CS197207B2 - Herbicide means and method of making the active agent - Google Patents

Abstract

N-substd. haloacetanilides of formula (I) and their acid addn. salts and metal salt complexes are new. In (I) R is an opt. substd. N-contg. heterocyclic gp.; X and Y are each alkyl; Z is halogen; and n is 0, 1 or 2). (I) are selective herbicides, with better herbicidal activity against grasses such as Alopecurus myosuroides and Arena fatua than known chloroacetanilides. It is possible to control arena fatua and/or Alopecurus simultaneously with other grasses e.g. digitaria, echinochloa, Panicum and/or Setaria in crops esp. beet, soyabeans, beans, cotton, rape, ground nuts, vegetables and maize. (I) influence plant growth and can therefore be used as defoliants, desiccants, weed-killers, germination inhibitors, but esp. to destroy weeds. (I) is usually applied in amts. of 0.1-10 kg/ha, pref. 0.1-5 kg/ha.

Description

The present invention relates to a herbicidal composition comprising as active ingredient a novel N-substituted haloacetanilide. The invention furthermore relates to a process for the preparation of these novel N-substituted haloacetanilides and to their use as. herbicides, in particular as selective herbicides.

It is already known that chloroacetanilides such as 2,6-diethyl-N-methoxymethylchloroacetanilide and 2-ethyl-6-methyl-N- (1-methyl-4'-methoxyethyl) chloroacetanilide can be used as herbicides (cf. U.S. Pat. No. 3,442,945 and DE Publication No. 2,328,340).

These compounds are effective mainly against grasses prosovitým species, for example as crabgrass (Digitaria), barnyard grass ¹ foot (Echinochloa), wild millet (Panicum) -N- (BER Seteria). However, other important grassy weeds such as field fox (Alopecurus myosuroides) and deaf oats (Avena fatua) are only combated with the above-mentioned active substances at higher application rates. However, at these higher doses, considerable damage occurs on crop plants, such as sugar beet, soybeans or corn, so that the active substances cannot be selectively used in these cultures.

It has now been found that the novel N-substituted haloacetanilides of formula I

R is pyrazol-1-yl, imidazol-1-yl, 1,2, -

4-triazol-1-yl, 1,2,3-triazol-1-yl, 1,3,4-triazol-1-yl and 1,2,3,44-triazol-11-yl or pyrrol-1-yl, each of which may be substituted one or more times with fluorine, chlorine, bromine and / or C 1 -C 4 alkyl,

X and Y are the same or different and are C1 -C4 alkyl,

Z is chlorine or bromine, and n is 0, 1 or 2, and their acid addition salts have potent herbicidal, particularly selective herbicidal properties.

According to the invention, the novel N-substituted haloacetanilides of the formula I as well as their acid addition salts are prepared by the formation of the N-halomethyl-haloacetanilides of the formula II

₇ CH £ Hal

N 2 CO-CH 2 Z

(ID in which

X, Y, Z and n are as defined above and Hal represents halogen, especially chlorine or bromine, by the heterocyclic compounds of formula III

R-M (III) wherein

R is as defined above and

M is hydrogen or an alkali metal, optionally in the presence of a diluent and an acid-binding agent at temperatures between 0 and 120 degrees Celsius, followed by the addition of an acid, optionally, to the compound obtained.

Surprisingly, the N-substituted haloacetanilides of the invention exhibit considerably better herbicidal activity against important grass weeds such as field fox (Alopecurus myosuroides) and deaf oats (Avena fatuaj) than the prior art chloroacetanilides, i.

2,6-diethyl-Nt _m ethoxymethylchloracetanilid and

2-Ethyl-6-methhl-N- (β-methyl-4-methoxymethyl) chloroacetanilide, which are the closest chemically and efficiently related active ingredients. deaf (Avena fatuaj and / or feathertail (Alopecurus mhosuгoides)) along with other grassy weeds such as the dew (Digitaria), hedgehog corn millet (Panicům) and / or rind (Setaria) in crops such as beet, soybean beans, beans, cotton, canola, peanuts, vegetables and maize, the active ingredients according to the invention thus represent a substantial enrichment of herbicidal compositions against grasses in the aforementioned crop plants.

