Synthesis and transformations of aziridinesulfonamide derivatives and their investigation as lubricant additives

Article abstract of DOI:10.1134/S0965544109030128

The methods for the synthesis of aziridinesulfonamide derivatives by chlorine substitution in N-β-chloroalkylsulfonamides were developed. It was found that the chlorine atom in the 3-position of aziridinesulfonamides is more reactive than that in the 4-po

Full text of DOI:10.1134/S0965544109030128

ISSN 0965-5441, Petroleum Chemistry, 2009, Vol. 49, No. 3, pp. 254–260. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © S.A. Mamedov, F.A. Fatali-zade, N.P. Ladokhina, M.F. Farzaliev, M.E. Musaeva, 2009, published in Neftekhimiya, 2009, Vol. 49, No. 3, pp. 272–277.
Synthesis and Transformations of Aziridinesulfonamide
Derivatives and Their Investigation as Lubricant Additives
S. A. Mamedov, F. A. Fatali-zade, N. P. Ladokhina, M. F. Farzaliev, and M. E. Musaeva
Institute of Chemistry of Additives, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
e-mail: nina_fuad@rambler.ru
Received April 08, 2008
Abstract—The methods for the synthesis of aziridinesulfonamide derivatives by chlorine substitution in N-β-
chloroalkylsulfonamides were developed. It was found that the chlorine atom in the 3-position of aziridine-
sulfonamides is more reactive than that in the 4-position. It was found that the reactions of 3- and 4-chloroalky-
laziridinesulfonamides with amylmercaptan in the presence of alkali lead to the replacement of the chlorine
atom with the hydroxyl group along with the opening of the aziridine cycle. The reaction of 4-chloroalkylazir-
idinesulfonamides with 2 moles of amylmercaptan results in both chlorine substitution and aziridine cycle
opening. The investigation of the synthesized compounds as additives for lubricants showed their high anticor-
rosive, antioxidant, and antiwear efficiency.
DOI: 10.1134/S0965544109030128
Previously [1], we have investigated conditions for
the synthesis of β-chloroalkylarenelsulfonamides via
the reaction of N-β-chlorosulfonamides with α-olefins.
The reactivity of chlorine in the N-β position towards
various nucleophiles has been investigated. Among N-
β-chloroalkylarenesulfonamide derivatives, their aziri-
dine derivatives are of particular interest. These com-
pounds are widely used for the synthesis of aminopyr-
roles [2, 3] and imidazoles [4, 5].
2-Alkyl(or 2-chloroalkyl, or 3-chloroalkyl)-N-(4-
chlorobenzenesulfonyl)aziridines (4–6)
General procedure. To a solution of 0.5 mol of N-
(2-chlorohexyl)-4-chlorobenzenesulfonamide (1), or
N-(1,5-dichloro-2-nonyl)-4-chlorobenzenesulfona-
mide (2), or N-(2,4-dichlorononyl)-4-chlorobenzene-
sulfonamide (3) in 200–250 ml of benzene, 190 ml of
10% aqueous NaOH solution was added at 10–20°ë.
The mixture was stirred at 20°ë for 60 min. The ben-
zene layer was separated, washed with water until neu-
tral reaction, and dried. Benzene was distilled off, and
the residue was distilled under a vacuum.
The aziridine cycle is easily opened even by potas-
sium thiocyanate to form thiazolidines [6, 7], which
demonstrates its high reactivity.
2-(3-Hydroxyheptyl)-N-(4-
The synthesis of aziridinesulfonamides is usually
carried out by the reaction of sulfonyl chlorides with
ethyleneimine at 30–35°ë in the presence of a base [8].
However, the most practical reagents for the synthesis
of aziridinesulfonamides are N-β-chlorosubstituted sul-
fonamides (1–3) previously described in [1].
chlorobenzenesulfonyl)aziridine (7)
To a solution of 38.6 g (0.1 mol) of N-(1,5-dichloro-
2-nonyl)-4-chlorobenzenesulfonamide (2) in 100 ml of
benzene, 32 ml of 20% NaOH aqueous solution was
added at 30–32°ë. The mixture was left to stay over-
night; then, the benzene layer was separated, washed
with water, and dried. Benzene was distilled off, and the
residue was distilled under a vacuum.
EXPERIMENTAL
All NMR spectra were recorded on Varian and Tesla
spectrometers operating at 60 and 90 MHz in CCL4, or
CF3CééH solutions with HMDS as an internal stan-
dard. IR spectra were recorded on UR-20 and Specord
2-(4-Hydroxyheptyl)-N-(4-
chlorobenzenesulfonyl)aziridine (8)
To a solution of 38.6 g (0.1 mol) of N-(2,4-dichlo-
rononyl)-4-chlorobenzenesulfonamide (3) in 100 ml of
75 IR spectrometers. The physicochemical characteris- benzene, 32 ml of 20% NaOH aqueous solution was
added. The mixture was refluxed at 78–80°ë for 60 min.
After cooling, the benzene layer was separated and
dried. Benzene was distilled off, and the residue was
distilled under a vacuum.
tics of the compounds are given in Table 1.
The synthesized compounds were examined as
additives according to standard procedures.
254

