CZ294453B6 - Use of hydrazine derivatives for controlling pest - Google Patents

Abstract

In the present invention, there is disclosed the use of hydrazine derivative of the general formula I, in which Re1 represents hydrogen H or alkyl group having 1 to 6 carbon atoms; Re2 and Re3 are each hydrogen, OH, an alkyl group containing 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, an alkylcarbonyl group containing 1 to 6 carbon atoms or a phenylcarbonyl group; Re4 denotes hydrogen or an alkyl group containing 1 to 6 carbon atoms; X represents 1 to 5 substituents being selected from the group consisting of hydrogen, a halogen, an alkyl group containing 1 to 6 carbon atoms and a haloalkyl group; Y denotes 1 to 5 identical or different substituents being selected from the group consisting of a nitro group and a cyano group; Z represents a halogen, a cyano group, an alkyl group containing 1 to 6 carbon atoms, a haloalkyl group containing 1 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms, a haloalkoxy group containing 1 to 6 carbon atoms, a haloalkylthio group containing 1 to 6 carbon atoms, a haloalkylsulfinyl or haloalkylsulfonyl group containing each 1 to 6 carbon atoms; and W represents oxygen or sulfur, for controlling pest being selected from strains consisting of Isoptera, Hymenoptera, Orthoptera and Psocoptera. Further claimed is the use of he hydrazine derivative of the general formula I for protecting buildings, building materials, furniture, leather, fibers, vinyl products, electrical wires or cables from pest of the class Rhinotermitidae, Termitidae, Kalotermitidae and Termopsidae, and for the use for fighting pest of the Formicidae family.

Description

Use of hydrazine derivatives for pest control

Technical field

The present invention relates to the use of hydrazine derivatives for controlling pests.

BACKGROUND OF THE INVENTION

WO 92/11340 discloses insecticides of different formulas.

WO 92/06076 and EP 0 500 111 disclose similar compounds to the present invention but disclose their general insecticidal effects, without any indication of their specific use against the four insects of the present invention against which the use of these compounds is particularly effective.

The hydrazine derivatives of the formula I which can be used according to the invention are known from European patent applications EP-A 462 456 and EP-A 486 937. of the order LIPODOPTERA, such as, for example, field bitch, the order of HEMIPTERA, the line of COLEOPTERA, such as Sphenophorus maidis, DIPTERA, such as Sphenophorus maidis, DIPTERA, such as Dacus cucurbitae, housefly, Culex pipiens and TYLENCHIDodera, such as .

However, it is not known that the hydrazine derivatives of formula I have considerable insecticidal activity against the order of ISOPTERA, such as Coptotermes formosanus, Retgiculitermes speratus, HYMENOPTERA, ORTHOPTERA, such as Acheta assimilis Fabricius and PSOCOPTERA, and so on.

SUMMARY OF THE INVENTION

The present invention relates to the use of hydrazine derivatives of the general formula I:

where

R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

R ² and R ³ , which may be the same or different, represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 1 to 6 carbon atoms in the alkyl moiety or phenylcarbonyl a group;

R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

X represents 1 to 5 identical or different substituents selected from the group consisting of hydrogen, halogen, alkyl of 1 to 6 carbon atoms and haloalkyl of 1 to 6 carbon atoms;

Y represents 1 to 5 identical or different substituents selected from the group consisting of nitro and cyano;

Z is halogen, cyano, (C1-C6) alkyl, (C1-C6) haloalkyl, (C1-C6) alkoxy, (C1-C6) haloalkoxy, (C1-C6) haloalkylthio, haloalkylsulfinyl (C 1 -C 6) or (C 1 -C 6) haloalkylsulfonyl; and

W represents an oxygen atom or a sulfur atom, for controlling pests selected from the order of the Isoptera, Hymenoptera, Orthoptera and Psocoptera.

The invention also relates to the use of the compounds of the formula I as defined above for the protection of wooden materials against pests of the family Rhinotermitidae, Termitidae, Kalotermitidae and Termopsidae.

It is an object of the present invention to provide a method for controlling pests from the group consisting of the orders Isoptera, Hymenoptera, Orthoptera and Psocoptera.

It is also an object of the present invention to provide a method of protecting woody materials against pests of the family Rhinotermitidae, Termidae, Kolatermitidae and Termopsidae.

It has surprisingly been found that these objectives can be achieved by the application of the compounds defined above. Furthermore, the use of the compounds of formula I for controlling pests as defined above has been found.

The present invention provides a new method of controlling ants damaging wooden materials from which houses, furniture and so on are built or harmful to crops and humans. The hydrazine derivatives of the general formula I have been found to have a considerable insecticidal activity against termites and ants.

The compounds of the present invention can be used to protect wooden materials such as trees, wooden fences, sleepers and so on and buildings such as chapels, mansions, houses, farm buildings, and so on from ants such as termites, and to control ants harmful to crops and humans.

Y is as defined above for the term "halogen" means a chlorine atom, a bromine atom, an iodine atom and a fluorine atom; the term "C 1 -C 6 alkyl" means a straight or branched C 1 -C 6 alkyl group; and the term "C 1 -C 6 haloalkyl" means an C 1 -C 6 alkyl group substituted with at least one halogen atom, and may be the same or different when substituted with more than one halogen atom.

Examples of preferred hydrazine derivatives of formula I of the present invention are hydrazine derivatives of formula I wherein W is oxygen, X is trifluoromethyl,

Y is cyano, Z is trifluoromethoxy and each R ¹ , R ² , R ³ and R ⁴ is simultaneously hydrogen.

Further preferred examples are compounds of formula I wherein X is substituted at the position and Y is substituted at the 4-position of the phenyl ring.

-2GB 294453 B6

The most preferred example is the hydrazine derivative of formula I wherein R ^1, R ^2, R ³ and R ⁴ are simultaneously hydrogen, X is trifluoromethyl substituted in the 3-position of the phenyl ring, Y is cyano substituted in the 4-position of the phenyl ring, and Z is trifluormethoxy5 group.

Typical examples of hydrazine derivatives of formula (I) of the present invention are shown in Table 1, but these examples do not limit the scope of the compounds of the invention.

Table 1

bs ss I & = u

I «•« s «

N

at 0 μ 4J 199 W '»w 206 rCb r4 * * R-4 CN 00 CN KX> r4 rH 214 E-form 159 Z-form 222 206 cn 00 r ~ 4 139 | 200 3t O O O O O CA X O O O w O CA O N rH u fc 8 r4 O <n fc 8 r-4 O r- <O to fc U O m fc O O n fc O O r— <u r-C U <* »Fc o fc Q O fc Q ω X 03 / X rH u r-4 O 1 xT X Cj> X » X o 1 x * X y e · X o 1 xř N O X 1 XT <N % ÍN O X 1 XT <N O X t xr CN O X 1 XI X x x X x X X X X X X X X X X x X 03 / x x X X X X X X X X X X X »» X X 03 / X X X X X X X X X X Řk x X X X X X X X X X X X X X X X with x x X X X X X X X X X X > ó r4 <N xť m \O Γ ' 00 O\ o r-4 r-i rH CN r- ( M r < * <3 * Η

-4GB 294453 B6

Table 1 - continued

«· **. u o • 4J • 4) 212 rH O (N 206 187 E-form ¹⁴⁸ Z-form σι cn rH tn rH CN 205 I 212 191 209 205 1 176 206 216 215 206 200 191 208 CN O CN te O O O O O Cn O O O O O O O O O O O O O O O N CO fa O o cn fa O o rH O cn fa O O m Cm U O cn fa O O cn fa υ cn í *> fa υ o cn Cm O 'N O ω rH O m fa U O rH υ f0 Cm U O cn fa CJ cn r> Cu 8 cn m ÉM U N O ω rH u Cm 8 n fa 8 i — 10 O ω fa U O fa X r4 O 1 xr z o 1 'sr z Q I «a · z u 1 -a · z u 4-CN 4-CN z υ 1 <a · X X z u 1 z o 1 4-CN δ 1 z CJ 1 -a · X X 4-Cl 4-Cl ZO 1 «and ¹ fa rH U i ΓΏ rH υ 1 cn 3-Cl 3-Cl rH υ 1 CO rH CJ 1 í *> 3-Cl 3-Cl 3-Cl 3-Br 3-Br M X 1 Γ0 3-Br 3-Br 3-Br 3-Br fa t m Pm i co fa 2 m fa 1 m fa 2 m and x x 03 / X X X X X X X X X X X X X X X X X X <* » X tfl »» and X X X X X X X X X X X X X X X and X X w 93 »» X X X X X X X X X X X X X X X X X « w X 91 X X X X X X X X X X X X X X X X X X > d m rH V0 rH ΓrK co rH o rH o CN rH CN CN (N m <N CN m CN kD CN r * CN co CN σ> CN about what rH WHAT CN CO m n what lA co

-5GB 294453 B6

Table 1 - continued

C 9 • u • P 213 201 185 00 <Λ r — 4 200 189 206 210 191 <Λ rH I 132 108 what 85 1 M 10 m 1 tS) ω m rH rH 0 Ψ4 w tn σ> 66 z-form 121 105 140 CO o> SE O O O O O O O O O ω O O O O O O O O O O O <0 cn <n <n <n m cn m cn cn n cn N fc r-l Em r-i fa r — 1 fc Cm fc r <4 fc r-4 fc to r-4 fc rH fc CJ at O CJ at at CJ CJ CJ CJ CJ CJ Q »» O CJ CJ CJ CJ CJ CJ O O O O O O O O O O O O OF the the the the x «“ 4 r4 X X tM 4-C at AND O: x at and CJ I 33 X υ 1 O 1 X X X X X X X at 1 CJ t CJ 1 CJ 1 M * Φ M * · <Φ Tt * Cř m m m cn r> <n cn H H 03 / 03 / 03 / 03 / fc fc & 4 fc CJ l ro · —1 CJ 1 CO 1 co cn O 1 co 3-C 3-C U 1 co CJ 1 WHAT 3-C CJ 1 co at 1 co X X X X X X X X X £ m ttí 03 / 03 / 03 / 03 / 03 / x X X X X X pers X X X X X X X fc 03 / 03 / 03 / 03 / O: 03 / 03 / 03 / X X X X X X X X X X X X X n cn m cn m m cn tn cn fc 03 / 03 / X X 03 / 01 X 03 / 03 / X X X X X X X X X X X X CJ O at CJ CJ at O O at cn m «Í Whi 03 / x 03 / 33 01 03 / 01 03 / 01 X X o CH X X X X X X X X X • 10 Γ * 00 σ » O <N what ’Φ in what C what <Λ O ** 4 (N WHAT m it KJ cn what cn what «Φ ’Φ ’Φ nj » «Η tn tn tn tn m in

-6GB 294453 B6

Table 1 - continued

o o • +> »» 4J 188 and | 170 β N '0 Λ 4 01 • H > 0 M-t 1 M in 00 95 z-form V4 and N Ό λ; ot H > 113 | 164 ! 118 183 ! 181 155 <*> ςΚ i ~ 4 176 184 182 168 115 130 214 m · r-t CM X O O O O O O O O w O © O O © O O O O O O O N rH O r *> Pm 8 r4 O n fc-4 8 m fe, O r-4 υ -5 Pm 8 r-4 o <n Cu U O r-H O <n Pm 8 rH O m I <J O r4 O í *) Pm 8 PM u o <* ϊ Cm O O HIM CO Pm 8 m I AM U « m Pm O O a X « « O 1 r4 O 1 <—1 o 1 nr z o 1 • Ď O 1 <* and and and and X and and and and and X X of IN • M * z u 1 Ό · X X X X and and and and and and and and X and and and and and X X íxr 1 CO Pm 2 m <* « X ca X and and and and and and and and and and and and X and m X Q <n X O X X Bi and o m o »O and o and o § and o and o and u <n and O o n and u o • H 1 rx r 8 • H 1 r- 33 ro 8 • H <n a · * U o -H 1 <T> a > # 8 m X u ? O O-CO-Ph X O X o and X B · and and and and and as and and and and and and and and and X X X X and X X x the and and and and and and and and and and and and X X X X X X > u c * ΙΛ co in σ> in O 90 ^ 0 <N <© m \ © \ 0 in \ 0 M3 M5 © <© C0 X0 o r- r-4 r * <N <*> r- * ϊ »r m r * Kť> r * tr-

Table 1 - continued

at • • P • P 165 157 ï> r- <OJ 210 152 Z-form m M9 T “< WITH O O O O O O N <»» Em U S CO (*> fa 8 co m fa O cO m fa υ o CO r> fa O O r4 O X as u t ta Q 1 o · ES CJ tr ta u O" and o 1 ta u 1 M fa 1 · » r-o O I n <*> fa O 2 m ro fa U t ro <O fa o 2 m r> fa O 1 co ca ca 03 / ca 03 / 03 / & ca w 03 / S3 »» % ca ca « oa »» 03 / w 0 $ 03 / 03 / ca ca 03 / m *> o CO r * cn r- About what r4 CO CN co what

Note: Ph is a phenyl group

-8EN 294453 B6

Some of the compounds listed in Table 1 are viscous or glassy.

Their Η NMR data is shown in Table 2:

C. 'H NMR [CDCh / TMS, δ (ppm)] 59 6.29 (s, 1H), 7.65 to 7.92 (m, Í3H), 9.14 (bs, 1H), 10.70 (brs, 1H) (DMSO-d ₆₎ 62 3.88 (bs, 1H), 3.87 (s, 1H), 6.91-7.55 (m, 13H), 7.73 (s, 1H), 8.13 (bs, 1H)

The compounds of formula I have a considerable killing effect at low doses on all termites detrimental to houses, construction materials, furniture, leather, fibers, vinyl objects, electrical wires and cables. They are suitable, for example, against the following pests: RHINOTERMITIDAE, including Coptotermes formosanus Shiraki, Reticulitermes speratus (Kolbe), Reticulitermes hesperus, which lives in North America, Reticulitermes tibialis, Reticulitermes flavipes, Reticulitermes lucifugus, which sits on the shoreline of the Mediterranean, (Hagen), TERMITIDAE including Odontotermes formosanus (Shiraki), KALOTERMITIDAE including Cryptotermes domesticus (Haviland), TERMOPSIDAE including Hodotermopsis japonica (Holmgren), etc.

Further, the ant control compound of the invention exhibits a very high killing effect at low doses on all ants harmful to crops or humans when they reach homes or public areas such as parks. The compounds are particularly useful against the following pests: FORMICIDAE, including Monomoriumpharaonis Linne, Monomorium nipponense Wheelex, Camponotus kiusiuensis Santschi, Formica japonica Motschulsky, Lasius fuliginosus (Latreille), Solenopsis richteri, Solenopsis invicta, Solenopsis gem.

For use in controlling pests selected from the order of Isoptera, Hymenoptera, Orthoptera and Psocoptera according to the present invention, the hydrazine derivatives of the general formula I are formulated with a suitable solid carrier and / or liquid carrier. If appropriate, they are formulated with the ingredients in the appropriate proportions according to conventional procedures for the preparation of such compositions and homogenized with the carrier by dissolution, suspension, mixing, impregnation, adsorption or adhesion to form a suitable composition, such as an oily solution. , an emulsifiable concentrate, a dissolved concentrate, a powder, granules, a wettable powder, an aerosol, a smoke composition, a liquid composition, and the like. It is also possible to formulate the compounds of formula I into edible baits by mixing with the bait containing the attractant or the like.

Examples of solid carriers for use in the present invention include clays such as kaolin, bentonite, acid clays and the like; talc such as talc, pyrophilite and the like; silica-based substances such as diatomaceous earth, silica sand, mica, synthetic silicate, synthetic highly dispersed silica and the like; and inorganic mineral powders such as pumice, sand and the like; organic substances such as pieces of wood, wood chips, cereal flour, sugars and the like. Examples of liquid carriers include alcohols such as methanol, ethanol, ethylene glycol and the like; ketones such as acetone, methyl ethyl ketone, cyclohexanone and the like; ethers such as ethyl ether, dioxane, tetrahydrofuran, Cellosolve and the like; aliphatic hydrocarbons such as light oil, kerosene and the like; aromatic hydrocarbons such as benzene, toluene, xylene, naphtha, cyclohexanone, methylnaphthalene and the like; and halogenated hydrocarbons such as chloroform, carbon tetrachloride, chlorobenzene and the like. These solid and liquid carriers can be used either alone or in the form of mixtures.

Among the additives that can be used according to the present invention are surfactants, dispersants, tackifiers and so on. Examples of surfactants include polyoxyethylene alkyl aryl ethers, polyoxyethylene sorbitan monolaurates, alkylarylsorbitan monolaurates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, lignin sulfonates, higher alcohol ester salts and sulfuric acid, and so on. These surfactants can be used either alone or as a mixture.

-9EN 294453 B6

As dispersing and tackifying agents, for example, casein, gelatin, starch, alginic acid, carboxymethylcellulose, agar, polyvinyl alcohol, turpentine oil and so on can be used as appropriate.

The compounds of the formula I according to the present invention are not applied only by application to the ground surface in order to protect wooden materials such as trees, wooden fences, sleepers and so on and buildings such as chapels, churches, houses, farm buildings, factories and so on. or on the floor, but can also be applied to wooden items such as concrete floor surfaces, supports, beams, furniture and so on, wooden items such as planks and so on and vinyl items such as insulated electric wires, pieces of vinyl, heat insulating materials such as styrene foams and so on. When used against ants harmful to crops and humans, the ant control agent of the invention is applied to the crops or surrounding soil or directly to the anthill or the like.

The present invention is not limited to the embodiments mentioned above, but also includes an embodiment wherein the ant control means of the invention is applied preventively to the sites where ants are expected to occur.

When administering the compounds of formula (I) of the present invention, the dosage may be suitably selected according to the desired use. When applied to wood materials, the amount of active ingredient is in the range of 0.1 to 50 g per m ² ; and in the case of soil treatment or anthill application, the amount of active ingredient is in the range of 1 to 500 g per m.

DETAILED DESCRIPTION OF THE INVENTION

The following are typical examples of compositions and test compositions of the invention. The invention is not limited to these examples.

In the examples, the term "part" means a part by weight.

Formulation Example 1

Any hydrazine derivative listed in Table 1 Xylene Parts Parts

The above ingredients are homogeneously dissolved to give an oily solution.

Formulation Example 2

Any hydrazine derivative listed in Table 1 Polyoxyethylenstyrylphenyl ether Cyclohexanone parts parts parts

The ingredients listed above are mixed homogeneously and dissolved to give an emulsifiable concentrate.

-10GB 294453 B6

Formulation example 3

Any hydrazine derivative listed in Table 1 Sodium alkylbenzenesulfonate White carbon black

Clay Parts Parts Parts Parts

The ingredients listed above are mixed homogeneously and milled to obtain a wettable powder.

Formulation Example 4

Any hydrazine derivative listed in Table 1 8 parts Cyclohexanone 4 parts Mixture of polyoxyethylene nonyl ether and alkylbenzenesulfonic acids 3 parts

The granular composition is prepared by homogeneously mixing and dissolving the ingredients mentioned above and spraying the resulting solution onto 85 parts by weight of granular pumice stone followed by drying.

Testing example 1

A filter paper is placed in a 9 cm diameter glass dish and dripped with 1 ml of a 500ppm solution of the compounds of Formula I. Then the filter paper is placed with Coptotermes formosanus Shiraki.

Seven days after the inoculation, the percent insect mortality was calculated from which the mortality was calculated. The results were evaluated according to the following criteria. The test was performed in triplicate with ten pests per group.

Criterion Mortality (%) AND 100 ALIGN! (B) 99-90 C 89-80 D 79-50

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The results are shown in Table 3:

Merge. C. Effect on killing termites Merge. C. / ........ '—...... Effect on weight loss termites 1 AND 5 AND 2 (B) 6 AND 3 AND 7 AND 4 AND 8 C 9 (B) 32 AND 10 AND 33 C 11 AND 34 AND 12 AND 35 AND 13 AND 36 (B) 14 AND 37 AND 15 Dec (B) 38 (B) 16 C 39 AND 17 AND 40 D 18 AND 41 AND 19 Dec AND 42 AND 20 May AND 43 AND 21 AND 44 C 2 (B) 45 AND 23 AND 46 AND 24 C 47 AND 25 D 48 AND 26 AND 49 C 27 Mar: AND 50 AND 28 C 51 AND 29 C 52 AND 30 AND 53 (B) 31 AND 54 AND 55 AND 73 AND 56 AND 74 AND 57 D 75 AND 58 AND 76 AND 59 C 77 AND 60 C 78 AND 61 AND 79 (B) 62 AND 80 AND 63 AND 81 AND 64 AND 82 (B) 65 C 83 D 66 AND 67 AND 68 AND 69 (B) 70 AND 71 AND 72 AND

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Testing example 2

The compounds of the formula I are applied to the anthill of the ant Solenopsis geminata by pouring 1 g of active substance on the anthill. 14 days after treatment, activity in the anthill is evaluated according to the following criteria. The test was performed with one block on the anthill.

Criterion Effect AND The anthill is completely destroyed or the activity in the anthill is extremely low (B) The anthill is active C The anthill is very active D Activity in the anthill is extremely high

Compound No. 44 of the present invention has an "A" effect in this assay.

Claims (8)

PATENT CLAIMS Use of a hydrazine derivative of the general formula I: (I), wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ² and R ³ , which may be the same or different, represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 1 to 6 carbon atoms in the alkyl moiety or phenylcarbonyl a group; R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; X represents 1 to 5 identical or different substituents selected from the group consisting of hydrogen, halogen, alkyl of 1 to 6 carbon atoms and haloalkyl of 1 to 6 carbon atoms; Y represents 1 to 5 identical or different substituents selected from the group consisting of nitro and cyano; Z represents a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms 6 carbon atoms or a haloalkylsulfonyl group containing 1 to 6 carbon atoms; and -13GB 294453 B6 W represents an oxygen atom or a sulfur atom for controlling pests selected from the order of the Isoptera, Hymenoptera, Orthoptera and Psocoptera. Use of a hydrazine derivative of the general formula I according to claim 1 in which R ^1, R ^2, R ³ and R ⁴ are hydrogen atoms; X is trifluoromethyl; Y is cyano; Z is trifluoromethoxy; and W represents an oxygen atom. Use according to claim 1 or 2, wherein the pests are ants or termites. Use of a hydrazine derivative of the general formula I as defined in claim 1 or 2 for the protection of houses, building materials, furniture, leather, fibers, vinyl products, electric wires or cables from Rhinotermitidae, Termitidae, Kalotermitidae and Termopsidae pests. Use of a hydrazine derivative of the formula I as defined in claim 1 or 2 for controlling pests of the family Formicidae. Use according to claim 5, wherein the hydrazine derivative is applied to the plants, to the surrounding soil or to a pest deposit. A method for controlling pests of the Rhinotermitidae, Termitidae, Kalotermitidae and Termopsidae families, characterized in that 0.1 to 50g / m ^{2 of} a hydrazine derivative of the formula I as defined in claim 1 or 2 is applied to the wood material. A method for controlling pests of the family Formicidae, characterized in that 1 to 500 g / m ^{2 of} a hydrazine derivative of the formula I as defined in claim 1 or 2 is applied to the soil surrounding the plants or to the pest.