CN102161659A - 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
- Publication number
- CN102161659A CN102161659A CN201110003054XA CN201110003054A CN102161659A CN 102161659 A CN102161659 A CN 102161659A CN 201110003054X A CN201110003054X A CN 201110003054XA CN 201110003054 A CN201110003054 A CN 201110003054A CN 102161659 A CN102161659 A CN 102161659A
- Authority
- CN
- China
- Prior art keywords
- chloro
- bromo
- pyridyl
- pyrazole
- carboxamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC=CC(Cl)=C([n](c(C(Nc1c(C)cc(*)cc1C(OC)=O)=O)c1)nc1Br)N=C Chemical compound CC=CC(Cl)=C([n](c(C(Nc1c(C)cc(*)cc1C(OC)=O)=O)c1)nc1Br)N=C 0.000 description 2
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
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 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, C1～C5 acyl group or C1～C5 amide group respectively independently.C1～C5 in above-mentioned each substituting group is C1～C3 more preferably.
X among the present invention
1Or X
2Be preferably independently respectively H, F, Cl, Br or-CN; X
1Or X
2Respectively independently more preferably Cl, Br or-CN.
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 amide group respectively independently; C1～C5 in aforementioned each substituting group is C1～C3 more preferably.R concretely
1Or R
2Can be independently selected from following group :-CH respectively
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 are 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 are C1～C3 alkyl, amino, C1～C3 alkylamino, C1～C3 alkylsulfonamido or C1～C3 amide group.
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) with corresponding alkyl hydrazides reagent react open loop and slough a water molecules and obtain the compound shown in the general formula (I1), its reaction scheme is with intermediate M1:
R
1During for C1～C5 haloalkyl or C1～C5 acyl group, 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 amide 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) obtains the compound shown in the general formula (I2) with intermediate M2 and triphosgene or phosgene reaction closed loop, 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) obtains intermediate M3 with intermediate M2 and dithiocarbonic anhydride, halohydrocarbons reaction, make catalyzer with organic monoacid again in toluene, M3 reaction dehydrating condensation Cheng Huan obtains the compound shown in the general formula (I4); Perhaps use intermediate M1 and reagent corresponding NH
2NHCSR
1Obtain M3 after the 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 I4 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 and corresponding reaction reagent HON=CNH
2R
2Cyclic condensation obtains the compound shown in the general formula (II), 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-(5-methyl-2-1,3,4-oxadiazole)-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
Get 2.0g (4.4mmol) 2-(3-bromo-1-(3-chloro-2-pyridyl)-1H-5-pyrazoles)-8-methyl-4H-3,1-benzoxazine-4-ketone (M1) is suspended among the 40mLDMF, 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-(2-(5-methyl-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
Press embodiment 1 compound N synthetic method O.1,2-(3-bromo-1-(3-chloro-2-pyridyl)-1H-5-pyrazoles)-6-chloro-8-methyl-4H-3,1-benzoxazine-4-ketone (M1) obtains title compound (NO.2) 1.51g with the acethydrazide reaction.
Compound N is (X=CN, R=CH O.23
3): 3-bromo-N-(2-(5-methyl-2-1,3,4-oxadiazole)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
Obtain compound N O.23 by embodiment 1 compound N synthetic method O.1.
Embodiment 2:
Reaction expression:
Compound N O.3 (X=CL, R=OH): 3-bromo-N-(2-(5-hydroxyl-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide 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-(2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide 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-(2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-bromo-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
Synthesize by embodiment 3 compound Ns synthetic method O.4.
Compound N O.24 (X=CN, R=SH): 3-bromo-N-(2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React the synthetic corresponding compounds NO.24 that obtains 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-(2-(5-thiopurine methyltransferase-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide 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=CH (CH
3)
2): 3-bromo-N-(2-(5-mercapto sec.-propyl base-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound 1.20g by embodiment 4 compound Ns synthetic method O.5.
Compound N is (X=Br, R O.8
1=CH
3): 3-bromo-N-(2-(5-thiopurine methyltransferase-2-1,3,4-oxadiazole)-4-bromo-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound by embodiment 4 compound Ns synthetic method O.5.
Compound N is (X=CN, R O.25
1=CH
3): 3-bromo-N-(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 synthetic
React synthetic corresponding title compound by embodiment 4 compound Ns synthetic method O.5.
Embodiment 5:
Reaction expression
Compound N is (X=CL, R=SCH O.9
3): 3-bromo-N-(2-(5-thiopurine methyltransferase-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
Get 2.0g (4.4mmol) 2-(3-bromo-1-(3-chloro-2-pyridyl)-1H-5-pyrazoles)-6-chloro-8-methyl-4H-3,1-benzoxazine-4-ketone (M1) is suspended among the 50mL DMF, adds 0.8gNH
2NHCSSCH
3, 55-60 ℃ is reacted 24h, gets settled solution next day, stirs down reaction solution is slowly added in the 100mL water, slowly separates out solid, continues to stir 2h, filtration, washing, dry finished product 1.60g (compound M3, the R:SCH of getting
3).
(R is SCH with 0.97g (1.70mmol) M3
3) add 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=CN, R=SCH O.26
3): 3-bromo-N-(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 synthetic
React synthetic corresponding title compound by embodiment 5 compound Ns synthetic method O.9.
Compound N is (X=CL, R=NH O.10
2): 3-bromo-N-(2-(5-amino-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
Get 2.0g (4.4mmol) 2-(3-bromo-1-(3-chloro-2-pyridyl)-1H-5-pyrazoles)-6-chloro-8-methyl-4H-3,1-benzoxazine-4-ketone (M1) is suspended among the 40mL DMF, adds 0.6gNH
2NHCSNH
2, 30-40 ℃ is reacted 24h, gets settled solution next day, stirs down reaction solution is slowly added in the 100mL water, slowly separates out solid, continues to stir 2h, filtration, washing, dry finished product 2.0g (compound M3, the R:NH of getting
2).
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.
Compound N is (X=Br, R=NH O.27
2): 3-bromo-N-(2-(5-amino-2-1,3,4-thiadiazoles)-4-bromo-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound by embodiment 5 compound Ns synthetic method O.10.
Compound N is (X=CN, R=NH O.28
2): 3-bromo-N-(2-(5-amino-2-1,3,4-thiadiazoles)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound by embodiment 5 compound Ns synthetic method O.10.
Compound N is (X=CN, R=CH O.39
3): 3-bromo-N-(2-(5-methyl-2-1,3,4-thiadiazoles)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound by embodiment 5 compound Ns synthetic method O.9.
Compound N O.40 (X=Br, R=OH): 3-bromo-N-(2-(5-hydroxyl-2-1,3,4-thiadiazoles)-4-bromo-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound by embodiment 5 compound Ns synthetic method O.9.
Compound N O.41 (X=CI, R=SH): 3-bromo-N-(2-(5-sulfydryl-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound by embodiment 5 compound Ns synthetic method O.9.
Embodiment 6:
Reaction expression:
Compound N is (X=CL, R=CH O.11
3): 3-bromo-N-(4-chloro-2-(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 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-(3-methyl-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide
React synthetic corresponding title compound by embodiment 6 compound Ns synthetic method O.11.
Compound N is (X=Cl, R=NH O.30
2): 3-bromo-N-(4-chloro-2-(3-amino-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide
Press embodiment 6 compound Ns synthetic method O.11, with M4 and HON=CNH
2NH
2Synthesize corresponding title compound.
Embodiment 7
Reaction expression:
Compound 13 (X
1=CL, R
1=NH
2): 3-bromo-N-(2-(5-amino-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
Get 2.0g (4.2mmol) 2-(3-bromo-1-(3-chloro-2-pyridyl)-1H-5-pyrazoles)-6-chloro-8-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
1=Br, R
1=NH
2): 3-bromo-N-(2-(5-amino-2-1,3,4-oxadiazole)-4-bromo-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound by embodiment 7 compound Ns synthetic method O.13.
Embodiment 8
Reaction expression:
Compound N is (X=CL, Z=O, R O.15
1=CH
3): 3-bromo-N-(2-(5-methylamino--2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide 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-(2-(5-methylamino--2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound by embodiment 8 compound Ns synthetic method O.16.
Compound N is (X=CL, Z=O, R O.17
2=SO
2CH
3): 3-bromo-N-(2-(5-methanesulfonamido-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
2.0g (4mmol) I 5 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=S0
2CH
3): 3-bromo-N-(2-(5-methanesulfonamido-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound by embodiment 8 compound Ns synthetic method O.17.
Compound N is (X=CL, Z=O, R O.21
2=COCH
3): 3-bromo-N-(2-(5-acetyl amido-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
2.0g (4mmol) I 5 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-(2-(5-acetyl amido-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound by the synthetic method of above-claimed cpd NO.21.
Embodiment 9
Reaction expression:
Compound N is (X=CL, Z=O, R O.19
1=R
2=CH
3): 3-bromo-N-(2-(5-dimethylamino-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
2.0g (4mmol) I 5 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-(2-(5-dimethylamino-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide synthetic
React synthetic corresponding title compound by embodiment 9 compound Ns synthetic method O.19.
Embodiment 10
Reaction expression:
Compound N is (X=Br, R O.42
1=COCH
3): 3-bromo-N-(4-bromo-2-(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 the 1mL triethylamine solution, adds 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 1.5g.
Compound N is (X=CN, R O.43
1=SO
2CH
3): 3-bromo-N-(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 the 1mL triethylamine solution, adds 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 1.4g.
Compound N is (X=CN, R O.44
1=CH
3): 3-bromo-N-(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%, 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 1.4g.
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 | 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 ratios under 10mg/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 concentration 10mg/L.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, C1～C5 acyl group or C1～C5 amide 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
2Respectively be independently Cl, Br or-CN.
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 amide 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 amide group, described R
2Be C1～C5 alkyl, amino, C1～C5 alkylamino, C1～C5 alkylsulfonamido or C1～C5 amide group.
6. neighboring Heterocyclic formanilide compound according to claim 4 is characterized in that being selected from:
3-bromo-N-(2-(5-methyl-2-1,3,4-oxadiazole)-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-methyl-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-methyl-2-1,3,4-oxadiazole)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-hydroxyl-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-bromo-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-sulfydryl-2-1,3,4-oxadiazole)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-thiopurine methyltransferase-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-mercapto sec.-propyl base-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-thiopurine methyltransferase-2-1,3,4-oxadiazole)-4-bromo-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(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,
3-bromo-N-(2-(5-thiopurine methyltransferase-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(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,
3-bromo-N-(2-(5-amino-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-amino-2-1,3,4-thiadiazoles)-4-bromo-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-amino-2-1,3,4-thiadiazoles)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-methyl-2-1,3,4-thiadiazoles)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-hydroxyl-2-1,3,4-thiadiazoles)-4-bromo-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-sulfydryl-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(4-chloro-2-(3-methyl-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide,
3-bromo-N-(4-bromo-2-(3-methyl-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide,
3-bromo-N-(4-chloro-2-(3-amino-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-amino-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-amino-2-1,3,4-oxadiazole)-4-bromo-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-methylamino--2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-methylamino--2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-methanesulfonamido-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-methanesulfonamido-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-acetyl amido-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-acetyl amido-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-dimethylamino-2-1,3,4-oxadiazole)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(2-(5-dimethylamino-2-1,3,4-thiadiazoles)-4-chloro-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1-H-pyrazole-4-carboxamide,
3-bromo-N-(4-bromo-2-(3-acetyl amido-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-is than azoles-4-methane amide,
3-bromo-N-(4-cyano group-2-(3-methanesulfonamido-5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide,
3-bromo-N-(4-cyano group-2-(3-methylamino--5-1,2,4-oxadiazole))-6-aminomethyl phenyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-4-carboxamide.
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, with corresponding alkyl hydrazides reagent react open loop and slough a water molecules and obtain the compound shown in the general formula (I1), its reaction scheme is with intermediate M1:
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, intermediate M2 and triphosgene or phosgene reaction closed loop being obtained the compound shown in the general formula (I2), reaction scheme is:
Z is an oxygen, R
1Be sulfydryl, X is X
1The time, under alkaline condition, in the polar aprotic solvent, intermediate M2 and dithiocarbonic anhydride reaction closed loop being obtained the compound shown in the general formula (I3), reaction scheme is:
Z is S, and X is X
1The time, under alkaline condition, in the polar aprotic solvent,, obtain intermediate M3 with intermediate M2 and dithiocarbonic anhydride, halohydrocarbons reaction, in toluene, make catalyzer again with organic monoacid, M3 reacts dehydrating condensation Cheng Huan and obtains the compound shown in the general formula (I4); Perhaps use intermediate M1 and reagent corresponding NH
2NHCSR
1Obtain M3 after the 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 is characterized in that under alkaline condition, in the polar aprotic solvent, under 70-80 ℃ or reflux temperature, and intermediate M4 and corresponding reaction reagent HON=CNH
2R
2Cyclic condensation obtains the compound shown in the general formula (II), 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110003054.XA CN102161659B (en) | 2010-01-15 | 2011-01-07 | Ortho heterocyclic formanilide type compounds and synthesis method and applications thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010018397.9 | 2010-01-15 | ||
| CN201010018397A CN101747325A (en) | 2010-01-15 | 2010-01-15 | Neighboring Heterocyclic formanilide compound and synthesis method and application thereof |
| CN201110003054.XA CN102161659B (en) | 2010-01-15 | 2011-01-07 | Ortho heterocyclic formanilide type compounds and synthesis method and applications thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102161659A true CN102161659A (en) | 2011-08-24 |
| CN102161659B CN102161659B (en) | 2015-01-07 |
Family
ID=42475001
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010018397A Pending CN101747325A (en) | 2010-01-15 | 2010-01-15 | Neighboring Heterocyclic formanilide compound and synthesis method and application thereof |
| CN201110003054.XA Active CN102161659B (en) | 2010-01-15 | 2011-01-07 | Ortho heterocyclic formanilide type compounds and synthesis method and applications thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010018397A Pending CN101747325A (en) | 2010-01-15 | 2010-01-15 | Neighboring Heterocyclic formanilide compound and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN101747325A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749225A (en) * | 2017-01-10 | 2017-05-31 | 青岛科技大学 | A kind of pyrazol acid amide compounds of difluoroethoxy containing thiadiazoles and its application |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747325A (en) * | 2010-01-15 | 2010-06-23 | 江苏省农药研究所股份有限公司 | Neighboring Heterocyclic formanilide compound and synthesis method and application thereof |
| WO2011085575A1 (en) * | 2010-01-15 | 2011-07-21 | 江苏省农药研究所股份有限公司 | Ortho-heterocyclyl formanilide compounds, their synthesis methods and use |
| 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 |
| CN101946785A (en) * | 2010-11-03 | 2011-01-19 | 青岛海利尔药业有限公司 | Insecticidal composition containing JS 9117 and abamectin |
| CN102047915B (en) * | 2011-01-11 | 2013-03-13 | 海利尔药业集团股份有限公司 | Insecticidal composition containing thiacloprid amide |
| CN102037977B (en) * | 2011-01-18 | 2013-06-26 | 陕西上格之路生物科学有限公司 | Insecticidal composition containing thiacloprid amide and synthetic pyrethroid insecticide |
| EP2649879A1 (en) | 2012-04-10 | 2013-10-16 | Basf Se | Pesticidal mixtures containing fluxapyroxad |
| WO2013156331A1 (en) | 2012-04-16 | 2013-10-24 | Basf Se | Synergistic compositions comprising pyraclostrobin and an insecticidal compound |
| CN103444747A (en) * | 2013-09-26 | 2013-12-18 | 江苏省绿盾植保农药实验有限公司 | Pesticide containing thiamethoxam amide and hexaflumuron |
| CN105753856B (en) * | 2016-03-08 | 2019-01-22 | 南通大学 | A kind of preparation and application of the difluoromethyl pyrazole class compound of the structure of oxadiazoles containing 1,3,4- |
| CN106831752B (en) * | 2017-01-10 | 2019-06-21 | 青岛科技大学 | One kind propoxyl group pyridine of tetrafluoro containing thiadiazoles connects pyrazol acid amide compounds |
| GB201810581D0 (en) | 2018-06-28 | 2018-08-15 | Ctxt Pty Ltd | Compounds |
| CN109912585B (en) * | 2019-03-23 | 2021-09-17 | 江苏耘农化工有限公司 | Pyridine pyrazole-4-formamide compound based on sulfur-containing functional group and preparation method and application thereof |
| PL3986890T3 (en) | 2019-06-18 | 2024-03-11 | Pfizer Inc. | Benzisoxazole sulfonamide derivatives |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995027700A1 (en) * | 1994-04-08 | 1995-10-19 | Sumitomo Chemical Company, Limited | Ether compound, use thereof, and intermediate for producing the compound |
| CN1543460A (en) * | 2001-08-15 | 2004-11-03 | ��Ļ���Ű˾ | Ortho-heterocyclic substituted aryl amides for controlling invertebrate pests |
| CN101497602A (en) * | 2008-01-30 | 2009-08-05 | 中国中化集团公司 | Anthranilic acid compound and use thereof |
| CN101747325A (en) * | 2010-01-15 | 2010-06-23 | 江苏省农药研究所股份有限公司 | Neighboring Heterocyclic formanilide compound and synthesis method and application thereof |
| CN101845043A (en) * | 2010-01-15 | 2010-09-29 | 江苏省农药研究所股份有限公司 | Ortho heterocycle formanilide compound and synthesis method and application thereof |
-
2010
- 2010-01-15 CN CN201010018397A patent/CN101747325A/en active Pending
-
2011
- 2011-01-07 CN CN201110003054.XA patent/CN102161659B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995027700A1 (en) * | 1994-04-08 | 1995-10-19 | Sumitomo Chemical Company, Limited | Ether compound, use thereof, and intermediate for producing the compound |
| CN1543460A (en) * | 2001-08-15 | 2004-11-03 | ��Ļ���Ű˾ | Ortho-heterocyclic substituted aryl amides for controlling invertebrate pests |
| CN101497602A (en) * | 2008-01-30 | 2009-08-05 | 中国中化集团公司 | Anthranilic acid compound and use thereof |
| CN101747325A (en) * | 2010-01-15 | 2010-06-23 | 江苏省农药研究所股份有限公司 | Neighboring Heterocyclic formanilide compound and synthesis method and application thereof |
| CN101845043A (en) * | 2010-01-15 | 2010-09-29 | 江苏省农药研究所股份有限公司 | Ortho heterocycle formanilide compound and synthesis method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| DONG WEILI，等: "Synthesis, Structure and Biological Activities of Some Novel Anthranilic Acid Esters Containing N-Pyridylpyrazole", 《CHINESE JOURNAL OF CHEMISTRY》, vol. 27, no. 3, 31 March 2009 (2009-03-31), pages 579 - 586, XP055117659, DOI: doi:10.1002/cjoc.200990095 * |
| 张自义,等: "肼类衍生物在五元唑类杂环合成中的应用进展", 《有机化学》, vol. 24, no. 11, 31 December 2004 (2004-12-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749225A (en) * | 2017-01-10 | 2017-05-31 | 青岛科技大学 | A kind of pyrazol acid amide compounds of difluoroethoxy containing thiadiazoles and its application |
| CN106749225B (en) * | 2017-01-10 | 2019-06-18 | 青岛科技大学 | One kind containing thiadiazoles-difluoroethoxy pyrazol acid amide compounds and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102161659B (en) | 2015-01-07 |
| CN101747325A (en) | 2010-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102161659B (en) | Ortho heterocyclic formanilide type compounds and synthesis method and applications thereof | |
| CN101935291B (en) | Cyano phthalic diamide compounds, preparation method thereof and use thereof as agricultural chemical pesticide | |
| WO2011085684A1 (en) | O-heterocyclyl formanilide compounds, their synthesis methods and use | |
| KR0172650B1 (en) | Insecticidal tetrahydrofuran derivatives | |
| CN101845043A (en) | Ortho heterocycle formanilide compound and synthesis method and application thereof | |
| CZ279334B6 (en) | 5-aminopyrimidine derivatives, process of their preparation and their use against pest, as well as an agent for pest fighting | |
| CN103755700B (en) | A kind of pyrazol acid amide compounds and uses thereof | |
| CN106432081A (en) | Preparation method and application of pyrazole oxime ether compound containing 4-Cl-3-ethyl-1-methylpyrazole structure | |
| CN105669549A (en) | Naphthalenedicarboxamide ethylnaphthalene acetic ester type compound and application thereof | |
| EP0555183A1 (en) | Pesticides | |
| CN102127065B (en) | Ortho-heterocyclic formyl substituted aniline compound as well as synthetic method and application thereof | |
| JP3580594B2 (en) | Insecticidal fungicidal composition | |
| CN101735199B (en) | O-formamidebenzoyl-pyrazole compound as well as preparation method and application thereof | |
| CN101570535A (en) | O-amino benzoyl hydrazine compounds and preparation method and application thereof | |
| JPH09506876A (en) | N-substituted aryl-trifluoromethyl imidazoles | |
| JPH11500428A (en) | Insecticidal 1-arylpyrazoles | |
| CN104725348B (en) | Anthraniloyl alkyl iso (thio) urea compound and synthesis method and application thereof | |
| CN112010836A (en) | 2-substituent imidazolidine derivative containing aryl bipyridyl oxygen structure and preparation method and application thereof | |
| JPH0678339B2 (en) | Fused heterocycle derivative | |
| CN101348464B (en) | Dihalo propene compound, and preparation and use thereof | |
| US4596893A (en) | 2-trifluoromethyl-4,6-dinitro-phenol and derivatives thereof, process for the preparation thereof and herbicidal, acaricidal and crop regulation compositions containing same | |
| CN102911131A (en) | Double-bond trifluoromethyl isoxazole compound, preparation method and application thereof | |
| JPH0526781B2 (en) | ||
| CN101362720A (en) | Pyrazole methanol esters compounds, preparation method and application thereof | |
| CN104761499A (en) | 1, 1-dichloropropene ether compound containing N-substituent-3-methylpyrazole oxime unit structure, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 210047 Changfeng Road 269, chemical industry park, Jiangsu, Nanjing Applicant after: Jiangsu Pesticide Research Institute Co., Ltd. Address before: 210046, No. 31-1, Heng Jing Road, Qixia District, Jiangsu, Nanjing Applicant before: Jiangsu Pesticide Research Institute Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |