Hydrazine derivatives or their salts

 

(57) Abstract:

Usage: in agriculture, as they have pesticidal activity. The inventive product-hydrazine derivatives or their salts of the formula specified in the description. table 4.

The invention relates to new compounds of hydrazine or its salts, methods for their production and pesticides containing them.

It is known that the compound hydrazine having the structure formula

- - where Q1a hydrogen atom, -CN, -R', -S,-N(R)COOR' or the like, where each of R' and R", which are independent of each other, is an alkyl group, and Q2tert-bucilina group or substituted alkyl group, have insecticidal activity.

However, these prior art references do not disclose the compounds of formula (I), the data below with the Deputy As defined below, such compounds of the invention.

The invention provides compounds of hydrazine following formula (I) or their salts,

A (I) where benzofuranyl group, hyalinella group, benzothiazoline group which may be substituted by a halogen atom, a C1-C6is an alkyl group, possibly substituted by halogen atom, alkoxy group or nitro group is ilen group, dihydrobenzofuranyl group, tetrahydrobenzo - thienyl group, indayla group or hexahydroquinoline group, R is a halogen atom, a C1-C6is an alkyl group or a nitro-group, n is an integer from 1 to 3, provided that when n is 2 or 3, R may be the same or different.

Most preferred are the following compounds: N'-t-butyl-N'-3,5-dimethylbenzoyl-N-benzo/b/ thiophene-2-carbohydrazide (compound 5), N'-t-butyl-N'-3,5-dimethylbenzoyl-N-5,6-Digi - DRO-4H-cyclopent/b/ thiophene-2-carbohydrates (compound 34) and N'-t-butyl-N'-3,5-dimethylbenzoyl-N-4,5,6,7-tetrahydrobenzo-zo/b/thiophene-2 - carbohydrazide (compound 35, described below).

Among the compounds of formula (I) compounds in which W is a hydrogen atom, can be obtained, for example, by the method according to the following reaction stages: stage reactions and

< / BR>
___ A-

In the above formulas, A, R and n are the same as defined above, and X a hydrogen atom, alkoxygroup or THISTLES, where T is an alkyl group.

Stage of the reaction and is conducted usually in the presence of a solvent and base. As a solvent of a solvent inert to the reaction such as water; an aromatic hydrocarbon such as benzene or toluene; an ether such as di is ton polar solvent, such as acetonitrile, dimethylformamide or pyridine, can be mentioned. These solvents may be used separately or in combination as a mixture. Particularly preferred is a solvent mixture of water and toluene, or a solvent mixture of water and methylene chloride. As the base, a tertiary amine, such as triethylamine; alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; a carbonate of an alkali metal such as sodium carbonate or potassium carbonate, an alkoxide such as sodium methoxide or ethoxide sodium; or pyridine, can be mentioned. Especially preferred is sodium hydroxide. Pyridine as a base, which can also be used as solvent, is preferred. The reaction temperature is usually from -50 to 100aboutC, preferably from 0 to 30aboutIn the case when X in the compound of formula (III) is a halogen atom or THISTLES, or from 50 to 100aboutIn the case when X is an alkoxy group. The reaction time is usually 0.1 to 24 hours, preferably 0.5 to 3 hours

The compound of formula (II) can be obtained, for example, by the method according to the following reaction stage b: reaction stage b

(IV (II)aboutC, preferably from 0 to 50aboutIn the case when Y in the compound mentioned formula (IV) represents a halogen atom, or from 80 to 100aboutIn the case when Y alkoxygroup. The reaction time is usually 0.1 to 24 hours, preferably 0.5 to 5 hours

The compound of formula (IV) can be obtained according to the stages of the reactions C and d, using the original substance mentioned after the formula (Y), which can be obtained according to the method, opened in, for example, J. Org.Chem. vol 21, 39-44 (1956) and J. Chem.Soc. C. 1225-1227 (1968). Reaction stage with
< the, Z1is a halogen atom and Z2alkyl group.

In reaction stage with a halogenation agent can be, for example, thionyl chloride, phosphorus oxychloride or thionyl bromide. In reaction stage d base, for example, may be a tertiary amine such as triethylamine, or pyridine, and the solvent may be, for example, other than water among the solvents suitable for this reaction stage.

Examples of synthesis of compounds of the invention in which W represents a hydrogen atom.

P R I m e R 1. Synthesis of N'-t-butyl-N'-3,5-dimethylbenzoyl-N-benzo/b/thiophene-2-CT - bohydrate (compound 5)

(1) 1.0 g of benzo/b/thiophene-2-carboxylic acid is subjected to interaction with 2 ml thionyl chloride by boiling under reflux overnight, and then the excess thionyl chloride is distilled off under reduced pressure to obtain benzo/b/thiophene-2-carbonyl chloride in the form of a solid product.

