CN102715172B - Application of dibenzyl acryloyl aminated compound as agricultural bactericide - Google Patents
Application of dibenzyl acryloyl aminated compound as agricultural bactericide Download PDFInfo
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- CN102715172B CN102715172B CN201110079042.5A CN201110079042A CN102715172B CN 102715172 B CN102715172 B CN 102715172B CN 201110079042 A CN201110079042 A CN 201110079042A CN 102715172 B CN102715172 B CN 102715172B
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- AEKSRNHSOYGPMP-UHFFFAOYSA-N CC(C)(C)Oc(cc1)ccc1C(c(cc1)cc(OC)c1OC)=O Chemical compound CC(C)(C)Oc(cc1)ccc1C(c(cc1)cc(OC)c1OC)=O AEKSRNHSOYGPMP-UHFFFAOYSA-N 0.000 description 1
- LAPISKJSGXLBQD-PYCFMQQDSA-N CCC(C)(C)Oc(cc1)ccc1/C(/c(cc1)cc(OC)c1OC)=C/C(N1CCOCC1)=O Chemical compound CCC(C)(C)Oc(cc1)ccc1/C(/c(cc1)cc(OC)c1OC)=C/C(N1CCOCC1)=O LAPISKJSGXLBQD-PYCFMQQDSA-N 0.000 description 1
- ZAWIHPQSOJGMOW-UHFFFAOYSA-N COc(ccc(C(c(cc1)ccc1F)=O)c1)c1OC Chemical compound COc(ccc(C(c(cc1)ccc1F)=O)c1)c1OC ZAWIHPQSOJGMOW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an application of a dibenzyl acryloyl aminated compound as an agricultural bactericide. The structure of the compound is as shown in the formula (I). Bioactivity assay shows that: the compound as shown in the formula (I) has a good effect of controlling diseases such as oomycete diseases generated from fungi in agriculture. The compound was found in impurities of an agricultural fungicide flumorph for the first time and was utilized for sterilization, thus changing waste into treasure. The invention is of great significance for environmental protection and simultaneously provides a new species in the field of agricultural fungicides.
Description
Technical field
The invention belongs to disinfectant use in agriculture field.Particularly, relate to the purposes of a kind of diphenylprop acrylamide compound as disinfectant use in agriculture.
Background technology
Flumorph belongs to diphenylprop acrylamide compound, is a kind of systemic fungicide, and protection and therapeutic action are had both, and suppresses spore germination effect obvious.Oomycete disease, especially downy mildew and phytophthora root rot on grape, potato and tomato are had to special efficacy." agricultural chemicals " 2009,48 (5): reported first in 341-343, from the former medicine of flumorph, isolate structure impurity as follows---formula (I) compound and stereoisomer thereof.
All the time, formula (I) compound is taken as prepares the impurity producing in flumorph process, and research staff makes great efforts to carry out process modification, to remove as possible.
Summary of the invention
The object of the invention is to the biologically active of heuristic (I) compound, particularly study its purposes as agricultural chemicals, to turn waste into wealth.Research discovery, the diphenylprop acrylamide compound shown in formula (I) has good bactericidal activity, can be for the preparation of disinfectant use in agriculture, therefore this compound has the purposes as disinfectant use in agriculture.
Technical scheme of the present invention is as follows:
One is the purposes as disinfectant use in agriculture suc as formula the diphenylprop acrylamide compound shown in (I):
Described formula (I) compound comprises stereoisomer and composition thereof, and chemical name is: (E, Z)-4-[3-(3,4-Dimethoxyphenyl)-3-(4-tert-butoxy phenyl) acryloyl group] morpholine.
Biological activity test shows, formula of the present invention (I) compound is a kind of effectively fungicide, be particularly suitable for control by the microbial disease of Oomycete cause of disease as downy mildew, phytophthora root rot, rotten mildew etc., especially downy mildew is had to good control efficiency.The present invention makes the refuse that is originally considered as impurity obtain a kind of new purposes, for disinfectant use in agriculture has increased new varieties.
Formula of the present invention (I) compound and stereoisomer thereof can be prepared by the following method: compound (III) is reacted with potassium tert-butoxide and obtains compound (II), and compound (II) reacts with acetyl morphine and obtains compound (I) under alkali condition.
The suitable condition of preparing compound (II) is: the potassium tert-butoxide that adds excessive (1.2-2 doubly), with oxolane, 1,4-dioxane, DMF, toluene or acetonitrile are solvent, react 30 minutes～20 hours to solvent boiling point in room temperature.More preferably solvent is toluene; More suitable reaction temperature is 0～130 ℃, and further preferred reaction temperature is 100-110 ℃.Under optimum condition, reaction completed at 1～10 hour.Reaction can utilize thin layer chromatography (TLC) monitoring.After having reacted, obtain compound (II) through extraction, recrystallization.
Compound (III) can be made by known method, specifically referring to EP0219756, US4910200 etc.
The suitable condition of preparing compound (I) is: in above-mentioned solvent, under suitable alkali exists, (the two feed molar ratio is 1 to compound (II): 1.5-2) react 30 minutes～20 hours to solvent boiling point in room temperature with acetyl morphine.More preferably solvent is toluene; More suitable reaction temperature is 0～130 ℃, and further preferred reaction temperature is 100-110 ℃.Under optimum condition, reaction completed at 1～10 hour.Reaction end monitoring and post-processing approach are the same, obtain target compound (I).
The suitable alkali that reacts used comprises organic base and inorganic base.Organic base is selected from pyridine or DMAP etc.; Inorganic base is selected from sodium hydroxide, potassium hydroxide, potassium tert-butoxide, sodium tert-butoxide, sodium hydride or Sodamide etc.The preferred alkali of the present invention is potassium tert-butoxide or Sodamide.
The purposes of formula provided by the invention (I) compound comprises also a kind of bactericidal composition take formula (I) compound as active component, and in composition, the weight percentage of active component is 0.1-99%.
The type of service of composition can be dry powder, wetting powder, missible oil, microemulsion, granule, suspending agent, water dispersible granules etc.Concrete application is depended in the selection of types of compositions.
Composition is prepared with known method, for example optional under the existence of surfactant, by diluting or lytic activity material with solvent medium and/or solid diluent.
Available solid diluent or carrier are for example: silica, kaolin, bentonite, talcum, diatomite, dolomite, calcium carbonate, magnesia, clay, synthetic silicate, Attagel, sepiolite etc.
Beyond dewatering, available liquid diluent also comprises as aromatics organic solvent (mixture, the chlorobenzene etc. of dimethylbenzene or alkylbenzene), paraffin (petroleum distillate), alcohols (methyl alcohol, propyl alcohol, butanols, octanol, glycerine), ester class (ethyl acetate, isobutyl acetate etc.), ketone (cyclohexanone, acetone, acetophenone, isophorone, ethyl pentyl group ketone etc.), amide-type (DMF, 1-METHYLPYRROLIDONE etc.).
Available surfactant is sodium, calcium, triethylamine or the triethanolamine salt of polyoxyethylene ester, the lignosulfonates etc. of alkylsulfonate, alkylaryl sulfonates, polyoxyethylene alkylphenol, sorbierite.
Composition also can containing special additive for specific object, for example, contain adhesive as gum Arabic, polyvinyl alcohol, polyvinylpyrrolidone etc.
In above-mentioned composition, the concentration of active component can change according to the preparation type of active component, application target, environmental condition and employing in wide region.The concentration range of active component is generally 0.5-90%, preferably 5-60%.
If needed, can to add in composition can with other active components of structural formula (I) compound compatibility, for example other bactericide are as mancozeb, white urea cyanogen, flumorph, dimethomorph, cyazofamid, fluopicolide, benzene metsulfovax, fluopicolide, pyrimorph, fluazinam etc., there is the effect of synergy or delaying drug resistance, also can with miticide/insecticide, plant growth regulator, antibiotic, weed killer herbicide, fertilizer.Like this, the purposes of formula of the present invention (I) compound also comprises the sterilization of binary that one contains formula (I) compound or ternary active component and/or desinsection, miticide composition.
The present invention discloses preparation method, biologically active and the purposes as disinfectant use in agriculture of the compound shown in formula (I) and stereoisomer thereof first.Preparation method provided by the invention is simple to operate, yield is high.The bactericidal activity of compound is good, can be used as disinfectant use in agriculture extensive use; When it is during as by-product in flumorph production process, be no longer also useless impurity, but a kind of bactericidal active constituent has really been realized " turning waste into wealth ".
Embodiment
By following concrete example, the present invention will be described in detail, but the present invention only limits to absolutely not these embodiment.Synthetic example
Example 1: Compound I synthetic
(1): intermediate II synthetic
26.0 grams of (0.1 mole) compound III are joined in 500 milliliters of three mouthfuls of reaction bulbs that 250 milliliters of toluene and 16.8 grams of (0.15 mole) potassium tert-butoxides are housed, be heated to back flow reaction, when backflow, separate the tert-butyl alcohol of generation, react 4 hours, TLC monitoring reaction is complete.Cooling, toluene layer is washed successively, anhydrous magnesium sulfate drying, filtration, precipitation, and recrystallizing methanol obtains 26.7 grams of (yields: 85%) of light yellow solid.Fusing point: 86-88 ℃.
1H?NMR(300MHz，CDCl
3)δppm：1.42(s，9H)，3.95(d，6H)，6.90(d，1H)，7.06(d，2H)，7.38(m，1H)，7.46(d，2H)，7.75(d，2H).
(2): Compound I synthetic
31.4 grams of (0.10 mole) Compound I I are joined in 500 milliliters of there-necked flasks that 380 milliliters of toluene and 22.4 grams of (0.20 mole) potassium tert-butoxides are housed, be heated to reflux, after 15 minutes, drip wherein 50 milliliters of toluene solutions of 23.2 grams of (0.18 mole) acetyl morphines, dropping process is 30 minutes, when back flow reaction, separate the tert-butyl alcohol, react after 6 hours, TLC monitoring reaction is complete.Cooling, toluene layer is washed successively, anhydrous magnesium sulfate drying, filtration, precipitation, placement crystallization solid, and recrystallizing methanol, obtains 36.2 grams of (yields: 85%) of white solid.Fusing point: 144-146 ℃ (Z/E mixture ratio 85/15).
1H?NMR(300MHz，CDCl
3)δppm：1.37(s，9H)，3.13(m，4H)，3.52(m，4H)，3.80(s，3H)，3.90(s，3H)，6.17(s，1H)，6.83(m，3H)，6.94(d，2H)，7.21(d，1H)，7.27(s，1H).
FORMULATION EXAMPLE (following component addition is parts by weight, is metered into after active component folding hundred)
Example 2
40 parts of compounds of the present invention, 10 parts of ethylene glycol, 4 parts of sodium lignin sulfonates, 6 parts of Nonoxynol-9s, 1 part of carboxymethyl cellulose, 37% 0.2 part of formalin, 75% 0.8 part of silicone oil aqueous emulsion, 38 parts, water, evenly mixes above composition, dissolve, must be containing the suspending agent of active ingredient 40%.
Example 3
15 parts of compounds of the present invention, 75 parts of cyclohexanone, 10 parts of Nonoxynol-9s, evenly mix above composition, dissolve, must be containing the missible oil of active ingredient 15%.
Example 4
10 parts of compounds of the present invention, 89 parts of talcum powder, 1 part of polyxyethylated propyl ether, evenly mixes above composition, pulverizes, must be containing the dry powder of active ingredient 10%.
Example 5
5 parts of compounds of the present invention, 73 parts of clays, 20 parts of bentonites, 1 part of dioctyl sulfo-sodium succinate, 1 part of sodium phosphate, evenly mixes above composition, after fully pulverizing, adds suitable quantity of water.Fully mix again, granulation, after being dried, must be containing the granule of active ingredient 5%.
Example 6
40 parts of compounds of the present invention, 53 parts, diatomite, C
12-204 parts, alcohol sulfuric acid phenol, 3 parts of neopelexes, evenly mix above composition, pulverize, must be containing the wetting powder of active ingredient 40%.
Example 7
8 parts of the compounds of this invention, 50 parts of mancozebs, 30 parts of kaolin, 4 parts of neopelexes, 8 parts of sodium lignin sulfonates, mix mentioned component, after fully pulverizing, obtain mixture content and be 58% wetting powder.
Example 8
10 parts of the compounds of this invention, 30 parts, white urea cyanogen, 45 parts of kaolin, 6 parts of neopelexes, 9 parts of sodium lignin sulfonates, evenly mix above composition, after fully pulverizing, obtain mixture content and be 40% wetting powder.
Example 9
10 parts of the compounds of this invention, 30 parts of flumorphs, 45 parts of kaolin, 6 parts of neopelexes, 9 parts of sodium lignin sulfonates, evenly mix above composition, after fully pulverizing, obtain mixture content and be 40% wetting powder.
Example 10
10 parts of the compounds of this invention, 30 parts of dimethomorphs, 45 parts of kaolin, 6 parts of neopelexes, 9 parts of sodium lignin sulfonates, evenly mix above composition, after fully pulverizing, obtain mixture content and be 40% wetting powder.
Example 11
10 parts of the compounds of this invention, 30 parts of cyazofamids, 45 parts of kaolin, 6 parts of neopelexes, 9 parts of sodium lignin sulfonates, evenly mix above composition, after fully pulverizing, obtain mixture content and be 40% wetting powder.
Example 12
10 parts of the compounds of this invention, 30 parts of fluopicolides, 45 parts of kaolin, 6 parts of neopelexes, 9 parts of sodium lignin sulfonates, evenly mix above composition, after fully pulverizing, obtain mixture content and be 40% wetting powder.
Example 13
10 parts of the compounds of this invention, 30 parts of benzene metsulfovax, 45 parts of kaolin, 6 parts of neopelexes, 9 parts of sodium lignin sulfonates, evenly mix above composition, after fully pulverizing, obtain mixture content and be 40% wetting powder.
Example 14
10 parts of the compounds of this invention, 30 parts of fluopicolides, 45 parts of kaolin, 6 parts of neopelexes, 9 parts of sodium lignin sulfonates, evenly mix above composition, after fully pulverizing, obtain mixture content and be 40% wetting powder.
Example 15
30 parts of the compounds of this invention, 30 parts of pyrimorphs, 10 parts of kaolin, 5.6 parts of neopelexes, 9.4 parts of naphtholsulfonic acid formaldehyde condensation products, 15 parts of soluble starches, above composition is evenly mixed, after fully pulverizing, obtain mixture content and be 60% water dispersible granules.
Example 16
30 parts of the compounds of this invention, 30 parts of fluazinams, 10 parts of kaolin, 5.6 parts of neopelexes, 9.4 parts of naphtholsulfonic acid formaldehyde condensation products, 15 parts of soluble starches, above composition is evenly mixed, after fully pulverizing, obtain mixture content and be 60% water dispersible granules.
Biological activity determination embodiment
Example 17 cucumber downy mildew control efficiency are measured
With compound sample of the present invention, cucumber downy mildew is carried out to live body and protected effect test.Test method is as follows:
Test medicine establishes 40,20,10,5, five concentration of 2.5mg/L.Adopt the potted plant assay method of live body, dissolve by a small amount of acetone for testing compound sample (volume ratio of acetone consumption and spouting liquid is equal to or less than 0.05), with the water dilution that contains 0.1% Tween 80, be mixed with desired concn liquid to be measured.On crops sprayer, liquid to be measured is sprayed on cucumber seedling (host plant is the potted plant seedling of standard of cultivating in greenhouse), after 24 hours, carry out disease inoculation, be then placed in phytotron and cultivate, until disease complete infect after (24 hours), move into hot-house culture.After solvent control and blank are fully fallen ill (being generally week age), carry out the assessment of compound protection effect.Test result is as follows:
When 400ppm, compound (I) is 95% to the control efficiency of downy mildew;
When 20ppm, compound (I) is 70% to the control efficiency of downy mildew, and contrast medicament flumorph is 100% to the control efficiency of downy mildew.
Claims (3)
1. diphenylprop acrylamide compound as shown in the formula (I), as a purposes for disinfectant use in agriculture, is characterized in that: the diphenylprop acrylamide compound shown in formula (I) is used for preventing and treating on crop by the microbial downy mildew of Oomycete cause of disease,
2. according to purposes claimed in claim 1, it is characterized in that: the form using formula (I) compound as the bactericidal composition of active component is used, and in composition, the weight percentage of active component is 0.1-99%.
3. according to purposes claimed in claim 2, it is characterized in that: described composition is mixed with dry powder, wetting powder, missible oil, microemulsion, granule, suspending agent or water dispersible granules.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110079042.5A CN102715172B (en) | 2011-03-30 | 2011-03-30 | Application of dibenzyl acryloyl aminated compound as agricultural bactericide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110079042.5A CN102715172B (en) | 2011-03-30 | 2011-03-30 | Application of dibenzyl acryloyl aminated compound as agricultural bactericide |
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| CN102715172B true CN102715172B (en) | 2014-06-18 |
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| CN103992294B (en) * | 2014-05-29 | 2016-06-08 | 常州大学 | A kind of synthetic method of acrylic amide reactive diluent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4753934A (en) * | 1983-02-28 | 1988-06-28 | Celamerck Gmbh & Co. Kg | Acrylic acid heterocyclic amides, fungicidal compositions and use |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4753934A (en) * | 1983-02-28 | 1988-06-28 | Celamerck Gmbh & Co. Kg | Acrylic acid heterocyclic amides, fungicidal compositions and use |
Non-Patent Citations (2)
| Title |
|---|
| 王远 等.高速逆流色谱在氟吗啉原药杂质分离中的应用.《农药》.2009,第48卷(第5期),341-343. |
| 高速逆流色谱在氟吗啉原药杂质分离中的应用;王远 等;《农药》;20090531;第48卷(第5期);341-343 * |
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Effective date of registration: 20160125 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Patentee after: SHENYANG SINOCHEM PESTICIDE CHEMICAL RESEARCH AND DEVELOPMENT CO., LTD. Address before: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28 Patentee before: Sinochem Corporation Patentee before: Shenyang Research Institute of Chemical Industry |