If 2,6-2-ethyl-N-chloromethyl-chloro-acetanilide and pyrazole are used as starting materials, the reaction scheme can be illustrated as follows:

+ b ^ ze

-HCl

The N-halomethylhaloacetanilides used as starting materials are generally defined by Formula II. In this formula, X and Y are the same or different and are preferably straight or branched (C 1 -C 4) alkyl. Z is preferably chloro or bromo and n is as defined in Formula I.

Starting compounds of formula II include, for example, the following compounds:

2-methyl-4-methyl-2-methyl-2-chloroacetanilide,

2-methyl-N-bromomethylbromomacetanilide,

2-ethyl-N-bromomethylbromoacetanilide,

2mthhlcN-chloгmetmhlcmloracetc anilide,

2-prophl-N-chloromethylcmloroacetanilide,

2-Isopropyl-N-trifluoromethylchloroacetanilide

2-Butyl-N-chloromethylchloroacetanilide,

2-isobutyl-N-cyclo-chloroacetate,

2-sec-butyl-N-chloromethyl] chloroacetanilide,

2-methylbuthl-N-chloromethyl-chloroacetanilide,

2.6- 2-Methyl-N-chloromethyl-chloroacetanilide,

Dietmyl ^{2,6-N-chloromethyl-l} hhlchloracet- anilide,

2,6-diethyl-N-bromomethylbromoacetanilide,

2-ethyl-6-methyl-N-halo-methyl-chloroacetanilide,

2.6- 2-Isoprophl-N-chloromethyl-chloroacetanilide

2,6-di-sec-butyl-N-chloromethylchloroacetanilide,

2,3-dimethyl-N-chloromethylchloroacetanilide,

2,4-dimethyl-N-chloromethylchloroacetanilide,

2,5-dimethyl-N-chloromethylchloroacetanilide,

2-ethyl-3-methyl-N-chloromethylchloroacetanilide,

2-ethyl-4-methyl-N-chloromethylchloroacetanilide,

2-ethyl-5-methyl-N-chloromethylchloroacetanilide,

2.4.6-trimethyl-N-chloromethylchloroacetanilide,

2.4.5-trimethyl-N-chloromethylchloroacetanilide,

2.3.5-trimethyl-N-chloromethylchloroacetanilide,

2-ethyl-4,6-dimethyl-N-chloromethylchloroacetanilide,

2,6-diethyl-4-methyl-N-chloromethylchloroacetanilide,

2,6-diisopropyl-4-methyl-N-chloromethylchloroacetanilide;

The N-halomethylhaloacetanilides of the formula II are known or can be prepared according to known methods (cf. U.S. Patent Nos. 3,630,716 and 3,637,847). They are obtained, for example, by reacting the corresponding anilines with paraformaldehyde in the presence of a catalytic amount of potassium hydroxide and mixing the resulting phenylazomethines with the addition of a haloacetyl halide, for example chloroacetyl chloride.

The N-halomethylhaloacetanilides of the formula II can also be obtained according to the novel

organic acids and a water-binding agent, such as sodium sulfate, in a manner known per se at temperatures between -10 ° C and 150 ° C, preferably between 10 ° C and 70 ° C, optionally in the presence of an inert organic solvent such as toluene (cf. DOS 2,119,518 and 2,210,603). When using inorganic acid halides such as thionyl chloride, it is possible to dispense with the use of a special water-binding agent (cf. also examples illustrating the production process).

Heterocyclic compounds, which are further used as starting materials, are generally defined by Formula III. In this formula, R is pyrazol-1-yl, imidazol-1-yl, 1,2,4-triazol-1-yl, 1,2,3-triazol-1-yl, 1,3,4-triazole- 1-yl and 1,2,3,4-tetrazol-1-yl or pyrrol-1-yl, wherein these radicals are optionally substituted one or more times with fluorine, chlorine, bromine, and / or C 1 -C 4 alkyl. M is preferably hydrogen and alkali metals such as sodium and potassium.

