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DOI: http://dx.doi.org/10.20534/AJT-16-9.10-100-104
Choriev Azimjon Uralovitch, Karshi State University, Senior Lecturer the Faculty of Natural Sciences, Department of Chemistry E-mail: azimjon-organik@mail.ru Abdushukurov Anvar Kabirovitch, National University of Uzbekistan named after Mirzo Ulug'bek, professor the Department of Organic Chemistry E-mail: abdushukurov-ximik@mail.ru
Synthesis of 4-hydroxy-u-chloracetophenones
Abstract: This paper reports a synthesis of 4-hydroxy-w-chloracetophenone as a catalyst using MoCI5, WCI6, SnCI4, VCI3 The mechanism has not been studied. It was studied the influence of the ratio of reactants, catalysts' concentration and the time ofsynthesis in the reaction of obtaining 4-hydroxy-w-chloracetophenone from phenol and chloride chloracetyl. The purified 4-hydroxy-w-chloracetophenone is characterized in terms of physical-chemical properties.
Keywords: 4-hydroxy-w-chloracetophenone, chloracetyl chloride, small quantities Lewis acids, IR spectrum.
4-Hydroxy-w-chloracetophenone is an aromatic ketone formula C8H7O2CI and an important photochemical reaction used in perfumery and as a reagent in organic chemistry. 4-Hydroxy-w-chloracetophenone acts as an optical filter being able to use the energy of UV radiation (promoting electrons into an excited state) and release this energy as heat to the environment (electrons returning to the initial state). This is possible because 4-hydroxy-w-chloracetophenone singlet and triplet have close states in terms of energy.
4-Hydroxy-w-chloracetophenone is used as a flavor ingredient, a flavor enhancer, perfume fixative in perfumery industry. In the composition of perfumes, cologne and scented soaps and UV light does not degrade the smell and color of these products. It is used as an additive for plastics, coatings and adhesive formulations [1, 5005-5010]. It is a component of sunscreen prod-
ucts and a plastic packaging can be added to block UV rays, protecting products within them [2, 3909-3916]. It is used in textile to protect them against degradation under the action of ultraviolete radiation [3, 53-62]. In preparations for solar protection, 4-hydroxy-w-chloracetophenone is intended to absorb UV-A and UV-B, protecting the skin from the negative effects of tanning (sun). It is known that structure is unstable in terms of photochemical because under the influence of sunlight it forms reactive radicals, aggressive, in which scientists associates with oxidative stress in human cells, skin damage, etc. 4-hydroxy-w-chloracetophenone and its derivatives are used as intermediates for dyes, in the manufacture of insecticides and pharmaceuticals, etc. [4, 145-149]. In the pharmaceutical industry are used for their anesthetic [5, 4818-4825] and anti-inflammatory properties [6, 3505-3514] etc. [7, 4046-4051]. It is a white solid
with the smell of rose, insoluble in water but soluble in benzene, tetrahydrofuran, methanol, and propylene glycol. 4-hydroxy-w-chloracetophenone and its derivatives are synthesized by Friedel-Crafts reaction of aromatics. Acylation is done with acid chlorides or anhydrides. The reaction is catalyzed by Lewis acids, BF3, AlCl3, FeCl3, TiCl4 or ZnCl2 [8, 1609-1610]. Nowadays, restrictions are imposed for waste minimization requiring the development of new catalytic technologies often based on
OH
CICH2COCI
solid catalysts. Various research groups have reported the use as a catalyst of the Friedel-Crafts acylation of phenole derivatives of various different metal oxides, for example a mixture of thorium dioxide, magnesium oxide, ZnO, etc. [9, 3442-3447].
Friedel-Crafts reaction of phenole and chloracetyl chloride in the presence ofLewis acid type catalysts (AlCl3) or MoCI5, WCI6, SnCI4, VCI3 is used for the preparation of w-chlor-para-hydroxyacetophenone (Scheme 1).
OCOCH2CI
HCI
OH
OCOCH2CI
+
OH )
OCOCH2CI
Scheme 1.
