CC BY
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ISSN 2522-1841 (Online) AZERBAIJAN CHEMICAL JOURNAL № 4 2023 ISSN 0005-2531 (Print)
UDC 547.56.56.563:264
AMINOMETHOXY DERIVATIVES OF 1-BENZYLTHIOOCTANE AS A BIOCORROSION INHIBITOR
LA.Jafarov1, E.H.Mammadbayli2, A.Z.Zalov\ KO.Iskenderova1, A.G.Habibova3
Azerbaijan State Pedagogical University 2 Y.Mammadaliyev Institute of Petrochemical Processes, Ministry of Science and Education of Azerbaijan 3Azerbaijan State Oil and Industry University
jafarov. [email protected]
Received 07.07.2022 Accepted 30.03.2023
Based on benzylthioctane-2-ol, heterocyclic amines (piperidine, morpholine, hexamethyleneimine), and formaldehyde, new Mannich bases were synthesized. The reaction was carried out at a temperature of 45-500C for 3-4 h. in an equimolar ratio of starting compounds. The yield of target products was 70-74%. The physicochemical data of the synthesized compounds were determined. The composition and structure of the target products were confirmed by elemental analysis, IR and 1H NMR spectroscopy. Their influence on the vital activity of sulfate-reducing bacteria of the Desulfovibrio desulfiricans type at three concentrations (25, 50, 100 mg/l) was studied. The obtained compounds showed high bactericidal properties, since 1% solutions of these compounds in isopropyl alcohol at a concentration of 100 mg/l showed a 100% bactericidal effect. Given that the aminomethoxy derivatives of 1-benzylthiooctane affect bacteria at very low concentrations, they can be proposed as effective inhibitors of sulfate reducing bacteria (SRB).
Keywords: l-benzylthiooctane-2-ol, heterocyclic amines, Mannich bases, sulfate-reducing bacteria, in-hibitor-bactericides, biocorrosion.
doi.org/ 10.32737/0005-2531-2023-4-31-39
Introduction
Mannich bases containing various functional groups and heteroatoms, such as sulfur, nitrogen, in particular, aminomethylated derivatives of alkyl(aryl)sulfanylalkanes, play a huge role both in the development of synthetic organic chemistry and in applied research. They are widely used as biologically active substances and medicines [1, 2]. One of the economic and environmental problems of oil companies is the difficulties that arise due to corrosion during oil production and transportation of oil. A significant part of the corrosion damage is due to the presence of sulfate reducing bacteria, which enter the oil areas with river, lake, sea, and waste water pumped into it previously untreated from bacteria [3]. In this case, the wells become infected with sulfate reducing bacteria (SRB) and other microorganisms. This complicates the operation of the field and thereby accelerates the corrosion of oil industry equipment, and also significantly reduces the quality of oil, thereby complicating its processing [4].
Among the biologically active compounds of a number of sulfur-containing substances, their amine-containing derivatives stand out, the value of which is associated with the presence of two pharmacophore groups in their molecules [5].
One of the easy and widely used methods for obtaining nitrogen-containing compounds is the aminomethylation reaction. Mannich bases, having pronounced antimicrobial and antifungal properties, have found their application as bactericide inhibitors [6, 7]. On the other hand, there are numerous reports showing the possibility of using Mannich bases as corrosion inhibitors.
Thus, in [8], three new Mannich bis bases were synthesized by the condensation reaction of acetophenone and formaldehyde with various aliphatic diamines. Their corrosion inhibition behavior for N80 steel in 15% HCl solution was evaluated by weight loss measurements, electrochemical tests, scanning electron microscope (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contact angle measurements. The results showed that
the inhibition efficiency increased with increasing concentration as well as the length of the alkyl chain of the inhibitor, with the best inhibitor efficiency reaching 98.20% for 0.3% M-8-M in 15% HCl at 900C. Electrochemical tests have shown that these inhibitors are of the mixed control type. XPS results and contact angle measurements showed that the inhibitors form a dense adsorption layer on the surface of N80 steel. The mechanism of inhibitor adsorption obeys the Langmuir isotherm, while physical adsorption and chemical adsorption exist simultaneously. M-8-M was compared with two commercial inhibitors at elevated temperature and gave a satisfactory corrosion rate of 15.13 mm/yr on N80 steel in 15% HCl at 1200C.
