Synthesis of aminomethylated derivatives of allylphenols and study of their antimicrobial characteristics in motor oil

Article abstract of DOI:10.1134/S1070427207040295

A series of nitrogen-containing compounds was synthesized by Mannich condensation of allylsubstituted derivatives of phenol and o-and p-cresols with formaldehyde and secondary amines. These compounds were studied as antimicrobial additives to motor oil (at a content of 1-2 wt %).

Full text of DOI:10.1134/S1070427207040295

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 4, pp. 665 668.
Pleiades Publishing, Ltd., 2007.
Original Russian Text A.M. Magerramov, M.R. Bairamov, G.M. Mekhtieva, M.A. Agaeva, P.Sh. Mamedova, D.M. Kulieva, I.G. Mamedov, 2007,
published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80, No. 4, pp. 681 685.
CHEMISTRY
OF FOSSIL FUEL
Synthesis of Aminomethylated Derivatives of Allylphenols
and Study of Their Antimicrobial Characteristics in Motor Oil
A. M. Magerramov, M. R. Bairamov, G. M. Mekhtieva, M. A. Agaeva,
P. Sh. Mamedova, D. M. Kulieva, and I. G. Mamedov
Baku State University, Baku, Azerbaijan
Institute of Chemistry of Fuel Additives, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Received November 29, 2006
Abstract A series of nitrogen-containing compounds was synthesized by Mannich condensation of allyl-
substituted derivatives of phenol and o- and p-cresols with formaldehyde and secondary amines. These com-
pounds were studied as antimicrobial additives to motor oil (at a content of 1 2 wt %).
DOI: 10.1134/S1070427207040295
Nitrogen-containing derivatives of phenols, and in
particular Mannich’s bases are the subject of systemat-
ic studies and, despite numerous papers in this field,
still attract researchers’ interest, which is caused by
their useful functional characteristics [1 5].
reaction proceeds well at the equimolar ratio of reac-
tants at 70 75 and duration of 4 5 h to give the cor-
responding aminomethylated allyl-containing phenols.
The target compounds were isolated from the reaction
mixture by vacuum distillation. The reaction scheme
is as follows:
With the aim to synthesize new nitrogen-containing
phenols in whole structure an allyl fragment is pres-
ent, along with aminomethyl group, we examined in
this study the reactions of ternary Mannich condensa-
tion of 2-allyl-substituted derivatives of phenol and
also o- and p-cresols with formaldehyde and sec-
ondary amines.
OH
R
+ CH2O + (R")2NH
R
OH
(1)
(R")2N CH2
As can be suggested, the presence of the above sub-
stituents in the aromatic core of phenols should impart
additional functional properties and, in particular,
antimicrobial properties to phenols. Biological protec-
tion of oils, fuels, polymers, and other materials is
topical problem, since the microbial corrosion of
the above materials adversely affects the national
economy [6].
I IV
OH
CH3
(2)
V VIII
CH2 N(R")2
OH
(3)
(R")2N CH2
EXPERIMENTAL
IX XII
With the aim to synthesize phenol compounds si-
multaneously containing an allyl group and amine
fragment, we carried out ternary condensation of allyl-
substituted derivatives of phenol and o- and p-cresols
with formaldehyde and secondary amines (under
the conditions of Mannich’s reaction).
CH3
where (1) at R and R = H; R = CH3 (I), C2H5 (II);
(IV); (2) at R = CH3;
N O
R = H; R = CH3 (V), C2H5 (VI); NR2 =
(VIII); (3) at R = H; R = CH3; R =
CH3; R = CH3 (IX), C2H5 (X); NR
NR2
=
(III),
N
N
N
(VII),
N O
=
Formaldehyde was used in the form of a 37% aqu-
eous solution (Formalin). It was found that the above
2
(XI),
(XII).
N O
665

