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ГОМОГЕННАЯ КАТАЛИТИЧЕСКАЯ ВИНИЛИРОВАНИЯ 2,4,6-ТРИГИДРОКСИ-1,3,5-ТРИАЗИНА АЦЕТИЛЕНОМ ПРИ ВЫСОКОМ ДАВЛЕНИИ
Зиядуллаев А.Э.
Докторант 3-курса Ташкентский химико- технологический института
Нурманов С.Э.
Доктор технических наук, профессор, факультет химия Национального университета Узбекистана
Калядин В.Г.
Кандидат химических наук, доцент, факультет химия Национального университета Узбекистана
Парманов А.Б.
Преподаватель химического факультета Национальный Университет Узбекистана
Жумартова У.У.
Магистрантка 2-курса химического факультета Национальный Университет Узбекистана
HOMOGENEOUS CATALYTIC VINYLATION OF 2,4,6-TRIHYDROXY-1,3,5-TRIAZINE BY
ACETYLENE AT HIGH PRESSURE
Ziyadullaev A.
Doctorate of 3-course of the
Tashkent Chemical Technology Institute Nurmonov S.
Doctor of technical sciences, professor, Faculty of ^emistry of the National University of Uzbekistan
Kalyadin V.
Candidate of chemical sciences, dosent, Faculty of ^emistry of the National University of Uzbekistan
Parmonov A.
Lecturer at the Faculty of Chemistry of National University of Uzbekistan
Jumartova U.
Student of 2-course of the Faculty of Chemistry National University of Uzbekistan
Аннотация
В работе исследована синтез виниловых эфиров путем винилирования 2,4,6-тригидрокси-1,3,5-триазина ацетиленом при высоком давлении в присутствии каталитических систем на основе ДМСО, ДМФА и оксида цинка исследована. Влияние растворителей природы катализаторов, температуры и продолжительности реакции на выход продуктов; энергия активации веществ, средние скорости реакции; состав полученных соединений был проанализированы спектральными методами ИК, :Н и 13С- ЯМР.
Abstract
In this work, the synthesis of vinyl ethers, by vinylation of 2,4,6-trihydroxy-1,3,5-triazine by acetylene at high-pressure in presence of catalytic systems on the base DMSO, DMFА and zinc oxide has been investigated. Influence of solvents, and nature of the catalyst, the temperature and duration of reaction was investigated on the yield of the products; the activation energy of reaction, the average reaction rates, were determined structure of obtained compounds by was analyzed spectral methods of IR, 1Н and 13C-NMR.
Ключевые слова: 2,4,6-тригидрокси-1,3,5-триазин, ацетилен, виниловый эфир, 4,6-дигидрокси-6-биц (винилокси) -1,3,5-триазин, 2-гидрокси-4,6-би (винилокси) -1,3,5-триазин, 2,4,6-триц (винилокси) -1,3,5-триазин.
Keywords: 2,4,6-trihydroxy-1,3,5-triazine, acetylene, vinyl ether, 4,6-dihydroxy-6-bic (vinyloxy) 1,3,5-triazine, 2-hydroxy-4,6-bic (vinyloxy ) 1,3,5-triazine, 2,4,6-three (vinyloxy) -1,3,5-triazine.
Introductions: The crystal structure of 2,4,6- [1]. 2,4,6-trihydroxy-1,3,5-triazine and its derivatives
trihydroxy-1,3,5-triazine (cyanuric acid) was first in- have been used in various sectors of the chemical
vestigated by scientists of Amsterdam University of industry as anti-sun for chlorine-stabilizers for open
Crystallography, E.H. Wiebenga and N.F.Moerman. reservoirs and large industrial water system, dyeing
materials, optical bleaching, surfactants, pesticides and herbicides in agriculture[2-3].
