Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxxx

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Journal of Analytical and Applied Pyrolysis

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Decomposition course of anticancer active imidazolidine-based hybrids with

diethyl butanedioate studied by TG/FTIR/QMS-coupled method
Marta Worzakowskaa, , Małgorzata Sztankeb, Krzysztof Sztankec
⁎

a
Department of Polymer Chemistry, Faculty of Chemistry, Maria Curie-Skłodowska University, 33 Gliniana Street, 20-614 Lublin, Poland
b
Chair and Department of Medical Chemistry, Medical University, 4A Chodźki Street, 20-093 Lublin, Poland
c
Laboratory of Bioorganic Synthesis and Analysis, Chair and Department of Medical Chemistry, Medical University, 4A Chodźki Street, 20-093 Lublin, Poland

ARTICLE INFO ABSTRACT

Keywords: The course of pyrolysis and combustion processes of four diethyl (2E)-2-{(2E)-[1-(R-phenyl)imidazolidin-2-yli-
Imidazolidine-based hybrids dene]hydrazinylidene}butanedioates which act as anticancer agents was studied using simultaneous thermal
Anticancer agents analysis method (TG/DSC) coupled online with Fourier transform infrared spectroscopy (FTIR) and Quadrupole
Decomposition course mass spectrometry (QMS) analyzers in helium and synthestic air atmospheres. It was found that the decom-
Thermal studies
position processes of the tested compounds in inert and oxidative conditions were complex and included some of
the simultaneous reactions. The following decomposition reactions were observed: (i) pyrolysis of CeO, CeC
and CeN bonds, partial decarboxylation and dehydration (ii) further partial fragmentation and pyrolysis of CeO,
CeC and CeN bonds connected with decarboxylation and dehydration of intermediate products; (iii) simulta-
neous cracking of CeN and partial pyrolysis of formed aromatic-rich residue and additional oxidation processes
in air conditions; (iv) fragmentation and pyrolysis processes (in inert conditions) and additional combustion
processes (in oxidative conditions) of fused aromatic rings in connection with some chemical reactions between
the decomposition fragments.

1. Introduction imines constitute an important group of molecules with prospective

Diethyl (2E)-2-{(2E)-[1-(R-phenyl)imidazolidin-2-ylidene]hydrazi-
nylidene}butanedioates (1–4) (Fig. 1) are a class of imidazolidine-based
hybrids with diethyl butanedioate whose structures in solution are fully
defined. All these small molecules are of particular importance in re-
lation to the patented medical utility since their remarkable anti-
proliferative effects are of benefit in the treatment of human multiple
myelomas (both resistant and susceptible to thalidomide) and human
tumours of breast and cervix [1,2]. In addition, all the title compounds
have been utilized in cyclization reactions aimed at obtaining antic-
ancer active heterobicyclic esters that contain a privileged 7,8-dihy-
droimidazo[2,1-c][1,2,4]triazin-4(6H)-one scaffold [2].
Despite the above-mentioned utilities, both thermal properties in
inert or oxidative conditions and the mechanism of thermal degradation
of the investigated anticancer agents (1–4) (possessing within their
structure two ester functional groups and two azomethine moieties of
the ketimine-type in the > C]NeN]C < grouping) are still unknown.
However, there are research papers describing the thermal stability and
decomposition pathways for various bioactive compounds bearing the
ester functional group/groups [3–5]. Besides, pharmacologically active
pharmaceutical utility that have been much less thermally tested [6–8]
than their metal complexes. Furthermore, the thermal stability, pyr-
olysis and combustion processes of succinic acid (1,4-butanedioic acid)
and its sodium succinate dibasic hexahydrate salt are described [9].
Hence, the assessment of thermostability, using the coupled TG/DSC/
FTIR/QMS thermal analysis techniques, will be especially important for
a further characterization of the title compounds as they have an ap-
plicative potential in medicine. The TG/DSC method enables in-
vestigating every phenomenon when the change in mass of the sample
heated occurs as well as the purity control, and therefore it is commonly
employed in thermal studies of pharmaceutics and drug-like molecules
[5,10–12]. Therefore, the purpose of the present investigation is to
determine the range of thermal stability in inert and oxidative condi-
tions as well as the main properties under pyrolysis of four - differently
substituted on the phenyl moiety -molecules with antitumour field of
relevance (1–4). The article focusses on valuable thermal properties of
candidates for medical application, by investigating their thermal de-
composition. Moreover, the present paper explains the thermal de-
gradation mechanism showing pathways of the thermal decomposition
and degradation products of the title compounds (1–4).

⁎
Corresponding author.
E-mail address: marta.worzakowska@poczta.umcs.lublin.pl (M. Worzakowska).

https://doi.org/10.1016/j.jaap.2019.104686
Received 31 March 2019; Received in revised form 27 August 2019; Accepted 28 August 2019
0165-2370/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Marta Worzakowska, Małgorzata Sztanke and Krzysztof Sztanke, Journal of Analytical and Applied Pyrolysis,
https://doi.org/10.1016/j.jaap.2019.104686
M. Worzakowska, et al.
Fig. 1. Structures in the solution of the investigated imidazolidine-based hy-
brids with diethyl butanedioate: 1. R = 4-CH3, 2. R = 3-Cl, 3. R = 4-Cl, 4.
R = 3,4-Cl2.
2. Experimental
2.1. Short description of the investigated compounds (1–4)
All the compounds (1–4) that were subjected to thermal studies
have been synthesized using efficient approaches previously patented
and published [1,2]. The structures of all molecules under thermal in-
vestigation have been confirmed by consistent spectroscopic data (in-
cluding 1H NMR and 13C NMR spectra), elemental analyses comprised
within ± 0.4 percent of the theoretical values for C, H, N (in the case of
1–4) and Cl (in the case of 2–4). The structural assignment of diethyl
(2E)-2-{(2E)-[1-(3-chlorophenyl)imidazolidin-2-ylidene]hy-
drazinylidene}butanedioate (2) – shown in Fig. 1 – has been ad-
ditionally supported by 13C,1H HMBC and HMQC correlations. All data
concerning the structural characterization of the title compounds have
been published in a previous paper [2]. The structures assigned to 1–4
have also been supported by their well-tried cyclizations [1,2]. The
studied pure compounds, isolated as white (1, 2) and creamy (3, 4)
solids having sharp melting points, have been reported to possess not
only enhanced anticancer effects in malignant human multiple mye-
loma cells (MM1R, MM1S), but also antiproliferative activities against
Fig. 2. DSC curves for compounds 1–4 in helium.
2
Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxxx
human tumours of breast (T47D) and cervix (HeLa). In addition, their
effects on normal human skin fibroblasts have been previously docu-
mented [2].
2.2. TG/DSC/FTIR/QMS analysis
The thermogravimetric analysis together with differential scanning
calorimetry (TG/DSC) was performed with a use of a STA 449 Jupiter
F1 instrument (Netzsch, Germany) coupled on-line with a FTIR TGA
585 analyzer (Bruker, Germany) and a QMS 403 C Aëolos (Netzsch,
Germany) analyzer. The TG/DTG instrument was calibrated with
standards weights according to the manufacturer proceedings. The
following metals (mass ca. 10 mg): In, Sn, Bi, Zn, Al, and Au were used
for the temperature and sensitivity calibrations. The results were
checked with calcium oxalate monohydrate. The compounds 1–4 were
heated between 40 °C and 850 °C (synthetic air atmosphere, a flow rate
100 mL/min) or 40 °C and 900 °C (helium atmosphere, a flow rate
40 mL/min) in Al2O3 crucibles. The sample mass was ca. 10 mg and the
heating rate was 10 K/min. The analysis for each sample was repeated
three times. Simultaneously, the gaseous FTIR and QMS spectra were
gathered by a FTIR TGA 585 analyzer and QMS 403C Aëolos analyzer in
order to evaluate the gaseous decomposition products emitted as a re-
sult of the thermal decomposition of the tested compounds. The FTIR
spectrometer with IR cell maintained at 200 °C was connected on-line to
STA instrument by Teflon transfer line with a diameter of 2 mm heated
to 200 °C. The FTIR spectra were collected within the range of 600-4000
cm−1 with 16 scans per spectrum and with a resolution 4 cm-1. The
QMS analyzer was connected on-line to STA instrument by quartz ca-
pillary heated to 300 °C. The QMS was operated under electron ioni-
zation with energy 70 eV. The QMS measurements in scan mode for m/
z, where m is the mass of molecule and z is a charge of molecule in
electron charge units in the range 10–300 m/z were performed.
3. Results and discussion
3.1. Melting temperature of compounds 1–4 evaluated by the use of DSC
According to the DSC studies, Fig. 2, S2a and S2b, compounds 1 and
2 melt within two temperature ranges. On the DSC curves, two en-
dothermic, asymmetrical signals distributed by one exothermic signal
for compound 1 appear, Fig. 2 and S2a. At this temperature range, no
mass loss is observed which directly indicate the melting process of
compounds. As mentioned above, the two low-temperature en-
dothermic peaks on DSC curves (at Tmax1 ca. 96 °C and Tmax2 ca. 131 °C)
are probably referred to the melting events of two tautomeric forms of
compound 1, whereas the exothermic signal (at Tmax ca. 102 °C) – to an
M. Worzakowska, et al. Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxxx

Fig. 3. TG and DTG curves for compounds 1–4 in helium.

Table 1
TG data of compounds 1–4 (helium atmosphere)a.
Sample Degradation process

First decomposition stage Second decomposition stage

First step Second step Third step First step

Tonset1 Tmax1 Tfinal1 Δm1 Tonset2 Tmax2 Tfinal2 Δm2 Tonset3 Tmax3 Tfinal3 Δm3 Tonset4 Tmax4 Tfinal4 Δm4
/°C /°C /°C /% /°C /°C /°C /% /°C /°C /°C /% /°C /°C /°C /%

1 197 ± 220 ± 251 ± 15.07 ± 251 ± 310 ± 355 ± 30.09 ± 355 ± ca.366-435 493 ± 15.23 ± 493 ± 675 ± 2.1 886 ± 39.61 ±
1.2 2.1 1.8 0.3 1.5 1.2 1.7 0.5 1.9 1.5 0.4 1.5 /730 ± 2.2 2.4 0.5
2 207 ± 233 ± 260 ± 15.76 ± 260 ± 298 ± 360 ± 28.26 ± 360 ± 388 ± 2.4 523 ± 21.38 ± 523 ± 793 ± 2.3 925 ± 34.60 ±
1.9 1.5 1.5 0.2 0.9 1.5 1.8 0.3 2.1 1.8 0.5 1.0 2.3 0.6
3 202 ± 230 ± 257 ± 15.11 ± 257 ± 299 ± 362 ± 28.52 ± 362 ± ca.391-433 555 ± 22.56 ± 555 ± 854 ± 3.0 < 991 33.81 ±
1.5 2.0 2.0 0.5 2.0 1.1 1.2 0.2 2.0 1.7 0.5 1.0 0.3
4 211 ± 240 ± 266 ± 15.33 ± 266 ± 301 ± 362 ± 25.61 ± 362 ± 402 ± 2.0 811 ± 34.68 ± 811 ± – < 990 3.42 ±
1.3 2.0 0.8 0.3 1.0 0.8 1.5 0.4 2.0 2.5 0.7 2.4 0.1

Tonset - the onset point decomposition temperatures, Tmax - the peak maximum temperatures, Tfinal - the final decomposition temperatures, Δm - the mass loss.
a
Values are the means ± SEMs.

3
M. Worzakowska, et al.
Fig. 4. The FTIR spectra of the gaseous decomposition products for compounds
1–3 (a) and compound 4 (b) in helium and the FTIR spectra of ethanol in the gas
state (c) (a - reference spectra [19]) and b - gaseous products for compound 1
registered at Tmax1 in helium).
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Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxxx
intermediate exothermic process which corresponds to the crystal-
lization called as “cold crystallization” of one of the tautomer. This was
confirmed visually during identification of this compound using
melting points on a Boetius apparatus. It was observed that compound 1
melts at 96–97 °C, then recrystallizes from the melt at ca. 102 °C, and
finally the other newly crystallized tautomeric solid phase melts again
at 130–131 °C. A similar behaviour with the two consecutive and se-
parate melting events has already been previously reported by Le Count
and Greer [13] in the case of the tautomeric dimethyl 2-[2-(4,5-di-
hydro-1H-imidazol-2-yl)hydrazinylidene]succinate.
In turn, two, sharp, endothermic, asymmetrical signals at Tmax1 ca.
68 °C and Tmax2 ca. 120 °C for compound 2 are well visible, Fig. 2 and
S2b. It suggests the melting process of two different solid phases of
compound 2.
On the other hand, the melting process of compounds 3 and 4 is
described by one, sharp endothermic signal visible at Tmax 96 °C for
compound 3 and 109 °C for compound 4. It directly confirms the pre-
sence of only one, isomeric form of those substances as well as their
high purity.
3.2. Decomposition course of compounds 1–4 in inert conditions
It is well seen that the compound 1, where R is the CH3 group in
para position of the phenyl moiety, is characterized by the lowest
thermal stability in inert atmosphere. Its thermal decomposition starts
at the temperature ca. 196 °C, Fig. 3, Table 1. However, the thermal
stability of compound 4, which contains two chlorine substituents at the
benzene ring, seems to be the highest, the Tonset value equals to 211 °C.
The compounds 2 and 3 are thermally stable up to the temperature ca.
207 °C and ca. 202 °C, respectively. The results indicate a little higher
thermal stability of the meta-chloro derivative than para-chloro deri-
vative.
Heating the studied compounds above the Tonset1 causes their de-
composition, Fig. 3, Table 1. The first decomposition step for com-
pounds 1–4 between the Tonset1 and Tfinal1 with Tmax1 centred at 220 °C,
233 °C, 230 °C and 240 °C, respectively, is observed. The values of the
mass loss (Δm1) for compounds 1–4 are comparable and equal to ca.
15%. On the DSC curves, the presence of only one, endothermic signal
testifies to the pyrolysis processes of the weak bonds in compounds 1–4.
According to the FTIR data, the first decomposition step for all the
studied compounds proceeds through the same mechanism, Fig. 4.
Heating the studied compounds up to the Tfinal1 temperature is con-
nected with the random breaking of the CeO and CeC bonds and the
emission of the mixture of gaseous decomposition products. The emis-
sion of alcohol and alkene at the beginning of the decomposition is
confirmed by the presence of the following absorption signals on the
FTIR spectrum gathered at Tmax1: 3580-3680 cm−1 (ν OH), 2921-
2990 cm−1 (ν CeH), 1380-1490 cm−1 (δ CeH), 1038-1066 cm−1 (ν
CeO), 1224–1250 cm−1 (ν CeO) and 901 cm−1 (ν CeCeO). In turn,
the emission of alkene is affirmed by the presence of the bands at ca.
1595-1630 cm−1 (ν C]C) and the bands below 900 cm−1 (γ]CH) on
the FTIR spectra, Fig. 4. In addition, some emission of aldehyde visible
as weak absorption bands at 2740 cm−1 (ν CeH in CHO group) and
1726-1776 cm−1 (ν C]O), is detected [14,15], Figs. 4, S4a and S4b.
Besides the emission of those main pyrolysis products, the appearance
of the emission of CO2 (peaks at 2300-2365 cm−1 (valence vibration)
and 669 cm−1 (deformation vibration)) and low H2O amount (several,
jagged, weak signals at the range 3450–4000 cm−1 and 1300-
1950 cm−1) [16–18] is confirmed, Figs. 4 and S4c. It may indicate the
partial decarboxylation and dehydration processes of the created in-
termediate volatiles, Scheme 1.
The second decomposition step occurs between the Tfinal1 and Tfinal2
with the corresponding Tmax2: 310 °C, 298 °C, 299 °C and 301 °C. The
evaluated mass losses are from 30.09% to 25.61%. However, the third
M. Worzakowska, et al.
Scheme 1. The proposed decomposition path of the studied compounds in helium.
decomposition step appears from the Tfinal2 up to the Tfinal3. At this
temperature range, the evaluated Δm3 is from 15.23% to 34.68%. DSC
curves show the presence of only endothermic signals which proves the
further pyrolysis processes of some bonds in the structure of those sub-
stances. From the Tonset2, the further emission of alkohol, alkene and
aldehyde, CO2, and H2O is noticed. These results were confirmed by the
QMS analysis (Fig. 5). According to the QMS data and NIST database
[19], the main organic pyrolysis product of compounds 1–4 under the
first and second decomposition steps is ethanol (m/z: 31,45,29,27,
46,43,26,30,15,42). The emission of small amount of ethylene (m/z:
28,27,26,25,24,14,12,13,15), ethanal (m/z: 29,44,43,15,42,16,26,
41,27), formaldehyde (m/z values: 29,30,28,15,12,13,14,31) and H2O
(m/z: 18,17,16,19,20) and the emission of CO2 (m/z: 44,28,16,12,22) is
also seen. However, the intensities of the FTIR bands and the m/z ions
characteristic for ethanol and ethylene decrease during the second de-
composition step. On the other hand, the increase in the intensity of the
FTIR bands and QMS signals characteristic for CO2 and H2O as well as a
comparable intensity of the signals for aldehyde confirm the continuous,
simultaneous reactions of the random breaking of CeO and CeC bonds
and some decarboxylation and dehydration processes of the formed in-
termediate fragments [17,18,20,21] and thus the creation of the some
aromatic-rich intermediates. Moreover, on the QMS spectra, one can
clearly see the presence of the m/z ions with the values 28, 14 and 29
when heating the compounds at the temperature range from Tonset1 to ca.
315 °C (first and second decomposition steps). This may suggest the
creation of N2 as a result of the cleavage of NeC bonds. The N2 molecule
has a symmetric structure and it is not visible by the gaseous FTIR
analyser. However, it is well visible by the QMS analyser. In addition, the
m/z ions 28 and 29 are also characteristic for CO. However the emission
of CO is not detected from the gaseous FTIR spectra at this temperature
range. As a result, the most presumable gaseous decomposition product
5
Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxxx
referred to above is N2. The emission of the above mentioned gaseous
decomposition products, is observed up to the temperature ca. 315 °C for
all the studied compounds.
From the temperature ca. 300 °C up to ca. 500 °C (compounds 1–3)
and ca. 650 °C (compound 4), the beginning of the emission of other
organic gaseous decomposition products is indicated. Moreover, the
increase in the intensity of the emission of CO2, H2O and an appearance
of the absorption signals characteristic for CO (2050–2270 cm−1) are
noticed. According to the FTIR results, the emission of low molecular
mass gas containing in the structure a nitrogen such as NH3 (several
bands with two characteristic maxima at 932 and 963 cm−1 [16,22]) is
clearly observed, Figs. 4 and S4d. The emission of this gas is also
confirmed by the QMS results. The presence of the characteristic m/z
ions for NH3 (m/z: 17,16,15,14,18) under the third decomposition step
is detected (Fig. 5). In addition, taking into account the structure of the
tested compounds, the formation of aromatic compounds is expected.
The type of the created aromatics is completely dependent on the initial
structure of the tested compounds. For the compound 1, the most likely
aromatics are p-toluidine, toluene and fused aromatic rings. The crea-
tion of the aromatic compounds is affirmed by the presence of the ab-
sorption bands at 1492 and 1597 cm−1 (νCAr=CAr), 1046–1086
(βCArH), 690-704 cm−1 (γCArH), Figs. 4 and S4e. In turn, m-chlor-
oaniline (compound 2), p-chloroaniline (compounds 3 and 4), chlor-
obenzene or fused aromatic rings (compounds 2–4) are expected as
main aromatic volatiles. The emission of m-chloroaniline and p-chlor-
oaniline is confirmed by the presence of the following absorption bands
on the FTIR: 1626–1640 cm−1 (δ NeH), 1595 and 1465-1497 cm−1
(νCAr=CAr), 1231-1267 cm−1 (νCN), 1088 cm−1 (βCArH), 1008 cm−1
(ring), 818-825 cm−1, 885 and 770 cm−1 (γCArH), 669 cm−1 (νCCl).
However, the absorption bands at 1579 cm−1 (νCAr=CAr for alkyl
substituted rings, compound 1), 689–704 cm−1 and 719–760 cm−1,
M. Worzakowska, et al.
Fig. 5. The QMS spectra for the decomposition product for compounds 1–3 (a) and compound 4 (b) in helium.
(γCArH, for compound 1), 1000-1045 cm−1 (in-plane δ aromatic
]CeH, for compound 1) and 1512-1617 cm−1 (νCAr=CAr for com-
pounds 2–4), 719-818 cm−1 (γCArH, for compounds 2–4), 1008-
1060 cm−1 (in-plane δ aromatic ]CeH for compounds 2–4) and at 669
cm−1 (νCCl) may be due to the emission of chlorobenzene and fused
aromatic rings in the case of all the studied compounds, Figs. 4, S4f and
S4g. The type of the emitted volatiles may indicate on the simulatneous
cracking of C–N bonds connected to the partial pyrolysis of formed
aromatic-rich residues and some dexarboxylation and dehydration
processes of the intermediates in this step. Moreover, the FTIR and QMS
analyses confirm the creation of an additional decomposition product
such as gaseous HCl for compound 4 (Figs. 4, S4h and 5). Its emission
from the temperature ca. 380 °C is noticed. The formation of this new
gas product is affirmed by the presence of several absorption bands in
the range 2640-3100 cm−1 on the FTIR spectrum and by the appear-
ance of the characteristic ions with the following m/z values
36,38,35,37 [14,19]. Unfortunately, the emission of aromatic frag-
ments is unseen from the QMS results. It may be due to two reasons:
their extremely low concentration which is not detected by the QMS
analyzer or the formation of fused aromatic rings containing functional
groups (eCH3, eCl, eNH) at the higher temperatures [23] which
cannot be detected by the QMS due to their high molecular masses.
The second degradation stage is composed of one, main step which
appears above the Tonset4 temperature. At this decomposition stage, the
mass loss is from ca. 33 to ca. 39%. Heating the compounds 1–3 under
inert conditions up to the temperature of 900 °C leads to their full de-
composition. In contrast to the thermal degradation of compounds 1–3,
the decomposition process of compound 4 is not finished. The mass loss
for compound 4 is only ca. 3.5% when it is heated to 900 °C. Analyzing
the results obtained based on the simultaneous TG-FTIR-QMS analysis,
it can be noted the emission of inorganic species such as CO (FTIR:
2050-2270 cm−1, QMS: m/z 28,12,16,29), CO2 (FTIR: 2300-2365 cm−1
6
Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxxx
and 669 cm−1, QMS: m/z 44,12,45,46,22), H2O (FTIR: 3450-
4000 cm−1 and 1300-1950 cm−1, QMS: m/z 18,17,16) and small
emission of aldehyde in the case of compounds 1–3, Figs. 4, S4i, S4j and
5. The presence of only exothermic signals on DSC curves for com-
pounds 1–3 demonstrates the occurrence of some chemical reactions
between the intermediate products and the residues. Probably, the
formed fused aromatic ring residues from compounds 1–3 undergo
fragmentation and destruction processes connecting with some che-
mical reaction between the decomposition fragments. However, for
compound 4, the additional emission of aromatic type fragments is
observed at the temperatures higher than 650 °C which indicates the
further slow pyrolysis processes of the remaining part of compound 4.
The proposed decomposition path of the studied compounds is pre-
sented in Scheme 1.
3.3. Decomposition course of compounds 1–4 in oxidative conditions
Similarly to the results obtained when heating the compounds in
inert atmosphere, the oxidative degradation happens in two main
stages, the first one is composed of at least three, non-well separated
decomposition steps, Fig. 6, Table 2. The DSC curves recorded in air
atmoshere are placed in Fig. 6a. The first decomposition step happens
up to the Tfinal1 with the Tmax1 at 212–231 °C and with the comparable
mass losses (14–15%) for all the studied compounds. As it is well seen
from the gaseous FTIR spectra gathered under the first decomposition
step, Fig. 7, the emission of alcohol and alkene is confirmed by the
presence of the following characteristic absorption bands above
3500 cm−1 (ν OH), at 2828-2985 cm-1 (ν C-H), 1378-1480 cm-1 (δ
CeH), 907–920 (ν CeCeO) and at 1024–1080 and 1223-1260 cm-1
(νCeO) at 1595-1640 cm-1 (νC]C) and below 900 cm−1 (γ]CeH)
(Fig. 7) [14]. The emission of these gases is also confirmed by the QMS
analysis (Fig. 8). The m/z ions characteristic for ethanol
M. Worzakowska, et al.
Fig. 6. TG and DTG curves for compounds 1–4 in air.
(31,45,29,27,46,43,26,30,15,42) and ethylene (28,27,26,25,24,
14,12,13,15) are detected [19]. Moreover, the FTIR spectra show the
emission of low concentration of carbonyl compounds which is affirmed
by the occurrence of the absorption bands at ca. 1720-1780 cm−1 (ν
C]O) and the beginning of the emission of CO2 (peaks at 669 and
2300-2365 cm−1) and further emission of H2O (peaks above
3500 cm−1) [22]. The emission of aldehyde (m/z: 29,44,43,15,
42,16,26,41,27), CO2 (m/z: 44,28,16,12,22) and low H2O amount (m/z:
18,17,16,19,20) is also well visible from the QMS spectra. In addition,
the formation of N2, as a result of the breaking of CeN bonds, is seen
from the QMS analysis as the ions with the following m/z values: 28,
29, 14. The formation of the above mentioned gases may be the result
7
Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxxx
of the partial destruction of the samples comprising simultaneous,
random breaking of CeC, CeO and NeH bonds and some decarbox-
ylation and dehydration processes of the created intermediate products.
This indicates the same decomposition mechanism of the studied
compounds (1–4) in inert and oxidative atmospheres under the first
decomposition step. As a result gaseous decomposition products and
unstable intermediate products are formed. Under this decomposition
step, mainly the pyrolysis processes of the bonds happen without the
oxidation of the formed volatile species. On the DSC curves no exo-
thermic signals (which can indicate the oxidation processes), only one,
asymmetrical, poorly marked endothermic signal with Tmax ca.
290–293 °C are observed, Fig. 6a.
M. Worzakowska, et al. Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxxx

Table 2
TG data of compounds 1–4 (air atmosphere)a.
Sample Degradation process

First decomposition stage Second decomposition stage

First step Second step Third step First step

Tonset1 Tmax1 Tfinal1 Δm1 Tonset2 Tmax2 Tfinal2 Δm2 Tonset3 Tmax3 Tfinal3 Δm3 Tonset4 Tmax4 Tfinal4 Δm4
/°C /°C /°C /% /°C /°C /°C /% /°C /°C /°C /% /°C /°C /°C /%

1 188 ± 212 ± 241 ± 15.48 ± 241 ± 293 ± /1.8 365 ± 30.64 ± 365 ± 379 ± /1.7 482 ± 11.98 ± 482 ± 581 ± /2.5 705 ± 44.53 ±
1.5 1.3 2.2 0.3 1.7 324 ± 2.2 2.1 0.5 1.5 428 ± 1.5 2.0 0.2 1.8 657 ± 2.6 1.4 0.6
2 199 ± 225 ± 253 ± 14.27 ± 253 ± 293 ± /1.6 345 ± 24.83 ± 345 ± 365 ± /1.7 470 ± 16.93 ± 470 ± 561 ± /1.9 711 ± 43.97 ±
1.3 1.5 1.8 0.4 1.9 318 ± 2.0 2.5 0.8 1.9 392 ± 1.9 1.5 0.4 1.7 656 ± 2.2 2.4 0.5
3 196 ± 222 ± 251 ± 14.66 ± 251 ± 294 ± /1.3 367 ± 26.72 ± 367 ± 383 ± /1.5 452 ± 13.91 ± 452 ± 563 ± /1.9 714 ± 44.71 ±
1.2 1.9 1.3 0.4 2.1 353 ± 1.5 1.8 0.4 1.4 404 ± 2.1 1.5 0.3 1.9 676 ± 1.5 1.9 0.5
4 205 ± 231 ± 253 ± 14.52 ± 253 ± 293 ± /1.1 345 ± 24.14 ± 345 ± 375 ± 2.0 468 ± 14.00 ± 468 ± 540 ± /2.0 722 ± 47.34 ±
1.8 2.0 1.0 0.2 1.5 326 ± 1.2 1.6 0.4 1.8 1.3 0.5 2.1 670 ± 1.1 1.5 0.3

*aValues are the means ± SEMs.

Fig. 6a. DSC curves for compounds 1–4 in air.

The second decomposition step is visible from Tonset2 to Tfinal2 and
the mass losses from ca. 24% to 30%. On the DTG curve, the presence of
one, asymmetrical peak with main Tmax2 temperature and a shoulder
above 300 °C suggests the occurrence of the simultaneous decomposi-
tion processes at this step. The third step appears between the Tonet3 and
Tfinal3 with the mass loss between 12% and 17%. When the compounds
are heated between the temperatures Tonset2 and 300 °C, the continuous
emission of alcohol and alkene is confirmed based on the presence of
the absorption bands above 3500 cm−1 (ν OH), at 2861-2985 cm-1 (ν
C–H), 1364–1480 cm-1 (δ CeH), 910–920 (ν CeCeO) and at
1017–1099 and 1223-1260 cm-1 (νCeO) at 1590-1630 cm-1 (νC]C)
and below 900 cm−1 (γ]CeH) on the FTIR spectra as well as by the
presence of the following m/z ions: 31,45,29,27,46,43,26,30,15,42
(ethanol) and 28,27,26,25,24,14,12,13,15 (ethylene) [14,19]. Besides
the emission of alcohol and alkene, some aldehyde compounds are also
created. The bands characteristic for aldehyde are seen as low intensity
signals at 1708-1786 cm-1 (νC]O) on the FTIR spectra and as the fol-
lowing m/z ions: 29,44,43,15,42,16,26,41,27 on the QMS spectra.
However, according to the QMS analysis, the concentration of above
mentioned gases decreases at this step as compared to their con-
centration at the first decomposition step. Moreover, the creation of
CO2, H2O and N2 is also visible from the FTIR and/or QMS spectra
(Figs. 7 and 8). In addition, from the temperature ca. 290 °C where
onset of the first exothermic DSC signal happens, the beginning of the
emission of other volatiles is detected. Their emission is continued up to
ca. Tfinal3. Among the volatiles, the formation of NH3 (two characteristic
absorption bands at 930 and 965 cm−1) and H2O, CO2, nitrogen oxides
and CO (the bands at 2050-2270 cm−1) is affirmed [24–27]. In contrast
to the analyses in helium atmosphere, in this temperature range, the
oxidation process of some NH3 fragments with oxygen is expected.
According to the literature data, NH3 in the presence of an oxidative
atmosphere can undergo oxidation to the corresponding nitrogen oxide
and water [28]. In addition, the emission of aromatic compounds is
suspected. It is affirmed by the results obtained from the analysis of the
gaseous FTIR spectrum gathered at 300 °C-Tfinal3 where the absorption
bands characteristic for aromatics are detected. The most presumable
aromatic compounds are the following: p-toluidine and toluene (com-
pound 1), m-chloroaniline and chlorobenzene (compound 2), p-chlor-
oaniline and chlorobenzene (compounds 3 and 4) or their fused aro-
matic ring forms. The emission of the above mentioned molecules is
affirmed by the occurrence of the following characteristic bands
at 3018-3080 cm−1 (νCAreH), 1636 cm−1 (δNH), 1580–1610 cm−1
(νCAr]CAr), 1225-1300 cm−1 (νCN) and 740-870 cm−1 (γCAr-H)
[14,19,29], (Fig. 7). The QMS analysis affirms the creation of NH3 (m/z:
17,16,15,14,18), nitrogen oxides: NO (m/z: 30,14,15,16,31,32), N2O
(m/z: 44,30,14,28,45,15,29,31), aldehydes (m/z: 12,13,14,15,16,
26,28,29,30,31,41,43), CO2 (m/z: 44,12,45,46,22), low H2O amount
(m/z: 18,17,16) and CO (m/z: 12,16,28,19). Similarly as for the results
received under inert conditions, the creation of aromatics under oxi-
dative conditions is not seen from the QMS spectra. It can distinguish
that the most realistic aromatics are fused aromatic rings instead of
single aromatic rings, Scheme 2. In the case of compound 4, the addi-
tional decomposition product which is created is HCl. Its emission is
visible from ca. 390 °C and it is confirmed by the presence of the bands
at 2640–3100 cm−1 on the FTIR spectrum and the characteristic ions
with the m/z values 36,38,35,37. These results confirm the

8
M. Worzakowska, et al. Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxxx

Fig. 7. The FTIR spectra of the gaseous decomposition products for compounds 1–3 (a) and compound 4 (b) in air.a).

9
M. Worzakowska, et al. Journal of Analytical and Applied Pyrolysis xxx (xxxx) xxxx

Fig. 8. The QMS spectra for the decomposition product for compound 1–3 (a) and compound 4 (b) in air.

Scheme 2. The proposed decomposition path of the studied compounds in air.

10
M. Worzakowska, et al.
simultaneous fragmentation and pyrolysis processes of CeO, CeC and
CeN bonds, partial pyrolysis of the formed aromatic-rich residues,
dexarboxylation, dehydration and some oxidation processes of am-
monia to the corresponding nitrogen oxides between the temperatures
Tonset2 and Tfinal3.
The second decomposition stage spreads from Tonset4 to Tfinal4 with the
mass loss from ca. 44% to 47%. Heating the substances in air atmosphere
causes their full decomposition at the Tfinal4 temperature. Generally, at
this temperature range, the creation of CO2 (FTIR: 2300–2365 cm−1 and
669 cm−1, QMS: m/z: 44,12,45,46,22), H2O (FTIR: 3450-4000 cm−1 and
1300-1950 cm−1, CO (FTIR: 2050–2270 cm−1, QMS: m/z: 28,12,16,29)
and nitrogen oxides is observed. On the DSC curves, only the exothermic
signals Tonset4 and Tfinal4 appear, Fig. 6a. This demonstrates some che-
mical reactions comprising the fragmentation, pyrolysis and combustion
processes of the remaining parts of the tested compounds (aromatic-rich
residues).
4. Conclusions
The course of pyrolysis and combustion processes of imidazolidine-
based hybrids with diethyl butanedionate containing the following
substituents: 4−CH3, 4-Cl, 3-Cl and 3,4-Cl2 attached to the phenyl
moiety has been studied by the use of the simultaneous TG/DSC/FTIR/
QMS method. The thermal stabilities of the tested compounds in helium
and in air atmospheres can be ordered as follows: 4-CH3 < 4-Cl < 3-
Cl < 3,4-Cl2 in relation to the substituent attached at the phenyl
moiety. It testified that the thermal stability of the tested compounds
was strictly connected with the type and position of the substituent
attached to the benzene ring. Generally, on the basis of obtained results,
it can be concluded that the presence of electron-donating group at the
benzene ring decreases the thermal resistance of the tested compounds.
However, the electron-withdrawing groups attached to the benzene
ring caused a slight increase in their thermal stability. The results prove
that the pyrolysis and combustion processes of the studied substances
can be subdivided into two main stages preceded by their melting
where the first decomposition stage is composed of at least three steps.
The main gaseous decomposition products in inert and oxidative at-
mospheres were as follows: alcohol, alkene, aldehyde, CO2, H2O, N2,
CO, NH3, aromatics, fused aromatic rings and HCl (in the case of the
compound containing a 3,4-Cl2 substitution) and nitrogen oxides (in the
case of oxidative atmosphere). It indicated their complex decomposi-
tion mechanism comprising simultaneous pyrolysis, decarboxylation,
dehydration and oxidation processes under their heating in inert and
oxidative conditions.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jaap.2019.104686.
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