CN108003054A - A kind of chrysanthemum amide compound containing diphenyl ether and preparation method and application - Google Patents
A kind of chrysanthemum amide compound containing diphenyl ether and preparation method and application Download PDFInfo
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- CN108003054A CN108003054A CN201711399976.0A CN201711399976A CN108003054A CN 108003054 A CN108003054 A CN 108003054A CN 201711399976 A CN201711399976 A CN 201711399976A CN 108003054 A CN108003054 A CN 108003054A
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- 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
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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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- 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
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- 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
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- 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
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- 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)
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- General Health & Medical Sciences (AREA)
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- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of chrysanthemum amide compound containing diphenyl ether and preparation method and application, the compound is (Z) 3 (2 chlorine 3,3,3 trifluoropropyl, 1 alkene, 1 base) 2,2 dimethyl N (4 Phenoxyphenyl) cyclopropane carboxamide, and the new chrysanthemum amide compound containing diphenyl ether has been synthesized using specific preparation method.The compound synthesis method of the present invention is simple, mild condition, it is of low cost, the compound has certain bioactivity to maize army worm etc., when its dosage is 500mg/L, the inhibiting rate to mythimna separata is 80%, it can be as the active ingredient of insecticide or composition pesticide, new selection is provided for insecticide, there is potential application prospect.
Description
Technical field
The present invention relates to a kind of preparation method and application of chrysanthemum amide compound, concretely relates to one kind and contains diphenyl ether
Chrysanthemum amide compound preparation method and application.
Background technology
Mythimna separata is the common insect pest of corn field, when corn enters three leaves to the jointing stage, and the stage of mythimna separata breeding, at present
The country has had the sprayings such as 5% Beta-cypermethrin EC, 50% imidacloprid suspending agent to prevent mythimna separata.
Chrysanthemum acidamide compounds have extensive desinsection, bactericidal activity.Sun Nabo etc. [CN1974561] reports compound
A and B, for trying to have mythimna separata certain preventive effect under concentration.
[organic chemistry, 2010,30 (5) such as Zhao Jinhao:719-725] report N- (substituted thiazole -2- bases)-chrysanthemum acidamide
Compound C has inhibitory activity in 600mg/L to diamondback moth；Zhang Landong is when the compound D of report is in 500mg/L, to diamondback moth
There is certain insecticidal activity, also there is certain preventive effect to aphid.
However, the insecticide due to frequently using these kinds, dosage are continuously increased, times for spraying gradually increases,
Maize army worm has produced resistance to them, causes crops Severe Reduction, and the economic benefit to peasant brings heavy losses, and
And the quality safety on agricultural product and the next immeasurable influence of the safety belt of ecological environment.Therefore, it is efficiently and low there is an urgent need for developing
The mythimna separate compound of resistance.
The content of the invention
An object of the present invention is to provide a kind of chrysanthemum amide compound (Z) -3- (chloro- 3,3,3- tri- of 2- containing diphenyl ether
Fluorine propyl- 1- alkene -1- bases) -2,2- dimethyl-N -s (4- Phenoxyphenyls) cyclopropane carboxamide or it is pharmaceutically acceptable
Salt, it has insecticidal activity to mythimna separata.
The second object of the present invention is to provide the preparation method of above-claimed cpd or its pharmaceutically acceptable salt.
The third object of the present invention be to provide above-claimed cpd or its pharmaceutically acceptable salt is preparing insecticidal materials
The application of aspect.
The fourth object of the present invention be to provide more than one state compound or its pharmaceutically acceptable salt for effectively into
The composition pesticide divided.
What an object of the present invention was realized in：
Chrysanthemum amide compound containing diphenyl ether or its pharmaceutically acceptable salt, shown in its chemical structural formula such as formula (I)：
Chemical name is：(Z) -3- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -2,2- dimethyl-N -s (4- phenoxy groups
Phenyl) cyclopropane carboxamide.
