CN103382169B - Emodin methyl sulfonic ester, and preparation method and applications thereof - Google Patents
Emodin methyl sulfonic ester, and preparation method and applications thereof Download PDFInfo
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Abstract
The invention belongs to the field of pesticide application, and more specifically relates to emodin methyl sulfonic ester, and a preparation method and applications thereof. Emodin methyl sulfonic ester is represented by formula 1, and is used as an agricultural bactericide, especially as a bactericide for wheat powdery mildew or rice blast. The emodin derivative emodin methyl sulfonic ester possesses excellent bactericidal activity on plant pathogens, and is suitable to be used as an active compound of a novel agricultural bactericide; raw materials are easily available; and synthesis is convenience. So that, comprehensive utilization of emodin and derivatives of emodin is expanded, and reliable data basis is provided for the development of plant source pesticides. The formula 1 is shown in the description.
Description
Technical field
The invention belongs to pesticides application field, specifically Schuttgelb methanesulfonate ester and its preparation method and application.
Background technology
Mainly concentrate on medically the research of Schuttgelb and derivative rheochrysidin thereof, research is more late also less in agricultural, and in recent years, due to the variety of problems of chemical pesticide, people come in diversion to botanical pesticide.Zhang Hong is at " biological activity of Schuttgelb methylated derivative " agricultural chemicals, 2008,47 (7), 537-539 page is modified the derivatize of Schuttgelb methyl and is obtained the compound that a series of derivative obtains the replacement of 3-OH group, and carry out biological activity test, show cucumber downy mildew Be very effective.Also find simultaneously trimethoxy Schuttgelb to beet exigua larvae take food and growth has obvious restraining effect, especially under 4000mg/L, larva almost takes food without any, and the rheochrysidin that Schuttgelb and monomethyl replace is then without this effect.Yang Lijun is at " rheochrysidin is to the activity of several nosophyte fungi " agricultural chemicals, 2010,02,133-135 page report adopts mycelial growth rate method and spore germination to send out and determines the bacteriostatic activity of rheochrysidin to several pathogenic fungi such as rice blast and cucumber downy mildew, and adopts pot-culture method to measure its activity to wheat and powdery mildew of cucumber germ.Rheochrysidin is obvious to botrytis cinerea pers and rice blast fungus mycelia bacteriostatic activity, its suppress in concentration (EC
50value) be respectively 3.74,1.14mg/L; To wheat powdery mildew and cucumber powdery mildew's pathogen, there is excellent activity, EC
50value is respectively 0.68,0.33mg/L.Results from pot experiment test also shows that rheochrysidin has good protection and result for the treatment of to cucumber powdery mildew's pathogen.Yang Li army " novel plant source pesticide 0.5% rheochrysidin aqua is to the toxicity test of cucumber powdery mildew's pathogen and field efficacy " plant protection subsequently; 2010; 05; 168-170 page report had once carried out toxicity test and the field control effectiveness test of cucumber powdery mildew's pathogen to the rheochrysidin aqua of 0.5%; indoor spore germination inhibition test result shows, rheochrysidin is to concentration EC in the suppression of cucumber powdery mildew's pathogen spore germination
50be 0.37 μ g/mL; Field control effectiveness test result shows, 0.5% rheochrysidin aqua has good protection and prevention effect to cucumber powdery mildew's pathogen, effective ingredient consumption 18-45g/hm
2prevention effect apparently higher than 15% trazodone wettable powder 135g/hm
2preventive effect.The disinfectant use in agriculture innovation technical manual of latest edition in 2011 has had the introduction about 0.5% rheochrysidin aqua, and some company is at this series products of production.As Beijing Kingbo Biotech Co., Ltd..
Summary of the invention:
The object of the present invention is to provide Schuttgelb methanesulfonate ester and its preparation method and application.
For achieving the above object, the technical solution used in the present invention is:
A kind of Schuttgelb methanesulfonate ester: Schuttgelb methanesulfonate ester such as formula shown in one,
Formula one.
