CN105646421B - A kind of sulfonic acid esters acaricide containing loop coil - Google Patents
A kind of sulfonic acid esters acaricide containing loop coil Download PDFInfo
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- CN105646421B CN105646421B CN201610102604.6A CN201610102604A CN105646421B CN 105646421 B CN105646421 B CN 105646421B CN 201610102604 A CN201610102604 A CN 201610102604A CN 105646421 B CN105646421 B CN 105646421B
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- sulfonic acid
- acid esters
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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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- 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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- 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)
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- General Health & Medical Sciences (AREA)
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- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of sulfonic acid esters acaricides containing loop coil, and structure is shown in formula I：
Description
The invention belongs to acaricide fields in pesticide for technical field, and in particular to a kind of sulfonic acid esters mite killing containing loop coil
Agent.
Background technology plant evil mite easily generates resistance to acaricide, can make a variety of because reproductive capacity is strong, life cycle is short
Crops Severe Reduction.Under common acaricide such as pyridaben, fenpyroximate, propargite, etoxazole, Envidor preventive effect is gradual
Drop, lasting period gradually shorten.It is to solve the preferred approach of resistance problem to develop new acaricide kind.
102060818 B of patent CN disclose a kind of reacted with Formula II compound with alkyl chloroformate and prepare series
Spiromesifen derivative, which part compound have preferable acaricidal activity.103664850 B of patent CN disclose one kind such as
Acaricide shown in formula III, single use or is applied in combination with other bioactive compound, has to Agricultural Mites preferably anti-
Control effect.In the prior art, the sulfonic acid esters acaricide containing loop coil and its acaricidal activity be at home and abroad as described in the present invention
Not disclosed report.
Invention content
The object of the present invention is to provide a kind of structure novel, efficient spiral shell mite sulfonic acid esters acaricides.
Technical scheme is as follows：
The present invention provides a kind of sulfonic acid esters acaricides containing loop coil, and structure is shown in formula I：
Compound of formula I can be made by following reaction：
Formula II compound in the presence of acid binding agent, reacts generation the compounds of this invention (formula with butyl sulfochlorides in solvent
I)。
Acid binding agent is selected from triethylamine, pyridine, picoline, sodium carbonate (potassium), sodium bicarbonate (potassium)；Solvent be selected from toluene,
Dimethylbenzene, ethyl acetate, dichloromethane, chloroform, 1,2- dichloroethanes；Butyl sulfochlorides are added in a manner of being added dropwise, and control temperature
It it is 0 DEG C -5 DEG C, method of purification is recrystallization, and solvent selects isopropanol.
The preparation method of Formula II compound is shown in 6436988 B1 of US.
Compound of formula I is subjected to indoor acaricidal ovum activity experiment, under 1 μ g/mL and 0.1 μ g/mL concentration, activity is all high
In Envidor, therefore, it is used to prevent the purposes of Agricultural Mites the invention also includes compound of formula I.
The advantages and positive effects of the present invention：
As Envidor etc. is conventional acaricidal a large amount of and frequently uses, evil mite produces in various degree conventional acaricide
Drug resistance.Under equivalent assay concentration, the sulfonates compounds of the invention containing loop coil are in 1 μ g/mL and 0.1 μ g/mL concentration
Under be 95% and 75% respectively to the corrected mortality of Tetranychus cinnabarinus mite ovum, higher than the 88% of comparison medicament Envidor and 33%
(being shown in Table 1).The compounds of this invention preparation process is simple, reaction condition is mild, is the new acaricide with good industrialization prospect.
The compounds of this invention can be used alone when preventing evil mite, can also be used with other active substance combinations, in favor of
Improve the comprehensive function of product.The invention also includes the miticide composition of compound of formula I crop active component, wrapped in the composition
Include compound of formula I and agriculturally acceptable carrier.
The composition of the present invention can be used in the form of preparation：Compound of formula I is dissolved or dispersed in as active component
In carrier or solvent, add suitable surfactant and aqua, missible oil, microemulsion, aqueous emulsion, suspending agent, dispersible oil is made
Suspending agent etc..
It should be appreciated that in scope defined by the claims of the present invention, various transformation and change can be carried out.
Specific embodiment
Following synthesis example, formulation examples and raw test result can be used to further illustrate the present invention, but do not mean that
The limitation present invention.
Synthesize example
The preparation of example 1, compound of formula I
100mL ethyl acetate, 15.7g (0.05mol) 3- (2,4 dichloro benzenes are sequentially added in 250mL three-necked flasks
Base) -2- oxo -1- oxaspiros [4,5]-decyl- 3- alkene -4- alcohol, 6.1g (0.06mol) triethylamine, after stirring and dissolving, use ice-water bath
The solution being made of 9.40g (0.06mol) butyl sulfochlorides and 30mL ethyl acetate is added dropwise down in 0 DEG C -5 DEG C of temperature control, stirring, drips
Finish, reaction 2h~3h, TLC monitoring reaction is stirred at room temperature.Reaction solution is poured into saturation NaHCO after reaction3(pH 8 is left for solution
It is right), it stirs ten minutes, liquid separation, with 40mL~60mL water washing organic layers, organic phase anhydrous Na 2SO4It is dry, vacuum rotary steam
It removes solvent ethyl acetate and obtains rufous viscous liquid, with 50mL recrystallisation from isopropanol, obtain 19.6g white crystals, receive
Rate 90.3%, fusing point：85℃-87℃.
1H NMR (500MHz, DMSO-d6), δ (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
5g compound of formula I and 20g ethyl acetate are separately added into 250mL beakers, stirring and dissolving adds in 10g agriculture breasts
1601# and 15g NP-7 are stirring evenly and then adding into 50g water, are sufficiently stirred 0.5h, obtain 5% compound of formula I microemulsion.
The preparation of example 3,25% compound of formula I suspending agent
Be separately added into 250mL beakers 25g compound of formula I, 5g Morwet D-500,7g Tween 80s, 2g white carbons,
Xanthan gum solution, 4g ethylene glycol and the 42g water of 15g0.1%, stirs evenly, is transferred in sand mill and is fully ground 3h, obtain 25%
Compound of formula I suspending agent.
The preparation of example 4, the dispersible oil-suspending agent of 25% compound of formula I
25g compound of formula I, 15g SP-OF3404,5g EL-40, the organic swellings of 3g are separately added into 250mL beakers
Soil, 52g methyl oleates, stirs evenly, and is transferred in sand mill and is fully ground 3h, obtains the dispersible oil-suspending agent of 25% compound of formula I.
Biological activity determination
Example 5 measures acaricidal ovum activity using infusion process and the method for statistical correction Mortality of insect.Detailed process is：
Reagent agent is diluted to required concentration by active ingredient respectively, being loaded with Tetranychus cinnabarinus mite ovum, (mite ovum is by indoor standardized side
The group that method is normally raised) blade leaching it is into the liquid, gently vibrate 5s after take out.Liquid extra on blade is sucked, is placed in
It is covered in the culture dish of wetting filter paper, is covered with preservative film, blank control is done with the processing for being free of medicament, culture dish is placed on
It raises in (25 ± 1) DEG C constant incubator and observation, the investigation hatching number when compareing egg hatching and be developed to the weak mite stage, statistics
The death rate.3 repetitions are often handled, results are averaged, and result of the test is shown in Table 1.
1 the compounds of this invention of table (Formulas I) is to the activity of Tetranychus cinnabarinus mite ovum
By 1 test data of table as it can be seen that under same dose, formula Compound I is equal to the activity of Tetranychus cinnabarinus mite ovum
It is higher than or is same as Envidor.
Claims (2)
1. a kind of sulfonic acid esters acaricide containing loop coil, structure is shown in formula I：
2. a kind of miticide composition, contain compound of formula I described in claim 1 as can in active component and agricultural or forestry
The carrier of receiving.
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 |
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| CN105646421A CN105646421A (en) | 2016-06-08 |
| CN105646421B true CN105646421B (en) | 2018-06-15 |
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| WO (1) | WO2017143892A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
|---|---|---|---|---|
| EP0528156B1 (en) * | 1991-07-16 | 1997-03-26 | 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 |
|---|---|---|---|---|
| AU7159994A (en) * | 1993-09-17 | 1995-03-30 | Bayer Aktiengesellschaft | 3-aryl-4-hydroxy-delta3-dihydrofuranone derivatives |
| 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
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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 |
|---|---|---|---|---|
| EP0528156B1 (en) * | 1991-07-16 | 1997-03-26 | 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 |
|---|
| 螺环季酮酸的羧酸酯衍生物的合成及其杀螨活性;高树坤等;《应用化学》;20120831;第29卷(第8期);885-891 * |
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| Publication number | Publication date |
|---|---|
| CN105646421A (en) | 2016-06-08 |
| 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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