Substituted N-(2-Hydroxyethyl)-1,3-thiazolidin-4-ones: Synthesis and anticorrosive properties

Article abstract of DOI:10.1023/A:1019545904261

A one-pot procedure was developed for synthesis of N-(2-hydroxyethyl)-1,3- thiazolidin-4-ones in 64-68% yield by reactions of monoethanolamine with carbonyl compounds and mercaptoacetic acid. The synthesized compounds were characterized by IR and ¹H NMR spectra, and their anticorrosive properties were studied.

Full text of DOI:10.1023/A:1019545904261

Russian Journal of Applied Chemistry, Vol. 75, No. 4, 2002, pp. 665 666. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 4, 2002,
pp. 680 681.
Original Russian Text Copyright
2002 by Kukharev, Stankevich, Klimenko, Kovalyuk, Bayandin.
BRIEF
COMMUNICATIONS
Substituted N-(2-Hydroxyethyl)-1,3-thiazolidin-4-ones:
Synthesis and Anticorrosive Properties
B. F. Kukharev, V. K. Stankevich, G. R. Klimenko, E. N. Kovalyuk, and V. V. Bayandin
Favorskii Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Angarsk State Technological Institute, Angarsk, Irkutsk oblast, Russia
Received December 28, 2001
Abstract A one-pot procedure was developed for synthesis of N-(2-hydroxyethyl)-1,3-thiazolidin-4-ones
in 64 68% yield by reactions of monoethanolamine with carbonyl compounds and mercaptoacetic acid.
1
The synthesized compounds were characterized by IR and H NMR spectra, and their anticorrosive prop-
erties were studied.
Nitrogen-containing alcohols and some sulfur-
When developing the synthesis procedure, we took
containing organic compounds are known to exhibit into account the conditions under which the separate
anticorrosive properties [1 3]. In this work, we pre-
pared, with the aim to reveal anticorrosive properties
of other amino alcohol derivatives, a series of substi-
tuted N-(2-hydroxyethyl)-1,3-thiazolidin-4-ones and
studied them as inhibitors of carbon dioxide and hy-
drogen sulfide corrosion of steel. One of routes to
N-(2-hyroxyethyl)-1,3-thiazolidin-4-ones is reaction
of oxazolidinies with mercaptoacetic acid [4]. Ox-
azolidines are, in turn, prepared by condensation of
carbonyl compounds with 1,2-amino alcohols [5 7]:
stages were performed in [4, 6, 7]. We used benzene
as solvent. Condensation of monoethanolamine with
carbonyl compounds I and II was performed by re-
fluxing an equimolar mixture of the reactants, with
azeotropic distillation of water. After the release of
water was complete, a stoichiometric amount of mer-
captoacetic acid was added, and the mixture was re-
fluxed until the release of the next portion of water
was complete.
The yield of N-(2-hydroxyethyl)-1,3-thiazolidin-
4
-ones III and IV under these conditions was 70 and
68%, respectively. The yield of thiazolidinones is the
O
R
NH
R
R C=O + HOCH CH NH
2
2
2
2
_
highest at the equimolar ratio of monoethanolamine
and carbonyl compounds. With 10% molar excess of
the carbonyl compound, the yield decreased by 6
10%, and with 10% molar excess of monoethanol-
amine, it decreased by 20 25%.
H O
2
I, II
O
HSCH COOH
,
2
S
N
_
H O
OH
2
R
R
III, IV
To evaluate the inhibiting power of III and IV, we
studied their effect on steel corrosion under condi-
tions simulating steel corrosion in petroleum produc-
tion [8].
where R = H (I, III): R + R = (CH ) (II, IV).
2
5
With this synthesis scheme, the yield of N-(2-hy-
droxyethyl)-1,3-thiazolidin-4-ones III and IV is 62
3% [4]. The initial oxazolidines were prepared from
monoethanolamine and the corresponding carbonyl
compounds in 90 94% yield [6, 7].
The anticorrosive activity was evaluated gravimet-
rically with St. 3 steel samples of size 2 20 6 mm,
according to GOST (State Standard) 9.505 86, in a
6
1
% NaCl solution saturated with CO in the presence
2
of hydrogen sulfide. Tests were performed at 20, 40,
and 60 C for 3 h. At a 10 3 M concentration of III or
IV and varied temperature, we obtained the following
protective effect Z (%): III, 95.9 (20 C), 80.5 (40 C),
and 45.5 (60 C); IV, 96.3 (20 C), 83.3 (40 C), and
In this study, we examined the possibility of com-
bining in one-pot synthesis the stages of preparation
of oxazolidines and their subsequent transformation
into N-(2-hydroxyethyl)-1,3-thiazolidin-4-ones.
1
070-4272/02/7504-0665 $27.00 2002 MAIK Nauka/Interperiodica

666
KUKHAREV et al.
6
2.7 (60 C). Thus, search for new corrosion inhibitors
CONCLUSIONS
among thiazolidinone alcohols shows much promise.
(
1) Conditions were found for one-pot synthesis
EXPERIMENTAL
of N-(2-hydroxyethyl)-1,3-thiazolidin-4-ones from
monoethanolamine, carbonyl compounds, and mercap-
toacetic acid. The product yield is higher than that in
the two-stage synthesis with intermediate isolation of
oxazolidines.
In syntheses, we used commercial paraform (99.3%
purity), cyclohexanone, monoethanolamine, and mer-
captoacetic acid, which were purified by distillation
to the main substance content of no less than 99.8%.
(2) The protective effect of N-(2-hydroxyethyl)-
N-(2-Hydroxyethyl)-1,3-thiazolidin-4-one III.
A mixture of 30.5 g (0.5 mol) of monoethanolamine,
5.1 g (0.5 mol) of paraform, and 100 ml of benzene
1
,3-thiazolidin-4-ones against carbon dioxide and
hydrogen sulfide corrosion of steel reaches 96%.
1
was refluxed with a Dean Stark trap until the release
of water was complete. Then, 46.1 g (0.5 mol) of
mercaptoacetic acid was added, and the mixture was
refluxed until the release of water was complete.
The mixture was cooled and distilled to give 47.9 g
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1
2
. Grigor’ev, V.P. and Ekilik, V.V., Khimicheskaya struk-
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hibitors), Rostov-on-Don: Rostov. Gos. Univ., 1978.
(
65%) of II; bp 176 178 C at 3 mm Hg; mp 63
1
6
3
4 C. IR spectrum (thin film, , cm ): 1630 (C=O),
1
. Kukharev, B.F., Stankevich, V.K., Klimenko, G.R.,
et al., Zh. Prikl. Khim., 2000, vol. 73, no. 1,
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300 (OH). H NMR spectrum (CDCl , 90 MHz), ,
3
4
ppm: 3.49 t (2H, NCH ), 3.56 d (2H, SCH CO, J
2
2
.4 Hz), 3.76 t (2H, OCH ), 4.0 s (1H, OH), 4.54 d
2
4
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Khimiya organicheskikh soedinenii sery i kremniya
2
Found, (%): C 40.97, H 6.03, N 9.28, S 21.63.
C H NO S.
5
9
2
(
Russian Symp. Chemistry of Organic Compounds of
Sulfur and Silicon ), Irkutsk, 2001, p. 184.
Calculated, (%): C 40.80, H 6.16, N 9.52, S 21.78.
N-(2-Hydroxyethyl)-1-thia-4-azaspiro[4.5]decan-
-one IV was prepared similarly from 30.5 g (0.5 mol)
of monoethanolamine, 49.1 g (0.5 mol) of cyclohex-
anone, and 46.1 g (0.5 mol) of mercaptoacetic acid.
4. Kukharev, B.F., Stankevich, V.K., and Klimenko, G.R.,
Izv. Ross. Akad. Nauk, Ser. Khim., 1997, no. 12,
pp. 2221 2223.
3
5
6
7
8
. Bergman, E.D., Chem. Rev., 1953, vol. 53, no. 2,
pp. 309 352.
Yield 73.5 g (68%); bp 200 203 C at 2 mm Hg; mp
1
8
(
9
(
6 87 C. IR spectrum (thin film, , cm ): 1630
. Laurent, P.A., Bull. Soc. Chim. Fr., 1967, no. 2,
pp. 571 575.
1
C=O), 3420 (OH). H NMR spectrum (CDCl3,
0 MHz), , ppm: 1.08 1.79 m [10H, (CH ) ], 3.44 t
2
5
. Cope, A.C. and Hancock, E.M., J. Am. Chem. Soc.,
2H, NCH ), 3.50 s (2H, SCH CO), 3.74 t (2H,
2 2
1
942, vol. 64, pp. 1503 1506.
OCH ), 4.08 s (1H, OH).
2
. Saakiyan, A.S. and Efremov, A.P., Zashchita nefte-
promyslovogo oborudovaniya ot korrozii (Corrosion
Protection of Petroleum Extraction Equipment),
Moscow: Nedra, 1982.
Found, (%): C 55.63, H 7.88, N 6.55, S 14.99.
C H NO S.
1
0
17
2
Calculated, (%): C 55.78, H 7.96, N 6.51, S 14.89.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 4 2002