HU212628B - Herbicidal compositions comprising 3-(substituted phenyl)-pyrazole derivatives or their salts, process for their use and preparation of a part of the active ingredients - Google Patents

Abstract

According to the process of the present invention, compounds of formulas (1-2) and (1-4) are prepared, wherein X, R1, R2, R3, B and D are as defined above for R6-1 and R8. 1 has the same meaning as R6 and R8 with the exception of hydrogen atoms HU 212 628 BA description: 80 pages (including 24 sheets)

Description

In the general formula (I) for the 3- (substituted phenyl) pyrazole derivatives, X is halogen,

R ¹ is optionally halogenated alkyl, R ² is methylsulfinyl or -AR ⁵ where A is -O- or -S- and R ⁵ is optionally halogenated alkyl,

R ³ is hydrogen or halogen,

R ⁴ is formyl, nitro, -CO-BR ⁶ , or -DR ⁸ ; where

B is -O-, -S-, or -NR ⁷ -, wherein

R ^{7 is} alkyl, R ⁶ is hydrogen, alkali metal, alkyl, alkenyl, alkynyl, alkoxycarbonylalkyl;

t IA) a kilo or ammonium group; D is -O-, S (O) _n -, -NR ⁹ - wherein n is 0, 1 or 2, R ^{9 is} hydrogen, alkyl, alkenyl or alkynyl; R ⁸ is hydrogen, cycloalkyl, [CH (R ¹⁰ )] _m -C (O) ER ¹² or optionally substituted alkyl, alkenyl or alkynyl.

The process of the present invention provides compounds of the formulas (1-2) and (1-4), wherein X, R ¹ , R ² , R ³ , B and D are the same as R ⁶ above ^{. 1} and R ^{8 1} have the same meaning as for R ⁶ and R ⁸ above, except hydrogen.

HU 212 628 B

Description: 80 pages (including 24 pages)

HU 212 628 Β

BACKGROUND OF THE INVENTION This invention relates to herbicidal compositions containing 3- (substituted phenylpyrazole) derivatives or their acid addition salts as active ingredients, to processes for their use and to the preparation of some of the active compounds. The 3 (substituted phenyl) pyrazole derivatives of formula (I)

X is halogen;

R ¹ is optionally halogenated C 1-4 alkyl;

R ² is methylsulfinyl or -AR ⁵ where A is -O- or -S-;

R ⁵ is optionally halogenated C 1-4 alkyl;

R 'is hydrogen or halogen;

R ⁴ is formyl or nitro, -CBR ⁶ or II p

-DR ⁸ . where

B is -O-. -S- or -NR ⁷ . wherein R ⁷ is C 1-4 alkyl;

R ⁶ is hydrogen. C 1-4 alkyl. C 3-6 alkenyl. C 3-6 alkynyl. (C 1 -C 4 alkoxy) carbomyl (C 1 -C 4 alkyl), and when B is -O-, R ^h may also be an alkali metal or quaternary ammonium group.

D is -O-. -S (O) 'or -NR ⁹ -. where n is 0. 1 or 2 and

R ⁹ is hydrogen. C 1-4 alkyl. C 3-6 alkenyl or C 36 alkynyl;

R ⁸ is hydrogen, optionally halogenated

C 1-8 alkyl. C 3-6 alkenyl. or C 3-6 alkynyl:

C 3-6 cycloalkyl. cyano (C 1 -C 4 alkyl) -. (C 1-4 alkyl) - (C 1-4 alkyl) -. (C 1-4 alkyl) thio (C 1-4 alkyl) -. di- (C 4 -C 4 alkyl) isosinyl (C 1 -C 4) alkyl or tri- (C 1 -C 4) alkylsilyl (C 1 -C 4) alkyl, the phenyl moiety optionally substituted by a halogen atom; (C1-C4 alkyl) or phenoxy (C1-C4 alkyl) Z-CHVC-E1R / O

R ¹² wherein m is 0, 1.2 or 3,

R ^l0 is a hydrogen atom or ham is 1, then R can also ^IU C1-4alkyl also

E is -O-, -S-, or -N-, wherein I

R

R ¹¹ is hydrogen, C 1-4 alkyl or C 3-6 alkenyl, or

And R ¹² together with the nitrogen to which they are attached form piperidino or morpholino.

R ¹² is hydrogen, C 1 -C 12 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, halogenated C 1 -C 4 alkyl, cyano (C 1 -C 4 alkyl) - , (C 1-4 alkoxy) (C 1-4 alkyl), (C 1-4 alkoxy) (C 1-4 alkoxy) -! C 1-4 alkyl, C 1-4 alkylthio (C 1-4 alkyl), di (C 1-4 alkoxy) phosphinyl (C 1-4 alkyl), or tri (1-4) alkyl. C 1 -C 4 alkyl) silyl-C 1 -C 4 alkyl, phenyl optionally substituted with one or two halogen atoms, phenyl-C 1 -C 4 alkyl optionally substituted on one or two halogen atoms and when E represents 0, then R ¹² may also represent an alkali metal atom or quaternary ammonium groups, or in the case where -E- is a group of formula N. R ¹² mean

I

R

Also C 1-4 alkylsulfonyl; when D is -S-. R ⁸ may also be 2- (ethoxycaronyl) -2-propyl.

if D is -SO ₂ - then R ⁸ can still be amino,

C 1-4 alkylamino. also di-C 1-4 alkylamino or C 1-4 alkylsulfonylamino, or

R ⁹

I when D is -N-. then R ⁸ may also be C 1-4 alkylsulfonyl. C 1-4 alkylaminosulfonyl. di (C 1-4 alkyl) aminosulfonyl.

C 3-6 -alkynyl-amino-sulfonyl or C 1-4 -alkyl-C 3-6 -alkynyl-amino-sulfonyl.

In-depth studies have been conducted to develop new herbicides, resulting in the discovery of 3- (substituted phenylpyrazole) derivatives of the formula (I) and their salts, which are not yet known in the literature and have excellent herbicidal activity at low doses. The present invention is based on these findings.

It is analogous to the compounds of the invention. herbicidal compounds are disclosed in Japanese Patent Laid-Open Publication Nos. 50117 936, 52-91 861, 54-70 270 and 55-9062 and in other literature. However, the 3- (substituted phenylpyrazole) derivatives and their salts prepared according to the invention have never been known to exhibit excellent herbicidal activity even at lower doses than the known compounds.

Among the 3- (substituted phenyl) pyrazole derivatives of the formula (I) and their salts, R ¹ is a C 1-4 alkyl group. among them, the methyl group is preferred.

The substituent R 'may be hydrogen or halogen. of these halogen atoms are preferred, especially chlorine.

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The substituent R ⁴ may be formyl, nitro, -CO-BR ⁶ where B and R ⁶ are as defined above, and -DR ⁸ where D and R ⁸ are as defined above. Preferred examples of the -CO-BR ⁶ group include C 1-4 alkoxycarbonyl groups and C 1-4 alkoxycarbonyl (C 1-4 alkoxy) carbonyl groups which are methoxy, ethoxy, propoxy, - butoxy, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl methyl group, methoxycarbonyl group, ethoxycarbonyl group or propoxycarbonyl ethoxycarbonylethyl groups of -DR ⁸ is preferred. represented by alkoxy and alkylthio groups having a methyl, ethyl, propyl or butyl moiety; alkenyloxy groups containing a propenyl, butenyl or pentenyl moiety; those alkynyloxy groups containing a propynyl, butynyl or pentynyl moiety, and alkenylamino groups containing a propenyl, butenyl or pentenyl moiety.

X is halogen, which may be fluorine, bromine, chlorine or iodine, preferably chlorine or fluorine.

However, in the process of the invention, the meaning of R ¹ , R ² , R ¹ , R ⁴ or X is not limited to the above examples; 3- (substituted phenyl) pyrazole derivatives and their salts also exhibit significant herbicidal activity which contains substituents other than those given above, provided that the substituents are as defined above.

Salts of the 3- (substituted phenyl) pyrazole derivatives of formula (I) are salts with mineral acids such as sulfuric acid or hydrochloric acid, and salts with organic acids such as p-toluenesulfonic acid.

The 3- (substituted phenyl) pyrazole derivatives of formula (I) may be formed by reaction with a suitable mineral acid or an organic acid.

The preparation of the 3- (substituted phenyl) pyrazole derivatives of the formula (I) and their salts is illustrated in Schemes 1, 2 and 3.

In the formulas in Scheme ¹ , R ¹ , R ² , R ³ , R ⁶ , X and B are as defined above, Y ¹ and Z are halogen, p and q are each 1 or 2, with the proviso that p and q are 3, As described in Scheme 1, the 3- (substituted phenyl) pyrazole derivatives (1-4) can be prepared by reacting a pyrazole derivative (II-2) in an inert solvent with a halogenating agent (II-3). A pyrazole derivative of the formula (II) is subjected to a Sommelet reaction in an inert solvent with hexamethylenetetramine followed by hydrolysis with an acid to give the corresponding 3- (substituted phenyl) pyrazole derivative (1-5) which is oxidized in an inert solvent. The compound of formula (1-6) is prepared and converted to the acid halide of formula (Π-4) by halogenation in an inert solvent. For the preparation of 3- (substituted phenyl) pyrazole derivatives of general formula 1-4, a pyrazole compound of general formula 1-3 wherein R ¹ , R ² , R ³ , R ^6-1 , X and B are as defined above. Y is a halogen atom or a hydroxy group of formula 1-6 and a compound of formula II-4 wherein Y ¹ is halogen with a halide of formula Π-III. or reacting a compound of formula II-1 in an inert solvent in the presence or absence of a base to give a compound of formula 1-4-1 or 1-4.

(1) Preparation of compounds of formula (II-3) from compounds of formula (II-2)

The reaction may be carried out using any inert solvent which does not substantially interfere with the reaction. Examples of such solvents include halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; aromatic hydrocarbons such as benzene, toluene or xylene; nitriles such as acetonitrile or benzonitrile; linear ethers such as methylcellulose and diethyl ether; cyclic ethers such as dioxane and tetrahydrofuran; sulforan; dimethylsulfone and dimethylsulfoxide. These solvents may be used alone or in combinations thereof.

Suitable halogenating agents for the above reaction are, for example, N-bromosuccinimide (NBS), N-chlorosuccinimide (NCS), bromine, chlorine, tert-butyl hypohalide and trichloromethanesulfonyl halide. When NBS or NCS is used as the halogenating agent, preferably an organic peroxide such as benzoyl peroxide or light is used as the catalyst or as an accelerator.

The halogenating agent is used in a molar amount or more relative to the pyrazole derivative of formula II-2.

The reaction is carried out at a temperature between 0 ° C and the boiling point of the inert solvent used.

The reaction takes about a few minutes to 48 hours to complete.

After completion of the reaction, the 3- (substituted phenyl) pyrazole derivative of formula (II-3) can be recovered from the reaction mixture by conventional means, such as solvent extraction, and, if desired, purified by various purification methods, such as recrystallization or column chromatography.

(2) Preparation of compounds of formula (I-5) from compounds of formula (II-3)

The first step of the reaction is a Sommelet reaction, the second step is acid hydrolysis. Suitable inert solvents for carrying out the first reaction step include organic acids such as glacial acetic acid, mineral acids such as hydrochloric or sulfuric acid, water, and mixtures of these solvents.

The hexamethylenetetramine is used in an equimolar amount with the pyrazole derivative (II-3). An excess of hexamethylene tetramine can also be used.

The reaction is carried out at a temperature between 10 'C and the boiling point of the inert solvent used, preferably 30180' C.

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After completion of the reaction, the solution containing the reaction product of the first step is subjected to acid hydrolysis in the second step.

The reaction product of the acid hydrolysis is subjected to the reaction product alone, or a large excess of a mineral acid such as hydrochloric acid or sulfuric acid is added as the situation requires, the latter being preferred.

The reaction is carried out at a temperature in the range of 80 to 180 ° C, and the reaction takes a few minutes to 48 hours to complete.

After completion of the reaction, the 3- (substituted phenyl) pyrazole derivatives (I-5) can be recovered from the reaction mixture by conventional means such as solvent extraction and, if desired, purification by purification methods such as recrystallization or column chromatography.

(3) Preparation of compounds of formula (1-6) from compounds of formula (1-5)

Inert solvents useful in this reaction include aromatic hydrocarbons such as benzene, toluene and xylene, pyridine and its derivatives, and water. These solvents may be used alone or in combination.

The oxidizing agent used is, for example, potassium permanganate or potassium dichromate in an amount of 1-5 moles, preferably 1-2 moles, per mole of the 3- (substituted phenyl) pyrazole derivative (1-5).

The reaction is carried out at a temperature between 0 ° C and the boiling point of the inert solvent used, preferably 30180 ° C. The reaction takes a few minutes to 48 hours to complete.

After completion of the reaction, the resulting 3- (substituted phenyl) pyrazole derivatives (I-6) can be recovered from the reaction mixture by known methods, such as solvent extraction, and, if desired, purification procedures such as recrystallization or column chromatography.

(4) Preparation of compounds of formula (11-4) from compounds of formula (1-6) In this reaction for the preparation of the acid halide, for example, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride may be used; aromatic hydrocarbons such as benzene, toluene and xylene; linear ethers such as methylcellulose, diethyl ether and diisopropyl ether; and cyclic ethers such as dioxane or tetrahydrofuran.

Suitable halogenating agents include, for example, thionyl chloride, phosphorus pentachloride and phosphorus trichloride.

The halogenating agent may be used in an amount equimolar to or greater than the 3- (substituted phenyl) pyrazole derivative (1-6).

For example, catalytic amounts of triethylamine, pyridine, dimethylformamide or the like can be used to accelerate the reaction.

The reaction is carried out at room temperature to the reflux temperature of the solvent used. The reaction time ranges from a few minutes to 48 hours, depending on the amount of reagents used and the reaction temperature.

After completion of the reaction, the excess halogenating agent and solvent are removed by evaporation from the reaction mixture to isolate the desired compound, which can be carried on to the next reaction after purification, optionally after recrystallization, distillation or other purification.

(5) Preparation of compounds of formula (1-4) from compounds of formula (1-6) or (ΙΙ-4)

The above conversion is an esterification or amide formation reaction. The esterification may be carried out using an excess of the alcohol corresponding to the desired ester in the presence of a mineral acid such as concentrated sulfuric acid, the alcohol being both a reagent and a solvent. The 3- (substituted phenyl) pyrazole derivatives (I-6) may also be present in the form of their alkali metal salts in the esterification reaction.

The esterification or amide formation reaction is carried out in the presence of an inert solvent and a halogen scavenger. Suitable inert solvents for this reaction are those solvents mentioned as suitable in the acid-halide formation reaction.

The alcohol or amine or halide of formula (II-1-1) is used in equimolar amounts or in excess. Inorganic or organic bases may be used as halogen deprotecting agents in the reaction. Inorganic bases include, for example, alkali metal salts such as sodium hydroxide or potassium hydroxide, organic bases include tertiary amines such as triethylamine or 4- (dimethylamino) pyridine, and 1,8-diazabicyclo [5. , 4,0] -7-undecene (DBU).

The reaction is carried out at a temperature between 0 'C and the boiling point of the solvent, preferably between 0 and 150' C. The reaction time ranges from a few minutes to 48 hours, depending, inter alia, on the amount of reagents used and the reaction temperature.

After completion of the reaction, the 3- (substituted phenyl) pyrazole derivatives (I-4) can be recovered from the reaction mixture by conventional techniques, such as solvent extraction, and, if desired, purification by purification methods such as recrystallization or column chromatography.

In Schemes A and B of Scheme ² , R ¹ , R ² , R ³ , R ¹ , D, X and Z are as defined above.

Reaction Scheme 2, Method A: Reaction of a pyrazole derivative of formula II-5 with a nitrating agent in an inert solvent affords a 3- (substituted phenyl) pyrazole derivative of the general formula 1-7, which is reduced in an inert solvent. 3- (substituted phenyl) pyrazole of formula 8) 4

It is then diazotized in an inert solvent and decomposed to give the 3- (substituted phenyl) pyrazole derivatives of formula (1-9).

On the other hand, according to Scheme B, Method B, a pyrazole derivative of the formula (Π-5) is converted into a pyrazole derivative of the general formula II-6 in an inert solvent to give the corresponding pyrazole derivative of the general formula I-10. - (substituted phenyl) pyrazole.

The 3- (substituted phenyl) pyrazole derivatives (1-8), (1-9) or (ΙΙΟ) prepared above may be prepared by reacting (1-2) with a halide (II) in the presence of a base in the presence of a base. 3- (substituted phenyl) pyrazole derivatives of the general formula (I).

When the compound (1-2) a 3- (substituted phenyl) pyrazole derivative of ^R8 is ^one substituent of - [CH · R ^10I m-COE-R ¹² - wherein R ^10, R ¹² and E are as defined above and m 1, this 3- (substituted phenyl) pyrazole derivative can be prepared by converting an acid containing - [CHR ^{, 0} ] _m CO-EH to an acid halide as described in Scheme 1, followed by esterification of the acid halide, thiolesterification or amide formation reaction.

(1) Preparation of compounds of formula (I-7) from compounds of formula (I-5)

Nitrating agents useful in the reaction include acetyl nitrate obtained by mixing concentrated nitric acid, a mixture of fuming nitric acid with concentrated sulfuric acid, and concentrated nitric acid with acetic anhydride.

The solvent used in the process may be mineral acids such as sulfuric acid or hydrochloric acid. Since this is an equimolar reaction, the use of an equimolar amount of nitrating agent is sufficient, although excess nitrating agent may be used.

The reaction is carried out at a temperature of -10 to 140 ° C, preferably -10 to 20 ° C. The reaction time ranges from a few minutes to 48 hours, depending, inter alia, on the amount of reagents used and the reaction temperature.

After completion of the reaction, the desired 3- (substituted phenyl) pyrazole derivative (1-7) is swallowed from the reaction mixture by pouring the reaction mixture into ice water and filtering off the precipitated crystals or extracting the reaction mixture with a solvent or other solvent. a separation process is used to isolate the desired product and, if desired, the product is purified, for example by recrystallization.

(2) Preparation of compounds of formula (I-8) from compounds of formula (I-7)

The reaction may be carried out using any inert solvent which does not substantially interfere with the reaction. Examples of such inert solvents are alcohols such as methanol, ethanol and propanol; linear ethers such as diethyl ether and methylcellosolve; cyclic ethers such as dioxane and tetrahydrofuran; organic acids such as acetic acid; and mineral acids such as hydrochloric acid; and water.

Zinc, iron, tin, and tin chloride can be used as the reducing agent in the acidic medium. Zinc powder may be used in a neutral or alkaline medium. Catalytic hydrogenation may also be carried out at atmospheric or elevated pressure in the presence of a suitable catalyst, such as Raneynikkel, palladium on carbon, palladium oxide, platinum, platinum carbon black, platinum sulfide carbonate and rhodium aluminum oxide.

The reducing agents used in the acidic medium may be used in equimolar amounts, although generally in excess. The amount of Raney nickel or similar catalyst used in the catalytic hydrogenation, when used, is from 5 to 20% by weight of the 3- (substituted phenyl) pyrazole derivative of the general formula (1-7), the noble metal catalyst such as platinum or palladium. if used, from 0.02 to 5% by weight, also with respect to the above compound.

The reaction is usually carried out at a temperature between 0 and 150 'C, preferably between 10 and 100' C. The reaction time ranges from a few minutes to 48 hours, depending, inter alia, on the amount of reagents used and the reaction temperature.

After completion of the reaction, the desired 3- (substituted phenyl) pyrazole derivative (1-8) can be obtained as follows: If the reaction is carried out in an acidic medium, the reaction mixture is poured into ice water, made basic and the desired product for example, solvent extraction. In the case of catalytic hydrogenation, the catalyst is filtered off from the reaction mixture and the desired product is recovered by evaporation of the filtrate. If desired, the product may be further purified, for example, by recrystallization or column chromatography.

(3) Preparation of Compounds of Formula (I-9) from Compounds of Formula (I-8) This reaction consists of two steps, the diazotization step and the resolution. A mineral acid such as sulfuric acid or hydrochloric acid may be used as the inert solvent for the diazotization step. For diazotization, sodium nitrite in powder form or in aqueous solution is used in the appropriate concentration, equimolar amount or excess.

The reaction is carried out at a temperature of -5 to 5 ° C.

The resulting diazonium salt is subjected to the reaction without separation.

The inert solvent used in the decomposition step is 30-70% sulfuric acid.

The decomposition is carried out in the presence of a catalyst at a temperature between 10 and 180 ° C. If the diazonium salt in solution is added dropwise to aqueous sulfuric acid, the reaction is carried out at 50-180 ° C. When copper (I) oxide is used as the catalyst, the reaction is carried out at a temperature of 10-50 ° C.

Catalysts include copper nitrate and

EN 212 628 Β copper (I) oxide. Copper nitrate is added to the reaction mixture, followed by copper (I) oxide in appropriate amounts.

Copper nitrate is used in an amount of from 1 to 20 moles per mole of the diazonium salt, preferably from 30 to 60 moles, and copper (I) oxide is also used in a catalytic amount from 1 mole to 1 mole per mole of the diazonium salt.

The total duration of the diazotization and cleavage reactions ranges from a few minutes to 48 hours, depending on the amount of reagents used and the reaction temperature.

After completion of the reaction, the 3- (substituted phenyl) pyrazole derivative (1-9) is obtained by pouring the reaction mixture into ice water, isolating the desired product from the mixture, for example by solvent extraction, and optionally for example, recrystallization or column chromatography.

(4) Preparation of compounds of formula (11-6) from compounds of formula (11-5) In this reaction, any solvent which does not significantly inhibit the reaction may be used. For example, halogenated hydrocarbons such as methylene chloride, chloroform or carbon tetrachloride, aliphatic nitriles such as acetonitrile; linear ethers such as methylcellulose; cyclic ethers such as dioxane or tetrahydrofuran; and mineral acids such as concentrated sulfuric acid.

Chlorosulfonyl acid or the like may be used in the chlorosulfonyl substitution reaction. Another possible method is to sulfonate the starting compound of formula (Π-5), for example by reaction with fuming sulfuric acid, and then convert the resulting sulfonic acid to an alkali metal salt and then chlorinate with the phosphorus pentachloride to the desired target compound. In another process, the starting compound is reacted with fuming sulfuric acid and then treated with carbon tetrachloride to give the desired product.

Chlorosulfonic acid is used in equimolar amounts or in excess, preferably in excess.

Fuming sulfuric acid is also used in equimolar amounts or in excess, preferably in excess.

Carbon tetrachloride is generally used in equimolar amounts or in excess.

The reaction temperature is between 0 and 180 'C, preferably between 15 and 100' C. The reaction time ranges from a few minutes to 48 hours, depending on the amount of reagents used and the reaction temperature.

After completion of the reaction, the 3- (substituted phenyl) pyrazole derivatives II-6 are recovered from the reaction mixture by pouring it into water, isolating the desired product from the reaction mixture by solvent extraction and, if desired, recrystallizing the isolated product. , column chromatography or other known purification methods.

(5) Preparation of compounds of formula (1-10) from compounds of formula (11-6)

This reduction step is carried out in an inert solvent such as glacial acetic acid. Reducing agents used in the reaction include, for example, zinc, tin, tin chloride in amounts of 1 mol or more, preferably 5 mol or more, per mole of the compound (II-6).

The reaction temperature is between 0 and 180 'C, preferably between 15 and 120' C. The reaction time ranges from a few minutes to 48 hours, depending on the amount of reagents used and the reaction temperature.

After completion of the reaction, the 3- (substituted phenyl) pyrazole derivatives (I-10) are obtained by pouring the reaction mixture into water, isolating the desired compound from the mixture by solvent extraction and, if desired, recrystallizing the product from the mixture by column chromatography. or other known purification procedure.

(6) Preparation of compounds of formula (1-2) from compounds of formula (1-9) or (1-10)

The reaction is carried out as described in Reaction Scheme 1, Reaction 5, to give the 3- (substituted phenyl) pyrazole derivatives (1-2).

Preparation of salts of 3- (substituted phenyl) pyrazole derivatives of formula (I) The above salts are formed with acids such as mineral acids including hydrochloric and sulfuric acids and organic acids such as p-toluenesulfonic acid. The salts are prepared by reacting the 3- (substituted phenyl) pyrazole derivatives of formula (I) obtained by the above processes with the above acids.

Representative examples of the 3- (substituted phenyl) pyrazole derivatives of the formula (I) and their salts and their physical constants are set forth in Table I below.

Table 1

Number of compound R ¹ R ² R ³ R ⁴ X Physical characteristics First -ch _{3 CH3} s- H MONTH- cl She. p. 157.1 'C Second -ch _{3 CH3} s- cl MONTH- cl She. p. 163.2 'C Third -ch _{3 CH3} s- cl iC ₃ H ₇ O- cl nD 1.5882 (26.5'C) 4th -ch _{3 CH3} s- cl ch ₂ = chch ₂ o- cl nD 1.6131 (25.3'C)

HU 212 628 Β

Number of compound R ¹ R ² R ³ R ⁴ X Physical characteristics 5th -ch ₃ CH ₃ S- cl CH = CCH ₂ O- cl 0. p. 71.5-72.5 ° C 6th -ch _{3 CH3} s- cl c ₂ h ₅ och ₂ ch ₂ o- cl nD 1.5944 (25.8 'C) 7th -ch _{3 CH3} s- cl A group of formula (1) cl nD 1.6075 (25.6 'C) 8th -ch _{3 CH3} s- cl A group of formula (2) cl nD 1.5988 (25.9 'C) 9th -ch _{3 CH3} s- cl HOOC (CH,) O cl 0. p. 191-194'C 10th -ch _{3 CH3} s- cl CH ₃ OOCCH (CH ₃ ) O- cl 0. p. 90-93 'C 11th -ch _{3 CH3} s- cl C ₂ H ₅ OOCCH (CH ₃ ) O- cl nD 1.5763 (28.8 'C) 12th -ch ₃ CH, S cl -C ₃ H ₇ OOCCH (CH ₃ ) O- cl 0. p. 87-90 'C 13th -ch _{3 CH3} s- cl CH ₂ = CHCH ₂ OOCCH (CH ₃ ) O- cl nD 1.5802 (23.4'C) 14th -ch _{3 CH3} s- cl CH = CCH ₂ OOCCH (CH,) O- cl nD 1.5858 (23.7 'C) 15th -ch _{3 CH3} s- cl HS cl nD 1.6303 (24.3'C) 16th -ch _{3 CH3} s- cl 1-C3H7S- cl 0. p. 91.8 'C 17th -ch _{3 CH3} s- cl CHF ₂ S- cl 0. p. 87.2 'C 18th -ch _{3 CH3} s- cl chf ₂ cf ₂ s- cl nD 1.5820 (24.7 'C) 19th -ch ₃ ch, s- cl ch ₂ = chch ₂ s- cl viscous material 20th -ch ₃ CH, S cl _CH2 = C (C1) _CH2 S- cl nD 1.6370 (25.1'C) 21st CH, CH, S cl ch = cch ₂ s- cl 0. p. 94.5 'C 22nd CH, CH, S cl A group of formula (3) cl nD 1.6528 (24.9 'C) 23rd CH, _CH3 s- cl C ₂ H ₅ OOCCH ₂ S- cl mp 112.1 'C 24th -ch _{3 CH3} s- cl c ₂ h ₅ oocch ₂ ch ₂ s- cl 0. p. 74.8 'C 25th CH, _CH3 s- cl HO ₂ CCH (CH ₃ ) S- cl 0. p. 180.0 'C 26th CH, _CH3 s- cl I-C, _H7 N®®H, CX3CCH _(CH3) S cl nD 1.5878 (22.1'C) 27th CH, _CH3 s- cl (CH ₃ ) ₂ N ^e ®H ₂ OOCCH (CH 3) S- cl 0. p. 176.1 'C 28th -ch ₃ ch, s- cl CH ₃ OOCCH (CH,) S- cl nD 1.6131 (24.9 'C) 29th CH, _CH3 s- cl C ₂ H ₅ OOCCH (CH ₃ ) S- cl nD 1.6010 (25.0 'C) 30th CH, CH, S cl -C ₃ H ₇ OOCCH (CH ₃ ) S- cl nD 1.5936 (25.0 'C) 31st CH, CH, S cl C1 _{(CH2) 3} OOCCH _(CH3) S cl nD 1.6025 (25.2 'C) 32nd CH, CH, S cl CH ₂ = CHCH ₂ OOCCH (CH ₃ ) S- cl nD 1.6030 (25.0 'C) 33rd CH, CH, S cl CH = CCH ₂ OOCCH (CH ₃ ) S- cl nD 1.5954 (25.0 'C) 34th CH, CH, S cl C ₂ H ₅ CH (CH ₃ ) CH ₂ OOCCH- (CH ₃ ) S- cl nD 1.5834 (25.0 'C) 35th -ch ₃ CH ₃ S- cl (C ₂ H _{5) 2} NCOCH (CH ₂ ) S - cl nD 1.5983 (26.4'C) 36th -ch ₃ CH, S cl H ₂ NSO ₂ - cl 0. p. 203.5 ° C 37th -ch ₃ CH, S cl ch ₃ nhso ₂ - cl 0. p. 79.1 'C 38th CH, CH ₃ S- cl (CH ₃ ) ₂ NSO ₂ - cl 0. p. 135.7 'C 39th -ch _{3 CH3} s- cl nC ₃ H ₇ NHSO ₂ - cl 0. p. 102-105 'C 40th CH, _CH3 s- cl CH ₃ SO ₂ NHSO ₂ - cl 0. p. 184-187 41st CH, _CH3 s- cl h ₂ n- cl nD 1.6403 (25.0 'C) 42nd -ch _{3 CH3} s- cl α ^θ Η ₃ Ν ^φ - cl 0. p. 174.5 'C 43rd -ch _{3 CH3} s- cl CH ₃ NH- cl nD 1.6368 (21.7 'C) 44th CH, _CH3 s- cl (CH ₃ ) ₂ N- cl nD 1.6241 (22.1'C) 45th CH, _CH3 s- cl ch ₂ = chch ₂ nh- cl nD 1.6238 (22.2'C) 46th -CH _{3 CH3} s- cl (CH ₂ = CHCH ₂ ) ₂ N- cl nD 1.6088 (21.6 'C) 47th -ch _{3 CH3} s- cl ch = cch ₂ nh- cl 0. p. 140.8 'C 48th CH, _CH3 s- cl ch ₃ oocnh- cl nD 1.6301 (22.2 'C) 49th CH, CH, S cl HOOC- cl 0. p. 213-214'C

HU 212 628 Β

Number of compound R ¹ R ² R ³ R ⁴ X Physical characteristics 50th CH, _CH3 s- cl C ₂ H ₅ OOC- cl nD 1.6029 (20.1'C) 51st -ch _{3 CH3} s- cl ch ₃ so ₂ nh- cl nD 1.6002 (25.9 'C) 52nd -ch _{3 CH3} s- cl ch ₃ nhso ₂ nh- cl ο. p. 134.5 'C 53rd -ch _{3 CH3} s- cl CH ₃ NHSO ₂ N (CH ₃ ) - cl nD 1.5763 (26.4 'C) 54th CH, _CH3 s- cl (CH ₃ ) ₂ NSO ₂ N (CH ₃ ) - cl nD 1.5839 (26.0'C) 55th -ch ₃ CH, S cl -C, H ₇ NHSO ₂ NH- cl She. p. 148.6 'C 56th -ch _{3 CH3} s- cl CHsCCH ₂ N (CH ₃ ) SO ₂ N - (CH = CCH ₂ ) - cl She. p. 111.5 'C 57th CH, _CH3 s- cl CH ₃ OCH ₂ CH ₂ OOCNH- cl She. p. 112-115 58th -uh, _CH3 s- cl BrCH ₂ CH ₂ OOCNH- cl She. p. 119.5'C 59th -ch _{3 CH3} s- cl NCCH ₂ CH ₂ OOCNH- cl nD 1.5938 (24.7 'C) 60th CH, _CH3 s- cl CH ₂ = C (CH ₃ ) CH ₂ OOCNH- cl She. p. 125.8 'C 61st -ch _{3 CH3} s- cl A group of formula (4) cl She. p. 103-105 C 62nd CH, _CH3 s- cl CH ₂ = CHCH ₂ OOCCH ₂ NH- cl She. p. 112.0 'C 63rd CH, _CH3 s- cl CHsCCH ₂ OOCCH ₂ NH- cl She. p. 127.0 'C 64th CH, CH, S cl C ₂ H ₁₀ OCHCH (CH ₃ ) NH- cl viscous material 66th CH, _CH3 s- cl hoocch ₂ nh- cl mp 207.1 'C 67th CH, _CH3 s- cl ch, oocch ₃ nh- cl She. p. 132,4'C 68th CH, CH, S cl HOOCCH (CH ₃ ) NH- cl She. p. 218.7 'C 69th CH, CH ₃ S- cl CH ₃ OOCCH (CH ₃ ) NH- cl She. p. 144.2 'C 70th CH, CH, SO cl She z cl She. p. 168.1 'C 71st CH, CH, SO cl CH ₃ SO ₂ NH- cl She. p. 168.0 'C 72nd -ch ₃ ch ₃ so- cl ch ₃ nhso ₂ nh- cl She. p. 146.3 'C 73rd -ch ₃ ch ₃ so- cl -C, H ₇ NHSO ₂ NH- cl She. p. 184.8 'C 74th CH, ch ₃ so- cl CH, NHSO ₂ N (CHCCH ₂ ) - cl She. p. 192.5 'C 75th CHF, _CH3 s- cl -nh ₂ cl She. p. 87.4 'C 76th -chf ₂ CH, S cl ch, nhso ₂ nh- cl She. p. 133.3 'C 77th -chf ₂ CH, S cl CH, NHSO ₂ N (CH = CCH ₂ ) - cl nD 1.5625 (25.6'C) 78th -chf ₂ CH, S cl CH, N (CHsCCH ₂₎ SO ₂ N 1 ₍₂ 1 CHhCCH cl nD 1.5675 (25.6'C) 79th -chf ₂ CH ₃ SO- cl -nh ₂ cl mp 187.1 'C 80th -chf ₂ ch ₃ so- cl -No ₂ cl She. p. 165.1 'C 81st -ch ₃ chf ₂ o- cl ch ₃ o- cl nD 1.5567 (23.4 'C) 82nd CH, chf ₂ o- cl c ₂ h ₅ o- cl nD 1.5434 (23.5'C) 83rd -ch ₃ chf ₂ o- cl nC ₃ H ₇ O cl nD 1.5410 (25.1'C) 84th CH, chf ₂ o- cl iC ₃ H ₇ O- cl nD 1.5422 (23.5'C) 85th CH, chf ₂ o- cl A group of formula (5) cl nD 1.5482 (25.4 'C) 86th CH, chf ₂ o- cl CH ₂ = CHCH ₂ O- cl nD 1.5536 (28.4'C) 87th -ch ₃ chf ₂ o- cl CH = CCH ₂ O- cl She. p. 84.0 'C 88th -ch ₃ chf ₂ o- cl c ₂ h ₅ och ₂ ch ₂ o- cl She. p. 79.5'C 89th CH, chf ₂ o- cl ncch ₂ o- cl She. p. 98.9 'C 90th CH, chf ₂ o- cl ch ₃ ooco- cl nD 1.5387 (23.2'C) 91st -CH ₃ chf ₂ o- cl ch ₃ oocch ₂ o- cl She. p. 119.8 'C) 92nd CH, chf ₂ o- cl nC, H ₇ OOCCH ₂ O- cl She. p. 89.7 'C 93rd CH, chf ₂ o- cl iC, H ₇ OOCCH ₂ O- cl She. p. 105.0 'C

HU 212 628 Β

Number of compound R ' R ² R ^? R ⁴ X Physical characteristics 94th CH, CHF ₂ O- cl nC ₄ H ₉ OOCCH ₂ O- cl She. p. 75.3 'C 95th -CH ₃ chf ₂ o- cl CH, CH ₂ CH (CH,) OOCCH ₂ O-! cl She. p. 107.8 'C 96th CH, chf ₂ o- cl nC ₆ H |, OOCCH ₂ O- cl nD 1.5244 (23.0'C) 97th CH, chf ₂ o- cl CH ₂ = CHCH ₂ OOCCH ₂ O- cl She. p. 84.7 'C 98th CH, chf ₂ o- cl CH = CCH ₂ OOCCH ₂ O- cl mp 119.6 'C 99th CH, chf ₂ o- cl A group of formula (6) cl She. p. 91.8 'C 100th CH, chf ₂ o- cl C ₂ H ₅ O (CH ₂ ) ₂ OOCCH ₂ O- cl nD 1.5261 (22.9 'C) One hundred and first CH, chf ₂ o- cl C, H _s O (CH, bOiCH, b-OOCCHsO- cl nD 1.5287 (23.0'C) 102nd -CH; CHF-, Ο- Cl (7) cl She. p. 139.1 'C 103. -CH, chf ₂ o- cl HOOC (CH,) O cl She. p. 158.7 'C 104. ΐ -CH, chf ₂ o- cl iC, H ₇ N®H, OO0CCH (CH,) O- cl viscous material 105. -CH, CHFnO- cl C ₂ H ₅ OOCCHiCH,) O- cl nD 1.5238 (25.7 'C) 106.! CH, CHF ₂ O-Cl nC ₄ H ₉ OOCCH (CH,) O- cl nD 1.5253 (18.5'C) 107. -CH, CHF ₂ O-Cl CH ₂ = CHCH ₂ OOCCH (CH,) O- cl She. p. 84.3 'C 108. -CH, i cm o- cl CH = CCH ₂ OOCCH (CH,) O- Cl! She. p. 109.7 'C 109.! -CH, CHF, O- cl CH NHCOCH (CH,) O Cl nD 1.5365 (35.2'C) 110. ¹ -CH, CHF ₂ O- cl (CH,) ₂ NCOCH (CH,) O- Cl o. p. 148.9 ° C 111. -CH, CHF ₂ O- cl HS Cl nD 1.5828 {21.8 Cl 112. -CH, ¹ CHF, O- Cl CH, S-Cl: o.p. 95.7'C 113. -CH, CHF, O- Cl C-1US Í Cl o. p. 110.5 ° C 114. -CH, CHF, O- Cl i-C; ll · S Cl o. p. 83.8 'C 115. -CH,! CHF, O-! Cl n-CJLS Cl o.p. 155.4 C 116. -CH; 'CHF-, Ο- Cl! CHFnS-Cl! mp 123.4 ° C 117 -CH, CHF ₂ O- Cl CH ₂ = CHCH ₂ S-Cl o p. 52.0-55.0'C 118. -CH, CHF, O-Cl CH ₂ = CHCH ₂ SO-Cl op 91.5 ° C 119 -CH, CHF ₂ O-Cl CH = CClI ₂ S- cl ο. p. 127-129 120. '-CH, CHF, O-: Cl A group of formula (8) cl nD 1.5972 (20.2 'C) 121. -CH, <CHF ₂ O- i Cl (C ₂ H ₅ O) ₂ P (O ₂ CH ₂ S- cl nD 1.5245 (25.3 'C) 122. -CH, {Ί11-40- ι Cl CH OOCS- Cl - nD 1.5656 (17.2 C ^e) 123. -CH, CHF ₂ O- Cl CH, OOCCH ₂ S-Cl She. p. 102.0 'C 124. ¹ -CH, CHF ₂ O-! cl C ₂ H ₅ OOCCH ₂ S- 'Cl She. p. 171.5 'C 125. -CH, CHF2O-Cl CH ₂ = CHCH ₂ OOCCH ₂ S- 'Cl She. p. 102.4 'C 126. -CH, 'CHF ₂ O-; cl HOOCCH (CH,) S-Cl o. p. 188,9'C 127th CH, CHF ₂ O- cl Na®®OOCCH (CH,) S Cl 1 o. p. 205.4 ° C __ ____j___1 128th CH, chf ₂ o- cl iC, H ₇ N®H, O®OCCH (CH,) S- cl viscous material 129th CH, chf ₂ o- cl CH, OOCCH (CH,) S cl nD 1.5654 (19.8 'C) 130th CH, chf ₂ o- cl C ₂ H ₅ OOCCH (CH,) S- cl nD 1.5565 (28.0 'C) 131st CH, chf ₂ o- cl C ₂ H ₅ OOCCH (CH, S (O) - cl nD 1.5582 (20.0 'C) 132. ί -CH, CHF, O- cl C ₂ H _s OOCCH (CH,) SO ₂ - cl She. p. 105.8 'C 133 -CH, CHF ₂ O- cl iC, H ₇ OOCCH (CH,) S- Cl nD 1.5417 (22.1 'C} 134. -CH, CHF ₂ O- cl nC ₄ H ₉ OOCCH (CH,) S- Cl nD 1.5458 (20.2'C) 135th CH, chf ₂ o- cl (CH,), CH (CH, hOOCCH- (CH,) S cl nD 1.5437 (22.2 'C) 136th CH, chf ₂ o- cl CH ₂ = CHCH ₂ OOCCH (CH,) S- cl nD 1.5600 (20.4 'C) 137. -CH, CHF, O- cl CH = CCH ₂ OOCCH (CH,) S- Cl! nD 1.5602 (22.2 'C)

HU 212 628 Β

Number of compound R ¹ R ² R ³ R ⁴ X Physical characteristics 138th CH, CHF ₂ O- cl CH, O (CH ₂ ) ₂ O (CH ₂ ) ₂ OOCCCH (CH,) S- cl nD 1.5431 (23.5'C) 139th CH, chf ₂ o- cl (C ₂ H ₅ O) ₂ P (O) CH ₂ OOCCH (CH,) S- cl nD 1.5386 (21.2 'C) 140th CH, chf ₂ o- cl CH NHCOCH (CH,) S cl She. p. 99.9 ° C 141st CH, chf ₂ o- cl (CH,) ₂ NCOCH (CH,) S- cl nD 1.5672 (19.9 'C) 142 .. CH, chf ₂ o- cl (C ₂ H ₅ ) ₂ NCOCH (CH ₂ ) S - cl nD 1.5532 (19.8 'C) 143rd CH, chf ₂ o- cl iC, H ₇ NHCOCH (CH,) S- cl She. p. 99.9 'C 144th CH, chf ₂ o- cl A group of formula (9) cl She. p. 132.3 'C 145th CH, chf ₂ o- cl Is a group of formula (10) cl nD 1.5457 (19.9 'C) 146th CH, chf ₂ o- cl -No ₂ cl She. p. 99.1 'C 147th CH, chf ₂ o- cl -nh ₂ cl nD 1.5743 (20.8 'C) 148th CH, chf ₂ o- cl ch, so ₂ nh- cl She. p. 142.9 'C 149th CH, chf ₂ o- cl ch, nhso ₂ nh- cl She. p. 133.0 'C 150th -ch ₃ chf ₂ o- cl CH, NH cl nD 1.4952 (25.2 'C) 151st CH, chf ₂ o- cl (CH,) ₂ N- cl nD 1.5561 (24.9 'C) 152nd -ch ₃ chf ₂ o- cl ch ₂ = chch ₂ nh- cl nD 1.5719 (25.3'C) 152nd CH, chf ₂ o- cl CHsCCH ₂ NH- cl She. p. 76.3 'C 154th -ch ₃ chf ₂ o- cl CH OOCNH- cl She. p. 162.3 'C 155th CH, chf ₂ o- cl αθΗ, Ν® cl She. p. 137.1 'C 156th CH, chf ₂ o- cl A group of formula (11) cl She. p. 244.1 'C 157th CH, chf ₂ o- cl ch, oocch ₂ nh- cl She. p. 96.2 'C 158th CH, chf ₂ o- cl HOOC (CH) NH cl She. p. 192.3 'C 159th CH, chf ₂ o- cl Na®O®OCCH (CH) NH cl She. p. 248.0 (decomposition) 160 CH, chf ₂ o- cl iC, H ₇ N®H, O®OCCH (CH,) NH- cl viscous material 161st CH, chf ₂ o- cl C ₂ H ₅ OOCCH (CH,) NH- cl nD 1.5371 (23.4'C) 162nd CH, chf ₂ o- cl CH, NHOCCH (CH) NH cl nD 1.5500 (25.6 'C) 163rd CH, chf ₂ o- cl (CH,) ₂ NOOCCH (CH,) NH- cl nD 1.5510 (25.2 'C) 164th CH, chf ₂ o- cl ch, nhso ₂ - cl nD 1.5461 (17.9 'C) 165th CH, chf ₂ o- cl (CH,) ₂ NSO ₂ - cl She. p. 135,2'C 166th CH, chf ₂ o- cl (C ₂ H ₅ ) NCOS- cl nD 1.5623 (17.7 'C) 167th CH, CHF ₂ s- cl CH, O- cl nD 1.5767 (21.9 'C) 168th CH, CHF ₂ s- cl C ₂ H ₅ O- cl nD 1.5810 (23.8 'C) 169th CH, CHF ₂ s- cl iC, H ₇ O cl nD 1.5536 (24.2 'C) 170th CH, CHF ₂ s- cl η-Ο ^ Ηι, Ο- cl nD 1.5460 (24.2'C) 171st CH, CHF ₂ s- cl CH ₂ = CHCH ₂ O- cl nD 1.5791 (19.8 'C) 172nd CH, CHF ₂ s- cl ch = cch ₂ o- cl nD 1.5720 (20.0'C) 173rd CH, CHF ₂ s- cl Is a group of formula (12) cl nD 1.6226 (24.3'C) 174th CH, CHF ₂ s- cl ch, oocch ₂ o- cl nD 1.5629 (23.1'C) 175th CH, CHF ₂ s- cl C ₂ H ₅ 00 CCH (CH ₂ ) O- cl nD 1.5569 (23.6'C) 176th CH, CHF ₂ s- cl HS cl nD 1.6218 (23.5'C) 177th CH, CHF ₂ s- cl CH, S cl nD 1.6069 (21.7 'C) 178th CH, CHF ₂ s- cl c ₂ h ₅ s- cl nD 1.6047 (24.1'C) 179th CH, CHF ₂ s- cl I- cl nD 1.5893 (23.6'C) 180th CH, CHF ₂ s- cl NC ₅ H 'S- cl nD 1.5881 (25.0 'C) 181st CH, CHF ₂ s- cl CHF ₂ s- cl nD 1.5869 (24.2'C)

HU 212 628 Β

Number of compound R ¹ R ² R ³ R ⁴ X Physical characteristics 182nd -CH ₃ CHF ₂ s- cl ch ₂ = chch ₂ s- cl nD 1.6173 (21.3'C) 183rd -ch ₃ CHF ₂ s- cl CHsCCH ₂ S- cl nD 1.6261 (23.4'C) 184th -ch ₃ CHF ₂ s- cl c ₂ h ₅ and ₂ ch ₂ s- cl nD 1.5816 (22.3'C) 185th CH, CHF ₂ s- the ch ₃ sch ₂ s- cl nD 1.6222 (24.2'C) 186th -ch ₃ CHF ₂ S- cl NCCH ₂ s- cl She. p. 95.9 'C 187th -ch ₃ CHF ₂ S- cl A group of formula (3) cl nD 1.6273 (24.3'C) 188th -ch ₃ CHF ₂ s- cl C ₂ H ₅ OOCS- cl nD 1.5720 (21.8 'C) 189th -ch ₃ CHF ₂ s- cl ch ₃ oocch ₂ s- cl She. p. 112.1 'C 190th -ch ₃ CHF ₂ s- cl c ₂ h ₂ oocch ₂ s- cl She. p. 97.8 'C 181st -ch ₃ CHF ₂ s- cl Is a group of formula (13) cl She. p. 104.4 ° C 192nd -ch ₃ CHF ₂ s- cl ch ₃ nhocch ₂ s- cl She. p. 138,6'C 193rd -ch ₃ CHF ₂ s- cl (CH ₃ ) ₂ NOOCCH ₂ S- cl She. p. 138.3 'C 194th -ch ₃ CHF ₂ s- HOOC (CH,) S cl She. p. 149.5'C 195th -ch ₃ CHF ₂ s- s- Na®O®OCCH (CH,) S cl She. p. 220.8 ° C 196th -ch ₃ CHF ₂ s- cl i-CCH, H ₇ N ^e H, O®OCCH (CH,) S- cl viscous material 197th -ch ₃ CHF ₂ s- cl C ₂ H ₅ OOCCH (CH ₃ ) S- cl nD 1.5788 (23.4 'C) 198th -ch ₃ CHF ₂ s- cl nC ₃ H ₇ OOCCH (CH ₃ ) S- cl nD 1.5643 (19.4 ^- C) 199th -ch ₃ CHF ₂ s- cl iC ₃ H ₇ OOCCH ₂ S- cl nD 1.5695 (19.4'C) 200th -ch ₃ CHF ₂ s- cl (CH ₃ ) ₂ CHCH ₂ OOCCH ₂ S- cl nD 1.5812 (21.2 'C) Two hundred and first -ch ₃ CHF ₂ s- cl CH 2 = CHCH ₂ OOCCH _(CH3) S cl nD 1.5800 (19.4 'C) 202nd -ch ₃ CHF ₂ s- cl C ₂ HjOOC (CH ₂ ) ₃ S- cl She. p. 110.7 'C 203rd -ch ₃ CHF ₂ s- cl CH ₃ NHOCCH (CH ₃ ) S- cl She. p. 140.8 'C 204th CH, CHF ₂ s- cl (CH ₃ ) ₂ NOCCH (CH ₃ ) S- cl nD 1.5791 (21.0'C) 205th CH, chf ₂ s ~ cl C4 She z 1 cl She. p. 109.6 'C 206th -ch ₃ CHF ₂ s- cl -nh ₂ cl nD 1.5837 (20.3 'C) 207th -ch ₃ CHF ₂ s- cl (CH ₃ ) ₂ N- cl nD 1.5838 (21.6 'C) 208th -ch ₃ CHF ₂ s- cl ch ₂ = chch ₂ nh- cl nD 1.6060 (21.2 'C) 209th -ch ₃ CHF ₂ s- cl (CH ₂ = CHCH ₂ ) ₂ N- cl nD 1.5884 (24.0 'C) 210th -ch ₃ CHF ₂ s- cl ch = cch ₂ nh- cl nD 1.6052 (23.1'C) 211th CH, CHF ₂ s- cl ch ₃ so ₂ nh- cl She. p. 165.7 'C 212th CH, CHF ₂ s- cl ch ₃ nhso ₂ nh- cl nD 1.5812 (20.4 'C) 213th CH, CHF ₂ s- cl CHjOOCNH- cl She. p. 144.5 'C 214th CH, CHF ₂ s- cl (C ₂ Hj) ₂ NCOS- cl nD 1.5753 (21.5'C) 215th CH, CH, S cl C ₂ H ₅ OOCCH (CH ₃ ) O- cl nD 1.5584 (25.7 'C) dimethyl sulfate quaternary ammonium salt 216th -ch ₃ chf ₂ o- cl (CH ₃ ) ₃ SiCH ₂ S- cl nD 1.5568 (22.8 'C) 217th CH, _CH3 s- cl NOj- F She. p. 151.0 'C 218th -ch _{3 CH3} s- cl NHj- cl nD 1.6260 (27.3 'C) 219th -CH _{3 CH3} s- cl SH cl viscous material 220th CH, _CH3 s- cl CH = CCH ₂ O- cl nD 1.5980 (25.2 'C) 221st CH, _CH3 s- cl ch = cch ₂ s- cl She. p. 93-96 222nd CH, _CH3 s- cl C ₂ H ₅ OOCCH (CH ₃ ) S- F nD 1.5880 (26.4 'C) 223rd CH, -sch ₃ cl CH ₃ O-COCH ₂ O- cl She. p. 126.2 'C 224th CH, -sch ₃ cl C ₂ H ₅ O-COCH ₂ O- cl She. p. 106.5 'C

HU 212 628 Β

Number of compound R ¹ R ² R ³ R ⁴ X Physical characteristics 225th -ch ₃ OCHF2- H CH ₂ = CHCH ₂ O- cl 0. p. 56.2 ° C 226th -ch ₃ OCHF ₂ - H ch = cch ₂ o- cl 0. p. 100.0 'C 227th -ch ₃ OCHF2- cl OHC cl 0. p. 138.2 'C 228th -ch ₃ OCHF2- cl CH ₂ = C (CH ₃ ) CH ₂ O- cl nD 1.5387 (24.3'C) 229th -ch ₃ OCHF2- cl (CH ₃ ), SiCH ₂ O- cl nD 1.5271 (23.9'C) 230th -ch ₃ OCHFj- cl ho-coch ₂ o- cl 0. p. 162.0 ° C 231st -ch ₃ OCHFj- cl Na ⁰ ® O-COCH ₂ O- cl 0. p. 238.0 'C 232nd -ch ₃ OCHF2- cl K ⁰ O®-COCH ₂ O- cl 0. p. 194.0 'C 233rd -ch ₃ ochf ₂ - cl í-c ₃ h ₇ nh ⁰ 3 o®-coch ₂ o- cl 0. p. 131.0 'C 234th -ch ₃ OCHFj- cl C ₂ H ₅ O-COCH ₂ O- cl 0. p. 102.3 'C 235th -ch ₃ ochf ₂ - cl tC ₄ H ₉ O-COCH ₂ O- cl 0. p. 92.2 'C 236th ch ₃ -ochf ₂ cl CH ₂ = CHC (CH ₃ ) ₂ O - coch ₂ o - cl 0. p. 92.8 'C 237th ch ₃ -ochf ₂ cl CH, C = CCH ₂ O-COCH ₂ O- cl 0. p. 104.3 'C 238th ch ₃ -ochf ₂ cl ch, s-coch ₂ o- cl 0. p. 117.5'C 239th CH -ochf ₂ cl C ₂ H ₅ S-COCH ₂ O- cl 0. p. 86.0 'C 240th CH -ochf ₂ cl -C ₃ H ₇ S-COCH ₂ O- cl 0. p. 98.0 'C 241st ch ₃ -ochf ₂ cl ch ₃ nhcoch ₂ o- cl 0. p. 149.7 'C 242nd CH -ochf ₂ cl (CH ₃ ) ₂ NCOCH ₂ O- cl 0. p. 153.3 'C 243rd CH -ochf ₂ cl nC ₄ H ₉ NHCOCH ₂ O- cl 0. p. 106.9 'C 244th ch ₃ -ochf ₂ cl H ₂ C = CHCH ₂ NHCOCH ₂ O- cl 0. p. 127.7 'C 245th CH -ochf ₂ cl (H ₂ C = CHCH ₂ ) ₂ NCOCH ₂ O- cl 0. p. 80.0 'C 246th ch ₃ -ochf ₂ cl A group of formula (14) cl 0. p. 205.6 'C 247th ch ₃ -ochf ₂ cl Is a group of formula (15) cl nD 1.5570 (18.7 'C) 248th CH -ochf ₂ cl CH, SO ₂ NHCOCH ₂ O- cl 0. p. 124.5 'C 249th CH -OCHF, cl (CH ₃ ) ₃ SiCH ₂ O-COCH ₂ O- cl nD 1.5223 (29.5'C) 250th CH, -ochf ₂ cl ch ₃ oc ₂ h ₄ oc ₂ h ₄ o- COCH (CH,) O- cl nD 1.5142 (23.9 'C) 251st CH, -ochf ₂ cl C ₂ H ₅ O-COCH (C ₂ H ₅ ) O- cl nD 1.5286 (26.5'C) 252nd -CH ₃ -ochf ₂ cl C ₂ H ₅ O-CO (CH ₂ ), O- cl nD 1.5238 (17.3'C) 253rd CH, -ochf ₂ cl CH, O-COOCH (-C ₃ H ₇ ) O- cl nD 1.5273 (24.3'C) 254th CH, -ochf ₂ cl CH, SO ₂ NHCOCH (CH,) 0- cl mp 51.6 'C 255th CH, -ochf ₂ cl OHC F 0. p. 107.3 'C 256th CH, -ochf ₂ cl CH ₂ = CHCH ₂ O- cl 0. p. 63.7-64.1 'C 257th -ch ₃ -ochf ₂ cl CH ₂ = C (CH ₃ ) CH ₂ O- cl nD 1.5376 (17.3'C) 258th CH, -ochf ₂ cl CHsCCH ₂ O- cl 0. p. 98.0-98.1 'C 259th CH, -ochf ₂ cl ch, c = cch ₂ o- cl 0. p. 108.5 'C 260th -CH ₃ -ochf ₂ cl HO-COCH ₂ O- cl 0. p. 143.7 'C 261st CH, -ochf ₂ cl ch ₃ o-coch ₂ o- cl 0. p. 122.8-123.1 'C 262nd CH, -OCHF2 cl C ₂ H ₅ O-COCH ₂ O- cl 0. p. 127.6 'C 263rd CH, -ochf ₂ cl nC ₃ H ₇ O-COCH ₂ O- cl 0. p. 97.6-97.8 'C 264th -ch ₃ -ochf ₂ cl iC, H ₇ O-COCH ₂ O- cl 0. p. 120.3-120.5 ° C 265th -uh ₃ -ochf ₂ cl nC ₄ H ₉ O-CO ₂ CH ₂ O- F 0. p. 91.4-91.6 'C 266th CH, -ochf ₂ cl CH ₂ = CHCH ₂ O-COCH ₂ O- F 0. p. 89.2-89.4 'C 267th CH, -ochf ₂ cl CH = CCH ₂ O-COCH ₂ O- F 0. p. 99.0 'C 268th -ch ₃ -ochf ₂ cl c ₂ h ₅ s-coch ₂ o- F 0. p. 69.3 'C

HU 212 628 Β

Number of compound R ¹ R ² R ³ R ⁴ X Physical characteristics 269th CH, -OCHF ₂ cl iC ₃ H ₇ S-COCH ₂ O- F She. p. 83.8 'C 270th CH, -OCHF ₂ cl HO-COCH (CH ₃ ) O- F She. p. 94.5 'C 271st CH, -OCHF ₂ cl ch ₃ o-cochch ₃ o- F She. p. 95.6 'C 272nd CH, -ochf ₂ cl C ₂ H ₅ O-COCH (CH ₃ ) 0- F She. p. 67.0-67.2 'C 273rd CH, -ochf ₂ cl CH ₂ = CHCH ₂ O- COCH (CH ₃ ) O- F viscous material 274th CH, -ochf ₂ cl CHeCCH ₂ O-CO ₂ CH (CH ₃ ) 0- F nD 1.5266 (25.8 'C) 275th -ch ₃ -ochf ₂ cl _C2 H5O COCH _{(C2 H5)} O- F nD 1.5105 (22.6'C) 276th -ch ₃ -ochf ₂ cl CH2 = C _{(CH3) 2} S cl nD 1.5775 (21.7 'C) 277th CH, -ochf ₂ cl _CH2 = C (C1) _CH2 S- cl nD 1.5865 (21.5'C) 278th CH, -ochf ₂ cl cich = chch ₂ s- cl nD 1.5867 (21.2'C) 279th CH, -ochf ₂ cl C1CH = C (C1) _CH2 S- cl nD 1.5926 (22.8 'C) 280th -CH ₃ -ochf ₂ cl NCCH ₂ s- cl She. p. 122.3 'C 281st CH, -ochf ₂ cl Na® O®-COCH ₂ S- cl She. p. 232.0 'C 282nd -ch ₃ -OCHF? cl (iC, H ₇ ) NH® ₃ o -coch ₂ s- cl mp 113.0 'C 283rd CH, -ochf ₂ cl ho-coch ₂ s- cl She. p. 164.2 'C 284th -ch ₃ -ochf ₂ cl iC ₃ H ₇ O-COCH ₂ S- cl She. p. 99.1 'C 285th -ch ₃ -ochf ₂ cl nC ₄ H ₉ O-COCH ₂ S- cl She. p. 62.0 'C 286th CH, -ochf ₂ cl C ₁₂ H ₂₅ O-COCH ₂ S- cl nD 1.5010 (27.2 'C) 287th CH, -ochf ₂ cl ch ₃ s-coch ₂ s- cl She. p. 98.3 'C 288th CH, -ochf ₂ cl c ₂ h ₅ s-coch ₂ s- cl She. p. 73.1 'C 289th CH, -ochf ₂ cl -C, H ₇ S-COCH ₂ S- cl She. p. 97.0 'C 290th CH, -ochf ₂ cl CHsCCH ₂ O-COCH ₂ S- cl She. p. 85.9 'C 291st CH, -ochf ₂ cl C ₂ H ₅ OC ₂ H ₄ OC ₂ H ₄ O- COCHjS- cl She. p. 76.5 ° C 292nd CH, -ochf ₂ cl A group of formula (16) cl She. p. 87.8 'C 293rd -ch ₃ -ochf ₂ cl A group of formula (17) cl She. p. 82.8 'C 294th CH, -ochf ₂ cl (CH ₃ ) ₃ SiCH ₂ O-COCH ₂ S- cl nD 1.5387 (29.1'C) 295th -ch ₃ -ochf ₂ cl CH ₃ NHCOCH ₂ S- cl She. p. 177.8 'C 296th CH, -ochf ₂ cl (CH,) ₂ NCOCH ₂ S- cl She. p. 121.6 'C 297th CH, -ochf ₂ cl h ₂ c = chch ₂ nhcoch ₂ s- cl She. p. 146.6 'C 298th CH, -ochf ₂ cl (H ₂ C = CHCH ₂ ) ₂ NCOCH ₂ S- cl She. p. 71.8 'C 299th CH, -ochf ₂ cl HC = CCH ₂ .NHCOCH ₂ S- cl mp 172,0'C 300th CH, -ochf ₂ cl Is a group of formula (18) cl She. p. 178.1 'C Three hundred and first CH, -ochf ₂ cl Is a group of formula (19) cl nD 1.5661 (21.5'C) 302nd CH, -ochf ₂ cl Is a group of formula (20) cl She. p. 120.4 'C 303rd CH, -ochf ₂ cl Is a group of formula (21) cl She. p. 126.5 'C 304th CH, -ochf ₂ cl iC ₄ H ₉ O-COCH (CH ₃ ) S- cl viscous material 305th CH, -ochf ₂ cl tC ₄ H ₉ CH ₂ O-COCH (CH ₃ ) S- cl nD 1.5462 (13.9 'C) 306th -CH ₃ -ochf ₂ cl nC ₆ H, ₃ O-COCH (CH ₃ ) S- cl nD 1.5210 (23.2'C) 307th CH, -ochf ₂ cl A group of formula (22) cl viscous material 308th CH, -ochf ₂ cl C ₂ H ₅ S-COCH (CH ₃ ) S- cl nD 1.5790 (24.0 'C) 309th CH, -ochf ₂ cl iC ₃ H ₇ S-COCH (CH ₃ ) S- cl nD 1.5669 (24.2'C) 310th CH, -ochf ₂ cl NCCH (CH ₃ ) O-COCHCH ₃ S- cl nD 1.5501 (23.1'C) 311th -ch ₃ -ochf ₂ cl CH ₃ SC ₂ H ₄ O-COCH (CH ₃ ) S- cl nD 1.5609 (23.1'C) 312th CH, -ochf ₂ cl A group of formula (23) cl viscous material

HU 212 628 Β

Number of compound R ¹ R ² R ³ R ⁴ X Physical characteristics 313th -ch ₃ -ochf ₂ cl A group of formula (24) cl nD 1.5956 (14.3 'C) 314th -ch ₃ -ochf ₂ cl (CH ₃ ) ₃ SiCH ₂ O- COCH (CH ₃ ) S- cl nD 1.5429 (26.8 'C) 315th -ch ₃ -ochf ₂ cl CH ₂ = CHCH ₂ NHCOCH (CH ₃ ) s- cl nD 1.5619 (22.6'C) 316th -ch ₃ -ochf ₂ cl (H ₂ C = CHCH ₂ ) ₂ NCOCH (CH ₃ ) s - cl nD 1.5603 (22.9 'C) 317th -ch ₃ -ochf ₂ cl HOCCH, NHCOCH (CH ₃ ) S- cl nD 1.5496 (23.1'C) 318th -ch ₃ -ochf ₂ cl CH ₃ O-CO- (CH 2) ₂ S- cl nD 1.5603 (26.9 'C) 319th -ch ₃ -ochf ₂ cl C ₂ H ₅ O-COC (CH ₃ ) ₂ S- cl She. p. 96.4 'C 320th -ch ₃ -ochf ₂ cl CH ₃ O-COCH (-C ₃ H ₇ ) S- cl nD 1.5572 (23.4 'C) 321st -ch ₃ -ochf ₂ cl C ₂ H ₅ O-COCH (CH ₃ ) N (CH ₃ + cl nD 1.5365 (22.8 'C) 322nd -ch ₃ -ochf ₂ cl HO-CO cl She. p. 216.7 'C 323rd -ch ₃ -ochf ₂ cl ch ₃ o-co- cl She. p. 63.9 'C 324th -ch ₃ -ochf ₂ cl C, H ₅ O-CO- cl nD 1.5446 (26.8 'C) 325th CH, -ochf ₂ cl CH ₂ = CHCH ₂ O-CO- cl nD 1.5317 (26.8 'C) 326th CH, -ochf ₂ cl CH ₃ O-COCH (CH ₃ ) O-CO- cl nD 1.5370 (25.7 'C) 327th -ch ₃ -ochf ₂ cl C ₂ H ₅ O-COCH (CH ₃ ) O-CO- cl nD 1.5672 (26.0'C) 328th -ch ₃ -OCHF, cl ch = cch ₂ o-co- cl She. p. 78.5 'C 329th -ch ₃ -OCHF ₂ Br BrCH ₂ CH (Br) CH ₂ O- cl nD 1.5862 (22.3'C) 330th -ch ₃ -OCHFj Br BrC = CCH ₂ O- cl nD 1.5603 (22.9 'C) 331st CH, -ochf ₂ Br CH ₃ O-COCH ₂ O- cl She. p. 133.8 'C 332nd -CH ₃ -ochf ₂ Br C ₂ H ₅ O-COCH (CH,) O- cl nD 1.5396 (20.8 'C) 333rd -ch ₃ -SCHF, cl ncch ₂ o- cl nD 1.5571 (26.1'C) 334th -ch ₃ -SCHF, cl CH ₂ = C (CH ₃ ) CH ₂ 0- cl nD 1.5767 (26.3'C) 335th CH, -schf ₂ cl C1CH = CHCH ₂ O- cl nD 1.5930 (25.8 'C) 336th -CH ₃ -schf ₂ cl ch ₃ och ₂ o- cl nD 1.5765 (23.8 'C) 337th -ch ₃ -schf ₂ cl c ₂ h ₅ oc ₂ h ₄ o- cl nD 1.5713 (23.4 'C) 338th -ch ₃ -SCHF, cl ch ₃ och ₂ s- cl She. p. 82.6 'C 339th CH, -SCHF, cl cich = chch ₂ s- cl nD 1.6194 (26.3'C) 340th CH, -schf ₂ cl _CH2 = C (C1) -CH, S- cl nD 1.6137 (26.2'C) 341st -ch ₃ -ochf ₂ cl HS F She. p. 72.6 'C 342nd -CH ₃ -ochf ₂ cl CH, S F She. p. 84.5 'C 343rd CH, -ochf ₂ cl f ₂ hcs- F nD 1.5377 (24.0 'C) 344th CH, -OCHF, cl ch ₂ = chch ₂ s- F nD 1.5670 (17.9 'C) 345th CH, -ochf ₂ cl CH2 = C _{(CH3) 2} S F nD 1.5637 (19.1'C) 346th CH, -ochf ₂ cl ch = cch ₂ s- F She. p. 82.8 ° C 347th CH, -ochf ₂ cl c ₂ h ₅ oc ₂ h ₄ s- F nD 1.5523 (24.0 'C) 348th CH, -ochf ₂ cl ho-coch ₂ s- F She. p. 132.2 'C 349th CH, -ochf ₂ cl ch ₃ o-coch ₂ s- F nD 1.5579 (24.0 'C) 350th -ch ₃ -ochf ₂ cl c ₂ h ₅ o-coch ₂ s- F nD 1.5342 (17.9 'C) 351st CH, -ochf ₂ cl C ₂ H ₂ O-COCH ₂ S (O) - F nD 1.5420 (25.0 'C) 352nd CH, -ochf ₂ cl nC ₄ H ₉ O-COCH ₂ S- F nD 1.5391 (24.1'C) 353rd CH, -ochf ₂ cl CH 2 = CHCH ₂ O-COCH ₂ S F nD 1.5562 (24.1'C) 354th -ch ₃ -ochf ₂ cl ch ₃ sch ₂ o-coch ₂ s- F She. p. 57.9 'C 355th CH, -ochf ₂ cl A group of formula (16) F She. p. 58.9 'C

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Number of compound R ¹ R ² R ³ R ⁴ X Physical characteristics 356th CH, -OCHF ₂ cl A group of formula (17) F nD 1.5794 (17.9'C) 357th CH, -ochf ₂ cl CH, NHCOCH ₂ S- F She. p. 147.0 'C 358th CH, -ochf ₂ cl (CH ₃ ) ₂ NCOCH ₂ S- f She. p. 141.2 'C 359th -ch ₃ -ochf ₂ cl HO-COCH (CH,) S f nD 1.5463 (19.1'C) 360th CH, -ochf ₂ cl CH ₃ O-CO 2 CH (CH 2) S- f nD 1.5494 (25.0 'C) 361st CH, -ochf ₂ cl C ₂ H ₅ O-COCH (CH ₃ ) S- f nD 1.5328 (18.0'C) 362nd CH, -ochf ₂ cl nC ₄ H ₉ O-COCH (CH,) S- F nD 1.5343 (25.1'C) 363rd CH, -ochf ₂ cl CH 2 = CHCH ₂ O-COCH _(CH3) S F nD 1.5471 (25.0'C) 364th CH, -ochf ₂ cl CHsCCH ₂ O-COCHCH, S- F viscous material 365th CH, -ochf ₂ cl ch, oc ₂ h ₄ oc ₂ h ₄ o- COCH (CH ₃ ) S- F nD 1.5355 (18.4'C) 366th CH, -ochf ₂ cl CH ₃ SO ₂ NH- F She. p. 146.9 'C 367th CH, -ochf ₂ cl CH ₃ NHSO ₂ NH- F She. p. 131.2 'C 368th CH, -ochf ₂ cl ch ₂ = chch ₂ nh- F nD 1.5424 (23.6'C) 369th CH, -ochf ₂ cl CHsCCH ₂ NH- F nD 1.5510 (27.1'C) 370th CH, -ochf ₂ cl c ₂ h ₅ o-coch ₂ nh- F She. p. 111.5 'C 371st CH, -ochf ₂ cl C ₂ H ₅ O-CO ₂ CH (CH 2) NH- F nD 1.5264 (26.6'C) 372nd CH, -ochf ₂ cl CH, O-CO- F nD 1.5430 (17.0'C) 373rd CH, -ochf ₂ cl C ₂ H ₅ O-CO- F nD 1.5320 (21.0'C) 374th CH, -ochf ₂ cl CH ₂ = CHCH ₂ O-CO- F nD 1.5218 (20.5 'C) 375th CH, -ochf ₂ cl ch = cch ₂ o-co- F nD 1.5820 (24.5'C) 376th CH, -ochf ₂ cl CH, O-COCH (CH) -O-CO- F nD 1.5314 (23.0 'C 377th CH, -ochf ₂ cl C ₂ H ₅ O-COCH (CH,) O-CO- F nD 1.5212 (14.1'C) 378th CH, -schf ₂ cl <^ J / —oc ₂ h ₄ o- cl She. p. 102.9 'C 379th CH, -schf ₂ cl <^> - o-coch ₂ s- cl She. p. 104.4 'C 380th CH, -schf ₂ cl HO-COCH ₂ O- cl She. p. 157.7 'C 381st CH, -schf ₂ cl Na® O®-COCH ₂ O- cl She. p. 135.2 'C 382nd CH, -schf ₂ cl c ₂ h ₅ o-coch ₂ o- cl nD 1.5736 (24.0 'C) 383rd CH, -schf ₂ cl í-c, h ₇ o-coch ₂ o- cl She. p. 113.3 'C 384th CH, -schf ₂ cl cf, ch ₂ o-coch ₂ o- cl She. p. 117.5'C 385th CH, -schf ₂ cl ch ₂ = chch ₂ o-coch ₂ o- cl She. p. 77.2 'C 386th CH, -schf ₂ cl Oy — o-coch ₂ o- cl nD 1.5619 (28.3'C) 387th CH, -schf ₂ cl ch, nhcoch ₂ o- cl She. p. 116.8 'C 388th CH, -schf ₂ cl CH ₃ O-COCH (CH,) O- cl nD 1.5620 (23.4 'C) 389th CH, -schf ₂ cl iC, H ₇ O-COCH (CH,) O- cl nD 1.5496 (24.5'C) 390th CH, -schf ₂ cl CH ₂ = CHCH ₂ O- COCH (CH ₃ ) O- cl nD 1.5643 (23.5'C) 391st CH, -schf ₂ cl CH ₃ NHCOCHC (CH ₃ ) O- cl nD 1.5641 (23.5'C) 392nd CH, -SCHF2 cl CH 3 O-COCH (nC ₄ H ₉₎ O cl nD 1.5488 (28.1'C) 393rd CH, -schf ₂ cl NCCH2O-COCH ₂ O- cl nD 1.5694 (28.0'C) 394th CH, -schf ₂ cl CH, O-C0CH (CH,) S cl nD 1.5891 (26.4'C)

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Number of compound R ¹ R ² R ³ R ⁴ X Physical characteristics 395th -ch ₃ -SCHF ₂ cl NCCH ₂ O-COCH (CH ₃ ) S- cl nD 1.5801 (26.5'C) 396th -ch ₃ -schf ₂ cl C ₂ H ₅ O-CO (CH ₂ ) ₃ S- cl mp 107,0'C 397th CH, -schf ₂ cl Is a group of formula (15) cl She. p. 136.9 'C 398th -ch ₃ -schf ₂ cl ho-coch ₂ nh- cl She. p. 204.0 'C (dec.) 399th CH, -schf ₂ cl c ₂ h ₅ o-coch ₂ nh- cl She. p. 110.0 'C 400th CH, -schf ₂ cl C ₂ H ₅ O-COCH (CH ₃ ) NH- cl nD 1.5730 (23.9 'C) Four hundred and first CH, -ochf ₂ cl A group of formula (6) cl She. p. 91.8 'C 402nd CH, -ochf ₂ cl (7) cl mp 139.1 'C 403rd -c « ₃ -ochf ₂ cl HO-CO F solid material 404th -ch ₃ -ochf ₂ cl -No ₂ F solid material 405th CH, -ochf ₂ cl -nh ₂ F viscous material 406th CH, -ochf ₂ cl MONTH- F solid material 407th CH, -ochf ₂ cl N-CO- ^whether O® cl She. p. 246.4 'C 408th CH, -ochf ₂ cl ch, o-co-ch ₂ s-co- cl nD 1.5727 (24.1'C) 409th CH, -ochf ₂ cl (CH ₃ ) ₂ NCO- F viscous material 410th CH, -ochf ₂ cl -C ₃ H ₇ N®H, o®oc- F nD 1.5269 (23.5'C)

NMR data for the viscous or crystalline materials in Table I are shown in Table II below. See Table 1. In the table, "br" has a broad meaning.

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Number of compound NMR (δ) CDCl / TMS, ppm 19th 2.38 (3H, s), 3.50 (2H, br), 3.96 (3Η, s), 4.93-5.33 (2Η, m), 5.46-6.23 (1H, m) , 7.25 (1H, s). 7.43 (1H, s) 64th 1.23 (3H, t), 1.51 (3H, d), 2.40 (3H, s). 3.97 (3H, s), 4.18 (2H, q), 3.80-4.16 (1H, m), 4.90 (1H, d), 6.64 (1H, s), 7 , 40 (1H, s) 104th 1.13 (6H, d), 1.58 (3H, d), 2.83-3.45 (1H, m), 3.80 (3H, s), 4.59 (1H, q), δ , 75 (1H, t), 6.92 (1H, s), 7.51 (1H, s), 7.75-8.35 (3H, br) 128th 1.18 (6H, d), 1.49 (3H, d), 2.92-3.58 (1H, m), 3.81 (3H, s), 4.06 (1H, q). 6.68 (1H, t), 7.43 (2H, s). 7.62-8.32 (3H, br) 160th 1.12 (6H, d), 1.48 (3H, d), 2.60-3.30 (1H, m), 3.73 (3H, s), 3.91 (1H, q), δ , 55 (1H, s), 6.68 (1H, s), 7.33 (1H, s), 7.98 (3H, s). 196th 1.20 (6H, d). 1.48 (3H, d), 3.28 (1H, m), 3.90 (1H, m), 4.00 (3H, s), 6.74 (1H, t, J = 56 Hz), 7.45 (2H, s), 8.00 (3H, s) 219th 2.28 (3H, t), 3.91 (1H), 3.99 (3H, s), 7.21 (1H, d), 7.50 (1H, d) 273rd 1.70 (3H, d), 3.80 (3H, s), 4.5-4.9 (2H), 5.0-5.5 (2H), 5.5-5.2 (1H) , 6.70 (1H, t, J = 73 Hz), 7.0-7.4 (2H) 304th 0.82 (6H, d), 1.56 (3H, d), 3.80 (2H, d), 3.73-4.23 (2H, m), 6.70 (1H, t), 7.20 (1H, s), 7.23 (1H, s) 307th 1.53 (3H, d), 3.75 (3H, s), 4.06 (1H, q), 5.10 (2H, s), 6.61 (1H, t), 7.18 (5H) , s), 7.41 (1H, s) 312th 1.53 (3H, d), 0.68-2.11 (10H, m), 3.80 (3H, s), 4.10 (1H, q), 4.33-4.90 (1H, br), 6.70 (1H, t), 7.20 (1H, s), 7.23 (1H, s). 364th 1.54 (3H, d), 2.42 (1H, t), 3.80 (3H, s), 3.98 (1H, q), 4.61 (2H, d), 6.71 (1H) , t, J = 72 Hz), 7.31 (1H, d, J = 9Hz), 7.80 (1H, d, J = 7.6Hz) 404th (CDCl 3 + + ^ DMSO) 3.80 (3H, s), 6.70 (1H, t, J = 72Hz), 7.2 (1H, d, J = 10Hz), 8.12 (1H, d, J = Hz) 405th 3.83 (3H, s), 6.67 (1H, t, J = 72Hz), 7.36 (1H, d, J = 10Hz), 8.20 (1H, d, J = Hz) 406th 3.73 (3H, s), 3.85 (2H, s, br), 6.64 (1H, t, J = 72Hz), 6.82 (1H, d, J = 8Hz), 7, 04 (1H, d, J = 10Hz) 407th 3.80 (3H, s), 6.00 (1H, Br), 6.65 (1H, t, J = 72 Hz), 7.01 (1H, d, J = 10 Hz), 7.01 ( 1H, d, J = 8Hz) 409th 3.10 (6H, s), 3.80 (3H, s), 6.70 (1H, t, J = 72Hz), 7.23 (1H, d, J = 30Hz), 7.53 ( 1H, d, J = 8Hz)

HU 212 628 Β

The pyrazole derivatives (Π-2) used as starting materials for the preparation of the 3- (substituted phenyl) pyrazole derivatives of the formula (I) and their salts can be prepared, for example, according to Scheme 3. The pyrazole derivatives of the formula II-2 are, depending on their raw materials, the groups II-7, (Π-8), (II-9) and (Π-10), depending on the groups (II-7), (II-8) ), (II—

9) and (II-10). In the equations of Scheme 3, R ¹ , R ² , R ⁵ , X and Z are as defined above, R ^3-1 is halogen and 10 R ^5-1 are C 1 -C 4 alkyl or halogenated C 1 -C 4 alkyl.

As shown in the Scheme, the pyrazole derivatives II-8 'can be prepared by reacting a compound of formula VI with diethyl carbonate 15 and then reacting the resultant compound of formula V-2 with hydrazine IV followed by reacting the resulting pyrazole derivative (Π-7 ') with Lawesson's reagent. 20

The pyrazole derivative (Π-10) can be prepared from the pyrazole derivative (Π-7), which is a tautomer of the pyrazole derivative (II-7 '), or it can be prepared from a pyrazole derivative (II-8) Tautomer of the pyrazole derivative of formula 8 'by reacting one of the above starting materials with a halide of formula III-1 and then halogenating the resulting pyrazole derivative of formula II-9.

Thus, the pyrazole derivatives of formula II-2 which are used as starting materials in Scheme 1 above can be prepared.

The pyrazole derivatives of formula II-5, which serve as starting materials for process A in Scheme 2, may be prepared as described above using the starting compound of formula V-3.

The ΠΙ. Table III shows representative examples of the compounds of formula II-2 prepared by the above process and their physical characteristics.

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Number of compound R ¹ R ² R ³ X Physical characteristic II. First CH, OCH, cl F nD: 1.5633 (26.5'C) II.2. -CH ₃ -OCHF ₂ Η cl nD: 1.5467 (24.4'C) II.3. -ch ₃ -ochf ₂ H F Oily substance II.4. -ch ₃ -OCHF2 cl cl nD: 1.5511 (24.5'C) II.5. -ch ₃ -OCHF2 cl F m.p. 93.7 ° C II.6. -ch ₃ -ochf ₂ Br cl nD: 1.5627 (24.8 'C) II.7. CH, -OCHF2 Br F 126.4 ° C II.8. I-C3H7 SCH, H F Oily substance 11.9. iC ₃ H ₇ SCH, cl F nD: 1.5830 (15.1 ° C) II. 10th terc-C ₄ H ₉ -ochf ₂ cl F nD: 1.5402 (24.8 'C) 11:11. terc-C ₄ H ₉ -ochf ₂ Br F nD: 1.4848 (24.2'C)

AIV. Table III shows representative examples of the pyrazole derivatives II and 5 and their physical constants.

ARC. spreadsheet

Number of compound R ¹ R ² R ³ X Physical characteristic 11:12. -CH ₃ -och ₃ Η cl m.p. 79.4 'C 11:13. CH, SCH, Η cl m.p .: 59.5 to 60.0 ^- C 11:14. -ch ₃ SCH, Η F mp: 40.8 ° C 11:15. -ch ₃ OCH, cl cl m.p. 71-73 ° C 11:16. -ch ₃ -sch ₃ cl cl mp 62.5-63.5 ° C 11:17. -ch ₃ -sch ₃ cl F nD: 1.6066 (21.5 ° C) 11:18. CH, -och ₃ Br cl m.p. 83-85 'C 11:19. CH, -sch ₃ Br cl m.p. 70.0-75.5 ° C II.20. -ch ₃ -och ₃ Η c m.p. 39.2 C 11:21. -ch ₃ -schf ₂ H cl nD: 1.6001 (20.2 'C) 11:22. CH, -ochf ₂ H F m.p. 41.2-41.5 ° C

HU 212 628 Β

Number of compound R ¹ R ² R ³ X Physical characteristic 11:23. CH, -ochf ₂ cl cl m.p. 27-28 ° C 11:24. CH, -schf ₂ cl cl nD: 1.5900 (20.2 'C) 11:25. CH, -ochf ₂ cl F mp: 35.9-36.2 ° C 11:26. -ch ₃ -ochf ₂ Br cl nD: 1.5664 (21.0'C) 11:27. CH, -SCHF ₂ Br cl nD: 1.5993 (18.3'C) 11:28. -ch ₃ -ochf ₂ Br F m.p. 63.9 ° C 11:29. CH, -OCHF ₂ F cl nD: 1.5441 (20.8 'C) 11:30. CH, -OCF ₂ CHF ₂ H cl nD: 1.5237 (20.5 'C) 11:31. -ch ₃ -ocf ₂ chf ₂ cl cl nD: 1.5283 (10.6'C) 11:32. -ch ₃ -ocf ₂ cf ₂ ci cl cl m.p. 68-70 ° C 11:33. -ch ₃ -ocf ₂ chfcf ₃ H cl m.p. 68-70 ° C 11:34. -c ₂ h ₅ -ochf ₂ cl cl nD: 1.5422 (27.3'C)

The following examples illustrate the invention. the examples are not limiting. In each of the examples, "%" refers to weight%.

Example 1

Preparation of 2-Chloro-5- [4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl] -4-fluorobenzoic acid (Compound 403).

Preparation of 1-1 3- / 5- (Bromomethyl) -4-chloro-2-fluorophenyl / -4-chloro-5-difluoromethoxy-1-methyl-1-H-pyrazole (Scheme 4) )

6.9 g (20 mmol) of 4-chloro-3- (4-chloro-2-fluoro-5-methylphenyl) -5- (difluoromethoxy) -1-methyl-1H-pyrazole are suspended in 100 ml of carbon tetrachloride, and 3.97 g (22 mmol) of N-bromosuccinimide and a catalytic amount of benzoyl peroxide were added and the reaction mixture was refluxed for 5 hours. The insoluble material is filtered off, the filtrate is evaporated and the residue is purified by column chromatography. 5.64 g of a viscous product are obtained in 70% yield.

NMR (CDCl 3 / TMS), (ppm): 3.83 (3H, s), 4.53 (2H, s),

6.67 (1H, t, J = 72Hz), 7.22 (1H, d, J = 10Hz),

7.60 (1H, d, J = 8Hz).

Preparation of 1-2-Chloro / 4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl / -4-fluorobenzaldehyde (Compound 255) (Scheme 5) )

14.4 g (30 mmol) of 4-chloro-3- (4-chloro-5- (dibromomethyl) -2-fluorophenyl) -5- (difluoromethoxy) -1-methyl-1H-pyrazole. The reaction mixture was slurried in concentrated hydrochloric acid (ml) and the reaction mixture was refluxed for 5 hours. The mixture was poured into ice water and extracted with ethyl acetate. The extract was washed with 5% aqueous sodium bicarbonate followed by water, dried and evaporated. The residue was purified by column chromatography. 6.0 g of the title compound are obtained in 59% yield. M.p. 107.3 ° C.

Preparation of 1-3 2-Chloro-5- / 4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -4-fluorobenzoic acid (Compound 403).

A solution of potassium permanganate (1.1 g, 7 mmol) in water (22 mL) was slowly added dropwise to 2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-1.7 g, 5 mmol). pyrazol-3-yl / 4-fluorobenzaldehyde in 18 ml of water at 70-80 ° C. After the completion of the dropwise addition, the reaction was continued for an additional hour at 70-80 ° C, then the reaction mixture was cooled to room temperature and made basic with 10% aqueous sodium hydroxide. The by-product manganese dioxide was filtered off and washed with warm water. The filtrate and washings were combined, acidified with hydrochloric acid and extracted with ether. The ether phase is washed with water, dried and evaporated to dryness. 1.0 g of the title compound is obtained in the form of a solid in 56% yield.

Example 2

Preparation of ethyl 5- (4-chloro-1-methyl-5- (methylthio) -1H-pyrazol-3-yl) -2,4-dichlorobenzoate (Compound 50) (Scheme 6)

Ethyl 5- (4-chloro-1-methyl-5- (methylthio) -1H-pyrazol-3-yl) -2,4-dichlorobenzoate (0.30 g, 0.85 mmol) and 0.10 g A mixture of thionyl chloride (0.85 mmol) in methylene chloride (20 mL) was heated under reflux for 2 hours. The reaction mixture was then evaporated in vacuo and the resulting acid chloride was reacted with a large excess of ethanol under reflux for 1.5 hours. The solvent was evaporated in vacuo and the residue was chromatographed on a silica gel column. Yield: 33.9% (11 g) of the title compound as a paste.

nD (20, 1 'C): 1.6029.

Example 3

Preparation of methyl 2-chloro-5- / 4-chloro-5- (difluoromethoxy) -1-methyl-1 H -pyrazol-3-yl / -4-fluorobenzoate (Compound 372) (Scheme 7)

Potassium hydroxide (0.1 g, 1.8 mmol) and methyl iodide (0.26 g, 1.8 mmol) were added (0.8 g, 0.8 mmol).

EN 212 628 old Chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-ΙΗ-pyrazol-3-yl) -4-fluorobenzoic acid in 20 ml of acetone and reflux the reaction mixture for 3 hours. boil for an hour. The mixture was extracted with ethyl acetate, and the extract was washed with water, dried and evaporated, and the residue was purified by column chromatography. Yield: 0.15 g (48%).

nD (17.0'C): 1.5430.

Example 4

Preparation of 5- (4-Chloro-4- (difluoromethoxy) methyl-1H-pyrazol-3-yl] -2,4-dichlorobenzaldehyde (Compound 227) (Scheme 8)

26.60 g (63.3 mmol) of 3- (5- (bromomethyl) -2,4-dichlorophenyl) -4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazole in 100 ml glacial acetic acid Water (100 mL) was added followed by hexamethylenetetramine (8.87 g, 63.3 mmol) and the reaction mixture was refluxed for 2 hours. Concentrated sulfuric acid (40 ml) was then added and the mixture was refluxed for 13 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The extract was washed with 5% aqueous sodium bicarbonate followed by water, dried and evaporated. The residue was purified by column chromatography. Yield: 12.66 g (56.3%). The product obtained has a melting point of 138.2 ° C.

Example 5

Preparation of 4-Chloro-3- (4-chloro-2-fluoro-5-nitrophenyl) -5- (difluoromethoxy) -1-methyl-1H-pyrazole (Compound 404) (Scheme 9)

To a solution of 3.11 g (0.01 mol) of 4-chloro-3- (4-chloro-2-fluorophenyl) -5-difluoromethoxy-1-methyl-1H-pyrazole in 6 ml of concentrated sulfuric acid, A mixture of 1.58 g (0.015 mol) of 60% nitric acid and 4.90 g (0.05 mol) of concentrated sulfuric acid is added dropwise at a temperature of 10 to +10 ° C. After stirring for an additional 3 hours at room temperature, the reaction mixture was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with 5% aqueous sodium bicarbonate followed by water, dried and evaporated to dryness. This gave 3.0 g (84%) of the title compound.

NMR, δ (ppm): 3.83 (3H, s), 6.67 (1H, t, J = 72 Hz),

7.36 (1H, d, J = 10Hz), 8.20 (1H, d, J = 8Hz).

Example 6

Preparation of 4-Chloro-3- (4-chloro-2-fluoro-5-nitrophenyl) -1-methyl-5- (methylsulfinyl) -1H-pyrazole (Compound 217) (Scheme 10)

To a solution of 0.98 g (3.4 mmol) of 4-chloro-3- (4-chloro-2-fluorophenyl) -1-methyl-5- (methylthio) -1H-pyrazole in 2 ml of concentrated sulfuric acid under ice-cooling a solution

A mixture of 1.65 g of concentrated sulfuric acid and 8.4 mmol of concentrated nitric acid (density 1.38) was added and the mixture was stirred at room temperature for a further 2 hours and allowed to stand overnight. The mixture was then poured into ice water and the crystals formed were filtered off, washed with water and then with ether, and dried. so

Yield: 87.4% (1.04 g) in crystalline form. 151.0 ° C.

Example 7

Preparation of 3- (5-Amino-4-chloro-2-fluorophenyl) -4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazole (Compound 405) (Scheme 11)

4-Chloro-3- (4-chloro-2-fluoro-5-nitrophenyl) -5- (difluoromethoxy) -1-methyl-1H-pyrazole (3.0 g, 8.5 mmol) in ethanol (15 mL) and 15 ml of concentrated hydrochloric acid are added tin (II) chloride (7.70 g, 34 mmol), and the reduction is carried out under reflux for 8 hours. The reaction mixture was poured into ice water, basified with 20% aqueous sodium hydroxide, and the desired product was extracted with ethyl acetate. The extract was dried and evaporated, and the residue was purified by column chromatography. Yield: 2.15 g (78%).

δ (ppm): 3.73 (3H, s), 3.85 (2H, s, broad), 6.64 (1H, t,

J = 72 Hz), 6.82 (1H, d, J = 8 Hz), 7.04 (1H, d, J =

Hz).

Example 8

Preparation of 4-chloro-3- (2,4-dichloro-5-hydroxyphenyl) -1-methyl-5- (methylthio) -1H-pyrazole (Compound 2) (Scheme 12)

5.67 g (17 mmol) of 4-chloro-3- (5-amino-2,4-dichlorophenyl) -1-methyl-5- (methylthio) -1H-pyrazole in 20 ml of 50% To a solution of sulfuric acid in sulfuric acid was added dropwise a solution of 1.33 g of sodium nitrite in 4.5 ml of water, keeping the temperature of the solution between -5 and +5 ° C. After the addition was complete, the mixture was stirred for an additional 20 minutes at 0 to 5 ° C, and the resulting solution was poured into a 1 liter Erlenmeyer flask and first of about 100 g of a total of 318.8 g of 40% aqueous copper nitrate solution. is added dropwise to the solution while maintaining the temperature between about 0 and 10 ° C, and then the remaining copper nitrate solution is added dropwise. After stirring for 30 minutes at room temperature, copper (I) oxide (2.51 g, 17 mmol) was added portionwise and the reaction continued for 1 hour at room temperature. The resulting solution was poured into ice water and the desired product was extracted with ethyl acetate. The extract was washed with water and evaporated. The residue was purified by recrystallization from methylene chloride to give 2.61 g (46.4%) of the title compound in crystalline form. Melting point: 163.2 'C.

Example 9

Preparation of 4-Chloro-3- (2,4-dichloro-5-mercaptophenyl) -1-methyl-5- (methylthio) -1H-pyrazole (Compound 15) (Scheme 13)

7.71 g (19 mmol) of 4-chloro-3- / 5- (chlorosulfonyl) -2,4-dichlorophenyl / -1-methyl-5- (methylthio) -1H-pyrazole in 80 ml glacial acetic acid and a mixture of 24.8 g (380 mmol) of zinc powder was refluxed for 3.5 hours. The resulting solution

Pour into ice water and extract the desired product with ethyl acetate. The extract was washed with water. dried and evaporated. Yield: 5.75 g (89.1%) as an oily substance.

nD (24.3 'C): 1.6303.

Example 10

4-Chloro-3- [4-chloro-2-fluoro-5- (2-propynylthio) phenyl] -1-methyl-5- (methylthio) -1H-pyrazole (Preparation of Compound 221) Reaction Scheme)

4-Chloro-3- (4-chloro-2-fluoro-5-mercapto-phenyl) -1-methyl-5- (methylthio) -1H-pyrazole (0.60 g, 1.86 mmol), 30 mL acetone, 2.04 mmol of potassium carbonate powder and 2.23 mmol of propargyl bromide are heated under reflux for 2 hours. The resulting solution is then filtered off with acetone insoluble material, the filtrate is evaporated and the residue is chromatographed on a silica gel column. Yield: 0.54 g (80.5%). M.p. 93-96 ° C.

Example 11

Preparation of 4-Chloro-3- [2,4-dichloro-5- (2-propynyloxy) phenyl] -1-methyl-5- (methylthio) -1H-pyrazole (Compound 5) (Scheme 15) )

4.00 g (6.2 mmol) of 4-chloro-3- (2,4-dichloro-5-hydroxyphenyl) -1-methyl-5- (methylthio) -1H-pyrazole, 20 ml of acetone,

Anhydrous potassium carbonate (1.28 g, 9.3 mmol) and

A mixture of propargyl bromide (1.10 g, 9.3 mmol) was refluxed for 2 hours. The resulting solution was filtered to remove the insoluble material in acetone. The filtrate was evaporated and the residue was chromatographed on a silica gel column. Yield: 1.89 g (84.3%). M.p. 71.5-72.5 ° C.

Example 12

Preparation of Ethyl 2- [5- / 4-chloro-1-methyl-5- (methylthio) - 1 H -pyrazol-3-yl] -2,4-dichlorophenoxy] propionate (Compound II) (Scheme 16) )

4.50 g (10.8 mmol) of 4-chloro-3- (2,4-dichloro-5-hydroxyphenyl) -1-methyl-5- (methylthio) -1H-pyrazole, 50 ml of acetone, anhydrous potassium of carbonate and 2.06 g (11.4 mmol) of ethyl 2-bromopropionate are heated under reflux for 2 hours. The resulting solution is then filtered off with acetone insoluble material, the filtrate is evaporated and the residue is chromatographed on a silica gel column. The title compound was obtained as an oily substance in 70.0% yield.

nD (28.8 'C): 1.5763

Example 13

Preparation of 2- [5- (4-chloro-1-methyl-5- (methylthio) -1H-pyrazol-3-yl / 2,4-dichlorophenylthio) -propionic acid (Compound 25). Scheme 17)

Ethyl 2- [5- / 4-chloro-1-methyl-5- (methylthio) -1H-pyrazol-3-yl] -2,4-dichloro (2.28 g, 5.18 mmol). To a solution of phenylthio] propionate in 50 ml of ethanol was added 0.31 g of 95% sodium hydroxide particles, followed by a few drops of water and the reaction was carried out for 3 hours at room temperature. The solvent was then evaporated in vacuo. Water and ethyl acetate were added to the residue and the aqueous layer was separated. The aqueous phase is acidified with hydrochloric acid and the desired product is extracted from the solution with ethyl acetate. The extract was washed with water, dried and evaporated to dryness. 1.74 g (81.6%) of the title compound are obtained in crystalline form. The product obtained has a melting point of 180.0 ° C.

Example 14

Preparation of 4-Chloro-3- (2,4-dichloro-5- (dimethylamino) phenyl) -5-difluoromethylthio-1-methyl-1H-pyrazole (Compound 207). Reaction Scheme)

0.72 g (2 mmol) of 3- (5-amino-2,4-dichlorophenyl) -4-chloro-5- (dichloromethylthio) -1-methyl-1H-pyrazole, 15 mL of sulfurane, A mixture of 18 g (2.2 mmol) of sodium bicarbonate and 0.34 g (2.4 mmol) of methyl iodide was reacted at 80 ° C for 16 hours. The reaction mixture was poured into water and the desired product was extracted with ether. The extract was washed with water, dried and evaporated to dryness. Yield: 0.62 g (80.2%) as a paste.

nD (21.6'C): 1.5838.

Example 15

N, N-Dimethyl-2- [5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl] -2,4-dichlorophenoxy] -propionamide (# 110) (Scheme 19)

O, 80 g (1.78 mmol) 2- [5- (4-chloro-5- (difluoromethoxy) 1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenoxy] -propionyl chloride A solution of anhydrous tetrahydrofuran (20 ml) was added dropwise at room temperature to a solution of 50% dimethylamine (0.32 g, 3.56 mmol) in tetrahydrofuran (20 ml) and the reaction was continued for an additional hour. Ethyl acetate was added to the solution and the mixture was washed with water. The organic layer was separated, dried and evaporated in vacuo. The residue is chromatographed on silica gel. Yield: 0.24 g (27%) of the title compound in crystalline form. The product obtained had a melting point of 148.9 ° C.

Example 16

Preparation of 4-Chloro-3- (2,4-dichloro-5- (methylaminosulfonylamino) phenyl) -5- (difluoromethoxy) -1-methyl-1H-pyrazole (Compound 149). (Scheme 20)

N-Methylaminosulfonyl chloride (0.22 g, 1.67 mmol) was added dropwise to 3- (5-amino-2,4-dichlorophenyl) -4-chloro-5- (0.44 g, 1.28 mmol). (difluoromethoxy) -1-methyl-1H-pyrazole and triethylamine (0.17 g, 1.67 mmol) in ice-cooled tetrahydrofuran (20 mL). After the addition was complete, the reaction was continued for a further 2 hours. Ethyl acetate was added and the reaction mixture was washed with water. The organic layer was separated, dried, evaporated and then back to dryness

The residue was recrystallized from a mixture of n-hexane and ether. Yield: 71.7% (0.40 g). The product obtained had a melting point of 133.0 'C.

Example 17

Preparation of 5- (4-Chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl] -N-methyl-2,4-dichlorobenzenesulfonamide (Compound 164) (Scheme 21) ml 0.43 g (1 mmol) was added dropwise to a 40% aqueous solution of methylamine in tetrahydrofuran.

A solution of 4-chloro-3- (5- (chlorosulfonyl) -2,4-dichlorophenyl) -5- (difluoromethoxy) -1-methyl-1H-pyrazole in 2 ml of tetrahydrofuran. After the addition was complete, the reaction was continued at room temperature for an additional 30 minutes. Ethyl acetate was then added to the reaction mixture to extract the desired product. The extract was washed with water, dried and evaporated to dryness. 0.42 g of the title compound is obtained in the form of a paste in 100% yield.

nD (17.9 'C): 1.5461

Example 18

Preparation of 2- [5- (4-Chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichloroanilino] isopropylammonium propionate (Compound 160) (Scheme 22)

2- [5- (4-Chloro-5- (difluoromethoxy) 1-methyl-1H-pyrazol-3-yl) -2,4-dichloroanilino] propionic acid (0.33 g, 0.8 mmol) To a solution of tetrahydrofuran (20 mL) was added isopropylamine (0.05 g, 0.88 mmol) and the mixture was reacted for 30 minutes at room temperature. The solvent was evaporated in vacuo to give the title compound as an oil (100%).

δ (ppm): 1.12 (6H, d), 1.48 (3H, d), 2.60-3.30 (1H, m),

3.73 (3H, s), 3.91 (1H, q), 6.55 (1H, s), 6.68 (1H, s),

7.73 (1H, s), 7.98 (3H, s).

Example 19

Ethyl 2- [5- / 4-chloro], 2-dimethyl-5- (methylthio) -1H-pyrazolum-3-yl / -2,4-dichlorophenoxy] -propiondt-methylsulfate (215). (Scheme 23)

2- [5- (4-Chloro-1-methyl-5- (methylthio) -1H-pyrazol-3-yl) -2,4-dichlorophenoxy] propionate (0.22 g, 0.52 mmol) To a solution of benzene (1 ml) in dimethyl sulfate (0.13 g, 1.04 mmol) was added and the mixture refluxed for 5 days. The solvent was evaporated in vacuo and the residue was dissolved in ethyl acetate, washed with a little water, dried over the organic phase and evaporated to dryness. The title quaternary salt is obtained in the form of a paste in a yield of 52.6%.

nD (25.7 'C): 1.5548.

The present invention provides a compound of formula (I)

3- (substituted phenyl) pyrazole derivatives and their salts are suitable for killing annual and perennial weeds in rice, highlands, orchards and marshlands, for example, weeds: Echinochloa crus-galli Beauv. lawn weeds that grow in rice fields), Cyperus serotinus Rottb., (a perennial weed of the Cyperaceae family that grows in wetlands, ditches and rice fields), arrow grass (Sagittaria pygmaea Mig., a pest of the Alismataceae family, in ditches and rice fields), Scirpus juncoides Roxb. subsp. juncoides, (which grows on perennial weeds in marshlands, in watercourses and on rice paddies), wild oats (Avena fatua L., perennial weed on grasses, in highlands, highlands and lowland areas), large-leaved thistle (Digitara) ., a herbaceous herbaceous herbaceous herbaceous herbaceous herbaceous in the highlands and orchards, and herbaceous horse rum (Rumex japonicus Houtt, a herbaceous herbaceous herbaceous herbaceous and herbivore), umbrella sedge (Cyperus Iria L.) perennial weed, which grows on highlands and along roads, red-footed porpoise (Amaranthus vetroflexus L., an annual weed of the family Amaranthaceae, which grows on highlands, along roads and in open fields), gall (Galium aparine L., Rubiaceae a very harmful weed of the family ny, female in the highlands), veronica (Veronica persica L., a very harmful weed of the family Scorphulariaceae, growing in the highlands and orchards); (Abutilon theophrasti L., a very harmful weed of the family Malvaceae, grows in the highlands), sea buckthorn (Xanthium strumarium L ', a very harmful annual herbaceous weed, grows in the highlands), high dawn (Ipomoea purpurea Voigt, a species of Convolvul very harmful weeds, growing in highlands).

Since the 3- (substituted phenyl) pyrazole derivatives of the formula I and their salts have excellent herbicidal activity both before and immediately after germination, the characteristic physiological activity of these compounds can be achieved if or a salt thereof, before or after planting of the crop (including lands where crop plants are already present), either in the pre-emergence state of the weed or in the initial or middle state of the weed growth. However, the use of the herbicides of the invention is not limited to the modes described above. The herbicides of the invention may be applied not only to herbicides in rice fields or highlands, but generally also to herbicides in other areas such as meadow or harvested lands, seasonally uncultivated rice fields and highlands, ridge fields, farm roads, watercourses, pastures, playgrounds, land not occupied by buildings, lands suitable for cultivation,

EN 212 628 Β railways and forests. It is economically most desirable to treat these areas prior to the initial stage of weed development, but the treatment is not limited to this period, but can also be carried out in the middle stage of the weed.

The 3- (substituted phenyl) pyrazole derivatives of the formula (I) and their salts are generally formulated as suitable herbicides for use in conventional agricultural formulations. The pyrazole derivatives or salts thereof are admixed with a suitable inert carrier and, if desired, further excipients, and formulated into a suitable formulation, for example, as a suspension, emulsifiable concentrate, solution, wettable powder, granule, powder or tablet; the compositions are prepared using dissolution, dispersion, suspension, mixing, impregnation, adsorbent or adhesives. Solid or liquid inert carriers may be employed. Solid carriers include, for example, soybean flour, cereal flour, wood flour, bark flour, sawdust, powdered tobacco stalks, powdered nutshells, bran, pulverized cellulose, residues of extracted plants, powdered synthetic polymers or resins, clays or agglomerates such as kaolin, agglomerates; talc, such as talc and pyrophyllite, silica powders or flakes such as diatomaceous earth, quartz sand, mica or white carbon (i.e., highly dispersed silica, also referred to as finely divided hydrated silica or hydrated silica), activated carbon, diatomaceous earth, shredded bricks, fly ash, sand, calcium carbonate powder. calcium phosphate powder. as well as other inorganic and organic powders, chemical fertilizers such as ammonium sulfate, ammonium nitrate, urea or ammonium chloride, and compost. These materials may be used singly or in combination.

Liquid carriers which may be used are liquids which are soluble in themselves and liquids which do not dissolve the active ingredient but which can be converted into dispersions by the use of excipients. Examples of such liquids are water, alcohols such as methanol, ethanol, isopropanol, butanol or ethylene glycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone or cyclohexanone; ethers such as ethyl ether, dioxane, cellosolve, dipropyl ether or tetrahydrofuran; aliphatic hydrocarbons such as gasoline and mineral oils; aromatic hydrocarbons such as benzene, toluene, xylene, naphtha and alkylnaphthalenes; halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride; esters such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate, or dioctyl phthalate, amides such as dimethylformamide, diethylformamide or dimethylacetamide; nitriles such as acetonitrile; and dimethylsulfoxide. The above solvents may be used alone or in combinations thereof.

The following are representative excipients which may be used alone or in combination, but are not required to be used. Suitable emulsifiers, dispersants, solubilizers, and / or wetting agents include surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene ethers with higher fatty acids. , polyoxyethylene resinates, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylarylsulfonates, naphthalenesulfonic acid condensation products, lignin sulfonates and higher alcohols sulfate.

Excipients which can be used to stabilize, disperse and / or bind active ingredient dispersions include, for example, casein, gelatin, starch, methylcellulose, carboxymethylcellulose, acacia, polyvinyl alcohol, turpentine. , bran oil, bentonite and lignin sulfonates.

Waxes, stearates, and alkyl phosphates may be used as adjuvants to improve the flow properties of solid herbicidal compositions.

In the case of dispersible herbicidal compositions, excipients such as condensation products of naphthalenesulfonic acid and polyphosphates may be used as absorption enhancers.

For example, silicone oil antifoams may be used as an excipient.

The active ingredient content can be varied as required, for example, in the form of powders or granules, and in the form of emulsifiable concentrates or wettable powders, from 0.01% to 50% by weight of the active ingredient.

The 3- (substituted phenyl) pyrazole derivatives of the formula (I) or their salts are used as an active ingredient in an appropriate dilution or suspension in water or other medium to kill or inhibit the growth of various weeds, in an amount which kills the weed or inhibits growth. applied to the foliage or stalk or to a surface where weed growth is not desired.

The amount of herbicidal composition to be applied will depend on a number of factors, such as the purpose of application, the weeds to be killed, whether or not the weed or crop has matured, the weather, environmental factors, how the herbicidal composition is formulated, depending on the application, the nature or condition of the site of application and the time of application, these and other factors, an amount of 1.0 g to 10 kg of active ingredient per hectare is applied.

When the herbicidal composition is applied to rice or highlands, it is desirable to select a low dose so as not to damage the crop, but to kill or inhibit the growth of the weed. When applied to a non-cultivated area, application rates of 100 g / ha or more are suitable for weed control.

HU 212 628 Β

The herbicidal compositions of the present invention may be used in combination with other herbicides, thereby extending the range of species of weeds to be inhibited and extending the period during which the herbicides may be used effectively, and may also serve to reduce the dose of the herbicides.

The following is a non-limiting example of the action and formulation of the herbicidal compositions of the present invention.

In the test examples, the test compounds are used in the form of spray mixtures obtained by diluting the formulation of Formulation Example 3 with water.

The formulations were prepared by combining 50 parts by weight of the test compound with 40 parts by weight of xylene and 10 parts by weight of a mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzene sulfonate.

The resulting composition is diluted with water as described in Figures 5-8. is applied to the area to be treated.

1. Test Example

Pre-emergence herbicidal effect on weeds in rice soil Pots (0.01 m ² ) are filled with soil to simulate rice field conditions and then separately planted with cotyledon, Monochoria vaginalis (Burm. F.) Presl var plantaginae) and Scirpus juncoides Roxb. subsp. juncoides seeds, each of which is a harmful weed of rice fields, and providing conditions for the seeds to reach a pre-emergent state. Each pot is sprayed with soil. spraying at the dosage given in Table V using the active compounds of the present invention. After 21 days, the herbicidal activity is examined, the number of weeds killed is compared to the number of weeds on the untreated soil, and the herbicidal effect is evaluated and the chemical effect on rice plants is determined. The following aspects will be taken into account in the evaluation:

* Herbicidal activity

degree % Of weeds killed 5 95% or more 4 70-95% 3 50-70% 2 30-50% 1 10-30% 0 Below 10%

* Phytotoxic effect

degree The degree of phytotoxic effect 0 No phytotoxic effects 1 Staring occurs, but disappears during initial growth, no inhibition of growth is observed

degree The degree of phytotoxic effect 2 Staring and noticeable growth inhibition are observed, but normal conditions are soon restored 3 Staring and growth inhibition are observed, and normal recovery is slow 4 Staring and growth inhibition are observed, and some rice plants die 5 All rice plants are destroyed

The following compounds were tested as comparative samples:

Compound A: 3-phenyl-5- (methylthio) pyrazole (disclosed in Japanese Patent Application Laid-Open No. 52-91 861);

Compound (B): described in the first example of the above patent;

Compound (C): Compound No. 8 in Japanese Patent No. 54-70270;

Compound D: Compound No. 159 of Japanese Patent Application 55-9062.

The results of the tests are shown in Table V.

Table V.

Number of compound The application rate is kg / ha Phytotoxic effect Preemergent treatment Rice Rooster- foot grass Scirpus juncoi- des Roxb. subsp. juncoi- des Mono- Chorin vagina- lis (Burm. F.) Presl var plantaginae 86th 0.8 5 5 5 5 0.1 4 5 5 5 87th 0.8 5 5 5 5 0.1 4 5 5 5 117th 0.8 4 5 5 5 0.1 3 5 5 5 119th 0.8 4 5 5 5 0.1 2 5 5 5 152nd 0.8 3 5 5 5 0.1 2 5 5 5 153rd 0.8 5 5 5 5 0.1 3 5 5 5 253rd 0.8 5 5 5 5 0.1 1 3 5 5 256th 0.8 5 5 5 5 0.1 4 5 5 5 257th 0.8 5 5 5 5 0.1 3 5 5 5

HU 212 628 Β

Number of compound The application rate is kg / ha Phytotoxic effect Preemergent treatment Rice Rooster- foot grass Scirpus juncoi- des Roxb. subsp. juncoi- des Mono- Chorin vagina- lis (Burm. F.) Presl var plantaginae 258th 0.8 5 5 5 5 0.1 4 5 5 5 259th 0.8 5 4 5 5 0.1 3 2 4 4 260th 0.8 5 5 5 5 0.1 3 2 5 5 268th 0.8 5 5 5 5 0.1 3 5 5 5 269th 0.8 5 5 5 5 0.1 3 2 5 5 275th 0.8 5 5 5 5 0.1 2 3 5 5 344th 0.8 5 5 5 5 0.1 4 5 5 5 346th 0.8 5 5 5 5 0.1 4 5 5 5 359th 0.8 5 5 5 5 0.1 3 5 5 5 368th 0.8 5 5 5 5 0.1 2 5 5 5 369th 0.8 5 5 5 5 0.1 3 5 5 5 370th 0.8 5 5 5 5 0.1 2 2 5 5 371st 0.8 5 5 5 5 0.1 2 1 5 5 Formula (A) 5 0 0 0 0 Formula (B) 5 0 0 2 0 (C) drawing wherein 5 0 0 0 0 Formula (D) 5 0 0 0 0

As can be seen from the results in Table V, the 3- (substituted phenyl) pyrazole derivatives of the formula (I) according to the invention and their salts have a better herbicidal activity in pre-emergent rice pads than in (A), (B). ), Comparative Compounds of Formulas (C) and (D). In the case where certain derivatives have a herbicidal activity at a given dose and at the same time are phytotoxic to the crop, sufficient herbicidal activity may be maintained by selecting a suitable lower dose while significantly reducing the phytotoxic effect on the crop.

2. Test Example

Herbicidal effect on rice field weeds in post-emergence state

To simulate rice field conditions, pots (0.01 m ² ) were filled with soil and then individually planted with cockroach grass, Scirpus juncoides Roxb. subsp. juncoides, and Cyperus Serotinus Rottb. tubers and arrow grass (Sagittaria pygmaea Miq.), all of which are harmful weeds in rice fields, and create conditions for the weeds to grow to a leafy state of development.

Spray the soil of each well with the test compound solution and apply the test compound dose as shown in Table VI. The compound numbers are as given in Table I below. After 21 days, the herbicidal activity is evaluated, the number of weeds killed is calculated in the same way as in Test Example 1, the phytotoxic effect on the rice plant is also assessed and evaluated in Test Example 1.

Our results are shown in Section VI. See Table 1.

VI. spreadsheet

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- The main leg THE* B ** Grass arrow Second 5 1 4 1 0 0 Third 5 2 5 4 2 3 4th 5 5 5 5 3 4 0.8 3 5 3 1 2 5th 5 5 5 5 5 5 0.8 4 5 4 4 3 6th 5 3 5 4 5 3 7th 5 4 5 4 3 1 0.8 2 4 1 0 1 8th 5 3 5 4 1 2 9th 5 5 5 5 5 5 0.8 4 5 4 5 5 10th 5 5 5 5 5 5 0.8 5 5 4 5 5 0.1 2 5 2 3 4 11th 5 5 5 5 5 5 0.8 4 5 4 5 4 0.1 2 5 3 5 2

HU 212 628 Β

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- lábfU THE* B ** Grass arrow 12th 5 5 5 5 5 5 0.8 4 5 4 5 5 0.1 0 3 2 0 3 13th 5 4 5 5 5 5 0.8 4 5 4 5 5 0.1 1 3 1 0 2 14th 5 5 5 5 5 5 0.8 5 5 4 5 5 16th 5 1 3 2 0 3 18th 5 1 4 2 1 3 19th 5 2 5 2 0 3 20th 5 1 5 1 0 2 21st 5 2 5 2 5 3 23rd 5 2 5 3 2 4 25th 5 5 5 5 3 5 0.8 3 4 2 3 4 26th 5 5 5 5 4 5 0.8 2 3 3 3 4 27th 5 4 5 5 4 5 0.8 3 3 2 3 3 28th 5 5 5 5 2 5 0.8 2 5 2 0 4 29th 5 5 5 5 4 5 0.8 3 5 3 2 4 30th 5 5 5 5 2 5 0.8 2 5 2 0 4 31st 5 5 5 5 4 5 0.8 3 5 2 1 4 32nd 5 5 5 5 2 5 0.8 2 5 2 0 4 33rd 5 5 5 5 2 5 0.8 2 5 2 0 4 34th 5 5 5 5 2 5 0.8 2 5 2 0 4 35th 5 5 5 5 2 5 0.8 2 5 2 0 4 37th 5 5 5 4 5 5 0.8 2 5 2 2 5 38th 5 2 5 4 3 5 41st 5 1 5 2 2 4 42nd 5 1 4 2 0 2

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Grass arrow 43rd 5 1 5 2 4 5 44th 5 1 5 2 1 4 45th 5 1 5 2 1 4 46th 5 1 5 2 2 4 47th 5 1 2 1 2 4 48th 5 1 5 2 1 4 49th 5 5 5 5 5 5 0.8 3 5 5 3 5 50th 5 5 5 5 5 4 0.8 4 5 3 3 4 0.1 1 5 2 0 2 51st 5 5 5 5 5 5 0.8 2 0 1 0 3 52nd 5 3 5 4 4 4 53rd 5 4 5 5 5 5 0.8 2 3 1 0 2 54th 5 2 5 4 5 3 55th 5 2 5 2 2 2 57th 5 0 2 2 0 1 59th 5 2 5 3 4 2 62nd 5 3 5 3 2 5 0.8 1 2 0 0 5 63rd 5 3 5 3 2 5 0.8 1 2 0 0 5 64th 5 5 5 5 2 5 0.8 2 5 3 0 5 66th 5 3 3 2 1 5 67th 5 3 5 3 2 5 0.8 1 2 0 0 5 68th 5 5 3 2 1 5 0.8 2 0 0 0 5 69th 5 5 5 5 3 5 0.8 2 5 3 0 5 71st 5 5 5 5 5 5 0.8 5 5 5 5 4 0.1 2 5 3 3 1 72nd 5 5 5 5 5 5 0.8 3 3 5 5 2 73rd 5 2 4 4 4 2 74th 5 5 5 4 4 4 0.8 3 3 1 0 1

HU 212 628 Β

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Arrow grass 75th 5 2 0 2 4 0 76th 5 2 4 4 5 2 77th 5 2 5 4 1 2 78th 5 1 5 2 2 0 81st 5 5 5 5 5 5 0.8 3 5 5 5 5 82nd 5 5 5 5 5 5 0.8 3 5 4 5 5 83rd 5 3 5 4 4 5 84th 5 5 5 5 5 5 0.8 3 5 4 5 5 85th 5 2 5 3 5 5 86th 5 5 5 5 5 5 0.1 3 5 0 5 1 87th 5 5 5 5 5 5 0.1 3 5 3 5 4 88th 5 5 5 5 5 5 0.8 3 5 4 5 5 89th 5 5 5 5 5 5 0.8 4 5 5 5 5 90th 5 5 5 5 5 5 0.8 3 5 3 3 3 91st 5 5 5 5 5 5 0.1 3 4 3 5 5 92nd 0.8 5 5 5 5 5 0.1 3 4 5 5 5 93rd 0.8 5 5 5 5 5 0.1 2 2 2 0 5 94th 0.8 5 5 5 5 5 0.1 3 5 4 5 5 95th 5 5 5 5 5 5 0.8 4 5 5 5 5 96th 5 5 5 5 5 5 0.8 4 5 5 5 5 97th 0.8 5 5 5 5 5 0.1 2 4 4 5 5 98th 0.8 5 5 5 5 5 0.1 2 4 3 5 5 99th 5 5 5 5 5 5 0.8 3 5 5 5 5 100th 5 5 5 5 5 5

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B * ' Arrow grass 0.8 4 5 5 5 5 One hundred and first 0.8 5 5 5 5 5 0.1 2 3 1 0 5 102nd 5 5 5 5 5 5 0.8 4 5 5 5 5 103rd 0.8 5 5 5 5 5 0.1 2 0 0 1 5 104th 0.8 5 5 5 5 5 0.1 2 0 0 0 5 105th 0.8 5 5 5 5 5 0.1 4 4 4 1 5 106th 0.8 ⁵ 5 5 5 5 0.1 3 4 0 0 5 108th 5 5 5 5 5 5 0.1 3 4 4 5 5 109th 5 5 5 5 5 5 0.1 3 5 5 5 5 110th 5 5 5 5 5 5 0.1 4 5 3 0 5 111th 5 5 5 4 5 5 0.8 2 5 2 4 3 112th 0.8 5 5 5 5 5 0.1 2 5 0 4 1 113th 5 5 5 5 3 5 0.8 3 5 2 1 5 114th 5 5 5 5 5 5 0.8 3 5 5 5 5 115th 5 5 5 5 4 5 0.8 2 5 2 3 4 116th 5 5 5 5 5 5 0.1 3 5 0 5 0 117th 5 5 5 5 5 5 0.8 2 5 3 5 5 118th 5 5 5 3 2 5 0.8 3 5 0 0 5 119th 5 5 5 5 5 5 0.8 2 5 3 5 3 120th 5 3 5 3 5 5 121st 5 5 5 5 5 5 0.8 3 5 3 5 5 122nd 5 4 5 5 5 5

HU 212 628 Β

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Arrow grass 0.8 3 5 3 3 4 123rd 5 5 5 5 5 5 0.1 2 5 3 0 5 125th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 4 3 3 4 126th 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 3 5 2 1 4 127th 5 5 5 5 5 5 0.8 5 5 4 5 5 0.1 3 3 3 2 4 128th 5 5 5 5 5 5 0.8 5 5 5 4 5 0.1 3 1 2 0 4 129th 5 5 5 5 5 5 0.8 5 5 5 5 5 129th 0.1 5 5 4 2 5 130th 0.8 5 5 5 5 5 0.1 2 5 5 2 5 131st 5 5 5 5 5 5 0.8 3 5 2 0 3 132nd 5 5 5 5 5 5 0.8 3 4 3 1 3 133rd 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 3 5 0 5 5 134th 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 3 5 5 0 5 135th 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 3 5 4 3 5 136th 5 5 5 4 5 5 0.8 5 5 3 5 5 0.1 3 5 2 2 5 137th 5 5 5 5 5 5 0.8 5 5 5 5 5 137th 0.1 3 5 5 3 5 138th 5 5 5 5 5 5 0.8 3 5 5 5 5

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Grass arrow 139th 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 3 5 2 0 5 140th 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 3 5 5 5 5 141st 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 4 5 3 0 5 142nd 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 3 5 0 3 4 143rd 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 3 5 3 0 5 144th 5 4 5 4 5 5 0.8 3 5 4 5 4 145th 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 3 5 2 0 4 146th 5 2 5 4 5 5 147th 5 2 5 5 5 5 148th 5 5 5 5 5 5 0.8 3 5 5 5 5 149th 5 5 5 5 5 5 0.8 3 5 5 5 5 150th 5 5 5 5 5 5 0.8 4 5 3 4 5 0.1 2 5 2 2 5 151st 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 3 5 1 0 3 152nd 5 5 5 5 5 5 0.8 3 5 5 3 5 153rd 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 3 5 2 3 3 154th 5 3 5 4 - 5 155th 5 5 5 5 5 5 0.8 3 4 2 5 5 156th 5 5 5 5 5 5

HU 212 628 Β

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Grass arrow 0.8 2 4 2 5 5 157th 5 5 5 5 5 5 0.8 3 5 5 5 5 158th 5 5 5 5 3 5 0.8 3 5 4 1 5 159th 5 5 5 5 2 5 0.8 3 4 3 0 4 160th 5 5 5 3 2 5 0.8 3 5 0 0 5 161st 5 5 5 5 5 5 0.8 5 5 5 4 5 0.1 2 5 4 2 5 162nd 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 3 5 5 163rd 0.8 5 5 5 5 5 0.1 3 5 5 3 5 164th 5 5 5 5 5 5 0.8 5 5 5 5 5 0.1 2 5 3 0 5 165th 5 3 5 5 4 4 166th 5 3 5 4 5 4 167th 5 5 5 5 2 5 0.8 3 5 3 0 5 168th 5 5 5 5 4 5 0.8 3 5 2 2 4 169th 5 5 5 4 5 5 0.8 2 5 2 5 3 170th 5 5 5 2 2 5 0.8 2 4 0 0 5 171st 5 3 5 0 4 5 172nd 5 3 5 4 5 5 173rd 5 5 5 2 5 5 0.8 2 4 0 4 4 174th 5 2 5 5 5 5 175th 5 3 5 5 5 5 176th 5 3 3 2 1 5 177 5 2 5 3 5 5 178th 5 2 5 3 5 4 179th 5 5 5 3 4 2 0.8 2 5 0 2 0

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- lábfu THE* B ** Grass arrow 180th 5 3 5 2 2 5 181st 5 2 5 4 5 2 182nd 5 5 5 5 5 5 0.8 3 5 4 5 5 183rd 5 5 5 4 5 5 0.8 3 5 4 0 5 184th 5 2 5 3 5 3 185th 5 3 5 4 5 5 186th 5 2 5 4 5 5 187th 5 1 5 2 4 0 188th 5 5 5 2 4 2 0.8 2 5 0 2 0 189th 0.8 5 5 5 3 5 0.1 1 4 0 1 1 190th 5 5 5 5 5 5 0.8 2 5 3 5 5 191st 5 5 5 5 3 5 0.8 3 4 4 - 5 192nd 5 5 5 5 3 5 0.8 3 4 3 1 5 193rd 5 3 3 2 1 4 194th 5 5 5 5 5 5 0.8 3 3 3 5 5 195th 5 4 5 5 5 5 0.8 3 3 3 3 4 196th 5 5 5 5 5 5 0.8 2 3 2 2 3 197th 5 5 5 5 5 5 0.8 3 5 5 3 5 198th 5 5 5 5 3 5 0.8 3 5 2 - 5 199th 5 5 5 5 5 5 0.8 3 5 2, 4 5 200th 0.8 5 5 5 2 5 0.1 1 3 0 0 5 Two hundred and first 0.8 5 5 3 5 5 0.1 3 4 0 0 5 202nd 5 5 5 5 2 5 0.8 2 3 2 0 5 203rd 5 5 5 4 4 5 0.8 2 4 2 2 5

HU 212 628 Β

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Nyflfű 204th 5 5 5 5 4 5 0.8 3 5 2 2 5 205th 5 2 5 4 0 4 206th 5 5 5 5 4 5 0.8 1 5 3 1 5 207th 5 2 5 2 5 2 208th 5 2 5 4 5 5 209th 5 5 5 4 5 5 0.8 2 5 1 5 5 210th 5 3 5 5 5 5 211th 5 5 5 5 5 5 0.8 2 4 4 4 5 212th 5 5 5 5 5 5 0.8 3 5 5 5 5 213th 5 4 5 4 3 3 214th 5 4 5 3 3 3 216th 5 5 5 5 2 5 0.8 2 5 5 0 5 218th 5 1 5 2 0 5 220th 5 5 5 5 5 5 0.8 3 5 5 3 5 221st 5 5 5 5 5 2 0.8 3 5 3 5 1 222nd 5 5 5 5 5 5 0.8 3 5 4 5 5 223rd 5 5 5 5 5 5 0.8 3 5 - 4 5 224th 5 5 5 5 5 5 0.8 3 5 5 5 5 225th 5 2 5 2 4 2 226th 5 2 5 2 5 2 227th 0.8 3 4 5 5 5 228th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 1 2 5 229th 5 5 5 5 5 5 0.8 3 5 2 2 5 230th 0.8 5 5 5 5 5 0.1 2 2 3 0 5 231st 0.8 5 4 5 5 5 0.1 3 3 2 2 3

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Nyflfű 232nd 5 5 5 5 5 5 0.8 3 5 5 5 5 233rd 0.8 5 5 5 5 5 0.1 2 1 0 2 5 234th 0.8 5 5 5 5 5 0.1 2 0 0 0 5 235th 0.8 5 5 5 5 5 0.1 3 5 5 2 5 236th 5 5 5 5 5 5 0.8 2 5 5 5 5 237th 0.8 5 5 5 5 5 0.1 3 4 5 5 5 238th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 5 5 5 239th 0.8 5 5 5 5 5 0.1 3 5 5 5 5 240th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 5 0 5 241st 0.8 3 5 5 5 5 242nd 0.8 5 5 5 5 5 0.1 3 5 4 3 5 243rd 5 3 5 5 5 5 0.8 1 5 4 5 5 244th 5 5 5 5 5 5 0.8 3 5 0 5 5 245th 0.8 5 5 5 5 5 0.1 1 5 0 5 5 246th 5 3 2 4 2 3 247th 0.8 5 5 5 5 5 0.1 2 3 2 0 5 248th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 5 0 5 249th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 2 5 5 2 5 250th 0.8 5 5 5 5 5 0.1 ³ 2 3 1 5 251st 0.8 5 5 5 5 5

HU 212 628 Β

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B * Arrow grass 0.1 2 3 5 0 5 252nd 5 5 5 5 5 5 0.8 3 5 5 5 5 253rd 0.8 5 5 5 5 5 0.1 4 5 5 5 5 254th 0.8 5 5 5 5 5 0.1 4 5 5 2 5 255th 0.2 5 5 5 5 5 0.1 5 5 5 0 5 256th 0.2 5 5 5 5 5 0.1 3 5 5 5 5 257th 0.2 5 5 5 5 5 0.1 3 5 3 5 5 258th 02 5 5 5 5 5 0.1 4 5 5 5 5 259th 0.8 5 5 5 5 5 0.2 4 4 5 5 5 0.1 3 3 0 5 5 260th 0.8 5 5 5 5 5 0.2 3 4 5 5 5 261st 0.2 5 5 5 5 5 0.1 3 3 5 5 5 262nd 0.2 5 5 5 5 5 0.1 5 5 5 5 5 263rd 0.2 5 5 5 5 5 0.1 5 5 5 5 5 264th 0.2 5 5 5 5 5 0.1 5 5 5 5 5 265th 0.2 5 5 5 5 5 0.1 5 5 5 5 5 266th 0.2 5 5 5 5 5 0.1 5 5 5 5 5 267th 0.2 5 5 5 5 5 0.1 4 5 5 5 5 268th 0.8 5 5 5 5 5 0.2 4 5 5 5 5 0.1 3 5 5 5 5 269th 0.8 5 5 5 5 5 0.2 4 5 5 5 5 0.1 3 5 3 5 5 270th 0.8 5 5 5 5 5

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Grass arrow 0.2 3 4 5 4 5 271st 0.2 5 5 5 5 5 0.1 3 5 5 5 5 272nd 0.2 5 5 5 5 5 0.1 3 5 5 5 5 273rd 0.8 5 5 5 5 5 0.2 4 5 5 5 5 0.1 3 5 5 5 5 274th 0.2 5 5 5 5 5 0.1 4 5 5 5 5 275th 0.8 5 5 5 5 5 0.2 3 5 5 5 5 0.1 2 5 3 3 5 276th 5 5 5 5 5 5 0.8 3 5 5 4 5 277th 5 5 5 5 5 5 0.8 2 5 5 4 5 278th 5 5 5 5 2 5 0.8 2 5 5 0 5 279th 5 4 5 5 4 5 0.8 1 5 4 2 4 280th 5 5 5 5 5 5 0.8 3 5 5 5 5 281st 5 5 5 5 5 5 0.8 3 4 4 4 5 282nd 5 5 5 5 5 5 0.8 3 5 5 4 5 283rd 5 5 5 5 5 5 0.8 3 5 5 5 5 284th 5 5 5 5 5 5 0.8 3 5 5 5 5 285th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 3 0 3 5 286th 5 5 5 5 5 5 0.8 4 4 3 5 5 287th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 3 5 5 288th 0.8 5 5 5 5 5 0.1 3 5 5 0 5

HU 212 628 Β

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Arrow grass 289th 0.8 5 5 5 5 5 0.1 3 5 4 0 5 290th 5 5 5 5 5 5 0.8 3 5 5 4 5 291st 5 5 5 5 5 5 0.8 3 5 5 5 5 292nd 5 5 5 5 5 5 0.8 4 5 5 4 5 0.1 3 5 2 0 5 293rd 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 2 0 5 294th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 2 5 3 0 5 295th 5 5 5 5 5 5 0.8 3 5 5 5 5 296th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 2 4 0 0 5 297th 5 5 5 5 5 5 0.8 3 5 3 4 5 298th 5 5 5 5 4 5 0.8 3 5 3 2 5 299th 5 5 5 5 5 5 0.8 3 5 5 5 5 300th 5 5 5 5 2 5 0.8 3 4 4 0 5 Three hundred and first 5 5 5 5 5 5 0.8 3 5 4 4 5 302nd 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 2 5 3 0 5 303rd 5 5 5 5 5 5 0.8 3 5 5 3 5 304th 0.8 5 5 5 5 5 0.1 3 5 4 0 0 305th 0.8 5 5 5 5 5 0.1 3 5 3 0 5 306th 5 5 5 5 5 5 0.8 3 5 5 4 5

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Grass arrow 307th 0.8 5 5 5 0 5 0.1 3 3 2 0 0 308th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 5 3 5 309th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 5 0 5 310th 5 5 5 5 5 5 0.8 4 5 5 4 5 0.1 2 5 0 0 5 311th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 2 4 3 0 5 312th 5 5 5 5 2 4 0.8 4 5 5 0 2 0.1 2 3 3 0 0 313th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 3 0 5 314th 5 5 5 5 5 5 0.8 4 5 5 4 5 0.1 2 3 0 4 5 315th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 5 0 5 316th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 3 5 4 0 5 317th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 2 5 4 0 5 318th 5 5 5 5 5 5 0.8 4 5 5 4 5 0.1 2 3 2 0 5 319th 5 5 5 5 5 5 0.8 4 5 4 3 5 0.1 2 4 2 3 5 320th 5 5 5 5 5 5 0.8 3 5 4 5 5 321st 5 3 5 5 2 5

HU 212 628 Β

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B * Arrow grass 0.8 1 5 2 0 5 322nd 0.8 5 4 5 5 5 0.1 3 1 3 0 5 323rd 0.8 5 5 5 5 5 0.1 5 5 5 5 5 324th 0.8 5 5 5 5 5 0.1 5 5 5 5 5 325th 0.8 5 5 5 5 5 0.1 5 5 5 5 5 326th 0.8 5 5 5 5 5 0.1 5 5 5 5 5 327th 0.8 5 5 5 5 5 0.1 5 5 5 5 5 328th 0.8 5 5 5 5 5 0.1 5 5 5 5 5 329th 5 5 5 5 5 5 0.8 2 5 3 2 5 330th 5 3 5 4 2 5 0.1 1 3 2 0 4 331st 0.8 5 5 5 5 5 0.1 2 3 5 0 5 332nd 0.8 5 5 5 5 5 0.1 3 5 5 0 5 333rd 5 5 5 5 5 5 0.8 2 5 5 5 5 334th 5 5 5 5 5 5 0.8 2 5 3 4 5 335th 5 4 5 5 2 4 0.8 1 5 4 0 2 336th 5 5 5 5 5 5 0.8 3 5 5 5 5 337th 5 5 5 5 5 5 0.8 3 5 4 5 5 338th 5 5 5 5 5 5 0.8 2 5 5 5 5 339th 5 3 5 5 2 5 0.8 1 5 3 0 4 340th 5 4 5 5 4 5 0.8 2 5 3 2 3 341st 0.8 5 5 5 4 5 0.2 2 4 4 2 5

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- lábfiű THE* B ** Grass arrow 342nd 0.2 5 5 5 5 5 0.1 3 5 5 3 5 343rd 0.2 5 5 5 5 5 0.1 5 5 5 3 5 344th 0.2 5 5 5 5 5 0.1 5 5 5 5 5 345th 0.8 5 5 5 5 5 0.2 4 5 5 5 5 0.1 3 5 5 3 5 346th 0.2 5 5 5 5 5 0.1 4 5 5 5 5 347th 0.2 5 5 5 5 5 0.1 1 1 0 0 5 348th 0.2 5 5 5 5 5 0.1 5 5 3 3 5 349th 0.2 5 5 5 5 5 0.1 5 5 5 5 5 350th 0.2 5 5 5 5 5 0.1 3 5 4 0 5 351st 0.8 3 5 5 5 5 0.2 1 5 4 5 5 352nd 0.2 5 5 5 5 5 0.1 5 5 5 5 5 353rd 0.2 5 5 5 5 5 0.1 5 5 5 5 5 354th 0.8 5 5 5 5 5 0.2 3 5 4 5 5 355th 0.2 5 5 5 5 5 0.1 3 5 4 0 5 356th 0.2 5 5 5 5 5 0.1 3 4 2 0 5 357th 0.2 5 5 5 5 5 0.1 4 5 4 4 5 358th 0.2 5 5 5 5 5 0.1 3 4 0 0 5 359th 0.8 5 5 4 5 5 0.2 3 5 - 4 5 360th 0.2 5 5 5 5 5 0.1 3 5 5 5 5 361st 0.2 5 5 5 5 5 0.1 3 5 3 5 5

HU 212 628 Β

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Grass arrow 362nd 0.2 5 5 5 5 5 0.1 3 5 3 3 5 363rd 0.2 5 5 5 5 5 0.1 3 5 5 0 5 364th 0.2 5 5 5 5 5 0.1 3 5 3 0 5 365th 0.2 5 5 5 5 5 0.1 3 5 0 0 5 366th 0.2 5 5 5 5 5 0.1 3 5 5 3 5 367th 0.8 5 5 5 5 5 0.2 3 5 5 5 5 368th 0.8 5 5 5 5 5 0.1 3 5 2 0 5 369th 0.2 5 5 5 5 5 0.1 3 5 2 5 5 370th 0.2 5 5 5 2 5 0.1 1 3 3 0 4 371st 0.2 5 5 5 2 5 0.1 2 4 5 0 4 372nd 0.2 5 5 5 5 5 0.1 5 5 5 5 4 373rd 0.8 5 5 5 5 5 0.1 5 5 5 5 5 374th 0.8 5 5 5 5 5 0.1 5 5 5 5 5 375th 0.8 5 5 5 5 5 0.1 5 5 5 5 5 376th 0.8 5 5 5 5 5 0.1 5 5 5 5 5 377th 0.2 5 5 5 5 5 0.1 5 5 5 0 5 378th 5 5 5 5 5 5 0.8 2 5 2 4 5 379th 5 5 5 5 3 5 0.8 4 4 4 - 5 380th 5 5 5 5 5 5 0.8 2 5 5 4 5 381st 5 5 5 5 5 5 0.8 3 4 5 5 5 382nd 5 5 5 5 5 5

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Grass arrow 0.8 3 5 5 5 5 383rd 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 1 5 0 0 5 384th 5 5 5 5 5 5 0.8 4 5 5 5 5 385th 5 5 5 5 2 5 0.8 5 5 5 0 5 0.1 0 5 2 0 5 386th 5 5 5 5 5 5 0.8 3 5 4 2 5 387th 5 5 5 5 5 5 0.8 3 5 5 5 5 388th 0.8 5 5 5 5 5 0.1 2 4 3 0 5 389th 5 5 5 5 5 5 0.8 4 5 5 5 5 0.1 2 5 5 0 5 390th 5 5 5 5 5 5 0.8 3 5 5 5 5 391st 5 5 5 5 5 5 0.8 3 5 4 5 5 392nd 5 4 5 5 2 5 0.8 2 5 3 0 5 393rd 5 5 5 5 5 5 0.8 4 4 5 5 5 394th 5 5 5 5 2 5 0.8 3 5 5 0 5 395th 5 5 5 5 3 5 0.8 4 5 5 0 5 0.1 1 4 2 0 5 396th 5 3 5 5 2 5 0.8 1 3 2 0 5 397th 5 5 5 5 5 5 0.8 3 5 4 2 5 398th 5 3 2 4 2 5 0.8 1 0 2 0 5 399th 5 5 5 5 2 5 0.8 2 5 4 0 5 400th 5 5 5 5 5 5 0.8 2 5 5 5 5

HU 212 628 Β

Number of compound Quantity of the active substance Fitoto- of toxic effect rice Effect of post-emergence treatment Rooster- foot grass THE* B ** Arrow grass Four hundred and first 5 5 5 5 5 5 0.8 4 5 5 5 5 402nd 5 5 5 5 5 5 0.8 4 5 5 5 5 403rd 0.2 5 5 4 5 5 0.1 4 3 2 0 5 404th 0.2 5 5 5 5 5 0.8 5 5 5 0 5 405th 0.2 5 5 4 5 5 0.1 3 3 3 0 4 406th 0.2 4 4 3 4 5 0.1 3 3 0 0 3 Compound of Formula (A) 5 0 0 0 0 0 Compound (B) 5 0 2 0 0 0 Compound of Formula (C) 5 0 0 0 0 0 Compound IDD 5 0 0 0 0 0

As shown in VI. Table 3 shows that the 3- (substituted phenyl) pyrazole derivatives of the formula (I) and their salts have a better herbicidal activity in comparison with the comparative formulas (A), (B), (C) or (D) compounds. If a derivative exerts a herbicidal activity on the weeds in a single dose and at the same time on the crop, sufficient herbicidal activity is maintained at a suitably selected lower dose, but the phytotoxic effect on the crop is significantly reduced.

3. Test Example

Effect on weeds of highland areas In preemergent treatment, boxes of cm wide, 20 cm long and 5 cm deep are filled with soil and planted separately with seeds of cocksfoot, marshmallow, buckthorn, burbot, veronica and gala, which are planted with weeds of the highlands and wheat seeds as crops for the highlands.

Spray the soil of each pot with the apparatus described in Figure VII. At the dose indicated in Table I, the test compounds are tested for herbicidal activity after 14 days with a solution of the test compounds (numbered according to Table I). The percentage of weeds killed was determined as in Test Example 1, the phytotoxic effect on soybean and wheat plants was also evaluated and evaluated as in Test Example 1. Our results are shown in Table VII. See Table 1.

VII. spreadsheet

Number of compound THE authorities the- Nyagan Tieny- lymph of kg / ha Phytotoxic effect Effect of pre-emergent treatment wheat weave- JA puppet K- kas- foot grass Neither- lyem- mály- va Serbian thorn rugged Lag Vero nika lady's bedstraw Third 5 1 0 5 5 5 5 - 5 4th 5 2 1 5 5 0 4 - 5 5th 5 3 0 5 4 2 5 - 5 6th 5 1 2 5 3 0 2 - 3 7th 5 0 1 4 4 0 2 - 2 8th 5 0 0 3 3 0 1 - 1 9th 5 4 4 5 5 - 5 - 5 0.8 2 0 5 4 3 5 - - 10th 5 5 4 5 5 5 5 - 5 0.8 3 2 3 5 5 5 - - 11th 5 5 5 5 4 4 5 - 5 12th 5 4 4 5 4 - 5 - 5 0.8 3 1 5 2 - 5 - - 13th 5 4 4 5 5 5 5 - 5 0.8 3 1 5 5 5 5 - - 14th 5 5 3 5 5 - 5 - 5 0.8 3 0 5 5 - 5 - - 16th 5 1 - 4 3 2 4 - 5 17th 5 0 0 1 0 0 4 - 0 18th 5 1 2 4 4 2 4 - 5 19th 5 1 1 5 - 1 4 - 4 20th 5 1 0 3 0 0 3 - 5 21st 5 0 0 4 2 0 1 - 0 23rd 5 0 0 4 0 0 1 - 0 24th 5 0 1 0 0 0 4 - 4 25th 5 1 0 3 2 0 5 - 4 26th 5 4 3 5 5 - 5 - 5 0.8 2 1 4 4 0 4 - 4 27th 5 4 4 5 5 - 5 - 5 0.8 2 2 4 4 - 5 - 4 28th 5 4 2 4 5 - 5 - 5

HU 212 628 Β

0.8 2 0 3 4 0 5 - 5 29th 5 2 3 5 - 2 5 - 4 30th 5 3 3 4 5 - 5 - 5 0.8 1 1 3 4 1 5 - 3 31st 5 3 2 5 4 3 5 - 5 32nd 5 3 2 4 5 - 5 - 4 0.8 1 0 3 4 0 5 - 3 33rd 5 4 2 4 4 - 5 - 5 0.8 2 0 3 3 0 5 - 5 34th 5 3 2 3 5 - 5 - 5 0.8 1 0 2 4 0 5 - 4 35th 5 3 2 5 4 - 5 - 3 0.8 1 0 4 3 0 5 - 2 37th 5 3 3 5 5 4 5 - 5 38th 5 2 1 5 5 0 5 - 5 40th 5 0 0 0 3 0 5 - 0 41st 5 2 2 2 4 - 4 - 4 42nd 5 0 0 3 1 0 0 - 0 43rd 5 0 0 4 2 0 3 - 5 44th 5 0 0 4 3 0 5 - 5 45th 5 0 0 4 2 0 2 - 4 46th 5 0 0 3 3 0 4 - 4 47th 5 0 0 4 5 1 5 - 5 48th 5 0 0 1 2 0 2 - 4 49th 5 3 5 5 4 0 5 - 5 50th 5 2 5 5 4 - 5 - 5 51st 5 2 5 5 5 5 5 - 5 52nd 5 0 3 5 5 - 5 - 5 54th 5 1 5 5 5 5 5 - 5 55th 5 0 0 3 1 0 2 - 1 57th 5 0 0 3 2 0 0 - 0 59th 5 0 0 4 1 0 2 - 0 71st 5 3 5 5 5 - 5 - 5 72nd 5 1 1 5 4 4 5 - 5 73rd 5 1 1 4 5 0 4 - 4 74th 5 2 2 5 5 2 5 - 5 76th 5 1 1 5 5 1 5 - 2 77th 5 0 1 5 5 - 3 - 4 78th 5 0 0 5 4 0 2 - 2 81st 5 5 4 5 5 5 5 - 5 0.8 3 2 5 5 4 5 - - 82nd 5 5 4 5 5 5 5 - 5 0.8 3 2 5 5 4 5 - - 83rd 5 4 3 5 5 - 5 - 5 0.8 2 2 5 4 4 5 - 5

84th 5 5 4 5 5 5 5 - 5 0.8 3 2 5 5 4 5 - - 85th 5 5 4 5 5 5 5 - 5 0.8 2 1 4 5 4 5 - 4 86th 5 5 5 5 5 5 5 - 5 0.8 3 3 5 5 5 5 - 5 87th 5 5 4 5 5 5 5 - 5 0.8 3 3 5 5 5 5 - 5 88th 5 4 3 5 5 5 5 - 5 0.8 3 0 5 4 3 5 - - 89th 5 4 3 5 5 3 - 5 5 0.8 1 1 5 3 1 - 5 5 90th 5 4 2 5 5 - 5 - 0 0.8 2 0 4 4 3 4 - 0 91st 5 4 4 5 5 5 5 - 5 0.8 2 2 4 5 5 5 - 5 92nd 5 4 3 5 5 5 - 5 5 0.8 1 1 5 4 4 - 5 5 93rd 5 4 2 5 5 5 - 5 5 0.8 1 1 4 3 4 - 5 5 94th 5 4 2 5 5 5 - 5 5 0.8 2 1 5 5 5 - 5 5 95th 5 3 2 5 4 3 - 5 5 0.8 1 1 5 2 1 - 5 5 96th 5 4 4 5 5 5 - 5 5 0.8 1 1 5 5 5 - 5 5 97th 5 3 3 5 5 5 - 5 5 0.8 1 1 4 5 3 - 5 5 98th 5 4 3 5 5 5 - 5 5 0.8 1 1 4 5 4 - 5 5 99th 5 3 3 5 5 5 - 5 5 0.8 1 1 4 3 4 - 5 5 100 5 4 3 5 5 3 - 5 5 0.8 1 1 3 4 1 - 5 5 One hundred and first 5 4 3 5 5 3 - 5 5 0.8 1 1 4 5 1 - 5 5 102nd 5 4 4 5 5 5 - 5 5 0.8 1 1 4 5 4 - 5 5 103rd 5 4 3 5 5 2 5 - 5 0.8 3 1 5 4 0 - - 5 104th 5 4 4 5 5 - 5 - 5 0.8 3 2 4 5 0 - - 5 105th 5 4 3 5 5 - 5 - 5 0.8 3 1 5 5 - 5 - 5 106th 5 4 3 5 5 2 - 5 5

HU 212 628 Β

0.8 3 1 5 5 - - 5 4 107th 5 5 3 5 5 3 - 5 5 0.8 3 1 5 4 - - 5 5 108th 5 4 3 5 5 3 - 5 5 0.8 3 1 5 5 - - 5 5 109th 5 4 3 5 5 2 5 - 5 0.8 3 1 5 5 - 5 - 5 110th 5 5 3 5 5 2 5 - 5 0.8 3 1 5 5 - 5 - 5 111th 5 4 2 2 5 1 4 - 5 0.8 1 0 1 4 - 2 - 3 112th 5 4 4 5 5 5 5 - 5 0.8 3 2 5 5 3 5 - - 113th 5 5 4 5 5 5 5 - 5 0.8 3 2 5 5 4 5 - - 114th 5 3 3 5 5 5 5 - 5 0.8 0 1 3 5 4 5 - 4 115th 5 3 3 5 5 2 5 - 5 0.8 0 0 4 5 - 2 - 3 116th 5 4 4 5 5 2 5 - 5 0.8 3 2 5 5 - 5 - 5 117th 5 4 3 5 5 2 5 - 5 0.8 2 0 5 5 0 5 - 5 118th 5 4 2 5 5 3 - 5 5 0.8 2 0 4 4 1 - 5 5 119th 5 4 2 5 5 4 5 - 5 0.8 2 0 5 4 2 5 5 120th 5 3 3 5 5 2 5 - 5 0.8 1 1 4 5 - 4 - 4 121st 5 4 3 5 5 3 5 - 5 0.8 2 1 4 5 1 5 - 5 122nd 5 4 3 5 5 2 5 - 5 0.8 2 0 4 4 - 5 - 5 123rd 5 4 3 5 5 2 5 - 5 0.8 2 1 4 5 - 5 - 5 125th 5 4 3 5 5 2 - 5 5 0.8 2 1 5 4 1 - 5 5 126th 5 4 4 5 5 - 5 - 5 0.8 2 2 5 5 - 5 - 5 127th 5 4 4 5 5 - 5 - 5 0.8 2 1 4 5 - 5 - 5 128th 5 4 4 5 5 0 4 - 5 0.8 2 1 4 4 0 3 - 4 129th 5 4 4 5 5 - 5 - 5 0.8 2 1 5 5 - 5 - 5

130th 5 4 4 5 5 0 5 - 5 0.8 1 0 5 4 0 5 - 5 131st 5 4 4 5 4 - 5 - 5 0.8 0 0 4 3 - 4 - 4 132nd 5 3 3 4 3 - 2 - 2 0.8 0 0 3 1 - 0 - 0 133rd 5 4 4 5 5 - 5 - 5 0.8 2 2 4 5 - 5 - 4 134th 5 4 3 4 5 - 5 - 5 0.8 2 1 3 5 - 4 - 5 135th 5 4 4 5 5 - 5 - 5 0.8 2 2 4 5 - 4 - 4 136th 5 4 4 5 5 - 5 - 5 0.8 2 2 4 5 - 5 - 4 137th 5 4 4 5 5 - 5 - 5 0.8 2 2 4 5 - 5 - 5 138th 5 4 4 5 5 5 5 - - 0.8 2 2 4 5 1 5 - - 139th 5 4 4 5 5 5 5 - 5 0.8 2 2 5 5 3 5 - 5 140th 5 4 4 5 5 - 5 - 5 0.8 3 2 5 5 - 5 - 5 141st 5 4 3 5 5 - 5 - 5 0.8 2 1 5 5 - 5 - 5 142nd 5 4 4 5 5 - 5 - 5 0.8 3 3 5 5 - 5 - 5 143rd 5 5 4 5 5 - 5 - 5 0.8 3 2 5 5 - 5 - 5 144th 5 3 3 5 5 - 5 - 5 0.8 1 1 4 4 - 5 - 4 145th 5 5 5 5 5 2 5 - 5 0.8 3 3 4 5 0 5 - 5 146th 5 3 4 5 5 4 5 - 5 147th 5 2 2 5 5 3 5 - 5 148th 5 2 0 5 5 2 5 - 5 149th 5 3 5 5 5 5 5 - 5 150th 5 4 3 5 5 4 5 - 5 0.8 2 1 5 5 2 5 - 5 151st 5 5 3 5 5 3 5 - 5 0.8 3 1 5 5 1 5 - 5 152nd 5 4 4 5 5 5 5 - 5 0.8 2 2 5 5 4 5 - 5 153rd 5 4 4 5 5 5 5 - 5 0.8 3 2 5 5 3 5 - 4 154th 5 3 2 5 4 3 5 - 5

HU 212 628 Β

0.8 1 0 4 2 2 4 - 4 155th 5 3 3 5 5 4 5 - 5 0.8 1 0 4 4 3 4 - 5 156th 5 3 3 5 4 2 5 - 5 0.8 1 0 4 3 0 4 - 4 157th 5 3 3 4 3 5 - - 5 0.8 1 0 3 2 4 - - 5 158th 5 3 3 4 5 0 5 - 3 0.8 1 0 3 4 0 4 - 0 159th 5 3 3 4 5 0 5 - 2 0.8 1 0 3 4 0 5 - 0 160th 5 3 3 4 5 0 5 - 2 0.8 0 0 3 3 0 3 - 0 161st 5 3 3 5 5 2 4 - 4 0.8 1 1 4 5 0 3 - - 162nd 5 5 3 5 5 4 5 - 5 0.8 3 1 5 4 3 5 - 4 163rd 5 5 3 5 5 2 5 - 5 0.8 3 1 5 4 0 3 - 4 164th 5 3 3 5 5 - 5 - 5 0.8 1 1 5 4 - 5 - 5 165th 5 4 3 5 5 - 5 - 5 0.8 2 1 4 5 - 4 - 4 166th 5 4 3 5 5 - 5 - 5 0.8 2 0 4 4 - 4 - 4 167th 5 3 3 5 5 3 5 - 5 0.8 1 1 4 4 1 5 - 4 168th 5 3 3 5 5 2 5 - 5 0.8 0 0 4 4 1 4 - 4 169th 5 3 3 5 5 5 2 - 5 0.8 1 0 4 4 3 0 - 4 170th 5 3 3 4 4 5 5 2 - 0.8 0 0 2 2 3 0 - 4 171st 5 3 5 5 4 0 - - 5 0.8 1 3 4 2 0 - - 5 172nd 5 4 3 5 5 - 5 - 5 0.8 2 1 4 4 0 - - 4 173rd 5 3 3 3 2 0 2 - 4 0.8 0 0 1 0 0 0 - 3 174th 5 3 3 5 4 0 2 - 5 0.8 1 0 4 3 0 - - 4 175th 5 4 4 5 5 - 5 - 5 0.8 2 2 4 4 0 - - 5 176th 5 2 2 3 2 0 2 1 177th 5 3 2 5 4 0 3 1

0.8 0 0 4 3 0 2 - 0 178th 5 3 3 5 4 0 2 - 1 0.8 1 1 4 3 0 0 - 0 179th 5 3 3 5 4 0 5 - 5 0.8 1 0 4 3 0 5 - 3 180th 5 3 2 2 4 - 3 - 4 0.8 1 0 1 2 0 1 - 2 181st 5 3 3 4 5 - 5 - 2 0.8 0 0 3 4 0 3 - 0 182nd 5 3 3 5 4 - 5 - 5 0.8 0 0 4 3 0 5 - 5 183rd 5 3 2 4 3 - 5 - 5 0.8 1 0 4 1 - 3 - 5 184th 5 3 2 4 2 - 2 - 2 185th 5 3 2 5 2 0 2 - 1 186th 5 3 2 5 5 0 2 - 1 187th 5 2 2 2 3 0 2 - 1 188th 5 2 2 3 2 - 2 5 1 189th 5 3 3 5 4 - 5 - 5 0.8 1 0 4 2 0 4 - 4 190th 5 3 3 4 4 - - 5 5 0.8 1 1 3 2 - 0 5 5 191st 5 3 3 4 5 2 - 5 5 0.8 1 1 3 3 ¹ - 5 5 192nd 5 3 3 5 2 - 5 5 0.8 0 0 2 1 0 - 5 5 193rd 5 2 1 2 3 - 2 - 1 194th 5 4 3 5 5 5 5 - 5 0.8 2 1 4 5 2 5 - 5 195th 5 3 3 5 5 - 4 - 1 0.8 1 1 4 5 0 3 - 0 196th 5 3 3 5 5 - 4 - 1 0.8 0 1 4 5 0 3 - 0 197th 5 3 3 5 4 - 5 - 5 0.8 1 0 4 3 - 5 - 3 198th 5 3 3 4 5 - - 5 5 0.8 1 1 3 3 - - 5 5 199th 5 3 3 4 4 2 - 5 2 0.8 1 1 3 2 1 - 5 1 200th 5 3 3 3 3 - - 5 5 0.8 1 0 2 1 0 - 5 5 Two hundred and first 5 3 3 4 4 - - 5 5 0.8 0 1 3 2 0 - 5 5 202nd 5 2 2 3 2 - - 5 1 0.8 0 0 2 0 0 - 5 0

HU 212 628 Β

203rd 5 2 2 3 2 - - 5 1 0.8 0 0 2 0 0 - 5 0 204th 5 3 3 3 4 2 - 5 5 0.8 1 1 2 2 1 - 5 5 206th 5 3 3 4 2 - 4 - 5 0.8 1 1 3 0 0 2 - 4 207th 5 2 2 4 4 - 2 - 1 0.8 0 0 3 2 0 0 - 0 208 5 2 2 4 5 - 5 - 1 0.8 0 0 3 3 0 4 - 0 209th 5 2 2 4 5 - 4 - 1 0.8 0 0 3 3 0 2 - 0 210th 5 1 1 4 1 - 4 - 4 212th 5 2 1 4 3 0 0 - 5 216th 5 3 2 4 3 5 2 - 5 0.8 1 0 2 2 4 0 - 5 220th 5 3 4 5 5 5 5 - 5 0.8 0 2 5 4 1 5 - 5 221st 5 3 3 5 4 0 5 - 5 0.8 1 1 5 3 - 4 - 5 222nd 5 3 3 5 3 3 5 - 5 0.8 3 0 5 2 1 5 - 5 224th 5 3 2 4 4 1 - 5 1 0.8 1 0 3 1 0 - 5 1 225th 5 5 3 5 5 2 - 5 5 0.8 3 1 4 5 0 - 5 5 227th 5 3 3 3 4 0 - 5 2 229th 5 3 2 4 5 1 - 5 5 0.8 1 0 2 3 0 - 5 4 230th 5 4 4 5 5 1 - 5 5 0.8 2 2 4 5 0 - 5 5 231st 5 3 3 4 5 1 - 5 5 0.8 1 1 3 4 0 - 5 5 232nd 5 3 3 5 5 1 - 5 5 0.8 1 1 4 5 0 - 5 5 233rd 5 3 2 4 5 2 - 5 5 0.8 1 0 3 5 1 - 5 5 234th 5 3 3 5 5 1 - 5 5 0.8 1 1 4 4 0 - 5 5 235th 5 3 2 3 5 0 - 5 2 0.8 1 0 2 4 0 - 5 0 236th 0.8 2 1 4 5 1 - 5 4 0.2 0 0 2 4 0 - 5 1 237th 5 3 2 3 5 1 - 5 5 0.8 1 0 2 3 0 - 5 4

238th 5 4 4 5 5 2 - 5 5 0.8 2 2 4 5 - - 5 5 239th 5 3 3 5 5 2 - 5 5 0.8 1 1 4 5 - - 5 5 240th 5 3 3 5 5 2 - 5 5 0.8 1 1 4 5 - - 5 5 241st 5 3 2 5 5 1 - 5 5 0.8 1 0 3 4 0 - 5 3 242nd 5 ³ 2 5 5 1 - 5 4 0.8 1 0 4 5 0 - 5 3 243rd 0.8 2 1 4 5 1 - 5 4 0.2 0 0 2 4 0 - 5 1 244th 5 3 3 5 5 5 - 5 5 0.8 1 1 4 4 3 - 5 5 245th 5 3 3 5 5 1 - 5 5 0.8 1 1 3 4 0 - 5 5 247th 5 3 3 3 4 0 - 5 2 0.8 1 1 2 1 0 - 5 1 248th 5 3 2 5 5 2 - 5 5 0.8 1 0 3 3 0 - 5 4 249th 5 3 3 5 5 2 - 5 5 0.8 1 1 3 4 0 - 5 5 250th 5 4 3 5 5 1 - 5 5 0.8 2 1 5 5 0 - 5 5 251st 5 4 3 5 5 4 - 5 5 0.8 2 1 5 5 2 - 5 5 252nd 5 3 2 4 4 1 - 5 4 0.8 1 0 3 2 0 - 5 2 253rd 5 4 3 5 5 3 - 5 5 0.8 2 1 4 5 2 - 5 4 254th 5 3 3 5 5 2 - 5 5 0.8 1 1 4 4 0 - 5 5 255th 0.8 5 5 5 5 4 - 5 5 0.2 3 3 4 5 2 - 5 5 256th 0.2 5 3 5 5 2 - 5 5 0.1 3 2 4 5 1 - 5 5 257th 0.8 3 2 5 5 2 - 5 5 0.2 1 0 5 5 0 - 5 4 258th 0.2 5 4 5 5 4 - 5 5 0.1 3 3 4 5 2 - 5 5 259th 0.8 3 3 4 3 1 - 5 4 0.2 0 0 2 1 0 - 4 2 260th 0.8 3 2 4 5 1 - 5 3 0.2 1 0 3 3 0 - 5 1 261st 0.8 4 3 5 5 4 - 5 5

HU 212 628 Β

0.2 2 1 4 5 3 - 5 5 262nd 0.8 2 1 4 5 1 - 5 4 0.2 0 0 2 3 0 - 5 2 263rd 0.8 2 1 3 4 1 - 5 3 0.2 0 0 0 2 0 - 5 2 264th 0.8 2 1 3 4 1 - 5 3 0.2 0 0 0 1 1 - 5 0 265th 0.8 3 1 4 5 1 - 5 3 0.2 1 0 2 4 0 - 5 0 266th 0.8 2 1 4 3 1 - 5 5 0.2 0 0 2 0 0 - 5 5 267th 0.8 2 2 3 4 1 - 5 5 0.2 0 1 0 2 0 - 5 3 269th 0.8 3 1 5 4 0 - 5 4 0.2 1 0 2 2 0 - 5 3 270th 0.8 3 1 5 5 1 - 5 4 0.2 1 0 5 3 0 - 5 2 271st 0.8 3 1 5 5 3 - 5 5 0.2 1 0 4 5 3 - 5 3 272nd 0.8 3 2 5 5 2 - 5 5 0.2 2 1 5 5 0 - 5 5 273rd 0.8 3 1 5 4 1 - 5 5 0.2 1 0 4 2 0 - 5 1 274th 0.8 3 1 5 5 1 - 5 5 0.2 1 0 3 5 1 - 5 4 275th 0.8 3 1 5 5 1 - 5 5 0.2 1 0 3 4 0 - 5 5 276th 5 4 3 4 4 1 - 5 4 0.8 2 1 3 4 0 - 5 3 277th 5 3 3 4 5 1 - 5 4 0.8 1 1 3 5 0 - 5 2 278th 5 3 3 4 5 1 - 5 4 0.8 1 1 3 4 0 - 5 3 279th 5 3 3 4 5 1 - 5 4 0.8 0 0 2 3 0 - 5 3 280 5 4 2 5 5 1 - 5 5 0.8 2 0 4 3 0 - 5 5 281st 5 3 3 5 5 1 - 5 5 0.8 1 I 4 5 0 - 5 5 282nd 5 3 3 5 5 2 - 5 5 0.8 1 1 4 5 0 - 5 5 283rd 5 3 3 5 5 2 - 5 5 0.8 1 1 4 5 0 - 5 5 284th 5 3 3 5 5 I - 5 5 0.8 1 1 4 3 0 - 5 5

285th 5 3 3 5 5 3 - 5 5 0.8 1 1 4 5 2 - 5 5 286th 5 3 3 5 5 2 - 5 5 0.8 1 1 3 4 0 - 5 5 287th 5 4 2 5 5 2 - 5 5 0.8 2 0 4 5 - - 5 5 288th 5 4 3 5 5 2 - 5 5 0.8 2 1 4 5 - - 5 5 289th 5 4 3 5 5 2 - 5 5 0.8 2 1 4 5 - - 5 4 290th 5 3 3 5 5 2 - 5 5 0.8 1 1 5 5 1 - 5 5 291st 5 3 3 5 3 2 - 5 5 0.8 1 1 4 1 1 - 5 5 292nd 5 3 2 5 5 4 - 5 5 0.8 1 0 3 4 2 - 5 5 293rd 5 3 1 3 5 2 - 5 5 0.8 1 0 2 4 0 - 5 5 294th 5 3 1 4 3 1 - 5 5 0.8 1 0 3 1 0 - 5 5 295th 5 3 2 5 5 1 - 5 5 0.8 1 0 4 4 0 - 5 5 296th 5 4 3 5 5 1 - 5 5 0.8 2 1 4 4 0 - 5 5 297th 5 3 3 5 5 1 - 5 5 0.8 1 1 4 4 - - 5 5 298th 5 3 3 4 5 1 - 5 5 0.8 1 1 3 4 - - 5 5 299th 5 4 3 5 5 1 - 5 5 0.8 2 1 3 4 0 - 5 4 300th 5 3 2 4 5 1 - 5 5 0.8 1 0 2 3 0 - 5 5 302nd 5 4 2 5 5 2 - 5 5 0.8 2 0 4 5 0 - 5 5 Three hundred and first 5 3 2 4 5 1 - 5 5 0.8 1 0 3 3 0 - 5 5 303rd 5 4 2 4 5 1 - 5 5 0.8 2 0 3 3 0 - 5 5 304th 5 3 3 5 5 2 - 5 5 0.8 1 1 4 4 1 - 5 5 305th 5 3 3 5 5 1 - 5 5 0.8 1 1 4 5 0 - 5 3 306th 5 4 3 4 5 2 - 5 5 0.8 2 1 3 3 1 - 5 5 307th 5 3 2 5 5 2 - 5 5

HU 212 628 Β

0.8 1 0 4 4 0 - 5 5 308th 5 4 3 5 5 2 - 5 5 0.8 2 1 4 5 - - 5 4 309th 5 4 4 5 5 2 - 5 5 0.8 2 2 4 5 - - 5 5 310th 5 4 5 5 5 2 - 5 5 0.8 2 3 3 5 0 - 5 5 312th 5 3 2 3 4 1 - 5 5 0.8 1 0 2 2 0 - 5 5 313th 5 3 3 5 5 2 - 5 5 0.8 1 1 4 5 0 - 5 5 314th 5 3 2 4 5 2 - 5 5 0.8 1 0 2 5 0 - 5 5 315th 5 3 3 5 5 1 - 5 5 0.8 1 1 3 4 0 - 5 5 316th 5 4 3 5 5 2 - 5 5 0.8 2 1 3 4 1 - 5 5 317th 5 4 3 5 5 2 - 5 5 0.8 2 1 3 4 1 - 5 5 318th 5 3 2 5 3 2 - 5 5 0.8 1 0 4 1 1 - 5 5 319th 5 3 3 5 5 5 - 5 5 0.8 1 1 5 5 3 - 5 5 320th 5 3 3 5 5 2 - 5 4 0.8 0 0 4 5 1 - 5 2 321st 5 3 2 4 5 1 - 5 5 0.8 1 0 2 3 0 - 5 4 322nd 5 2 1 3 4 1 - 5 4 0.8 0 0 0 1 0 - 3 2 323rd 5 4 4 5 5 5 - 5 5 0.8 2 2 5 4 3 - 5 4 324th 5 5 4 5 5 4 - 5 5 0.8 3 2 5 4 3 - 5 3 325th 5 3 4 5 5 - - 5 5 0.8 1 2 4 5 - - 5 4 326th 5 4 3 5 5 5 - 5 5 0.8 2 1 4 5 3 - 5 5 327th 5 4 3 5 5 5 - 5 5 0.8 2 1 4 5 2 - 5 5 328th 5 3 4 5 5 4 - 5 5 0.8 1 2 4 5 2 - 5 4 329th 5 2 1 3 3 1 - 5 4 0.8 0 0 1 0 0 - 5 1 330th 5 3 1 4 5 1 - 5 5 331st 5 5 5 5 5 5 - 5 5

0.8 3 4 5 5 5 - 5 5 332nd 0.8 5 5 5 5 5 - 5 5 0.2 3 3 3 4 3 - 5 4 333rd 5 3 2 4 5 1 - 5 2 0.8 1 0 3 3 1 - 5 - 334th 5 2 2 3 4 1 - 5 5 0.8 0 0 2 2 0 - 5 5 335th 5 2 1 4 5 1 - 5 5 0.8 0 0 0 0 0 - 4 - 336th 5 2 2 5 5 2 - 5 5 0.8 0 0 4 5 1 - 5 4 337th 5 2 2 4 3 1 - 5 5 0.8 0 0 3 1 0 - 5 3 338th 5 3 2 4 5 1 - 5 5 0.8 1 0 3 3 0 - 5 5 339th 5 2 1 4 4 0 - 5 4 340th 5 2 2 3 4 1 - 5 5 0.8 0 0 2 2 0 - 5 5 341st 0.8 3 1 3 4 1 - 5 4 0.2 1 0 0 1 0 - 3 3 342nd 0.8 3 1 5 5 1 - 5 4 0.2 1 0 4 5 0 - 5 2 343rd 0.8 3 1 5 5 1 - 5 4 0.2 1 0 4 5 0 - 5 2 344th 0.8 3 1 5 5 1 - 5 4 0.2 1 0 3 3 0 - 5 2 345th 0.8 3 2 5 5 1 - 5 4 0.2 1 1 3 4 0 - 5 2 346th 0.8 3 1 5 5 1 - 5 4 0.2 1 0 3 4 0 - 5 2 347th 0.8 3 1 5 5 1 - 5 4 0.2 1 0 3 4 0 - 5 1 348th 0.8 3 1 5 5 1 - 5 4 0.2 1 0 3 5 0 - 5 1 349th 0.8 3 1 4 5 1 - 5 4 0.2 1 0 2 4 0 - 5 1 350th 0.8 3 1 4 5 1 - 5 4 0.2 1 0 2 3 0 - 5 4 351st 0.8 2 1 3 4 1 - 5 4 0.2 0 0 0 3 - - 5 1 352nd 0.8 3 1 4 5 1 - 5 5 0.2 1 0 2 4 0 - 5 4 353rd 0.8 2 1 4 5 1 - 5 3 0.2 0 0 2 4 0 - 5 0 354th 0.8 3 1 4 4 0 - 5 4

HU 212 628 Β

0.2 1 0 2 2 0 - 5 4 355th 0.8 2 1 4 4 0 - 5 4 0.2 0 0 2 2 0 - 5 0 356th 0.8 2 1 4 4 0 - 5 4 0.2 1 0 1 1 0 - 5 0 357th 0.8 2 1 4 4 1 - 5 4 0.2 0 0 3 1 0 - 5 0 358th 0.8 2 1 4 5 1 - 5 3 0.2 0 0 3 4 0 - 5 0 359th 0.8 3 1 5 5 1 - 5 4 0.2 1 0 3 5 0 - 5 1 360th 0.8 3 1 5 5 1 - 5 5 0.2 1 0 4 5 - - 5 3 361st 0.8 3 1 4 4 1 - 5 4 0.2 1 0 3 3 0 - 5 0 362nd 0.8 3 1 4 5 1 - 5 5 0.2 1 0 3 5 0 - 5 3 363rd 5 5 3 5 5 2 - 5 5 0.8 3 1 4 5 1 - 5 4 364th 0.8 3 1 5 5 1 - 5 4 0.2 1 0 3 5 0 - 5 2 365th 0.8 2 1 5 5 1 - 5 4 0.2 0 0 4 5 0 - 5 1 366th 0.8 3 1 4 4 1 - 5 3 0.2 1 0 3 2 0 - 5 0 367th 0.8 2 1 4 4 1 - 5 3 0.2 0 0 3 2 0 - 0 0 368th 5 4 3 5 5 2 - 5 5 0.8 2 1 5 5 1 - 5 5 369th 0.8 3 2 5 5 2 - 5 5 0.2 1 2 4 5 0 - 5 2 370th 0.8 3 2 4 5 2 - 5 4 0.2 0 1 2 4 0 - 4 0 371st 0.8 3 1 5 5 1 - 5 4 0.2 1 0 3 4 0 - 5 2 372nd 0.8 4 4 5 5 5 - 5 5 0.2 2 2 5 4 4 - 5 4 373rd 0.8 4 4 5 5 4 - 5 5 0.2 2 2 5 5 3 - 5 4 374th 0.8 5 4 5 5 4 - 5 5 0.2 3 2 5 5 2 - 5 5 375th 0.8 5 4 5 5 4 - 5 5 0.2 3 2 5 5 2 - 5 5 376th 0.8 5 4 5 5 4 - 5 5 0.2 3 2 5 5 2 - 5 5

377th 0.8 3 3 5 5 5 - 5 5 378th 5 3 1 5 5 1 - 5 5 0.8 0 0 1 0 0 - 4 - 379th 5 3 3 4 5 2 - 5 5 0.8 1 1 3 3 1 - 5 5 380th 5 3 1 3 4 1 - 5 3 0.8 1 0 2 2 0 - 4 2 381st 5 2 3 3 5 1 - 5 3 0.8 0 1 2 4 0 - 5 2 382nd 5 2 2 5 5 1 - 5 5 0.8 0 0 4 3 0 - 5 5 383rd 5 3 2 5 5 1 - 5 3 0.8 1 0 3 4 0 - 5 - 384th 5 3 2 4 4 1 - 5 2 0.8 1 0 3 2 0 - 5 - 385th 5 4 3 4 4 1 - 5 2 0.8 2 1 3 2 0 - 5 - 386th 5 3 1 4 5 1 - 5 5 0.8 0 0 2 3 0 - 5 4 388th 5 3 2 4 5 1 - 5 5 0.8 1 0 3 4 0 - 5 5 389th 5 3 2 4 5 1 - 5 5 0.8 1 0 3 4 0 - 5 5 390th 5 3 3 4 5 1 - 5 5 0.8 1 1 3 5 0 - 5 5 391st 5 3 2 4 3 0 - 5 5 0.8 1 0 3 1 0 - 5 5 392nd 5 2 1 4 4 1 - 5 5 0.8 0 0 2 1 0 - 5 4 393rd 5 3 2 4 4 1 - 5 5 0.8 0 0 2 2 0 - 5 5 394th 5 3 3 4 4 0 - 5 5 0.8 1 1 2 2 0 - 5 5 395th 5 3 2 4 5 1 - 5 5 0.8 1 0 2 2 0 - 5 5 396th 5 2 1 4 3 1 - 5 4 0.8 0 0 2 0 0 - 5 0 398th 5 2 1 3 3 1 - 5 3 399th 5 2 1 4 3 1 - 5 3 0.8 0 0 2 1 0 - 5 0 400th 5 2 1 4 4 1 - 5 4 0.8 0 0 3 2 0 - 5 2 Four hundred and first 5 3 3 5 5 5 - 5 5 0.8 1 1 4 3 4 - 5 4 402nd 5 3 3 5 5 5 - 5 5

HU 212 628 Β

0.8 1 1 4 5th 1 - 5 5 403rd 0.8 4 3 5 5 2 - 5 5 0.2 2 1 4 5 1 - 5 4 404th 4 5 4 5 5 3 - 5 5 0.8 3 2 5 5 1 - 5 5 405th 5 4 3 4 5 1 - 5 5 0.8 2 1 3 4 0 - 5 4 406th 5 4 3 4 5 1 - 5 5 0.8 2 1 3 4 0 - 5 4 (THE) picture write off ve- fruit being 5 0 0 0 0 0 0 0 0 (B) picture write off ve- fruit being 5 0 0 0 0 0 0 0 0 (C) picture write off ve- fruit being 5 0 0 0 0 0 0 0 0 ID) picture write off ve- fruit being 5 0 0 0 0 0 0 0 0

As shown in FIG. Table 3 shows that the 3- (substituted phenyl) pyrazole derivatives of formula (I) and their salts have significantly better activity against weeds in pre-emergence test in rice soil than in (A), (B), (C) and (D). ). If the derivatives exert a herbicidal action on the weeds in a single dose and at the same time have a phytotoxic effect on the crop, at a suitably selected lower dose they will still have sufficient herbicidal activity and substantially reduce the phytotoxic effect on the crop.

4. Test Example

Herbicidal effect on weeds of highland areas in postemergent treatment is filled with soil cm wide, 20 cm long and 5 cm deep and planted with the seeds of the weeds and soybean and wheat listed below. These plants are allowed to grow to the condition also indicated below, after which the weeds and crop plants are sprayed separately with the active compounds VIII according to the invention.

The dose is given in Table I (compound numbering according to Table I) and after 14 days the herbicidal activity is tested. The percentage of dead weeds was evaluated as in Test Example 1, and the phytotoxic effect on soybeans and wheat was evaluated as in Test Example 1.

The weeds included in the study are listed below and the state of development at which the spraying took place is given:

Cocksfoot 2-stage development stage

Silkworm 2-stage development stage

Strawberry 1 leaf stage

Maturity 1 leaf stage of development

Veronica 1-leaf stage of development

Galaj 2-stage development stage

Wheat 2-leaf development stage

Soya beans 1 leaf development stage

Our results are shown in Table VIII. See Table 1. Vili. spreadsheet

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian- thorn rugged Lag Vero nika lady's bedstraw Second 5 1 2 2 5 4 5 - - Third 5 2 4 5 4 4 4 - 4 4th 5 5 5 5 5 5 5 - 5 0.2 3 4 4 5 5 5 - 5 5th 5 5 5 5 5 5 5 - 5 0.2 3 4 5 5 5 5 - 5 6th 5 3 5 5 5 5 5 - 5 7th 5 2 4 4 5 5 5 - 4 8th 5 1 4 2 5 2 5 - 1 9th 5 5 5 4 5 5 5 - 5 0.8 3 5 2 5 5 5 - 5 10th 0.8 5 5 5 5 5 5 - 5 0.1 4 5 4 5 5 5 - 5 11th 5 5 5 5 5 5 5 - 5 0.1 4 4 4 5 5 5 - 5 12th 0.8 5 5 4 5 5 5 - 5 0.2 3 4 3 5 5 5 - 5 13th 0.8 5 5 4 5 5 5 - 5 0.1 4 4 3 5 5 5 - 5 14th 0.8 5 5 4 5 5 5 - 5 0.2 3 4 3 5 5 5 - 5 15th 5 2 3 2 5 5 5 - 5 16th 5 2 3 3 5 4 5 - 4

HU 212 628 Β

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian thorn rugged Lag Vero nika lady's bedstraw 17th 5 2 2 3 5 4 5 - 4 18th 5 2 5 3 5 4 5 - 5 19th 5 5 5 5 5 5 5 - 5 0.8 3 3 3 5 4 5 - 5 20th 5 3 5 4 5 5 5 - 5 21st 5 5 5 4 5 5 5 - 5 0.8 2 3 2 5 5 4 - 5 22nd 5 1 2 2 5 3 5 - 4 23rd 5 2 2 2 5 5 5 - 5 24th 5 2 2 1 5 3 4 - 4 25th 5 3 5 4 5 5 5 - 5 26th 0.8 5 5 4 5 5 5 - 5 0.2 3 5 2 5 5 5 - 5 27th 5 5 5 5 5 5 5 - 5 0.8 4 5 3 5 5 5 - 5 28th 0.8 5 5 4 5 5 5 - 5 0.1 3 4 2 5 5 5 - 5 29th 5 5 5 5 5 5 5 - 5 0.1 4 5 4 5 5 5 - 5 30th 5 5 5 5 5 5 5 - 5 0.8 4 5 3 5 5 5 - 5 31st 5 5 5 5 5 5 5 - 5 0.2 3 5 2 5 5 5 - 5 32nd 0.8 5 5 3 5 5 5 - 5 0.1 3 4 3 5 5 5 - 5 33rd 5 5 5 5 5 5 5 - 5 0.8 3 5 3 5 5 5 - 5 34th 5 5 5 5 5 5 5 - 5 0.8 3 5 3 5 5 5 - 5 35th 5 4 4 4 5 5 5 - 5 0.8 2 2 2 5 5 5 - 5 36th 5 0 1 0 4 4 5 - 3 37th 5 2 5 4 5 5 5 - 5 38th 5 2 5 3 5 5 5 - 5 40th 5 0 2 2 5 4 5 - 5 41st 5 0 3 0 5 0 5 - 5 42nd 5 2 5 3 5 5 5 - 5 43rd 5 2 3 2 5 3 5 - 5 44th 5 2 3 3 5 4 5 - 5

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian- thorn rugged Lag Vero nika lady's bedstraw 45th 5 2 5 3 5 5 5 - 5 46th 5 3 4 3 5 4 5 - 5 47th 5 1 2 3 5 4 5 - 5 48th 5 2 5 2 5 4 5 - 5 49th 5 4 5 5 5 5 5 - 5 50th 5 5 5 5 5 5 5 - 5 0.2 3 5 5 5 5 5 - 5 51st 5 3 5 5 5 5 5 - 5 52nd 5 2 4 3 5 5 5 - 5 54th 5 2 5 4 5 5 5 - 5 55th 5 0 2 1 5 3 5 - 4 56th 5 0 3 1 5 2 5 - 1 57th 5 0 2 2 4 2 5 - 4 58th 5 0 2 0 4 3 5 - 4 59th 5 1 2 2 4 4 5 - - 60th 5 0 2 0 3 4 4 - 3 62nd 5 4 5 4 5 5 - 5 5 0.8 2 3 2 5 5 - 5 5 63rd 5 4 5 4 5 5 - 5 5 0.8 2 4 2 5 5 - 5 5 64th 5 5 5 5 5 5 - - 6 0.8 3 3 3 5 5 - 5 5 66th 5 4 5 4 5 5 - 5 5 0.8 2 4 2 5 5 - 5 5 67th 5 3 5 3 5 5 - 5 5 0.8 1 3 1 5 5 - 5 5 68th 0.8 3 5 3 5 5 - 5 5 70th 5 0 1 0 1 1 3 - 0 71st 5 3 5 5 5 5 5 - 5 72nd 5 2 4 4 5 5 5 - 5 73rd 5 1 3 1 5 3 5 - 2 74th 5 1 3 1 5 2 5 - 2 75th 5 1 2 1 5 2 5 - 1 76th 5 2 1 2 5 2 5 - 2 77th 5 2 5 4 5 5 5 - 4 78th 5 1 4 3 5 4 5 - 3 79th 5 1 2 1 5 2 5 - 3 81st 0.8 5 5 5 5 5 5 - 5 0.2 3 5 5 5 5 5 - 5

HU 212 628 Β

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian thorn rugged Lag Vero nika lady's bedstraw 82nd 0.8 5 5 5 5 5 5 - 5 0.2 3 5 5 5 5 5 - 5 83rd 0.8 5 5 5 5 5 5 - 5 0.2 3 4 3 5 5 5 - 5 84th 0.8 5 5 5 5 5 5 - 5 0.2 3 5 4 5 5 5 - 5 85th 0.8 5 5 5 5 5 5 - 5 0.2 3 3 4 5 5 5 - 5 86th 0.8 5 5 5 5 5 5 - 5 0.2 3 5 5 5 5 5 - 5 87th 0.8 5 5 5 5 5 5 - 5 0.1 4 5 5 5 5 5 - 5 88th 0.8 5 5 5 5 5 5 - 5 0.1 3 5 5 5 5 5 - 5 89th 5 5 5 5 5 5 - 5 5 0.8 4 5 4 5 5 - 5 5 90th 0.8 5 5 5 5 5 5 - 5 0.2 3 3 3 5 5 5 - 5 91st 5 5 5 5 5 5 5 - 5 0.8 3 5 5 5 5 5 - 5 92nd 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 93rd 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 94th 5 5 5 5 5 5 - 5 5 0.8 3 5 5 5 5 - 5 5 95th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 96th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 97th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 98th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 99th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 100th 5 5 5 4 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 One hundred and first 5 5 5 5 5 5 - 5 5

Number of compound THE authorities the- Nyagan · ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab Rooster leg grass Neither- lyem- mály- va Serbian thorn rugged Lag Vero nika lady's bedstraw 0.8 2 5 4 5 5 - 5 5 102nd 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 103rd 5 5 5 5 5 5 5 - 5 0.8 3 4 3 5 5 5 - 5 104th 5 5 5 5 5 5 5 - 5 0.8 3 4 3 5 5 5 - 5 105th 5 5 5 5 5 5 5 - 5 0.8 4 5 5 5 5 5 - 5 106th 5 5 5 5 5 5 - 5 5 0.8 3 5 5 5 5 - 5 5 107th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 108th 5 5 5 5 5 5 - 5 5 0.8 3 5 5 5 5 - 5 5 109th 5 5 5 5 5 5 5 - 5 0.8 4 5 5 5 5 5 - 5 110th 5 5 5 5 5 5 5 - 5 0.8 4 5 5 5 5 5 - 5 111th 5 4 5 4 5 5 5 - 5 0.8 2 5 2 5 4 5 - 4 112th 0.8 5 5 5 5 5 5 - 5 0.2 3 5 4 5 5 5 - 5 113th 0.8 5 5 5 5 5 5 - 5 0.2 3 5 5 5 5 5 - 5 114th 5 4 5 5 5 5 5 - 5 0.8 2 5 4 5 5 5 - 5 115th 5 4 5 5 5 5 5 - 5 0.8 2 5 4 5 5 5 - 5 116th 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 117th 0.8 5 5 5 5 5 5 - 5 0.2 3 3 3 5 5 5 - 5 118th 5 5 5 5 5 5 - 5 5 0.8 3 5 3 5 5 - 5 5 119th 0.8 5 5 5 5 5 5 - 5 0.2 3 5 3 5 5 5 - 5 120th 5 4 5 4 5 5 5 - 5 0.8 2 3 3 5 5 5 - 5

HU 212 628 Β

Number of compound THE authorities the- Nyagan meny- lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian thorn Masz Lag Vero nika lady's bedstraw 121st 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 122nd 0.8 5 5 5 5 5 5 - 5 0.2 3 5 3 5 5 5 - 5 123rd 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 124th 5 3 3 2 5 5 5 - 4 0.8 0 1 0 4 4 5 - 3 125th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 126th 0.8 5 5 5 5 5 5 - 5 0.2 3 5 4 5 5 5 - 5 127th 5 5 5 5 5 5 5 - 5 0.8 3 5 5 5 5 5 - 5 128th 5 5 5 5 5 5 5 - 5 0.8 3 5 5 5 5 5 - 5 129th 0.8 5 5 5 5 5 5 - 5 0.2 3 5 5 5 5 5 - 5 130th 5 5 5 5 5 5 5 - 5 0.8 3 5 5 5 5 5 - 5 131st 0.8 5 5 5 5 5 5 - 5 0.2 3 5 3 5 5 5 - 5 132nd 5 5 5 5 5 5 5 - 5 0.8 3 5 5 5 5 5 - 5 133rd 0.8 5 5 5 5 5 5 - 5 0.2 3 5 4 5 5 5 - 5 134th 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 135th 5 5 5 5 5 5 5 - 5 0.8 3 5 5 5 5 5 - 5 136th 5 5 5 5 5 5 5 - 5 0.8 3 5 5 5 5 5 - 5 137th 5 5 5 5 5 5 5 - 5 0.8 3 5 5 5 5 5 - 5 138th 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 139th 5 5 5 5 5 5 5 - 5 0.8 3 5 5 5 5 5 - 5 140th 5 5 5 5 5 5 5 - 5

I

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- Maly va Serbian thorn Masz Lag Vero nika lady's bedstraw 0.8 4 5 5 5 5 5 - 5 141st 5 5 5 5 5 5 5 - 5 0.8 3 5 5 5 5 5 - 5 142nd 5 5 5 5 5 5 5 - 5 0.8 3 4 5 5 5 5 - 5 143rd 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 144th 5 5 5 5 5 5 5 - 5 0.8 3 4 3 5 5 5 - 5 145th 5 5 5 5 5 5 5 - 5 0.8 3 4 5 5 5 5 - 5 146th 5 3 5 5 5 5 5 - 5 147th 5 4 5 5 5 5 5 - 5 148th 5 3 5 5 5 5 5 - 5 149th 5 3 5 4 5 5 5 - 5 150th 5 5 5 5 5 5 5 - 5 0.8 4 5 5 5 5 5 - 5 151st 5 5 5 5 5 5 5 - 5 0.8 4 5 5 5 5 5 - 5 152nd 5 5 5 5 5 5 5 - 6 0.8 4 5 5 5 5 5 - 5 153rd 0.8 5 5 5 5 5 5 - 5 0.2 4 5 5 5 5 5 - 5 154th 5 3 5 4 5 5 5 - 5 0.8 1 3 3 5 4 5 - 4 155th 5 5 5 5 5 5 5 - 5 0.8 3 4 4 5 5 5 - 5 156th 5 4 5 5 5 5 5 - 5 0.8 2 4 4 5 5 5 - 5 157th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 158th 5 5 5 5 5 5 5 - 5 0.8 3 3 4 5 5 5 - 5 159th 5 5 5 5 5 5 5 - 5 0.8 3 4 3 5 4 5 - 5 160th 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 161st 5 5 5 5 5 5 5 - 5 0.8 4 5 5 5 5 5 - 5

HU 212 628 Β

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian· thorn rugged Lag Vero nika lady's bedstraw 162nd 5 5 5 5 5 5 5 - 5 0.8 4 5 4 5 5 5 - 5 163rd 5 5 5 5 5 5 5 - 5 0.8 4 5 4 5 5 5 - 5 164th 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 165th 5 4 5 4 5 5 5 - 5 0.8 2 3 2 5 4 5 - 4 166th 5 5 5 5 5 5 5 - 5 0.8 2 5 3 5 5 5 - 5 167th 5 5 5 5 5 5 5 - 5 0.8 3 4 3 5 5 5 - 5 168th 5 5 5 5 5 5 5 - 5 0.8 3 5 3 5 5 5 - 5 169th 5 5 5 5 5 5 - 5 5 0.8 3 3 3 5 5 - 5 5 170th 5 3 5 4 5 5 - 5 5 0.8 1 4 2 5 5 - 5 4 171st 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 172nd 5 5 5 5 5 5 5 - 5 0.8 4 5 4 5 5 5 - 5 173rd 5 3 5 4 5 5 - 5 5 0.8 1 3 2 5 5 - 5 4 174th 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 175th 0.8 5 5 4 5 5 5 - 5 0.2 3 3 2 5 4 3 - 5 176th 5 3 5 4 5 5 5 - 5 0.8 1 5 2 5 5 5 - 5 177th 5 5 5 5 5 5 5 - 5 0.8 3 5 3 5 5 5 - 5 178th 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 179th 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 180th 5 3 4 4 5 4 5 - 5 0.8 1 2 2 5 3 5 - 4 181st 5 4 5 4 5 5 5 - 5

Number of compound THE authorities the- Nyagan meny- lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian thorn rugged Lag Vero nika lady's bedstraw 0.8 2 4 3 5 4 5 - 4 182nd 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 183rd 5 5 5 5 5 5 5 - 5 0.8 3 5 5 5 5 5 - 5 184th 5 4 5 5 5 5 5 - 5 0.8 2 5 3 5 5 5 - 5 185th 5 4 5 4 5 5 5 - 5 0.8 2 5 2 5 5 5 - 5 186th 5 5 5 5 5 5 5 - 5 0.8 3 5 3 5 5 5 - 5 187th 5 3 5 4 5 5 5 - 5 0.8 0 3 2 4 3 4 - 3 188th 5 4 5 4 5 5 5 - 5 0.8 2 5 3 5 5 5 - 5 189th 5 5 5 5 5 5 5 - 5 0.8 3 5 3 5 5 5 - 5 190 5 5 5 5 5 5 - 5 5 0.8 4 5 4 5 5 - 5 5 191st 5 5 5 5 5 5 - 5 5 0.8 3 5 3 5 5 - 5 5 192nd 5 3 5 4 5 5 - 5 5 0.8 1 3 2 5 5 - 5 5 193rd 5 3 3 3 5 4 - 4 4 0.8 0 0 1 4 2 - 2 2 194th 5 5 5 5 5 5 5 - 5 0.8 2 5 3 5 5 5 - 5 195th 5 5 5 5 5 5 5 - 5 0.8 3 5 3 5 5 5 - 5 196th 0.8 5 5 4 5 5 5 - 5 0.2 3 3 3 5 5 5 - 5 197th 5 5 5 5 5 5 5 - 5 0.8 4 5 4 5 5 5 - 5 198th 5 5 5 5 5 5 - 5 5 0.8 3 5 3 5 5 - 5 5 199th 5 5 5 5 5 5 - 5 5 0.8 3 4 3 5 5 - 5 5 200th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5

HU 212 628 Β

A ve- THE authorities Phytotoxic effect The effect of post-emergent treatment fruit being Ups- today the- Nyagan ling lymph of kg / ha Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian thorn rugged Lag Vero nika lady's bedstraw Two hundred and first 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 202nd 5 4 5 4 5 5 - 5 5 0.8 2 5 2 5 5 - 5 5 203rd 5 4 4 3 5 4 - 5 5 0.8 2 2 1 5 3 - 5 4 204th 5 5 5 5 5 5 - 5 5 0.8 3 5 3 5 5 - 5 5 205th 5 3 5 4 5 5 5 - 5 0.8 1 5 3 5 3 5 - 4 206th 5 4 5 4 5 5 5 - 5 0.8 2 5 2 5 5 5 - 5 207th 5 4 5 5 5 5 5 - 5 0.8 2 3 3 5 4 5 - 5 208th 5 5 5 5 5 5 5 - 5 0.8 3 4 4 5 5 5 - 5 209th 5 4 5 4 5 5 5 - - 0.8 2 3 2 5 4 5 - - 210th 5 3 4 4 5 5 5 - 5 0.8 1 2 3 5 3 5 - 4 211th 5 3 5 4 5 5 5 - 5 0.8 1 4 2 5 4 5 - 5 212th 5 5 5 5 5 5 5 - 5 0.8 3 5 4 5 5 5 - 5 213th 5 3 2 3 5 4 5 - 5 0.8 1 0 1 3 3 5 - 3 214th 5 3 5 4 5 5 5 - - 0.8 1 4 2 5 4 5 - - 215th 5 2 5 3 5 5 5 - 5 216th 5 5 5 5 5 5 - 5 5 0.8 3 4 3 5 5 - 5 5 218th 5 4 5 3 5 5 5 - 5 220th 5 5 5 5 5 5 5 - 5 0.8 4 5 4 5 5 5 - 5 221st 5 5 5 5 5 5 5 - 5 0.8 3 5 3 5 5 5 - 5 222nd 0.8 5 5 4 5 5 5 - 5 0.1 4 4 3 5 5 5 - 5 223rd 5 5 5 5 5 5 - 5 5

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian- thorn rugged Lag Vero nika lady's bedstraw 0.8 5 5 5 5 5 - 5 5 224th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 225th 5 5 5 5 5 4 - 5 5 0.8 2 2 3 4 2 - 4 3 226th 5 5 5 5 5 4 - 4 5 0.8 3 2 3 4 2 - 4 3 227th 5 5 5 5 5 5 - 5 5 0.8 3 3 3 5 4 - 4 4 228th 0.8 5 3 5 5 5 - 5 5 0.2 3 3 4 5 5 - 5 5 229th 5 5 5 5 5 5 - 5 5 0.8 3 2 4 5 5 - 5 5 230th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 231st 5 4 5 5 5 3 - 5 5 0.8 2 5 4 5 - - 5 5 232nd 5 5 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 233rd 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 234th 5 5 5 5 5 5 - 5 5 0.8 2 5 5 5 5 - 5 5 235th 5 5 5 5 5 5 - 5 5 0.8 3 5 3 5 5 - 5 5 236th 0.8 3 5 4 5 5 - 5 5 0.2 1 4 2 5 5 - 5 5 237th 5 4 5 5 5 5 - 5 5 0.8 1 5 4 5 5 - 5 5 238th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 239th 5 5 5 5 5 5 - 5 5 0.8 2 5 5 5 5 - 5 5 240th 5 5 5 5 5 5 - 5 5 0.8 2 5 5 5 5 - 5 5 241st 5 4 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 4 242nd 5 5 5 5 5 5 - 5 5 0.8 3 5 3 5 5 - 5 5

HU 212 628 Β

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect Effect of post-irritant treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian thorn rugged Lag Vero nika lady's bedstraw 243rd 0.8 3 4 4 5 5 - 5 5 0.2 1 2 2 5 5 - 3 5 244th 5 5 5 5 5 5 - 5 5 0.8 3 3 3 5 5 - 5 5 245th 5 5 5 5 5 5 - 5 5 0.8 2 3 2 5 5 - 5 5 246th 5 4 4 4 5 5 - 5 5 0.8 2 2 2 5 4 - 4 4 247th 5 4 5 4 5 5 - 5 5 0.8 2 5 3 5 5 - 5 4 248th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 249th 5 4 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 250th 0.8 3 5 5 5 5 - 5 5 251st 5 5 5 5 5 5 - 5 5 0.8 3 3 5 5 5 - 5 5 252nd 5 5 5 5 5 5 - 5 5 0.8 3 5 5 5 5 - 5 5 253rd 0.8 5 5 4 5 5 - 5 5 0.1 3 4 3 5 5 - 5 5 254th 5 5 5 5 5 5 - 5 5 0.8 3 5 5 5 5 - 5 5 255th 0.8 5 5 5 5 5 - 5 5 0.2 3 5 5 5 5 - 5 5 256th 0.2 5 5 5 5 5 - 5 5 0.1 4 4 4 5 5 - 5 5 257th 0.2 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 258th 0.2 5 5 5 5 5 - 5 5 0.1 4 4 4 5 5 - 5 5 259th 0.8 3 5 5 5 5 - 5 5 0.2 1 3 3 5 5 - 5 5 260th 0.8 4 5 5 5 5 - 5 5 0.2 2 4 4 5 5 - 5 5 261st 0.8 4 5 5 5 5 - 5 5 0.2 2 5 4 5 5 - 5 5 262nd 0.8 4 5 5 5 5 - 5 5 0.2 2 4 3 5 5 - 5 5

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- lábfiS Neither- lyem- mály- va Serbian thorn rugged Lag Vero nika lady's bedstraw 263rd 0.8 4 5 5 5 5 - 5 5 0.2 2 5 4 5 5 - 5 5 264th 0.8 4 5 5 5 5 - 5 5 0.2 2 5 3 5 5 - 5 5 265th 0.8 4 5 5 5 5 - 5 5 0.2 2 5 3 5 5 - 5 5 266th 0.8 4 5 5 5 5 - 5 5 0.2 2 5 3 5 5 - 5 5 267th 0.8 4 5 5 5 5 - 5 5 0.2 2 5 4 5 5 - 5 5 268th 0.8 5 5 5 5 5 - 5 5 0.2 2 5 4 5 5 - 5 5 269th 0.8 5 5 5 5 5 - 5 5 0.2 2 5 4 5 5 - 5 5 270 0.8 5 5 5 5 5 5 5 0.2 3 4 4 5 4 - 5 4 271st 0.2 5 5 5 5 5 - 5 5 0.1 4 5 5 5 5 - 5 5 272nd 0.2 5 5 5 5 5 - 5 5 0.1 4 5 5 5 5 - 5 5 273rd 0.8 5 5 5 5 5 - 5 5 0.2 3 3 5 5 5 - 5 5 274th 0.2 5 5 5 5 5 - 5 5 0.1 4 5 5 5 5 - 5 5 275th 0.2 5 5 5 5 5 - 5 5 0.1 3 4 3 5 5 - 5 5 276th 0.8 5 5 4 5 5 - 5 5 0.2 3 3 2 5 5 - 5 4 277th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 278th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 279th 5 5 5 5 5 5 - 5 5 0.8 3 5 3 5 5 - 5 5 280th 5 5 5 5 5 5 - 5 5 0.8 2 3 3 5 5 - 5 5 281st 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 282nd 5 5 5 5 5 5 - 5 5

HU 212 628 Β

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot brake Neither- lyem- mály- va Serbian thorn Masz Lag Vero nika Gala aj 0.8 2 5 4 5 5 - 5 5 283rd 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 284th 5 5 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 285th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 286th 5 5 5 5 5 5 - 5 5 0.8 2 3 2 5 5 - 5 5 287th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 288th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 289th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 290th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 291st 5 5 5 4 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 292nd 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 293rd 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 294th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 295th 5 5 5 4 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 296th 0.8 4 5 4 5 5 - 5 5 0.2 3 3 3 5 5 - 5 5 297th 5 5 5 5 5 5 - 5 5 0.8 2 4 3 5 5 - 5 5 298th 5 5 5 5 5 5 - 5 5 0.8 3 3 3 5 5 - 5 5 299th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 300th 5 5 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 Three hundred and first 5 5 5 5 5 5 - 5 5 0.8 3 4 3 5 5 - 5 5

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian- thorn rugged Lag Vero nika lady's bedstraw 302nd 5 5 5 5 5 5 - 5 5 0.8 3 5 3 5 5 - 5 5 303rd 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 304th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 305th 5 5 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 306th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 307th 5 5 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 308th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 309th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 310th 5 5 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 311th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 312th 5 5 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 313th 5 5 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 314th 5 5 5 5 5 5 - 5 5 0.8 3 4 4 5 5 - 5 5 315th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 - - 5 5 316th 5 5 5 5 5 5 - 5 5 0.8 3 5 3 5 - - 5 5 317th 5 5 5 5 5 - - 5 5 0.8 3 5 4 5 - - 5 5 318th 5 5 5 5 5 5 - 5 5 0.8 2 3 3 5 5 - 5 5 319th 5 5 5 5 5 5 - 5 5 0.8 3 3 3 5 5 - 5 5 320th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 321st 5 4 5 4 5 5 - 5 5

HU 212 628 Β

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- The main leg Neither- lyem- mály- va Serbian thorn rugged Lag Vero nika lady's bedstraw 0.8 2 3 3 5 5 - 5 5 322nd 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 323rd 0.8 5 5 5 5 5 - 5 5 0.1 4 5 5 5 5 - 5 5 324th 0.8 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 325th 0.8 5 5 5 5 5 - 5 5 0.2 3 5 5 5 5 - 5 5 326th 0.8 5 5 5 5 5 - 5 5 0.2 4 5 4 5 5 - 5 5 327th 0.8 5 5 5 5 5 - 5 5 0.2 4 5 4 5 5 - 5 5 328th 5 5 5 5 5 5 - 5 5 0.8 4 5 5 5 5 - 5 5 329th 5 5 5 5 5 5 - 5 5 0.8 2 3 3 5 5 - 5 5 330th 5 4 5 5 5 5 - 5 5 0.8 1 2 2 5 3 - 5 5 331st 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 332nd 0.8 5 5 5 5 5 - 5 5 0.2 3 4 3 5 5 - 5 5 333rd 5 4 5 4 5 5 - 5 5 0.8 2 4 2 5 5 - 5 5 334th 5 4 4 5 5 5 - 5 5 0.8 2 2 4 5 5 - 5 5 335th 5 4 5 5 5 5 - 5 5 0.8 2 3 3 5 4 - 5 5 336th 5 5 5 5 5 5 - 5 5 0.8 4 4 4 5 5 - 5 5 337th 5 4 5 5 5 5 - 5 5 0.8 2 4 3 5 5 - 5 - 338th 5 5 5 5 5 5 - 5 5 0.8 3 4 4 5 5 - 5 5 339th 5 4 4 4 5 5 - 5 5 0.8 2 2 2 5 5 - 5 5 340th 5 4 5 5 5 5 - 5 5 0.8 2 3 3 5 5 - 5 5

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- The main leg Neither- lyem- mály- va Serbian thorn rugged Lag Vero nika lady's bedstraw 341st 0.8 3 3 3 5 5 - 5 5 0.2 1 1 2 5 4 - 5 4 342nd 0.2 5 5 5 5 5 - 5 5 0.1 3 5 3 5 5 - 5 5 343rd 0.2 5 5 5 5 5 - 5 5 0.1 3 4 3 5 5 - 5 4 344th 0.2 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 345th 0.2 5 5 5 5 5 - 5 5 0.1 3 5 4 5 5 - 5 5 346th 0.2 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 347th 0.2 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 348th 0.8 4 5 4 5 5 - 5 5 0.2 2 3 3 5 5 - 5 5 349th 0.8 5 5 5 5 5 - 5 5 0.2 4 5 4 5 5 - 5 5 350th 0.8 5 5 5 5 5 - 5 5 0.2 4 5 3 5 5 - 5 5 351st 0.2 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 352nd 0.8 5 5 5 5 5 - 5 5 0.2 3 5 5 5 5 - 5 5 353rd 0.2 5 5 5 5 5 - 5 5 0.1 4 5 5 5 5 - 5 5 354th 0.8 5 5 5 5 5 - 5 5 0.2 3 5 3 5 5 - 5 5 355th 0.8 5 5 5 5 5 - 5 5 0.2 3 5 4 5 5 - 5 5 356th 0.8 5 5 5 5 5 - 5 5 0.2 3 5 4 5 5 - 5 5 357th 0.8 4 5 4 5 5 - 5 5 0.2 2 3 2 5 4 - 5 5 358th 0.8 4 4 5 5 5 - 5 5 0.2 2 2 3 5 5 - 5 5 359th 0.8 5 5 5 5 5 - 5 5 0.2 3 5 5 5 5 - 5 5 360th 0.2 5 5 5 5 5 - 5 5

HU 212 628 Β

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian thorn Masz Lag Vero nika lady's bedstraw 0.1 4 5 4 5 5 - 5 5 361st 0.2 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 362nd 02 5 5 5 5 5 - 5 5 0.1 4 4 4 5 5 - 5 5 363rd 0.8 5 5 5 5 5 - 5 5 0.2 3 5 4 5 5 - 5 5 364th 0.2 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 365th 0.8 5 5 5 5 5 - 5 5 0.2 3 5 5 5 5 - 5 5 366th 0.8 4 5 5 5 5 - 5 5 0.2 2 4 3 5 4 - - 5 367th 0.8 4 5 5 5 5 - 5 5 0.2 2 5 3 5 5 - 5 5 368th 0.8 5 5 4 5 5 - 5 5 0.1 4 4 3 5 5 - 5 5 369th 0.2 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 370th 0.8 4 5 5 5 5 - 5 5 0.2 2 5 4 5 5 - 5 4 371st 0.2 5 5 5 5 5 - 5 5 0.1 4 5 5 5 5 - 5 5 372nd 0.2 5 5 5 5 5 - 5 5 0.1 4 5 5 5 5 - 5 5 373rd 0.8 5 5 5 5 5 - 5 5 0.2 4 5 4 5 5 - 5 5 374th 0.2 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 375th 0.2 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 376th 0.2 5 5 5 5 5 - 5 5 0.1 4 5 4 5 5 - 5 5 377th 0.2 5 5 5 5 5 - 5 5 0.1 4 5 5 5 5 - 5 5 378th 5 4 4 4 5 5 - 5 5 0.8 2 2 2 5 5 - 5 5 379th 5 5 5 5 5 5 - 5 5 0.8 3 5 3 5 5 - 5 5

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- mály- va Serbian thorn rugged Lag Vero nika lady's bedstraw 380th 5 4 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 381st 5 4 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 382nd 5 5 5 5 5 5 - 5 5 0.8 3 5 5 5 5 - 5 5 383rd 5 4 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 384th 5 5 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 385th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 386th 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 387th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 388th 0.8 5 5 4 5 5 - 5 5 0.1 4 4 3 3 5 5 - 5 389th 0.8 5 5 4 5 5 - 5 5 0.2 4 4 4 5 5 - 5 5 390th 0.8 5 5 4 5 5 - 5 5 0.1 4 4 3 5 5 5 - 5 391st 5 5 5 4 5 5 - 5 2 0.8 3 5 2 5 5 - 5 0 392nd 5 5 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 393rd 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 394th 5 5 5 5 5 5 - 5 5 0.8 3 5 4 5 5 - 5 5 395th 5 5 5 5 5 5 - 5 5 0.8 2 5 3 5 5 - 5 5 396th 5 4 5 4 5 5 - 5 5 0.8 2 5 2 5 5 - 5 5 397th 5 5 5 5 5 5 - 5 5 0.8 3 4 2 5 5 - 5 5 398th 5 4 5 4 5 5 - 5 5 0.8 2 5 2 5 5 - 5 5 399th 5 5 5 5 5 5 - 5 5

HU 212 628 Β

Number of compound THE authorities the- Nyagan ling lymph of kg / ha Phytotoxic effect The effect of post-emergent treatment Wheat Weave- jabab K- kas- foot grass Neither- lyem- · opacification va Serbian thorn Masz Lag Vero nika lady's bedstraw 0.8 2 5 3 5 5 - 5 5 400th 0.8 5 5 4 5 5 - 5 5 0.2 4 5 4 5 5 - 5 5 Four hundred and first 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 402nd 5 5 5 5 5 5 - 5 5 0.8 2 5 4 5 5 - 5 5 403rd 0.8 5 5 4 5 5 - 5 5 0.2 4 5 3 5 5 - 5 5 404th 5 5 5 4 5 5 - 5 5 0.8 3 4 3 5 5 - 5 5 405th 5 5 5 4 5 5 - 5 5 0.8 3 4 3 5 5 - 5 5 406th 5 5 5 4 5 5 - 5 5 0.8 3 4 3 5 4 - 5 5 (THE) picture write off ve- Gyula 5 0 2 0 3 1 2 - 3 (B) picture write off ve- Gyula 5 0 1 0 2 0 3 - 2 (C) picture write off ve- Gyula 5 0 1 0 1 0 1 - 1 (D) picture write off ve- fruit being 5 0 2 2 3 1 3 - 3

As shown in FIG. Table 3 shows that the 3- (substituted phenyl) pyrazole derivatives of the formula (I) according to the invention and their salts have a higher herbicidal activity in the highlands than in (A), (B), (C) and ( Comparative compounds of formula D.

If a derivative has both herbicidal activity and a phytotoxic effect on the crop at a given concentration, a suitably selected lower dose will still suffice with a herbicidal effect and substantially reduce the phytotoxic effect on the crop.

]. Formulation example

A wettable powder composition is prepared by uniformly mixing and grinding the following ingredients:

Compound # 1 is 50 parts

Clay - white carbon mixture 45 parts (clay is the main component)

Poly (oxyethylene) nonylphenyl ether 5 parts

Formulation Example 2

A granular composition is prepared by uniformly mixing, grinding, and then kneading and granulating the resulting material with an appropriate amount of water:

Compound # 7 is 5 parts

Bentonite-clay mixture 90 parts

Calcium lignin sulfonate 5 parts

3. Formulation example

An emulsifiable concentrate is prepared by uniformly mixing the following ingredients:

Compound # 12 is 50 parts

Xylene 40 parts

A mixture of poly (oxyethylene) nonylphenyl ether and calcium alkylbenzene sulfonate 10 parts

4. Formulation example

A wettable powder composition can be prepared by uniformly mixing and milling the following components:

Compound # 33 50 parts

Clay-white carbon 45 parts (clay is the main component)

Poly (oxyethylene) nonylphenyl ether 5 parts

5. Formulation example

A granulated preparation is prepared by uniformly mixing and grinding the following ingredients, then kneading the resulting material with a sufficient amount of water and granulating it:

Compound 122 is 5 parts

Bentonite-clay mixture 90 parts

Calcium lignin sulfonate 5 parts

6. Formulation Example

An emulsifiable concentrate is prepared by uniformly mixing the following ingredients:

Compound 381 is 50 parts

Xylene 40 parts

A mixture of poly (oxyethylene) nonylphenyl ether and calcium alkylbenzene sulfonate 10 parts

Claims (10)

PATENT CLAIMS CLAIMS 1. A herbicidal composition, wherein the 3- (substituted phenyl) pyrazole derivative of formula (I) is present in an amount of 0.01% to 50% by weight as an active ingredient. Or their physiologically acceptable acid addition salts and / or agricultural and horticultural acceptable surfactants and / or carriers and, if desired, other auxiliaries - in the formula (I) X is halogen; R ¹ is optionally halogenated C 1-4 alkyl; R ² is methylsulfinyl or -AR ⁵ where A is -O- or -S-; R ⁵ is optionally halogenated C 1-4 alkyl; R ³ is hydrogen or halogen; R ⁴ is formyl or nitro, -CBR ⁶ or II p -DR ⁸ . where B is -O-, -S-, or -NR ⁷ wherein R ⁷ is C 1 -C 4 alkyl; R ⁶ is hydrogen, C 1-4 alkyl. C 3-6 alkenyl. C 3-6 alkynyl. (C1-C4) alkoxy-carbonyl (C1-C4) -alkyl. and if B is -O-. R ⁶ may also be an alkali metal or quaternary ammonium group. D is -O-, -S (O) _n, or -NR ⁹ -. where n is 0. 1 or 2 and R ⁹ is hydrogen. C 1-4 alkyl. C 3-6 alkenyl or C 36 alkynyl; R ⁸ is hydrogen. optionally halogenated C 1 -C 8 alkyl. C 3-6 alkenyl. or C 3-6 alkynyl; C 3-6 cycloalkyl. cyano (C1-C4 alkyl) -. (C 1 -C 4 alkoxy) - (C 1 -C 4 alkyl) -. (C 1-4 alkyl) thio (C 1-4 alkyl) -. di- (C4-alkyl) -phosphinyl (C1-C4-alkyl) or tri- (C1-C4-alkyl) silyl (C1-C4) -alkyl. the phenyl moiety optionally substituted by a halogen atom of phenyl (C1-C4 alkyl) or phenoxy (C1-C4 alkyl) ACH1-C-E ( R ¹ is a group of the formula wherein m is 0. 1.2 or 3, R ¹⁰ is hydrogen or when m is 1, R ¹⁰ may also be C 1-4 alkyl, E is -O-, -S-, or -N-, wherein I R R ^H is hydrogen, (C 1 -C 4) alkyl or (C 3 -C 6) alkenyl, or R ¹² together with the nitrogen to which they are attached form piperidino or morpholino. R ¹² is hydrogen, C 1 -C 12 alkyl, C 3 -C 6 cycloalkyl. C 3-6 alkenyl. C 3-6 alkynyl. halogenated (C 1 -C 4) alkyl, cyano (C 1 -C 4) alkyl, ((C 1 -C 4) alkoxy) (C 1 -C 4) alkyl, (C 1 -C 4) alkoxy (C 1 -C 4) alkoxy (C 14) alkyl, C 1-4 alkylthio (C 1-4 alkyl), di (C 1-4 alkoxy) phosphinyl (C 1-4 alkyl), or tri (C 1-4 alkyl) ) silyl (C1-C4) alkyl, phenyl optionally substituted by one or two halogens, optionally phenyl (C1-C4) alkyl optionally substituted on the phenyl portion, and when E is -O-, then R ¹² may also be an alkali metal or quaternary ammonium group, or, when -E- is -N-, R ¹² may be I R ¹¹ Also C 1-4 alkylsulfonyl; when D is -S-, R ⁸ may also be 2- (ethoxycarbonyl) -2-propyl. when D is -SCU-. then R ⁸ may also be amino, C 14 alkylaminosulfonyl, di (C 1 -C 4 alkyl) amino. also di (C 1-4 alkyl) amino or (C 1 alkyl) sulfonylamino; obsession R ⁹ I when D is -N-. then R ⁸ may also be C 1-4 alkylsulfonyl. C 1-4 alkyl-antinosulfonyl. di (C 1-4 alkyl) aminosulfonyl, C 3-6 -alkynyl-amino-sulfonyl or (C 1-4 -alkyl) - (C 3 -C 6 -alkynyl) -aminosulfonyl. The herbicidal composition according to claim 1. characterized in that, in the formula (I), X is halogen. R ¹ is C 1 -C 4 alkyl; R ² is -AR ⁵ where R ⁵ is C 1-4 alkyl or halogenated C 1-4 alkyl and A is -O or -S-; R ³ is halogen; R ⁴ represents i) -CO-BR ⁶ . wherein B is -O-, -S-, or NR ⁷ . R ⁷ is C 1 -C 4 alkyl, R ⁶ is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, or (C 1 -C 4 alkoxy) carbonyl (C 1 -C 4) alkyl (- ii) -R ⁸ where D is -O-, -S- or -NR ⁹ -, R ⁹ is C 1 -C 4 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl, R ⁸ is C 1-4 alkyl, halogenated C 1-4 alkyl, C 3-6 alkenyl. halogenated C 3-6 alkenyl, C 3-6 alkynyl. C 1 -C 4 cyanoalkyl. C3-C6 cycloalkyl, C1-C4 alkoxy-C1-C4 alkyl, or HU 212 628 Β -CHR ¹⁰ -CO-ER ¹² where E is -O-, -S- or NR ¹¹ -, R ¹⁰ is hydrogen or C 1-4 alkyl or C 3-6 alkenyl, R ¹² is C 1-4 alkyl, halogenated C 1-4 alkyl, C 3-6 alkenyl, halogenated C 3-6 alkenyl, C 3-6 alkynyl, halogenated C 3-6 alkynyl, (C 1-4 alkoxy) C 1-4 alkyl, 3 -C 6 -cycloalkyl or tri (C 1-4 -alkyl) silylalkyl. The herbicidal composition according to claim 1, wherein X is halogen, R * is C 1 -C 4 alkyl; R ² is -AR ⁵ wherein R ⁵ is halogenated C 1-4 alkyl and A is -O- or -S-; R ³ is halogen and R ⁴ is i) -CO-BR ⁶ where B is -O- or -S- and R ⁶ is C 1-4 alkyl or C 1-4 alkoxy-carbonyl- (1-4). (ii) -DR ⁸ wherein D is -O-, -S- or -NR ⁹ -, R ⁹ is hydrogen, C 3-6 alkenyl or C 3-6 alkynyl, and R ⁸ is hydrogen; , C3-6 alkenyl or C3-6 alkynyl, or iii) -CHR ^l0) where _m -CO-ER ¹² wherein E is O or S, ^R10 is hydrogen or m = 1 1- 4 carbon atoms, ^R12 represents a C1-12 alkyl or a halogenated C1-4 alkyl group and m is 0 or the first 4. The herbicidal composition according to claim 3, wherein X is halogen; R ¹ is methyl; R ² is difluoromethoxy; R ³ is halogen; R ⁴ is i) -CO-BR ⁶ wherein R ⁶ is C 1 -C 4 alkyl or C 1 -C 4 alkoxy-carbonyl-C 1 -C 4 alkyl and B is -O- or -S-, ii) -R ⁸ where D is -O-, -S- and -NR ⁹ - and R ⁹ is C 3 -C 6 alkenyl or hydrogen, C 3 -C 6 alkynyl, R ⁸ is hydrogen, C 3 -C 6 alkenyl, or C 3-6 alkynyl or - (CHR ¹⁰ ) _m -CO-ER ¹² where E is -O- or -S-, R ¹⁰ is hydrogen or C 1-4 alkyl with m = 1 and m is 0 or 1 . 5. The herbicidal composition according to claim 4, characterized in that the active ingredient is methyl 5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichloro- benzoate, ethyl 5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichlorobenzoate, methyl 2-chloro-5- (4- chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -4-fluorobenzoate, ethyl 2-chloro-5- (4-chloro-5- (difluoromethoxy) -1- methyl 1 H -pyrazol-3-yl) -4-fluorobenzoate [1- (methoxycarbonyl) ethyl] -2- 4-dichloro-5- (4-chloro-5- / difluoromethoxy) -1 methyl-1H-pyrazol-3-yl) -benzoate, [1- (ethoxycarbonyl) ethyl] -2,4-dichloro-5- (4-chloro-5- / difluoromethoxy) -1- methyl 1 H -pyrazol-3-yl) benzoate, [1- (methoxycarbonyl) ethyl] -2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1 H -pyrazole -3-yl) -4-fluorobenzoate, [1- (ethoxycarbonyl) ethyl] -2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazole), 3-yl) -4-fluorobenzoate, 4-chloro-3- [2,4-dichloro-5- (2-propenyloxy) phenyl] -5- (difluoromethoxy) -1-methyl-1H-pyrazole, 4-chloro-3- [2,4-dichloro-5- (2-propyloxy) phenyl] -5- (difluoromethoxy) -1-methyl-1H-pyrazole, 4-Chloro-3- [4-chloro-2-fluoro-5- (2-propynyloxy) phenyl] -5-difluoromethoxy-1-methyl-1H-pyrazole, 4-chloro-3- [4-Chloro-2-fluoro-5- (2-propynyloxy) phenyl] -5-difluoromethoxy-1-methyl-1H-pyrazole, 4-chloro-3- [4-chloro-2 -fluoro-5- (2-propenylthio) phenyl] -5 (difluoromethoxy) -1-methyl-1H-pyrazole, 4-chloro-3- [4-chloro-2-fluoro-5- ( 2-propynylthio) phenyl] -5-difluoromethoxy-1-methyl-1H-pyrazole, 4-chloro-3- [4-chloro-2-fluoro-5- (2-propenylamino) -phenyl] -5 (difluoromethoxy) -1-methyl-1H-pyrazole, 4-chloro-3- [4-chloro-2-fluoro-5- (2-propynylamino) phenyl] -5 ( difluoromethoxy) -1-methyl-1H-pyrazole, methyl 5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenoxy acetate, ethyl 5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenoxyacetate, n-propyl-5- (4- chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenoxyacetate, isopropyl-5- (4-chloro-5- / difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenoxyacetate, methyl 2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl- 1H-pyrazol-3-yl) -4-fl fluorophenoxyacetate, ethyl 2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -4-fluorophenoxyacetate, -propyl-2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -4-fluorophenoxyacetate, isopropyl-2-chloro-5 - (4-chloro-5- (difluoromethoxy) -1-methyl-H-pyrazol-3-yl) -4-fluorophenoxyacetate, methyl 5- (4-chloro-5- (difluoromethoxy) - 1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenylthioacetate, ethyl 5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) - 2,4-dichlorophenylthioacetate, methyl 2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -4-fluorophenylthioacetate, ethyl 2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -4-fluorophenylthioacetate, ethyl 2- [5- ( 4-Chloro-5- (difluoromethoxy--1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenoxy] -propionate, methyl 2- [5- (4-chloro-5) - (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenylthio] propionate, ethyl 2- [5- (4-chloro-5- / difluoro-) methoxy (-1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenylthio] propionate, methyl 2- [2-chloro-5- (4- chloro-5-difluoromethoxy-1-methyl-H-pyrazol-3-yl) -4-fluoro-phenoxy] -propionate, ethyl 2- [2-chloro-5- (4-chloro-5- / difluoro) -methoxy-1-methyl-1H-pyrazol-3-yl) -4-fluorophenoxy] propionate, methyl 2- [2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-) methyl 1 H -pyrazol-3-yl) -4-fluorophenylthio] propionate or ethyl 2- [2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1 H -pyrazole) -3-yl) -4-fluorophenyl-thio] propionate. A method for controlling weeds, characterized in that a composition according to claim 1 is effective at 1.0 g / ha 54 EN 212 628 Β to 10 kg / ha of active substance is applied to the area to be treated. The process for use in rice soil according to claim 6, wherein the active ingredient is 4-chloro-3- [2,4-dichloro-5- (2-propenyloxy) phenyl-5- / difluoromethoxy] -. 1-methyl-1H-pyrazole, 4-Chloro-3- [2,4-dichloro-5- (2-propynyloxy) phenyl] -5- (difluoromethoxy) -1-methyl-1H-pyrazole, 4-chloro-3- [ 4-chloro-5- (2-propenyloxy) phenyl] -5- (difluoromethoxy) -1-methyl-1H-pyrazole, 4-chloro-3- [4-chloro-5- (2-propynyl) oxy) phenyl] -5- (difluoromethoxy) -1-methyl-1H-pyrazole, 4-chloro-3- [4-chloro-5- (2-propenylthio) phenyl] -5- (difluoromethoxy) -1-methyl-1H-pyrazole, 4-chloro-3- [4-chloro-5- (2-propynylthio) phenyl] -5- (difluoromethoxy) -1-methyl-1H-pyrazole, -chloro-3- [4-chloro-2-fluoro-5- (2-propynylamino) phenyl] -5-difluoromethoxy-1-methyl-1H-pyrazole or 4-chloro-3- [ A composition containing 4-chloro-2-fluoro-5- (2-propynylamino) phenyl] -5-difluoromethoxy-1-methyl-1H-pyrazole is used. 8. A process according to claim 6, for use in the highlands, especially in wheat, wherein the active ingredient is methyl 5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2. , 4-dichlorophenoxyacetate, ethyl 5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenoxyacetate, n-propyl -5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenoxyacetate, isopropyl-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenoxyacetate, methyl 2-chloro-5- (4-chloro-5- (difluoromethoxy) - 1-methyl-1H-pyrazol-3-yl) -4-fluorophenoxyacetate, ethyl 2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3) -yl) -4-fluorophenoxyacetate, n-propyl-2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methylH-pyrazol-3-yl) -4-fluoro- phenoxyacetate, isopropyl 2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -4-fluorophenoxyacetate. methyl 5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenylthioacetate, ethyl 5- (4-chloro-5- difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenylthioacetate, methyl 2-chloro-5- (4-chloro-5- / difluoromethoxy) -1- methyl-1H-pyrazol-3-yl) -4-fluorophenylthioacetate or ethyl-2-chloro-5- (4-chloro-5- (difluoromethoxy-1-methyl-1H-pyrazol-3-yl). A composition containing -4-fluorophenylthioacetate is used. The process for use in non-productive areas according to claim 6, wherein the active ingredient is methyl 5- (4-chloro-5- / difluoromethoxy / -1-methyl-1H-pyrazol-3-yl) -2 , 4-dichlorobenzoate, ethyl 5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) 2,4-dichlorobenzoate, methyl 2-chloro-5 - (4-Chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -4-fluorobenzoate, Ethyl 2-chloro-5- (4-chloro-5- / difluoromethoxy) (-1-methyl-1H-pyrazol-3-yl) -4-fluorobenzoate, 1 - [(methoxycarbonyl) ethyl] -5- (4-chloro-5-difluoromethoxy) -1 methyl-lH-pyrazol-3-yl) -2,4-dichlorobenzoate, 1 - [(ethoxycarbonyl) ethyl] -5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichlorobenzoate, 1- [(methoxycarbonyl) ethyl] -2-chloro-5- (4-chloro-5-difluoromethoxy--1-methyl-1H-pyrazol-3-yl) -4-fluorobenzoate, 1- [ (ethoxycarbonyl) ethyl] -2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -4-fluorobenzoate, ethyl 2- [ 5- (4-Chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenoxy] -propionate, methyl 2- [5- (4-chloro) -5- (difluoromethoxy) -1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenylthio] propionate, ethyl 2- [5- (4-chloro-5- difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -2,4-dichlorophenylthio] propionate, methyl 2- [2-chloro (4-chloro-5-difluoro) methoxy (-1-methyl-1H-pyrazol-3-yl) -4-fluorophenoxy] propionate, ethyl 2- [2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl) - 1H-pyrazol-3-yl) -4-fluorophenoxy] -propionate, methyl 2- [2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazole); 3-yl) -4-fluorophenylthio] propionate or ethyl 2- [2-chloro-5- (4-chloro-5- (difluoromethoxy) -1-methyl-1H-pyrazole) A composition containing -3-yl) -4-fluorophenylthio] propionate. 10. A process for the preparation of 3- (substituted phenyl) pyrazole derivatives of the formula (I) and their acid addition salts X is halogen; R ¹ is optionally halogenated C 1-4 alkyl; R ² is methylsulfinyl or -AR ⁵ where A is -O- or -S-; R ⁵ is optionally halogenated C 1-4 alkyl; R ³ is hydrogen or halogen; R 1 'is -DR ⁸ -1 or -CBR ^{6-1 in} General II wherein B is -O-, -S-, or -NR ⁷ where R ⁷ is C 1 -C 4 alkyl; R 1 'is C 1 -C 4 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, (C 1 -C 4 alkoxy) carbonyl (C 1 -C 4) alkyl, and when B is -O-, R ^6-1 can also be an alkali metal or quaternary ammonium group, D is -O-, -S (O) _n, or -NR ⁹ -, wherein n is 0, 1 or 2 and R ⁹ is hydrogen, C 1-4 alkyl, C 3-6 alkenyl, or C 36 alkynyl; R 1 'is hydrogen, optionally halogenated C 1-8 alkyl, C 3-6 alkenyl, or C 3-6 alkynyl; C 3-6 cycloalkyl, cyano (C 1-4 alkyl), (C 1-4 alkoxy) (C 1-4 alkyl), (C 1-4 alkyl) thio (C 1-4) HU 212 628 Β alkyl) -. di (C 1-4 alkyl) phosphine-3- (C 1-4 alkyl) - or tri- (C 1-4 alkyl) silyl- (C 1-4 alkyl) optionally substituted on the phenyl by phenyl ( (C 1 -C 4 alkyl) - or R ¹² wherein m is 0, 1, 2 or 3, R ¹⁰ is hydrogen or when m is 1, R ¹⁰ may also be C 1 -C 4 alkyl. E is -O-, -S-, or -N-. where I R ' R is hydrogen, (C 1 -C 4) alkyl or (C 3 -C 6) alkenyl, or R ¹² together with the nitrogen to which they are attached form piperidino or morpholino. R ¹² is hydrogen. C 1 -C 12 alkyl. C 3-6 cycloalkyl, C 3-6 alkenyl. C 3-6 alkynyl. halogenated C 1-4 alkyl. cyano (C 1-4 alkyl) -. (C 1 -C 4 alkoxy C 1 -C 4 alkyl) -. (C 1 -C 4 alkoxy) - (C 1 -C 4 alkoxy) - (C 14 alkyl) -. (C 1 -C 4 alkyl) thio (C 1 -C 4 alkyl) -. di (C1-C4 alkoxy) phosphinyl (C1-C4 alkyl) or tri (C1-C4 alkyl) silyl-C1-C4 alkyl, optionally substituted with one or two halogen atoms. in the case of the phenyl moiety the phenyl (C 1 -C 4) alkyl substituted by one or two halogens. and when E is -N-, R ¹² may be II R ¹¹ Also C 1-4 alkylsulfonyl; when D is -S (O) ₂ - then R ^8-1 may also be amino, C 1-4 alkylamino. also di (C1-C4 alkylamino) or (C1-C4 alkyl) sulfonylamino, or R ⁹ If D is -N- then R ⁸ ' ¹ may also be C 1-4 alkylsulfonyl, C 1-4 alkylaminosulfonyl. di (C 1 -C 4 alkyl) aminosulfonyl. C 3 -C 6 alkynyl-amino-sulfonyl or (C 14 -alkyl) - (C 3 -C 6 -alkynyl) -aminosulfonyl, characterized in that (a) for the preparation of compounds of the formula (I-1-2), wherein R ^{1 is a} compound of the formula (I); R ² . R 'and X are as defined herein. R ^J is -R ⁸ ' ¹ . wherein D is and R ⁸ ' ¹ is as defined in the preceding disclosure. reacting a compound of formula (I-1), wherein the substituents have the meanings given above, with a compound of formula (II), wherein R ^8-1 is as defined for formula (1-2). Z present-