What the second object of the present invention was realized in：
The preparation method of chrysanthemum amide compound containing diphenyl ether or its pharmaceutically acceptable salt, it is at 20~30 DEG C
Under, after 4- phenoxybenzamines are dissolved in solvent, time acid is added, after stirring evenly, triethylamine is added dropwise, and add 1- (3- diformazans
Aminopropyl) -3- ethyl-carbodiimide hydrochlorides and I-hydroxybenzotriazole, after reacting 2~5h, after washed, dry, obtain
Crude product, is then dissolved in the second solvent, after being separated on silica gel column chromatography by crude product, you can obtains shown in formula (I)
Chrysanthemum amide compound containing diphenyl ether.
The reaction equation of the preparation method is：
Preferably, the molar ratio of 4- phenoxybenzamines and time acid is 1: 1~1.2.
Preferably, the molar ratio of 4- phenoxybenzamines and triethylamine is 1: 2.
First solvent is selected from dichloromethane or chloroform, preferably dichloromethane.
Preferably, second solvent is the body of petroleum ether and the mixed solution of dichloromethane, petroleum ether and dichloromethane
Product is than being 3: 1~5: 1, preferably 4: 1.
What the third object of the present invention was realized in：
Chrysanthemum amide compound containing diphenyl ether shown in formula (I) or its pharmaceutically acceptable salt can be used for preparing desinsection
Medicine, i.e., the application in terms of insecticidal materials are prepared, the insecticidal materials live mythimna separata such as maize army worm etc. with stronger desinsection
Property.
What the fourth object of the present invention was realized in：
A kind of composition pesticide, its active ingredient are the chrysanthemum amide compound or its medicine containing diphenyl ether shown in formula (I)
Acceptable salt on, and one or more pharmaceutically acceptable auxiliary materials.
The composition pesticide contains chrysanthemum amide compound containing diphenyl ether shown in formula (I) or it is pharmaceutically acceptable
The carrier permitted on salt, pharmaceutics or using the compound or its pharmaceutically acceptable salt as the mixed with medicinal tax of active ingredient
Shape agent or the combination of diluent.
The various formulations of the composition pesticide can be prepared according to the conventional production process of pesticide field, such as by active ingredient
Mixed with one or more carriers, required formulation is then made.
The present invention has synthesized new chrysanthemum amide compound (Z) -3- (2- containing diphenyl ether by using specific preparation method
Chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases) -2,2- dimethyl-N -s (4- Phenoxyphenyls) cyclopropane carboxamide, its synthetic method
Simply, mild condition, of low cost, which has certain bioactivity to maize army worm etc., when its dosage is
During 500mg/L, the inhibiting rate to mythimna separata is 80%, can be as the active ingredient of insecticide or composition pesticide, to eliminate corn
Mythimna separata provides new selection, has potential application prospect, is expected to solution China's mythimna separata insecticide and relies primarily on external import, into
The problems such as this high and maize army worm produces resistance to existing insecticide.
Embodiment
With reference to embodiment, the present invention is further elaborated, and following embodiments are only as explanation, not with any
Mode limits the scope of the invention.
The process and method not being described in detail in the following embodiments are conventional methods well known in the art, institute in embodiment
It is to analyze pure or chemical pure and commercially available or prepared by method well known within the skill of those ordinarily skilled with reagent.
Embodiment 1
(Z) -3- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -2,2- dimethyl-N -s (4- Phenoxyphenyls) cyclopropane
The preparation of formamide：
The chemical structural formula of the compound is：
The reaction equation of the compounds process for production thereof is：
Specifically, its preparation method is as follows：
At normal temperatures, 4- phenoxybenzamines (200mg, 1.08mmol) and 30mL dichloromethane are added in reaction bulb,
Under stirring condition, time acid (314mg, 1.29mmol) is added, after stirring 10min, Et is added dropwise3N (218mg, 2.16mmol), and
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDCI, 219mg, 1.62mmol), 1- hydroxy benzenes is added portionwise
And triazole (HOBt, 310mg, 1.62mmol), 3.0h is reacted, the reaction was complete for TLC detections.
50mL dichloromethane is added into reaction bulb, to be diluted to reaction product, is then washed three times using 30mL,
Washed one time with 30mL salt, dried afterwards using organic layer anhydrous sodium sulfate again, and dichloromethane is removed with revolving, reacted
Product crude product.Use the mixed solution of petroleum ether and dichloromethane (volume ratio=4: 1) thick as solvent, dissolving reaction product
Product, are separated on silica gel column chromatography afterwards, obtain reaction product 300mg, m.p.66-68 DEG C, yield 68%.
