CS204050B2 - Means for protection of cultural plants against damaging by the herbicide active thiolcarbamates and/or acetanilides and method of making the n-dichloracetyl-1,2,3,4-tetrahydrochinaldine - 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

The present invention relates to novel N-dichloroacetyl-1,2,3,4-tetrahydroquinaldine, to a process for its preparation and to its use as an agent (antidote) for the protection of crop plants against herbicide damage.

In this context, the abovementioned compositions (antidotes, antidotes) refer to substances capable of specifically antagonizing the harmful effects of herbicides on crop plants, i. to protect crop plants while not appreciably affecting the herbicidal activity on the weed control.

It is known that certain thiolcarbamates and acetanilides when used to control weeds in maize and other crops cause less or greater damage to crop plants. Furthermore, certain compounds, such as N-dichloroacetyl-2-methylindoline and N-dichloroacetyl-cis, trans-decahydroquinoline, are known to be useful in mitigating the damage caused by thiolcarbamates or acetanilides to crop plants (see DOS number: 2 218 097 ). However, the efficacy of these substances as antidotes is not always entirely satisfactory.

A new N-dichloroacetyl-1,2,3,4-tetrahydroquinoline of the formula I has now been found.

, 4-tetrahydroquinaldine

(AT

Furthermore, it has been found that the novel N-dichloroacetyl-1,2,3,6-tetrahydroquinoline of the above-mentioned formula I is obtained by obtaining 1,2,3,4-tetrahydroquinoline of the formula II

(II) reacting with dichloroacetyl chloride, optionally in the presence of an acid binding agent and optionally in the presence of a diluent.

In addition, it has been found that N-dichloroacetyl-1,2,3,4-tetrahydroquinaldine of formula I is excellently suited to protect crop plants from damage by herbicidally active thiolcarbamates and / or acetanilides.

Surprisingly, damage to crop plants by herbicidally active thiolcarbamates or acetanilides is surprisingly better suppressed by the concomitant use of N-dichloroacetyl-1,2,3,4-tetrahydroquinidine than by the use of the known N-dichloroacetyl-2-methylindoline or N-dichloroacetyl-cis, trans-decahydroquinoline, which compounds represent the chemically closest related substances of the same type of effect. Thus, the compound of the invention represents a valuable enrichment of the prior art.

The preparation of N-dichloroacetyl-1,2,3,4-tetrahydroquinaldine by reaction of 1,2,3,4-tetrahydroquinnaldine with dichloroacetyl chloride can be described by the following reaction scheme:

+ CLjWC-CO-CI

---->

-HCt

The 1,2,3,4-tetrahydroquinaldine of formula (II) used as starting material in the process of the present invention can be obtained by hydrogenating the quinine with hydrogen gas in the presence of a supported catalyst such as Raney nickel or ruthenium on a support, and optionally in the presence of a diluent such as methanol. or ethanol, at a temperature between 100 and 250 ^° C, preferably between 150 and 200 ° C. The hydrogen pressure may vary within wide limits. In general, pressures of between 10 and 22 MPa, preferably between 15 and 19 MPa, are employed. The hydrogenation of quinaldine is preferably carried out in the absence of another diluent, using ruthenium on alumina as a catalyst.

In the process according to the invention, all conventional acid acceptors, which preferably include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium bicarbonate and lower tertiary amines such as triethylamine, dimethylbenzylamine, pyridine and diazabicyclooctane. However, an excess of the starting 1,2,3,4-tetrahydroquinoline of formula II used may also serve as the acid binding agent, in which case the addition of an additional acid binding agent is unnecessary.

The diluents used in the process according to the invention are water and inert organic solvents, which preferably include ketones such as diethyl ketone or methyl isobutyl ketone, nitriles 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, such as in particular dimethylformamide.

The reaction temperatures of the process according to the invention can be varied within a wide range. In general, the reaction is carried out at a temperature of between about 0 and 60 ° C, preferably between 20 and 50 ° C.

In the process according to the invention, 1 mol of dichloroacetyl chloride and 1 mol of an acid binding agent are preferably used per mole of 1,2,3,4-tetrahydroquinaldine of the formula II. Isolation of the reaction product is carried out in a conventional manner. In general, the reaction mixture is poured into water after completion of the reaction, the aqueous mixture is shaken with a low water-soluble organic solvent such as methylene chloride, the combined organic phases are washed successively with dilute hydrochloric acid and water, dried and evaporated, the remainder is subjected to traction distillation.

Practical preparation of N-dichloroacetyl-1,2, -

The following examples illustrate 3,4-tetrahydroquininaline.

Example 1

and O-C * _from CHCl

14.8 g (0.1 mol) of dichloroacetyl chloride are added to a solution of 29.4 g (0.2 mol) of 1,2,3,4-tetrahydroquinaldium in 200 ml of acetonitrile at room temperature with stirring. The mixture was extracted several times with methylene chloride, the combined organic phases were washed successively with dilute hydrochloric acid and water, dried over sodium sulfate and evaporated under reduced pressure. by distillation of 20 grams of N-dichloroacetyl-1,2,3,4-tetrahydroquinaldine with a refractive index n _D ²⁰ = 1.5728.

Calcd for C12H13ONCI2:

C 55.83 O / o, H 5.08%, Cl 27.47%, δ 5.43%; found *

C 55.6%, H 5.1%, Cl 27.3%, N 5.3%.

Example 2

143 g (1 mol) of quinaldine are hydrogenated at 195 DEG C. under a hydrogen pressure of 17 to 19 MPa for 2 hours in the presence of 15 g of ruthenium catalyst on alumina. The reaction mixture was filtered and subjected to fractional distillation. 123 g

1.2.3.4- tetrahydroquininal, boiling at 75 ° C / 133 Pa.

As mentioned above, N-dichloroacetyl-1, 4-tetrahydroquinidine of formula I is useful for protecting crop plants from damage by herbicidally active thiolcarbamates or acetanilides, without significantly affecting the weed activity of these herbicides.

Preferably, N-dichloroacetyl-1,2, -

3,4-tetrahydrochinaldi of the formula I to be used as an antidote for herbicidally active thiolcarbamates of the formula III,

R2 z

R ¹ —S — C — N II \ OR ³ (И1) in which

R ¹ represents an alkyl group having 1 to 4 carbon atoms, benzyl, chlorobenzyl or alkoxybenzyl having from 1 to 4 carbon atoms in the alkoxy part,

R ² and R ³ are each independently C 2 -C 4 alkyl or cyclohexyl, or

R ² and R ³ together with the nitrogen atom to which they are attached form a 5- to 7-membered heterocyclic ring.

Examples of thiolcarbamates of the formula III are:

S-ethyl-N, N-dipropylthiocarbamate,

S-ethyl-N, N-diisobutylthiocarbamate,

S-propyl-N-butyl-N-ethylthiocarbamate,

S-propyl-N, N-diisopropylthiocarbamate,

S-ethyl-N, N-diethylthiocarbamate,

S-ethyl-N-ethyl-N-cyclohexylthiocarbamate,

S-ethyl-hexahydroazepine-1-thiocarbamate,

S-p-methoxybenzyl-N, N-diethylthiocarbamate,

S-p-chlorobenzyl-N, N-diethylthiocarbamate

S-benzyl-N, N-diethylthiocarate,

S-benzyl-N, N-di-sec-butylthiocarbamate,

S-propyl-N-ethyl-N-butylthiocarbamate.

The thiolcarbamates of formula III and their herbicidal activity are already known (see U.S. Pat. Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,314).

