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CHEMICAL PROBLEMS 2023 no. 3 (21) ISSN 2221-8688
UDC 547.279(088.8)
SYNTHESIS OF ALKOXYCARBONYLMETHYL ESTERS OF THIOACETIC AND THIOBENZOIC ACIDS AND THEIR INVESTIGATION AS ADDITIVES TO
LUBRICATING OILS
11 2 2 2 K.Z. Huseynov1, P.A. Aliyev1, M.A. Mirzoyeva2, I.M. Eyvazova2, N.A. Aliyev2
1Baku State University Academician Z .Khalilov Str. 23, AZ1148, Baku, 2Acad.A.M.Guliyev Institute of Chemistry of Additives Boyukshore Highway, Block 2062, AZ 1029, Baku, e-mail: [email protected]
Received 18.05.2023
Accepted 27.07.2023
Abstract: The method for obtaining alkoxycarbonylmethyl esters of thioacetic acid, based on the interaction of mercaptoacetic acid esters with acetic anhydride in an alkaline medium was proposed. It showed that an alternative way to obtain alkoxycarbonylmethyl esters of thioacetic acid is the reaction of mercaptoacetic acid esters with acetyl chloride in the presence of equimolar quantities of triethylamine. The interaction of mercaptoacetic acid esters with benzoyl chloride in the presence of equimolar amounts of triethylamine was used to synthesize appropriate alkoxycarbonylmethyl esters of thioacetic and thiobenzoic acids. Study into synthesized compounds as additives to lubricating oils revealed that addition of butoxycarbonyl methyl ester of thioacetic acid at a concentration of 1% in M-8 oil practically eliminated its corrodibility, while butoxycarbonyl methyl esters of thioacetic and thiobenzoic acids also had some lubricating and antimicrobial properties.
Keywords: esters of mercaptoacetic, thioacetic and thiobenzoic acids, acetic anhydride, acetyl chloride, lubricating oils, corrodibility, lubricating properties, antimicrobial additives DOI: 10.32737/2221-8688-2023-3-294-300
Introduction
As the mechanical engineering and the tightening of requirements for lubricating oils develops, there is a need to develop more effective additives for them. In this aspect, any study related to the directed synthesis of new multifunctional additives and the identification of the relationship between their structure and properties is undoubtedly relevant.
Previously, we studied the effect of the ester group on the functional properties of
various sulfides and found that just alkoxycarbonylmethylthio fragment largely contributed to enhancing the anticorrosion activity of the compounds [1-3]. In order to study the effect of the acyl group attached to a sulfur atom, on the properties of the compound, there were studied alkoxycarbonylmethyl esters of thioacetic and thiobenzoic acids with the following formula
r-0-c-ch2-s-c-r' r - alkyl radicals, R1 = CH3, C6H5
0 2 0
CHEMICAL PROBLEMS 2023 no. 3 (21)
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As compared to the alkyl esters of thiocarboxylic acids, their alkoxycarbonyl methyl esters are poorly studied compounds [4,5].
There is no information in the literature on the interaction of alkyl esters of mercaptoacetic
acid with acetic anhydride. We revealed that in an alkaline medium, this reaction leads to the formation of alkoxycarbonylmethyl derivatives of thioacetic acid, which are of interest both as additives to lubricating oils and biologically active substances [6,7].
R-O-C-CH-SH +
CH3—C
CH3-C O
O
O
R = i-C3H7 (I), C4H9 (II)
R-O-C-CH2-S-C-CH3 + CH3COOH
O
O
The structure of the synthesized compounds was confirmed by the data of IR and NMR spectra [8, 9], as well as chemically. So, in the IR spectrum of
isopropoxycarbonylmethyl ester of thioacetic acid (comp.I), the absence of a band with a frequency of 2600-2500 cm-1 indicates the interaction of the mercapto-group of the isopropyl ester of mercaptoacetic acid with acetic anhydride. The IR spectrum of comp.I
contains absorption bands at 1740 and 1136 cm-1, indicating the presence of C=O and C-S bonds, respectively.
1H NMR spectrum of comp.I (CDCb, 5, ppm): 1.28 d. (6H, 2CH3), 2.35 s. (3H, CH3) , 3.78 s. (2H, CH2), 4.96 m. (1H, CH).
13C NMR spectrum of comp.I (CDCh, 5, ppm): 22.3 (2CH3), 33.6 (CH2), 70.2 (CH), 169.9 (COO), 195.3 (CO).
Fig.1.IR spectra of isopropoxycarbonylmethyl ester of thioacetic acid Experimental Part
The starting esters of mercaptoacetic acid were obtained by the well-known method [10].
The IR spectra of substances were taken on a Specord M-80 spectrophotometer in a thin layer of 4000-400 cm"1'
The NMR spectra were taken on AS-200 spectrophotometers (Bruker 1H-200 MHz, 13C-50 MHz). Internal standard was TMS. 1-5%
solutions of the studied compounds in CDCl3 were used.
Butoxycarbonylmethyl ester of thioacetic acid (II). A mixture of 4 g of NaOH, 8 ml of water and 17.76 g (0.12 g-mol) of mercaptoacetic acid butyl ester was poured onto 50 g of finely crushed ice, and 12.75 g (0.125 g-mol) of acetic anhydride was quickly added
with vigorous stirring. Stirring continued for another 1 hour at a temperature of 40-500C. Then the reaction mixture is extracted with benzene, washed with water to neutral, dried
over calcium chloride, and after distillation of benzene, comp.II was isolated by vacuum distillation, yield is 14.8 g (65%).
Fig.2. NMR spectra of isopropoxycarbonylmethyl ester of thioacetic acid
The isopropoxycarbonylmethyl ester of thioacetic acid comp.I was obtained by a similar procedure with yield of 64%. By interaction of isopropyl and butyl esters of
mercaptoacetic acid with acetyl chloride in the presence of equimolar amounts of triethylamine compounds identical to comp.I and II, respectively were obtained:
(coh^n
r-o-c-ch2-sh + ch3-c-ci —2 5 3 » r-o-c-ch2-s-c-ch3 + (c2h5)3n . hcl
o o
R = i-C3H7 (I), C4H9 (II)
"2 w jj "3 V3'
o o
Isopropoxycarbonylmethyl ester of thioacetic acid (I). 3.93 g (0.05 g-mol) of acetyl chloride was added dropwise to cooled to -5°C solution of 6.7 g (0.05 g-mol) of isopropyl ester of mercaptoacetic acid and 5.1 g (0.05 g-mol) of triethylamine in 50 ml of anhydrous benzene, so that the mixture temperature didn't rise above 5°C. The reaction mixture was stirred for
1 hour at 50-60°C. The separated precipitate of the hydrochloric acid salt of triethylamine was filtered off, after distillation of benzene, comp.I was isolated by vacuum distillation, yield was 6.6 g (75%).
Alkoxycarbonylmethyl esters of thiobenzoic acid were obtained by a similar procedure (7480%)
R-0-C-CH2-S-C-C6H5 R = С2H5 (III) i-C3Hy (IV), C4H9 (V)
O 0
The synthesized compounds (I - V) organic solvents and lubricating oils, insoluble
(Table1) are liquids that are readily soluble in in water.
Table 1. Characterization of alkoxycarbonylmethyl esters of thioacetic and thiobenzoic acids
s! Q iSl 13.09 1/1 CO 14.30 en 12.71
OJ s 3 CJ EU oo Os >jn OS i/i Os
■cJ o O o o OS CO >-in CO o 'O CO CO
Formula iSl O r-* EU r-— u o EB eg O o EU O o 'T EU O O EU o
DO CT", ^ so iN wn so en m H
■ö' o EU o Q r^i ITl >jn CO Wl SQ
MH o CO c^l oo o O SD fin Q SD m
CJ os co CO O OS in CO so en o fin CO
s, ^r cO <vn Os r--. CO un Os
r-5 Q o c— m fm ^r en un OS CO on m
O a OS OS o CO fn o OS fin OS ^r fin
^ B '■■ 1 s=L, .. tu pq F-* r"N —1 o ^ -CS r"N f-- ■ vn m * OS y_^ —1 o A Ci OS un i en in ' m Os O OS
Ori eu1 u eu1 tri' o EU* o EU' o
Bri EU u 1 £ a EU u EU u I E^ u
Comp. 1—1 1—1 i—i i—i i—i £ >
Results and Discussions
The influence of the synthesized compounds on the anticorrosive, lubricating and antimicrobial properties of M-8 oil was studied.
The anticorrosive properties of derivatives of thioacetic and thiobenzoic acids were determined by the rigorous NAMI method in the presence of 0.02% copper naphthenate for 25 hours at 140°C (lead plates). As a result of the
tests, it was found that the addition of 1% of comp.II practically eliminated the corrosiveness of M-8 oil.
The lubricating properties of the studied compounds were studied on a four-ball friction machine according to GOST 9490-75.The test results are shown in Table 2.