2.2 g of 28% methanolic solution of sodium methoxide are added dropwise with ice cooling to a solution with 1.4 g of N-t-butylhydrazine hydrochloride, dissolved in 15 ml of methanol, and the mixture was stirred at the same temperature for 15 minutes Then it gradually add 2 ml of Viseu the Oh temperature for 1 h under stirring, and the reaction mixture was poured into water and extracted with ethyl acetate. Then the organic layer is washed with water and dried over anhydrous sodium sulfate. The solvent is then distilled off under reduced pressure, and the crude product, thus obtained, purified chromatography using a column with silica gel (eluting solution: methylene chloride/ethyl acetate 2/1) to give 1.1 g of N'-t-butyl-N-benzo/b/thiophene-2-carbohyd-razida (intermediate 5, described below), having a melting point of 147-148aboutC.

(2) 220 g of 3,5-dimethylbenzoyl chloride is added dropwise under ice cooling to a solution with 300 mg of N'-t-butyl-N-benzo/b/-thiophene-2-carbohydrazide obtained in the above stage (1), dissolved in 3 ml of pyridine. The mixture is subjected to interaction at the same temperature for 1 h under stirring. Then the reaction mixture is placed in water and extracted with ethyl acetate. Then the organic layer is washed with water and dried over anhydrous sodium sulfate. The solvent is then distilled off under reduced pressure, and the resulting crude product is purified chromatographically on a column of silica gel (eluting solution: methylene chloride/ethyl acetate 95/5) to give 400 mg of the desired product (compound 5) with to-carbohydrazide (compound 22)

(1) 10 g of 4-forventelige added dropwise at room temperature to a solution with 10.8 g of rhodanine and 20 g of sodium acetate, suspended in 100 ml of acetic acid. The resulting mixture is subjected to interaction with boiling under reflux for 2 h and then cooled to room temperature. Then this reaction mixture is then poured into about 500 ml of water and the resulting solid product is collected by filtration, washed with water and dried, obtaining a 16.4 g of 5-(4-formanilide)rhodanine.

(2) of 8.3 g of sodium hydroxide dissolved in 700 ml of water and the solution is heated to about 70aboutC. Then, 10 g of 5-(4-formanilide) rhodanine obtained in the above stage (1) is placed in the solution, and the mixture is subjected to interaction at the same temperature for 20 minutes after the reaction, the reaction solution is cooled to a temperature of at most 10aboutAnd it added dropwise 20 ml of concentrated hydrochloric acid. Thus obtained solid product is collected by filtration, washed with water and dried, obtaining of 6.1 g of 3-(4-forfinal)-2-mercaptoacetic acid.

(3) a Mixture of 12 g of iodine and 80 ml of nitrobenzene is heated to about 190aboutWith obtaining a solution. Then 1.5 g of 3-(4-ftoh the interaction for 2 min with stirring. After completion of the reaction, the reaction solution is cooled to room temperature and extracted with 100 ml of 1% aqueous solution of sodium hydroxide. The appropriate amount of acid semitecolo sodium is added to the extract, and then added dropwise concentrated hydrochloric acid, bringing the pH to 1. The precipitate was separated by filtration, washed with water and then with hexane and dried, obtaining 910 mg 6 toranzo/b/-thiophene-2-carboxylic acid.

(4) 700 mg 6 toranzo/b/thiophene-2-carboxylic acid obtained in the aforementioned stage (3), is subjected to the interaction with 2 ml thionyl chloride by boiling during the night. Then the excess thionyl chloride is distilled off under reduced pressure, obtaining 6-toranzo/b/thiophene-2-carbonyl chloride.

1.4 g of 28% methanolic solution of sodium methoxide are added dropwise with ice cooling to a solution with 900 mg of N-t-butylhydrazine hydrochloride, dissolved in 9 ml of methanol, and the mixture was stirred at the same temperature for 15 minutes and Then 2 ml of the solution mentioned 6 toranzo(b)thiophene-2-carbonyl chloride in methylene chloride gradually add there. The mixture is subjected to interaction at the same temperature for 1 h under stirring. Then the reaction mixture by Phatom sodium. The solvent is then distilled off under reduced pressure and the thus obtained crude product is purified on a chromatographic column with silica gel (eluting solution: methylene chloride/ethyl acetate 2/1) to give 720 mg of N'-t-butyl-N-6-toranzo/b/-thiophene-2-carbohydrazide (intermediate 16), having a melting point 175-176aboutC.

(5) 0.5 ml of a solution of methylene chloride containing 210 mg of 3,5-dimethylbenzoyl chloride dropwise under ice cooling are added to a solution with 300 mg of N'-t-butyl-N-6-toranzo/b/thiophene-2-carbohydrazide received on the said stage (4), dissolved in 3 ml of pyridine. The mixture is subjected to interaction at the same temperature for one hour under stirring. Then the reaction mixture is placed in water and extracted with ethyl acetate. Then the organic layer is washed with water and dried over anhydrous sodium sulfate. The solvent is then distilled off under reduced pressure and the resulting crude product is purified on a chromatographic column with silica gel (eluting solution: methylene chloride/ethyl acetate 95/5) to give 420 mg of the desired product (compound 22), having a melting point 243-244aboutC.

