CN1654456A - Pyrazole-containing bishydrazide compound and its preparation method and use - Google Patents
Pyrazole-containing bishydrazide compound and its preparation method and use Download PDFInfo
- Publication number
- CN1654456A CN1654456A CN 200510048934 CN200510048934A CN1654456A CN 1654456 A CN1654456 A CN 1654456A CN 200510048934 CN200510048934 CN 200510048934 CN 200510048934 A CN200510048934 A CN 200510048934A CN 1654456 A CN1654456 A CN 1654456A
- Authority
- CN
- China
- Prior art keywords
- pyrazole
- methyl
- ethyl
- compound
- containing bishydrazide
- 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.)
- Pending
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention relates to one kind of pyrazolyl dihydrazide containing compound and its preparation process and use. The pyrazolyl dihydrazide containing compound is shown in I, and its preparation process includes the following steps: the condensation between 1-methyl-3-ethyl-4-substitutent-pyrazolyl dihydrazide and substituted phenyl formyl chloride inside organic solvent at 0-20 deg.c, and the post-treatment. The pyrazolyl dihydrazide containing compound has certain preventing effect on rice blast, cucumber botrytis and wheat powdery mildew and certain pesticidal activity on armyworm.
Description
(1) technical field
The present invention relates to a kind of pyrazole-containing bishydrazide compound, preparation method and its usage.
(2) background technology
Pyrazole compound is being played the part of important role in heterocyclic pesticide.Because that pyrazole compound shows is efficient, low toxicity and diversity structure, thereby has boundless research and development prospect.Before the present invention makes, there is the pesticide patent of relevant bishydrazide structure to occur abroad, tertiary butyl structure is arranged in the bishydrazide structure and do not have heterocycle structure.Domestic Lee rectifies name etc. pyrazole heterocycle and non-benzene ring structure is replaced two phenyl ring in two heterocycle structures, obtains a series ofly having-bishydrazide compound of CONH-structure, shows certain insecticidal activity.
(3) summary of the invention
The object of the invention is to provide a kind of pyrazole-containing bishydrazide compound of biologically active.
Described pyrazole-containing bishydrazide compound is suc as formula shown in (I):
Wherein X represents Cl, Br, R represent methylidene, nitro or chlorine atom.
A kind of preparation method of above-mentioned pyrazole-containing bishydrazide compound, comprise the steps: suc as formula the substituted-phenyl formyl chloride shown in the 1-methyl shown in (II)-3-ethyl-4-replacement-pyrazole-containing bishydrazide and the formula (III) under the acid-capture agent effect, carry out condensation reaction at 0～20 ℃ in organic solvent, aftertreatment gets product;
Wherein X and R definition is the same.
Based on the consideration of productive rate and cost, described condensation reaction time was good with 1～50 hour.
Described substituted-phenyl formyl chloride: 1-methyl-3-ethyl-4-replacement-pyrazole-containing bishydrazide: the molar ratio of acid-capture agent is preferably 1: 1.0～and 1.5: 1.0～2.0, described consumption of organic solvent is preferably 20～60 times of 1-methyl-3-ethyl-4-replacement-pyrazole-containing bishydrazide quality.
It is one of following that described acid-capture agent is preferably: triethylamine, pyridine, lutidine, Anhydrous potassium carbonate.
It is one of following that described organic solvent is preferably: tetrahydrofuran (THF), ethyl acetate, toluene, chlorobenzene, trichloromethane.
Described aftertreatment can be: use dilute hydrochloric acid washing reaction liquid to neutral, and layering, the organic phase drying is filtered, and concentrates, and column chromatography for separation gets described pyrazole-containing bishydrazide compound.
The preparation method of described pyrazole-containing bishydrazide compound recommends to be undertaken by following parameter:
The substituted-phenyl formyl chloride: 1-methyl-3-ethyl-4-replacement-pyrazole-containing bishydrazide: the molar ratio of acid-capture agent is 1: 1.0～1.1: 1.2～1.4, and consumption of organic solvent is 5～20 times of 1-methyl-3-ethyl-4-replacement-pyrazole-containing bishydrazide quality; Setting-up point is 0～20 ℃, and the reaction times is 10～20 hours.
Described 1-methyl-3-ethyl-4-replacement-pyrazole-containing bishydrazide can adopt following method to make:
1-methyl-3-ethyl-4-replacement-5-pyrazole carboxylic acid ethyl ester and excess hydrazine hydrate are carried out the stirring and refluxing reaction, and reaction finishes the back concentrating under reduced pressure, uses ethyl alcohol recrystallization, gets white, needle-shaped crystals and is described product.