Furthermore, N-Dichloroacetyl-1,2,3,4-tetrahydroquinaldine of the formula I can advantageously be used as an antidote in the case of herbicidally active acetanilides of the formula IV,

in which

R is an optionally substituted nitrogen-containing heterocyclic radical,

X and Y, which may be the same or different, each represent an alkyl group,

Z represents a halogen atom and n has a value of 0, 1 or 2, as well as their herbicidally active acid addition salts and metal salt complexes.

The following compounds are exemplified as acetanilides of formula IV:

2-methyl-6-ethyl-N- (1-pyrazolylmethyl) chloroacetanilide,

2,6-diethyl-N- (1-pyrazolylmethyl) chloroacetanilide,

2,6-Diethyl-N- (1,2,4-triazol-1-ylmethyl) chloroacetanilide

2,6-dimethyl-N- (1,2,4-triazol-1-ylmethyl) chloroacetanilide,

2-methyl-N- (1-pyrazolylmethyl) chloroacetanilide,

2,5-dimethyl-N- (1-pyrazolylmethyl) chloroacetanilide,

2,3-dimethyl-N- (1-pyrazolylmethyl) chloroacetanilide,

2-methyl-6-ethyl-N- (1-pyrazolylmethyl) chloroacetanilide hydrochloride,

2,6-diethyl-N- (1-pyrazolylmethyl) - • chloroacetanilide hydrochloride,

2,6-diethyl-N - ((3,5-dimethylpyrazole-1 -)

-yl) methyl] chloroacetanilide

2,6-diethyl-N - [(3-chloro-1,2,4-triazol-yl) methyl] chloroacetanilide,

2-methyl-6-ethyl-N - [(3,5-dimethylpyrazol-1-yl) methyl] chloroacetanilide,

2-tert-butyl-N- (1-pyrazolylmethyl) chloroacetanilide,

2-methyl-6-ethyl-N - [(3-bromo-5-methylpyrazol-1-yl) methyl] chloroacetanilide, 2-methyl-6-ethyl-N - [(3-chloro-1,2,4- triazolyl) methyl] chloroacetanilide,

2,6-Diethyl-N - [(4-chloropyrazol-1-ylmethyl) chloroacetanilide.

Furthermore, N-dichloroacetyl-1,2,3,4-tetrahydroquinoline of the formula I can advantageously be used as an antidote in the case of herbicidally active acetanilides of the formula V,

(V) in which

R 4 represents an alkyl group, a halogen atom, a haloalkyl group, an alkylthio group, an alkylsulfonyl group, an aminosulfonyl group, a cyano group or a nitro group, each of R ⁵ and R ⁶ which may be the same or different; hydrogen, alkyl, halogen, haloalkyl or an optionally substituted phenyl group,

R 7 represents an alkyl group or an optionally substituted phenyl group and m is an integer of 0 to 5.

The following compounds are exemplified as acetanilides of formula (V):

2,6-dimethyl-N- (benzoylmethyl) chloroacetanilide,

2,6-Dimethyl-N- (4-chlorobenzoylmethyl) cm-oraceanilide,

Z-methyl-4-ethyl-N- [benzoylmethyl] chloroacetanilide.

In addition, the N-dichloroacetyl-1,2,3,4-tetrahydroquinaldine of the formula I can advantageously be used as an antidote for the herbicidally active acetanilides of the formula VI,

(VI)

OF

NR13,

OF

R 10 represents a hydrogen atom or an alkyl group,

R11 represents a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkenyl group, a cycloalkyl group, a halogen atom, an optionally substituted aryl or aralkyl group, or a group -OR14, -SR14 or NR13R14,

R 13 represents a hydrogen atom, an alkyl group or an optionally substituted aryl group,

R14 represents a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group or an optionally substituted aralkyl group,

R ⁸ represents an alkyl group,

R ⁹ represents an alkyl group or a halogen atom,

R 12 represents a halogen atom and p is 0, 1 or 2.

The following compounds are exemplified as acetanilides of formula VI:

2,6-diethyl-N - [(2-methyl-1,3,4-oxadiazole-

-5-yl) methyl] cm-oracetanilide,

2,6-dimethyl-N - [(2-methyl-1,3,4-oxadiazol-5-yl) methyl] chloroacetanilide,

2-ethyl-6-methyl-N - [(2-methyl-1,3,4-oxadiazol-5-yl) methyl] chloroacetanilide, 2-tert-butyl-N - [(2-methyl-1,3, 4-Oxadiazol-5-yl] methyl] chloroacetanilide.

In addition, the N-dichloroacetyl-1,2,3,4-tetrahydrohydrolinaldine of formula I can be advantageously used as an antidote in the case of the herbicidally active ocetonides summarized below:

N- (2'-methoxyethyl) -2,6-dimethylaminococanilide,

N- (2'-ol-e-oxoethyl) -2,6-dimetmelchloaocetanilide,

N- (2'-n-propyloxyethyl) -2,6-dimethyl-ch-oaocetonilide,

N- (2'-isopropyloxyethyl) -2,6-dimethyloloocetonilide,

N- (2'-methoxyethyl) -4-methyl-5-ethylchloroacetanilide,

N- ^{(2'-methoxyethyl)} -2,6-diethylcmloracetanilid,

N - [2‘-Etmoxylmethyl) -4-methyl-β-ethylchloaocetone,

N- (1'-ethoxykaabonylethyl) -2,6-dimethylChloaocetonilide,

N- (3‘-Methoxe-2‘-paopyl) -2-methylchloroacetanilide,

N- (3‘-Methoxe-2‘-paopyl) -2,6-dimethyloloocetonilide,

N- (3‘-Methoxy-2‘-propyl) -2-methyl-6-ethylchromoacetamide,

N- (3'-methoxe-2'-prope-) -2,6-diethelcho-oocetanidide,

in which

A is oxygen, sulfur or a grouping

N- (3‘-methoxy-2‘-propyl) -2-ethylchloroacetanilide,

N- (2‘-ethoxyethyl) -2,6-diethylchloroacetanilide,

N- (2‘-n-propoxyethyl) -2-methyl-6-ethylchloroacetanilide,

N- (2‘-n-propoxyethyl) -2,6-diethylchloroacetanilide,

N- (2'-isopropyloxyethyl) -2-methyl-G-ethylchloroacetanilide, N-chloroacetyl-2,6-dimethylaneneacetic acid ethyl ester and methyl ester, β- (N-chloroacetyl-2,6-dimethylanilino) propionic acid methyl ester, and ethyl- (N-chloroacetyl-2-methyl-6-ethylanilino) propionic acid, N- (3'-methoxy-2'-propyl) -2,3-dimethylchloroacetanilide,

N- (2'-ethoxyethyl) -2-methyl-6-chloro chloroacetanil,

N- (2‘-Methoxy-ethyl) -2-methyl-6-chloro-chloroacetanilide,

N- (2'-methoxyethyl) -2-methyl-6-methoxychloroacetanilide.

The herbicidally active acetanilides of the formula IV, as well as their acid addition salts and metal salt complexes, are not yet known. These compounds can be prepared by:

(a) N-halo (m -tetyl) -1-halo (III) (III),

X

(VID in which

X, Y, Z and n are as defined above and

Hal represents a halogen atom, in particular chlorine or bromine, reacted with heterocyclic compounds VIII, compounds of the general formula R-M (VIII), as defined above, and in which:

R is from above

M represents a hydrogen atom or an alkali metal, optionally in the presence of a diluent and an acid binding agent, whereupon an acid or a metal salt is optionally added to the resulting product.

When 2,6-diethyl-N-chloromethylchloroacetanilide is used as starting material. and pyrazole, the course of the reaction according to process (a) can be described as follows:

following reaction scheme -

♦ co-cw ^ ct

+ baze

HCl

The N-haloethylthiazolidines used as starting materials in the process of the variant (and are generally defined by the above formula VII. In this formula, the symbols X and Y may be the same or different and are preferably C 1 -C 4 alkyl groups, which groups may be straight or branched Z is preferably chlorine or bromine and n is as defined above.

