CN109942664B - Preparation method of plant molluscacide spirocarb - Google Patents
Preparation method of plant molluscacide spirocarb Download PDFInfo
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Abstract
The invention discloses a preparation method of a plant molluscacide, namely, spirocarb, which takes oil-tea saponin as a raw material and utilizes Ca (OH)2Hydrolyzing oil tea saponin to obtain 2-methyl-2-butenoic acid, acetic acid and Ca2+Forming soluble calcium salt, carboxyl of glycosyl part of sasanqua saponin is also mixed with Ca2+Generating insoluble calcium saponin decarboxylation calcium precipitate, filtering, dispersing the insoluble saponin decarboxylation calcium precipitate with deionized water, acidifying calcium salt with sulfuric acid, filtering to remove CaSO4Precipitating, and distilling the filtrate under reduced pressure to obtain spirocarb H2B. The invention obtains the high-quality RoxWire by taking the tea saponin as the raw material, changes the surplus oil tea saponin into valuable, can be widely applied to industrial production, and provides technical support for the popularization of the RoxWire.
Description
Technical Field
The invention relates to a synthesis method of a known compound, in particular to a preparation method of a plant molluscacide-RoxWis.
Background
Schistosomiasis is one of the most serious parasitic diseases endangering human health, about 70 more countries and regions prevail around the world, about 31 hundred million people are affected, about 2 hundred million people are infected, and the people die of the schistosomiasis every year[1-2]. Schistosomiasis control practice shows that oncomelania is the only intermediate host of schistosomiasis, and controlling oncomelania can effectively control schistosomiasisPropagation, therefore, in the region with multiple schistosomiasis, snail killing is one of the direct effective measures for preventing schistosomiasis infection.
Through years of research and practice, a series of effective technologies and methods are summarized in the process of controlling oncomelania in China, and the methods mainly comprise ecological oncomelania killing, biological oncomelania killing, drug oncomelania killing and plant oncomelania killing. The ecological snail killing project has long lasting effect and resource saving, but the one-time investment is large and the snail killing effect is slow; the biological molluscacide conforms to the concept of sustainable development, is an effective measure for controlling oncomelania and realizing the fundamental prevention and control of schistosomiasis, but is not much about the mechanism research and the large-scale field application of the biological molluscacide such as predation molluscacide, microbial molluscacide, competitive molluscacide and the like; the chemical molluscacidal in the drug molluscacidal is still the most main molluscacidal method at present, but most of the common molluscacidal in China are chemical synthetic agents at present, and the problems of toxicity of other target organisms (such as freshwater fishes), environmental pollution, high price and the like exist[3-4]. At present, a novel plant molluscicide appears on the market, the effective component of the molluscicide is the extract of plant organs such as roots, stems, leaves, flowers, fruits or seeds, the molluscicide has the advantages of low toxicity and easy degradation, and the molluscicide is more and more concerned by WHO and disease control departments of various countries[5]。
The spirocarb (formula shown in formula 1) is a pentacyclic triterpenoid substance from Camellia oleifera Abel of Camellia, is a novel botanical molluscicide[6]. The spirocarb is obtained by removing 2-methyl-2-butenoic acid and acetic acid from sasanqua saponin, hydrolyzing to remove ester groups corresponding to the above two acids, and converting corresponding part of sasanqua saponin into hydroxyl (the component is hereinafter referred to as H)2B represents). Although the oil tea saponin has a certain snail killing effect, the activity of killing oncomelania by removing 2-methyl-2-butenoic acid and acetic acid components is higher, so that the higher the decarboxylation component content is, the better the snail killing effect is. The spirocarb is used as a novel plant molluscacide, and is mainly combined with cholesterol on red cell walls of mollusks to generate water-insoluble compound precipitate, so that the normal permeability of red blood cells is destroyed, the intracellular osmotic pressure is increased to disintegrate, the hemolysis phenomenon is caused, and the mollusks are killed. A large number of indoor and outdoor drug effect tests show that the molluscacide has killing effect on oncomelaniaGood, has the advantages of high efficiency, low toxicity, low price, environmental protection, convenient use and the like, has better biological safety of the spirocarb compared with the strong toxicity of the existing niclosamide serving as a molluscicide, and has higher popularization and application values[7]. In 2013, the Rouwei products are registered by pesticides of Ministry of agriculture, and the registration numbers are PD20131345 and PD 20131346.
Camellia saponin (molecular formula shown in formula 2) is oleanane type triterpene saponin mixture in Theaceae (Camellia sinensis, Camellia japonica, Camellia oleifera Abel) plant[8]Its basic structure is composed of aglycone (beta-amyrin derivative), saccharide and organic acid. The oil tea saponin is mainly stored in tea seeds and tea leaves, wherein the content of dried tea seeds is 4% -6%, and the oil tea saponin is insoluble in conventional anhydrous solvents such as ethanol, methanol and acetone, and is easily soluble in water, tert-butyl alcohol and other large polar solvents. Tea resources in China are rich, the sasanqua saponin is used as a main byproduct in tea production, the storage capacity is large, the price is low, the sasanqua saponin is easy to obtain, and important research and development and utilization values are achieved[9]The plant molluscacide spirocarb is prepared by taking tea saponin as a raw material, and the method is simple and has low cost.
Although methods for synthesizing snails have been reported in patents by Zhangjie, Chenjiafeng, etc., there are problems in the method for preparing snails in high content, high quality and high efficiency because the water solubility of the snails is good, the thermal stability is poor, the snails are easily deteriorated during heating, the solution is blackened and smelled, and the aqueous solution of the snails is easily foamed during the treatment as a good foaming agent. Zhangjie et al directly uses tea saponin as molluscicide, though simple and convenient, the molluscicidal activity of the tea saponin needs to be improved, a large amount of drug is needed to achieve satisfactory molluscicidal effect, and the use of raw materials in large batch can cause environmental pollution,the utilization rate of tea saponin raw material is low[10]. The method can not determine the hydrolysis condition of acetate and 2-methyl-2-butenoate in tea saponin, further can not ensure the content of active components in a final product, and can not ensure the killing effect of a spirocarb product[11]. Liu Rui Hua and the like directly use tea seed powder as raw materials, sodium hydroxide solution and alkaline protease are used for hydrolysis, and then decompression dehydration is carried out to prepare the spirocarb, but the spirocarb active component is easily decomposed and deteriorated by heating in the dehydration process, the product quality can not be ensured, and further the content of the spirocarb active ingredient in the product can not be ensured[12]. Zhang Nenermin etc. utilizes sodium hydroxide and alkaline protease to hydrolyze tea saponin, and then obtains the active component H of spirocarb by acidification and precipitation with hydrochloric acid2B, but the decarboxylated product of the tea saponin has high solubility in water, the separation efficiency of directly acidifying and precipitating to recover the active component of the spirocarb is low, and the product yield is low[13]. The method for preparing the spirocarb by using the dipolar solvent N, N-dimethylformamide through aminolysis reaction has the defects that the reaction condition needs to be strictly controlled, the used solvent, raw materials and the like need to be strictly subjected to anhydrous treatment, and the final yield is only 21.6 percent[14]. In addition, the oil tea saponin is purified by a two-stage precipitation method in Liqingchuan and the like, firstly, the crude extract of the tea saponin is primarily purified by an alcohol precipitation method, and then, the purified tea saponin is obtained by utilizing the principle that the tea saponin reacts with metal ions to generate a tea saponin metal ion complex to form complex precipitation[15]. Unfortunately, the scholars only produce tea saponin with 87.58% of purity under milder environment and shorter time, and do not go deep into the process of preparing the spirocarb from the tea saponin.
Reference documents:
[1] schistosomiasis research committee of the medical academy of health, committee on the science of parasitosis, parasitosis (brochure) [ M ]. shanghai: shanghai science and technology press, 1964: 860-885.
[2] General research of drugs for killing mollusks and thinking [ J ] of application research thereof, medical animal prevention, 2002, 18 (4): 189- -191.
[3] Zhongnong, practical oncomelania study [ M ]. Beijing: science publishers, 2005: 266-290.
[4] Chenchang, snail killer in China and application thereof [ J ] Chinese schistosomiasis control J, 2003, 15 (5): 321.322.
[5] wang balance, operating country, lindane, etc. during the twelve five's period, the scientific research focus and direction of schistosomiasis in China [ J ]. the journal of schistosomiasis control in China, 2011, 23 (2): 11l to 113.
[6] Jiming mountain, Guzuanmin, Zhangyang. research and application status and development prospect of biological pesticide [ J ]. Shenyang university of agriculture, 2006,37(4): 555-.
[7] Dongwang, fangjia jue, huangyi, luoyang, luzhou region, dansheng county, sichuan province, snail and niclosamide molluscicidal control test [ J ] parasitic diseases and infectious diseases, 2017, 15 (1): 8-13.
[8]Murakami T,Nakamura J,Masuda H,et a1.Bioactive saponins and glycosides.XV.Saponin constituents with gastroprotective effect from the seeds of tea plant,Camellia Sinensis L.vat.Assamica Pierre,cultivatein Sri Lanka；structures of assamsaponins A,B,C,D,and E[J].Chem.Pharm.Bull.(tokyo),1999,47(12):1759-1764.
[9] The study of tea saponin has been advanced by Limoniwu, Guo morning, san Yi Fan, Showwen. tea saponin research [ J ]. tea communication 2016,43(1):14-22.
[10] Zhangjie, Hu Wen, botanical molluscicides and uses of their tea saponin [ P ]. Chinese patent: CN101524067,2009-09-09.
[11] Liuruihua, plant biological compound molluscicide and preparation method [ P ]. Chinese patent: CN1579168,2005-02-16.
[12] Chenjiafeng, a preparation method of plant molluscicide [ P ]. Chinese patent: CN1973633,2006-12-15.
[13] Zhang Neanmin, a plant molluscacide and its preparation method and use [ P ]. Chinese patent: CN104521968A,2015-04-22.
[14] Preparation and properties of tea saponin de-esterified [ J ]. biomass chemical engineering, 2011, 45 (3): 8-10.
[15] The study on the effect of extraction and purification process of tea saponin from Liqingchuan and on the activity of alcohol dehydrogenase [ D ]. Fertilizer industry university, 2016.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a plant molluscacide-Roxwell. Based on the characteristics that the camellia saponin and decarboxylated components thereof have good water solubility, poor thermal stability and large polarity, and saponin calcium precipitates have low solubility in water and are easy to be converted into the spirocarb, the invention uses the tea saponin as the raw material to obtain the high-quality spirocarb, changes the surplus camellia saponin into valuable, can be widely applied to industrial production, and provides technical support for popularization of the spirocarb.
The invention relates to a preparation method of a plant molluscacide, namely, spirocarb, which takes oil-tea saponin as a raw material and utilizes Ca (OH)2Hydrolyzing oil tea saponin to obtain 2-methyl-2-butenoic acid, acetic acid and Ca2+Forming soluble calcium salt, carboxyl (A) of glycosyl part of sasanqua saponin is also reacted with Ca2+Generating insoluble calcium saponin decarboxylation calcium precipitate (formula 3), filtering, dispersing the insoluble saponin decarboxylation calcium precipitate with deionized water, acidifying calcium salt with sulfuric acid, filtering to remove CaSO4Precipitating, and distilling the filtrate under reduced pressure to obtain spirocarb H2B。
The preparation method of the plant molluscacide, namely the spirocarb, comprises the following steps:
step 1: hydrolysis and calcification
Taking 60% of oil-tea saponin and calcium hydroxide as raw materials, taking water as a solvent, hydrolyzing the oil-tea saponin in an alkaline environment under a heating condition, removing acetic acid, 2-methyl-2-butenoic acid, carboxyl on glycosyl of the oil-tea saponin and Ca (OH)2Reacting to obtain tea saponin calcium decarboxylation precipitate, performing suction filtration on water-soluble calcium acetate, calcium 2-methyl-2-butenoate and the solution, and drying the precipitate to obtain khaki tea saponin calcium decarboxylation precipitate;
in the step 1, the mass ratio of 60% of the oil tea saponin to the calcium hydroxide is 8: 1-5, preferably 4: 1.
In the step 1, the temperature of the hydrolysis reaction is 25-90 ℃, and preferably 40-60 ℃; the time of the hydrolysis reaction is 5 to 30 hours, preferably 15 hours.
Step 2: acidification
Adding the tea saponin calcium decarboxylation precipitate obtained in the step (1) into a dispersing agent for uniform dispersion, adjusting the pH value by using a dilute sulfuric acid solution, and converting the tea saponin calcium decarboxylation precipitate into a calcium sulfate solid and a spirocarb solution;
in the step 2, dispersing the tea saponin calcium decarboxylation precipitate by using a dispersing agent, adding a dilute sulfuric acid solution with the mass concentration of 10-20%, adjusting the pH value of the mixed solution, and converting the tea saponin calcium decarboxylation precipitate into a Roxwell solution and CaSO4Precipitating, and filtering to separate the two.
In the step 2, the dispersing agent is selected from one or more of low-boiling point and large-polarity solvents, such as deionized water, dimethyl sulfoxide, ethylene glycol, acetic acid, nitromethane, acetone, pyridine and the like. Deionized water is preferred according to the solubility difference of the tea saponin calcium decarboxylation precipitate, the spirocarb and the calcium sulfate.
In the step 2, the pH value of the mixed solution is adjusted to 2-4.
And step 3: refining
According to the characteristic that the RoxWire is easily soluble in a large polar solvent and is hardly soluble in a small polar solvent, the small polar solvent is added into the RoxWire solution obtained in the step 2, the polarity of the solution is reduced, the polar environment of the RoxWire solution is changed, the RoxWire solid can be separated out from the solution, the RoxWire solid is obtained by filtering, the filtrate is subjected to reduced pressure distillation to recover the small polar solvent, and the residual liquid after the recovery of the small polar solvent can be returned to the link of hydrolysis and calcification reaction of the oil tea saponin to be used as the solvent.
In the step 3, the small polar solvent is one or a mixture of more of acetone, diethyl ether, ethyl acetate, n-butanol, tetrahydrofuran and the like, and acetone is preferred.
Glycosyl and sapogenin in the sasanqua saponin molecule are connected through glycosidic bonds, the glycosidic bonds are easy to break under a strong acid environment, so that the sasanqua saponin is deteriorated, and meanwhile, the sasanqua saponin has poor thermal stability and is easy to oxidize under a high-temperature environment, so that the solution is blackened and has bad odor. The invention utilizes proper alkali as a hydrolysis reagent, obtains the optimal reaction temperature, reactant feed ratio, reaction time, acidification pH and separation conditions for preparing the spirocarb by using the oil-tea saponin through experiments, ensures that a glycosyl part and a sapogenin part are not damaged during hydrolysis of the oil-tea saponin molecules, and only removes acetic acid and a 2-methyl-2-butenoic acid part to generate a tea saponin decarboxylation component. The product is detected by Molish reaction, and glycosyl is not destroyed, and the sapogenin part is not destroyed by Libermann Burchard experiment.
According to the invention, the tea saponin calcium decarboxylation precipitate is directly obtained by hydrolyzing the tea saponin by calcium hydroxide in one step, the process is simple and operable, the energy consumption is low, the conversion rate is high, the side reactions are few, and the reaction product is easy to separate; after the tea saponin calcium decarboxylation precipitate is acidified to obtain the RoxWiy solution, water can be removed through reduced pressure distillation, and high-purity RoxWiy solid is obtained.
The method can realize one-time completion of ester hydrolysis of the tea saponin and decarboxylation calcium precipitation of the tea saponin, is convenient for separation and purification of products, and reduces the separation cost. And (4) carrying out next reaction on the filtered tea saponin calcium decarboxylation precipitate, and returning the reaction liquid to the previous step for recycling. The by-product calcium acetate and calcium 2-methyl-2-butenoate solution can be concentrated and then acidified by sulfuric acid, and then purified by rectification under reduced pressure to be used as a by-product, and the by-product calcium sulfate is also an important chemical raw material.
