CHEMICAL PROBLEMS 2023 no.

2 (21) ISSN 2221-8688 161

UDC 547.452 + 620.197

SYNTHESIS OF β-KETOSULFIDES BASED ON BENZALACETONE AND RESEARCH

INTO THEIR INHIBITORY PROPERTIES

V.М. Kyazimov, G.Z. Guseynov, N.S. Madji, М.А. Mirzoyeva, О.G. Nabiyev,
G.S. Kyazimova, L.К. Vahid-zadeh

Acad. A.M. Kuliyev Institute of Chemistry of Additives under the Ministry of Science and Education of
Azerbaijan Republic, Boyukshor highway, quarter 2062, АZ 1029, Baku, Azerbaijan
e-mail: [email protected]

Received 06.12.2022
Accepted 26.04.2023

Abstract: The interaction of benzalacetone with mercaptoacetic acid and its alkyl esters was used to
synthesize and characterize new representatives of β-ketosulfides, the structure of which was proved by 1H
and 13С NMR- spectroscopy. The gravimetric method was used to study the influence of the synthesized
compounds on the corrosion rate of St-3 in various aggressive medium. It was established that the studied
compounds inhibit the corrosion process both in single-phase acidic (0.1N HCl и 0.1N H2SO4), and in two-
phase (electrolyte-hydrocarbon) media. In the latter case, they are more effective - the corrosion rate of St-3
decreases from 2.1 to 0.06-0.35 g/m 2 hour, while the degree of protection against corrosion is 83.3-97.1 %.
The studied compounds exhibit a greater protective effect in hydrochloric acid solution (97.1-92.45%), than
in sulfuric acid (76.9-87.1%). Among the tested compounds, β-ketosulfide obtained on the basis of
mercaptoacetic acid showed the highest inhibitory efficiency in both mediums.
Keywords: benzalacetone, mercaptoacetic acid, alkyl esters of mercaptoacetic acid, β- ketosulfide, inhibitors
of corrosion, single-phase medium, two-phase medium, gravimetric method.
DOI: 10.32737/2221-8688-2023-2-161-167

Introduction

Ketosulfides are of interest as corrosion α-, β-unsaturated carbonyl compounds in the

inhibitors [1, 2], growth stimulators of presence of various catalysts [6–14]. Obtaining
agricultural crops [3], and synthesis of new representatives of ketosulfides and studying
biologically active compounds [4, 5]. their useful properties is relevant. For this
One of the convenient ways to obtain purpose, we carried out reactions of
ketosulfides is the addition of thiols to benzalacetone with mercaptoacetic acid and its
unsaturated ketones by the Michael reaction. A alkyl esters. The synthesized β-ketosulfides
number of β-ketosulfides were synthesized and were studied as steel corrosion inhibitors in
characterized by conjugate addition of thiols to various aggressive media.

Experimental part

NMR spectra were taken on a Bruker the literature data.

instrument with an operating frequency of 300 The reagents used - benzalacetone,
MHz (1H) and 75 MHz (13С) in С6D6 solvent. mercaptoacetic acid, and triethylamine - were
TMS was used as an internal standard. purified by distillation.
Alkyl esters of mercaptoacetic acid were 4-Methoxycarbonylmethylthio-4-
synthesized by the reaction of mercaptoacetic phenylbutan-2-one (I). To a mixture of 10.6 g
acid with the corresponding alcohols in an (0.1 mol) of methyl ester of mercaptic acid and
acidic medium [15]. The physicochemical 3 ml of triemidylamine in 50 ml of benzene
constants of the synthesized esters comply with when mixing , are added 14.6 g (0.1 mol) of
www.chemprob.org CHEMICAL PROBLEMS 2023 no. 2 (21)
162 V.М. KYAZIMOV et al.

benzalacetone in 50 ml of benzene. While an (3Н, O=C-CH3); 1.29 d (6H, CH3-C- CH3).

increase in the temperature of the reaction NMR spectra 13С, δ, ppm.:205.7 (C=O); 168.9
mixture by 6-8°C is observed. (O=C-O); 139.3 (C1, Ph); 128.5(C2, C3, C5 и C6,
Stirring is continued for 2 hours at room Ph); 127.2 (C4, Ph); 69.1 (OCH); 38.5 (SCH2);
temperature. Then the temperature is raised to 37.5 (CHS); 29.2 (O=C-CH3); 21.3 (CH3-C-
60-65°C and the reaction is continued for CH3). Found, %: C 44.68; H 7.26; S 23.69.
another 3 hours. C5H10O2S. Calculated, %: C 44.78; H 7.46; S
The benzene solution was washed with 23.88.
water until neutral, dried over sodium sulfate, 4-Carboxymethylthio-4-phenylbutan-2-one
and then filtered. After distilling off the solvent, (1V). Yield: 67.5%, Тb.128-130о/1.0 mm,
the target product was isolated by vacuum 1.5690. NMR spectra 1H (fig.1), δ, ppm.: 10.29
distillation. Yield of 18.82 g (74.5 %), Тb. 115- s (1Н, СООН): 7.02-7.13 m (5H, C6H5); 4.59-
116оС/1.5 mm, 1.5403. NMR spectra 1H, δ, 4.64 m (1H, PhCHS); 2.79 c (2H, SCH2); 2.58-
м.д.: 7.13-7.26 m (5H, C6H5), 4.41-4.46 t (1H, 2.64 m (2Н, С-СН2-С); 1.58 s (3Н, СН3). NMR
PhCHS); 3.55 s (3H, OCH3); 3.02 s (2H, SCH2); spectra 13С (fig.2), δ, ppm.: 204.5 (C=O); 175.4
2.61-2.80 m (2H, CCH2C); 2.02 s (3H, O=C- (СООН); 140.8 (C1, Ph); 128.5 (C2, C3, C5 and
CH3). NMR spectra 13C, δ, м.д.: 205.2 (C=O); C6, Ph); 127.2 (C4, Ph); 48.8 (СH2); 44.23
173.4 (O=C-O); 14.1 (C1, Ph); 128.6 (C2, C3, C5 (SCH2); 32.3 (CH); 29.5 (CH3). Found,% : С
и C6, Ph); 127.3 (C4, Ph); 51.2 (CH2); 50.6 26.15; H 4.19; S 34.53. C2H4O2S. Calculated,%
(OCH3); 38.9 (SCH2); 37.7 (CH); 29.2 (CH3). : C 26.09; H 4.35; S 34.78.
Found, %: C 33.81; H 5.72; S 29.99. C3H6O2S. The inhibitory properties of the synthesized
Calculated, %: C 33.96; H 5.66; S 30.19. compounds were studied gravimetrically
Other β-ketosulfides (II-IV) were according to the State Standard (ГОСТ) 9.502-
synthesized by a similar procedure. 82 n single-phase acidic media and in two-phase
Other β-ketosulfides (II-IV) were electrolyte-hydrocarbon media (3%
synthesized by a similar procedure (II). NaCl+0.02% СН3СООН + kerosene 5:1),
Yield: 73.2 %, Тb.123-125оС/1.5 mm, saturated with carbon dioxide.
1.5321. NMR spectra 1H, δ, ppm.: 7.10-7.23 m Before testing, the plates were ground on
(5H, C6H5), 4.31-4.36 m (2H, OCH2); 4.10-4.15 a grinding machine, polished, washed with
t (1H, PhCHS); 3.12 s (2H, SCH2); 2.65-2.84 m distilled water, alcohol, hexane, and then with
(2H, CCH2C); 2.01 s (3H, O=C-CH3); 1.27-1.32 acetone.
t (3H, O-C-CH3). NMR spectra 13С δ, ppm.: The plates (40 x 20 x 5) were placed in a
205.2 (C=0); 168.2 (O=C-O); 139.5 (C1, Ph); beaker with 200 ml of an acid solution so that
128.3 (C2, C3, C5 and C6, Ph); 127.4 (C4, Ph); they did not come into contact with each other.
60.2 (OCH2); 52.1 (CH2); 39.8 (SCH2); 37.2 After 3 hours, the plates were removed from the
(CHS); 28.9 (O=C-CH3); 14.3 (O CH2CH3). solution and washed with running water, dried
Found, %: C 39.83; H 6.52; S 26.59. C4H8O2S. and a thin coating was removed from the
Calculated, %: C 40.00; H 6.67; S 26.67. surface of the plates with an elastic band,
4-i-Propoxycarbonylmethylthio-4- washed with hexane, and dried with acetone.
phenylbutan-2-one (III). Yield: 70.1%, Тb.131- Then the plates were weighed on an analytical
133оC/1.5 mm, 1.5300. NMR spectra 1H, δ, balance with an accuracy of 0.0001 g.
ppm.: 7.11-7.24 m (5H, C6H5), 4.86-5.00 m (1 The corrosion rate (ρ) was determined in
2
H, OCH); 4.31-4.38 t (1H, Ph CH S); 3.31 s g/m ∙h using the following formula:
(2H, SCH2); 2.52-2.77 m (2H, С-СН2-С); 1.95 с

m1 – mass of plates before testing, g

m2 - mass of plates after testing, g
S – plate area, m2
τ - test time, hour.

CHEMICAL PROBLEMS 2023 no. 2 (21)

 SYNTHESIS OF β-KETOSULFIDES BASED 163

The degree of protection (Z, %) was determined by the following formula:

Z
ρ fon - plate corrosion rate without inhibitor, g/m2 h.
ρ - plate corrosion rate with inhibitor, g/m2 h.

Fiq. 1. 1H NMR spectra of 4-carboxymethylthio-4-phenylbutan-2-one

Fiq. 2. 13С NMR spectra of 4-carboxymethylthio-4-phenylbutan-2-one

Results and their discussion

The reaction of benzalacetone with benzene solution in equimolar ratios of reagents

mercaptoacetic acid and its esters proceeded in a in the presence of triethylamine.
Reaction scheme:

O + HSCH2COOR O
N(C2H5)3
R= CH3 (I), C2H5 (II), i-C3H7 (III), H (IV) SCH2COOR

I-IV

CHEMICAL PROBLEMS 2023 no. 2 (21)

164 V.М. KYAZIMOV et al.

Synthesized β-ketosulfides (I-IV) are carbon and carbonyl groups, four p-electrons are
light yellow liquids, soluble in organic solvents, delocalized on three carbon atoms and an
stable during storage. Their structure and oxygen atom. The influence of -I and -M -
composition were confirmed by 1H, 13C NMR effects of carbonyl oxygen leads to the
spectroscopy and elemental analysis. polarization of the conjugated system, as a
The reaction mechanism is presented as result of which the ß-carbon atom acquires a
follows. Benzalacetone belongs to α, ß- partially positive charge, and carbonyl oxygen
unsaturated ketones, in the molecule of which, acquires a partially negative charge:
by conjugation of π-bonds of the double carbon-

Such a distribution of electron density in which, after subsequent protonation, turns into
the conjugated system leads to the addition of enol. Further, the unstable enol formed as a
nucleophilic thiolate ion to carbon at the β- result of conjugated addition is isomerized into
position of the ketone, forming an enolate ion, a more stable keto form:

_
+
HSCH2COOR + N(C2H5)3 HN(C2H5)3 + SCH2COOR

CH3
_ _ +H+
SCH2COOR + Ph-C=C-C=O Ph-CH-CH=C-O
H H CH3 SCH2COOR

CH3 CH3

Ph-CH-CH=C-OH Ph-CH-CH2-C=O
SCH2COOR SCH2COOR

Thus, the final product corresponds to a metal surface. In this regard, it was of interest to
formal addition at carbon-carbon double bonds study their inhibitory properties.
without affecting the carbonyl group. The inhibitory properties of β-
The molecules of β-ketosulfides we ketosulfides were studied in a single-phase acid
synthesized contain various functional groups, medium (0.1N HCI and 0.1 N H2SO4) and in a
including ester and carbonyl groups, as well as a two-phase system: electrolyte-hydrocarbon
sulfur heteroatom havingan unshared electron saturated with carbon dioxide. The gravimetric
pair, which can be used to interact with the test results are presented in Table 1.

Table 1. Inhibitory properties of β-ketosulfides

0.1N HCl 0.1N H2SO4 3% NaCl+0.02%
t= 20°C t= 20°C CH3COOH+kerosene
5:1, CO2, t= 20°C
№№ Formula and name of the Conc., ρ, Z, % ρ, Z, % ρ, Z, %
compound mg/l g/m2 g/m2 g/m2 h
h h

CHEMICAL PROBLEMS 2023 no. 2 (21)

 SYNTHESIS OF β-KETOSULFIDES BASED 165

O
I CH CH2 C 50 0.71 79.1 0.97 76.9 0.35 83.3
CH 100 0.55 83.8 0.87 79.3 0.27 87.1
SCH2COOCH3 3
4-Methoxycarbonylmethyl-
thio-4-phenylbutan-2-one
O
II CH CH2 C 50 0.66 80.6 0.92 78.1 0.31 85.2
CH 100 0.52 84.7 0.84 80.2 0.23 89.0
SCH2COOC2H5 3
4-Ethoxycarbonylmethyl-
thio-4-phenylbutan-2-one
O
III CH CH2 C 50 0.60 82.4 0.87 79.3 0.29 86.2
100 0.50 85.3 0.79 81.2 0.20 90.5
CH3
SCH2COOC3H7-i

i-Propoxycarbonylmethyl-
thio-4-phenylbutan-2-one
O
IV CH CH2 C 50 0.37 89.1 0.66 84.3 0.17 91.9
CH3 100 0.26 92.4 0.54 87.1 0.06 97.1
SCH2COOH
4-Carboxymethylthio-4-
phenylbutan-2-one

V Without the inhibitor – 3.40 – 4.20 – 2.10 –

As can be seen from the data in Table 1, phase system.

the studied compounds effectively inhibit the The studied compounds exhibit a greater
corrosion of steel in a two-phase system: protective effect in a solution of hydrochloric
electrolyte-hydrocarbon saturated with carbon acid (79.1-92.4%) than in sulfuric acid (76.9-
dioxide. At that, the corrosion rate decreases 87.1%).
from 2.1 to 0.06-0.35 g/m2 h, while the degree It should be noted that among the studied
of protection is 83.3-97.1%. These compounds compounds, β-ketosulfide, obtained on the basis
have inhibitory properties in acidic medium in of mercaptoacetic acid itself, turned out to be
0.1N HCI and 0.1 N H2SO4, solutions, but the most effective.
exhibit less inhibitory activity than in a two-

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BENZALASETON ƏSASINDA β-KETOSULFİDLƏRİN SİNTEZİ VƏ İNHİBİTOR

XASSƏLƏRİNİN TƏDQİQİ

V.M. Kazımov, Q.Z. Hüseynov, N.S. Məcdi, M.Ə. Mirzəyeva,

O.Q. Nəbiyev, G.S. Kazımova, L.K. Vahidzadə

Azərbaycan Respublikası Elm və Təhsil Nazirliyi akad. Ə.M.Quliyev adına Aşqarlar Kimyası İnstitutu
AZ 1029 Bakı, Böyükşor şosesi, 2062-ci məhəllə,
e-mail: [email protected]

Xülasə: Benzalasetonun merkaptosirkə turşusu və onun alkil efirləri ilə qarşılıqlı təsirindən β-
ketosulfidlərin yeni nümayəndələri sintez edilmiş və xarakterizə olunmuşdur. Onların quruluşu 1H
və 13C-spektroskopiya ilə təsdiq edilmişdir. Sintez olunmuş birləşmələrin qravimetrik üsulla
müxtəlif aqressiv mühitlərdə Cт-3-ün korroziya sürətinə təsiri öyrənilmişdir. Məlum olmuşdur ki,
onlar həm birfazalı elektrolit (0.1N HCl və 0.1N H2SO4 məhlulları), həm də ikifazalı elektrolit–

CHEMICAL PROBLEMS 2023 no. 2 (21)

 SYNTHESIS OF β-KETOSULFIDES BASED 167

karbohidrogen mühitində poladın korroziyasını ləngidirlər. Sonuncu halda onlar daha effektlidirlər
– korroziyanın sürəti 2.1-dən 0.06-0.35 q/m2 saat-dək azalır, mühafizə effekti 83.3-97.1% təşkil
edir. Tədqiq olunan birləşmələr sulfat turşusu məhlulu (76.9-87.1%) ilə müqayisədə xlorid turşusu
məhlulunda (79.1-92.4%) daha yüksək mühafizə effekti nümayiş etdirirlər. Həm elektrolit, həm də
elektrolit–karbohidrogen mühitində ən yüksək effektivlik merkaptosikə turşusu əsasında alınmış β-
ketosulfidə məxsusdur.
Açar sözlər: benzalaseton, merkaptosirkə turşusu, merkaptosirkə turşusunun alkil efirləri, β-
ketosulfidlər, korroziya inhibitorları, mühafizə effekti, birfazalı mühit, ikifazalı mühit, qravimetrik
üsu

СИНТЕЗ β-КЕТОСУЛЬФИДОВ НА ОСНОВЕ БЕНЗАЛЬАЦЕТОНА И

ИССЛЕДОВАНИЕ ИХ ИНГИБИРУЮЩИХ СВОЙСТВ

В.М. Кязимов, Г.З. Гусейнов, Н.С.Маджди, М.А. Мирзоева,

О.Г. Набиев, Г.С. Кязимова, Л.К. Вахид-заде

Институт химии присадок им.акад. А.М. Кулиева Министерства науки и образования

Азербайджанской республики
АZ 1029 Баку, Беюкшорское шоссе, 2062-й квартал; e-mail: [email protected]

Аннотация: Взаимодействием бензальацетона с меркаптоуксусной кислотой и ее

алкильными эфирами синтезированы и охарактеризованы новые представители β-
кетосульфидов, строение которых доказано 1H и 13С ЯМР-спектроскопией. Методом
гравиметрии изучено влияние синтезированных соединений на скорость коррозии Ст-3 в
различных агрессивных средах. Установлено, что исследуемые соединения ингибируют
процесс коррозии как в однофазной кислотной (0.1N HCl и 0.1N H2SO4), так и в двухфазной
(электролит-углеводород) средах. В последнем случае они более эффективны – скорость
коррозии Ст-3 уменьшается от 2.1 до 0.06-0.35 г/м 2 час, при этом степень защиты от
коррозии составляет 83.3-97.1 %. Исследуемые соединения проявляют большее защитное
действие в растворе соляной кислоты (97.1-92.45%), чем в серной кислоте (76.9-87.1%).
Среди испытанных соединений наибольшую ингибирующую эффективность в обеих средах
проявил β-кетосульфид, полученный на основе меркаптоуксусной кислоты.
Ключевые слова: бензальацетон, меркаптоуксусная кислота, алкильные эфиры
меркаптоуксусной кислоты, β-кетосульфиды, ингибиторы коррозии, однофазная среда,
двухфазная среда, гравиметрический метод.

CHEMICAL PROBLEMS 2023 no. 2 (21)