CN104592210B - Pyrazol acid amide compounds and its application - Google Patents
Pyrazol acid amide compounds and its application Download PDFInfo
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- CN104592210B CN104592210B CN201510059961.4A CN201510059961A CN104592210B CN 104592210 B CN104592210 B CN 104592210B CN 201510059961 A CN201510059961 A CN 201510059961A CN 104592210 B CN104592210 B CN 104592210B
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- acid amide
- amide compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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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)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a kind of pyrazol acid amide compounds and its application, are related to disinfectant use in agriculture field.As shown in logical formula (I), in formula, X is oxygen atom, sulphur atom to the compound structure；R1For hydrogen atom, halogen, the alkyl of C1 C4 or alkoxyl, nitro.R2For hydrogen atom, halogen atom, the alkyl of C1 C4 or alkoxyl, nitro.The compound structure is simple, and there is preferable inhibitory activity to the various plants pathogenic fungi such as southern corn leaf blight and fusarium graminearum, can be used for preventing and treating plant pathogenic fungi, is its new application in pesticide field.
Description
Technical field
The present invention relates to disinfectant use in agriculture field, more particularly to pyrazol acid amide compounds and its as disinfectant use in agriculture
Application.
Background technology
Pesticide resistance is problems faced of having in control of agricultural pest all the time.As pesticide is using one section
After time, insect or pathogen can produce resistance to which, and especially for the strong pesticide of some targets, its resistance is produced more
Hurry up.Therefore, in the face of this problem, need constantly to invent new and improved tool parasite killing or sterilization in control of agricultural pest
The compound of activity and compositionss.Meanwhile, the day with people's needs growing to agricultural and animal products etc. and to environmental conservation
Benefit is paid attention to, and also has always a demand for that use cost is lower, environment amenable novel agrochemical.
Since being succeeded in developing from first acid amide fungicides carboxin in 1966 by Chemtura Corporation, such compound is made
It is that antibacterial uses existing more than 40 years history, its chemical constitution is as follows：
In order to delay the Drug resistance of this series bactericidal agent, people studying the surrogate-data technique of this kind of medicament always, constantly there is knot
Structure is novel, model of action is unique, performance is more preferable, efficient to harmful organism, safe, degradable in the environment to non-target organism and
Degraded is produced solution thing and the kind of human health and ecological environment security is reported.
Up to the present, the report that pyrazol acid amide compounds are used as disinfectant use in agriculture yet there are no.
Content of the invention
Object of the present invention is to provide pyrazol acid amide compounds, it can be as disinfectant use in agriculture in control agricultural
Application in phytopathogen.
Technical scheme is as follows：
The invention provides a kind of pyrazol acid amide compounds, its general structure is as follows：
In logical formula (I), X is oxygen atom or sulphur atom；
R1For hydrogen atom, halogen atom, the alkyl of C1-C4 or alkoxyl, nitro；
R2For hydrogen atom, halogen atom, the alkyl of C1-C4 or alkoxyl, nitro.
Preferably, in the logical formula (I),
X is oxygen atom or sulphur atom；
R1For hydrogen atom, chlorine atom, bromine atoms, methyl, methoxyl group or nitro；
R2For hydrogen atom, chlorine atom, bromine atoms, methyl, methoxyl group or nitro.
Formula is that the key reaction equation in the preparation of compounds of (I) is：
X, R in formula1、R2Implication ibid.
Its preparation method is：General formula III compound and thionyl chloride are heated to 80 DEG C of backflow 1-3 hours, and reaction obtains formula
II compound.Pyrazoles and dichloromethane are mixed, catalyst of triethylamine or pyridine is added, under stirring at room temperature, is added dropwise over leading to
Formula II compound reacts 2-4 hours at 30-50 DEG C, and the mixture of reaction is washed to neutrality, cools down after solid is separated out,
Filter, washing, with dimethyl sulfoxide and water recrystallization, obtains cream-white crystals product, as the logical formula (I) compound pyrazoles acyl of the present invention
Aminated compoundss.
The pyrazol acid amide compounds of the present invention have higher inhibitory activity to various plants pathogen.Therefore, this
Bright also include that logical formula (I) compound is used for the purposes for controlling phytopathogen.
Present invention additionally comprises to lead to formula (I) compound as the bactericidal composition of active component.Living in the bactericidal composition
The weight percentage of property component is between 1-10%.Also include agricultural, forestry, acceptable in health in the bactericidal composition
Carrier.
