DD144350A5 - MEANS OF PREVENTING HERBICIDES ON CULTURAL PLANTS - Google Patents

Abstract

1. Claims for the contracting states : BE, CH, DE, FR, GB, IT, NL N-Dichloroacetyl-1,2,3,4-tetrahydro-quinaldine of the formula see diagramm : EP0006540,P18,F2 1. Claims for the contracting state AT Process for the preparation of N-dichloroacetyl-1,2,3,4-tetrahydro-quinaldine of the formula see diagramm : EP0006540,P19,F2 characterised in that 1,2,3,4-tetrahydro-quinaldine of the formula see diagramm : EP0006540,P19,F4 is reacted with dichloroacetyl chloride, if appropriate in the presence of an acid-binding agent and if appropriate in the presence of a diluent.

Description

Agent for preventing herbicide damage to crop plants

Applicability of the invention

The present invention relates to antidotes for preventing herbicide damage to crop plants.

By "antidote" ("safener", "antidote") herein is meant substances which are capable of specifically antagonizing adverse effects of herbicides on crop plants, d. H. to protect the crops without appreciably affecting the herbicidal action on the weeds to be controlled.

Characteristic of the known technical solutions

It is known that certain thiocarbamates and acetanilides cause more or less severe damage to the crop when used for weed control in maize and other crops. Furthermore, it is known that compounds such. B, li-Dichloro = acetyl-2-methyl-indoline and ET-dichloroacetyl-cis, trans-decahydroquinoline are suitable to reduce damage by thiolcarbamates or acetanilides to crop plants (see DE-OS 22 18 097). However, the effectiveness of these substances as an antidote is not always entirely satisfactory.

Object of the invention .

The aim of the invention is the provision of agents with improved protective effect for crops against herbicide damage caused by thiocarbamates and / or acetanilides.

the invention.

The object of the invention is based on finding _s suitable compounds which are excellently suited to prevent Herbisidsohä'den by thiocarbamates, and / or acetanilides, "

It has now become the new n-dichloroacetyl-1,2,3,4-tetrahydroquinaldehyde of the formula

(D

found"

Furthermore, it has been found that the novel W-dichloroacetyl-1 ₉ 2,3 »4-tetrahydro-quinaldine of the formula (I) is obtained when 1,2,3,4-tetrahydroquinaldine of the formula

(II)

with dichloroacetyl chloride, optionally in countercurrent

213771

an acid binder and, if appropriate, in the presence of a diluent.

In addition, it has been found that N-dichloroacetyl-1,2,3,4-tetrahydro-quinaldine of formula (I) is excellently suited to protect crops from herbicidal damage by thiolcarbamates and / or acetanilides.

Surprisingly, herbicidal damage by thiolcarbamates or acetanilides to crop plants with the concomitant use of N-dichloroacetyl-1,2,3,4-tetrahydroquinaldine better suppressed than when using the known from the prior art compounds N-dichloroacetyl-2-methyl-indoline or N- Dichloroacetyl-cis, transdecahydroquinoline, which are the chemically most similar substances of the same mode of action. The substance according to the invention thus represents a valuable enrichment of the technique.

The preparation of N-dichloroacetyl-1,2,3,4-tetrahydroquinaldine by reacting 1,2,3,4-tetrahydro-quinaldine with dichloroacetyl chloride can be illustrated by the following formula scheme:

-O _u + Cl ₀ HC-CO-Cl

Cn- ί

3 -HCl

The 1,2,3,4-tetrahydroquinone required as starting material in carrying out the process according to the invention.

Le A 18 886

-A-

quinaldine of the formula (II) can be by hydrogenation of quinaldine with gaseous hydrogen in the presence of a catalyst such as Raney nickel or ruthenium on a. Carrier, and optionally in the presence of a diluent, such as methanol or ethanol, at tempera, doors between 100 ° C and 250 ° C / preferably between 1 50 ° C and 200 ° C produce. The hydrogen pressure can be varied within a wider range. In general, one works at pressures between TO 100 and 220 bar, preferably between 150 and 190 bar. Preferably, the hydrogenation of quinaldine is carried out in the absence of additional diluents using ruthenium on alumina catalyst.

When carrying out the process according to the invention, all customary acid acceptors are suitable as acid binders. These include, preferably, alkali hydroxides, such as sodium hydroxide and potassium hydroxide, furthermore alkali metal carbonates, such as sodium carbonate, potassium carbonate and sodium bicarbonate, and also lower tertiary amines, such as triethylamine, dimethylbenzylamine, pyridine and diazabicyclooctane. However, it may also function in excess of 1,2,3,4-tetrahydro-chinaldine of the formula (II) act simultaneously as an acid binder. In this case, the addition of an additional acid binder is unnecessary.

As diluents, water and inert organic solvents can be used in the reaction according to the invention. These include, preferably, ketones, such as diethyl ketone, such as methyl isobutyl ketone; nitrites,

Le A 18 886

21 37 7ί

such as propionitrile and acetonitrile; Ethers, such as tetrahydrofuran or dioxane; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene, halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; Esters, such as ethyl acetate; and formamides, in particular dimethylformamide.

The reaction temperatures can be varied within a substantial range in the process according to the invention. In general, one works between about 0 and 60 C, preferably between 20 and 50 C.

When carrying out the process according to the invention, preference is given to 1 mol of 1,2,3,4-tetrahydroquinaldine of the formula (II), preferably 1 mol of dichloroacetyl chloride and 1 mol of acid binder. The isolation of the reaction product is carried out by customary methods. In general, by pouring the reaction mixture into water after the reaction is complete, the mixture is treated with a sparingly soluble organic solvent, e.g. Shaking methylene chloride, the combined organic phases washed successively with dilute hydrochloric acid and water, then dried and evaporated and the remaining residue subjected to a fractional distillation.

The practical preparation of the N-dichloroacetyl-1,2,3,4-tetahydro-quinaldine according to the invention is evident from the following examples.

Le A 18 886

example 1

O = C-CHCl ₂

A solution of 29.4 g (0.2 mol) of 1,2,3,4-tetrahydroquinaldine in 200 ml of acetonitrile is added at room temperature while stirring with 14.8 g (0.1 mol) of dichloroacetyl chloride. Thereafter, it is stirred for 2 more hours at 40.degree. Then allowed to cool and gives the reaction mixture in water. The resulting mixture is extracted several times with methylene chloride. The combined organisehen phases are washed successively with dilute hydrochloric acid and water, dried over sodium sulfate and concentrated under reduced pressure. The remaining residue is fractionally distilled. This gives 20 g of N-dichloroacetyl-1,2,3,4-tetrahydro-chinaldine.

Refractive index: η = 1.5728

Analysis:

Calculated: 55.83% C; 5.08% H; 27.47% Cl; 5.43% Cl Found: 55.6% C; 5.1% H? 27.3% Cl; 5.3% Cl

20 Example 2

143 g (1 mol) of quinaldine are mixed with 15 g of a catalyst mixture consisting of ruthenium on aluminum

Le A 18 886

213771

oxide, added and hydrogenated for 2 hours at 195 C under a hydrogen pressure of 170-190 bar. Thereafter, the reaction mixture is filtered and subjected to fractional distillation. This gives 123 g of 1,2,3,4-tetrahydro-chinaldine. Boiling point: 75 ° C at 1 mm Hg

Le A 18 886

The N-dichloroacetylene-1,2,3,4-tetrahydro-quinaldine of the formula (I) is suitable, as already mentioned, for the protection of crop plants from damage by herbicidally active thiolcarbamates or acetanilides, without noticeably influencing their weed effect.

Preferably, the N-dichloroacetyl-1,2,3,4-tetrahydro quinaldine of the formula (I) as antidote herbicidally active thiolcarbamates of the formula

r'-s-c-nCT ο you)

O ^R

10 uses v / earth,

in which

R ^{1 is} C ₁ -C ₄ alkyl, benzyl, chlorobenzyl or C ₁ -C 4 alkoxybenzyl,

R and R are independently alkyl of 2 to 4 carbon atoms or cyclohexyl and

also

2 3

R and R, together with the adjacent nitrogen atom, represent a five- to seven-membered heterocyclic ring.

Specific examples of thiolcarbamates of the formula (III) are:

Le A 18 886

Berlin, October 22, 1979 AP ^ü 07 D / 213 GZ 55 605

-9- 21 37

S-ethyl-HjH-dipropylthiocarbamate S-ethyl-1H-IT-diisobutylthiocarbamate S-propyl-ST-butyl-1-ethylthiocarbamate S-propyl-N, N-diisopropylthiocarbainate S-ethyl-1-IT-diethylthiocarbamate S-ethyl-IJ- ethyl-H-cyclohexylthiocarbamate S-ethyl-hexahydro-acepin-1-thlocarbamate "Sp-methoxybenzyl" -lijN-diethylthiocarbamate Sp-chlorobenzyl-lijU-diethylthiocarbamate S-benzyl-hjir-diethyl-thiocarbamate S-benzyl-N, N-di-sec , butylthiocarbamate S-propyl-N-ethyl-N-butylthiocarbamate

The thiolcarbamates of the formula (III) and their herbicidal activity are already known (cf., US Pat. Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,339).

