KR820002066B1 - Process for the preparation of benzophenone hydrazone derivatives - Google Patents

Abstract

Title hydrazones I(R1,R5,R7=halogen, alkyl, haloalkyl, alkoxy; R1 or R5 makes naphthyl group with adjacent benzene; R2,R4=H, alkyl, acyl, ester, thioester group, optionally substituted carbamoyl or thiocarbamoyl; R2 and R4 make C5-7 cycle with adjacent N; R3=substituted alkyl, alkenyl, N,N-dialkylamino, substituted phenyl; when p is zero, R2 and R4 are not H; m,n,x= 0, 1; P= 0, 2, 3), useful insecticides, were prepd. by reacting compd. II with NH2NR2R4. Thus, 4-chloro-4'-methylsulfonylbenzophenone ethoxycarbonyl hydrazone (m.p. 132.5-140≰C) was prepd. from phenol, p-chlorobenzoyl chloride, and ethylcarbozate.

Description

Method for preparing benzophenone hydrazone derivative

The present invention relates to compounds having pesticidal action.

Commercially useful pesticides are generally divided into four main categories: chlorine-based compounds such as DDT, camphorchloro and BHC, organophosphorus-based compounds such as parathion, carbamates such as carbaryl, and more recently synthetic pyridoids such as fermedrin have.

Resistance to pesticides appears after use and it requires new pesticides and especially new groups of pesticides.

It has been found that many groups of compounds shown in the literature have insecticidal properties but are sometimes not commercially acceptable as pesticides.

We have newly discovered benzophenone hydrazones that are insecticidal against a wide range of pests.

Some benzophenone hydrazones are already known.

For example, U.S. Patent Nos. 3,732 and 307 describe compounds of the general formula

Where

X is selected from the group consisting of perfluoroalkyl, perfluoroalkoxy and perfluoroalkylthio containing up to 4 carbon atoms,

Y is selected from the group consisting of perfluoro alkylthio and perfluoroalkoxy, perfluoroalkyl, alkylthio, alkoxy, alkyl, fluorine, cancelled, chlorine, hydrogen containing up to 4 carbon atoms.

JR DoAmaral et. al. J. Med. Chem. The benzophenone hydrazones described in 12, 21 (1969) and the compounds of US Pat. No. 3,732,307 are clearly distinguished by the unsubstituted NH ₂ of hydrazine. The compounds in that specification are primarily described as plant growth regulators, but are also mentioned in US Pat. No. 3, 732, 307 that they have activity against pests. In the twenty four examples given in the specification, the compounds of the twenty examples did not contain alkylthio as well as perfluoroalkylthio groups. Emphasis is placed on the specification that compounds having perfluoroalkyl, in particular trifluoromethyl as substituents, or compounds having an alkylthio or perfluoroalkylthio in the 4-position in one of the benzene rings are not proposed for any particular use. Not only that, but also 4-substituted compounds containing substituents not mentioned in the specification have no particular use.

According to the invention a compound of formula (I) is prepared.

In the above formula

m is 0 and n is 0 or m is 1 and n is 0 or 1;

p is 0, 2 or 3, x is 0 or 1;

R ¹ , R ⁵ and R ⁷ are halogen, alkyl, haloalkyl or alkoxy or R ¹ and adjacent R ⁵ groups together with adjacent benzene form a naphthyl group;

R ² and R ^{4, which} are the same or different, are hydrogen, alkyl, acyl, ester or thioester groups, optionally substituted carbamoyl or optionally substituted thiocarbamoyl or R ² and R ⁴ are one or more heteroatoms with adjacent nitrogen; To form a 5 to 7 membered ring optionally containing; R ³ is optionally substituted alkyl, alkenyl, N, N-dialkylamino or phenyl optionally substituted with alkyl or hydrogen; When p is 0 both R ² and R ⁴ are not hydrogen.

