CN105646421A - Sulfonate miticides containing spiro - Google Patents
Sulfonate miticides containing spiro Download PDFInfo
- Publication number
- CN105646421A CN105646421A CN201610102604.6A CN201610102604A CN105646421A CN 105646421 A CN105646421 A CN 105646421A CN 201610102604 A CN201610102604 A CN 201610102604A CN 105646421 A CN105646421 A CN 105646421A
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- formula
- compound
- acaricide
- sulfonate
- miticides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses sulfonate miticides containing spiro. The structure of the sulfonate miticides is shown in the formula I in the specification. The compound has inhibiting and killing functions on pest mites and mite eggs and can serve as a miticide for controlling pest mites in agriculture.
Description
Present disclosure belongs to acaricide field in pesticide, is specifically related to a kind of sulfonic acid esters acaricide containing volution.
Acaricide, because reproductive capacity is strong, life cycle is short, is very easily produced resistance, can make multiple kinds of crops Severe Reduction by background technology plant evil demodicid mite. Preventive effect is gradually reduced conventional acaricide such as pyridaben, fenpyroximate, propargite, etoxazole, Envidor etc., the lasting period shortens gradually. Developing new acaricide kind is the preferred approach solving resistance problem.
Patent CN102060818B disclose one Formula II compound react with alkyl chloroformate prepare series Spiromesifen derivative, wherein part of compounds has good acaricidal activity. Patent CN103664850B discloses a kind of acaricide as shown in formula III, single use or use with other bioactive compound combination, and Agricultural Mites has better prevention effect. In the prior art, sulfonic acid esters acaricide containing volution and acaricidal activity not disclosed report at home and abroad thereof as described in the present invention.
Summary of the invention
It is an object of the invention to provide a kind of novel structure, efficient spiral shell demodicid mite sulfonic acid esters acaricide.
Technical scheme is as follows:
The invention provides a kind of sulfonic acid esters acaricide containing volution, structure shown in formula I:
Compound of formula I can be prepared by following reaction:
Formula II compound and butyl sulfochlorides are under acid binding agent exists, and in solvent, reaction generates the compounds of this invention (Formulas I).
Acid binding agent is selected from triethylamine, pyridine, picoline, sodium carbonate (potassium), sodium bicarbonate (potassium); Solvent is selected from toluene, dimethylbenzene, ethyl acetate, dichloromethane, chloroform, 1,2-dichloroethanes; Butyl sulfochlorides adds in dropping mode, and controlling temperature is 0 DEG C-5 DEG C, and method of purification is recrystallization, and isopropanol selected by solvent.
The preparation method of Formula II compound is shown in US6436988B1.
Compound of formula I carries out indoor acaricidal ovum activity test, and under 1 �� g/mL and 0.1 �� g/mL concentration, its activity all higher than Envidor, therefore, present invention additionally comprises compound of formula I for preventing and treating the purposes of Agricultural Mites.
Advantages of the present invention and good effect:
Along with the routines such as Envidor are acaricidal a large amount of and frequently use, conventional acaricide is created Drug resistance in various degree by evil demodicid mite. Under equivalent assay concentration, the sulfonates compounds containing volution of present invention corrected mortality to Tetranychus cinnabarinus demodicid mite ovum under 1 �� g/mL and 0.1 �� g/mL concentration is 95% and 75% respectively, higher than 88% and 33% (see table 1) of comparison medicament Envidor. The compounds of this invention preparation technology is simple, reaction condition is gentle, is the new acaricide with good industrialization prospect.
The compounds of this invention, when preventing and treating evil demodicid mite, can be used alone, it is possible to use with other active substance combination, is beneficial to improve the comprehensive function of product.Present invention additionally comprises the miticide composition of compound of formula I crop active component, said composition includes compound of formula I and agriculturally acceptable carrier.
The compositions of the present invention can use using the form of preparation: compound of formula I is dissolved or dispersed in as active component in carrier or solvent, adds appropriate surfactant and makes water preparation, cream, microemulsion, aqueous emulsion, suspending agent, dispersibles oil-suspending agent etc.
It should be appreciated that, in the claim limited range of the present invention, various conversion and change can be carried out.
Detailed description of the invention
Following synthesis example, formulation examples and raw result of the test of surveying can be used to further illustrate the present invention, but are not intended to limit the present invention.
