CN105541794A - Heptafluoroisopropyl-containing pyridyl pyrazole amide derivative and application thereof - Google Patents
Heptafluoroisopropyl-containing pyridyl pyrazole amide derivative and application thereof Download PDFInfo
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- CN105541794A CN105541794A CN201610012973.6A CN201610012973A CN105541794A CN 105541794 A CN105541794 A CN 105541794A CN 201610012973 A CN201610012973 A CN 201610012973A CN 105541794 A CN105541794 A CN 105541794A
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- cucumber
- pyridyl
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- propyls
- heptafluoroisopropyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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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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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to preparation and application of a heptafluoroisopropyl-containing pyridyl pyrazole amide derivative which is shown as a general formula (I). The compound represents a broad spectrum and efficient insecticidal and bactericidal agent structure type. When the heptafluoroisopropyl-containing pyridyl pyrazole amide derivative is used as a novel insecticidal and bactericidal agent, the heptafluoroisopropyl-containing pyridyl pyrazole amide derivative can well prevent and control oriental armyworms, plutella xylostella and beet armyworms and also can be well used for preventing and controlling cucumber target leaf spot, cucumber bacterial angular leaf spot, cucumber fusarium wilt, cucumber downy mildew, cucumber powdery mildew, tomato bacterial leaf spot and a rice sheath blight disease. The meaning of R1, R2 and R3 in the formula is shown in the description.
Description
One, technical field
The present invention relates to pyridyl pyrazoles amide derivatives containing seven fluorine sec.-propyls and the application as sterilant and sterilant aspect thereof, belong to technical field of pesticide.
Two, background technology
In recent years, field of agrochemicals is that the research and development of target sterilant achieve breakthrough with ryanodine receptor.Agricultural chemicals company of Japan, Beyer Co., Ltd and E.I.Du Pont Company have found two class high reactivity sterilant-phthalic diamides and O-formammidotiazol-benzamides respectively, this is the synthetic pesticide that Late Cambrian acts on target ryanodine receptor, it makes endogenous Ca store discharge by the activation of induction insect ryanodine receptor, and then causes insect death.This insecticides shows efficiently, wide spectrum, to non-target organism safety and and conventional pesticides without features such as cross resistances.
Chlorantraniliprole (chlorantraniliprole); the bromo-N-of chemical name 3-[4-chloro-2-methyl-6-[(methyl-carbamoyl) benzene]-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-methane amide, trade(brand)name health wide (Ryanxypyr).It is a kind of Novel ortho formamido-benzamide insecticides that du pont company develops, belong to insect ryanodine receptor inhibitor, have and tag and stomach poison function, show efficient, wide spectrum, the features such as holding effect and mechanism of action novelty, can be used for preventing and treating each Species of Lepidopterous Insect Pests, its prevention effect is obviously better than other commercialization insecticide variety used in current production, cross resistance is not existed to other sterilant, and to natural enemy insect safety, can be used for vegetables, beet, the crop control beet armyworms such as cotton, lopper worm, small cabbage moth, small white, the various insect such as bollworm, good prevention effect is had to each instar larvae.The focus of ryanodine receptor insecticides research at present.
Commercial ryanodine receptor insecticides has with three at present:
Each major company is also all devoted to the research of this compounds, the new texture as the initiative of Bayer agriculture section:
The new texture of E.I.Du Pont Company:
The new texture of Syngenta Co., Ltd:
Three, summary of the invention
The object of this invention is to provide pyridyl pyrazoles amide derivatives and application thereof that a class contains seven fluorine sec.-propyls, this compounds has excellent desinsection, fungicidal activity.
The present invention is the preparation and application of the pyridyl pyrazoles amide derivatives containing seven fluorine sec.-propyls shown in general formula (I),
In formula, R
1represent the alkyl of hydrogen, halogen, 1-6 carbon alkyl, the replacement of one or more identical or different halogen atoms; R
2represent the alkyl of hydrogen, halogen, 1-6 carbon alkyl, the replacement of one or more identical or different halogen atoms; R
3represent substituted or unsubstituted alkyl, thiazolinyl, alkynyl, cycloalkyl.
The pyridyl pyrazoles amide derivatives containing seven fluorine sec.-propyls that the present invention narrates can be prepared as follows: compound 1 obtains compound 2 through potassium persulfate oxidation, compound 2 and corresponding halohydrocarbons reaction obtain compound 3, compound 3 hydrolysis obtains acid 4, and the aniline that compound 4 and seven corresponding fluorine sec.-propyls replace obtains the pyridyl pyrazoles amide derivatives containing seven fluorine sec.-propyls of target general formula (I).
Compound 1 is commercially available or prepares by currently known methods.
