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AZ9RBAYCAN KIMYA JURNALI № 1 2016
83
UDC 547.64:621.892
SYNTHESIS AND ANTIMICROBIAL PROPERTIES OF N,N-bis-(p-DIMETHYLAMINOBENZYLIDENE)DIAMINOPROPANE AND ITS METAL COMPLEXES
A.R.Rahimova, P.Sh.Mammadova, T.M.Ilyasly, Z.I.Ismayilov, M.N.Aliyeva
Baku State University A.Guliyev Institute of Chemistry of Additives NAS ofAzerbaijan
rahimova_aysel@mail.ru
Received 01.10.2015
The synthesis of complexes of Cu(II) and Ni(II) with N,N-bis-(p-dimethylaminobenzylidene)diami-nopropane obtained by condensation of N,N-(p-dimethylaminobenzaldehyde with diaminopropane has been realized. All obtained compounds were characterized by their spectra (IR, NMR). Antimicrobial properties of initial azomethine and its complexes with Cu and Ni were analyzed. It was established that they showed high bactericidal and fungicidal activity in M-8 oil.
Keywords: Schiff bases, metal complexes, antibacterial, antifungous.
One of the main methods of making metal parts is machining. The most important element of the process of metal cutting is using cutting fluids (CF). As CF for metal cutting there are proposed various compositions of organic and inorganic compounds, most of which are oil-based liquids (CFs). Oil-based CFs meet a series of requirements: in particular, they must not cause a pronounced biological effect on the skin and respiratory system of employee, must have a minimal irritating effect when exposing to the mucous membranes, have low oil mist, not contain 3,4-benzpyrene and certain other hazardous substances. It is important to know the molecular composition of the oil-based CF to identify individual compounds of potential environmental pollutants.
Such data are needed to create industrial environmental conditions in the workplace. Currently, CF, along with high efficiency, must meet stringent environmental requirements. In this connection conducting research on the creation of clean and safe CF is of great importance. The concept of ecologically friendly CFs includes technological means, the composition of which does not contain compounds that have a negative impact on the environment and the health of staff. To solve this problem, it is suggested to replace the environmentally harmful components with harmless ones. It should be noted that despite the availability of a wide range of different CFs, some
of the commodity produced liquids are ineffective, often do not meet the requirements imposed on them, multi-component, stable enough to contain unsafe ingredients. Modern CFs contain combinations of additives for various applications. To obtain certain high-performance CF it is important to use the original components of quality have scientifically grounded composition and production technology.
Taking into account the above mentioned, our research is oriented to improving cost-effective, low-component and environmentally friendly compositions [1-5]. Compositions were developed considering the analysis of the available literature data on the CF compositions and components of the functional purpose.
Experimental part
IR spectra were investigated by use of UR-20 spectrometer at the 400-4000 sm-1 zone, NMR spectra by use of Bruker-spectrometer in the solvent of C2D5OD.
N,N-bis-(p-dimethylaminobenzylidene)di-aminopropane (I). The ligand was synthesized by the condensation of p-dimethylaminobenzal-dehyde with bis-aminopropane in 1:1 molar ratio using absolute alcohol as the reaction medium. The mixture was refluxed on a water bath for 1 and a half an hour and then allowed to stand overnight at room temperature. The product was crystallized from the same solvent.
NMR spectrum of N,N-b/'s-(p-dimethylaminobenzylidene)diaminopropane (L).
Melting point - 1120C, yield - 65%. Found, %: C - 74.8, H - 7.6, N-17.6, C21H28N4. Calculated, % : C- 75, H - 7.5, N - 17.5.
IR spectra (v, sm-1): 1650 (C=N), 1610 (C=C), 1470, 1180 (C-N)(CH3)2. NMR spectra (5, ppm): 8.146 (C=N), 3.641-3.028 (CH3)2N, 2.050 (4H), 1.205-1.131 (CH2).