The Mannich base 1-((cyclohexylami-no)methyl)urea was synthesized and characterized using FT-IR, H1 NMR and C13 NMR spectra and tested as a mild steel corrosion inhibitor in 1 N HCl and H2SO4 solutions using poten-tiodynamic polarization and alternating current impedance in the temperature range of 303-333 K [9]. Inhibition efficiency increased with inhibitor concentration and temperature in 1 N. HCl, while inhibition efficiency increased with inhibitor concentration and decreased with temperature. The results of potentiodynamic polarization showed that the inhibitor acts as a mixed type inhibitor. A study of the AC impedance shows that the corrosion of steel was mainly controlled by the charge transfer process. Surface analysis was performed using the SEM method. The adsorption of the inhibitor follows the Langmuir adsorption isotherm. To obtain information about the mechanism of the inhibitory action, the parameters of activation and adsorption were calculated.
The inhibitory effect of the Mannich base, #-(1-morpholinobenzyl)semicarbazide (MBS), was studied for the corrosion of AA6061 in a 0.5 M HCl solution at various temperatures of 303323 K [10]. Testing was carried out by poten-tiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) methods. The efficiency of MBS inhibition improved with an increase in its concentration (0.01-2.56 mM) and an increase in temperature. MBS demonstrated mixed behavior of the inhibitor in all studied ranges of concentrations and temperatures.
MBS showed a maximum inhibition efficiency of 98% at 2.56 mM and 323 K. The inhibitor followed mixed adsorption on the alloy surface and obeyed the Langmuir isotherm model. The results obtained with the EIS were in good agreement with the results of the PDP. A corresponding AA6061 corrosion inhibition mechanism has been proposed. The adsorption of inhibitor molecules on the alloy surface was confirmed by studying the surface morphology using a scanning electron microscope and an atomic force microscope (AFM). Theoretical studies using density functional theory (DFT) confirmed the experimental results.
keto and enol form of MBs
In [11], a corrosion inhibitor containing nitrogen atoms and a conjugated n-bond was synthesized, and its final product, synthesized under optimal conditions of orthogonal test results, was called a multi-Mannich base (MBT). The inhibitory effect of the corrosion inhibitor on N80 steel sheet was evaluated in a CO2-saturated solution containing 3 wt.% NaCl; the corrosion rate was 0.0446 mm/year, and the corrosion inhibition rate was 90.4%. According to research in electrochemistry and adsorption theory, MBT is a mixed corrosion inhibitor that mainly exhibits cathodic suppression ability. The adsorption of MBT on the surface of the steel sheet proceeds according to the Langmuir adsorption isotherm; it can be spontaneously adsorbed on the surface of N80 steel sheet, which provides a good corrosion inhibiting effect. The surface of steel sheet N80 was microscopically characterized using an atomic force microscope (AFM). It can be seen from the results that the MBT-added N80 steel sheet is significantly different from the blank control group; the surface of the steel sheet is relatively smooth, indicating that the MBT forms an effective protective film on the surface of the N80 steel, which inhibits the steel sheet.
Mannich bases ZG/ZH (acid corrosion inhibitors) were synthesized using benzaldehyde,
2-aminothiazole, acetophenone/cyclohexanone as raw materials and choosing the appropriate proportion of reaction time, temperature and raw material ratio [12]. The corrosion inhibition efficiency of two types of Mannich base on steel N80 was studied by the mass loss method and the electrochemical method. The result of the mass loss method showed that both kinds of inhibitors had an excellent effect on N80 steel in
15% hydrochloric acid solution. The electrochemical method showed that both ZG and ZH are mainly composite corrosion inhibitors controlling the anodic interaction, and their corrosion inhibiting effect was further confirmed by the AC impedance method. The behavior of adsorption between inhibitors and the steel surface corresponds to the Langmuir isotherm model.
cr-c^o^-cr^
0
Mannich base ZG Mannich base ZH
In [13], an aliphatic amine, formaldehyde, and sodium lignosulfonate were used to synthesize a new acidic corrosion inhibitor. They were used as raw materials for the production of new Mannich bases as environmentally friendly corrosion inhibitors. The corrosion inhibition of mild steel by these Mannich bases in 2M HCl solution was investigated by the weight loss method. Using one-factor experiments, the optimal molar ratio was determined. At the same time, the effect of temperature and inhibitor dosage on the corrosion inhibition performance of products was studied. Adsorption on the surface of mild steel and the mechanism of inhibition were also discussed. Potentiodynamic polarization studies show that the extracts are mixed type inhibitors.