Table 2. Lubricating properties of synthesized com
Comp. Formula of compounds Concentration, % Is Pw, H Pc, H Dws ,mm
II ii 2 ii 3 o o 1 38 784 1568 0.49
V c4h9-0-c-ch2-s-c-<(=) o o 1 38 784 1568 0.44
M-8 oil 32 617 1235 0.62
pounds
The lubricating properties of the compounds are characterized by the scuffing index (Is), the welding load (Pw), the critical seizing load (Pc) and the wear spot diameter (Dws). The anti-wear property index is determined at a load of 392 Newton and test duration of 30 minutes.
According to Table 2, butoxycarbonyl methyl esters of thioacetic and thiobenzoic acids significantly improve the lubricating properties
of M-8 oil. So, introducing 1% of these compounds into M-8 oil decrease the wear scar diameter from 0.62 mm to 0.44 - 0.49 mm. The antimicrobial properties of the synthesized compounds (II, V) are established by the method MEC - 1954 under conditions simulating tropical atmosphere (in a thermostat at 28-320C and relative air humidity 90-100%). Fungal and bacterial cultures were used as test microbes. The test results are shown in Table 3.
Table 3. Antimicrobial properties o: synthesized compounds
Comp. Formula Concen-tr., % Zone of microbial growth inhibition, cm
Bacteria Fungi
Pseudomonas aeruginosa Candida tropicalis Aspergillu s niger
II c4h9-o-c-ch2-s-c-ch3 o o 0.5 1.5 + + + + 0.1 - 0.2 0.3 - 0.4 0.7 - 0.9 1.5 - 1.7
V c4h9-o-c-ch2-s-c-<(—) 4 9 ii 2 ii ^^ o o 0.5 1.5 + + 0.1- 0.2 0.1- 0.2 0.2 - 0.3 0.6 - 0.8 0.8 - 1.5
+ Abundant growth of microorganisms around the well in the Petri dish
As can be seen from Table 2, the studied compounds (II, V) show a certain antifungal activity: the inhibition zone of fungi is 1.5-1.7 cm.
Thus a one-stage method for the synthesis of alkoxycarbonylmethyl esters of thioacetic and thiobenzoic acids was developed, which consists in the interaction of alkyl esters of mercaptoacetic acid with acetic anhydride in an alkaline medium.
It found that the interaction of
mercaptoacetic acid esters with acetyl and benzoyl chlorides in the presence of equimolar amounts of triethylamine leads to the formation of alkoxycarbonylmethyl esters of thioacetic and thiobenzoic acids, respectively.
It was established that
alkoxycarbonylmethyl esters of thioacetic and thiobenzoic acids had some anticorrosive, lubricating and antimicrobial properties in relation to lubricating oils.
References
1. Huseynov G.Z., Aliyev P.A., Mirzoyeva M.A. Alkoxycarbonylmethyl sulfides as lubricant additives. Oil Refining and Petrochemistry, 2022, no. 1, pp. 23-25. (In Russian).
2. Huseynov G.Z. Synthesis and properties of mercaptoacetic acid. Processes of Petrochemistry and Oil Refining, 2022, no. 2, pp. 233-240.
3. Guryanova N.E., Mirzoyeva M.A., Romm I.P., Huseynov G.Z., Mamedov F.A. Dipole moments and electron-donating properties of some derivatives of esters of mercaptocarboxylic acids. Journal of Organic Chemistry, 1978, vol. 48, no. 1, pp.114-119. (In Russian).
4. Weigand-Hilgetag. Experimental methods in organic chemistry. Moscow: Chemistry Publ., 1968, 944 p. (In Russian).
5. .Wenzel F.W., Reid E.E. The preparation and properties of a series of alkyl thiolacetates. J.Am.Chem.Soc., 1937, vol. 59, no. 6, pp. 1089-1090.
6. Garmash S.N., Skulskaya E.A., Priymenko
B.A., Klyuev N.A. Synthesis and properties of 7-aroylalkylxanthinyl-8-thioacetic acid derivatives. Chemistry of Heterocyclic Compounds, 1990, no. 7, pp. 967-970. (In Russian).
7. Shirai A, Fumoto Y, Shouno T, Maseda H, Omasa T. Synthesis and biological activity of thiazolyl-acetic acid derivatives as possible antimicrobial agents. Biocontrol Sci. 2013, vol. 18(2), pp. 59-73. doi: 10.4265/bio.18.59. PMID: 23796637.
8. Bellamy L. New data on the IR spectra of complex molecules. Moscow: Mir Publ., 1971, 318 p. (In Russian).
9. Ionin B.I., Ershov B.A., Koltsov A.I. NMR spectroscopy in organic chemistry. Leningrad: Chemistry Publ., 1983, 269 p. (In Russian).
10. Huseynov K.Z., Gambarov D.G., Mirzoyeva M.A., Mamedov F.N., Fatizade R.F. Synthesis of thioglycolic acid esters and their application in analytical chemistry. Azerbaijan Chemical Journal, 1977, no. 6, pp. 103-107. (In Russian).
TiOSiRKO УЭ TiOBENZOY TURÇULARININ ALKOKSiKARBONiLMETiL EFiRLORiNiN SiNTEZi УЭ ONLARIN SÜRTKÜ YAGLARINA AÇQAR KÎMi TODQiQi
K.Z. Hüseynov1, P.A. Oliyev1, М.Э. Mirzayeva 2, i.M. Eyvazova2, N.O. Oliyev2
1 Baki Dövlst Universiteti 2Akademik d.Quliyev adina A§qarlar Kimyasi institutu AZ1148, Baki, akademik Z.Xdlilov kûç.23 AZ1029, Baki, Böyük^or çosesi, тэкэПд 2062 e-mail: [email protected]
Xulasa: Tiosirka tur§usunun alkoksikarbonilmetil efirlarinin alinmasi ифип qalavi muhitda merkaptosirka tur§usu efirlarinin sirka anhidridi ila qar§iliqli tasirina asaslanan usul taklif edilmi§dir. Gostarilmi§dir ki, tiosirka tur§usunun alkoksikarbonilmetil efirlarini almaq u9un alternativ usul merkaptosirka tur§usu efirlarinin ekvimolyar miqdarda trietilaminin i§tiraki ila asetilxloridla reaksiyasidir. Tiosirka va tiobenzoy tur§ularinin muvafiq alkoksikarbonilmetil efirlarinin sintezi u9un ekvimolyar miqdarda trietilaminin i§tiraki ila merkaptosirka tur§usu efirlarinin benzoilxloridla qar§iliqli tasirindan istifada edilmi§dir. Sintez edilmi§ birla§malarin surtku yaglarina a§qar kimi tadqiqi naticasinda muayyan edilmi§dir ki, tiosirka tur§usunun butoksikarbonilmetil efirinin 1% qatiliqda M-8 yagina alava edilmasi onun korroziyasini praktiki olaraq aradan qaldirir, tiosirka va tiobenzoy tur§ularinin butoksikarbonilmetil efirlari ham da muayyan yaglayici va antimikrob xassalar gostarir.
A?ar sozlar: merkaptosirka-, tiosirka- va tiobenzoy tur§ularinin efirlari, sirka anhidridi, asetilxlorid, surtku yaglari, korroziyaya ugrama, yaglayici xassalar, antimikrob a§qarlar
СИНТЕЗ АЛКОКСИКАРБОНИЛМЕТИЛОВЫХ ЭФИРОВ ТИОУКСУСНОЙ И ТИОБЕНЗОЙНОЙ КИСЛОТ И ИССЛЕДОВАНИЕ ИХ В КАЧЕСТВЕ ПРИСАДОК К
СМАЗОЧНЫМ МАСЛАМ
11 2 2 2 К.З. Гусейнов , П.А. Алиев , М.А. Мирзоева , И.М. Эйвазова , Н.А. Алиев
1 Бакинский Государственный Университет AZ1148, Баку, ул.академика З.Халилова 23 2Институт химии присадок им.академика А.М.Кулиева AZ1029, Баку, Беюкшорское шоссе , квартал 2062 e-mail: [email protected]
Аннотация: Предложен способ получения алкоксикарбонилметиловых эфиров тиоуксусной кислоты, основанный на взаимодействии эфиров меркаптоуксусной кислоты с уксусным ангидридом в щелочной среде. Показано, что альтернативным путем получения алкосикарбонилметиловых эфиров тиоуксуснй кислоты являются реакции эфиров меркаптоуксусной кислоты с хлористым ацетилом в присутствии эквимолярных количеств триэтиламина. Взаимодействием эфиров меркаптоуксусной кислоты с хлористым бензоилом в присутствии эквимолярных количеств триэтиламина синтезированы соответствующие алкоксикарбонилметиловые эфиры тиоуксусной и тиобензойной кислот. В результате исследования синтезированных соединений в качестве присадок к смазочным маслам установлено, что добавление бутоксикарбонилметилового эфира тиоуксусной кислоты в концентрации 1% в масло М-8 практически устраняет его коррозионность, бутоксикарбонилметиловые эфиры тиоуксусной и тиобензойной кислот также обладают определенными смазывающими и антимикробными свойствами.
Ключевые слова: эфиры меркаптоуксусной, тиоуксусной и тиобензойной кислот, уксусный ангидрид, ацетилхлорид, смазочные масла, коррозионность, смазывающие свойства, антимикробные присадки.