Modification of plasma and thermal surface energy modification of polymers, for active modification of the initial polymeric materials based on 2,4,6-trigi-droxy-1,3,5-triazine [4], increase of hydrophobicity of polymers, regulation of their adhesion properties have been widely used [5].
Investigations of russian scientists V. Zhorin, M.R. Kiselev and V.A. Kotenev have been developed to determination influence of main factors on thermal processes of mixtures of polymers based on cyanuric acid under high pressure [6-8].
Purpose and task: To study the process of synthesizing vinyl compounds of cyanuric acid based on catalytic vinylation with the participation of a solvent and a catalyst under high pressure.
The reaction mechanism can be presented as:
Research materials: Cyanuric acid vinyl ethers, homogeneous catalysis, catalysts, solvents and high atmospheric pressure.
Results and discussions:Synthesis of vinyl compounds of 2,4,6-trihydroxy 1,3,5-triazine was first carried out by catalytic vinyl in high-base system due to the active hydrogen atom in the molecule with the presence of acetylene at atmospheric pressure [9-10]. Reaction was carried out under high pressure to study the effect of pressure on the synthesis of vinyl compounds of cyanuric acid. Dimethylformamide (DMF) and dimethylsulfoxide (DMSO) were used as a solvents, the pressure to was equaled from 10-20 atm. zinc oxide was used as catalyst and at this formation of mono, di and three-vinyl ethers of 2,4,6-trigidroxy 1,3,5-triazine was observed.
OH
O—CH = CH2
N
N
+ HC = CH ZnO,DMSO
N
N
H
N
OH
"OH
In this reaction 2,4,6-trihydroxy 1,3,5-triazine has dissociated under action of the solvent:
OH O-
N
N
N
N
H
+ H
N ^H HO/ ^OH
In the reaction process acetylene interacts with zinc oxide with formation of n-complex: HC^CH + ZnO -HC =
: CH
▼
ZnO
In resulting p-complex one n-acetylene bond was disconnected and the c-complex-vinyl zinc hydroxide cation was formed.
©
-»- CH = HC
HC = CH
I
ZnO
H
\ / ZnOH
The vinyl zinc hydroxide cation interacts with anionic acid with formation of vinyl zinc hydroxide complex:
O— ZnOH
CH
= HC
v©7 + \ /
ZnOH
N
H
H
H
+ H
H
The resulting vinyl zinc binds with hydrogen ions in the complex of hydroxide to form the mono-vinyl ether of the acid. (4,6-digidroxy-6-bits (vinyl-oxy) - 1,3,5-triazine):
O — HC = CH2
O — CH = CH—ZnOH
HO
N^ N
JN
+
H
+
N
N
N^ OH
HO
N
+
+ ZnOH
OH
Di-vinyl ether is first synthesized by addition more acetylene into system containing the acid mono-vinyl ether at increasing the reaction duration and temperature:
N
O — HC = CH2 N
H
N
+ 2 HC
CH
ZnO
N
OH
DMSO
H
O — HC = CH2 N
—HC = CH2
ZnO
DMSO
H2C = CH-
N^ N
1
N^O—HC = CH2
The resulting divinyl ether was turn into three-ivinyl ether by further increasing in system amount of acetylene and time of reaction:
O- HC = CH2 O_ HC = CH2
T 2
pN + HC = CH
HO/^^^NO—HC = CH2
The vinyl reaction of 2,4,6-trihydroxy 1,3,5-triazine at 10 atm. was carried out in drying of 2-6 h and 100-160 oC in the presence of catalysts DMSO, DMF and zinc oxide in the liquid phase. In order to accelerate the reaction to increase product yield and reduce the risk of acetylene decomposition, the system was diluted by inert gas (nitrogen).
Vinylation of 2, 4, 6- trihydroxy 1, 3, 5-triazine was carried out in the presence of systems DMSO+ZnO and DMF+ZnO. It was investigated the in flense effect of reaction duration and temperature on carring out reaction and yields of forming compounds.
As mentioned above, zinc oxide reacts which 2,4,6-trigidroxy 1,3,5-triazine with formation of intermediate in the system which further has accelerated the vinyl process as an active catalyst. In the system zinc cyanurate acts as an active catalyst and prevents the addition of anions into the reaction mixture. However zinc oxide is more effective catalyst at using in combination with organic solvents. (DMSO and DMF).
The reaction was carried and will formation of mono-vinyl ether at 2 h; di-vinyl ether at 4 h, three-vinyl ether at 6 h with high yields and at 8 h yields of all vinyl ethers sharply decreased. (Table 1)
Table 1
The influence of reaction duration in presence of DMSO + ZnO on the yield vinyl ethers of 2,4,6-triglycer-
ide 1,3,5-triazine
Temperature, °C The products and the reaction time is 2 hour yield,% Totally %
I II III
100 34.6 8.4 6.2 49.2
120 40.4 10.8 8.6 59.8
140 52.6 12.4 10.2 75.2
160 20.8 6.8 4.6 32.2
The reaction time is 4 hour
100 14.3 28.8 10 55.1
120 15.8 34.6 12 64.7
140 16.4 46.8 18 81.2
160 6.6 20.8 8.6 35.4
The reaction time is 6 hour
100 4.2 8.4 46.6 59.2
120 4.2 10.3 58.4 72.9
140 4.8 8.2 76.6 89.6
160 - - 37.8 37.8
Analysis of the results has show that when reaction was carried is the precense catalyst DMSO + ZnO at 2 h and 140 0C (I) -monovinyl ether 52.6, (II) di-vinyl ether 12.4, (III) -three-vinyl ether 10, 2 %. At synthesis of at 4 h and 140 0C yields of mono-vinyl ether was 16.4, divinyl ether 46,8, three vinyl ether
18%; at synthesis 6 h and 140 0C yields of ethers were monovinyl ether 4.8, divinyl ether 8.2, trivinyl ether 76.6% of time at vinyulation of correspondence.
The effect of 2,4,6-trigidroxy 1,3,5-triazine in the presence of DMF + ZnO for 2,4,6 h. at high pressure in the temperature range 120-160 °C, was studied.
Table 2
The effect of reaction duration in presence of DMF + ZnO on the yield of vinyl ethers of 2,4,6-triglyceride _1,3,5-triazine_
Temperature °C The products and the reaction time is 2 hour yield,% Totally %
I II III
100 32.6 8.2 4.8 45.6
120 38.5 8.6 7.4 54.5
140 46.4 12.2 9.6 68.4
160 18.6 4.8 4.2 27.6
The reaction time is 4 hour
100 10.8 23.8 8.8 43.4
120 13.6 27.5 10.2 51.3
140 14.4 42.8 16.7 73.9
160 6.0 14.8 7.6 28.4
The reaction time is 6 hour
100 3.8 6.2 41.4 51.4
120 3.2 8.5 46.8 58.5
140 3.4 7.2 70.6 81.2
160 2.6 6.4 17.8 37.8
With an increase in duration at a constant temperature of 140 oC, the yields of mono-vinyl ethers resembles through a maximum with a duration of 4 hours, and the three vinyl ethers increase continuously. It should be noted that at combination of zinc oxide will of
DMSO products were synthesis with higher yields in comparison with system ZnO + DMF.
The kinetic parameters of the synthesis of 2,4,6-trigidroxy 1,3,5-triazine mono, di and three-vinyl ethers, that is the activation energy and the average reaction rate were calculated (Table 3).
