Synthesis of N-substituted derivatives of arylsulfonyl hydrazides and their investigation as additives for lubricating oils

Article abstract of DOI:10.1134/S0965544112040068

The reaction between arylsulfonyl chlorides and hydrazine has been studied, and it has been found that in the presence of excess hydrazine, the bis-derivatives are produced in small amounts along with monoarylsulfonyl hydrazides. It has been revealed that the reaction of monosulfonyl hydrazides with alkyl bromides in the presence of a base results only in N-alkylation of the sulfamide nitrogen, although the reaction in the presence of HCl proceeds at the amine group with the formation of quaternary ammonium salts. A method for the preparation of sulfonyl hydrazides by oxidation of N-alkyl sulfamides in the presence of iodine has been developed. Some arylsulfonyl hydrazide derivatives have been examined as antioxidant, anti-rust, and antiwear additives. These sulfonyl hydrazides also exhibit a high bactericidal and fungicidal activity.

Full text of DOI:10.1134/S0965544112040068

ISSN 0965ꢀ5441, Petroleum Chemistry, 2012, Vol. 52, No. 4, pp. 284–287. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © S.A. Mamedov, S.I. Mamedova, I.Sh. Guseinov, N.P. Ladokhina, F.A. Fatalizade, M.F. Farzaliev, 2012, published in Neftekhimiya, 2012, Vol. 52, No. 4,
pp. 317–320.
Synthesis of NꢀSubstituted Derivatives of Arylsulfonyl Hydrazides
and Their Investigation as Additives for Lubricating Oils
S. A. Mamedov, S. I. Mamedova, I. Sh. Guseinov, N. P. Ladokhina,
F. A. Fatalizade, and M. F. Farzaliev
Institute of Chemistry of Additives, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
eꢀmail: nina_fuad@rambler.ru
Received April 13, 2011
Abstract—The reaction between arylsulfonyl chlorides and hydrazine has been studied, and it has been found
that in the presence of excess hydrazine, the bisꢀderivatives are produced in small amounts along with
monoarylsulfonyl hydrazides. It has been revealed that the reaction of monosulfonyl hydrazides with alkyl
bromides in the presence of a base results only in
tion in the presence of HCl proceeds at the amine group with the formation of quaternary ammonium salts.
A method for the preparation of sulfonyl hydrazides by oxidation of ꢀalkyl sulfamides in the presence of
Nꢀalkylation of the sulfamide nitrogen, although the reacꢀ
N
iodine has been developed. Some arylsulfonyl hydrazide derivatives have been examined as antioxidant, antiꢀ
rust, and antiwear additives. These sulfonyl hydrazides also exhibit a high bactericidal and fungicidal activity.
DOI: 10.1134/S0965544112040068
The products of the reaction of arylsulfonyl chloꢀ ous NaOH solution was vigorously stirred for 30 min
rides with polyamines are being currently studied as
additives for lubricating oils and greases. It is also
known that they exhibit antiarrhythmic, antitumor,
and antibacterial activities [1–3].
at 90–98°С. Afterwards, 0.06 mol of nꢀbutyl or nꢀoctyl
bromide was added dropwise to the reaction mixture at
this temperature, and the resulting mixture was addiꢀ
tionally stirred for 3 h and then cooled. The obtained
crystals were filtered off, washed with water, and
recrystallized from an ethanol–benzene blend (2 : 1).
EXPERIMENTAL
Quaternary salts of arylsulfonyl hydrazides (comꢀ
pounds 6–8). Arylsulfonyl hydrazide 1–3 (0.1 mol)
was dissolved in a mixture of diethyl ether and benzene
(1 : 1), and hydrogen chloride was bubbled through the
resulting mixture until complete precipitation of crysꢀ
tals. The obtained crystals were filtered off and recrysꢀ
tallized from ethanol. The crystals were hydroscopic
(deliquescent plates).
Procedures for the synthesis of various arylsulfonyl
hydrazides are described below.
Arylsulfonyl hydrazides (compounds 1–3) Hydraꢀ
zine sulfate in an amount of 0.1 mol was added to
0.05 mol of arylsulfonyl chloride and the resultant
mixture was diluted with water at 20°С. Afterwards,
the reaction was initiated by adding drop wise 0.2 mol
of 30% NaOH solution until pH 7.3. During the addiꢀ
tion of the alkali, the temperature of the medium
N,N'ꢀDialkylꢀN,N'ꢀbis(arylsulfonyl
(compounds 9–11). The corresponding
hydrazides)
ꢀalkylꢀ
increased to 25–35
for 2–2.5 h. Then the temperature was slowly elevated
to 90 and maintained for 9 h. The precipitate
°С and was maintained at this level
N
Nꢀ
arylsulfonyl hydrazide (0.1 mol) was mixed with
0.12 mol of 30% aqueous NaOH solution and heated
until its complete dissolution. Then, 0.2 mol of crysꢀ
talline iodine was added to the reaction mixture; the
mixture was heated for 2 h, and 10 mL of diluted HCl
(1 : 1) was added. If the resultant medium was colored,
it was treated with 0.1 N sodium sulfite solution till
disappearance of the color. The obtained crystals were
filtered off with a sinteredꢀglass funnel, washed with
water, and recrystallized from ethanol.
°
С
formed was washed with water to neutral reaction, and
the resulting crystals were dissolved in benzene. The
benzene solution was filtered and concentrated by
evaporation. Isooctane was added to the concentrated
solution, and arylsulfonyl hydrazides 1–3 were isoꢀ
lated.
The products insoluble in benzene were recrystalꢀ
lized from ethanol. A study of their structure and comꢀ
position showed them to be N,N'ꢀbisarylsulfonyl
hydrazides.
1
Analysis methods. The H NMR spectra the synꢀ
thesized compounds were recorded on a Varian Tꢀ60
and Teslaꢀ467 spectrometers operating at frequencies
N
ꢀAlkylꢀ
Nꢀ4ꢀmethylpenylsulfonyl hydrazides (comꢀ
pounds 4, 5) A mixture contained 0.05 mol of 4ꢀmethꢀ
ylpenylsulfonyl hydrazide 1 and 0.1 mol of 20% aqueꢀ of 60 and 90 MHz.
284

SYNTHESIS OF
N
ꢀSUBSTITUTED DERIVATIVES OF ARYLSULFONYL HYDRAZIDES
285
RESULTS AND DISCUSSION
Despite the excess of hydrazine, the yield of arylꢀ
sulfonyl hydrazides does not exceed 30–32% and
depends on the nature of arylsulfonyl chloride. Thus,
the yields of sulfonyl hydrazides obtained by the reacꢀ
tion of 4ꢀmethylphenyl, 4ꢀbromophenyl, and 2,5ꢀ
dimethylphenyl sulfonyl chlorides with hydrazine are
16.5, 18.5, and 31%, respectively, thereby providing
evidence for the effect of the substituent nature.
The available published data on the reaction of
arylsulfonyl chloride with hydrazines are controverꢀ
sial. For example, it was shown that the reaction
between arylsulfonyl chloride and hydrazine results in
the formation of monosulfonyl hydrazides [4] of disulꢀ
fonyl hydrazides when the reactants are used in the
1 : 1 or 2 : 1 molar ratio, respectively . However, we
have shown that the reaction in the presence of excess
hydrazine yields bisꢀarylsulfonyl hydrazides along
with monoarylsulfonyl hydrazides (see the scheme
below):
The reaction of 4ꢀmethylphenylsulfonyl hydrazide
with alkyl bromides in the presence of the base resulted
in the formation of
Nꢀalkyl derivatives of sulfonyl
hydrazides. The spectral data confirmed the fact of
alkylation of the sulfamide nitrogen via the following
reaction:
N
ꢀ
R2
R1
+ NH NH ⋅ H2SO4
2 2
SO2Cl
R2
+ R⎯Br
SO2NH NH2
R
CH3
R2
OH
R1
SO2N NH2
CH3
SO2NH NH2
R = C4H9 (4); C8H17 (5)
R2
(1–3)
The reaction of arylsulfonyl hydrazides 1–3 with
hydrogen chloride gives the quaternary ammonium
salts:
R1 = CH3, R2 = H (1); R1 = H, R2 = CH3 (2);
R1 = Br, R2 = H (3).
R2
R2
R1
R1
⋅ HCl
SO2NH NH2
+ HCl
SO2NH NH2
R2
R2
(6–8)
R1 = CH3, R2 = H (6); R1 = H, R2 = CH3 (7);
R1 = Br, R2 = H (8).
To compare and study the influence of the a series of
alkylradical on the hydrazine nitrogen atoms on hydrazide)s by oxidation of
the performance characteristics, we synthesized famides:
N
,
N
'ꢀdialkylꢀ
N
,
N
'ꢀbis(arylsulfonyl
N
ꢀalkylꢀ ꢀarylsulꢀ
N
R2
R2
R2
R3
J
R1
2
R1
R1
SO2N
R3
H
SO2N NSO2
R3
R2
R2
R2
(9–11)
R1 = H, R2 = H; R3 = C2H5 (9); R1 = H, R2 = CH3,
R3 = C2H5 (10); R1 = CH3, R2 = H, R3 = C4H9 (11).
Arylsulfonyl hydrazides are synthons in synthesis of various heterocyclic compounds that have promise as
bactericides [5].
PETROLEUM CHEMISTRY Vol. 52
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2012

286
MAMEDOV et al.
Table 1. Results of testing arylsulfonyl hydrazides as additives for lubricating oils and greases
Antiwear properties at load of 392 N
Induction period
for sludge formation,
precipitate, %
Additive content
in oil or grease
Compound no.
Corrosion, g/m2
d
, mm
–
A
p
Oil Mꢀ8
–
–
3
0
–
160
–
–
AKꢀ15
0.68
0.60
0.55
0.50
0.60
0.51
0.55
0.50
0.48
0.61
0.59
0.51
0.50
20.1
56
60
66
46
56
52
66
68
62
48
68
67
4
5
0.75
0.09
0.15
2.5
1.1
1.2
0.8
–
21.2
13.8
6.1
1
3
9
1
30.5
19.8
20.7
14.5
4.0
3
11
3
5
DFꢀ11
2
VNIINPꢀ300
Grease 141/l
Compound 5
Compound 11
2.4
–
3
–
3.9
–
58.9
5.6
–
3
–
6.2
Our preliminary studies showed [6, 7] that comꢀ compositions obtained previously [10, 11]. From the
pounds containing simultaneously the sulfamide data Table 1 it follows that a 3% concentration of comꢀ
group together with other functional groups and hetꢀ pound 5 or 11 sharply reduces the corrosiveness and
erocyclic moieties exhibit good antirust, antioxidant, enhances the tribological properties of the oil; and
and tribological properties as components of lubricatꢀ they decrease the corrosion in the 141/L sealing grease
ing oils. To improve these properties of lubricating from 58.9 to 5.6 g/m2 (the absence of corrosion).
greases, sulfamide compounds were also used [8, 9]. In These compounds can be used as antirust and antiwear
light of this information, the arylsulfonyl hydrazides additives for greases.
synthesized in the present study that are soluble in the
Note that in contrast to the known methods, these
Mꢀ8 and AKꢀ15 oils were screened as additives for
sulfamide compounds were added to the grease during
lubricating oils and greases.
its preparation at130–140°С.
The oil solubility of compounds 1–3 does not
exceed 2%; therefore, they were not tested as lubricatꢀ
ing oil additives. Wellꢀsoluble compounds 4, 5, 9, 11
displayed high antioxidant and antiwear properties
(Table 1).
Synthesized arylsulfonyl hydrazides were also studꢀ
ied as antimicrobial additives in the Mꢀ8 oil (compds.
4, 5, 11) and in the Azerol cutting fluid (compds. 9,
10). Bactericidal activity of the synthesized comꢀ
pounds was determined according to GOST 9.052ꢀ88
Sulfonyl hydrazides 4, 5, 9, 11 were also studied as using the following microorganisms: a mixture of fungi
antirust and antiwear additives in lubricating grease
(
Aspergillus niger
,
Penicillium chrysogenum
,
Penicilꢀ
PETROLEUM CHEMISTRY Vol. 52
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2012

SYNTHESIS OF
N
ꢀSUBSTITUTED DERIVATIVES OF ARYLSULFONYL HYDRAZIDES
287
Table 2. Results of testing arylsulfonyl hydrazides 4–7and
11 as antimicrobial additives to lubricating oils and cutting
fluids
As follows from the data in Table 2,
N
ꢀalkyl subꢀ
stituted derivatives of monosulfonyl hydrazides 4, 5
and 'ꢀdibutylꢀ 'ꢀbis(4ꢀmethylphenylsulfoꢀ
N
,
N
N,N
nyl hydrazide) 11 have a high antibacterial and antiꢀ
fungal activity. Compounds 4, 5, and 11 are oilꢀsolꢀ
uble; hence, they can be used for protection of
petroleum products against biodegradation. Quaꢀ
ternary ammonium salts of monosulfonyl
hydrazides 6 and 7 also exhibit a high bactericidal
and fungicidal activity; this fact proves that ammoꢀ
nium salts are promising for protection of lubricatꢀ
ing fluids from biological degradation.
In summary, it has been found that the investigaꢀ
tional arylsulfonyl hydrazides exhibit good antimicroꢀ
bial properties and their performance is higher than
that of the known biocides used in industry.
Diameter of microorꢀ
ganism suppression
Mꢀ8 oil or
cutting fluid pound no tion, %
Comꢀ Concentraꢀ
zone, cm
Bacterial Fungi
mixture mixture
Mꢀ8 oil
Mꢀ8 oil
Mꢀ8 oil
4
5
1
2.6
2.3
1.8
1.4
3.2
2.4
2.0
1.8
0.5
0.25
0.1
1
2.8
2.5
2.0
1.8
3.5
2.8
2.5
2.0
0.5
0.25
0.1
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11
6
1
3.4
3.0
3.0
2.4
3.8
3.5
2.8
2.6
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0.25
0.1
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1
3.8
3.6
3.2
2.8
3.2
3.0
2.8
2.3
0.5
0.25
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PETROLEUM CHEMISTRY Vol. 52
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2012