CN102161659B - Ortho heterocyclic formanilide type compounds and synthesis method and applications thereof - Google Patents
Ortho heterocyclic formanilide type compounds and synthesis method and applications thereof Download PDFInfo
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Abstract
The invention discloses ortho heterocyclic formanilide type compounds and a synthesis method and applications thereof. The ortho heterocyclic formanilide type compounds are shown in the formula I and the formula II, wherein X1 or X2 is hydrogen, halogen or cyano respectively; R1 or R2 is C1-C5 alkyl, C1-C5 halogenated alkyl, hydroxyl, C1-C5 alkoxy, C1-C5 halogenated alkoxy, mercapto, C1-C5 alkylthio, amino, C1-C5 alkylamino, C1-C5 halogenated alkylamino, C1-C5 alkoxyamino, C1-C5 alkylsulphonylamino, C1-C5 acyl or C1-C5 acylamino. The new ortho heterocyclic formanilide type compounds disclosed by the invention has good prevention and controlling effect on harmful insects; and the compounds can be used to prepare pesticides used in the fields such as agriculture and horticulture and have the advantages of high efficiency, low toxicity and environmental friend.
Description
Technical field
The invention belongs to pesticide field, be specifically related to a kind of can as neighboring Heterocyclic formanilide compound of 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 pest obtain effective improvement.Along with continuing to increase of sterilant application scale, the problems such as the resistance that organic synthesis sterilant in use produces also more highlight.Therefore, the low toxicity compounds acting on brand-new target spot becomes the inexorable trend of sterilant research.
Summary of the invention
The object of this invention is to provide, for various insect, there is excellent prevention effect, and there is a class neighboring Heterocyclic formanilide compound of the feature such as efficient, safety, Environmental compatibility are good, to meet the demand of Crop protection to highly effective and safe sterilant.
Another object of the present invention is to provide a kind of preparation method of above-claimed cpd.
A further object of the invention is to provide above-claimed cpd and is preparing the purposes in sterilant.
Object of the present invention can be reached by following measures:
Formula (I), the neighboring Heterocyclic formanilide compound shown in (II),
In formula, X
1or X
2be separately hydrogen, halogen or cyano group; Z is oxygen or sulphur;
R
1or R
2be separately 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, N-dialkylamino), C1 ~ C5 haloalkane amino, C1 ~ C5 alkoxyamino, C1 ~ C5 alkylsulfonamido, C1 ~ C5 acyl group or C1 ~ C5 amide group.C1 ~ C5 in above-mentioned each substituting group can more preferably C1 ~ C3.
X in the present invention
1or X
2separately be preferably H, F, Cl, Br or-CN; X
1or X
2separately more preferably Cl, Br or-CN.
R in the present invention
1or R
2separately be preferably C1 ~ C5 alkyl, hydroxyl, C1 ~ C5 alkoxyl group, sulfydryl, C1 ~ C5 alkylthio, amino, C1 ~ C5 alkylamino, C1 ~ C5 alkylsulfonamido or C1 ~ C5 amide group; C1 ~ C5 in aforementioned each substituting group can more preferably C1 ~ C3.R concretely
1or R
2can separately be selected from following group :-CH
3,-C
2h
5,-CH (CH
3)
2,-OH ,-OCH
3,-OC
2h
5,-OCH (CH
3)
2,-SH ,-SCH
3,-8C
2h
5,-SCH (CH
3)
2,-NH
2,-NHCH
3,-NHC
2h
5,-N (CH
3)
2,-NHCH (CH
3)
2,-NHOCH
3,-NHOC
2h
5,-NHOCH (CH
3)
2,-N (CH
3)
2,-NHCF
3,-NHCHF
2,-NHCH
2f ,-NHCOCH
3,-NHCOC
2h
5,-NHSO
2cH
3or-NHSO
2c
2h
5deng.
R
1more preferably C1 ~ C5 alkyl, hydroxyl, sulfydryl, C1 ~ C5 alkylthio, amino, C1 ~ C5 alkylamino, C1 ~ C5 alkylsulfonamido or C1 ~ C5 amide group, most preferably is C1 ~ C3 alkyl, hydroxyl, sulfydryl, C1 ~ C3 alkylthio, amino, C1 ~ C3 alkylamino, C1 ~ C3 alkylsulfonamido or C1 ~ C3 amide group.
R
2more preferably C1 ~ C5 alkyl, amino, C1 ~ C5 alkylamino, C1 ~ C5 alkylsulfonamido or C1 ~ C5 amide group, most preferably is C1 ~ C3 alkyl, amino, C1 ~ C3 alkylamino, C1 ~ C3 alkylsulfonamido or C1 ~ C3 amide group.
The preparation method of general formula (I) and the neighboring Heterocyclic formanilide compound shown in (II) is as follows respectively:
Z is oxygen, R
1for C1 ~ C5 alkyl or amino, X is X
1time, in neutral conditions, in polar aprotic solvent, (at room temperature) is by intermediate M1 and corresponding alkyl hydrazine reagent react open loop and slough a water molecules and obtain the compound shown in general formula (I1), and its reaction scheme is:
R
1during for C1 ~ C5 haloalkyl or C1 ~ C5 acyl group, also can be prepared by above formula.R
1during for C1 ~ C5 alkylamino, C1 ~ C5 haloalkane amino, C1 ~ C5 alkoxyamino, C1 ~ C5 alkylsulfonamido or C1 ~ C5 amide group, by R
1compound I 1 for amino is carried out reaction with alkylating reagent, alkoxide reagent, alkylsulfonylated reagent or acylting agent and can be prepared.
Z is oxygen, R
1for hydroxyl, X is X
1time, first reacted by intermediate M1 and hydrazine hydrate and prepare intermediate M2, in neutral conditions, in polar aprotic solvent, intermediate M2 and triphosgene or phosgene reaction closed loop are obtained the compound shown in general formula (I2) by (at a reflux temperature), and reaction scheme is:
R
1during for C1 ~ C5 alkoxyl group or C1 ~ C5 halogenated alkoxy, formula I2 compound and alkylating reagent are reacted and can prepare.
Z is oxygen, R
1for sulfydryl, X is X
1time, in the basic conditions, in polar aprotic solvent, (at a reflux temperature) intermediate M2 and dithiocarbonic anhydride react closed loop and obtain the compound shown in general formula (I3), and reaction scheme is:
R
1during for C1 ~ C5 alkylthio, formula I3 compound and alkylating reagent are reacted and can prepare.
Z is S, X is X
1time, in the basic conditions, in polar aprotic solvent, (at a reflux temperature) with intermediate M2 and dithiocarbonic anhydride, halohydrocarbons reaction, obtain intermediate M3, in toluene, make catalyzer with organic monoacid again, M3 reacts dehydrating condensation Cheng Huan and obtains the compound shown in general formula (I4); Or with intermediate M1 and corresponding reagent N H
2nHCSR
1obtain M3 after reaction, then make catalyzer with organic monoacid in toluene, M3 reacts dehydrating condensation Cheng Huan and obtains the compound shown in general formula (I4), and reaction scheme is:
The preparation of formula I4 compound when Z is S can be prepared by above formula, as R
1for the approach of M2-M3-I4 directly can be adopted when alkyl or haloalkyl, R be amino or other groups (as hydroxyl, sulfydryl) time, also can adopt M1-M3-I4 approach.Work as R
1during for C1 ~ C5 alkoxyl group, C1 ~ C5 halogenated alkoxy, C1 ~ C5 alkylamino, C1 ~ C5 haloalkane amino, C1 ~ C5 alkoxyamino, C1 ~ C5 alkylsulfonamido or C1 ~ C5 acyl group etc., corresponding alkylation, sulfoamido or acylting agent and I4 can be adopted to react preparation further.
In the basic conditions, in polar aprotic solvent, under 70-80 DEG C or reflux temperature, intermediate M4 and corresponding reaction reagent HON=CNH
2r
2cyclic condensation obtains the compound shown in general formula (II), and reaction scheme is:
R
2definition described above, be preferably C1 ~ C5 alkyl, C1 ~ C5 haloalkyl, hydroxyl, sulfydryl or amino, work as R
2the compound prepared for adopting above formula during other groups reacts with corresponding alkylation, sulfoamido or acylting agent further to be prepared.
Acidic conditions described in the present invention or weak acid adopt the organic acid 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 DMF equal solvent.
Intermediate M2 is by-10 ~ 30 DEG C of temperature, and raw material (M1) and hydrazine hydrate are reacted obtained (with reference to patent CN200910033297), reaction scheme is:
It is active that general formula (I) and (II) compound have excellent control to insect, and thus compound of the present invention can be used as preparing sterilant, and then the plant such as protecting agriculture, gardening.Described insect has lepidoptera pest as bollworm, beet armyworm, small cabbage moth, cabbage caterpillar, Cnaphalocrocis medinali(rice leaf roller) and striped rice borer etc., homoptera pest is as leafhopper, plant hopper, aphid, aleyrodid etc., Diptera pest as housefly, Liriomyza, mosquito class etc., the insect such as Orthoptera and Coleoptera etc.Certainly, the harmful organism that compound of the present invention can be prevented and treated is not limited to the scope of above-mentioned citing.
When being used as the sterilant in the fields such as agricultural, gardening when the compound of the present invention represented by general formula (I) and (II), can be used alone, or use in the mode of insect-killing composition, as with formula (I) or formula (II) for activeconstituents, add that the conventional inert ingredient in this area is processed into aqueous emulsion, suspension agent, water dispersion granule, missible oil etc.
Conventional inert ingredient comprises: liquid vehicle, as water; Organic solvent is as toluene, dimethylbenzene, hexanaphthene, methyl alcohol, butanols, ethylene glycol, acetone, dimethyl formamide, ether, methyl-sulphoxide, animal and plant oil and lipid acid; Conventional tensio-active agent, as emulsifying agent and dispersion agent, comprises anion surfactant, cats product, nonionogenic tenside and amphoterics; Other auxiliary agent, as wetting agent, thickening material etc.
When the compound of the present invention represented by general formula (I) and (II) is used as the activeconstituents in sterilant, content in described sterilant can be selected in the scope of 0.1% to 99.5%, and can determine suitable active component content according to dosage form and application process.Usually, containing the activeconstituents described in 5% to 50% (weight percent, lower same) in aqueous emulsion, preferably its content is 10% to 40%; Containing the activeconstituents of 5% to 50% in suspension agent, preferably its content is 5% to 40%.
Such as, for described aqueous emulsion, suspension agent, can carry out Homogeneous phase mixing using as the compounds of this invention of activeconstituents and the auxiliary agent such as solvent and tensio-active agent and make, during use, dilutable water be to prescribed concentration.For described water dispersion granule, can mix as the compounds of this invention of activeconstituents, solid carrier and tensio-active agent etc. and carry out pulverizing and make, during use, use water dilutes.Certainly, the working method of preparation is never limited to foregoing.Those skilled in the art according to described activeconstituents and application target etc., can select suitable method.
Except as except the described compound represented by general formula (I) and (II) of activeconstituents, sterilant of the present invention can comprise any applicable 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, the application method commonly used can be selected, as cauline leaf spraying, used for ponds, soil treatment and seed treatment etc.Such as, when adopting cauline leaf spraying, as activeconstituents the compound represented by general formula (I) and (II) can working concentration scope be aqueous emulsion, suspension agent, water dispersion granule, the missible oil of 1 to 1000mg/L, preferably its concentration is 1 to 500mg/L.
Novel ortho Heterocyclic formanilide compound disclosed by the invention has excellent prevention effect to harmful insect, and therefore this compound with the sterilant in the fields such as preparation agricultural, gardening, can have efficient, low toxicity, eco-friendly advantage.
Embodiment
For the ease of to further understanding of the present invention, the embodiment provided below has done more detailed description to it.These embodiments only are not used for limiting scope of the present invention or implementation principle for describing.
Embodiment 1:
Reaction expression:
Compound N is (X=H, R=CH O.1
3): the synthesis of the bromo-N-of 3-(2-(5-methyl-2-1,3,4-oxadiazole)-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Get 2.0g (4.4mmol) 2-(the bromo-1-of 3-(3-chloro-2-pyridyl)-1H-5-pyrazoles)-8-methyl-4H-3,1-benzoxazine-4-ketone (M1) is suspended in 40mLDMF, add 0.4g acethydrazide, room temperature reaction spends the night, next day obtains settled solution, is slowly added in 100mL water by reaction solution, slowly separate out solid under stirring, continue to stir 2h, filter, dry finished product 1.45g.
Compound N is (X=CL, R=CH O.2
3): the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-methyl-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
By embodiment 1 compound N synthetic method O.1,2-(the bromo-1-of 3-(3-chloro-2-pyridyl)-1H-5-pyrazoles) the chloro-8-methyl of-6--4H-3,1-benzoxazine-4-ketone (M1) and acethydrazide are obtained by reacting title compound (NO.2) 1.51g.
Compound N is (X=CN, R=CH O.23
3): the synthesis of the bromo-N-of 3-(2-(5-methyl-2-1,3,4-oxadiazole)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Compound N is obtained O.23 by embodiment 1 compound N synthetic method O.1.
Embodiment 2:
Reaction expression:
Compound N is (X=CL, R=OH) O.3: the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-hydroxyl-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
1.0g (2.07mmol) M2 and 0.8g (2.68mol) triphosgene is added to the reflux in toluene reaction 4h of 20mL, by in slow for filtrate impouring water after concentrated, stir more than 2h, leave standstill, filter, be washed to filtrate pH=7, filter, after Diethyl ether recrystallization, namely obtain 1.0g solid phase prod.
Embodiment 3:
Reaction expression
Compound N is (X=CL, R=SH) O.4: the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
0.97g (2.0mmol) intermediate M2 and 5mL dithiocarbonic anhydride are added in 20mL pyridine, be heated to 50 DEG C of isothermal reactions 3 days, leave standstill after fully stirring 2h in this reaction solution impouring frozen water after terminating, wait solid fully to separate out rear filtration, alcohol wash, washing, dry product 0.85g.
Compound N is (X=Br, R=SH) O.7: the synthesis of the bromo-N-of 3-(the bromo-6-aminomethyl phenyl of 2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Synthesize by embodiment 3 compound N synthetic method O.4.
Compound N is (X=CN, R=SH) O.24: the synthesis of the bromo-N-of 3-(2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 3 compound N synthetic method O.4 and obtain corresponding compound N O.24.
Embodiment 4:
Reaction expression
Compound N is (X=CL, R O.5
1=CH
3): the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-thiopurine methyltransferase-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
By 1.3g (2.4mmol) I
3be dissolved in the sodium hydroxide solution of 5mL 10%, then add containing methyl iodide 0.2mL (3.0mmol) ethanolic soln 20mL.After room temperature reaction 10h in impouring 50mL water, stir after 2h and leave standstill, filter, washing, dry corresponding title compound 0.88g after ethyl alcohol recrystallization.
Compound N is (X=CL, R O.6
1=CH (CH
3)
2): the synthesis of the bromo-N-of 3-(2-(5-mercapto sec.-propyl base-2-1,3,4-oxadiazole) the chloro-6-aminomethyl phenyl of-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 4 compound N synthetic method O.5 and obtain corresponding title compound 1.20g.
Compound N is (X=Br, R O.8
1=CH
3): the synthesis of the bromo-N-of 3-(the bromo-6-aminomethyl phenyl of 2-(5-thiopurine methyltransferase-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 4 compound N synthetic method O.5 and obtain corresponding title compound.
Compound N is (X=CN, R O.25
1=CH
3): the synthesis of the bromo-N-of 3-(2-(5-thiopurine methyltransferase-2-1,3,4-oxadiazole)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 4 compound N synthetic method O.5 and obtain corresponding title compound.
Embodiment 5:
Reaction expression
Compound N is (X=CL, R=SCH O.9
3): the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-thiopurine methyltransferase-2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Get 2.0g (4.4mmol) 2-(the bromo-1-of 3-(3-chloro-2-pyridyl)-1H-5-pyrazoles) the chloro-8-methyl of-6--4H-3,1-benzoxazine-4-ketone (M1) is suspended in 50mL DMF, adds 0.8gNH
2nHCSSCH
3, 55-60 DEG C of reaction 24h, next day obtains settled solution, is slowly added in 100mL water by reaction solution, slowly separate out solid under stirring, continues to stir 2h, filter, washing, dry finished product 1.60g (compound M3, R:SCH
3).
By 0.97g (1.70mmol) M3, (R is SCH
3) add in 20mL toluene with 0.38g (1.97mmol) tosic acid, be heated to back flow reaction 2h, after precipitation, use hexanaphthene recrystallization, dry must corresponding title compound (NO.9) 0.82g.
Compound N is (X=CN, R=SCH O.26
3): the synthesis of the bromo-N-of 3-(2-(5-thiopurine methyltransferase-2-1,3,4-thiadiazoles)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 5 compound N synthetic method O.9 and obtain corresponding title compound.
Compound N is (X=CL, R=NH O.10
2): the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-amino-2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Get 2.0g (4.4mmol) 2-(the bromo-1-of 3-(3-chloro-2-pyridyl)-1H-5-pyrazoles) the chloro-8-methyl of-6--4H-3,1-benzoxazine-4-ketone (M1) is suspended in 40mL DMF, adds 0.6gNH
2nHCSNH
2, 30-40 DEG C of reaction 24h, next day obtains settled solution, is slowly added in 100mL water by reaction solution, slowly separate out solid under stirring, continues to stir 2h, filter, washing, dry finished product 2.0g (compound M3, R:NH
2).
(R is NH containing 1.0g (2.73mmol) M3 0.2mL methylsulphonic acid to be dropped to 20mL
2) toluene solution in, be chilled to room temperature after being heated to back flow reaction 3h, continue reaction and spend the night, this reaction solution is suspended in 35mL ethyl acetate by next day, adds the ammonia soln of 20mL 10% under vigorous stirring, filters and to obtain corresponding title compound 0.5g.
Compound N is (X=Br, R=NH O.27
2): the synthesis of the bromo-N-of 3-(the bromo-6-aminomethyl phenyl of 2-(5-amino-2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 5 compound N synthetic method O.10 and obtain corresponding title compound.
Compound N is (X=CN, R=NH O.28
2): the synthesis of the bromo-N-of 3-(2-(5-amino-2-1,3,4-thiadiazoles)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 5 compound N synthetic method O.10 and obtain corresponding title compound.
Compound N is (X=CN, R=CH O.39
3): the synthesis of the bromo-N-of 3-(2-(5-methyl-2-1,3,4-thiadiazoles)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 5 compound N synthetic method O.9 and obtain corresponding title compound.
Compound N is (X=Br, R=OH) O.40: the synthesis of the bromo-N-of 3-(the bromo-6-aminomethyl phenyl of 2-(5-hydroxyl-2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 5 compound N synthetic method O.9 and obtain corresponding title compound.
Compound N is (X=CI, R=SH) O.41: the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-sulfydryl-2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 5 compound N synthetic method O.9 and obtain corresponding title compound.
Embodiment 6:
Reaction expression:
Compound N is (X=CL, R=CH O.11
3): the bromo-N-of 3-(the chloro-2-of 4-(3-methyl-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide
1.0g (2.07mmol) M4 and 0.33g (4.46mol) N '-hydroxyl acetamidine is added in the ethanol of 15mL, after ice bath is cooled to 0 DEG C, the ethanolic soln (being added to stirring reaction 30min in the ethanol of 10mL to obtain by the sodium Metal 99.5 of 0.1g) of slow dropping sodium ethylate, be chilled to room temperature after complete 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 2h, leave standstill, filter, washing, is drying to obtain white solid product 0.6g.
Compound N is (X=Br, R=CH O.12
3): the bromo-N-of 3-(the bromo-2-of 4-(3-methyl-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 6 compound N synthetic method O.11 and obtain corresponding title compound.
Compound N is (X=Cl, R=NH O.30
2): the bromo-N-of 3-(the chloro-2-of 4-(3-amino-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide
By embodiment 6 compound N synthetic method O.11, by M4 and HON=CNH
2nH
2carry out synthesizing to obtain corresponding title compound.
Embodiment 7
Reaction expression:
Compound 13 (X
1=CL, R
1=NH
2): the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-amino-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Get 2.0g (4.2mmol) 2-(the bromo-1-of 3-(3-chloro-2-pyridyl)-1H-5-pyrazoles) the chloro-8-methyl of-6--4H-3,1-benzoxazine-4-ketone (M1) is suspended in 40mL DMF, add 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, after precipitation, use hexanaphthene recrystallization, dry corresponding title compound (NO.13) 1.2g.
Compound 14 (X
1=Br, R
1=NH
2): the synthesis of the bromo-N-of 3-(the bromo-6-aminomethyl phenyl of 2-(5-amino-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 7 compound N synthetic method O.13 and obtain corresponding title compound.
Embodiment 8
Reaction expression:
Compound N is (X=CL, Z=O, R O.15
1=CH
3): the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-methylamino--2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
2.0g (4mmol) I 5 is dissolved in the sodium hydroxide solution of 5mL 10%, then adds containing methyl iodide 0.4mL (6.0mmol) ethanolic soln 20mL.After room temperature reaction 10h in impouring 50mL water, stir after 2h and leave standstill, filter, washing, dry corresponding title compound (NO.15) 1.4g after ethyl alcohol recrystallization.
Compound N is (X=CL, Z=S, R O.16
2=CH
3): the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-methylamino--2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 8 compound N synthetic method O.16 and obtain corresponding title compound.
Compound N is (X=CL, Z=O, R O.17
2=SO
2cH
3): the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-methanesulfonamido-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
2.0g (4mmol) I 5 is dissolved in 20mL toluene and 1mL triethylamine solution, then 0.7g (6mmol) Methanesulfonyl chloride is added, after room temperature reaction 2h in impouring 50mL water, leave standstill after stirring, branch vibration layer, pressure reducing and steaming solvent, dry corresponding title compound (NO.17) 1.8g after ethyl alcohol recrystallization.
Compound N is (X=CL, Z=S, R O.18
2=S0
2cH
3): the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-methanesulfonamido-2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 8 compound N synthetic method O.17 and obtain corresponding title compound.
Compound N is (X=CL, Z=O, R O.21
2=COCH
3): the synthesis of the bromo-N-of 3-(2-(5-acetyl amido-2-1,3,4-oxadiazole) the chloro-6-aminomethyl phenyl of-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
2.0g (4mmol) I 5 is dissolved in 20mL toluene and 1mL triethylamine solution, then 0.47g (6mmol) Acetyl Chloride 98Min. is added, after room temperature reaction 2h in impouring 50mL water, leave standstill after stirring, branch vibration layer, pressure reducing and steaming solvent, dry corresponding title compound (NO.21) 1.8g after ethyl alcohol recrystallization.
Compound N is (X=CL, Z=S, R O.22
2=COCH
3): the synthesis of the bromo-N-of 3-(2-(5-acetyl amido-2-1,3,4-thiadiazoles) the chloro-6-aminomethyl phenyl of-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by the synthetic method of above-claimed cpd NO.21 and obtain corresponding title compound.
Embodiment 9
Reaction expression:
Compound N is (X=CL, Z=O, R O.19
1=R
2=CH
3): the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-dimethylamino-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
2.0g (4mmol) I 5 is added in 10mL30% formaldehyde and 10mL formic acid solution, back flow reaction 5h, add 10% aqueous sodium hydroxide solution after cooling to pH=10, filter, water washing, dry, obtain corresponding title compound (NO.19) 1.6g.
Compound N is (X=CL, Z=S, R O.20
1=R
2=CH
3): the synthesis of the bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-dimethylamino-2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide
Carry out Reactive Synthesis by embodiment 9 compound N synthetic method O.19 and obtain corresponding title compound.
Embodiment 10
Reaction expression:
Compound N is (X=Br, R O.42
1=COCH
3): the bromo-N-of 3-(the bromo-2-of 4-(3-acetyl amido-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide
2.2g (4mmol) I8 is dissolved in 20mL toluene and 1mL triethylamine solution, then 0.47g (6mmol) Acetyl Chloride 98Min. is added, after room temperature reaction 2h in impouring 50mL water, leave standstill after stirring, branch vibration layer, pressure reducing and steaming solvent, dry corresponding title compound 1.5g after ethyl alcohol recrystallization.
Compound N is (X=CN, R O.43
1=SO
2cH
3): the bromo-N-of 3-(4-cyano group-2-(3-methanesulfonamido-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide
2.0g (4mmol) I8 is dissolved in 20mL toluene and 1mL triethylamine solution, then 0.7g (6mmol) Methanesulfonyl chloride is added, after room temperature reaction 2h in impouring 50mL water, leave standstill after stirring, branch vibration layer, pressure reducing and steaming solvent, dry corresponding title compound 1.4g after ethyl alcohol recrystallization.
Compound N is (X=CN, R O.44
1=CH
3): the bromo-N-of 3-(4-cyano group-2-(3-methylamino--5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide
2.0g (4mmol) I8 is dissolved in the sodium hydroxide solution of 5mL 10%, then adds containing methyl iodide 0.4mL (6.0mmol) ethanolic soln 20mL.After room temperature reaction 10h in impouring 50mL water, stir after 2h and leave standstill, filter, washing, dry corresponding title compound 1.4g after ethyl alcohol recrystallization.
Compound obtained by each embodiment is as shown in table 1,2:
Table 1
Table 2
Take the compounds of this invention as the formulation example of activeconstituents by describing below, described formulation example can be used as the sterilant of agricultural, gardening and field of flower culture.But embodiments of the present invention are not limited to following content.
Example of formulations 1: aqueous emulsion
By the compounds of this invention 20 parts, toluene 12 parts, ethylene oxide-propylene oxide block copolymer 6 parts, xanthan gum 6 parts, ethylene glycol/propylene glycol compound antifreezer 8.5 parts, organosilicon 0.8 part, 46.7 parts, water, obtains by aqueous emulsion complete processing the aqueous emulsion that activeconstituents is 20%.
Example of formulations 2: suspension agent:
By the compounds of this invention 25 parts, wetting agent to Methyl fatty amide group benzene sulfonic acid sodium salt 6 parts, suspending agent alkylphenol polyoxyethylene formaldehyde condensation products 2 parts, tackifier cellulose sodium carboxymethyl 6 parts, sanitas sodium salicylate 1 part, frostproofer propylene glycol 2 parts, defoamer silicone oil 1 part, 57 parts, water, obtains by suspension agent complete processing the suspension agent that activeconstituents is 25%.
Example of formulations 3: missible oil
By the compounds of this invention 10 parts, dimethylbenzene 40 parts, dimethyl formamide 35 parts, tween 80 emulsifying agent 15 parts, obtain by oil slick complete processing the missible oil that activeconstituents is 10%.
Example of formulations 4: water dispersion granule
The compounds of this invention 80 parts, wetting agent PO-EO block polyether 2 parts, dispersion agent naphthalene sulfonic acid condensate sodium salt 10 parts, disintegrating agent are gathered second and forge pyrrolidone 1 part, 7 parts, diatomite, obtains by water dispersion granule complete processing the water dispersion granule that active ingredient is 80%.
The test example of the sterilant being activeconstituents will be described with the compounds of this invention 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, adopt leaching leaf feeding method to carry out insecticidal effect test.According to the building form of example of formulations 3, the compound of the embodiment of the present invention is made sterilant respectively.Diluted by obtained insecticide emulsifiable concentrate with pure water, Homogeneous phase mixing obtains the liquid of desired concn.Choose luxuriant dish, clean and dry, make leaf dish with punch tool, in liquid, soaked for 10 seconds take out, load in culture dish after naturally drying.Every ware access small cabbage moth 3 instar larvae 10, repeat for 3 times, 1d, 3d investigate dead borer population, and statistics mortality ratio, evaluates its insecticidal effect.Mortality statistics is as following table.
| NO. | Dosage mg/L | 1d mortality ratio % | 2d mortality ratio % | 3d mortality ratio % |
| 1 | 50 | 0.00 | 11.00 | 20.00 |
| 2 | 10 | 0.00 | 42.00 | 100.00 |
| 3 | 50 | 19.15 | 76.49 | 90.48 |
| 4 | 10 | 0.00 | 65.30 | 100.00 |
| 5 | 10 | 100 | 100.50 | 100.00 |
| 6 | 10 | 4.36 | 80.95 | 100.00 |
| 7 | 50 | 5.56 | 68.52 | 94.74 |
| 8 | 50 | 0.00 | 80.95 | 47.62 |
| 9 | 100 | 0 | 0 | 50.00 |
| 10 | 10 | 31.72 | 72.63 | 100.00 |
| 11 | 10 | 42.66 | 71.73 | 100.00 |
| 12 | 10 | 9.52 | 85.51 | 100.00 |
| 13 | 50 | 12.44 | 77.52 | 95.33 |
| 14 | 50 | 7.30 | 53.45 | 82.33 |
| 15 | 10 | 22.40 | 66.60 | 95.00 |
| 16 | 50 | 18.53 | 57.42 | 90.12 |
| 17 | 50 | 7.22 | 51.36 | 80.23 |
| 18 | 50 | 9.14 | 60.53 | 87.66 |
| 19 | 50 | 2.35 | 45.57 | 82.00 |
| 20 | 50 | 4.78 | 55.75 | 88.22 |
| 21 | 50 | 8.63 | 32.45 | 80.11 |
| 22 | 50 | 7.47 | 27.43 | 77.75 |
| 23 | 10 | 18.35 | 46.33 | 95.12 |
| 24 | 50 | 7.29 | 30.42 | 66.06 |
| 25 | 50 | 5.62 | 37.53 | 64.23 |
| 26 | 50 | 8.75 | 30.43 | 70.32 |
| 27 | 10 | 21.51 | 57.56 | 96.32 |
| 28 | 10 | 23.65 | 67.62 | 100.00 |
| 30 | 50 | 10.23 | 45.52 | 80.78 |
| 39 | 50 | 4.35 | 27.32 | 70.66 |
| 40 | 50 | 2.48 | 38.23 | 78.54 |
| 41 | 50 | 7.32 | 18.48 | 67.03 |
| 42 | 50 | 6.48 | 34.33 | 82.24 |
| 43 | 50 | 11.36 | 29.25 | 87.82 |
| 44 | 50 | 8.52 | 32.42 | 78.23 |
Compound N o.2, No.4, No.5, No.6, the 3rd day kill ratio under 10mg/L concentration such as No.10, No.11, No.12 all reaches 100%.
Test example 2: to the insecticidal effect of black bean aphid
Select the indoor black bean aphid 3 age in days nymph raised continuously, adopt pickling process to carry out insecticidal effect test.
According to the building form of example of formulations 3, compound of the present invention is made sterilant respectively.With pure water, obtained insecticide emulsifiable concentrate is diluted, the liquid of preparation 400mg/L.Become aphid to be inoculated on the high broad bean seedling of 30 ~ 50mm by 5, after 24h, remove into aphid, if each broad bean seedling about has about 30 primiparity aphids, if obtained 3 age in days aphids to the 3rd day, along basal part of stem, broad bean seedling is cut, if record aphid radix.If take out after the broad bean seedling of tool aphid is soaked 5s in liquid, insert to be equipped with in the bottle of clear water and cultivate (each concentration in triplicate).Move to observation ward after process, 72h checks borer population anyway, statistics mortality ratio (stiff for death standard with aphid).Compound N o.2 under 400mg/L concentration the mortality ratio of the 3rd day reach 96.04%.
Test 3: snout moth's larva effect is killed to striped rice borer
Adopt striped rice borer 3 instar larvae, adopt leaching rice seedling feeding method to carry out insecticidal effect test.According to the building form of example of formulations 3, the compound of the embodiment of the present invention is made sterilant respectively.Diluted by obtained insecticide emulsifiable concentrate with pure water, Homogeneous phase mixing obtains the liquid of concentration 10mg/L.Choose rice seedling, point will 10 strains/group, in liquid, soaked for 10 seconds take out, load in dactylethrae after naturally drying.Often pipe access striped rice borer 3 instar larvae 10, repeat for 3 times, 1d, 3d, 5d, 7d investigate dead borer population, and statistics mortality ratio, evaluates its insecticidal effect.Compound N o.11 after treatment 1d, 3d, 5d, 7d investigate mortality ratio be respectively 16.67,36.67,43.33,90.00%.
Claims (4)
1. formula I, the neighboring Heterocyclic formanilide compound shown in (II),
In formula,
X
1or X
2be separately Cl, Br or-CN;
Z is oxygen or sulphur;
R
1for sulfydryl, amino or C1 ~ C5 alkylsulfonamido;
R
2for amino or C1 ~ C5 alkylsulfonamido.
2. neighboring Heterocyclic formanilide compound according to claim 1, is characterized in that being selected from:
The bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
The bromo-N-of 3-(the bromo-6-aminomethyl phenyl of 2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
The bromo-N-of 3-(2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
The bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-amino-2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
The bromo-N-of 3-(the bromo-6-aminomethyl phenyl of 2-(5-amino-2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
The bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-sulfydryl-2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
The bromo-N-of 3-(the chloro-2-of 4-(3-amino-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide,
The bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-amino-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
The bromo-N-of 3-(the bromo-6-aminomethyl phenyl of 2-(5-amino-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
The bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-methanesulfonamido-2-1,3,4-oxadiazole)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
The bromo-N-of 3-(the chloro-6-aminomethyl phenyl of 2-(5-methanesulfonamido-2-1,3,4-thiadiazoles)-4-)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
The bromo-N-of 3-(4-cyano group-2-(3-methanesulfonamido-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide.
3. in claim 1 ~ 2, arbitrary described compound is preparing the purposes in sterilant.
4. an insect-killing composition, with described compound arbitrary in claim 1 ~ 2 for activeconstituents, adds that inert ingredient makes aqueous emulsion, suspension agent, water dispersible granules or emulsifiable concentrate.
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| CN102450276A (en) * | 2010-11-01 | 2012-05-16 | 海利尔药业集团股份有限公司 | Pesticide composition containing thiazide insect amide and thiamethoxam |
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