The compositionss of the present invention can be applied in the form of preparation.Logical formula (I) compound dissolves as active component or disperses
In carrier or be configured to preparation so as to use as antibacterial when more readily dispersible.For example：These chemicals can be made into
Wettable powder or suspending agent.In these compositionss, a kind of liquid or solid carrier is at least added, and when needed can be with
Add appropriate surfactant.
The bactericidal composition of the present invention is imposed on described pathogen or its somatomedin.For some are applied, for example
One or more other antibacterial, Insecticides (tech) ＆ Herbicides (tech), plant agriculturally can be being added in the bactericidal composition of the present invention
Growth regulator or fertilizer etc., thus can produce additional advantage and effect.
The compound structure of the logical formula (I) of the present invention is simple, novel, it is easy to synthesize, low cost, plant pathogenic fungi is had compared with
Good prevention effect.Report is had no in the plant pathogenic fungi inhibitor being currently known.
Specific embodiment
Embodiment in below in conjunction with the present invention, to the embodiment of the present invention in technical scheme carry out clear, complete
Description, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiment.It is based on this
Embodiment in bright, the every other enforcement obtained under the premise of creative work is not made by those of ordinary skill in the art
Example, belongs to the scope of protection of the invention.
Embodiment 1：
Compound(C8H6N2OS preparation)
(1) 0.01mol thiophene -2-carboxylic acids and 15mL thionyl chlorides are added in 50mL three-necked bottles, are heated to 80 DEG C of backflows 2
Hour, vacuum distillation removes excessive thionyl chloride, till no liquid flows out, is cooled to room temperature, obtains final product thiophene -2- formyls
Chlorine.
(2) 0.01mol pyrazoles and 10mL dichloromethane are added in 50mL three-necked bottles, adds 3mL triethylamines, stir in room temperature
Mix down, be added dropwise over the thiophene -2- formyl chlorides of brand-new.After completion of dropping, at 30-50 DEG C, continue reaction 3 hours, reaction is completed
Afterwards, successively with 10% hydrochloric acid, 10%NaOH and distilled water wash reactant mixture to neutrality, place in 2-6 DEG C of refrigerator, until
After solid is separated out, filter, washing, with dimethyl sulfoxide and water recrystallization, obtains cream-white crystals product, and yield is 54%.Product
Spectral data is as follows：
1H NMR(300MHz,DMSO-d6)(ppm):6.71 (1H, s), 7.30 (1H, t, J=4.5Hz), 8.02 (1H,
S), 8.19 (1H, d, J=5.1Hz), 8.38 (1H, d, J=3.0Hz), 8.57 (1H, d, J=2.7Hz).
13C NMR(300MHz,DMSO-d6)(ppm):110.81(1C),128.31(1C),130.68(1C),132.15
(1C),139.06(1C),139.34(1C),145.26(1C),158.62(1C).
Embodiment 2：
Compound(C8H5N2O2Br preparation)
(1) 0.01mol furan -2- formic acid and 15mL thionyl chlorides are added in 50mL three-necked bottles, are heated to 80 DEG C of backflows 2
Hour, vacuum distillation removes excessive thionyl chloride, till no liquid flows out, is cooled to room temperature, obtains final product furan -2- formyls
Chlorine.
(2) 0.01mol 4- bromines pyrazoles and 10mL dichloromethane are added in 50mL three-necked bottles, adds 3mL pyridines, in room
Under temperature stirring, the furan -2- formyl chlorides of brand-new are added dropwise over.After completion of dropping, continue reaction 2 hours, reaction at 30-50 DEG C
After the completion of, successively with 10% hydrochloric acid, 10%NaOH solution and distilled water wash reactant mixture to neutrality, in 2-6 DEG C of refrigerator
Place, after solid is separated out, filter, washing, with dimethyl sulfoxide and water recrystallization, obtains White crystalline product, and yield is 55%.
The spectral data of product is as follows：
1H NMR(300MHz,DMSO-d6)(ppm):6.84 (1H, dd, J=1.2Hz, J=1.5Hz), 7.97 (1H, d, J
=3.6Hz), 8.12 (1H, s), 8.23 (1H, s), 8.81 (1H, s)；
13C NMR(300MHz,DMSO-d6)(ppm):98.61(1C),113.13(1C),125.02(1C),130.46
(1C),143.21(1C),145.17(1C),150.01(1C),153.13(1C).