In one aspect of the invention, when p is 0, the substituent in one benzene ring is SR ³ and the hydrazine NH ₂ must be substituted. It is surprising, for example, that R ⁴ must be substituted with alkyl, in particular acyl, ester or thioester or carbamoyl or thiocarbamoyl, to obtain useful compounds.

Another aspect of the invention is when p is 2 or 3.

는 치환기

를 의미한다는 것은 판단할 만할 것이다. p가 3인 화합물이 본 발명에서 특히 바람직하다.Substituent-(O) ₂ SR ³ is a substituent

Is a substituent

Means to be judged. Particularly preferred in the present invention are compounds in which p is 3.

Furthermore, these substituents are completely different from any substituents proposed in US Pat. No. 3,732,307.

In this specification, halo or halogen shall be interpreted as fluorine, chlorine, cancellation or oxo, in particular fluorine, chlorine, cancellation.

Preferred compounds in the first aspect of the invention are compounds wherein p, n, x = 0, m = 1, R ¹ is halo, R ² is hydrogen, R ³ is alkyl and R ⁴ is acyl or alkoxycarbonyl.

Preferred compounds in the second aspect of the invention are p = 3, x = 0, R ² is hydrogen, R ¹ and R ⁵ are halo, R ⁴ is hydrogen, acyl or alkoxycarbonyl, R ³ is alkyl, optionally substituted phenyl or Optionally substituted benzyl compound.

In general formula (I), R <^1> , R <^5> and R <^7> are preferable halogen and especially chlorine is preferable. When one of these groups is alkyl or alkoxy, preference is given to those having from 1 to 4 carbon atoms, in particular methyl or methoxy. In general, m is preferably 1, n and x are 0.

When they are haloalkyl they are preferably trifluoromethyl.

R ² is preferably hydrogen and R ⁴ is preferably hydrogen, which is usually a carbonyl derivative. When R ² or R ⁴ is alkyl, alkyl having 1 to 4 carbon atoms is particularly preferred.

When R ² or R ⁴ together with adjacent nitrogen form a ring, examples are piperidine, pyrrolidine, thiamorpholin, in particular morpholine.

If R ² or R ⁴ is an ester or thioester group it has the general formula of R ⁸ XCO, where x is oxygen or sulfur, in particular oxygen and R ⁸ is alkyl having 1 to 12 carbon atoms, in particular 1 to 8 carbons (especially ethyl Organic radicals are optionally substituted (e.g., C1-4 alkoxy; C3-7 cycloalkyl; halogen or phenyl, aryl such as substituted phenyl or naphthyl, phenoxy and substituted Substituted with aryloxy, such as phenoxy); cycloalkyl having 3 to 7 carbon atoms, in particular cyclopentyl; optionally substituted alkenyl having 2 to 12 carbon atoms (e.g. substituted with aryl such as phenyl or substituted phenyl); Alkynyl of 2 to 6; aryl, such as optionally substituted phenyl or 2-naphthyl; heteroaryl, such as furyl, thienyl, pyridyl; hetero, such as morpholinyl, piperidyl and thiamorpholinyl When phenyl is substituted, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms, nitro, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms And phenyl is selected from the group of halogen and substituted if R ² or R ⁴ is acyl, which forms the general formula of R ⁹ CO, wherein R ⁹ is R ⁸ or hydrogen as defined above.

R ³ is preferably optionally substituted alkyl having 1 to 4 carbon atoms. Preferred substituents are halogen. When R ³ is alkenyl it is usually 1-propenyl. When R ³ is dialkylamino this is preferably dimethylamino. Especially preferred are R ³ methyl or trifluoro methyl.

Preferred compound groups are those in which p is 3.

