CN101613318A - Dihalo-propylene compound and preparation method thereof, application - Google Patents
Dihalo-propylene compound and preparation method thereof, application Download PDFInfo
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- CN101613318A CN101613318A CN200910183287A CN200910183287A CN101613318A CN 101613318 A CN101613318 A CN 101613318A CN 200910183287 A CN200910183287 A CN 200910183287A CN 200910183287 A CN200910183287 A CN 200910183287A CN 101613318 A CN101613318 A CN 101613318A
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Abstract
The invention discloses the dihalo-propylene compound shown in the general formula (I), wherein, R
1Be C
1-C
5Alkyl, phenyl or substituted-phenyl; R
2Be C
1-C
5Alkyl or C
1-C
5Haloalkyl; R
3Be hydrogen, halogen, C
1-C
3Alkyl, C
1-C
3Alkoxyl group, nitro, cyano group, thiocyanogen, trifluoromethyl sulfonyl or trifluoromethyl sulphinyl base; R
4Be halogen, C
1-C
5Alkyl, cyano group or nitro; X is a halogen; N is 2-4, and m is 2-4.The invention also discloses the preparation method of dihalo-propylene compound.Dihalo-propylene compound compounds of the present 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.
Description
Technical field
Dihalo-propylene compound of the present invention and preparation method thereof, application belong to technical field of pesticide, are specifically related to a class and can be used as dihalo-propylene compound of pest control agent activeconstituents and preparation method thereof.
Background technology
Because human attention, to the toxicity of agricultural chemicals and more and more tighter to the requirement of environmental influence, efficient, low toxicity thereof, selectivity is good, safe, Environmental compatibility becomes the pesticide research exploitation well target to environment protection.In recent years, part is new and effective, the sterilant of low toxicity is used to substitute high malicious organophosphorus pesticide, and the dihalo-propylene insecticides is a class wherein.
To be SUMITOMO CHEMICAL chemical company proposed in 1997 dihalo-propylene insecticides pyridalyl (Pyridalyl) (JPn, kokai tokkyo koho JP09194418, insecticides US5922880), efficient, low toxicity, safety.Its chemical structure is as follows:
Pyridalyl has remarkable prevention effect to the various lepidoptera pests on vegetables and the cotton, and does not have cross resistance with the existing sterilant of preventing and treating lepidoptera pest, to the insect that has developed immunity to drugs, has good effect equally.Opposite with its high reactivity, pyridalyl is very little to various arthropodan influences, so it is expected to become the effective tool of a pest control in the insect comprehensive regulation (IPM) or sterilant resistance management.
U.S. Pat 5872137 discloses the dihalo-propylene compound that contains benzoates, under 500ppm effective concentration, spodoptera litura (prodenia litura) is had preventive effect more than 80%:
Chinese patent CN101348464A discloses the dihalo-propylene compound that contains pyrazole carboxylic acid ester class, under 400ppm effective concentration, small cabbage moth is had 100% preventive effect:
U.S. Pat 5922880 discloses the dihalo-propylene compound that minority contains the heterocycle formate ester, and furans is arranged, thiophene, and pyridine, quinoline etc. under 500ppm effective concentration, have preventive effect more than 80% to spodoptera litura (prodenia litura);
U.S. Pat 5952386 discloses the dihalo-propylene compound of aryl carboxamides class, under 500ppm effective concentration, spodoptera litura (prodenia litura) is had preventive effect more than 80%.
Summary of the invention
The purpose of this invention is to provide at various insects and have good prevention effect, and have a class dihalo-propylene compound of characteristics such as efficient, low toxicity, low residue, 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 application of above-claimed cpd aspect the preparation sterilant.
Dihalo-propylene compound and preparation method thereof, application are to take following technical scheme to realize:
Dihalo-propylene compound shown in the general formula (I):
Wherein,
R
1Be C
1-C
5Alkyl, phenyl or substituted-phenyl, the substituting group of substituted-phenyl is selected from halogen, C
1-C
3Alkyl or C
1-C
5In the haloalkyl one or more; R
1Be preferably C
1-C
5Alkyl;
R
2Be C
1-C
5Alkyl or C
1-C
5Haloalkyl is preferably C
1-C
5Alkyl;
R
3Be hydrogen, halogen, C
1-C
3Alkyl, C
1-C
3Alkoxyl group, nitro, cyano group, thiocyanogen, trifluoromethyl sulfonyl or trifluoromethyl sulphinyl base are preferably hydrogen, halogen, C
1-C
3Alkyl or nitro;
R
4Be halogen, C
1-C
5Alkyl, cyano group or nitro are preferably halogen; (R
4) m more preferably 2, the 6-dichloro;
X is a halogen, is preferably chlorine;
N is 2-4, is preferably 3; M is 2-4.
C among the present invention
1-C
5Alkyl is meant C straight chain or side chain
1-C
5Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, isopentyl, 1-ethyl propyl, neo-pentyl, 2,2-dimethyl propyl or 2-methyl-isobutyl.
Substituted-phenyl is generally to fluorophenyl, rubigan, to bromophenyl, adjacent fluorophenyl, Chloro-O-Phenyl, o-bromophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2,4-dibromo phenyl, p-methylphenyl, o-methyl-phenyl-or 2,6-dichlor-4-trifluoromethyl phenyl etc.
C
1-C
5Haloalkyl is meant C straight chain or side chain
1-C
5Haloalkyl, as methyl fluoride, chloromethyl, brooethyl, difluoromethyl, trifluoromethyl, trichloromethyl, trisbromomethyl, 2-fluoro ethyl, 2,2,2-trifluoroethyl, 1-(trifluoromethyl) ethyl etc.
Halogen is meant fluorine, chlorine, bromine or iodine.
C
1-C
3Alkyl is as methyl, ethyl, n-propyl or sec.-propyl; C
1-C
3Alkoxyl group is as methoxyl group, oxyethyl group, positive propoxy or isopropoxy; Nitro; Cyano group; Thiocyanogen; Trifluoromethyl sulfonyl or trifluoromethyl sulphinyl base.
The dihalo-propylene compound of general formula (I) is a class novel cpd, can make according to for example following reaction process is synthetic:
Wherein, substituent R
1, R
2, R
3, R
4, X, m and n be identical with definition in the general formula (I).
According to above-mentioned reaction equation, under the situation that has alkali or alkali-free to exist, make the reaction of pyrazol formyl chloride (II) and dihalo allyloxy phenoxyalkyl amine (III), described reaction is preferably with an organic solvent carried out under-10 to 60 ℃ of conditions, and its preferable reaction temperature is 0 to 30 ℃.
Above-mentioned reaction equation, with respect to pyrazol formyl chloride (II), dihalo allyloxy phenoxyalkyl amine (III) mol ratio be 1～3, preferred molar ratio is 1～1.5, the mol ratio of alkali is 1-5, preferred molar ratio is 1～2.
Described alkali is alkalimetal hydride, alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate or organic bases.
Described alkalimetal hydride is a sodium hydride; Described alkali metal hydroxide is sodium hydroxide or potassium hydroxide; Described alkaline carbonate is yellow soda ash or salt of wormwood; Described alkali metal hydrocarbonate is sodium bicarbonate or saleratus; Described organic bases is pyridine or triethylamine;
Described organic solvent is aromatic hydrocarbons, ketone, halohydrocarbon, ester class or polar solvent.
Described aromatic hydrocarbons is benzene, toluene or dimethylbenzene; Described ketone is acetone, methylethylketone or mibk; Described halohydrocarbon is chloroform, methylene dichloride or ethylene dichloride, described ester class is methyl acetate or ethyl acetate, described polar solvent is tetrahydrofuran (THF), acetonitrile, diox, N, dinethylformamide, N-Methyl pyrrolidone or methyl-sulphoxide or pyridine.
For the target compound shown in the separate type after reaction (I), under the situation of using water-soluble solvent, decompression earlier removes solvent, in resistates, add water, use water-fast aromatic hydrocarbons (as benzene, toluene and dimethylbenzene) then, halohydrocarbon (as chloroform, methylene dichloride and ethylene dichloride), or the described resistates of ester class (as ethyl acetate) solvent extraction, and with the resulting extraction liquid of saturated common salt water washing, with anhydrous sodium sulphate or anhydrous magnesium sulfate organic phase is carried out drying again, decompression removes solvent then.When using water-immiscible solvent, then in the gained reaction mixture, add water and saturated common salt water washing successively, precipitation reduces pressure after the organic phase drying.After boiling off solvent, can carry out purification processes to the resistates that obtains by methods such as recrystallization and column chromatographies, thereby obtain target compound by general formula (I) expression.
The pyrazol formyl chloride by general formula (II) expression as intermediate can adopt currently known methods, for example at Bull.Soc.Chim.France, 293 (1996) and US4950668 described in method synthesize and make.
The dihalo-allyloxy phenoxyalkyl amine by general formula (III) expression as intermediate can adopt currently known methods, for example synthesizes in the method described in the US5952386 to make.
General formula (I) compound has good control activity to insect, thereby compound of the present invention can be used as the sterilant of 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.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 the compound of the present invention by general formula (I) expression is used as the sterilant in fields such as agricultural, gardening, can use separately, or use in the mode of insect-killing composition, as being activeconstituents, adopt this area inert ingredient commonly used to be processed into aqueous emulsion, microemulsion, missible oil and wettable powder etc. with formula (I).
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.
During as pesticide active ingredient, the content in described sterilant can be selected in 0.5% to 99.5% scope, and can determine suitable active component content according to dosage form and application process by the compound of the present invention of general formula (I) expression.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 microemulsion, preferably its content is 10% to 30%; Contain 1% to 90% activeconstituents in missible oil, preferably its content is 10% to 80%.
For example, for described aqueous emulsion, microemulsion, 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 wettable powder, 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 the described compound by general formula (I) expression as activeconstituents, 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 the working concentration scope of the compound of expression is 1 to 1000ppm aqueous emulsion, microemulsion or missible oil, preferably its concentration is 1 to 500ppm.
Novel dihalo-propylene compound compounds 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:
1, the preparation of 3-methylpyrazole-5-formic acid-(2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy benzene oxygen) propionic acid amide
With 1,3-dimethyl pyrazole-5-formyl chloride (0.348g, 0.0022mol) and the solution formed of toluene (10ml), under stirring and ice-water bath cooling, slowly be added drop-wise to by 2,6-two chloro-4-(3 ', 3 '-dichloro) the allyloxy phenoxy propylamine (0.630g, 0.0022mol), (0.222g is 0.0022mol) and in the mixed solution formed of toluene (20ml) for triethylamine.After dropwising, reaction mixture is warmed up to about 30 ℃, and continues to stir under this temperature, chromatogram tracking to reactant transforms fully substantially, needs 2～3 hours approximately.Pour resulting reaction mixture into (30ml) in the water, standing demix.Organic layer is with saturated common salt water washing and behind anhydrous sodium sulfate drying, the decompression precipitation, and resistates is title compound (compound N is o.10 in the table 1), heavy 0.97g, yellow oil No.1.
1HNMR(CDCl
3)(ppm)：2.116(m，2H)，2.239(s，3H)，3.724(m，2H)，4.095(t，2H，J＝5.4Hz)，4.113(s，3H)，4.600(d，2H，，J＝6.3Hz)，6.121(t，1H，，J＝6.3Hz)，6.237(s，1H)，6.727(br，1H)，6.874(s，2H)
Embodiment 2
Press the method for embodiment 1, with 1,3-diethyl pyrazoles-5-formyl chloride and 2, o.2 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 1.259 (t, 3H, J=7.5Hz), 1.420 (t, 3H, J=7.5Hz), 2.110 (m, 2H), 2.640 (q, 2H, J=7.5Hz), 3.705 (m, 2H), 4.076 (t, 2H, J=5.4Hz), 4.566 (d, 2H, J=6.0Hz), 4.581 (q, 2H, J=7.5Hz), 6.102 (t, 1H, J=6.0Hz), 6.309 (s, 1H), 6.749 (br, 1H), 6.853 (s, 2H)
Embodiment 3
Press the method for embodiment 1, with 3-sec.-propyl-1-methylpyrazole-5-formyl chloride and 2, o.3 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 1.227 (d, 6H, J=7.5Hz), 2.110 (m, 2H), 2.968 (m, 1H, J=7.5Hz), 3.719 (m, 2H), 4.093 (t, 2H, J=5.4Hz), 4.123 (s, 3H), 4.585 (d, 2H, J=6.0Hz), 6.117 (t, 1H, J=6.0Hz), 6.294 (s, 1H), 6.758 (br, 1H), 6.868 (s, 2H)
Embodiment 4
Press the method for embodiment 1, with 3-isobutyl--1-methylpyrazole-5-formyl chloride and 2, o.4 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 0.926 (d, 6H, J=7.5Hz), 1.893 (m, 1H, J=7.5Hz), 2.113 (m, 2H), 2.447 (d, 2H, J=7.5Hz), 3.724 (m, 2H), 4.096 (t, 2H, J=5.4Hz), 4.132 (s, 3H), 4.590 (d, 2H, J=6.0Hz), 6.117 (t, 1H, J=6.0Hz), 6.250 (s, 1H), 6.724 (br, 1H), 6.868 (s, 2H)
Embodiment 5
Press the method for embodiment 1, with 4-chloro-3-isobutyl--1-ethyl pyrazoles-5-formyl chloride and 2, o.5 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 0.935 (d, 6H, J=7.5Hz), 1.403 (t, 3H, J=7.5Hz), 2.012 (m, 1H, J=7.5Hz), 2.145 (m, 2H), 2.519 (d, 2H, J=7.5Hz), 3.792 (m, 2H), 4.093 (t, 2H, J=5.7Hz) 4.555 (q, 2H J=7.5Hz), 4.601 (d, 2H, J=5.7Hz), 6.119 (t, 1H, J=5.7Hz), 6.894 (s, 2H), 7.186 (br, 1H)
Embodiment 6
Press the method for embodiment 1, with 4-bromo-3-isobutyl--1-ethyl pyrazoles-5-formyl chloride and 2, o.6 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl3) is (ppm): 0.954 (d, 6H, J=7.5Hz), 1.406 (t, 3H, J=7.5Hz), 2.019 (m, 1H, J=7.5Hz), 2.152 (m, 2H), 2.478 (d, 2H, J=7.5Hz), 3.793 (m, 2H), 4.092 (t, 2H, J=5.7Hz), 4.600 (q, 2H J=7.5Hz), 4.610 (d, 2H, J=6.0Hz), 6.118 (t, 1H, J=6.0Hz), 6.892 (s, 2H), 7.118 (br, 1H)
Embodiment 7
Press the method for embodiment 1, with 4-bromo-3-isobutyl--1-methylpyrazole-5-formyl chloride and 2, o.7 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl3) is (ppm): 0.957 (d, 6H, J=7.5Hz), 2.012 (m, 1H, J=7.5Hz), 2.163 (m, 2H), 2.472 (d, 2H, J=7.5Hz), 3.797 (m, 2H), 4.095 (t, 2H, J=5.7Hz), 4.127 (s, 3H), 4.591 (d, 2H, J=6.0Hz), 6.119 (t, 1H, J=6.0Hz), 6.894 (s, 2H), 7.180 (br, 1H)
Embodiment 8
Press the method for embodiment 1, with 4-bromo-3-sec.-propyl-1-ethyl pyrazoles-5-formyl chloride and 2, o.8 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 1.308 (d, 6H, J=7.5Hz), 1.427 (t, 3H, J=7.5Hz), 2.149 (m, 2H), 3.020 (m, 1H, J=7.5Hz), 3.803 (m, 2H), 4.110 (t, 2H, J=5.7Hz) 4.520 (q, 2H, J=7.5Hz), 4.627 (d, 2H, J=6.0Hz), 6.139 (t, 1H, J=6.0Hz), 6.894 (s, 2H), 7.085 (br, 1H)
Embodiment 9
Press the method for embodiment 1, with 4-chloro-3-sec.-propyl-1-methylpyrazole-5-formyl chloride and 2, o.9 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 1.284 (d, 6H, J=7.5Hz), 2.158 (m, 2H), 3.043 (m, 1H, J=7.5Hz), 3.790 (m, 2H), 4.084 (t, 2H, J=6.0Hz), 4.172 (s, 3H), 4.591 (d, 2H, J=6.0Hz), 6.119 (t, 1H, J=6.0Hz), 6.896 (s, 2H), 7.187 (br, 1H)
Embodiment 10
Press the method for embodiment 1, with 4-chloro-1,3-diethyl pyrazoles-5-formyl chloride and 2, o.10 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 1.234 (t, 3H, J=7.5Hz), 1.420 (t, 3H, J=7.5Hz), 2.142 (m, 2H), 2.628 (q, 2H, J=7.5Hz), 3.791 (m.2H), 4.086 (t, 2H, J=5.7Hz), 4.517 (q, 2H, J=7.5Hz), 4.541 (d, 2H J=6.0Hz), 6.121 (t, 1H, J=6.0Hz), 6.856 (s, 2H), 7.185 (br, 1H)
Embodiment 11
Press the method for embodiment 1, with 3-ethyl-1-methylpyrazole-5-formyl chloride and 2, o.11 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 1.418 (t, 3H, J=7.5Hz), 2.123 (m, 2H), 2.243 (s, 3H), 3.738 (m.2H), 4.087 (t, 2H, J=5.7Hz), 4.537 (q, 2H, J=7.5Hz), 4.591 (d, 2H J=6.0Hz), 6.116 (t, 1H, J=6.0Hz), 6.724 (br, 1H), 6.867 (s, 2H)
Embodiment 12
Press the method for embodiment 1, with 4-bromo-1,3 dimethyl pyrazole-5-formyl chloride and 2, o.12 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 2.167 (m, 2H), 2.259 (s, 3H), 3.790 (m, 2H), 4.072 (t, 2H, J=5.7Hz), 4.120 (s, 3H), 4.588 (d, 2H, J=6.0Hz), 6.116 (t, 1H, J=6.0Hz), 6.892 (s, 2H), 7.183 (br, 1H)
Embodiment 13
Press the method for embodiment 1, with 3-isobutyl--1-ethyl pyrazoles-5-formyl chloride and 2, o.13 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 0.907 (d, 6H, J=7.5Hz), 1.413 (t, 3H, J=7.5Hz), 1.890 (m, 1H, J=7.5Hz), 2.098 (m, 2H), 2.458 (d, 2H, J=7.5Hz), 3.722 (m, 2H), 4.080 (t, 2H, J=5.4Hz), 4.554 (q, 2H, J=7.5Hz), 4.586 (d, 2H, J=6.0Hz), 6.087 (t, 1H, J=6.0Hz), 6.323 (s, 1H), 6.833 (s, 2H), 6.992 (br, 1H)
Embodiment 14
Press the method for embodiment 1, with 1-ethyl-3-methylpyrazole-5-formyl chloride and 2, o.14 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 1.216 (t, 3H, J=7.5Hz), 2.121 (m, 2H), 2.635 (q, 2H, J=7.5Hz), 3.718 (m, 2H), 4.097 (t, 2H, J=5.7Hz), 4.131 (s, 3H), 4.597 (d, 2H, J=6.0Hz), 6.120 (t, 1H, J=6.0Hz), 6.286 (s, 1H), 6.729 (br, 1H), 6.891 (s, 2H)
Embodiment 15
Press the method for embodiment 1, with 4-bromo-3-sec.-propyl-1-methylpyrazole-5-formyl chloride and 2, o.15 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 1.285 (d, 6H, J=7.5Hz), 2.154 (m, 2H), 3.020 (m, 1H, J=7.5Hz), 3.796 (m, 2H), 4.095 (t, 2H, J=6.0Hz), 4.127 (s, 3H), 4.597 (d, 2H, and J=6.0Hz) 6.125 (t, 1H, J=6.0Hz), 6.861 (s, 2H), 7.131 (br, 1H)
Embodiment 16
Press the method for embodiment 1, with 4-chloro-1,3-dimethyl pyrazole-5-formyl chloride and 2, o.16 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N.
1HNMR(CDCl
3)(ppm)：2.148(m，2H)，2.200(s，3H)，3.798(m，2H)，4.097(t，2H，J＝6.0Hz)，4.134(s，3H)，4.599(d，2H，J＝6.0Hz)，6.126(t，1H，J＝6.0Hz)，6.861(s，2H)，7.230(br，1H)
Embodiment 17
Press the method for embodiment 1, with 4-bromo-1,3-diethyl pyrazoles-5-formyl chloride and 2, o.17 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 1.266 (t, 3H, J=7.5Hz), 1.419 (t, 3H, J=7.5Hz), 2.160 (m, 2H), 2.634 (q, 2H, J=7.5Hz), 3.799 (m, 2H), 4.121 (t, 2H, J=5.4Hz), 4.520 (q, 2H, J=7.5Hz), 4.599 (d, 2H, J=6.0Hz), 6.125 (t, 1H, J=6.0Hz), 6.861 (s, 2H), 7.107 (br, 1H)
Embodiment 18
Press the method for embodiment 1, with 4-nitro-1,3-diethyl pyrazoles-5-formyl chloride and 2, o.18 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl
3) (ppm): 1.262 (t, 3H, J=7.5Hz), 1.458 (t, 3H, J=7.5Hz), 2.151 (m, 2H), 2.635 (q, 2H, J=7.5Hz), 3.827 (m, 2H), 4.110 (t, 2H, J=5.4Hz), 4.537 (q, 2H, J=7.5Hz), 4.598 (d, 2H, J=6.0Hz), 6.123 (t, 1H, J=6.0Hz), 6.665 (br, 1H), 6.881 (s, 2H)
Embodiment 19
Press the method for embodiment 1, with 4-chloro-3-sec.-propyl-1-ethyl pyrazoles-5-formyl chloride and 2, o.19 the reaction of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy propylamines makes compound N,
1HNMR (CDCl3) is (ppm): 1.296 (d, 6H, J=7.5Hz), 1.405 (t, 3H, J=7.5Hz), 2.155 (m, 2H), 3.125 (m, 1H, J=7.5Hz), 3.793 (m, 2H), 4.088 (t, 2H, J=5.7Hz), 4.561 (q, 2H, J=7.5Hz), 4.627 (d, 2H, J=6.0Hz), 6.120 (t, 1H, J=6.0Hz), 6.858 (s, 2H), 7.0635 (br, 1H)
Embodiment 20
1, the preparation of 3-methylpyrazole-5-formic acid-(2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy benzene oxygen) propionic acid amide
With 1,3-dimethyl pyrazole-5-formyl chloride (0.348g, 0.0022mol) and the solution formed of toluene (10ml), under stirring and ice-water bath cooling, slowly be added drop-wise to by 2,6-two chloro-4-(3 ', 3 '-dichloro) the allyloxy phenoxy propylamine (1.890g, 0.0066mol), (1.11g is 0.011mol) and in the mixed solution formed of toluene (20ml) for triethylamine.After dropwising, reaction mixture is warmed up to about 30 ℃, and continues to stir under this temperature, chromatogram tracking to reactant transforms fully substantially, needs 2～3 hours approximately.Pour resulting reaction mixture into (30ml) in the water, standing demix.Organic layer is with dilute hydrochloric acid washing, saturated common salt water washing and behind anhydrous sodium sulfate drying, the decompression precipitation, and resistates is title compound (compound N is o.10 in the table 1), heavy 0.85g, yellow oil No.1.
1HNMR(CDCl
3)(ppm)：2.116(m，2H)，2.239(s，3H)，3.724(m，2H)，4.095(t，2H，J＝5.4Hz)，4.113(s，3H)，4.600(d，2H，，J＝6.3Hz)，6.121(t，1H，，J＝6.3Hz)，6.237(s，1H)，6.727(br，1H)，6.874(s，2H)
Embodiment 21
1, the preparation of 3-methylpyrazole-5-formic acid-(2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy benzene oxygen) propionic acid amide
With 1,3-dimethyl pyrazole-5-formyl chloride (0.348g, 0.0022mol) and the solution formed of toluene (10ml), under stirring and ice-water bath cooling, slowly be added drop-wise to by 2,6-two chloro-4-(3 ', 3 '-dichloro) the allyloxy phenoxy propylamine (0.945g, 0.0033mol), (0.555g is 0.0055mol) and in the mixed solution formed of toluene (20ml) for triethylamine.After dropwising, reaction mixture is warmed up to about 30 ℃, and continues to stir under this temperature, chromatogram tracking to reactant transforms fully substantially, needs 2～3 hours approximately.Pour resulting reaction mixture into (30ml) in the water, standing demix.Organic layer is with dilute hydrochloric acid washing, saturated common salt water washing and behind anhydrous sodium sulfate drying, the decompression precipitation, and resistates is title compound (compound N is o.10 in the table 1), heavy 0.91g, yellow oil No.1.
1HNMR(CDCl
3)(ppm)：2.116(m，2H)，2.239(s，3H)，3.724(m，2H)，4.095(t，2H，J＝5.4Hz)，4.113(s，3H)，4.600(d，2H，，J＝6.3Hz)，6.121(t，1H，，J＝6.3Hz)，6.237(s，1H)，6.727(br，1H)，6.874(s，2H)
The prepared compound of each embodiment is as shown in the table:
| Compound N O. | ??R 1 | ??R 2 | ??R 3 | ??(R 4)m | ??n | ??X | Physical behavior |
| ??1 | ??CH 3 | ??CH 3 | ??H | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??2 | ??C 2H 5 | ??C 2H 5 | ??H | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??3 | ??CH 3 | ??(CH 3) 2CH | ??H | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??4 | ??CH 3 | ??(CH 3) 2CH ??CH 2 | ??H | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??5 | ??C 2H 5 | ??(CH 3) 2CH ??CH 2 | ??Cl | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??6 | ??C 2H 5 | ??(CH 3) 2CH ??CH 2 | ??Br | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??7 | ??CH 3 | ??(CH 3) 2CH ??CH 2 | ??Br | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??8 | ??C 2H 5 | ??(CH 3) 2CH | ??Br | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??9 | ??CH 3 | ??(CH 3) 2CH | ??Cl | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??10 | ??C 2H 5 | ??C 2H 5 | ??Cl | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??11 | ??C 2H 5 | ??CH 3 | ??H | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??12 | ??CH 3 | ??CH 3 | ??Br | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??13 | ??C 2H 5 | ??(CH 3) 2CH ??CH 2 | ??H | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??14 | ??CH 3 | ??C 2H 5 | ??H | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??15 | ??CH 3 | ??(CH 3) 2CH | ??Br | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??16 | ??CH 3 | ??CH 3 | ??Cl | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??17 | ??C 2H 5 | ??C 2H 5 | ??Br | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??18 | ??C 2H 5 | ??C 2H 5 | ??NO 2 | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
| ??19 | ??C 2H 5 | ??(CH 3) 2CH | ??Cl | ??2，6-diCl | ??3 | ??Cl | Yellow oil |
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
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, to obtain activeconstituents be 20% aqueous emulsion to uniform mixing together.
Example of formulations 2: microemulsion:
20 parts of The compounds of this invention, 10 parts of triphenylethylene phenol Soxylat A 25-7s, 5 parts of alkyl benzene sulfonate calcium salts, 5 parts in acetone, 10 parts of Virahols, 3 parts of Soxylat A 25-7 methane amides, 47 parts in water, to obtain activeconstituents be 20% microemulsion to uniform mixing together.
Example of formulations 3: missible oil
10 parts of The compounds of this invention are dissolved in the mixed solvent of being made up of 40 parts of dimethylbenzene and 35 parts of dimethyl formamides, add 15 parts of soil temperature 80 emulsifying agents then, stir and uniform mixing to obtain activeconstituents be 10% missible oil.
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.
Compound is to the insecticidal activity result of small cabbage moth
Compound N o.5, the mortality ratio of No.6, No.7, No.8, No.9, No.10, No.12, No.14, No.15, No.16 and No.19 3d under 400ppm concentration reaches 100%.
Test example 2: to the insecticidal effect of beet armyworm
Beet armyworm 3 instar larvaes of selecting the indoors artificial feed to raise adopt and soak leaf and add the synthetic method of soaking worm and carry out the insecticidal effect test.The medicament configuration: take by weighing new compound sample 10mg in the 10ml volumetric flask, be settled to scale with acetone and obtain mother liquor, mother liquor obtains the soup of required dosage with the dilution of 0.05% tween 80 water.Ready fresh luxuriant dish leaf dish was flooded in soup 10 seconds, take out nature and dry.24 orifice plates of packing into.1 of beet larva at night soaking soup, 24 larvas of every processing are inserted in every hole.Processing is placed under the normal condition and raises, the life or death borer population of investigation 72h, statistics mortality ratio.
Compound is to the insecticidal activity result of beet armyworm
| ??NO. | Dosage ppm | Radix | 3d mortality ratio % | ??NO. | Dosage ppm | Radix | 3d mortality ratio % |
| ??1 | ??400 | ??24 | ??37.50 | ??11 | ??400 | ??24 | ??83.33 |
| ??2 | ??400 | ??24 | ??50.00 | ??12 | ??400 | ??24 | ??100 |
| ??3 | ??400 | ??24 | ??50.00 | ??13 | ??400 | ??24 | ??100 |
| ??4 | ??400 | ??24 | ??100 | ??14 | ??400 | ??24 | ??95.83 |
| ??5 | ??400 | ??24 | ??100 | ??15 | ??400 | ??24 | ??100 |
| ??6 | ??400 | ??24 | ??100 | ??16 | ??400 | ??24 | ??79.16 |
| ??7 | ??400 | ??24 | ??100 | ??17 | ??400 | ??24 | ??62.50 |
| ??8 | ??400 | ??24 | ??100 | ??18 | ??400 | ??24 | ??58.33 |
| ??9 | ??400 | ??24 | ??100 | ??19 | ??400 | ??24 | ??100 |
| ??10 | ??400 | ??24 | ??100 | Pyridalyl | ??400 | ??24 | ??100 |
Compound N o.4, the mortality ratio of No.5, No.6, No.7, No.8, No.9, No.10, No.12, No.13, No.15 and No.19 3d under 400ppm concentration reaches 100%.
Test example 3: to the insecticidal effect of culex pipiens pollens
Select 3 instar larvaes of indoor continuous raising, adopt continuous immersion method to carry out the insecticidal effect test.
According to the composition mode of example of formulations 3, compound of the present invention (table 1) is made sterilant respectively.With pure water resulting insecticide emulsifiable concentrate is diluted, prepare the soup of 100mg/L.Fish for 20 of 3 instar larvaes, drop into and fill in the enamel basin of soup continuous immersion liquid 72h (each concentration triplicate).Move to observation ward after the processing, 72h checks borer population anyway, statistics mortality ratio (stiff with larva is death standard).
Compound N o.1, No.17, the No.19 mortality ratio under 100mg/L concentration is 100%.
Claims (10)
1, the dihalo-propylene compound shown in the general formula (I):
Wherein,
R
1Be C
1-C
5Alkyl, phenyl or substituted-phenyl;
R
2Be C
1-C
5Alkyl or C
1-C
5Haloalkyl;
R
3Be hydrogen, halogen, C
1-C
3Alkyl, C
1-C
3Alkoxyl group, nitro, cyano group, thiocyanogen, trifluoromethyl sulfonyl or trifluoromethyl sulphinyl base;
R
4Be halogen, C
1-C
5Alkyl, cyano group or nitro;
X is a halogen;
N is 2-4, and m is 2-4.
2, dihalo-propylene compound according to claim 1, wherein
R
1The substituting group of middle substituted-phenyl is selected from halogen, C
1-C
3Alkyl or C
1-C
5In the haloalkyl one or more.
3, dihalo-propylene compound according to claim 1, wherein
R
1Be C
1-C
5Alkyl;
R
2Be C
1-C
5Alkyl;
R
3Be hydrogen, halogen, C
1-C
3Alkyl or nitro;
R
4Be halogen.
4, dihalo-propylene compound according to claim 1, wherein
(R
4) m is 2, the 6-dichloro;
X is a chlorine;
N is 3.
5, the preparation method of the described dihalo-propylene compound of a kind of claim 1, having in the presence of alkali or the alkali-free, pyrazol formyl chloride and dihalo-allyloxy phenoxyalkyl amine are being reacted under-10～60 ℃, in the organic solvent, separating, obtain formula (I) compound, its reaction equation is as follows:
Wherein,
R
1Be C
1-C
5Alkyl, phenyl or substituted-phenyl;
R
2Be C
1-C
5Alkyl or C
1-C
5Haloalkyl;
R
3Be hydrogen, halogen, C
1-C
3Alkyl, C
1-C
3Alkoxyl group, nitro, cyano group, thiocyanogen, trifluoromethyl sulfonyl or trifluoromethyl sulphinyl base;
R
4Be halogen, C
1-C
5Alkyl, cyano group or nitro;
X is a halogen;
N is 2-4, and m is 2-4.
Wherein, with respect to pyrazol formyl chloride (II), dihalo allyloxy phenoxyalkyl amine (III) mol ratio be 1～3, the mol ratio of alkali is 1-5.
6, the preparation method of dihalo-propylene compound according to claim 5, wherein said alkali is alkalimetal hydride, alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate or organic bases; Described organic solvent is aromatic hydrocarbons, ketone, halohydrocarbon, ester class or polar solvent.
7, the preparation method of dihalo-propylene compound according to claim 6, wherein said alkalimetal hydride is a sodium hydride, described alkali metal hydroxide is sodium hydroxide or potassium hydroxide, described alkaline carbonate is yellow soda ash or salt of wormwood, described alkali metal hydrocarbonate is sodium bicarbonate or saleratus, and described organic bases is pyridine or triethylamine; Described aromatic hydrocarbons is benzene, toluene or dimethylbenzene; Described ketone is acetone, methylethylketone or mibk; Described halohydrocarbon is chloroform, methylene dichloride or ethylene dichloride, described ester class is methyl acetate or ethyl acetate, described polar solvent is tetrahydrofuran (THF), acetonitrile, diox, N, dinethylformamide, N-Methyl pyrrolidone or methyl-sulphoxide or pyridine.
8, the preparation method of dihalo-propylene compound according to claim 5, wherein temperature of reaction is 0～30 ℃.
9, the application of each described dihalo-propylene compound aspect the preparation sterilant in the claim 1～4.
10, a kind of insect-killing composition is an activeconstituents with each described dihalo-propylene compound in the claim 1～4, adds that inert ingredient makes aqueous emulsion, microemulsion or missible oil.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Publication Number | Publication Date |
|---|---|
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ID=41493226
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|---|---|
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