Reagents and materials
The reagents used were: phenole (99.5%), chloracetyl chloride (98%), MoCI5 (98.5%), WCI6 (99%), SnCI4 (99%), VCI3 (99.5%). Merck, Sigma Aldrich. In this paper reagents are used as such without further purification. Concentrated hydrochloric acid (37%) Sigma Aldrich, carbonyl sulphide and other materials are used without special treatment. Melting point determination is made using the device "Melting Point Meter" KRS-P1, the company Kruss Optronic GmbH. The IR spectrum was carried out using a Perkin Elmer FT-IR spectrophotometer — Spectrum 100.
Syntheses
In the syntheses with Lewis catalysts was used the classical method of synthesis. The work was done with phenole, chloracetyl chloride, carbon disulfide, anhydrous aluminum chloride and the mixture was heated at 40-45 °C. In the syntheses where MoCI5, WCI6, SnCI4, VCI3 was used it was also used a catalyst system for stirring the reaction mixture in order to obtain the most intimate contact between the catalyst and the reactants. After completion of the synthesis the catalyst is removed by filtration (MoCI5, WCI6, SnCI4, VCI3). MoCI5, WCI6, SnCI4, VCI3 powder is reused after washing it with dichloromethane and dried. Crude 4-hydroxy-w-chloracetophenone obtained after syntheses was purified by recrystallization from ethanol, filtered and dried under vacuum.
Getting 4-hydroxy-w-chloracetophenone is achieved by Friedel-Crafts reaction in the presence of AlCl3 catalyst in good yields, and we tested the MoCI5, WCI6, SnCI4, VCI3 as
catalyst. Laboratory syntheses were carried out in order to determine the influence of various parameters on the efficiency of the reaction of 4-hydroxy-w-chloracetophenone: the variation ratio of the reactants, the variation in the catalyst concentration, reaction time, type of catalyst reaction.
The influence of the variation ratio of reactants
The syntheses were conducted with different molar ratios of the reactants chloracetyl chloride phenole, ratios ranging from 1:1 to 1:2 and 1:3. The chloracylation is generally used, working at reflux. The reaction temperature is 130-135 °C. The concentration of MoCI5, WCI6, SnCI4, VCI3 catalyst was 0.2% compared with chloracetyl chloride. The reaction is given by the excess phenole. The duration of the synthesis is 3 hours. In Table 1 is shown the variation of the yield depending on the ratio of re-actants. As may be seen in Table 1 the yield increases with the increasing molar ratio of reactants. By working with a large excess of phenole (molar ratio chloracetyl dechlorinated phenole) of1: 3 is obtained a high yield of 85.6% of 4-hydroxy-w-chloracetophenone. Using a large excess of one reactant leads to increased reaction yields, but increases are not very spectacular and taking into account the need for recovery of phenole leading to increased costs it would be preferable to work with a ratio of chloracetyl chloride: phenole 1:2.
Influence ofchanges in concentration ofthe catalyst
To track variation's influence the concentration of MoCI5, WCI6, SnCI4, VCI3 catalyst use the following values;: 0.001%, 0.002%, 0.005%, 0.01% (percentage by mass) from chloracetyl chloride. Synthesis duration is
two hours. Temperature is 130-135 °C. All syntheses were carried out with a molar ratio of chloracetyl chloride: phenole 1:2. The results are shown in Table 1.
Watching the graph in Table 1 shows that with increasing concentration of catalyst (MoCI5, WCI^ SnCI4,
VCI3) increases the reaction yield, but the yield is very small increased after increasing the concentration from 0.2 to 1% yield increase by only 9%. It is therefore preferred to work with a concentration of catalyst (MoCI5, WCL, SnCI, VCI) of 0.002%.