Compared with the prior art, the invention has the beneficial effects that:
1. the calcium hydroxide hydrolyzes the tea saponin to directly obtain the tea saponin decarboxylation calcium precipitate in one step, the reaction process is simple, and the product separation is convenient. The reaction takes the oil tea saponin as a raw material, eliminates the interference of protein macromolecules, saccharides and the like in the tea seed powder, can obtain the high-quality spirocarb, and can realize continuous production.
2. When the tea saponin decarboxylated calcium salt is acidified to obtain the spirocarb, water is used as a solvent, and the relationship between the solubility of the spirocarb and the polarity of the solvent is utilized, so that the spirocarb can be conveniently separated from other substances, and the method is simple to operate and low in cost.
3. The raw materials and the byproducts can be recycled, and the byproducts calcium sulfate, acetic acid and 2-methyl-2-butenoic acid are important chemical raw materials. The invention has extremely low environmental pollution and meets the requirements of green chemical production.
4. Compared with the prior art, the high-content RoxWiy bulk drug (the content is 53.26% as shown in figure 3 detected by high performance liquid chromatography) can be obtained by using the tea saponin as the raw material, the quality of the RoxWiy is guaranteed (the purity of the purified RoxWiy can reach more than 90% detected by high performance liquid chromatography), and support is provided for further application of the RoxWiy in the field of biological pesticides.
5. The domestic oil tea saponin has huge annual output and low price, but the application range is limited. The invention can prepare pure spirocarb, changes the oil-tea saponin into valuable, and greatly improves the economic value and the agricultural value of the oil-tea saponin.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the present invention.
FIG. 2 is a Roxwell infrared spectrum. The characteristic absorption spectrum was 3427cm-1，2927cm-1，1727cm-1，1645cm-1，1375cm-1，1234cm-1，1078cm-1，1045cm-1，640cm-1。
FIG. 3 is a high performance liquid chromatogram of Roxwell.
Detailed Description
Example 1:
1. hydrolysis and calcification of sasanqua saponin
Weighing 1.1g of calcium hydroxide into a three-neck flask, adding 75ml of deionized water, uniformly stirring with water, weighing 8.3g of sasanqua saponin (the mass fraction is 60 percent and the amount of sasanqua saponin is 5g), uniformly stirring and mixing, heating to 40 ℃, stirring with a stirrer, performing stable reaction for 12 hours to obtain khaki saponin calcium, and washing with a small amount of deionized water for 1-2 times. Vacuum-filtering with vacuum pump, and drying in vacuum drying oven at 50-75 deg.C for 12 hr to obtain 6.4g of dried calcium saponin with yield of 77.1%.
2. Acidification preparation of spirocarb solution of saponin calcium
Dispersing the saponin calcium solid obtained in the last step by using 100mL of deionized water, stirring by using a magnetic stirrer, dropwise adding sulfuric acid with the mass fraction of 10% by using a separating funnel at room temperature, gradually dissolving the yellowish brown solid, and generating white calcium sulfate precipitate at the bottom of the solution. And when the pH value of the solution is stabilized to be 4-5, stopping adding the sulfuric acid, and performing suction filtration to obtain a mixed solution of calcium sulfate solid, the spirocarb and the oil tea saponin.
3. Refining of Roxwei
Acetone is added into the mixed solution of the RoxWipe and the oil tea saponin obtained in the previous step, so that the polarity of the solution is reduced, and the solubility of the calcium sulfate, the RoxWipe and the oil tea saponin is reduced in sequence. With the gradual addition of acetone, when the volume of the added acetone is 50mL, the precipitation amount of calcium sulfate is maximum, the calcium sulfate is removed by suction filtration, and the acetone is continuously added into the solution. When the volume of the added acetone is 130mL, the maximum precipitation amount of the RoxWir is obtained, the RoxWir solid and the filtrate are obtained through suction filtration, and the solid RoxWir is placed into a vacuum drying oven to be dried for 12 hours at the temperature of 50-75 ℃ to obtain 3.3g of dried RoxWir solid, wherein the yield is 40%. And (3) putting the filtrate into a reduced pressure distillation device, distilling to recover acetone, and taking residual liquid after distillation as a solvent for hydrolyzing and calcifying the sasanqua saponin for the next time.
Example 2:
1. hydrolysis and calcification of sasanqua saponin
Weighing 1.1g of calcium hydroxide into a three-neck flask, adding 75ml of deionized water, uniformly stirring water, weighing 8.3g of oil tea saponin (the mass fraction is 60 percent and the oil tea saponin content is 5g), uniformly mixing, heating to 50 ℃, carrying out stable reaction for 12h to obtain khaki saponin calcium, and washing with a small amount of deionized water for 1-2 times. Vacuum-filtering with vacuum pump, and drying in vacuum drying oven at 50-75 deg.C for 12 hr to obtain 7.1g of dried calcium saponin with yield of 85.5%.
2. Acidification preparation of spirocarb solution of saponin calcium
The saponin obtained in the previous step was calcium-acidified according to the procedure of example 1 to obtain a Roxwell solution.
3. Refining of Roxwei
The RoxWine solution was treated according to the procedure of example 1 to obtain 3.8g of RoxWine solid in a yield of 46%. The filtrate was distilled under reduced pressure as in example 1.
Example 3:
weighing 1.1g of calcium hydroxide into a three-neck flask, adding 75ml of deionized water, uniformly stirring with water, weighing 8.3g of sasanqua saponin (the mass fraction is 60%, and the weight fraction is 5g of sasanqua saponin), uniformly stirring and mixing, and heating to 90 ℃. Stirring by using a stirrer, reacting stably for 12h, not obtaining saponin calcium precipitate, blackening reaction liquid with foul smell, performing Molish experiment Libermann Burchard experiment on the reaction liquid, finding no characteristic color, and judging that the oil tea saponin is deteriorated after reacting for 12h at the temperature of 90 ℃.
Example 4:
1. hydrolysis and calcification of sasanqua saponin
1.7g of calcium hydroxide is weighed, 75ml of deionized water is added, the mixture is stirred to prepare a saturated solution, and the saturated solution is filled into a three-neck flask. Weighing 8.3g of sasanqua saponin (with the content of 60 percent and the sasanqua saponin content of 5g), placing into a three-neck flask, stirring and mixing uniformly, and heating to 50 ℃. Stirring by using a stirrer, carrying out stable reaction for 12 hours to obtain khaki saponin calcium, and washing for 1-2 times by using a small amount of deionized water. Vacuum-filtering with vacuum pump, and drying in vacuum drying oven at 50-75 deg.C for 12 hr to obtain 7.3g of dried calcium saponin with yield of 87.9%.
2. Acidification preparation of spirocarb solution of saponin calcium
The saponin obtained in the previous step was calcium-acidified according to the procedure of example 1 to obtain a Roxwell solution.
3. Refining of Roxwei
The RoxWine solution was treated according to the procedure of example 1 to obtain 4.2g of RoxWine solid in 51% yield. The filtrate was distilled under reduced pressure as in example 1.
Example 5:
1. hydrolysis and calcification of sasanqua saponin
2.2g of calcium hydroxide is weighed, 75ml of deionized water is added, the mixture is stirred to prepare a saturated solution, and the saturated solution is filled into a three-neck flask. Weighing 8.3g of sasanqua saponin (with the content of 60 percent and the sasanqua saponin content of 5g), placing into a three-neck flask, stirring and mixing uniformly, and heating to 50 ℃. Stirring by using a stirrer, carrying out stable reaction for 12 hours to obtain khaki saponin calcium, and washing for 1-2 times by using a small amount of deionized water. Vacuum-filtering with vacuum pump, and drying in vacuum drying oven at 50-75 deg.C for 12 hr to obtain 8.1g of dried calcium saponin with yield of 97.6%.
2. Acidification preparation of spirocarb solution of saponin calcium
The saponin obtained in the previous step was calcium-acidified according to the procedure of example 1 to obtain a Roxwell solution.
3. Refining of Roxwei
The RoxWine solution was treated according to the procedure of example 1 to obtain 4.4g of RoxWine solid in a yield of 53%. The filtrate was distilled under reduced pressure as in example 1.
Example 6:
1. hydrolysis and calcification of sasanqua saponin
2.2g of calcium hydroxide is weighed, 75ml of deionized water is added, the mixture is stirred to prepare a saturated solution, and the saturated solution is filled into a three-neck flask. Weighing 8.3g of sasanqua saponin (with the content of 60 percent and the sasanqua saponin content of 5g), placing into a three-neck flask, stirring and mixing uniformly, and heating to 50 ℃. Stirring by using a stirrer, carrying out stable reaction for 5 hours to obtain khaki saponin calcium, and washing for 1-2 times by using a small amount of deionized water. Vacuum-filtering with vacuum pump, and drying in vacuum drying oven at 50-75 deg.C for 12 hr to obtain 6.5g of dried calcium saponin with yield of 78.3%.
2. Acidification preparation of spirocarb solution of saponin calcium
The saponin obtained in the previous step was calcium-acidified according to the procedure of example 1 to obtain a Roxwell solution.
3. Refining of Roxwei
The RoxWine solution was treated according to the procedure of example 1 to obtain 3.2g of RoxWine solid in a yield of 38.6%. The filtrate was distilled under reduced pressure as in example 1.
Example 7:
1. hydrolysis and calcification of sasanqua saponin
2.2g of calcium hydroxide is weighed, 75mL of deionized water is added, the mixture is stirred to prepare a saturated solution, and the saturated solution is filled into a three-neck flask. Weighing 8.3g of sasanqua saponin (with the content of 60 percent and the sasanqua saponin content of 5g), placing into a three-neck flask, stirring and mixing uniformly, and heating to 50 ℃. Stirring by using a stirrer, carrying out stable reaction for 15h to obtain khaki saponin calcium, and washing for 1-2 times by using a small amount of deionized water. Vacuum-filtering with vacuum pump, and drying in vacuum drying oven at 50-75 deg.C for 12 hr to obtain 8.2g of dried calcium saponin with yield of 98.8%.
2. Acidification preparation of spirocarb solution of saponin calcium
The saponin obtained in the previous step was calcium-acidified according to the procedure of example 1 to obtain a Roxwell solution.
3. Refining of Roxwei
The RoxWine solution was treated according to the procedure described in example 1 to obtain 4.7g of RoxWine as a solid in a yield of 57%. The filtrate was distilled under reduced pressure as in example 1.
Example 8:
1. hydrolysis and calcification of sasanqua saponin
8.2g of dry calcium saponin was obtained according to the procedure of example 7.
2. Preparation of snail-shaped solution by acidifying saponin calcium
8.2g of saponin calcium was acidified to give a Roxwell solution according to the procedure in example 1.
3. Refining of Roxwei
And adding diethyl ether into the mixed solution of the RoxWipe and the oil tea saponin obtained in the previous step, reducing the polarity of the solution, separating out solids, and when the volume of the added acetone is 30mL, maximizing the precipitation amount of calcium sulfate, performing suction filtration to remove the calcium sulfate, and continuously adding the diethyl ether into the solution. When the volume of the added ether is 90mL, the maximum precipitate amount of the RoxWir is obtained, the RoxWir solid and the filtrate are obtained by suction filtration, and the solid RoxWir is put into a vacuum drying oven to be dried for 12 hours at the temperature of 50-75 ℃ to obtain 2.1g of dried RoxWir solid with the yield of 25%. And (3) putting the filtrate in a reduced pressure distillation device, distilling to recover ether, and taking residual liquid after distillation as a solvent for hydrolyzing and calcifying the camellia saponin for the next time.
Example 9:
1. hydrolysis and calcification of sasanqua saponin
8.2g of dry calcium saponin was obtained according to the procedure of example 7.
2. Preparation of snail-shaped solution by acidifying saponin calcium
8.2g of saponin calcium was acidified to give a Roxwell solution according to the procedure in example 1.