The N-halomethylhaloacetanilides of formula VII are either known or can be prepared by known methods (see U.S. Patent Nos. 3,630,716 and 3,637,847). Said substances are obtained, for example, by reacting the corresponding aniline with paraformaldehyde in the presence of a catalytic amount of potassium hydroxide and reacting the resulting phenylazomethine with a haloacetyl halide such as chloroacetyl chloride.

However, the N-halomethyl haloacetanilides of the general formula VII can also be prepared by a novel process, which comprises the known haloacetanilides of the general formula IX, _Z (IX) in which:

X, Y, Z and n are as defined above, reacted with at least 1 mole of formaldehyde or formaldehyde releasing agent, for example paraformaldehyde, and a halogenating agent such as hydrohalic acid or an inorganic or organic acid halide, in the presence of a water-binding agent such as sulfate % sodium, in a manner known per se at a temperature of between -10 and 150 ° C, preferably between 10 and 70 ° C, optionally in the presence of an inert organic solvent such as toluene (see DOS Nos. 2119 518 and 2 210 603). When working with an inorganic acid halide such as thionyl chloride, it is not necessary to use a special water-binding agent (see also examples).

The heterooyl compounds used as further starting materials are generally defined by the above formula (VIII). In this formula, R is preferably optionally substituted azolyl radicals selected from the group consisting of 1-pyrazolyl, 1-imidazolyl, 1,2,4-triazol-1-yl, 1,2,3-triazol-1-yl, 1,1-triazolyl, 1,2,3-triazol-1-yl, 3,4-triaxyl-11-yl and 1,2,3,4-tetrazol-1-yl radicals as well as an optionally substituted 1-pyrrolyl radical. Suitable substituents for these radicals are preferably halogen atoms such as fluorine, chlorine and bromine, as well as alkyl groups having 1 to 4 carbon atoms. Preferably M represents a hydrogen atom or an alkali metal such as sodium or potassium.

The heterocyclic compounds of formula (VIII) are generally known in organic chemistry.

Suitable solvents for the reaction according to variant (a) are inert organic solvents, which preferably include ketones such as diethyl ketone and in particular methyl isobutyl ketone, nitriles such as propionitrile and especially 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 such as especially dimethylformamide.

As the acid binding agent, all of the commonly used inorganic and organic acid acceptors, including preferably alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium bicarbonate, can be used in the process of variant (a) below. tertiary alkylamines, aralkylamines, aromatic amines and cycloalkylamines such as triethylamine, dimethylbenzylamine, pyridine and diazabicyclooctane. In the present case, an excess of azole, meaning a compound of the above formula (VIII), may also be used.

The reaction temperatures during operation in the sense of variant (a) can be varied within wide limits. In general, the reaction is carried out at a temperature of between about 0 and 120 ° C, preferably between 20 and 80 ° C.

In the process according to variant (a), preferably 1 to 2 mol of the heterocyclic compound of formula (VIII) and 1 mol of the acid binding agent are used per mole of the compound of the formula VII. To isolate the compound of formula (IV), the reaction mixture is filtered, the filtrate is washed with water and, after drying, evaporated. The residue is then optionally purified by fractional crystallization or distillation.

In accordance with a special embodiment, the reaction mixture is cooled to about 9 ° C, filtered and hydrogen chloride is introduced into the filtrate at a temperature of from 5 to -15 ° C. The precipitated hydrochloric acid salts are suctioned off, washed with an organic solvent, for example ethyl acetate, and partitioned between a mixture of an organic solvent, for example ethyl acetate and water of about pH 12. The organic phase is separated and the compound of formula IV is isolated in conventional manner .

All salts resulting in the formation of physiologically tolerable salts are suitable for the preparation of acid addition salts of the compounds of the formula IV. These acids include, preferably, hydrohalic acids such as hydrochloric and hydrobromic acids, in particular hydrochloric acid, phosphoric, nitric, sulfuric, mono- and dibasic carboxylic and hydroxycarboxylic acids, such as acetic, maleic, succinic, fumaric, tartaric, citric, salicylic, sorbic and lactic as well as sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.

Salts of compounds of formula (IV) may be prepared in a simple manner by conventional salt-preparation methods, for example by dissolving a compound of formula (IV) in a suitable inert solvent and adding an acid such as hydrochloric acid and isolated in a manner known per se, for example by filtration and optionally purified washing with an inert organic solvent.

For the preparation of complexes of the compounds of the formula IV with metal salts, preference is given to using metal salts II. to IV. the main groups and I. and II. as well as IV. to VIII. side groups of the Periodic Table of Elements, including, but not limited to, copper, zinc, manganese, magnesium, tin, iron, and nickel. Suitable salt anions are those derived from those acids which lead to the formation of physiologically tolerable salts. Such acids preferably include hydrohalic acids such as hydrochloric and hydrobromic acids, phosphoric acid, nitric acid and sulfuric acid.

Complexes of compounds of formula IV with metal salts may be prepared in a conventional manner, for example by dissolving a metal salt in an alcohol such as ethanol and adding a compound of formula IV. The metal salt complexes can be isolated in a manner known per se, for example by filtration, and optionally purified by recrystallization.

The following examples illustrate the preparation of the acetanilide IV.

Example 3

To 274.2 g (1 mol) of 2,6-diethyl-N-chloromethylchloroacetanilide in 250 ml of anhydrous ethyl acetate was added with stirring a mixture of 68 g (1 mol) of pyrazole and 106 g (1.05 mol) of triethylamine in 150 ml of anhydrous ethyl acetate. The temperature rises to 30 ° C. The mixture is stirred for an additional 1 hour at room temperature and is then worked up in either of the following two ways:

1. The reaction mixture is filtered, the filtrate is washed neutral with water, dried over sodium sulphate and evaporated in vacuo. After fractional crystallization from ligroin, 171.2 g (56% of theory) of 2,6-diethyl-N- (1-pyrazolylmethyl) chloroacetanilide are obtained in the form of colorless crystals of m.p.

2. Cool the reaction mixture to 0 ° C, filter and wash the residue on the filter with 10 mL of cold ethyl acetate. 50 g (1.4 mol) of dry hydrogen chloride are introduced into the filtrate at 0 to -10 DEG C., the precipitated hydrochloric acid salts are filtered off with suction, washed with 50 ml of cold ethyl acetate and the solid residue is partitioned between 0.5 liters of ethyl acetate and 0.1 ml. The organic phase was separated, washed twice with 0.5 L of sodium chloride solution each time, dried over sodium sulfate and evaporated in vacuo. The colorless oily residue crystallized upon addition of 60 ml of gasoline. 220.2 g (72% of theory) of 2,6-diethyl-N- (1-pyrazolylmethyl) chloroacetanilide are obtained in the form of colorless crystals, melting at 67 ° C.

The compounds summarized in Table 1 are also prepared in an analogous manner.

