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Structure of the synthesized alcohol identified IR-spectral analysis. In IR-spectrum of the obtained unsaturated alcohol on the base of 2-methyl-1-pentene with formaldehyde new absorption bands of valence oscillation ofC-О bond in the field of1031-1170 sm-1; valence oscillation of olefinic bond С=С are manifested in the field of 1605 sm1; absorption bands СН3, СН2 groups at 2661-2731 sm1 and a wide absorption band vOH car-bonyl groups in the field of 2900-2958 sm-1.
Thus, condensation process of 2-methyl-1-pentene, 2-ethyl-1-pentene, 3-methyl-1-pentene, 3-methyl-2-pen-tene, heptene-1 with formaldehyde is studied. Optimum conditions of obtaining monatomic unsaturated alcohols are determined. Influence of the nature and concentration of the catalyst, temperature and dissolvent on the product yield is investigated.
References:
1. Касимова К. А., Шарф В. З., Литвин Е. Ф. Алкилбензол-сульфокислоты - эффективные катализаторы кислотно-катализируемого взаимодействия олефинов с формальдегидом (реакция Принса)//Тез. докл. УП Всесоюзной конференции: «ПАВ и сырьё для их производства. Химия и технология ПАВ», 1988. - С. 10.
2. Шеманаева М. Н., Мельник Л. В., Крюков С. И., Москвичев Ю. А., Среднев С. С., Суровцев А. А., Карпов О. П. Способ получения кислородсодержащих органических соединений - смеси кетонов и непредельных спиртов и возможно альдегидов. Патент РФ № 2174113. Дата публикации 27.09.2001.
3. Астахова А. С., Хидекель М. Ф. Способ получения непредельных спиртов. Авторское свидетельство № 232966, 1969.
In the capacity of subjects of investigation there have been chosen tertiary olefines 2-methyl-1-pentene, 2-eth-yl-1-pentene, 3-methyl-1-pentene, 3-methyl-2-pentene that have been separated by the method of fractionation from hexine fractions of the Shurtan gas-chemical complex, formaldehyde, sulphuric acid.
In the capacity of dissolvent there have been chosen dioxane and diethyl ether, the catalyst of halogenide metals: ZnCl2, CuCl2.
IR-spectrums of the synthesized alcohols and their initial reagents have been removed on IK- Fourier spectrophotometer SISTEM-200.
Purity of the synthesized compounds has been controlled thin-layer chromatography on plates Silufol: elu-ent -benzol-acetone.
DOI: http://dx.doi.org/10.20534/AJT-17-1.2-126-129
Мirkhamitova Dilorom, candidate of chemical science, dotsent E-mail: [email protected] Nurmanov Suvonkul, doctor of technical sciences, chair of department Halimova Oygul, magister National University of Uzbekistan, Tashkent
Investigation of catalytical reaction of acetylene with morpholine
Abstract: Method of N-vinylmorpholine synthesis by vinylation of morpholine was elaborated in homogeneous and heterogeneous conditions and also in the presence of nanostructural catalysts on the base of activated coal and potassium hydroxide.
Keywords: morpholin, heterogeneous catalyse, nanostructural catalysers, vinylation, kinetics of this process, energy of activation.
In last years a great progress has been achieved in ob- It is known that vinyl compounds are used in different
tain and investigation of properties of modified nano- braches of industry and agriculture and ther are synthe-
structural heterogeneous catalysts for vinylation of or- sized by different methods, among which by importance
ganical compounds having in their composition an active and actuality is vinylation of corresponding organical
atoms of hydrogen [1]. compounds by action on them by acetylene [2-4].
Investigation of catalytical reaction of acetylene with morpholine
From above-mentioned reaction of vinylation of (DMSO-dimethylsulfoxide; DMF-dimethylformamide) morpholine in the presence of KOH with using super has been investigated and it was determined that reac-base systems such as KOH-DMSO and KOH-DMF tion is carried out according to following scheme:
/-\
0n_/nh + hc=ch
KOH-DMSO -*
90-95°C
/-\
on_/n-ch=ch2
At this influence of solvent nature on carring out of this reaction was investigated. Experimental results have shown that in absence of dipolar aprotonical solvents vinylmorpholine also has been obtained but in small quantities (before 2.0 %). In solution of DMF at 70 °C and duration 4 h. aproduct was obtained with yield 8-10 %. At substitution of DMF and DMSO the yield of forming N-vinylmorpholine has increased in high degree (at the same conditions as at using DMF the maximal yield of product was equaled 22 %). In all cases yield of N-vinylmorpholine has been increased with increasing of reaction duration (1-4 h.).
Influence of quantity of catalyst on vinylation was investigated by chanding it's quantity in reaction system from 10 to 20 % from mass of morpholine in the presence of solvent — DMSO. Obtained results have shown that quantity of catalyst has influenced on the yield of forming N-vinylmorpholine with increasing of it's contant in interval 10-15 % yield of product also was increased. The following increasing of catalyst quantity negatively influenced on formation of N-vinylmorpholine what canbe explained by following fact — at content of KOH in system more 15 % quantity of oligomers or polymers has increasing of resinous compounds during reaction of vinylation. Correspondenly it is possible to conclude, that optimal contance of catalyst (KOH) for vinylation of morpholine by acetylene is 15 mass. %.
Also it was investigated influence of nature of using catalysts hydroxides LiOH, NaOH and KOH (in solid state) on the vinylation of morpholine. It was determined that in all cases N-vinylmorpholine was formed but KOH was the most active catalyst — in it's presence yield of N-vinylmorpholine was equaled 23.0 % (in the presence of LiOH or NaOH yield of product was equaled 16.6 and 19.4 % correspondenly).
Kinetics of vinylation of morpholine with acetylene at atmospheric presence in the presence of system KOH-DMSO and different temperatures and durations of reaction carring out has been investigated. On the base of obtained kinetical data the graph in coordinates lgW-1/T has been constructed (fig. 1) and also value of the activation energy (E) of vinylation of morpholine has been calculated which was equaled 55.6 kDj/mole.
Fig. 1. Dependence of lgW from 1/T for reaction of morpholine vinylation
Also heterogeneous — catalytical vinylation of morpholine in running reactor in the presence of heterogeneous catalyst (KOH) beared on granulated activated coal (30 % from mass of bearer) has been carried out. It was determined that in these conditions also N-vinyl-morpholine was formed.
For optimization of conditions of morpholine vinylation influence of temperature on it's carring out in heterogeneous system that is on yield of the forming at this N-vinylmorpholine has been investigated. Obtained results are presented in table 1.
Table 1. - Effect of temperature on vinylation of morpholine
№ Temperature, °C Yield of N-vinyl-morpholine, % № Temperature, °C Yield of N-vinyl-morpholine, %
1 65-70 - 6 210-215 23.2
2 100-105 10.6 7 225-230 25.0
3 120-125 18.4 8 250-255 31.7
4 140-160 19.8 9 280-285 19.0
5 180-190 21.5 10 290-300 12.0
Obtained results have shown that with increasing of temperature in interval 100-255 °C yield of forming N-vinylmorpholine was increased from 10.0 to 31.7 % correspondenly. Than increasing temperature above 225 °C has carried out to shar decreasing of yield of syn-thesised compound and for example at temperatures 280-285 °C and 290-300 °C it was equaled 19 and 12 % correspondenly.
Structure of synthesised N-vinylmorpholine was prowed by method of IR-spectroskopy.
In IR-spectrum of N-vinylmorpholine there ar following bands: 1520-1610 sm-1 - valent vibrations C=C bond of vinyl group; 1050-1250 sm-1 valent vibrations C-O-C fragment of morpholine molecule; 2950-2960 sm-1 simmetrical and unsimmetrical vibrations of methylenic group (-CH2-).
Determined experimental data have shown that catalyst KOH/activate coal has an enough activity at synthesis of N-vinylmorpholine by heterogeneous-cat-alytical vinylation of morpholine by acetylene.
Dor development of catalytical systems for reaction of acetylene with morpholine some nanostructural matrixes of activated coal were obtained which were used as bearer of catalysts. It was determined influence of initial dimensions of obtained activated coal on carring out synthesis of N-vinylmorpholine. The optimal dimensions of using of activated coal were equaled 1-3 m.
Dispersion analysis was carried out by method of microscopy. With in of decreasing of dimensions of particles of activated coal sample be for fractionation were undergone to ultrasonic treatment, for which water suspension of activated coal has been prepared (150 ml. H2O : 5g. of activated coal) and than it was undergone to ultrasonic treatment in regime 0.6 A; 38 kGc. during 60 min. Through every 3 min. the treatment was stoped and glass with mixture was cooled in during 30 sec. in water. Through 10, 20, 30 and 60 min. probes were separated and dimensions of particles of activated coal were determined by method of microscopy.
Analysis of obtained results has shown that dimensions of dispergated particles of activated coal were equaled 700-900 nm.
Sedimension fractionation of particles of activated coal during 20, 30, 40 and 60 min. has shown that in investigated intervals of time their distribution by dimension has changed markedly.
Dimensions of particles of obtained fraction after 20 min. dispergation were equaled 500-750 nm, and after intervals 30, 40 and 60 min. of dispergation they were equaled 300-350; 200-320 and 200-250 nm. cor-respondenly. Obtained results are presented in table 2.
Such the results of dispersion analysis by method of microscopy have shown that in installation of ultrasonic dispergater UZDH2T by dispergation of suspension of activated carbon by water it is possible to active of dimensions of particles of activated coal to 200-250 nm. durining 60 minutes. Increasing of dispergation time didu't influenced on dimensions of obtained particles.
Table 2. - Influence of dispergation time on dimensions of particles of activated coal
Time of dispergation, min. Dimensions of particles of activated coal, nm.
- 1-3 mkm.
10 700-900
20 500-750
30 300-550
40 200-320
60 100-250
Heterogeneous — catalytical reaction of acetylene with morpholine in the presence of catalyst on the base of nanostructural activated coal with dimensions of particles 200-250 nm. has been investigated. Conditions of carring reaction were the same as in the presence of catalyst activated coal/KOH. Quantity of KOH in the presence of catalyst was equaled 30 mass. %. Influence of temperature on reaction of acetylene with morpholine in heterogeneous conditions in the presence of catalyst on the base of activated coal winy dimension of particles 200-250 nm. has been determined.
It was determined that in this case also N-vinylmor-pholine was synthesised. Obtained results are presented in table 3.
Table 3. - Influence of temperature on yield of N-vinylmorpholine in the presence of catalyst activated coal/KOH with particles dimensions of activated coal 200-250 nm
№ Теmperature Yield of N-vinylmor-
of reaction, oC pholine, %
1 160 24.3
2 180 27.0
3 200 29.5
4 220 34.4
5 240 38.2
6 260 25.6
7 280 20.4
Obtained results have shown that in this case temperature in interval 160-180 °C in gratedegree has influenced on the yield of forming N-vinylmorpholine. In investigated interval of temperatures yield of N-vinyl-morpholine was carried out through maximum (38.2 %) observed at 240 °C. With increasing of temperature in interval 160-240 °C yield of product has increased from 24.3 to 38.2 %. The following increasing of temperature has negative influence of yield of N-vinylmorpholine for example it's yield at 260 °C and 280 °C was equaled 25.6 and 20.4 % correspondenly.
Analysis of obtained data has shown that for reaction of acetylene N-vinylmorpholine in the presence of
Synthesis of vinyl esters of some carbonic acids
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