The IR spectra of the complexes C=N zone is observed at 1650 sm-1. In comparison with its position in the spectrum of the ligand (1637 sm-1) it is shifted to low-frequency zone. Such a change proves presence of coordination of metal with N atom C=N bond (635-620 sm-1, M=N). On the base of above-mentioned we can conclude that complexes should have such a structure: M(L)2X2, where X - anion.
The complex of Cu(II) (II). They were prepared by reacting ethanolic solution of the ligand with ethanolic solution of metal acetate in 1:2 molar ratio. The precipitated solid coloured complexes were filtered, washed with ethanol, dried in oven. Melting point - 1550C, yield -62%. Found, %: C 62.50, H 3.40, N 13.53. Calculated, %: C 62.37, H 3.0, N 13.73.
The complexes of Ni(II) (III). They were prepared by reacting ethanolic solution of the ligand with ethanolic solution of metal acetate in 1:2 molar ratio. The settled down solid coloured complexes were filtered, washed with
ethanol, dried in oven. Melting point - 1450C, yield - 60 %. Found,%: C 62.70, H 3.90, N 12.93. Calculated, %: C 62.20, H 3.2, N 13.67.
At studying antimicrobial properties of the synthesized compounds there was used the cavity method on agar medium with using suspension of different cultures (Pseudomonas Aeruginosa, Mycobacterium lacticolium, Aspergillus niger, Cladasporium resinale, Penicillium Chrosegenum, Chastomium gloloodium Trichoderma viride). The sterilized (autoclaved 1210C for 15 min), medium (40-500C) was poured into the Petri dishes at a depth of 3-4 mm and allowed to solidify. The plates were pre-incubated forth at room temperature and incubated at 370 C for 24 hours.
Antiwear properties of synthesized compounds were determined by use of Four-ball friction machine (ГОСТ 9490-75) and evaluated on dimensions of wear spot.
Results and discussion
The perspective N-containing compounds present a wide class of organic chelate forming compounds containing hetero atoms. Such compounds are able to coordinate with metals, and complexes obtained on their basis often have an effective biological activity [6, 7].
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As is known from literature, ligands and their metal complexes are considerably active against Baccilus megaterium and Candida tropicalis, but the effect of metal complexes is stronger than influence of ligands. It was also reported that ligands and their metal complexes are active against Fuherica Coli, Barilum sp and Pseudomanan acurtuginan. Morever, Cu complexes of ligands were reported to be inhibiting active against bacteria and fungi. It was also determined that ligands could produce an inhibiting effect on the development of Aspergillus niger, Penisilum rubium and Augergillus ferreus. Furthermore, it was also established that ligands had an antibacterial and antifungal effect.
There was developed the method for obtaining N,N-£is-(p-dimethylaminobenzylidene)di-aminopropane. Its structure was proved by methods of IR and NMR spectroscopy.
The functional properties of the compounds were studied in M-8 oil by use of the standard laboratory methods. Results of studying antimicrobial and antiwear properties of the synthesized compounds are indicated in the table. As follows from the table in condition of friction regime synthesized Schiff base and its complexes at 1% concentration have high antimicrobial properties (0.47-0.40 mm) and improve lubricating properties of the oil. Studied additives are better than the well-known additive (tricresilphosphate).
Antimicrobial efficiency of studied compounds in M-8 oil was evaluated by diameters of the degradation zone around the cavity both with additive and without it: increasing diameters leads to improving antimicrobial ef-
References
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ficiency. M-8 oil itself doesn't have biostability. Results of the study are indicated in the table. As follows from the table synthesized azomethine and its metal complexes have antimicrobial properties. They overbalance known additive -sodium pentachlorophenolate (etalon) by efficiency (at the same concentrations).