Gained compound is carried out1H NMR and elemental analysis, it is as a result as follows：
1H NMR(400MHz,CDCl3)δ：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 for
C21H19ClF3NO2: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 for 409.1056).
Embodiment 2
(Z) -3- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -2,2- dimethyl-N -s (4- Phenoxyphenyls) cyclopropane
Formamide insecticidal activity is tested
General sieve compound evaluates its insecticidal activity to the virulence of worm target under for examination concentration indoors.Target is mythimna separata
(Mythima separata)；Experimental concentration：Screening concentration is 500mg/L.
Test method：Compound prepared by embodiment 1 is configured to 5.0%EC systems with emulsifying agent (Tween-80) and DMF
Agent, adds distilled water dilution to be configured to measure required concentration liquid.Chemicals treatment liquid volume 10mL.Reference《National south pesticide wound
Give birth to mark quasi-ordering in center processed》, its desinsection to mythimna separata Plutella xylostella is tested using (blade, seedling) infusion process
Activity.
Mythimna separata：Dry in the shade naturally after the maize leaves section sheared in right amount is fully infiltrated in the liquid prepared, be put into and be lined with filter
In the culture dish of paper, mythimna separata 3 age mid-term larva, 15/ware is connect, capping mark is placed on observation indoor feeding and observation.Examined after 3d
Come to an end fruit.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.
General sieve has higher the result shows that target compound is 80% to the eradicative rate of mythimna separata under the concentration of 500mg/L
Insecticidal activity.
Claims (9)
1. a kind of chrysanthemum amide compound containing diphenyl ether or its pharmaceutically acceptable salt, it is characterised in that chemical structural formula
Such as formula（I）It is shown：
。
2. the preparation method of compound described in claim 1 or its pharmaceutically acceptable salt, it is characterised in that 20 ~ 30
At DEG C, after 4- phenoxybenzamines are dissolved in the first solvent, time acid is added, after stirring evenly, triethylamine is added dropwise, and be added portionwise
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and I-hydroxybenzotriazole, it is washed, dry after reacting 2 ~ 5h
After dry, crude product is obtained, then crude product is dissolved in the second solvent, after being separated on silica gel column chromatography, you can obtain formula
（I）The shown chrysanthemum amide compound containing diphenyl ether.
3. compound or the preparation method of its pharmaceutically acceptable salt according to claim 2, it is characterised in that 4- benzene
The molar ratio of epoxide aniline and time acid is 1: 1 ~ 1.2.
4. compound or the preparation method of its pharmaceutically acceptable salt according to claim 2, it is characterised in that 4- benzene
The molar ratio of epoxide aniline and triethylamine is 1: 2.
5. compound or the preparation method of its pharmaceutically acceptable salt according to claim 2, it is characterised in that described
First solvent is selected from dichloromethane or chloroform.
6. compound or the preparation method of its pharmaceutically acceptable salt according to claim 2, it is characterised in that described
Second solvent is the mixed solution of petroleum ether and dichloromethane, and the volume ratio of petroleum ether and dichloromethane is 3: 1 ~ 5: 1.
7. compound or the preparation method of its pharmaceutically acceptable salt according to claim 6, it is characterised in that described
Second solvent is the mixed solution of petroleum ether and dichloromethane, and the volume ratio of petroleum ether and dichloromethane is 4: 1.
8. compound any one of claim 1 ~ 7 or its pharmaceutically acceptable salt in terms of insecticidal materials are prepared
Using.
9. a kind of composition pesticide, it is characterised in that it is compound any one of claim 1 ~ 7 that it, which includes active ingredient,
Or its pharmaceutically acceptable salt, 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 |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711399976.0A CN108003054B (en) | 2017-12-22 | 2017-12-22 | Chrysamide compound containing diphenyl ether and preparation method and application thereof |
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| CN108003054A true CN108003054A (en) | 2018-05-08 |
| CN108003054B CN108003054B (en) | 2020-07-10 |
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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 |
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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 |
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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 |
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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 |
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