Synthesis example
Example 1, compound of formula I preparation
250mL there-necked flask is sequentially added into 100mL ethyl acetate, 15.7g (0.05mol) 3-(2,4-Dichlorobenzene base)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-alcohol, 6.1g (0.06mol) triethylamine, after stirring and dissolving, with ice-water bath temperature control 0 DEG C-5 DEG C, stirring drips the solution being made up of 9.40g (0.06mol) butyl sulfochlorides and 30mL ethyl acetate down, drips and finishes, reaction 2h��3h, TLC monitoring reaction is stirred at room temperature. React and after terminating, reactant liquor is poured into saturated NaHCO3Solution (about pH8), stirs ten minutes, separatory, with 40mL��60mL water washing organic layer, organic facies anhydrous Na 2SO4Dry, vacuum rotary steam removes solvent ethyl acetate and obtains rufous viscous liquid, uses 50mL recrystallisation from isopropanol, obtains 19.6g white crystal, yield 90.3%, fusing point: 85 DEG C-87 DEG C.
1HNMR (500MHz, DMSO-d6), �� (ppm): 0.81-0.84 (m, 3H), 1.27-1.33 (m, 2H), 1.58-1.62 (m, 6H), 1.76-1.90 (m, 4H), 1.85-1.94 (m, 2H), 3.51-3.54 (m, 2H), 7.32-7.33 (d, 1H), 7.44-7.45 (d, 1H), 7.75 (s, 1H).
Formulation examples
The preparation of example 2,5% compound of formula I microemulsion
In 250mL beaker, it is separately added into 5g compound of formula I and 20g ethyl acetate, stirring and dissolving, adds 10g agriculture breast 1601# and 15gNP-7, be stirring evenly and then adding into 50g water, be sufficiently stirred for 0.5h, obtain 5% compound of formula I microemulsion.
The preparation of example 3,25% compound of formula I suspending agent
25g compound of formula I, 5gMorwetD-500,7g Tween 80,2g white carbon, the xanthan gum solution of 15g0.1%, 4g ethylene glycol and 42g water it is separately added in 250mL beaker, stir, proceed to and sand mill is fully ground 3h, obtain 25% compound of formula I suspending agent.
Example 4,25% compound of formula I dispersibles the preparation of oil-suspending agent
In 250mL beaker, it is separately added into 25g compound of formula I, 15gSP-OF3404,5gEL-40,3g organobentonite, 52g methyl oleate, stirs, proceed to and sand mill is fully ground 3h, obtain 25% compound of formula I and dispersible oil-suspending agent.
Biological activity determination
The method of example 5, employing infusion process and statistical correction Mortality of insect measures acaricidal ovum activity. Detailed process is: reagent agent is diluted to respectively desired concn by effective ingredient, and the blade leaching that will be loaded with Tetranychus cinnabarinus demodicid mite ovum (colony that demodicid mite ovum is normally raised) by indoor standardized method is into the liquid, takes out gently after vibration 5s. Suck medicinal liquid unnecessary on blade, it is placed in the culture dish being covered with moistening filter paper, cover with preservative film, blank is done with the process without medicament, culture dish is placed in (25 �� 1) DEG C constant incubator and raises and observe, in time compareing egg hatching and be developed to the weak demodicid mite stage, investigation hatching number, adds up mortality rate.Often processing 3 times and repeat, results averaged, result of the test is in Table 1.
The table 1 the compounds of this invention (Formulas I) activity to Tetranychus cinnabarinus demodicid mite ovum
From table 1 test data, under same dose, the activity of Tetranychus cinnabarinus demodicid mite ovum is above or is same as Envidor by formula I.
Claims (3)
1. the sulfonic acid esters acaricide containing volution, structure shown in formula I:
2. a kind of sulfonic acid esters acaricide containing volution according to claim 1, it is characterised in that compound of formula I can be used for preventing and treating Agricultural Mites as acaricide.
