Biocidal and anticorrosive effect of 2-aminothiazole derivatives used as additives to jet fuels

Article abstract of DOI:10.1023/A:1013081926468

The effect of 2-aminothiazole derivatives on the biological resistance and corrosion activity of jet fuels was studied under conditions of water condensation.

Full text of DOI:10.1023/A:1013081926468

Russian Journal of Applied Chemistry, Vol. 74, No. 6, 2001, pp. 998 1001. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 6, 2001,
pp. 971 974.
Original Russian Text Copyright
2001 by Karpov, Nazarenko, Pekarevskii, Potekhin.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Biocidal and Anticorrosive Effect of 2-Aminothiazole
Derivatives Used as Additives to Jet Fuels
K. A. Karpov, A. V. Nazarenko, B. V. Pekarevskii, and V. M. Potekhin
St. Petersburg State Technological Institute, St. Petersburg, Russia
Received April 16, 2001
Abstract The effect of 2-aminothiazole derivatives on the biological resistance and corrosion activity of
jet fuels was studied under conditions of water condensation.
2
-Aminothiazole derivatives are widely used in
the possibility of fuel contamination [7]; it can be
fully precluded only by using special additives.
pharmacology [1]. Aminothiazoles exhibit antimicro-
bial [1 3] and antioxidant [4] activity. Some disubsti-
tuted aminothiazole derivatives are used as antioxidant
additives to hydrocarbon fuels, mineral and synthetic
lubricating oils, solid paraffins, polyolefins, and ani-
mal and vegetable fats [5]. sym-Triazine derivatives
containing substituents with 2-aminothiazole frag-
ments are effective anticorrosive, antiwear, and anti-
scuff additives to lubricating oils [6].
EXPERIMENTAL
Compounds I IV were prepared by the Hansch
procedure, namely, by reactions of thiourea with , -
dichlorodiethyl ether (I) [10], with iodine and acetone
(II) [11, 12], with iodine and acetophenone (III)
[10, 11], and with iodine and 1 -acetonaphthone (IV).
The purity and structures of I IV were proved by
TLC and by IR and NMR spectroscopy. The relevant
physicochemical data are listed in Table 1.
With the aim to look for high-performance addi-
tives of polyfunctional effect among 2-aminothiazole
derivatives, we studied the compounds of the general
formula
The biological resistance of jet fuels RT anbd TS-1
[
GOST (State Standard) 10227 86, intended for use
R
N
in different climatic zones] protected with biocidal
additives was determined according to GOST 9.023
7
NH2 ,
S
4 within the framework of a common system of meas-
ures for corrosion and aging protection. The proce-
dure involves incubation of fuels with additives in
contact with an aqueous-mineral medium containing
test microorganisms which actively grow in the fuel
with no additive. Incubation was performed for 15
where R = H (I), Me (II), Ph (III), and 1-naphthyl
IV).
(
In this work, we studied the biocidal and anticor-
rosive properties of 2-aminothiazole derivatives I IV
when used as additives to jet fuels.
Table 1. Yields, melting points, and retention factors of
Biocidal additives to fuels are used to suppress
the biological damage by microorganisms, impairing
the service properties of fuels [7 9]. The effect of
these additives is based on inhibiting the activity of
microorganisms contaminating the fuel and living in
hydrocarbon medium. Biocidal additives are active in
concentrations that do not exceed the level prescribed
for additives serving for other purposes. In any proc-
esses of fuel purification, the danger of fuel de-
terioration by microorganisms is decreased. However,
these measures can only diminish, but not prevent
2
-aminothiazole derivatives I IV
Compound no. Yield, %
mp,
C
Rf*
I
II
III
90
60
80
88 1, 90 [10]
40 41, 42 [11]
152 153, 151 152 0.61
[11]
0.44
0.49
IV
80
165
1
0.68
*
Eluent 2-propanol octane, 1 : 1.
070-4272/01/7406-0998 $25.00 2001 MAIK Nauka/Interperiodica
1

