CN101747325A - Neighboring Heterocyclic formanilide compound and synthesis method and application thereof - Google Patents
Neighboring Heterocyclic formanilide compound and synthesis method and application thereof Download PDFInfo
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Abstract
The invention discloses a neighboring Heterocyclic formanilide compound and a synthesis method and an application thereof. The neighboring Heterocyclic formanilide compound is as shown in formulas I and II. In the formulas, X1 and X2 are respectively and independently hydrogen, halogen or cyan; Z is oxygen or sulfur; R1 or R2 are respectively and independently C1-C5 alkyl, C1-C5 haloalkyl, hydroxyl, C1-C5 alkoxy, C1-C5 halogenated alkoxy, sulfhydryl, C1-C5 alkylsulphide radical, amino, C1-C5 alkylamino, C1-C5 halogenated alkylamino, C1-C5 alkoxy amido, C1-C5 alkyl sulfoamido or C1-C5 acyl. The novel neighboring Heterocyclic formanilide compound has superior prevention and treatment effect for harmful insects, can be used for preparing insecticide in the fields such as agriculture and gardening, and has the advantages of high efficiency, low toxicity and environment friendliness.
Description
Technical field
The invention belongs to pesticide field, be specifically related to a kind of neighboring Heterocyclic formanilide compound that can be used as sterilant and preparation method thereof.
Background technology
The control of insect is the core realm of pesticide science research all the time, and the generally use of sterilant makes most insect pests obtain effective improvement.Along with sterilant is used continuing to increase of scale, the problems such as resistance that the organic synthesis sterilant in use produces also more highlight.Therefore, the low toxicity compounds that acts on brand-new target spot becomes the inexorable trend of sterilant research.
Summary of the invention
The purpose of this invention is to provide at various insects and have good prevention effect, and have a class neighboring Heterocyclic formanilide compound of characteristics such as efficient, safety, Environmental compatibility are good, to satisfy the demand of Crop protection the highly effective and safe sterilant.
Another object of the present invention provides a kind of preparation method of above-claimed cpd.
A further object of the invention provides the purposes of above-claimed cpd aspect the preparation sterilant.
Purpose of the present invention can reach by following measure:
Neighboring Heterocyclic formanilide compound shown in formula (I), (II),
In the formula, X
1Or X
2Be hydrogen, halogen or cyano group independently respectively; Z is oxygen or sulphur;
R
1Or R
2Be C1～C5 alkyl, C1～C5 haloalkyl, hydroxyl, C1～C5 alkoxyl group, C1～C5 halogenated alkoxy, sulfydryl, C1～C5 alkylthio, amino, C1～C5 alkylamino (comprising N, the N-dialkylamino), C1～C5 haloalkane amino, C1～C5 alcoxyl amino, C1～C5 alkylsulfonamido or C1～C5 acyl group respectively independently.
X among the present invention
1Or X
2Be preferably independently respectively H, F, Cl, Br or-CN; X
1Or X
2Respectively more preferably H, F, Cl or Br independently; X wherein
2Most preferably be Cl or Br.
R among the present invention
1Or R
2Be preferably C1～C5 alkyl, hydroxyl, C1～C5 alkoxyl group, sulfydryl, C1～C5 alkylthio, amino, C1～C5 alkylamino, C1～C5 alkylsulfonamido or C1～C5 acyl group respectively independently, tool this as-CH
3,-C
2H
5,-CH (CH
3)
2,-OH ,-OCH
3,-OC
2H
5,-OCH (CH
3)
2,-SH ,-SCH
3,-SC
2H
5,-SCH (CH
3)
2,-NH
2,-NHCH
3,-NHC
2H
5,-NHCH (CH
3)
2,-NHOCH
3,-NHOC
2H
5,-NHOCH (CH
3)
2,-N (CH
3)
2,-NHCF
3,-NHCHF
2,-NHCH
2F or-NHSO
2CH
3Deng.
R
1More preferably C1～C5 alkyl, hydroxyl, sulfydryl, C1～C5 alkylthio, amino, C1～C5 alkylamino, C1～C5 alkylsulfonamido or C1～C5 acyl group most preferably are C1～C3 alkyl, hydroxyl, sulfydryl, C1～C3 alkylthio, amino, C1～C3 alkylamino, C1～C3 alkylsulfonamido or C1～C3 acyl group; R
2More preferably C1～C5 alkyl most preferably is C1～C3 alkyl.
General formula (I) and (II) shown in the preparation method of neighboring Heterocyclic formanilide compound respectively as follows:
Z is an oxygen, R
1Be C1～C5 alkyl or amino, X is X
1The time, under neutrallty condition, in the polar aprotic solvent, at room temperature, intermediate M1 being obtained the compound shown in the general formula (I1) with corresponding alkyl hydrazides reagent react open loop, its reaction scheme is:
R
1During for C1～C5 haloalkyl, also can be prepared by following formula.R
1During for C1～C5 alkylamino, C1～C5 haloalkane amino, C1～C5 alcoxyl amino, C1～C5 alkylsulfonamido or C1～C5 acyl group, with R
1For the Compound I 1 of amino is reacted and can be prepared with alkylating reagent, alkoxide reagent, alkyl sulfonyl reagent or acylting agent.
Z is an oxygen, R
1Be hydroxyl, X is X
1The time, earlier by intermediate M1 and hydrazine hydrate prepared in reaction intermediate M2, under neutrallty condition, in the polar aprotic solvent, under reflux temperature, intermediate M2 and triphosgene or phosgene reaction closed loop obtain the compound shown in the general formula (I2), and reaction scheme is:
R
1During for C1～C5 alkoxyl group or C1～C5 halogenated alkoxy, formula I2 compound and alkylating reagent reaction can be prepared.
Z is an oxygen, R
1Be sulfydryl, X is X
1The time, under alkaline condition, in the polar aprotic solvent, under reflux temperature, intermediate M2 and dithiocarbonic anhydride reaction closed loop obtain the compound shown in the general formula (I3), and reaction scheme is:
R
1During for C1～C5 alkylthio, formula I3 compound and alkylating reagent reaction can be prepared.
Z is S, and X is X
1The time, under alkaline condition, in the polar aprotic solvent, under reflux temperature, with intermediate M2 and dithiocarbonic anhydride, halohydrocarbons reaction, obtain intermediate M3, make catalyzer with organic monoacid again in toluene, M3 reaction dehydrating condensation Cheng Huan obtains the compound shown in the general formula (I4); Perhaps with obtaining M3 after intermediate M1 and the reagent corresponding reaction, make catalyzer with organic monoacid again in toluene, M3 reaction dehydrating condensation Cheng Huan obtains the compound shown in the general formula (I4), and reaction scheme is:
The preparation of the formula I compound when Z is S can prepare by following formula, as R
1The approach of M2-M3-I4 can be directly adopted during for alkyl or haloalkyl, when R is amino or other groups (as hydroxyl, sulfydryl), also the M1-M3-I4 approach can be adopted.Work as R
1During for C1～C5 alkoxyl group, C1～C5 halogenated alkoxy, C1～C5 alkylamino, C1～C5 haloalkane amino, C1～C5 alcoxyl amino, C1～C5 alkylsulfonamido or C1～C5 acyl group etc., can adopt the further prepared in reaction of corresponding alkylation, sulfoamidoization or acylting agent and I4.
Under alkaline condition, in the polar aprotic solvent, under 70-80 ℃ or reflux temperature, intermediate M4 obtains the compound shown in the general formula (II) with corresponding reaction reagent together with hydroxyl oxime cyclic condensation, and reaction scheme is:
R
2Definition as mentioned above, be preferably C1～C5 alkyl, C1～C5 haloalkyl, hydroxyl, sulfydryl or amino, work as R
2The compound that can adopt following formula preparation during for other groups further with corresponding alkylation, sulfoamidoization or acylting agent prepared in reaction.
Acidic conditions described in the present invention or weak acid adopt organic acids such as methylsulfonic acid, tosic acid; Described alkaline condition adopts highly basic or weak base, and highly basic is sodium hydroxide, potassium hydroxide, sodium alkoxide etc.; Described weak base is pyridine, triethylamine etc.; Described polar aprotic solvent is alcohol, toluene, benzene equal solvent; Described polar aprotic solvent is the DMF equal solvent.
Intermediate M2 makes (with reference to patent CN200910033297) by under-10～30 ℃ of temperature with raw material (M1) and hydrazine hydrate reaction, and reaction scheme is:
General formula (I) and (II) compound insect is had good control activity, thereby compound of the present invention can be used as the preparation sterilant, and then plants such as protection agricultural, gardening.Described insect has lepidoptera pest such as bollworm, beet armyworm, small cabbage moth, cabbage caterpillar, Cnaphalocrocis medinali(rice leaf roller) and striped rice borer etc., homoptera pest such as leafhopper, plant hopper, aphid, aleyrodid etc., Diptera pest such as housefly, Liriomyza, mosquito class etc., insects such as Orthoptera and Coleoptera etc.Certainly, the compound of the present invention harmful organism that can prevent and treat is not limited to above-mentioned scope of giving an example.
When by general formula (I) and (II) compound of the present invention of expression is as the sterilant in fields such as agricultural, gardening, can use separately, or use in the mode of insect-killing composition, as being activeconstituents, add that this area inert ingredient commonly used is processed into aqueous emulsion, suspension agent, water dispersion granule, missible oil etc. with formula (I) or formula (II).
Inert ingredient commonly used comprises: liquid vehicle, as water; Organic solvent such as toluene, dimethylbenzene, hexanaphthene, methyl alcohol, butanols, ethylene glycol, acetone, dimethyl formamide, ether, methyl-sulphoxide, animal and plant oil and lipid acid; Tensio-active agent such as emulsifying agent and dispersion agent commonly used comprise anion surfactant, cats product, nonionogenic tenside and amphoterics; Other auxiliary agent is as wetting agent, thickening material etc.
When by general formula (I) and (II) compound of the present invention of expression is as the activeconstituents in the sterilant, content in described sterilant can be selected in 0.1% to 99.5% scope, and can determine suitable active component content according to dosage form and application process.Usually, contain the described activeconstituents of 5% to 50% (weight percent, down together) in aqueous emulsion, preferably its content is 10% to 40%; Contain 5% to 50% activeconstituents in suspension agent, preferably its content is 5% to 40%.
For example, for described aqueous emulsion, suspension agent, can will carry out uniform mixing as the The compounds of this invention of activeconstituents and auxiliary agents such as solvent and tensio-active agent and make, dilutable water be to prescribed concentration during use.For described water dispersion granule, can be with as mixing such as The compounds of this invention, solid carrier and the tensio-active agents of activeconstituents and pulverize and make, water dilutes during use.Certainly, the working method of preparation never is limited to foregoing.Those skilled in the art can select suitable method according to described activeconstituents and application target etc.
Except as activeconstituents by general formula (I) and (II) expression described compound, sterilant of the present invention can comprise any suitable activeconstituentss such as other sterilant, miticide, sterilant, insect growth regulator(IGR), plant-growth regulator and soil improvement agent.
For Utilization of pesticides of the present invention, can select the application method used always, as cauline leaf spraying, used for ponds, soil treatment and seed treatment etc.For example, when adopting the cauline leaf spraying, as activeconstituents by general formula (I) but and the working concentration scope of the compound of (II) representing be 1 to 1000mg/L aqueous emulsion, suspension agent, water dispersion granule, missible oil, preferably its concentration is 1 to 500mg/L.
Novel neighboring Heterocyclic formanilide compound disclosed by the invention has good prevention effect to harmful insect, so this compound can have efficiently with the sterilant in fields such as preparation agricultural, gardening, low toxicity, eco-friendly advantage.
Embodiment
For the ease of to further understanding of the present invention, the embodiment that provides has below done more detailed description to it.These embodiment are not to be used for limiting scope of the present invention or implementation principle for narration only.
Embodiment 1:
Reaction expression:
Compound N is (X=H, R=CH O.1
3): 3-bromo-N-{2-[2-(5-methyl isophthalic acid, 3,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
Get 2.0g (4.4mmol) 2-(3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazoles)-5-methyl-4H-3,1-benzoxazine-4-ketone (M1) is suspended among the 40mL DMF, add the 0.4g acethydrazide, room temperature reaction spends the night, get settled solution next day, under stirring reaction solution is slowly added in the 100mL water, slowly separate out solid, continue to stir 2h, filtration, the dry finished product 1.45g that gets.
Compound N is (X=CL, R=CH O.2
3): 3-bromo-N-{4-chloro-2-[2-(5-methyl isophthalic acid, 3,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
Press embodiment 1 compound N synthetic method O.1,2-(3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazoles)-7-chloro-5-methyl-4H-3,1-benzoxazine-4-ketone (M1Cl) obtains title compound (NO.2) 1.51g with the acethydrazide reaction.
Embodiment 2:
Reaction expression:
Compound N O.3 (X=CL, R=OH): 3-bromo-N-{4-chloro-2-[2-(5-hydroxyl-1,3,4-oxadiazole)]-the 6-aminomethyl phenyl-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
1.0g (2.07mmol) M2 and 0.8g (2.68mol) triphosgene are added to the reflux in toluene reaction 4h of 20mL, with in the slow impouring water of filtrate, stir more than the 2h after concentrating, leave standstill, filter, be washed to filtrate pH=7, filter, promptly get the 1.0g solid phase prod behind the ether recrystallization.
Embodiment 3:
Reaction expression
Compound N O.4 (X=CL, R=SH): 3-bromo-N-{4-chloro-2-[2-(5-sulfydryl-1,3,4-oxadiazole)]-the 6-aminomethyl phenyl-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
0.97g (2.0mmol) intermediate M2 and 5mL dithiocarbonic anhydride are added in the 20mL pyridine, be heated to 50 ℃ of isothermal reactions 3 days, after fully stirring 2h in this reaction solution impouring frozen water, leave standstill after the end, wait solid fully to separate out after-filtration, alcohol is washed, is washed, the dry product 0.85g that gets.
Compound N O.7 (X=Br, R=SH): 3-bromo-N-{4-bromo-2-[2-(5-sulfydryl-1,3,4-oxadiazole)]-the 6-aminomethyl phenyl-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
Synthesize by embodiment 3 compound Ns synthetic method O.4.
Embodiment 4:
Reaction expression
Compound N is (X=CL, R O.5
1=CH
3): 3-bromo-N-{4-chloro-2-[2-(5-thiopurine methyltransferase-1,3,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
With 1.3g (2.4mmol) I
3Be dissolved in the sodium hydroxide solution of 5mL 10%, add then and contain methyl iodide 0.2mL (3.0mmol) ethanolic soln 20mL.In the impouring 50mL water, leave standstill behind the stirring 2h behind the room temperature reaction 10h, filter, washing, the ethyl alcohol recrystallization after drying gets corresponding title compound 0.88g.
Compound N is (X=CL, R O.6
1=S CH (CH
3)
2): 3-bromo-N-{4-chloro-2-[2-(5-mercapto sec.-propyl-1,3,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
By embodiment 4 compound Ns synthetic method O.5 synthesize corresponding title compound 1.20g.
Compound N is (X=Br, R O.8
1=SCH
3): 3-bromo-N-{4-bromo-2-[2-(5-thiopurine methyltransferase-1,3,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
By embodiment 4 compound Ns synthetic method O.5 synthesize corresponding title compound.
Embodiment 5:
Reaction expression
Compound N is (X=CL, R=SCH O.9
3): 3-bromo-N-{4-chloro-2-[2-(5-thiopurine methyltransferase-1,3,4-thiadiazoles)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
0.97g (1.70mmol) M3 (R is SCH3) is added in the 20mL toluene with 0.38g (1.97mmol) tosic acid, be heated to back flow reaction 2h, use the hexanaphthene recrystallization behind the precipitation, dry corresponding title compound (NO.9) 0.82g that gets.
Compound N is (X=CL, R=NH O.10
2): 3-bromo-N-{4-chloro-2-[2-(5-amino-1,3,4-thiadiazoles)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
The 0.2mL methylsulphonic acid is dropped to 20mL to be contained 1.0g (2.73mmol) M3 (R is NH
2) toluene solution in, be chilled to room temperature after being heated to back flow reaction 3h, continue reaction and spend the night, be suspended in this reaction solution in the 35mL ethyl acetate next day, adds the ammonia soln of 20mL 10% under the vigorous stirring, filter corresponding title compound 0.5g.
Embodiment 6:
Reaction expression:
Compound N is (X=CL, R=CH O.11
3): 3-bromo-N-{4-chloro-2-[2-(5-methyl isophthalic acid, 2,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
1.0g (2.07mmol) M4 and 0.33g (4.46mol) N '-hydroxyl acetamidine are added in the ethanol of 15mL, after ice bath is cooled to 0 ℃, slowly drip the ethanolic soln (add to stirring reaction 30min obtains in the ethanol of 10mL) of sodium ethylate by the sodium Metal 99.5 of 0.1g, be chilled to room temperature after intact and keep reaction 2h, heating reflux reaction spends the night.After being chilled to room temperature next day, filter, in the slow impouring water of filtrate, stir more than the 2h, leave standstill, filter, washing is drying to obtain white solid product 0.6g.
Compound N is (X=Br, R=CH O.12
3): 3-bromo-N-{4-bromo-2-[2-(5-methyl isophthalic acid, 2,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
By embodiment 6 compound Ns synthetic method O.11 synthesize corresponding title compound.
Embodiment 7
Reaction expression:
Compound 13 (X=CL, R=NH
2): 3-bromo-N-{4-chloro-2-[2-(5-amino-1,3,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
Get 2.0g (4.2mmol) 2-(3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazoles)-5-methyl-4H-3,1-benzoxazine-4-ketone (M1) is suspended among the 40mL DMF, add the 0.8g Urea,amino-, room temperature reaction spends the night, add tosic acid 1.0g and 20mL toluene, be heated to back flow reaction 4h, use the hexanaphthene recrystallization behind the precipitation, dry corresponding title compound (NO.13) 1.2g that gets.
Compound 14 (X=Br, R=NH
2): 3-bromo-N-{4-bromo-2-[2-(5-amino-1,3,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
By embodiment 7 compound Ns synthetic method O.13 synthesize corresponding title compound.
Embodiment 8
Reaction expression:
Compound N is (X=CL, Z=O, R O.15
1=CH
3): 3-bromo-N-{4-chloro-2-[2-(5-methylamino--1,3,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
2.0g (4mmol) I 5 is dissolved in the sodium hydroxide solution of 5mL 10%, adds then and contain methyl iodide 0.4mL (6.0mmol) ethanolic soln 20mL.In the impouring 50mL water, leave standstill behind the stirring 2h behind the room temperature reaction 10h, filter, washing, the ethyl alcohol recrystallization after drying gets corresponding title compound (NO.15) 1.4g.
Compound N is (X=CL, Z=S, R O.16
2=CH
3): 3-bromo-N-{4-chloro-2-[2-(5-methylamino--1,3,4-thiadiazoles)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
By embodiment 8 compound Ns synthetic method O.16 synthesize corresponding title compound.
Compound N is ((X=CL, Z=O, R O.17
2=SO
2CH
3): 3-bromo-N-{4-chloro-2-[2-(5-methanesulfonamido-1,3,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
2.0g (4mmol) I5 is dissolved in 20mL toluene and the 1mL triethylamine solution, add 0.7g (6mmol) Methanesulfonyl chloride then, behind the room temperature reaction 2h in the impouring 50mL water, leave standstill after the stirring, branch vibration layer, pressure reducing and steaming solvent, ethyl alcohol recrystallization after drying get corresponding title compound (NO.17) 1.8g.
Compound N is ((X=CL, Z=S, R O.18
2=SO
2CH
3): 3-bromo-N-{4-chloro-2-[2-(5-methanesulfonamido-1,3,4-thiadiazoles)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
By embodiment 8 compound Ns synthetic method O.17 synthesize corresponding title compound.
Compound N is ((X=CL, Z=O, R O.21
2=COCH
3): 3-bromo-N-{4-chloro-2-[2-(5 acetyl amidos-1,3,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
2.0g (4mmol) I5 is dissolved in 20mL toluene and the 1mL triethylamine solution, add 0.47g (6mmol) Acetyl Chloride 98Min. then, behind the room temperature reaction 2h in the impouring 50mL water, leave standstill after the stirring, branch vibration layer, pressure reducing and steaming solvent, ethyl alcohol recrystallization after drying get corresponding title compound (NO.21) 1.8g.
Compound N is ((X=CL, Z=S, R O.22
2=COCH
3): 3-bromo-N-{4-chloro-2-[2-(5-acetyl amido-1,3,4-thiadiazoles)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
By the synthetic method of above-claimed cpd NO.21 synthesize corresponding title compound.
Embodiment 9
Reaction expression:
Compound N is ((X=CL, Z=O, R O.19
1=R
2=CH
3): 3-bromo-N-{4-chloro-2-[2-(5-dimethylamino-1,3,4-oxadiazole)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
2.0g (4mmol) I5 is added in 10mL30% formaldehyde and the 10mL formic acid solution, back flow reaction 5h, the cooling back adds 10% aqueous sodium hydroxide solution to pH=10, filters, water washing, drying obtains corresponding title compound (NO.19) 1.6g.
Compound N is ((X=CL, Z=S, R O.20
1=R
2=CH
3): 3-bromo-N-{4-chloro-2-[2-(5-dimethylamino-1,3,4-thiadiazoles)]-the 6-aminomethyl phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-methane amide synthetic
By embodiment 9 compound Ns synthetic method O.19 synthesize corresponding title compound.
The prepared compound of each embodiment is shown in table 1,2:
Table 1
Table 2
To narrate below with the The compounds of this invention is the formulations of active ingredients example, and described formulation example can be used as the sterilant in agricultural, gardening and flower culture field.But embodiments of the present invention are not limited to following content.
Example of formulations 1: aqueous emulsion
With 20 parts of The compounds of this invention, 12 parts of toluene, 6 parts of ethylene oxide-propylene oxide block copolymers, 6 parts of xanthan gum, 8.5 parts of ethylene glycol/propylene glycol compound antifreezers, 0.8 part of organosilicon, 46.7 parts in water, obtaining activeconstituents by the aqueous emulsion complete processing is 20% aqueous emulsion.
Example of formulations 2: suspension agent:
With 25 parts of The compounds of this invention, wetting agent to 6 parts of methyl fatty acyl amido benzene sulfonic acid sodium salts, 2 parts of suspending agent alkylphenol polyoxyethylene formaldehyde condensation products, 6 parts of tackifier cellulose sodium carboxymethyls, 1 part of sanitas sodium salicylate, 2 parts of frostproofer propylene glycol, 1 part of defoamer silicone oil, 57 parts in water, obtaining activeconstituents by the suspension agent complete processing is 25% suspension agent.
Example of formulations 3: missible oil
With 10 parts of The compounds of this invention, 40 parts of dimethylbenzene, 35 parts of dimethyl formamides, 15 parts of tween 80 emulsifying agents, obtaining activeconstituents by the oil slick complete processing is 10% missible oil.
Example of formulations 4: water dispersion granule
The poly-second of 80 parts of The compounds of this invention, 2 parts of wetting agent PO-EO block polyethers, 10 parts of dispersion agent naphthalene sulfonic acid condensate sodium salts, disintegrating agent is forged 1 part of pyrrolidone, 7 parts in diatomite, and obtaining active ingredient by the water dispersion granule complete processing is 80% water dispersion granule.
To narrate with the The compounds of this invention test example of the sterilant that is activeconstituents below.But embodiments of the present invention are not limited to following content.
Test example 1: to the insecticidal effect of small cabbage moth
Select 3 instar larvaes, employing is soaked the leaf feeding method and is carried out the insecticidal effect test.According to the composition mode of example of formulations 3, the compound of the embodiment of the invention is made sterilant respectively.With pure water resulting insecticide emulsifiable concentrate is diluted, uniform mixing obtains the soup of desired concn.Choose luxuriant dish, clean and dry, make the leaf dish, in soup, soaked for 10 seconds and take out, in the culture dish for the treatment of to pack into after nature dries with punch tool.Every ware inserts 10 of small cabbage moth 3 instar larvaes, 3 repetitions, and 1d, 3d investigate dead borer population, and the statistics mortality ratio is estimated its insecticidal effect.Mortality statistics such as following table.
| ??NO. | Dosage mg/L | 1d mortality ratio % | 2d mortality ratio % | 3d mortality ratio % |
| ??1 | ??100 | ??0.00 | ??10.00 | ??20.00 |
| ??2 | ??100 | ??0.00 | ??40.00 | ??100.00 |
| ??3 | ??100 | ??19.05 | ??76.19 | ??90.48 |
| ??4 | ??100 | ??0.00 | ??65.00 | ??100.00 |
| ??5 | ??100 | ??100 | ??100.00 | ??100.00 |
| ??6 | ??100 | ??4.76 | ??80.95 | ??100.00 |
| ??7 | ??100 | ??5.26 | ??68.42 | ??94.74 |
| ??8 | ??100 | ??0.00 | ??80.95 | ??47.62 |
| ??9 | ??100 | ??0 | ??0 | ??50.00 |
| ??10 | ??100 | ??31.82 | ??72.73 | ??100.00 |
| ??11 | ??100 | ??42.86 | ??71.43 | ??100.00 |
| ??12 | ??100 | ??9.52 | ??85.71 | ??100.00 |
| ??13 | ??100 | ??12.54 | ??77.22 | ??95.33 |
| ??14 | ??100 | ??7.00 | ??53.25 | ??82.33 |
| ??15 | ??100 | ??22.00 | ??66.00 | ??95.00 |
| ??16 | ??100 | ??18.13 | ??57.32 | ??90.12 |
| ??17 | ??100 | ??7.32 | ??51.66 | ??80.23 |
| ??18 | ??100 | ??9.44 | ??60.23 | ??87.66 |
| ??NO. | Dosage mg/L | 1d mortality ratio % | 2d mortality ratio % | 3d mortality ratio % |
| ??19 | ??100 | ??2.55 | ??45.67 | ??82.00 |
| ??20 | ??100 | ??4.88 | ??55.45 | ??88.22 |
| ??21 | ??100 | ??8.53 | ??32.55 | ??80.11 |
| ??22 | ??100 | ??7.77 | ??27.63 | ??77.75 |
Compound N o.2, No.4, No.5, No.6, the 3rd day kill ratios under 100mg/L concentration such as No.10, No.11, No.12 all reach 100%.
Test example 2: to the insecticidal effect of black bean aphid
Select the black bean aphid 3 age in days nymphs of indoor continuous raising, adopt pickling process to carry out the insecticidal effect test.
According to the composition mode of example of formulations 3, compound of the present invention is made sterilant respectively.Resulting insecticide emulsifiable concentrate is diluted the soup of preparation 400mg/L with pure water.5 one-tenth aphids are inoculated on the high broad bean seedling of 30～50mm, remove into aphid behind the 24h, 30 left and right sides primiparity are arranged approximately if aphid got 3 ages in days if aphid is cut the broad bean seedling along basal part of stem to the 3rd day on each broad bean seedling, record is as if the aphid radix.Tool if take out the broad bean seedling of aphid soaks 5s in soup after, is inserted and cultivates (each concentration triplicate) in the bottle that clear water is housed.Move to observation ward after the processing, 72h checks borer population anyway, statistics mortality ratio (stiff with aphid is death standard).Compound N o.2 under 400mg/L concentration the 3rd day mortality ratio reach 96.04%.
Test 3: to the snout moth's larva effect extremely of striped rice borer
Adopt striped rice borer 3 instar larvaes, employing is soaked the rice seedling feeding method and is carried out the insecticidal effect test.According to the composition mode of example of formulations 3, the compound of the embodiment of the invention is made sterilant respectively.With pure water resulting insecticide emulsifiable concentrate is diluted, uniform mixing obtains the soup of desired concn.Choose rice seedling, divide will 10 strain/groups, in soup, soaked for 10 seconds and take out, in the dactylethrae for the treatment of to pack into after nature dries.Every pipe inserts 10 of striped rice borer 3 instar larvaes, 3 repetitions, and 1d, 3d, 5d, 7d investigate dead borer population, and the statistics mortality ratio is estimated its insecticidal effect.Compound N o.11 after processing 1d, 3d, 5d, 7d investigation mortality ratio be respectively 16.67,36.67,43.33,90.00%.
Claims (10)
1. the neighboring Heterocyclic formanilide compound shown in formula (I), (II),
In the formula,
X
1Or X
2Be hydrogen, halogen or cyano group independently respectively;
Z is oxygen or sulphur;
R
1Or R
2Be C1～C5 alkyl, C1～C5 haloalkyl, hydroxyl, C1～C5 alkoxyl group, C1～C5 halogenated alkoxy, sulfydryl, C1～C5 alkylthio, amino, C1～C5 alkylamino, C1～C5 haloalkane amino, C1～C5 alcoxyl amino, C1～C5 alkylsulfonamido or C1～C5 acyl group independently respectively.
2. neighboring Heterocyclic formanilide compound according to claim 1 is characterized in that described X
1Or X
2Respectively be independently H, F, Cl, Br or-CN.
3. neighboring Heterocyclic formanilide compound according to claim 2 is characterized in that described X
1Or X
2Be H, F, Cl or Br independently respectively.
4. neighboring Heterocyclic formanilide compound according to claim 1 is characterized in that described R
1Or R
2Be C1～C5 alkyl, hydroxyl, C1～C5 alkoxyl group, sulfydryl, C1～C5 alkylthio, amino, C1～C5 alkylamino, C1～C5 alkylsulfonamido or C1～C5 acyl group independently respectively.
5. neighboring Heterocyclic formanilide compound according to claim 4 is characterized in that described R
1Be C1～C5 alkyl, hydroxyl, sulfydryl, C1～C5 alkylthio, amino, C1～C5 alkylamino, C1～C5 alkylsulfonamido or C1～C5 acyl group.
6. neighboring Heterocyclic formanilide compound according to claim 4 is characterized in that described R
2Be C1～C5 alkyl.
7. the preparation method of arbitrary described neighboring Heterocyclic formanilide compound in the claim 1～6 is characterized in that
Z is an oxygen, R
1Be C1～C5 alkyl or amino, X is X
1The time, under neutrallty condition, in the polar aprotic solvent, at room temperature, intermediate M1 being obtained the compound shown in the general formula (I1) with corresponding alkyl hydrazides reagent react open loop, its reaction scheme is:
Z is an oxygen, R
1Be hydroxyl, X is X
1The time, earlier by intermediate M1 and hydrazine hydrate prepared in reaction intermediate M2, under neutrallty condition, in the polar aprotic solvent, under reflux temperature, intermediate M2 and triphosgene or phosgene reaction closed loop obtain the compound shown in the general formula (I2), and reaction scheme is:
Z is an oxygen, R
1Be sulfydryl, X is X
1The time, under alkaline condition, in the polar aprotic solvent, under reflux temperature, intermediate M2 and dithiocarbonic anhydride reaction closed loop obtain the compound shown in the general formula (I3), and reaction scheme is:
Z be S,, X is X
1The time, under alkaline condition, in the polar aprotic solvent, under reflux temperature, with intermediate M2 and dithiocarbonic anhydride, halohydrocarbons reaction, obtain intermediate M3, make catalyzer with organic monoacid again in toluene, M3 reaction dehydrating condensation Cheng Huan obtains the compound shown in the general formula (I4); Perhaps with obtaining M3 after intermediate M1 and the reagent corresponding reaction, make catalyzer with organic monoacid again in toluene, M3 reaction dehydrating condensation Cheng Huan obtains the compound shown in the general formula (I4), and reaction scheme is:
8. the preparation method of the described neighboring Heterocyclic formanilide compound of claim 1, it is characterized in that under alkaline condition, in the polar aprotic solvent, under 70-80 ℃ or reflux temperature, intermediate M4 obtains the compound shown in the general formula (II) with corresponding reaction reagent together with hydroxyl oxime cyclic condensation, and reaction scheme is:
In the claim 1～6 arbitrary described compound in the purposes of preparation aspect the sterilant.
10. an insect-killing composition is an activeconstituents with arbitrary described compound in the claim 1～6, adds that inert ingredient makes aqueous emulsion, suspension agent, water dispersible granules or emulsifiable concentrate.
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| PCT/CN2010/073303 WO2011085575A1 (en) | 2010-01-15 | 2010-05-27 | Ortho-heterocyclyl formanilide compounds, their synthesis methods and use |
| CN201110003054.XA CN102161659B (en) | 2010-01-15 | 2011-01-07 | Ortho heterocyclic formanilide type compounds and synthesis method and applications thereof |
| PCT/CN2011/070267 WO2011085684A1 (en) | 2010-01-15 | 2011-01-14 | O-heterocyclyl formanilide compounds, their synthesis methods and use |
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