SYNTHESIS AND TRANSFORMATIONS OF AZIRIDINESULFONAMIDE DERIVATIVES
Table 1. Physicochemical characteristics of compounds 4–13
Found/calculated, %
255
Compound no. Yield, %
Tbp, °C (mmHg)
d240
n2D0
C
H
H
52.69
------------
52.46
5.98
---------
5.86
5.42
---------
5.09
4
5
88.5
80.2
76.4
74.9
81.8
78.9
76.8
72.6
75.0
77.9
65–66/0.4
130–132/0.1
142–143/0.4
142–143/0.1
161–163/0.2
174–175/0.3
1.0788
1.2159
1.2183
1.2219
1.2259
1.1766
1.4719
1.5332
1.5340
1.5380
1.5399
1.5266
1.5238
1.5267
1.5300
1.5288
51.80
------------
51.27
6.55
---------
6.02
3.80
---------
3.99
51.60
------------
51.27
6.35
---------
6.02
3.66
---------
3.99
6
54.55
------------
54.29
6.92
---------
6.68
4.22
---------
4.22
7
54.41
------------
54.29
6.92
---------
6.68
4.48
---------
4.22
8
60.88
------------
60.58
7.67
---------
7.34
4.17
---------
3.92
9
55.45
------------
55.09
8.14
---------
7.85
3.48
---------
3.21
10
11
12
13
198–199/0.45 1.0834
55.41
------------
55.09
8.11
---------
7.85
3.52
---------
3.21
200–202/0.4
1.1340
53.85
------------
53.59
7.62
---------
7.25
3.19
---------
2.84
215–216/0.55 1.1729
57.87
------------
57.49
8.83
---------
8.49
2.98
---------
2.68
193–194/0.4
1.1150
2-(3-Oxyallylheptyl)-N-(4-
of benzene was added dropwise at 50°ë. The mixture
was refluxed for 2.5–3 h, the benzene layer was sepa-
rated, washed with water, and dried. Benzene was dis-
tilled off, and the residue was distilled under a vacuum.
In a similar way, 2-(4-chlorobenzenesulfonamido)-
1-amylthio-4-hydroxynonane (11) was prepared from
2-(3-chloroheptyl)-N-(4-chlorobenzenesulfonyl)aziri-
dine (6).
chlorobenzenesulfonyl)aziridine (9)
To a mixture of 5.6 g (5.5 mmol) of triethylamine
and 2.9 g (50 mmol) of allyl alcohol, a solution of
16.6 g (50 mmol) of 2-(3-chloroheptyl)-N-(4-chlo-
robenzenesulfonyl)aziridine (6) in 50 ml of benzene
was added dropwise at 20–30°ë. The mixture was
heated at 50–60°ë for 1–2 h, cooled, and filtered. The
resulted benzene solution was washed with water and
dried. Benzene was distilled off, and the residue was
distilled under a vacuum.
2-(4-Chlorobenzenesulfonamido)-1-amylthio-5-
(carboxymethyloxy)nonane (12)
To a solution of 8.2 g (20 mmol) of 2-(4-chloroben-
zenesulfonamido)-1-amylthio-4-hydroxynonane (11)
in 20 ml of benzene, 2.5 g (2.5 mmol) of triethylamine
2-(4-Chlorobenzenesulfonamido)-1-amylthio-5-
hydroxynonane (10)
To a solution of 1.6 g (40 mmol) of NaOH in 6 ml of was added. Then, a solution of 2.36 g of chloroacetic
water, 4.16 g (40 mmol) of amylmercaptan was added. acid in 20 ml of ethanol was added and the mixture was
Then, a solution of 15.4 g (40 mmol) of 2-(4-chlorohep- refluxed for 2–3 h. After the addition of 50 ml of water,
tyl)-N-(4-chlorobenzenesulfonyl)aziridine (5) in 50 ml the benzene layer was separated and dried. Benzene
PETROLEUM CHEMISTRY Vol. 49 No. 3 2009

256
MAMEDOV et al.
was distilled off, and the residue was distilled under a dried. Benzene was distilled off, and the residue was
vacuum.
distilled under a vacuum.
The structures of compounds 10, 11, and 13 were
confirmed by their 1H NMR spectra.
2-(4-Chlorobenzenesulfonamido)-1,5-
bis(amylthio)nonane (13)
RESULTS AND DISCUSSION
To a solution of 4 g (100 mmol) of NaOH in 50 ml
of ethanol, 20.8 g (200 mmol) of amylmercaptan was
added. Then, a solution of 34.6 g (100 mmol) of 2-(4-
chloroheptyl)-N-(4-chlorobenzenesulfonyl)aziridine
(5) in 50 ml of ethanol was added dropwise at 40–50°ë.
The mixture was heated at 50–60°ë for 2.5–3 h, ethanol
Because of the electrophilic character of the sul-
fonamide group, the treatment of N-(β-chloroalkyl)are-
nesulfonamides with potassium alcoholate or a KOH
ethanolic solution, even in the cold, results in the elim-
ination of hydrogen chloride to give aziridine deriva-
tives. Further investigations have shown that hydrogen
was distilled off, and 100 ml of benzene was added. The chloride elimination is caused even by treatment with a
benzene layer was separated, washed with water, and 10% alkali aqueous solution at room temperature.
Cl
C H
4
9
–HCl
C H
4
9
N
NHSO C H Cl-n
2
6
4
SO C H Cl-n
2
6 4
(1)
(4)
Cl
Cl
C H
4
9
C H
4
9
–HCl
Cl
N
(5)
NHSO C H
Cl-n
2
6
4
SO C H Cl-n
2
6
4
(2)
Cl
Cl
C H CH
2
4
9
C H
–HCl
4
9
Cl
(6)
SO C H
N
NHSO C H
6 4
Cl-n
2
Cl-n
(3)
2
6 4
In the case of concentrated alkali solution or long-term product 6 is readily replaced with the hydroxyl group
storage in a dilute solution, the second chlorine atom in owing to the inductive effect of the sulfonamide group.
C H CH
2
Cl
C H CH OH
4
9
4
9
2
–HCl
N
N
SO C H Cl-n
SO C H Cl-n
(7)
2
6 4
(6)
2
6 4
However, the hydrolytic substitution chlorine in 90°ë) or with the use of a more concentrated alkali
product 5 proceeds at higher temperatures (80– solution.
PETROLEUM CHEMISTRY Vol. 49 No. 3 2009

SYNTHESIS AND TRANSFORMATIONS OF AZIRIDINESULFONAMIDE DERIVATIVES
257
Cl
OH
C H
C H
4
9
4
9
–HCl
N
N
(5)
(8)
SO C H
SO C H Cl-n
Cl-n
2
6 4
2
6 4
The substitution of other nucleophilic agents for chlo- is easy to open by nucleophiles. However, we revealed that
rine in products 5 and 6 also proceeds easily. Depending the aziridine cycle opening reaction depends on the nature
on the reagents and reaction conditions, the opening of the of the nucleophile. For example, the reaction of 6 with
aziridine ring can take place along with the chlorine sub- allyl alcohol under mild conditions in the presence of tri-
stitution reaction, in agreement with published data. It has ethylamine or pyridine leads only to chlorine substitution
been shown [9, 10] that the aziridine cycle in sulfonamides with the obtainment of ether 9.
OCH CH CH
Cl
2
2
C H CH
2
C H CH
2
4
9
4
9
HOCH2CH=CH2
N
N
SO C H Cl-n
SO C H Cl-n
(6)
(9)
2 6 4
2
6 4
In the reaction of 5 and 6 with amylmercaptan in the by the hydroxyl group occurs along with the opening of
presence of alkali, the substitution of the chlorine atom the aziridine cycle.
Cl
OH
C H
4
9
C H
4 9
C5H11SH + KOH
SC H
5
11
N
NHSO C H Cl-n
(10)
2
6
4
SO C H Cl-n
2
6 4
(5)
Cl
OH
C H CH
2
4
9
C5H11SH + KOH
NHSO C H Cl-n
C H CH
2
2
6
4
4
9
N
SC H
(11)
5
11
SO C H Cl-n
2
6 4
(6)
The presence of hydroxyl in compounds 10 and 11 transformation of 10 into the ester by its reaction with
was proven by 1H NMR spectroscopy, as well as by the chloroacetic acid.
OH
OCH COOH
2
ClCH2COOH
C H
SC H
5 11
4
9
SC H
C H
4 9
5
11
NHSO C H
Cl-n
2
6
4
NHSO C H Cl-n
2
6 4
(10)
(12)
PETROLEUM CHEMISTRY Vol. 49 No. 3 2009

258
MAMEDOV et al.
Table 2. Results of testing compounds 4–13 as additives for M-11 oil
Content of additives
in 100 g of M-11 oil
Antiwear and extreme pressure Thermooxidative stability
characteristics, 392 N, 1 h by a DK NAMI test
Corrosion,
g/m2
Compound no.
Viscosity
mmol
2
g
3
WSD, mm
5
LWI
6
Deposit, %
7
increment
1
4
4
8
3
5
0.82
1.37
2.74
1.05
1.75
3.5
120.1
97.9
33.5
61.3
38.7
16.1
51.2
30.1
8.1
0.78
0.71
0.64
0.73
0.67
0.50
0.52
0.46
0.41
0.75
0.69
0.62
0.52
0.48
0.42
0.48
0.40
0.38
0.50
0.40
0.38
0.63
0.40
–
–
–
12.9
12.8
4.0
22.1
29.9
16.7
21.1
19.8
10.4
12.5
9.8
10
3
–
5
6
34
9
7.66
4.8
5
10
3
46
36
40
48
–
2.0
1.05
1.75
3.5
6.4
5
3.7
10
3
1.4
8.9
8
1.0
32.5
26.8
10.9
48.7
34.6
10.1
5.89
2.30
1.10
6.91
4.2
4.1
11.2
8.5
5
1.66
3.32
1.12
1.86
3.72
1.48
2.47
4.94
1.56
2.13
5.22
1
–
3.3
10
3
–
1.73
6.0
7.3
9
47
50
54
45
59
68
47
59
70
–
13.9
9.8
5
4.3
10
3
1.1
8.7
12
13
1.6
8.9
5
0.6
7.0
10
3
0.25
1.65
0.81
0.30
–
6.1
8.6
5
7.1
10
–
1.4
6.4
DF-11*
24.7
4.0
–
–
2
–
–
–
VNIINP-300*
IKhP-21*
–
2.4
3.9
–
–
–
–
2
5.1
–
13.27
10.46
2.6
65.4
78.1
75.4
–
4
2.2
0.61
Ionol*
–
1.0
–
PETROLEUM CHEMISTRY Vol. 49 No. 3 2009

SYNTHESIS AND TRANSFORMATIONS OF AZIRIDINESULFONAMIDE DERIVATIVES
259
By treatment of 5 with two moles of amylmer- aziridine ring opening reactions proceed simulta-
captan at 50–60°ë, the chlorine substitution and neously.
Cl
SC H
5
11
C H
4
9
SC H
5
11
2(C5H11SH + KOH)
C H
4
9
N
NHSO C H
Cl-n
2
6
4
SO C H Cl-n
2
6 4
(5)
(13)
The analogous reaction of 6 leads to product 11,
The study of the effect of aziridinesulfonamides and
their derivatives on the extreme-pressure characteristics
has shown that the aziridine moiety worsens the
extreme-pressure properties, although they are superior
to the initial chlorinated sulfonamides 1–3 in antiwear
characteristics. Aziridine 6 is more effective than 4. In
addition, the replacement of chlorine in aziridine 4 with
the hydroxyl group (compound 7) worsens and the
presence of the allyl group (compound 9) improves the
antiwear and extreme-pressure characteristics. In con-
trast to aziridines 4–6, their transformation products 9,
12, and 13 exhibit a high antiwear and extreme-pres-
sure efficiency.
regardless of the reaction conditions.
Analysis of the published data shows that, despite a
wide variety of sulfonamide compounds, they have
been investigated as lubricant additives to a lesser
extent compared to other application areas. A large
group of sulfanilides [11–15] has been investigated as
antioxidant, detergent, corrosion-inhibiting, antiwear,
and extreme-pressure additives for lubricants. Taking
this into account, we have comprehensively investi-
gated anticorrosive, antiwear, extreme-pressure, and
antioxidant characteristics of the synthesized com-
pounds 4–13.
The study of the influence of the concentration of
compounds 4–13 on the antiwear characteristics of the
M-11 oil has shown that the optimal concentration pro-
viding a minimum wear scar diameter is 10 mmol per
100 g of oil for compounds 4–6 and is even lower
(5 mmol) for compounds 9, 12, and 13. The antiwear
efficiency of the latter compounds, even at a 5 mmol
concentration, is about 1.5–2 times that of other deriv-
atives. Regarding the concentration effect of these com-
pounds on oil M-11 extreme pressure characteristics, it
should be pointed out that their efficiency is highly
dependent on concentration. Compounds 12 and 13 are
more effective than the other compounds, even at con-
centrations of 5 mmol per 100 g of oil.
The results of testing the properties of the synthe-
sized compounds in comparison with the industrial
additives are represented in Table 2. As can be seen,
there are very effective additives among the compounds
prepared. Their performance depends on their structure
and composition. The aziridine moiety has an unfavor-
able effect on the corrosion-inhibiting properties of the
compounds. The presence of a long-chain alkyl radical
(compounds 5 and 6) enhances the anticorrosive effi-
ciency. The replacement of chlorine with the hydroxyl
(compound 7) or the allyl (compound 9) group does not
influence the anticorrosive characteristics of the com-
pounds. However, the compounds prepared via reac-
tions involving aziridine cycle opening (compounds 9,
12, and 13) display a very high anticorrosive activity.
Testing the aziridinesulfonamides and their trans-
The investigation into the influence of the concen- formation products has shown their high antioxidant
tration of aziridinesulfonamides and their derivatives efficiency. The compounds containing the chlorine
on the corrosion-inhibiting properties of oils has shown atom and a functional group in the 1,3-positions are
that the optimal concentration for preventing corrosion more efficient than those containing the substituents in
(5 g/m2) in the M-11 oil is 10 mmol and even lower (3– the 1,4-positions, because of the interplay with the sul-
5 mmol) for compounds 12 and 13.
fonamide group.
X
X
C H
4
9
C H CH
4 9 2
<
N
N
SO C H Cl-n
2
6 4
SO C H
6 4
Cl-n
2
PETROLEUM CHEMISTRY Vol. 49 No. 3 2009

260
MAMEDOV et al.
7. M. Weitzberq, Z. Aizenshtat, and J. Blum, J. Heterocycl.
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Chem. 21, 1597 (1984).
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additives. In their performance, they are superior to
some extent to other sulfonamide derivatives, as well as
certain industrial additives.
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