Studying functional properties of compounds
Zone of
ö o degradation of Antiwear
Ligand and complexes "Sa Ö 1) O Ö microorganisms, sm property of M-8
Mixed Mixed oil,
o O Bacteria (MPA) Fungi (SA) mm
N,N-fa's-(p-dimethyl-aminobenzylidene)di-aminopropane (L) 1.0 0.5 0.25 3.0-3.0 2.5-2.5 2.3-2.3 3.3-3.3 2.4-2.4 1.6-1.8 0.47
1.0 3.2-3.2 3.2-3.2
L2CuX2 0.5 2.6-2.6 2.6-2.8 0.4
0.25 2.5-2.5 2.0-2.0
1.0 3.3-3.3 3.0-3.0
L2NiX2 0.5 2.6-2.6 2.3-2.2 0.45
0.25 2.4-2.4 2.1-2.1
Sodium pentachloro-phenolate 1.0 0.5 1.3 0.7 1.4 0.7
Tricresilpho sphate 1.0 0.65
M-8 oil - ++ ++
++ - ample growth of microorganisms around cavity?
Thus, synthesized compounds are of certain interest as multifunctional additives to lubricating oils improving their antimicrobial and antiwear properties. Use of them in the CF composition will allow to reduce amount of the components at keeping their exploitation properties.
Synthesized compounds with antimicrobial properties were studied in the compositions of additives to CFs. In compositions there were used the known industrial additives (S-75 -detergent, DF-11 - multifunctional additive).
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5. Radnakrishnan S., Manghatai K. S. Investigation on Microoorganisms and their Degradation efficiency in Paper and Pulp Mill Effluent // J. Water Resource and Protection. 2010. V. 2. No 3. P. 660-664.
6. Raj B.K., Arun Kumar. Synthesis and Characterization and Biocidal Activity of some Schiff Base and its Metal Complexes of Co(II), Co(III) and Ni(II) //Oriental J. of Chem. 2013. V. 29. No 3. P. 1187-1191.
7. Мамедова П.Ш., Меджидов А.А., Шапиро А. Комплексные соединения переходных металлов Cu(II), Co(II), Co(III), Ni(II) с парамагнитными основаниями Шиффа // Изв. АН СССР. 1977. № 3. С. 538-541.
N,N-Ais-(p-DÍMETÍLAMÍNOBENZÍLÍDEN)DÍAMÍNOPROPAN VO ONUN METAL KOMPLEKSLORÍNÍN
SÍNTEZÍ VO antímíkrob xassolorí
A.R.Rahimova, P.^.Mammadova, T.M.Ilyasli, Z.I.Ismayilov, M.N.Oliyeva
Cu(II) va Ni(II) metallannin N,N-bis-(^-dimeülaminobenzaldehid)in diaminopropanla kondensasiyasindan alinmiç N,N-b/'s-(^-dimetylaminobenziliden)diaminopropanla komplekslari sintez edilmiçdir. Bütün sintez edilmiç maddalar (ÍQ, NMR) spektrlarina göra xarakteriza edilmiçdir. ilkin azometin va onun Cu va Ni ila komplekslarinin antimikrob xassalari ôyranilmiçdir. Onlarin M-8 yaginda yüksak bakterisid va fungisid xassasi nûmayiç etdirmasi müayyan edilmiçdir.
Açar sözlar: §iff asaslari, metal komplekslari, bakteriya aleyhina, göbalak э1еуЫпэ.
СИНТЕЗ И БАКТЕРИЦИДНЫЕ СВОЙСТВА ^^6ис-(и-ДИМЕТИЛАМИНО-БЕНЗИЛИДЕН)ДИАМИНОПРОПАНА И ЕГО МЕТАЛЛИЧЕСКИХ КОМПЛЕКСОВ
A.P.ParaMOBa, P.Ш.Maмедова, T.M. Ильяслы, З.И.Исмаилов, M-Н.Алиева
Синтезированы комплексы Cu(II) и Ni(II) с ^^бис-(п-диметиламинобензилиден)диаминопропаном, полученного конденсацией ^^п-диметиламинобензальдегида с диаминопропаном. Все полученные соединения были охарактеризованы по их спектрам (ИК, ПМР). Изучены антимикробные свойства исходного азометина и его комплексов с Cu и Ni. Установлено, что они проявляют высокую бактерицидную и фунгицидную эф -фективность в масле М-8.
Ключевые слова: основания Шиффа, металлкомплексы, антибактериальные, противогрибковые.
