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11CHEMICAL SCIENCES
SYNTHESIS OF AMINOMETYLSUBSTITUTED THIOCARBAMIDES AND ANTIOXIDANT PROPERTIES
Rahimova A.R.
Baku State University, Azerbaijan, Baku
Ismailov Z.I.
Baku State University, Azerbaijan, Baku Guseynova G.A.
Baku State University, Azerbaijan, Baku Shukurova G.M.
Baku State University, Azerbaijan, Baku Dzhafarova E.K.
Baku State University, Azerbaijan, Baku
Sultanova S.G.
Baku State University, Azerbaijan, Baku
ABSTRACT
Synthesized some aminometylsubstituted thiocarbamides and investigated as antioxidants. It has been established that they have shown a high antioxidant properties and are inhibitors of complex action. Studies have shown that the investigated aminometylsubstituted thiocarbamide are effective inhibitors of the oxidation of complex action: Terminated chain oxidation reaction with peroxide radicals and hydroperoxides are catalytically decomposed Aminometylsubstituted derivatives have been found to be more effective standarts oxidants as the process dominantly affects the overall antioxidant behavior of..
Keywords: thiocarbamide, antioxidant properties, aminometylsubstituted compounds.
Introduction.
The literature survey reveals that the thiocar-bamides and derivatives have nucleus enhanced pharmaceutical, agricultural and industrial values so, the medicines containing thiadiazines nucleus are now used extensively in medical, biomedical and biotechno-logical faculties[1]. It has been shown to posses industrial, fungicidial, insecdicidial, medicinal values. The synthetic applications of N-aryl/alkyllisocyanodichlo-rides have been investigated and shown to have enough potential in the synthesis of nitrogen and sulfur containing heterocyclic compounds[2].Benzothiazoles have been known from long ago to be biologically features are still of great scientific interest. They are becyclic ring system with multiple applications. Some derivatives of benzothiazoles posses antituberculoses, anticancer, antitumor, antipyretic activities. In view of application of benzothiazoles and derivatives in medicinal chemistry and in many other ways[3]. The literature survey reveals that the heterotcyclic compounds having thiadiazole nucleus enhanced pharmaceutical, medicinal, agricultural and industrial values. So the medicines containing thiadiazole nucleus are now used extensively in medicinal, agricultural, pharmaceutical, bio-technological faculties[4]. These drugs have been shown to posses a diverse range of physiological activities, plant growth, promoting activity, antitumor, antibacterial, antidiabetic values some thiadiazole were also found to be active against S. aureus, E. coli, and C. albicans [5]. In the literature it is known that a number thiocarbamides and their various derivatives are widely
used in industry as a monomers, copolimers, corrosion inhibitor, herbicides and fungicides in agriculture[6,7].
Experimental Part.
3-amino-1-thiocarbamidoprophan.
Three-necked flask equipped with a mechanical stirrer and a thermometer was charged with 10 ml of hydrochloric acid, 7,2g (0,1 mol) of tiocarbamide and 8,9 g (0,1 mol) of 2-aminoprophanol. Then the reaction mixture was stirred at 800 C for 3 hours. The reaction was montored by TLC. As a eluent is used isopropanol hexane (3:5). The reaction product was washed with water, extracted with ether, and dried over sodium sulfate. After distilling off the ether recovered white crystals. Appearing crystals were recrystallized from etha-nol. Obtained 10,3 g of 3-aminothiocarbamido-prophan in 75% yield, Tmelt=80 0 C,Rf=0,62.
Founded:%C 36.08;H 8.28; N 31.56; S 21.92; C4H11N3S.
Calculated:0/« C36.09; H 8.27 ; N 31.57; S 24.06.
Structure of the synthesized compounds proved IR, NMR spectroscopy and cleanliness-elemental analysis, thin layer chromatography. The IR spectra of the synthesized aminometylsubstituted thiocarbamides revealed the characteristic absorption band 3380, 3270, 3240, and 3180 corresponding to the shetching vibrations of related NH-group. Absorption band corresponding to the fragment NHCS, appears in the 1535sm-1. In the NMR spectrum of the protons are in the NHCSNH2 fragment and appear in 6.3-7.4 ppm methane proton in the fragment was detected in 2.1-
2.2ppm. metylene proton fragment was found in 2.752.95 ppm.
Antioxidant properties.
Antioxidant effect of synthesized aminometylsub-stituted studied in model reactions. As a model reaction initated by a-a^azobisizobutylnitrole (AiBN) used oxidation reaction in a solution of chlorobenzene at 600C. Inhibitory properties of the compounds studied the kinetics of the reaction with radicals cumylperoxde and cumylperoxide cumyl. Chlorobenzene, cumyl and cumyl hydroperoxide was purified by the standart procedure.
Reaction with radicals cumylperoxide studied initiates (AIBN) cumyl oxidation in the presence of these compounds. Initiator was injected at a concentration of 2xl0-2 mol/l inhibitor concentration was 5x10-5 mol/l. Reaction cumyl hydroperoxide with aminometylsubsti-tuted thiocarbamides was performed in a glass reactor
Figure l has shown cumene oxidation in the presence of the initiator kinetic curves thiocarbamide listed derivatives. We can see from the picture, the curves of compounds with kumolhidroperoxide/. In addition to the compounds studied has not been going at a steady
thermostated at chlorobenzene solution while bubbling nitrogen. Samples periodically analyzed for cumylhi-droperoxide iodometric. On the spending of ROOH measured reaction rate of interaction with hydroperoxides aminometylsubstituted thiocarbamide. As can be seen from Figurel, with the study initiated by AIBN cumyl oxidation at 1100 Cs in the presence of the synthesized compounds inhibited the oxidation of studied inhibitors react with radicals cumylperoxide. Studies have shown that all compound shaving as a part of thiocarbamide fragment inhibit initated oxidation. Largest induction period (t) calculated stoichiometric factor y, equal to the number of oxidation chains terminating in one molecule of the inhibitor and its transformation products. To calculate the rate constants for the interaction of inhibitors with peroxide radicals-k7 kinetic curves of oxygen uptake of the transformed coordinates into [O2]-1t to [O-]-1 t.
pace and induction period of oxidation of cumene is not observed. However, in response to a concentrated environment thiocarbamide into derivatives when the absorption rate of 5 10-4 moll reduced.
№ T = 600C T= 1100C X, minutes
compounds Formula of the compounds f K710-4l/mol san K,10-4l/mol san V
c4h9 s ch2 -ch-ch2n(c4h9)2
1 nh-c-nh2 s 6,0 5,22 16 32000 250
c4h9o ch2 ch-ch2n (c4h9)
2 nh — c—nh2 || s 1,8 2,2 11 22000 110
c3h7och2 ch-ch2n(ch2)6
3 nh-c-nh2 s 1,6 1,8 9 18000 60
4 Cu-2[NH2-C6H4-C=N-C6H4-OH]2 4,8 3,7 3,6 6800 200
5 Ni-2[NH2-C6H4-C=N-C6H4-OH]2 8.0 6.8 4,3 8000 300
Fig. 1 Cumene oxidation kinetic curves in the presence of synthesized compounds (XV, XVIXVIII) with initiator T = 60 0 C: 11 [lnH] = 0; [AIBN] = 2 10-2 mol /1, O2-absorbing oxygen volume (ml); T-induction period.
Figure 2 under the influence of the synthesized compounds were cumene autooxidation kinetic curves. As shown in the picture cumene induced cycle inhibitor for 40 minutes. In comparison with the first picture we
V,
100.9 0.8 0.7 -0.6 -0.5 0.4 -0.3 -
0.2 0.1-
can see that the decomposition of cumene without initiator the period of induction equal 20 minutes. As can be seen, the highest result determined thiocarbamide derivative was dibutylamino-3-thiobutyl-thiokarbami-doprophan/
40 80 120 160 200 240 280 360
r,daq
Figure 2. The kinetic curves of cumene autooxidation with prescence of synthesized compounds (XV, XVI and XVIII) T = 110 0 C: 11, [ln H] = 0: [lnH} = 5 10-5 mol/l:VO2-absorbed oxygen volume (ml); T-induction
period.
As a result of studies have found that all the tested compounds (1-5) actively decomposed HPC figure 3. Kinetic curve of HPC decomposition under the action of the compound consists of two parts. At the beginning of the reaction revealed some induction period during which there is very little decay HPC and then goes fast catalytic decomposition of HPC.
This suggest that the reaction of the compound (1) of HPC is complex. First antioxidant reacts with cumyl hidroperixide turning into active products which are then catalytic decomposition of HPC. The catalytic decomposition of hydroperoxide in the presence of ami-nometilsubstituted thiocarbamides flows under the influence is not the source of the antioxidant and its conversion products.
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[ROOH] m0|/m|
-1-1-1-1-1-
20 40 60 80 100 fdeq
Fig/3/Kinetic curves of kumil hidroperoxide division with synthesis compounds
The results showed that one molecule of the compound capable of decomposing to a few tens of thousands of molecules HPC. The value of the kinetic parameters of the catalytic decomposition of HPC by the action of the compounds are shown in Table 2.
Results and discussion.
In model reactions, we studied the reactions of different thiocarbamides with cumylperoxide and cumylperoxide radicals established that they have exhibit high antioxidant activity. Continuing studies on the synthesis of various derivatives thiocarbamides and studied the relationship between structure and antioxi-dant properties in this paper the synthesis a ami-nometylsubstitued thiocarbamides based on the reaction of amino alcohols with thiocarbamide
Analysis of the kinetic parameters of the HPC cleavage is seen that the catalyst factor is observed for the compound which in the molecule, together with a thiocarbamide moity also contains a primary amine fragment.Antioxidant (1) has high antioxidant properties, along with its inherent high catalys factor also has a high value of the reaction rate constant. For example, the value for the compounds (1) is 9 and for compounds (2-4) 2,2-5,22 l/mols.
Thus studies have shown that the investigated ami-nometylsubstituted thiocarbamide are effective inhibitors of the oxidation of complex action:Terminated
chain oxidation reaction with peroxide radicals and hydroperoxides are catalytically decomposed.
Conclusion.
From the result of antioxidant effect we can conclude that all compounds exhibited strong to moderate activity. Aminometylsubstituted derivatives have been found to be more effective standarts oxidants as the process dominantly affects the overall antioxidant behavior of.
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