GlUSHKO et al., Orient. J. Chem., Vol. 33(4), 1689-1697 (2017)
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alcohol and heated to 500 0C, followed by dripping
34 ml hydrazine hydrate. In one hour’s time it was
filtered off the catalyst, with solution boiled out and
residue recrystallized from 30-ml ethyl alcohol. The
yield of AB15C5 was 70%, with its melting point of
79.5-80.5 0C.
Reaction products were identified using
chromate-mass spectrometry
It was found out that there were two
impurities, identified as compounds A and B, which
formed alongside with benzo-15-crown-5.The
formation of impurity A was the result of tetraethylene
glycol dichloride hydrolysis, while impurity B was
2-(2-(2-(2-(2-chlorethoxy)ethoxy)ethoxy)ethoxy)
phenol. Structural formulas of these side products
are shown in Figures 2 and 3 below.
Infrared spectrum (KBr, ν, cm-1): 497
(weak), 581 (weak), 631 (weak), 712 (weak), 766
(weak), 793 (weak) (NH2), 847 (medium) (NH2),
917 (weak), 940 (medium), 987 (medium), 1060
(medium) (C-O-C), 1079 (medium), 1127 (strong)
(C-O-C), 1181 (medium), 1217 (medium) (C-N),
1251 (medium), 1294 (medium), 1332 (weak),
1355 (weak), 1452 (medium), 1511 (strong) (CH2),
1589 (weak) (aromatic C-C), 1610 (medium) (NH2),
2878 (medium) (C-H), 2921 (medium) (C-H), 2957
(medium) (C-H), 3056 (aromatic C-H), 3346 (strong)
(NH2), 3396 (strong) (NH2).
In case of Synthesis 1, apart from
target product (i.e. benzo-15-crown-5 (80.09%)),
intermediate and side products, the reaction mixture
also contained initial catechol and tetraethylene
glycol dichloride (4.149% and 8.106% respectively)
at 6.5 h, time after the reaction had started. As
synthesis duration increased to 8.5 h, the content
of target product reached 82.097%, with its further
formation taking place at extremely low rate.
1HNuclear@ magnetic resonance
(DMSO-d6, 300 MHz): 3.60 (broad singlet, 8H,
CH2+CH2+CH2+CH2), 3.68-3.77 (multiplet, 4H,
CH2+CH2), 3.85-3.97 (multiplet, 4H, CH2+CH2), 4.67
(broad singlet, 2H, NH2), 6.05 (double doublet, 1H,
J=8.4, J=2.5, CH), 6.22 (doublet, 1H, J=2.5, CH),
6.63 (doublet, 1H, J=8.4, CH).
In case of tetraethylene glycol dichloride
addition in three equal parts every 10 minutes, the
concentration of target product under the same
conditions was 80.192%.In case of adding the whole
amount of tetraethylene glycol dichloride at once, the
concentration of target product was 78.431%.
13C Nuclear magnetic resonance (DMSO-
d6, 75 MHz): 67.77, 68.84, 69.27, 69.71, 70.09,
70.16, 70.30, 100.96, 105.53, 117.49, 139.35,
143.95, 149.92.
The curve of dependence between reaction
mixture and synthesis duration 1 is shown in
Figure 4.
Thus, benzo-15-crown-5 forms only
RESULTS AND DISCUSSION
after reaction mixture has been heated to its
boiling point (107 C), which takes 1.3 h. Then,
0
Reaction products were identified using gas
chromatograph«ChromatecCrystal500.2»,equipped
with mass spectrometry detector ThermoISQ and
15 m long fused silica column TR-5MS, with its
inner diameter and fixed-phase film thickness of
0.25 mm and 0.25µm respectively. Carrier has:
helium (rate: 2.8 ml/min, split ratio: 1:25, column
temperature range:150-280 0C, temperature setting:
20 0C/min. Mass spectrums of an electronic
impact were determined at the 70-eV energy of
the temperature of reaction mixture decreases to
102 0C, followed by formation of two side products,
A and B, in comparatively small quantities (4.211%
and 3.554% respectively).
Benzo-15-crown-5 is extracted from boiling
reaction mass by hexane. The mass fraction of
Fig. 2: 1-chlorine-11-hydroxy-
tetraethyleneglycol, m/z 212.5
0
ionizing electrons and 280 C temperature of ion
source. Reaction products were identified mainly
by comparing registered spectrum with that of
NISTUSA (2008) and also by molecular ion based
on the correlation between mass, spectrum and
structure.
Fig. 3: 2-(2-(2-(2-(2-chlorethoxy)ethoxy)ethoxy)
ethoxy)phenol, m/z 304.11