3. Refining of Roxwei
And adding ethyl acetate into the mixed solution of the RoxWipe and the oil tea saponin obtained in the previous step, so that the polarity of the solution is reduced. When the volume of the added ethyl acetate is 60mL, the precipitation amount of calcium sulfate is maximum, the calcium sulfate is removed by suction filtration, and the ethyl acetate is continuously added into the solution. When the volume of the added ethyl acetate is 160mL, the maximum precipitation amount of the RoxWir is obtained, the RoxWir solid and the filtrate are obtained through suction filtration, and the solid RoxWir is placed into a vacuum drying oven to be dried for 12 hours at the temperature of 50-75 ℃ to obtain 2.6g of dried RoxWir solid, wherein the yield is 31%. And (3) putting the filtrate in a reduced pressure distillation device, distilling to recover ethyl acetate, and taking residual liquid after distillation as a solvent for hydrolyzing and calcifying the sasanqua saponin for the next time.
Claims (3)
1. A preparation method of a plant molluscacide, namely, Roxwell, is characterized in that:
using sasanquasaponin as raw material, Ca (OH)2Hydrolyzing oil tea saponin to obtain 2-methyl-2-butenoic acid, acetic acid and Ca2+ Forming soluble calcium salt, carboxyl of glycosyl part of sasanqua saponin is also mixed with Ca2+Generating insoluble calcium saponin decarboxylation calcium precipitate, filtering, dispersing the insoluble saponin decarboxylation calcium precipitate with deionized water, acidifying calcium salt with sulfuric acid, filtering to remove CaSO4Precipitating, and distilling the filtrate under reduced pressure to obtain spirocarb H2B; the method comprises the following steps:
step 1: hydrolysis and calcification
Taking 60% of oil-tea saponin and calcium hydroxide as raw materials, taking water as a solvent, hydrolyzing the oil-tea saponin in an alkaline environment under a heating condition, removing acetic acid, 2-methyl-2-butenoic acid, carboxyl on glycosyl of the oil-tea saponin and Ca (OH)2Reacting to obtain tea saponin calcium decarboxylation precipitate, performing suction filtration on water-soluble calcium acetate, calcium 2-methyl-2-butenoate and the solution, and drying the precipitate to obtain khaki tea saponin calcium decarboxylation precipitate;
step 2: acidification
Adding the tea saponin calcium decarboxylation precipitate obtained in the step (1) into a dispersing agent for uniform dispersion, adjusting the pH value by using a dilute sulfuric acid solution, and converting the tea saponin calcium decarboxylation precipitate into a calcium sulfate solid and a spirocarb solution;
and step 3: refining
According to the characteristic that the RoxWirb is easily soluble in a large polar solvent and hardly soluble in a small polar solvent, adding the small polar solvent into the RoxWir solution obtained in the step 2, reducing the polarity of the solution, changing the polar environment of the RoxWir solution, separating out RoxWir solid from the solution, and filtering to obtain the RoxWir solid;
in the step 1, the mass ratio of 60% of the oil tea saponin to the calcium hydroxide is 8: 1-5;
in the step 1, the temperature of the hydrolysis reaction is 40-60 ℃, and the time of the hydrolysis reaction is 15 hours;
in the step 2, dispersing the tea saponin calcium decarboxylation precipitate by using a dispersing agent, adding a dilute sulfuric acid solution with the mass concentration of 10-20%, adjusting the pH value of the mixed solution to 2-4, and converting the tea saponin calcium decarboxylation precipitate into a RoxWis solution and CaSO4Precipitating, and filtering to separate the two.
2. The method of claim 1, wherein:
in the step 2, the dispersing agent is one or a mixture of more of deionized water, dimethyl sulfoxide, ethylene glycol, acetic acid, nitromethane, acetone and pyridine.
3. The method of claim 1, wherein:
in the step 3, the small polar solvent is one or a mixture of acetone, diethyl ether, ethyl acetate, n-butanol and tetrahydrofuran.
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| JPH0761998A (en) * | 1993-08-24 | 1995-03-07 | Itouen:Kk | New saponin compound and desacyl saponin compound |
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| JPH0761998A (en) * | 1993-08-24 | 1995-03-07 | Itouen:Kk | New saponin compound and desacyl saponin compound |
| CN1579168A (en) * | 2004-04-21 | 2005-02-16 | 湖北金海潮科技有限公司 | Plant-biological composite trepone micide |
| CN1973633A (en) * | 2006-12-15 | 2007-06-06 | 福州大学 | Prepn process of botanical molluscacide |
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