CN106810535A - One class substituted benzene formyl amine derivative, its preparation method and application - Google Patents
One class substituted benzene formyl amine derivative, its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
Abstract
The invention provides the heterocyclic carbamate derivatives of a class pyrazolyl containing polyfluoro substitution, with below general formula A-1：
Description
Technical field
The invention belongs to agricultural insecticide field, and in particular to a class substituted benzene formyl amine derivative.
Background technology
Due to the long-term use of existing pesticide species, result in disease and resistance is generated to existing pesticide species, therefore it is required that constantly finding that there is the new new varieties of pesticides with the different mechanisms of action.Simultaneously as existing insecticide consumption is excessive, pressure more is brought to environment, therefore require the new varieties of pesticides of the more efficient consumption of exploitation.
In recent years, with the raising of fluorine chemistry technology, increasing full-fluorine group is introduced in organic compound, by negative and fat-soluble effectively using such as pseudo- plan effect of the unique physical property of fluorine atom and chemical property, BE, electricity high, the new organic compound of introducing full-fluorine group can be made has special only performance, and and then can develop new pesticide species.
For the noval chemical compound with insecticidal activity for introducing fluorine-containing heterocyclic group, prior art has following report：
PCT Patent Application WO2010069502A discloses the substituted benzene formyl amine compound of triazol radical containing trifluoromethyl, and disclosed compound has excellent insecticidal activity, can do and be developed as agricultural insecticide.
The substituted benzene formyl amine compound of heterocyclic radical containing polyfluoro is disclosed in PCT Patent Application WO2011098408A, disclosed compound has excellent insecticidal activity, can do and be developed as agricultural insecticide.
The benzamide compound that not publicly pyrazolyl containing polyfluoro replaces in the prior art.
The content of the invention
The present invention provides the heterocyclic carbamate derivatives of a class pyrazolyl containing polyfluoro substitution, with below general formula A-1：
Wherein：
R is selected from C1-C10 alkyl, C1-C10 haloalkyls, C1-C10 alkane alkenyl, at least one substituted aryl being selected from hydrogen, halogen, C1-C10 haloalkyls, C1-C10 halogenated alkoxies, C1-C10 alkylthio groups and C1-C10 halogenated alkylthios, at least one substituted heteroaryl that is selected from hydrogen, halogen, C1-C10 haloalkyls, C1-C10 halogenated alkoxies, C1-C10 alkylthio groups and C1-C10 halogenated alkylthios；
R1 is selected from hydrogen or halogen；
R2, R4 are independently selected from hydrogen, halogen, C1-C10 alkyl, C1-C10 alkoxies, C1-C10 alkylthio groups, C1-C10 haloalkyls, C1-C10 halogenated alkoxies, C1-C10 halogenated alkylthios, nitro, itrile group, C1-C10 carboxylates, formamide, thioformamide；
C1-C10 alkyl, C1-C10 chloro alkyl that R5, R6 replace independently selected from hydrogen, C1-C10 alkyl, C1-C10 cycloalkyl, the C1-C10 cycloalkyl of itrile group substitution, itrile group；
T1, T2, T3, T4 are independently selected from hydrogen, halogen, C1-C10 alkyl, C1-C10 haloalkyls, nitro, itrile group, C1-C10 alkoxies, C1-C10 alkylthio groups, C1-C10 sulfoxide groups, C1-C10 sulfuryls；
X is selected from nitrogen or C-Y, and Y is selected from halogen, C1-C10 alkyl, nitro, C1-C10 haloalkyls.
The heterocyclic carbamate derivatives of the substitution of pyrazolyl containing polyfluoro that the present invention is provided, the substituent R is selected from C1-C10 alkyl, C1-C10 haloalkyls, C1-C10 alkane alkenyl, at least one substituted aryl being selected from hydrogen, halogen, C1-C10 haloalkyls, C1-C10 halogenated alkoxies, C1-C10 alkylthio groups and C1-C10 halogenated alkylthios, at least one substituted heteroaryl that is selected from hydrogen, halogen, C1-C10 haloalkyls, C1-C10 halogenated alkoxies, C1-C10 alkylthio groups and C1-C10 halogenated alkylthios.Preferably, R is selected from C1-C6 alkyl, C1-C6 haloalkyls, C1-C6 alkane alkenyl, at least one substituted aryl being selected from hydrogen, halogen, C1-C6 haloalkyls, C1-C6 halogenated alkoxies, C1-C6 alkylthio groups and C1-C6 halogenated alkylthios, at least one substituted heteroaryl that is selected from hydrogen, halogen, C1-C6 haloalkyls, C1-C6 halogenated alkoxies, C1-C6 alkylthio groups and C1-C6 halogenated alkylthios.It may further be preferable that R is selected from methyl, ethyl.