6 4 3/
Table 1. - Chloracetylation of phenol in the presence of small quantities of MoCI5, WCL, SnCI4, VCI3
№ Molar ratio of phenole: chloracetyl Reaction time, hour Temperature, ^ Yield,% Reaction product by column chromatography,%
chloride: katalysator PCА 4-HCА
MoCI5
1 1:1:2,5.10-3 3 118-120 80 15 85
2 1:1:5.10-4 2 118-120 85 23 77
3 3:1:1,2.10-2 2 130-135 74 28 72
wci6
4 1:1:1,5.10-3 3 118-120 78 30 70
5 1:1:3.10-3 3 118-120 82 20 80
6 3:1:7,4.10-3 2 130-135 73 32 68
SnCI 4
7 1:1:1,1.10-3 3 118-120 81 24 76
8 1:1:2,2.10-3 3 118-120 83 35 65
9 3:1:7,4.10-3 2 130-135 66 51 49
VCI3
10 1:1:1,4.10-3 3 118-120 60 31 69
11 1:1:2,8.10-3 3 118-120 72 36 64
12 3:1:1,6.10-3 2 130-135 55 38 62
* - phenylchloracetate
** - 4-hydroxy-v-chloracetophenone.
The influence of reaction time
The observation of the influence of reaction time on the 4-hydroxy-w-chloracetophenone synthesis by the Friedel-Crafts reaction in the presence of catalytic MoCI5, WCI6, SnCI4, VCI3 synthesis was accomplished by carrying out the reaction at different times. It increases the reaction time from 1, 2, 3 and 5 hours. The concentration of catalyst working with is 0.002% MoCI5, WCI6, SnCI4, VCI3 related to the amount of chloracetyl chloride. Synthesis temperature is the reflux (130135 °C). The synthesis was carried out with a molar ratio of the reactants: Chloracetyl chloride: phenole 1:2. Low yield of the reaction is observed after one hour of synthesis. With increasing reaction time and yields are higher, but the increase is not significant. After 5 hours of synthesis the yield of 4-hydroxy-w-chloracetophenone obtained practically is 88.20%. The influence of the catalyst type on the yield of reaction The influence of catalyst type synthesis by the reaction of 4-hydroxy-w-chloracetophenone Friedel-Crafts acylation has been found by working with the acylation catalysts AlCl3 as compared to the catalytic action of MoCI5, WCI6, SnCI4,
VCI3. The reaction time is 3 hours. The concentration of catalyst which is employed is 0.002% related to the amount of chloracetyl chloride. Synthesis temperature is the reflux. The MoCI5, WCI6, SnCI4, VCI3 synthesis with synthesis temperature is 130-135 °C. When working with AlCl3 catalyst, the reaction temperature is 40-45 °C, because it is currently working in the reaction of solvent carbon disulfide. (40% by mass in relation to the reaction mixture). The syntheses were carried out with a molar ratio of the reactants: Chloracetyl chloride: phenole 1:2.
Synthesized 4-hydroxy-w-chloracetophenone was processed. In the first stage of the reaction mixture is filtered to remove the catalyst MoCI5, WCI6, SnCI4, VCI3. Then the clear solution is treated with water. Solution is treated with hydrogen chloride and passed into a separating funnel to separate the organic layer containing 4-hydroxy-w-chloracetophenone. The solution is heated to remove the excess phenole. The resulting crude in the synthesis of 4-hydroxy-w-chloracetophenone was made subj ect to a process ofrecrystallization for obtaining a pure
compound. As the recrystallization solvent used is etha-nol. 4-hydroxy-w-chloracetophenone obtained and puri-
fied by recrystallization has been characterized from the chloracetophenone is soluble in alcohol, chloroform, ether, physical-chemical point of view, the results are as follows: and very slightly soluble in water. In the IR spectrum can be white crystals m. p. 58 °C, density 1.1 g/cm3. 4-hydroxy-w- observed some characteristic absorption bands (Figure 1).
Figure 1. Is shown the IR spectra of 4-
The FT-IR spectrum of crystal w-chlor-para-hydroxyacetophenone shows bands characteristic to uC-H stretching vibration at 3056 cm-1 aromatic (m) and 3010 cm-1 (m) respectively the characteristic band of deformation at SC-H 1447 cm-1 (s). Bands characteristic to uC=C stretching vibrations assigned to aromatic ring at 1594 cm-1 were confirmed at 1594 cm-1 (i) and 1493 cm-1 (vi), and between 944-764 cm-1 appears characteristic bands to SC-H bending vibrations (characteristic to aromatic nucleus). At 1759 cm-1 band appears very intense band attributed to uC=O stretching vibration (for ketones). In the spectrum appear intense and very intense bands at 1275-1135 cm-1range, assigned to the stretching vibrations uC-O.
Interesting results have been obtained in the synthesis of4-hydroxy-w-chloracetophenone as a catalyst using
hydroxy-Q-chloracetophenone purified
MoCI5, WCI6, SnCI4, VCI3 It is a heterogeneous catalyst which may be easily separated from the reaction mixture and re-used. It is not corrosive and does not produce secondary products. The mechanism has not been studied. It was studied the influence of the ratio of reactants, catalysts' concentration and the time of synthesis in the reaction of obtaining 4-hydroxy-w-chloracetophenone from phenol and chloride chloracetyl. A comparison was made between the catalyst and catalysts' Friedel-Crafts chloracetylation classics: aluminum chloride, respectively. Under the same reaction conditions as those used in the synthesis of MoCI5, WCI6, SnCI4, VCI3 the yield was smaller than classical catalysts, which can be explained by a too low concentration of catalyst. The purified 4-hydroxy-w-chloracetophenone is characterized in terms of physical-chemical properties.
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DOI: http://dx.doi.org/10.20534/AJT-16-9.10-104-107
Yuldasheva Mukhabbat Razzoqberdievna, National university of Uzbekistan, the Faculty of Chemistry E-mail: ymuxabbat@bk.ru
Synthesis and analysis of aryl methyl amines
Abstract: Synthesis of alkyl amines derivatives of aromatic hydrocarbons. The structure of the obtained 2,4-de-methylbenzylamine, 2,5- dimethybenzylamine, 2,4,6-threemethyl 3,5-di (N-aminomethyl) nitrobenzene was determined by means of IR spectroscopy and chromato-mass-spectrometry.
Keywords: aromatic hydrocarbons, xylenes, nitro-mesitylene, amidoalkylation, N-hydroxyalkylimide, alkyl amines of aromatic hydrocarbons.
Aromatic compounds and their functional derivatives are the most widen and important class of organic compounds on the base of the chemical transformations of which can be solved the fundamental problems influential ability reflectional reactivity of aromatic substrates and alkylating reagents by using various catalysts.
Continuing systematically investigation of reaction amidoalkylation of aromatic hydrocarbons [1-3], we have studied the amidoalkylation of xylenes and nitro-mezitilena in the presence of proton catalysts, also synthesized aryl alkyl amines.
We investigated synthesis arylalkylimides from ami-dalkyl reaction using from m-xylene which is substitutents of the aromatic ring methyl groups in a consistent orientation and easy reacts with N-hydroxymethylftalimide (N-MFI) by electrophilic substitution. Starting materials for this reaction: m-xylene, N-MFI, cons H2SO4:H3PO4 were taken 6:1:2:1 mol and reaction was continued by string at 120 ° C for four hours. The result of this reaction 1,3-dimethyl-4-(N-phthalimidomethyl)benzene
is obtained in yield 73%. Experimental section contains the IQ-spectrum of compound and H^spectra were obtained 2,29d (6H, 2CH3), 4,6 s (2H, CH2), 6,9d (3H, Ar3H3), 7,75 m (4H, ArR2H4). Subsequent treatment with ^-hydroxoethylphthalimide under the usual reaction conditions afforded substance in 76% yield.
Similarly, the compound of p-xylene's with phthalimidialkyl synthesized as an ordered stages above. The reaction of para- xylene's with N-MFI, H3PO4 and H2SO4 is prolonged for six hours. The result of this reaction 1,4-dimethyl 2-(N-phthalimidomethyl) benzene is obtained in yield 78%.
The reaction of nitrogen mezitilen with N-methylol-phthalimid is carried by one mol out. Phosphoric acid is used as a catalysis. It is defined that in this reaction all substitutents of benzene ring have obtained consistent orientation so that reason it gives a opportunity to make bis-amidalkyle and separate 2,4,6- threemethyl 3,5-di-(N-phthalimidomethyl) nitro benzene by string at 120 ° C in 65% yield.