TABLE 1 <^ - < ^CVR (IVl

example number X Y " OF R melting point (° C) 4 C2H5 6-С2Н5 Cl 1,2,4-triazol-1-yl 112 5 I-C3H7 6-1-C3H7 Cl 1-pyrazolyl 134 6 СНз 6-С2Н5 Cl 1,2,4-triazol-1-yl 92 7 СНз 6-С2Н5 Cl 1-pyrazolyl 57 8 C2H5 4,6- (СНз) 2 Cl 1-pyrazolyl 82 9 СНз 4,6- (СНз) 2 Cl 1-pyrazolyl 92 10 C2H5 4-СНз, 6-С2Н5 Cl 1-pyrazolyl 78 11 I-C3H7 6-1-C3H7 Cl 1,3,4-triazol-1-yl 196 12 I-C3H7 6-1-СЗН7 Cl 1,2,4-triazol-1-yl 138 13 C2H5 6-С2Н5 Cl 1-pyrrolyl oil 14 1-C3H7 - Cl 1,2,4-triazol-1-yl 118 15 Dec СНз 6-С2Н5 Cl 1-pyrazolyl oil 16 I-C3H7 Cl 1,2,3,4-tetrazol-1-yl oil 17 С2Н5 - Cl 1,2,4-triazol-1-yl 81 18 СНз 6-СНз Cl 1-pyrazolyl 82 19 Dec СНз 6-СНз Cl 1,2,4-triazol-1-yl 110 20 May СНз 5-СНз Cl 1,2,4-triazol-1-yl oil

example number X Yn OF R melting point (° C 21 CH3 - Cl 1-pyrazolyl 56 22nd СНз - Cl 1,2,4-triazol-1-yl 88 23 СНз 5-CH3 Cl 1-pyrazolyl oil 24 СНз 3-CH3 Cl 1 H -carbol-1-yl 114 25 СНз 3-CH3 Cl 1-pyrazolyl 102 26 C2H5 6-CH3 Cl 1-pyrazolyl (xHCl) 87 27 Mar: C2H5 6-C2H5 Cl 1-pyrazolyl (xHCl) 67 28 C2H5 6-C2H5 Cl 3,5-dimethylpyugazol-1-yl 111 29 C2H5 6-C2H5 Cl bromomethylipyrazolyl 145 30 C2H5 6-C2H5 Cl 3-Chloro-1,2,4-triazol-1-yl 110 31 CH3 6-C2H5 Cl 3,5-dimethylpyrazol-11-yl 90 32 C2H5 6-C2H5 Cl 3-Methylpyrazol-1-yl 89 33 C2H5 6-CH3 Cl 3-Methylpyrazol-1-yl 113 34 C (CH 3) 3 . - Cl 1-pyrazolyl oil 35 C (CH 3) 3 - Cl ^ Д-ШагоМ ^ 118 36 C2H5 6-CH3 Cl bromomethylpyrazolyl 80 37 CH3 6-C2H5 Cl 4-chloropyrazol-1-yl 91 38 CH3 6-C2H5 Cl 3-chloro-1,2,4-triazol-1-yl 121 39 C2H5 6-CH3 Cl 2,4,5-trichloroimidazol-11-yl 158 40 C2H5 6-C2H5 Cl d-chloropyrazol-1-yl 110 41 C2H5 6-C2H5 Cl 1,2,3,4-tetrazol-1-yl 110 42 C2H5 6-C2H5 Br 1-pyrazolyl 68 43 CH3 6-C2H5 Br 1-pyrazolyl 67 44 C2H5 6-C2H5 Cl 1-imidazolyl oil 45 C2H5 6-C2H5 Br ^^ - ШагоМ ^ 90 46 CH3 6-C2H5 Br 78

Preparation of starting materials

Example 3 a ^ΓΗΐ: 7 ^CH _Z ^Cl ^CO-C ^Cl (Variant a)

To a solution of 225.7 g (1 mol) 2,6-diethylchloroacetanilide in 1.5 L toluene was added 45 g (1.5 mol) paraformaldehyde. The mixture was heated to 40 ° C and 179 g (1.5 mol) of thionyl chloride was added dropwise with stirring, with slight gas evolution. The reaction mixture was stirred at 40 ° C until gas evolution ceased, then filtered and the filtrate evaporated in vacuo. After drying the residue in a high vacuum, 268.7 g (98% of theory) of 2,6-diethyl-N-chloromethylchloroacetanilide are obtained in the form of a colorless oil.

(Variant / 3)

To a solution of 225.7 g (1 mol) of 2,6-diethylchloroacetanilide in 1.5 L of anhydrous toluene was added 45 g (1.5 mol) of paraformaldehyde and -100 g of anhydrous sodium sulfate. Dry hydrogen chloride was introduced into the mixture with stirring and heating to 50 ° C until the milky suspension of paraformaldehyde disappeared, then 100 g of anhydrous sodium sulfate was added to the mixture, the reaction mixture was stirred at 50 ° C for 1 hour. then - it is filtered. The filtrate was evaporated in vacuo and the residue dried under high vacuum. 263.2 g (96% of theory) of 2,6-diethyl-N-chloromethylchloroacetanilide are obtained in the form of a colorless oil. ,

Analogous to the procedure as in the example

3a, the compounds summarized in Table 2 are obtained.

X

Hal melting point (° C) example number

5a I-C3H7 6-1-С3N7 С1 С1 not insulated 6a СНз 6-С2Н5 С1 С1 91 8 a C2H5 4,6- (СНз) а С1 С1 not insulated · 9a СНз 4,6- (СНз) 2 С1 С1 not insulated 10 a C2H5 4-СНз 6-С2Н5 С1 С1 not insulated ’ 14a 1-C3H7 - С1 С1 90 17a C2H5 - С1 С1 not insulated · 18a СНз 6-СНз С1 С1 88 20a СНз 5-СНз С1 С1 not insulated 24a СНз 3-СНз С1 С1 40 34a С (СНз) з - С1 С1 not insulated ’ 42a С2Н5 6-С2Н5 Вг Вг not insulated · 43a СНз 6-С2Н5 Вг Вг not insulated ·

The acetanilides of the formula IV show a strong herbicidal action, in particular against grasses. They can therefore be used for the selective control of weeds, in particular grass weeds.

Herbicidally active acetanilides of formula V are also not yet known. These substances can be obtained by:

b) N-acylmethylanilines of the general formula X, in which

R ⁴ , R ⁵ , R ⁶ , R ^{7 and} m are as defined above, reacted with chloroacetyl chloride in the presence of a diluent.

When 2,6-dimethyl-N-benzoylmethylaniline and chloroacetyl chloride are used as starting materials, the reaction scheme described in variant (b) can be described as follows:

The N-acylmethylanines used as starting materials in the process of variant (b) are generally defined by the above formula X. In this formula, R ⁴ preferably represents a straight or branched alkyl group having 1 to 6, in particular 1 to 4 carbon atoms, a halogen atom, in particular fluorine, chlorine or bromine, a haloalkyl group containing up to 3 carbon atoms and up to 5 identical or different halogen atoms, in particular fluorine and chlorine, for example trifluoromethyl, further preferably an alkylthio or C 1 -C 4 alkylsulfonyl group, as well as an amino sulfonyl, cyano and nitro group. R5 and R6 may be the same or different and preferably each represent a hydrogen atom, a straight or branched alkyl group having 1 to 4 carbon atoms, a halogen atom, in particular fluorine, chlorine and bromine, a halogenalkyl group containing up to 3 carbon atoms and up to 5 identical or different halogen atoms, in particular fluorine and chlorine atoms, as well as a phenyl group optionally substituted by one or more substituents, these substituents being preferably those mentioned in the meaning of R4. R7 is preferably a straight or branched alkyl group having from 1 to 6, in particular from 1 to 4, carbon atoms, and a phenyl group optionally substituted by one or more substituents, preferably those mentioned for the meaning of the symbol R ⁴ , as well as phenyl and phenoxy, which may also be substituted by the radicals R 4.

The N-acylmethylanilines of formula X are known [see, inter alia, Chem. Ber. 25, 2865 (1892) and Chem. Soc. 1943, 63] or can be prepared by known methods. Said compounds are obtained, for example, by reacting the corresponding anilines with α-haloketones in the presence of an organic solvent, for example ethanol (see also examples).