666
MAGERRAMOV et al.
The initial allylphenols were synthesized by the
The characteristics of the compounds synthesized
are listed in Table 1. Their yield varies from 48.0
to 70.6%, depending on the nature of amine and ini-
tial phenol compound. All these compounds, except
4-methyl-2-morpholinomethyl-6-allylphenol (XII), are
well-known procedure [7], Claisen thermal rearrange-
ment of allyl ethers of phenol and o- and p-cresols,
within 3 6 h and were isolated from the reaction
mixture by distillation in a high vacuum.
Table 1. Characteristics of aminomethylated allylphenols
n2D0
d420, kg m
3
Compound
OH
Yeld, % of theoretical
bp, C/P, mm Hg
48.4
70.6
110 111/0.8
1.5298
1015.9
(CH3)2N CH2
(C2H5)2N CH2
N CH2
CH2 CH CH2
I
OH
113 114/0.7
118 120/0.8
1.5285
1.5010
993.4
CH2 CH CH2 II
OH
OH
CH2 CH CH2 III
CH2 CH CH2 IV
50.0
1048.5
O
N CH2
OH
70.8
45.3
118 119/0.6
111 113/0.7
1.5030
1.5012
1091.3
1023.8
CH3
CH2 CH CH2
V
CH2 N(CH3)2
OH
CH3
CH3
CH2 CH CH2
VI
60.0
58.5
64.0
119 120/0.7
124 126/0.6
126 128/0.5
1.5040
1.5047
1.5040
1007.9
1051.4
1143.5
CH2 N(C2H5)2
OH
CH2 CH CH2
VII
CH2
OH
N
CH3
CH2 CH CH2
VIII
CH2
N
O
OH
(CH3)2N CH2
CH2 CH CH2 IX
48.0
110 112/0.6
1.5240
973.2
CH3
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 4 2007

SYNTHESIS OF AMINOMETHYLATED DERIVATIVES OF ALLYLPHENOLS
Table 1. (Contd.)
Compound
667
3
Yeld, % of theoretical
bp, C/P, mm Hg
n2D0
d420, kg m
OH
(C2H5)2N CH2
CH2 CH CH2 X
63.2
118 120/0.6
1.5210
971.8
CH3
OH
N CH2
CH2 CH CH2 XI
52.7
65.2
127 129/0.7
128 130/0.6
1.5064
1033.4
CH3
OH
O
N CH2
CH2 CH CH2 XII
CH3
Table 2. Results of studying antimicrobial characteristics of aminomethylated derivatives of allylphenols in M-12 motor oil
Area of bacterium
annihilation
Area of fungus
annihilation
Concentration
in oil, wt %
Compound
cm
2-Dimethylaminomethyl-6-allylphenol (I)
2-Diethylaminomethyl-6-allylphenol (II)
1.0
2.0
1.0
2.0
1.0
2.0
1.0
2.0
1.0
2.0
1.0
2.0
1.0
2.0
1.0
2.0
1.0
2.0
1.0
2.0
1.0
2.0
1.0
2.0
1.0
2.0
+ +
+ +
+ +
+ +
+ +
0.8 1.0
1.6 2.0
0.9 1.0
1.9 2.0
+ +
1.0 1.2
0.7 0.8
1.5 1.7
0.8 1.0
1.7 2.0
0.6 0.7
1.3 1.5
+ +
1.0 1.1
0.7 1.0
1.5 2.1
+ +
1.0 1.1
0.7 1.0
1.4 2.0
0.6 0.9
1.3 1.9
0.6 0.9
1.3 1.9
+ +
2-Piperidinomethyl-6-allylphenol (III)
+ +
2-Morpholinomethyl-6-allylphenol (IV)
0.9 1.0
1.9 2.0
+ +
+ +
+ +
1.0 1.1
+ +
+ +
+ +
+ +
+
+ +
+ +
+ +
+ +
+ +
1.1 1.4
2.2 2.9
0.7 1.0
1.5 2.0
+ +
2-Allyl-4-dimethylaminomethyl-6-methylphenol (V)
6-Methyl-2-allyl-4-diethylaminomethylphanol (VI)
6-Methyl-2-allyl-4-piperidinomethylphenol (VII)
6-Methyl-2-allyl-4-morpholinomethylphenol (VIII)
4-Methyl-2-dimethylaminomethyl-6-allylphenol (IX)
4-Methyl-2-diethylaminomethyl-6-allylphenol (X)
4-Methyl-2-piperidinomethyl-6-allylphenol (XI)
4-Methyl-2-morpholinomethyl-6-allylphenol (XII)
8-Quinolinol (reference) (XIII)
+ +
+ +
M-12 motor oil (XIV) (without additive)
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 4 2007

668
MAGERRAMOV et al.
viscous liquid substances colored from light yellow
to brown and readily soluble in aromatic solvents.
4-Methyl-2-morpholinomethyl-6-allylphenol is a light-
straw-colored crystalline substance with mp 43 C.
interest and can find application as antimicrobial ad-
ditives to lubricating oils.
CONCLUSION
The structures of all the synthesized aminometh-
ylated derivatives of allylphenols were confirmed by
the IR and NMR data.
Aminomethylated derivatives of allylphenols syn-
thesized by ternary Mannich condensation of allyl-
substituted derivatives of phenol and o- and p-cresols
with formaldehyde and secondary amines, when added
at a content of 1 2 wt %, have high fungicidal activity
with respect to mold fungi. Compounds IV and XII
containing cyclic amine fragment in their structures
have also high bactericidal properties (in comparison
with the reference, 8-quinolinol).
All the compounds were tested as antimicrobial
additives to the M-12 motor oil at a content of 1 and
2 wt %. The operations were performed according to
GOSTs (State Standards) 9.082 77 and 9.052 88.
The nutrient medium for growing the bacterial cul-
ture was meat-extract agar (MEA), and for growing
the fungus culture, wort agar (WA). The comparison
was performed with 8-quinolinol (reference). The res-
ults of the tests are presented in Table 2.
REFERENECES
1. US Patent no. 6179885. Compositions Containing
Mannich’s Aromatic Compounds and Procedures of
Their Synthesis, 2001, Ref. Zh. Khim., 2002,
0202-19P187P.
2. Kondrat’ev, V.V., Kirillov, N.S., and Bobyr’, O.V.,
Khim. Tekhnol., 2005, no. 7, pp. 13 14.
3. Zui Baoyou and Xu Danqion, J. Chem. Ind. Eng., 2004,
As can be seen from Table 2, all the studied amino-
methylated derivatives of allylphenols exhibit a fun-
gicidal activity. The diameter of the area of depression
of fungus growth, depending on the compound struc-
ture and its concentration, is, on the average, 0.8 1.0
(at a content of 1 wt %) and 1.4 2.0 cm (at a content
of 2 wt %).
vol. 55, no. 12, pp. 2043 2046.
4. Terada Masahiro, J. Am. Chem. Soc., 2004, vol. 126,
Morpholine-substituted allylphenols also have bac-
tericidial properties and are second in these properties
only to 8-quinolinol (reference). As can be seen from
Table 2, the latter has no fungicidal activity and
the fungus growth was not suppressed in its presence
even at a content of 2 wt %. As regards spent M-12
oil, it shows no resistance to fungi and bacteria.
The results of comparison tests show that the amino-
methylated derivatives of allylphenols are of practical
no. 17, pp. 5356 5357.
5. Kharitonova, N.I., Burilov, A.N., and Pudovik, M.A.,
Izv. Ross. Akad. Nauk, Ser. Khim., 2003, no. 3,
pp. 694 696.
6. Andreyuk, E.I., Bilai, V.M., and Koval’, E.Z., Mikrob-
naya korroziya i ee vozbuditeli (Microbial Corrosion
and Its Pathogens), Kiev: Naukova Dumka, 1980.
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tierkunst, Leipzig: Johann Ambrosius Barth, 1964.
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