BIOCIDAL AND ANTICORROSIVE EFFECT OF 2-AMINOTHIAZOLE DERIVATIVES
999
Table 2. Microbial resistance of jet fuels in the presence of 2-aminothiazole derivatives I IV (1 10 3 M)
*
4
-Substituent in aminothiazole
Test culture
Unprotected fuel
Ionol
H
Me
Ph
1-naphthyl
RT jet fuel
+
Pseudomonas aeruginosa
Candida utilis
Cladosporium resinae
++
++
+
+
+
+
+
+
+
+
++
++
+
+
TS-1 jet fuel
Pseudomonas aeruginosa
Candida utilis
Cladosporium resinae
++
++
+
+
+
+
++
++
+
*
(
) No growth, (+) slight pigmentation and/or turbidization of the medium, and (++) turbid medium and/or formation
of a flaky suspension.
Table 3. Sensitivity of test microorganisms to 2-aminothiazole derivatives I IV (4 10 4 M), evaluated by diffusion
into agar
Diameter of the spot of microorganism growth delay, mm
Test culture
4-substituent in aminothiazole
Ionol
H
Me
Ph
1-naphthyl
Staphylococcus aureus
Escherichia coli
Bacillus cereus
Pseudomonas aeruginosa
Candida utilis
Penicillium aurantiogriseum
Aspergillus niger
0
2
4
1
0
0
0
8
4
8
2
0
6
8
0
0
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
days under conditions optimal for the microbial growth.
The extent of fuel protection with a biocidal additive
was evaluated by comparing the samples with unpro-
tected fuel (control). The results of the tests are listed
in Table 2.
Table 3 shows how 2-aminothiazole derivatives
affect the microbial growth. With respect to the effi-
ciency of the bactericidal effect the compounds can
be ranked in the order II > I > III.
According to our results, the structure of the 4-sub-
stituent in 2-aminothiazole derivatives affects the
activity toward test microorganisms. Compound II,
containing the methyl substituent, is characterized by
the largest diameters of growth delay spots. Aromatic
substituents drastically decrease the biocidal effect of
the additives. Compound IV showed no biocidal prop-
erties under the experimental conditions.
Our results show that 2-aminothiazole derivatives
I IV are fairly effective biocidal additives. In this
connection, it is of interest to compare the microbial
resistance of jet fuels containing additives I IV and
commercial additive Ionol (2,6-di-tert-butyl-4-methyl-
phenol). As seen from Table 2, this additive shows no
biocidal properties, and the microbial impact tests
give results identical with those for the control sample.
The biological activity of 2-aminothiazole deriva-
tives I IV correlates with the electron-donor and
electron-acceptor power of substituents. According to
[14], compounds containing heteroatoms and multiple
bonds can enter into donor acceptor interactions with
biopolymers, disturbing the normal vital activity of
a microorganism. In our case, compound II containing
To obtain quantitative characteristics of the bio-
cidal effect of I IV, we evaluated the sensitivity of
test microorganisms to 2-aminothiazole derivatives by
the method of duffusion into agar [13]. For the tests
we used the standard culture media: Czapek agar and
meat peptone agar.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 74 No. 6 2001

1000
KARPOV et al.
Table 4. Corrosion resistance of St.3 steel in hydrated RT
K
K
=
,
(2)
jet fuel in the presence of 2-aminothiazole derivatives
K
4
I IV (98 C, additive concentration 5 10 M)
where K is the corrosion activity of the fuel contain-
ing an additive (g m ).
Additive
K, g m 2
2
1
.71
The corrosion activities and corrosion inhibition
factors are listed in Table 4.
I
II
III
IV
Ionol
1.32
1.24
0.78
0.57
1.36
0.30
0.38
1.19
2.00
0.26
Thus, 2-aminothiazole derivatives show high anti-
corrosive power and surpass commercial inhibitor
Ionol in performance. Along with the already noted
inhibition of acid formation in fuel, the mechanism of
the anticorrosive effect of 2-aminothiazole derivatives
may also involve formation of a monomolecular layer
of compounds (as a rule, coordination compounds) on
the metal surface, insulating it from the hydrocarbon
medium [19].
an electron-donor methyl substituent exhibits the
strongest biocidal effect, whereas compounds III and
IV, containing aromatic substituents lowering the
electron density in the thiazole ring, show a weak
biological activity.
CONCLUSIONS
It is believed that antioxidants mainly behave as
biocides [15]. However, as shown in Table 3, com-
mercial oxidation inhibitor Ionol shows no biocidal
effect at all.
(1) 2-Aminothiazole derivatives exhibit biocidal
properties and can be used as additives to RT and
TS-1 jet fuels.
As biocidal additives are used ammonia and amine
derivatives, potassium permanganate, copper sulfate,
zinc chloride, and a number of organic compounds
(2) The biocidal properties of I IV depend on the
nature of a 4-substituent.
(3) Aminothiazoles I IV exhibit anticorrosive
[
[
16]. However, many of them stimulate corrosion
17]. The corrosion activity of hydrocarbon media
activity in RT fuel under conditions of water conden-
sation.
toward metal surfaces is, in particular, due to acids
18] formed by oxidation. 2-Aminothiazole deriva-
[
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