CN103724292A - N-alcoxyl (sulfur) alkyl benzoheterocycle derivative and application thereof - Google Patents
N-alcoxyl (sulfur) alkyl benzoheterocycle derivative and application thereof Download PDFInfo
- Publication number
- CN103724292A CN103724292A CN201310670142.4A CN201310670142A CN103724292A CN 103724292 A CN103724292 A CN 103724292A CN 201310670142 A CN201310670142 A CN 201310670142A CN 103724292 A CN103724292 A CN 103724292A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- halogen
- compound
- group
- cyano group
- 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.)
- Granted
Links
- 0 **C(*)NC1=Nc2ccccc2*1 Chemical compound **C(*)NC1=Nc2ccccc2*1 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/82—Nitrogen 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
Abstract
The invention relates to an N-alcoxyl (sulfur) alkyl benzoheterocycle derivative and application thereof to being used as a farm-oriented bactericide, and belongs to the technical field of pesticides. The N-alcoxyl (sulfur) alkyl benzoheterocycle derivative, provided by the invention, adopts the structure show in the general formula I in the Specification, in the formula, R1, R2, R3, m, X and Y have the implication described in the Specification.
Description
Technical field
The invention belongs to disinfectant use in agriculture field.Be specifically related to a kind of N-alcoxyl (sulphur) alkyl Benzheterocyclic derivatives and uses thereof.
Background technology
N-alcoxyl provided by the invention (sulphur) alkyl Benzheterocyclic derivatives novel structure, preparation method is simple, and the mode of action is various.Compound provided by the invention both can stop the invasion of pathogenic bacteria to plant by melanic synthesizing of Antifungi, thereby reached the effect of indirect control, also various plants pathogenic fungi was shown to strong direct sterilization effect simultaneously.
Summary of the invention
The object of the invention is to N-alcoxyl (sulphur) the alkyl Benzheterocyclic derivatives of developing a kind of novel structure and can effectively controlling plant pathogenic fungi.Benzheterocyclic derivatives (as benzothiazole, benzoxazoles and benzoglyoxaline etc.) is the very important compound of a class in pesticide field, and many pesticide species are as all contained benzheterocycle in the structures such as derosal, thiabendazole, F-1991 and tricyclazole.Although carry out the existing history for many years of research that composition optimizes obtains bacteriostatic activity compound on benzheterocycle, and the current study hotspot that is still, in document, do not see the research report of introducing N-alcoxyl (sulphur) alkyl 2 of benzheterocycles.
By the amino benzheterocycle replacing of 2-, aldehyde, alcohol (or phenol), under acidic conditions, in room temperature, next step generates N-alcoxyl (sulphur) alkyl Benzheterocyclic derivatives to compound provided by the present invention.The method mild condition, cheap, yield is high, aftertreatment is simple.
N-alcoxyl provided by the invention (sulphur) the alkyl Benzheterocyclic derivatives mode of action is various.Both can reach by check melanin biosynthesizing the effect of indirect diseases prevention; also the various plants pathogenic fungies such as botrytis cinerea, fusarium graminearum, apple anthrax bacteria, phytophthora infestans, verticillium dahliae, rice blast, bacterium of downy mildew of cucumber and cotton-wilt fusarium are had to strong inhibition active, to had concurrently protection and result for the treatment of by the caused Plant diseases of above-mentioned fungal infection simultaneously.
