HU184684B - Acaricide compositions and process for producing substituted tetrazine derivatives utilizable as active agents too - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to acaricidal compositions and the preparation of their active ingredient. The acaricidal composition of the present invention comprises as active ingredient one or more substituted tetrazine derivatives of formula (I) or a tautomer thereof, wherein R 1 is hydrogen or C 1-4 alkyl, R 2 is hydrogen or C 1-4 alkyl, or R 1 and R R2 is a single bond, R3 is a C4-C6 tertiary alkyl group, or a phenyl group optionally substituted with a halogen atom or a C1-4 alkyl group, R6 is a phenyl group substituted at the 2-position with a halogen atom, liquid or solid carriers, preferably kaolin, xylene or water; and surfactants, preferably lignin sulfonates, sulfonated naphthalene formaldehyde condensates salts, sulfonated phenol-formaldehyde condensates, or nonylphenol / ethylene oxide condensate; with at least one. The active ingredient is prepared by reacting a substituted azine of formula (III) with a hydrazine of formula (IV) or oxidizing a compound of formula (I) wherein R1 and R2 are hydrogen or alkyl. r3-c = n-n = c-r6 R NH-NHR * cm) (iv)

Description

(57) EXTRAS

The present invention relates to acaricidal compositions and to their preparation.

The acaricidal composition according to the invention comprises as active ingredient one or more substituted tetrazine derivatives of the formula (I) or a tautomer thereof, wherein:

R ¹ is hydrogen or C 1-4 alkyl,

R ² is hydrogen or C 1-4 alkyl, or

R ¹ and R ² together represent a single bond,

R ³ is C 4 -C 6 tertiary alkyl or phenyl optionally substituted with halo or C 1 -C 4 alkyl,

R ⁶ is phenyl substituted at the 2-position by a halogen atom, liquid or solid carriers, preferably kaolin, xylene or water; and surfactants, preferably lignin sulfonates, salts of sulfonated naphthalene-formaldehyde condensates, salts of sulfonated phenol-formaldehyde condensates, or nonylphenol / ethylene oxide condensate; with at least one of them.

The active ingredient is prepared by reacting a substituted azine of formula (III) with a hydrazine of formula (IV) or oxidizing a compound of formula (I) wherein R ¹ and R ^{2 are} hydrogen or alkyl.

r ³ -c = nn = cr ⁶ cm)

R NH-NHR * (arc)

184,684

The present invention relates to a process for the preparation of a substituted tetrazine derivative which can be used as an active ingredient in an acaricidal composition.

The agents of the invention are effective against mites, their eggs and larvae.

The active compounds of the present invention may be substituted tetrazine derivatives of formula (I) and tautomers thereof. In the formula (I), R * is hydrogen or C 1-4 alkyl,

R ² is hydrogen or C 1-4 alkyl,

R * and R ² together represent a single bond,

R ³ is C 4 -C 6 tertiary alkyl, C 3 -C 7 cycloalkyl, or phenyl optionally substituted with halo or C 1 -C 4 alkyl

R ⁶ is phenyl substituted at the 2-position by a halogen atom.

Preferred compounds are those compounds of formula I wherein R ^{6 represents} a 2-fluorophenyl group when R ¹ R ^{2 represents a} single bond and R ³ represents a non-2-fluorophenyl group and when R ¹ and R ² each represent a hydrogen atom.

Many compounds of Formula I also exist in tautomeric forms of Formula II. Compositions containing tautomeric compounds as active ingredients are preferably acaricidal agents.

In the general formula (II)

R ³ , R ⁶ and R ¹ are as defined for the compound of formula (I), and

R ⁴ has the same meaning as R ² .

Some of the compounds of the present invention are exemplified. Particularly mentioned are the most preferred active ingredients a

3.6-bis (2-chlorophenyl) -1,2-dihydro-1-methyl-1,2,4,5-tetrazine,

3.6-bis (2-chlorophenyl) -1,2,4,5-tetrazine;

3- (2-bromophenyl) -6- (2-chlorophenyl) -1,2,4,5-tetrazine compounds.

Compounds of formula (I) wherein R ¹ and R ² have different meanings from each bond are prepared by substituting a substituted azine of formula (III) wherein R ³ and R ⁶ are as defined above and X is each a cleavable group. , with a hydrazine of formula IV wherein R ¹ and R ² are as defined above but do not form a bond to give the desired compounds.

The reaction is conveniently carried out at elevated temperatures, such as 30 to 100 ° C, especially 50 to 80 ° C, in a suitable solvent such as an alkanol such as ethanol, ether such as tetrahydrofuran or a hydrocarbon such as toluene.

Preferably X represents a halogen atom, preferably a chlorine or bromine atom, a cyano group or a C 1-4 alkoxy group, in particular a methoxy group.

The substituted azines of formula (ban) used as starting materials in the process of the invention are prepared by reacting a compound of formula (V) wherein R ³ and R ⁶ are as defined above and A is -CONH-HNCO-CONH-N = CH. -, -CH = NN = = CH-, is halogenated to give a compound of formula (III) wherein X is halogen 2 and the product is optionally reacted with an anion-forming compound to give a corresponding compound wherein X is not halogen, but also other alkoxy groups, e.g.

The halogenating agent is preferably a halogen atom such as chlorine, phosphorus pentahalide, especially phosphorus pentachloride or phosphorus pentabromide, or thionyl halide such as thionyl chloride, and preferably a suitable organic solvent such as acetic acid, a hydrocarbon or a halogenated hydrocarbon such as benzene is used as the reaction medium. The reaction is conveniently carried out at elevated temperatures, such as 70-150 ° C, preferably 90-110 ° C.

Compounds of formula (V) wherein A represents a CONH-NHCO- group may be prepared by reacting a hydrazide of formula R ³ CONHNH _{2 with} a compound of formula R ⁶ COY wherein R ³ and R ⁶ are as defined above and Y represents a halogen atom, preferably a chlorine or bromine atom, a hydroxy group, a C 1-6 alkoxy group or a R 1 COO group to give the desired compound.

Compounds of formula (V) wherein A represents CONH-NHCO- and R ³ has the same meaning as R ⁶ are prepared by reacting a halide of formula R'COHal wherein Hal represents a halogen atom, preferably a chlorine or bromine atom, is reacted directly with hydrazine.

Compounds of formula (V) wherein A is -CH = NN = CH- and R ³ and R ⁶ are identical may be prepared by reacting an aldehyde of formula R'CHO wherein R ³ is as defined above reaction with hydrazine in a suitable solvent to give the desired compound.

Compounds of formula (V) wherein A is -CNH-N = CH- or CH = N-NHCO- can be prepared by hydrazide of R ³ CONHNH 2 or R ⁶ CONHNH 2 with R ⁶ CHO or The reaction is conducted with an aldehyde of the formula R ³ CHO.

The hydrazides R ³ CONHNH ₂ used as starting materials can be prepared by conventional methods.

(I) compounds wherein represents a single bond, R 'and R ² together may be the corresponding compound (I) of the formula is prepared by reacting the compounds with an oxidizing agent.

The preferred oxidizing agent is an alkali metal nitrite, such as sodium nitrite, used in the presence of an acid, and the reaction is carried out, if desired, in a suitable solvent which is inert under the reaction conditions used, such as glacial acetic acid. Other oxidizing agents may also be used, such as nitric acid, hydrogen peroxide, bromine or isoamyl nitrile. The oxidizing agents are used in a suitable solvent such as acetic acid in an alkanol such as ethanol or an optionally halogenated hydrocarbon such as ethanol or an optionally halogenated hydrocarbon such as ethanol or an optionally halogenated hydrocarbon such as carbon tetrachloride or chloroform.

The reaction may conveniently be carried out at 5 to 30 ° C, preferably at 10 to 20 ° C.

184,684

Compounds of formula II are prepared by reacting a thiadiazolium salt of formula VI wherein R ¹ , R ³ and R ⁶ are as defined above and Χθ represents an anion with a hydrazine of formula R ⁴ NHNH ₂ , wherein R ⁴ is as defined above to give the desired compound.

The reaction may be carried out, if desired, in the presence of a solvent such as an alkanol such as ethanol, preferably at a temperature between 20 ° C and a reflux temperature, for example 100 ° C.

X ° may represent any suitable anion, but is preferably halogen, especially chlorine, sulfate or ptoluenesulfonate.

The thiadiazolium salts of formula (VI) are prepared by reacting a corresponding thiadiazole of formula (VII), wherein R ³ and R ⁶ are as defined above, with a compound of formula R'X.

The thiadiazoles of formula (VII) may be prepared by reacting a compound of formula (V) wherein A is a -CONH-NHCO- group with phosphorus pentasulfide or a compound of formula (dal) with a sulfide, preferably diphosphorus pentasulfide, or a hydrosulfide. reaction to give the desired compound.

Compounds of formula (II) wherein R ³ and R ⁶ are the same, R ¹ and R ^{4 are} also the same are prepared by reacting a compound of formula (VIII) wherein R ⁴ and R ⁶ are as defined above, oxidizing with the oxidizing agent to the desired compound.

Conveniently, the oxidizing agent is a halogen atom such as iodine or an alkali metal hypochlorite or ferricyanide, preferably sodium hypochlorite or ferricyanide, and is conveniently carried out in a suitable solvent such as pyridine at a temperature of 60 ° C to 120 ° C.

Alternatively, compounds of formula II wherein R ³ and R ⁶ are the same, R ¹ and R ⁴ are the same, may alternatively be prepared by reacting a compound of formula IX wherein R ⁴ and R ⁶ are alkylating with the above alkylating agent in the presence of an alkali metal base such as sodium hydroxide or sodium carbonate.

The alkylating agent is preferably a haloacetic acid such as iodoacetic acid or a dialkyl sulfate such as dimethyl sulfate and the reaction is preferably carried out in a suitable solvent such as an alkanol such as ethanol. The temperature employed is preferably 5 to 80 ° C.

Compounds of formula II wherein R ¹ and R ^{4 are} other than hydrogen, R ³ and R ⁶ are the same, R ¹ and R ^{4 are} also the same can be prepared by reacting a compound of formula X wherein R ⁴ and R ⁶ are dimerized in a suitable solvent in the presence of a base to give the desired compound.

The reaction is preferably carried out in a suitable solvent, namely a polar proton-free solvent such as acetonitrile or dimethylformamide, and at elevated temperatures, for example from 50 ° C to reflux (for example 120 ° C).

Preferably, the fish represents a chlorine atom.

The base is preferably a tertiary amine such as triethylamine and the solvent is preferably a polar solvent such as acetonitrile.

The active compounds containing tetrazines of the formula I are particularly active against the eggs and larvae of mites, especially the eggs of the red spider mite (Tetranychus cinnabarinus), but other mite species such as Tetranychus urticae, Panonychus ulmi, Phyllocoptrata oleivora, and Tetranychus medanieli. In all cases, the compounds are used in the form of preparations.

The compositions of the present invention are initially prepared in the form of agents containing from 0.5 to 90% and usually from 10 to 50% by weight of the active ingredient which can be diluted to the desired concentration prior to application to the surface to be treated, e.g. can be used in the form of solutions.

The substituted tetrazines of formula (I) and their tantomers are insoluble in water and can be prepared by conventional methods for the formation of insoluble compounds.

These compounds, for example, are soluble in a water immiscible solvent, such as high boiling hydrocarbons (e.g. xylene), which contain suitable emulsifiers and thus, when added to water, act as a self-emulsifying oil.

Alternatively, the substituted tetrazines may be admixed with or without a wetting agent and a solid carrier to form wettable powders which are soluble or dispersible in water or even mixed with a solid carrier to form a solid product.

Aqueous suspension concentrates may also be prepared by grinding the active ingredient with water, a wetting agent and a suspending agent (e.g., xanthan gum).

The surfactant may be a nonionic, anionic or cationic surfactant.

Preferred surfactants include ethoxylated fatty alcohol sulfates, lignin sulfonates, alkylaryl sulfonates, sulfonated naphthalene-formaldehyde condensate salts, sulfonated phenol-formaldehyde condensate salts, sodium oleoyl-N-methyl tauride, phenol ethoxylates and fatty alkyl ethoxylates.

In addition to the substituted tetrazines, the compositions of the present invention may contain other active substances such as insecticidal, acaricidal, ovicidal, bactericidal and fungicidal agents.

Formulations containing the active compounds of formula (I) may be applied to any site where mite infection is present, or where eggs or larvae are present or are expected to occur. The compositions of the invention can be used, for example, on plants, animals or soil.

The plants to be treated with the compositions of the present invention include cereals, plantations and ornamental plants such as cotton, tobacco, rice, fruit trees and cereals such as apple, pear, apricot, citrus, corn, barley or wheat, beans, sugar beet, potato, carrot, or greenhouse. plants and fruits such as pepper, tomato, cucumber, melon or strawberry.

For different applications, compositions containing the compounds of the formula I can be used in various amounts, for example, for controlling harmful pests, the compositions can be applied to the plants in amounts of 17-120 g / ha or applied in concentrations of 1-2000 ppm, preferably 100-1000 ppm. 3

And 184,684 in quantities of 35-280 g / ha. The compositions of the invention are generally applied to the plants, but systemic effects can also be observed when the compositions are applied to the soil around the plant.

It has now been found that the compositions of the present invention, in particular those containing 3,6-bis (2-chlorophenyl) -1,2-dihydro-1-methyl-1,2,4,5-tetrazine, generally control them. mites that parasitize their crops but do not kill predatory mites that devour those mites. Those mites that survive treatment with the compositions of the invention are killed by these predatory mites so that the fruits are substantially free of the mites breeding on them.

In addition to their action against mites, the compositions of the invention containing the compounds of Formula I as active ingredients are also active against aphids, such as Aphis fabae (black aphid), Megoura viciae (beech aphid), Sitobion avenae (cereal aphid). and Myzus persicae (peach aphid).

The preparation of the compounds of formula (I) and their tautomers and the compositions thereof are illustrated by the following examples. In the examples, temperatures are given in degrees Celsius, and parts and percentages are given in parts by weight and percent by weight.

Example 1 (variant of procedure (a))

3,6-bis (2-chlorophenyl) -1,2-dihydro-1-methyl-1,2,4,5-tetrazine

a) A solution of N, N-bis (2-chlorobenzoyl) hydrazine g hydrazine hydrate in 500 ml of water is treated with stirring by adding dropwise a solution of 43.6 g of sodium hydroxide in 150 ml of water. 25 g of 2-chlorobenzoyl chloride. The mixture was stirred at room temperature for two hours. The resulting solid was collected by filtration, washed with 1: 1 acetone / water and recrystallized from acetic acid. 97.5 g of product are obtained.

217-219 °

b) bis (ce: 2-dichlorobenzylidene) hydrazine

443.5 g of phosphorus pentachloride in 850 ml of 1,2-dichlorobenzene are heated to 110 and 164.7 g of N, N-bis (2-chlorobenzoyl) hydrazine are added portionwise with stirring. The mixture was stirred and heated at 110 for 1 hour. After this time, excess phosphorus pentachloride and 1,2-dichlorobenzene are distilled off under reduced pressure to give a viscous oil which solidifies. The crude solid was recrystallized twice from methanol to give 58.0 g of bis (a: 2-dichlorobenzylidene) hydrazine as a white crystalline solid.

105-107 °.

c) 3,6-bis (2-chlorophenyl) -1,2-dihydro-1-methyl-1,2,4,5-tetrazine

Methylhydrazine (31.0 g) in ethanol (550 mL) was heated to reflux (78) and bis (a: 2-dichlorobenzylidene) hydrazine (58.0 g) was added portionwise. During the addition, the mixture was heated at reflux for 1/2 hour.

The ethanol was evaporated in vacuo and the residue was washed with water and then recrystallized from ethanol / water. 37.0 g of product are obtained.

116-118 °

2nd-5th examples

The following compounds were prepared in the same manner as in Example 1, but using the appropriate o-halobenzoyl chloride in step a) and using the appropriate hydrazine or substituted hydrazine in step c). The temperatures used in step c) are 30 °, 70 ° and 100 °, and the solvents a. They are methanol, ethanol, tetrahydrofuran, acetonitrile, toluene, dioxane and petroleum ether.

2. 3,6-bis (2-chlorophenyl) -1,2-dihydro-1,2,4,5-tetrazine, m.p. 168-169 °.

3. 3,6-bis (2-fluorophenyl) -1,2-dihydro-1-methyl-1,2,4,5-tetrazine, m.p. 93-94 °.

4. 3,6-bis (2-fluorophenyl) -1,2-dihydro-1,2,4,5-tetrazine, m.p. 145-148 °.

5. 3,6-bis (2-chlorophenyl) -1,2-dihydro-1- (2-hydroxyethyl) -1,2,4,5-tetrazine, m.p. 50-55 °.

Example 6

3- (4-methylphenyl) -6- (2-chlorophenyl) -1,2-dihydro-1-methyl-1,2,

4.5-Tetrazine

a) N- (2-Chlorobenzoyl) -N- (4-methylbenzoyl) hydrazine

38.8 g of 2-chlorobenzhydrazide are dissolved in sodium hydroxide solution (9.18 g in 125 ml of water). The solution was stirred and 35.2 g of 4-methylbenzoyl chloride was added dropwise. After stirring for 2 hours, the precipitated solid was collected by filtration and recrystallized from ethanol to give 30.0 g of the desired product.

Mp 204-206 °.

b) 3- (4-Methylphenyl) -6- (2-chlorophenyl) -1,2-dihydro-1-methyl-1,2,4,5-tetrazine

The procedure of Example 1 (b) and (c) is followed to obtain the desired compound from the product of (a) above. 152-154 °.

7-13. examples

The following compounds were prepared as described in Example 6. The solvent for the final step is methanol, ethanol, tetrahydrofuran, acetonitrile, toluene, dioxane or petroleum ether.

7. 3- (4-methylphenyl) -6- (2-chlorophenyl) -1,2-dihydro-1,2,

4.5-Tetrazine, m.p. 194-197 °.

8. 3- (tert-butyl) -6- (2-chlorophenyl) -1,2-dihydro-1,2,4,5-tetrazine, m.p. 172-174 °.

9. 3-tert-Butyl-6- (2-chlorophenyl) -1,2-dihydro-1 (or 2) methyl-1,2,4,5-tetrazine, m.p. 105-120 °.

10. 3-Phenyl-6- (2-chlorophenyl) -1,2-dihydro-1,2,4,5-tetrazine, m.p. 206-210 °.

11. 3- (2-Fluorophenyl) -6- (2-chlorophenyl) -1,2-dihydro-1 (or 2) methyl-1,2,4,5-tetrazine, m.p. 97 °.

12. 3- (3-methylphenyl) -6- (2-chlorophenyl) -1,2-dihydro-2-methyl-1,2,4,5-tetrazine, m.p. 163-165 °.

13. 3- (2-Bromophenyl) -6- (2-chlorophenyl) -1,2-dihydro-2-methyl-1,2,4,5-terazine, m.p. 102-104 °.

Example 14 (Process variant b)

3.6-bis (2-chlorophenyl) -1,2,4,5-tetrazine

Dihydrotetrazine of Example 2 (0.8 g) was dissolved in glacial acetic acid (50 ml) and a solution of sodium nitrite (2.0) in water (10 ml) was added dropwise with stirring at 10 °. After the addition, the mixture was poured into water and the solid was collected by filtration and recrystallized from ethyl acetate. The above product is obtained, m.p. 179-182.

184,684

15th-18th examples

In the same manner as in Example 14, the following compounds are prepared by oxidation (at the temperatures used: 5 °, 15 ° and 30 °, oxidizing agents are nitric acid, bromine and hydrogen peroxide, and the corresponding 1,2-dihydrotetrazines are solvents). acetic acid, ethanol and carbon tetrachloride):

15. 3- (tert-butyl) -6- (2-chlorophenyl) -1,2,4,5-tetrazine,

86-90 °.

16. 3-phenyl-6- (2-chlorophenyl) -1,2,4,5-tetrazine,

120-122 °.

17. 3- (2-Bromophenyl) -6- (2-chlorophenyl) -1,2,4,5-tetrazine, m.p.

18. 3- (4-methylphenyl) -6- (2-chlorophenyl) -1,2,4,5-tetrazine, m.p. 129-132 °.

Example 19

3.6-bis (2-chlorophenyl) -1,2-dihydro-1-methyl-1,2,4,5-tetrazine

a) 2,5-Bis (2-chlorophenyl) thiadiazole

30.9 g of bis (2-chlorophenyl) hydrazine in 250 ml of pyridine were treated with 22.2 g of diphosphorus pentasulfide in portions. The mixture was heated at reflux for 12 hours, then cooled and poured into 1 liter of ice / water. The resulting solid was collected by filtration, washed with water, dried in vacuo and recrystallized from isopropanol. 18.3 g of the desired product are thus obtained in the form of colorless needles.

Mp 111-113 °.

b) 2,5-bis (2-chlorophenyl) thiadiazole - other version 103.8 g (lb). The dichloroazin of Example 1 is treated with 90.0 g of sodium sulfide monohydrate in 500 ml of ethanol and heated at reflux for 2 hours. The mixture was poured while warm into 2 L of ice / water. The resulting solid was collected by filtration, washed with water and dried in vacuo to give 90.2 g of the desired product.

110-112 °.

c) 1,5-bis (2-chlorophenyl) -3 (or 4) methylthiadiazolium sulfate

16.0 g of the product of a) and 6.56 g of dimethyl sulfate are heated together in a water bath for 30 minutes and then the mixture is cooled. The resulting solid was triturated with acetone, collected by filtration, washed with acetone, then washed again with diethyl ether and dried in vacuo. 16.8 g of the expected product are obtained.

146-148 °

d) 3,6-bis (2-chlorophenyl) -1,2-dihydro-1-methyl-1,2,4,5-tetrazine

6.0 g of the product of b) is suspended in 30 ml of ethanol and 1.5 g of hydrazine hydrate are added to the suspension. The mixture was heated at reflux for 50 minutes, cooled and filtered. The filtrates were concentrated to a small volume and diluted with water to give a semi-solid which solidified during trituration. The solid was collected by filtration and dried in vacuo to give 3.1 g of the desired product.

Mp 115-116 °, identical to the product of Example 1.

Example 20

3.6-bis (2-chlorophenyl) -1,4-dihydro-1,4-dimethyl-1,2,4,5-tetrazine

6.0 g 19b). The product of Example 1b is suspended in 30 ml of ethanol and 1.40 g of methyl hydrazine are added. The mixture was heated at reflux for 30 minutes, then cooled and filtered. The filtrate was then concentrated to a small volume and diluted with water. The resulting solid was collected by filtration, washed with water and dried in vacuo, then recrystallized from petroleum ether (petroleum ether 80-100 ° C). 3.40 g of the expected product are obtained.

Mp 148-149 °.

21st-23rd examples

The following compounds were also prepared as described in Examples 19 and 20;

21. 3,6-bis (2-chlorophenyl) -1,2-dihydro-1-ethyl-1,2,4,5-tetrazine, m.p. 106-108 °.

22. 3,6-Bis (2-chlorophenyl) -1,4-dihydro-1-ethyl-4-methyl-1,2,4,5-tetrazine, m.p. 92-94 °.

23. 3,6-Bis (2-chlorophenyl) -1,4-dihydro-1- (2-hydroxyethyl) -1,2,4,5-tetrazine, m.p. 149-152 ° C.

Example 24

3.6-bis (2-chlorophenyl) -1,4-dihydro-1,4-dimethyl-l, 2,4- _t 5-tetrazine - other variant mole N- (2-chlorobenzylidene) -N ^L methyl- hydrazine, 1 mole of iodine and sufficient pyridine to dissolve are heated at reflux for 10 hours. The pyridine is then evaporated to give the desired product which is recrystallized from petroleum ether. The recrystallized product has a melting point of 148 °. The procedure is repeated using sodium hypochlorite and sodium ferricyanide instead of iodine at temperatures between 60 ° C and 120 ° C, such as 60 °, 80 °, 100 and 120 ° C.

Example 25

3, & bis (2-bromophenyl) -l, 2,4,5-tetrazine

Example 14 gave the above product, m.p. 166 ° C.

example

3.6-bis (2-chlorophenyl) -1,4-dihydro-1,4-dimethyl], 2,4,5-tetrazine mole of N- (a: 2-dichlorobenzylidene-N-methylhydrazine) and Triethylamine (1 mol) was added to acetonitrile and the mixture was heated under reflux for 6 hours, then the solvent was evaporated and the resulting solid was recrystallized from petroleum ether to give the desired product.

Mp 148 °.

The process is repeated at various temperatures, such as 50 ° C and reflux temperature, such as 50 °, 70 °, 90 ° and 110 °. The procedure was repeated with α-bromo starting material.

Example 27

A 50% wettable powder formulation was prepared using the active ingredient of Example 1.

weight%

Example 1 50

Reax 45L (lignin-based wetting and dispersing agent) 5

Polyphone H (Sulfonated Kraft Lignin Sodium 2 Neosyl (Precipitated Silica) 10

Kaolin 33

Similar formulations were prepared using the compounds of Examples 14 and 17.

184,684

Example 28

50% wettable powder formulations were prepared using the compounds of Examples 1, 14 and 17.

weight%

Example compound 50

Reax 45L 5

Kaolin 45th

Example 29

An 85% wettable powder formulation was prepared using the active ingredient of Example 14.

weight%

Example 14 85

Reax 45L 10

Kaolin 5

Example 30

Aqueous suspension concentrates were prepared which contained 10, 20 and 50% 1 to 26%. containing the active ingredient of Example 1, mixed with water, xanthhangum (0.2-3% by weight of the composition) and a surfactant (5% by weight of the composition). The formulations may be readily diluted with water into ready-to-use solutions or suspensions containing from 0.05 to 5% of the active ingredient. The surfactant may be ethoxylated fatty alcohol sulfate, lignin sulfonate, alkylaryl sulfonate, sulfonated naphthalene formaldehyde condensate salt, sulfonated phenol formaldehyde condensate salt, sodium oleoyl-N-methyltaxylate and dialkylethyl sulfate fatty alcohol ethoxylate.

Example 31

Emulsifiable concentrates of 5, 10, 15 and 20% by weight of 1 to 26% by weight are prepared. and the surfactant of Example 30 (1, 2 or 5% by weight). The formulations are readily dispersible in water to provide 0.05 to 5% by weight of ready-to-use dispersions.

The example

Formulations containing the compounds listed in the table below at 1000, 300, 100, 10 and 3 ppm in concentrations of 500 ppm Lissapol NX (nonylphenol / ethylene oxide condensate) wettable agent are applied to 2 cm diameter discs of carob bean (Phaseolus vulgaris) leaves, which were infected with 50-100 eggs of the green spider mite Tetranychus telarius. Treated leaf discs and mite aphids, together with control leaf discs treated with wetting agent only, were kept on wet filter paper for 5 days. Mortality of the mite eggs was then measured, and the LC ₅₀ values. The evaluation was performed according to the following scale.

LC ₅₀ (ppm) Indication

1000 0

300-1000 1

100-299 2

30-99 3

10-29 4

3-9.9 5

1-2,9 6

The results obtained are as follows:

Example number Marking

6

5

1

3

2

2

2

1 '3

4

1

6

6

3

2

6

2

5

4

4

The control leaf discs treated with water and wetting agent had less than 5% mortality over the same period.

Example B

Carob beans with two fully developed cotyledons were sprayed with an aqueous acetone solution containing 1000 pp w / v of the compounds of Examples 1 and 14 and 500 ppm Lissapol NX wetting agent. After 24 hours and 35 days for 7 days, discs were cut from the treated leaves and planted with 10 to 10 adult female Tetranychus cinnabarinus mites. The mites were removed after 24 hours, during which time the mites laid about 100-100 eggs on each disk. The mortality of these eggs was examined after 5 days and found that each disk had greater than 95% mortality.

Example 32

Following the procedure of Examples 21 and 22, the following compounds were prepared:

(a) 3-cyclohexyl-6- (2-chlorophenyl) -1,2-dihydro-1 (or 2) methyl-1,2,4,5-tetrazine, m.p. 130-132 ° C;

(b) 3-cyclohexyl-6- (2-chlorophenyl) -1,2,4,5-tetrazine, m.p. 90-91 ° C;

(c) 3- (2-iodophenyl) -6- (2-chlorophenyl) -1 (or 2) methyl-1,2-dihydro-1,2,4,5-tetrazine, m.p. 165 ° C;

(d) 3- (2-iodophenyl) -6- (2-chlorophenyl) -1,2,4,5-tetrazine, m.p. 145 ° C;

(e) 3- (2- (methylthio) phenyl) -6- (2-chlorophenyl) -1 (or 2) methyl-1,2-dihydro-1,2,4,5-tetrazine , op. 170 ° C;

(f) 3- (2,5-Dichlorophenyl) -6- (2-chlorophenyl) -1,2-dihydro-1 (or 2) methyl-1,2,4,5-tetrazine, m.p. . 166-168 ° C;

(g) 3- (2,5-Dichlorophenyl) -6- (2-chlorophenyl) -1,2,4,5-tetrazine, m.p. 180-182 ° C;

(h) 3-cyclohexyl-6- (2-bromophenyl) -1,2-dihydro-1 (or 2) -methyl-1,2,4,5-tetrazine, m.p. 108 ° C;

(i) 3-Cyclohexyl-6- (2-bromophenyl) -1,2,4,5-tetrazine, m.p. 89-91 ° C;

184,684 (j) 3-Cyclohexyl-6- (2-fluorophenyl) -1,2-dihydro-1 (or 2) -methyl-1,2,4,5-tetrazine, m.p. 94 ° C;

(k) 3-Cylohexyl-6- (2-fluorophenyl) -1,2,4,5-tetrazine, m.p. 53-56 ° C;

(1) 3- (1-methylcyclohexyl) -6- (2-chlorophenyl) -1,2,4,5-tetrazine, m.p. 69 ° C.

The results of the tests according to Example A are as follows:

compound designation (a) 6 (b) 7 (d) 6 (>) 7

(The 7 marks are LC ₅₀ = 0.1— Means -0.299 ppm.) comparative effect example The following compounds are active against three mite species efficacy was similar to that described in Example A. The test results are as follows: Compound Tetranychus cinnabarinus Tetranychus urticae (Susceptible) Tetranychus urticae (Resistant) dicofol / Compound of formula (4) 4 1 cyhexatin / Compound of formula XI / 2 not tested not tested amitraz / Compound of Formula XIII / 5 not tested 3 Example 14 of Compound 7 7 5 Example 1 of Compound 6 6 5

(The signal 7 represents LC ₅₀ = 0.3 to 1 parts per million.)

A difference of 2 in the indications in the table means that the compound with the greater symbol is ten times more active with a symbol with a value of less than 2.

From the above data it is evident that the compounds of the present invention have a higher activity than the other three compounds used to date.

Claims (2)

PATENT CLAIMS An acaricidal composition for controlling mites, their eggs or larvae, characterized in that it contains from 0.5 to 90% by weight of the substituted tetrazine derivative of the formula (I) or a tautomeric derivative thereof, R ¹ is hydrogen or C 1-4 5 alkyl groups, R ² is hydrogen or C 1-4 alkyl, or R 'and R ² together represent a single bond, R ³ is C 4 -C 6 tertiary alkyl, 10 C 3 -C 7 cycloalkyl or phenyl optionally substituted with halo or C 1 -C 4 alkyl, R ⁶ is in the 2-position with a halogen atom Substituted phenyl, liquid or solid carriers, preferably kaolin, xylene or water; and surfactants, preferably lignin sulfonates, salts of sulfonated naphthalene-formaldehyde condensates, sulfonated phenol-formaldehyde condensed salts, or nonylphenol / ethylene oxide condensate; with at least one of them. 2. The composition of claim 1, wherein the composition is as an active ingredient 3.6-bis (2-chlorophenyl) -1,2-dihydro-1-methyl-1,2,4,5-tetra25zine or 3.6-bis (2-chlorophenyl) -1,2,4,5-tetrazine, or 3- (2-bromophenyl) -6- (2-chlorophenyl) -1,2,4,5- contains tetrazine. A process for the preparation of a substituted tetrazine30 derivative of formula (I) wherein: R ¹ is hydrogen, C 1-4 alkyl or hydroxy (C 1-4 alkyl) R ² is hydrogen or C 1-4 Or an alkyl group R * and R ² together represent a single bond, R ³ is C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, or phenyl optionally substituted with up to 2 times more than halogen, C 1 -C 4 alkyl or C 1 -C 4 alkylthio, R ⁶ is phenyl substituted at the 2-position by a halogen atom, 45 characterized in that a) for the preparation of compounds of formula I wherein R ¹ and R ² are other than a single bond, a substituted azine of formula III wherein R ³ and R ⁶ are as defined above and X is a cleavable group, preferably chlorine; represents a bromine atom, a cyano group or a C 1-4 alkoxy group with a hydrazine of formula IV wherein R ¹ and R ² are as defined above, at a temperature of from 30 ° C to 100 ° C in a suitable solvent, or B) for the preparation of compounds of formula I wherein R ¹ and R ² together represent a single bond, compounds of formula I wherein R ¹ and R ² each represent hydrogen or C 1-4 alkyl, in a suitable solvent with a suitable oxidizing agent oxidized. 2 drawing -7184 684 NGO ₃ : A 01 Ν 43/64; C 07 D 275/08 r'nh-nhr (III)