CC BY
70CHEMISTRY SCIENCES
СИНТЕЗ АРОМАТИЧЕСКОГО АЦЕТИЛЕНОВОГО СПИРТА НА ОСНОВЕ КЕТОНОВ И ФЕНИЛАЦЕТИЛЕНА И ИХ БИОЛОГИЧЕСКИЕ СВОЙСТВА
Буриев Ф.Х.
преподаватель факультета естественных наук, Чирчикский государственный педагогический институт, Узбекистан Абдурахманова С.С. докторант, Чирчикский государственный педагогический институт, Узбекистан Зиядуллаев О.Э.
доктор химических наук, профессор, Чирчикский государственный
педагогический институт, Узбекистан
SYNTHESIS OF AROMATIC ACETYLENE ALCOHOL BASED ON KETONES AND PHENYLACETYLENE AND THEIR BIOLOGICAL PROPERTIES
Buriyev F.
Teacher of the Faculty of Natural Sciences, Chirchik State Pedagogical Institute, Uzbekistan Abdurakhmanova S. doctoral student, Chirchik State Pedagogical Institute, Uzbekistan Ziyadullaev O.
Doctor of Chemical Sciences, professor, Chirchik State Pedagogical Institute, Uzbekistan
Аннотация
Синтезированы ароматические ацетиленовые спирты (ААС) взаимодействием ацетиленового углеводорода- фенилацетилена с кротоновым альдегидом кетонами (ацетон, метилэтилкетон, метилизопропил-кетон, ацетофенон и понокалин) по методу Фаворского. Научно обосновано влияние различных факторов-мольное соотношения исходных веществ, температуры, продолжительности реакции и природы растворителей на выход продукта. Найдено оптимальное условие синтеза продукта с высоким выходом. Предложен механизм реакции, основываясь на литературные источники. С помощью кванто-химических методов и их расчетов определено распределение электронов молекулярно-динамические показатели, фазовые строение, рассчитана энергии активации процесса и показано стадии реакций. Синтезированные ароматические ацетиленовые спирты впервые использованы в качестве биоцидов для биокоррозии стальных и металлических конструкций нефтегазовой промышленности.
Abstract
Aromatic acetylene alcohols (AAA) synthesized by reacting acetylene with phenylacetylene- croton aldehyde and ketones (acetone, methylethylketone, methylizopropylketone, acetophenone and pinokalin) by the method of Favorsky. Scientifically proven influence of various factors-the molar ratio of the starting materials, temperature and the nature of the solvent on the yield of the product itself. The reaction mechanism based on literary sources. Structure, composition and purity of the quantum-chemical values of aromatic acetylenic alcohols and vinyl ester proved by physico-chemical methods and modern computer programs that calculate the activation energy for processes and to identify the mechanisms of reactions carried out. First proved synthesized aromatic acetylenic alcohols exhibits inhibitory activity against biological corrosion of steel and metal structures of the oil and gas industry and proved their high activity as biocides.
Ключевые слова: фенилацетилен, ароматические ацетиленовые спирты, катализатор, растворители, кинетика, механизм реакции, выход продукты, биологический активность.
Keywords: phenylacetylene, aromatic acetylenic alcohols, catalyst, solvent, kinetics, reaction mechanism, yield products, bioactivity.
INTRODUCTION
Systematic investigations about the manufacture of various new products on the process of oil, oil products and hydrocarbons or be applying catalysts with higher base in the process for the purpose of subsequent development of classical reactions on the bases of acetylene and its homologs in the near future have been carrying out within the last ten years [1-3]. Being of great
importance AAA and such group substances are used on a large scale in different fields, including inhibitors-antibiocorrosion of metal installation in oil-gas industry [4, 5], ionites purifying poisonous and polluted sewage in the enterprises of metallurgy and oil-gas refinery, as additives increasing low-temperature resistance of aviation gasoline, and in the paint and varnish industry, textile, agriculture, medicine and radio engineering for
the various purposes [6, 7]. Being the presence of tri-bond and hydroxyl group in the molecule of AAA causes the expansion of their application fields and their chemical properties [8]. They are mainly synthesized with the various methods - Favorsky, Grignard-Jocich and diazotization reactions on the bases of acetylene hydrocarbons [9-13]. The reaction of phenyl acetylene with aldehyde and ketones in the tetrahydrofuran solution in the presence of the catalysts has not been studied in the Favorsky method.
EXPERIMENTAL
Reagents: Alkalies- LiOH, NaOH and KOH, solvents- methanol, ethanol, tetrahydrophuran (THP), diethylesther (DEE), potash, hydroquinone, benzene, chloroform, phenylacetylene, croton aldehyde, acetone, methylethylketone, methylizopropylketone, pinokaline, acetophenone.
Instruments: PMR spectra of the structure of synthesized compounds have been studied in the spectro-photometer Jeol FX-90Q (90 millihertz), and IR structure has been studied in the spectrophotometer Bruker JFS-25. In the room temperature NMR1H structure has
O
been determined with the help of spectrophotometer Bruker DPX-400 (working frequency 400.13 millhertz, solvent- CDCl3, inner standard- GMDS). The content of mixture has been analyzed GLCh with the help of device LXM-80 (gas-carrier-helium, (column) geyser 3000x3 mm, 1% solution of liquid phase polyethylene glycol in NaCl), filters- Extraction Thimbles Grade 603. (3,2-20,0 mm.), Pressure-Regulators Kayzer K98, thormemetrs- Thorm. of 2-Channel (-50- +300), strurrer- RW 28 basic.
Methods of research modern computer's programs: Phase structure of synthesized AAA molecules, distribution of charges and electron density in the molecules, quantum - chemical granularity of compounds have been determined with the help ofquantum-chem-ical half-empiric PM3 of STAT program Hyper Chem Activation 7,0 packet and the processes have been mathematical modeled.
Experiments of synthesis aromatic acetylene alcohols: Synthesis reaction scheme of AAA is offered in the following view on the references [14].
Ar-
+ R-C
MOH+solvent
R
R'
Here: R= -CH3, R'= -CH3; R= -CH3, R'= -C2H5; R= -CH3, R'= izo -C3H7, R= -CH3, R'= -C(CH3)3; R= -CH3, R'= -C6H3, R= -H, R'= -CH=CH-CH3, M= Na and K, Solvent- methanol, ethanol, DEE and THP.
Powdery KOH of 5,6 g (0,1 mole) is placed into the three-necked flask in volume of 500 ml, supplied with a mechanical mixer, the reverse refrigerator and a drop funnel, and at once THP of 200 ml is added, in the flask cooled a mix of ice and salt to temperature-5 °C and through a drop funnel within 1 hour PhA of 10,2 g (0,1 mole) is added and 0,1 mole of dissolved croton aldehyde in 25 ml of DEE then a mix is left for a night. The reactionary mix is hydrolyzed at cooling by ice water, the ether bed and ether extractions are dried over potash and subjected to distillation at the presence of hydroquinone. 19g (70,4%) 1-phenylhex-4-en-1-yn-3-olTboil. =153 °C is allocated (released). The obtained spirit is dissolved in benzene, acetone, chloroform and other organic solvents, but it is badly dissolve in water [15].
In the similar way 2-methyl-4-phenylbut-3-yn-2-ol (81,4%) is synthesized from 10,2 g (0,1 mole) of PhA and 5,8 g (0,1 mole) of acetone, Tboil. =147 °C., 3-methyl-1-phenylpent-1-yn-3-ol (72,1%) is synthesised from 10,2 g (0,1 mole) of PhA and 7,2 g (0,1 mole) of methylethylketone, Tboil. =160-162 °C., 3,4-dimethyl-1-phenylpent-1-yn-3-ol (65,3%) is synthesised from 10,2 g (0,1 mole) of PhA and 8,6 g (0,1 mole) of methylizopropylketone, Tboil=137 °C., 3,4,4-trimethyl-1-phenylpent-1-yn-3-ol (57,6%) is synthesised from
10,2 g (0,1 mole) of PhA and 10,0 g (0,1 mole) of pinokaline, Tboil=134 °C., 2,4-diphenylbut-3-yn-2-ol (85,3%) is synthesised from 10,2 g (0,1 mole) of PhA and 12,0 g (0,1 mole) acetophenone, Tboil. =183-185 °C.
RESULTS AND DISCUSSION
In this work available AAA- 2-methyl-4-phenylbut-3-yn-2-ol (I), 3-methyl-1-phenylpent-1-yn-3-ol (II), 3,4-dimethyl-1 -phenylpent-1 -yn-3-ol (III), 3,4,4-trimethyl-1 -phenylpent-1 -yn-3 -ol (IV), 2,4-diphenylbut-3-yn-2-ol (V) Ba 1-phenylhex-4-en-1-yn-3-ol (VI) is synthesized by the influence of acetone, methylethylketone, methylizoprophylketone, pinokaline, acetophenon, croton aldehyde the aromatic acetylene hydrocarbon- PhA on the Favorsky method.
For the purpose of the synthesis of AAA with higher yield, the influences of various factors on the process, temperature, duration of reaction, nature of solvent and catalysts, mole rate of initial substances, have been analyzed systematically.
Influences of the nature of catalysts and the duration of reaction on AAA yield have been studied. Obtained results are exposed in Table 1.
It has been observed that influences of temperature, nature of solvent and catalysts on the AAA yield in the following on the basis of the exposed investigation results in Table 1.
Table 1
The influence of the nature of catalysts and the reaction duration on the yield of ААA (Temperature 0 °Q sol_ vent THP and the amount of initial substances in equimolar ratio) ^__
Catalyst Duration of reaction, hour I II III IV V VI
NaOH 4 29,8 27,0 25,5 22,4 39,8 48,5
6 46,8 43,0 39,0 36,5 49,7 57,2
8 52,4 50,5 47,3 43,2 55,8 65,2
10 51,1 49,3 45,8 41,3 54,2 62,0
12 29,9 26,4 21,2 17,4 31,4 36,2
KOH 4 54,4 45,5 41,9 38,6 61,2 56,2
6 73,3 67,6 55,3 51,3 78,4 62,2
8 81,4 72,1 65,3 57,6 85,3 70,4
10 80,0 71,3 64,0 55,7 83,8 67,5
12 46,7 38,3 34,6 29,7 50,1 40,5
Alongside with going up of the duration of reaction from 4 hours to 8 hours the yield of product increases. When the reaction proceeds for 4-6 hours, initial products aren't able to react fully and on the account of staying in the mixture, and forming acetylenids reacting with catalyst, it reduces the amount of catalyst and catalytic activity, and this affects the yield of product.
When the reaction proceeds for 8 hours, initial products interact sufficiently and it is observed the increase in the yield of AAA. Alcohols produced as a result of reaction form alcoholates with alkalis and having hydrolyzed under the influence of water it turns into AAA again. Herein, the nature of catalyst is of great importance, i.e. the more active catalyst is, the more quickly AAA being formed in the process turns into alcohol ate, consequently favorable condition is created for the interlink age of nonreacted initial products.
As soon as the duration of reaction increases even more for 10 hours, AAA gets into oligomerization, and also it leads to fall in the product yield as a result of producing additional products on the account of water release from the molecule of alcohols.
Besides, it is observed that AAA, produced in the mixture, turns into initial products again and initial substances (aldehyde and ketons) get into condensation, partly polymerization [16].
When the process is carried out for 12 hours, it is observed the sharp fall in the yield of product as a result of turning into interval products of AAA and unreacted initial products in the system by the influence of solvent and catalysts.
In particular, protonation process comes into being from the formation of carbcations thirsty for electrons in the solution. Consequently it is observed the sharp decrease in the yield of product on the account of
R
Ars
R'
OH
AAA's turning into alcohol ether or unsaturated tri-bond- and doublebond-bearing hydrocarbons dehydrating, also procedure of binding reactions of ketons to the bond of ^=O, formation of vinyl group-bearing ethers by the interaction of AAA produced in the system with unreacted PhA, the condensation of ketons by the influence of alkalis.
We can interpret the generation of interval and additional production in the process of synthesizing AAA on the Favorsky method as the following:
- normally alcohols are dehydrated in the acid state, but it has been observed that as a result of this reaction generating AAA gets into the dehydration reaction partly in alkali state and it produces mixed (heterogeneous) -bond-bearing unsaturated hydrocarbons at about 3-19% favorably. In particular, it has been defined that 2-methyl-4-phenylvinylacetylene from the hydration of 2,4-diphenylbut-3-yn-2-ol, and also 3-methyl-5-phenylpropenylacetylene and 2,3-dimethyl-5- phenylpropenylacetylene and in very little amount 2-methyl-4-phenylvinylacetylene and 2 -isopropyl-4-henylvinylacetylenes from 3-methyl-1-phenylpent-1-yn-3-ol and 3,4-dimethyl-1-phenylpent-1-yn-3-ol are produced .
It has been determined that AAA containing tertiary buthyl radical and aromatic link in its molecule i.e. higher inclined to the hydration 3,4,4-trimethyl-1-phenylpent-1-yn-3-ol and relatively difficult hydrating 2,4-diphenylbut-3-yn-2-ol, in turn 2- tertiary buthyl-4-phenylvinylacetylene and 2,4-diphenylvinylacetylenes, and 1-phenylhex-4-en-1-yn-3-ol obtained on the basis of croton aldehyde changes into 1-phenylhexyn-1-diene-3,4 removing one molecule mater from its molecule.
Reaction is offered as following:
Arv
R
= R' + H2O
- they get changed into alcohol ether as a result of synthesized AAA remaining i solution
R R'
Ar.
R'
R
OH
Ar
R'
O
R
+ H2O Ar
- besides it has been observed that AAA reproduces initial substances in the solvent Arv ,R Ar.
-+ R—
R'
OH
O
R'
- AAA changes into favorable alcoholates easily reacting with catalytic active alkalis in the system and at the same time increases the amount of water in the solvent
R Ar R
R'
+
OH
MOH
+ H2O
R'
OM
- it can be observed that PhA, unreacted and reproduced in the process, has changed into unstable vinyl alcohol at first bonding with water, then into methylphenylketone. It has been clarified through tje intercom-parision of the investigation results that this process can influence on the product yield both positively and negatively, i.e. 2,4-diphenylbut-3-yn-2-ol (85,3%) has been synthesized with higher yield, from negative side the fall of the amount of water in the system causes the hydrolysis of AAA alcolates is complicated and influences on the decrease in the amount of product yield
,O
H2O -«-Ar-^ -Ar-
OH
- Unreacted PhA reacts with AAA and it leads to the occurance of vinyloxy compounds. In particular, 2-methyl-4-phenylbut-3-yn-2-ol produces 1-phenyl-3-methyl-3-(2-phenylvinyloxy)-buthyn-1 reacting with PhA
Ar Ar.
Ar-
+
OH
O-
y
Ar
Among the used catalysts in alkali of KOH which has more higher basicity that LiOH and NaOH AAA is produced with maximum yield.
And alcoholates generating in the process gets into hydrolysis easily, herein it has been defined that on account of easy hydrolysis of potassium AAA may be synthesized with higher yield by using catalyst KOH.
The influence of solvents on the yield of AAA has been investigated. Here, the process is carried out for 8 hours at 00C, initial substances are chosen in equimolar ratio.
Table 2
The influence of the nature of solvents on the yield of AAA (Catalyst KOH, duration of reaction - 8 hours, tem-
The table shows that the yield of AAA is released very highly when the solution of THP is used. The main reasons of producing of AAA with higher yield in the absolute diethylether (DEE) than in ethanol and methanol: used catalysts change into alcoholates reacting with ethanol & methanol as they form suspension with ethanol and methanol, the amount of catalyst decreases, its catalytic role disappears partly and this leads to the complication of interaction of initial substances, consequently the productivity of AAA yield decreases.
perature - 0 oC)
Solvent I II III IV V VI
Ethanol 41,3 39,0 34,2 28,7 47,3 36,2
Methanol 54,0 48,4 38,9 33,0 62,0 46,0
DEE 74,1 66,2 62,3 54,1 78,3 65,0
THF 81,4 72,1 65,3 57,6 85,3 70,4
Because of being hydrogen bond forming proton solution, ethanol and methanol produce potassium ion in free state in the system linking with catalysts' hy-droxyl group removing H+ in their molecule. Ion of metal is very active and strong reductant, so it creates an opportunity for the generation of alcoholates with alcohols which are being synthesized and accelerates the process. But along with this, these metals (lithium, sodium, potassium) produce acetylenids with the initial substance- PhA, and changes croton aldehyde into tar, with the solvent produces potassium methylate and eth-ylates. It complicates the process solvating the solvent
and reducing its basicity i.e. nucleophility. Although dielectric constancy in DEE is lower than methanol and ethanol, it doesn't catch acidity hydrogen atom, as a result initial substances keep their higher reaction activity, and this objective influences on the generation of AAA.
It can be explained the release of product with sufficiently higher yield in DEE and THP which are considered aproton solvents among the used solvents as the following:
- on account of the formation of activated complexes because of the increase of polarity of state in THP (e= 7,5) which has higher dielectric constancy
than DEE (e= 4,5) reaction rate constant goes up, and this serves the release of AAA with higher yield [17];
- catalysts transfer to th esolvent state quickly and easily in THP and this creates comfortable homogen catalytic state for the reaction process i.e. for the formation of active centre in initial substances;
- DEE and THP are considered base solvents, and hydrogen atoms in them save generalized electron pairs. These generalized electron pairs of hydrogen atom is distributed on the plain, and in THP negative charge is in the view of delocalized along the ring. In turn it leads to the growth in product yield as a result of alkalis' catalytic activity i.e. basecity increasing more and more;
- THP possessing relatively higher dielectric constancy increases the hydrolysis of interval and additional products (acetales, acetylenides and alcoholates) generating in the reaction;
- dipole moment of aproton solvents which form donor-acceptor bond, polarity in them goes up, and this leads to the maximum passage of product yield. And methanol and ethanol are proton solvents and they produce alcoholates exchanging with metal ions of catalyst releasing H+ from themselves easily on account of possessing acidity property and forming hydrogen bond. And this decreases the activity of catalysts, consequently the activity energy of reaction rises, the reaction velocity falls down, and this affects the product yield;
- it has been defined that the increase of the influence of investigation results on the reaction velocity, selectivity of process and the occurrence of space collision on the following series ethanol < methanol < DEE < THP.
It has been defined that the fall in the product yield alongside with the growth of carbon atoms and branching number in the molecule of ketones and phenyl radical-bearing ketone (acetaphenon) the synthesis of alcohol with the very maximum yield (85,3%).
- in PhA electron clouds have removed towards triatry bond from phenyl radical because carbon atom is sp in acetylene and in phenyl radical it is sp2. It has been observed that ketones PhA reaction undergoes easily in the presence of catalyst owing to being movable of electron cloud of n-bonds, the inductive effect in n-bond compounds is stronger than ones in c-bond compounds [18];
- along with saving high electro negativity radicals in its molecule, the yield of AAA decreases. The cause of this case is that unstable interval products arevgenerated in a large amount;
- carbcations are known not to be separated in free state, but it can be observed their generation in practice. Stability of carbcations of ketones used in the research goes up on the series of methylethyl < isopropyl < trit-buthyl. In turn it creates an opportunity for the generation of interval and additional products under the influence of various factors decreasing the amount of positive charge of carbcations. The more stable carbcations are the more easily interval and additional products generate and their reaction activity is higher. Car-bcations producing in the Favorsky reaction associate
with catalyst and interval products in the system and increase the amount of additional products;
-C=0 - in organic chemistry, especially in the synthesis of organic compounds -C=0 various factors influence on the reaction procedure and the yield of product, in particular the generation of carbcations at the synthesis of AAA and their stability is of great importance. when the reaction undergoes in THP solution the generation, stability and life of carbonions are longer. And this gives a chance to reagent to influence from any sides. The fall in AAA yield on the series 2-methyl-4-phenylbut-3-yn-2-ol > 3-methyl-1-phenylpent-1-yn-3-ol > 3,4-dimethyl-1-phenylpent-1-yn-3-ol > 3,4,4-trimethyl-1-phenylpent-1-yn-3-ol depends on the stability and stereo-structure of carbonions producing in the process i.e. methyl radicals in acetone is symmetry than -C=0, salvation is stronger, and also recemation happens and optic activity is kept. This is considered a comfortable condition for the H+ coming from PhA molecule. It is observed the same condition in ethyl - isopropyl - and triatry buthyl -bearing ketons as is acetone. But no symmetry salvation appears in them, because of branching of radicals it prevents spatial combination of H+ towards to the combination of H+ towards -C=0 and the procedure of nucleophilic association reaction gets complicated. The second point of the matter: carbon atom in carbonyl group is trigonal (sp2) hybridized; carbon of carbonyl group and groups bonded with it are flat structural i.e. lay on the plain, especially two methyl radicals in acetone on one plain, at the same distance, so hydrogen atom approaches easily to its molecule. In other on account of number and branching of carbon atoms are more polarization and hydrogen of carbonyl group is passive i.e. electron acceptor property gets weaker under the influence of radicals, and this is a cause of the fall in the product yield;
- among the being synthesized the yield of 2,4-diphenylbut-3-yn-2-ol is relatively high. There is phe-nyl group possessing high dissociation constant strong inductive effect in the molecule of initial product ace-tophenon;
- the yield of main product becomes little because of solubility of alcoholates, which are generating as interval and additional product in the Favorsky reaction, gets complicated alongside with the growth in the number of main chain and branching, but alcoholate of tri-atry bond- and double bond-bearing 1-phenylhex-4-en-1-yn-3-ol alcohol is hydrolyzed easily, so selectivity of alcohol generation is higher than 3,4-dimethyl-1-phenylpent-1-yn-3-ol and 3,4,4-trimethyl-1-phenylpent-1 -yn-3 -ol;
- it has been observed that the yield of 1-phenylhex-4-en-1-yn-3-ol synthesized on the basis of the reaction of kroton aldehyde with PhA releases less than 2-methyl-4-phenylbut-3-yn-2-ol, 3-methyl-1-phenylpent-1-yn-3-ol and 2,4-diphenylbut-3-yn-2-ol. It can be observed: the stimulant towards polymerization of double-bond in the kroton aldehyde molecule; the generation of 1-phenylhexin - 3-in-1-ol-3 isomer of synthesized 1-phenylhex-4-en-1-yn-3-ol in large amount and their partly polymerization, transferring to
tarlike substance in alkali state and 1-phenylhex-4-en-1-yn-3-ol and its isomer turn into two-atom alcohols;
- releasing of 1-phenylhex-4-en-1-yn-3-ol with higher yield than 3,4-dimethyl-1-phenylpent-1-yn-3-ol and 3,4,4-trimethyl-1-phenylpent-1-yn-3-ol, molecular weight of methylisopropylketon and methyltriatry-buthylketones is higher than kroton aldehyde, owing to this movability and the number of colliding are little.
Also, stereo structure re of ketones, their interaction level orientating definitely with the molecule of PhA i.e. the number of effective colliding is little.
The influence of the duration of reaction and temperature on the product yield has been investigated in order to choose the most effective method for the synthesis of AAA. Obtained results have been presented in table 3.
Table 3
The influence of the duration of reaction and temperature on the yield of AAA (Catalyst KOH, solvent THP and
the amount of initial substances in equimolar ratio)
Duration reac- I II III IV V VI
tion, hour
temperature, 10 oC
6 64,1 56,6 46,3 43,2 65,0 49,4
8 68,4 61,1 53,7 47,0 71,3 58,2
10 67,6 60,0 52,0 45,8 70,7 55,6
temperature, 0 oC
6 73,3 67,6 55,3 51,3 78,4 62,2
8 81,4 72,1 65,3 57,6 85,3 70,4
10 80,0 71,3 64,0 55,7 83,8 67,5
temperature, 10 oC
6 61,1 52,3 49,2 46,3 70,0 52,2
8 73,0 64,7 56,2 52,0 76,8 63,0
10 72,2 63,1 55,5 51,1 76,2 58,0
It has been observed the fall in the productivity on account of partly polymerization of synthesizing AAA, the interaction of initial products, the generation of additional products which are tarlike and difficult-soluble in the system. also, when the temperature is high, the solvent and initial products turn into donor-acceptor-bearing additional products interacting.
The influence of main factors, temperature, duration of reaction, effecting the procedure of process has been studied, average velocity of reaction has been determined. On the basis of obtained results the relation of lgW with 1/T has been expressed and activation energy (E) of formation reaction of 2-methyl-4-phenylbut-3-yn-2-ol Ba 3-methyl-1-phenylpent-1-yn-3-ol has been calculated on the Arrhenius method, its value is favourably equal to 10,06 kcal/mole and 9,16 kcal/mole.
Table 4
The kinetic results of AAA synthesizing (Catalyst KOH, temperature, 0 oC, solvent DEE, initial substances in __equimolar ratio)*_
Duration reaction, hour Product yield Average speed of reaction (W)
I II I II
% mole/hour % mole/hour %/hour mole/hour %/hour mole/hour
4 46,4 2,26 39,4 1,80 11,6 0,56 9,85 0,45
6 69,5 3,17 65,1 2,89 11,5 0,31 10,8 0,48
8 74,1 3,15 66,2 2,91 9,26 0,39 8,27 0,36
When the reaction is done between -10- 10 oC the product yield is released with the very maximum. When PhA and ketone-aldehydes are reacted at 0 oC, the yield is released maximum. When the reaction undergoes at -10 oC, solubility of catalysts in the solvent gets passive, as a result it has been observed less generation of catalytic active centers in the system, the interaction of particles goes slowly, consequently relatively lower release is observed in the AAA yield.
At 0 oC the velocity of motion in the molecules of initial substances and solution increases. Owing to this their particles possess higher energy and they form active molecules, the procedure of interconnection reaction between them starts to go easily, instability of acet-ylenides and alcoholates goes up, and this serves more synthesis of general product.
* - as the sample the process of synthesis of
2-methyl-4-phenylbut-3-yn-2-ol and 3-methyl-1-phenylpent-1-yn-3-ol has been shown.
Anticorrosion properties of AAA, synthesized on microorganisms, including bacterium and funguses oc-the basis of phenyl acetylene, anti (erosion) decay of curring in the content of oil have been studied. metal and metal installation under the affect of alive
Table 5
_Bacteria stimulating biocorrosion of metal installation in the oil-gas industry_
Kinds of bacterium Oil fields
and funguses Kukdumalok Umid Kruk Northern Urtabulok
Rate of microorganism existence (occurrence)
Pseudomonasstutzeri 22 26 28 24
Pseudomonasputida 23 25 25 26
Micrococcusalbum 27 29 24 28
Desulfovibrio vulgaris 25 24 26 23
Micrococcussulfurous 26 28 25 25
Desulfotmaculumsp. 28 29 31 27
Desulfovibriosp. 23 18 29 25
Acinetobacter sp. 26 23 19 26
Gallionellasp. 27 25 26 25
Desulfomaculum 29 32 31 30
Basillius sp. 31 33 29 31
Pseudomonas turcosa 21 18 20 17
Pseudomonas aeroginoza 17 18 22 20
Rhodococcace luteus 26 24 26 25
Biocorrosion is also called bacteriological or fungous corrosion [19]. It is cleared that 30% of biocorrosion of metals is caused by micro funguses, 70% by micro bacteria. These microorganisms call metal biocorrosion into being and it is observed that it creates opportunity for the growth of chemical corrosion [20]. As a result of microbiological corrosion of metal pipes and apparatus oil industry is suffering losses in general manufacture for 5-10% [21, 22]. Alongside with being cause of corrosion of installation, microorganisms are reasons for the damage of oil composition- hydrogen sulphide corrosion. Studying the reasons of biological corrosion and their occurrence, and creating chemical preparations preventing corrosion are considered one of important tasks in front of science. Inhibitor properties
Results of investigation show that it has been defined the influence of sulfate -reducing bacteria removed from AAA samples on the stimulants of biocorrosion of oil industry pipes (Table 6). It has been defined that among the suggested biocides microorganisms in the composition of V and I oil and oil products are the most active biocide anti funguses and bacteria.
CONCLUSION
On the obtained results the influence of the nature of solvents on the generation of product yield has been systematically analyzed, and the most favorable homo-gen-catalytic state has been defined for the procedure of process. Selective family of the influence of solvents
of synthesized AAA anti bacterium and funguses causing the decay of metal installation in oil fields by the influence of microorganisms have been studied. Kinds of microorganisms-bacterium and funguses originating the process of biocorrosion in the metal installation, machines, tools of drilling, storage, delivery, and also in the refinery have been determined.
As the object of investigation Kukdumalok, Umid, Kruk and Northern Urtabulak in the system of «Uz-bekneftegaz» NHC have been chosen. As a result of investigations more than 100 hydrocarbon oxidizing bacteria sludge (slime) have been isolated from filings removed from water-oil emulsions, pipes and machines. It has been defined that more than 40 of them affect the quality of oil and oil products and metal installation biocorrosion.
Table 6
on the AAA yield has been offered in the following state: ethanol < methanol < DEE < THF.
To sum up it, when PhA or aldehyde - ketons are takenin equimolar ratio with each-other, the productivity in product yield has been increased when initial products are taken in equimolar ratio, but alongside with this it has been observed the growth in the amount of interval and additional products as well, and also it has been created possibility of the occurrence of waste products. And when initial products have been taken with equal amount, AAA yield has generated less than when initial products have been taken in unequal amount though, the suggested state ethanol < methanol < DEE < THF has been chosen as the very alternative
Microbiological activity of AAA
Offered inhibitors Bacteriostatic activity Bactericidal activity
Concentration, mg/l Cell of bacterium,% Concentration, mg/l Cell of bacte-rium,%
alive dead alive dead
I 40 0 100 30 25 75
II 20 0 100 30 40 60
III 20 6 94 60 25 75
IV 20 15 85 60 35 65
VI 20 25 75 60 50 50
V 10 0 100 30 0 100
state. Firstly, in this state the generation amount of interval and additional products has been less, secondly, the possibility of resending unreacted PhA, aldehyde and ketons into the system has been kept.
On the investigations it has been observed that the amount of the generation of additional products is less in the process of DEE. And at used catalysts, and at KOH with high basicity AAA has been synthesized with maximum amount and additional products have been synthesized with minimum amount.
Synthesis process of alcohols gets completive along with appearing of volume radicals around the carbon in carbonyl group and falling down of general energy in them. Consequently, the heat-energy of AAA is higher, and this leads to the generation of additional products in the reaction on account of the generation of active centers.
On the nature, properties and structure of initial products relative productivity series of AAA generation, and it has been offered as the following: 3,4,4-trimethyl-1-phenylpent-1-yn-3-ol < 3,4-dimethyl-1-phenylpent-1-yn-3-ol < 1-phenylhex-4-en-1-yn-3-ol < 3-methyl-1-phenylpent-1-yn-3-ol < 2-methyl-4-phenylbut-3-yn-2-ol < 2,4-diphenylbut-3-yn-2-ol.
On the results of carried out research it has been achieved the synthesis of AAA on the Favorsky method and it has been defined the very alternative state for the process. In accordance with it, when the reaction undergoes in THF solution at 0 oC using catalyst KOH, initial substances in inter equimolar ratio for 8 hours AAA is synthesized with the very high yield I=81,4%; II=72,1%; III=65,3%; IV=57,6%; V=85,3% Ba VI=70,4% favorably.
References
1. Vannot R.W. Some reaction of acetylenic alcohols. New Zealand, 1983; 177.
2. Temkin O.N. The chemistry of acetylene. Properties, electronic structure and reactivity of alkynes. Journal Sorosov of Science, 1998; 2: 52-63.
3. Trofimov B.A, Gusarova N.K. Acetylene: new possibilities of classical reactions. Journal Success of Chemistry, 2007; I(6): 551-586.
4. Frignani A, Moniicelli C, Zicchi F, Trabanelli K. Acetylenic alcohols as inhibitors of iron acid corrosion. International Journal Corrosion Scale Inhibitors, 2014; 3(2): 105-109.
5. Moneses M.A. and Valle L.M. Temperature dependence of corrosion inhibitors of steels used oil well stimulation using acetylenic compound and halide ion salt mixtures. Brazilian Journal of Petroleum and Gas, 2007; 1(1): 8-15.
6. Karakhanov E.A. and KapaxaH°B E.A. What is petrochemistry. Journal Sorosov of Science, 1996; 2: 65-73.
7. Temkin O.N. Acetylene chemistry: "Acetylene tree" in organic synthesis on the eve of XXI century. Journal Sorosov of Science, 2001; 6: 32-76.
8. Potkin V.I., Dikusar E.A. and Kozlov N.G. Tertiary acetylenic alcohols and diols on the basis of
phenylacetylene and 2-methyl-3-buthyl-2-ola. Journal of Organic Chemistry, 2002; 9: 13-16.
9. Yin Ngai Sum, Dingli Yu and Yugen Zhang. Synthesis of acetylenic alcohols with calcium carbide as the acetylene source. Journal the Royal Society of Chemistry, 2013; 4: 4126-4149.
10. Shchelkunov S.A., Sivolobova A.O., Mataeva S.O., Minbaev D.B. and Muldahmedov Z.M. Grignard reacting the 2-methyl-4-chlorobut-3-yn-2-ol in environments substituting diethyl ether. Journal of Organic Chemistry. 2001; 1: 17-37.
11. Bare W.D. and Andrews L. Formation of Grignard species from the reaction of methyl halides with laser-ablated magnesium atoms. Journal of American Chemical Society. 2001; 19(98): 7293-7301.
12. Ziyadullaev O.E., Turabdzanov S.M., Juraev R.S. and Abdurakhmanova S.S. Synthesis of aromatic acetylenic alcohols on the basis of aniline. XI International scientific- practical conference "Actual Problems of Modern Science - 2015". Przemysl, Poland. 2015; 15: 91-94.
13. Diederich E.F., Stang P.J. and Tykwinski R.R. Acetylene Chemistry. Journal of Chemistry, Biology, and Material Science. Weinheim. 2005; 5: 156-162.
14. Ziyadullaev O.E. Synthesis and technological of aromatic acetylenic alcohols, their vinyl ethers on the base of phenylacetylene: Authors abstract of the dissertation for candidate of chemical sciences. Tashkent; 2011: 213.
15. Ziyadullaev O.E. Synthesis of Aromatic Acetylene Alcohols Journal of Chemistry and Chemical Technology. 2016; Special Issue 3: 34-42.
16. Ziyadullaev O.E., Turabjanov S.M., Ikramov A.A. and Mahatova G.B. Theoretical foundations of homogeneous reaction of catalytic vinylation of aromatic acetylene alcohols. XV International scientific conference «High-Tech in Chemical Engineering -2014» 2014; Zvenigorod (Moscow region, Russia) 124.
17. Iskandarov S.A. and Sadikov B.D. Theoretical foundation of organic chemistry. Tashkent. 1987: 436.
18. Trofimov B.A. and Gusarova N.K. Acetylene: New possibilities of classical reactions. Journal Success of Chemistry, 2007; I(6): 551-586.
19. Nurmanov S.E., Mavloni M.E. and Khamidova O.Sh. Synthesis and bacteriostatic and bactericidal activities of acetylene alcohols. Journal of Reports of the Academy of Sciences of Uzbekistan, 2011; 2: 66-69.
20. Micheil W., Jarle H., Robert K .and Ulf X. Probing the enantioselectivity of Bacillus subtilis esterase BS2 for tert. alcohols. Journal of Molekular Catalisis B: Enzymatic. 2009; 60: 82-86.
21. Mavlaniy M.E., Nurmanov S.E. and Ziyadullaev O.E. The bacterial flora of oil fields Kukdumalak and North Urtabulak. Uzbek Oil and Gas Journal. 2013; 2: 73-78.
22. Ziyadullaev O.E. Synthesis of Aromatic Acetylenic Alcohols and their Vinyl Ethers. Abstract of doctoral dissertation, Tashkent, 2016., 43-72.
