N
CH Ph
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 11 2009

2
344
VORONKOV et al.
+
–
Table 4. Elemental analysis of PA I–VI [HN(CH
2
2
CH OH)
3
] X
Elemental analysis, %
–
Comp. no.
X
F
mp, °С
found
calculated
I
C 32.55; H 7.61; F 26.58; N 7.01
(for adduct TEА·3HF)
–
C 34.45; H 8.60; F 27.22; N 6.76
C 38.82; H 8.69; Cl 19.10; N 7.54
C 31.32; H 7.01; Br 34.73; N 6.09
C 26.01; H 5.82; I 45.80; N 5.05
C 33.96; H 7.60; N 13.20
II
Cl
Br
I
C 35.92; H 8.01; Cl 19.20; N 7.46
C 31.38; H 6.73; Br 36.20; N 6.42
C 25.94; H 5.83; I 47.42; N 5.02
C 31.65; H 7.27; N 12.13
160
III
IV
V
180
125
NO
3
75
VI
ClO
4
C 26.33; H 6.21; Cl 15.11; N 5.46
C 28.87; H, 6.46; Cl 14.20; N 5.61
250 (decomp)
Similar structure, apparently, has PA VII with Х =
EXPERIMENTAL
СН СОО, for which the value of ∆ν(COO) in the IR
spectrum is 174 cm .
3
–
1
1
13
15
Н, С, N NMR spectra of solutions of PA II–
XIV in DMSO-d were registered on a Bruker DPX
6
In the spectra of PA IX–XIV the values of ∆ν
COO) (209–240 cm ) are higher than in PA VII,
4
00 spectrometer (400.13, 100.61 and 40.56 MHz,
–
1
(
respectively). IR absorption spectra (KBr pellets) and
FTIR spectra were taken on a Varian 3100 FT–IR
spectrophotometer.
VIII, being characteristic of the same structure C,
established for PA XI by the XRD method [4]. The
oxygen atoms of the carboxylic group in these PA
form nonequivalent Н-bonds: one with two OH groups
of the cation, and another, with that OH group, whose
PA II was prepared by the reaction of TEA with
saturated boiling aqueous solution of NH Cl (molar
4
…
hydrogen atom is also involved in the OH Cl bonding
ratio of the reagents 1:1) until the evolution of
ammonia ceased. After evaporation of water, the
crystals of PA II were kept for one more day over
P O in a vacuum. The yield of PA II was quantitative.
with the second molecule of the anion.
2
5
C
Note that with butanol as a solvent as well as under
solvent-free conditions (finely dispersed powder of
O
O
H
O
NH Cl was heated with TEA on a water bath) the yield
4
H
H
H1
−
of PA II also exceeded 95%.
COO
CH2
S
Cl
O
PA I [1], III–V were synthesized similarly by the
reaction of TEA with the corresponding ammonium
salt. The elemental composition and the properties of
PA I–VI are given in Table 4.
O
N
C
Compounds VII–XIV were synthesized by the
reaction of TEA with acetic acid, 2-methylphenoxy-,
-methyl-4-chlorophenoxy-, 2-methylphenylsulfanyl-,
-chlorophenylsulfanyl-, 4-chlorophenylsulfanyl-, indol-
-ylsulfanyl-, and 1-benzylindol-3-ylsulfanylacetic acids
A wide vibration band ν(ОН) in the IR spectra of
PA VII–XIV is located at lower frequencies (3130–
2
4
3
–1
3
190 cm ) than that of PA II–VI containing an
–
inorganic anion X . This is indicative of a larger strength
of hydrogen bonds of the hydroxy groups with the car-
boxylate anion. The largest strength of this bond in PA
[
16–20].
–1
VII corresponds to the lowest frequency of 3133 cm .
ACKNOWLEDGMENTS
The work was performed with a financial support
The shifts of vibration bands of TEA in the range
–1
1
500–700 cm in the spectra of PA VII–XIV are
similar to those observed in the spectra of PA II–VI
containing inorganic anions X . This fact points to the
similarity of structure of the cation in all PA II–XIV
regardless of the character of hydrogen bonds formed
by its OH groups.
from the Council on Grants of the President of RF
(grant no. NSh-255.2008.3) and the Program of Basic
Research of Presidium RAS “Elaboration of methods
of preparation of chemical substances and new
materials,” 2009.
–
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TRIS(2-HYDROXYETHYL)AMMONIUM SALTS
2345
REFERENCES
21. Nefedova, T.V., Kazimirovskaya, V.B., Levkov-
skaya, G.G., Bryuzgin, A.A., Guseva, S.A., Mirsko-
va, A.N., and Voronkov, M.G., Pharm. Chem. J., 1986,
vol. 20, no. 3, p. 176.
1
. Voronkov, M.G., Kochina, T.A., Vrazhnov, D.V., and
Litvinov, M.Yu., Russ. J. Gen. Chem., 2008, vol. 78,
no. 11, p. 2160.
. Wiechert, D., Mootz, D., Franz, R., and Siegmund, G.,
Chem. Eur. J., 1998, vol. 4, no. 6, p. 1043.
. Starova, G.L., Frank-Kamenetskaya, O.V., Funda-
menskii, V.S., Semenova, N.V., and Voronkov, M.G.,
Dokl. Akad. Nauk SSSR, 1981, vol. 260, no. 4, p. 888.
. Sklover, V.E., Gridunova, G.V., Struchkov, Yu.T.,
Voronkov, M.G., Kryukova, Yu.I., and Mirskova, A.N.,
Dokl. Akad. Nauk SSSR, 1983, vol. 269, no. 2, p. 387.
22. Nefedova, T.V., Kubatiev, A.A., Martynov, A.V.,
Guseva, S.A., Kazimirovskaya, V.B., Mirskova, A.N.,
Novikova, N.V., Lobanova, E.G., Nepsha, V.D.,
Moskvitina, L.T., and Voronkov, M.G., Pharm. Chem.
J., 1987, vol. 21, no. 9, p. 648.
2
3
23. Nefedova, T.V., Kubatiev, A.A., Kazimirovskaya, V.B.,
Chernyakhovskaya, B.I., Mirskova, A.N., Guseva, S.A.,
Levkovskaya, G.G., and Voronkov, M.G., Pharm.
Chem. J., 1988, vol. 22, no. 10, p. 759.
4
5
6
7
8
9
. Mootz, D., Brodalla, D., and Wiebke, M., Acta Cryst.,
Sect. C, 1990, vol. 46, p. 797.
. Párkányi, L., Hencsei, P., Nyulászi, L., and Baryshok, V.P.,
Kemiai Közlemenyek, 1991, vol. 73, p. 279.
. Párkányi, L., Hencsei, P., and Nyulászi, L., J. Mol.
Struct., 1996, vol. 377, no. 1, p. 27.
. Yilmaz, V.T., Icbudak, H., Olmez, H., and Howie, R.A.,
Turk, J. Chem., 1996, vol. 20, p. 69.
. Bracuti, A.J., Crystallogr. Spectrosc. Res., 1993, vol. 23,
p. 669.
24. Kazimirovskaya, V.B., Nefedova, T.V., Annenkova, V.M.,
Annenkova, V.Z., and Voronkov, M.G., Pharm. Chem.
J., 1989, vol. 23, no. 7, p. 581.
25. Nefedova, T.V., Boiko, M.I., Kazimirovskaya, V.B.,
Ivanov, A.A., Levkovskaya, G.G., Guseva, S.A., and
Voronkov, M.G., Dokl. Akad. Nauk SSSR, 1990,
vol. 310, no. 5, p. 1256.
26. Nefedova, T.V., Korytov, L.I., Oshchepkova, O.M.,
Malyshev, V.V., Vvedenskii, V.Yu., Kolbaseeva, O.V.,
Noskova, L.K., and Voronkov, M.G., Dokl. Akad. Nauk
SSSR, 1994, vol. 334, no. 1, p. 115.
1
1
0. Naiini, A.A., Pinkas, J., Plass, W., Young, V.G., Jr., and
2
7. Nefedova, T.V., Oshchepkova, O.M., Malyshev, V.V.,
Mirskova, A.N., Levkovskaya, G.G., Vvedenskii, V.Yu.,
and Voronkov, M.G., Dokl. Akad. Nauk SSSR, 1995,
vol. 344, no. 5, p. 700.
Verkade, J.G., Inorg. Chem., 1994, vol. 33, no. 10, p. 2137.
1. Lukevics, E., Arsenyan, P., Shestakova, I., Domrache-
va, I., Kanepe I, Belyakov, S., Popelis, J., and Pudo-
va, O., Appl. Organometal. Chem., 2002, vol. 16, no. 4,
p. 228.
28. Voronkov, M.G., Gubanova, L.I., D’yakov, V.M.,
Kazimirovskaya, V.B., and Platonova, A.T., Author’s
Certificate no. 944286, 1979; Byull. Izobret., 1982,
no. 15.
1
1
2. Steiner, T., Schreurs, A.M.M., Lutz, M., and Kroon, J.,
New J. Chem., 2001, vol. 25, no. 1, p. 174.