Suitable diluents for use according to variant (b) are preferably inert organic solvents, which preferably include ketones, such as diethyl ketone and in particular acetone and methyl ethyl ketone, nitriles such as propionitrile and 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 during operation in the sense of variant (b) can be varied within wide limits. In general, the reaction is carried out at a temperature between 0 and 120 ° C, preferably between 20 and 100 ° C.

In the process of variant (b), preferably 1 to 3 moles of chloroacetyl chloride are used per mole of the compound of the formula (X). The isolation of the compounds of formula (V) is carried out in a conventional manner.

The following examples illustrate the practical preparation of the acetanilides of formula (V).

Example 47

To a solution of 18.5 g (0.068 mol) 2,6-dimethyl-N- (4-chlorobenzoylmethyl) aniline in 150 ml benzene was added dropwise 16 ml - (0.2 mol) chloroacetyl chloride. The mixture was stirred at reflux for 15 hours, after which time the solvent and excess chloroacetyl chloride were distilled off in vacuo. The residue was triturated in a 1: 3 mixture of ether and petroleum ether, the precipitated crystalline material was filtered off with suction and dried. 17.7 g (75% of theory) of chloroacetanilide, m.p. 128 DEG C., are obtained.

Preparation of the starting material

CHj

To 48.4 g (0.4 mole) of 2,6-imethylethylamine in 40 ml of ethanol was added 46.7 g (0.2 mole) of N-bromo-4-chloroacetophenone in 40 ml of ethanol, the mixture was stirred for 20 minutes The mixture was heated to 50 ° C, then cooled to 0 ° C, the precipitated crystals were filtered off and washed with a small amount of ethanol. 30 g (55% of theory) of 2,6-dimethyl-N- (4-chloro-benzoylmethyl) aniline of melting point 82 DEG C. are obtained.

Example 48

ch _of co-c (ch ₃ j ₃

CO-CH 2 Cl

23.3 g (0.1 mol) of 2-ethyl-6-methyl-N-pivaloylmethylaniline are dissolved in 100 ml of benzene and 24 ml (0.3 mol) of chloroacetyl chloride are added. The mixture was stirred at reflux for 15 hours, after which time the solvent and excess chloroacetyl chloride were distilled off in vacuo. The oily residue is stirred with petroleum ether, the solution is decanted off, stirred with activated carbon and, after filtration, evaporated in vacuo. The residue is stirred with n-hexane, the solid material is filtered off with suction and dried. It is obtained

13.7 g [45 ° / o of theory) of 2-ethyl-6-methyl-N-pivaloylmethylchloracetanilidu mp 86 ^o C.

Preparation of the starting material

108 g (0.8 mol) of 2-ethyl-6-methylaniline and 53.8 g (0.4 mol) of monochlorpinacoline in 300 ml of toluene are heated at 110 ° C for 25 hours. The mixture was allowed to cool, filtered, the filtrate was washed with water, dried over sodium sulfate and the solvent was distilled off in vacuo. The residue was subjected to fractional distillation. 24.1 g (26% of theory) of 2-ethyl-6-methyl-N-pivaloylmethylaniline having a boiling point of 138-150 ^c / 93 Pa and a refractive index n _D20 = 1.5168 are obtained.

The compounds summarized in Table 3 are obtained in an analogous manner.

сн _ъ

CH 2 CO-C (CH ₃ n -1 ⁾

TABLE 3

RR \> CO-R ^?

N ^ CO-CH ^ Cl (V)

R _m 4 R ⁵ R6

Example number

R7

Melting point (° C) or refractive index

49 2-CH3 H H © 138 50 2-CH3 H H 140 51 2,6- (C2 H5) 2 H H - © - ^a 134 52 2,6- (C2 H5) 2 H H © 116 53 2-C1 H H 124 54 2,6- (CH 3) 2 H H 100 ALIGN! 55 4-C1 H H - © ~ ^a 114 56 2,6- (CH 3) 2 CH3 H CHs 104 57 2,6- (1-C3H7) 2 H H 200

Example number Rm ⁴ R ⁵ R ⁶ R ⁷ . Melting point (° C), refractive index 58 2,6- (C2H5) 2, 4-СНз н H <2> 112 59 2,6- (1-S7) 2 н H 140 60 2,6- (СНз) 2 н H - © - ^CH 3 90 61 2-C2H5,6-N-N н H - 70 62 2,6- (СНз) 2 н H - ^ - OCH ₃ 114 OCHj 63 2-C2H5 н H © η ₀ 2θ = 4,6- (СНз) 2 = 1.5680 64 2,6- (СНз) г. н H - © 7 104 65 2,4,6- (СНз) з н H 134 66 2,4,6- (СНз) з н H ~ © n _D ²⁰ = 1.5610 67 2,6- (СНз) г. н Y2> - @ - ^a 149 68 2,6- (СНз) 2 н СНз 84 An analogous way is compounds can be summarized See Table 4 below.

RR,> -what-R ^? / 2 / \ _co- cw ct 'm.

(IN)

Example number Rm ⁴ R5 R ⁶ R ⁷ 69 3,5- (CF 3) 2 Н Н @ ^а 70 2,6- (СНз) ₂ н Н 71 2,6- (СНз) г. н Н 72 2,6- (СНз) 2 н Н 73 2,6- (СНз) 2, 4-SO 2 NH 2 н Н 74 2-С1,6-СНз н Н 75 2-С2Н5,6-СНз СНз СНз © 76 2-С2Н5,6-СНз СНз СНз 77 2-С2Н5,6-СНз СНз СНз 78 2-С2Н5,6-СНз СНз СНз 79 2-С2Н5,6-СНз СНз СНз 80 2-С2Н5,6-СНз н СНз 81 2-С2Н5,6-СНз н СНз - <2Η2> ^α 82 2,6- (СНз) г. Н 83 2,6- (СНз) 2 н · <Θ> ^η 84 2,6- (СНз) 2 н <2> 85 2,6- (СНз) г. н © © 86 2,6- (СНз) 2 н © 87 2,6- (СНз) 2 н СНз

2O4DSO

The acetetanllides of the general formula V have potent herbicidal properties. The compounds are therefore suitable for controlling weeds. These substances can be used in particular for the selective control of weeds and grass weeds.

The herbicidally active acetanilides of the general formula (VI) are not yet also intended. These compounds can be obtained by:

c) N-azolylalkylanilines of the general formula XI,

in which

R 8, R ^9, R ^10, R 11, A and p have the above meanings, are reacted with chlorides or anhydrides haloacetic acid of general formula XIIa, respectively. Xllb,

R ¹² —CH 2 —CO — Cl, fXIIa) (R ¹² —CH 2 —CO ₃ O, (X 11b) in which:

R ¹² is as defined above, optionally in the presence of a diluent and optionally in the presence of an acid binding agent.

If 2,6-diethyl-N- (3-methylthio-4-methyl-1,2,4-triazol-5-ylmethyl) aniline and chloroacetyl chloride are used as starting materials, the reaction may be carried out according to variant (c) described by the following reaction scheme:

The N-azolylalkylanilines used as starting materials in the process of variant (c) are generally defined by the above formula XI. In this formula, A is preferably oxygen, sulfur or a group.

NR13, /

wherein R 13 is preferably a hydrogen atom, a straight or branched alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 10 carbon atoms, in particular a phenyl group, each of which aryl groups may be substituted by halogen, alkyl (C až-C 4), (Cx-C 2) alkoxy, (C nebo-C nebo) alkylthio, cyano, nitro and / or haloalkyl of up to 2 2 carbon atoms and up to 5 5 identical or different halogen atoms, in particular fluorine and chlorine. R ¹⁰ is preferably hydrogen or methyl. R11 in formula XI is preferably hydrogen, straight or branched (C1-C4) alkyl, haloalkyl of up to 3 carbon atoms and up to 5 identical or different halogen atoms, in particular fluorine and chlorine, for example trifluoromethyl, preferably an alkenyl or alkynyl group having from 2 to 4 carbon atoms, a cycloalkyl group of 5 to 7 carbon atoms, and a halogen atom, in particular fluorine, chlorine or bromine. The symbol R ⁱⁿ is further preferably an aryl group having 6 to 10 carbon atoms, especially phenyl, each of these · aryl groups may be substituted by halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, cyano, nitro and / or haloalkyl containing up to 2 carbon atoms and up to 5 identical or different halogen atoms, in particular fluorine or chlorine, for example trifluoromethyl. R ^u is further preferably an aralkyl group having 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl, in particular benzyl, each of these aralkyl groups may be substituted in the aryl moiety 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 containing up to 2 carbon atoms and up to 5 identical or different halogen atoms, in particular fluorine or chlorine, for example trifluoromethyl.

R11 can also preferably mean a grouping -OR ^U, -SR 14 and - NR R ^{n M,} wherein R13 is preferably the same radicals which have already been designated for this radical to be advantageous R14 are such groups are hydrogen, straight or branched (C 1 -C 4) alkyl, haloalkyl of up to 3 carbon atoms and up to 5 identical or different halogen atoms, in particular fluorine and chlorine, for example trifluoromethyl, further preferably alkenyl or alkynyl of 2 to 4 carbon atoms, cycloalkyl a C5-C7 group as well as an aralkyl group of 6 to 10 carbon atoms in the aryl portion and 1 to 4 carbon atoms in the alkyl portion, especially a benzyl group, each of which aralkyl groups may be halogen-substituted in the aryl portion; (C 1 -C 4) alkyl, (C 1 -C 2) alkoxy, (C 1 -C 4) alkylthio or 2 carbon atoms, cyano, nitro and / or haloalkyl containing up to 2 carbon atoms and up to 5 identical or different halogen atoms, in particular fluorine or chlorine, in particular trifluoromethyl.

Preferably, R ⁸ in formula XI represents a straight or branched (C 1 -C 4) alkyl group. R ⁹ in formula XI is preferably a straight or branched (C 1 -C 4) alkyl group or fluorine, chlorine or bromine. Index p is a number of 0, 1, or 2.

The N-azolylalkylanilines of the general formula (XI) used as starting materials in the process of variant (c) are not yet known. These compounds can be obtained by:

d) anilines of formula XIII, reacted with azolylderivatives of formula XIV,

(XIV I in which

A, R 10 and R 11 are as defined above, Hal 'represents chlorine or bromine in the presence of an acid binding agent such as potassium carbonate or sodium carbonate and in the presence of an inert organic solvent such as dimethylformamide or toluene at a temperature between 20 and 160 ° C, wherein an excess of the aniline of general formula (XIII) (see also examples) is preferably used or is used

(e) hydrazine derivatives of formula XV,

R9

(XV) in which

R8, R9, R10 and p are as defined above, reacted with isocyanates or isothiocyanates of formula XVI,

R 13 - N = C = B, (XVI) wherein

B is oxygen or sulfur; and

R13 is as defined above, in the presence of an organic solvent, for example an alcohol, an ether or a hydrocarbon, at a temperature between 0 and 80 ° C, of the resulting compound of formula XVII,

_R 10

CH-CO-NH-NH-CB-NHR-N ⁷ '(XVII)

in which

B, R8, R9, R10, R13 and p are as defined above, subjected to cyclization in the presence of a strong base such as sodium or potassium hydroxide solution and in the presence of a solvent such as ethanol or water at a temperature between 20 and (XIII).

R ⁸ , R 9 and p are as defined above,

100 ° C, and the triazolones or triazolthiones obtained, of the general formula (XVIII),

' in which

B, R ^8, R ^9, R 10, R 13 and p have the above meanings, are reacted with halides of the formula XIX

Hal — Ris, (XIX) in which

Hal * represents chlorine or bromine, and

R15 is as R14, except for hydrogen, in the presence of a strong base such as sodium hydroxide and in the presence of an inert organic solvent such as toluene or methylene chloride at a temperature between 20 and 80 ° C, and catalysts may also be used phase transfer and work with other alkylating agents, for example dimethyl sulfate (see also examples), or that

f) reacting the hydrazine derivatives of the aforementioned general formula (XV) with the acid chlorides or anhydrides of the general formula (XXa) and (II); XXb,

R ¹⁶ —CO — C1, (XXa) (R16 — CO—) 2 O, (XXb) in which

R 16 represents an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, in the presence of an inert organic solvent such as an ether, hydrocarbon or halogenated hydrocarbon at between 50 and 50 ° C , and the resulting compounds of formula XXI,

№

CO-NH'NH-CO-R (XX1) wherein

R ⁸ , R 9, R 10, R 16 and p are as defined above, either by treatment with phosphorus sulfide in a manner known per se [see Chem. Ber. 32, 797 (1899) and J. Prakt. Chemie 69, 145 (1904)] cyclize to thiadiazole derivatives or are reacted with conventional dehydrating agents to produce oxadiazole derivatives also in a known manner [see Elderfield, Heterocyclic Compounds, Vol. . 7 (1961)] or that

g) reacting the hydrazine derivatives of the aforementioned general formula (XV) in a manner known per se with nitriles of the general formula XXII,

R 17_ _C = N, (XXII) wherein

R 17 represents an alkyl group, a haloalkyl group, or an optionally substituted aryl group, to give triazole derivatives [see Chem. Ber. 96, 1064- (1963)] or that

h) reacting the hydrazine derivatives of formula XV with the iminoethers of formula XXIII in a manner known per se;

NH

OF

R16_ _C x HCl, \

OR18 (XXIII) wherein

R 16 represents an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, and

R18 represents a methyl or ethyl group, at reflux in the presence of an inert organic solvent such as ethanol to form oxadiazole derivatives, or

j) reacting the anilines of the above formula XIII with the azolylaldehydes of the formula XXIV,

(XXIV) in which

A and R ¹¹ have the above meanings, in an inert organic solvent such as toluene at a temperature between 80 and 120 ° C, and the resulting compound of formula XXV,

(XXV) in which

A, R ^8, R ^9, R ¹¹ and p are as defined above, is generally known manner reduced, for example by reaction with complex hydrides, such as sodium borohydride, optionally in the presence of a polar organic solvent such as methanol at a temperature between 0 ^C and 80 C.

The compounds of formulas XIII and XIV required as starting materials in the work of variant (d) are known or can be prepared in a manner known per se [see Helv. Chim. Acta 55,199 et al. (1972), Chem. Ber. 32, 797 et al. (1899) and Chem. Ber. 96, 1049 et al. (1963)].

The starting materials of the formula (XV) used in the process according to variant (e) are not yet known. However, these compounds can be prepared in a manner known per se by employing known esters (see, inter alia, DOS Nos. 2,350,944 and 2,513,730) of the general formula XXVI,

R *

CH 2 COOR ¹⁸ (XXVI) wherein

R ⁸ , R ⁹ , R ¹⁰ and p are as defined above, and

R ¹⁸ represents methyl or ethyl, reacted with hydrazine hydrate, preferably in the presence of an organic solvent such as ethanol, dioxane or dimethylformamide, at a temperature between 20 and 120 ° C (see also examples).

The reactants of formulas XVI and XIX used in the process of variant (e) are commonly known compounds in the field of organic chemistry.

Compounds of formulas XXa, XXb, XXII and XXIII, used as reactants in the work of variants (f), (g) and (h), are also known.

The azolylaldehydes of formula XXIV, used as reactants in the process of variant [j], are also known or can be prepared in a manner known per se [see Elderfield, "Heterocyclic Compounds", Vol. 7 (1961) and "Advances in Heterocyclic Chemistry", Vol. 9 (1968)].

The chlorides or anhydrides of haloacetic acids used as further starting materials in the reaction according to variant (c) are generally defined by the above formulas XHa and X11b. In these formulas, R ¹² is preferably chloro, bromo or iodo.

The chloroacetic acid chlorides and anhydrides of the above formulas XHa and X11b are generally known compounds in organic chemistry.

Suitable diluents for use according to variant (c) are preferably inert organic solvents, which preferably include ketones such as diethyl ketone and in particular acetone and methyl ethyl ketone, nitriles such as propionitrile and 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.

Optionally, the reaction of variant (c) may be carried out in the presence of acid binding agents (hydrogen chloride acceptors). All of the customary acid acceptors which are preferably organic bases, such as tertiary amines, such as triethylamine or pyridine, and inorganic bases, such as alkali metal hydroxides and carbonates, can be used as these reagents.

The reaction temperatures during operation in the sense of variant (c) can be varied within wide limits. In general, the reaction is carried out at a temperature between 0 and 120 ° C, preferably at a temperature between 20 and 100 ° C.

When working in accordance with variant (c), preferably 1 to 1.5 moles of a haloacetylating agent and 1 to 1.5 moles of an acid binding agent are used per mole of the compound of the formula XI. Isolation of general compounds

^ C / γ-ÍÍmJ SCW-COCH ₃ ^ ^ Ct formula VI is carried out in conventional manner.

The following examples illustrate the practical preparation of acetanilides of formula VI.

Гм Example 88, N-CH ³ N ^{+ CH-M-} 3 Э С-СО ^ ^ c _{of H5}

16.3 g (0.07 mole) of 2-ethyl-6-methyl-N - [(2 - [(2 - [1 H] 2], 3,4] oxadiazol-4-yl] -4- (4-carboxylic acid)] l) methyl] aniline and 6 g (0.076 mol) of anhydrous pyridine are heated to boiling under stirring in 100 ml of absolute tetrahydrofuran and a solution of 8 g (0.07 mol) of chloroacetyl chloride in 20 ml of tetrahydrofuran is added dropwise. After stirring for 10 minutes, the solvent was distilled off and the residue was stirred with 150 ml of water, and the crystallized reaction product was filtered off with suction, washed with water and dried to give 18.7 g (87% of theory) of beige-colored crystals. 2-Biphenyl-6-methyl-1 - [(2-methyl-1,3,4-oxadiazol-5-yl) methyl] chloroacetanilide, m.p. 67-70 ° C.

Preparation of the starting material

N .CH * Ji 1L. CH aX 2.-Ч ₀ > ~ ^сн Э «5 #

A mixture of 101.2 g (0.76 mol) of 2-ethyl-6-methylaniline; · 40 g (0.3 mol) of 2-methyl-l-5chloromethyl, 3-, ^and 4 oxadiazole, {41.4 g 0.3 mol) · · · powdered potassium carbonate and 76 ml of dimethylformamide is heated for 5 hours under stirring, at 100 ° C. The reaction mixture was filtered. The filtrate is diluted with methylene chloride and several times. Wash with water. The methylene chloride phase is dried over sodium sulfate and the solvent is distilled off in vacuo. Vacuum distillation of the residue yielded 46.8 g (67.5% of theory) of a yellow oily 2-ethyl-6-methyl-N- [(2-methyl-1,3,4-oxadiazol-S-yl) methyl] aniline. boiling point of 140-142 ° C / 13 Pa, the purity of which, according to gas chromatography, is 94%.

C, W _£ 4 “tys

To a mixture of 5 g (0.017 mol) 2,6-diethyl-N - [(1-methyl-2-methylthio-1,3,4-traazol-5-yl) ethyl] aniline and 1.6 g (0.02) mol) of pyridine in 100 ml of absolute tetrahydrofuran was stirred at room temperature with stirring

2.3 g (0.02 mol) of chloroacetyl chloride are added dropwise, the temperature rising to about 30 ° C.

The reaction mixture was stirred for a further 2 hours, then partially concentrated by distilling off the solvent

and add water. The crystallized product is filtered off with suction, dried and recrystallized from a mixture of diisopropyl ether and ethyl acetate. 5 g (80% of theory) of 2,6-diethyl-N - [(1-methyl-2-methylthio-1,3,4-triazol-5-yl) methyl] chloroacetanilide are obtained.

Preparation of starting materials

and)

you with

To 13,9 g (0,05 mol) 2,6-β-β-methyl-Ν - [(1-methyl-2-thiono-1,3,4-triazol-5-yl) methyl] aniline in a two-phase mixture consisting of 150 ml of toluene and 40 ml of 50% sodium hydroxide solution with the addition of 1.5 g of triethylbenzylammonium chloride as catalyst are added dropwise at room temperature with rapid stirring to 6.3 g (0.05 mol) of dimethyl sulphate, Deň: 32 ° C. The reaction mixture is stirred for 5 hours, then the toluene phase is separated, washed several times with water, dried over sodium sulphate and the solvent is distilled off. The oily residue is crystallized by addition of petroleum ether. After recrystallisation from petroleum ether yielded 6.7 g (40 o / ₀ yield) of 2,6-diethyl-N- {(1-methyl-methylthio-l ^ a-triazol-yl-methyl] aniline, mp 65 to 67 ac.

Example- 89

b]

Suspend 29.6 g (0.1 mole of 1-methyl-4 - [(2,6-diethylanilino) acetyl] thiosemicar base) in 150 ml of ethanol, add 7 g of potassium hydroxide in 20 ml of water to the suspension. After heating for one hour at reflux, most of the solvent was distilled off and 250 ml of water were added to the residue, acidified to pH 5 with acetic acid and the precipitate was filtered off with suction and washed thoroughly with water. 2,6-diethyl-N ((1-methyl-2-thiono-1,3,4-triazol-5-yl) methyl) aniline, m.p. 117-121 ° C.

c) ^{C C, HS} c CO CO-HH-NH-CS-NHCH 2 _H

44.2 g (0.2 mol) of 2,6-diethylanilinoacetic acid hydrazide and 14.8 g (0.2 mol) of methyl isothiocyanate are dissolved in 250 ml of ethanol and the solution is refluxed for 1 hour. After cooling to room temperature, the precipitate formed is filtered off with suction and washed twice with 50 ml of ethanol each time. After drying, 46 g (78% of theory) of 1-methyl-4- ((2,6-diethylanilino) acetyl) thiosemicarbazide are obtained as a colorless crystalline solid, m.p. 166 ° C.

58.7 g (0.25 mol) of 2,6-diethylanilinoacetic acid ethyl ester and 25 g of hydrazine hydrate are allowed to stand in 200 ml of ethanol for 24 hours, the solvent is distilled off and the residue is stirred with water. After drying, 50.5 g (91% of theory) of 2,6-diethylanilinoacetic acid hydrazide are obtained, m.p. 71-73 ° C.

The compounds shown in Table 5 are obtained in an analogous manner.

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TABLE 6

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The acetanilides of the general formula (VI) have potent herbicidal, especially selective herbicidal properties. These substances are therefore suitable for controlling weeds, in particular for selective control of herbal and grassy weeds. However, the selectivity of these compounds is not always entirely satisfactory in some cultures.

The antidote used for the purposes of the invention, namely 1-dichloroacetyl-1,2,3,4-tetrahydroquinaldine of the formula I, is particularly suitable for the protection of important crop plants such as corn, soybean, cotton, sugar beet, cereals, rice and sugar cane, against damage by herbicidally active thiolcarbamates and acetanilides, in particular herbicides of the formulas IV, V and VI.