Profitable new Mannich bases 1-(pyridin-4-yl(pyrrolidin-1-yl)methyl)urea (UPyP), 1-(mor-pholino(pyridin-4-yl)methyl)urea (UMP) and 1-(piperidin-1-yl(pyridin-4-yl)methyl)urea (UPP) were synthesized, characterized and investigated as inhibitors for mild steel surface corrosion in 1.0 M hydrochloric acid solution using weight loss, potentiodynamic polarization mea-
surement and electrochemical impedance spec-troscopy (EIS). X-ray structures of UMP and UPP are shown. The efficiency of inhibition increases with an increase in the concentration of the inhibitor and decreases with an increase in the temperature of the solution. Potentiody-namic polarization measurements showed that all inhibitors are of mixed type. The values of thermodynamic and activation parameters are calculated and discussed. The adsorption of inhibitors on mild steel surfaces in the presence of HCl follows the Langmuir adsorption isotherm. The relationship between molecular structure and their inhibition efficiency was studied using density functional theory (DFT) calculations. It is shown that the experimental and theoretical results are in good agreement [14].
Undoubtedly, the value and importance of using computational methods in the science of corrosion is gradually being recognized [15]. Delving into the thought that certain molecular electronic descriptors such as ionization potential, electron affinity, HOMO-LUMO gap, and dipole moment matter because they represent a unique solution to the problem of understanding
the inhibitory properties of corrosion inhibitors leads us to the next predicament. The reliability of such parameters is a matter of intense debate, and thus the present study is a continuation of this attempt to review earlier experimental results reported for some Schiff and Mannich bases as steel corrosion inhibitors in neutral aqueous solutions using density functional theory calculations. Based on sources of uncertainty such as the structure of the molecular model, the description of environmental efforts, and the errors associated with the nature of quantum chemical methods, it was concluded that it was not possible to obtain a complete picture of the corrosion inhibition mechanism and properties of the compounds under study through computed descriptors.
The corrosion-inhibiting behavior of P110 steel in 20% HCl solution with and without Mannich base as an inhibitor was investigated by electrochemical measurements and soaking experiments [16]. Thermodynamic parameters showed that the dissolution of P110 in HCl solution is an endothermic process. EIS studies have shown that the proposed Mannich base can effectively inhibit corrosion by forming an adsorption layer that acts as a barrier. The polarization curves showed that it is a mixed type inhibitor that can reduce the reactions of anodic dissolution and cathodic hydrogen evolution at the same time.
Thus, the presented analysis of literature reports shows that Mannich bases can be used as inhibitors for various types of corrosion.
Mannich bases based on sulfur-containing alcohols and heterocyclic amines, which have a wide range of properties, also exhibit bactericidal properties, but their effect against the growth of SRBs has been little studied [17, 18].
Discussion of the results
Continuing research in the field of chemistry of biologically active arylsulfanylalkanes, the presented work presents the results of the synthesis and study of the properties of ami-nomethoxy derivatives of 1-(benzylsulfanyl)-octane-2-ol. At the first stage, the initial active hydrogen-containing substrate, previously unknown sulfur-containing seconddary alcohol 1-(benzylsulfanyl)octane-2-ol (III), was synthesized by the reaction of benzylthiol (I) with 1-bromooctanol (II) in an equimolar ratio, in an alkaline medium (40% solution of NaOH in water), at 50-600C for 3-4 h. The reaction proceeds according to Scheme 1.
Next, the Mannich condensation reaction of alcohol (III) with formaldehyde and hetero-cyclic [piperidine (IV), morpholine (V), hexa-methyleneimine (VI)] amines was carried out.
The reaction was carried out at a temperature of 45-500C for 3-4 h in an equimolar ratio of starting compounds, and new representatives of aminomethoxy derivatives of 1-(benzylsulfanyl)octane-2-ol (VII-IX) were obtained according to Scheme 2. The yield of the obtained compounds was 68-75%.
c6h5ch2sh + i
Scheme 1
NaOH, 50-60°C
OH
II
-NaBr, H20 The yield of alcohol (III) was 65%.