The heterocyclic carbamate derivatives of the substitution of pyrazolyl containing polyfluoro that the present invention is provided, the substituent R 1 is selected from hydrogen or halogen.Preferably, R1 is selected from hydrogen, fluorine, chlorine, bromine.
The heterocyclic carbamate derivatives of the substitution of pyrazolyl containing polyfluoro that the present invention is provided, the substituent R 2, R4 is independently selected from hydrogen, halogen, C1-C10 alkyl, C1-C10 alkoxies, C1-C10 alkylthio groups, C1-C10 haloalkyls, C1-C10 halogenated alkoxies, C1-C10 halogenated alkylthios, nitro, itrile group, C1-C10 carboxylates, formamide, thioformamide.Preferably, R2, R4 are independently selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxies, C1-C6 alkylthio groups, C1-C6 haloalkyls, C1-C6 halogenated alkoxies, C1-C6 halogenated alkylthios, nitro, itrile group, C1-C6 carboxylates, formamide, thioformamide.It may further be preferable that R2, R4 are independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxies, C1-C3 alkylthio groups, C1-C3 haloalkyls, C1-C3 halogenated alkoxies, C1-C3 halogenated alkylthios, nitro, itrile group, C1-C3 carboxylates, formamide, thioformamide.Still further preferably, R2, R4 are independently selected from hydrogen, chlorine, fluorine, bromine, C1-C3 alkyl, nitro, itrile group, C1-C3 carboxylates, formamide, thioformamide.
The heterocyclic carbamate derivatives of the substitution of pyrazolyl containing polyfluoro that the present invention is provided, C1-C10 alkyl, C1-C10 chloro alkyl that the substituent R 5, R6 replaces independently selected from hydrogen, C1-C10 alkyl, C1-C10 cycloalkyl, the C1-C10 cycloalkyl of itrile group substitution, itrile group.Preferably, R5, R6 replace independently selected from hydrogen, C1-C6 alkyl, C1-C6 cycloalkyl, the C1-C6 cycloalkyl of itrile group substitution, itrile group C1-C6 alkyl, C1-C6 chloro alkyl.It may further be preferable that C1-C5 alkyl, C1-C5 chloro alkyl that R5, R6 replace independently selected from hydrogen, C1-C5 alkyl, C1-C5 cycloalkyl, the C1-C5 cycloalkyl of itrile group substitution, itrile group.It is even furthermore preferable that R5, R6 are independently selected from hydrogen, C1-C3 alkyl, C1-C4 cycloalkyl, itrile group substitution C1-C5 cycloalkyl, itrile group substitution C1-C5 alkyl, C1-C4 chloro alkyl.
The heterocyclic carbamate derivatives of the substitution of pyrazolyl containing polyfluoro that the present invention is provided, described substitution base T1, T2, T3, T4 is independently selected from hydrogen, halogen, C1-C10 alkyl, C1-C10 haloalkyls, nitro, itrile group, C1-C10 alkoxies, C1-C10 alkylthio groups, C1-C10 sulfoxide groups, C1-C10 sulfuryls.Preferably, T1, T2, T3, T4 are independently selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyls, nitro, itrile group, C1-C6 alkoxies, C1-C6 alkylthio groups, C1-C6 sulfoxide groups, C1-C6 sulfuryls.It may further be preferable that T1, T2, T3, T4 are independently selected from hydrogen, fluorine, chlorine, bromine, C1-C2 alkyl, halo C1-C2 alkyl, nitro, itrile group, C1-C2 alkoxies, C1-C2 alkylthio groups, C1-C2 sulfoxide groups, C1-C2 sulfuryls.It is even furthermore preferable that T1, T2, T3, T4 independent preferably hydrogen, fluorine, chlorine, bromine.
The heterocyclic carbamate derivatives of the substitution of pyrazolyl containing polyfluoro that the present invention is provided, the substituent X is selected from nitrogen or C-Y, and Y is selected from halogen, C1-C10 alkyl, nitro, C1-C10 haloalkyls.Preferably, X is selected from nitrogen or C-Y, and Y is selected from halogen, C1-C6 alkyl, nitro, C1-C6 haloalkyls.It may further be preferable that X is selected from nitrogen or C-Y, and Y is selected from chlorine, fluorine, bromine, C1-C3 fluoro-alkyls.It is even furthermore preferable that X is selected from nitrogen or C-Y, and Y is selected from chlorine.
The heterocyclic carbamate derivatives of the substitution of pyrazolyl containing polyfluoro that the present invention is provided, used as highly preferred mode, the heterocyclic carbamate derivatives of the substitution of pyrazolyl containing polyfluoro are selected from least one in following compound：
The following Tables 1 and 2 of typical compound of the benzamide compound of the substitution of pyrazolyl containing polyfluoro shown in formula A-1.In table 1, the substituent X in formula A-1 is nitrogen, T1 is chlorine, T2, T3 and T4 are hydrogen, R1 for hydrogen.In table 2, substituent X in formula A-1 is that chlorine, T2 and T4 are that hydrogen, R1 are hydrogen for nitrogen, T1 and T3.
