Aminomethylated derivatives of 2-propenyl- and 4-isopropenylphenols as antimicrobial additives for petroleum products

Article abstract of DOI:10.1134/S096554411001010X

A number of aminomethylated derivatives of 2-propenyl-, 4-isopropenylphenols have been synthesized and their antimicrobial properties have been studied in M-12 engine oil and TS-1 jet fuel (at concentrations of 1-2% and 0.3-0.5%, respectively). They have been found to possess bactericidal and fungicidal properties and significantly improve the antimicrobial properties of both of the materials (as compared to the well-known antimicrobial additive, 8-hydroxyquinoline). The presence of an alkenyl substituent along with an aminomethyl group in the structure of the substances in question has been demonstrated to enhance the antimicrobial properties. The formation of an intermolecular and intramolecular hydrogen bond in the initial and synthesized phenolic compounds has been studied.

Full text of DOI:10.1134/S096554411001010X

ISSN 0965ꢀ5441, Petroleum Chemistry, 2010, Vol. 50, No. 1, pp. 68–71. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.R. Bairamov, A.M. Magerramov, G.M. Mekhtieva, R.A. Abushev, M.A. Agaeva, S.A. Gasanova, I.G. Mamedov, 2010, published in Neftekhimiya, 2010, Vol. 50,
No. 1, pp. 69–72.
Aminomethylated Derivatives of 2ꢀPropenylꢀ
and 4ꢀIsopropenylphenols as Antimicrobial Additives
for Petroleum Products
M. R. Bairamov, A. M. Magerramov, G. M. Mekhtieva, R. A. Abushev,
M. A. Agaeva, S. A. Gasanova, and I. G. Mamedov
Baku State University, Baku, Azerbaijan
eꢀmail: gunka@mail.ru
Received June 11, 2008
Abstract—A number of aminomethylated derivatives of 2ꢀpropenylꢀ, 4ꢀisopropenylphenols have been synꢀ
thesized and their antimicrobial properties have been studied in Mꢀ12 engine oil and TSꢀ1 jet fuel (at conꢀ
centrations of 1–2% and 0.3–0.5%, respectively). They have been found to possess bactericidal and fungiꢀ
cidal properties and significantly improve the antimicrobial properties of both of the materials (as compared
to the wellꢀknown antimicrobial additive, 8ꢀhydroxyquinoline). The presence of an alkenyl substituent along
with an aminomethyl group in the structure of the substances in question has been demonstrated to enhance
the antimicrobial properties. The formation of an intermolecular and intramolecular hydrogen bond in the
initial and synthesized phenolic compounds has been studied.
DOI: 10.1134/S096554411001010X
Functionally substituted phenols are an object of
systematic research. Compounds containing heteroaꢀ
toms, multiple bonds, and other moieties that allow
for their modification in order to obtain new comꢀ
pounds with useful properties are of the greatest interꢀ
est both theoretically and practically [1–5].
EXPERIMENTAL
Aminomethylated 2ꢀpropenylphenol and 4ꢀisoꢀ
propenylphenol derivatives have been synthesized
using a known technique [6, 7] by their triple condenꢀ
sation with formaldehyde and secondary amines (by
the Mannich reaction). The reaction was carried out at
We have previously synthesized aminomethyl 70–75°С and an equimolar reactant ratio for 4–5 h.
derivatives of allylphenols, which were studied as antiꢀ The desired substances were extracted from the reacꢀ
microbial additives for petroleum products [6, 7]. In a tion mixture by converting them into the correspondꢀ
continuation of these studies, we synthesized amiꢀ ing quaternary ammonium salts through treatment
nomethyl derivatives of 2ꢀpropenylꢀ and 4ꢀisopropeꢀ with hydrogen chloride and subsequent decomposiꢀ
nylphenols and also examined them as antimicrobial tion by aqueous ammonia. The following substances
additives.
have been synthesized:
OH
R''
R
R'
where (1) R' = H; R'' = –CH=CH–CH3
R = –CH2–N(C2H5)2 (I),
(II),
(III);
O
CH2
N
CH2
N
(2) R'' = H; R' =
C CH2
CH3
R = –CH2–N(C2H5)2 (IV),
(V),
(VI).
O
CH2
N
CH2
N
68

AMINOMETHYLATED DERIVATIVES
69
The structures of these substances have been estabꢀ nylphenols in Mꢀ12 engine oil (at a concentration of
lished by NMR spectroscopy.