Particularly preferred groups are m = 1, n and x = 0, p = 3, R ¹ is halogen, R ³ is C 1-4 alkyl optionally substituted with halogen and R ² is hydrogen. More preferred groups are R ³ is methyl or trifluoromethyl, R ⁴ is R ⁸ (O) q-CO, where q is 0, 1, R ⁸ is 1-4 alkoxy, 3-7 cycloalkyl, C1-C12 alkyl optionally substituted with halogen, phenoxy or substituted phenoxy: C3-C7 cycloalkyl; C2-C12 alkenyl optionally substituted by phenyl or substituted phenyl; C2-C6 alkynyl; Or optionally substituted phenyl wherein all substituted phenyl groups include 1 to 4 alkyl, 1 to 4 haloalkyl, nitro, 1 to 4 alkoxy, 1 to 4 alkylthio, 1 to 4 dialkylamino, phenyl Or substituted with halogen; R ⁸ is also hydrogen when q = 0.

The compounds of the invention act against economically important pests that cause serious and serious damage to crops, such as Chinese cabbage moth (Frutella makuripennis), Chinese cabbage butterfly (Pierris brassica), Egyptian cotton Lepidopteraceae, including caterpillars of leaf worms (Spodogerra litoraris) and pests of the genus Heliodes, such as H. amigera, H. vilisense, and H. branch. Many of the compounds also have an effect on other caterpillars, such as apple moth. Some of the compounds are colleptera including mustard (Pedon coflearia), cereal weevil (Sirophyllus granarius), powdery cockroach (tribolium castanium), and dark brown larvae (tenebrio molito) Neck beetle; Atoperaphid aphids, such as Blatella germana; It is also effective against other pests, such as Hemiptera aphids, including the beetle aphid (Megura Vichyea).

Many of the compounds are also active against pests and economically important mites of animals, including farm poultry. For example, it is active against larvae in pests of mosquitoes such as Deepiramox, such as sheep Blue Fly (Russilia), and Etes agusti. Some of the compounds (particularly when R ⁴ represents a carbamoyl or thiocarbamoyl group) show the pesticidal effect of the compound penetrating into the animal's internal tissues when the compound is treated. This property is important for the treatment of animals, such as cattle, in which pests such as sturgeons are prevalent in tissue-stationary states. Some of the compounds are active against these and ked and parasitic mites, in particular mites, such as the Bupillius microflues, and mites, such as the genus Sacoptes.

Some of the compounds exhibit bactericidal, herbicidal and plant growth regulation.

The present invention includes a pesticidal composition composed of a compound of formula (I) and an inert extender. One or more of the compounds of the invention may be included in the composition and the extenders may be surfactants of liquids, solids, gases such as, for example, dispersants, emulsifiers or wetting agents.

Known compounds having acaricide or pesticidal action may be added to one or more compounds of the invention to increase or broaden the range of activity of the pesticide.

Such additional insecticides include tetrachlorobinfos, phenythrothione, demethone-s-methyl, posalone, dioxanthone, chlorophenbinfos, dichlorbose, bromophosphethyl, diazinone, dimether, methyl Organophosphorus compounds such as parathion, bolstar 0-ethyl-0- (4-methylthiophenyl) -s-propyl phosphorodithioate, or chloro pyriphos; Carbamates such as metmill, carbaryl; Pyrimicab; Or promecarb; Crosslinked diphenyl compounds such as tetradipon, tetrasul or DDT; Chlorine hydrocarbons such as benzene hexachloride, endosulfane, endrin or toxaphene; Acaricides such as amitraz, chlorodimethylform, cholpyrine, chloromethiuron or nimidan; Synthetic pyridoids such as fermedrine, fenbarrerate or cyfemedrin or thin insecticides such as cyhexarin or fenbutatin oxa.

The composition of the present invention can be prepared in well-known forms such as, for example, a water-soluble dispersant, a water-soluble emulsion, an emulsified concentrate, a dispersion powder, a distribution powder or a granule. It may also be used at the required concentration by adding it with water or a suitable extender before spraying directly as a pesticide. It may be a dispersion solution consisting of dissolving the compound of the present invention in a solvent which can be mixed with water by adding a dispersing agent, or may be a dispersion powder consisting of the compound of the present invention and a dispersing agent. Alternatively, the compounds according to the invention in very fine powder form can be associated with a dispersant and then mixed with water to give a paste or cream which is then added to an oil-in-water emulsifier to give a dispersion of the active ingredient in an aqueous oil emulsion. Get

The emulsion is obtained by dissolving the compound of the invention dissolved in a solvent that cannot be mixed with water in water in the presence of an emulsifier to form an emulsion. Emulsions of the required concentration can be formed from concentrated emulsions by combining the compounds of the invention with emulsifiers, water and immiscible solvents. Alternatively, the compound of the invention can be supplied to the consumer in the form of an emulsion concentrate in the form of a solution in which a compound of the invention is dissolved in a water-insoluble solvent containing an emulsifier.

Distribution powders are obtained by vigorously mixing and grinding the compound of the invention with a kaolin and a ground solid powder extender.

Solid granules are obtained by mixing the compounds of the invention with extenders similarly used in distribution powders and granulating the mixtures in conventional manner. Alternatively, the active ingredient may be absorbed or adsorbed to a granular extender already formed of diatomaceous earth attapulgite, limestone grit.

The concentration of the active ingredient (when used alone) of the composition sprayed directly on the crop by conventional ground spraying methods is preferably within the range of 0.001 to 10% (particularly 0.005 to 5%) and 20% by weight of the composition. The above-mentioned more concentrated composition is preferable in the case of aerial spraying. The concentration of the active ingredient as the main concentrated composition can vary widely, such as from 5 to 95% by weight of the composition.

As already described, the compounds of the invention exhibit exceptional activity as insecticides and therefore the present invention includes methods of controlling pests by spreading the compound of formula (I) to the area of the pest, ie the pest or its habitat. The compounds of the present invention can be preferably applied alone or as one of the compositions already described.

The compound of the present invention has activity against Redodotera and Diptheramok, which damages the life of the plant, and protects the plant from damage caused by pests by spraying the compound of formula (I) on the habitat of the plant. For example, cabbage moths and cabbage moths and leaf worms that damage vegetables such as brassica are serious pests on cotton.

Spraying or distribution to pest-infested plants and direct grinding are generally preferred methods, but the active compounds can be sprayed onto the plants in granular form or by dipping. In this case, the plant is protected from pests because the active compound is absorbed by the roots of the plant. The amount of active compound to be sparged can vary greatly depending on the environment and usually the amount is in the range of 0.01 to 20 kg per hectare, particularly 0.1 to 10 kg per hectare.

Also included in the present invention is a method of protecting an animal from damage by pests by treating the animal with a compound of formula (I). Parasites are prevalent infectious agents in animals such as poultry and most can be controlled by external spreading of the compound of formula (I). The method is sprayed directly on the animals or partially sprayed on buildings and the like where the animals are raised.

The compound of the present invention can be prepared according to the following method.

1) The following compound of formula (II) is prepared by reacting with a compound of NH ₂ NR ² R ⁴ .

When both R ² and R ⁴ are hydrogen the product

a) acylating with an acyl halide or anhydrous acid such that R ² or R ⁴ is an acyl group, or

b) chloroformate or chlorothioformate acylated such that R ² or R ⁴ is an ester group, or

c) can be acylated with isocyanates or isothiocyanates such that R ² or R ⁴ is carbamoyl or thiocarbamoyl.

The term `` acylating agent '' as used herein includes these three types of compounds.

The reaction with hydrazine or hydrazine derivatives is usually carried out at temperatures of 50 ° to 100 ° C. in the presence of acetic acid.

The acylation reaction is preferably carried out at a temperature of 0 ° to 100 ° C in the presence of an inert organic liquid which also acts as a solvent of the reactants. More advantageously the reaction is carried out in the presence of a tertiary alkylamine, pyridine or alkali metal carbonate with a suitable acid binder. Chlorine is preferred when the acylating agent is a halide.

Compounds of formula (II) with P = 3 are novel compounds and can be prepared by reacting sulfonyl halides of the R ³ SO ₃ X structure with the corresponding 4′-high compound of formula (III) Where X is halogen, in particular chlorine.

This process is preferably carried out in the presence of an inert organic solvent and an acid binder.

The compound of formula (II) having P = 0 can be prepared by reacting the following compound (a) with compound (b) by Friedel-Crafts reaction.

Where Y is a halide, typically chlorine.

Compounds of formula (II) with P = 2 can be prepared by oxidizing the corresponding compound with P = 0 with an oxidizing agent such as hydrogen peroxide.

2) When P = 3, it may be prepared by reacting a compound of formula (IV) with a compound of formula RSO ₂ Y.

Wherein both R ² and R ⁴ are not hydrogen and Y is halogen, in particular chlorine. This reaction is usually carried out at a temperature of 0 to 100 ° C. in the presence of an acid binder.

Alternatively, compounds of formula (IV) can be prepared by reacting a suitable hydrazine derivative of NH ₂ NR ² R ⁴ formula with a compound of formula (III) in the presence of an inert organic solvent (optionally in the presence of acetic acid). General formula (IV), wherein R ² and R ⁴ are not both hydrogen, is not a new reactant and is included as part of the present invention.

In most of the reactions a product consisting of a mixture of E and Z isomers is obtained.

It is understood that general formula (I) representing the compound of the present invention includes all of these isomers. In all cases, all of the isomers can be separated by conventional methods such as chromatography or fractional recrystallization, but in general we do not find it advantageous to separate the isomers as they have more valuable pesticidal activity. Isomer activity for one compound is different and in some cases the activity of one isomer may be ignored; Pure isomers lacking kill activity are not part of the present invention. The new reactants of general formula (IV) also exist in isomeric form and the structures shown are intended to include all of the isomers.

The invention is illustrated in the following examples.

Compounds according to the invention are prepared according to one of the following schemes.

The term "acylating agent" includes acid halides, acid anhydrides, isocyanates and isothiocyanates.

Examples 1 to 6 are typical examples of preparations according to these schemes.

The structure of all compounds prepared according to the invention was confirmed by infrared analysis.

Example 1

Description of Scheme 1

The phenol is reacted with p-colobenzoyl chloride by Friedel-Crafts reaction in the presence of aluminum chloride to give 4-chloro-4'-hydroxy benzophenone having a melting point of 179 to 181 ° C (A). Methanesulfonyl chloride (2.5 g) is added to a pyridine solution containing this compound (5 g) at room temperature. The reaction is heated in a steam bath for 1 and a half hours and the liquid reaction product is poured into dilute hydrochloric acid, filtered and air dried to give a solid. The solid is recrystallized from industrial methyl alcohol to obtain 4-chloro-4'-methylsulfonyl-oxybenzophenol having a melting point of 120 ° to 121 ° C (B). A solution of glacial acetic acid (8 ml) and ethanol (200 ml) containing ethyl carbazate (7.8 g) and 9.4 g of this product is heated to reflux for 48 hours and evaporated to dryness in vacuo. The residue was extracted with methylene chloride (250 ml), the extract was washed with water and aqueous sodium hydroxide solution (2.5N) and evaporated to dryness. 4-chloro-4'-methylsulfonylbenzophenone ethoxycarbonyl with a melting point of 132.5 ° to 140 ° C. Obtain Hydrazone (C).

Example 2

Description of Scheme 2

Example 1 To a solution of ethanol (200 ml) containing B (9.35 g) compound was added hydrazine hydrate (8 ml) according to glacial acetic acid (1.5 ml). The mixture is heated with reflux for 17 hours. The solvent is evaporated under reduced pressure and extracted with chloroform to give an oil. The extract is washed with water, aqueous sodium hydroxide solution and then dried over magnesium sulfate. The solvent is evaporated under reduced pressure to give an oil. When this is left to crystallize, a melting point of 70 to 110 ° C yields 4-chloro-4'-methylsulfonyloxybenzophenone hydrazone (D).

Example 3

Description of Scheme 3

An ether (15 ml) solution containing propionyl chloride (2 g) was added dropwise over 30 minutes with stirring (at 0-5 ° C.) in a pyridine (20 ml) solution containing the D (6.2 g) compound of Example 2. . The mixture was stirred at room temperature for 1 and a half hours, cooled with water (1 liter), the solid was washed with dilute hydrochloric acid and water, filtered and dried under vacuum at 60 ° C. for 1 and a half to give a melting point of 128 to 144 ° C., 4-chloro-4 '-Ethylsulfonylbenzophenone propionylhydrazone is obtained (C).

Example 4

Description of Scheme 4

Example 1 A (92.8 g) compound of ethanol (1 L) solution, ethyl carbazate (100 g) and glacial acetic acid (100 ml) were heated under reflux for 48 hours with stirring. The solvent is evaporated under reduced pressure to form a slurry and the solid is separated from the liquid by filtration. This solid is washed with some cooled industrial methyl alcohol and dried in vacuo at 50 ° C.

The liquid is evaporated again under reduced pressure and the oil obtained is extracted with chloroform and the extract is washed with aqueous sodium carbonate solution and water. The extract is dried over magnesium sulfate and evaporated under reduced pressure to obtain a second batch of solids.

The combined solids are recrystallized from industrial methyl alcohol to obtain 4-chloro-4'-hypsioxy benzophenone ethoxy carbonylhydrazone having a melting point of 185 to 187 ° C (E). (E) Tetrahydrofuran (25 ml) solution containing methanesulfonyl chloride (44.7 g) was added dropwise for 35 minutes in a tetrahydrofuran (700 ml) solution containing (95.55 g) compound and triethylamine (90 ml). . A fine precipitate is formed by exotherm, which is left under stirring overnight. It is poured into water (500 ml) and extracted with methylene chloride (500 ml). The extract is washed five times with 500 ml of water and dried over magnesium sulfate. The semisolid residue obtained by evaporating the solvent under reduced pressure is immersed in industrial methylated alcohol. Filtration and washing with more solvent left the white solid under vacuum at 75 ° C. for 3 hours to obtain 4-chloro-4′-methylsulfonyl oxybenzophenone ethoxycarbonylhydrazone having a melting point of 132 to 142 ° C. .

Example 5

Description of Scheme 5

Isopropylphenyl sulfide is reacted with 4-chlorobezoyl chloride by Friedel-Crafts reaction in the presence of aluminum chloride to give 4-chloro-4'-isopropylthiobenzophenone having a melting point of 105 to 107 ° C (F).

Hydrazine hydrate was added to a solution of (F) (101 g) in ethanol (650 ml). The mixture is heated to reflux for 24 hours, after which the solvent is evaporated under reduced pressure. Water is added to the residue, which is extracted with chloroform and washed with aqueous sodium hydroxide and water. The organic extract is dried over magnesium sulfate and evaporated under reduced pressure to obtain 4-chloro-4'-isopropylthiobenzophenonehydrazone having a boiling point of 188 to 190 캜 at 0.1 atmosphere (G).

This was treated with ethylchloroformate in the same manner as described in Example 3 to obtain 4-chloro-4'-isopropylthiobenzophenone ethoxycarbonylhydrazone (H) having a melting point of 115 to 135 ° C.

Example 6

Description of Scheme 6

The Friedel-Craft reaction described in Example 5 was used to obtain 4-chloro-4'-propylthiobenzophenone having a melting point of 94-95 ° C (F). This (2.9 g) is dissolved in glacial acetic acid and hydrogen peroxide is added (3.5 ml of 100 masses).