Table 1
Table 2
Part of compounds nuclear magnetic data such as table 3 below in above-mentioned Tables 1 and 2.
Table 3
Present invention also offers the preparation method of the heterocyclic carbamate derivatives of the pyrazolyl containing polyfluoro substitution, including：
In above-mentioned preparation method, initiator, catalyst, alkali, solvent, condensing agent, condensation reagent, dehydrating agent commonly used in the art etc. could be used for the present invention.
In synthetic intermediate B-5, used as preferred mode, the dehydrating agent is selected from one kind, two or three combination of the above in C1-C5 alkyl acid anhydrides, C1-C5 haloalkyls acid anhydrides, C1-C5 alkyl sulfonic acids chlorine, phosphorus trichloride, POCl3, phosphorus pentachloride and thionyl chloride.Used as further preferred mode, the dehydrating agent is selected from one kind, two or three combination of the above in acetic anhydride, TFAA, methylsufonyl chloride, thionyl chloride, phosphorus trichloride and POCl3.
The heterocyclic carbamate derivatives of the substitution of pyrazolyl containing polyfluoro that the present invention is provided are suitable for agricultural insecticidal.It is particularly suitable for preventing and treating mite class, Lepidoptera, Homoptera, Semiptera or coleopteran pest.
The present invention also provides a kind of agricultural chemical insecticide, the heterocyclic carbamate derivatives of the substitution of pyrazolyl containing polyfluoro containing 1~99% weight/mass percentage composition.
When agricultural chemical insecticide is prepared, the agricultural chemical insecticide can be formulated into various liquors, missible oil, suspending agent, aqueous suspension, microemulsion, emulsion, aqueous emulsion, pulvis, wettable powder, soluble powder, granule, water-dispersion type granule or capsule.The agricultural chemical insecticide includes quinolines of the present invention and carrier.Carrier at least includes two kinds, and wherein at least one is surfactant.Carrier can be solid or liquid.Suitable solid carrier includes natural or synthesis clay and silicate, such as natural silica and diatomite；Magnesium silicate such as talcum；Magnesiumaluminumsilicate such as kaolinite, kaolin, montmorillonite and mica；White Carbon black, calcium carbonate, precipitated calcium carbonate；Calcium sulfate；Lime stone；Sodium sulphate；Amine salt such as ammonium sulfate, hexamethylene diamine.Liquid-carrier includes water and organic solvent, and when solvent or diluent is done with water, organic solvent can also be used as adjuvant or antifreeze additive.Suitable organic solvent includes aromatic hydrocarbons such as benzene, dimethylbenzene, toluene etc.；Chlorohydrocarbon, such as chlorobenzene, vinyl chloride, chloroform, dichloromethane etc.；Aliphatic hydrocarbon, such as petroleum distillate, hexamethylene, light mineral oil；Alcohols, such as isopropanol, butanol, ethylene glycol, glycerine and cyclohexanol etc.；And their ether and ester；Also ketone, such as acetone, cyclohexanone and dimethylformamide and N- methyl-pyrrolidons.
Surfactant can be emulsifying agent, dispersant or wetting agent；Can be ionic or nonionic.Nonionic emulsifier such as polyoxyethylene fatty acid fat, polyoxyethylene aliphatic alcohol ether, Polyoxyethylene fatty ammonia, and commercially available emulsifying agent：Agriculture breast 2201B, agriculture breast 0203B, agriculture breast 100#, agriculture breast 500#, agriculture breast 600#, agriculture breast 600-2#, agriculture breast 1601, agriculture breast 2201, agriculture breast NP-10, agriculture breast NP-15, agriculture breast 507#, agriculture breast OX-635, agriculture breast OX-622, agriculture breast OX-653, agriculture breast OX-667, peaceful breast 36#.Dispersant is including sodium lignin sulfonate, pull open powder, calcium lignosulfonate, condensation compound of methyl naphthalene sulfonic acid and formaldehyde etc..Wetting agent is：Sldium lauryl sulfate, neopelex, Negel etc..
Agricultural chemical insecticide can be prepared by general method.For example, active material is mixed with liquid flux and/or solid carrier, while adding surfactant such as emulsifying agent, dispersant, stabilizer, wetting agent, other auxiliary agents can also be added such as：Adhesive, defoamer, oxidant etc..
Specific embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these specific embodiments.One skilled in the art would recognize that present invention encompasses all alternatives, improvement project and the equivalents that are potentially included in Claims scope.
