Synthesis and study of vitrescent materials based on the alkoxybenzoic acids derivatives and triethanolamine

Article abstract of DOI:10.1134/S1070363213040075

Fifteen new branched triethanolamine esters of the benzoic acid derivatives were designed and the mesomorphism typical of discotic mesogens was forecast for them. In eight of the obtained compounds a manifestation of liquid crystal properties was predicted, for four derivatives equiprobable prognosis was given, and only three compounds were predicted not to form a mesophase. The obtained esters were characterized by elemental analysis, NMR and IR spectroscopy, gas chromatography-mass spectrometry. The main thermal characteristics that allow accounting for their phase behavior were determined.

Full text of DOI:10.1134/S1070363213040075

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 4, pp. 652–658. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © M.S. Gruzdev, O.B. Akopova, T.V. Frolova, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 4, pp. 564–570.
Synthesis and Study of Vitrescent Materials Based
on the Alkoxybenzoic Acids Derivatives and Triethanolamine
M. S. Gruzdeva, O. B. Akopovab, and T. V. Frolovac
a Krestov Institute of Solution Chemistry, Russian Academy of Sciences,
ul. Akademicheskaya 1, Ivanovo, 153045 Russia
b Ivanovo State University, ul. Ermaka 37; Ivanovo, 153025 Russia
c Ivanovo Institute of the State Fire Service of the Ministry of Emergency of Russia,
pr. Stroitelei 33, Ivanovo, 153043 Russia
e-mail: gms@isc-ras.ru
Received March 1, 2012
Abstract―Fifteen new branched triethanolamine esters of the benzoic acid derivatives were designed and the
mesomorphism typical of discotic mesogens was forecast for them. In eight of the obtained compounds a
manifestation of liquid crystal properties was predicted, for four derivatives equiprobable prognosis was given,
and only three compounds were predicted not to form a mesophase. The obtained esters were characterized by
elemental analysis, NMR and IR spectroscopy, gas chromatography-mass spectrometry. The main thermal
characteristics that allow accounting for their phase behavior were determined.
DOI: 10.1134/S1070363213040075
Among the priorities of modern organic chemistry
is the modeling and the creation of organic light-
emitting diodes and semiconductors, including those
based on discotic mesogens [1]. Organic light-emitting
diodes (OLEDs) are semiconductor devices based on
various organic compounds efficiently emitting light at
passing an electric current through them. The H. Bock
group was pioneering in the development of the
OLEDs based on discotic mesogens [2]. They created
two-layer sandwich red light emitting diodes with
stable electroluminescence. The main application of
the OLED technology is to create information displays,
where the matching of energy levels to the minimal
barriers of the injected charge carriers and the region
of luminescence is important [1]. It is assumed that the
production of such displays would be much cheaper
than the current production of liquid crystal displays. It
is also expected that the combination of the ordered
liquid crystalline state of the oligomeric structure of
branched macromolecules constructed on the basis of
branching of dendrimers would lead to an ordered
glassy state with a potential “hole” conductivity [3, 4].
amine (Ia–Id), the forecast of their possible meso-
morphism, the synthesis and study of phase behavior,
including the liquid crystalline state. It is assumed that
such compounds should have unique thermal charac-
teristics and the specific type of mesomorphism mani-
festation, useful later as a substrate in organic light-
emitting diodes.
OR
RO
N
OR
I
O
R =
OCnH2n+1, n = 3, 4, 6, 9, 12 (a);
O
O
(b);
O
CH2
The aim of this paper is designing new esters, the
derivatives of alkoxybenzoic, benzoic, cyclohexyl-
benzoic and benzyloxybenzoic acids with triethanol-
O
(d).
H
(c);
652

SYNTHESIS AND STUDY OF VITRESCENT MATERIALS
653
A forecast of possible manifestation of meso-
morphism characteristic of discotic mesogens was
performed by the method proposed in [5-8]. This
method requires the calculation of the dimensionless
molecular parameters: K, Kc, Kp, Ks, Kar, Mm, Mr,
which can be found from the molecular structure and
models constructed by the HyperChem, Ver. Pro 6.0
software and optimized by the method of molecular
mechanics (MM+). The calculation of these param-
eters for structures Ia–Id was carried out in automatic
mode using a software module ChemCard [9] (Table 1,
classification series I). The parameter K characterizes
anisomety of the whole molecule, and the parameters
Kc and Kp give the same for its separate parts (center
and periphery). The parameter Ks reflects a degree of
substitution of the central fragment with the peripheral
substituents, Kar takes into account the packing density
of the peripheral substituents, and the parameter Mm
accounts for the ratio of the masses of the central
fragment and the peripheral substituents. Parameter
Mr = Mm × Ks considers the number of substituents in
the central core of the discogene molecule.