Table 3
Kinetic parameters of the synthesis of 2,4,6-trigidroxy 1,3,5-triazine vinyl ethers (DMSO + ZnO)
Vinyl ethers Reaction time, h Temperature, 0C Yield of vinyl ethers of 2,4,6-trihydroxy 1,3,5-triazine Reaction rate
% gram % hour
I 2 100 34.6 3,35 17,3
120 40.4 3.92 20,2
140 52.6 5,10 26,3
160 20.8 2,01 10,4
II 4 100 28.8 2,79 7,2
120 34.6 3,35 8,65
140 46.8 4,54 11,7
160 20.8 2,01 5,2
III 6 100 46.6 4,52 7,8
120 58.4 5,66 9,7
140 76.6 7,43 12,8
160 37.8 3,66 9,45
Analysis shows that the temperature at 140 °C for °C for 4 hours 46,8%, 11,7 %/h, and at 140 °C for 6 2 hours at mono vinyl 52.6%, 26,3 %/h, di-vinyl at 140 hours three-vinyl 76.6%, 12,8 %/h.
Table 4
Vinyl ethers Reaction time, h Temperatur, "C Yield of vinyl ethers of 2,4,6-trihydroxy 1,3,5-triazine Reaction rate
% gram %/hour
I 2 100 32.6 3,16 16,3
120 38.5 3,73 19,25
140 46.4 4,50 23,2
160 18.6 1,80 9,3
II 4 100 23.8 2,35 5,95
120 27.5 2,64 6,9
140 42.8 4,17 10,7
160 14.8 1,43 3,7
III 6 100 41.4 4,09 6,93
120 46.8 4,54 7,8
140 70.6 6,85 12,8
160 17.8 1,72 2,96
Analysis of the vinyl ethers produced in the presence of DMF + ZnO showed that mono-vinyl ethers with a lower yield than DMSO-ZnO at 2 h and 140 ° C 46,4 %, 23,2 %/h, at 4 h, di-vinyl ethers 42.8%,
10,7 %/h, at 6 h three-vinyl ethers 70.6%, 12,8 %/h synthesis.
Influence of pressure on the yield of products was investigated. The reaction was carried out in DMSO and DMF solutions during 2,4,6 h (Table 5).
Table 5
Reaction Pressure, Yield,% Yield,%
duration (atm) in the presence of DMSO in the presence of DMF
1 - -
2 10 75,2 68,4
20 75,4 64,3
1 52,5 34,4
4 10 81,2 73,9
20 81,4 70,6
1 62,6 39,7
6 10 89,6 81,2
20 89,8 76,5
1 37,9 35,2
8 10 56,8 44,2
20 54,2 43,8
According to the results analysis of the yield of acetic vinyl ether at atmospheric pressure was 52,5 h for 4 h. 62,6 in 6 hours; There was a dramatic decrease at 8 h and 37,9%, when the reaction was carried out in the presence of a DMSO solvent at 10 atm. pressure; 75,2 in 2 hours; 81,2 in 4 hours; 89,6 in 6 hours. During hours at 2, 4, 6 hours at increased pressure to 20 atm. there was little change in product yields: 75,4; 81,4 only at reaction time 8 h was observed decreasing of yield from 89,8 to 54,2%. It is show from the table, that the product was synthesized with higher yields at using DMSO in comparison will such at carried out in the presence of DMF.
The structure of mono, di-vinyl and three-vinyl ethers of cyanuric acid synthesized on the basis of 2,4,6-trigidroxy 1,3,5-triazine was proved by spectral methods IQ-, 1H and 13C-NMR and also their physical constants were determined. The spectral results of obtain vinyl ethers are presented below.
4,6-digidroxy-6-bits (vinyloxy)-IR-spectrum of 1,3,5-triazine: 4,6-digidroxy-6-bits (vinyloxy) - IR-spectrum of 1,3,5-triazine to hydroxyl group ( OH) a
specific vibration signal was observed in the area of 3512 cm-1. The valence vibration signal of the carbonyl group (C = O) was seen in the area 1765 cm-1- The valence vibration signal of the group C = N of the heterocyclic ring was observed in the area 1384 cm-1, and in the area 1093 cm-1, the valence vibration signal specific to the C-OH group was observed. Valence vibrations of the ether (C-O-C) group in the field 1253 cm-1, vinyl band 864 cm-1 area deformation vibration of =CH2 group, 1471 cm-1 area = valence vibration of CH group, 1660 cm-1 area and vinyl band (-CH = CH2) was observed.
