TWI335208B - Novel insecticide composition - Google Patents

Abstract

The subject of the present invention is an insecticidal composition useful for controlling ravaging or pest arthropods, in particular insects, and more especially those which attack crops, the said composition combining at least one insecticidal compound of general formula (I) as in the description with an oil of plant origin possessing high drying power.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insecticide composition for controlling damaged or harmful arthropods, particularly comprising a phenylpyrazole compound as an active material and oily properties. The insecticide composition is used in combination with an adjuvant. [Prior Art] An insecticide composition comprising a stupid pyridinium compound is known, and in particular EP 0295 11 discloses an insecticide composition which comprises what is generally known and also known as fipronil The compound, 5-amino-3_cyano-(2,6-dichloro-4-trifluoromethylphenyl)_4•trifluoromethylsulfinylpyrazole. Recently, it has been known that the phenylpyrazole compound which can also be used as the active ingredient of the insecticide composition is 5-amino-3-cyano-I- (2,6-dioxa·4-trifluoromethylphenyl) _4_ethyl sulfinyl pyrazole. This compound is commonly referred to as ethipr〇ie, and is disclosed in U.S. Patent No. 5,814,652. It is desirable to reduce the dose of chemical products that are dispersed in the environment to control the infestation of the stolen goods, especially by reducing the dosage administered. Therefore, certain adjuvants (referred to as biological activators) such as mineral oils, wetting agents, penetrants are used in combination with commercially major products, and it is possible to use, for example, the combination of an inorganic oil adjuvant and an insecticidal compound. This has the advantage of reducing the dose of the compound used. And I have seen the possibility of choosing for the farmer, so I can find the solution that is most suitable for his special problem, and on the other hand, 'When some stolen goods t find tectonic 4, some of these main products will be affected. limit. When the Kun ==:! agent is used together with the phenyl hydrazine compound, the so-called sensitive grain is also

O:\80\80651 -930224. DOC -6- 公告 Announcement 1 π v々., , at the same time, for the subject matter of the attack: biological activity. SUMMARY OF THE INVENTION Accordingly, the present invention provides an insecticide composition comprising a compound of the formula (1) and an oil which is plant-derived and highly dry.

Wherein R1 represents a _ prime atom, a -CN group or a methyl group or a _C(S)NH2 group, a -C(=N·Y)Z group or a C(〇)CH3 group; R2 represents -S(0)nR3 or 4 , 5-dicyanoimidazole-2.yl or haloalkyl; R3 represents an alkyl group or a halogen group; the IU system includes a hydrogen atom, a halogen atom, a hydroxyl group or an alkoxy group and may be _NR5R6, C(0) R7-C(0)0R7, -S(0)mR7, alkyl, haloalkyl, -〇R8 or -n=c(r9)(r 丨〇) groups; R·5 and R_6 are independently selected From a hydrogen atom 'alkyl, halogen-based, -C(〇)alkyl, alkoxy group, methoxyalkyl-C(O)- or -S(0)rCF3 group; or R5 and Re- Forming a divalent group that can be inserted with one or more heteroatoms such as oxygen or sulfur

O:\80\80651 *930224. DOC 1335208 Announcement

R7 is selected from the group consisting of alkyl and haloalkyl;

Re is selected from the group consisting of an alkyl group, a dentate group and a gas atom; R9 is selected from a hydrogen atom and an alkyl group; and R1 is selected from one or more hydroxyl groups, hydrogen atoms, a certain S-alkyl group, and a cyano group. Or an alkyl group or a combination thereof substituted with a styl group and a heteroaryl group. The X system is selected from the group consisting of a nitrogen group and a C-R12 group; the arylcarbonyl group and the Y group are selected from the group consisting of a hydroxyl group, an amine group, an amine carbonyl group, an alkoxy group, and an alkane group. a carbonyl group, an alkoxycarbonyl group, an aminomethyl fluorenyl group, an arylaminomethyl fluorenyl group, an alkylaminomethyl fluorenyl group and a pyrazolyl group, which may be substituted or unsubstituted; the Z series is selected from the group consisting of a hydroxyl group and an amine. Alkyl, aminocarbonyl, alkoxy, arylcarbonyl, alkane, carbonylcarbonyl-alkylcarbonylcarbonyl, aminomethylmercapto, arylaminomethylhydrazine and alkylaminocarboxamidine; ^ is independently selected from a halogen atom or a hydrogen atom or alternatively /^^ or "N〇2; R" is selected from a halogen atom, a halogen atom group, a haloalkoxy group, a _s(〇) qCF3& _ SF5 group; m η ' q, r is independently selected from 〇, 1 and 2; the condition is that when R! represents a methyl group, R3 represents a haloalkyl group, r4 represents _NH2, R11 represents Cl, R13 represents _CF3, and X represents N. The present invention is an insecticide composition for protecting cereals mainly comprising a phenylpyrazole compound and an adjuvant of a plant derived oil having a high drying power. A number of examples of vegetable oils used in the formulation of insecticides, especially insecticide compounds, are known, for example, from U.S. Patent No. 6,149,913. However, it has not been proposed to use a vegetable oil with a high drying power in the insecticidal composition. because

O:\80\8065I-930224.DOC 1335208

In the insecticidal composition of the present invention, the Chinese version of the patent application No. 091121857 is replaced by a page (98 years 7 h. X_ and most surprisingly, it is possible to obtain extremely favorable results. The composition of the formulation provided makes it possible to obtain a plant protection mixture of excellent physical properties, and thus it can be used in conjunction with various other commercial combinations without physicochemical incompatibility. For use in the insecticide compositions of the present invention The stability of the mixture of protected plants can also be formulated as a specific active ingredient 'which is difficult and even impossible to apply. The insecticide composition of the present invention comprises a compound of the formula 植物 and a vegetable virgin oil. As for the compound of the formula 1, The alkyl group and the decyloxy group of (1) are preferably a lower alkyl group and an alkoxy group, that is, such groups have a fluorene to 4 carbon atoms; and a haloalkyl group and a halane having 1 to 4 carbon atoms are also preferred. An oxy group; a haloalkyl group and a dentate group which may have one or more halogen atoms; preferred groups of the group include -CF3 and -OCF3. Preferred compounds of the formula 1 are when R1 represents a term; Cheng, R3 generation Episulfidyl or !i alkyl; R4 represents 5r6, RJR6 is independently selected from a chlorine atom, an alkyl group, a halogen group, a -c(0)alkyl group, and a c(9)0R7 group; ^ is a burnt group or a dentate group J represents - C-R12; R13U fluorenyl; R11 and R12 are independently selected from a halogen atom or a hydrogen atom or the other. The first compound of the formula i is (1) tR1 represents a table rs(Q)2CF374 represents side 2, and x represents a heart. Ch" is chlorine and Rl3 is difluorodecyl. The chemical definition of the compound is 5_Amino_3-cyano-Η2,6-dichloro-4-mphenyl)_4^曱ylsulfin Stuffed with tons of bark, and called fipronil.

The second best compound is when R Qiaotian I stands for -CN; R2 stands for _s(〇)2C2H5

80651-980710.DOC •9- 1335208.. (, brother 091121857 patent application ('Chinese manual replacement page (98 years): Λ • · : * ; :: table 2 ' χ 代表 ' thought to be three汔. The chemical name of the compound is 5-amino-3-cyano-small phenyl) ice ethyl sulfite-, and is called the yuppo (10) ipl). The second component of the bismuth composition is plant native. oil. The advantage of using the vegetable oil of the present invention is that it is non-toxic or at least very less toxic than the inorganic oil and has a lower phytotoxicity' higher biodegradability. Suitable oils are unsaturated vegetable oil mash, structured oil, vegetable oil vinegar or a mixture of these organic phases. The oil may be of various native species, but is preferably derived from linseed, pilomo, dadan, corn, cotton, safflower and oil scorpion. These oils are sold in different grades, ie crude oils, refined oils or isomerized oils. The polyunsaturated vegetable oils contain a large number of unsaturated bonds. The polyunsaturated oil is understood to be a triglyceride having two or three double bonds in each chain of the linear aliphatic chain main body, or ci8: 2 or C18. Or 18 carbon atoms of 3 double bonds. In the case of the polyunsaturated oil, the triglyceride mentioned mainly contains a so-called oleic acid ester acid chain (C18: 3) such as linseed oil. Therefore, the weight composition of the oil (characterized by fatty acid) ranges as follows: 50 to 60% of C18: 3_1 to 17% of C18: 2-15 to 25% of C18: 1-2 to 4% of C18: 0 -5 to 8% of C16: 0. In the example of polyunsaturated oil, it is also mentioned that the triglyceride vinegar mainly contains linseed oil, such as sunflower, corn, soybean, safflower, cottonseed and rapeseed. oil. Therefore, the composition of these oils (characterized by fatty acids) is as follows: 45 to 7〇% of C18:2_0” to

80651-980710.DOC -10· 1335208 ...__________J f] y, ,. 10%^LC18 . 3-10 ^ 40〇/〇C18 : 1-O.ljL 1〇〇/〇C18 : 〇-i ^ 26/❶C16. 〇. In the case of Lu, the oil in the scope of the present invention is a dry oil. The drying power is natural (dry or semi-drying oil) with or by chemical treatment with only a small or undried oil (so-called semi-dried or undried oil) produced by <isomerization. The isomerization reaction involves the double bond of the fatty acid chain ch2-ch-ch· to obtain the co-consumption of the heart such as ·ch=ch ch=ch.c, thus increasing its drying power (reactivity with air) Therefore, the percentage of the isomerization of the isomerized oil to the Japanese oil is between 16 and 18%, but the isomerized linseed oil contains uu% of the total light dilute. For the spent composition of the present invention, the vegetable oil having a value of (9) greater than 70, preferably greater than, ..., dryness, greater than (10), and preferably greater than (10), and preferably greater than the oil is preferably refined and/or Isomerization of the oil to the sun. In the compound of the present invention, the ratio of the weight of the compound of the mountain and the compound is too. · 6' is preferably from 0.2 to 1.35', more preferably from the 〇 · 25μ The composition of the present invention is „, and may be concentrated, that is, a commercially available product combined with two substances. The formula also contains two substances... 1 In the example, 'diluted with water, ο shrinking composition (the mixture) Said mixture), or by a mixture containing each substance ": ready to use. A barrel of the composition of the market = composition = liquid composition of Ming Form of a solution, a suspension of the concentrate. J Rong Li yield an oil solution of the composition is also preferred are, because it can

O:\80\80651 -930224.DOC ^35208 Easy to use and because it is easy to manufacture. Preferably, it is used as an aqueous concentrate in the form of an oil-in-water emulsion using vegetable oil. The compositions of the present invention correspond to conventional techniques used to protect plant formulations, and include solid or liquid addition sigma agents. The composition may also include conventional additives or adjuvants for all plant protection compositions, especially carriers, surfactants, adhesion promoters and flow enhancers, and anti-agents. The δ hai composition may also contain additional ingredients such as protective colloids, adhesives, thickeners, thixotropic agents, penetration enhancers, stabilizers, release agents, pigments, colorants, polymers, anti-foaming The term "carrier" refers to a natural or synthetic organic or inorganic substance, substance that is combined with an active ingredient to aid in its application to plants. The carrier is usually inert and should be treated on plants. The carrier can be solid (grey stone, natural or synthetic salt in emulsified stone, resin, bad, solid fertilizer, etc.) or liquid (water, alcohol, class, petroleum alkaloid, aromatic or paraffin, gasification hydrocarbon , liquefied gas, etc.). The beta surfactant can be an ionic or nonionic emulsification, dispersing or conditioning agent. The extract may be, for example, a salt of poly(tetra) acid, a salt of xyloic acid, a salt of acid or κ酉, a polycondensate of ethylene oxide with a fatty alcohol or with a fatty acid or an aliphatic amine group, substituted Phenol (especially alkylphenol or arylphenol), thiobutyrate salt, taurine derivative (especially alkyl taurate), polyoxyethylated phenol or alcohol phosphate . In order to facilitate dispersion of the active ingredient in water and good application to plants, it is desirable to have at least one surfactant. The oil/water suspension concentrates listed are the aqueous suspensions of the crystalline form in the water- and oil-oil organic phase suspensions (the oils here plus the emulsified materials, which are oil-in-water emulsions). liquid. 0:\80\B065l-930224.D〇c -12- 1335208 M wide-">々:. Prepare a suspension concentrate (which can also be spray applied) to obtain a consistency that does not increase' and does not store after storage Forming a settled or phase separated stable fluid product comprising from 1 to 75% active ingredient, from 0.5 to 15% surfactant, from 1 to 10% of a thixotropic agent, to 10% of a suitable additive, such as a pigment' Coloring agent, anti-foaming agent 'corrosion inhibitor, stabilizer, penetration enhancer, adhesive, and water or organic liquid which is used as a carrier in which the active ingredient is almost insoluble or insoluble. Partial organic solid substance or inorganic salt can be dissolved Or dispersed in a carrier to avoid sedimentation or as a cryoprotectant for water. The insecticide composition of the present invention can be subjected to various known treatment methods such as crepe (applying a composition comprising the composition above the pretreated mash) Liquid, spray, infused into trees or applied to the grain. Spraying the liquid over the pretreated grain is a preferred method of treatment. According to another object of the invention, the invention also relates to the control of the knot Animal treatment A method characterized by applying an insecticide composition as defined before an effective and non-toxic dose to the upper portion of the crop. The term 'effective and non-phytotoxic dose' means that the composition of the invention is sufficient to present or appear to be present The arthropods on the boot are controlled or destroyed and are not phytotoxic to the grain. The amount can vary widely depending on the insect, grain type, weather conditions, and the compounds contained in the compositions of the present invention to be controlled; such amounts can be determined, for example, by systematic field testing, and are known to those skilled in the art. . The acaricidal composition of the present invention is preferably used in an amount of from 5 to 1 g/ha, preferably from 1 to 250 g/ha, to the compound of the formula. The appropriate amount for the oily component is the formula ^匕O:\80\80651-930224.DOC • 13· 1335208 yVf (4)||The amount is from 0.25 to 〇.45 times. The actual agent 4 is ^^..多# and 疋, such as the crop to be treated, the degree of damage, weather conditions, etc. Suitable: in the treatment of the method of the present invention, the reference is a moss, especially barley, protein-rich oil-rich crops, such as peas, rape: sunflower, corn, grapes, horses and potatoes , Fanzhuang, vegetable crops (Wanju, turmeric crops, etc.), rice, tree cultivation (apple, pear, cherry, etc.), citrus fruit, turf. In the treatment method of the present invention, the two components of the insecticide composition of the present invention are simultaneously administered by the composition of the present invention from a concentrate or a barrel mixture which can be easily mixed. Another aspect of the present invention relates to a product which can simultaneously and sequentially apply the compound of the formula 1 and the oil of the insecticide composition of the present invention. [Embodiment] k is provided by the following examples, but does not limit the preferred properties of the composition of the present invention. Preparation of Insect Compositions The insecticide compositions of the present invention comprise the following ingredients: - an insecticide active ingredient of formula (I). 375 - ethoxylated polyarylaryl phenol phosphate potassium salt 60 - thiobutane Dioctyl octanoate 10 - ethoxylated oleic acid 8.5 - polyunsaturated vegetable oil 170 - monopropanediol 50 - polysaccharide 1.4 -1,2-benziso n-sedrin-3-one 0.7 O: \80\8O651-93O224.DOC -14· 1335208

...isotrienol...citric acid monohydrate 1 -water (added to 1 liter) The composition is prepared according to known methods, the details of which are as follows: Monopropylene glycol, isotridecyl alcohol, ethoxylated polyaryl The aryl phenol phosphate potassium salt, the sodium dioctyl succinate salt, and the citric acid monohydrate are simultaneously added to the water under stirring. Stirring is continued to disperse and dissolve the ingredients. The active ingredient is then added with stirring. The suspension was pre-ground using a colloid mill and then ground to a final particle size using a ball mill. A solution containing 2% polysaccharide and 1% 1,2-benzoiso-p-pyridin-3-one was added to the milled suspension under stirring. Add oil, phase (including plant method and ethoxylated oleic acid) to form an oil-in-water emulsion. Example 2 Two compositions of the present invention containing rapeseed oil and soybean oil were prepared as described in Example 1. The ingredients contained in each formulation are detailed in Table 1 below. Table 1 Composition 1 Composition 2 g / kg / kg 5-amino-3-ranyl-1-(2,6-dioxa-4-trifluoromethylphenyl)-4-ethylsulfin醯基p ratio 11 sitting insecticide compound 105.26 103.63 selected rapeseed oil with high drying power of vegetable oil 200 selected soybean oil with high drying power of vegetable oil 100 Soprophor FLK dispersant 50 50 Garopon SDS wetting agent 10 10 O: \80\80651 -930224.DOC -15· 1335208 修ι£ί' Supplement,

Alkamul A ----- emulsifier 15 15 propylene glycol antifreeze 55 20 Rhodorsil 454 anti-foaming agent 5.0 5.0 Rhodopol G thickener 2.0 1.2 Proxel GXL fungicide 1.0 0.2 water 586.74 586.74 Example 3: treatment of rice in concentration About 50 g/ha of the inventive compositions 1 and 2 were applied to the leaves to treat a rice crop of about 16 to 17 cm height infested by the small brown crop pest (Laodelphax striatellus). The insecticide composition is applied as a spray gun. In the southern part of the country, observe the mortality rate of pests. The results are listed in Table 2 below: Table 2 Insecticide composition insecticidal efficacy (6 hours) insecticidal efficacy (24 hours) insecticidal efficacy (48 hours) Composition 1 31 100 100 Composition 2 27.6 100 100 Example 4 : Control of Rice The compositions 1 and 2 of the present invention at dose rates of 25 and 50 g/ha were applied to the leaves to treat rice crops of about 16 to 17 cm in height which were attacked by brown crop pests (Nilaoarvara lugens). Application of the insecticide composition with a spray gun As for the comparative example, a similar suspension composition comprising the same ingredients but no oil component was applied to the rice straw crop. O:\80\8O65l-930224.DOC • 16· 1335208 Bulletin_Repair? 0^/Ly Under the table, observe the number of insects per square meter of crops for 14 days: Table 3 Insecticide Composition 3 Hours 1 day 3 days 7 days 10 days 14 days Composition l (25 g/ha) 1166 495 204 319 259 154 Composition l (50 g/ha) 1194 495 165 358 215 110 Composition 2 (25 g/ha) 1249 363 182 281 297 77 Composition 2 (50 g/ha) 1089 336 160 176 110 55 Comparative composition (25 g/ha) 1056 605 248 462 325 172 Comparative composition (50 g/ha) 930 517 154 341 204 121 It can be seen that the oil-containing compositions of the present invention provide better activity reduction than the corresponding compositions without oil. O:\80\8065! -930224. DOC -17-

Claims (1)

1335208 Patent application No. 091121857 Replacement of patent application scope (October 99) Pick up, patent application scope: Announcement · i 1. A kind of prevention and control of sputum Ethiprole) (chemical name 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-ethylsulfinylpyrazole) for insecticidal purposes a compound, and a vegetable oil selected from the group consisting of soybean oil and rapeseed oil. A method of treating arthropods that infest cereals, characterized in that the insecticide composition according to claim 1 of the patent application is applied to the upper part of the plant. 80651-991018.doc