P R I m e R 3. Synthesis of N'-t-butyl-N'-3,5-dimethylbenzoyl-N-5,6-League is howling acid is subjected to interaction with 4 ml thionyl chloride within 3.5 h at boiling under reflux. Then the excess thionyl chloride is distilled off under reduced pressure, getting 5,6-dihydro-4H-cyclopent/b/thiophene-2-carbonyl chloride.

to 2.41 g of a 28% methanolic solution of sodium methoxide are added dropwise with ice cooling to a solution containing 1.48 g of N-t-butylhydrazine, dissolved in 17 ml of methanol. The mixture is stirred at the same temperature for 30 minutes Then a solution containing the above-mentioned 5,6-dihydro-4H-cyclopent/b/thiophene-2-carbonyl chloride dissolved in 7 ml of methylene chloride, gradually add to the mixture. The mixture is subjected to interaction at the same temperature for 1 h under stirring. Then the reaction mixture is placed in water and extracted with ethylacetate. Then the organic layer is washed with water and dried over anhydrous sodium sulfate. The solvent is then distilled off under reduced pressure, and the obtained crude product is purified column chromatography on silica gel (eluting solution: methylene chloride/ethyl acetate 3: 1), receiving 0,86 g of N'-t-butyl-N-5,6-dihydro-4H-cyclopent/b/thiophene-2-carb-hydrazide (intermediate 28) having a melting point of 163-164aboutC.

(2) a Solution containing 544 mg of 3,5-dimethylbenzoyl chloride, dissolved in 2 ml of methylene chloride, dropwise doba is the Zid, obtained in the above stage (1), dissolved in 9 ml of pyridine. The mixture is subjected to interaction at the same temperature for 1.5 hours Then the reaction mixture is placed in water and extracted with ethyl acetate. Then the organic layer is washed with water and dried over anhydrous sodium sulfate. The solvent is then distilled off under reduced pressure and the resulting crude product was then purified by the method of column chromatography with silica gel (eluting solution: methylene chloride/ethyl acetate 95/5) to give 0.88 g of the desired product (compound 34) having a melting point 231-232aboutC.

P R I m e R 4. Synthesis of N'-t-butyl-N-3,5-dimethylbenzoyl-N-4,5,6,7-tetrahydrobenzo/b/thiophene - 2-carbohydrazide (compound 35)

(1) 1.0 g of 4,5,6,7-tetrahydrobenzo/b/thiophene-2-carboxylic acid is subjected to interaction with 4 ml thionyl chloride within 3.5 h at boiling under reflux. Then the excess thionyl chloride is distilled off under reduced pressure, getting 4,5,6,7-tetrahydrobenzo(b)thiophene-2-carbonyl chloride.

2,22 g of a 28% methanolic solution of sodium methoxide are added dropwise with ice cooling to a solution containing of 1.37 g of N-t-butylhydrazine hydrochloride, dissolved in 16 ml of methanol. The mixture was stirred at the of IMT chloride, dissolved in 7 ml of methylene chloride, gradually add to the mixture. The mixture is subjected to interaction at the same temperature for 1 h under stirring. Then the reaction mixture is placed in water and extracted with ethyl acetate. Then the organic layer is washed with water and dried over anhydrous sodium sulfate. The solvent is then distilled off under reduced pressure, and the resulting crude product is purified by chromatography on a column of silica gel (eluting solution: methylene chloride/ethyl acetate 3/2), getting to 0.72 g of N'-t-butyl-N-4,5,6,7-tetrahydrobenzo/b/thiophene-2-carbohydrazide (intermediate compound 29) having a melting point 155-157aboutC.

(2) the Solution with 512 mg of 3,5-dimethylbenzoyl chloride, dissolved in 2 ml of methylene chloride, are added dropwise with ice cooling to a solution containing 700 mg of N'-t-butyl-N-4,5,6,7-tetrahydrobenzo(b)thiophene-2-carbohydrazide obtained in the above stage (1), dissolved in 8 ml of pyridine. The mixture is subjected to interaction at the same temperature for 1.5 hours Then the reaction mixture is placed in water and extracted with ethyl acetate. Then the organic layer is washed with water and dried over anhydrous sodium sulfate. Then the solvent is distilled at what ielem (eluting solution: methylene chloride/ethyl acetate 95:5), getting 0.96 g of the desired product (compound 35) having a melting point of from 243-244aboutC.

The new compounds include compounds of the above formula (II), (IV) and (Y) which are useful as intermediates to the compounds of the invention, and typical examples are given in the table. 1-3.

Below are typical examples of the compounds of formula (I) of the invention in which W is a hydrogen atom, are presented in table. 4.

Among the compounds of formula (I) compounds represented by the following formula (1-2), also exhibit high pesticidal activity

A (1-2) where A, R and n are as defined above, and a cyano group, -R', -S,-N(R)COOR' or-CH2R', where R' and R" are as defined above.

The compounds of formula (1-2) can be obtained, for example, by known methods

(I-I) + W1G____ (1-2) (1-2)

In the above formula W' is as defined above, and G, a chlorine atom or a bromine atom.

The above reaction is carried out usually in the presence of a solvent and a base at a reaction temperature of -100 to 150aboutC, preferably from -80 to 100aboutWith over a reaction time of 0.1 to 24 hours, preferably from 0.2 to 3 hours as a solvent of a solvent inert to the reaction, thiofuran; or aprotic polar solvent, such as acetonitrile, dimethylformamide, dimethylsulfoxide or triamide hexamethylphosphoric acid, can be used. These solvents may be used individually or in combination as a mixture.

The base can be selected from inorganic bases, such as sodium hydride and potassium hydride; organic lithium compounds such as n-butyl lithium, tert-butyl lithium and phenyl lithium; and organic bases such as triethylamine and pyridine.

The following describes specific examples of synthesis of compounds of the present invention, in which W, W', where W' has the values defined above.

P R I m e R 5. Synthesis of N'-t-butyl-N-cyano-N'-3,5-dimethylbenzoyl-N-5,6-dihydro-4H - cyclopent/b/thiophene-2-carbohydrazide (compound 61)

80 mg of 60% dispersion of sodium hydride in mineral oil is gradually added to a solution containing 500 mg of N'-t-butyl-N'-3,5-dimethylbenzoyl-N-5,6-dihydro-4H-cyclopent /b/thiophene-2-carbohydrazide (referred to compound 34), dissolved in a solvent mixture containing 5 ml of tetrahydrofuran and 1 ml of triamide hexamethylphosphoric acid. After adding the reaction solution was stirred at room temperature in those whom pachanee under reflux.

After completion of the reaction, the reaction solution is cooled to room temperature. The reaction product is placed in water and extracted with ethyl acetate. Then the organic layer is washed with water and dried over anhydrous sodium sulfate. The solvent is then distilled off under reduced pressure, and the resulting crude product is purified by chromatography on a column of silica gel (eluting solution: n-hexane/ethyl acetate 9:1) to give 310 mg of the desired product (compound 61) having a refractive index 1,5631 (20,6aboutC).

Following the method of the above-mentioned synthesis example, given the following compounds.

Compound 62: N'-t-butyl-N'-3,5-dimethylbenzoyl-N-ethoxalyl-5,5,-dihydro-4H - cyclopent/b/thiophene-2-carbohydrazide (refractive index: 1,5412 when 46,4aboutC).

Compound 63: N'-t-butyl-N'-3,5-dimethylbenzoyl-N[(N"-methyl-N"-n-butoxide-bonyl) aminosulfonyl] -N-5,6-dihydro-4H-cyclopent/b/thiophene-2-carbohydrazide (viscous oil).

The compounds of formula (I) of the invention exhibit excellent pesticidal activity as active ingredients for pesticides. For example, they are effective against plant parasitic mites such as bimaculated spider mite (Tetranychus urticae), s); agricultural insect pests, such as cabbage moth (Plutella xylostella), bollworm cabbage (Manustra brassicae), scoop usual (Spodoptera litura), rice moth (Chaphalocrocis medinalis), Adoxophyes sp. the Colorado potato beetle (Leptinotarsa decemlineata), the Apple moth (Laspeyresia pomonella), cotton bollworm (Heliothis zea), tobacco moth (Heliothis virescens), the weevil cotton (Anthonomus grandis), Gypsy moth (Lymantria dispar), pumpkin leaf (Aulacophora femoralis), aphids, insects, jumping on plants, insects, jumping in leaves, service, bugs, scale, thrips, insects, Bouncing on the grass, anthomyidae flies, scarabs, scoop-Upsilon (Agrotis ipsilon), a noctuid moth (Agrotis segetum), or ants; hygienic insect pests such as tropical rat mite (Ornithonyssus bacoti), cockroaches, fly room (Musca domestica), or bedroom mosquito (ulex pipiens pallens); insect pests of stored grain, such as grain moth (Sitotroga crealell), azuki bean weevil (llosobruchus chinensis), khruschak small flour (Tribolium confusum) or flour worms; household pests, such as moths clothing (Tinea pellionella), black Museum beetle (Anthrenus baridae) or subterranean termites; and other parasites of domestic animals, such as fleas, lice or fleas. In addition, they are also effective against soil in which the od such as millipedes or lice. Compounds of the invention exhibit excellent pesticidal activity against Lepidoptera pests among the aforementioned various pests. In addition, they are also effective against insect pests, such as cabbage moth and homemade mole with resistance to organophosphorus and PYRETHROID insecticides. In addition, the compounds of the invention have the system properties. Therefore, when applied to soil, it is possible to control not only harmful insects, mites, nematodes, gastropods and isopods in the soil, but also pests of foliage. Compounds of the invention have a high safety with respect to mammals, fish and beneficial insects and thus suitable for use as pesticides.

To use as ingredients for pesticides, the compounds of this invention can be formulated together with agricultural additives in various forms, such as dusty, granules, wettable powders, dispersible in water, granules, suspension concentrates, emulsifiable concentrates, aerosols or paste, such as conventional agricultural chemicals.

Such formulations about the -99,9 wt. 'clock preferably 10-99,5 wt.h. more preferably 20-99,5 wt.h. agricultural additives. When such formulations are to be used, they can be used in the form in which they are or after dilution with a suitable solvent such as water to a predetermined concentration.

As additives can be mentioned carriers, emulsifiers, suspendresume agents, dispersing agents, solvents, penetrating agents, wetting agents, thickeners, pinagsama agents, stabilizers and antifreeze agents. They can be added if necessary. Media can be divided into solid and liquid media. As solid carriers should be mentioned powders of animal and vegetable origin, such as starch, activated carbon, soybean flour, wheat flour, wood flour, fish flour, or milk powder; mineral powders such as talc, kaolin, bentonite, calcium carbonate, zeolite, diatomaceous earth, white carbon black, clay or alumina; powder sulfur; sulfur anhydrous sodium sulfate. As liquid carriers should be mentioned water; alcohols such as methyl alcohol or ethylene glycol; ketones, such as acetone, methyl ethyl ketone or N-me; aromatic hydrocarbons, such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane or benzene; halogenated hydrocarbons such as chloroform or chlorobenzene; acid amides such as dimethylformamide; esters such as ethyl acetate or glycerol ester of fatty acids; NITRILES, such as acetonitrile; serosoderjaschei compounds such as dimethyl sulfoxide; or a vegetable oil such as soybean oil or corn oil.

The following describes the prescription examples of pesticides containing the compounds of this invention as active ingredients. However, the compounds as active ingredients, types of agricultural additives, mixing ratio or types of formulations are not limited to these specific examples.

Prescription example 1 (wt.h.): Connection 5 20 Kaolin 52 Sodium lignin sulfonate 8 White black 20

The above compound is uniformly mixed, getting a wettable powder.

Prescription example 2 (wt.h.): The connection 34 5 Talc 95

The mentioned components are uniformly mixed, receiving the dust.

Prescription example 3 (wt.h.): The connection 35 20 N-methyl-2-pyrrolidone 10 Polyoxyethylenated - phenyl ether 10 Xylene 60

atorny example 4 (wt.h.): Kaolin 83 Sodium lignin sulfonate 2 Polyoxyethyleneglycol sulfate 5 Fine powder silica 10

A mixture of the above components is mixed with compound 17 in a mass ratio of 4:1, receiving a wettable powder.

Prescription example 5 (wt.h.): The connection 34 40 Atsilirovannye polyalkyl - phenol phosphatidylethanolamine 2 Silicone 0,2 Xanthographa resin 0.1 Glycol 5 Water 52,7

The mentioned components are uniformly mixed and dispersed, receiving a suspension concentrate, water-based.

Prescription example 6 (wt.h.): Connection 5 75 Sodium polycarboxylate 13,5 Anhydrous sodium sulfate 10 Dextrin 0.5 Sodium alkylsulfonate 1

The mentioned components are injected into the high-speed mixing dispenser, there is added 20% water mixture granularit and dried, obtaining granules, dispersible in water.

Prescription example 7 (wt. PM): Compound 22 5 Bentonite 37 Kaolin 57 Sodium lignin sulfonate 5

The aforementioned components add necessary for granulation amount of water, the mixture is stirred and granularit, receiving pellets.

Prescription example 8 (wt.h.): Connection 24 2,5 N-methyl-2-pyrrolidone 2,5 Soybean oil 95,0

The mentioned components are uniformly mixed and dissolved, receiving formula with ultra-low volume.

Prescription example 9 (wt.h.) the s uniformly mixed, give a concentrate capable of emulgirovanija.

Prescription example 10 (wt. PM): Compound 43 10 Corn oil 77 Polyoxyethylene - approved castor oil 12 Organic bentonite 1

The mentioned components are uniformly mixed and dispersed, receiving a suspension concentrate oil-based.

In addition, pesticides containing the compounds of the invention as active ingredients, can be used in mixture or in combination with other agricultural chemicals such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides or plant growth regulators, if necessary. In some cases, using the combination of the efficiency will increase.

For example, such as insecticides, acaricides or nematicides can be mentioned organophosphorus compounds, such as 0-(4-bromo-2-chlorophenyl) 0-ethyl S-propyl poportional, 0-(2,2 - dichlorovinyl) 0,0-dimethyl phosphate, 0-ethyl 0-/3-methyl-4-(petitio)phenyl N-isopropyl-phosphoramidate, 0,0-dimethyl 0-(4-nitro-m-tolyl) phosphorotioate, 0-ethyl 0-ethyl 0-(4-nitrophenyl) phenylphosphonium, 0,0-diethyl 0-(2-isopropyl-6-methylpyrimidin-4-yl) phosphorotioate, 0,0-dimethyl 0-(3,5,6-trichloro-2(RS)-S-terbutyl 0-ethyl 2-oxo-1,3-thiazolidin-3-Il phosphothioate; urethane compounds such as 1-naphthyl N-methylcarbamate, 2-isopropoxyphenyl N-methylcarbamate, 2-methyl-2-(methylthio)Propionaldehyde 0-methylcarbamoylmethyl, 2,3-dihydro-2-, 2-dimethylbenzofuran-7-yl-methylcarbamate, dimethyl N,N'-[THIOBIS{ (methylimino)carbonyloxy} resetanimation, S-methyl N-(methylcarbamoyl) thioacetimidate, N,N-dimethyl-2-methylcarbamoylmethyl-2-(methylthio)ndimethylacetamide, 2-(ethylthiomethyl) phenyl N-methylcarbamate, 2-dimethylamino-5,6-dimethylpyrimidin-4-yl N, N-dimethylcarbamate or 2-second-butylphenyl N-methylcarbamate; derivatives, such as S,S-2-dimethyl aminotrimethylene bis (THIOCARBAMATE) or N,N-dimethyl-1,2,3-trician-5-yl amine; organic chlorine compounds such as 2,2,2-trichloro-1-1-bis(4-chlorophenyl)ethanol or 4-chlorophenyl-2,4,5 - trichlorophenyl sulfon; ORGANOMETALLIC compounds, such as bis [Tris(2-methyl-2-phenylpropyl)tin] oxide; PYRETHROID compounds such as (RS) - a-cyano-3/phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate, 3-phenoxybenzyl (IRS)-CIS, TRANS-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, (RS)--cyano-3-phenoxybenzyl (IRS)-CIS,TRANS-3-(2,2 - dichlorovinyl)-2,2-dimethylcyclopropane - boxill, (S)--cyano-3-phenoxybenzyl (IP)-CIS-3-(2,3-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate, (RS)--cyano-3-phenoxybenzyl-chloro-3,3,3-Cryptor-1-propenyl)- 2,2-dimethylcyclopropane carboxylate or 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether (common name: etofenprox; below simply referred to as compound a-1); connection benzoyl urea, such as 1-(4-chlorophenyl)-3-(2,6-differentail)urea, 1-[3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy)Fe - Neil] -3- (2,6-differentail)urea or 1-(3,5-dichloro-2,4-differenl)-3-(2,6-differentail)urea; juvenile hormone analogues, such as isopropyl (2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienal; pyridazinone compounds such as 2-tert-butyl-5-(4-tert-butylbenzyl)-4-chloro-3(2H)-pyridazinone; pyrazol compounds such as tert-butyl-4[(1,3 - dimethyl-5-Phenoxyethanol-4-yl)methylene aminoacetyl] benzoate; nitro compounds such as 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-modename (common name: Imidacloprid; below referred to simply as Compound a-2), 1-[N-(6-chloro-3-pyridylmethyl)-N-ethylamino]-1-methylamino-2-nitroethylene (EP A; below referred to simply as compound a-3), 2-methylamino-2-[N-methyl-N-(6-chloro-3-Piri - dimethyl)-amino]-1-nitroethylene (EP A; below simply referred to as compound a-4), 1-(6-chloro-3-pyridylmethyl)amino-1-dimethylamino-2-nitroethylene (EP A; below referred to simply as compound a-5), 1-(6-chloro-3-pyridylmethyl)-2-(1-nitro-2-alkylthiomethyl)imidazolidin (EP A; below referred to simply as compound a-6), 1-(6-chloro-3-pyridylmethyl)-2-(1-NITR the SRW-2--methylallylthioquinoline)- imidazolidin (EP A; below simply referred to as compound a-8), 1-(6-chloro-3-pyridylmethyl)-3-methyl-2-nitroguanidine (EP A; below referred to simply as compound a-9), 1-(6-chloro-3-pyridylmethyl)-3,3-dimethyl-2-nitroguanidine (EP A; below referred to simply as the compound a-10), 3-(6-chloro-3-pyridylmethyl)-2-nitromethylene - thiazolidine (EP A; below referred to simply as compound a-11), 1-(6-chloro-3-pyridylmethyl)-2-(nitromethylene)-imidazolidin (EP A; referred to below simply compound A-12), 6-(6-chloro-3-pyridylmethylamine)-1,3-dimethyl-5-nitro-1,2,3,4 - tetrahydropyrimidin (EP A; below referred to simply as compound a-13) or 1-(6-chloro-3-pyridylmethyl)-5-nitro-3-methyl-6-methylamino-1,2,3,4 - tetrahydropyrimidin (EP A; below referred to simply as compound a-14); dinitro compounds; organic sulfur compounds; compounds of urea; compound of triazine; compounds of hydrazine; and other compounds such as 2-tert-Butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5 - thiadiazin-4-one (common name: buprofezin; below referred to simply as compound a-15), TRANS-(4-chlorophenyl)-N-cyclo - hexyl-4-methyl-2-oxothiazolidine - 3-carboxamide, N-methylbis-(2,4-xylylenediamine)amine, N'-(4-chloro-o-tolyl)-N, N - dimethylformamide or (4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl)propyl] (dimethyl)silane (normal Sacillus thurigiensis agent, or nuclear poligraphy virus; antibiotics, such as avermectin or milbemycin; or the like can also be used in mixture or in combination with pesticides of the present invention. Among these insecticides, acaricides and nematicides, compound a-1, a-2, a-3, a-4, A-5, A-6, a-7, a-8, A-9, A-10, A-11, A-12, A-13, A-14, a-15 and a-16 are preferred. More preferred are compounds a-1, a-2, A3, A-6, a-15 and a-16. Particularly preferably, when at least one of the compounds 5, 34 and 35 of the present invention and at least one of the compounds a-1, a-2, a-3, a-6, a-15 and a-16 are mixed, and the mixture is used so that the component contains from 50 to 5000 g/ha and the latter would contain from 10 to 5000 g/ha, this will be manifested excellent pesticidal activities against insect pests, such as rice moth (Chaphalocrocis medinalis), Adoxophyes sp. jumping insects on plants, hopping insects on the leaves.

As fungicides, may be mentioned phosphorus compounds, such as S-benzyl 0,0-aminobutiramida phosphorotioate, 0-ethyl S,S-diphenyl phosphorodithioate or aluminum ethyl hydride phosphate; chlorinated compounds such as 4,5,6,7-tetrachlorophthalic or tetrachloroisophthalonitrile; dithiocarbamate compounds such as polymerbased) manganese with zinc salt, dicing bis(dimethyldithiocarbamate)ethylenebis(dithiocarbamate) or polymer propylenebis(dithiocarbamate) zinc compounds N-halogenoalkane, such as 3A, 4,7,7-tetrahydro-N- (trichloromethylsulfuryl)phthalimide, 3A, 4,7 7a-tetrahydro-N-(1,1,2,2-tetrachloroethylene)-phthalimide or N-(trichloromethylsulfuryl) phthalimide; connection dicarboxy imide, such as 3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidin-1-carboxamid, (RS)-3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-OK-Catholicon-2-, 4-dione or N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarba-ximin; benzimidazole compounds such as methyl 1-(butylcarbamoyl)-benzimidazole-2-yl-carbamate or dimethyl 4,4'-(o-phenylene)bis-(3-tialian); connection azole, such as 1-(4-chlorphenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazole-1-yl) butanol, 1-(biphenyl-4-yloxy)-3,3-dimethyl-1-(1H-1,2,4-triazole-1-yl)butane-1-ol, 1-[N-(4-chloro-2-triptoreline)-2-propoxymethyl/imidazole, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolane-2-ylmethyl] -1H-1,2,4-triazole, 1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolane-2-ylmethyl] -1H-1,2,4-triazole or 1-[2(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole; carbinol compounds such as 2,4'-dichloro--(pyrimidine-5-yl)benzhydryl alcohol or ()-2,4'-debtor--(1H - 1,2,4-triazole-1-ylmethyl)benzhydryl alcohol; compounds benzanilide, so-methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-D-alaninate; connection pyridinoline, such as 3-chloro-N-(3-chloro-2,6-dinitro-4- , , -triptorelin)-5-trifluoromethyl-2-pyridylamine; piperazine compounds; compounds of the research; anthraquinone compounds; compounds cinoxacin; connection crotonic acid; compounds, sulfonic acids; compounds, urea and other compounds, such as aminobutiramida 1,3-ditiolan-2-aligenment, 5-methyl-1,2,4-triazole [3,4-b]benzothiazole, 1,2,5,6-tetrahydrofur - rol/3,2,1-ij/- quinoline-4-one, 6-(3,5-dichloro-4-were)-3(2H)-pyridazinone, 3 allyloxy-1,2-benzisothiazole-1,1-dioxide or 1-(4-Chlorobenzyl)- 1-cyclopentyl-3-finalisation. In addition, can also be used substances antibiotics, such as validamycin And in mixture or in combination with pesticides of the present invention.

The ratio in the mixture of compounds of the invention to another agricultural chemikalie is usually in the range from 1:100 to 100:1, preferably from 1: 50 to 50: 1. A pesticide containing the compound of the invention as the active ingredient, is used in the active concentration of an ingredient from 1 to 20,000 ppm, preferably from 1 to 2000 ppm, more preferably from 10 to 1000. The active concentration of the ingredient usually varies depending on the recipe, method, purpose, selection times is to monitor the application of the formulation, having mentioned concentration to the site of invasion, and thus, the concentration of active ingredient in water is less than said area.

The usage amount of the active ingredient per unit surface area is usually from about 1 to 50,000 g, preferably from 10 to 10000, more preferably from 50 to 5000 g per 1 hectare But in some special case, the amount of applied active ingredient may be outside the above area.

Various formulations containing the compounds of this invention or their diluted composition can be used generally accepted methods of application that are typically used, such as spraying (for example, spraying, injection jet, spray, spraying, splashing powder or grain or dispersion in water), the use of the soil (for example, mixing or irrigation) or impregnation, with the aim of obtaining poisonous food. In addition, it is possible feeding pet food containing the above active ingredient, and monitoring of invasion or growth of insect pests, particularly insect pests, with their excrement. Further, actinozoa, the composition may include up to 100% of the active ingredient.

And p s t a t e t h m s p R I m e R 1. Insecticidal test against normal Cutworm (Spodoptera litura).

Each formulation containing the active ingredient is dispersed in water, obtaining a dispersion containing the active ingredient at a concentration of 800 ppm. The cabbage leaves were immersed in the dispersion for about 10 s and then dried in air. A strip of moistened filter paper placed in a Petri dish having a diameter of 9 cm, and dried cabbage leaves placed on filter paper. Ten larvae usually Cutworm (Spodoptera litura), the second or third stages are placed on the leaves, and the Petri dish was closed and kept in a vessel at a constant temperature when the light 26aboutC. On the 5th day after placing the larvae on the leaves, considered dead insects, and mortality calculated according to the following equation.

Mortality (%) 100

As a result, the mortality was 100% for each of the compounds 1, 3, 5, 7-11, 13, 14, 17-20, 22-24, 27, 29, 30, 34, 35, 36, 37, 39-52 and 54-63, and the mortality was 90% for each of the compounds 2 and 6.

And p s t a t e t h m s p R I m m e R 2. Insecticidal test against the cabbage butterfly (Plutella xylostella).

Spanish is the second or third stages replace the cabbage butterfly (Plutella xylestella) in the second or third stages, and mortality calculated in the same way. Mortality was 100% for each of the compounds 1, 5, 7, 8, 10, 11, 14, 17, 19, 20, 22, 24, 27, 29, 30, 34, 35, 37, 39, 41, 43, 44, 47, 50, 57, 61, 62 and 63.

And p s t a t e t h m s p R I m e R 3. Insecticidal test against rice leafroller (Chaphalocrocis medinalis).

Each formulation containing the active ingredient is dispersed in water, obtaining a dispersion containing the active ingredient at a concentration of 50 ppm. The leaves of the corn immersed in the dispersion for about 10 s and then dried in air. A sheet of moistened filter paper placed in a container of ice cream, having a diameter of 8 cm, and the dried leaves are placed on filter paper. Five larvae of rice leafroller (Chaphalocrocis medinalis) in the second or third stages is placed on the sheet, and a glass of ice cream close and incubated in a chamber with constant temperature when the light 26aboutC. On day 5 after hatching of the larvae, consider the dead insects, and calculate the mortality in the same manner as in test example 1.

Mortality was 100% for each of the compounds 5, 17, 22 and 34.

And p s t a t e t h m s p R I m e R 4. Insecticidal test against Adoxophyes sp.

It is an ingredient in a concentration of 50 ppm. A small piece of artificial food (trade name: Insecta LF, manufactured by Nippon Nosan Kogyo K. K.) is immersed in the dispersion for about 60 seconds and then leave at standard room temperature for about one hour. A sheet of filter paper placed in a container of ice cream, having a diameter of 8 cm, artificial and processed foods are placed on filter paper. Ten larvae of Adoxophyes sp. in the second or third stages are placed on it, and a glass of ice cream close and kept in a vessel with constant temperature when the light 26aboutC. On the 8th or 9th day after placing the larvae count the dead insects and expect mortality in the same manner as in test example 1.

Mortality was 100% for each of the compounds 5, 34 and 35.

Hydrazine derivatives of General formula

< / BR>
where a is benzofuranyl group, hyalinella group, benzothiazoline group which may be substituted with halogen, C1- C6is an alkyl group, possibly substituted with halogen, alkoxy - or nitro-group, benzothiazolyl group, tentionally group, dihydrotestoterone group, dihydrocyclopenta group, dihydrobenzo is/BR> R is halogen, C1- C6is an alkyl group or the nitro-group;

n = 1 - 3 - integer;

provided that, when n = 2 or 3, R may be the same or different,

or their salts.

 

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