First, prepared by compound
Embodiment 1：Intermediate b-2 synthesizes：
To the hydrazine hydrate that 148.02g (1.0mol) b-1 and 500ml85% are added in the there-necked flask of 1L, flow back 4h under mechanical agitation, after backflow a period of time, reaction solution becomes clarification, TLC detection reactions, after raw material reaction is complete, stand, reaction solution separates out substantial amounts of white crystal, and reaction solution is poured into 800ml water, magnetic agitation, reaction separates out more crystal, and suction filtration, filter cake is washed three times with 200ml respectively, infrared lamp is dried to obtain white needle-like crystals B-2 weight 137g, yield 94%.
M.p.118~119 DEG C of the white needle-like crystals for obtaining, its nuclear magnetic data is：1HNMR (600MHz, DMSO-d6)δ：4.20 (s, 2H), 6.63 (dd, J=7.2,4.8Hz, 1H), 7.54 (s, 1H), 7.55 (dd, J=7.4,4.5Hz, 1H), 8.02 (d, J=4.8Hz, 1Hz)；EI-MS m/s:144.3(M+)
Embodiment 2：The synthesis of intermediate b-3
To the absolute ethanol that 250ml is added in the there-necked flask of 1L,8.85g metallic sodiums (0.38mol),Treat that metallic sodium is warmed up to backflow after being completely dissolved,And access drying tower dry-run protection,Add the crude product 68.02g (0.47mol) of intermediate b-2,After reaction solution flows back again,90ml diethyl maleates (0.55mol) is added dropwise,1h completion of dropping,After continuing backflow 1.5h,It is bronzing clarified solution to react,TLC tracking reactions,After raw material,Stand,It is cooled to 65 DEG C and adds 55ml (0.88mol) glacial acetic acid afterwards,Solid is separated out,In pouring the mixture into 700ml water,Magnetic agitation,The solid dissolving of precipitation,In placing reaction liquid into refrigerator,Product slowly separates out solid in 29 DEG C or so beginnings,Stood overnight in refrigerator,Suction filtration,Filter cake with 40% ethanol water drip washing (50ml × 3),With a small amount of ether drip washing filter cake,Pistac solid 59g is obtained after drying under infrared lamp,Yield 45%.
The nuclear magnetic data of the pistac solid for obtaining is：1HNMR (600MHz, DMSO-d6)δ：1.21 (t, 3H), 2.62 (m, 1H), 2.90 (m, 1H), 3.26 (m, 1H), 4.20 (d, 2H), 4.82 (m, 1H), 7.19 (m, 1H), 7.91 (m, 1H), 8.27 (m, 1H)
Implement 3：The synthesis of intermediate b-4
To addition intermediate 3140g (0.52mol) in the three neck round bottom flask of 2L,Add the acetonitrile of 700ml,Slow heating makes it slowly dissolve under mechanical agitation,After treating dissolution of raw material,It is slowly added dropwise 98% concentrated sulfuric acid 70ml (1.31mol),After completion of dropping stirring 20min,Potassium peroxydisulfate 168g (0.62mol) is slowly added in batches,During potassium peroxydisulfate is added,It is very violent due to reacting,To be slowly added in batches,Reaction solution is avoided to rush out,After treating that potassium peroxydisulfate addition is finished,Heat to backflow,Reaction solution starts in ecru,With the carrying out of reaction,Solution slowly becomes orange-yellow,Eventually become black,After back flow reaction 4.5h,TLC tracking reactions,Display raw material reaction is complete,Stop heating and be cooled to room temperature,Reaction solution is concentrated into after 150ml or so,Pour into 400ml water,There is substantial amounts of faint yellow solid to separate out under stirring,Suction filtration,Filter cake is washed with water (100 × 3),Dried under infrared lamp,Obtain 65.5g faint yellow solids,Yield：47.4%.
The nuclear magnetic data of the faint yellow solid for obtaining is：1HNMR(600MHz,CDCl3):δ 10.08 (s, 1H ,-OH), 8.51 (dd, J=1.2.0Hz, 3.4Hz, 1H, Pyridine-6-H), 7.90 (dd, J=1.5Hz, 6.0Hz, 1H, Pyridine-4-H), 7.41 (dd, J=4.7Hz, 7.8Hz, 1H,), Pyridine-5H 6.37 (s, 1H, Pyrazole-H), 4.22~4.18 (q, J=6.0Hz, 2H ,-CH 2-) 1.19 (t, J=6.0Hz, 3H ,-CH 3).
Implement 4：The synthesis of intermediate b-6
To compound b-4 and b-5 is added in the three neck round bottom flask of 250ml, wherein b-4 is 17.0g (0.064mol), and b-5 is 18.16g (0.064mol).The DMF solution of 70ml is added, by dissolution of raw material under magnetic agitation, granular potash solid 13.15g (0.095mol) is added; 120 DEG C, after reaction 3h are heated under dry-run protection, b-4 is reacted completely for TLC tracking reaction display raw materials; stop heating; room temperature is cooled to, reactant is poured into the water of 200ml, there is substantial amounts of solid to separate out; stirring half an hour; suction filtration, filter cake is washed with water (50ml × 3), and drying is not required to after draining directly carries out next one-step hydrolysis.
The nuclear magnetic data of the solid for obtaining is：1HNMR(600MHz,CDCl3):δ 8.51 (dd, J=1.5Hz, 4.6.0Hz, 1H,), Pyridine-6-H 7.92 (dd, J=1.5Hz, 8.0Hz, 1H, Pyridine-4-H), 7.46 (dd, J=4.5Hz, 8.0Hz, 1H, Pyridine-5-H), 6.69 (s, 1H, pyrazole-H), 4.27~4.23 (q, J=7.0Hz, 2H ,-CH2-)；3.89(s,3H,Pyrazole-CH 3), 1.24 (t, J=6.0Hz, 3H ,-CH2CH 3)
Embodiment 5：The synthesis of intermediate b-7
To being added the previous step undried intermediate b-6 crude products that obtain of reaction in 250ml round-bottomed flasks, add THF200ml, make it that prepare in advance 15% NaOH solution is added after dissolving under stirring, stirring reaction at room temperature, whole solution is in rufous, after reaction 2h, TLC point plates are shown without after raw material, solvent THF decompressions in reaction are steamed, the solid for now having paste is separated out, adding water dissolve it under stirring, now solution is kermesinus, stirring is lower to be added dropwise dense HCl, it is acidified to Ph=1~2, now there is substantial amounts of solid to separate out, suction filtration, filter cake is washed with water (50ml × 3), it is dried to obtain faint yellow solid powder 26.3g, yield 82.2% (two step yields).
The nuclear magnetic data of the faint yellow solid powder for obtaining is：1HNMR(600MHz,CDCl3):δ 8.46 (dd, J=1.6Hz, 4.5Hz, 1H,), Pyridine-6-H 7.90 (dd, J=1.8Hz, 8.0Hz, 1H, Pyridine-4-H), 7.44 (dd, J=4.6,8.0Hz, 1H, Pyridine-5-H), 6.71 (s, 1H, pyrazole-H), 3.85 (s, 3H, Pyrazole-CH 3)
Embodiment 6：The synthesis of intermediate b-9
Take 250ml there-necked flasks,The chloro- 3- trifluoromethyls -2- aminobenzoic acids of 2.37g (0.01mol) 5- are added at room temperature,Triethylamine 4g and 20ml acetonitrile,After treating that the chloro- 3- trifluoromethyls -2- aminobenzoic acids of 5- dissolve under stirring,Add intermediate b-7 (5.02g,0.01mol) with 20ml acetonitrile solutions,Reaction solution is cooled to -5 DEG C,The 20ml acetonitrile solutions of 4.53g (0.04mol) are slowly added dropwise under dry-run protection,Treat to be warmed up to room temperature naturally after completion of dropping,It is stirred at room temperature after reaction 3h,TLC tracking display raw material reactions are complete,Reaction solution is poured into 150ml,There is yellow solid to separate out,Solution is fitted into 500ml separatory funnels,Add 150ml ethyl acetate,Ethyl acetate layer is washed with saturated aqueous common salt (50ml × 3),Anhydrous MgSO4Dry, suction filtration, desolventizing obtains khaki solid 4.5g, yield 69.2%.
The nuclear magnetic data of the khaki solid for obtaining is：1HNMR(600MHz,CDCl3):δ 8.46 (dd, J=1.4Hz, 4.8Hz, 1H,), Pyridine-6-H 8.34 (d, J=2.4Hz, 1H,), Ar-4-H 7.93~7.95 (m, 2H, Pyridine-4-H,), Ar-6-H 7.49 (dd, J=4.8Hz, 1H,), Ar-5-H 6.97 (s, 1H, pyrazole-H), 3.88 (s, 3H, Pyrazole-CH 3)。
Embodiment 7：Target compound 60 synthesizes
Take 50ml round-bottomed flasks and add 6- chloro- 2- [1- (3- chloro-2-pyridyls) -3- ((1- methyl -3- perfluoro-ethyls) -4- Trifluoromethyl-1 H-5- pyrazoles epoxide) -1H-5 pyrazolyls] -8- trifluoromethyl -4H- benzos [d] [1, 3] oxazines -4- ketone 0.5g (0.76mmol), the lower addition 20mlTHF of stirring dissolves it, 30% dimethylamine solution 0.0.2g (0.99mmol) is added dropwise, it is stirred at room temperature after reaction 30min, TLC tracking reaction display raw material reactions are complete, add water 20ml, ethyl acetate 20ml is extracted, ethyl acetate layer saturated common salt water washing, anhydrous MgSO4After drying, suction filtration, decompression is spin-dried for partial solvent, and TLC separates [V (petroleum ether):V (ethyl acetate)=2:1], pistac solid 310mg is obtained.
Through nmr analysis, it is the compound that numbering is 60 to obtain pistac solid.
Embodiment 8：Target compound 6 synthesizes
Take 50ml round-bottomed flasks and add 6- chloro- 2- [1- (3- chloro-2-pyridyls) -3- ((1- methyl -3- perfluoro-ethyls) -4- Trifluoromethyl-1 H-5- pyrazoles epoxide) -1H-5 pyrazolyls] -8- methyl -4H- benzos [d] [1, 3] oxazines -4- ketone 0.5g (0.76mmol), the lower addition 20mlTHF of stirring dissolves it, 30% methylamine solution 0.11g (0.99mmol) is added dropwise, it is stirred at room temperature after reaction 30min, TLC tracking reaction display raw material reactions are complete, add water 20ml, ethyl acetate 20ml is extracted, ethyl acetate layer saturated common salt water washing, anhydrous MgSO4After drying, suction filtration, decompression is spin-dried for partial solvent, and TLC separates [V (petroleum ether):V (ethyl acetate)=2:1], pistac solid 250mg, yield 48% are obtained.
Through nmr analysis, it is the compound that numbering is 6 to obtain pistac solid.And the m.p. of pistac solid:196~198 DEG C.
2nd, preparation is prepared
In example 9 below~11, each component is prepared according to mass percent.
Embodiment 9,30% suspending agent
Compound 60 and other components are fully mixed, thus obtained suspending agent, dilute with water gained suspending agent can obtain the dilution of any required concentration.
Embodiment 10,30% missible oil
Phosphorous acid is dissolved in toluene, compound 5 and ethoxylated triglycerides are added, transparent solution is obtained.
Embodiment 11,60% wettable powder
Compound 23, dodecyl sodium naphthalene sulfonate, sodium lignin sulfonate and silicon bath soil are mixed, is crushed in pulverizer, until particle reaches standard.
3rd, biological activity test
Embodiment 12, the insecticidal activity to mythimna separata
Dried in the shade naturally after appropriate maize leaves are fully infiltrated in the liquid for preparing, be put into the culture dish for being lined with filter paper, connect mythimna separata 3 age mid-term larva, 10/ware, be placed in 24~27 DEG C of observation ward and cultivate, investigation result after 48h.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.Experimental concentration 20mg/L.
Compound 1~85 in result display table 1 shows 100% death rate under experimental concentration 20mg/L.
Embodiment 13, the insecticidal activity to diamondback moth
Chinese cabbage leaf will naturally be dried in the shade after fully being infiltrated in the liquid for preparing in right amount, be put into the culture dish for being lined with filter paper, connect diamondback moth 2 age mid-term larva, 10/ware, be placed in 24~27 DEG C of observation ward and cultivate, investigation result after 48h.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.Experimental concentration 20mg/L.
Compound 1~85 in result display table 1 shows 100% death rate under experimental concentration 20mg/L.
Embodiment 14, the insecticidal activity to aphis craccivora
The Broad Bean Leaves seedling of aphis craccivora will be connected in spraying treatment under Potter spray towers, aphis craccivora is placed in 20~22 DEG C of observation ward and cultivates after treatment, investigation result after 48h.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.Experimental concentration 200mg/L.
Compound 1~85 in result display table 1 shows more than 90% death rate under experimental concentration 200mg/L.
Embodiment 15, the insecticidal activity to planthopper
4~6 rice seedlings (being about 3~4cm, indoor culture) are fixed in the culture dish of Φ 7cm with crystobalite sand, CO is met2The Brown Planthopper 3 age mid-term nymph of anesthesia is some, and (pressure is 5lb/in for metered dose treatment under being placed in Potter spray towers2, settling amount is 4.35mg/cm2), it is control that experiment sets clear water, and often treatment is repeated 4 times, and is covered with transparent plastic cup after spraying, is put in observation ward (25~27 DEG C, 14h illumination), investigation result after 48h.During investigation, polypide is touched with writing brush, it is reactionless to be considered as dead worm.
Compound 1~85 in result display table 1 shows more than 90% death rate under experimental concentration 200mg/L.
Part of compounds preventing and treating mythimna separata under embodiment 16, low dosage, diamondback moth, prodenia litura prevention effect.