The N-dichloroacetyl-i ^^^ - tetrahydro-quinaldine of the formula (I) can also be used preferably as an antidote for herbicidally active acetanilides of the formula

CH ₂ -R

(IV)

in which

R is an optionally substituted N-containing heterocyclic radical,

X and Y are the same or different and are alkyl, Z is halogen and η is 0, 1 or 2,

and in their herbicidally active acid addition salts and metal salt complexes.

Specific examples of acetanilides of the formula (IV) are:

2-Methyl-6-ethyl-N- (pyrazol-1-ylmethyl) -chloroacetanilide 2,6-diethyl-N- (pyrazol-1-ylmethyl) -chloroacetanilide 2,6-diethyl-N- (1 , 2,4-triazol-1-yl-methyl) -chloroacetanilide 2,6-dimethyl-N- (1,2,4-triazol-1-ylmethyl) -chloroacetanilide

2-methyl-N- (pyrazol-1-ylmethyl) -chloroacetanilide

2,5-Dimethyl-N ~ (pyrazol-1-ylmethyl) -chloroacetanilide 2,3-Dimethyl-N- (pyrazol-1-ylmethyl) -chloroacetanilide 2-methyl-6-ethyl-N ~ (pyrazole-1 -yl-methyl) -chloracetanilid-

hydrochloride

2,6-Diethyl-N- (pyrazol-1-ylmethyl) -chloroacetanilide hydrochloride 2,6-diethyl-N, T3,5-dimethyl-pyrazol-1-yl) -methyl? -

chloroacetanilide

2.6 "diethyl-N ^ l3-chloro-1,2,4-triazolyl) -methyl7-chloro ~

acetanilide

2-methyl-6-ethyl-N- _< / T3, 5-dimethyl-pyrazol-1-yl) -. 5 methyl 7-chloroacetanilide

2-tert-butyl-N- (pyrazol-1-yl-methyl) -chloroacetanilide 2-methyl-6-ethyl-N-> T3-bromo-5-methyl-pyrazolyl) -methyl? "

chloroacetanilide '

2-methyl-5-ethyl-N-> T3-chloro-1,2,4-triazolyl) -methyl-chloroacetanilide

2,6-diethyl-N- ^ T4-chloro-pyrazol-1 ~ Z

acetanilide Le A 18 886

213771

Further, the N-dichloroacetyl-1,2,3,4-tetrahydroquinaldine of the formula (I) may preferably be used as an antidote agent for herbicidally active acetanilides of the formula

^ C - CO - R ⁷ · (ν)

f ^X C0 - CH ₂ Cl m

in which

R is alkyl, halogen, haloalkyl, alkylthio, alkylsulfonyl, aminosulfonyl, cyano or nitro,

R and R are the same or different and are hydrogen, alkyl, halogen, haloalkyl or optionally substituted phenyl,

R is alkyl or optionally substituted phenyl and

m stands for integers from 0 to 5.

Specific examples of acetanilides of the formula (V) are:

2,6-Dimethyl-N- (benzene-methyl) -chloroacetanilide 2,6-Dimethyl-N- (4-chlorobenzene-methyl) -chloroacetanilide 2-Methyl-6-ethyl-N- (benzoyl-methyl) -chloroacetanilide

In addition, the N-dichloroacetyl-1,2,3,4-tetrahydroquinaldine of the formula (I) may preferably be used as an antidote agent for herbicidally active acetanilides

Le A 18 886

the formula

(VI)

in which

1 A for oxygen, sulfur or the grouping> NR

5, R ^{10 is} hydrogen or alkyl,

R is hydrogen, alkyl, haloalkyl, alkenyl,

Alkynyl, cycloalkyl, halogen, optionally substituted aryl and aralkyl or the groupings -OR ¹⁴ , -SR ¹⁴ and NR ¹³ R ¹⁴ ,

R is hydrogen, alkyl or optionally substituted aryl, R ^{4 is} hydrogen, alkyl, haloalkyl, alkenyl,

Alkynyl, cycloalkyl or optionally substituted aralkyl, R ^{3 is} alkyl.

R is alkyl or halogen,

ι ο R ^{A is} halogen and

ρ stands for the numbers O, 1 or 2.

Specific examples of acetanilides of the formula (VI) are:

2,6-diethyl-N- (2-n-ethyl-1,3,4-oxadiazol-5-yl) -methyl 17-chloroacetanilide

2,6-dimethyl-NZ-2-methyl-1,3,4-oxadiazol-5-yl) -methyl-7-chloroacetanilide

Le A 18 886

- ". 213771

2 "ethyl 6-methyl-N-1,2-methyl-1,3,3-oxadiazol-5-yl) -methylj chloroacetanilide

2-tert-Butyl ~ N- £ T2-methyl-1,3,4-oxadiazcl-5-yl) -methyljchloracetanilid

In addition, the N-dichloroacetyl-1,2,3,4-tetrahydro-quinaldine of the formula (I) may preferably be used as an antidote to the following herbicidal acetanilides: N - ^ '- KethoxyäthyD ^ o-dimethyl-chloroacetanilide N- ( 2'-Allyloxyethyl) -2,6-dimethyl-chloroacetanilide N- (2'-n-propyloxyethyl) -2,6-dimethyl-chloroacetanilide K- (2'-isopropyloxyethyl) -2,6-dimethyl-chloroacetanilide N- ( 2'-Mothoxyethyl) -2-methyl-6-ethyl-chloroacetanilide N- (2'-mcthoxyethyl) -2,6-di-ethyl-chloroacetanilide N- ( ^2f- ethoxyethyl) -methyl-o-ethyl-chloroacetanilide N- (l'-Aethoxycarbonyl-Aethyl) -5-dimethylchloroacetanilide N- (3'-Methoxy-propyl- (2 ') - 2-methyl-chloroacetylamide N - O ' -methoxy-propyl- (2 ') - 2,6-dimethyl-chloroacetanilide N- (3'-methoxy-propyl- (2 ') -2-methyl-6-ethyl-chloroacetanilide N- (3'- ^v . Ethoxy-propyl- (2 ^/ ) -2 , 6-diethyl-chloroacetanilide N- (methoxy-propyl- (2 *) -2-ethyl-chloroacetanilide N- (2'-ethoxyethyl) -2,6-diethyl-chloroacetanilide N- (2'-n-propoxyethyl) - 2-methyl-6-ethyl-chloroacetanilide N- (2'-n-Pr opoxyethyl) -2,6, diethyl-chloroacetanilide N- (2'-isopropyloxyethyl) -2-methyl-6-ethyl-chloroacetani? id ^ HZhloracetyl 2,6 ·} -dimethy .anilino-essigsäυreäthyl- methylester and SS (N-chloroacetyl-2,6-dinethylanilino) -propionic acid methylester OC (N-chloroacetyl-2-methyl-6-ethyl anilino) -propionic acid ethyl ester N- (3 '-> iethoxy-propyl- (2') - 2,3-dimethyl-chloroacetanilide N- ( 2'-ethoxyethyl) -2-methyl-6-chloro-chloroacetanilide K ( 2'-methoxyethyl) -2-methyl-6-chloro-chloroacetanHd N- (2'-methoxyethyl) -2-methyl-6-methoxy-chloroacetanilide

Le A 18 8S6

The herbicidally active acetanilides of the formula (IV) 'and their acid addition salts and metal salt Konplexe are not yet known. They can be produced, however, by

a) N-halomethyl-haloacetanilides of the formula

X / ^Y n N \ CH ₂ - Shark (M) _ CO - CH ₂

(VII)

in which

X, Y, Z and η are as defined above and 'Hal is halogen, in particular chlorine or bromine,

with heterocycles of the formula

R-M (VIII)

in which

R has the abovementioned meaning and M is hydrogen or an alkali metal,

if appropriate in the presence of a diluent and of an acid binder, and if appropriate subsequently adding an acid or a metal salt.

If 2, e-diethyl-N-chloromethyl-chloroacetanilide and pyrazole are used as starting materials, the course of the reaction of process (a) can be represented by the following formula scheme:

Le A 18 886

«15 ~

Berlin, 22 October 10, 1979 AP C 07 D / 213 771 GZ 55 605 18

3771

C ₂ H

CO-CH ₂ Cl

The U-halomethyl-haloacetanilides to be used as starting materials in the process (a) are generally defined by the formula (VII). In this formula, X and Y are the same or different and are preferably straight-chain or branched alkyl having 1 to 4 carbon atoms, Z is preferably the halogens chlorine or bromine and the index η has the abovementioned meaning.

The N-halomethyl-haloacetanilides of the formula (VII) are known or can be prepared by known methods. (See U.S. Patents 3,630,716 and 3,637,847). Example, by reacting corresponding anilines with paraformaldehyde in the presence of catalytic amounts of potassium hydroxide and the resulting Phenylazomethine with a Halogenacetylhalogenid, for example, chloroacetyl chloride, added.

The N-halomethyl-haloacetanilides of the formula (VII) can also be obtained by a novel process by "known haloacetanilides of the formula

(IX)

CO - CH ₂ - Z

in which

X, Y, Z and η are as defined above,

with at least 1 mol of formaldehyde or formaldehyde donating substances, such as paraformal & ehyd, and a Halogenierungsmifc ^ tel, such as a hydrohalic acid or an inorganic or organic acid halide, and a water-binding agent, for example sodium sulfate, in a conventional manner at temperatures between -1Ö ° C. and 150 ° C, preferably between 10 and 70 ⁰ C, optionally in the presence of an inert organic solvent, for example toluene, reacted (see, German Offenlegungsschriften 2,119,518 and 2,102,603). When using inorganic acid halides, such as thionyl chloride, the use of

"5 5 The use of a special binding agent is not necessary (see also manufacturer's instructions).

The heterocycles also to be used as starting materials are generally defined by the formula (VIII). In this formula stands. R is preferably the optionally substituted Äzolylreste pyrazol-1-yl, imidazol-1-yl, 1,2,4-triazol-t-yl; 1,2,3-triazol-1-yl; 1,3,4-triazol-1-yl and 1,2,3,4.-tetrazol-1-yl and optionally substituted pyrrol-1-yl. Suitable substituents are preferably: halogen, in particular fluorine, chlorine and bromine, and also alkyl having 1 to 4 carbon atoms. M is preferably hydrogen and the alkali metals sodium and potassium.

The heterocycles of the formula (VIII) are generally known compounds of organic chemistry.

Le A 18 886

For the reaction according to process (a), suitable diluents are preferably inert organic solvents. These include preferably ketones, such as diethyl ketone, in particular methyl isobutyl ketone; Nitriles, such as propionitrile, in particular acetonitrile; Ethers, such as tetrahydrofuran or dioxane; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene, halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; Esters, such as ethyl acetate; and formamides, in particular dimethylformamide.

Acid binders which can be used in process (a) are all customary inorganic and organic acid acceptors. These include, preferably, alkali metal carbonates, for example, sodium carbonate, potassium carbonate, and sodium bicarbonate, further lower tertiary alkylamines, aralkylamines, aromatic amines, or cycloalkylamines, e.g. Triethylamine, dimethylbenzylamine, pyridine and diazabicyclooctane. It is also possible to use a corresponding excess of azole, which in the present case is to be understood as meaning a compound of the formula (VIII).

The reaction temperatures can be varied in a wider range in process (a). In general, one works between about 0 and 120 ° C, preferably between 20 and 80 ° C.

When carrying out the process (a), preference is given to 1 mol of the compounds of the formula (VII)

Le A 18 886

1 to 2 moles of the heterocycle of formula (VIII) and 1 mole of acid binder. To isolate the compounds of the formula (IV), the Reafctlonsgemiseh is filtered, the filtrate washed with water, dried and concentrated. The residue is optionally purified by fractional crystallization or distillation.

In a special Mafarbeitungsform cools the reaction mixture to about © C, filtered and passes into the filtrate at 5 to -15 ⁰ C hydrogen chloride. The precipitated chloride salts are filtered off with suction, washed with an organic solvent, for example ethyl acetate, and distributed in a mixture of an organic solvent, for example ethyl acetate and water, of a pH value around 12. The organic phase is separated off and

1b isolates the compounds of the formula (IV) in the usual way.

For the preparation of acid addition salts of the compounds of the formula (IV), all acids come into question which lead to physiologically acceptable salts. These include, preferably, the hydrohalic acids, e.g. the hydrobromic acid and the hydrobromic acid, in particular the hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such. Acetic, maleic, succinic, fumaric, tartaric, citric, salicylic, sorbic, lactic, and sulfonic acids, e.g. p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.

Le A 18 886

213771

The salts of the compounds of formula (IV) can be readily prepared by conventional salification methodologies, e.g. by dissolving a compound of formula (IV) in a suitable inert solvent and adding the acid, e.g. Hydrochloric acid, and in a known manner, e.g. by filtration, isolated and optionally purified by washing with an inert organic solvent.

For the preparation of metal salt complexes of the compounds of Forijiel (IV) are preferably salts of metals of II.Ibis IV. Main and the I. and II., And IV. To VIII. Subgroup in question, where copper, zinc, manganese, Magnesium, tin, iron and nickel are exemplified. Suitable anions of the salts are those derived from acids, which lead to physiologically acceptable salts. These include, preferably, the hydrohalic acids, e.g. hydrochloric acid and hydrobromic acid, phosphoric acid, nitric acid and sulfuric acid.

The metal salt complexes of the compounds of the formula (IV) can be obtained in a simple manner by conventional methods, e.g. by dissolving the metal salt in alcohol, e.g. Ethanol, and adding to the compound of formula (IV). Metal salt complexes may be prepared in known manner, e.g. by filtration, isolate and optionally by ücrystallization clean.

The practical preparation of acetanilides of the formula (IV) is evident from the following examples.

Le A 18 886

Example 3

C ₂ H ₃

CH ₂ -N

N V-CO - CH ₂ - Cl

C ₂ H ₃

To 274.2 g (1 mol) of 2,6-diethyl-N-chloromethyl-chloroacetanilide in 250 ml of anhydrous ethyl acetate is added with stirring a mixture au3 68 g (1 mol) of pyrazole and 106 g (1.05 mol) of triethylamine in 150 ml of anhydrous ethyl acetate, with the temperature rising to 30 ° C. The mixture is stirred for another hour at room temperature. For the workup, there are two possibilities:

1) The reaction mixture is filtered, the filtrate washed neutral with water, dried over sodium sulfate and evaporated in vacuo. After fractional crystallization with ligroin, 171.2 g (56% of theory) of 2,6-diethyl-N- (pyrazol-1-yl-methyl) -chloroacetanilide of melting point 67 ° C. are obtained in the form of colorless crystals.

2) The reaction mixture is cooled to ⁰ ° C., filtered and the filter residue is washed with 10 ml of cold ethyl acetate. In the filtrate (1.4 mol) of dry hydrogen chloride are introduced at 0 to ^'0 -10 C 50 g. The precipitated hydrochloride salts are then filtered off with suction, washed with 50 ml of cold ethyl acetate and the solid residue is partitioned between 0.5 l of ethyl acetate

Le A 18 886

2t 37 71

and 0.5 1 aqueous sodium hydroxide solution having a pH of 12. The organic phase is separated off, washed twice with 0.5 l Nati-iumchloridlösung, dried over sodium sulfate and evaporated in vacuo. The colorless oily residue is added with 60 ml of gasoline, where it crystallizes. This gives 220.2 g (72% of theory) of 2,6-diethyl-N- (pyrazol-1-yl-methyl) -chloracetanilii form of colorless crystals.

yl-methyl) -chloroacetanilide of melting point 67 C in

in an analogous manner, the compounds listed in the table below are prepared:

Table 1

X X ^Y n / CH ₂ ^x co - R (IV) -CH ₂ -Z Melting points ⁰ C) Esp. No. C ₂ H ₅ Yn Z R 112 4 i-Cj H ₇ 6-C ₂ H ₅ Cl 1,2,4-triazol-l-yl 134 5 CH ₅ 6-1-C ₅ H ₇ Cl Pyrazol-1-yl 92 6 CHj 6-C ₂ H ₅ Cl 1,2,4-triazol-l-yl "57 7 C ₂ H ₅ 6-C ₂ H ₅ Cl Pyrazol-1-yl 82 8th CH ₃ 4,6 (CHj); ι Cl Pyrazol-1-yl 92 9 C ₂ K ₅ 4,6- (CHj) ₅ ι Cl Pyrazol-1-yl 78 10 1-C ₃ H ₇ 4-CHj, 6-C ₂ H ₅ Cl Pyrazol-1-yl 196 11 1-C ₅ H ₇ 6-i-Cj H ₇ Cl 1,3,4-triazol-l-yl 138 12 18,886 6-1-C ₃ H ₇ Cl 1,2,4-triazol-l-yl Ls A

Tatel le l (continued) Yn z. R Shrimp pur.ktj ^ Oei Ex X 6-CGC. Cl Pyrrol-1-yl Oil 81 13 C; H ₅ - , Cl 1,2,4-triazol-l-yl 113 β2 14 1-C ₃ H ₇ 6-C ₂ H ₅ Cl 1,2,3,4-tctrazol-1-yl CcI 110 15 "• V - Cl Pyrazol-1-yl Oei 16 Cl 1,2,4-triazol-l-yl f> 6 17 C _z H ₅ 6-CH ₃ Cl Pyrazol-1-yl , 88 18 CH, 6-CH ₃ Cl 1,2,4-triazol-l-yl CfI 19 CK, 5-CHj Cl 1,2,4-triazol-l-yl 114 20 | Ch \ Cl Pyrazol-1-yl 102 21 ¹ CH ₃ Cl 1 ρ 2,4-triazol-1-yl 87. 22 CHj 5-CHj Cl Pyrazol-1-yl 67 23 CKj 3-CH ₃ Cl 1,2,4-triazol-l-yl 111 24 CHj 3-CH ₃ Cl Pyrazol-1-yl 25 CHj 6-CK ₅ Cl Pyrazol-1-yl (xiiCl) 14 ?. 26 CIH 6-C ₂ H ₃ Cl Pyrazol-1-yl (xl i Cl) 27 OgHj 6-C ₂ H ₅ Cl 3f5-dimethyl " no 28 C ₂ H ₅ pyrazol-1-yl 6-C ₂ H ₃ Cl Bromo-methyl- 90 29 C ₂ H ₅ pyrazolyl 6-C ₂ H ₅ Cl 3-chloro-l, 2,4- • 83 30 C _a H _s trlasol-l-yl 6-C ₂ H ₃ Cl 3,5-dimethyl- 113 31 CH ₃ pyrazol-1-yl 6-C ₂ H ₃ Cl 3-Methy1- Oei 32 C ₂ H ₅ pyrasol-l-yl IIS 6-CH ₃ Cl 3-Methy1- 80 33 Cg Hey pyrazol-1-yl - Cl Pyrasol-l-yl 34 C (CHs) ₃ - » Cl 1,2,4-triazol-l-yl- 35 C (CH ₅ ) ₃ 6-CH _s ca, BRCM-methyl 36 C ₂ H ₅ pyrazolyl

Le A 18 886

213771

Table_l (continued)

Example Sr, X

CH,

CH ₃

39 C _z 'u

C, H,

Yn 6-C ₂ H,

6-C ₂ K ₅

6-CH ₅

6-C _£ H ₅

6-C ₂ H ₅

42 C ₂ H ₅ 6-C-Hs He 43 CH ₃ 6-C ₂ H ₅ br 44 C ₂ H ₅ DC ₂ H ₅ Cl 45 C ₂ H ₅ 6-C, H ₃ br 46 6-C ₂ H ₅ br

4-chloropyrazole-1-yl

Khlor-1,2,4-triazol-1-yl

2,4,5-trichloropimidazol-1-yl 4-chloropyrazol-1-yl 1,2,3,4-tetrazol-1-yl

Pyrazol-1-yl pyrazol-1-yl imidazole-1-yl 1,2,4-triazol-1-yl 1,2,4-triazol-1-yl

Melting point ( ⁰ Cj

91

153 110 110

63 67

CeI SO

73

Le A 18 886

Preparing ^{o n} Ausganqsprodukten Example 3a

C ₂ H,

CO - CH ₂ Cl

(Variant & C)

To eiger solution of 225.7 g (1 MpI) of 2,6-diethyl-chloroacetanilide in 1.5 1 of toluene are 45 g (1.5 mol) of para

ο given formaldehyde. It is heated to 40 C and dripped

179 g (1.5 mol) of thionyl chloride with stirring. a lively gas development begins. The mixture is stirred at 40 ° C until the gas evolution is complete. It is then filtered and the filtrate is concentrated in vacuo. After degassing the residue in a high vacuum, 268.7 g (98% of theory) of 2,6-diethyl-N-chloromethyl-chloroacetanilide are obtained as a colorless oil.

(Variant ß)

To a solution of 225.7 g (1 mol) of 2,6-diethyl-chloroacetanilide in 1.5 1 of anhydrous toluene 45 g (1.5 mol) of paraformaldehyde and 10Og anhydrous sodium sulfate given with stirring and heating to 50 ° C. Initiate dry hydrogen chloride until the milky suspension of paraformaldehyde has disappeared. Thereafter, 100 g of anhydrous sodium sulfate are added again, stirred a Stuna © @ 50 ° C and filtered «The filtrate is concentrated in vacuo. Mach

Le A 18 886

213771

Degassing of the residue gives 263.2 g (96% of theory) of 2, e-diethyl-chloroacetanilid as a colorless oil.

Analogously to Example 3a, the compounds of Table 2 below are obtained.

5 Table 2

CH ₂ -HaI CO-CH ₂ -Z

(VII)

Example no. X Yn Z Hal SC ₁ -LT. egg. z-point or refractive index 5 a 1-C ₃ H ₇ 6 -! - C ₃ H ₇ Cl Cl not isolated 6 a CH ₃ 6-C ₂ H ₅ Cl Cl 91 8 a ^C 2 ^H 5 4,6- (CH ₃ ) ₂ Cl Cl not isolated 9 a CH ₃ 4,6- (CH ₃ ) ₂ Cl Cl Il 10a C ₂ H ₅ 4-CH ₃ Cl Cl π 6-C ₂ H ₅ 14a XC ₃ H ₇ - Cl Cl 9O 17a C ₂ H ₅ - Cl Cl not isolated 18a CH ₃ 6-CH ₃ Cl Cl 88 20a CH ₃ 5-CH ₃ Cl Cl not isolated 24a CH ₃ 3-CH, Cl Cl 40 34a C (CH ₃ ) ₃ Cl Cl not isolated 42a C ₂ H ₅ 6-C ₂ H ₅ br br Il 43a CH ₃ 6-C ₂ H ₅ br br Il Le A 18 886

The acetanilides of the formula (IV) have strong herbicidal effects, in particular against grasses. They can therefore be used for selective weed and especially weed control.

The herbicidally active acetanilides of the formula (V) are also not yet known. They can be produced, however, by

b) N-Acylmethylaniline of the formula

(X)

in which

R, R, R, R and m are as defined above,

reacted with chloroacetyl chloride in the presence of a diluent.

If 2,6-dimethyl-N-benzoylmethyl-aniline and chloroacetyl chloride are used as starting materials, the course of the reaction of process (b) can be represented by the following formula scheme:

, CH ₃

^f ^ O> N-CH ₂ -CO- <g

H CH ^

Cl-CO-CH ₂ Cl

-HCl

H.

N-CH ₂ -CO- (O, CO-CH ₀ Cl

Le A 18 886

213771

The N-acylmethyl-anilines to be used as starting materials in the process (b) are generally defined by the formula (X). In this formula, R preferably represents straight-chain or branched alkyl having 1 to 6, in particular 1 to 4, carbon atoms, halogen, in particular fluorine, chlorine and bromine, haloalkyl having up to 3 carbon atoms and up to 5 identical or different halogen atoms, as halogens are in particular fluorine and chlorine, by way of example trifluoromethyl may be mentioned; further preferably alkylthio and alkylsulfonyl having 1 to Kohlenstpffatomen in the alkyl moiety and aminosulfonyl, cyano unh nitro. R and R are the same or different and are preferably hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, halogen, in particular fluorine, chlorine and bromine, haloalkyl having up to 3 carbon and up to 5 identical or different halogen atoms, wherein Halogens, in particular fluorine and chlorine, and preferably optionally mono- or polysubstituted phenyl,

wherein as substituents preferably the radicals mentioned for R come into question. R is preferably straight-chain or branched alkyl having 1 to 6, in particular 1 to 4, carbon atoms and optionally mono- or polysubstituted phenyl, where

Substituents preferably the radicals already mentioned in R as well as phenyl and phenoxy, which may also be substituted by R, come into question.

The N-acylmethyl-anilines of the formula (X) are known (cf., inter alia, Chem. Ber Z5, 2865 (1892) and Chem. Soc., 1943, 63) or can be prepared by known methods

Le A 18 886

produce. They are obtained, for example, by reacting anilines with α-haloketones in the presence of an organic solvent, e.g. Ethanol, converts (see also the Hersteliungsbeispiele).

Suitable diluents for the reaction according to process (b) are preferably inert organic solvents. These include preferably ketones, such as diethyl ketone, in particular acetone and methyl ethyl ketone; Nitriles, such as propionitrile, in particular acetonitrile; Ethers, such as tetrahydrofuran or dioxane; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; and esters, such as ethyl acetate.

The reaction temperatures can be varied within a substantial range when carrying out the process (b). In general, one works between 0 and 120 ° C _f, preferably between 20 and 100 ⁰ C.

In carrying out the process (b) is preferably used for 1 mol of the compound of formula (X) 1 to 3 moles of chloroacetyl chloride. The isolation of the compounds of formula (V) is carried out in the usual manner.

The practical preparation of acetanilides of the formula (V) is shown by the following examples:

Le A 18 886

Example 47

.-Α

16 ml (0.2 mol) of chloroacetyl chloride are added dropwise to a solution of 18.5 g (0.068 mol) of 2,6-dimethyl-N- (4-chloro-benzoylmethyl) -aniline in 1 "of benzene Stirring for 15 hours under reflux and concentrated by distilling off the solvent and the excess chloroacetyl chloride in vacuo.The residue is triturated with a mixture ether / petroleum ether (1: 3), the resulting crystalline residue filtered off with suction and dried to give 17.7 g ( 75% of theory) 2,6-dimethyl-N- (4-chlorobenzomethyl) -chloroacetanilide of melting point 128 ° C.

