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CHEMICAL PROBLEMS 2019 no. 1 (17) ISSN 2221-8688 81
UDC 547.426:621.892
METAL COMPLEX COMPOUNDS AS EFFECTIVE ADDITIVES
TO CUTTING FLUIDS
V.M. Farzaliyev1, M.P. Bayramov2, S.Kh. Jafarzadeh2, P.Sh. Mammadova1,
E.R. Babayev1, I.M. Eyvazova1
1Acad. A.Guliyev Institute of Chemistry of Additives of ANAS Beyukshor Highway, Block 2062, AZ1029, Baku, e-mail: pervin_mammadova@mail. ru
2Baku State University Acad. ZahidKhalilov 23 str., Baku, AZ 1148, e-mail: info@bsu.az
Received 11.02.2019
Among the numerous classes of organic compounds used as additives, transition metal complexes with aromatic azomethines, Schiff bases have proven their worth. Note that Azomethins and their various functionally substituted derivatives exhibit high biological activity. These compounds effectively inhibit the growth of various microorganisms and can be used in microbiology, pharmacology, food and manufacturing industries, as well as additives to lubricating oils. The paper describes the synthesis and study of azomethine compounds based on benzaldehyde and amines (aniline, benzylamine), as well as their transition metals complexes. The antimicrobial and antiwear properties of the original azomethines and their complexes with transition metals (Cu2+, Ni2+, Co2+) were studied. It found that they show effective antiwear properties in lubricating oil AK-15, high bactericidal and fungicidal efficiency in emulsion cutting fluid Azerol-5.
Keywords: azomethine, Schiff bases, metal complexes, cutting fluid, antimicrobial efficiency, antiwear property, lubricating oil, multifunctional additive. Doi.org/10.32737/2221-8688-2019-1-81-86
INTRODUCTION
In recent years there has been an intensified search for new compounds, including metal-organic ones simultaneously possessing different functional properties. Exhibiting high biological activity, these compounds [1-5] are widely used as additives to fuels and lubricating oils, polymer stabilizers, metal corrosion inhibitors [6] and can also serve as a source for the synthesis of other compounds. All things considered, the
synthesis and study of coordination compounds of transition metals with aromatic azomethines are problems of today both from scientific and practical points of view.
The purpose of the research was to synthesize and study effective complexes of Cu2+, Ni2+, Co2+ with Schiff bases obtained through the condensation of benzaldehyde with aniline and benzylamine used as additives to CF.
EXPERIMENTAL PART
Benzylidenaniline (Li). 21.2 g (0.2 mol) of benzaldehyde and 18.7 g (0.2 mol) of aniline, separately dissolved in a minimum amount of methanol were placed into a reaction flask with a magnetic stirrer and reflux condenser. The reaction mass was stirred for 2 hours. After completion of the reaction, the mixture was filtered and left to crystallize. Precipitated beige crystals were re-crystallized from
hexane as follows: MP (melting point) = 92-940C, yield 17 g (47%), C13H11N; IR spectrum (vcm-1), 1629 (CH = N); 1312 (N-C6H5) Benzylidenebenzylamine (L2) was synthesized in a similar manner. The resulting crystals were re-crystallized from benzene as follows: MP = 1150C, yield 62%; C14H13N; IR spectrum (vcm-1), 1625 (CH = N); 1312 (N-C6H5)
4-dimethylamino-1-benzilidenaniline (L3).
MP=1000C, yield 84.7% ; C15H16N2; Benzylideneaniline complex with copper (Li)2Cu. A mixture of methanol solutions of 3.62 g (0.02 mol) of benzylideneaniline and 1.8 g (0.01 mol) of copper acetate was heated at 650C in a reaction flask equipped with a reflux condenser for 2.5 hours. The obtained dark crystals were re-crystallized from methanol as follows: MP = 2200C, yield 37.7%; C26H22N2Cu; IR spectrum (vcm-1), 1627.6 (CH = N); 1313, 1578 (CH3COO-)
L1Me, L2Me and L3Me were obtained in a similar manner:
Benzylideneaniline complex with nickel (L^Ni. MP = 2350С, yield 46.4%; C26H22N2Ni;
Benzylideneaniline complex with cobalt (L1)2Co. MP = 2420С, yield 48.4%;
C26H22N2Co;
4-dimethylamino-i-benzilidenaniline complex with copper (L3)2Cu. MP = 1850С, yield 72%; C15H16N2Cu; 4-dimethylamino-1-benzilidenaniline complex with nickel (L3)2Ni. MP = 1300С, yield 59.1%; C^H^NNi; 4-dimethylamino-1-benzilidenaniline complex with cobalt (L3^Co. MP = 1550 C, yield 74.9% ; C^H^Co.