Claims (11)
1. the heterocyclic carbamate derivatives that a class pyrazolyl containing polyfluoro replaces, with below general formula A-1：
Wherein：
R is selected from C1-C10 alkyl, C1-C10 haloalkyls, C1-C10 alkane alkenyl, is selected from hydrogen, halogen, C1-C10 halos
At least one substituted aryl in alkyl, C1-C10 halogenated alkoxies, C1-C10 alkylthio groups and C1-C10 halogenated alkylthios,
It is selected from hydrogen, halogen, C1-C10 haloalkyls, C1-C10 halogenated alkoxies, C1-C10 alkylthio groups and C1-C10 alkyl halide sulphur
At least one substituted heteroaryl in base；
R1 is selected from hydrogen or halogen；
R2, R4 are independently selected from hydrogen, halogen, C1-C10 alkyl, C1-C10 alkoxies, C1-C10 alkylthio groups, C1-C10 halogen
Substituted alkyl, C1-C10 halogenated alkoxies, C1-C10 halogenated alkylthios, nitro, itrile group, C1-C10 carboxylates, formamide,
Thioformamide；
C1-C10 cycloalkyl, itrile group that R5, R6 replace independently selected from hydrogen, C1-C10 alkyl, C1-C10 cycloalkyl, itrile group
Substituted C1-C10 alkyl, C1-C10 chloro alkyl；
T1, T2, T3, T4 independently selected from hydrogen, halogen, C1-C10 alkyl, C1-C10 haloalkyls, nitro, itrile group,
C1-C10 alkoxies, C1-C10 alkylthio groups, C1-C10 sulfoxide groups, C1-C10 sulfuryls；
X is selected from nitrogen or C-Y, and Y is selected from halogen, C1-C10 alkyl, nitro, C1-C10 haloalkyls.
2. the heterocyclic carbamate derivatives for replacing according to the pyrazolyl containing polyfluoro described in claim 1, it is characterised in that：
R be selected from C1-C6 alkyl, C1-C6 haloalkyls, C1-C6 alkane alkenyl, be selected from hydrogen, halogen, C1-C6 haloalkyls,
At least one substituted aryl in C1-C6 halogenated alkoxies, C1-C6 alkylthio groups and C1-C6 halogenated alkylthios, be selected from hydrogen,
At least one in halogen, C1-C6 haloalkyls, C1-C6 halogenated alkoxies, C1-C6 alkylthio groups and C1-C6 halogenated alkylthios
Substituted heteroaryl；
R1 is selected from hydrogen or halogen；
R2, R4 are independently selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxies, C1-C6 alkylthio groups, C1-C6 alkyl halides
Base, C1-C6 halogenated alkoxies, C1-C6 halogenated alkylthios, nitro, itrile group, C1-C6 carboxylates, formamide, thio formyl
Amine；
R5, R6 take independently selected from hydrogen, C1-C6 alkyl, C1-C6 cycloalkyl, the C1-C6 cycloalkyl of itrile group substitution, itrile group
The C1-C6 alkyl in generation, C1-C6 chloro alkyl；
T1, T2, T3, T4 are independently selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyls, nitro, itrile group, C1-C6
Alkoxy, C1-C6 alkylthio groups, C1-C6 sulfoxide groups, C1-C6 sulfuryls；
X is selected from nitrogen or C-Y, and Y is selected from halogen, C1-C6 alkyl, nitro, C1-C6 haloalkyls.
3. the heterocyclic carbamate derivatives for replacing according to the pyrazolyl containing polyfluoro described in claim 2, it is characterised in that described：
R is selected from methyl, ethyl；
R1 is selected from hydrogen, fluorine, chlorine, bromine；
R2, R4 are independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxies, C1-C3 alkylthio groups, C1-C3 alkyl halides
Base, C1-C3 halogenated alkoxies, C1-C3 halogenated alkylthios, nitro, itrile group, C1-C3 carboxylates, formamide, thio formyl
Amine；
R5, R6 take independently selected from hydrogen, C1-C5 alkyl, C1-C5 cycloalkyl, the C1-C5 cycloalkyl of itrile group substitution, itrile group
The C1-C5 alkyl in generation, C1-C5 chloro alkyl；
T1, T2, T3, T4 are independently selected from hydrogen, fluorine, chlorine, bromine, C1-C2 alkyl, halo C1-C2 alkyl, nitro, nitrile
Base, C1-C2 alkoxies, C1-C2 alkylthio groups, C1-C2 sulfoxide groups, C1-C2 sulfuryls；
X is selected from nitrogen or C-Y, and Y is selected from chlorine, fluorine, bromine, C1-C3 fluoro-alkyls.
4. the heterocyclic carbamate derivatives for replacing according to the pyrazolyl containing polyfluoro described in claim 3, it is characterised in that described：
R is selected from methyl, ethyl；
R1 is selected from hydrogen, fluorine, chlorine, bromine；
R2, R4 independently selected from hydrogen, chlorine, fluorine, bromine, C1-C3 alkyl, nitro, itrile group, C1-C3 carboxylates, formamide,
Thioformamide；
R5, R6 are independently selected from hydrogen, C1-C3 alkyl, C1-C4 cycloalkyl, itrile group substitution C1-C5 cycloalkyl, itrile group substitution
C1-C5 alkyl, C1-C4 chloro alkyl；
T1, T2, T3, T4 independent preferably hydrogen, fluorine, chlorine, bromine；
X is selected from nitrogen or C-Y, and Y is selected from chlorine.
5. the heterocyclic carbamate derivatives for replacing according to the pyrazolyl containing polyfluoro described in claim 4, it is characterised in that the pyrazoles containing polyfluoro
The heterocyclic carbamate derivatives of base substitution are selected from least one in following compound：
6. the heterocyclic carbamate derivatives for replacing according to the pyrazolyl containing polyfluoro described in claim 1, it is characterised in that the pyrazoles containing polyfluoro
The preparation method of the heterocyclic carbamate derivatives of base substitution includes：
7. the heterocyclic carbamate derivatives for replacing according to the pyrazolyl containing polyfluoro described in claim 6, it is characterised in that：
In synthetic intermediate B-5, the dehydrating agent is selected from C1-C5 alkyl acid anhydrides, C1-C5 haloalkyls acid anhydrides, C1-C5 alkane
One kind, two or three combination of the above in base sulphonic acid chloride, phosphorus trichloride, POCl3, phosphorus pentachloride and thionyl chloride.
8. the heterocyclic carbamate derivatives for replacing according to the pyrazolyl containing polyfluoro described in claim 7, it is characterised in that：
In synthetic intermediate B-5, the dehydrating agent be selected from acetic anhydride, TFAA, methylsufonyl chloride, thionyl chloride,
One kind, two or three combination of the above in phosphorus trichloride and POCl3.
9. the heterocyclic carbamate derivatives for replacing according to the pyrazolyl containing polyfluoro described in claim 1, it is characterised in that the pyrazoles containing polyfluoro
The heterocyclic carbamate derivatives of base substitution are used for agricultural insecticidal.
10. the heterocyclic carbamate derivatives for replacing according to the pyrazolyl containing polyfluoro described in claim 9, it is characterised in that the pyrazoles containing polyfluoro
The heterocyclic carbamate derivatives of base substitution are used to prevent and treat mite class, Lepidoptera, Homoptera, Semiptera or coleopteran pest.
A kind of 11. agricultural chemical insecticides, it is characterised in that containing containing 1~99% weight/mass percentage composition in the agricultural chemical insecticide
The heterocyclic carbamate derivatives of polyfluoro pyrazolyl substitution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019123195A1 (en) | 2017-12-20 | 2019-06-27 | Pi Industries Ltd. | Pyrazolopyridine-diamides, their use as insecticide and processes for preparing the same. |
| WO2019123194A1 (en) | 2017-12-20 | 2019-06-27 | Pi Industries Ltd. | Anthranilamides, their use as insecticide and processes for preparing the same. |
| WO2019150220A1 (en) | 2018-01-30 | 2019-08-08 | Pi Industries Ltd. | Novel anthranilamides, their use as insecticide and processes for preparing the same. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711255A (en) * | 2002-11-15 | 2005-12-21 | 杜邦公司 | Novel anthranilamide insecticides |
| CN102883606A (en) * | 2010-02-09 | 2013-01-16 | 拜尔农作物科学股份公司 | Hydrazine-substituted anthranilic acid derivatives |
| CN103068813A (en) * | 2010-06-15 | 2013-04-24 | 拜耳知识产权有限责任公司 | Anthranilic acid diamide derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711255A (en) * | 2002-11-15 | 2005-12-21 | 杜邦公司 | Novel anthranilamide insecticides |
| CN102883606A (en) * | 2010-02-09 | 2013-01-16 | 拜尔农作物科学股份公司 | Hydrazine-substituted anthranilic acid derivatives |
| CN103068813A (en) * | 2010-06-15 | 2013-04-24 | 拜耳知识产权有限责任公司 | Anthranilic acid diamide derivatives |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019123195A1 (en) | 2017-12-20 | 2019-06-27 | Pi Industries Ltd. | Pyrazolopyridine-diamides, their use as insecticide and processes for preparing the same. |
| WO2019123194A1 (en) | 2017-12-20 | 2019-06-27 | Pi Industries Ltd. | Anthranilamides, their use as insecticide and processes for preparing the same. |
| WO2019150220A1 (en) | 2018-01-30 | 2019-08-08 | Pi Industries Ltd. | Novel anthranilamides, their use as insecticide and processes for preparing the same. |
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