The present invention goes back the compound that free list 1 lists and illustrates, but does not limit the present invention.
The compound of general formula of the present invention (I) has excellent bactericidal and insecticidal activity, as sterilant, can be used for preventing and treating lepidopteran class, Coleoptera class, Homoptera class, Diptera class and Orthoptera class pest; As sterilant, can be used for preventing and treating Cucumber Target Leaf Spot, cucumber bacterial angular leaf spot, cucumber fusarium axysporum, cucumber downy mildew, powdery mildew of cucumber, bacterial spot of tomato, rice sheath blight disease.
The compound of general formula of the present invention (I) can directly use, and also can add that the carrier agriculturally accepted uses, also can use bactericide compounded with other types sterilant.
Four, embodiment
The present invention is further illustrated below in conjunction with embodiment:
Embodiment one: the synthesis of intermediate 2
Compound 1 (37mmol) is dissolved in 100mL acetonitrile, add sulfuric acid (74mmol) stirring at room temperature 10min, add Potassium Persulphate (56mmol), after temperature rising reflux 4h, be cooled to 55 DEG C, filter, precipitation under filter vacuum, add water 100mL, use dichloromethane extraction (3 × 150mL) again, organic layer merges, dry, and filtrate concentrates, residuum is through silica gel chromatographic column reduced pressure chromatography, elutriant is ethyl acetate and sherwood oil mixed solvent, obtains white solid 2 (62.4%), m.p.136-138 DEG C.
1hNMR (CDCl
3, 400M) and δ: 9.35 (s, 1H, NH); 8.52 (d, J=4.4Hz, 1H, pyridyl-H); 7.90 (d, J=8.0Hz, 1H, pyridyl-H); 7.43 (dd, J
1=4.4Hz, J
2=8.0Hz, 1H, pyridyl-H); 6.36 (s, 1H, pyrazolyl-H); 4.19 (q, 2H, J=7.2Hz, CH
2); 1.19 (t, 3H, J=7.2Hz, CH
3).
Embodiment two: the synthesis of intermediate 3-methyl isophthalic acid-(3-chloro-2-pyridyl)-1H-pyrazole-5-ethyl formate
Compound 2 (7.5mmol) is dissolved in 30mLDMF, add Anhydrous potassium carbonate (11mmol), be heated to 100 DEG C, slowly drip the DMF solution of methyl iodide (9mmol), drip and finish, 3h is reacted at 100 DEG C, extraction into ethyl acetate (3 × 50mL), washing, organic layer is dry, filtrate concentrates, and obtains oily liquids 3-methyl isophthalic acid-(3-chloro-2-pyridyl)-1H-pyrazole-5-ethyl formate.
1HNMR(CDCl
3，400M)δ：8.54(d，J＝4.6Hz，1H，pyridyl-H)；8.21(d，J＝8.0Hz，1H，pyridyl-H)；7.65(dd，1H，J
1＝4.6Hz，J
2＝8.0Hz，1H，pyridyl-H)；6.63(s，1H，pyrazolyl-H)；4.20(q，J＝7.0Hz，2H，CH
2)；3.80(s，3H，CH
3)；1.07(t，J＝7.0Hz，3H，CH
3).
Embodiment three: the synthesis of intermediate 3-methyl isophthalic acid-(3-chloro-2-pyridyl)-1H-pyrazoles-5-formic acid
In 100mL round-bottomed flask, add ester (2.10g, 7.5mmol), 20mL methyl alcohol, 5mL water and NaOH (0.36g, 9mmol), reaction mixture stirring at room temperature reaction 6h, most of solvent is sloughed in decompression, add the dilution of 50mL water, ethyl acetate (10mL) extracts unreacted organism, water layer concentrated hydrochloric acid is adjusted to pH1.5, separate out solid, stirring at room temperature 30min, extraction into ethyl acetate (3 × 50mL), washing, organic layer is dry, filtrate concentrates, obtain 1.09g white solid 3-methyl isophthalic acid-(3-chloro-2-pyridyl)-1H-pyrazoles-5-formic acid, productive rate 57.6%, m.p.245-247 DEG C.
1hNMR (DMSO-d
6, 400M) and δ: 13.50 (s, 3H, CH
3), (8.51 d, J=4.6Hz, 1H, pyridyl-H), (8.18 dd, J=8.0Hz, 1H, pyridyl-H), 7.61 (dd, J
1=4.6Hz, J
2=8.0Hz, 1H, pyridyl-H), (6.54 s, 1H, pyrazolyl-H), 3.85 (s, 3H, CH
3).
