CN102690257A - Anthranilamide compound and application thereof - Google Patents
Anthranilamide compound and application thereof Download PDFInfo
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- CN102690257A CN102690257A CN2012101611094A CN201210161109A CN102690257A CN 102690257 A CN102690257 A CN 102690257A CN 2012101611094 A CN2012101611094 A CN 2012101611094A CN 201210161109 A CN201210161109 A CN 201210161109A CN 102690257 A CN102690257 A CN 102690257A
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- 0 CNC(c(cc(*)cc1*)c1NC(c1cc(*)n[n]1-c1ncccc1*)=O)=O Chemical compound CNC(c(cc(*)cc1*)c1NC(c1cc(*)n[n]1-c1ncccc1*)=O)=O 0.000 description 5
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Abstract
The invention discloses a novel anthranilamide compound and application thereof. A structure of the compound is shown as a general formula I: wherein R1, R2, R3, R4 and R5 are defined as a specification. The compound of the general formula I has a broad-spectrum insecticidal activity and particularly has a good effect for killing lepidoptera pests and coleoptera pests.
Description
Technical field
The present invention relates to a kind of Anthranilamide compound and application thereof.The invention belongs to agriculture desinsection field.
Background technology
Du pont company is one of sterilant of the effectively preventing lepidoptera pest developed in recent years in disclosed Arthropodicidal anthranilamide of calendar year 2001 (WO2001070671A2).After this, German BASF, the U.S. just reaches earlier, and the me too class drug patent that the Shenyang Chemical Engineering Inst of China, Hunan Chemical Research Institute, Zhejiang chemical research institute have all carried out this medicine discloses.
The present invention and the disclosed compound structure of above-mentioned patent have similarity, but structure still has tangible difference.The compound of general formula I of the present invention does not appear in the newspapers, and is one type of novel fully Anthranilamide compound.The maximum characteristics of the present invention are on the nitrogen-atoms of acid amides, to introduce diverse group.
The action target spot of clear and definite Anthranilamide compound is the ryania acceptor at present; This receptor is to know maximum calcium channel albumen a few days ago; Ryania combines with this compounds, can cause a large amount of releases of calcium ion in the insect muscle tissue sarcoplasmic reticulum chamber, makes Muscle contraction dead.
Summary of the invention
A kind of Anthranilamide compound compound provided by the invention, its purpose is to prevent and treat effectively Agricultural pests, especially lepidopteran and coleopteran pest.
Technical scheme of the present invention is following:
The Anthranilamide compound compound of a kind of novelty provided by the invention is shown in general formula I:
In the formula,
R
1Be selected from H, CH
3, or halogen;
R
2Be selected from H, halogen, CF
3Or cyano group;
R
3Be selected from halogen, CF
3, OCH
2CF
3, or OCF
2H;
R
4Be selected from H or halogen;
R
5Be selected from
Or be selected from the arbitrary group of following G1-G6:
When G1:E was selected from N, Z was selected from S; When E was selected from S, Z was selected from NH;
G2:R
8Be selected from CH
2Or can be by phenyl ring, benzheterocycle, or heterocyclic substituted; M is selected from acid or ester;
G3:L is selected from halogen, cyanic acid;
G4:A is selected from H, the C1-C4 alkyl; B is selected from straight chain, or the C of band side chain
0-C
5Alkyl;
G5:D is selected from straight chain, or band side chain C
5Alkyl; R
6, R
7Be selected from identical or different C
1-C
4Alkyl;
G6: be selected from straight chain, or band side chain C
7-C
10Alkyl
N is: 1-5;
Various isomer, the N-oxide compound, or be applicable to agricultural and non-agricultural salt.
The present invention relates to a kind of compsn of preventing and treating Agricultural pests, comprise the biologic effective dose and at least a tensio-active agent of compound of Formula I, the component of solid diluent and liquid diluent.The invention still further relates to another kind of compsn, comprise the biologic effective dose or the preparation of biologic effective dose and other at least a compound of a kind of compound of general formula I.
The invention still further relates to a kind of method of preventing and treating Agricultural pests, this method is with the biologic effective dose contact Agricultural pests and the environment thereof of formula I compound.And the biologic effective dose of the biologic effective dose of a kind of compound of general formula I and other at least a compound or preparation control Agricultural pests, especially prevent and treat lepidoptera pest.
Compound of Formula I involved in the present invention exists with the form of one or more steric isomers.Various steric isomers comprise enantiomer, diastereo-isomerism, body atropisomer, and geometrical isomer.When a kind of steric isomer is an enrich body, or when from other isomer, separating, this isomer can demonstrate more high reactivity, or shows favourable effect.And those skilled in the art also know how to separate, and prepare described steric isomer.Therefore, the present invention includes compound of Formula I, various isomer, the N-oxide compound, or be applicable to agricultural and non-agricultural salt.Compound of the present invention can be a raceme, single steric isomer, or exist with optically pure active body form.
The salt of The compounds of this invention comprises inorganic salt or organic acid additive salt, example hydrochloric acid salt, nitrate salt, phosphoric acid salt, vitriol, acetate, butyrates, oxalate, propionic salt, fumarate, tartrate.
According to biological activity, synthetic route, cost, preferred compound is:
R
1Be selected from CH
3R
2Be selected from Cl or cyanic acid; R
3Be selected from Br; R
4Be selected from Cl;
R
5Be selected from
Or be selected from following G1, G2, or the arbitrary group of G3:
Preferred especially formula I compound is selected from:
Formula I compound, wherein R
1Be selected from CH
3R
2Be selected from Cl; R
3Be selected from Br; R
4Be selected from Cl; R
5Be selected from
Formula I compound, wherein R
1Be selected from CH
3R
2Be selected from cyanic acid; R
3Be selected from Br; R
4Be selected from Cl; R
5Be selected from
Formula I compound, wherein R
1Be selected from CH
3R
2Be selected from Cl; R
3Be selected from CF
3R
4Be selected from Cl; R
5Be selected from
Formula I compound, wherein R
1Be selected from CH
3R
2Be selected from cyanic acid; R
3Be selected from Br; R
4Be selected from Cl; R
5Be selected from
Formula I compound, wherein R
1Be selected from CH
3R
2Be selected from cyanic acid; R
3Be selected from CF
3R
4Be selected from Cl; R
5Be selected from
Formula I compound, wherein R
1Be selected from CH
3R
2Be selected from cyanic acid; R
3Be selected from Br; R
4Be selected from Cl; R
5Be selected from
Formula I compound, wherein R
1Be selected from CH
3R
2Be selected from Cl; R
3Be selected from Br; R
4Be selected from Cl; R
5Be selected from
Formula I compound, wherein R
1Be selected from CH
3R
2Be selected from cyanic acid; R
3Be selected from CF
3R
4Be selected from Cl; R
5Be selected from
The preparation method of compound of Formula I of the present invention is following:
General formula I-a compound can be used benzoxazinone and the mercaptoethylamine prepared in reaction of general formula I I:
General formula I-b compound can be used benzoxazinone and the amido alkyl alcohol prepared in reaction of general formula I I:
General formula I-c compound can be used benzoxazinone and amino acid or the corresponding esters prepared in reaction of general formula I I:
General formula I-d compound can be used benzoxazinone and the Malonamide nitrile of general formula I I, or the Haloacetamide prepared in reaction:
General formula I-e compound can be used benzoxazinone and the 2-hydroxyethylhydrazine prepared in reaction of general formula I I:
General formula I-f compound can be used benzoxazinone and the Plaquenil side chain prepared in reaction of general formula I I:
General formula I-g compound can pass through benzoxazinone and the chloroquine side chain prepared in reaction of general formula I I:
General formula I-h compound can be used benzoxazinone and the C7-C10 alkylamino prepared in reaction of general formula I I:
Each group see claim book of general formula I a-Ih;
This reaction can be solvent-free, or in the solvent that is fit to, carry out, and comprises THF, ether, methylene dichloride, chloroform.Temperature of reaction is carried out in the Optimal Temperature of room temperature to solvent refluxing.Reaction times 1-24 hour.The preparation method of general formula I I is with reference to Biorganic and Medicinal Chenmistry 2000,8,2095-2103 and J.Heterocyclic Chemistry 1999.36,563-588.
According to above-mentioned described method and method well known in the art, the compound below can preparing among the table 1-7, but do not limit the present invention.The abbreviation of using in the table as: t refers to uncle, and s refers to the second month in a season, and n makes a comment or criticism, and i refers to different, Me nail base, Et refers to ethyl, Pr refers to propyl group, i-Pr refers to sec.-propyl, Bu refers to butyl.
Table 1
Table 2
Table 3
Table 4
Table 5
The compound embodiment
Further specify the present invention through embodiment below, but be not to limit the present invention with these embodiment.All umbers and percentage are in weight ratio among the embodiment.
Embodiment, the typical compound reaction expression:
The preparation of compound a:
80% Hydrazine Hydrate 80 (5mL) joined under room temperature contain 2, and the 3-dichloropyridine (0.5g, 3mmol) in the anhydrous alcohol solution (30mL), reflux 24h.Ice bath is cooled to 0 ℃, has a large amount of solids to separate out, suction filtration, and filtration cakes torrefaction gets white solid.Yield 80%.
The preparation of compound b:
(0.06g 3mmol) slowly joins in absolute ethyl alcohol (15mL) reaction flask, treats sodium piece complete reaction, and solution is heated to backflow with sodium.(0.3g 2.1mmol), continues backflow 10min to add 1 then.Reflux state drips ethyl maleate down, and (1.4g 8.4mmol), detects 1 completely dissolve, stopped reaction after the 5min.Decompression steams most of ethanol in the reaction bulb, adds DCM(10mL then).Organic phase is added drop-wise to water (30mL, hydrochloric acid is regulated pH and maintained about 4).DCM (30mL) extracted twice merges organic phase, drying, and recrystallization gets light yellow solid, yield 50-55%.
Compound c 1:
Under condition of ice bath, POCl3 (5mL) dripped (0.5g is 1.9mmol) and in acetonitrile (30mL) reaction flask in containing 2.Dropwise, with reaction solution reflux 2h.The major part that boils off normal pressure contains the acetonitrile solution of tribromo oxygen phosphorus, adds DCM (10mL) then.Organic phase is added drop-wise to (30mL, pH transfers to about 8) in the saturated sodium carbonate solution.The DCM extracted twice merges organic phase, and drying is crossed post and got brown oil matter, yield 90-93%.
Compound c 2:
Under condition of ice bath, (0.8g adds to contain 2 2.9mmol) that (0.5g is 1.9mmol) and in acetonitrile (30mL) reaction flask with tribromo oxygen phosphorus.Dropwise, with reaction solution reflux 5h.The major part that boils off normal pressure contains the acetonitrile solution of tribromo oxygen phosphorus, adds DCM (10mL) then.Organic phase is added drop-wise to (30mL, pH transfers to about 8) in the saturated sodium carbonate solution.The DCM extracted twice merges organic phase, and drying is crossed post and got white solid, yield 90-95%.
Compound d 1:
(0.33g 3.4mmol) is added drop-wise to and contains 3a (0.5g is 1.7mmol) and in acetonitrile (20mL) reaction flask with 98% vitriol oil under the room temperature.Dropwise, after reaction solution stirs about 5min, the adding Potassium Persulphate (0.69g, 2.6mmol).Then reaction solution is refluxed about 5h.Filter, filtrating concentrating removed most of acetonitrile, and saturated sodium carbonate solution transfers pH in about 8.The DCM extracted twice merges organic phase, and drying is crossed post and got white solid, yield 80%.
Compound d 2:
(0.17g 1.8mmol) is added drop-wise to and contains 3b (0.3g is 0.9mmol) and in acetonitrile (15mL) reaction flask with 95% vitriol oil under the room temperature.Dropwise, stir reaction solution about 5min after, add Potassium Persulphate (0.36g, 1.35mmol).Then reaction solution is refluxed about 5h.Filter, filtrating concentrating removed most of acetonitrile, and saturated sodium carbonate solution transfers pH in about 8.The DCM extracted twice merges organic phase, and drying is crossed post and got white solid, yield 75%.
Verbindung 1:
The water intaking close Lithium Hydroxide MonoHydrate (0.294g, 7mmol) in contain 4a (0.5g, 1.75mmol), in water (15mL) and THF (15mL) reaction flask.Stir 5h under the room temperature.THF is gone out in underpressure distillation, then water pH is transferred to about 1.DCM (30mL) extracted twice merges organic phase, drying, concentrate white solid, yield 60%.
Verbindung 2:
The water intaking close Lithium Hydroxide MonoHydrate (0.254g, 6mmol) in contain 4b (0.5g, 1.5mmol), in water (15mL) and THF (15mL) reaction flask.Stir 5h under the room temperature.THF is gone out in underpressure distillation, then water pH is transferred to about 1.DCM (30mL) extracted twice merges organic phase, drying, concentrate white solid, yield 64%.
Compound f1:
Under condition of ice bath with methylsulfonyl chloride (0.18g, dropwise add in acetonitrile solution 1.55mmol) 5a (0.4g, 1.55mmol) and triethylamine (0.157g, acetonitrile mixture 1.55mmol).After stirring 20min, and adding 2-amino-3-methyl-5-chloro phenylformic acid (0.288g, 1.55mmol), restir 5min.Then by low add triethylamine (reaction solution stirs 45min for 0.31g, acetonitrile solution 3.1mmol), add again methylsulfonyl chloride (0.18g, 1.55mmol).Reaction solution rises to room temperature then, stirs 8h.Reaction solution is cooled to 0 ℃, crosses to filter yellow solid.Yellow solid is dissolved among the DCM (30mL), removes by filter yellow insolubles, add gac in the filtrating, stir 20min, diatomite filtration.Filtrating is dry concentrate faint yellow solid, can be used for next step reaction, yield 50%.
Compound f2:
Under condition of ice bath to methylsulfonyl chloride (0.189g, dropwise add in acetonitrile solution 1.65mmol) 5b (0.5g, 1.65mmol) and triethylamine (0.167g, acetonitrile mixture 1.65mmol).After stirring 20min, and adding 2-amino-3-methyl-5-chloro phenylformic acid (0.3g, 1.65mmol), restir 5min.Then by low add triethylamine (reaction solution stirs 45min for 0.334g, acetonitrile solution 3.3mmol), add again methylsulfonyl chloride (0.189g, 1.65mmol).Reaction solution rises to room temperature then, stirs 8h.Reaction solution is cooled to 0 ℃, crosses to filter yellow solid.Yellow solid is dissolved among the DCM (30mL), removes by filter yellow insolubles, add gac in the filtrating, stir 20min, diatomite filtration.Filtrating is dry concentrate faint yellow solid, can be used for next step reaction, yield 55%.
Compound 9f (seeing table 5):
Under the room temperature to f1 (0.2g dropwise adds 1-N among DCM 0.49mmol) (5mL), N-diethylammonium-1, (0.077g, dichloromethane solution 0.49mmol) (3mL) stir about 6h 4-diamino-6 pentanes.Reaction solution is used alkali liquid washing, DCM (30mL) extraction, and drying concentrates, and recrystallization gets white solid, yield 65%.
Compound 10f (seeing table 5):
Under the room temperature to f2 (0.2g dropwise adds 1-N among DCM 0.442mmol) (5mL), N-diethylammonium-1, (0.07g, dichloromethane solution 0.442mmol) (3mL) stir about 6h 4-diamino-pentane.Reaction solution is used alkali liquid washing, DCM (30mL) extraction, and drying concentrates, and recrystallization gets white solid, yield 60%.
The nuclear magnetic data of part of compounds is following:
Compound 2a:
1H-NMR(CDCl3)δ1.00(s，1H，SH)，2.18(s，3H，Ph-CH3)，2.86(t，2H，CH2SH)，3.50(t，2H，NHCH2)，7.15(s，1H，Pyrazole-H)，7.48(s，1H，Ph-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.93(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.45(d，J＝4.8Hz，1H，NH).
Compound 9a:
1H-NMR(CDCl3)δ1.00(s，1H，SH)，2.18(s，3H，Ph-CH3)，2.86(t，2H，CH2SH)，3.50(t，2H，NHCH2)，7.15(s，1H，Pyrazole-H)，7.48(s，1H，Ph-H)，7.23(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.44(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.45(d，J＝4.8Hz，1H，NH).
Compound 10a:
1H-NMR(CDCl3)δ1.00(s，1H，SH)，2.18(s，3H，Ph-CH3)，2.86(t，2H，CH2SH)，3.50(t，2H，NHCH2)，7.15(s，1H，Pyrazole-H)，7.48(s，1H，Ph-H)，7.23(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.44(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.45(d，J＝4.8Hz，1H，NH).
Compound 26a:
1H-NMR(CDCl3)δ1.00(s，1H，SH)，2.18(s，3H，Ph-CH3)，2.86(t，2H，CH2SH)，3.50(t，2H，NHCH2)，7.15(s，1H，Pyrazole-H)，7.48(s，1H，Ph-H)，7.23(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.44(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.45(d，J＝4.8Hz，1H，NH).
Compound 34a:
1H-NMR(CDCl3)δ1.00(s，1H，SH)，2.18(s，3H，Ph-CH3)，2.86(t，2H，CH2SH)，3.50(t，2H，NHCH2)，7.15(s，1H，Pyrazole-H)，7.54(s，1H，Ph-H)，7.23(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.99(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.45(d，J＝4.8Hz，1H，NH).
Compound 2b:
1H-NMR(CDCl3)δ2.00(s，1H，NH)，2.35(s，3H，Ph-CH3)，2.47(s，3H，NHCH3)，7.15(s，1H，Pyrazole-H)，7.48(s，1H，Ph-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.93(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.0(s，1H，NHCS)，8.45(d，J＝4.8Hz，1H，NH).
Compound 10b:
1H-NMR(CDCl3)δ2.00(s，1H，NH)，2.35(s，3H，Ph-CH3)，2.47(s，3H，NHCH3)，7.15(s，1H，Pyrazole-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，.J＝4.8Hz，8Hz，1H，Pyridine-H)，7.44(s，1H，Ph-H)，7.48(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyri?dine-H)，8.0(s，1H，NHCS)，8.45(d，J＝4.8Hz，1H，NH).
Compound 34b:
H-NMR(CDCl3)δ2.00(s，3H，SCH3)，2.35(s，3H，Ph-CH3)，7.15(s，1H，Pyrazole-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.44(s，1H，Ph-H)，7.48(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.0(s，1H，NHCO).
Compound 10c:
1H-NMR(CDCl3)δ2.00(s，1H，OH)，2.18(s，3H，Ph-CH3)，4.14(s，2H，NHCH2)，7.15(s，1H，Pyrazo1e-H)，7.23(s，1H，Ph-H)，7.23(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.44(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.45(d，J＝4.8Hz，1H，NH)，11.0(s，1H，COOH)
Compound 18c:
1H-NMR(CDCl3)δ2.00(s，1H，OH)，2.18(s，3H，Ph-CH3)，4.14(s，2H，NHCH2)，7.15(s，1H，Pyrazole-H)，7.23(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.54(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，7.99(s，1H，Ph-H)，8.45(d，J＝4.8Hz，1H，NH)，11.0(s，1H，COOH)
Compound 34c:
1H-NMR(CDCl3)δ2.35(s，3H，Ph-CH3)，3.67(s，3H，OCH3)，7.15(s，1H，Pyrazole-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.44(s，1H，Ph-H)，7.48(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.0(s，1H，NHCO).
Compound 10d:
1H-NMR(CDCl3)δ4.98(s，2H，CH2)，2.18(s，3H，Ph-CH3)，4.07(m，1H，CH)，7.15(s，1H，Pyrazole-H)，7.23(s，1H，Ph-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.44(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.45(d，J＝4.8Hz，1H，NH).
Compound 10e:
1H-NMR(CDCl3)δ2.00(s，1H，OH)，2.00(s，1H，NH)，2.18(s，3H，Ph-CH3)，2.84(t，2H，NHCH2)，3.79(t，2H，CH2OH)，7.15(s，1H，Pyrazole-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.30，1H，Ph-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.75，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.00(s，1H，NH)，8.45(d，J＝4.8Hz，1H，NH).
Compound 42e:
1H-NMR(CDCl3)δ2.00(s，1H，OH)，2.00(s，1H，NH)，2.18(s，3H，Ph-CH3)，2.74(t，2H，CH2NH)，2.85(t，2H，NHCH2)，3.32(t，2H，CH2NH)3.65(t，2H，CH2OH)，7.15(s，1H，Pyrazole-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.30，1H，Ph-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.75，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.00(s，1H，NH)，8.45(d，.J＝4.8Hz，1H，NH).
Compound 78e:
1H-NMR(CDCl3)δ1.00(t，2H，CH2CH3)，1.30(d，3H，CHCH3)，1.39(m，2H，CH2CH2CH2)，1.55(m，2HCH2CH2CH)，2.00(s，1H，OH)，2.18(s，3H，Ph-CH3)，2.36(t，2H，NCH2CH2)，2.40(q，2H，CH2CH3)，2.55(t，2H，CH2CH2N)，2.74(t，2H，CH2NH)，3.63(t，2H，CH2OH)，3.76(m，1H，NHCHCH3)，7.15(s，1H，Pyrazole-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.30，1H，Ph-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.75，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.00(s，1H，NH)，8.45(d，J＝4.8Hz，1H，NH).
Compound 9f:
1H-NMR(CDCl3)δ1.00(t，J＝7.2Hz，6H，2CH2CH3)，1.18(d，J＝6.4Hz，3H，CHCH3)，1.54(m，2H，CH2)，1.55(m，2H，CH2)，2.18(s，3H，Ph-CH3)，2.46(q，J＝7Hz，4H，2CH2CH3)，2.53(t，J＝6.8Hz，2H，CH2)，4.07(m，1H，CH)，7.15(s，1H，Pyrazole-H)，7.23(s，1H，Ph-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.44(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.45(d，J＝4.8Hz，1H，NH).
Compound 10f:
1H-NMR(CDCl3)δ1.00(t，J＝7.2Hz，6H，2CH2CH3)，1.19(d，J＝6.4Hz，3H，CHCH3)，1.55(m，2H，CH2)，1.57(m，2H，CH2)，2.18(s，3H，Ph-CH3)，2.46(q，J＝7Hz，4H，2CH2CH3)，2.53(t，J＝6.8Hz，2H，CH2)，4.07(m，1H，CH)，7.15(s，1H，Pyrazole-H)，7.23(s，1H，Ph-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.44(s，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.45(d，J＝4.8Hz，1H，NH).
Compound 10f:
1H-NMR(CDCl3)δ1.06(s，9H，3CHCH3)，1.35(s，6H，2CCH3)，1.43(s，2H，CCH2C)，2.18(s，3H，PhCH3)，7.15(s，1H，Pyrazole-H)，7.26(d，J＝5.6Hz，1H，Pyridine-H)，7.30，1H，Ph-H)，7.37(dd，J＝4.8Hz，8Hz，1H，Pyridine-H)，7.75，1H，Ph-H)，7.84(d，J＝8Hz，1H，Pyridine-H)，8.00(s，1H，NH)，8.45(d，J＝4.8Hz，1H，NH)
Preparation and application:
Compound of the present invention generally will be used for and be suitable for agricultural carrier being made into preparation, and carrier comprises liquid or solid thinner or organic solvent.The useful preparation of this case compound can prepare in a usual manner.These preparations comprise: pulvis, granula, bait formulation, pill, solution, suspension agent, emulsion, wettable powder, missible oil, dried flowing agent etc.Wherein there are many preparations directly to use.Sprays can be diluted in the suitable medium, the sprayed volume when using as per hectare 100 to several hectolitres.High concentration composition is mainly as supplying the further midbody of preparation usefulness.In a broad sense, these amount of formulation contain the activeconstituents that is less than about 1%-99% (weight) and at least one in following two components: (a) about 0.1%-20% tensio-active agent; (b) about 5%-99% solid or liquid diluent.More particularly, the general proportions of contained significant quantity mentioned component is following in the preparation:
Certainly, the content of activeconstituents can be lower or higher, and this depends on the desired use and the physical properties of compound.The ratio of hoping tensio-active agent and activeconstituents sometimes is higher, and this can realize through being incorporated into tensio-active agent in the preparation or mixing through bucket.
The preferred stronger thinner of water-absorbent concerning wettable powder, the bigger thinner of preferred density concerning pulvis.Concerning suspension concentrate, preferably be lower than 0.1% solubleness; Solution concentration liquid is preferably under 0 ℃ and is not separated.All preparations can contain minor amounts of additives to reduce foaming, caking, burn into microorganism growth etc.Each composition preferably EPA approval is used for the material of this desired use.
It is known preparing these method for compositions.Simple each composition that mixes can make solution.The fine-grained solids compsn prepares with hybrid system, normally in sledge mill or fluid energy mill, grinds.Suspension agent prepares with wet milling process.Granula and pill can prepare through active substance is sprayed onto on the preformed particulate vector, also can prepare with agglomeration technique.
Embodiment A
Mixing each stirs with accelerate dissolution down very much and slightly warm.In packaging operation, add one 7 pore filter, to guarantee not contain any unnecessary not molten thing in the product.
Embodiment B
In the blending machine, activeconstituents is mixed with inert material.After in sledge mill, grinding, material is mixed and through 50 mesh sieves once more.
Embodiment C
Pulvis
The wettable powder 10% of Embodiment B
Pyrophyllite (powder) 90%
With agent of wetting properties numerical value and pyrophyllite thinner thorough mixing, pack then.This product is suitable for as pulvis.
Embodiment D
Activeconstituents is dissolved in volatile solvent such as the acetone, in double-cone mixer, is sprayed onto on the attapulgite particle through dedusting and preheating.Acetone is evicted in heating from then.Make particle cooling then and pack.
Embodiment E
In rotary blender, mix each composition and water spray, granulate to accomplish.When most of materials reach desired 0.1-0.42mm scope (18-40 USS sieve), take out particle, dry and screening.Excessive material is broken, obtain the material that another batch is in institute's claimed range.These particles contain 4.5% activeconstituents.
Embodiment F
Solution
This case compound 25%
N-Methyl pyrrolidone 75%
Each composition is mixed and stirring, obtain being suitable for the direct solution of using with short run.
Embodiment G
Each composition mixes in sand milling and grinds, and obtains granularity and all is in the particle below 5 microns basically.
Embodiment H
In sand milling, each composition is mixed together and grinds, obtain all being in basically the particle below 5 microns.This product can directly use, and looses with oil content, also can use emulsifying water.
Example I
Activeconstituents and surfactant mixt are dissolved in the suitable solvent such as acetone, and are sprayed on the broken corn cob.Then with particle drying and packing.
This case compound also can mix with a kind of or more kinds of other insecticides, mycocide, nematocides, bactericide, miticide or other biological active compound, forms multi-component agricultural chemicals, produces more wide-spectrum effective agricultural protection effect.Can have with other agricultural protectant examples that The compounds of this invention fits over together: insecticide; Mycocide; Nematocides; Bactericide; Miticide; Biotechnological formulation.
Practicality
The characteristic of some compound of the present invention is to have favourable metabolism and/or pedo relict form; They have broad spectrum of activity to the insect that habit occupies leafage, and these insects belong to the growth farm crop or store insect, forestry pest, chamber crop insect, ornamental plant pest, the nursery crop pest of farm crop.The compounds of this invention demonstrates activity to some important economic insects, and these insects belong to Agricultural pests, forestry pest, greenhouse insect, ornamental plant pest, nursery pest, for example:
Lepidoptera pest comprises autumn mythimna separata and beet armyworm and other Spodoptera insects; Oriental tobacco budworm, corn earworm, bollworm and other Noctua insects; European corn borer, navel orangeworm, handle/stem snout moth, striped rice borer, yellow rice borer, Cnaphalocrocis medinali(rice leaf roller) and other snout moths; Trichoplusia ni, purple line geometrid moth and other geometrid moths; The moth-eaten moth of apple, grape steinernema and other volume moths; Black cutworm, Eight characters cutworm, other cutworms and other noctuids; Small cabbage moth, pink bollworm.
Species in order to illustrate control action kou have: bollworm, sweet bud noctuid, Ostrinia furnacalis, rice-stem borer, Cnaphalocrocis medinali(rice leaf roller).But the insect that The compounds of this invention produced control provide protection is not limited only to these species.
Use
Use a kind of or more kinds of this case compound of the present invention with significant quantity; Can control the agriculture insect; And realize farm crop, the healthy protection of animal and human's class; Can be applied to and comprise agricultural and the non-agricultural insect environment that infects the place, be applied to claimed area, also can directly be applied to the insect that will control.Because habitat and the habit of these agriculture insects are varied, adopt many different application methods.Preferred application method is that this apparatus can intersperse among compound in the insect environment with the apparatus spraying, intersperses among in the soil or in the animal body, intersperses among the part that is infected on the plant or need protection.In addition, the granula of these toxic chemicals also can be applied to soil or mix in the soil.Also other application methods be can adopt, direct spraying and residual spray, aerial spraying, poison bait, ear tag, bolus, aerosol and many additive methods comprised.
The compounds of this invention can be used with its pure state, but modal be that a preparation is used, contain a kind of in the preparation or more compounds and suitable carriers, thinner and tensio-active agent.Preferred application method relates to the aqueous dispersions or the treated oil solution of compound sprays.With the concentration of the mixing of spray oils, spray oils, synergistic agent such as Piperonyl Butoxide, usually can strengthen the effectiveness of this case compound.
This case compound reaches the required rate of application of effective control action kou will depend on following like this some factors: kind, the insect life history, life stage, its size, habitat, season, host crop or animal, feeding habits, mating behavior, ambient moisture, the temperature etc. of the insect that will control.In general, the rate of application of per hectare 0.01-2 kilogram activeconstituents just is enough under normal circumstances the insect in the Agro-ecology is produced large-scale effectively control action kou, but also possibly be low to moderate 0.001 kg/ha or up to the rate of application of 8 kg/ha.
Following experiment confirm this case compound the control of concrete insect is renderd a service, compound is described and numbering is seen specification sheets table 1-5
Test A
Bollworm
Prepare some test units, each unit is made up of one 230 milliliters plastic cup, and every cup has the growth cotton seedling plant in three weeks.Put into 10 bollworm third-instar larvaes in every glass.With three cups is one group, in cup, sprays into the solution (volume is acetone/zero(ppm) water 75/25) of each experimental compound, and every group of cup only sprays a kind of solution.Spray method is, with each glass place make on the travelling belt its pass through a fan-shaped mist awl hydraulicefficiency pressure nozzle under, the speed of the about 20g/ hectare of nozzle activeconstituents is sprayed, spray pressure is 30 pounds/207 kPas.Then with on each bowl cover, 27 ℃ and 50% relative humidity held 72 hours, image data then.In the compound of being tested, following compounds causes the mortality ratio more than or equal to 80%:
Compound 2a; 5a; 9a; 10a; 14a; 17a; 18a; 37a; 38a; 2b; 3b; 6b; 10b; 17b; 18b; 34b; 41b; 50b; 2c; 6c; 8c; 10c; 18c; 34c; 37c; 42c; 54c; 2d; 10d; 1e; 9e; 20e; 22e; 34e; 42e; 49e; 66e; 73e; 81e; 9f; 14f; 18f; 10g; 18g; 45g.Structrual description and numbering are seen specification sheets table 1-5.
Test B
Sweet bud noctuid
The TP of revision test A, test compounds still were the evaluation mortality ratio at 48 hours to the effectiveness of sweet bud noctuid third-instar larvae.In the compound of being tested, following compounds causes the mortality ratio more than or equal to %:
Compound 2a; 5a; 9a; 10a; 14a; 17a; 18a; 37a; 38a; 2b; 3b; 6b; 10b; 17b; 18b; 34b; 41b; 50b; 2c; 6c; 8c; 10c; 18c; 34c; 37c; 42c; 54c; 2d; 10d; 1e; 9e; 20e; 22e; 34e; 42e; 49e; 66e; 73e; 81e; 9f; 14f; 18f; 10g; 18g; 45g.Structrual description and numbering are seen specification sheets table 1-5.
Test C
Ostrinia furnacalis
Prepare some test units, each unit has one 230 milliliters plastic cup to constitute, and every cup has a grain germination corn seed.With three test units is one group, and every group like a kind of test compound spraying of said usefulness of test A.After treating the spraying fluid drying on the cup, in every glass, put into five Ostrinia furnacalis third-instar larvaes.In every glass, insert a wetted dentistry gauze in case drying, then on each bowl cover.Then with each glass 27 ℃ and 50% relative humidity held 48 hours, gather the mortality ratio data then.In the compound of being tested, following compounds causes more than or equal to 80% mortality ratio:
Compound 2a; 5a; 9a; 10a; 14a; 17a; 18a; 37a; 38a; 2b; 3b; 6b; 10b; 17b; 18b; 34b; 41b; 50b; 2c; 6c; 8c; 10c; 18c; 34c; 37c; 42c; 54c; 2d; 10d; 1e; 9e; 20e; 22e; 34e; 42e; 49e; 66e; 73e; 81e; 9f; 14f; 18f; 10g; 18g; 45g.Structrual description and numbering are seen specification sheets table 1-5.
Test D
Rice-stem borer
Cup by one group 350 milliliters is prepared some test units, and every cup has the solution spray of long some paddy rice seedling test units in the sterilization soil of 2.54 cm thicks like said a kind of following compounds of usefulness of test A.After treating the spraying fluid drying on the paddy rice, in each cup with cover, suck 10 to 15 rice-stem borers.Each glass 27 ℃ and 50% relative humidity held 48 hours, gathered the mortality ratio data then.In the compound of being tested, following compounds causes the mortality ratio more than or equal to 80%:
Compound 2a; 5a; 9a; 10a; 14a; 17a; 18a; 37a; 38a; 2b; 3b; 6b; 10b; 17b; 18b; 34b; 41b; 50b; 2c; 6c; 8c; 10c; 18c; 34c; 37c; 42c; 54c; 2d; 10d; 1e; 9e; 20e; 22e; 34e; 42e; 49e; 66e; 73e; 81e; 9f; 14f; 18f; 10g; 18g; 45g.Structrual description and numbering are seen specification sheets table 1-5.
Test E
Cnaphalocrocis medinali(rice leaf roller)
Get one group 260 milliliters cup, put into 5 Cnaphalocrocis medinali(rice leaf roller) adults in every cup.The TP that is adopted is identical with test in other respects, three cups of each treatment group.Handle and gather the mortality ratio data after 48 hours.In the compound of being tested, following compounds causes the mortality ratio more than or equal to 80%:
Compound 2a; 5a; 9a; 10a; 14a; 17a; 18a; 37a; 38a; 2b; 3b; 6b; 10b; 17b; 18b; 34b; 41b; 50b; 2c; 6c; 8c; 10c; 18c; 34c; 37c; 42c; 54c; 2d; 10d; 1e; 9e; 20e; 22e; 34e; 42e; 49e; 66e; 73e; 81e; 9f; 14f; 18f; 10g; 18g; 45g.Structrual description and numbering are seen specification sheets table 1-5.
Claims (8)
1. compound of the present invention comprises various isomer, N-oxide compound, and be applicable to agricultural non-agricultural salt, the agricultural composition of this compound and in agricultural and non-agricultural insecticidal action.
General structure I:
Wherein,
R
1Be selected from H, CH
3, or halogen;
R
2Be selected from H, halogen, CF
3Or cyano group;
R
3Be selected from halogen, CF
3, OCH
2CF
3, or OCF
2H;
R
4Be selected from H or halogen;
R
5Be selected from
Or be selected from the arbitrary group of following G1-G6:
Wherein,
When G1:E was selected from N, Z was selected from S; When E was selected from S, Z was selected from NH;
G2:R
8Be selected from CH
2Or can be by phenyl ring, benzheterocycle, or heterocyclic substituted; M is selected from acid or ester;
G3:L is selected from halogen, cyanic acid;
G4:A is selected from H, the C1-C4 alkyl; B is selected from straight chain, or the C of band side chain
0-C
5Alkyl;
G5:D is selected from straight chain, or band side chain C
5Alkyl; R
6, R
7Be selected from identical or different C
1-C
4Alkyl;
G6: be selected from straight chain, or band side chain C
7-C
10Alkyl
N is: 1-5.
2. compound as claimed in claim 1 is characterized in that said compound is preferably certainly:
R
1Be selected from CH
3
R
2Be selected from Cl or cyanic acid;
R
3Be selected from Br or Cl;
R
4Be selected from Cl;
R
5Be selected from
Or be selected from following G1, G2, or the arbitrary group of G3:
3. like claim 1, the compound of 2 described general formula Is is characterized in that this compounds is used to prevent and treat the effect of Agricultural pests, comprises lepidopterous larvae and adult, Coleoptera food leaf larva and adult.
4. like claim 1, the compound of 2 described general formula Is is characterized in that can be used as the compsns of control Agricultural pests, can with one or more tensio-active agents, solid diluent, liquid diluent combination.
5. method as claimed in claim 4 is characterized in that can be used as the compsn of preventing and treating invertebrate pests, can make up with one or more other bioactive compoundss or preparation; Comprise pyrethroid, amino formate; The class nicotinoids, neural sodium channel blockers, parasiticidal macrolide; Propalanine is tied anti-agent, the desinsection ureas.
6. compsn as claimed in claim 5 is characterized in that the combination of one or more other bioactive compoundss or preparation is selected from sterilant, nematocides, miticide, or biotechnological formulation.
7. compsn as claimed in claim 6 is characterized in that using separately or being made into mixture and uses, and its effective constituent shared part by weight in preparation is 0.5-90%.
8. preparation as claimed in claim 7 is characterized in that being made into emulsion, and oil-suspending agent, solution comprise missible oil, wettable powder, pulvis, granula, bait formulation, pill and high concentration composition.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013136073A1 (en) * | 2012-03-13 | 2013-09-19 | Redx Pharma Limited | Agricultural chemicals |
| CN104725348A (en) * | 2013-05-20 | 2015-06-24 | 江苏省农药研究所股份有限公司 | Anthraniloyl alkyl iso (thio) urea compound and synthesis method and application thereof |
| CN105712973A (en) * | 2014-12-02 | 2016-06-29 | 沈阳中化农药化工研发有限公司 | Pyrazole amide compound and application thereof |
| CN114790190A (en) * | 2022-01-25 | 2022-07-26 | 内蒙古灵圣作物科技有限公司 | Purification method of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-ethyl formate |
-
2012
- 2012-05-15 CN CN2012101611094A patent/CN102690257A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013136073A1 (en) * | 2012-03-13 | 2013-09-19 | Redx Pharma Limited | Agricultural chemicals |
| CN104725348A (en) * | 2013-05-20 | 2015-06-24 | 江苏省农药研究所股份有限公司 | Anthraniloyl alkyl iso (thio) urea compound and synthesis method and application thereof |
| CN104725348B (en) * | 2013-05-20 | 2017-05-10 | 江苏省农药研究所股份有限公司 | Anthraniloyl alkyl iso (thio) urea compound and synthesis method and application thereof |
| CN105712973A (en) * | 2014-12-02 | 2016-06-29 | 沈阳中化农药化工研发有限公司 | Pyrazole amide compound and application thereof |
| CN114790190A (en) * | 2022-01-25 | 2022-07-26 | 内蒙古灵圣作物科技有限公司 | Purification method of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-ethyl formate |
| CN114790190B (en) * | 2022-01-25 | 2024-03-22 | 内蒙古灵圣作物科技有限公司 | Purification method of 3-bromo-1- (3-chloropyridine-2-yl) -1H-pyrazole-5-ethyl formate |
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Application publication date: 20120926 |