Technical scheme of the present invention is as follows:
N-alcoxyl alkane (virtue) base Benzheterocyclic derivatives, as shown in general formula I:
In formula:
R
1be selected from hydrogen; C
1～C
8alkyl; Or optionally by cyano group, halogen, phenyl ring, C
1～C
4alkoxyl group or C
1～C
4the C that alkylthio replaces
1～C
8alkyl, C
3～C
8alkenyl or C
3～C
8alkynyl;
m=0～4；
X is selected from S, O or NH;
Y is selected from O or S;
R
2be selected from hydrogen; C
1～C
8alkyl; Or optionally by cyano group, halogen, phenyl ring, C
1～C
4alkoxyl group or C
1～C
4the C that alkylthio replaces
1～C
8alkyl, C
3～C
8alkenyl or C
3～C
8alkynyl; Or optionally by cyano group, halogen, C
1～C
4alkoxyl group or C
1～C
4the C that alkylthio replaces
3～C
8alkenyl or C
3～C
8alkynyl;
R
3be selected from C
1～C
8alkyl; Or optionally by cyano group, halogen, phenyl ring, C
1～C
4alkoxyl group or C
1～C
4the C that alkylthio replaces
1～C
8alkyl, C
3～C
8alkenyl or C
3～C
8alkynyl; Phenyl or by being selected from the optional phenyl replacing of 1～3 following substituting group: halogen, C
1～C
8alkyl, C
3～C
8cycloalkyl, hydroxyl, C
1～C
4alkoxyl group, C
1～C
4haloalkyl, C
1～C
4halogenated alkoxy, C
1～C
4halogenated alkylthio, C
1～C
4halogenated alkyl sulfonyl, carboxyl, nitro, cyano group, phenyl, phenoxy group, benzoyl.
The present invention more preferably compound is in general formula I:
R
1be selected from C
1～C
4alkyl;
m=1～2；
X is selected from S or O;
Y is selected from O;
R
2be selected from C
1～C
4alkyl;
R
3be selected from C
1～C
4alkyl.
Further compound is in general formula I:
R
1be selected from methyl, ethyl;
m=1；
X is selected from S;
Y is selected from O;
R
2be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-;
R
3be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-.
Compounds process for production thereof provided by the invention is suc as formula shown in II:
R in formula II
1, R
2, R
3, m, X, the implication of Y is identical with formula I.
Reaction is carried out in suitable solvent, the optional tetrahydrofuran (THF) freely of suitable solvent, acetonitrile, methylene dichloride, toluene, dimethylbenzene, benzene, DMF or methyl-sulphoxide; Especially, with under normal temperature being the alcohol (or mercaptan) of liquid during as reactant, also can add excessive this alcohol (or mercaptan) as reaction solvent.
Suitable acid is optional from example hydrochloric acid, sulfuric acid, acetic acid or formic acid etc.
Temperature of reaction can, in room temperature between solvent boiling point temperature, be generally 20～100 ℃.
Reaction times is 10 minutes to 2 hours, is generally 30 minutes to 1 hour.
Reaction intermediate therefor II, III, IV all can commercially obtain.
This preparation method's concrete steps are as follows:
Take the amino benzheterocycle of 1mmol2-, 1mmol aldehyde, 1mmol alcohol (or mercaptan) is in 100mL pear shape bottle, add 5mL tetrahydrofuran (THF), stirring at room is dissolved, add again 0.2mL formic acid (or acetic acid, concentrated hydrochloric acid, the vitriol oil) to continue under room temperature and stir, after having reacted, add saturated sodium bicarbonate solution 20mL, ethyl acetate 20mL, continues to stir 10 minutes, and mixing solutions is proceeded in separating funnel, aqueous phase discarded, organic phase is through anhydrous sodium sulfate drying, and concentrating under reduced pressure is sloughed solvent, obtains target compound.
Compound provided by the invention can be processed into missible oil, aqueous emulsion, microemulsion, wettable powder, water dispersible granules, suspension agent, or other suitable dosage forms, for preventing and treating by botrytis cinerea, fusarium graminearum, apple anthrax bacteria, phytophthora infestans, verticillium dahliae, rice blast, bacterium of downy mildew of cucumber and cotton-wilt fusarium etc. infect caused plurality of plant diseases.
Embodiment
By following concrete Preparation Example and biological Examples, contribute to understand the present invention, but do not limit content of the present invention.
The preparation of embodiment 1 Compound I-A-1
Take 1.64g (10mmol) II-1,1mL37% formaldehyde solution, 1mL methyl alcohol, 0.2mL acetic acid is in 50mL pear shape bottle, stirring at room 30min, silica gel thin-layer plate detection reaction is complete, add each 10mL of saturated sodium bicarbonate solution and ethyl acetate, under room temperature, continue to stir 10min, turn aqueous phase discarded in separating funnel, organic phase concentrating under reduced pressure after anhydrous sodium sulfate drying reclaims solvent, enriched material crystallization in ethanol/water (volume ratio 1/1), obtain faint yellow needle-like crystal, yield 78%, fusing point 98-99 ℃.Nuclear magnetic data
1h NMR (500MHz, CDCl
3, δ ppm): 2.58 (s, 3H, CH
3), 3.40 (s, 3H, CH
3), 4.83 (s, 2H, CH
2), 6.62 (s, 1H, NH), 7.04 (t, J=7.5Hz, 1H, Ar-H), 7.14 (d, J=7.5Hz, 1H, Ar-H), 7.47 (t, J=7.5Hz, 1H, Ar-H).
The preparation of embodiment 2 Compound I-A-2
Take 1.64g (10mmol) II-1,1.2mL40% acetaldehyde solution, 1mL methyl alcohol, 0.2mL acetic acid is in 50mL pear shape bottle, stirring at room 30min, silica gel thin-layer plate detection reaction is complete, add each 10mL of saturated sodium bicarbonate solution and ethyl acetate, under room temperature, continue to stir 10min, turn aqueous phase discarded in separating funnel, organic phase concentrating under reduced pressure after anhydrous sodium sulfate drying reclaims solvent, enriched material crystallization in ethanol/water (volume ratio 1/1), obtain faint yellow needle-like crystal, yield 72%, fusing point 95-97 ℃.Nuclear magnetic data
1h NMR (500MHz, CDCl
3, δ ppm): 1.46 (d, J=7.0Hz, 3H, CH
3), 2.58 (s, 3H, CH
3), 3.42 (s, 3H, CH
3), 4.54 (q, J=7.0Hz, 1H, CH), 6.58 (s, 1H, NH), 7.04 (t, J=7.5Hz, 1H, Ar-H), 7.14 (d, J=7.5Hz, 1H, Ar-H), 7.47 (t, J=7.5Hz, 1H, Ar-H).
The preparation of embodiment 3 Compound I-A-3
Take 1.64g (10mmol) II-1, 1.2mL40% acetaldehyde solution, 1.08g phenylcarbinol (10mmol), 0.2mL acetic acid is in 50mL pear shape bottle, add tetrahydrofuran (THF) 10mL, stirring at room 60min, silica gel thin-layer plate detection reaction is complete, concentrating under reduced pressure removes after about 5mL tetrahydrofuran (THF), in pear shape bottle, add each 10mL of saturated sodium bicarbonate solution and ethyl acetate, under room temperature, continue to stir 10min, turn aqueous phase discarded in separating funnel, organic phase concentrating under reduced pressure after anhydrous sodium sulfate drying reclaims solvent, enriched material crystallization in ethanol/water (volume ratio 1/1), obtain faint yellow needle-like crystal, yield 65%, fusing point 110-112 ℃.Nuclear magnetic data
1h NMR (500MHz, CDCl
3, δ ppm): 1.42 (d, J=7.0Hz, 3H, CH
3), 2.58 (s, 3H, CH
3), 4.47 (s, 2H, CH
2), 4.56 (q, J=7.0Hz, 1H, CH), 6.56 (s, 1H, NH), 7.04 (t, J=7.5Hz, 1H, Ar-H), 7.14 (d, J=7.5Hz, 1H, Ar-H), 7.29 (m, 3H, Ar-H), 7.47 (t, J=7.5Hz, 1H, Ar-H), 7.56 (d, J=7.5Hz, 2H, Ar-H).
The preparation of embodiment 430% Compound I-A-1 wettable powder
Take Compound I-A-130g, sodium lauryl sulphate 2g, sodium lignosulfonate 3g, naphthalene sulfonic acidformaldehyde condensation product 5g, light calcium carbonate complements to 100g, after above-mentioned material is fully mixed, after ultra-fine pulverizer disintegrating, obtains 30% wettable powder product.
The preparation of embodiment 550% Compound I-A-1 water dispersible granules
Take Compound I-A-150g; N-methyl-N-oleoyl-Sodium taurine salt 6g; polyvinylpyrrolidone 3g, Xylo-Mucine 2g, naphthalene sulfonic acidformaldehyde condensation product 10g; kaolin complements to 100g; by the abundant co-grinding of above-mentioned material, then after adding water and mediating, add in the tablets press of 1-100 eye mesh screen and carry out granulation; and then drying, screening, obtain 50% water dispersible granules product.
The Determination of Antibacterial Activity of embodiment 6 Compound I-A-1 to botrytis cinerea
Taking reagent agent 2mg is dissolved in 1mL methyl-sulphoxide (DMSO), by deionized water proportional diluted, become series concentration gradient, the PDA substratum for reagent liquid 1mL and 9mL thawing of getting different concns mixes, and pours into while hot in aseptic culture dish and makes and be with medicine culture medium flat plate.After culture medium solidifying, put into 1 make to be attached to media surface with the one side of mycelia for examination bacterium bacterium cake (diameter is 4mm) in each substratum plane, every processing repeats for 3 times.Cultivate after 72h, by right-angled intersection method, measure for examination bacterium colony growth diameter, calculate inhibiting rate.Result shows, when drug concentration is 10mg/L, Compound I-A-1 can reach more than 90% the mycelial growth inhibition rate of botrytis cinerea.
The impact of embodiment 7 Compound I-A-1 on fungi melanin biosynthesis
Take verticillium dahliae as supplying examination fungi, taking reagent agent 2mg is dissolved in 1mL methyl-sulphoxide (DMSO), by deionized water proportional diluted, become series concentration gradient, the PDA substratum for reagent liquid 1mL and 9mL thawing of getting different concns mixes, and pours into while hot in aseptic culture dish and makes and be with medicine culture medium flat plate.After culture medium solidifying, put into 1 make to be attached to media surface with the one side of mycelia for examination bacterium bacterium cake (diameter is 4mm) in each substratum plane, every processing repeats for 3 times.Cultivate after 144h, observe bacterium colony melanochrome in each plate and generate situation.Result shows, when drug concentration is 5mg/L, the melanochrome that Compound I-A-1 can suppress verticillium dahliae completely generates.
Embodiment 850% Compound I-A-1 water dispersible granules control cucumber downy mildew field test
With reference to the method for " GB/T17980.26-2000 pesticide field efficacy medicine test criterion () bactericidal agent for preventing and treating cucumber downy mildew ", 50% Compound I provided by the invention-A-1 water dispersible granules has been carried out to control graw mold of tomato field control effectiveness test.Result shows, when drug concentration is 1500 μ g/mL, its protection effect and result for the treatment of are respectively 76.7% and 68.5%; When spraying medicine concentration is 1000 μ g/mL, its protection effect and result for the treatment of are respectively 92.3% and 85.6%.
N-alcoxyl of the present invention (sulphur) alkyl Benzheterocyclic derivatives and being described by concrete example as disinfectant use in agriculture purposes, those skilled in the art can use for reference content of the present invention, the links such as appropriate change raw material, processing condition realize corresponding other object, its relevant change does not all depart from content of the present invention, within all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included in scope of the present invention.
Claims (5)
1. a N-alkoxyalkyl Benzheterocyclic derivatives, as shown in general formula I:
In formula:
R
1be selected from hydrogen; C
1～C
8alkyl; Or optionally by cyano group, halogen, phenyl ring, C
1～C
4alkoxyl group or C
1～C
4the C that alkylthio replaces
1～C
8alkyl, C
3～C
8alkenyl or C
3～C
8alkynyl;
m=0～4；
X is selected from S, O or NH;
Y is selected from O or S;
R
2be selected from hydrogen; C
1～C
8alkyl; Or optionally by cyano group, halogen, phenyl ring, C
1～C
4alkoxyl group or C
1～C
4the C that alkylthio replaces
1～C
8alkyl, C
3～C
8alkenyl or C
3～C
8alkynyl; Or optionally by cyano group, halogen, C
1～C
4alkoxyl group or C
1～C
4the C that alkylthio replaces
3～C
8alkenyl or C
3～C
8alkynyl;
R
3be selected from C
1～C
8alkyl; Or optionally by cyano group, halogen, phenyl ring, C
1～C
4alkoxyl group or C
1～C
4the C that alkylthio replaces
1～C
8alkyl, C
3～C
8alkenyl or C
3～C
8alkynyl; Phenyl or by being selected from the optional phenyl replacing of 1～3 following substituting group: halogen, C
1～C
8alkyl, C
3～C
8cycloalkyl, hydroxyl, C
1～C
4alkoxyl group, C
1～C
4haloalkyl, C
1～C
4halogenated alkoxy, C
1～C
4halogenated alkylthio, C
1～C
4halogenated alkyl sulfonyl, carboxyl, nitro, cyano group, phenyl, phenoxy group, benzoyl.
2. according to the compound of claim 1, it is characterized in that, in general formula (I),
R
1be selected from C
1～C
4alkyl;
m=1～2；
X is selected from S or O;
Y is selected from O;
R
2be selected from C
1～C
4alkyl;
R
3be selected from C
1～C
4alkyl.
3. according to the compound of claim 1, it is characterized in that, in general formula (I),
R
1be selected from methyl, ethyl;
m=1；
X is selected from S;
Y is selected from O;
R
2be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-;
R
3be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-.
4. the arbitrary described compound of claim 1-3 is for preventing and treating the purposes by the caused Plant diseases of following plants pathogenic fungi: botrytis cinerea, fusarium graminearum, apple anthrax bacteria, phytophthora infestans, verticillium dahliae, rice blast, bacterium of downy mildew of cucumber, cotton-wilt fusarium or other phytopathogenic fungi.
5. according to the purposes of claim 4, described compound can be processed into missible oil, aqueous emulsion, microemulsion, wettable powder, water dispersible granules, suspension agent, or other suitable dosage forms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310670142.4A CN103724292B (en) | 2013-12-03 | 2013-12-03 | N-alcoxyl (sulphur) alkyl Benzheterocyclic derivatives and uses thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310670142.4A CN103724292B (en) | 2013-12-03 | 2013-12-03 | N-alcoxyl (sulphur) alkyl Benzheterocyclic derivatives and uses thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103724292A true CN103724292A (en) | 2014-04-16 |
| CN103724292B CN103724292B (en) | 2015-08-19 |
Family
ID=50448626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310670142.4A Expired - Fee Related CN103724292B (en) | 2013-12-03 | 2013-12-03 | N-alcoxyl (sulphur) alkyl Benzheterocyclic derivatives and uses thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103724292B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965138A (en) * | 2014-04-30 | 2014-08-06 | 西北农林科技大学 | N-alcoxyl (sulfur) alkyl benzo heterocyclic derivative and use thereof as herbicide |
| CN111087363A (en) * | 2020-01-07 | 2020-05-01 | 湖南科技大学 | N-heterocyclic substituted-2-bromoacetamide compound for crop bacteriostasis and preparation method thereof |
| CN112209894A (en) * | 2020-10-23 | 2021-01-12 | 贵州医科大学 | 5-aryl substituted 2-aminobenzoxazole derivative, preparation method and application thereof |
-
2013
- 2013-12-03 CN CN201310670142.4A patent/CN103724292B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965138A (en) * | 2014-04-30 | 2014-08-06 | 西北农林科技大学 | N-alcoxyl (sulfur) alkyl benzo heterocyclic derivative and use thereof as herbicide |
| CN103965138B (en) * | 2014-04-30 | 2016-01-20 | 西北农林科技大学 | N-alcoxyl (sulphur) alkyl Benzheterocyclic derivatives and the purposes as weedicide thereof |
| CN111087363A (en) * | 2020-01-07 | 2020-05-01 | 湖南科技大学 | N-heterocyclic substituted-2-bromoacetamide compound for crop bacteriostasis and preparation method thereof |
| CN112209894A (en) * | 2020-10-23 | 2021-01-12 | 贵州医科大学 | 5-aryl substituted 2-aminobenzoxazole derivative, preparation method and application thereof |
| CN112209894B (en) * | 2020-10-23 | 2023-06-06 | 贵州医科大学 | 5-aryl substituted 2-aminobenzoxazole derivative, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103724292B (en) | 2015-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5089581B2 (en) | 1,2-Benzisothiazole derivatives and plant disease control agents for agriculture and horticulture | |
| PL182711B1 (en) | Derivatives of amino acids, method of obtaining them, fungicides for use in agriculture or horticulture and method of killing fungi | |
| WO2013064079A1 (en) | Use of compound of pyrazole amides as agricultural fungicide | |
| JPS6147403A (en) | Method of repelling plant pathoginic fungi by use of fungicidal composition containing n-acetonylbenzamide | |
| CN103059006B (en) | Chrysin-1,2,3-triazole compound with anti-microbial activity and preparation method thereof | |
| CN103724292B (en) | N-alcoxyl (sulphur) alkyl Benzheterocyclic derivatives and uses thereof | |
| CN102503896A (en) | Methylacryloyl-benzimidazole (sulfur) ketone derivative and application of serving as antibacterial agent thereof | |
| CN106397422A (en) | Nicotinamide compound containing chiral oxazoline and application of same as agricultural bactericide | |
| PT97919B (en) | PROCESS FOR THE PREPARATION OF PESTICIDE COMPOSITION, ESPECIALLY FUNGICIDE CONTAINING 2-METHOXYININOCARBOXYL ACID ESTERS, AND INTERMEDIATE PRODUCTS | |
| CN105541745B (en) | 1- (fragrant amino ethyl) -2- aryl -3,1- benzoxazine compounds and its preparation and use with bactericidal activity | |
| JPH09505315A (en) | 3-Methoxy-2-phenyl-methyl acrylate | |
| CN104725276B (en) | Heptafluoroisopropyl-containing carbonyl oxime ether compound, preparation method and applications thereof | |
| CN103382169B (en) | Emodin methyl sulfonic ester, and preparation method and applications thereof | |
| CN103408465B (en) | A kind of N-disubstituted benzenes ylmethyl valine amide carbamate derivatives and application | |
| JPS63146856A (en) | Cyclohexane derivative, production thereof and herbicide comprising said derivative as active ingredient | |
| CN104926751A (en) | Benzisothiazolone derivatives and synthetic method thereof | |
| CN103965138B (en) | N-alcoxyl (sulphur) alkyl Benzheterocyclic derivatives and the purposes as weedicide thereof | |
| CN104910094A (en) | 1-amido-2-aryl-2,4-dihydro-3,1-benzoxazine compounds with bactericidal activity and application thereof | |
| JPH0948750A (en) | Phenylalkanoic acid amide derivative and agricultural and horticultural fungicide | |
| US8987170B2 (en) | Succinimide compound | |
| CN108440510A (en) | A kind of acid amide fungicides | |
| CN110818707B (en) | Compound containing fused heterocyclic structure, preparation method and application thereof, and bactericide | |
| TW513413B (en) | Substituted 4-(3-alkenylbenzoyl) pyrazoles | |
| CN103651352B (en) | New application of N-(2-phenoxy benzene) benzamide compound as agricultural bactericide | |
| CN104529900A (en) | Bactericidal activity of 1-substituted-N-substituted phenyl-5-amidogen-1H-pyrazole-4-formamide compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150819 Termination date: 20151203 |
|
| EXPY | Termination of patent right or utility model |