AROXY DERIVATIVES OF TRIS-(2-HYDROXYETHYL)AMMONIUM
341
2800–3075 cm–1 (N+–H) in the IR spectra. Phenol
itself, as a more weak acid, gives with triethanolamine
a
15 mL of methanol 0.94 g (0.01 mol) of phenol in
10 mL of methanol was added dropwise at stirring, the
mixture was kept at 30–50°С for 6 h, the solvent was
removed, the residue was washed with ether and dried
hydrogen-bonded complex (HOCH2CH2)3NH…
ОС6H5 (I), as witnessed by a small downfield shift of
15
1
the N NMR signal (∆δN = 4.6 ppm) and the absence
in a vacuum. Yield 2.30 g (95%). Transparent oil. H
of the ν(N+–H) band in the IR spectrum.
NMR spectrum, δ, ppm: 8.09 s (5Н, С6Н5), 3.98 t (6Н,
ОСН2), 3.44 t (6Н, NСН2). 13С NMR spectrum, δС,
ppm: 158.9 (Ph), 56.0 (ОСН2), 55.9 (NСН2). 15N NMR
spectrum, δN, ppm: –350.4. IR spectrum, ν, cm–1: 1310
(νs, NO2), 1510 (νаs, NO2), 3326 (ОН). Found, %: С
59. 52; Н 8.99; N 5.88. С12Н21NО4. Calculated, %: С
59.23; Н 8.69; N 5.75. Compounds II–VIII were
synthesized in a similar way.
It is known that the replacement of the triethanol-
ammonium cation in protatranes [(HOCH2CH2)3NН]+ ·
–O(O)CR by the di- or monoethanolammonium cation
[(HOCH2CH2)n(RR')NН]+, where n = 1, 2; R = R' = H,
Alk may increase the physiological, e.g. cancerostatic,
activity [3]. With this in mind, we have synthesized the
analogs of aroxyprotatranes [(Et3NН]+ · –ОС6H2(NO2)3
–
(V), [(HOCH2CH2)2(Me)NН]+ · ОС6H4(NO2) (VI),
Tris(2-hydroxyethyl)ammonium 2-nitrophenolate
(II). Yield 91%, mp 55°С. 1H NMR spectrum, δ, ppm:
8.44–6.14 m (4Н, С6Н4), 3.80 t (6Н, ОСН2), 3.31 t
(6Н, NСН2). 13С NMR spectrum, δС , ppm: 158.2–
121.0 (С6Н4), 56.7 (ОСН2), 55.8 (NСН2). IR spectrum,
ν, cm–1: 1320 (νs, NO2), 1516 (νаs, NO2), 2809–3100
(N+H), 3345 (ОН). Found, %: С 50.28; Н 7.28; N
9.69. С12Н20N2О6. Calculated, %: С 49.99; Н 6.99; N
9.71.
–
[(HOCH2CH2)2(Me)NН]+ · ОС6H2(NO2)3
(VII),
[HOCH2CH2(Ме)2NН]+ · –ОС6H2(NO2)3 (VIII) by the
reaction of triethylamine (NEt3), N-methyldiethanol-
amine, and N,N-dimethylethanolamine with the cor-
responding nitrophenols.
One of specific features of salts (ionic liquids),
among which protatranes and aroxyprotatranes can be
placed, is ionic conductivity [2]. Electroconductivity of
0.1 N aqueous solutions of I, II, III, IV, VII varies in
the order (σ, mSm/cm): 1.70 (I) < 3.25 (II) < 3.36 (III) <
3.96 (IV) < 4.26 (VII), that is, increases with the
acidity of the starting phenol НОС6H5–n(NO2)n, which
follows the order (pKa): 9.98 (n = 0) < 7.23 (n = 1) <
4.01 (n = 2) < 0.42 (n = 3) as well as the basicity of
Tris(2-hydroxyethyl)ammonium
2,4-dinitro-
1
phenolate (III). Yield 94%, mp 119°С. H NMR
spectrum, δ, ppm: 8.50, 7.76, 6.44 m (3Н, С6Н3), 3.82
t (6 Н, ОСН2), 3.34 t (6 Н, NСН2). 13С NMR
spectrum, δC, ppm: 160.1, 141.0, 124.9, 122.8 (С6Н3),
56.6 (ОСН2), 55.9 (NСН2). 15N NMR spectrum, δN,
ppm: –339.5. IR spectrum, ν, cm–1: 1335 (νs, NO2),
1526 (νаs, NO2), 2857–3121 (N+H), 3355 (ОН). Found,
%: С 43.53; Н 5.46; N 12.51. С12Н19N3О8. Calculated,
%: С 43.24; Н 5.74; N 12.60.
amines increasing in the following order (рKавн ): 7.72
+
(triethanolamine) < 8.56 (methyldiethanolamine) <
9.22 (dimethylethanolamine) < 10.87 (NEt3).
Therefore, by the reaction of phenol, 2-, 2,4-di-,
and 2,4,6-trinitrophenol with triethanolamine, methyl-
diethanolamine, dimethylethanolamine and triethyl-
amine a series of new water soluble liquid and solid
aroxyprotatranes and their analogues I–VIII were
synthesized.
Tris(2-hydroxyethyl)ammonium 2,4,6-trinitro-
1
phenolate (IV). Yield 3.59 g (95%), mp 129°С. H
NMR spectrum, δ, ppm: 8.84 s (2Н, С6Н2), 4.01 t (6Н,
ОСН2), 3.55 t (6Н, NСН2). 13С NMR spectrum, δC,
ppm: 162.0, 142.1, 127.0, 125.2 (С6Н2), 55.5 (ОСН2),
55.1 (NСН2). 15N NMR spectrum, δN, ppm: –337.9. IR
spectrum, ν, cm–1: 1325 (νs, NO2), 1549 (νаs, NO2),
2870–3074 (N+H), 3354 (ОН). Found, %: С 38.40; Н
4.52; N 14.99. С12Н18N4О10. Calculated, %: С 38.10; Н
4.79; N 14.81.
IR spectra were recorded in KBr on a Varian
3100FT–IR75 spectrophotometer. NMR spectra were
registered in D2O on a DPX 400 spectrometer with
working frequencies 400.13 (1H), 101.62 (13С) and
40.53 MHz (15N). Electroconductivity was measured
for 0.1 N solutions in distilled Н2О at 20°С on a
Radelkis OK–102/1 conductometer. Amines were
purified by triple distillation. Phenols (99.8%) were
purchased from Aldrich. All reactions were carried out
in dry argon.
Triethylammonium 2,4,6-trinitrophenolate (V).
1
Yield 95%. Yellow powder, mp 174°С. H NMR
spectrum, δ, ppm: 8.79 s (2Н, С6Н2), 3.09 s (6Н, СН2),
1.15 t (9Н, NСН2). IR spectrum, ν, cm–1: 1349 (νs,
NO2), 1563 (νаs, NO2), 2750–3036 (N+H).
Tris(2-hydroxyethyl)ammonium phenolate (I).
To 1.49 g (0.01 mol) of tris(2-hydroxyethyl)amine in
N-Methyl-bis(2-hydroxyethyl)ammonium 2-nitro-
phenolate (VI). Yield 93%. Viscous oily liquid. H
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 2 2014