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CHEMICAL PROBLEMS 2025 no. 2 (23) ISSN 2221-8688
249
SYNTHESIS OF 3-PIPERIDINE-2-HYDROXYPROPYLISOBUTYL ETHER AND STUDY
OF ITS ANTI-RUST PROPERTIES
V.M. Farzaliyev, R.M. Babai, R.F. Mammadova, G.M. Guliyeva, G.Sh. Eyvazova
Institute of Chemistry of Additives after acad. A.M. Guliyev of MSE of AR AZ.1029, Baku, Boyukshor highway, 206 2th block [email protected]
Received 10.04.2024 Accepted 21.06.2024
Abstract: Lubricants used in technology should have sufficient protective properties to effectively protect metal parts from rust during operation, as well as during short and long-term idle stops. One of the effective ways to solve this problem is to add effective preservative (conservation) additives to lubricants, which do not adversely affect the operating properties of lubricants and improve their preservation properties. For the purpose of synthesis and research of effective protective additives for lubricating oils, 3-chloro-2-hydroxypropylisobutyl ether was obtained by treating isobutyl alcohol with epichlorohydrin. By adding NaOH to 3-chloro-2-hydroxypropylisobutyl ether, synthetic substance - 3,2-epoxypropylisobutyl ether was synthesized. 3-piperidine-2-hydroxypropylisobutyl ether was synthesized by treating 3,2-epoxypropylisobutyl ether with piperidine.
The structure of substancy was confirmed by H, 13C NMR spectroscopy.
The corrosion efficiency of the compound was studied. It became clear that these compounds are more effective than the industrial additive - alkenylsuccinimide urea.
Keywords: protective additive, corrosion, rust, lubricating oils, isobutyl alcohol, epichlorohydrin, binary amines.
DOI: 10.32737/2221-8688-2025-2-249-255
Introduction
Technical progress is related to the tightening of the working parameters of machines and mechanisms, their ability to provide reliable, long-term and economical work, which, in turn, leads to aggravation of the working conditions of the lubricating oils used in them and this leads to an increase in the requirements for the quality of oils. In order to create high-quality lubricating oils that can meet modern requirements, they add organic substances, i.e. additives, to their composition. In addition to choosing high-quality raw materials, additives with different functional effects should be used in the production of lubricating oils. The synthesis of new types of additives, the study of the dependence between their functional effect and chemical structure is of great theoretical and practical importance. No matter what kind of technical equipment, it is
impossible for them to work without lubricating oil.
It is well known that rusting or corrosion in a humid atmosphere severely harms the economy of a country. Conservation and working-conservation oils containing highly effective protective additives are used as the main method of combating damage to parts of working mechanisms in industry and agriculture.
The analysis of the results of recent studies in the field of protective additives shows that alkylphenols, heterocyclic amines, organic acids and other compounds containing various functional groups and heteroatoms (N, S, etc.) are used as promising protective additives for conservation or working-preservative oils [1-7].
These compounds are surfactants (SAMs) that protect metals from electrochemical
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CHEMICAL PROBLEMS 2025 no. 2 (23)
corrosion (rusting) in an electrolyte-lubricant-metal system.
In connection with the above, 3-piperidine-2-hydroxypropylisobutyl ether was synthesized and studied in order to improve the
protective properties of lubricating oils.
The structure and composition of the synthesized compound was confirmed by 1H, 13C NMR spectroscopy and elemental analysis [8].
Experimental part
1H and C13 NMR spectra of the compounds were recorded on a Bruker 300 spectrophotometer at 300 and 75 MHz, respectively. Hexamethylsilane (HMS) was used as internal standard and deuterium benzene (C6 H6 ) as solvent.
For targeted synthesis, 3,2-
epoxypropylisobutyl ether was taken as starting material. 3-piperidine-2-hydroxypropylisobutyl ether was synthesized by acting on this primary substance with a double amine - piperidine [9].
The reaction was carried out according to the following scheme:
CH3 I 3
CH3- CH-CH2OH + CH2-CH-CH2C1
3 2 2 2
o
H2so4 <fH3
CH3- CH-CH2-0-CH2-CH-CH2Cl (1) OH
CH3 CH3
I NaOH I
CH,-CH-CH20-CH2-<pH-CH2Cl -CH3-CH-CH2-0-CH2-CH-CH2 (2)
OH "HCI V
çh3
ch3- ch-ch2-o-ch2-ch-ch2 + hn;
V
\
CH,
I
CH3- CH-CH2-0-CH2-CH-CH2 N^
OH
(3)
Fig. 1. 1H NMR spectrum of 3-Chloro-2-hydroxypropylisobutyl ether
Preparation of 3-chloro-2-
hydroxypropyl isobutyl ether (1). 30 g of
epichlorohydrin and 36 g of isobutyl alcohol are added to a 100 ml three-necked reaction flask. Then 3 ml of 98% sulfuric acid is added dropwise to the mixture.
The mixture is stirred at a temperature of 90-95°C for 6 hours. After completion of the reaction, the mixture is extracted with toluene and the extract is washed with water, dried with CaCl2, and the toluene is expelled. The residue is driven off under vacuum in an oil bath.
Physico-chemical constants of the obtained substance : no20- 1.4425 ; d420 - 1.04 65 g/sm3; Tb. 95-105° C; yield 60%; MRd - calculated 33.45, found 33.16. Signals of !H , 13C NMR spectra of 3-Chloro-2-hydroxypropylisobutyl ether : NMR, 'H spectrum (Fig. 1), (C6D6, 5, ppm.): 0.78 d (CHs)2 CH(6H), 1.7 m CH-(CH3)2 (H), 2.93 d CH2Cl(2H), 3.24 d CH2O CH2(4H), 3.41 m CHOH(H). NMR, 13C spectrum (Fig. 2), (C6D6, 5, ppm.) : 18.94(CH3)2 CH-, 28.18 CH(CHs)2, 46.06 CH2Cl, 72.89 CH2O CH2-, 78.03CH0H.
IT". <.T HO 140 130 ISO 110 100 90 BO 70 60 SO 40 30 20 ppm
Fig. 2. 13C NMR spectrum of 3-Chloro-2-hydroxypropylisobutyl ether
Synthesis of 3,2-Epoxypropylisobutyl ether (2). To a 100 ml three-necked reaction flask equipped with a mechanical stirrer, reflux condenser and thermometer, add 10 g (0.07 mol) of 3-chloro-2-hydroxypropylisobutyl ether and 2.5 g of NaOH to 30 ml of benzene (dissolve 2.5 g of NaOH in 6 ml of water) 29% is given in the form of a solution. The reaction mixture is stirred at a temperature of 75-80°C for 5-6 hours. The mixture is extracted with benzene, the extract is washed with water, dried with
Na2SO4, and the benzene is expelled. The residue is expelled in a vacuum in an oil bath. Tb. = 100-1010 C, (10 mm c.st.) ; yield : 54%, (5 q) ; no20 - 1.4 1 45 ; d420 - 0.9242 g/sm3. Chemical formula of the substance C7 H14 O2 ; calculated, % : C - 64.61 ; H - 10.85 ; found, % : C - 64.54 ; H - 10.43
Signals of !H, 13C NMR spectra of 3,2-Epoxypropylisobutyl ether: NMR, !H spectrum (Fig. 3) (C6D6, 5, ppm.):
0.86 d (6H, (CH3)2 ) ; 1.78 m ( H, - CH ) ; 2.81m (H, H2C - HC -) ; 3.02 d (2H, OCH2) ;3.07 d
( 2H, CH20 ) ; 3.34 d ( 2H, H2C - HC - )• °
O
NMR, 13C spectrum (Fig. 4) (C6D6, 5, ppm.):
19.09 ( CH3 )2 ; 28.55 (- CH ) ; 43.19 ( - CH - CH3 - ) ; 50.39 ( H2C - HC ) ;
O
71.70 ( - OCH2 ) ; 78.00 ( CH20- ).
Fig. 3. 1H NMR spectrum of 3,2-Epoxypropylisobutyl ether
........... ............ ..........................................I .................. ~
<70 1*0 ISO 1*0 130 120 110 100 80 80 TO 80 SO 40 M 20 10 ppm "
Fig. 4. 13C NMR spectrum of 3,2-Epoxypropylisobutyl ether
Synthesis of 3-Piperidine-2-hydroxypropylisobutyl ether (3). 6 g (0.07 mol) of 3,2-epoxypropylisobutyl ether and 30 ml of benzene are added to a 100 ml three-necked reaction flask. Then, 4 g (0.04 mol) of piperidine is added dropwise to the mixture. At this time, the temperature of the mixture rises to 35°C. The mixture is stirred at a temperature of 75-80°C for 6 hours. After the reaction is complete, the mixture is extracted with benzene, the extract is washed several times with water, dried with Na2SO4, and the benzene is expelled.
The final product: Tb. = 109-110° C, (6 mm c.st.) ; yield : 64%, (4 q) ; no20 - 1.4665 ; d420 -0.9797 q/sm3. Chemical formula of the substance C12 H25 O2 N.