3. Fang, L., Numajiri, S., Kobayashi, D., Ueda, H.,
Nakayama, K., Miyamae, H., and Morimoto, Y.,
J. Pharm. Sci., 2004, vol. 93, p. 144.
2
9. Voronkov, M.G. and Rasulov, M.M., Pharm. Chem. J.,
007, vol. 41, no. 1, p. 1.
2
1
4. Odabasoglu, M. and Buyukgungor, O., Acta Crystal-
logr., Sect. E: Struct. Rep. Online., 2007, vol. 63, p. 186.
5. Verkade, J., Coord. Chem. Rev., 1994, vol. 137, p. 233.
6. Voronkov, M.G., D’yakov, V.M., Stetsenko, N.A,
Prokhoda, E.F., Aurtir’s Certificate no. 1954859, 1973;
Byull. Iizobret., 1976, no., 20.
7. Sof’ina, Z.P., Voronkov, M.G., D’yakov, V.M.,
Semenova, N.V., Platonova, A.T., Peretolchina, N.М.,
Lesnaya, N.A, and Smetankina, O.Z., Pharm. Chem. J.,
30. Voronkov, M.G., Kolesnikova, O.P., Rasulov, M.M.,
and Mirskova, A.N., Pharm. Chem. J., 2007, vol. 41,
no. 5, p. 244.
1
1
31. Voronkov, M.G., Mirskova, A.N., and Levkov-
skaya, G.G., Dokl. Biol. Sci., 2002, vol. 386, p. 404.
3
3
2. Shabanov, P.D., Ganapol’skii, V.P., Zarubin, I.V.,
1
1
Zhumasheva, A.B., and Elistratov, A.A., Neuroscience,
2
006, no. 3(5), p. 43.
3. Kolesnikova, O.P., Mirskova, A.N., Adamovich, S.N.,
Mirskov, R.G., Kudaeva, O.T., and Voronkov, M.G.,
Dokl. Biol. Sci., 2009, vol. 425, p. 107.
1
978, vol. 12, no. 4, p. 489.
8. Levkovskaya, G.G., Guseva, S.A., Kazimirov-
skaya, V.B., Kholdeeva, L.N., Voronkov, M.G., and
Mirskova, A.N., Pharm. Chem. J., 1986, vol., 20, no. 3,
p. 180.
9. Mirskova, A.N., Levkovskaya, G.G., and Tizenberg, G.M.,
RF Patent no. 2034540, 1992; Byull. Izobret., 1992,
no. 3.
3
3
4. Khankhodzhaeva, D.A. and Voronkov, M.G., Dokl.
Akad. Nauk SSSR, 1993, vol. 333, no. 1, p. 124.
5. Voronkov, M.G., Dolmaa, G., Tserenpil, S.,
Ugtakhbayar, О., and Chimidtsogzol, А., Dokl. Biol.
Sci., 2005, vol. 404, p. 367.
1
2
0. Levkovskaya, G.G., Rudyakova, E.V., and Mirskova, A.N.,
Russ. J. Org. Chem., 2002, vol. 38, no. 11, p. 1641.
36. Voronkov, M.G., Dyban, A.P., D’yakov, V.M., and
Simbirtsev, N.L., Dokl. Biol. Sci., 1999, vol. 364, p. 23.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 11 2009

2
3
346
VORONKOV et al.
7. Voronkov, M.G., Gorbalinskii, V.A., and D’yakov, V.M.,
Acids and Bases, New York: Wiley, 1962
Dokl. Biochemistry, 1999, vol. 369, p., 195.
4
4
1. Brannon, D.G., Morrison, R.H., Hall, J.L., Hum-
phrey, G.L., and Zimmerman, D.N., J. Inorg. Nucl.
Chem., 1971, vol. 33, no. 4, p. 981.
2. Adamovich, S.N., Kuznetsova, G.A., Kashik, T.V.,
Zykova, E.V., Chipanina, N.N., Aksamentova, T.N.,
Mirskov, R.G., Mirskova, A.N., and Voronkov, M.G.,
Russ. J. Gen. Chem., 2008, vol. 78, no. 9, p. 1754.
3
3
8. Makarova, L.E., Borovskii, G.B., Bulatova, A.M.,
Sokolova, M.G., Voronkov, M.G., and Mirskova, A.N.,
Agrokhimiya, 2006, no. 10, p. 1.
9. Witanowski, M., Stefaniak, L., and Webb, G.A.,
Nitrogen NMR Spectroscopy. In: Annual reports on
NMR spectroscopy, Webb, G.A., Ed., London:
Academic Press, 1981, vol. 11B, p. 33.
43. Deakon, G.B. and Phillips, R.J., Coord. Chem. Rev.,
4
0. Albert, A. and Sergeant, Е.P., Ionization Constants of
1980, vol. 33, p. 227.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 11 2009