OH
m
III + CH20 + HN
/ \
N_/
IV-VI
Scheme 2
C6H5H2C\
X
45-50°C ,
-h,o
VII-IX
X = CH2 (IV, VII); O (V, VIII); CH2-CH2 (VI, IX).
The resulting products are colorless liquids with a characteristic odor, insoluble in water, readily soluble in organic solvents (ethanol, acetone, benzene, toluene, CH2Cl2, CHCl3, CCl4, etc.).
The composition and structure of the obtained compounds were established on the basis of elemental analysis, IR and 1H NMR spec-tro-scopy, and mass spectrometry. The individuality of the starting and synthesized compounds, as well as the composition of the reaction mixtures, was controlled by GLC. In the IR spectrum of compound (III), a broad absorption band is observed in the region of 3630 cm-1, which is characteristic of the stretching vibrations of the hydroxyl group (vOH) of secondary sulfur-containing alcohol (III), which is absent in the corresponding spectra of compounds (VII-IX). The IR spectra of compounds (III, VII-IX) contain absorption bands at 2915-2895 and 2850-2830 cm-1, which are characteristic of vibrations of the C-H bond of CH3 and CH2 groups, respectively. Stretching vibrations of C-C bonds of the benzene end of compounds (VII-IX) give bands of moderate intensity at 1610-1590 and 1500-1400 cm-1. The vCh vibrations of the benzene nucleus appear as bands of medium intensity in the region of 3100-3050 cm-1. The spectra of these compounds contain intense bands of out-of-plane bending vibrations Sc-n in the region of 700-650 cm-1. Stretching vibrations vc-o appear in the region of 1100-1050 cm-1 in the form of an intense band, and vibrations of the C-N bond in the region of 1250-1200 cm-1 in the form of a band of medium intensity. In the IR spectra of compounds VII-IX, absorption bands were found in the region of 735-730 cm-1, which are characteristic of the stretching vibrations of the C-S bond.
The 1H NMR spectra of compounds VII-IX (see experimental part) also confirm the structure and structure of the synthesized compounds. The signal of the protons of the hydroxyl group (OH) of the initial sulfur-containing secondary alcohol III, which manifests itself as a broadened singlet in the region of 2.7 ppm, was not detected in the spectra of compounds VII-IX; instead, a signal in the form of doublets in the region of S 4.25 ppm was ob-
served, which refers to the protons of the OCH2N fragment. This confirms that the hydrogen of the hydroxyl (OH) group is in-volved in the aminomethylation reaction. The protons of the benzene ring (C6H5) give multiplet signals in the region of 5 7.30-7.34 ppm. The mass spectra of compounds III and VII-IX show the corresponding molecular ions, as well as their fragmentation products. The synthesized amino-methoxy derivatives of 1-(benzylsulfanyl)-octane-2-ol (VII-IX) were tested as biocorrosion inhibitors against sulfate-reducing bacteria.
The bactericidal-inhibiting properties were studied according to OCT 39-234-89 at three concentrations (25; 50; 100 mg/l), 1143 strains of Desulfovibrio desulfuricans were used as SRB, the nutrient medium was Postgate B, pH 7.0-7.5, the duration of incubation was thermostat at 30-320C - 15 days.
The synthesized compounds (VII-IX) were studied as inhibitor-bactericides against SRB according to the procedure [19]. For this purpose, 1% solutions of compounds (VII-X) in isopro-panol were prepared. The bactericidal effect of the reagents is studied mainly by observing for 15 days and calculating the amount of H2S formed at the end of the experiment. The formation of H2S is determined by iodometric titration. For comparison, two samples without reagent were taken: control 1 and control 2. Control 1 - only Postgate B nutrient medium, control 2 - nutrient medium and SRB cultures. The results of the study are presented in the Table.
The Table shows that all three samples showed high bactericidal properties. Moreover, 1% solutions of compound (IX) at a concentration of 100 mg/l showed 100% bactericidal effect. A 1% solution of compounds (VII) and (VIII) at a concentration of 100 mg/l showed 96.2% and 98% bactericidal effect. Compounds (VII-IX) at a concentration of 50 mg/l showed 60%, 76%, 91% bactericidal effect, respectively. And at a concentration of 25 mg/l, the bactericidal effect of compounds (VII-IX) was 16.4%, 36.4%, and 52.7%, respectively.
Inhibitor-bactericidal properties of 1% solutions of compounds (VII-IX) in isopropyl alcohol
Reagent Concentration, c, mg/l Number of bacteria (number of cells/mg) Amount of H2S, mg/l Bactericidal effect, Z-%
VII 25 107 213 16.4
50 104 89 60
100 101 9.6 96.2
VIII 25 106 162 36.4
50 103 57 76
100 101 8.2 98
IX 25 104 105 52.7
50 101 25 91
100 - - 100
Control 1 - 14.0 -
Control 2 108 222.0 -
Experimental part
The IR spectra of the synthesized compounds were recorded on Spektrum BX and Bruker instruments from Alpha IR Furye (Germany) in the range 4000-400 cm-1. 1H NMR spectra were recorded on a Bruker AM-300 spectrometer (Germany) at a frequency of 300 MHz in C6D6 solvent, HMDS as internal standard. Mass spectra were obtained on a VG-7070E mass spectrometer (ionizing voltage, 70 eV). The purity of the reaction products was determined from the boiling point, elemental analysis, and GLC. Elemental analysis was carried out on a CARLO ERBA instrument, model EA 1108 (Italy). GLC analysis was carried out on an HXM-8 Mfl, chromatograph (Russia), steel column (300x3 mm) with 5% PEGS on Dinochrome P, carrier gas helium (40 cm3/min), katharometer detector, column temperature 1500C, evaporator - 23 00C. The refractive index ( n 1°) was determined on an ABBEMAT 350/500 refractometer (Germany), specific gravity (d420) by the pycnometric method [20].
For the synthesis of amino derivatives, reactive benzylmercaptan (I), formaldehyde, and commercial secondary amines were used: piperi-dine (IV), morpholine (V), hexamethyleneimine (VI). Before use, the original components were distilled. Benzene was taken as a solvent, which was purified and dried according to a known method [21]. Paraform was used in the form of a reactive powder, which depolymerizes when
heated.
1-(Benzylsulfanyl)octane-2-ol (III). To a
mixture of 31 g (0.25 mol) of benzylmercaptan
(I) and 10 g (0.25 mol) of NaOH in 15 ml of water (40% solution) at 500C with vigorous stirring, 52.3 g (0.25 mol) of 1-bromooctane is added dropwise of 1-bromooctane-2-ol (II). The mixture was stirred at 50-600C for 3-4 h. After cooling, 30 ml of benzene was added to the mixture, the aqueous layer was separated, the organic layer was washed with water until neutral, and dried with anhydrous MgSO4. After distilling off the solvent, the residue was distilled in vacuo. Yield 41.02 g (65%), boil. temp. 162-1640C (1 mm Hg.), ng0 1.5352, dl01.0156, MRd 77.40, calc. 77.62. IR spectrum, v, cm-1: 3630 (OH), 2915 (CH3), 2850 (CH2), 3070 (CH of benzene cycle), 1590 (c=Carom), 1050 (C-O), 700 (C-S). NMR 1H, 5, ppm: 0.9 t (3H, C8H3, J 7.3 Hz), 1.35-1.45 m (10H, C3-7H2), 2.5 t (2H, SC1H2), 2.8 s (H, OH), 3.7 t (1H, OC2H), 3.9 c (2H, PhCH2), 7.30-7.36 m (5H, C6H5). Mass-spectra, m/z (IreL, %): 253
(II) [M + H]+, 252 (15) [M]+, 235 (100) [M-OH]+, 221 (3) [M- OH - CH2]+, 177 (72) [CUH13S]+, 129 (19) [M- C8H9 - H2O]+, 122 (6) [CyH6S]+, 95 (50) [PhCH2]+, 89 (15), 82 (51). Founded, %: C 71.15; H 9.51; S 12.61. C15H24OS. Calculated, %: C 71.37; H 9.58; S 12.70. M 252.42.
1-[Benzylsulfanyl]-2-piperidinomethoxy-
octane (VII) was obtained from 5.05 g (0.02 mol) of compound (III), 0.6 g of paraform, and
1.7 g (0.02 mol) of piperidine (IV). Yield 4.9 g (70%), boil. temp. 184-1860C (2 mm Hg.), nf 1.5244, d|° 0.9962, MRd 107.44, calc. 107.46. IR spectrum, v, cm-1: 3055 (CHarom.), 2900 (CH3), 2895 (CH2), 1585 (CHarom.), 1250 (C-N), 1050 (C-O), 650 (C-S). NMR 1H, 5, ppm.: 0.91 t (3H, C8H3; J 7.2 Hz), 1.34 m (10H, C3-7H2), 1.62 m (8H, 4CH2cycl), 2.45-2.90 m (6H, SCH2, 2NCH2), 3.35 t (1H, OCH), 3.8 s (2H, PhCH2), 4.20 d.d. (2H, OCH2N), 7.30-7.36 m (5H, C6H5). Mass-spectra, m/z (Irei., %): 350 (8) [M + H]+, 349 (10) [M]+, 331 (9) [M - H2O]+, 318 (27) [M - HO - CH2]+, 266 (6) [M -C5H9N] , 246 (70) [M - C5H11N - H2O]+, 226 (100) [M - CyHyS]+, 223 (51) [M - CyH^NOf, 193 (5) [C12H17S] , 91 (78) [PhCH2]+, 75 (60) [CsHyS]+. Founded, %: C 71.94; H 10.02; N 3.98; S 9.08. C21H35NOS. Calculated, %: C 72.15; H 10.09; N 4.01; S 9.17. M 349.58.
1-[Benzylsulfanyl]-2-morpholinometh-oxyoctane (VIII) was obtained from 5.05 g (0.02 mol) of compound (III), 0.6 g of paraform, and 1.74 g (0.02 mol) of morpholine (V). Yield 5.52 g (74%), boil. temp. 188-1900C (2 mm Hg.), n22° 1.5246, d\° 1.0282, MRd 104.71, calc. 104.68. IR spectrum, v, cm-1: 3060 (CHarom), 2900 (CH3), 2840 (CH2), 1600, 1500 (C=Carom),1250 (C-N), 1100 (C-O), 750 (C-S). NMR 1H, 5, ppm: 0.95 t (3H, C8Hs; J 7.2 Hz), 1.34 m (10H, C3-7H2), 2.35-2.60 m (2H, SCH2), 2.9-3.1 m (8H, 2OCH2cycl., 2NCH2cycl.), 3.35 t (1H, OCH), 3.8 s (PhCH2), 4.20 d.d. (2H, OCH2N), 7.30-7.35 m (5H, C6H5). Mass-spectra, m/z (Irel, %): 352 (10) [M + H]+, 351 (18) [M]+, 333 (13) [M - H2O]+, 319 (21) [M -H2O - CH2]+, 265 (27) [M - C4H8NO]+, 246 (53) [M - C4H9NO - H2O]+, 228 (18) [M -C7H7S]+, 198 (71) [M - C8H9OS]+, 193 (15) [C12H17S]+, 100 (100) [C5H10NO]+, 91 (40) [C6H5N]+, 75 (46) [CbH7S]+, 57 (35) [C2H3NO] . Founded, %: C 68.12; H 9.38; N 3.94; S 9.03. C20H33NO2S. Calculated, % C 68.33; H 9.46; N 3.98; S 9.12. M 351.56.
1-[Benzylsulfanyl]-2-hexamethyleneimi-nometh oxyoctane (IX) was obtained from 5.05 g (0.02 mol) of compound (III), 0.6 g (0.02
mol) of paraform, and 1.98 g (0.02 mol) of hex-amethyleneimine (VI). Yield 5.52 g (72%), boil. temp. 186-188°C (2 mm Hg.), n2D0 1.5242, df 0.9916, MRd 111.98, calc. 112.11. IR spectrum, v, cm-1: 3050 (CHarom), 2895 (CH3), 2830 (CH2), 1600, 1500 (C=Carom), 1200 (C-N), 1050 (C-O), 735 (C-S). NMR 1H, S, ppm: 0.95 t (3H, C8H3; J 7.3 Hz), 1.34 m (10H, C3-7H2), 1.62 m (8H, 4CH2cycl), 2.45-2.85 m (6H, SC1H2, 2NCH2cycl), 3.5 t (1H, OC2H), 3.8 s (2H, PhCH2), 4.20 d.d. (2H, OCH2N), 7.307.35 m (5H, C6H5). Mass-spectra, m/z (Irei, %): 364 (10) [M + H]+, 363 (13) [M]+, 345 (6) [M -H2O]+, 331 (14) [M - H2O - CH2]+, 272 (13) [M - C6H5NI+, 258 (7) [M - C4H9NO - H2O]+, 255 (17) [M - C6H6NO]+, 235 (51) [M -C17H14NO]+, 225 (8) [M - C8H^S]+, 138 (72) [C5H10S]+, 128 (56) [CyH14NO]+, 122 (100) [CyH6S]+, 91 (6) [C6H5N]+. Founded, %: C 72.46; H 10.18; N 3.82; S 8.73. C22H37NOS. Calculated, %: C 72.67; H 10.26; N 3.85; S 8.82. M 363.61.
Conclusion
1. Three-component Mannich reaction of 1-(benzylsulfanyl)octane-2-ol, formaldehyde and secondary heterocyclic amines gave aminometh-oxy derivatives of 1-(benzylsulfanyl)octane. The yield of compounds was 70-74%. Their physico-chemical properties were determined, the composition and structure of the obtained compounds were confirmed using elemental analysis data, IR and 1H NMR spectroscopy, and mass spectro-metry.
2. The effect of the synthesized compounds on SRBs of the Desulfoxibrio desulfofurcans type at three concentrations (25, 50, 100 mg/l) was tested. It was found that, at a concentration of 100 mg/l, the bactericidal effect of compounds (VII-IX) was 96.2%, 98%, and 100%, respectively. It has been determined that 1% solutions of aminomethoxy derivatives of 1-(benzylsulfa-nyl)octane exhibit high bactericidal activity, and they act on bacteria at very low concentrations.
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1-BENZiLTiOOKTANIN AMiNOMETOKSi TÖROMOLORi BÏOKORROZÏYA ÎNHÎBÎTORU KlMi
LA.Caf3rov, E.H. Mammadbayli, A.Z.Zalov, KO.iskandarova, A.Q.Habibova
Elmi adabiyyatda daha çox Mannix reaksiyasi kimi taninan aminometillaçma reaksiyasi ß-karbonil birlaçmalarinin alinmasinda an vacib üsullardan biridir. Bu reaksiyanin mahsullari (Mannix asaslari) sanaye va kand tasarrüfatinin müxtalif sahalarinda geniç istifada olunur. Mannix asaslarinin tatbiqinin an vacib sahalari arasinda onlarin korroziya inhibitorlari kimi istifadasi vurgulanmalidir. Taqdim olunan maqalada yeni Mannix asaslarinin sintezi aparilir va onlarin sulfat reduksiya edan bakteriyalann yaratdigi biokoroziyanin yeni inhibitorlari kimi istifadasinin mümkünlüyü göstarilir. 1-Benziltioktan-2-olun formaldehid va heterosiklik aminlarin (piperidin, morfolin, heksametilenamin)
asasinda yeni Mannix asaslari sintez edilmi§dir. Reaksiya 45-50°C temperaturda 3-4 saat muddatinda, ilkin maddalarin ekvimolyar nisbatinda apanlmi§dir. Alinan maddalarin giximi 70-74% ta§kil etmi§dir. Birla§malarin fiziki-kimyavi gostaricilari tayin edilmi§, qurulu§lari iQ va 1H NMR spektroskopiya usullan ili tasdiq edilmi§dir. Onlarin "Desulfovibrico desulfiricans" tipli sulfatreduksiyaedici bakteriyalara qar§i tasiri tadqiq edilmi§dir. Muayan edilmi§dir ki, alinmi§ aminometoksi birla§malar 1%-li qatiliqda yuksak qeyd olunan bakteriyalara qar§i yuksak bakterisid inhibitor xassaya malikdir.
Agar sozlar. 1-benziltioktan-2-ol, heterotsiklik aminbr, Mannix asaslari, sulfatreduksiyaedici bakteriyalar, inhibitor bakterisidbr, biokorroziya.
