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catalyst an the base of nanostructural activated coal with activated coal AV-L/KOH and nanostructural activated
dimensions ofparticles 20-250 nm. the optimal temper- coal/KOH has been investigated. It was shown that in
ature was 240 °С and at this yield of N-vinylmorpholine both cases N-vinylmorpholine was obtained. Activity
was equaled 38.2 %. of catalyst on the base of nanostructural activated coal
Such heterogeneous — catalytical reaction of was higher in comparasion with catalyst on the base
acetylene with morpholine in the presence of catalysts: activated coal AV-L.
References:
1. Mackenzie J. D., Bescher E. Chemical Routesin the Synthesis of Nanomaterials Using the Sol-Gel Process//Acc. Chem. Res. - 2007. - № 40. - Р. 810.
2. Темкин О. Н. Химия ацетилена, «Ацетиленовое дерево» в органической химии ХХ1века//Соросовский образовательный журнал. - Соросов, 2001. - Т. 7, № 6. - С. 35-38.
3. Трофимов Б. А. Некоторые аспекты химии ацетилена//ЖОХ. - Л., 1995. - № 9. - С. 1368-1370.
4. Трофимов Б. А., Нестеренко Р. Н., Михалева А. И. Новые примеры винилирования NH-гетероциклов ацетиленом в системе КОН-ДМСО//ХГС. - Рига, 1986. - № 4. - С. 481-485.
D OI: http://dx.doi.org/10.20534/AJT-17-1.2-129-132
Parmanov Askar Basimovich, Senior researcher fellow, National University of Uzbekistan, Tashkent E-mail: [email protected]
Nurmanov Suvonkul Erxonovich, doctor of technical sciences, chair of department, National University of Uzbekistan, Tashkent
Phayzullaeva Mariya Phayzullaevna, teacher of the Karaganda State University named after Korkyt Ata
Abdullaev Jakhongir Urozolievich, magister National University of Uzbekistan
Soliev Mukhammadjon Ismatullaevich, teacher Namangan Engineering Pedagogical Institute
Synthesis of vinyl esters of some carbonic acids
Abstract: Heterogeneous-catalytical vinylation of some carbonic acids (enanthic, pelargonic and cyclohexancarbonic) was investigated. In each case the influence of the catalyst nature, temperature and mole ratio of reagents on the yield of the obtained vinyl esters of the corresponding acids was investigated.
Keywords: Heterogeneus-catalytical, acetilen, acids: enanthic, pelargonic and cyclohexancarbonic, energy activation.
Vinyl esters are used in different branches as solvents, bactericidal preparates in perfumery [1; 2]. Polymers obtained on their base have a specifical properties and are used as glue for different materials [3; 4].
From carbonic acids acetic acid as reagent for obtain vinyl esters has been investigated in large degree. Fat carbonic acids in this plane aren't investigated [5].
It is necessary to note that in Republik of Uzbekistan during last years the output of oil has been increased. Extraction from oil composition heteroatom-containing compounds such as fat carbonic acids and their processing has a great importance and future [6; 7].
In this work hetero-catalytical vinylation of acids such as enantic, pelargonic and cyclohexanic extracted from oil
composition of our Republic was investigated. Acetylene was used as vinylation agent. All reactions were carried out in flowing reactor in presence of following catalysts:
A1203; Zn (CH3COO)2 and Cd (CH3COO)2bearing on
Al2O3; Zn (C6H13COO)2/Al2O3 pelargonic and cyclo-hexanic acids bearing on Al2O3. It was determined that in all cases vinyl esters ofcorresponding acids were obtained with different yields according to following scheme:
O
R—c:
^OH
.0
r—c;
W^re: R = -C6Hn; -C6Hi3 and -C8Hi7.
Their yields have been depended on nature of catalysts, temperature of process and mole ratio of carbonic acids and acetylene.
It was investigated a mole ratio of initial reagents on yield of vinyl ester enantic acid in presence of catalysts Zn (CH3COO)2/Al2O3 and Zn (C6H13COO)2/Al2O3. Obtained data are presented in table 1.
Table 1. - Influence of mole ratio enantic acid and acetylen on yield of it's vinyl ester (temperature 300 °C)
Molar ratio of enantic Yield of vinyl ester of
acid : acetylene enantic acid
catalyst Zn (CH3COO)2/Al2O3
3 : 1 6.3
2 : 1 10.4
1 : 1 35.8
1 : 2 45.0
1 : 3 56.2
1 : 4 61.3
1 : 5 61.8
catalyst Zn (CfH13COO)2/Al2O3
3 : 1 11.2
1 : 1 38.6
1 : 2 51.0
1 : 2.5 54.3
1 : 4 62.7
1 : 5 63.4
Obtained results have shown that molar ratio of initial reagent has influenced on yield of vinyl ester of enantic acid. In presence of used catalysts when molar ratio of acid is higher then acetylen the vinyl ester was formed with low yields but in case when content of acetylen was more then acid yields of product were higher. At using of catalyst Zn (CH3COO)2/Al2O3 and molar ratio of regents 3 : 1 - 6.3 %. With incresing of molar ratio enantic acid: acetylen 1 : 4 the yield of forming vinyl ester of enantic acid was increased to 61.3 %. Following increasing of acetylen practically didn't influenced on yield of product. The same dependence was observed at using catalytical system Zn (C6H13COO)2/Al2O3. For example in it's presence at molar ratios enantic acid: acetone 3 : 1 and 4 : 1 yields of formed vinyl ester were
t>—ch=cho
11.2 and 62.7 % correspondenly. Thus for synthesis ofvi-nyl ester of enantic acid the most active catalyst was Zn (C6H13COO)2/Al2O3 and at this optimal ratio of enantic acid : acetylen was 1 : 4-5.
For carring out of reactions especially heterogeneous-catalytical at high temperatures investigation of their ki-netical constants in practical ratio is very important. By this reason kinetics of vinylation of enantic acid by acetylen in the presence of catalyst Zn (CH3COO)2/Al2O3 was investigated at temperatures 150, 200, 250 and 300 °C and at duration of 0.5; 1.0; 1.5 and 2.0 houres. Obtained kineti-cal data are presented on fig. 1.
Fig. 1. Dependence of yield of vinyl ester of enantic acid from duration of reaction at temperatures (°C): 1 - 150; 2 - 200; 3 - 250; 4 - 300; (catalyst — Zn (C16H33COO)2/Al2O3)
On the base of these data the rate of reaction of vinylation of enantic acid was calculated and also graph of dependence on oflgW/1/T was constructed (fig. 2), from which by equation ofArrenius the activation energy of this rection was determined which was equaled 4090J/mole.
For determination of influence of nature of carbonic acids on vinylation and yields of forming vinyl esters vi-niylation of pelargonic acid by acetylen in presence of following catalysts; Al2O3; Zn (CH3COO)2/activated coal; Zn (CH3COO)2/Al2O3 Cd (CH3COO)2/Al2O3 and Zn (C6H13COO)2/Al2O3 also was investigated. Obtained maximal yields of vinyl ester of pelargonic acid in presence of these catalysts are presented in table 2.
Fig. 2. Dependence of logariphm of rate from reverse
temperature (1/T) for vinylation of enantic acid at duration of rection (h.): 1 - 0.5; 2 - 1.0; 3 - 1.5; 4 - 2.0
Table 2. - Yields of vinyl ester of pelargonic
№ Temperature, °С Yield of vinyl ester of pelargonic acid, %
1. 230 15.4
2. 260 43.5
3. 280 49.8
4. 300 55.4
5. 320 57.2
6. 350 48.3
Zn (CH3COO)2/activated coal Zn (CH,COO)„/ALO_
cd (ch3coo)2/ai2o3
Zn (C8H17CO°)2/Al2O3
Yield of vinyl ester of pelargonic acid, %
33.2
51.3
37.4
55.4
Obtained results have shown that between investigated catalysts for vinylation of pelargonic acid catalyst Zn (C6H13COO)2/Al2O3 was the most active; in it's presence yield of vinyl ester of pelargonic acid was equaled 55.4 %. Also influence of temperature on yield of this ester in the presence of the most active catalyst has been investigated (table 3).
Table 3. - Influence of temperature on yield of vinyl ester of pelargonic acid (catalyst Zn (CRH13COO)2/ALO3)
№
Temperature, °С
230
260
280
300
320
350
Yield of vinyl ester of pelargonic acid, %
15.4
43.5
49.8
55.4
57.2
48.3
For determination of influence of presence of carbo-cyclical ring in molecule of carbonic acid on it's vinylation also it was investigated reaction of cyclohexancarbonic acid
by acetylene in the presence of some above-mentiened catalysts and also influence of temperature on yields ofob-tained vinyl ester of this acid have been investigated in the presence of catalyst Zn (C6H13COO)2/Al2O3 Obtained data are presented in table 4.
Table 4. - Vinylation of cyclohexancarbonic acid at different temperatures (catalyst Zn (C6H13COO)2/Al2O3)
Temperature, °С
220
240
260
280
300
320
340
Yield of vinyl ester of cyclo hexancarbonic acid, %
22.5
33.2
38.7
45.3
53.0
51.4
43.6
Results have shown that in investigated temperature interval (220-340 °C) yield of obtained vinyl ester was carried out throught maximum (53.0 %) at 300 °C. On fig. 3 comparasional data by influence of temperature on yields of vinyl esters of investigated carbonic acids in the presence of the most active catalyst are presented.
Fig. 3. Comporasional data by dependence on yield of vinyl esters from temperature (catalyst Zn (C6H13COO)2/Al2O3): 1 — Vinyl ester of cyclohexancarbonic acid; 2 — Vinyl ester of enantic acid; 3 — Vinyl ester of pelargonic acid
Also yields of vinyl esters of investigated acids in presence of some elaborated catalytical systems also were determined (table 5). From these data it is possible to conclude that alyphatical carbonic acid are more active than cyclic acid at heterogeneous-catalytical vinylation of them by acetylene. Also it is shown that with increasing of molecular mass of alyphatical carbonic acids the vinylation is carried out at higher temperatures and yields of their obtained vinyl esters at this have been deacreased.
Table 5. - Yields of vinyl esters of investigated
carbonic acids in the presence of elaborated catalysts (mole ratio of carbonic acid : acetylene — 1 : 4-5, temperature 300 °C)
Catalysts Yields of products, %
I II III
AW trace - -
Zn (CH3COO)2/activated coal 43.4 33.2 31.4
Zn (CH3COO)2/Al2O3 61.8 51.3 48.5
Cd (CH3COO)2/Al2O3 52.7 37.4 35.2
Zn (C6H13C°°)2/A12°3 63.4 - -
Zn (C8H17COO)2/Al2O3 - 55.4 -
Zn (C6H11COO)2/Al2O3 - - 53.0
In table 5 — I, II and III vinyl esters of enantic, pel-argonic and cyclohexancarbonic acids.
This is caused by fact that with increasing of molecular mass of carbonic acids their acidity has decreased what is carried out to decreasing of yields of their vinyl esters. Results have shown that investigated acids by of their ratio to vinylation by acetylene can be presented by following raw:
c,h cooh < chcooh < c h cooh.
6 11 8 17 6 13
Maximal yields of their vinyl esters were 53.0 and 63.4 %. At investigation of nature of catalysts at vinyl-ation above mentioned acids by acetylene it was determined that zink salt of every acid is active catalyst for vinylation namely of this acid.
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2. Раднаева Л. Д. Полимеры на основе ненасышенных карбоновых кислот и их производных. - Улан-Удэ, 2005. - 354 c//[Electronic resource]. - Available from: http://bankrabot.com
3. Плате Н. А., Сливинский Е. В. Основы химии и технологии мономеров. - М.: Наука, 2002. - 415 с.
4. Нарметова Г. Р., Хамидов Б. Н., Рябова Н. Д., Арипов Э. А. Очистка, идентификация и применение нефте-новых кислот. - Ташкент, 1983. - 144 с.
5. Муратова С. Х., Нурманов С., Нарметова Г. Р., Сирлибаев Т. С. Винилирование карбоновых (нефтяных) кислот//Узб. хим. журн. - Ташкент, 2003. - № 6. - С. 13-17.
6. Бродская Е. С. Нефтяные и синтетическые нефтеновые кислоты, их свойств и применение//Журн. орг. хим. -1999. - Т. 35, Вып. 2. - С. 221-226.
7. Наметкин Н. С., Егорова Г. М., Хамаева В. Х. Нафтеновые кислоты и продукты их химической переработка/Химия. - 1982. - С. 182-186.
D OI: http://dx.doi.org/10.20534/AJT-17-1.2-132-134
Smanova Zulaykho, National University of Uzbekistan E-mail: smanova. chem @mail.ru
Yangibayev Azim,
Yakhshieva Khurniso E-mail: [email protected]
Raximov Samariddin, National University of Uzbekistan named after Mirzo Ulugbek
Chemism of complex formation of pyridine and anabasine dyes
Abstract: Between problems standing befor investigators working in field of synthesis of organic reagents one of the important is finding of general principls of selection analytical reagents with help of which it is possible to determine content of different ions of metals with high sensibility. Decision of this problem is connected with investigation of particulities of spacial and electronical structure of reagents, ions of different metals, their complexes and also changing carring ont at their interaction.