The mixture is stirred and heated at 60 ° C. for 5 hours and then poured into water. Dry and recrystallize with ethanol to give 4-chloro-4'-propylsulfonylbenzophenone having a melting point of 140.5 to 142.5 ° C. This was treated with hydrazine hydrate as described in Example 5 to obtain 4-chloro-4'-propylsulfonyl benzophenone hydrazone having a melting point of 110 to 120 ° C (J), which was similar to that of Example 3. Treatment with propionyl chloride to obtain 4-chloro-4'-propylsulfonylbenzophenone propionylhydrazone having a melting point of 155 to 170 ° C.

Example 7

Description of Scheme 7

(F) solution of Example 5 (14.52 g) was treated with ethyl carbazate in a similar manner as described in Example 1 to 4-chloro-4'-isopropyl-thio benzophenone ethoxy having a melting point of 155 to 135 ° C. Carbonylhydrazone is obtained.

The products of the above and below examples are generally obtained as a mixture of geometric isomers, and the ratio of the two isomers varies from product to product.

[Example 8-22]

The compounds shown in the following table were prepared by one of the above schemes in a similar manner as described above in the appropriate examples.

Physical values (melting point in ° C.) are given in section J for the final product, section K in the starting material and section L in the intermediate.

When using Scheme 3 the starting material is the product of the previous example.

The starting material (paragraph K) is form A when schemes 1,2 or 4 are used and form F when schemes 5 or 7 are used.

The intermediate (L term) is type B when Scheme 1 or 2 is used, type E when Scheme 4 is used and type G when Scheme 5 is used.

The type of acylating agent or hydrazine derivative used given in the term indicated by A is as follows.

TABLE 1

Example 223

The product of Example 4 separated the geometric isomers by high pressure liquid chromatography. E-isomers have a melting point of 160 to 161 ° C and Z-isomers have a melting point of 152 to 156 ° C.

Due Diligence 224

This example illustrates the activity of the compounds of the present invention against diamond back moths (plutella maculipennis) and larvae.

Ten larvae are immersed in the test solution and placed in a test tube with a dry square cabbage (cabbage). After 24 hours, untreated cabbage is added and after 24 hours the larval mortality is evaluated.

Repeat the test twice with each test compound and several concentrations of test solution to calculate the LD ₅₀ value.

The compound of Example 1-223 has less LD ₅₀ than 5000 ppm.

Example 225

The following form of concentrate was formulated as follows.

1. NonylPhenol Ethoxylate.

2. AH is an ethoxylated cast oil.

3. Sodium salt of cresol sulfonic acid / formaldehyde condensation product.

4. Ethylene oxide / propylene oxide copolymer.

5. Silicone in Emulsion.

6. High molecular weight polysaccharides.

7. Alkyl phenol ethoxylates.

8. Silicones in Emulsion.

9. Dioctyl ester of sodium sulfosuccinic acid.

10. Polyvinyl Alcohol.

Claims (1)

A process for preparing a compound of formula (I) by reacting a compound of formula (II) with formula NH ₂ NR ² R ⁴ .

In the above formula m is 0 and n is 0, m is 1 and n is 0 or 1; P is 0, 2 or 3, X is 0 or 1; R ¹ , R ⁵ and R ⁷ are halogen, alkyl, haloalkyl, or alkoxy, or R ¹ and adjacent R ⁵ together with the benzene to which they are linked form a naphthyl group; R ² and R ⁴ may be the same or different and are hydrogen, alkyl, acyl, ester or thioester groups, optionally substituted carbamoyl or optionally substituted thiocarbamoyl, or R ² and R ⁴ together with the nitrogen to which they are linked form a 5-7 membered ring having one or more heteroatoms; R ³ is phenyl optionally substituted by optionally substituted alkyl, alkenyl, N, N-dialkylamino, alkyl or halogen; When P is 0, both R ² and R ⁴ are not hydrogen.