K 2.00–8.50; Kc 1.0–2.6; Kp 0.20–0.70; Ks 0.25–1.00; Kar 0.080–0.450; Mm 0.30–0.80; Mr 0.15–0.80 (1) [8].
The results of calculation and the analysis of
molecular parameters (Table 1) show that the esters
that include the mesogenic fragments of alkoxybenzoic
acids Ia, the homologs from first to eighth are
predicted to be able to form columnar supramolecular
packing in the mesophase. Four homolog, with n = 9 to
12, according to the forecast have an equal probability
of transforming to the liquid-crystalline state, and to
show no mesomorphism characteristic of discotic
mesogens. The presence on the periphery of the more
“rigid” fragments (unsubstituted benzene or cyclo-
hexane ring) (Table 1, Ib-Id) are predicted to lead to
the disappearance of liquid-crystalline properties. The
forecast was confirmed by the experimental data,
which are discussed below.
The synthesis of branched esters Ia–Id was per-
formed in several stages. Triethanolamine, a viscous
liquid capable of vitrification, was chosen as the
branching center. Alkoxybenzoic acids II were ob-
tained along the Scheme 1 according to methods [10,
11] by the reaction of ethyl 4-hydroxybenzoate with
alkyl bromides followed by the ester hydrolysis.
As the basis of the synthesis of alkoxybenzoic II,
benzyloxybenzoic III, cyclohexsylbenzoic IV and
benzoic V esters with triethanolamine VI was the
Table 1. Molecular parameters and mesomorphism prediction of triethanolamine derivatives Ia–Ida
Comp. no.
Е, kcal mol–1
K
Kp
Kar
Mm
PCol+N
Ia, n = 1
Ia, n = 2
Ia, n = 3
Ia, n = 4
Ia, n = 5
Ia, n = 6
Ia, n = 7
Ia, n = 8
Ia, n = 9
Ia, n = 10
Ia, n = 11
Ia, n = 12
Ib
39.54
40.24
42.85
45.57
48.25
51.02
53.72
56.41
59.11
61.81
64.51
67.21
58.13
57.40
32.68
4.42
4.36
5.04
5.16
5.56
5.66
6.04
6.03
6.38
6.36
6.66
6.71
4.11
3.92
3.57
0.57
0.49
0.42
0.38
0.33
0.31
0.28
0.26
0.24
0.22
0.21
0.20
1.47b
1.41b
0.79b
0.116
0.112
0.106
0.101
0.096
0.091
0.083
0.083
0.079b
0.070b
0.073b
0.066b
0.044b
0.074b
0.143
0.72
0.63
0.57
0.51
0.47
0.43
0.40
0.37
0.35
0.33
0.31
0.31
2.19b
1.84b
1.00b
+
+
+
+
+
+
+
+
±
±
±
±
–
–
–
Ic
Id
a
Ks = 1.0 for all compounds, Kc = 1.11 for Ia, n = 1, Kc = 1.07 for the other homolog; PCol + N is forecast of mesomorphism characteristic
of discotic mesogens. b Parameters that go beyond the classification series I.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 4 2013

654
GRUZDEV et al.
Scheme 1.
O
O
O
O
K2CO3
CnH2n+1Br + HO
H2n+1CnO
DMF
C2H5
C2H5
O
EtOH
H2n+1CnO
NaOH
OH
n = 3, 4, 6, 9, 12.
Scheme 2.
O
3CnH2n+1
O
OH
а
n = 3, 4, 6, 9, 12
O
CH2
O
3
OH
OH
b
DSC, DMAP
CH2Cl2
Iа−Id
+
HO
N
O
H
3
OH
OH
c
O
3
OH
d
method developed in [12], where the reaction was
carried out under the action of dicyclohexylcar-
bodiimide on the carboxy and phenol groups of the
initial reagents II–V and VI in the presence of
dimethylaminopyridine as a catalyst, Scheme 2.
two components due to the presence in these esters of
an ether group.
Table 3 shows the values of the thermodynamic
parameters of the synthesized compounds obtained by
the method of differential scanning calorimetry (DSC)
in a heating cycle. Esters of structure Ia have in their
structure mesogenic fragments of alkoxybenzoic acids
with the alkyl substituent from propyl to dodecyl. It
was assumed that the range of the mesophase
temperature of new derivatives will be substantially
dependent on the length of the hydrocarbon radical.
However, the study showed that the length of the
hydrocarbon substituent weakly affected the and the
vitrification of the mesophase (Table 3).
The structure of the synthesized compounds Ia-Id
was confirmed by elemental analysis, NMR and IR
spectroscopy, and GC-MS method. Table 2 lists the IR
spectral parameters of the synthesized esters Ia-Id.
Compounds Ia–Id are fully substituted esters of
triethanolamine and derivatives of benzoic acid. In the
IR spectra they are characterized by three bands (Fig.
1, Table. 2) of the usual esters, due to the stretching
vibrations of C=O (s), CO–O (s, as), and OCC (s, as)
groups [13]. The peculiarity of the IR spectra of these
compounds is that the band OCC (s, as) of compounds
Ia, Ib, in contrast to that of the esters Ic, Id, is split in
We succeeded to fix the phase transitions, which
can be attributed to the enantiotropic mesophase
followed by vitrification in the triethanolamine deri-
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SYNTHESIS AND STUDY OF VITRESCENT MATERIALS
655
vatives Ia, n = 3, 4, 6, 9, 12. The data in Table 1 show
that the use of the longest alkyl group (dodecyl
derivative) leads to the most significant result, namely,
the sustainable mesophase in the glassy state.
Т 88.23°C
ΔH 75.26 J g–1 K–1
Тg –17.99°C
ΔCp 0.074 J g–1 K–1
At the first heating of the sample Ia, n = 12 the
crystal–mesophase and mesophase–isotropic liquid
transitions are observed (Fig. 1). In the cooling cycle a
gradual vitrification of the sample occurs while
maintaining the texture of the mesophase, which is
confirmed by the data of polarization thermo-
microscopy (Fig. 2). Thus, we found that all the
synthesized derivatives of triethanolamine with
structure Ia exhibited mesomorphism with the
transition from the liquid crystalline to the vitreous
state upon cooling, which agreed quite well with the
results of the forecast presented in Table 1.
Temperature, °C
Т 30.72°C
ΔH 2.738 J g–1 K–1
Т 57.4°C
ΔH 0.739 J g–1 K–1
Temperature, °C
Fig. 1. DSC curves of tris[2-(4-dodecyloxybenzoyloxy)ethyl]-
amine (Ia, n = 12): (1) heating and (2) cooling.
The derivatives of triethanolamine 1b-Id did not
exhibit the properties of liquid crystal, which is also in
good agreement with the prediction (Table 1). Varying
the substituent in the para position results only in the
change in the melting temperature. The triethanol-
amine benzoate Id melted at the temperature of about
38°C. The introduction of cyclohexyl fragment in-
creases the melting temperature of Ic to 123°C, while
the introduction of the benzyloxy substituent (Ib)
imparts amorphous structure to the material without a
stable melting point, existing mostly in the glassy
state.
Tris[2-(4-propyloxybenzoyloxy)ethyl]amine (Ia,
n = 3). A 4.25 g portion of propyloxybenzoic acid was
dissolved in 75 ml of chloroform in a round-bottom
250 ml flask, and at permanent stirring 1.17 g of
triethanolamine was added. The mixture was stirred for
10 min, then 3.47 g of 1,3-dicyclohexylcarbodiimide
and a catalytic amount of dimethylaminopyridine was
added. The mixture was stirred for 12 h. The reaction
mixture was then filtered through a glass frit filter. The
filtrate was washed with 5% acetic acid (2×25 ml), 5%
sodium chloride solution (2×25 ml), distilled water
(2×25 ml), and dried over sodium sulfate. The solvent
was removed on a rotary evaporator, the residue was
chromatographed on silica gel, eluent chloroform,
EXPERIMENTAL
IR spectra were recorded on a Bruker Vertex 80
instrument in the range of 7500–350 cm–1 from KBr
tablets or films between two KRS-5 plates. 1H and 13C
NMR spectra were registered on Bruker AC-200
(200.13 MHz) and Bruker 500 instruments, solvent
CDCl3, internal reference TMS. Thin layer chromato-
graphy was performed on the chromatographic plates
Silufol UV 254, Czech Republic. The spots were
developed under UV irradiation, λ = 254 nm.