Described Schuttgelb methanesulfonate ester extracts by giant knotweed the Schuttgelb obtained to carry out derivatize synthesis, silicagel column separating-purifying, Schuttgelb methanesulfonate ester shown in the formula one obtaining having agricultural bactericidal activity:
Formula one.
Described Schuttgelb methanesulfonate ester obtains as follows:
1) Schuttgelb:
Mixed in the ratio of 1:4-6 with ether (ml) by the ethanol extraction (g) of polygoni cuspidati,radix powder, carrying out surname extraction after mixing, to be back to ether colourless, is then the NaHCO of 3-6% with massfraction
3repeatedly extract, combining extraction liquid also adjusts pH<4, and then Precipitation, filters and obtains dry powder, then be the Na of 3-6% through massfraction
2cO
3repeatedly extract, combining extraction liquid also adjusts pH<4, Precipitation, detects namely obtain the Schuttgelb with standard control content ﹥ 98% through thin-layer chromatography.
2) synthesis of Schuttgelb p-dimethylamino-azo-benzene acid esters
Add toluene, acid binding agent triethylamine in above-mentioned gained Schuttgelb, then drip Methanesulfonyl chloride, reflux, no longer increase through liquid chromatography determination product, stopped reaction, reaction formula is as follows:
3) purifying of Schuttgelb methanesulfonate ester
Silicagel column is adopted to carry out separation and purification to product the product of above-mentioned gained, silicagel column mixes sample, solvent in product is volatilized, using sherwood oil: ethyl acetate=20:1-10:1(volume ratio) mixed solution be separated as elutriant, collect the larger component of polarity (second component), obtain target product Schuttgelb methanesulfonate ester.
Further, the ethanol extraction (g) of polygoni cuspidati,radix powder mixes in the ratio of 1:5 with ether (ml) by described step 1), and carrying out surname extraction after mixing, to be back to ether colourless, is then the NaHCO of 5% with massfraction
3repeatedly extract, combining extraction liquid also adjusts pH<4, and then Precipitation, filtration obtains dry powder, then dry powder is crossed silicagel column, be that the sherwood oil of 15:1-10:1 and ethyl acetate carry out gradient elution as elutriant by volume ratio, collect the larger component of polarity (second component), then again through massfraction be the Na of 5%
2cO
3repeatedly extract, combining extraction liquid also adjusts pH<4, Precipitation, detects namely obtain the Schuttgelb with standard control content ﹥ 98% through thin-layer chromatography.
The ethanol extraction of described polygoni cuspidati,radix powder is by extract obtained through surname extraction as Extraction solvent using ethanol for polygoni cuspidati,radix powder.
The application of Schuttgelb methanesulfonate ester, described Schuttgelb methanesulfonate ester is as the application of disinfectant use in agriculture.Described Schuttgelb methanesulfonate ester is as the sterilant of wheat powdery mildew or rice blast.
The advantage that the present invention has: emodin derivates Schuttgelb methanesulfonate ester novel structure of the present invention, to phytopathogen, there is stronger fungicidal activity, raw material is easy to get, synthesis is convenient, the suitable active ingredient as a kind of novel disinfectant use in agriculture, and Schuttgelb methanesulfonate ester has good fungicidal activity to wheat powdery mildew or rice blast.Therefore, this compound has expanded the comprehensive utilization of Schuttgelb and derivative thereof, and the exploitation for botanical pesticide provides reliable data foundation.
Embodiment:
Below embodiment is used for further describing the present invention.Agricultural bactericidal active testing will be carried out according to the method described above to Schuttgelb methanesulfonate ester.
Embodiment 1
Schuttgelb methanesulfonate ester, concrete experimental technique is as follows:
Extract to giant knotweed the Schuttgelb (with standard control content ﹥ 98%) obtained and carry out derivatize synthesis, silicagel column separating-purifying, obtain the Schuttgelb methanesulfonate ester with agricultural bactericidal activity, detailed process is as follows:
1. the synthesis of Schuttgelb p-dimethylamino-azo-benzene acid esters
Get 1g Schuttgelb and be placed in 100ml round-bottomed flask, add 50ml toluene, the triethylamine of 0.56g is as acid binding agent, then (relative to Schuttgelb) Methanesulfonyl chloride of 1.5 equivalents is dropwise dripped, reflux 3h, liquid chromatography display reaction product occurs, when the ratio of product no longer increases, and stopped reaction.
Wherein Schuttgelb is that raw material carries out extracting the Schuttgelb obtained with standard control content ﹥ 98% with giant knotweed, namely the ethanol extraction taking polygoni cuspidati,radix powder is about 100g, in apparatus,Soxhlet's, adding 500mL ether, extract that to be back to ether colourless, is then the NaHCO of 5% with massfraction
3repeatedly extract, combining extraction liquid also adjusts pH<4, and then Precipitation, filters and obtains dry powder, then be the Na of 5% through massfraction
2cO
3repeatedly extract, combining extraction liquid also adjusts pH<4, Precipitation, detects namely obtain the Schuttgelb with standard control content ﹥ 98% through thin-layer chromatography.
Wherein the ethanol extraction of polygoni cuspidati,radix powder is that polygoni cuspidati,radix powder passes through, and surname extraction obtains, and Extraction solvent is ethanol, and extraction time is 4h, and withdrawal ratio is giant knotweed quality: ethanol contend=1:10.
2. the purifying of Schuttgelb methanesulfonate ester
Liquid-phase chromatographic analysis (methyl alcohol: water=60:40(v/v) is carried out to product), display proportion of products is 85%, has part to have neither part nor lot in the raw material of reaction, therefore need carry out separation and purification to product.The present embodiment adopts silicagel column to carry out separation and purification to product, silica gel mixed sample, product solvent is volatilized, using sherwood oil: ethyl acetate=10:1(v/v) mixing solutions be separated as elutriant, collect the larger component of polarity (second component), obtain target product, identify that it is Schuttgelb methanesulfonate ester through nuclear-magnetism.
Adopt aforesaid method, carrying out derivatize to Schuttgelb, to synthesize the compound obtained be Schuttgelb methanesulfonate ester, mp.199-200 DEG C.Its structure is as follows:
1H NMR(300MHz，CDCl3)：δ12.22，12.04（2H，s，1-OH，8-OH），7.57（1H，s，H-4），7.31（1H，s，H-5），7.03（1H，s，H-2），6.64（1H，s，H-1），5.30（3H，s，H-SCH3），2.45（3H，s，6-CH3）。
Embodiment 2
The mensuration of Schuttgelb methanesulfonate ester fungicidal activity
Indoor biometrics test is carried out to the Schuttgelb methanesulfonate ester of embodiment 1, using Schuttgelb methanesulfonate ester as medicament, medicament acetone is fully dissolved, be diluted to series concentration (400mg/L, 100mg/L, 25mg/L, 6.25mg/L) fungicidal activity with the water containing 0.1%Tween80 again measure the potted plant seedling assay method of employing and suppress spore germination method in vitro: cucumber downy mildew, wheat powdery mildew, corn rust use potted plant seedling assay method, reagent agent is made into different concentration, if the blank of not dispenser agent.Repeat for 3 times, the foliar spray process of 2 leaf phases, spraying is placed on shady and cool place, inoculates pathogenic bacteria after 24h, and dispenser is placed on greenhouse (temperature is 25 ± 1 DEG C) and cultivates, normal water and fertilizer management, 7 days " Invest, Then Investigate " state of an illness.
Rice blast and gray mold of cucumber use and suppress spore germination method in vitro, liquid (25mg/L, 6.25mg/L) is attached on slide glass or in other planes, spore liquid is dripped after liquid is dry, after moisturizing certain hour. microscopy spore germination rate, with the virulence suppressing spore germination how much to measure medicament, judge the activity of compound.During microscopy generally under low power lens, often process casual inspection 200 spores, calculate sprouting when spore germ tube is greater than the short radius of spore, otherwise not very sprout.As carpospore cyst produces zoospore, its sprouting is not easily observed under the microscope, then whether observable sporocyst produces zoospore as sprouting standard.
After measured, when target be wheat powdery mildew and rice blast time, synthesize by Schuttgelb derivatize the Schuttgelb methanesulfonate ester obtained and have good fungicidal activity, test result is as follows:
"/" represents not to be surveyed.
The preventive effect of wheat powdery mildew spore is suppressed to be 95% when compound concentration is 6.25mg/L (Schuttgelb under comparable sodium be 20% to the preventive effect of wheat powdery mildew).Compound concentration is that to suppress the germination rate of the sick spore of rice blast to be 100% be 80% to the inhibiting rate of rice blast to 25mg/L under comparable sodium).
Claims (4)
1., as a Schuttgelb methanesulfonate ester for the sterilant of wheat powdery mildew or rice blast, it is characterized in that: Schuttgelb methanesulfonate ester such as formula shown in one,
2. the preparation method of Schuttgelb methanesulfonate ester described in a claim 1, it is characterized in that: described Schuttgelb methanesulfonate ester extracts by giant knotweed the Schuttgelb obtained to carry out derivatize synthesis, silicagel column separating-purifying, Schuttgelb methanesulfonate ester shown in the formula one namely obtaining having agricultural bactericidal activity:
Described Schuttgelb methanesulfonate ester obtains as follows:
1) Schuttgelb:
Step 1) ethanol extraction of polygoni cuspidati,radix powder is mixed with the ratio of ether in 1:4-6g/ml, carrying out surname extraction after mixing, to be back to ether colourless, is then the NaHCO of 3-6% with massfraction
3repeatedly extract, combining extraction liquid also adjusts pH<4, and then Precipitation, filters and obtains dry powder, then be the Na of 3-6% through massfraction
2cO
3repeatedly extract, combining extraction liquid also adjusts pH<4, Precipitation, detects namely obtain the Schuttgelb with standard control content ﹥ 98% through thin-layer chromatography;
2) synthesis of Schuttgelb p-dimethylamino-azo-benzene acid esters
Add toluene, acid binding agent triethylamine in above-mentioned gained Schuttgelb, then drip Methanesulfonyl chloride, reflux, no longer increase through liquid chromatography determination product, stopped reaction, reaction formula is as follows;
3) purifying of Schuttgelb methanesulfonate ester
Silicagel column is adopted to carry out separation and purification to product the product of above-mentioned gained, silicagel column mixes sample, solvent in product is volatilized, using sherwood oil: the mixed solution of ethyl acetate=20:1-10:1 volume ratio is separated as elutriant, collect i.e. second component of the larger component of polarity, obtain target product Schuttgelb methanesulfonate ester.
3. by the preparation method of Schuttgelb methanesulfonate ester described in claim 2, it is characterized in that: the ethanol extraction of described polygoni cuspidati,radix powder is by extract obtained through surname extraction as Extraction solvent using ethanol for polygoni cuspidati,radix powder.
4. by the application of Schuttgelb methanesulfonate ester described in claim 1, it is characterized in that: described Schuttgelb methanesulfonate ester is as the sterilant of wheat powdery mildew or rice blast.
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| CN106857511A (en) * | 2017-02-28 | 2017-06-20 | 江苏辉丰农化股份有限公司 | A kind of microbicide compositions comprising emodin derivates Yu pyrazol acid amide compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102010316A (en) * | 2009-09-04 | 2011-04-13 | 中国药科大学 | Method for extracting high-purity frangula emodin from polygonum cuspidatum |
| CN102595885A (en) * | 2009-10-05 | 2012-07-18 | 玛珑生物创新有限公司 | Anthroquinone containing derivatives as biochemical agricultural products |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102010316A (en) * | 2009-09-04 | 2011-04-13 | 中国药科大学 | Method for extracting high-purity frangula emodin from polygonum cuspidatum |
| CN102595885A (en) * | 2009-10-05 | 2012-07-18 | 玛珑生物创新有限公司 | Anthroquinone containing derivatives as biochemical agricultural products |
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| Title |
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| 大黄素的化学合成及结构修饰研究进展;梁英等;《有机化学》;20111231;第31卷(第8期);第1324—1333页 * |
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