Calculated , % : C - 54.19 ; H - 16.12 ; O - 20.64 ; N - 9.03
Found , % : C - 54.34 ; H - 15.63 ; O -20.14 ; N - 10.01
Signals of !H, 13C NMR spectra of 3-piperidine-2-hydroxypropylisobutyl ether: NMR, !H spectrum (Fig. 5) (C6D6, 5, ppm.):
I
0.8Id (6H, ( CH3)2 ); 1.2 m (2H, -CH2-CH2-CH2-); 1.78 m (H-CH);
ch ^
1.37 m ( 4H,-CH2-CH2-CH2 ) ; 2.28 t ( 4H, f< ); 3.10 d(2H, - CH2-N\ );
CH2
3.4 d ( 2H, -CH2 -O ) ; 3.79 s ( OH ) ; 3.86 t ( H, - O-CH- ).
OH
NMR,
13
C spectrum (Fig. 6) (C6D6, 5, ppm.):
25.97 ( -CH2-CH2-CH2- ); 28.46 (-0- CH - ) ; 54.81 (I<CH ); 62 49 ( CH2 " NC ) '
i cho
OH
66.49 (-CH2 - O - ) ;74.01 (O-CH- ).
OH
Fig. 5. 1H NMR spectrum of 3-Piperidine-2-hydroxypropylisobutyl ether
Fig. 6. 13C NMR spectrum of 3-Piperidine-2-hydroxypropylisobutyl ether
It is known, some organic compounds containing N, O and S have high adsorption activity, passivating them in contact with metal and showing effective protective properties [1012].
Tests of 3-piperidine-2-
hydroxypropylisobutyl ether based on 3,2-epoxypropylisobutyl ether as protective anti-rust additives were conducted and evaluated in the humidity chamber (r-4) included in the complex research system according to GOST 9.054-75, under the influence of sea water and 0.1% solution of HBr acid. Steel-10 plates are ground, polished, washed with hexane or heptane, cleaned with alcohol and dried before testing, and the surface of the plates is not touched by hand. Then the anti-rust additive is added to the oil at a concentration of 1% and mixed.
Steel plates are immersed in this additive oil for 1 minute and hung in the open air for 1 hour. Then r-4 is placed in a humidity chamber and corrosion is observed and evaluated.
Tests according to the 1st method were carried out in the humidity chamber r-4 on samples made of steel (steel-10) in the mode of periodic condensation of moisture. First, the samples are exposed to a regime consisting of a temperature of 40 + 20 and a relative humidity of 95 + 3% for 7 hours. Then conditions are created for moisture condensation on the samples (by cooling them to a temperature lower than the chamber temperature, i.e. 5-10°C). During the test, from the start of the
process to the appearance of the first corrosion center, the samples are visually inspected at regular intervals.
In the 4th method, a steel plate immersed in oil is kept in sea water for 24 hours, and the corrosion process on the steel plate is observed.
Tests according to the 5th method are carried out under the influence of a 0.1% solution of HBr acid. So, for the test, 2 glasses are taken, one is filled with added oil, and the other is filled with a 0.1% solution of HBr acid. The steel plates are first immersed in the solution of HBr acid for 1 second at room temperature, then taken out and immersed in a beaker containing added oil 12 times for 1 minute and suspended in the air for 4 hours. Then the corrosion on the steel plate is reviewed and evaluated. The results of the tests are given in the table.
The results of the tests revealed that when 3-piperidine-2-hydroxypropylisobutyl ether is added to M-12 lubricating oil at a concentration of 1%, the anti-rust property of the oil increases dramatically. In the presence of 3-piperidine-2-hydroxypropylisobutyl ether, corrosion in a humidity chamber begins after 20 days and corrosion on a steel plate is 3.5%, corrosion after 24 hours in seawater is 4.5%, corrosion after 4 hours under the influence of a 0.1% solution of HBr acid is 3%. In comparison, the results of 3-piperidine-2-hydroxypropylisobutyl ether are higher than those of the benchmark industrial additive alkenylsuccinimide urea (SIM).
Table. Test results of 3-piperidine-2-hydroxypropylisobutyl ether as protective anti-rust
additive in M-12 oil
Simple mines Additive viscositv. Humi dir.- chamber (method!) Sei^ita 24iioun (mrthod-4) HBr effect 4 hours (inethod-5)
Duration of the onset of conosjco foci. div$ The number of coaoaon foci ootrosion % The cumber of corrosion foci Corrosion % Ihe iumbei of :otrosicm foci LOTTOS«) %
1 M-12 oil without additiv e * 4 SO 40 90 45 8S 44
5 M12+ CB, . "II CJKCH-C!M>-CHVCH-CH- ' 6h 1.0 20 7 33 9 43 6 3
6 M-12- SIM (sUndard) 10 15 12 6 20 10 16 8
Conclusion
Thus, it was determined that 3-piperidine-2-hydroxypropylisobutyl ether has high anti-rustprotection efficiency. Based on the results of the tests, it can be said that the synthesized 3-
piperidine-2-hydroxypropylisobutyl ether can be recommended for extensive testing for the purpose of creating working-preservative oils.
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