The heterocyclic compounds of formula III are generally known compounds of organic chemistry.

Suitable diluents for the reaction according to the invention are preferably inert organic solvents. These preferably include ketones such as diethyl ketone, especially methylisobutyl ketone, nitriles such as propionitrile, 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 or chloroform chlorobenzene, esters such as ethyl acetate, and formamides such as especially dimethylpharmamide.

Suitable acid-binding agents are all inorganic and organic acid-binding agents which can be used. These preferably include alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium phosphate, as well as lower tert.alkylamines, aralkylamines, aromatic amines or cycloalkylamines such as triethylamine, dimethylbenzylamine, pyridine and diazabicyclooctane. It is also possible to use an appropriate excess of azole, which in this case is a compound of formula III.

The reaction temperatures can be varied within a wide range in the process according to the invention. Generally the reaction is carried out at temperatures between about 0 and 120 and DEG C., preferably between 20 and 80 ° C ^d

In the process according to the invention, preferably 1 to 2 moles of the heterocyclic compounds of formula (III) and 1 mol of the acid binding agent are used per mole of the compounds of the formula II. In order to isolate the compounds of formula I, the reaction mixture is filtered, the filtrate is washed with water, dried and concentrated. Optionally, the residue is purified by fractional crystallization or distillation.

In a particularly preferred form of treatment, the reaction mixture is cooled to about 0 ° C, the cooled reaction mixture is worked up and the filtrate is

X, Y, Z and n are as defined above, reacting with at least 1 mole of formaldehyde or formaldehyde donors such as paraformaldehyde and a halogenating agent such as hydrohalic acid or inorganic halide 197207 hydrogen chloride at 5 to -15 ° C. The precipitated chlorides are filtered off, washed with an organic solvent such as ethyl acetate and the phases are separated in a mixture consisting of an organic solvent such as ethyl acetate and water having a pH of about 12. The organic phase is separated and the compounds of formula I are isolated by conventional means.

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

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

Examples of particularly active agents of the active compounds according to the invention are, in addition to the compounds given in the examples illustrating the production process and in the examples of Table I, the following compounds:

2,6-diethyl-N- [imidazol-1-ylmethyl] chloroacetanilide,

2,6- -е-ЬуУЫ- (1,3, d-triazolyl-methyl) chlorocetyl,

2,6-diethyl-ht (уyгг □ Уl1yimetdyi) chloroacetanilide,

2,6-Dimethyl-4- (pyrazol-1-ylmethyl) cdloroacetanide

2,6-dimethyl-h- (imidazol-1-ylmethyl) chloroacetanilide

2,6-dimethyl-h- (1,2,4-thiazolil-ylmethyl) cdloroacetanilide,

2,6-dimethyl-h- (pyrrolidylimethyl) chloroacetanilide

2-methyl-6-methyl-h- (imidazol-1-ylmethyl) cdioracetamide,

2ο31 ^-1-6-π-Η-1-(- (1,3,4-trans-1-methyl) cdioracetanilide,

2-Ethyl-6-m-methyl- (1-chloro-1-ol) cdloroacetanilide,

2-ethyl-4,6-dimethyl-ht (1,2,4-rlazol-1-ylmethyl) -cycloacetanilide,

2 ι γ -4 ,6 ,6 4,6 - Π · Η Η Η γ γ-Ν - (З ^ ^ Ь l l l l l methyl) l l methyl methyl) methyl lor lor cd,

2.4.6-thlmethyl-N- (1,2,4-triazolyl-ylethoxy) cdioracetanilide,

2.4.6- [1,3-Triazolylmethyl] chloroacetanilide;

2,6-Diddd4-mdtdd-N- (1,1,2-4,8ζο1- (1-methyl) cdloroacetanilide, d, 6-diethyl-4-ethoxy-N- (1,3,4-piperazin-14,447) chloroacetanilide,