Analyzed by above-mentioned spectral data, it may be determined that the structural formula of obtained product is
Embodiment 3：
Compound(C8H5N2OSBr preparation)
(1) 0.01mol thiophene -2-carboxylic acids and 15mL thionyl chlorides are added in 50mL three-necked bottles, are heated to 80 DEG C of backflows 2
Hour, vacuum distillation removes excessive thionyl chloride, till no liquid flows out, is cooled to room temperature, obtains final product thiophene -2- formyls
Chlorine.
(2) 0.01mol 4- bromines pyrazoles and 10mL dichloromethane are added in 50mL three-necked bottles, adds 3mL triethylamines,
It is stirred at room temperature down, is added dropwise over the thiophene -2- formyl chlorides of brand-new.After completion of dropping, continue reaction 4 hours at 30-50 DEG C, instead
After the completion of answering, put in 2-6 DEG C of refrigerator to neutrality with 10% hydrochloric acid, 10%NaOH and distilled water wash reactant mixture successively
Put, after solid is separated out, filter, washing, with dimethyl sulfoxide and water recrystallization, obtains cream-white crystals product, and yield is 67%.
The spectral data of product is as follows：
1H NMR(300MHz,DMSO-d6)(ppm):7.32 (1H, t, J=4.8Hz), 8.16 (1H, s), 8.22 (1H, d,
), J=4.8Hz 8.36 (1H, d, J=3.9Hz), 8.83 (1H, s)；
13C NMR(300MHz,DMSO-d6)(ppm):99.58(1C),128.45(1C),130.80(1C),131.24
(1C),139.44(1C),139.67(1C),145.35(1C),157.71(1C).
Embodiment 4：
Antibacterial Activity of the pyrazol acid amide compounds to plant pathogenic fungi
1st, test plant pathogenic fungi
Rhizoctonia solani Kuhn, fusarium graminearum, southern corn leaf blight, Sclerotinia sclerotiorum, botrytis cinerea, Ma Ling
Potato late disease bacteria, Colletotrichumlagenarium, fruit white rot of grape bacterium, citrus common green mold bacterium and Botryosphaeria berengeriana f. sp.
2nd, experimental technique
Test compound is dissolved in dimethyl sulfoxide, is then added in the tap water containing 0.1% tween 80, mixing is
The test solution of 200mg/L is made into after even.This solution is added in sterilized PDA culture medium, while add concentration being
The streptomycin of 50mg/L.With the corresponding solution without test compound as blank, the uniform pastille flat board of thickness is made standby
With in triplicate.Ф 5mm well-growns, the uniform bacteria cake of pollution-free, growing way are chosen with sterilized card punch, in aseptic bar
The center (one bacteria cake of each plating) of toxic culture medium and control medium is accessed under part, is trained under 28 DEG C of constant temperatures
Support.When the colony diameter of blank grows to 50mm or so, using the diameter of crossing method measurement bacterium colony, which is taken average
Value, calculates relative bacteriostasis rate with following equation：
3rd, experimental result
Pyrazol acid amide compounds are to the Antibacterial Activity result of plant pathogenic fungi as shown in table 1, table 2 and table 3.
Inhibitory activity of 1 embodiment of table, 1 compound in 200mg/L to plant pathogenic fungi
| Strain | Suppression ratio (%) | Strain | Suppression ratio (%) |
| Fusarium graminearum | 92.1 | Phytophthora infestans | 86.2 |
| Southern corn leaf blight | 95.8 | Colletotrichumlagenarium | 57.5 |
| Rhizoctonia solani Kuhn | 80.6 | Fruit white rot of grape bacterium | 52.4 |
| Botrytis cinerea | 87.3 | Citrus common green mold bacterium | 67.7 |
| Sclerotinia sclerotiorum | 90.9 | Botryosphaeria berengeriana f. sp | 63.2 |
As known from Table 1,1 compound of embodiment has very to fusarium graminearum, southern corn leaf blight and Sclerotinia sclerotiorum
Good inhibition；There is preferable inhibition to Rhizoctonia solani Kuhn, botrytis cinerea and phytophthora infestans.
Inhibitory activity of 2 embodiment of table, 2 compound in 200mg/L to plant pathogenic fungi
| Strain | Suppression ratio (%) | Strain | Suppression ratio (%) |
| Fusarium graminearum | 93.7 | Phytophthora infestans | 61.6 |
| Southern corn leaf blight | 90.4 | Colletotrichumlagenarium | 83.3 |
| Rhizoctonia solani Kuhn | 81.5 | Fruit white rot of grape bacterium | 63.9 |
| Botrytis cinerea | 91.8 | Citrus common green mold bacterium | 72.6 |
| Sclerotinia sclerotiorum | 85.1 | Botryosphaeria berengeriana f. sp | 74.4 |
As known from Table 2,2 compound of embodiment has very to fusarium graminearum, southern corn leaf blight and botrytis cinerea
Good inhibition；There is preferable inhibition to Rhizoctonia solani Kuhn, Sclerotinia sclerotiorum and Colletotrichumlagenarium.
Inhibitory activity of 3 embodiment of table, 3 compound in 200mg/L to plant pathogenic fungi
| Strain | Suppression ratio (%) | Strain | Suppression ratio (%) |
| Fusarium graminearum | 92.9 | Phytophthora infestans | 72.0 |
| Southern corn leaf blight | 85.7 | Colletotrichumlagenarium | 62.4 |
| Rhizoctonia solani Kuhn | 91.5 | Fruit white rot of grape bacterium | 82.1 |
| Botrytis cinerea | 96.3 | Citrus common green mold bacterium | 65.2 |
| Sclerotinia sclerotiorum | 83.6 | Botryosphaeria berengeriana f. sp | 64.8 |
As known from Table 3,3 compound of embodiment has very to fusarium graminearum, Rhizoctonia solani Kuhn and botrytis cinerea
Good inhibition；There is preferable inhibition to southern corn leaf blight, Sclerotinia sclerotiorum and fruit white rot of grape bacterium.
It can be that professional and technical personnel in the field realize or use that above-mentioned embodiment is intended to illustrate the present invention, to above-mentioned
Embodiment is modified, therefore the present invention is included but is not limited to
Above-mentioned embodiment, any meet the claims or description description, meet with principles disclosed herein and novelty,
The method of inventive features, technique, product, each fall within protection scope of the present invention.
Claims (5)
1. a kind of pyrazol acid amide compounds, it is characterised in that the structure of the compound is as shown in logical formula (I)：
In formula,
X independently is oxygen atom or sulphur atom；
R1For hydrogen atom；R2For bromine atoms.
2. application of the pyrazol acid amide compounds as claimed in claim 1 in control fungal diseases of plants.
3. application according to claim 2, it is characterised in that described pyrazol acid amide compounds are in control rice banded sclerotial blight
Pathogenic bacteria, fusarium graminearum, southern corn leaf blight, Sclerotinia sclerotiorum, botrytis cinerea, phytophthora infestans, melon
Application on anthrax bacteria, fruit white rot of grape bacterium, citrus common green mold bacterium and Botryosphaeria berengeriana f. sp.
4. a kind of bactericidal composition containing compound described in claim 1, it is characterised in that the bactericidal composition is with described
Compound of Formula I is active component, also includes acceptable carrier in agricultural, forestry or health, active component in compositionss
Weight percentage is 1-10%.
5. a kind of suppress plant pathogenic fungi method, it is characterised in that bactericidal composition described in claim 4 is imposed on needs
On the medium of the pathogenic fungi of control or its growth.
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| CN112174948A (en) * | 2019-07-01 | 2021-01-05 | 南京农业大学 | Novel thiazoline-tryptamine amide compound and application thereof as agricultural bactericide |
| CN115010641B (en) * | 2022-07-18 | 2023-04-11 | 青岛农业大学 | Beta-substituted pyrrole derivative, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0206523B1 (en) * | 1985-06-18 | 1991-12-04 | Imperial Chemical Industries Plc | Heterocyclic compounds as fungicides |
| JPS63119463A (en) * | 1986-11-06 | 1988-05-24 | Nissan Chem Ind Ltd | Amide-substituted acetonitrile derivative, production thereof and agricultural and horticultural fungicide containing the same |
| AU1988692A (en) * | 1991-04-24 | 1992-12-21 | E.I. Du Pont De Nemours And Company | Fungicidal pyrazoles, pyrazolines and tetrahydropyridazines |
| EP2373313A4 (en) * | 2008-11-26 | 2012-06-13 | Miikana Therapeutics Inc | Substituted pyrazole compounds |
| TWI654180B (en) * | 2012-06-29 | 2019-03-21 | 美商艾佛艾姆希公司 | Fungicidal heterocyclic carboxamide |
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