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DOI: http://dx.doi.org/10.20534/AJT-17-1.2-124-126
Makhmudova Feruza Akhmadjanova, The senior scientific researcher, Tashkent chemical-technological institute E-mail: [email protected] Maksumova Oytura Sitdikovna, The Doctor of Chemistry sciences, professor E-mail: [email protected]
Synthesis on a basis olefines
Abstract: possibility of obtaining unsaturated monatomic alcohols by the condensation reaction of olefines with formaldehyde in the presence of catalysts is shown. Kinetic regularity of reaction interacting of olefines with formaldehyde from the relationship of initial reagents, the nature of catalyst and temperature are studied.
Keywords: olefins, unsaturated alcohols, the catalyst, condensation, solvent, formaldehyde.
Liquid olefines are important inter-mediats in organic to obtain organic compounds of different classes, including unsaturated alcohols. The analysis of this data shows the possibility of two regimes of process with anhydrous formaldehyde:
1) at 20-100 °C in the presence of catalysts and dissolvents;
2) thermal condensation at 150-240 °C, 5-10 atm. pressure. For our researches the first regime as in the laboratory environment it is technologically more preferable chosen.
The purpose of the present work is the synthesis of unsaturated alcohols by the condensation reaction tertiary isomers of hexene with formaldehyde.
During the undergone reactions by interacting of tertiary olefines: 2-methyl-1-pentene, 2-ethyl-1-pentene, 3-methyl-1-pentene, 3-methyl-2-pentene with formaldehyde at rather low temperatures in the presence of the catalysts have been detected unsaturated alcohols under following circuit designs:
synthesis. As chemical raw materials, they draw attention of researchers in the respect that at the synthesis on their basis, reactions can undergo at atmospheric pressure in milder conditions. Liquid olefines enter into various reactions which compounds of other classes, including unsaturated alcohols are formed. Unsaturated alcohols can be used in various spheres of national economy. In chemical, food and other industries for allocation of firm suspended matters, for the separation of synthetic organic ion exchangers, for clearing of industrial flow and intermediate products in organic synthesis etc [1,10].
Unsaturated alcohols can be synthesized in the various ways [2, 3]. Among them Prins reaction, which is understood as interaction of olefines with aldehydes in the presence of catalysts, is a convenient method. However, in Prins reactions depending on the nature of olefine and aldehyde, from reaction conditions, and also on the character of the catalyst and dissolvent it is possible
Synthesis on a basis olefines
For the purpose of detection of optimum conditions of process, the influence of the nature of dissolvent, the catalyst, olefine, and temperatures on the reaction product yield is investigated. In the capacity of dissolvent are chosen dioxane-1,4 and diethyl ether, the catalyst of halogenide metals: ZnCl2, CuCl2.
A series of experiments have been carried out and solvent has been chosen for the condensation reaction of olefines with formaldehyde (tab. 1).
Table 1. - Influence of the nature of solvents on the yield of obtained alcohol; T = 80 °C
Compound Names of solvents The yield of alcohol, %
2-methyl-1-pentene Dioxane 63.0
Diethyl ether 82.6
2-ethyl-1-pentene Dioxane 52.0
Diethyl ether 72.5
3-methyl-1-pentene Dioxane 48.7
Diethyl ether 65.3
3-methyl-2-pentene Dioxane 36.0
Diethyl ether 54.8
It is found out that is smooth also good exits condensation chosen olefines with formaldehyde proceeds at presence of diethyl ether. Comparison of relative activity of the specified catalysts is carried out in condensation reactions on an example of 2-methyl-1-pentene at 60-80°C in diethyl ether.
Fig. 1. Relative activity of catalysts at the condensation of 2-methyl-1-pentene. T = 80 0C, [K] = 0.25 mole/l: 1 - ZnCl2; 2 - CuCl2
The gained results show that CuCl2 manifests the best catalytic activity (fig. 1). These results allow to have catalysts for the given reaction in the following row of relative activity: CuCl2 > ZnCl2.
The influence of a molar relationship of olefine, formaldehyde and catalyst is studied. At equimole relationship of olefine, formaldehyde and catalyst is equal to 1 : 1 : 0.25 within 14-18 hours the yoeld of appropriate unsaturated alcohols made only 20-30 %. Intensive formation of coproducts has been observed. With increase in the molar relation of olefine to formaldehyde the maintenance of alcohols in reaction particles increased. At quintuple excess of olefine the quantity of coproducts decreased and an yield of unsaturated alcohols formed within 70-85 %.
Study of the influence of temperature on the obtaining process of unsaturated alcohols shows that alongside with increase in reaction temperature of condensation the alcohol yield increases. At the temperature of 80 °C the yield of alcohol attains to 82 %, the further increase in temperature does not promote increase in the yield of alcohol.
Fig. 2. Dependence of an yield of alcohol on the base of 2-methyl pentene-1 on the reaction temperature, °C: 1 - 60; 2 - 70; 3 - 80
On the basis of the gained results and the literary data the codensation reaction mechanism of 2-methyl pentene-1 with formaldehyde in the presence of CuCl2 it is possible to present as follows: in the presence ofLewis acids the intermediate compound III, stabilized as a result of detachment of Lewis acid and proton transfer, is formed:
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].
