CN107629005A - Polysubstituted phenylpyrazole derivatives and its production and use - Google Patents
Polysubstituted phenylpyrazole derivatives and its production and use Download PDFInfo
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- CN107629005A CN107629005A CN201710725456.8A CN201710725456A CN107629005A CN 107629005 A CN107629005 A CN 107629005A CN 201710725456 A CN201710725456 A CN 201710725456A CN 107629005 A CN107629005 A CN 107629005A
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- 0 *C(CNc1c(C=*)c(C#N)n[n]1-c(c(Cl)cc(C(F)(F)F)c1)c1Cl)=O Chemical compound *C(CNc1c(C=*)c(C#N)n[n]1-c(c(Cl)cc(C(F)(F)F)c1)c1Cl)=O 0.000 description 4
- DMIZGMXOBGAMEZ-UHFFFAOYSA-N CCc1cc(Cl)ccc1OCC(Cl)=O Chemical compound CCc1cc(Cl)ccc1OCC(Cl)=O DMIZGMXOBGAMEZ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a kind of polysubstituted phenylpyrazole derivatives and preparation method thereof and the application in insecticide is made, its structure is：
Description
Technical field
The invention belongs to technical field of pesticide, in particular to a kind of polysubstituted phenylpyrazole derivatives and preparation method thereof and
Purposes.
Background technology
French Luo Na-Rhone-Poulenc discloses one kind in Application No. CN86108643.0 Chinese patent within 1986
The method of N- Phenylpyrazole insecticides, and developed in 1989 Chinese name " ethiprole ", trade name " Regent " it is wide
Insecticide is composed, its structural formula is as shown in formula I；French Luo Na-Rhone-Poulenc formula II disclosed in patent US6015910 in 2000
Shown compound, Chinese name " ethiprole ", trade name " Kirappu ", some features of the compound have exceeded ethiprole.
As people are more and more strict to environment, food safety requirements, some old pesticide species, it is inadaptable to be particularly some
Environment and the kind for having potential risk to person poultry safety, progressively be eliminated.Thus, develop active high, Environmental compatibility
Pesticide new variety good, the mode of action is unique, it is the only way of Agrochemicals.
The content of the invention
Present invention aims at a kind of polysubstituted phenylpyrazole derivatives are provided, its insecticidal effect is better than or equivalent to market
Existing commercial agricultural chemicals.This kind of compound can be used for agricultural, forestry or the preventing and treating of sanitary insect pest, especially resistanc pest
Preventing and treating, its preparation method high income, step are few, simple to operate.
To achieve the above object, polysubstituted phenylpyrazole derivatives of the invention, as shown in formula I, formula I is its structure：
Wherein,
R1For one kind in ethyl, trifluoromethyl；
Z is one kind in C, S；
N is 0,1,2；
R2For halogen, CN, C1-C4Alkyl and haloalkyl, C1-C4Alkoxy and halogenated alkoxy, C2-C4Alkenyl and halo
Alkenyl, C2-C4Alkoxy-carbonyl, phenyl and substituted-phenyl, heterocyclic radical and substituted heterocyclic radical, benzoyl and substituted benzene formyl
One kind in base, aryloxyalkyl group carbonyl, benzyloxy and substitution benzyl benzyloxy.
Meanwhile present invention also offers the preparation method of polysubstituted phenylpyrazole derivatives described in formula I, it includes following
Step：
Structural formula is used to substitute for compound 5- amino -1- (2,6- dichlor-4-trifluoromethyls phenyl) -4- shown in II sub-
Sulfonyl pyrazole -3- nitriles, with intermediate halides of the structural formula as shown in III in reaction dissolvent and add basic species under conditions of
Reaction, that is, obtain polysubstituted phenylpyrazole derivatives of the structural formula as shown in I, its reaction equation is：
Wherein, R1、Z、n、R2It is defined as described above, R3For one kind in chlorine, bromine.
Wherein, the solvent be benzene,toluene,xylene, chlorobenzene, pyridine, acetone, acetonitrile, ethyl acetate, tetrahydrofuran,
One kind in dioxane, N,N-dimethylformamide, dichloromethane, 1,2- dichloroethanes；
The basic species are sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, triethylamine, pyridine, methyl pyrrole
One kind in pyridine.
Wherein, structural formula be the mol ratio of compound shown in II and halides of the structural formula as shown in III be 1 ︰ 0.9~
3.0。
Present invention also offers application of the polysubstituted phenylpyrazole derivatives in insecticide is made, the insecticide
In, the concentration of polysubstituted phenylpyrazole derivatives is 0.1mg/L~9.9 × 105mg/L；When making insecticide, particular compound
Can be the enantiomters of the polysubstituted phenylpyrazole derivatives, diastereoisomer, racemic modification, pharmaceutically acceptable
Salt, crystalline hydrate or solvate etc..The insecticide can be used for the preventing and treating of the insect, evil mite of agricultural, forestry or hygienic industry, especially
It is the preventing and treating of resistanc pest, evil mite, and existing common insecticides no interactions resistance, and with hypotoxicity, it is environment-friendly,
Safe to use, the features such as wide spectrum and lasting period are long, be a kind of active material having a extensive future.
Embodiment
Polysubstituted phenylpyrazole derivatives of the present invention and its production and use are made with reference to specific embodiment
It is further described.
Embodiment 1
The polysubstituted phenylpyrazole derivatives part representative compound structural formula of the present invention is as follows：
Embodiment 2
The preparation for the compound that numbering is I -1, its reaction equation are in above-described embodiment 1：
Its preparation method comprises the following steps：
5mmol ethiprole [chemical names are added in 50ml flasks：5- amino -1- (2,6- dichlor-4-trifluoromethyl benzene
Base) -4- trifluoromethyl sulfinyl pyrazole -3- nitriles], dissolved with 10ml ethyl acetate, to less than 2 DEG C, stirring adds ice bath in batches
Enter 6mmol sodium hydrides, the ethyl acetate solution of 6mmol ortho-nitrophenyl sulfonic acid chlorides is slowly added dropwise, react at room temperature 4 hours, use successively
Ammonium chloride and sodium carbonate liquor washing, organic layer anhydrous sodium sulfate drying, precipitation, (volume ratio is for petroleum ether and ethyl acetate
5：1) column chromatography can obtain white solid N- [3- itrile group -1- (2,6- bis- fluoro- 4- trifluoromethylbenzene of the structural formula as shown in I -1
Base) -4- trifluoromethyl sulphinyls base) -1H- pyrazoles -5- bases] 2.46 grams of -2- nitrobenzophenones sulfonamide, 167~169 DEG C of fusing point,
Reaction yield 79.3%.
Embodiment 2
The preparation for the compound that numbering is I -4, its reaction equation are in embodiment 1：
Its preparation method comprises the following steps：
5mmol ethiprole [chemical names are added in 50ml flasks：5- amino -1- (2,6- dichlor-4-trifluoromethyl benzene
Base) -4- ethylsulfinyl pyrazoles -3- nitriles], lower addition 5mmol methylsufonyl chlorides and 5ml pyridines are stirred, is stirred overnight at room temperature,
System is poured into frozen water, there is solid precipitation, by gained solid with petroleum ether and ethyl acetate (volume ratio 5：1) column chromatography must be tied
Faint yellow solid N- [3- itrile groups -1- (the fluoro- 4- trifluoromethyls of the 2,6- bis-) -4- ethyl sulfenyls of structure formula as shown in I -4
Base) -1H- pyrazoles -5- bases] 1.90 grams of-methylsulfonamides, 126~127 DEG C of fusing point, reaction yield 80.1%.
Embodiment 3
The preparation for the compound that numbering is I -7, its reaction equation are in embodiment 1：
Its preparation method comprises the following steps：
9mmol ethiprole [chemical names are added in 100ml flasks：5- amino -1- (2,6- dichlor-4-trifluoromethyl benzene
Base) -4- trifluoromethyl sulfinyl pyrazole -3- nitriles], dry tetrahydrofuran 40ml, under nitrogen protection, it is added portionwise 0.8 gram
Sodium hydride, stirring reaction 30 minutes, bromoacetyl bromide 7ml is added dropwise, reacts at room temperature 3 hours, add 0.01mol 4- diformazan ammonia
Yl pyridines, continue stirring 1 hour.Reaction system filters, filtrate decompression distillation, gained grease petroleum ether and ethyl acetate
(volume ratio 5：1) column chromatography obtains pale yellow oily liquid N- [3- itrile group -1- (2,6- bis- fluoro- 4- of the structural formula as shown in I -7
Trifluoromethyl) -4- trifluoromethyl sulphinyls base) -1H- pyrazoles -5- bases]-amino carbonyl methyl-DMAP season
2.55 grams of ammonium salt, using ethiprole rate of collecting as 47.3%.
Embodiment 4
The preparation for the compound that numbering is I -13, its reaction equation are in embodiment 1：
Its preparation method comprises the following steps：
3mmol ethiprole [chemical names are added in 50ml flasks：5- amino -1- (2,6- dichlor-4-trifluoromethyl benzene
Base) -4- trifluoromethyl sulfinyl pyrazole -3- nitriles], dry tetrahydrofuran 10ml, ice bath is cooled to less than 0 DEG C, and nitrogen is protected
Under shield, 3mmol NaH is added portionwise, after reacting half an hour, 9mmol 2-vhloro-5-chloromethylpyridine is added dropwise, drips
Cheng Hou, be warmed to room temperature naturally, continue stirring 3 hours, concentration, with dichloromethane 20ml dissolve, 40ml wash 3 times, organic phase without
Aqueous sodium persulfate is dried, precipitation, and gained grease is with petroleum ether and ethyl acetate (volume ratio 5：1) column chromatography obtain structural formula such as I-
Pale yellow oily liquid 5- (6- chloropyridine-3- vlmethyls)-1- (2,6- dichlor-4-trifluoromethyls phenyl) shown in 13-
4- trifluoromethyl sulfinyl pyrazole -3- nitriles] 0.71 gram, reaction yield 42.3%.
Embodiment 5
The preparation for the compound that numbering is I -27, I -28, I -29, its reaction equation are in embodiment 1：
Its preparation method comprises the following steps：
5mmol ethiprole [chemical names are added in 50ml flasks：5- amino -1- (2,6- dichlor-4-trifluoromethyl benzene
Base) -4- trifluoromethyl sulfinyl pyrazole -3- nitriles], dry DMF 20ml, 15mmol stir-frys are added portionwise
The Anhydrous potassium carbonate of heat, 70 DEG C or so are heated to, the 5ml DMF solution of 10mmol bromoacetates are added dropwise,
It is added dropwise, 75 DEG C or so are reacted 20 hours.50ml water and 10ml5% watery hydrochloric acid are added after reaction solution cooling, with 50ml second
Acetoacetic ester extracts, organic layer saturated common salt water washing 3 times, anhydrous sodium sulfate drying, precipitation, with petroleum ether and ethyl acetate (body
Product is than being 5：1) column chromatography obtains white solid 3- itrile group -1- (2,6- dichlor-4-trifluoromethyl benzene of the structural formula as shown in I -27
Base) 0.54 gram of -4- trifluoromethyl sulphinyl base -5- ethoxycarbonylmethylamino -1H- pyrazoles, yield 20.6%；And structural formula
As shown in I -28 white solid 2- [3- itrile groups -1- (2,6- dichlor-4-trifluoromethyls phenyl) -4- trifluoromethyl sulphinyls base -
1H- pyrazoles -5- bases] 0.77 gram of amion acetic acid, yield 31.2%；And white solid 3- itrile group of the structural formula as shown in I-29-
Double (ethoxycarbonylmethyl group) amino -1H- pyrazoles of 1- (2,6- dichlor-4-trifluoromethyls phenyl) -4- trifluoromethyl sulphinyl bases -5-
0.49 gram, yield 16.2%.
Embodiment 6
The preparation for the compound that numbering is I -33, its reaction equation are in embodiment 1：
Its preparation method comprises the following steps：
Acyl chlorides is prepared first, and method is as follows：
5mmol parafluorobenzoic acids and 25mL thionyl chlorides are added in the 100mL three-necked bottles equipped with magnetic agitation, plus returning
After flowing condensing unit and drying and device for absorbing tail gas, oil bath heating is warming up to 65~70 DEG C, back flow reaction 4 hours, Ran Houyong
Water pump depressurizes (condition：52 DEG C/1.5h/0.09M Pa) a large amount of excessive thionyl chlorides are steamed, crude product is produced, in light yellow liquid
Body, it is directly used in and reacts in next step.
Then, the preparation of target compound, method are as follows：
4.8mmol ethiprole [chemical names are added in the 50mL three-necked bottles equipped with magnetic agitation：5- amino -1- (2,6-
Dichlor-4-trifluoromethyl phenyl) -4- trifluoromethyl sulfinyl pyrazole -3- nitriles], the dichloromethane (DCM) that 10ml is dried, ice
Bath adds 0.5mmol DMAP (DMAP) and 6.5mmol triethylamines, the 5ml bis- of acyl chlorides is added dropwise to less than 0 DEG C
Chloromethanes solution, drips and removes ice bath, is to slowly warm up to flow back, and reacts 10 hours, is cooled to room temperature, 2 are washed with 1% watery hydrochloric acid
It is secondary, wash 2 times, organic phase anhydrous sodium sulfate drying, precipitation, with petroleum ether and ethyl acetate (volume ratio 5：1) column chromatography obtains
[3- itrile groups -1- (2,6- dichlor-4-trifluoromethyls phenyl) -4- trifluoromethyls are sub- by white solid N- of the structural formula as shown in I -33
Sulfonyl -1H- pyrazoles -5- bases] 1.88 grams of -4- fluorobenzamides, using ethiprole rate of collecting as 70.2%.
Embodiment 7
The preparation for the compound that numbering is I -41, its reaction equation are in embodiment 1：
Its preparation method comprises the following steps：
The preparation of acyl chlorides, with the method for embodiment 6；
The preparation of target compound, method are：
4.8mmol ethiprole [chemical names are added in the 50mL three-necked bottles equipped with magnetic agitation, thermometer and constant pressure funnel
Claim：5- amino -1- (2,6- dichlor-4-trifluoromethyl phenyl) -4- trifluoromethyl sulfinyl pyrazole -3- nitriles], what 20m was dried
1,2- dichloroethanes (DCE), ice bath add 0.5mmol DMAP (DMAP) and 6.5mmol tri- to less than 0 DEG C
Ethamine, the 5ml of acyl chlorides 1,2- dichloroethane solutions are added dropwise, drips and removes ice bath, are to slowly warm up to flow back, react 8 hours,
Room temperature is cooled to, is washed 2 times with 1% watery hydrochloric acid, is washed 2 times, organic phase anhydrous sodium sulfate drying, precipitation, with petroleum ether and acetic acid
Ethyl ester (volume ratio 5：1) column chromatography obtains white solid N- [3- itrile group -1- (2,6- bis- chloro- 4- tri- of the structural formula as shown in I -41
Trifluoromethylphenyl) -4- trifluoromethyl sulphinyl base -1H- pyrazoles -5- bases] 2.26 grams of -2- (2,4- Dichlorophenoxy) acetamide, with
Ethiprole rate of collecting is 73.5%.
Embodiment 8
The biological activity determination of part representation compound
To bollworm determination of activity, using conventional manual's feed surface rubbing method：Specifically entered using 24 porocyte culture plates
Row screening active ingredients, 300 microlitres of man-made feeds being added per hole, 20 microlitres of decoction is added per hole, screening decoction uses various concentrations, point
Wei not 10mg/L, 3.33mg/L, 1.11mg/L, 0.37mg/L；
To aphid determination of activity, using conventional impregnation method：Specifically the sample of precise is dissolved in ethanol respectively and being prepared
Into certain density mother liquor, finite concentration is diluted to the aqueous solution of the emulsifying agent containing 0.1mg/L as needed, is respectively
50mg/L、16.66mg/L、5.56mg/L、1.85mg/L。
Take the part of compounds of the present invention to be tested, and select four kinds of control compounds to carry out interior under the same conditions
Insecticidal activity data (%, concentration unit：Mg/L) determination test, result of the test are shown in Table 1.
Control compound is respectively：
Chlorantraniliprole (compound that E.I.Du Pont Company Application No. CN02815924.1 Chinese patent is recorded, Chinese：
Chlorantraniliprole, trade name：Health is wide)；
Ethiprole (compound that Luo Na-Rhone-Poulenc Application No. CN86108643.0 Chinese patent is recorded, Chinese
Title：Ethiprole, trade name：Frontline Regent)；
Ethiprole (compound of Luo Na-Rhone-Poulenc Application No. US6015910 patent notes, Chinese：Second
Worm nitrile, trade name：Kirappu))；
Nitenpyram (compound of Japanese Wu Tian companies Application No. EP302389 patent notes, Chinese：Alkene pyridine
Worm amine, trade name：Bestguard).
Table 1 biocidal activity test result (killing rate %, concentration unit：mg/L)
The as shown by data of table 1：Test compound is respectively provided with excellent prevention effect to bollworm, aphid etc..Which part
Compound is very notable to the prevention effect of bollworm, and such as I -17, I -30 in concentration as little as 0.37mg/L, and the death rate reaches
100%, it is suitable with active best control compound ethiprole, chlorantraniliprole on existing market under same concentrations；Partization
Compound is very notable to the prevention effect of aphid, and such as I -27, I -17, I -42 in concentration as little as 1.85mg/L, and the death rate reaches
40%, it is suitable with active best control compound ethiprole, Nitenpyram under same concentrations.
Claims (7)
- A kind of 1. polysubstituted phenylpyrazole derivatives, it is characterised in that：As shown in formula I, formula I is its structure：Wherein,R1For one kind in ethyl, trifluoromethyl；Z is one kind in C, S；N is 0,1 or 2；R2For halogen, CN, C1-C4Alkyl and haloalkyl, C1-C4Alkoxy and halogenated alkoxy, C2-C4Alkenyl and haloalkenyl group, C2-C4Alkoxy-carbonyl, phenyl and substituted-phenyl, heterocyclic radical and substituted heterocyclic radical, benzoyl and substituted benzoyl, fragrant oxygen One kind in alkyl-carbonyl, benzyloxy and substitution benzyl benzyloxy.
- A kind of 2. preparation method of polysubstituted phenylpyrazole derivatives described in claim 1, it is characterised in that：This method is to use Structural formula be II shown in compound 5- amino -1- (2,6- dichlor-4-trifluoromethyls phenyl) -4- substituted sulfinyls pyrazoles - 3- nitriles, with halides of the structural formula as shown in III in a solvent and add basic species under conditions of react, obtain structural formula as shown in I Polysubstituted phenylpyrazole derivatives, the reaction equation of preparation process is：Wherein, R3For chlorine or bromine.
- 3. the preparation method of polysubstituted phenylpyrazole derivatives according to claim 2, it is characterised in that：Structural formula is II The mol ratio of shown compound and halides of the structural formula as shown in III is 1 ︰ 0.9~3.0.
- 4. the preparation method of the polysubstituted phenylpyrazole derivatives according to Claims 2 or 3, it is characterised in that：It is described anti- It is -2~40 DEG C to answer temperature, and the reaction time is 2~5h.
- 5. the preparation method of the polysubstituted phenylpyrazole derivatives according to Claims 2 or 3, it is characterised in that：It is described molten Agent is benzene, toluene, pyridine, dimethylbenzene, chlorobenzene, acetone, acetonitrile, ethyl acetate, tetrahydrofuran, dioxane, N, N- dimethyl One kind in formamide, dichloromethane, 1,2- dichloroethanes.
- 6. the preparation method of the polysubstituted phenylpyrazole derivatives according to Claims 2 or 3, it is characterised in that：The alkali Property thing is：One kind in sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, triethylamine, pyridine, picoline or It is several.
- 7. application of the polysubstituted phenylpyrazole derivatives described in claim 1 in insecticide is made, it is characterised in that：It is described to kill In worm agent, the concentration of polysubstituted phenylpyrazole derivatives is 0.1mg/L~9.9 × 105mg/L。
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Application publication date: 20180126 |