2-: isopropyl-h- (pyrazole-1-1 ^ 61471) chloroacetanilide,

2-isouroylh- (1,2,4-para-1-ylmethyl) chloroacetanilide,

2-Isopropyl-1H- (1,3,4-azoyl-1-ylmethyl) -cycloacetanilide

2-Ethyl- (propyl-Х-уУпеНлу!) Cdloroacetanilide,

2-Etdyl-ht (1,2,4-nazoyl-ylmethyl) chloroacetanide;

2-Etdyl-h- [1,3,4-triazolyl-ylmethyl] chloroacetanilide,

2,3-Dimethyl-4- (γ-pyrazol-1-ylmethyl) chloroacetanilide

2.3-Dimethyl 1-N- (1,2,44пα2оУ1-у1те1Й1у1) chloroacetanilide

2,3-dimethyl (1,3,4- [18201-1-ylmethyl] chloroacetanilide),

2,4-dimetdyl-N- (pyrazo-^ ^уan У У) chloroacetanilide,

2,4-dimethyl-N- (1,2,4-triazol-1-ylmethyl) cdloroacetanilide,

2,41-Dimethyl-1,2,3,4-triazol-1-ylmethyl-chloroacetanilide,

2,5-dimethyl-N- (1) 11 (01-1-14 (11,171)) chloroacetanilide,

2,5-trans-(1,2,4-riazol-1-ylmethyl) cdloroacetanilide,

2,5-Dimethyl-N- (1,3,4-riazol-1-ylmethyl) -bromoacetanilide

9 7 207

2-methyl-N- ^{(pyrazol-ylmethyl)} chloroacetanilide

2-methyl-N- (1,2,4-triazol-1-ylmethyl) chloroacetanilide,

2-methyl-N- (1,3,4-triazol-1-ylmethyl) chloroacetanilide,

2-sec-Butyl 1-N- (pyrazol-1-ylmethyl) chloroacetanilide,

2-sec-butyl-N- (1,2,4-triazol-T-yl) chloroacetanilide,

2-sec-butyl-N- (1,3,4-triazol-1-yl) chloroacetanilide.

The active compounds according to the invention have potent herbicidal effects, in particular against grasses. They can therefore be used to selectively control weeds and in particular grassy weeds. Possible crops are: beet, soybeans, beans, cotton, canola, peanuts, vegetables and maize.

The active compounds according to the invention can be applied both after and in particular before the emergence of the plants. They can also be worked into the soil before sowing.

The active compounds according to the invention influence the growth of plants and can therefore be used as defoliation agents, desiccants, weed control agents, germinating agents and in particular as weed control agents.

Weed, in the broadest sense, means all plants that grow in places,. where they are undesirable. Whether the compounds of the invention act as total or selective herbicides depends essentially on the amount applied.

For example, the active compounds according to the invention can be used in the following plants:

Dicotyledonous weeds of genera:

Sinapis, Lepidium, Bedstraw (Galium), Chickweed (Stellaria), Chamomile (Matricaria), Stem (Anthemis), Five-spot (Galinsoga), Goosefoot (Chenopodium), Nettle (Urtica), Ragwort (Senecio), Amaranthus, Portulaca, Xanthium, Convulvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Eggplant (Solanum), Mustard (Rorippa), Rotala,

Lindernia, Lamium,. Veronica, Abutilon, Emex, Durman (Datura), Violet (Viola), Hemp (Galeopsia), Poppy (Papaver), Cornflower (Centaurea).

Dicotyledonous plants of the genera: cotton (Gossypium), soybean (Glycine), beet (Beta), carrot (Daucus), bean (Phaseolus), peas (Pisum), potatoes (Solanum ·), flax (Ltnum), mulch (Ipomoea) , vetch (Vicia), tobacco (Nicotiana), tomatoes (Lycopersicon), peanuts (Arachis), kale (Brassica), lettuce (Lactuca), cucumber (Cucumis), gourd (C ^ c ^ i ^ rbita).

Monocotyledonous weeds of the genera: hedgehog (Echinochloa), shear (Setaria), millet (Panicum), dew (Digita ^ a), timothy (Phleum), meadow-grass (Poa), fescue (Festuca), eleusine (Eleusine), Brachiaria, rye ( Lolium), Brome (Bromus), Oats (Avena), Cyperus, Sorghum, Agropyron, Troskut. (Cynodon), Monocharia, Fimbristylis, arrowhead

Eleocharis, Scirpus, Paspalum, Ischaemum, Sphlenoclea, Dactyloctenium, distemper (Agrostis), foxtail (Alopecurus), chundelka (Apera).

Monocotyledonous plants of genera:

rice (Oryza), maize (Zea), wheat (Triticum), barley (Hordeum), oats (Avena), rye (Secale), sorghum (Sorghum), millet (Panicům), sugarcane (Saccharum), pineapple (An. an-as), asparagus (Asparagus), garlic (Allium).

However, the use of the active compounds according to the invention is by no means restricted to these genera but also to other plants in the same way.

The compounds according to the invention are suitable, depending on the concentration, for the total control of weeds, for example on industrial and railway surfaces and on roads and squares, possibly with trees. The compounds of the invention may also be used to control weeds in long-term crops such as forest crops, ornamental trees, fruit trees, vineyards, citrus, butternut, banana, coffee, tea, rubber, coconut, cocoa, berry and hop plants, and to selectively control weeds in annual crops.

The active compounds according to the invention can be converted into the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These compositions are prepared in a known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using 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, benzene 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, and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethylsulfoxide, and water. By liquefied gaseous fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane: as solid carriers there are suitable: natural stone meal such as kaolins, alumina, talc, chalk , quartz, attapulgite, mortmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silicic acid, aluminum oxide and silicates. Suitable emulsifiers are non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, e.g.

The active compounds according to the invention can be used as such or can be combined with other herbicidal active compounds in the formulations for enhancing and supplementing the spectrum of activity, depending on the intended use, and can be admixed with the ready-to-use formulations or added immediately before use. In particular, the following active substances are also suitable for this purpose, as well as other representatives of the active substance groups which are characterized by these active substances, and it is not excluded that some of these active substance combinations also show synergistic activity.

Of particular note is the combination of the active compounds according to the invention with 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one (Metamitron) for beet cultures, with 4-amino-6- tert-butyl-3-methylthio-1,2,4-triazin-5 (4H) -one (Metribuzin) for corn, soybeans, tomatoes and. with 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (Atrazine) for maize and sorghum.

The active compounds according to the invention can be present in the compositions in mixtures with other known active compounds, such as fungicides, insecticides and acarlides.

The compositions generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90% by weight of active ingredient.

The active compounds may be used as such, in the form of their concentrates or of the use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. Application is carried out in the usual manner, for example by spraying, dusting, sprinkling and dressing.

The amount of active ingredient used may vary within wide limits. This amount depends essentially on the type of effect desired. In general, the application rate is between 0.1 and 10 kg of active substance per ha, preferably between 0.1 and 5 kg / ha.

The good herbicidal activity of the active compounds according to the invention is illustrated by 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 prepare an effective active ingredient, 1 part by weight of active ingredient is mixed with the indicated 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 covered with the active ingredient.

The amount of water per unit area is expediently kept constant. The concentration of active ingredient in the composition is of no importance, only the amount of active ingredient used per unit area is critical. After three weeks, the degree of damage to the plants was assessed as% damage compared to the development of untreated control plants. 0% means no effect (as in the untreated control) and 100% means complete destruction of the plants.

The following table shows the active substances, the amounts used and the results:

Table А:

Pre-emergence test in greenhouse

Active Substance Used Sugar Soya Corn Avena Echinochloa Alopecurus amount of beet fatua crus galii myosuroides active ingredients

001 001 00ΐ 0 0 0 SE9‘0 1Э-МЭ-ОЭ

Pre-emergence test in greenhouse

Active Substance Used Sugar Soya Corn Avena Echinochloa Alopecurus amount Corn fatua crus galii myosuroides active ingredients ________________________________________ kg / ha _______________________________________________________________________________

LO cn

LO CD o o — I

O O rH

O O O O

o o

LO LO OJ OJ CD CD CD θ '

CO-CHrCl

Continuation of Table

Active substance Amount Cukrová Soya Corn Echinochloa Alopecurus according to effectively- beet Crus galii myosuroides Example no. substances kg / ha

(16) 0.625 40 0 90 100 ALIGN! 100 ALIGN! (17) 0.625 0 0 0 90 90 (19) 0.625 0 0 0 90 90 Italy (21) 0.625 0 0 0 100 ALIGN! 90 Italy (23) 0.625 0 10 0 90 80 Italy (26) 0.625 0 0 30 100 ALIGN! 90 (28) 0.625 0 0 0 100 ALIGN! 70 (29) 0.625 0 10 20 May 100 ALIGN! 90 (30) 0.625 0 0 20 May 100 ALIGN! 80 (31) 0.625 0 0 50 100 ALIGN! 90 (32) 0.625 0 0 0 90 80 (34) 0.625 0 0 0 90 70 (35) 0.625 0 20 May 0 90 90 (36) 0.625 0 10 D 100 ALIGN! 80 (38) 0.625 0 0 0 90 70 (40) 0.625 0 0 0 90 70 (41) 0.625 0 0 0 90 70

Examples illustrating the method of production of active ingredients:

Example 1

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 consisting of 68 g (1 mol) of pyrazole and 106 g (1.05 mol) of triethylamine in 150 ml. -bezvodého 'ethyl acetate, whereupon the temperature rises to ^{30! 0} C. the mixture was stirred for 1 hour at room temperature. Two options are available for processing the reaction mixture:

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

2) Cool the reaction mixture to 0 ° C, filter, and wash the residue on the filter additionally 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 ° C. The hydrochloride salts formed are then filtered off, washed with 50 ml of cold ethyl acetate and the solid residue is partitioned between 0.5 liters of ethyl acetate and 0.5 liters of aqueous sodium hydroxide solution at pH 12. The organic phase is separated, washed twice in each case 0.5 liters of sodium chloride solution, dried over sodium sulphate and evaporated under vacuum. The colorless oily residue was mixed with 60 ml of gasoline and the product crystallized. 220.2 g (72% of theory) of 2,6-diethyl-N- (pyrazol-1-ylmethyl) chloroacetanilide, m.p. 67 DEG C., are obtained in the form of colorless crystals.

The compounds shown in Table 1 are prepared in an analogous manner:

Table I

Yfi X Нсо- R CH 2 Z (!) Example # X Yn OF R Melting point ГС) 2 C2H5 6-С2Н5 Cl 1,2,4-triazol-1-yl 112 3 1-C3H7 6-C5H7 Cl pyrazol-1-yl 134 4 СНз 6-С2Н5 Cl 1,2,4-triazol-1-yl 92 5 СНз 6-С2Н5 Cl pyrazol-1-yl 57 6 C2H5 4,6- (СНз) г. Cl pyrazol-1-yl 82 7 СНз 4,6- (СНз) 2 Cl pyrazol-1-yl 92 8 C2H5 4-СНз 6-С2Н5 Cl pyrazol-1-yl 78 9 I-C3H7 6-1-C3H7 Cl 1,3,4-triazol-1-yl 196 10 1-C3H7 6-1-C3H7 Cl 1,2,4-triazol-1-yl 138 11 C2H5 6-С2N5 - Cl pyrrol-1-yl oil 12 I-C3H7 - Cl 1,2,4-triazol-1-yl 118 13 СНз 6-С2Н5 Cl 1,2,3,4-tetrazol-1-yl oil 14 I-C3H7 - Cl pyrazol-1-yl oil 15 Dec С2Н5 - Cl 1,2,4-triazol-1-yl 81 16 СНз 6-СНз Cl pyrazol-1-yl 82 17 СНз 6-СНз Cl 1,2,4-triazol-1-yl 110 18 СНз 5-СНз Cl 1,2,4-triazol-1-yl oil 19 Dec СНз - Cl pyrazol-1-yl 56 20 May СНз - Cl 1,2,4-triazol-1-yl 88 21 СНз 5-СНз Cl pyrazol-1-yl oil 22nd СНз 3-СНз Cl 1,2,4-triazol-1-yl 114 23 СНз 3-СНз Cl pyrazol-1-yl 102 24 С2Н5 6-СНз Cl pyrazol-1-yl (xHCl) 87 25 С2Н5 6-С2Н5 Cl pyrazol-1-yl (xHCl) 67 26 С2Н5 6-С2Н5 Cl 3,5-dimethyl-pyrazol-1-yl 111 27 Mar: С2Н5 6-С2Н5 Cl bromomethylpyrazolyl 145 28 С2Н5 6-С2Н5 Cl 3-chloro-1,2,4-triazol-1-yl 110 29 СНз 6-С2Н5 Cl 3,5-dimethyl-pyrazol-1-yl 90 30 · С2Н5 6-С2Н5 Cl 3-Methylpyrazol-1-yl 89 31 С2Н5 6-СНз Cl 3-Methylpyrazol-1-yl 113 32 С (СНз) з - Cl pyrazol-1-yl oil 33 С (СНз) з - Cl 1,2,4-triazol-1-yl 118 34 С2Н5 6-СНз Cl bromomethylpyrazolyl 80 35 СНз 6-С2Н5 Cl 4-chloropyrazol-1-yl 91 36 СНз 6-С2Н5 Cl 3-chloro-1,2,4-triazol-1-yl 121 37 С2Н5 6-СНз Cl 2,4,5-trichloroimidazol-1-yl 158 38 С2Н5 6-С2Н5 Cl 4-chloropyrazol-1-yl 110 39 С2Н5 6-С2Н5 Cl 1,2,3,4-tetrazol-1-yl 110 40 С2Н5 6-С2Н5 Br pyrazol-1-yl 68 41 СНз 6-С2Н5 Br pyrazol-1-yl 67 42 С2Н5 6-С2Н5 Cl imidazol-1-yl oil 43 С2Н5 6-С2Н5 Br 1,2,4-triazol-1-yl 90 44 СНз 6-С2Н5 Br 1,2,4-triazol-1-yl 78

Production of starting materials

Example la:

(Variant A)): Example number X Yn of 39 C2H5 6-С2Н5 Cl 40 C2H5 6-С2Н5 Br 41 СНз 6-С2Н5 Br 42 C2H5 6-С2Н5 Cl 43 C2H5 6-С2Н5 Br 44 СНз 6-С2Н5 Br 45 C2H5 6-СНз Cl 46 C2H5 6-С2Н5 Cl 47 С [СНз] з - Cl 48 СНз 6-СНз Cl 49 СНз 6-СНз Cl 50 С (СНз) з - Cl 51 СНз 6-СНз Cl 52 С (СНз) з - Cl 53 СНз 6-СНз Cl 54 С (СНз) з - Cl 55 СНз - Cl 56 СНз - Cl 57 СНз - Cl 58 СНз 3-СНз Cl 59 СНз 3-СНз Cl 60 СНз 3-СНз Cl 61 СНз - Cl 62 СНз 3-СНз Cl

Production of starting materials

R Melting point (° C)

1,2.3.4-Tetrazol-1-yl110 Pyrazol-1-yl68 Pyrazol-1-yl67 Imidazol-1-yl oil

1,2.4-triazol-1-yl90

1,2,4-triazol-1-yl78

4-chloro-3,5-dimethylpyrazole-1-74

-yk

4-chloro-3,5-dimethylpyrazole-1-94

-yl

4-chloro-3,5-dimethyl-pyrazole-1-

-yl

4-chloro-3,5-dimethyl-pyrazole-1,107

-yi

3,5-dimethylpyrazol-1-yl 110

Chloro-1,2,4-triazolyl-3,5-dimethylpyrazol-1-yl oil chloro-1,2,4-triazolyl-136

4-chloropyrazol-1-yl 105

4-chloropyrazol-1-yl chloro-1,2,4-triazolyl oil

3,5-dimethylpyrazol-1-yl98

4-chloro-3,5-dimethylpyrazole-1-

-yl chloro-1,2,4-triazole oil

4-chloro-3,5-dimethylpyrazole-93

-1-yl

3,5-dimethylpyrazol-1-yl124

4-chloropyrazol-1-yl

4-chloropyrazol-1-yl 1a:

(1.5 mol) of thionyl chloride with vigorous gas evolution. The mixture was further stirred at 40 ° C until gas evolution ceased. The mixture was then filtered and the filtrate was concentrated in vacuo. After degassing the residue in a high vacuum, 268.7 g (98% of theory) of 2,6-diethyl-N (Variant a)) are obtained:

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 of chloromethyl chloroacetanilide as a colorless oil was added dropwise with stirring.

(Variant bj):

To a solution of 225.7 g (1 mol) of 2,6-chloroacetanilide in 1.5 liters of anhydrous toluene was added 45 g (1.5 mol) of paraformaldehyde and 100 ml of anhydrous sodium sulfate. While stirring and heating to 50 ° C, dry hydrogen chloride is introduced until the milk solids of the paraformaldehyde pension disappear. Then, 100 g of anhydrous sodium sulfate was added again, the mixture was further stirred for 1 hour at 50 ° C and filtered. The filtrate was concentrated in vacuo. After degassing of the residue, 263.2 g (96% of theory) of 2,6-diethylchloroacetanilide are obtained in the form of a colorless oil.

In analogy to Example 1a, the compounds shown in Table 2 are obtained:

Table 2

N

Xco-chjZ (III

Example # X Y " OF Hal Melting point or refractive index 3a I-C3H7 e-i-csH? Cl Cl product not insulated 4a CH3 6-C2H5 Cl Cl 91 6a C2H5 4,6- (CH 3) 2 Cl Cl product not insulated 7a CH3 4,6- (CH 3) 2 Cl Cl product not insulated 8a C2H5 4-CH3 6-C2H5 Cl Cl product not insulated 12a 1-C3H7 - Cl Cl 90 15a C2H5 - Cl Cl product not insulated 16a СНз 6-CH3 Cl Cl 88 18a СНз 5-CH3 Cl Cl product not insulated 22a CH3 3-CH3 Cl Cl 40 32a C (CH 3) 3 - Cl Cl product not insulated 40a C2H5 6-C2H5 Br Br product not insulated 41a CH3 6-C2H5 Br Br product not insulated

OBJECT OF THE INVENTION

Claims (2)

OBJECT OF THE INVENTION 1. A herbicidal composition characterized in that it contains as active ingredient at least one compound of formula I, ^N-CO-CH ^ £ Yfi (J in which R is pyrazol-1-yl, imidazol-1-yl, R, R, R ' 1,2.3-triazol-1-yl 1,3.4-trlazol-1-yl a 1,2.3.4-tetrazol-1-yl or pyrrol-1-yl, each of which may be substituted one or more times with fluorine, chlorine, bromine and / or C 1 -C 4 alkyl, X and Y are the same or different and are C1 -C4 alkyl, Z is chlorine or bromine and n is 0, 1 or 2, or an acid addition salt thereof. 2. A process for the preparation of an active ingredient according to claim 1, wherein the N-halomethyl haloacetanilides of the formula II are: N = co-cHjp (10 in which X, Y, Z and n are as defined above and Hal represents halogen, especially chlorine or bromine, with heterocyclic compounds of the general formula III R — Μ (III), in which R is as defined above and M is hydrogen or an alkali metal, optionally in the presence of a diluent and an acid-binding agent at temperatures of from 0 to 120 degrees Celsius, followed by addition of an acid to the compound optionally obtained.