2-hydroxy-4,6-bits (vinyloxy) -1,3,5, - IR spectrum of triazine: 2-hydroxy-4,6-bits (vinyloxy) -1.3,5, - hydroxyl in the IR spectrum of triazine (OH) vibration signal was observed in the area 3493 cm-1. The valence vibration signal of the carbonyl group (C = O) was seen in the area 1759 cm-1, and the valence vibration signals of the C = N group of the ring were seen in the area 1386 cm-1. In the 1091 cm-1 area, the valence vibration signal specific to the C-OH group was observed. In the 1253 cm-1 area, the valence vibration signal of the ether
(C-O-C) group, the vinyl band 862 cm-1 area deformation vibration of the =CH2 group, 2929 and 1438 cm-
1 area the valence oscillations of the CH group, 1654 sm-1 in the area, the valence vibration signal (-CH = CH2) was observed.
IR-spectrum of 2,4,6-trieth (vinyloxy) -1,3,5-triazine: 2,4,6-tritium (vinyloxy) in the IR spectrum of -1,3,5-triazine of carbonyl group (C = O) the valence vibration signal was in the field 1791 cm-1, and the valve vibration signals of the C = N group of the ring were in the 1400 cm-1 area. In the 1056 cm-1 area was the valence vibration signal of the ether (C-O-C) group, vinyl band 761 cm-1 area deformation vibration band CH2, 3053 and 1463 cm-1 area = CH valence oscillations; 1693 sm-1 in the area, was observed the valence vibration signal (-CH = CH2).
PMR spectrum of 2,4,6-trieth (vinyloxy) -1,3,5-triazine: 2,4,6-tritium (vinyloxy) in the PMR spectrum of -1,4,5-triazine in the vinyl group (-CH = CH2) quartet signal of one proton (-CH =) is 7.41 m.p. in the field, the duplex-duplex signals of two protons (= CH2) are 5.03 and 5.06 m. areas. Three-vinyl ether of cyanuric acid in the 13C spectrum signals of carbon atoms in the 2,4,6-position in the triazine ring at 166 m. in the field, the carbon of the vinyl group is 145.5 (-CH=) and 94.6 (=CH2) ppm areas.
CONCLUSION
After analyation of kinetic parameters of the synthesis of cyanuric acid vinyl ethers, the average reaction rate was determined and it's activation energy was calculated. Using analysis of graphs of analytical functions and diagrams of kinetic parameters of synthesis it is possible to established that at a reaction time of 2, 4, 6 hours and a temperature of 140 ° C the yields of vinyl ethers have reached a maximum values: mono-vinyl, in
2 h, 75,2; di-vinyl, in 4 h, 81,2 and in 6 hours 89,6 %.
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SOLVING DIRECT AND INVERSE PROBLEMS FOR AUTOCATALYTIC REACTIONS
Bondarchuk I.
Postgraduate student, Department of Chemistry, Tomsk State University Bondarchuk S.
Doctor of Physical and Mathematical Sciences, Professor, Department of Biology and Chemistry, Tomsk State Pedagogical University
Abstract
This article proposes a new method and algorithm for identifying the kinetic parameters of autocatalytic reactions through solving inverse problems. The proposed method can be classified as integral. A simple algorithm and code is presented, which is easy to test and which is based on the MS Excel Solver add-on without using macros of Visual Basic. A detailed description of the implementation of the algorithm and the results of determining the kinetic parameters for identifying the kinetic parameters of typical autocatalytic reactions are given.
Keywords: chemical kinetics, autocatalytic reaction, inverse problems, spreadsheet.