The investigated compounds were studied as antimicrobial and anti-wear additives to CF and oils.
Antimicrobial efficiency of the samples was determined by the method of zonal diffusion according to ГОСТ 9.052-88 and ГОСТ 9.082-77 (tab.1). Pure cultures of the
following types of bacteria and fungi as aggressive destroyers of oil products were used for testing: Bacteria: Mycobacterium lacticolium, Pseudomonas aeruginosa; Fungi: Aspergillus niger, Cladosporium-resinae, Penicillium chrosegenum, Chactomium globosum, Trichoderma viride.
These microorganisms were grown at a temperature of 28 ± 20C in a special thermostat with 90-100% humidity: fungi for 3-4 days, and bacteria for 2-3 days. Meat-peptone agar (MPA) was used for the cultivation of bacterial cultures, and suslo-agar (SA) - for fungi.
The studied compounds and the standard were added to CF Azerol-5 in mass (1.0-0.25%) percents.
The effectiveness of the antimicrobial effect of the compounds was determined by the diameter of the zone of inhibition of the microorganism' growth around the hole with/without additive: the larger it is, the more effective is the antimicrobial action. The analyzed oil and CF are not biostable.
The anti-wear properties of the tested compounds were determined on a four-ball friction machine ЧШМ -3.2 through the use of balls made of SH-15 grade steel with a diameter of 12.7 m at a constant load of 137 N within 4 hours and 392 N within 1 hour; the speed of rotation of the upper ball was 1500 rev /min and evaluated by the diameter of the wear spot (Dw) according to ГОСТ 9490-75 (tab.).
IR spectra were recorded on UR-20 spectrometer in the range of 400-4000 cm-1.
RESULTS AND DISCUSSION
Schiff bases were synthesized through the interaction of benzaldehyde with aniline and benzylamine in the 1:1 ratio in methanol together with their transition metal complexes obtained. The reaction was carried out at the boiling point of alcohol for 2 hours.
The structure of the synthesized compounds was confirmed by IR spectra. The bands of the stretching vibrations of azomethine (C = N) bonds, deformation (= CH) and stretching (C = C) bonds of aromatic fragments of the obtained ligands and stretching vibrations of (Me - N)
bond were identified. As follows from the analysis of the spectral characteristics of the original Schiff bases (Li and L2) and their complexes with Cu2+, Ni2+, Co2+ the position of the main analytical absorption bands, except for the C = N bond remains practically unchanged. In the IR spectra of complexes (35,7-9) the C = N band is observed in the region 1627 cm- 1 and, as compared with its position in the spectrum of the ligand (1629 cm- 1), it slightly shifted (2 cm- 1) toward the low frequency region of the aromatic absorption fragments. Such a character of changes in the
position of the C = N bond is interpreted in the nitrogen atom of C = N bond [7]. literature as coordination of the metal with the
h2nc6h5
CHO
(Li)
NH2CH2C6H5
(CH3COO)2Me
ch=nch2c6h5
2 6 5
(L,)
'(1-1)2 Me ^Me
Me = Cu2+, Ni2+, Co2+
Earlier, it was noted that in the most cases complex compounds are biologically active [3] and have antimicrobial properties. It was interesting to study the influence of the structure of the investigated compounds on the bio-stability of CF.
As mentioned above, the antimicrobial properties were determined in the emulsion composition CF Azerol-5 [8,9] at concentrations of 0.25-1.0%. For comparison, Schiff bases previously derived from dimethylaminobenzaldehyde and their metal complexes [10] were tested. As follows from the test results (table), the Schiff bases and their metal complexes with their antimicrobial properties in terms of their efficiency are at the
level of the selected standard - biocide, and in some cases (4,7-9) they surpass it. It should be noted that 4-dimethylamino-1-
benzilidenaniline and its complexes with Cu2+, Ni2+, Co2+ (6-9) even at low concentrations (0.25-0.5%) possess both bactericidal and fungicidal properties in CF which is due to the presence of additional dimethylamine fragment in the molecule.
The results of the study of anti-wear properties indicate that in the studied friction mode the synthesized Schiff bases are effective at 1.5% concentration both with a load of 137H within 4 h (0.40-0.62) and with a load of 392 N within 1 h (0.43-0.67).
Table i. Physicochemical and antimicrobial properties of the synthesized compounds
H=NC6H5
Concen- Zone of inhibition of Anti-wear
№ Compound tration, microorganisms growth, cm properties
% Mixed bacteria Mixed fungi 137 N 4 392 N 1
(MPÄ) (SA) h h
1 1 1.6-1.8 2.5-2.7
0.5 1.0-1.2 2.4-2.4 0.62 0.67
Q 0.25 1.7-1.7 2.0-2.2
ch=nch2c6h5
2 1 1.2-1.4 1.6-1.6
í J 0.5 1.0-1.0 1.2-1.4 0.58 0.60
ch=nc6h5 6 5 0.25 0.8-1.0 + +
3 [0 1 ch=nc6h5 Cu 2 1 0.5 0.25 1.8-1.8 1.4-1.5 1.2-1.2 1.2-1.3 1.0-1.0 + + 0.50 0.53
4 ID CH=NC6H5 Ni -2 1 0.5 0.25 1.6-1.7 1.5-1.6 1.2-1.4 1.2-1.2 0.8-1.0 + + 0.56 0.66
5 0 " ch=nc6h5 Co 2 1 0.5 0.25 1.4-1.4 1.0-1.0 + + 1.0-1,0 + + + + 0.53 0.60
6 C ( H3 CH3 X / N $ CH=NC6H5 1 0.5 0.25 3.0-3.0 2.6-2.8 1.6-1.8 2.4-2.4 2.0-2.2 1.7-1.7 0.48 0.55
7 CH3 CH3 \ / N Cu 1 0.5 0.5 3.3-3.5 3.0-3.0 2.8-2.8 2.6-2.8 2.0-2.2 1.6-1.6 0.40 0.43
CH=NC6H5 2
8 CH3 CH3 \ / N 0 CH=NC6H Ni 2 1 0.5 0.25 3.2-3.2 1.4-1.6 1.0-1.0 2.2-2.4 1.8-2.6 1.4-1.6 0.42 0.45
9 CH3 CH3 N C 1 0.5 0.25 2.4-2.4 2.0-2.0 1.7-1.8 2.0-2.0 1.2-1.2 + + 0.45 0.47
CH=NC6 H5 2
Sodium pentachlorofenolat e (standard) 1.0 0.5 0.25 1.3 0.7 + 1.4 0.8 +
CF Azerol-5 + + + +
Tricresyl phosphate 0.65 0.68
+ + full microorganism growth around a hole in the Petri dish
REFERENCES
1. Ray B.K. and Arun Kumar. Synthesis, characteriration and biological activity of some Schiff base and its metal complexes of Cu(II), Co (II), Ni (II).
Oriental Journal of Chemistry. 2013, vol.29, no3, pp.1187-1191. 2. Tsublova E.G., Ivanova T.T., Ivanova T.N., Yasnetsov V.V. Farmakolo-
gicheskie svoystva shiffovykh osnovaniy iz gruppy proizvodnykh etoksi aminobenzoti azola. Vestnik Ivanovskoy Meditsinskoy Akademii. 2012, vol.17, no. 4, pp. 12-15.(In Russian).
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4. Litvinov V.P. Khimiya i biologiches-kaya aktivnost 1,8-naftiridinov. Russian Chem.Rev. 2004, vol. 73, no. 7, pp. 717-725.
5. Kuliyev A.M. Khimiya i tekhnologiya prisadok t toplivam i maslam [Chemistry and technology of additives to fuels and oils]. Leningrad: Khimiya Publ. 1985, 312 p. (In Russian).
6. Xul., Qix., Kim S.-I. Synthesis and crystal structure of a second polymorph of N, N -bis (salicybidene) 3,5,3',5' -tetramethyl-4,4' -diamine. Journal of Structural Chemistry. 2006, vol.47, no. 5, pp. 999-1002.
7. Kwik W.L., Alice W.N.Tay. Mixed-ligand complexes of copper(II) containing a monocondensed schiff base and an amino acid or amine. Polyhedron. 1990, Vol. 9, no 10, pp.1293-1296.
8. Pat. I 2008 0203 Azerbaijan.
9. Mamedova P.Sh., Mamedova Z.R., Soltanova Z.G., Dzhafarov G.M., Agaeva Eh.A. Synthesis and antimicrobic properties of complexes of transition metals with Shiff bases. Chemical Problems. 2008, no. 3, pp. 543-546.
10. Pat. I 2001 0074 Azerbaijan.
This work was supported by the Science Development Foundation under the President of the Republic of Azerbaijan - Grant № EiF-BGM-4-RFTF-1/2017-21/12/4
METAL-KOMPLEKS BiRLd$MdLdR YAGLA YICI-SOYUDUCUMA YELORd
EFFEKTiV A§QAR KiMi
12 2 1 V.M. Fdzrzdliyev , M.P. Bayramov , S.X. Jdfdrzadd , P.§. Mdmmddova ,
E.R. Babayev1, I.M. Eyvazova1
1AMEA akademik d.Quliyev adina A^qarlar Kimyasi institutu AZ1029, Baki §., Böyük§or §osesi, mah.2062, e-mail:pervin_mammadova@mail.ru
2Baki Dövlat Universiteti AZ 1148, Baki, akad.ZahidXdlilov küg.23, e-mail: info@ bsu.az
Kegid metallarmm aromatik azometinlarla - §iff dsaslari ila kompleks birla§malari a§qar kimi istifada olunan goxsayli üzvi birla§ma sinifldri arasinda perspektiv hesab olunur. Azometinlar vd onlarin müxtalif funksionalavazli töramalari yüksak bioloji aktivliya malikdir. Bu cür birla§malar müxtalif mikroorqanizmlarin inki§afini effektiv §akilda inhibirla§dirir va mikrobiologiya, farmakologiya, yeyinti va emal sanayesinda, elaca da sürtkü yaglarina a§qar kimi istifada edila bilar. Maqalada aromatic sira azin birla§malarin (benzaldehid, N-dimetilbenzaldehid), elaca da onlarin kegid metallarla komplekslarinin sintezi va yaglayici-soyuducu mayelara effektiv goxfunksiyali, o cümladan antimikrob a§qar kimi tadqiqi tasvir olunmu§dur. ilkin madda olan azometinlar va onlarin kegid metallarla komplekslarinin mikroba va yeyilmaya qar§i xassalari tadqiq edilmi§dir. Onlarin AK-15 yaginda effektiv yeyilmaya qar§i, emulsiya yaglayici-soyuducu maye Azerol-5-da yüksak bakterisid va fungisid xassalara malik olmasi a§kar edilmi§dir. Agar sözlw. azometin, §iff asaslari, metal-komplekslar, yaglayici-soyuducu maye, antimikrob effektliliyi, yeyilmaya qar§i xassa, sürtkü yagi, goxfunksiyali a§qar.
МЕТАЛЛОКОМПЛЕКСНЫЕ СОЕДИНЕНИЯ В КАЧЕСТВЕ ЭФФЕКТИВНЫХ ПРИСАДОК К СМАЗОЧНО-ОХЛАЖДАЮЩИМЖИДКОСТЯМ
12 2 1 В.М. Фарзалиев , М.Р. Байрамов , С.Х. Джафарзаде , П.Ш. Мамедова ,
Э.Р. Бабаев1, И.М. Эйвазова1
1 Институт химии присадок им. акад. А.Кулиева Национальной АН Азербайджана AZ1029, Баку, Беюкшорское шоссе, кв.-л 2062; e-mail: pervin_mammadova@mail.ru 2Бакинский государственный университет AZ1148, Баку, ул.акад. ЗахидаХалилова 23; e-mail: info@bsu.az
Среди многочисленных классов органических соединений, используемых в качестве присадок, перспективными зарекомендовали себя комплексные соединения переходных металлов с ароматическими азометинами - основаниями Шиффа. Азометины и их различные функциональнозамещенные производные обладают высокой биологической активностью. Подобные соединения эффективно ингибируют рост различных микроорганизмов и могут быть использованы в микробиологии, фармакологии, пищевой и обрабатывающей промышленностях, а также как присадки к смазочным маслам. В работе описаны синтез и исследование азометиновых соединений, полученных на основе бензальдегида и аминов (анилин, бензиламин), а также их комплексов с переходными металлами (Cu2+, Ni2+, Co2+). Изучены антимикробные и противоизносные свойства исходных азометинов и их комплексов с переходными металлами. Показано, что в масле АК-15 они проявляют эффективные противоизносные, а в эмульсионной СОЖ Азерол-5 -высокую бактерицидную и фунгицидную эффективность.
Ключевые слова: азометины, основания Шиффа, металлокомплексы, смазочно-охлаждающая жидкость, антимикробная эффективность, противоизносное свойство, смазочное масло, многофункциональная присадка
