CN108003054B - Chrysamide compound containing diphenyl ether and preparation method and application thereof - Google Patents
Chrysamide compound containing diphenyl ether and preparation method and application thereof Download PDFInfo
- Publication number
- CN108003054B CN108003054B CN201711399976.0A CN201711399976A CN108003054B CN 108003054 B CN108003054 B CN 108003054B CN 201711399976 A CN201711399976 A CN 201711399976A CN 108003054 B CN108003054 B CN 108003054B
- Authority
- CN
- China
- Prior art keywords
- pharmaceutically acceptable
- compound
- acceptable salt
- dichloromethane
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C233/60—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a chrysanthemic amide compound containing diphenyl ether and a preparation method and application thereof, wherein the compound is (Z) -3- (2-chloro-3, 3, 3-trifluoroprop-1-en-1-yl) -2, 2-dimethyl-N- (4-phenoxyphenyl) cyclopropane formamide, and a specific preparation method is adopted to synthesize the novel chrysanthemic amide compound containing diphenyl ether.
Description
Technical Field
The invention relates to a preparation method and application of a chrysanthemic amide compound, in particular to a preparation method and application of a chrysanthemic amide compound containing diphenyl ether.
Background
Armyworm is a common pest in a corn field, is also a stage of armyworm propagation when corn enters three leaves to an elongation stage, and is prevented and controlled by spraying of 5% of high-efficiency cypermethrin emulsifiable solution, 50% of imidacloprid suspending agent and the like at present in China.
The chrysanthemide compounds have wide insecticidal and bactericidal activity. Sunnabo et al [ CN1974561] reported that compounds A and B have some control of armyworm at the concentrations tested.
N- (substituted thiazole-2-yl) -chrysanthemide compounds C reported by Zhaojinhao et al (organic chemistry, 2010,30(5): 719-725) have inhibitory activity to diamondback moth at 600 mg/L, and compounds D reported by Zhangdong et al have certain insecticidal activity to diamondback moth at 500 mg/L and certain control effect to aphid.
However, due to the frequent use of these varieties of pesticides, the dosage of the pesticides is increasing, the times of the pesticides are increasing, the corn armyworms have already developed resistance to them, the crops are seriously reduced in yield, the economic benefits of farmers are greatly lost, and the quality safety of agricultural products and the safety belt of the ecological environment are inestimable. Therefore, there is a need to develop highly effective and low resistant, insecticidally active compounds.
Disclosure of Invention
It is an object of the present invention to provide a bisamide compound (Z) -3- (2-chloro-3, 3, 3-trifluoroprop-1-en-1-yl) -2, 2-dimethyl-N- (4-phenoxyphenyl) cyclopropanecarboxamide or a pharmaceutically acceptable salt thereof containing diphenyl ether, which has insecticidal activity against armyworms.
The invention also aims to provide a preparation method of the compound or the pharmaceutically acceptable salt thereof.
The invention also aims to provide the application of the compound or the pharmaceutically acceptable salt thereof in preparing the pesticide.
The fourth object of the present invention is to provide a pesticidal composition containing the above-mentioned compound or a pharmaceutically acceptable salt thereof as an active ingredient.
One of the objects of the invention is achieved by:
a chrysanthenamide compound containing diphenyl ether or a pharmaceutically acceptable salt thereof, the chemical structural formula of which is shown as the formula (I):
the chemical name is: (Z) -3- (2-chloro-3, 3, 3-trifluoroprop-1-en-1-yl) -2, 2-dimethyl-N- (4-phenoxyphenyl) cyclopropanecarboxamide.
The second purpose of the invention is realized by the following steps:
a preparation method of a chrysanthemum amide compound containing diphenyl ether or a pharmaceutically acceptable salt thereof comprises the steps of dissolving 4-phenoxyaniline in a solvent at the temperature of 20-30 ℃, adding cyhalothrin acid, stirring uniformly, dropwise adding triethylamine, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1-hydroxybenzotriazole, reacting for 2-5 hours, washing and drying to obtain a crude product, dissolving the crude product in a second solvent, and separating on a silica gel chromatographic column to obtain the chrysanthemum amide compound containing diphenyl ether shown in the formula (I).