Elemental analysis was performed using a FlashEA
1112 analyzer. Chromatograms and mass spectra were
recorded on GC-MS Saturn 2000R instrument, carrier
gas helium. Thermogravimetric analysis (TG) was
performed on a NETZCH TG 209 F1 analyzer, in an
argon flow of 20 ml min–1 at a heating rate 10°C min–1.
Differential scanning calorimetry (DSC) was
performed on a NETZCH DSC 204 F1 instrument,
capsule material Al, the sample weight ≈ 20 mg,
heating in N2 atmosphere from -110 to 100°C, heating
rate 10°C min–1.
Table 2. Absorption bands of ester groups in the IR spectra
of esters Ia–Id
Compound
Ia, n = 3
Ia, n = 4
Ia, n = 6
Ia, n = 9
Ia, n = 12
Ib
C=O
CO–O
1233.47
1232.91
1233.03
1231.01
1232.97
1213.26
1230.71
1218.78
O–C–C
1703.39
1664.34
1666.43
1672.01
1668.54
1786.88
1627.86
1781.31
1178.49–1172.59
1177.48–1173.33
1177.53–1171.33
1177.51–1171.61
1179.92–1171.47
1186.54–1168.13
1185.93
Ic
1168.39
Id
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656
GRUZDEV et al.
Table 3. The values of thermodynamic parameters of triethanolamine derivatives Ia–Ida
Compound
mp, °С
ΔНm, J g–1
Тcr, °С
ΔНcr, J g–1
Тg, °С
ΔСр, J g–1 K–1
Тph, оС
ΔНph, J g–1
Ia, n = 3
Ia, n = 4
Ia, n = 6
118.97
123.84
127.23
65.94
81.16
75.49
77.89
79.79
–57.9
17.86
12.41
–7.86
0.79
0.4
88.93
–
–57.9
–
–77.51
0.164
53.76
76.77
–
–59.9
Ia, n = 9
94.18
88.23
81.9
28.43
–
–20.45
–
–
–
–
–
–
Ia, n = 12
75.26
30.72
57.40
–
2.73
0.74
–
–
–
–
–
–59.4
7.29
0.211
0.203
Ib
122.69
38.18
72.29
4.02
–
–
–2.13
–61.27
23.47
23.47
53.87
–
–65.49
–
Ic
10.06
4.021
0.524
0.077
0.052
Id
a Data are given for the heating cycle.
followed by recrystallization from acetonitrile. The
synthesized compound is a crystalline white substance,
yield 85%, M 635.76. IR spectrum, ν, cm-1: 3147, 3032
s (C–H, Ar), 2971, 2889 s [(CH2)nCH3], 2798 w,
[(CH2)nCH3], 1703.39 s, (C=O), 1233.47 s, (CO–O as),
PhOCH2CH2, JHH 6.1 Hz,), 4.14 m (6H, NCH2CH2,
J
HH 12,2 Hz); 6.90 d (6H, H2, 6–Ph, JHH 8.5 Hz); 7,55 d
(6H, H2,5–Ph, JHH 8.5 Hz). 13C NMR spectrum
(CDCl3), δC, ppm: 10.44 (CH3); 22.44 (PhOCH2);
57.48 (NCH2); 63.51 (NCH2CH2); 69.70 (PhOCH2);
114.29 (C2,6-Ph); 129.10 (C3,5-Ph); 166.2 (OCPh);
166.95 (PhCOO). Found, %: C 67.76, H 7.92, N 2.03.
C36H45NO9. Calculated, %: C 68.01, H 7.13, N 2.20.
1
1178.49–1172.59 s (O–C–C as), 1398 s (Ar, s). H
NMR spectrum (CDCl3), δ, ppm: 1,04 m (9H, CH3,
JHH 7.32 Hz,), 1.83 m (6H , PhOCH2CH2, JHH 6.11
Hz), 3.52 m (6H, NCH2, JHH 7.34 Hz), 3.95 m (6H,
Tris[2-(4-butyloxybenzoyloxy)ethyl]amine (Ia,
n = 4) was obtained similarly. Yield: 81%, M =
677.84. IR spectrum, ν, cm-1: 3147, 3032 s (C–H, Ar),
2971, 2889 s [(CH2)nCH3], 2798 w, [(CH2)nCH3],
1664.34 s (C=O), 1232.91 s, (CO–O as), 1177.48–
1
1173.33 s (O–C–C as), 1398 s (Ar, s). H NMR
spectrum (CDCl3) δ, ppm: 0.98 m (9H, CH3, JHH 7.324
Hz), 1.24 m (6H, CH2CH2, JHH 12.5 Hz), 1.79 m (6H,
PhOCH2CH2, JHH 17.4 Hz), 3.49 m (6H, NCH2, JHH
14.3 Hz); 3.99 t (6H, PhOCH2, JHH = 6.7 Hz); 4.15 t
(6H, NCH2CH2, JHH 11.9 Hz), 6.86 d (6H, Ph–H, JHH
8.24 Hz); 7.53 d (6H, Ph–H, JHH = 8.5 Hz). 13C NMR
spectrum (CDCl3), δC, ppm: 13.71 (CH3); 19.25 (CH2);
30.68 (PhOCH2); 49.99 (CH2); 57.47 (NCH2); 68.28
(NCH2CH2); 114.38 (C2,6-Ph); 129.05 (C3,5-Ph);
154.85 (C–Ph); 161.6 (OCPh); 170.85 (PhCOO).
Found, %: N 7.15, C 70.09; N 2.17. C39H51NO9.
Calculated, %: N 7.56, C 69.11; N 2.07.
Tris[2-(4-hexyloxybenzoyloxy)ethyl]amine
(I,
n = 6) was obtained similarly. Yield 78%. M = 761.49.
IR spectrum, ν, cm–1: 3147, 3032 s (C–H, Ar), 2971,
2889 s [(CH2)nCH3], 2798 w [(CH2)nCH3], 1666.4 s
Fig. 2. Flower texture of tris[2-(4-dodecyloxybenzoyloxy)
ethyl]amine (Ia, n = 12), 25°C, the cooling cycle, crossed
nicols.
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SYNTHESIS AND STUDY OF VITRESCENT MATERIALS
657
(C=O), 1233.03 s, (CO–O as), 1177.53–1171.33 s
(O–C–C as), 1398 s (Ar, s). 1H NMR spectrum
(CDCl3), δ, ppm: 0.92 t (9H, CH3, JHH 7.019 Hz), 1.25
m (6H, CH2, JHH 10.17 Hz), 1.59 m (6H, CH2, JHH
11.597 Hz), 1.80 (m, 6H, CH2 , JHH 12.817 Hz) 2. 05
m, (6H, OCH2CH2, JHH 16.479 Hz); 3.99 t (6H, OCH2,
JHH = 6.7 Hz); 3.55 m (6H, NCH2CH2, JHH 14.0 Hz);
4.21 m (6H, NCH2, JHH 11.9 Hz), 6.87 d (6H, Ph–H,
JHH 8.545 Hz); 7.52 d, (6H, Ph–H, JHH 8.50 Hz). 13C
NMR spectrum (CDCl3), δC, ppm: 15.16 (CH3); 30.23
(PhOCH2); 31.83 (CH2); 41.09 (CH2); 41.13; 53.71
(CH2); 61.11 (NCH2); 66.05 (NCH2CH2); 114.38
(C2,6-Ph); 128.02 (C3,5-Ph); 131.01 (C–Ph); 134.47 (C–
Ph); 161.9 (OCPh); 165.98 (PhCOO). Found, %: N
8.19, C 70.12; N 1.79. C45H63O9N.Calculated, %: N
8.57, C 70.75; N 1.83.
(CH3); 22.71 (CH2); 24.85 (CH2); 29.38 (CH2); 29.76
(CH2); 30.98 (PhOCH2); 32.98 (CH2); 49.44 (CH2);
57.54 (NCH2); 68.22 (NCH2CH2); 114.22 (C2,6-Ph);
128.82 (C3,5-Ph); 155.04 (C–Ph); 161.43 (OCPh);
171.24 (PhCOO). Found, %: N 9.93, C 74.71; N 1.24.
C63H99O9N. Calculated, %: N 9.84, C 74.57; N 1.38.
Tris[2-(benzoyloxy)triethyl]amine (Id) was ob-
tained similarly. Yield 77%. M = 461.52. IR spectrum,
ν, cm–1: 3147, 3032 s (C–H, Ar), 2971, 2889 s [(CH2)nCH3],
1786.88 s(C=O), 1213.26 s, (CO–O as), 1173.41 s (O–
C–C as), 1398 s (Ar, s). 1H NMR spectrum (CDCl3), δ,
ppm: 3.40 t (6H, NCH2, JHH 14,04 Hz); 7.03 m (6H,
NCH2CH2, JHH 11.56 Hz); 7.31 m (3H Ph4-H, JHH
7.32 Hz); 7.46 m, (6H, Ph1,5-H, JHH 6.71 Hz,); 8.08 d
(6H, Ph2,6-H, JHH 6.71 Hz). 13C NMR spectrum
(CDCl3), δC, ppm: 58.01 (NCH2); 62.23 (NCH2CH2);
129.04 (C2,6-Ph); 130.59 (C3,5-Ph); 131.67 (C–Ph);
162.37 (OCPh); 171.59 (PhCOO). Found, %: N 5.85,
C 70.12; N 3.02. C27H27O6N. Calculated, %: N 5.90, C
70.27; N 3.03.
Tris[2-(4-nonyloxybenzoyloxy)ethyl]amine (Ia,
n = 9) was obtained similarly. Yield: 76%. M =
888.24. IR spectrum, ν, cm–1: 3147, 3032 s (C–H, Ar),
2971, 2889 s [(CH2)nCH3], 2798 w, [(CH2)nCH3],
1672.01 s (C=O), 1231.01 s, (CO–O as), 1177.51–
Tris[2-(4 benzyloxybenzoyloxy)ethyl]amine (Ib)
was obtained similarly. Yield: 75% . M = 779.89. IR
spectrum, ν, cm–1: 3147, 3032 s (C–H, Ar), 2971, 2889
s [(CH2)nCH3], 2798 w [(CH2)nCH3], 1627.86 s (C=O),
1230.71 s, (CO–O as), 1185.93 s (O–C–C as), 1398 s
1
1171.61 s (O–C–C as), 1398 s (Ar, s). H NMR
spectrum (CDCl3), δ, ppm: 0.89 t (9H, CH3, JHH 7.3
Hz), 1.28 m (12H, CH2CH3, JHH 25.02 Hz), 1.54 m
(12H, CH2, JHH 16.48 Hz); 1.78 m (12H, CH2, JHH 7.94
Hz); 2,04 m (6H, OCH2CH2, JHH 12.21 Hz); 3.51 m
(6H, NCH2CH2, JHH 14.04 Hz); 3.98 t (6H, OCH2, JHH
6.1Hz), 4.14 m (6H, NCH2, JHH 11.59); 6.87 d (6H,
Ph–H, JHH 9.16 Hz,); 7.52 d (6H, Ph–H, JHH 9.1 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 13.89 (CH3);
22.59 (CH2); 24.78 (CH2); 29.19 (CH2); 30.69
(PhOCH2); 32.57 (CH2); 49.37 (CH2); 57.48 (NCH2);
68.05 (NCH2CH2); 114.76 (C2,6-Ph); 128.78 (C3,5-Ph);
155.21(C–Ph); 161.43 (OCPh); 171.42 (PhCOO).
Found, %: N 9.27, C 73.05; N 1.66. C54H81O9N.
Calculated, %: N 9.20, C 73.01; N 1.58.
1
(Ar, s). H NMR spectrum (CDCl3), δ, ppm: 4.08 t
(6H, NCH2, JHH 12,07 Hz); 4. 38 m (6H, NCH2CH2,
JHH 6.71 Hz), 5,14 s (6H, PhOCH2Ph, JHH 7.32 Hz);
7.00 d (6H, Ph–H, JHH 8.55 Hz), 7.4 m (15H, Ph–H,
J
HH 7.32 Hz,); 7.99 d (6H, Ph–H, JHH = 9.155 Hz). 13C
NMR spectrum (CDCl3), δC, ppm: 41.70 (CH2); 58.99
(NCH2); 61.83 (NCH2CH2); 126.06 (C–Ph); 126.23
(C–Ph); 128.04 (C2, 6-Ph); 128.7 (C2,6-Ph); 129.11
(C3,5-Ph); 129.13 (C3,5-Ph); 176.46 (PhCOO). Found,
%: N 5.79, C 73.89; N 1.78. C42H36O9N. Calculated,
%: N 5.82, C 73.92; N 1.79.
Tris[2-(4-dodecyloxybenzoyloxy)ethyl]amine (Ia,
n = 12) was obtained similarly. Yield 75% . M =
1014.48. IR spectrum, ν, cm–1: 3147, 3032 s (C–H,
Ar), 2971, 2889 s [(CH2)nCH3], 2798 w, [(CH2)nCH3],
1668.54 s (C=O), 1232.97 s, (CO–O as), 1179.92–
Tris[2-(4-cyclohexanebenzoyloxy)ethyl]amine (Ic)
was obtained similarly. Yield 80%. M = 707.95. IR
spectrum, ν, cm–1: 3147, 3032 s (C–H, Ar), 2971, 2889
s [(CH2)nCH3], 2798 s [(CH2)nCH3], 1781.31 s (C=O),
1218.78 s, (CO–O as), 1168.39 s (O–C–C as), 1398 s
1
1
1171.47 s (O–C–C as), 1398 s (Ar, s). H NMR
(Ar, s). H NMR spectrum (CDCl3), δ, ppm: 1.42 m
spectrum (CDCl3), δ, ppm: 0.88 t (9H, CH3, JHH 6.1
Hz,), 1.26 m (18H, CH2, JHH 25.02 Hz); 1.54 m,(18H,
CH2, JHH 15.87 Hz); 1.78 m (18H, CH2, JHH 7.94 Hz);
2.03 m (6H, OCH2CH2, JHH 12.21 Hz); 3.51 m (6H,
NCH2CH2, JHH 14,04 Hz); 3.98 t (6H, OCH2, JHH
6.71 Hz); 4.14 m (6H, NCH2, JHH 11.59 Hz); 6.87 d
(6H, Ph–H, JHH 9,16 Hz); 7.52 d (6H, Ph–H, JHH
9.16 Hz). 13C NMR spectrum (CDCl3), δC, ppm: 14.41
(12H, cyclo-CH2, JHH 10.38 Hz,); 1.76 m (6H, cyclo-
CH2, JHH 12.82 Hz); 1.86 m (12H, cyclo-CH2, JHH
10.99 Hz); 2.50 t (6H, NCH2, JHH 11.59 Hz); 4.08 m
(6H, NCH2CH2, JHH 7.32 Hz); 7.34 d (6H, Ph–H, JHH
7.94 Hz); 8.06 d (6H, Ph–H, JHH 7.94 Hz). 13C NMR
spectrum (CDCl3), δC, ppm: 25.91 (cyclo-CH2); 26.71
(cyclo-CH2); 34.14 (cyclo-CH2); 44.96 (CH); 81.98
(NCH2); 83.38 (NCH2CH2); 114.78 (C–Ph); 127.21
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658
GRUZDEV et al.
(C2,6-Ph); 131.19 (C3,5-Ph); 155.27 (C–Ph); 162.09
(PhCOO). Found, %: N 8.15, C 76.41; N 2.04.
C45H57O6N. Calculated, %: N 8.12, C 76.35; N 1.98.
6. Akopova, O.B., Frolova, Т.V., and Kotovich, L.N., Zh.
Obshch. Khim., 2006, vol. 76, no. 2, p. 274.
7. Akopova, O.B., Kurbatova, Е.V., and Gruzdev, M.S.,
Zh. Obshch. Khim., 2010, vol. 80, no. 2, p. 243.
8. Akopova, O.B., Bulavkova, М.G., Gruzdev, M.S., and
Frolova, Т.V., Zh. Obshch. Khim., 2011, vol. 81, no. 4,
p. 622.
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