Embodiment four: the synthesis of intermediate 3-trifluoro ethoxy-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-ethyl formate
Intermediate 2 (3.7mmol) is dissolved in 30mLDMF, add Anhydrous potassium carbonate (5.5mmol), be heated to 100 DEG C, slow dropping 2, 2, the DMF solution of 2-trifluoro iodoethane (4.4mmol), drip and finish, 3h is reacted at 100 DEG C, extraction into ethyl acetate (3 × 50mL), washing, organic layer is dry, filtrate concentrates, residuum is through silica gel chromatographic column reduced pressure chromatography, elutriant is ethyl acetate and sherwood oil mixed solvent, obtain 1.28g white solid 3-trifluoro ethoxy-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-ethyl formate, productive rate 99%, m.p.63-65 DEG C.
1hNMR (CDCl
3, 400M) and δ: 8.52 (dd, J
1=1.6Hz, J
2=4.8Hz, 1H, pyridyl-H), 7.91 (dd, J
1=1.6Hz, J
2=8.0Hz, 1H, pyridyl-H), 7.43 (dd, 1H, J
1=4.8Hz, J
2=8.0Hz, 1H, pyridyl-H), (6.54 s, 1H, pyrazolyl-H), 4.66 (q, J=16.4Hz, 2H, CH
2cF
3), 4.20 (q, J=7.2Hz, 2H, CH
2), 1.22 (t, J=7.2Hz, 3H, CH
3).
Embodiment five: the synthesis of intermediate 3-trifluoro ethoxy-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-formic acid
In 100mL round-bottomed flask, add ester (3.7mmol), 20mL methyl alcohol, 5mL water and NaOH (4.5mmol), reaction mixture stirring at room temperature reaction 6h, most of solvent is sloughed in decompression, add the dilution of 50mL water, ethyl acetate (10mL) extracts unreacted organism, water layer concentrated hydrochloric acid is adjusted to pH1.5, separate out solid, stirring at room temperature 30min, extraction into ethyl acetate (3 × 50mL), washing, organic layer is dry, filtrate concentrates, obtain 0.84g white solid 3-trifluoro ethoxy-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-formic acid, productive rate 71.3%, m.p.165-167 DEG C.
1hNMR (CDCl
3, 300M) and δ: 8.51 (dd, J
1=1.6Hz, J
2=4.8Hz, 1H, pyridyl-H), 7.92 (dd, J
1=1.6Hz, J
2=8.0Hz, 1H, pyridyl-H), 7.44 (dd, 1H, J=4.8Hz, 8.0Hz, pyridyl-H), (6.59 s, 1H, pyrazolyl-H), 4.65 (q, J=16.4Hz, 2H, CH
2cF
3).
Embodiment six: general formula (I) compou nd synthesis
Acid 4 (1.0mmol) is dissolved in 20mL methylene dichloride, adds oxalyl chloride (3mmol), reaction mixture, at room temperature reaction 3h, removes solvent under reduced pressure and obtains crude acid chloride.Under ice bath, acyl chlorides is dissolved in 10mL methylene dichloride in the 20mL dichloromethane solution slowly instilling intermediate 5 (1.3mmol), then drips triethylamine (1.5mmol) and makes acid binding agent, stirring at room temperature 4h.Question response terminates, precipitation, in reaction flask, add methylene dichloride (60mL), then using saturated sodium bicarbonate aqueous solution (20mL), saturated sodium-chloride water solution (20mL) and water (50mL) to wash respectively has organic layer, anhydrous Na
2sO
4drying, filters, and filtrate concentrates, and residuum is through silica gel chromatographic column reduced pressure chromatography, and elutriant is ethyl acetate and sherwood oil mixed solvent, and obtain the compound of general formula (I), particular compound is in table 1.
Embodiment six: active to diamondback moth larvae
A certain amount of testing compound is dissolved in appropriate DMF, is made into 400mgL with the water containing TW-20
-1liquid, and be diluted to certain concentration as required, fresh cabbage leaves cut into slices, in liquid to be measured, floods cabbage leaves, time 3-5 second, get rid of remaining liquid.After liquid is dry, put into the long straight type of the markd 10cm of tool in vitro, access 3 age diamondback moth larvae, build the mouth of pipe with gauze.Test process be placed in standard treatment chamber, 72h check result touches polypide with pulling needle, and motionless person is dead, under each concentration in triplicate.Calculate and corrected mortality.Table 2 is the test result of part of compounds.
Embodiment seven: control vegetable disease live body microscreen test
Select 2 cotyledon period cucumber seedlings, Cucumber Target Leaf Spot, Powdery Mildew, oidium adopt spore suspension spray inoculation, cucumber bacterial angular leaf spot, bacterial spot of tomato adopt bacteria suspension spray inoculation, cucumber fusarium axysporum disease adopts radicle seed soaking inoculation method, and rice sheath blight disease adopts mycelia spray inoculation method.Reagent agent and contrast medicament are evenly sprayed in cucumber cotyledons the morning in fine day, inoculate pathogenic bacteria after 2 hours, moisturizing is cultivated.According to grade scale after contrasting fully morbidity, the investigation state of an illness, calculates disease index and preventive effect.Table 3 is the test result of part of compounds.
Pyridyl pyrazoles amide derivatives (I) list of table 1 containing seven fluorine sec.-propyls
aThevalueofHRMS[M+Na]
+.
Table 2 part of compounds is to small cabbage moth active testing result test-results
Table 3 part of compounds control vegetable disease live body microscreen test-results (500mgkg
-1)
Claims (4)
1. the pyridyl pyrazoles amide derivatives containing seven fluorine sec.-propyls, is characterized in that it has structure shown in following general formula (I):
In formula, R
1represent the alkyl of hydrogen, halogen, 1-6 carbon alkyl, the replacement of one or more identical or different halogen atoms; R
2represent the alkyl of hydrogen, halogen, 1-6 carbon alkyl, the replacement of one or more identical or different halogen atoms; R
3represent substituted or unsubstituted alkyl, thiazolinyl, alkynyl, cycloalkyl.
2. the pyridyl pyrazoles amide derivatives containing seven fluorine sec.-propyls according to claim 1, is characterized in that.R
1for hydrogen, methyl, ethyl, sec.-propyl; R
2for hydrogen, methyl, ethyl, sec.-propyl; R
3for methyl, ethylisopropyl base, allyl group, propargyl, trifluoroethyl.
3. the application containing the pyridyl pyrazoles amide derivatives of seven fluorine sec.-propyls according to claim 1, is characterized in that it is as sterilant, can be used for preventing and treating lepidopteran class, Coleoptera class, Homoptera class, Diptera class and Orthoptera class pest.
4. the application containing the pyridyl pyrazoles amide derivatives of seven fluorine sec.-propyls according to claim 1, it is characterized in that it is as sterilant, can be used for preventing and treating Cucumber Target Leaf Spot, cucumber bacterial angular leaf spot, cucumber fusarium axysporum, cucumber downy mildew, powdery mildew of cucumber, bacterial spot of tomato, rice sheath blight disease.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128410A (en) * | 2019-04-30 | 2019-08-16 | 南通大学 | Pyrazole Oxime Esters of the structure containing difluoromethyl pyrazole and its preparation method and application |
| WO2023006634A1 (en) | 2021-07-27 | 2023-02-02 | Syngenta Crop Protection Ag | Method for controlling diamide resistant pests & compounds therefor |
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| CN1659160A (en) * | 2002-06-13 | 2005-08-24 | 纳幕尔杜邦公司 | Pyrazolecarboxamide insecticides |
| CN101298435A (en) * | 2007-04-30 | 2008-11-05 | 中国中化集团公司 | O-formammidotiazol-benzamide compounds and use thereof |
| CN101659655A (en) * | 2009-09-15 | 2010-03-03 | 南开大学 | Pyrazole amide derivative and application thereof |
| CN101967139A (en) * | 2010-09-14 | 2011-02-09 | 中化蓝天集团有限公司 | Fluoro methoxylpyrazole-containing o-formylaminobenzamide compound, synthesis method and application thereof |
| CN105061396A (en) * | 2015-08-13 | 2015-11-18 | 南阳师范学院 | Amide derivative and preparation method thereof |
-
2016
- 2016-01-08 CN CN201610012973.6A patent/CN105541794A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1659160A (en) * | 2002-06-13 | 2005-08-24 | 纳幕尔杜邦公司 | Pyrazolecarboxamide insecticides |
| CN101298435A (en) * | 2007-04-30 | 2008-11-05 | 中国中化集团公司 | O-formammidotiazol-benzamide compounds and use thereof |
| CN101659655A (en) * | 2009-09-15 | 2010-03-03 | 南开大学 | Pyrazole amide derivative and application thereof |
| CN101967139A (en) * | 2010-09-14 | 2011-02-09 | 中化蓝天集团有限公司 | Fluoro methoxylpyrazole-containing o-formylaminobenzamide compound, synthesis method and application thereof |
| CN105061396A (en) * | 2015-08-13 | 2015-11-18 | 南阳师范学院 | Amide derivative and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128410A (en) * | 2019-04-30 | 2019-08-16 | 南通大学 | Pyrazole Oxime Esters of the structure containing difluoromethyl pyrazole and its preparation method and application |
| WO2023006634A1 (en) | 2021-07-27 | 2023-02-02 | Syngenta Crop Protection Ag | Method for controlling diamide resistant pests & compounds therefor |
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