CC BY
3SYNTHESIS OF COMPOUNDS WITH HIGH BIOLOGICAL ACTIVITY J.Ergashev, Sh.Omonov, L.Yusupova, S.Nurmanov https://doi.org/10.5281/zenodo.8371988
Abstract. Acetylene derivatives are substances with biochemical activity. They actively participate in oxidation-reduction processes, protein metabolism and increase the activity of enzymatic processes. Among the investigated compounds, vinyl ether of butyn-2-diol-1.4 has a relatively high defoliant property (92%) and it was recommended for use as a cotton defoliant. The created defoliant reduced cotton defoliation time by 30-40%, the effect on immature bolls by 50% and increased yield by 2-3%.
Keywords: acetylene, butyn-2-diol-1.4, vinylation, 4-vinyloxybutyn-2-ol-1, 1.4-divinyloxybutyn-2, hydroquinone, defoliant, defoliant activity, cotton.
Аннотация. Ацетилен уосилалари биокимёвий фаолликка эга булган моддалар уисобланади. Улар оксидланиш-цайтарилиш жараёнларида, оцсил алмашинувида ва ферментатив жараёнлар активлигини оширишда фаол иштирок этади. Тадциц цилинган бирикмалар ичида 2-бутин-1,4-диолнинг винил эфири нисбатан юцори дефолиантлик хоссасига эга (92%) ва у гуза дефолианти сифатида цуллашга тавсия этилди. Яратилган дефолиант гузанинг баргини тушириш вацтини 30-40% га, пишмаган кусакларга таъсирини 50% га камайтириш ва уосилдорлигини 2-3% га оширди.
Калит сузлар: ацетилен, 2-бутин-1,4-диол, виниллаш, 4-винилокси-2-бутин-1-ол, 1,4-дивинилокси-2-бутин, гидрохинон, дефолиант, дефолиантлик фаоллиги, гуза.
Аннотация. Производные ацетилена - вещества с биохимической активностью. Они активно участвуют в окислительно-восстановительных процессах, белковом обмене и повышают активность ферментативных процессов. Среди исследованных соединений относительно высоким дефолиантным свойством (92%) обладает виниловый эфир 2-бутин-1,4-диола, который был рекомендован для использования в качестве дефолианта хлопка. Созданный дефолиант сократил время дефолиации хлопчатника на 30-40%, воздействие на незрелые коробочки на 50% и повысил урожайность на 2-3%.
Ключевые слова: ацетилен, бутин-2-диола-1,4, винилирование, 4-винилоксибутин-2-ол-1, 1,4-дивинилоксибутин-2, гидрохинон, дефолиант, дефолиантная активность, хлопок.
Introduction
It is known to us that mankind obtains all the products needed for daily life from agricultural crops. Therefore, non-stop scientific research is being carried out in the development of the agricultural sector. At the same time, the position of cotton raw materials grown in our republic in the world market and the number of its buyers increasing year by year can be an example of this. Speaking about cotton, it should be noted that this plant is biologically a perennial crop that requires moderate temperatures. Naturally, the plants will not ripen until they get a temperature that is good enough for them. The climatic conditions of our republic are strongly continental, and the precipitation in the mountainous regions in the spring season lasts until May, the seepage water of the cultivated fields cannot withstand the sowing of seeds in the nearby lands, and the autumn frost comes early and the precipitation begins, causing some difficulties for the full ripening of the crops. For this reason, deep scientific researches are conducted on cotton varieties by our breeding scientists, and today, as a result of these scientific
works, new varieties of cotton are being created that meet the demands of the world market for quick cooking and fiber. In addition, agrotechnologies suitable for these new varieties have been developed, reducing the labor force, using resource-saving agrotechnologies, and using chemical preparations that are harmless to greenhouses. Therefore, each agrotechnical event is of great importance in increasing productivity and reducing costs. If the performed action adds yield to the cultivated crop or is deemed necessary based on the biology of the plant, this action can be considered as an agrotechnical action of the specified crop. A lot of scientific research on defoliation agro-measures has been carried out and is being continued today. So, we can consider cotton defoliation and retail agro-measures as important agro-measures in cotton care. [1,2,3].
Currently, defoliants based on magnesium chlorate, which are widely used in agriculture, have a negative effect on cotton leaves and young buds, causing the leaves to curl and the buds to burn. First of all, this leads to a decrease in productivity, contamination of cotton with dried leaves, and a decrease in fiber quality. It is known from scientific sources that the cotton plant is saturated with organic oxycarbonic acids, especially citric and malic acids, at the end of the growing season, that is, before the leaves are shed. Therefore, the inclusion of these acids in the defoliant increases the effectiveness of the defoliation process. Acetylene derivatives are substances with biochemical activity. They actively participate in oxidation-reduction processes, protein metabolism and increase the activity of enzymatic processes. Therefore, creating new defoliants based on local raw materials that have a "gentle" effect on the cotton leaf and its bolls, are highly effective, less toxic, accelerate the shedding of cotton leaves and the full ripening of the bolls, and are one of the urgent problems facing chemists. Acetylene diol 2-butyn-1,4-diol has been used as a defoliant with high biological activity. Currently, it is not used due to its high toxicity.
Research and methodology
4-Vinyloxy-2-butyn-1-ol and 1,4-divinyloxy-2-butyn were synthesized at atmospheric pressure. 0.215 g of KOH and 40 ml of DMSO were placed in a flask equipped with a reflux condenser, a stirrer and a tube for supplying acetylene, then the mixture was heated with constant stirring to 97-100 °C, after which it was slowly cooled to 35 °C, 4.3 g (0.05 mol) butyn-2-diol-1,4 and acetylene was passed through the reaction mixture at a temperature of 110 °C. After 8 hours, the process was stopped and, after cooling, the reaction mixture was extracted with ether and dried with MgSO4. Then the solvent was distilled off and the distillation was carried out in the presence of the hydroquinone inhibitor. After that, a fraction with a boiling point of 177-178
°C was obtained (at 10 mm Hg) corresponding to 2.69 g of monovinyl ether of butyn-2-diol-1,4
20
with Bp = 92-93 °C (at 10 13 mm Hg). Product yield - 2.69 g, 48.1% (of theory), d—0,870
4
g/cm
3 n 2 = 1,4615
Results and discussion
In this part of the study, an attempt was made to carry out the vinylation of butyn-2-diol-1,4 with acetylene in a super basic medium. It was found that in the reaction mono- and divinyl ethers of diol were formed. Reaction scheme: CH3
:S=O + KOH
» KOH --K+
:O=S^ 3 CH3
OH
o CH3
OH"_^CH2-C=C-CH2-O:K++ >OH2O
I "" / 2
OH CH^
CH^ c=C-CH2-OGk+ + HC=CH->-CH2- C=C—CH2-O—
1 •• 1 2 2 .. | |
OH OH H H
CH2- C=C-CH2-OH
•• - + OH CH2-C=C-CH2-O-C=C:K ->-
I 2 "II
OH H H
•• - +
CH2- C=C-CH2-O- CH=CH2 + CH2- C=C-CH2-O- ^CK I 2 - 2 I 2 2 I I
OH OH H H
The kinetics of butyn-2-diol-1.4 monovinyl ether synthesis was studied. The effects of solvent nature and catalyst amount were studied for this process. Benzene, dioxane, DMSO and DMFA were used as solvents. LiOH, NaOH and KOH were used as catalysts. According to the obtained results, the catalytic activity of the above-mentioned systems increases. Among the cited catalysts, relatively active for the studied process is KOH (Table 1).
Table 1.
The effect of the nature of the catalyst on the course of the reaction
Catalyst The yield of the vinyl ester of butyn-2-diol-1,4, %.
LiOH 24.2
NaOH 35.3
KOH 48.1
Product yield is also affected by the amount of catalyst. Therefore, the process was studied in the presence of 2-10% of KON compared to the initial diol. The obtained results are presented in Table 2.
Table 2.
Production of vinyl ethers of 2-butyne-1,4-diol Effect of amount of catalyst (KOH)
The amount of catalyst KOH,% (based on the mass of butyn-2-diol-1.4) The yield of vinyl esters of butyn-2-diol-1,4,%
monovinyl ether divinyl ether
2 34.0 36.6
3 30.4 39.5
4 28.5 41.8
5 27.1 43.4
7 25.6 44.6
10 25.3 45.7
12 24.5 46.8
15 24.0 47.3
I 2 2
OH
K+
:O=S:
\
XH3
CH
When the amount of KOH is increased from 2 to 5%, the yield of monovinyl ester of butyn-2-diol-1.4 increases from 34.0 to 48.1%, respectively. A further increase in the amount of catalyst has almost no effect on the product yield. When the amount of KOH was increased to 10%, a partial increase in product yield was observed and was 49.0%. So, the economically alternative amount of KOH as a catalyst is 5% compared to the amount of butyn-2-diol-1.4. The results of the study of the effect of the nature of the solvent (benzene, dioxane, DMSO, DMFA) on the yield of the product are presented in Table 3.
Table 3
Influence of the nature of solvents on the yield of monovinyl ester of butyn-2-diol-1,4. (The reaction time is 8 hours, the temperature is 130 °C, the catalyst is KOH (5%)).
Solvent Product yield,%
monovinyl ether divinyl ether
Benzene 12,5 5,4
Dioxan 20,6 15,3
DMFA 29,5 32,6
DMSO 27,1 43,4
From the ana lysis of the results, it can be seen that among the solvents used, DMSO
is relatively active for the process of vinylation of 2-butyn-1,4-diol. Product yield with his participation is 48.1%. In the solution of benzene, dioxane and DMFA, the yield of monovinyl ether of 2-butyn-1.4-diol is 12.5, respectively; It consisted of 30.6 and 39.5%.
The role of DMSO in this is that, firstly, it acts as a strong solvent for the starting materials, and secondly, it forms a highly basic system with KOH. That is, the basic property of KOH and the corresponding dissociation of the system and the formation of alcohol by alcohol will increase. As a result of nucleophilic addition of potassium alcohol of diol to acetylene, monovinyl ether is formed.
Based on the results of scientific research, the use of catalyst KOH and solvent DMSO for the process of vinylation of 2-butyne-1,4-diol is effective.
Product yield and purity were determined using gas-liquid chromatography, IR- and NMR-spectroscopic methods. Based on this, the biological activity and toxicity of synthesized 2-butyn-1.4-diol mono- and divinyl esters were investigated. It was experimentally determined that 2-butyn-1.4-diol vinyl esters are less toxic. Synthesized vinyl ethers take an active part in oxidation-reduction processes, protein metabolism and increase the activity of enzymatic processes. Accordingly, based on local raw materials, new defoliants with a "gentle" effect on the cotton leaf and its bolls, high efficiency, low toxicity, accelerating the shedding of cotton leaves and the full ripening of the bolls, and economically cheap, were created. Considering the above, the defoliant activity of these synthesized compounds was tested. Synthesized acetylene compounds are biologically active compounds, their use as a defoliant allows the tissues of the cotton body to dry out and only shed its leaves. The synthesized defoliant was more effective when the soil was wet. In this case, the biologically active compound was absorbed into the cotton tissue for 12-15 hours. The result began to be felt after 2-4 days. New leaves were not allowed to form on the cotton body, resulting in no contamination of the cotton during picking. When the cotton bolls were 50-55% opened, the newly synthesized drug was sprayed on the cotton. The results of the latest research on the proposed defoliant are given. The results of the
research on the use of defoliants in the perennial cotton season showed that "Andijan" had a good effect on the leaves of the cotton variety and caused them to shed uniformly.
1. 1.4-vinyloxy-2-butyn- 1-ol-1 -BDMVE
2. 1,4-divinyloxy-2-butyne- BDDVE
3. Monovinyl ether of resorcinol - RMVE
4. Divinyl ether of resorcinol - RDVE
5. Hydroquinone monovinyl ether - GMVE
6. Hydroquinone divinyl ether-GDVE
Experiments to determine the defoliant activity of the synthesized substances were carried out by spraying cotton with different percentage solutions of the preparations. Aqueous 0.025% emulsions of mono- and divinyl esters of 2-butyne-1.4-diol, resorcinol, and hydroquinone were used separately. After defoliation (8-10 days), green, dry and shed leaves, opened and half-opened bolls were counted on cotton plants. Table 4 shows the effectiveness of defoliants on cotton leaves (after 10 days) in percent (%).
Table 4
Defoliant activity of synthesized vinyl ethers
Experiment option Consumption dose of defoliant, according to active substance, kg/ha Defoliation activity, %
BDMVE 5/0.5 89.0
BDDVE 5/0.5 92.0
RMVE 5/0.5 82.0
RDVE 5/0.5 86.0
GMVE 5/0.5 84.0
GDVE 5/0.5 90.0
butyne-2-diol-1.4 5/0.5 85.0
"Avguron Extra" 5/0.5 92.9
Spraying of cotton defoliant (-0.5 ha for each preparation) was carried out in dry weather conditions, the dose of the preparation was 5 kg/ha, and the percentage of fallen leaves was determined after 8-10 days. In this case, it was observed that the color of the leaves did not change, and the cotton stem did not dry out. At the same time, the introduction of mono- and divinyl esters of butyn-2-diol-1,4 as a defoliant for defoliation of cotton reduced the defoliation time of cotton by 30-40% and the effect on unripe bolls by 50%. Increased productivity by 2-3%.
The results of the analysis of the obtained data showed that the studied vinyl esters have defoliant activity, and their values are butyn-2-diol-1,4; 89 for mono- and divinyl esters of resorcinol, respectively; 92; 82 and 86%.
Conclusion
Acetylene derivatives are compounds with biochemical activity. They actively participate in oxidation-reduction processes, protein metabolism and increase the activity of enzymatic processes. Among the studied compounds, vinyl esters of butyn-2-diol-1.4 have a relatively high defoliant property (92%) and it was recommended for use as a cotton defoliant. It was thoroughly studied by specialists of the Ministry of Agriculture and Water Management of the Republic of Uzbekistan, which serves the development of the chemical and technological fields.
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