6ꢀDiethylaminomethylꢀ2ꢀpropenylphenol (I): yield
88.3%, nD20 1.5114; d420 1003.6 kg/m3, 1Н NMR (aceꢀ
1–2%) and TSꢀ1 jet fuel (at a concentration of 0.3–
0.5%) were tested by zone diffusion assay according to
GOST (State Standard) 9.052ꢀ88 and GOST 9.082ꢀ
77. The following microorganisms were studied:
tone d6,
δ
, ppm): 1.18 t (6Н, 2СН3); 1.89 d (3Н, СН3);
Mycobacterium lacticolium
, Staphyilococcus albus,
2.58 (4Н, 2СН2); 3.75 s (2H, СН2ꢀN); 6.29 m (1H,
q
E. coli, Mucor Pinicillium, and Aspergillus niger
,
.
CH=); 6.63 (1H, CH=); 6.65–7.3 (3H, aromatic);
10.5 s (1H, OH). 13C NMR spectrum: 12.3; 18.7; 46.8;
57.1; 118.7; 123.1; 123.9; 124.6; 125.2; 126.8; 128.5;
157.5.
6ꢀPiperidinomethylꢀ2ꢀpropenylphenol (II): yield
76.0%; nD20 1.5085; d420 1043.4 kg/m3; 1Н NMR (aceꢀ
Meatꢀpeptone agar (MPA) and wort agar (WA)
were taken to cultivate bacterial cultures and fungi,
respectively. In order to compare and detect the antiꢀ
microbial activity of these compounds, 8ꢀhydroxꢀ
yquinoline, a wellꢀknown antimicrobial additive for
lubricants and fuels, was used. Inoculation and cultiꢀ
vation were carried out as described in [6]. The effiꢀ
ciency of the antimicrobial action of the compounds
was determined in terms of the diameter of the microꢀ
organism growth inhibition area.
Microorganisms were inoculated in Petri dishes on
the surface of an agarized culture medium; then, pits
of a 4ꢀ to 5ꢀmm depth were made with a sterile 10ꢀmm
drill bit into which 0.3–0.5 ml of the samples were
introduced. The dishes were subsequently placed in a
thermostat and left to stay at 29–30°С over 2 days (for
tone d6,
СН3); 3.59
δ
, ppm): 1.35–1.71 m (6Н, 3СН2); 1.9
d (3Н,
s
(2Н,СН2–N); 6.15 m (1H, CH=); 6.62
(1H, CH=); 6.55–7.2 (3H, aromatic); 10.4 s (1H,
ÎH). 13C NMR spectrum: 18.9; 24.8; 26.7; 44.9; 62.8;
118.6; 123.4; 124.1; 124.8; 125.2; 128.1; 128.6; 156.9.
6ꢀmorpholinomethylꢀ2ꢀpropenylphenol (III): yield
80.7%, nD20 1.5085; d420 1043.4 kg/m3; 1Н NMR (aceꢀ
tone d6,
N(CН2)2); 3.65
δ
, ppm): 1.89 d (3Н, СН3); 2.55
t (4Н,
t
(4Н, О(СН2)2); 3.66
s (2Н, bacterial growth) or 3–4 days (for fungi).
СН2⎯N); 6.3 t (1H, CH=); 6.67 (1H, CH=); 6.7–7.4
13
(3H, aromatic); 10.55 s (1H, OH). C NMR: 18.3;
RESULTS AND DISCUSSION
43.4; 62.3; 66.7; 118.3; 118.9; 121.8; 125.7; 126.1;
126.9; 127.4; 135.8
The results of the study show that the yields of the
desired compounds vary from 65.0 to 88.3% dependꢀ
ing on the nature of the reactant amines and phenols.
The greatest yields can be achieved with the use of
morpholine or diethylamine and 2ꢀpropenylphenol.
The aminomethylated 2ꢀpropenylꢀ and 4ꢀisopropeꢀ
nylphenol derivatives and the reactant alkenylphenols
were investigated by the NMR spectroscopy techꢀ
nique. It was found that these phenols experience
intermolecular hydrogen bonding and the products’
Mannich bases contain a rather strong intramolecular
bond, supposedly due to the electron pair of the amiꢀ
2ꢀDiethylaminomethylꢀ4ꢀisopropenylphenol (IV)
yield 70%; nD20 1.5492; d420 1002.2 kg/m3; 1Н NMR
(acetone d6, , ppm): 1.04 t (6Н, 2СН3); 2.05 с (3Н,
СН3–С); 2.57 (4Н, N(CН2)2); 3.5 (2Н, N–CH2–
:
δ
q
s
Ar); 4.91 and 5.13 AB (2Н, СН2=); 6.8–7.2 (3Н,
С6Н3); 8.9 (1H, OH).
2ꢀPiperidinomethylꢀ4ꢀisopropenylphenol (V): yield
65.0%; nD20 1.5612; d420 1022.8 kg/m3; 1Н NMR (aceꢀ
tone d6, , ppm): 1.71 m (6H, of the 3СН2 cycle),
δ
nomethyl nitrogen atom located in the oꢀposition with
2.01 s (3Н, СН3–С); 2.62 m (4H, of the N(CН2)2
cycle); 3.49 s (2Н, NCН2–Ar); 4.90 and 5.12 AB (2Н,
СН2=); 6.96–7.3 (3Н, С6Н3); 9.2 (1H, OH).
2ꢀMorpholinomethylꢀ4ꢀisopropenylphenol
yield 75.7%; nD20 1.5645; d420 1021.8 kg/m3; 1Н NMR
respect to the phenol hydroxyl and the OH hydrogen.
The 1H NMR spectra of dilute solutions of 2ꢀproꢀ
penylꢀ and 4ꢀisopropenylphenols in CCl4 feature a
shift of hydroxyl proton signals from 6.5 to 4.8 ppm.
However, no such concentrationꢀinduced shift is
(VI):
observed for the oꢀaminomethyl derivatives. Owing to
(acetone d6,
N(CН2)2); 3.45
δ
, ppm): 1.99 s (3Н, СН3); 2.32
(2Н, NCН2⎯Ar); 3.55
m
m
(4Н,
(4Н,
the formation of the N…H intramolecular hydrogen
bond, hydroxyl group signals in these compounds are
detected in the range of 8.9–10.55 ppm.
s
О(СН2)2); 4.8 and 5.12 s (2Н, СН2=); 6.6–7.2 (3H,
aromatic); 9.5 (1H, OH). 13C NMR: 22.3; 53.6; 62.3;
66.7; 109.9; 116.4; 119.9; 126.4; 126.6; 133.1; 143.1;
157.4.
1
Furthermore, H NMR spectroscopic studies of
the aminomethyl derivatives of alkenylphenols up to
the boiling temperature of СCl4 revealed a minor shift
of the hydroxyl group signals, thereby unequivocally
confirming that the intramolecular hydrogen bond is
quite strong [8, 9].
The nature of the aminomethyl moiety in all derivꢀ
atives of both 2ꢀpropenylꢀ and 4ꢀisopropenylphenol
NMR spectroscopy was also used to investigate the
formation of an intermolecular and intramolecular
hydrogen bond in the precursors and products (I–VI)
in the temperature range of 25–70°С and at concenꢀ
trations of 0.1–50% in CCl4
.
The antimicrobial properties of the aminomethyꢀ does not have any significant influence on the strength
lated derivatives of 2ꢀpropenylꢀ and 4ꢀisopropeꢀ of the intramolecular hydrogen bond.
PETROLEUM CHEMISTRY Vol. 50
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2010

70
BAIRAMOV et al.
Table 1. Results of testing the substances in Mꢀ12 oil in MPA and WA culture media
Microorganism killing zone, cm
Bacteria
Fungi
Mycoꢀ
No.
Compound
Conc., %
bacteriꢀ Staphyꢀ
um lactiꢀ lococcus
colium
Penicilliꢀ Aspergilꢀ
E. coli Mucor
um
lus niger
I
2
1
1.3–1.5
0.8–0.9
+ +
2.0–2.4
1.1–1.2
+ +
+ +
+ +
OH
(C2H5)2N CH2
CH CH CH3
CH CH CH3
CH CH CH3
II
2
1
1.7–1.8
1.1–1.2
+ +
+ +
+ +
+ +
1.5–1.7
+ +
+ +
+ +
OH
OH
N CH2
N CH2
III
IV
2
1
1.7–1.9 1.9–2.1
1.2–1.4 1.1–1.3
2.1–2.5
1.3–1.6
O
2
1
1.7–1.8
0.9–1.2
+ +
+ +
+ +
+ +
2.0–2.5
1.5–1.8
+ +
+ +
1.3–1.5
0.5–0.6
OH
⎯
N(C H )
CH2 CH CH
2
5 2
3
CH3 C CH2
N CH2
V
2
1
2.2–2.7
1.1–1.3
2.5–2.7 1.8–2.2 2.6–3.0
1.2–1.5 0.8–1.1 1.5–1.7
+ +
OH
CH3 C CH2
VI
VII
2
1
2.5–2.8
1.2–1.6
2.8–3.3 2.9–3.3 2.5–2.7 0.9–1.1
1.5–1.8 1.3–1.5 1.5–1.8 0.4–0.5
OH
CH2
N
O
CH3 C CH2
OH
2
1
+ +
0.9–1.1
0.5–1.6
+ +
1.8–2.1
1.2–1.3
+ +
CH2
N
O
VIII 8ꢀHydroxyquinoline (reference)
IX Mꢀ12 oil (control)
2
1
–
0.7–0.9 0.9–1.1 1.6–1.8
+ +
+
+ +
+
+ +
+
+
+
+
+
0.7–1.0
+
As can be seen from the above NMR data, the that they consist of 95% transꢀ and 5% cisꢀisomers
intramolecular hydrogen bond in the structures of (this is proved by the corresponding signals).
aminomethylated 2ꢀpropenylphenol is stronger
The results of testing the aminomethylated derivaꢀ
(10.4–10.55 ppm) than in the derivatives of 4ꢀisoproꢀ
tives of 2ꢀpropenylꢀ and 4ꢀisopropenylphenols for
pylphenol (8.9–9.5 ppm).
antimicrobial properties are given in Tables 1 and 2.
The results of spectral analyses of aminomethyꢀ
The data of Tables 1 and 2 make it evident that all
lated derivatives of 2ꢀpropenylphenol also have shown of the substances in question (I–VI) in Mꢀ12 engine
PETROLEUM CHEMISTRY Vol. 50
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AMINOMETHYLATED DERIVATIVES
71
Table 2. Results of testing the substances in TSꢀ1 fuel in MPA and WA culture media (compound numbers as in Table 1)
Microorganism killing zone, cm
No.
Conc., %
Bacteria
Staphylococcus
Fungi
E. coli
Mucor
Penicillium
Aspergillus niger
I
0.5
0.3
0.5
0.3
0.5
0.3
0.5
0.3
0.5
0.3
0.5
0.3
0.5
0.3
0.5
0.3
–
1.5–2.0
0.7–0.9
3.7–3.0
1.0–1.3
+ +
+ +
+ +
3.7–3.8
1.8–1.9
3.1–3.5
1.7–1.8
+ +
2.7–3.5
1.6–1.8
3.3–3.8
1.4–1.7
3.3–3.7
1.7–1.8
2.9–3.5
1.5–1.6
3.1–3.5
1.5–1.7
2.2–2.5
1.3–1.4
1.9–2.0
1.0–1.1
+ +
II
+ +
+ +
3.7–3.9
1.8–2.0
3.9–4.1
1.9–2.3
3.7–4.0
1.8–2.1
3.1–3.4
1.6–1.9
2.6–2.9
1.7–2.0
+ +
III
IV
V
3.5–3.7
1.9–2.2
3.3–3.5
1.9–2.0
+ +
3.7–4.2
1.8–2.1
+ +
+ +
+ +
+ +
+ +
+ +
+
VI
VII
VIII
IX
+ +
+ +
2.2–2.5
1.1–1.2
3.3–3.5
1.7–1.8
+
2.9–3.0
1.5–1.6
+
+ +
+
+
oil and TSꢀ1 jet fuel at the investigated concentrations that unlike aminomethyl derivatives of allylphenols,
the substances in question exhibit fungicidal properꢀ
ties in addition to bactericidal properties at the same
concentrations in oil and fuel.
possess bactericidal and fungicidal properties. In
terms of efficiency, they are not inferior to the wellꢀ
known antimicrobial additive 8ꢀhydroxyquinoline and
often prove superior to it. Of the aminomethyl derivaꢀ
tives of alkenylphenols tested in Mꢀ12 oil, compound
I only has bactericidal properties, whereas compound
VI containing the morpholinomethyl moiety in the
Thus, the Mannich bases bearing alkenyl groups on
the aromatic ring synthesized in this work exhibit quite
a high antimicrobial activity and can be used for the
protection of petroleum products against microbial
degradation during their storage and transportation.
oꢀposition and the conjugate isopropenyl group in the
ꢀposition with respect to the hydroxyl group effiꢀ
p
ciently inhibits the growth of both bacteria and fungi.
REFERENCES
Studies of the phenol compounds in TSꢀ1 fuel
revealed that the best bactericidal and fungicidal propꢀ
erties are exhibited by compounds containing both
piperidine and propenyl (compound II), as well as
diethylaminomethyl and isopropenyl (IV) fragments.
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In order to clarify the contribution of the multiple
bond to the antimicrobial properties of aminomethyl
derivatives of 2ꢀpropenylꢀ and 4ꢀisopropenylphenols,
we examined 2ꢀmorpholinomethylphenol (VII),
which has been obtained by the condensation of pheꢀ
nol with formaldehyde and morpholine and does not
contain an alkenyl group. A comparison of the results
of the investigation shows that the presence of a subꢀ
stituent with a multiple bond on the phenyl ring
enhances the antimicrobial properties of the comꢀ
pounds.
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PETROLEUM CHEMISTRY Vol. 50
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2010