5 Preparation of the starting material

- CO

46.7 g (0.2 mol) of U / -bromo-4-chloroacetophenone in 40 ml of ethanol become 48.4 g (0.4 mol) of 2,6-dimethylaniline

Le A 18 8C6

in 40 ml of ethanol and heated to 50 ° C for 20 minutes. Then it is cooled to 0 ⁰ C, filtered from the crystals formed and washed with a little ethanol after. This gives 30 g (55% of theory) of 2,6-dimethyl-N- (4-chlorobenzomethyl) aniline of melting point 82 ° C.

Example 48

C ₂ H ₅

^ CH ₂ - CO - C (CH ₈ ), CO - CH ₃ Cl

23.3 g (0.1 mol) of 2 = ethyl-6-methyl-N-pivaloylmethyl-snilin are dissolved in 100 ml of benzene and mixed with 24 ml (0.3 mol) Chloracety! Chloride. Then allowed to stir for 15 hours under reflux and concentrated by distilling off the solvent and the excess Chloracetylchlorids in vacuo. The oily residue is stirred with petroleum ether, decanted, stirred with charcoal, filtered and concentrated in vacuo. The residue is stirred with n-hexane, the resulting solid is filtered off with suction and dried. This gives 13.7 g (45 % of theory) of 2-ethyl-6-methyl-N-pivaloylmethyl-chloroacetanilide of melting point 86 ° C.

Preparation of the ÄusganqsjgrodukteD

.CH ₂ -CO -

Le A 18 88β

213771

108 g (0.8 mol) of 2-ethyl-6-methyl-aniline and 53.8 g (0.4 mol) Monochlorpinakolin be heated in 300 ml of toluene at 110 ° C for 25 hours. It is allowed to cool, filtered, the filtrate is washed with water, dried over sodium sulfate and concentrated by distilling off the solvent in vacuo. The residue is fractionally distilled. This gives 24.1 g (26% of theory) of 2-ethyl-6-methyl-N-pivaloylmethyl-aniline of boiling point 138'- 15O ° C / O, 7 mm and a refractive index of n_ = 1.5168.

In an analogous manner, the compounds listed in Table 3 below are prepared.

Le A 18 886

Table 3

Ex.

49 50 51 52 53 54 55 56 57 58

-N

r " ⁵ r ^

^N c '~ co /

^ CO - Ci

- R

(V)

2-CH ₃ H

2-CH ₃ 'H

2,6- (C _g H _{3) 2} H

2,6- (C ₂ H _{3) 2} H

2-Cl H

2,6- (CHj) ₂ H

4-Cl

2,6- (CH _s ) ₂ CH ₃

2,6- (K ¹ ₃ H _? ) _Ii H

2,6- (C ₂ H ₉ ) *, H 4- »CK _s

2 _t 6 ~ (i <C _s H ₇ ) g H

3) β Η

2 ~ C >> Ha e H 6-CH _s

2,6- (CK _{3) 2} H

2-C h Hj, 4,6- (CH ₃

2,6- (CH ₃ ) _t H 2,4, S- (CH ₃ ) _s H

H H H H H H H H K

Cl

: O> ci

"-C1

Cl

D> CH ₈

CH ₃

: O> ci

-OCH ₃ " ^H OCH _S

D> ci

Melting point ( ⁰ C) or

138th

140

134

Ιΐβ

124

100

114

104

200

112

140 90

70 114

ng = 1.5680

104 134

La A 18 886

213771

Table 3 (continued)

Ex. 2 **. R ⁵ R ⁶ R ⁷ Melting point ( ⁰ C) or refractive index 66 2 4,6- (CH ₃ ) _; 5 ^H H n ^ ° = 1.5610 67 2 , 6- (CH ₇ J ₂ H ^> - © -ex 149 68 , 6- (CHj) ₂ H CHj 84

Le A 18 886

In an analogous manner, the compounds listed in Table 4 below can be obtained.

table

CO-CH ₂ Cl (V)

EeI game Kr.

74 75 76 77 78 79 80 81

s * 5-N ₁ CF ₅ ) ₂ H H 2,6- (CH ₃ ) ₂ H K 2,6- (CH ₅ ) ₂ H H 2,6-, CH ₃ ) j H H 2,6- (CH ₅ ) ₂ , 4-SC ₂ MH ₂ H H 2-Cl, 6-CH ₃ H H 2-C ₂ H ₅ , 6-CHj CH ₅ CH ₃ 2-C ₂ H _{5 t} 6 ~ CHj CH ₃ CH ₃ 2-C ₂ K ₅ , 6-CH ₃ CHj CH ₃ 2-C ₂ H ₃ * 6-CH _? CH ₃ CH ₃ 2-C ₂ H ₃ , 6-CH ₃ CH ₃ CH ₃ 2-C ₂ H ₃ , 6-CH ₃ H CH ₃ 2-C ₂ H ₅ , 6-CH ₃ H CH ₃

Cl

Le A 18

213771

Table 4 (continued)

Example No.,

R '

2,6- (CHj) ₂ 2,6- (CH ₃ ) _a 2,6- (CHj) ₂ 2,6- (CHj) ₂ 2,6- (CHj) ₂

2,6- (CHj) ₂

H H H H H

-Cl - <

-F -CH ₃

-Cl

-Cl-Cl

CH,

Le A 18 886

The acetanilides of the formula (V) have strong herbicidal properties. They are therefore suitable for weed control. In particular, they can be used for selective weed and grass weed control.

The herbicidally active acetanilides of the formula (VI) are also not yet known. They can be produced, however, by

c) N-Azolylalkylaniline of the formula

_D 9 R ¹⁰ Ν- ~ N

11

R. (XI)

10 in which

R, R, R, R, A, and ρ are as defined above

to have,

with haloacetic acid chlorides or anhydrides of the formulas

15 R ¹² -CH ₂ -CO-C1 (XIIa)

or

(R ¹² -CH ₂ -CO) ₂ O (XIIb)

in which

1 ο R has the meaning given above,

in the presence of a diluent and optionally in the presence of an acid binder.

Le A 18 886

213771

If 2,6-diethyl-N- (3-methylthio-4-methyl-1,2,4-triazol-5-yl-methyl) -aniline and chloroacetyl chloride are used as starting materials, the course of the reaction of process (c) can be carried out by the following equation scheme are reproduced:

C ₂ H ₅

N N

C ₂ H ₅

Il Η + Cl ^ N- ^ SCH ₃

CH

'C ₂ H ₅

-CO-CH, Cl

HCl

'C ₂ H ₅

N - N

CH ₃

CO-CH ₂ Cl

The N-Azolylalkylaniline required as starting materials in the implementation of the method (c) are generally defined by the formula (XI). In this formula, A is preferably oxygen, sulfur or the grouping

In which R is preferably hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms and aryl having 6 to 10 carbon atoms, in particular phenyl, where each of these aryl radicals may be substituted by halogen, alkyl having 1 to 4 coal

Le A 18 886

lenstoffatomen, alkoxy having 1 or 2 carbon atoms, alkylthio having 1 or 2 carbon atoms, cyano, nitro and / or haloalkyl having up to 2 carbon and up to 5 identical or different halogen atoms, wherein as halogens in particular fluorine and chlorine may be mentioned. R

11 is preferably hydrogen or methyl. R in the formula (XI) is preferably hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, haloalkyl having up to 3 carbon atoms and up to 5 identical or different halogen atoms, halogens being in particular fluorine and chlorine, by way of example Trif luorme.thyl called, further preferably for

Alkenyl and alkynyl having 2 to 4 carbon atoms, cycloalkyl having 5 to 7 carbon atoms and halogen, in particular fluorine, chlorine or bromine. R is furthermore preferably aryl having 6 to 10 carbon atoms, in particular phenyl, where each of these aryl radicals may be substituted by halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 or 2 carbon atoms, alkylthio having 1 or 2 carbon atoms, cyano, nitro and or haloalkyl having up to 2 carbon atoms and up to 5 identical or different halogen atoms, halogens being in particular fluorine or chlorine and trifluoromethyl being mentioned as an example of haloalkyl. R is further preferably aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety, especially benzyl, each of these aralkyl moieties in the aryl moiety may be substituted by halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 or 2 carbon atoms , Alkylthio having 1 or 2 carbon atoms, cyano, nitro and / or haloalkyl

Le A 18 886

3771

with up to 2 carbon atoms and up to 5 identical or different halogen atoms, halogens being in particular fluorine or chlorine and trifluoromethyl being mentioned as an example of haloalkyl. In addition, R ^{11 represents} the groupings -OR _f -SR and -NR R, wherein R is preferably those radicals which have already been mentioned above for this radical, R in these groups is hydrogen, straight-chain or branched alkyl having 1 to 4 Carbon atoms, haloalkyl having up to 3 carbon atoms land up to 5 identical or different halogen atoms, halogens being in particular fluorine and chlorine, by way of example trifluoromethyl, furthermore preferably alkenyl and alkynyl having 2 to 4

C 1 -C 4, cycloalkyl of 5 to 7 carbon atoms and aralkyl of 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety, in particular benzyl, where each of these aralkyl moieties in the aryl moiety may be substituted by halogen, alkyl of 1 to 4 carbon atoms, Alkoxy having 1 or 2 carbon atoms, alkylthio having 1 or 2 carbon atoms, cyano, nitro and / or haloalkyl having up to 2 carbon atoms and up to 5 identical or different halogen atoms, halogens being in particular fluorine or chlorine and trifluoromethyl being mentioned as an example of haloalkyl be.

In the formula (XI), R preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms.

ο R is preferably in the formula (XI) for geradkecti-

Le A 18 886

- 40 - £ Λ «3

branched or branched alkyl having 1 to 4 carbon atoms or for the halogens fluorine, chlorine and bromine; the index ρ stands for the numbers 0, 1 or 2.

The N-Azolylalkylaniline of formula (XI) required as starting materials in the process (c) are not yet known. You get them when you

d) Anilines of the formula

in which

8 9 R, R and ρ have the abovementioned meaning,

with azole derivatives of the formula

R ¹⁰ _

N # (XIV)

Hal '-

in which

A, R and R are as defined above and ^ 5 Hal "is chlorine or bromine,

in the presence of an acid binder such as potassium or sodium carbonate, and in the presence of an inert organic solvent such as dimethylformamide or toluene, at temperatures between 20 and 160 ° C, preferably a

Le A 18 886

1 3771

Excess of aniline of the formula (XIII) is used (see also Preparation Examples), or

e) hydrazine derivatives of the formula

.9

PH - PO - MW _ KTU

(XV)

CH-CO-NH-NH

in which

8 9 '10 R, R |, R and ρ have the abovementioned meaning

with isocyanates or mustard oils of the formula

R ¹³ -N = C = B. (XVI)

in which

B is oxygen or sulfur and R has the meaning given above,

in the presence of an organic solvent, such as an alcohol, ether or hydrocarbon, at temperatures between 0 and 80 ° C, 5, the resulting compounds of the formula

R ⁹ ? ¹⁰

CH-CO-NH-NH-CB-NHR '

in which

Le A 18 886

- 42 - ^^ ^ ⁶ *

ft Q 10 13 B, R, R, R, R and ρ are as defined above

to have,

cyclized in the presence of a strong base such as sodium or potassium hydroxide, and in the presence of a solvent, v / ie, for example, ethanol or water at temperatures between 20 and 100 ° C and the resulting triazolones or triazolothiones of the formula

P R ⁹ ? Ν- I 11 NH ύ in which -Ν B, R, R, R, R with halides and ρ the above ar igegeben to have, the formula Hal ¹

(XVIII)

(XIX)

in which

15 Hai ^{1 is} chlorine or bromine and

15 14

R is the radicals of the substituent R,

excluding hydrogen,

in the presence of a strong base, such as, for example, sodium hydroxide solution, and in the presence of an inert organic solvent, such as toluene or methylene chloride, at temperatures between 20 and 80 C, wherein also phase-transfer catalysed and with other alkylating reagents, such as dimethyl sulfate, worked v / earth (see also

25 position examples), or

Le A 18 886

f) hydrazine derivatives of the formula (XV) with formic acid or acid chlorides or acid anhydrides of the formulas

R ¹⁶ -CO-C1 (XXa)

or.

fR ¹⁶ -CO-) ₂ O (XXb)

in which

R is alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, optionally substituted aryl or optionally substituted aralkyl

in the presence of an inert organic solvent, such as an ether, hydrocarbon or semi-halogenated hydrocarbon, at temperatures between 0 and 50 ° C and the resulting compounds of the formula

~ ⁹ ι

CH-CO-NH-NH-CO-R ¹⁶ M / (XXI)

R ¹

, 8 p

in which

R, R, R, R and ρ are as defined above,

either cyclized with diphosphorus pentasulfide in known manner (see Chem.Ber. 2 [2, 797 (1899) and J.prakt. Chemie 9, 145 (1904) to thiadiazole derivatives, or also in a known manner with conventional

Le A 18 886

, - 44 -

dehydrating reagents to oxadiazole derivatives (see, for this Elderfield, Heterocyclic Compounds, Vol 7 (1961) or

g) hydrazine derivatives of the formula (XV) with nitriles of the formula

R ¹⁷ -C = N (XXII)

in which

R is alkyl, haloalkyl or optionally substituted aryl

in a conventional manner to triazole derivatives (see Chem.Ber. 9 ^, 1Ό64 (1963)), or

h) hydrazine derivatives of the formula (XV) with irino ethers of the formula

16 c ^

R -C ^ _1βxHCl (XXIII)

15 in which

R is alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, optionally substituted aryl or optionally substituted aralkyl and

1 8

R is methyl or ethyl,

in a conventional manner, under reflux and in the presence of an inert organic solvent such as ethanol, to form oxadiazole derivatives, or

Le A 18 886

j) the anilines of the formula (XIII) with azole aldehydes of the formula

in which

R has the meaning given above,

in the presence of an inert organic solvent, for example toluene, at temperatures between

as

80 and 120 ⁰ C and the resulting compounds of the formula

N = CH-A. JL-ρ 11 < ^XXV >

R 10

in which

A, R, R, R 'and ρ are as defined above,

reduced in a generally known manner; for example, by reaction with complex hydrides, such as sodium borohydride, if appropriate in the presence of a polar organic solvent, such as methanol, at temperatures between 0 and 80 ^° C.

The compounds of the formulas (XIII) and (XIV) required as starting materials in process d) are known or can be prepared by processes which are known in principle (cf., Kelv.Chim.Acta 55, 19 9 et seq.

Le A 13 886

Berlin, the .22. 10. 1979 AP C 0? D / 213 771 GZ 55 605 18

Chem. Ber, £ 2, 797 et seq. (1899) and Chem. Ber. 26, 1049 et seq. (1963)).

The starting materials of the formula (ZV) required in the process (e) are not yet known. However, they can be prepared by known processes using known esters (cf., inter alia, DI-OS 2 350 944 and 2 513 730). of the formula

10

CE - COOR

in which, 10

R ¹

and ρ have the abovementioned meaning and is methyl or ethyl,

with hydrazine hydrate, preferably in the presence of an organic Lösungamitteis, such as ethanol, dioxane or dimethylformamide, at temperatures between 20 and 120 ^ ^- C. (cf. also Preparation Examples *).

The reaction components of the formulas (P / I) and (XIX) required in the processes (e) are generally known compounds of organic chemistry.

The substances of the formulas (XXa) ₉ (XXb), (XXII) and (XXIII) required in the processes (f) "(g) and (h) as reaction components are also known *

The azole-aldehydes of the formula (XXIV) to be used as reaction components in the process (j) are likewise known or can be prepared by processes which are known in principle (compare Elderfield, "Heterocyclic Compounds", Vol 7 (1961) and " Advances in Heterocyclic Chemistry, Vol. £ (1968)).

The haloacetic acid chlorides or anhydrides also to be used as starting materials for the reaction according to process (c) are generally defined by the formulas (XIIa) and (XIIb). In this way for chlorine, bromine and iodine.

generally defined. In these formulas R stands for preference.

The haloacetic acid chlorides and anhydrides of formulas (XIIa) and (XIIb) are well known compounds of organic chemistry.

Suitable diluents for the reaction (c) are preferably inert organic solvents. These include preferably ketones, such as diethyl ketone, in particular acetone and methyl ethyl ketone; Nitriles, such as propionitrile, in particular acetonitrile; Ethers, such as tetrahydrofuran or dioxane; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; and esters, such as ethyl acetate.

The process (c) may optionally be carried out in the presence of acid binders (hydrogen chloride acceptors)

Le A 18 886

become. As such, all common acid binders can be used. These include 'preferably organic bases, such as tertiary amines, for example triethylamine, or pyridine; Further, inorganic bases, such as alkali metal hydroxides and alkali metal carbonates.

The reaction temperatures can be varied within a substantial range when carrying out the process (c). In general, one works between 0 and 120 ° C, preferably between 20 and 1OO ° C.

In carrying out the process (c) is preferably used for 1 mol of the compound of formula (XI) 1 to 1.5 mol Haiogenacetylierungsmittel and 1 to 1.5 moles of acid binder. The isolation of the compounds of formula (VI) is carried out in the usual manner.

The practical preparation of acetanilides of the formula (VI) is evident from the following examples.

Le A 18 886

Example 88

16.3 g (0.07 mol) of 2-ethyl-6-methyl-N- / O 2 -methyl-1,3,4-oxadiazol-6-yl) -methyl7-aniline and 6 g (0.076 mol) of anhydrous pyridine are heated in 100 ml of absolute tetrahydrofuran with stirring to boiling and treated dropwise with a solution of 8 g (0.07 mol) of chloroacetyl chloride in 20 ml of tetrahydrofuran. After completion of the dropwise addition is allowed to stir for 10 minutes, concentrated by distilling off the solvent and the residue is stirred with 150 ml of water. The crystallizing reaction product is filtered off with suction, washed with water and dried. This gives 18.7 g (87% of theory) of beige crystals of 2-ethyl-6-methyl-N-X-methyl-1,3-oxadiazol-5-yl-methyl. Chloroacetanilide of melting point 67 "to 70 ° C.

Preparation of the starting product

Le A 18 886

A mixture of 101.2 g (0.76 mol) of 2-ethyl-6-methylaniline, 40 g (0.3 mol) of 2-methyl-5-chloromethyl-1,3,4-oxadiazole, 41.4 g ( 0.3 mol) of powdered potassium carbonate and 76 ml of dimethylformamide is heated with stirring to 100 ⁰ C for 5 hours. Thereafter, the reaction mixture is filtered, the filtrate diluted with methylene chloride and washed several times with water. The methylene chloride phase is dried over sodium sulfate and concentrated in vacuo by distilling off the solvent. The residue is distilled in vacuo. This gives 46.8 g (67.5 % of theory) of yellowish oil of 2-ethyl-6? -Methyl-N - / (2-methyl-1,3,4-oxadiazol-5-yl) -Ciethy3 ₁ 7 Aniline of boiling point 14O to 142 ° C / O, 1 mm with a 94% purity (determined by gas chromatography).

15 Example 89

ru Il Il

SCH,

5 g (0.017 mol) of 2,6-diethyl-N-1,1-methyl-2-methylthio-1,3,4-triazol-5-yl) -methyl-7- ^aniline and 1.6 g (0.02 mol) Pyridine are stirred in 100 ml of absolute tetrahydrofuran and added dropwise at room temperature with 2.3 g (0.02 mol) of chloroacetyl chloride, the temperature rises to about 30 ⁰ C. It is allowed to stir for 2 hours, partially distilled by distilling off the solvent

Le Ä 18 88S

and mixed with water. The crystallizing product is filtered off, dried and recrystallized from diisopropyl ether / ethyl acetate. This gives 5 g (80% <3er theory) of 2,6-diethyl-N-ni-methyl-2-methylthio-1,3, 4-tria2ol-5-yl) -methyl-7-chloroacetanilide of melting point 121 to 123 ° C.

Preparation of precursors

 SCH, a)

13.9 g (0.05 mol) of 2,6-diethyl-N- [1-methyl-2-thiono-1, 3,4-triazol-5-yl) -methyl7-aniline are added at room temperature in a sweiphase mixture from 150 ml of toluene and 40 ml of 50% strength sodium hydroxide solution with the addition of 1.5 g of triethylbenzylammonium chloride (TEBA) as the catalyst was rapidly stirred and treated dropwise with 6.3 g (0.05 mol) of dimethyl sulfate, the temperature being maintained at about 35 ° C increases. The mixture is stirred for 5 hours, the toluene phase is separated off, washed several times with water, dried over sodium sulfate and concentrated by distilling off the solvent. The residual oil is brought to crystallization by the addition of petroleum ether. After recrystallization from petroleum ether, 6.7 g (40% of theory) of 2,6-diethyl-N- (1-methyl-2-methylthio-1, 3,4-triazol-5-yl-1-methyl-7-yl) are obtained. aniline of melting point 65 bi © 67 ° C.

Le A 18 886

29.6 g (0.1 mol) of 1-methyl-4- (2,6-diethylanilino) acetyl / thiosemicarbazide are suspended in 150 ml of ethanol and after addition of 7 g of potassium hydroxide in 20 ml of water for 1 hour heated to reflux. Thereafter, the major part of the solvent is distilled off and the residue is mixed with 250 ml of water. After acidification with glacial acetic acid to pH 5, the resulting precipitate is filtered off with suction and washed thoroughly with water. After drying, 27 g (97% of theory) of 2,6 ~ diethyl-N- £ M-methyl-2-thiono-1,3,4-triazol-5-yl) -methyl7-aniline of melting point 117 to i21 ° C.

0C ₂ H ₃ ^ CO-NH-NH-CS-NHCH ₃

44.2 g (0.2 mol) of 2,6-diethyl-anilino-acetic acid hydrazide and 14.8 g (0.2 mol) of methyl mustard oil are dissolved in 250 ml of ethanol and heated to reflux temperature for one hour. After the subsequent cooling to room temperature, the resulting precipitate is filtered off with suction and washed twice with 50 ml of ethanol. After drying, 46 g (78% of theory) of 1-methyl

Le A 18 88S

4j £ 2,6-dilethyl-anilino) -acetyl-7-thiosemicarbazid in the form of a colorless crystalline substance of melting point 166 ° C.

^d)

58.7 g 10%, 25 mol) 2,6-diethylanilino-acetic acid ethyl ester and 25 g of hydrazine hydrate are allowed to stand in 200 ml of ethanol for 24 hours. It is then concentrated by distilling off the solvent and the residue is stirred with water. After drying, 50.5 g (91% of theory) of colorless crystals of 2,6-diethyl-anilino-acetic acid hydrazide of melting point 71 to 73 ° C.

In a similar manner, those compounds are obtained which are listed in Table 5 in the formula.

Le A 18 886

table

CO - CH ₂ - R

12

(VI)

Ex.

10

90 91 92 93 94 95 96 97 98

j 2 chord I ¹ Z

H CH ₃

H CH ₅

H CH ₃

H H H H

99 H 100 H 101 H

C ₈ H ₃ 6-C ₂ H ₃ 0 CH ₃ 6 -CH ₃ 0

C (CH ₃ ) _s - 0

H -S-CH ₂ -CHsCH. C ₂ H ₉ 6-C ₂ H ₉ "" Ν

H -S-CH ₅

Cj Hg

iC ₃ H ₇ CH,

CH.

CH-

CH ₃

Chg

C ₈ H ₃

CH ₃

CK ₃ 6-CH, ti '

CH ₃

6_p ti «2 Jig

6-Cg H ₃ 0 6-C · E, 0

CH ₃

3-CH ₃

6 ™

Cl Cl Cl Cl Cl Cl Cl Cl Cl

CH ₃ 1-C ₃ H ₇

• 3 ⁿ 7

CH ₃

CH ₃

br

br

Cl

79-82 91-93 102-04 67-70 ° 115-20 57-59 43-47

zHhfl.Osl '

glassy solidifies

80 °

92-94 ° C 135-37 °

Le h 18

According to one or more of the processes described in the application, the starting materials listed in the table below are obtained in a formula.

Table 6

1P M-

(Χι)

Example no. R iO 1 H ] R ¹¹ R ⁹ _R 8 A Melting point Te / H 1 or refraction H index XI-1 H CH ₃ C ₂ H ₅ 6-C ₂ H, O n ²² = 1.540 XI-2 H CH ₃ CH ₃ 6-C ₂ H ^ O n | 2-1.S47 nj ^ - 1,552 XI-3 H CH ₃ CH ₃ 6-CH ₃ O 52-55 XI-4 H CH ₃ - (CH ₃ J ₃ - O 96-99 XI-5 H CH ₃ ⁱ " ^C 3 ^H 7 6-1 "C ₃ R O in - 1,534 xr-6 H C ₂ H ₅ C ₂ H ₅ 6-C ₂ H ₅ O Ο - 1.542 ι ¹ «1 531 XI-7 H C ₂ H ₅ CK ₃ 6-C ₂ H ₅ O S5-57 XI-8 1-C ₃ K ₇ CH ₃ 6-C ₂ H ₅ O n ²¹ «1,577 XI-9 H SCH ₃ C ₂ H ₅ 6-C ₂ H ₅ 2N-CH ₃ XI-10 S-CH ₂ -CH = C ₂ K ₅ 6-C ₂ H ₅ ^ M-CH ₃ Tough oil ^CH 2 F 142-143 XI-11 S-CH ₂ H ^) CH ₃ 6-C ₂ H ₅ ^ N-CH ₃ XI-12 CH ₃ CH ₃ 3-CH ₃

Le A 18 886

The acetanilides of the formula (VI) have strong herbicidal, especially selective herbicidal properties. They are therefore suitable for weed control. In particular, they can be used for selective weed and grass weed control. The selectivity in some cultures is not always satisfactory. The antidote according to the invention, the 1-dichloroacetyl-1,2,3,4-tetrahydro-quinaldln of formula (I) -, is particularly suitable for the protection of important crops, such as corn, soybeans, cotton, sugar beets, cereals, rice and Sugarcane against herbicide damage by thiolcarbamates and acetanilides, in particular from damage by herbicidal active compounds of the formulas (IV), (V) and (VI).

The active compound combinations according to the invention show a very good action against weeds and grass weeds in numerous crops. They can therefore be used for selective weed control in many crops. - Weeds in the broadest sense mean all plants that grow in places where they are undesirable.

The active compound combinations according to the invention can be used, for example, in the following plants.

Dicotyledonous weeds of the genera ; Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Se'sbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Le A 18 886

21377t

Dicotyledonous cultures of the genera : Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cuburbita.

Monocotyledonous weeds of the genera : Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monocharia, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ishaemum , Sphenoclea, Daciyloctenium, Agrostis, Alopecurus, Apera.

Monocotyledonous cultures of the genera : Oryza, Zea, Triticum, Hordeum, Avena, Secale _R Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

In particular, the active compound combinations according to the invention are suitable for selective weed control in corn, soybeans, cotton, sugar beet, cereals, rice and sugar cane. , ...

The antidote according to the invention can be converted into the customary formulations in admixture with the herbicidal active ingredients in which it is used, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, Suspension emulsion concentrates, seed powders, natural and synthetic substances, ultra-fine encapsulations in polymeric substances and in seed coating compositions.

Le A 18 886

- 58 - 2.

These formulations are produced in known manner, _t for example by mixing the antidote according to the invention optionally in admixture with the herbisiden active compounds with which it is used, with extenders, that is liquid solvents and / or solid carriers, optionally with the use of surfactants, that is emulsifiers and / or dispersants and / or foaming agents. In the case of using water as extender, it is also possible, for example, to use organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or mathylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; as solid carriers: natural minerals such as kaolins, clays, talc? Chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as fumed silica, alumina and silicates; as solid carriers for granules fractured and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic substances

Le A 18 886

and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-forming agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol A'ther, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolysates; as a dispersing agent: e.g. Lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-type polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate may be used in the formulations.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight of antidote or antidote and herbicidal active ingredient, preferably between 0.5 and 90%.

The antidote according to the invention can be used as such or in its formulations also in admixture with herbicidal active ingredients, wherein finished formulation or tank mixing is possible. Also a mixture with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, protective substances against

Le A 18 886

Bird disease, growth factors, plant nutrients and soil structurants are possible.

The antidote according to the invention or mixtures of antidote according to the invention and herbicidal active ingredient can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders and granules. The application is done in the usual way, e.g. by pouring, spraying, spraying, dusting, spreading, dry pickling, moist pickling, wet pickling, slurry pickling or encrusting.

The antidote according to the invention can be applied by the methods customary for such antidotes. Thus, the antidote according to the invention can either be applied before or after the herbicide or applied together with the herbicide. In addition, crops may be protected from damage by seed treatment with the antidote before sowing (seed dressing) when Herbi-ζid is applied before or after sowing. Another possible use is that you bring out the antidote during sowing in the seed furrow. If both plants are cuttings, they may be treated with the antidote before transplantation. "

25 the.

When using the antidote according to the invention, the local Aufv / and amounts of the respective herbicides are used. The application rates of herbicides

Le A 18 886

Berlin, October 22, 1979 AP C 07 D / 213 771 GZ 55 605 18

21377!

Active ingredient varies between 0.5 and 5 kg / ha _e The application rate of antidote is independent of the herbicide and Aufwaudinenge the herbicidal active ingredient * In general, the application rates of inventive antidote surface treatment between 0.1 and 5 kg / ha, preferably between 0 , 2 and 4 kg / ha. In seed treatment, the application rates of the antidote according to the invention are generally between 10 and 300 g per kilogram of seed, preferably between 25 and 200 g per kilogram of seed.

In the active compound combinations according to the invention, the weight ratios of antidote to herbicidal active ingredient can vary in relatively large ranges. In general, 1 part by weight of herbicidal active substance of the formula (III), (IV), (V) or (VI) accounts for 0.05 to 1.0 parts by weight, preferably 0.1 to 0.5 parts by weight an antidote of formula (I),

Execution, starting from I pie '

The good effectiveness of the antidote according to the invention is evident from the following example ♦

Example A

Pre-emergence test "

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of herbicidal active ingredient or antidote or a mixture of antidote and herbicidal active ingredient with the stated amount of solvent, '' the specified amount of emulsifier and dilute the concentrate with water to the desired concentration ,

Seeds of the test plants are sown in normal soil and watered after 24 hours with the herbicide preparation or with the antidote preparation or with the preparation of antidote and herbicidal active ingredient. It is advisable to keep the amount of water per unit area expediently constant. The concentration of active ingredient in the preparation does not matter, only the application rate of the active ingredient per unit area is decisive. After three weeks, the degree of damage of the plants is rated in% damage compared to the development of the untreated control. It means:

0% = no effect (as untreated control) 100% = total destruction

Active ingredients, application rates and results are shown in the following table:

Le A 18 886

Table A Pre-emergence test

Active ingredient herbicide

Drug cost of herbicide kg / ha

Active ingredient Active ingredient Antidote a «Antidote - kg / ha

Corn Echinochloa amaranthus

H.

O = C-CHCl, (known) '

Cp

O = C-CHCl. (known)

CH.

C-CH ₉ -Cl

• 1 =

CH-

O = C-CHCl ₂ (according to the invention)

100

100

co oa cn

Table A (continued) rre-emerccnce-Tcst

Active ingredient herbicide

Drug cost of herbicide kg / ha

Active substance active ingredient

Antidote to antidote. kg / ha

Corn Echinochloa amarunthus

3 C-CH ₂ Cl

H.

O = C-CHCl.

100

100

^Cil 3 ^ C-OLCl n:

CoH ^{2 x} -

-2 ^nc >

N-

CO

O = C-CHCl.

100

100

O = C-CHCl.

100

100

Claims (2)

Erfindimgsanspruch Agent for the protection of crop plants from herbicidal damage by thiolcarbamates and / or acetanilides, characterized by a content of IT-dichloroacetyl-Ί, 2,3,4-tetrahydro-chinaldine of the formula (D in addition to extenders and / or surface-active agents. 2 _# Process for the protection of crops from herbicidal damage by thiocarbamates and / or acetanilides, characterized in that N-dichloro-acetyl-1,2,3,4-tetrahydro-quinaldine is allowed to act on the crops and / or their habitat according to point 1 « Use of H-dichloroacetyl-1,2- _f 3, -tstrahydro-quinaldine according to item 1, characterized in that it is used for the protection of crop plants from herbicide damage by thiolcarbamates and / or acetanilides, 4 * Method for the preparation of agents: protection of crops from herbicidal damage by thiolcarbamates and / or acetanilides, characterized in that one mixes 1-dichloro-1-chloro-1,2-yl-4-tetrahydro-quinaldine with extenders and / or surface-active agents. Berlin, 22 * 10. 1979 AP C 07 D / 213 .771 GZ 55 605 18 - S6 « 5. Means according to item 1, characterized by a content of a) at least one herbicidally active acetanilide of the formula ~ -R- (IV) CO - CH ₂ - Z in which R is an optionally substituted H-containing heterocyclic radical, Z and Y are the same or different and are alkyl, Z 'is halogen and
η is 0, 1 or 2 _s or a herbicidally active acid addition salt or metal salt complex of an acetanilide of the formula (IV), or a herbicidally active acetanilide of the formula l CO - R? ^ CO Berlin, October 22, 1979 AP C 07 D / 213 771 GZ 55 605 18 in which R ^{4 is} alkyl, halogen, haloalkyl, alkylthio, alkylsulfonyl, aminosulfonyl, cyano or miro, R and R are the same or different and are hydrogen, alkyl, halogen, haloalkyl or optionally substituted phenyl, R is alkyl or optionally substituted phenyl and
m stands for integers from 0 to 5, or a herbicidally active acetanilide of the formula (TO CO-CH ₂ -R ¹² in which A is oxygen, sulfur or the group ^l3 , R ^{10 is} hydrogen or alkyl, R ^{11 is} hydrogen, alkyl,:. Haloalkyl, alkenyl, alkynyl, cycloalkyl, halogen, optionally substituted aryl and aralkyl or the moieties -OR ¹⁴ , -SR ¹⁴ and IJR ¹³ R ¹⁴ , R - * represents hydrogen, alkyl or optionally substituted aryl, R ¹ 4 represents hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl or optionally substituted aralkyl, R ^{8 is} alkyl, r 9 is alkyl or halogen, R is halogen and ρ stands for the numbers 0, 1 or 2, the herbicidally active acetanilide of the formula C ₅ H. or a herbicidally active thiocarbamate of the formula 2 R ¹ -SCK R ⁶ . _W 3 ti \ 3 (IH) in which R ^{1 is} C ₁ -C ₄ alkyl, benzyl, chlorobenzyl or C ₁ -C ₄ alkozybensyl » 2 3 R and R are independently alkyl of 2 to 4 carbon atoms or cyclohexyl, and also 2 3 R and R- together with the adjacent nitrogen atom represent a 5- to 7-membered hetero are cyclic ring, and b) the antidote N-dichloroacetyl-1,2,3,4-tetrahydro-quinaldine of the formula (I) *