The reaction formula of the preparation method is as follows:
preferably, the molar ratio of the 4-phenoxyaniline to the cyhalothrin acid is 1: 1-1.2.
Preferably, the molar ratio of 4-phenoxyaniline to triethylamine is 1: 2.
The first solvent is selected from dichloromethane or trichloromethane, preferably dichloromethane.
Preferably, the second solvent is a mixed solution of petroleum ether and dichloromethane, and the volume ratio of the petroleum ether to the dichloromethane is 3: 1-5: 1, preferably 4: 1.
The third purpose of the invention is realized by the following steps:
the chrysanthenamide compound containing diphenyl ether shown in the formula (I) or the pharmaceutically acceptable salt thereof can be used for preparing an insecticide, namely the application in the aspect of preparing the insecticide, and the insecticide has stronger insecticidal activity on armyworms such as corn armyworms and the like.
The fourth purpose of the invention is realized by the following steps:
a pesticide composition comprises effective components of a diphenyl ether-containing chrysanthemic amide compound shown in a formula (I) or a pharmaceutically acceptable salt thereof and one or more pharmaceutically acceptable auxiliary materials.
The pesticide composition contains a diphenyl ether-containing chrysanthemide compound shown in formula (I) or a pharmaceutically acceptable salt thereof, a pharmaceutically acceptable carrier or a combination of the compound or the pharmaceutically acceptable salt thereof as an active ingredient and a pharmaceutical excipient or a diluent.
The various dosage forms of the pesticidal composition may be prepared according to conventional production methods in the field of pesticides, for example, by mixing the active ingredient with one or more carriers and then making the desired dosage form.
The novel chrysanthemum amide compound (Z) -3- (2-chloro-3, 3, 3-trifluoroprop-1-en-1-yl) -2, 2-dimethyl-N- (4-phenoxyphenyl) cyclopropanecarboxamide containing diphenyl ether is synthesized by adopting a specific preparation method, the synthesis method is simple, the conditions are mild, the cost is low, the compound has certain bioactivity on corn armyworm and the like, when the dosage is 500 mg/L, the compound has an inhibition rate on the armyworm of 80 percent, can be used as an effective component of an insecticide or an agricultural chemical composition, provides a new choice for eliminating the corn armyworm, has a potential application prospect, and is expected to solve the problems that the armyworm insecticide in China is imported mainly by foreign countries, the cost, the corn armyworm generates high resistance on the existing insecticide and the like.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
Procedures and methods not described in detail in the following examples are conventional methods well known in the art, and the reagents used in the examples are either analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art.
Example 1
Preparation of (Z) -3- (2-chloro-3, 3, 3-trifluoroprop-1-en-1-yl) -2, 2-dimethyl-N- (4-phenoxyphenyl) cyclopropanecarboxamide:
the chemical structural formula of the compound is as follows:
the reaction formula of the preparation method of the compound is as follows:
specifically, the preparation method comprises the following steps:
at room temperature, 4-phenoxyaniline (200mg, 1.08mmol) and 30m L dichloromethane were added to a reaction flask, while stirring, cyhalothrin acid (314mg, 1.29mmol) was added, and after stirring for 10min, Et was added dropwise3N (218mg, 2.16mmol) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI, 219mg, 1.62mmol), 1-hydroxybenzotriazole (HOBt, 310mg, 1.62mmol) were added portionwise for 3.0h and T L C checked for completion.
The reaction flask was charged with 50m L dichloromethane to dilute the reaction product, then washed three times with 30m L water, washed once with 30m L brine, then dried over anhydrous sodium sulfate as the organic layer and the dichloromethane removed by rotary evaporation to give a crude reaction product, the crude reaction product was dissolved using a mixed solution of petroleum ether and dichloromethane (volume ratio 4: 1) as the solvent and then separated on a silica gel column to give 300mg of the reaction product, m.p.66-68 ℃, with a yield of 68%.
Subjecting the obtained compound to1H NMR and elemental analysis, results are as follows:
1H NMR(400MHz,CDCl3)：7.42(d,J＝8.4Hz,2H),7.28-7.33(m,3H,C6H4),7.16(d,J＝9.4Hz,1H C6H5),7.08(t,J＝7.1Hz,1H,C6H5),6.97-6.99(m,3H,C6H4,CH＝C),2.20(t,J＝8.2Hz,1H,CH),1.80(d,J＝8.2Hz,1H,CH),1.38(s,6H,2CH3)；Anal.calcd forC21H19ClF3NO2:C,61.54；H,4.67；N,3.42；found C 61.50,H 4.63,N 3.40.HR-ESI-MS m/z:409.1053(Calcd for409.1056).
example 2
Insecticidal activity test of (Z) -3- (2-chloro-3, 3, 3-trifluoroprop-1-en-1-yl) -2, 2-dimethyl-N- (4-phenoxyphenyl) cyclopropanecarboxamide
The toxicity of the indoor screening compound to a pest target is evaluated under the test concentration, and the insecticidal activity of the indoor screening compound is evaluated, wherein the target is Mythima seperata, and the test concentration is 500 mg/L.
Test method the compound prepared in example 1 was formulated into a 5.0% EC formulation using an emulsifier (tween-80) and DMF, and diluted with distilled water to prepare a drug solution at a desired concentration for measurement, the amount of the drug solution treated was 10m L, and its insecticidal activity against the armyworm Plutella xylostella was tested by the (leaf, shoot) dipping method in accordance with the national center for the creation of agricultural chemicals standards.
Insect sticking: and (3) fully soaking a proper amount of cut corn leaf sections in the prepared liquid medicine, naturally drying in the shade, putting into a culture dish padded with filter paper, inoculating 15 heads/dishes of larvae of 3-year-old midage of armyworms, covering with a mark, and then putting into an observation room for feeding and observing. The results were examined after 3 d. If the body of the insect is touched with a brush pen lightly, no response is regarded as dead insect.
The common sieve result shows that the target compound has 80 percent of killing rate on armyworm at the concentration of 500 mg/L and has higher insecticidal activity.
Claims (7)
1. A chrysanthenamide compound containing diphenyl ether or a pharmaceutically acceptable salt thereof, wherein the chemical structural formula is shown as formula (I):
2. the method for preparing the compound or the pharmaceutically acceptable salt thereof according to claim 1, characterized in that 4-phenoxyaniline is dissolved in a first solvent at 20-30 ℃, and then added with cyhalothrin acid, stirred uniformly, added with triethylamine dropwise, added with 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1-hydroxybenzotriazole in batches, reacted for 2-5 h, washed and dried to obtain a crude product, then dissolved in a second solvent, and separated on a silica gel chromatographic column to obtain the chrysanthemide compound containing diphenyl ether shown in formula (I);
the first solvent is selected from dichloromethane or trichloromethane; the second solvent is a mixed solution of petroleum ether and dichloromethane, and the volume ratio of the petroleum ether to the dichloromethane is 3: 1-5: 1.
3. The method for preparing a compound or a pharmaceutically acceptable salt thereof according to claim 2, wherein the molar ratio of 4-phenoxyaniline to cyhalofop acid is 1: 1-1.2.
4. The process for preparing a compound according to claim 2 or a pharmaceutically acceptable salt thereof, wherein the molar ratio of 4-phenoxyaniline to triethylamine is 1: 2.
5. The method for preparing a compound or a pharmaceutically acceptable salt thereof according to claim 2, wherein the second solvent is a mixed solution of petroleum ether and dichloromethane, and the volume ratio of petroleum ether to dichloromethane is 4: 1.
6. Use of a compound of claim 1 or a pharmaceutically acceptable salt thereof for the manufacture of a pesticidal medicament.