3. a miticide composition, containing the compound of formula I described in claim 1 as acceptable carrier in active component and agricultural or forestry.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610102604.6A CN105646421B (en) | 2016-02-25 | 2016-02-25 | A kind of sulfonic acid esters acaricide containing loop coil |
| PCT/CN2017/071622 WO2017143892A1 (en) | 2016-02-25 | 2017-01-19 | Sulfonic acid ester acaricide containing spiro rings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610102604.6A CN105646421B (en) | 2016-02-25 | 2016-02-25 | A kind of sulfonic acid esters acaricide containing loop coil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105646421A true CN105646421A (en) | 2016-06-08 |
| CN105646421B CN105646421B (en) | 2018-06-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610102604.6A Active CN105646421B (en) | 2016-02-25 | 2016-02-25 | A kind of sulfonic acid esters acaricide containing loop coil |
Country Status (2)
| Country | Link |
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| CN (1) | CN105646421B (en) |
| WO (1) | WO2017143892A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017143892A1 (en) * | 2016-02-25 | 2017-08-31 | 浙江博仕达作物科技有限公司 | Sulfonic acid ester acaricide containing spiro rings |
| CN107602515A (en) * | 2017-10-13 | 2018-01-19 | 南开大学 | One kind 5A5B6CTricyclic spiro lactone derivatives and its production and use |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0528156A1 (en) * | 1991-07-16 | 1993-02-24 | Bayer Ag | 3-Aryl-4-hydroxy-delta3-dihydrofuranone and 3-aryl-4-hydroxy-delta3-dihydrothiophenone derivatives |
| CN102060818A (en) * | 2011-01-07 | 2011-05-18 | 青岛科技大学 | Novel spirodiclofen compound and preparation method and application thereof |
| CN103664850B (en) * | 2013-12-26 | 2015-02-18 | 青岛科技大学 | Spirodiclofen sulfonate compound and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2127859T3 (en) * | 1993-09-17 | 1999-05-01 | Bayer Ag | DERIVATIVES OF 3-ARIL-4-HIDROXI-3-DIHIDROFURANONA. |
| TW201031327A (en) * | 2008-11-14 | 2010-09-01 | Bayer Cropscience Ag | Active compound combinations having insecticidal and acaricidal properties |
| CN105646421B (en) * | 2016-02-25 | 2018-06-15 | 浙江博仕达作物科技有限公司 | A kind of sulfonic acid esters acaricide containing loop coil |
-
2016
- 2016-02-25 CN CN201610102604.6A patent/CN105646421B/en active Active
-
2017
- 2017-01-19 WO PCT/CN2017/071622 patent/WO2017143892A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0528156A1 (en) * | 1991-07-16 | 1993-02-24 | Bayer Ag | 3-Aryl-4-hydroxy-delta3-dihydrofuranone and 3-aryl-4-hydroxy-delta3-dihydrothiophenone derivatives |
| CN102060818A (en) * | 2011-01-07 | 2011-05-18 | 青岛科技大学 | Novel spirodiclofen compound and preparation method and application thereof |
| CN103664850B (en) * | 2013-12-26 | 2015-02-18 | 青岛科技大学 | Spirodiclofen sulfonate compound and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高树坤等: "螺环季酮酸的羧酸酯衍生物的合成及其杀螨活性", 《应用化学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017143892A1 (en) * | 2016-02-25 | 2017-08-31 | 浙江博仕达作物科技有限公司 | Sulfonic acid ester acaricide containing spiro rings |
| CN107602515A (en) * | 2017-10-13 | 2018-01-19 | 南开大学 | One kind 5A5B6CTricyclic spiro lactone derivatives and its production and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105646421B (en) | 2018-06-15 |
| WO2017143892A1 (en) | 2017-08-31 |
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Address after: 314300 No. 1 Fangjiaduo Road, Haiyan Economic Development Zone, Jiaxing City, Zhejiang Province Patentee after: Zhejiang Yulong Biotechnology Co., Ltd. Address before: 314300 No. 1 Fangjiaduo Road, Haiyan Economic Development Zone, Zhejiang Province Patentee before: Zhejiang Boshida Crop Technological Co., Ltd. |
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Address after: Fang Tai Road Economic Development Zone, Haiyan County, Jiaxing city of Zhejiang Province, No. 1 314300 Patentee after: Zhejiang Yulong Biotechnology Co., Ltd Address before: Fang Tai Road Economic Development Zone, Haiyan County, Jiaxing city of Zhejiang Province, No. 1 314300 Patentee before: Zhejiang Yulong Biotechnology Co., Ltd. |
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Denomination of invention: Sulfonic acid ester acaricide containing spiro ring Effective date of registration: 20211222 Granted publication date: 20180615 Pledgee: Xitangqiao sub branch of Zhejiang Haiyan Rural Commercial Bank Co.,Ltd. Pledgor: Zhejiang Yulong Biotechnology Co.,Ltd. Registration number: Y2021330002593 |
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