Above-mentioned pyrazole-containing bishydrazide compound is as the application of insectofungicide.
Adopt toxic potato agar substratum (PDA) method that the fungicidal activity that the synthetic compound has carried out Pyricularia oryzae (Pyricularia oryzae), fusarium graminearum (Gibberella zeae), Phytophthora capsici germ (Phytophthora capsici) and botrytis cinerea pers (Botrytis cinerea) is measured, adopt potted plant stem and leaf of Wheat to preserve the spore method fungicidal activity that the synthetic compound has carried out wheat powdery mildew (Blumeria graminis) is measured.The result shows that described pyrazole-containing bishydrazide compound does not have the preventive effect effect substantially to fusarium graminearum, Phytophthora capsici germ, and rice blast fungus, botrytis cinerea pers, wheat powdery mildew are had different preventive effect effects.
Adopt the Potter spray method that the synthetic compound has been carried out the insecticidal activity assay of mythimna separata (Mythimna separata), adopt dipping plant method the synthetic compound to be carried out the insecticidal activity assay of green rice leafhopper (Nephotettix cincticeps).The result shows that described pyrazole-containing bishydrazide compound does not have insecticidal activity substantially to green rice leafhopper, and mythimna separata is had certain insecticidal activity, X=Cl especially, R=3-NO
2Formula (I) compound the inhibition activity of mythimna separata is reached 100%.
(4) embodiment
Below by embodiment the present invention is further specified, but protection scope of the present invention is not limited to this.
Embodiment 1
4.05g (20mmol) 1-methyl-3-ethyl-4-chloro-5-pyrazoles formyl hydrazine and 2.4g (24mmol) triethylamine are joined in the 40mL chloroform soln, drip 19mmol 3-nitrobenzoyl chloride under ice bath stirs, 30min drips complete, react 20h then in about 7 ℃, reaction is finished, and is extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, the organic phase drying is filtered, and concentrates, ethyl alcohol recrystallization, obtain white solid, fusing point 232-234 ℃, yield is 92%.
This compound
1H NMR and IR are as described below,
1H?NMR(DMSO-d
6，δ/ppm)1.26(3H，t，J＝4.4Hz，CH
2CH
3)，2.65(2H，q，CH
2CH
3)，4.16(3H，s，NCH
3)，7.27-8.72(4H，m，Ph-H)，9.5(1H，s，PyCONHNH)，9.59(1H，s，PyCONHNH)
IR(KBr，V
CO/cm-1)1606
Embodiment 2
4.05g (20mmol) 1-methyl-3-ethyl-4-chloro-5-pyrazoles formyl hydrazine and 2.0g (22mmol) lutidine are joined in the 70mL toluene solution, and ice bath stirs and drips 19mmol 3-methyl benzoyl chloride down, and it is complete that 40min drips, in about 3 ℃, react 10h then, reaction is finished, and is extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, the organic phase drying, filter, concentrate, use ethyl alcohol recrystallization, obtain white solid, fusing point 178-180 ℃.Yield is 90%.
This compound
1H NMR and IR are as described below,
1H?NMR(DMSO-d
6，δ/ppm)1.26(3H，t，J＝4.75Hz，CH
2CH
3)，2.40(3H，s，Ph-CH
3)，2.65(2H，q，CH
2CH
3)，4.12(3H，s，NCH
3)，7.32-7.69(4H，m，Ph-H)，9.21(1H，d，J＝3.5Hz，PyCONHNH)，9.63(1H，d，J＝3.75Hz，PyCONHNH)
IR(KBr，V
CO/cm-1)1602
Embodiment 3
4.05g (20mmol) 1-methyl-3-ethyl-4-chloro-5-pyrazoles formyl hydrazine and 1.85g (23mmol) pyridine are joined in the 40mL ethyl acetate solution, drip 19mmol 3-chloro-benzoyl chloride under ice bath stirs, 30min drips complete, in about 10 ℃, react 15h then, reaction is finished, and is extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, the organic phase drying, filter, concentrate, use ethyl alcohol recrystallization, obtain white solid, fusing point 186-188 ℃.Yield is 53%.
This compound
1H NMR and IR are as described below,
1H?NMR(DMSO-d
6，δ/ppm)1.16(3H，t，J＝4.6Hz，CH
2CH
3)，2.54(2H，q，CH
2CH
3)，3.91(3H，s，NCH
3)，7.45-7.58(4H，m，Ph-H)，10.50(1H，s，PyCONHNH)，10.59(1H，s，PyCONHNH)
IR(KBr，V
CO/cm
-1)1602
Embodiment 4
4.94g (20mmol) 1-methyl-3-ethyl-4-bromo-5-pyrazoles formyl hydrazine and 1.85g (23mmol) pyridine are joined in the 30mL chlorobenzene solution, drip 19mmol 3-nitrobenzoyl chloride under ice bath stirs, 30min drips complete, reacts 16h then in about 6 ℃, reaction is finished, extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, organic phase drying, filter, use ethyl alcohol recrystallization, obtain white solid, fusing point 207-208 ℃.Yield is 93%.
This compound
1H NMR and IR are as described below,
1H?NMR(DMSO-D
6，δ/ppm)1.20(3H，t，J＝4.5Hz，CH
2CH
3)，2.56(2H，q，CH
2CH
3)，3.94(3H，s，NCH
3)，7.84-8.78(4H，m，Ph-H)，10.76(1H，s，PyCONHNH)，11.19(1H，s，PyCONHNH)
IR(KBr，V
CO/cm
-1)1607
Embodiment 5
4.94g (20mmol) 1-methyl-3-ethyl-4-bromo-5-pyrazoles formyl hydrazine and 3.17g (23mmol) Anhydrous potassium carbonate are joined in the 50ml chlorobenzene solution, drip 19mmol 3-methyl benzoyl chloride under ice bath stirs, 30min drips complete, reacts 15h then in about 8 ℃, reaction is finished, extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, organic phase drying, filter, use ethyl alcohol recrystallization, obtain white solid, fusing point 183-185 ℃.Yield is 91%.
This compound
1H NMR and IR are as described below,
1H?NMR(DMSO-D
6，δ/ppm)1.26(3H，t，J＝4.75Hz，CH
2CH
3)，2.42(3H，s，Ph-CH
3)，2.66(2H，q，CH
2CH
3)，4.15(3H，s，NCH
3)，7.35-7.69(4H，m，Ph-H)，9.12(1H，d，J＝3.75Hz，PyCONHNH)，9.76(1H，d，J＝4.0Hz，PyCONHNH)
IR(KBr，V
CO/cm
-1)1607
Embodiment 6
4.94g (20mmol) 1-methyl-3-ethyl-4-bromo-5-pyrazoles formyl hydrazine and 2.4g (24mmol) triethylamine are joined in the 60mL ethyl acetate solution, drip 19mmol 3-chloro-benzoyl chloride under ice bath stirs, 30min drips complete, reacts 18h then in about 3 ℃, reaction is finished, extremely neutral with diluted hydrochloric acid aqueous solution washing reaction liquid, layering, organic phase drying, filter, use ethyl alcohol recrystallization, obtain white solid, fusing point 194-195 ℃.Yield is 92%.
This compound
1H NMR and IR are as described below,
1H?NMR(DMSO-D
6，δ/ppm)1.26(3H，t，J＝4.5Hz，CH
2CH
3)，2.66(2H，q，CH
2CH
3)，4.13(3H，s，NCH
3)，7.37-7.89(4H，m，Ph-H)，9.61(1H，d，J＝3.7Hz，PyCONHNH)，9.86(1H，d，J＝3.75Hz，PyCONHNH)
IR(KBr，V
CO/cm
-1)1600
Embodiment 7
The trichloromethane consumption changes 54ml (81g) into, and other is operated with embodiment 1, obtains white solid, and fusing point 232-234 ℃, yield is 89%.
Embodiment 8
The trichloromethane consumption changes 13.6ml (20.25g) into, and other is operated with embodiment 1, obtains white solid, and fusing point 232-234 ℃, yield is 90%.
Embodiment 9
Acid-capture agent changes 3.59g (26mmol) Anhydrous potassium carbonate into, and other are operated with embodiment 1, obtain white solid, and fusing point 232-234 ℃, yield is 90%.
Embodiment 10
3-nitrobenzoyl chloride consumption changes 20mmol into, and other are operated with embodiment 1, obtain white solid, and fusing point 232-234 ℃, yield is 91%.
Embodiment 11
Organic solvent changes the 80mL tetrahydrofuran (THF) into, and other are operated with embodiment 1, obtain white solid, and fusing point 232-234 ℃, yield is 89%.
Embodiment 12
Temperature of reaction is adjusted to 20 ℃, and other are operated with embodiment 1, obtain white solid, and fusing point 232-234 ℃, yield is 90%.
The test of embodiment 13 fungicidal activities
Adopt toxic potato agar substratum (PDA) method that the fungicidal activity that embodiment 1～6 synthetic compound has carried out Pyricularia oryzae (Pyricularia oryzae), fusarium graminearum (Gibberella zeae), Phytophthora capsici germ (Phytophthora capsici) and botrytis cinerea pers (Botrytiscinerea) is measured, general sieve concentration is 25ppm; Adopt the toxic potato agar substratum of excised leaf (PDA) method that the fungicidal activity that the synthetic compound has carried out Rhizoctonia solani Kuhn (Rhizoctoniasolani) is measured, general sieve concentration is 500ppm; Adopt potted plant toxic potato agar substratum (PDA) method that the fungicidal activity that the synthetic compound has carried out Sclerotinia sclerotiorum (Sclerotoniasclerotiorum) is measured, general sieve concentration is 500ppm; Adopt potted plant stem and leaf of Wheat to preserve the spore method fungicidal activity that the synthetic compound has carried out wheat powdery mildew (Blumeria graminis) is measured, general sieve concentration is 500ppm.Test result sees Table 1.
Table 1 pyrazole-containing bishydrazide compound is to the restraining effect of germ
| The embodiment title | Formula (I) compound | Concentration (ug/ml) | Fusarium graminearum | The Phytophthora capsici germ | Rice blast fungus | Botrytis cinerea pers | Concentration (ug/ml) | Wheat powdery mildew | |
| ??X | ?R | Preventive effect (%) | Preventive effect (%) | Preventive effect (%) | Preventive effect (%) | Preventive effect (%) | |||
| Embodiment 1 | ??Cl | ?3-CH 3 | ????25 | ????2.6 | ????0 | ????10.2 | ????6.4 | ????500 | ???10.0 |
| Embodiment 2 | ??Cl | ?3-NO 2 | ????25 | ????0 | ????0 | ????51.3 | ????6.4 | ????500 | ???10.0 |
| Embodiment 3 | ??Cl | ?2-Cl | ????25 | ????0 | ????0 | ????20.5 | ????19.1 | ????500 | ???10.0 |
| Embodiment 4 | ??Br | ?3-CH 3 | ????25 | ????18.6 | ????0 | ????20.5 | ????0 | ????500 | ???20.0 |
| Embodiment 5 | ??Br | ?3-NO 2 | ????25 | ????0 | ????0 | ????21.2 | ????15.9 | ????500 | ???0 |
| Embodiment 6 | ??Br | ??2-Cl | ???25 | ???0 | ???0 | ???56.1 | ???4.4 | ???500 | ???0 |
The test of embodiment 14 insecticidal activities
Adopt the Potter spray method that embodiment 1～6 synthetic compound has been carried out the insecticidal activity assay of mythimna separata (Mythimnaseparata), working concentration is 1000mg/L; Adopt dipping plant method that the synthetic compound has been carried out the insecticidal activity assay of green rice leafhopper (Nephotettix cincticeps), working concentration is 500mg/L.Test result sees Table 2.
Mortality ratio is being the A level more than 90%, is the B level between 70～90%, is the C level between 50～70%, is the D level between 0～50%.
Table 2 pyrazole-containing bishydrazide compound is to the killing action of insect
| The embodiment title | Formula (I) compound | Leafhopper | Mythimna separata | |||
| ????X | ??R | Mortality ratio (%) | The virulence rank | Mortality ratio (%) | The virulence rank | |
| Embodiment 1 | ????Cl | ??3-CH 3 | ????0 | ????D | ????0 | ????D |
| Embodiment 2 | ????Cl | ??3-NO 2 | ????100 | ????A | ????0 | ????D |
| Embodiment 3 | ????Cl | ??2-Cl | ????0 | ????D | ????0 | ????D |
| Embodiment 4 | ????Br | ??3-CH 3 | ????10.0 | ????D | ????0 | ????D |
| Embodiment 5 | ????Br | ??3-NO 2 | ????4.80 | ????D | ????0 | ????D |
| Embodiment 6 | ????Br | ??2-Cl | ????4.60 | ????D | ????0 | ????D |
Claims (10)
1, suc as formula the pyrazole-containing bishydrazide compound shown in (I),
Wherein X is Cl or Br, and R is methyl, nitro or chlorine.
2, pyrazole-containing bishydrazide compound as claimed in claim 1 is characterized in that described X is Br.
3, pyrazole-containing bishydrazide compound as claimed in claim 1 is characterized in that described X is Cl, and R is a nitro.
4, a kind of preparation method of pyrazole-containing bishydrazide compound according to claim 1, comprise the steps: suc as formula the substituted-phenyl formyl chloride shown in the 1-methyl shown in (II)-3-ethyl-4-replacement-pyrazole-containing bishydrazide and the formula (III) under the acid-capture agent effect, carry out condensation reaction at 0～20 ℃ in organic solvent, aftertreatment gets product;
Wherein X is Cl or Br, and R is methyl, nitro or chlorine.
5, the preparation method of pyrazole-containing bishydrazide compound as claimed in claim 4 is characterized in that described condensation reaction time is 1～50 hour.
6, the preparation method of pyrazole-containing bishydrazide compound as claimed in claim 4, it is characterized in that described substituted-phenyl formyl chloride: 1-methyl-3-ethyl-4-replacement-pyrazole-containing bishydrazide: the molar ratio of acid-capture agent is 1: 1.0～1.5: 1.0～2.0, and described consumption of organic solvent is 20～60 times of 1-methyl-3-ethyl-4-replacement-pyrazole-containing bishydrazide quality.
7, the preparation method of pyrazole-containing bishydrazide compound as claimed in claim 4, it is characterized in that described acid-capture agent is one of following: triethylamine, pyridine, lutidine, Anhydrous potassium carbonate, described organic solvent are one of following: tetrahydrofuran (THF), ethyl acetate, toluene, chlorobenzene, trichloromethane.
8, as the preparation method of the described pyrazole-containing bishydrazide compound of one of claim 4～7, it is characterized in that described 1-methyl-3-ethyl-4-replacement-pyrazole-containing bishydrazide makes by following method: 1-methyl-3-ethyl-4-replacement-5-pyrazole carboxylic acid ethyl ester and excess hydrazine hydrate are carried out the stirring and refluxing reaction, reaction finishes the back concentrating under reduced pressure, gets white, needle-shaped crystals and is 1-methyl-3-ethyl-4-replacement-pyrazole-containing bishydrazide.
9, the preparation method of pyrazole-containing bishydrazide compound as claimed in claim 8, it is characterized in that described substituted-phenyl formyl chloride: 1-methyl-3-ethyl-4-replacement-pyrazole-containing bishydrazide: the molar ratio of acid-capture agent is 1: 1.0～1.1: 1.2～1.4, and described consumption of organic solvent is 5～20 times of 1-methyl-3-ethyl-4-replacement-pyrazole-containing bishydrazide quality; Condensation reaction time is 10～20 hours.
10, the described pyrazole-containing bishydrazide compound of claim 1 is as the application of insectofungicide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510048934 CN1654456A (en) | 2005-01-19 | 2005-01-19 | Pyrazole-containing bishydrazide compound and its preparation method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510048934 CN1654456A (en) | 2005-01-19 | 2005-01-19 | Pyrazole-containing bishydrazide compound and its preparation method and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1654456A true CN1654456A (en) | 2005-08-17 |
Family
ID=34894493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510048934 Pending CN1654456A (en) | 2005-01-19 | 2005-01-19 | Pyrazole-containing bishydrazide compound and its preparation method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1654456A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483313A (en) * | 2013-09-03 | 2014-01-01 | 南开大学 | Novel hydrazide derivatives as well as preparation method and application thereof |
| CN104193681A (en) * | 2014-08-08 | 2014-12-10 | 一帆生物科技集团有限公司 | Preparation and application of 4-chlorine-3-ethyl-1-methyl-N'-(2-substituted phenoxy acetyl)-1H-pyrazol-5-carbohydrazide compounds |
| CN104744358A (en) * | 2014-07-24 | 2015-07-01 | 浙江工业大学 | Pyridine formylhydrazine compounds with insecticidal activity and preparation method and application thereof |
| CN105777639A (en) * | 2016-01-26 | 2016-07-20 | 浙江博仕达作物科技有限公司 | Pyrazole hydrazide compound and use thereof |
| CN110256361A (en) * | 2019-05-08 | 2019-09-20 | 湖南人文科技学院 | A kind of bishydrazide compounds and preparation method thereof of the structure fragment of ketone containing phenyl pyrimidine |
| WO2022147993A1 (en) * | 2021-01-05 | 2022-07-14 | 西北农林科技大学 | Diphenylpyrazole compound, and preparation method therefor and application thereof |
-
2005
- 2005-01-19 CN CN 200510048934 patent/CN1654456A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483313A (en) * | 2013-09-03 | 2014-01-01 | 南开大学 | Novel hydrazide derivatives as well as preparation method and application thereof |
| CN104744358A (en) * | 2014-07-24 | 2015-07-01 | 浙江工业大学 | Pyridine formylhydrazine compounds with insecticidal activity and preparation method and application thereof |
| CN104193681A (en) * | 2014-08-08 | 2014-12-10 | 一帆生物科技集团有限公司 | Preparation and application of 4-chlorine-3-ethyl-1-methyl-N'-(2-substituted phenoxy acetyl)-1H-pyrazol-5-carbohydrazide compounds |
| CN105777639A (en) * | 2016-01-26 | 2016-07-20 | 浙江博仕达作物科技有限公司 | Pyrazole hydrazide compound and use thereof |
| WO2017128942A1 (en) * | 2016-01-26 | 2017-08-03 | 浙江博仕达作物科技有限公司 | Pyrazole hydrazide compound and use thereof |
| CN110256361A (en) * | 2019-05-08 | 2019-09-20 | 湖南人文科技学院 | A kind of bishydrazide compounds and preparation method thereof of the structure fragment of ketone containing phenyl pyrimidine |
| CN110256361B (en) * | 2019-05-08 | 2023-06-16 | 湖南人文科技学院 | Bishydrazide compound containing phenylpyrimidinone structural fragment and preparation method thereof |
| WO2022147993A1 (en) * | 2021-01-05 | 2022-07-14 | 西北农林科技大学 | Diphenylpyrazole compound, and preparation method therefor and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1654456A (en) | Pyrazole-containing bishydrazide compound and its preparation method and use | |
| US9089139B2 (en) | Agri-horticultural pest control compositions comprising 4-(3-butynyl)aminopyrimidine derivatives | |
| CN1810808A (en) | New [1,2,3]-thiobiazole derivative and its synthesis and use | |
| CN106397422B (en) | Nicotinamide compound containing chiral oxazoline and the purposes as disinfectant use in agriculture | |
| CN107129498B (en) | Imidazoles arone compounds and the preparation method and application thereof | |
| Mao et al. | Synthesis and bioactivity of N-tert-butyl-N′-acyl-5-methyl-1, 2, 3-thiadiazole-4-carbohydrazides | |
| CN1288149C (en) | Double heterocyclic compound containing pyrazole and pyrazole ketone, preparing method and its use | |
| CN110372622A (en) | Phenyl acetanides containing chiral oxazoline and the purposes as disinfectant use in agriculture | |
| CN1300138C (en) | Diheterocyclic compound, its preparing method and use | |
| KR20040015097A (en) | Triazolopyrimidines | |
| CN1285589C (en) | Heterocyclic compound containing double pyrazole, preparing method and its use | |
| CN1709875A (en) | Pyrazole diacylhydrazine compound, and its preparing method and use | |
| CN107602496B (en) | Chiral complementary alkyl heterocyclic compound and application thereof as bactericide | |
| CN114805348B (en) | Triazolopyridine amide compound and preparation method and application thereof | |
| CN1648123A (en) | Double heterocyclic compound containing pyrazole and benzimidazole, preparing method and its use | |
| CN1644582A (en) | Pyrazole contained diheterocyclic compound, its preparation and use | |
| CN100398523C (en) | 2,4-dichlor phenoxyacetic amide pyrimidine derivative and its preparation method and agricultural composition | |
| CN107033082A (en) | A kind of acyl thiourea compound for containing 1,3 dimethyl 1H pyrrazole structures and its preparation method and application | |
| CN110734403B (en) | (S) -2- (1H-pyrazole-4-formamido) propyl benzoate compound and preparation method and application thereof | |
| CN1760189A (en) | Method for preparing N-alkoxy carbonyl, thiazolethioketone derivative,s and usage | |
| CN101250138B (en) | Benzyloxycarbonyl amino acid aryl esters having insecticidal and fungicidal activitives | |
| CN103333113A (en) | Preparation and application research of fluxapyroxad analogue derivative | |
| CN1974561A (en) | Cyhalothrin amide compound containing quinary nitrogen heterocycle ketone and its prepn and application | |
| CN114502551B (en) | Fluorine-containing pyrimidine compound and preparation method thereof | |
| CN101003502B (en) | Compound of amide chlorotrifluoro chrysanthemic acid containing thiourea, preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |