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    • 专利摘要:
    1-arylpyrazole of formula (I) wherein R 31 , R 32 , R 33 , R 4 , R 5 , R 12 , R 13 , R 14 , R 15 and Z are the same as defined in the specification It is useful as an intermediate of pesticides or other pesticides. Herein, a composition containing a compound of formula (I) and its use, in particular the use of agricultural and animal care as a pesticide, in particular a method for inhibiting arthropods, has been described.
    公开号:KR20000076074A
    申请号:KR1019997008162
    申请日:1998-03-05
    公开日:2000-12-26
    发明作者:우타이-테；매닝데이빗트레드웨이
    申请人:제닌 페트릭；롱-쁠랑 아그로；
    IPC主号:
    专利说明:

    Insecticidal 1-arylpyrazole {PESTICIDAL 1-ARYLPYRAZOLES}
    The present invention relates to novel derivatives of 1-arylpyrazole having utility as pesticides or as intermediates for preparing other pesticides. The present invention relates to the use of said compounds as intermediates for the preparation of said compounds, other pesticides, or for the inhibition of arthropod pests, in particular agricultural methods of said compounds or compositions, or protection of animals, In particular it relates to the use for the inhibition of arthropods as insecticides.
    International patents WO 87/03781 and European patents 0295117, 0154115, 0201852 describe insecticidal 1- (substituted phenyl) pyrazoles. Other prior art is also found in the patents or patents filed therefrom.
    International patents WO 93/06089 and WO 94/21606 also describe insecticidal 1- (4-SF 5 substituted phenyl) heterocycles which may be pyrrole as well as imidazole or pyrazole. The teaching of this patent is not substantially different from international patent WO 87/03781 or European patent 0295117 as far as pyrazole is concerned.
    Various pesticidal pyrazoles have been described in various patents: European Patents 0418016, 0403309, 0352944; US Patents 5104994, 5079370, 5047550, 5232940, 4810720, 4804675, 5306694, 4614533, 5187185, 5223525; International Patents 93/06089, 94/21606.
    Because of the many pests and crops present, and the damage status of crops by pests, there is a need for additional novel pesticidal compounds.
    It is an object of the present invention to provide novel pesticidal compounds of the 1-arylpyrazole group and methods for their preparation.
    A second object of the present invention is to provide a pesticidal method using insecticidal compositions and insecticidal pyrazole compounds for arthropods, in particular insects, particularly in crop or horticultural crops, forestry, veterinary medicinal or livestock raising, or public health. To provide.
    The third object of the present invention is not only very active compounds with a wide range of pesticidal activity, but also selective special activities such as pesticidal activity of aphids, mites, leaf pests, soil pesticides, tissues, taste avoidance or seed treatment It is to provide a compound having a compound.
    These and other objects, in whole or in part, fulfilling the invention will be readily apparent from the following detailed description of the invention.
    The present invention includes novel chemical compounds having pesticidal or acaricidal activity of insecticides, mites, nematodes.
    The present invention relates to compounds having the general formula (I) and to salts which are acceptable as pesticides thereof:
    [In the above meal,
    R 31 and R 32 can be individually OR 20 , S (O) n R 20 , or N (R 20 ) (R 21 ); Or R 31 and R 32 are also linked to O [C (R 22 ) (R 23 )] m O, S (O) n [C (R 22 ) (R 23 )] m S (O) a , O ( CH 2 ) m S (O) n , O [C (R 22 ) (R 23 )] m (NR 20 ), S (O) n [C (R 22 ) (R 23 )] m (NR 20 ), NR 21 [C (R 22 ) (R 23 )] m NR 20 , NR 21 [C (O) (CH 2 ) m ] NR 20 ;
    when m is greater than 1, the [C (R 22 ) (R 23 )] groups may be the same or different;
    R 20 , R 21 can be individually H, alkyl, aryl, benzyl, allyl, propazyl;
    R 22 , R 23 are individually H; halogen; OH; NH 2 ; COOR 20 ; C (O) NH 2 ; C (O) N (R 20 ) (R 21 ); C (S) NH 2 ; OC (O) N (R 20 ) (R 21 ); CN; NO 2 ; C (S) N (R 20 ) (R 21 ); Alkyl which may be optionally substituted with OH, NH 2 , halogen, CN, NO 2 , COOR 20 , C (O) NH 2 , C (S) NH 2 ; S (O) b alkyl; Alkoxy; May be S (O) c R 20 ;
    R 4 is R 26 ; S (O) d R 26 ; S (= R 27 ) (= NR 28 ) R 26 ;
    R 26 is alkyl optionally substituted with one or more halogen, which may be the same or different;
    R 5 is NH 2 , alkylamino wherein the alkyl may be substituted with NO 2 , halogen, CN, alkoxycarbonyl, OH, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or carbamoyl; Or R 5 is a radical of the formula (Ia):
    [In the above meal,
    R 4, R 12, R 13 , R 14, R 15, Z and R 33 are respectively equal to the R 4, R 12, R 13 , R 14, R 15, Z and R 33 of formula (I)] ;
    R 27 is NR 28 , O or a lone electron pair;
    R 28 is H; C 1-6 alkyl; C 1-6 haloalkyl; COR 24 ; S (O) e R 24 ; COOR 24 ; C (O) N (R 20 ) (R 21 ); C (O) SR 24 ; C (S) OR 24 ; SO 2 NR 20 R 21 ; P (O) q (R 20 ) (R 21 ); P (O) q (OR 20 ) (OR 21 ); C (= NR 20 ) NR 20 ) R 21 ; C (= NR 20 ) (OR 21 ); C (S) N (R 20 ) (R 21 ); C (O) C (O) R 20 ; C (O) C (O) OR 20 ; C (O) C (O) NR 20 R 21 ; And C (O) NR 20 SO 2 R 21 ;
    q is 0 or 1;
    R 24 is NO 2 , CN, halogen, alkoxy, amino, alkoxycarbonyl or alkyl optionally substituted with OH;
    Z is N or CR 16 ;
    R 12 , R 13 , R 14 , R 15 and R 16 are individually H; halogen; SF 5 ; CN; NO 2 ; R 25 ; S (O) f R 25 ; OH; OR 25 ; N (R 36 ) (R 37 ); CON (R 25 ) (R 37 ); Can be N 3 (azido);
    R 36 and R 37 can be individually H, alkyl;
    R 25 may be alkyl optionally substituted with one or more halogen, which may be the same or different;
    R 33 is C 1 to C 3 alkyl optionally substituted with one or more halogen, NO 2 , alkoxy, CN, COOH, COO-alkyl, C (O) NH 2 ;
    n, a, b, c, d, e and f are independently selected from 0, 1 or 2;
    m is an integer from 1 to 5;
    Stereoisomers of formula (I), such as diastereomers and optical isomers, are also included in the present invention.
    As used herein, without limitation, the term 'alkyl' generally refers to straight or branched chain alkyl having 1 to 6 carbon atoms. 'Aryl' is selected from the group consisting of C 6-10 aryl, for example halogen, C 1-6 alkyl, C 1-6 alkoxy, CN, NO 2 , C 1-6 haloalkyl and C 1-6 haloalkoxy It means phenyl or naphthyl which may have one or more substituents.
    Preferred compounds of formula (I) are those in which R 13 and R 15 are H or halogen; R 12 is halogen; R 16 is hydrogen or halogen; And / or R 14 is halogen; SF 5 ; R 25 ; S (O) n R 25 ; Or OR 25 . R 12 is chlorine; R 13 and R 15 are H; Particular preference is given to compounds in which R 14 is CF 3 and Z is C-Cl.
    Also preferred are compounds of formula (I), wherein R 4 is S (O) n R 26 and Z is CR 16 .
    m is preferably 2, 3 or 4, more preferably 2 or 3, most preferably 2.
    Other preferred compounds of formula (I) are those in which R 26 is CH 3 or CH 2 CH 3 ; Z is CR 16 ; R 13 and R 15 are H; R 12 is halogen; R 16 is H or halogen; R 14 is CF 3 , OCF 3 , SF 5 ; And / or a compound wherein R 33 is CH 3 .
    Most preferred compounds of formula (I) are those wherein R 31 and R 32 are each independently OCH 3 ; OC 2 H 5 ; SCH 3 ; May be SC 2 H 5 ; And R 31 and R 32 are linked to OCH 2 CH 2 O; O (CH 2 ) 3 O; S (CH 2 ) 2 S; S (O) (CH 2 ) 2 S; S (O) (CH 2 ) 2 S (O); S (O) 2 (CH 2 ) S (O); S (O) 2 (CH 2 ) 2 S (O) 2 ; S (CH 2 ) 2 O; S (O) (CH 2 ) 2 O; S (O) 2 (CH 2 ) 2 O; O (CH 2 ) [CH (CH 2 OH)] O; O (CH 2 ) [C (CH 2 OH) (CH 2 OH)] O; OCH (COOCH 3 ) CH (COOCH 3 ) O; OCH (COOC 2 H 5 ) CH (COOC 2 H 5 ) O; OCH 2 C (COOCH 3 ) (COOCH 3 ) CH 2 O; OCH 2 C (COOC 2 H 5 ) (COOC 2 H 5 ) CH 2 O; OCH 2 CH (CH 3 ) O; SCH 2 CH 2 NH; OCH 2 CH (CH 2 CH 2 OH) O; Or OCH 2 C (CH 2 OH) 2 CH 2 O; O (CH 2 ) CH (CH 2 SCH 3 ) O; O (CH 2 ) CH (CH 2 SOCH 3 ) O may be formed; In particular R 4 is S (O) n R 26 ; R 26 is CH 3 or CH 2 CH 3 ; Z is CR 16 ; R 13 and R 15 are H; R 12 is halogen; R 16 is H or halogen; R 14 is CF 3 , OCF 3 , SF 5 ; R 33 is CH 3 .
    Compounds of formula (I) preferably have one or more of the following aspects:
    R 12 is halogen;
    X is C-Cl;
    R 13 and R 15 are H;
    R 14 is CF 3 or SF 5 ;
    R 5 is NH 2 , CH 3 NH, or CH 3 CH 2 NH;
    R 4 is CH 3 S (O), CH 3 S (O) 2 or CH 3 S;
    R 31 and R 32 are OMe or are linked OCH 2 CH 2 O; OCH 2 CH (CH 3 ) O; S (CH 2 ) 2 S; S (O) (CH 2 ) 2 S; S (O) (CH 2 ) 2 S (O); S (O) 2 (CH 2 ) 2 S (O) 2 ; O (CH 2 ) [CH (CH 2 OH)] O; SCH 2 CH 2 NH; O (CH 2 ) CH (CH 2 SCH 3 ) O; O (CH 2 ) CH (CH 2 SOCH 3 ) is formed.
    The compound of formula (I) comprises a compound of formula (III) having at least one reactive functional group selected from the group consisting of alcohols, thiols, primary amines and secondary amines; In other words,
    Alcohols of the formula R 20 OH;
    Thiols of formula R 20 SH;
    Amines of the formula HN (R 20 ) (R 21 );
    Or HO [C (R 22 ) (R 23 )] m OH, HS [C (R 22 ) (R 23 )] m SH, HO [C (R 22 ) (R 23 )] m SH, HO [C (R 22 ) (R 23 )] m N (R 20 ) H, HS [C (R 22 ) (R 23 )] m N (R 20 ) H, or NHR 20 [C (R 22 ) (R 23 ) m mHHR 21 wherein R 22 and R 23 may be the same or different and R 20 and R 21 may be the same or different.
    [Wherein R 4 , R 5 , R 12 , R 13 , R 14 , R 15 , Z and R 33 are as defined above and R 34 is oxygen or sulfur].
    The reaction of the compound of formula (II) with the compound of formula (III) is characterized by the reaction of the compound of formula (II) with the compound of formula (III) in a liquid medium at Achievement is by direct reaction in the temperature range of from about 150 deg. It is desirable to remove the water. The liquid medium may be a reactant or a solvent. Solvents usable for the reaction include alcohols such as methanol, ethanol, isopropanol; Ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane; Nitriles such as acetonitrile; Aromatic solvents such as toluene, benzene, chlorobenzene; Haloalkanes such as chloroform, methylene chloride; Amides such as dimethylamide; Ketones such as acetone, methylisobutylketone; Esters such as ethyl acetate. The amount of reactant is generally about 50 to about 200% of the amount required for the reaction (except when the reactant is used as a solvent, the amount of reactant is much higher). The reaction can be carried out in the presence or absence of an acid catalyst. Acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid; Organic acids such as acetic acid, formic acid, p-toluenesulfonic acid; Lewis acids such as iron (II) chloride, ammonium chloride, boron trifluoride, aluminum chloride, zinc iodide, zinc chloride; Acidic ion exchange resins; Clay, such as montmorillonite.
    In the above process, when R 5 is -NH 2 and R 34 is oxygen in the starting material of formula (II), in addition to preparing a compound of formula (I) wherein R 5 is -NH 2 , Due to the reaction of the starting materials with other molecules, compounds of formula (I) can be prepared in which R 5 is a radical of the formula (Ia). Both products are active as pesticides.
    The sulfoxide and sulfone compounds of formula (I), ie compounds in which n, a, b, c, d, e or f are 1 or 2, are also not limited to peroxides such as hydrogen peroxide, t-butylperox Seed; Peracids such as metachloroperbenzoic acid; Acyl nitrates such as acetyl nitrate and other non-peroxide reagents such as sodium periodate, sodium perborate, magnesium oxide, potassium permanganate, N-bromosuccinimide, preferably hydrogen peroxide and sodium periodate It can be prepared by oxidizing the corresponding sulfide with an appropriate oxidant.
    In some cases, such as oxyketal sulfide where mild conditions are required, sodium periodate is the preferred sulfoxylating agent.
    The invention is illustrated by the following non-limiting examples.
    Example 1
    Preparation of 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3-[(1,1-dimethoxy) ethyl] -4-methylthio-1H-pyrazole
    3-acetyl-5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-1H-pyrazole 2.0 g (0.0052 mole), trimethyl orthoformate 1.7 ml (0.0156 mole), a mixture of para-toluenesulfonic acid monohydrate 0.060 g (0.0003 mole) and 10 ml of methanol are heated at 40 ° C. for about 8 hours and left at 20 ° C. for 64 hours. The mixture is mixed with saturated NaHCO 3 solution, extracted with dichloromethane, then dried, filtered, distilled and chromatographed with silica gel. 0.59 g of the title compound is obtained at a melting point of about 149 ° C.
    Example 2
    5-amino-1-[(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,3-dioxolan-2-yl) -4-methylthio- Preparation of 1H-pyrazole
    10.0 g (26.03 mmol) of [2,6-dichloro-4- (trifluoromethyl) phenyl] -3-acetyl-4-methylthio-1H-pyrazole, 1.94 g (31.23 mmol) of 1,2-ethanediol , a mixture of 0.49 g (2.6 mmol) of p-toluenesulfonic acid and 500 ml of benzene is heated and refluxed for 10 hours while removing water. The mixture is mixed with an aqueous sodium bicarbonate solution. The organic layer is washed with saturated aqueous potassium chloride solution, then dried, evaporated and chromatographed. 2.33 g of the title compound are obtained (melting point about 143 ° C.).
    Example 3
    5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,3-dioxolan-2-yl) -4-methylsulfinyl- Preparation of 1H-pyrazole
    At 0 ° C., 500 mg of compound 2 is added to a solution of 244 microliters 0.5 M sodium periodate in 2.5 ml of methanol. The mixture is stirred at 0 ° C. for 20 minutes and left at 20 ° C. for 10 hours. The mixture is successively extracted with methylene chloride and water, separated, dried and evaporated to afford the title compound. The result of mass spectrometry was M + H = 444 (molecular weight = 443).
    Example 4
    5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,3-dithioran-2-yl) -4-methylthio-1H- Preparation of Pyrazole
    5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3-acetyl-4-methylthio-1H-pyrazole 1 g (2.60 mmol), 1,2-ethanedithi A mixture of 0.26 ml (3.10 mmol), 0.084 g (0.5 mmol) iron (III) chloride and 25 ml methylene chloride is stirred at 20 ° C. for 6 days under inert atmosphere. The mixture is evaporated and chromatographed to give 100 mg of yellow title compound. As a result of mass spectrometry, the molecular weight was 460.
    Example 5
    5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methylthiazolidin-2-yl) -4-methylsulfinyl-1H-pyrazole Produce
    5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -3-acetyl-4-methylsulfinyl-1H-pyrazole 1 g (2.5 mmol), 2-aminoethanethiol A mixture of 0.284 g (2.5 mmol) of hydrochloride, 348 microliters (2.50 mmol) of triethylamine, 50 mg of p-toluenesulfonic acid and 30 ml of benzene is heated and refluxed overnight with water removal. The mixture is then cooled, filtered, evaporated and chromatographed to give 20 mg of the title compound as a white solid; Melting point 85 ° C.
    Example 6
    5-amino-1-[(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,3-oxathioran-2-yl) -4-methylsulfonyl Preparation of -1H-pyrazole
    54.34 g (0.131 mole) of 3-acetyl-5-amino-1-[(2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylsulfonyl-1H-pyrazole in 500 ml of dioxane 36.7 ml (0.522 mole) of mercaptoethanol, 71.1 g (0.522 mole) of anhydrous zinc chloride and 62.1 g (0.522 mole) of anhydrous sodium sulfide are added in this order in an ice cold bath with cooling at 0 ° C. The mixture is then warmed to room temperature and stirred for about 17 hours The mixture is filtered to remove salts, the filtrate is concentrated under reduced pressure and diluted with 40 ml of acetonitrile and filtered at 35 ° C. to recover the product. The filtrate is further diluted with acetonitrile to give a second harvested product .. Harvested harvested 5-amino-1-[(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- ( 2-methyl-1,3-oxathioran-2-yl) -4-methylsulfonyl-1H-pyrazole is 30.53 g and has a melting point of 201 ° C. From water to hereinafter as Compound 23.
    Example 7
    5-amino-1-[(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,1,3,3-tetraoxo-1,3-dithiolan- Preparation of 2-yl) -4-methylsulfonyl-1H-pyrazole
    5-amino-1-[(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1-oxo-1,3-dithiolan- in 4 ml of trifluoroacetic acid To 0.49 g (0.00096 mole) of an ice-cold solution of 2-yl) -4-methylsulfonyl-1H-pyrazole, 0.4 ml (0.004 mole) of 30% hydrogen peroxide was added dropwise and the mixture was allowed to warm to room temperature for about 17 hours. The mixture is partitioned between ethyl acetate and water, the organic phase is separated, washed with saturated aqueous sodium bicarbonate solution, then brine and dried over sodium sulfate The solution is filtered, concentrated under reduced pressure and chromatographed with silica gel. 5-amino-1-[(2,6-dichloro-4- (trifluoromethyl) phenyl] -3- (2-methyl-1,1,3,3-tetra as a cream colored powder having a melting point of 231 ° C 0.14 g of oxo-1,3-dithioran-2-yl) -4-methylsulfonyl-1H-pyrazole is obtained, which is referred to as compound 25 from below.
    Example 8
    1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-3- (4-hydroxymethyl-2-methyl-1,3-dioxolan-2-yl) -5-N-1-[[[2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-1H-pyrazol-3-yl] ethylidene] amino-1H-pyrazole Manufacture
    Condensation of 3-acetyl-5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-1H-pyrazole with glycerol using the method of Example 2 above In the synthesis of compound 6 in Table 1, 1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-3- (4-hydroxymethyl-2-methyl-1 , 3-dioxolan-2-yl) -5-N-1-[[[2,6-dichloro-4- (trifluoromethyl) phenyl] -4-methylthio-1H-pyrazole-3- The reaction mixture resulting from the separation of il] ethylidene] amino-1H-pyrazole is treated to give a byproduct of melting point 100 ° C. The said compound is called compound 9 from the following.
    The following compounds are prepared according to the methods described in Examples 1-5:
    compoundR 31 R 32 nMelting point OneOCH 3 OCH 3 0149 2OCH 3 OCH 3 One153
    compoundR 310 R 320 R 17 nMelting point 3OOH0143 4OOCH 3 0126 5OOH2194 6OOCH 2 OH071 7OOCH 2 OH2183 8OOCH 3 2202 10OOHOne68 11OOCH 3 One90 15SNHHOne85 16SSH0(M + H) + = 460 17SSH2207 18SSHOne127 19SOSH0179.5 20SOSHOne182 21SOSH2195 22SOSOH2175 23SOH2201 24SOH0(M + H) + = 444 25SO 2 SO 2 H2231 26OOCH 2 OHOne153 27OOCH 2 SCH 3 043 28OOCH 2 SOCH 3 068 29OOCH 2 SOCH 3 One82 30O0CH 2 SCH 3 268 31OOCH 2 SOCH 3 2110
    compoundR 5 nMelting point 34EtNH2119 35MeNH2188 36EtNH0(M + H) + = 456 37EtNHOne(M + H) + = 472 38MeNH0(M + H) + = 442 39MeNHOne(M + H) + = 458
    Compound 9
    compoundR 310 R 320 R 17 R 18 nMelting point 12OOHH0143 13OOHH2223 14OOCH 2 OHCH 2 OH085
    In addition, the present invention provides a method for inhibiting pests in a habitat, wherein the habitat is treated (eg, sprayed or administered) with an effective amount of a compound of formula (I), wherein the substituents are as defined above, or a salt that is acceptable as a pesticide thereof. It provides a method for suppressing pests (including)). Habitats include, for example, the pest itself or a place where the pest inhabits or feeds (plants, animals, fields, structures, land, forests, orchards, waterways, soil, plants or animal products, etc.). .
    In particular, the present invention provides a method of systematic inhibition of arthropods in the habitat, in particular some insects or mites that feed on the land above the plant. Inhibition of pests occurring on such leaves can be achieved by spraying the leaves directly, for example by spraying the soil or by spraying particulates on the roots or seeds of the plants, and then systematically transferring them to parts on the ground of the plants. Can be provided. Such systematic activity includes the inhibition of pests at distant parts as well as at the sparging site of the plant, for example by transferring from one side of the leaf to the other, or from the treated leaf to the untreated leaf. Examples of families of pests that can be systematically inhibited by the compounds of the present invention include cicada wood (cicada), stink bug (cicada) and coleopteran. The invention is particularly suitable for aphids and shovels.
    As is evident from the use as pesticides, the present invention provides compounds having activity as pesticides and methods of using said compounds for the inhibition of a wide variety of pests, including: arthropods, in particular insects or mites; Plant nematodes; Or parasites or protozoan pests. Thus, it is advantageous that the compound of formula (I) or a salt which is acceptable as a pesticide thereof is introduced in practical use, for example in crops or horticultural crops, forestry, veterinary medicine or dairy, or public health. From this point forward, when the term “compound of formula (I)” is used, the term always includes salts which have activity as compounds of formula (I) and their pesticides. The term "compound of formula (I)" includes salts having activity as compounds of formula (I) and pesticides thereof.
    In addition, the compounds of the present invention can also be used to inhibit soil insects such as corn rootworms, termites (especially for the protection of structures), root maggots, cockroaches, stem boraxes, wild bugs, root aphids, or slugs. Can be. The compounds may also be used to provide activity against plant pathogenic nematodes, such as root-knot nematodes, cyst nematodes, lancets, root rot nematodes, or stem or bulb nematodes. For example, for the suppression of soil pests such as corn rootworms, it is advantageous to spray or mix this compound in the soil in which the crop is planted or to be planted or in the roots of seeds or growing plants.
    In the public health arena, this compound is used in many insects, particularly in the fly or housefly, stable flies, soldier flies, horn flies, stag flies, on the backs, on the horns, back mosquitoes, aphids, or on other twins such as mosquitoes. It is particularly useful for inhibition.
    The compounds of the present invention can be used in the following uses and in the following pests, including arthropods, in particular insects or mites, nematodes, parasites or protozoan pests:
    For example, in the protection of stored products such as grains, peanuts, feed, wood or fines such as rugs and textiles, including grains or flours, the compounds of the present invention may be used as arthropods, more specifically, For example, weevil species, such as Efestia species (powdery moth), Antlerus species (Alkali worm), Tribolium species (rice thief), Cytophilus species (shell weevils) or Acarus species (mites) It is useful against attack by beetles, moths or mites containing.
    It is useful for suppression at home or industrial sites where cockroaches, ants or termites, or similar arthropod pests prevail, or for suppressing mosquito larvae in aqueducts, wells, reservoirs or other flowing or stagnant water.
    For example, it is useful for the treatment of foundations, structures or soils in the prevention of invasion of buildings by termites, such as reticulite species, heterotherm species, and Copto therms species.
    In agriculture, it is useful for adults, larvae and eggs, such as heliotis species (butterfly and moths), for example, heliotis species, such as heliotis biresins (cigarette beetle), king tobacco moth and corn chestnut moth. For example, coleophetas (beetles) such as antonomomus species, for example, Grandis (Mexicosom weevil), Leptinotarsa dessumita (Colorado potato beetle), Diabrotica species (corn root beetle) It is useful for adults and larvae of the tree. For example, Heterolopera species such as Psilla, Bemisia, Trialurodes, Apis, Missocus, Megoura, and Filoxera, Nepotetics, Stinkwood and cicada).
    For example, it is useful for twins such as the Musca species. It is useful for the locusts such as green onion worms. For example, grasshoppers such as Rocusta and Schistoserca species (grasshoppers and crickets), such as the Grilus species, and, for example, wing blades, dysentery wheels, German wheels, Rocusta migatoria migrating Useful for Arca species such as Oides and Scystocerca Gregaria. For example, it is useful for Toktogi, such as Periplaneta species and Blaterra species (wheels). For example, it is useful for termites, such as the Coptotermes species (termites).
    For example, it is useful for agriculturally important arthropods, such as Akari (mites), such as the tetranicus species and Panonicus species.
    It is useful against nematodes that attack crops or trees important in agriculture, forestry or horticulture, either directly or by spreading bacterial, viral, mycoplasma or fungal diseases of plants. For example, root-knot nematodes, such as a meloidogine species (for example, sweet potato root-gall nematode), are mentioned.
    For example, mites, for example, Ixodes species, Bifilus species, for example Bifilus microfluus, Lippipalus species, for example Lipificelus apendipulatus, Ornitodorus species (e.g. Mite, including ornitodorus mauvata) and mites (eg, damalia species); Flyfly (eg, homegrown species, Anopheles ja, Musca species, Hippoderma species); Stink wood; Dictioterra (eg, periplaneta spp., Blatella spp.); Arthropods, parasites that internally or externally parasite on vertebrates, especially warm-blooded vertebrates, such as, for example, cattle, sheep, goats, horses, pigs, poultry, dogs or cats, such as cattle In the veterinary or dairy industry for protozoa or in the maintenance of public health; For example, against infections of the gastrointestinal tract caused by members of the parasitic nematode, for example Trichostronilidae; For example, caused by Emerian species, such as Trifanosomes Cruzy, Leishaminian species, Plasmodium species, Barbesis species, Trichomonadidae species, Toxoplasma species and Taylorlia species Useful in the inhibition and treatment of protozoan diseases.
    Practical use for the inhibition of arthropods, in particular insects or mites, or nematode pests of plants, includes, for example, spraying an effective amount of a compound of the invention on a plant or on a medium in which the plant grows. For such methods, the active compounds are generally applied to the habitat where the arthropod or nematode infection is inhibited at an effective rate within the range of about 5 g to about 1 kg of active compound per hectare of the treated habitat. Under ideal conditions, depending on the pest being suppressed, lower rates may provide adequate protection. On the other hand, it may be necessary to use active ingredients at higher rates due to bad weather conditions, pest resistance or other factors. The optimum ratio usually depends on several factors, such as, for example, the type of pest being suppressed, the type or growth stage of the infected plant, the heat interval or the method of spreading. More preferably, the effective ratio of active compound ranges from about 50 g / ha to about 400 g / ha.
    If the pests are soily, the active compounds in the formulated compositions are generally distributed evenly (i.e., sprayed or zoned) in the area to be treated in any convenient manner, and from about 5 g to about 1 kg ai / ha, preferably at a rate of about 50 to about 250 g ai / ha. When applied as a seedling for seedlings or as a trickle irrigation for crops, the liquid solution or suspension contains from about 0.075 to about 1000 mg ai / l, preferably from about 25 to about 200 mg ai / l. If desired, it can be applied in close proximity to the field or to the seed or plant that is generally protected from attack or the area where the crop is growing. Spraying with water over the area can wash out the active ingredient into the soil or leave it to natural action by rainfall. If desired, during or after sparging, the formulated compounds can be mechanically distributed in the soil, for example by use of enteral, stationary or braking chains. Spraying can be carried out before planting, at planting time, after planting, but before or after germination.
    The compounds of the present invention and methods of inhibiting pests thereby can be used in the protection of paddy fields, feed crops, farm crops, greenhouse crops, orchard crops or vineyard crops, in the protection of decorative crops, or in the protection of plantation trees or forest trees. Particularly beneficial, examples include: grains (such as wheat or rice), cotton, vegetables (such as pepper), crops (such as sugar beet, soybean or oilseed rape), grassland or fodder crops (corn or Orchards or citrus orchards (such as nucleus or citrus), ornamental plants, flowers or vegetables or shrubs in greenhouses or gardens or parks, or trees in forests, plantations or nurseries (both deciduous and evergreen).
    It is also useful for protecting wood (wood, felling, timber, stored timber or lumber) from attacks such as bumblebees or beetles or termites.
    It is used to protect stored products such as cereals, fruits, nuts, spices or tobacco in intact, ground or mixed in products from the attack of moths, beetles, mites or bark weeds. In addition to protecting the stored meat, fish or cereals from attack by beetles, mites or flies, they may also be stored in natural or modified forms (e.g., as rugs or fabrics) such as cuticles, hairs, fleece or feathers. Protect animal products.
    In addition, the compounds of the present invention and methods of using the same can be used in the inhibition of arthropods, parasites or protozoa which are harmful to livestock as described above, or which spread disease vectors of livestock or serve as disease vectors. It is particularly valuable for the suppression of mites, mites, teeth, fleas, horns, or flies that are vampires, annoying or maggots. The compounds of the present invention are particularly useful in the inhibition of arthropods, parasites or protozoa which are present in or live on the epidermis or on the epidermis, or which suck the animal's blood, for this purpose oral, parenteral Administration, transdermal administration or topical administration.
    The compounds of the invention may also be useful for coccidiosis, a disease caused by infection from protozoan parasites of the genus Emeria. This is a significant potential source of economic losses in livestock and birds, especially those raised or stored under intensive conditions. For example, cattle, sheep, pigs or rabbits may be affected, but such diseases are particularly important in poultry, especially chicken. Small doses of the compounds of the present invention, preferably in combination with food, are effective in preventing or greatly reducing the onset of coccidiosis. This compound is effective for both cecum and intestinal forms. In addition, the compounds of the present invention may exhibit an inhibitory effect on oocytes by reducing the number of oocytes and reducing the sporulation of the resulting oocytes. Poultry disease is usually transmitted by birds that eat in or over contaminated infectious organisms in or on contaminated garbage, debris, food, or drinking water. The disease is manifested by bleeding, accumulation of blood in the caecum, passage of blood to feces, weakness and digestive problems. The disease often kills animals, but poultry that has survived severe infections has significantly reduced its value in the market.
    Compositions described later for the application of growing crops or habitats in which the crops are growing, or as seed fractions, are generally intended for local spreading to animals or alternatively for storage, household goods, general environment May be introduced at property or region. Suitable means for spreading the compounds of the invention include the following:
    For crops growing as foliar sprays, dusts, particulates, mists or foams, or as suspensions of finely divided or encapsulated compositions as soil or root therapeutics by liquid medicine, dust, particulates, smoke or foams; On seeds of the crop by spraying as seed fraction by liquid slurry or dust;
    For example, food or suitable oral ingestible pharmaceutical preparations, edible baits, livestock salt lumps, dietary supplements, preparations for infusion, sprays, baths, saliva, showers, sprays, dust, oils, shampoos, creams Arthropods by parenteral, oral or topical spraying of compositions which, by incorporation into wax stains or livestock self-treatment systems, exhibit an immediate and / or prolonged action of the active ingredient over time for arthropods, parasites or protozoa. For animals infected with or exposed to parasites or protozoa;
    As a spray, mist, dust, smoke, wax stains, lacquer, granules or bait for the general environment or for certain places where pests, including stored products, wood, household goods, or home or industrial sites may be lurking Or in trickle feeds, wells, reservoirs or other flowing or standing water directed towards the channel;
    For livestock within the feed to suppress fly larvae that feed their feces.
    The following non-limiting examples illustrate the use of the compounds of the present invention in the inhibition of pests.
    Species tested were:
    Genus speciesCommon name Apis GospyCotton Leaf Aphid Musca Domesticahousefly Diabrotica BirgiferaWestern Corn Roots Periplaneta AmericanaForeign wheel Spordogera EritaniaSouthern Beetle Skijapis GraminumBarley Bean Aphid Ctenose-Paperides FeliceCat flea Lipispalus San GuineusBrown Tick
    Soil irrigation test (systematic activity)
    Cotton and sugarcane trees are planted in pots. One day prior to treatment, each port was infected with about 25 aphids from the mixed population. Cotton trees were infected with aphids, and sugarcane trees were infected with barley aphids. Selected compounds of formula (I) were sparged against the soil in dilutions that delivered an equivalent of 10.0 ppm soil concentration by weight. Aphid counts were obtained at 5 DAT (= 5 days after treatment). The number of aphids on the treated tree was compared to the number on the untreated control tree. This test shows systematic activity (transfer of active ingredient).
    Housefly Bait / Contact Test
    About 25 4 to 6 days old grown housefly were anesthetized and placed in cages with a sugar water solution containing a compound of the present invention. The concentration of selected compound of formula (I) in the bait solution was 50 ppm. After 24 hours, flies that showed no movement for stimulation were considered dead.
    Spraying on leaves with aphids (contact test)
    The aphid-infected cotton tree was placed on a rotating turntable and sprayed with a 100 ppm formulation of the selected compound of formula (I). The treated apis gopipi infected trees were maintained for 3 days after treatment, after which dead aphids were counted.
    The obtained result is as follows. 'X' in the table means high activity; '+' Means intermediate activity; '-' Means low activity. 'NT' means not tested.
    Compound no.Systematic activity against aphidsSystematic Activity on Barley Bean AphidActivity against housefly by contactFoliar activity against aphids OneXXX+ 2+XXX 3XXXX 4XXXX 5XXXX 6+X-- 7XX+X 8XXXX 9--X- 10XXXX 11XXXX 12XXXX 13 XXX 14- -- 15XXX- 16-XX+ 17XXX+ 18-+XX 19-+XX 20--X- 21--X- 22X+-- 23X -24XX 25- -26-+X- 27X+X- 28X-XX 29X-XX 30X -31X ++ 32XXXX 33---- 34XXXX 35XXXX 36X X+ 37X XX 38XXX39+X-"X" = high activity, "+" = medium activity, "-" = low activity
    Indeed, the compounds of the present invention form very frequently part of the composition. The present invention therefore also relates to a pesticidal composition comprising a compound of formula (I) or a salt acceptable as a pesticide thereof and a carrier acceptable as a pesticide. These compositions can be introduced to inhibit: arthropods, especially insects or mites; eelworm; Or parasite or protozoan pests. The composition can be of any kind known in the art for application to any desired pest within any site or indoor or outdoor area, or for application by internal or external administration to vertebrates. These compositions combine the active ingredient with one or more other compatible ingredients suitable for the intended use, for example, as a solid or liquid carrier or diluent, adjuvant, surfactant, and the like, agriculturally or pharmaceutically acceptable, It contains at least one compound of formula (I) as described above, or a salt that is acceptable as a pesticide thereof. These compositions, which may be prepared by any method known in the art, similarly form part of the present invention.
    In addition, these compositions may contain other types of components such as protective colloids, adhesives, thickeners, thixotropic agents, penetrants, spray oils (especially as acaricides), stabilizers, preservatives (especially preservatives), promoters and pesticide properties (especially Insecticides, acaricides, nematicides, or fungicides) or other known active ingredients with properties that control the growth of plants. More generally, the compounds introduced in the present invention can be combined with all solid or liquid additives corresponding to conventional formulation techniques.
    Compositions suitable for use in agriculture, horticulture and the like include, for example, formulations suitable for use as sprays, dusts, particulates, mists, foams, emulsions and the like.
    The effective dosage of the compounds introduced in the present invention can vary within wide ranges, in particular depending on the nature of the pests to be removed or the degree of infection of, for example, crops infected with these pests. In general, compositions according to the invention usually contain from about 0.05% to about 95% (by weight) of an acceptable salt as a compound of formula (I) or a pesticide thereof according to the invention, about one or more of one or more solid or liquid carriers 1 to about 95%, and optionally, about 0.1 to about 50% of one or more of other compatible ingredients, such as surfactants and the like.
    In the description of the present invention, the term "carrier" denotes an organic or inorganic ingredient, natural or synthetic ingredient, which is combined with an active ingredient, for example, to facilitate spraying on a seed, seed or soil. . Therefore, this carrier is generally inert and should be acceptable (eg, agriculturally acceptable, especially for plants to be treated).
    The carrier may be, for example, clay, natural or synthetic silicate, silica, resin, wax, solid fertilizer (eg ammonium salt), kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, bentonite or diatomaceous earth Ground natural minerals such as, or solids such as silica, alumina, or silicate, especially surface synthetic minerals such as aluminum silicate or magnesium silicate. As particulate solid carriers, the following are suitable: pulverized or fractionated natural stones such as calcite, marble, pumice, calculi and dolomite; Synthetic particulates of inorganic or organic flours; Fine particles of organic materials such as sawdust, coconut husk, corncob, corn husk or tobacco stem; Diatomaceous earth, tricalcium phosphate, powdered cork, or absorbent carbon black; Water-soluble polymers, resins, waxes; Or solid fertilizers. If desired, such solid compositions may contain one or more compatible humectants, dispersants, emulsifiers or colorants that may also act as diluents when solid.
    The carrier may also be a liquid, for example: water; Alcohols, especially butanol or glycols, and ethers or esters thereof, especially methylglycol acetate; Ketones, in particular acetone, cyclohexanone, methylethylketone, methylisobutylketone, or isophorone; Petroleum fractional distillates such as paraffins or aromatic hydrocarbons, in particular xylene or alkylnaphthalenes; Mineral or vegetable oils; Aliphatic chlorinated hydrocarbons, in particular trichloroethane or methylene chloride; Aromatic chlorinated hydrocarbons, in particular chlorobenzene; Water-soluble or strong polar solvents such as dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone; Liquefied gas; Or mixtures thereof.
    The surfactant may be an emulsifier, dispersant or wetting agent in ionic or nonionic form or a mixture of such surfactants. Among these are, for example, salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide with aliphatic alcohols or fatty acids or fatty acid esters or aliphatic amines, substituted phenols (especially Alkylphenols or arylphenols), salts of sulfosuccinic esters, taurine derivatives (particularly alkyltaurates), phosphate esters of alcohols or polycondensates of ethylene oxide with phenols, esters of fatty acids with polyols, or sulfates of these compounds , Sulfonate or phosphate functional derivatives. The presence of at least one surfactant is generally essential when the active ingredient and / or the inert carrier are only water soluble or water insoluble and the carrier reagent of the composition for sparging is water.
    The composition of the present invention may further contain other additives such as adhesives or colorants. Adhesives such as carboxymethylcellulose or natural or synthetic polymers in powder, particulate or lattice form, such as gum arabic, polyvinyl alcohol or polyvinyl acetate, cephalin or lecithin, or synthetic phospholipids can be used in the formulation. It is possible to use colorants such as inorganic pigments, for example: iron oxides, titanium oxides or Prussian blue; Organic dyes such as alizarin dye, azo dye or metal phthalocyanine dye; Or trace nutrients such as iron, manganese, boron, copper, cobalt, molybdenum or zinc.
    Compositions containing a compound of formula (I) or a salt which is acceptable as a pesticide thereof that can be used for the inhibition of arthropods, plant nematodes, parasites or protozoan pests may also be used as synergists (e.g., piperonyl butoxide or seser). Mex), stabilizing substances, other insecticides, acaricides, plant nematode eliminators, insect repellents or anticoccidiosis agents, fungicides (e.g. agricultural or veterinary suitable such as benomil and iprodione), bacterial exterminators, arthropods or vertebrates It may also contain animal attractants or repellents or pheromones, deodorants, flavors, dyes, or adjuvant agents such as, for example, trace elements. These may be designed to improve titer, persistence, safety, absorption at the desired site, spectrum of pests that are inhibited or to perform other useful functions in the same animal or area where the composition is treated.
    Examples of compounds that have activity as other pesticides that may be included in or used with the compositions of the present invention include: Acetate, Chlorpyriphos, Demethone-S-methyl, Disulfotone, Etoprofos, phenythrothione, phenamifos, phonofos, isazofoss, isofenfoss, malathion, monocrotophos, parathion, forate, posalon, pyrimifos-methyl, terbufoss, triazo Force, cyfluthrin, cipermethrin, deltamethrin, phenpropatrine, penvalerate, permethrin, tefluthrin, aldicarb, carbosulfane, metomil, oxamyl, pyrimikav , Bendiocarb, teflubenzuron, dicopol, endosulfan, lindane, benzoxmate, cartope, cyhexatin, tetradipon, avermectin, ivermectin, milbemicin, thiophanate, trichlor Von, dichlorbos, diaberdine or dimethria Sol.
    For their agricultural spraying, the compounds of formula (I) or salts acceptable as pesticides thereof generally take the form of compositions in various solid or liquid forms.
    Solid forms of the compositions that can be used include dispersants (having a content of up to 80% of an acceptable salt as a compound of formula (I) or a pesticide thereof), wettable powders or granules (including water dispersible granules), in particular extrusion, consolidation , Granulation carriers, or granulation starting from the powder (the content of the salt of the compound of formula (I) or a pesticide thereof in this wettable powder or granule is from about 0.5 to about 80%). For example, a solid homogeneous or heterogeneous composition containing at least one compound of formula (I) or a salt which is acceptable as a pesticide thereof, such as particulates, pellets, briquettes or capsules, may be subjected to Can be used to manage. Similar effects can be obtained using trickle or intermittent feeding of the water dispersible concentrate as described herein.
    For example, liquid compositions include aqueous or non-aqueous solutions or suspensions (such as emulsifiable concentrates, emulsions, dispersible materials, dispersions, or solutions). In addition, the liquid compositions may in particular be emulsifiable concentrates, dispersions, emulsions, dispersible materials, aerosols, wettable powders (or spray powders), dry dispersible materials or pastes, liquids or for example aqueous sprays (less and In the form of a composition adapted to form a liquid composition when sprayed as a mist or aerosol.
    For example, liquid compositions in the form of emulsifiable or soluble concentrates contain from about 5 to 80% by weight of active ingredient, whereas for emulsions or solutions ready to be sprayed, from about 0.01 to about Contains 20%. In addition to the solvent, the emulsifiable or soluble concentrate may, if desired, contain from about 2 to about 50% of suitable additives such as stabilizers, surfactants, penetrants, corrosion inhibitors, colorants or adhesives. For example, any required concentration of emulsions particularly suitable for spraying plants can be obtained from such concentrations by dilution with water. These compositions are included within the scope of compositions that can be introduced in the present invention. The emulsion can be in oil-in-water or water-in-oil form and can be concentrated in concentration.
    Liquid compositions of the present invention, in addition to normal agricultural use, are for example inhibited by arthropods (or compounds of the present invention) comprising site, outdoor or indoor storage or processing areas, containers or installations or standing or running water. And other pests), which can be used to treat substrates or sites infected or susceptible to infection.
    All such aqueous dispersions or emulsions or spray mixtures can be sprayed onto the crops at a rate of from about 100 to about 1,200 liters per hectare of spray mixture, for example by any suitable means, mainly by spraying, More or less depending on (e.g. small volume or extremely small volume). The compounds or compositions according to the invention are easily applied to vegetation with pests to be removed, in particular to roots or leaves. Another method for spraying a compound or composition according to the invention is to add chemigation, ie a formulation containing the active ingredient, to irrigation water. The irrigation may be sprinkler irrigation for leaf insecticides or surface irrigation or underground irrigation for soil or tissue insecticides.
    Concentrated suspensions that can be sprayed with a spray are prepared to produce a stable liquid product that does not settle (finely ground) and is typically from about 10 to about 75 weight% of the active ingredient, from about 0.5 to about 30% of the surfactant, about 0.1 To about 10% thixotropic agent, about 0 to about 30% suitable additives, such as antifoaming agents, corrosion inhibitors, stabilizers, penetrants, adhesives, and carriers, containing water or organic liquids with little or no active ingredient active. . Some organic solids or inorganic salts help prevent sedimentation or dissolve in the carrier as antifreeze.
    Wettable powders (or spray powders) typically contain about 10 to about 80 weight% of the active ingredient, about 20 to about 90% solid carrier, about 0 to about 5% wetting agent, about 3 to about 10% dispersant, and If desired, it is prepared to contain from about 0 to about 80% of one or more stabilizers and / or other additives such as penetrants, adhesives, anti-tackifiers, colorants and the like. To prepare the wettable powder, the active ingredient is thoroughly mixed in a suitable mixer with additional materials that can be incorporated into the porous filler in the binder. This produces a wettable powder with advantageous wettability and susceptibility. They are suspended in water to give the desired concentration, which suspension can be very advantageously introduced, especially for spraying on plant foliage.
    "Water dispersible granules (WG)" (parts that are readily dispersed in water) have a composition that is quite similar to wettable powders. They may be wetted (contact with finely divided active ingredients and inert fillers and small amounts, for example from about 1 to about 20% by weight of water, or contacted with aqueous solutions of dispersants or binders, followed by drying and screening) or dry routes (Pulverization and screening after compaction), and by atomization of the formulations described for wettable powders.
    Composition ratios and concentrations of the formulated compositions may vary depending on the method of application or the nature or use of the composition. In general, compositions for use in inhibiting arthropods, plant nematodes, parasites or protozoan pests are typically one or more of the compounds of formula (I), or acceptable salts as pesticides thereof, or the entire active ingredient (i.e. From about 0.00001 to about 95% of the compound of (I), or an acceptable salt as an insecticide thereof, and other substances toxic to arthropods or insecticides, synergists, trace elements, or stabilizers of plant nematodes, hookworms and beetles), Especially about 0.0005 to about 50 weight percent. The actual composition introduced and the rate of their spreading are chosen so as to achieve the desired effect by the farmer, livestock worker, doctor or veterinarian, outbreak practitioner or those skilled in the art.
    Solid or liquid compositions for topical use in animals, wood, storage or household products are typically from about 0.00005 to about 90%, in particular from about 0.001 to about 10% by weight of one or more of the compounds of formula (I) or pesticides thereof As an acceptable salt. For parenteral administration, including oral or transdermal administration to an animal, the solid or liquid composition generally contains from about 0.1 to about 90 weight percent of an acceptable salt as one or more of the compounds of formula (I) or as pesticides thereof. Pharmaceutically treated feeds generally contain from about 0.001 to about 3 weight percent of an acceptable salt as one or more of the compounds of formula (I) or as pesticides thereof. Concentrates or preparations for mixing with the feed generally contain from about 5 to about 90%, preferably from about 5 to about 50% by weight of an acceptable salt as one or more of the compounds of formula (I) or as pesticides thereof. Mineral salt licks for livestock generally contain from about 0.1 to about 10% by weight of one or more of the compounds of formula (I) or salts acceptable as pesticides thereof.
    Powder or liquid compositions for spraying livestock, commodities, land or outdoors contain from about 0.0001 to about 15%, in particular from about 0.005 to about 2.0% by weight, of an acceptable salt as one or more of the compounds of formula (I) or as a pesticide thereof can do. Appropriate concentrations of treated water are from about 0.0001 to about 20 ppm, in particular from about 0.001 to about 5.0 ppm, of acceptable salts as one or more of the compounds of formula (I) or as pesticides thereof, and can be used in fish farming for treatment with suitable exposure times. have. Bait for ingestion may contain from about 0.01 to about 5%, preferably from about 0.01 to about 1.0% by weight of an acceptable salt as one or more of the compounds of formula (I) or as pesticides thereof.
    When administered to a parenteral parenterally, orally or transdermally or by other means, the dosage of a compound of formula (I) or a salt which is acceptable as an insecticide thereof is determined by the species, age or health of the vertebrate and the arthropod, nematode or protozoan pest It depends on the extent and nature of the actual or possible infection. One dose of about 0.1 to about 100 mg per day, preferably about 2.0 to about 20.0 mg per 1 kg body weight of the animal, or about 0.01 to about 20.0 mg, preferably 1 kg of body weight of the animal The daily dosage of about 0.1 to 5.0 mg is generally suitable for oral or parenteral administration for continuous treatment. The slow-release formulation or device may be used to administer the animal at one time in combination with the daily dose required for several months.
    Compositions Examples 2A-2M below illustrate compositions for use in arthropods, in particular mites or insects, plant nematodes, parasites or protozoal pests, wherein the compositions are formulas (I) as described in the reference examples as active ingredients. ) Or a salt which is acceptable as a pesticide thereof. Each of the compositions described in Examples 2A-M may be diluted with a sprayable composition at a concentration appropriate for use in the rice fields.
    The chemical general names of the components used in Examples 2A to 2M are as follows:
    Trade nameChemical description Ethylan BCPNonylphenol Ethylene Oxide Condensate Soprophor BSUTristyrylphenol Ethylene Oxide Condensate Arylan CA70% w / v solution of calcium dodecylbenzenesulfonate Solvesso 150Light C 10 Aromatic Solvent Arylan SSodium dodecylbenzenesulfonate Darvan No 2Sodium lignosulfonate Celite PFSynthetic Magnesium Silicate Carrier Sopropon T36Sodium salt of polycarboxylic acid Rhodigel 23Polysaccharide Xanthan Gum Bentone 38Organic Derivatives of Magnesium Montmorillonite AerosilUltrafine Silicon Dioxide
    Example 2A
    A water soluble concentrate was prepared with the following composition:
    Active ingredient7% Ethylan BCP10% N-methylpyrrolidone83%
    To an Ethylan BCP solution dissolved in some N-methylpyrrolidone, the active ingredient is added with heating and stirring until dissolved. The resulting solution is adjusted to the volume with the remaining amount of solvent.
    Example 2B
    An emulsifiable concentrate (EC) was prepared with the following composition:
    Active ingredient25% (max) Soprophor BSU10% Arylan CA5% N-methylpyrrolidone50% Solvesso 15010%
    The first three components are dissolved in N-methylpyrrolidone and then added to Solvesso 150 to final volume.
    Example 2C
    Wettable powder (WP) was prepared from the following composition:
    Active ingredient40% Arylan s2 % Darvan No 25% Celite PF53%
    The ingredients are mixed and ground into a powder having a particle size of less than 50 microns with a hammer mill.
    Example 2D
    An aqueous-flowable formulation was prepared with the following composition:
    Active ingredient40.00% Ethylan BCP1.00% Sopropon T3600.20% Ethylene glycol5.00% Rhodigel 2300.15% water53.65%
    The components are finely mixed and ground in a bead mixer until a particle diameter of less than 3 microns is obtained.
    Example 2E
    An emulsifiable suspension concentrate was prepared with the following composition:
    Active ingredient30.0% Ethylan BCP10.0% Bentone 380.5% Solvesso 15059.5%
    The components are finely mixed and ground in the bead mill until a particle diameter of less than 3 microns is obtained.
    Example 2F
    Water dispersible granules were prepared with the following composition:
    Active ingredient30% Darvan No 215% Arylan s8 % Celite PF47%
    The components are mixed, ground in a fluid energy mill, sprayed with water (up to 10%) and atomized in a rotary granulator. The resulting particulates are dried in a fluid bed dryer to remove excess water.
    Example 2G
    Dispersants were prepared with the following composition:
    Active ingredient1 to 10% Talc Powder-Ultrafine99 to 90%
    The components are mixed finely and further ground as necessary to obtain fine powder. This powder can be applied to areas infected with arthropods, such as garbage dumps, storage or household items, or animals infected with or at risk of arthropods to inhibit arthropods by oral ingestion. Suitable methods of dispersing dispersants in arthropod habitats include blowers, shakers or livestock self-treatment devices.
    Example 2H
    Ingestible baits were prepared with the following compositions:
    Active ingredient0.1 to 1.0% Wheat powder80% molasses19.9 to 19%
    The ingredients were mixed finely and formed as required in an ingestible form. Ingestible baits can be sprayed on areas such as homes, industrial lands, for example kitchens, hospitals or shops, or outdoors, infected by arthropods such as ants, fleas, cockroaches or flies, to inhibit arthropods by oral ingestion. have.
    Example 2I
    Solution formulations were prepared with the following compositions:
    Active ingredient15% Dimethyl sulfoxide85%
    The active ingredient is dissolved in dimethyl sulfoxide as necessary with mixing or heating. This solution is used for percutaneous use as a pour-on for arthropod-infected animals, or after sterilization by filtration through a polytetrafluoroethylene membrane (pore size 0.22 micrometers) by parenteral injection. It can be applied at a spreading rate of 1.2 to 12 ml per 100 kg.
    Example 2J
    Wettable powders were prepared with the following compositions:
    Active ingredient50% Ethylan BCP5% Aerosil5% Celite PF40%
    Ethylan BCP is absorbed into Aerosil, which is then mixed with other ingredients and ground with a hammer mill to yield a wettable powder, which can be diluted with water to a concentration of 0.001 to 2% by weight of the active compound, arthropods, for example Arthropods, for example, by spraying areas of fly larvae or plant nematodes, spraying or dipping into livestock infected with arthropods, parasites and protozoa, or by oral intake of drinking water Parasites or protozoa.
    Example 2K
    If necessary, the percentage was adjusted (similar to that described in the above composition) to form a slow-release pill composition from granules containing the following ingredients:
    Active ingredient Density agent A laxative bookbinder
    Finely mixed ingredients are formed into fine particles, which are compressed to a specific gravity of 2 or more. This callback is orally administered to ruminants to provide continuous efficacy of the active compound for extended periods of time, thereby inhibiting infection of arthropods, parasites or protozoa of ruminants.
    Example 2L
    Sustainable compositions in the form of particulates, pellets, briquettes and the like can be prepared from the following compositions:
    0.5-25% active ingredient Polyvinyl Chloride 75-99.5% Dioctyl phthalate (plasticizer)
    The components are mixed and formed into a suitable shape by melt extrusion or molding. The composition is useful for inhibiting pests by slow release, for example, by addition to purified water or by preparation with a collar or ear tag, or by attachment to livestock.
    Example 2M
    Water dispersible granules were prepared with the following composition:
    Active ingredient85% (max) Polyvinylpyrrolidone5% Aterpulzite Clay6% Sodium nauryl sulfate2 % glycerin2 %
    The components are mixed with water as a 45% slurry, wet milled to a particle diameter of 4 microns, and then spray dried to remove water.
    While the present invention has been described with respect to various preferred embodiments, those skilled in the art will recognize that various modifications, substitutions, omissions, and changes may be made without departing from the scope of the present invention. Accordingly, the scope of the invention is intended to be limited only by the scope of the following claims and equivalents thereof.
    权利要求:
    Claims (10)
    [1" claim-type="Currently amended] Salts acceptable as compounds of formula (I) and pesticides thereof:
    [Formula I]
    [In the above meal,
    R 31 and R 32 can be individually OR 20 , S (O) n R 20 , or N (R 20 ) (R 21 ); Or R 31 and R 32 are also linked to O [C (R 22 ) (R 23 )] m O, S (O) n [C (R 22 ) (R 23 )] m S (O) a , O ( CH 2 ) m S (O) n , O [C (R 22 ) (R 23 )] m (NR 20 ), S (O) n [C (R 22 ) (R 23 )] m (NR 20 ), NR 21 [C (R 22 ) (R 23 )] m NR 20 , NR 21 [C (O) (CH 2 ) m ] NR 20 ;
    when m is greater than 1, the [C (R 22 ) (R 23 )] groups may be the same or different;
    R 20 , R 21 can be individually H, alkyl, aryl, benzyl, allyl or propazyl;
    R 22 , R 23 are individually H; halogen; OH; NH 2 ; COOR 20 ; C (O) NH 2 ; C (O) N (R 20 ) (R 21 ); C (S) NH 2 ; OC (O) N (R 20 ) (R 21 ); CN; NO 2 ; C (S) N (R 20 ) (R 21 ); Alkyl which may be optionally substituted with OH, NH 2 , halogen, CN, NO 2 , COOR 20 , C (O) NH 2 or C (S) NH 2 ; S (O) b alkyl; Alkoxy; May be S (O) c R 20 ;
    R 4 is R 26 ; S (O) d R 26 ; S (= R 27 ) (= NR 28 ) R 26 ;
    R 26 is alkyl optionally substituted with one or more halogen, which may be the same or different;
    R 5 is NH 2 ; Alkyl is alkylamino which may be substituted by NO 2 , halogen, CN, alkoxycarbonyl, OH, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or carbamoyl; Or R 5 is a radical of the formula (Ia):
    Formula Ia

    [In the above meal,
    R 4, R 12, R 13 , R 14, R 15, Z and R 33 are respectively equal to the R 4, R 12, R 13 , R 14, R 15, Z and R 33 of formula (I)] ;
    R 27 is NR 28 , O or a lone electron pair;
    R 28 is H; C 1-6 alkyl; C 1-6 haloalkyl; COR 24 ; S (O) e R 24 ; COOR 24 ; C (O) N (R 20 ) (R 21 ); C (O) SR 24 ; C (S) OR 24 ; SO 2 NR 20 R 21 ; P (O) q (R 20 ) (R 21 ); P (O) q (OR 20 ) (OR 21 ); C (= NR 20 ) NR 20 R 21 ; C (= NR 20 ) (OR 21 ); C (S) N (R 20 ) (R 21 ); C (O) C (O) R 20 ; C (O) C (O) OR 20 ; C (O) C (O) NR 20 R 21 ; And C (O) NR 20 SO 2 R 21 ;
    q is 0 or 1;
    R 24 is NO 2 , CN, halogen, alkoxy, amino, alkoxycarbonyl or alkyl optionally substituted with OH;
    Z is N or CR 16 ;
    R 12 , R 13 , R 14 , R 15 and R 16 are individually H; halogen; SF 5 ; CN; NO 2 ; R 25 ; S (O) f R 25 ; OH; OR 25 ; N (R 36 ) (R 37 ); CON (R 25 ) (R 37 ); Can be N 3 (azido);
    R 36 and R 37 can be individually H or alkyl;
    R 25 may be alkyl optionally substituted with one or more halogen, which may be the same or different;
    R 33 is C 1 to C 3 alkyl optionally substituted with one or more halogen, NO 2 , alkoxy, CN, COOH, COO-alkyl, C (O) NH 2 ;
    n, a, b, c, d, e and f are independently selected from 0, 1 or 2;
    m is an integer from 1 to 5;
    [2" claim-type="Currently amended] The compound of claim 1, wherein R 13 and R 15 are H or halogen; R 12 is halogen; R 16 is H or halogen; R 14 is halogen; SF 5 ; R 25 ; S (O) n R 25 ; Or OR 25 .
    [3" claim-type="Currently amended] The compound according to claim 1 or 2, wherein m is preferably 2, 3 or 4, more preferably 2 or 3 and most preferably 2.
    [4" claim-type="Currently amended] The compound of claim 1, wherein R 31 and R 32 are each independently OCH 3 ; OC 2 H 5 ; SCH 3 ; May be SC 2 H 5 ; And R 31 and R 32 are linked to OCH 2 CH 2 O; O (CH 2 ) 3 O; S (CH 2 ) 2 S; S (O) (CH 2 ) 2 S; S (O) (CH 2 ) 2 S (O); S (O) 2 (CH 2 ) 2 S (O); S (O) 2 (CH 2 ) 2 S (O) 2 ; S (CH 2 ) 2 O; S (O) (CH 2 ) 2 O; S (O) 2 (CH 2 ) 2 O; O (CH 2 ) [CH (CH 2 OH)] O; O (CH 2 ) [C (CH 2 OH) (CH 2 OH)] O; OCH (COOCH 3 ) CH (COOCH 3 ) O; OCH (COOC 2 H 5 ) CH (COOC 2 H 5 ) O; OCH 2 C (COOCH 3 ) (COOCH 3 ) CH 2 O; OCH 2 C (COOC 2 H 5 ) (COOC 2 H 5 ) CH 2 O; OCH 2 CH (CH 3 ) O; SCH 2 CH 2 NH; OCH 2 CH (CH 2 CH 2 OH) O; Or OCH 2 C (CH 2 OH) 2 CH 2 O; O (CH 2 ) CH (CH 2 SCH 3 ) O; O (CH 2 ) CH (CH 2 SOCH 3 ) O may be formed; R 4 is S (O) n R 26 ; R 26 is CH 3 or CH 2 CH 3 ; Z is CR 16 ; R 13 and R 15 are H; R 12 is halogen; R 16 is H or halogen; R 14 is CF 3 , OCF 3 , SF 5 ; R 33 is CH 3 .
    [5" claim-type="Currently amended] A pesticidal composition containing a compound of formula (I) as described in claim 1 or a salt acceptable as a pesticide thereof, and a carrier acceptable as a pesticide.
    [6" claim-type="Currently amended] The insecticidal composition according to claim 5, which contains 0.05 to 95% by weight of the compound of formula (I).
    [7" claim-type="Currently amended] A method of inhibiting pests in a habitat, comprising spraying the habitat with a compound of formula (I) as described in claim 1, or an acceptable salt as a pesticide thereof, or a composition as defined in claim 5.
    [8" claim-type="Currently amended] 8. The method of claim 7, wherein the pest is an insect.
    [9" claim-type="Currently amended] A process for preparing a compound as described in claim 1, wherein the compound of formula (II) is reacted with a compound having at least one reactive functional group selected from the group consisting of alcohols, thiols, primary amines and secondary amines. How it was made:
    [Formula II]
    [Wherein, R 4 , R 5 , R 12 , R 13 , R 14 , R 15 , Z and R 33 are as defined in claim 1 and R 34 is oxygen or sulfur].
    [10" claim-type="Currently amended] The compound of claim 9, wherein the compound of formula (III) is an alcohol of formula R 20 OH, a thiol of formula R 20 SH, an amine of formula HN (R 20 ) (R 21 ), or HO [C (R 22 ) (R) 23 )] m OH, HS [C (R 22 ) (R 23 )] m SH, HO [C (R 22 ) (R 23 )] m N (R 20 ) H, HO [C (R 22 ) (R 23 )] m SH or HS [C (R 22 ) (R 23 )] m N (R 20 ) H.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-03-10|Priority to US4013697P
    1997-03-10|Priority to US60/040,136
    1998-03-05|Application filed by 제닌 페트릭, 롱-쁠랑 아그로
    1998-03-05|Priority to PCT/EP1998/001225
    2000-12-26|Publication of KR20000076074A
    2006-07-19|Application granted
    2006-07-19|Publication of KR100602814B1
    优先权:
    申请号 | 申请日 | 专利标题
    US4013697P| true| 1997-03-10|1997-03-10|
    US60/040,136|1997-03-10|
    PCT/EP1998/001225|WO1998040359A1|1997-03-10|1998-03-05|Pesticidal 1-arylpyrazoles|
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