The active compound combinations according to the invention show a very good action against herb and grass weeds in numerous crops of useful plants. Thus, these combinations can be used to selectively control weeds in numerous crop plants.

Weeds in the broadest sense mean all plants growing 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 genera:

Mustard (Sinapis), Watercress (Lepidium), Bedstraw (Galium), Chickweed (Stellaria, Chamomile (Matricaria), Stem (Anthemis), Stink (Galinsoga), Goosefoot (Chenopodium), Nettle (Urtica), Ragwort (Senecio), Pigweed (Amaranthus), purslane (Portulaca), beetroot (Xanthium), bindweed (Convolvulus), broom (Ipomoea), moss (Polygonum), gathering (Sesbania), ambrosia (Ambrosia), thistle (Cirsium), thistle (Carduus), milk (Sonchus), Eggplant (Solanum), Mustard (Rorippa), Rotala, Lindernia, Deadnettle (Lamium), Speedwell (Veronica), Abutilon (Abutilon), Emex, Durman (Datura), Violet (Viola), Hemp (Galeopsis), poppy (Papaver), cornflower (Centaurea).

Dicotyledonous plants of genera:

cotton (Gossypium), soybean (Glycine), beet (Beta), carrot (Daucus), bean (Phaseolus), peas (Pisum), potatoes (Solanum), flax (Linen), bitterwort (Ipomoea), vetch (Vicia), tobacco (Nicotiana), tomatoes (Lycopersicon), peanuts (Arachis), kale (Brassica), lettuce (Lactuca), cucumber (Cucumis), gourd (Cucurbita).

Monocotyledonous weeds of genera:

Hedgehog (Echinochloa), Shear (Setaria), Millet (Panicům), Rosette (Digitaria), Timothy (Phleum), Fennel (Poa), Fescue (Festuca), Eleusine (Eleusine), Brachiaria, Rye (Lolium), Brome (Bromus) ), oat (Avena), flathead (Cyperus), sorghum (Sorghum), wheatgrass (Agropyron), hawkfish (Cynodon), Monocharia, Fimbristylis, arrowhead (Sagittaria), Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactylnctenecen Agrostls), foxtail (Alopecurus), chundelka (Apera).

Monocotyledonous plants of genera:

rice (Oryza), maize (ZeaJ, wheat (Triticum), barley (Hordeum), oats (Avena), rye (Secale), sorghum (Sorghum), millet (Panicům), sugarcane (Saccharum), pineapple (Ananas), asparagus (Asparagus), garlic (Allium).

The active compound combinations according to the invention are particularly suitable for the selective control of weeds in maize, soya, cotton, sugar beet, cereals, rice and sugar cane.

The antidote used for the purposes of the invention may be converted, if desired in admixture with herbicidally active substances, into conventional compositions such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, concentrates based on suspensions and by emulsion, natural and synthetic materials impregnated with active ingredients, small particles coated with polymeric substances, and seed coatings.

These compositions are prepared in a manner known per se, for example by mixing the antidote to be used according to the invention, optionally in admixture with the herbicidally active substances in which it is used, with fillers, i.e. liquid solvents and / or solid carriers, optionally with surfactants, i.e. emulsifiers. and / or dispersants and / or foaming agents. If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. Basically suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol as well as 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. Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of granulates are crushed and fractionated natural stone materials such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of anor204050 ganic and organic flours and granules of organic material such as sawdust, coconut shells nuts, corn sticks and tobacco stems. Suitable emulsifiers and / or foaming agents are non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, e.g.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

In addition, these compositions may contain coloring agents such as inorganic pigments such as iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes and metallic azophthalocyanine dyes, as well as trace elements such as iron, manganese, boron, media, cobalt, molybdenum and zinc.

The concentrates generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight, of the antidote (s) and the herbicidally active substances.

The antidote used according to the invention can be applied as such or in the form of any of the above-mentioned compositions, even in admixture with herbicidally active substances. In this case, the ready-to-use formulations can be used or can be prepared prior to application (Tankmix). Mixtures with other known active ingredients, such as fungicides, insecticides, acaricides, nematocides, avian protective agents, growth agents, plant nutrients and soil conditioners can also be used.

The antidote to be used according to the invention or mixtures of the antidote and the herbicidally active compounds can be applied as such, in the form of concentrated formulations or further dilution forms prepared therefrom, such as ready-to-use solutions, suspensions, emulsions, powders and granules. The application is carried out in the usual manner, for example by watering, spraying, dusting or tossing, dry, wet or wet pickling, suspension pickling or incrustation.

The antidote used for the purposes of the invention may be administered by the methods customary for the administration of such antidotes. Thus, the antidote may be applied either before or after the application of the herbicide, or together with the herbicide. Further, the crop plants can be protected from damage by the herbicide applied before or after sowing, by treating the seed (pickling) before sowing. Another possibility is that the antidote is applied when sowing into the seed furrow.

Plant seedlings can then be treated with an antidote prior to planting. In this case, however, a generalized treatment is preferred.

In the application of the antidote according to the invention, the usual doses of the respective herbicides are suitable. The herbicidally active substance consumption is between 0.5 and 5 kg / ha. Consumption of the antidote does not depend on the herbicide and the herbicide dose used. In general, the consumption of the antidote used for the purposes of the invention varies between 0.1 and 5 kg / ha, preferably between 0.2 and 4 kg / ha, in a surface treatment. In the treatment of seed, the consumption of the antidote used according to the invention is 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 ratio of the antidote to the herbicidally active substance can be varied within a relatively wide range. Generally, 1 part by weight of the herbicidally active compound of the formula III, IV, V or VI is 0.05 to 1.0 part by weight, preferably 0.1 to 0.5 part by weight of the antidote of the formula I.

The good efficacy of the antidote used for the purposes of the invention, or the combination of active ingredients according to the invention, follows from the following example.

Example A

Preemergence test solvent: 5 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of the herbicidal active ingredient or antidote, or a mixture of the antidote and the herbicidal active ingredient, is mixed with said amount of solvent, the said amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The seeds of the test plants are sown in normal soil and after 24 hours are quenched with a composition containing the herbicidally active compound, optionally with a composition comprising an antidote or composition comprising an antidote and a herbicidally active compound. The amount of water per unit area is expediently constant. The concentration of the active ingredient in the composition is not critical, only the consumption of active ingredient per unit area is essential.

After 3 weeks, the degree of plant damage in% of the untreated control plants was evaluated. In this case, 0% means no effect (the same condition as the untreated control plants) and 100% complete destruction of the plants.

The active substances used, the consumption and the results obtained are shown in Table A.

preemergence test herbicidally active substance consumption consumption corn consumption Echinochloa Amaranthus herbicide antidote (pigweed) (amaranth) in kg / ha in kg / ha

X o

I o

II o co

0)

Ό O

Λ o O)

I herbicidally active substance consumption of antidote consumption of maize Echinochloa Amaranthus herbicide of antidote (hedgehog) (amaranth)

Claims (2)

-tetrahydroquinaline of formula I, characterized in that 1,2,3,4-tetrahydroquininaline of formula II A composition for the protection of crop plants from damage by herbicidally active thiol carbamates and / or acetanilides, characterized in that it contains, as an antidote, N-dichloroacetyl-1,2,3,4-tetrahydrochinaldin of the formula I 0 = C-CHCl _from (ut in a concentration of 0.1 to 95% by weight. 2. The process for the preparation of N-dichloroacetyl-1,2,3,4- is reacted with dichloroacetyl chloride, optionally in the presence of an acid binding agent and optionally in the presence of a diluent.