7. A pesticide composition, which is characterized by comprising the compound or the pharmaceutically acceptable salt thereof as an effective component according to claim 1 and one or more pharmaceutically acceptable auxiliary materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711399976.0A CN108003054B (en) | 2017-12-22 | 2017-12-22 | Chrysamide compound containing diphenyl ether and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711399976.0A CN108003054B (en) | 2017-12-22 | 2017-12-22 | Chrysamide compound containing diphenyl ether and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108003054A CN108003054A (en) | 2018-05-08 |
| CN108003054B true CN108003054B (en) | 2020-07-10 |
Family
ID=62060560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711399976.0A Active CN108003054B (en) | 2017-12-22 | 2017-12-22 | Chrysamide compound containing diphenyl ether and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108003054B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539694A (en) * | 2013-09-12 | 2014-01-29 | 中国农业科学院植物保护研究所 | Polysubstituted chrysanthemum acyl aniline derivative and application thereof |
-
2017
- 2017-12-22 CN CN201711399976.0A patent/CN108003054B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539694A (en) * | 2013-09-12 | 2014-01-29 | 中国农业科学院植物保护研究所 | Polysubstituted chrysanthemum acyl aniline derivative and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108003054A (en) | 2018-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5269609B2 (en) | Pest control agent | |
| CN103265527B (en) | Anthranilamide compound as well as preparation method and application thereof | |
| EP2256112B1 (en) | Anthranilamides, process for the production thereof and pest controllers containing the same | |
| DE60036290T2 (en) | PYRAZOL DERIVATIVES AND METHOD FOR THE PRODUCTION THEREOF AND PESTICIDES CONTAINING THESE AS ACTIVE INGREDIENTS | |
| ES2370534T3 (en) | PEST CONTROL AGENT CONTAINING A NEW PIRIDIL-METHANAMINE DERIVATIVE OR ONE OF ITS SALTS. | |
| KR20200031684A (en) | m-diamide-based compound and its manufacturing method and application | |
| DE102005048072A1 (en) | Thiazoles as fungicides | |
| KR20160074541A (en) | Processes for the preparation of pesticidal compounds | |
| EA015590B1 (en) | Alkoxyalkyl-substituted cyclic ketoenols | |
| CN104540845A (en) | Novel cyclic depsipeptide derivative and pest control agent comprising same | |
| DE60219643T2 (en) | Heterocyclic carboxanides and their use as fungicides | |
| BRPI0512580B1 (en) | n-phenylpyrazole derivatives as pesticides | |
| DE3713774A1 (en) | NEW PYRAZOLE DERIVATIVES, METHOD FOR THEIR PRODUCTION AND FUNGICIDES FOR AGRICULTURE AND GARDENING, WHICH CONTAIN THESE COMPOUNDS | |
| CN103214461A (en) | Quinoline derivative and application thereof | |
| CN110804040B (en) | Preparation method and application of pyrazole oxime compound containing difluoromethyl pyrazole bipyridyl | |
| CN110845478B (en) | Preparation and use of pyrazole formyloxime derivatives containing 1-substituted pyridyl-3-trifluoromethylpyrazole units | |
| CN108003054B (en) | Chrysamide compound containing diphenyl ether and preparation method and application thereof | |
| EP0065483B1 (en) | Acyl aniline and acylnaphthyl amine microbicides, processes for preparing them and their use | |
| DE3139298C2 (en) | ||
| DE2902832A1 (en) | MICROBICIDAL AGENTS | |
| DE2902861A1 (en) | MICROBICIDAL AGENTS | |
| CN108503599B (en) | Pyrazinamide compounds, and preparation method and application thereof | |
| JP4532340B2 (en) | Sulfonylamidine derivatives effective for pest control | |
| CN108503559B (en) | Synthesis and application of capsaicin halogenated derivative | |
| CN108148049B (en) | Preparation method and application of 5-pyrazole amide compound with triazinone structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Ji Yang Inventor after: Li Wan Inventor after: Yang Zihui Inventor after: Yi Shuai Inventor after: Wu Shijie Inventor before: Li Wan Inventor before: Yang Zihui Inventor before: Yi Shuai Inventor before: Wu Shijie |
|
| CB03 | Change of inventor or designer information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200611 Address after: 044100 Shanxi city of Yuncheng Province Linyi County Industrial Park Applicant after: SHANXI LVHAI AGROCHEMICAL Co.,Ltd. Address before: 071002, Hebei, No. 54 East Road, Hebei University, 180 Applicant before: Heibei University |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |