CN101092404A - Striazine derivative of fluoro alkene sulfenyl and fluoro alkene amido with notable biological activity - Google Patents

Abstract

This invention relates to a novel fluoroalkenylsulfur- or amino-substituted s-triazine derivative that can kill pests, mites, nematodes, bacteria and weeds, its preparation method, composition containing the derivative, and the method for killing or controlling pests, mites, nematodes, bacteria and weeds by using the composition containing the derivative.

Description

Fluoroathenylthio, fluoro enamino s-triazine derivative with notable biological activity

Technical field

The present invention relates to have desinsection, kill the novel fluoroathenylthio of mite, nematicide and sterilization and weeding activity, s-triazine derivative that the fluoro enamino replaces and preparation method thereof, the composition that contains this derivative, kill or control insect, mite class, nematode with this derivative, and the method for sterilization and weeding.

Background technology

Patent GB9219634, GB9219635, GB9316219, US5952359, GB9705120, US6448262, US7105524 disclose and have contained 4,4-two fluoro-3-butylene sulfo-heterocyclic derivatives, these derivatives have nematicide, desinsection, acaricidal activity, and some compound also has sterilization and weeding activity.Yet, do not see the report of seven kinds of fluoroathenylthios of the present invention, fluoro enamino s-triazine derivative.

Summary of the invention

In order to satisfy the requirement on the agricultural, the invention provides new fluoroathenylthio, fluoro enamino s-triazine derivative and on agricultural, prevent and treat the application of parasitosis crop smothering and contain the using method of these compound compositions.Fluoroathenylthio provided by the invention, fluoro enamino analog derivative be controlling plant insect, mite class, nematode, germ and weeds effectively.

Seven kinds of fluoroathenylthios of the present invention, fluoro enamino s-triazine derivative structural formula are as follows:

Compound among the present invention can be synthetic by several different methods, and for example figure below is depicted as wherein feasible synthetic route.

In the above-mentioned synthetic method, used intermediate is can be by known method synthetic or bought from market, for example:

1) with known method Synthetic 2,4-dichloro s-triazine

2) intermediate (D) and (E) can adopt following method synthetic

3) intermediate 1 reaction 2), 2-two fluoro-4-bromo-1-butylene have corresponding synthetic method in patent WO9406777, WO9406782, WO9524403 and GB9518111.

The invention described above compound can be controlled harmful insect such as lepidopteran, Diptera, Homoptera and Coleoptera and some other no vertebra insect of various agricultural, gardening, forest and storage, as the mite class.For example, seven kinds of above-mentioned compounds can be controlled following insect and mite class:

Myzus persicae (black peach aphid), Aphis gossypii (cotten aphid), Aphis fabae (vegetable aphid), Aedes aegypti (mosquito), Anopheles spp. (Anopheles), Culex spp. (Culex), Dysdercus fasciatus (band line red cotton bug), Muscadomestica (housefly), Pieris brassicae (large white butterfly), Plutella xlostella (small cabbage moth), Phaedon cochleariae (the horseradish ape is chrysomelid), Aonidiella spp. (kidney Aspidiotus genus), Trialeurodes spp. (Aleyrodes), Bemisia tabaci (sweet genus aleyrodid), Blattella germanica (Groton bug), Periplaneta americana (periplaneta americana), Blatta orientalis (East Africa Lian), Spodoptera littoralis (prodenia litura), Heliothis virescens (oriental tobacco budworm), Chortiocetes terminifera (Australian locust), Diabrotica spp. (the chrysomelid genus of bar), Agrotis spp. (Agrotis), Chilo partellus (Pyrausta nubilalis (Hubern).), Nilaparvata lugens (brown paddy plant hopper), Nephotettix cincticeps (rice green leafhopper), Panonychus ulmi (panonychus ulmi), Panonychus citri (tangerine Panonychus citri), Tetranychus urticae (Tetranychus urticae), Tetranychus cinnabarinus (carmine spider mite), Phyllcoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (white spider) and Brevipalpus spp. (short hairs mite).

The compounds of this invention also can be used for preventing and treating nematode, mainly prevents and treats plant nematode such as root knot nematode: Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica and other Meloidogyne kind; Roe deer capsule nematode: Globoderarostochiensis and other Globodera kind; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii and other Heterodera kind; Plant the knurl nematode: Anguina species; Stem and leaf bud nematode: Aphelenchoides species; Thorn nematode: Belonolaimus longicaudatus and other Belonolaimus kind; Pine wood nematode: Bursaphelenchus xylophilus and other Bursaphelenchus kind; Annular nematode: Criconema kind, Criconemella kind, Criconemoides kind, Mesocriconema kind; Bulb eelworm: Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus kind; Awl nematode: Dolichodorus kind; Helicotylenchus: Heliocotylenchusmulticinctus and other Helicotylenchus kind; Sheath nematode: Hemicycliophora kind and Hemicriconemoides kind; The Hirshmanniella kind; Hat nematode: Hoploaimus kind; Pseudo-root nodule nematode: Nacobbus kind; Needlework worm: Longidoruselongatus and other Longidorus kind; Nail nematode: Paratylenchus kind; Pratylenchus: Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus kind; Similes thorne: Radopholus similis and other Radopholus kind; Kidney shape nematode: Rotylenchus robustus and other Rotylenchus kind, Scutellonema kind; Undesirable root nematode: Trichodorus primitivus and other Trichodorus kind, Paratrichodorus kind; Downgrade nematode: Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus kind; Phase tangerine nematode: Tylenchulus kind; Sword nematode: Xiphinema kind and other plant nematode.

The compounds of this invention also can be used as sterilant, prevents and treats the various plants pathogenic bacteria.

The compounds of this invention is useful as herbicides also, the plant of preventing and kill off multiple weeds and not expecting, and prevent and kill off the plant that other weedicide is produced resistance.

The compounds of this invention is particularly useful for control to the deleterious insect of plant, mite class and nematode.

In order to use above-mentioned target compound control harmful insect, mite class, nematode etc., need be made into corresponding compositions, contain the described compound of claim 1 of 0.1-99% weight in the said composition.Compound can be made composition such as pulvis, wettable powder, granula (slowly-releasing or quick-release), missible oil, suspension agent, aqua, emulsifiable concentrate, microemulsion, coating agent for seed, smoke substance, may command release dosage form such as the microcapsule granula or the suspension agent etc. of various ways, be applied to soil, plant or seed, and mix in bait, or be put into the place that insect haunts.When in soil that is applied to plant or plantation or the water, be scattered in the water during use or in other liquid medium, effectively working concentration is usually at 0.1ppm to 10000ppm, preferred 1ppm to 5000ppm.

These compounds can the single-component pattern use, and also can use with as sterilant, synergistic agent, weedicide, sterilant or plant-growth regulator with suitable one or more biological activities.Other effective ingredient that is suitable for comprises the compound that can enlarge activity profile or prolong the lasting period, can strengthen the compound of the active of target compound or enhancing quick-acting.Other effective ingredient in the mixture, especially wanting can increase the result of use of target compound and will have the different mechanism of action.Target compound can be with desinsections such as pyrethroid, organic phosphates, amino formate, chlorinated cyclopentadiene class, formamidine, organic tin, chlorinated hydrocarbons, benzoyl area kind, pyroles, kill mite and nematocides is used with.

Embodiment

Following specific embodiment is used for further specifying the present invention.

Synthetic embodiment

Synthesizing of example 1 compound (I)

2,4-dichloro s-triazine (7.5g) is dissolved in the 50mL methylene dichloride, stir down, the 20ml dichloromethane solution that will contain aniline (4.7g) in the ice bath dropwise is added in the above-mentioned solution, adds the back and continues to stir, TLC follows the tracks of, when no longer including the product generation, termination reaction removes most of solvent under reduced pressure, separate (ethyl acetate: sherwood oil=5: 1) obtain product 4-chloro-2-(N-phenyl amido) s-triazine 8.4g (productive rate 82%), light yellow transparent liquid with column chromatography.

Get above-mentioned product, and acetate 4,4-two fluoro-3-alkene butyl alcohol esters (7.5g) are dissolved in the 60mL ethanol, add salt of wormwood 7g again, and reflux conditions reacted 6 hours down, filtered.The most of solvent of pressure reducing and steaming, column chromatography is separated (ethyl acetate: sherwood oil=2: 1), obtain compound (I) 9.6g (productive rate 77%), yellow jelly. ¹H?NMR(CDCl ₃)d：2.36(2H，m)，2.84(2H，m)，4.22(1H，t)，6.72(1H，t)，7.08(2H，t)，7.55(2H，d)，8.31(1H，s)，9.37(1H，s)ppm。

Synthesizing of example 2 compounds (IV)

2,4-dichloro s-triazine (7.5g) is dissolved in the 50mL methylene dichloride, stirs down, to contain 4 in the ice bath, the 20ml dichloromethane solution of 4-two fluoro-3-alkene butylamine (5.4g) dropwise is added in the above-mentioned solution, adds the back and continues to stir, and TLC follows the tracks of, when no longer including the product generation, termination reaction removes most of solvent under reduced pressure, separates (ethyl acetate: sherwood oil=5: 1) obtain product 4-chloro-2-(4 with column chromatography, 4 two fluoro-3-alkene butyl sulfo-s) s-triazine 7.6g (productive rate 69%), weak yellow liquid.

Get above-mentioned product, reach aniline (3.6g) and be dissolved in the 50mL methylene dichloride, add salt of wormwood 7g again, reflux conditions reacted 6 hours down, filtered.The most of solvent of pressure reducing and steaming, column chromatography is separated (ethyl acetate: sherwood oil=2: 1), obtain compound (I) 6.4g (productive rate 73%), the orange solid. ¹H?NMR(CDCl ₃)d：2.12(2H，m)，3.09(2H，m)，4.22(1H，t)，6.72(1H，t)，7.08(2H，t)，7.27(1H，t)，(7.55(2H，d)，8.36(1H，s)，9.37(1H，s)ppm。

Example of formulations (add-on of active ingredient is metered into after rolling over hundred in the prescription, and all percentage compositions are weight percentage)

Example 3 10% compound (I) missible oil

Compound (I) 10%, farming breast No. 500 5%, farming breast No. 601 5%, methyl alcohol 10%, dimethylbenzene complements to 100%.Above-mentioned material mixes, and promptly obtains transparence missible oil.

Example 4 10% compound (II) wettable powders

Compound (II) 10%, Sodium dodecylbenzene sulfonate 1.5%, carboxymethyl cellulose 1%, sulfonaphthol formaldehyde condensation products sodium salt 8%, light calcium carbonate complements to 100%.Above-mentioned material thorough mixing after ultrafine crusher is pulverized, promptly obtains converted products,

Example 5 15% compound (III) aqueous emulsions

Compound (III) 15%, polyvinyl alcohol 0.8%, alkylaryl polyoxyethylene poly-oxygen propylene aether 8%, farming breast No. 500 2%, Nongru-700 number 8%, dimethyl formamide 10%, ethylene glycol 5%, under the high-speed stirring, water complements to 100%, obtains the aqueous emulsion of favorable dispersity.

Example 6 60% compound (IV) water dispersible granules

Compound (IV) 60%, methyl naphthalene sulfonate formaldehyde condensate 12%, epoxidized polyether 5%, Zulkovsky starch 15%, gypsum complements to 100%.Above-mentioned material mixing after the kneading, adds in the tablets press that the certain specification screen cloth is housed and carries out granulation, and drying, screening obtain granule then.

Example 7 25% compound (V) suspension agents

Compound (V) 25%, calcium lignin sulphonate 5%, white carbon black 0.5%, ethylene glycol 4%, tributyl phosphate 1%, water complements to 100%, mixes, and carries out porphyrize in the sand milling still, obtains suspension agent.

Example 8 10% compound (VII) microemulsions

Compound (VII) 10%, agricultural chemicals No. 500 5%, farming breast No. 1,601 5%, farming breast No. 1,602 8%, azone 1%, water complements to 100%, and high-speed stirring obtains transparent microemulsion.

Biological activity determination

Example 9 pesticide and miticide actilities are measured

With The compounds of this invention several insects and mite class have been carried out the insecticidal activity assay test.Method for measuring is as follows:

After the mixed solvent dissolving of new compound with acetone/methanol (1: 1), be diluted to required concentration with the water that contains 0.1% tween 80.

With Myzus persicae (black peach aphid), Culex pippenspallens (culex pipiens pollens), Musca domestica (housefly), Plutella xlostella (small cabbage moth), Heliothis virescens (oriental tobacco budworm), Nilaparvata lugens (brown paddy plant hopper), Tetranychus cinnabarinus (carmine spider mite) is target, adopt airbrush spray method and immersion method (culex pipiens pallens larvae) to carry out insecticidal activity assay, airbrush spraying processing pressure is that 10psi (is roughly equal to 0.7kg/cm ²), spouting liquid is 0.5ml.Handle the mortality ratio that 2-3 day is investigated target in the back.

The partial test result is as follows:

When liquor strength was 50ppm, seven kinds of compounds were equal 100% to the mortality ratio of black peach aphid, carmine spider mite, housefly,, other target insect mortality ratio also surpasses 95%.

Claims (5)

1, fluoroathenylthio, fluoro enamino s-triazine derivative, structural formula is as follows:

2, the described compound of claim 1 the preparation method, by following trans should making:

3, the described compound of claim 1 is being prevented and treated plant insect, mite class, nematode, and the application of germ and weeds.

4, the described compound of claim 1 is particularly useful for pest control, mite class, nematode.

5, a kind of desinsection, kill mite, nematicidal composition, it is characterized in that: contain the described fluoroathenylthio of claim 1, fluoro enamino s-triazine derivative in the composition, the weight percentage of active ingredient is 0.1-99%.