CS196431B2 - Herbicide and method of producing the active constituent - Google Patents

Abstract

1. N-Alcylmethyl-chloroacetanilides of the formula see diagramm : EP0000051,P12,F1 in which R represents alkyl, halogen, halogenoalkyl, alkylthio, alkylsulphonyl, aminosulphonyl, cyano or nitro, R**1 and R**2 are identical or different and represent hydrogen, alkyl, halogen, halogenoalkyl or optionally substituted phenyl, R**3 represents alkyl or optionally substituted phenyl and n represents integers from 0 to 5.

Description

BACKGROUND OF THE INVENTION The present invention relates to a herbicidal composition comprising the novel N-acylmethychloroacetanilides as an active ingredient. The invention further relates to a process for the preparation of these novel herbicidally active compounds. .

It is already known that chloroacetanilides, such as 2-ethyl-6-methyl-N- (1'-methyl-2'-methoxyethyl) chloroacetanilide, can be used as herbicides, in particular for combating grass weeds (cf. - However, these compounds are not equally well effective against all grasses and their selectivity is not always entirely sufficient.

It has now been found that the novel N-acylmethylchloroacetanilides of the general formula I

R represents an alkyl group having 1 to 6 carbon atoms, fluorine, chlorine, bromine, halogenoalkyl with up to 3 carbon atoms, · · to the same or different halogen atoms, and ¹ ***** "· í * í '· further represents an alkylthio group and an alkylsulfonyl group having from 1 to 4 carbon atoms each, as well as an arylsulfonyl group, a cyano group or a nitro group,

R1 and ^R2 are the same or different and · hydrogen, · an alkyl group having 1 to 4 carbon atoms, fluorine, · chlorine, bromine, halogenoalkyl with up to 3 · atoms. and with up to 5 'of the same or different halogen atoms and optionally fluorine, chlorine, bromine, alkyl of 1 to 6 carbon atoms, haloalkyl. C až-C 3-C 3-Cas-C 5-C 5-C 5-C 5-C 5-C. alkyl, C alkyl-Can alkyl, aminosulfonyl, cyano, and / or nitro substituted phenyl · Group, and · ''

R ³ represents an alkyl group having 1 to 6 carbon atoms, and optionally fluorine, chlorine, bromine, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having up to 3 carbon atoms and up to 5 identical or different halogen atoms, (C1 -C4) alkylthio, (C1 -C4) alkylsulfonyl, aminosulfonynyl, phenyl, chlorophenyl, phenoxy, alkoxy. 1-4 carbon atoms

190431, a cyano, and / or nitro substituted phenyl group and n is an integer from 0 to 3, have potent herbicidal properties, in particular also selective herbicidal properties.

According to the invention, the novel N-acylmethylchloroacetanilides of the formula I are prepared by reacting the N-acylmethylanilides of the formula II

R ¹ R ^2, -CO-R ³

Ra

() in which

R, R ¹ , R ² , R ³ and n have the above-mentioned above

They are known to react with chloroacetyl chloride in the presence of a diluent.

Surprisingly, the N-acylmethylchloroacetanilides according to the invention predominate in the herbicidal action over known chloroacetanilides, such as 2-ethyl-6-methyl-N- (1'-methyl-2'-methoxyethyl) chloroacetanilide, since next to grasses such as ré (Šétaria), Jílek. (Lolium) and Hedgehog Corn (Echinochtoa) suppress also mustard (Sinapis). In addition, they show better selectivity in important crop plants. The substances according to the invention thus represent a substantial enrichment of the herbicidal compositions.

If 2,6-dimethyl-N-benzoybmethylanine and chlorination of ethyl chloride are used as starting materials, the following reaction scheme illustrates the course of the reaction:

The N-acylanilines used as starting materials are generally defined by formula II: In this formula, R is preferably a straight or branched alkyl group having 1 to 6, in particular 1 to 4 carbon atoms, a halogen, in particular fluorine, chlorine and bromine, haemgenalkyl a group of up to 3 carbon atoms and up to 5 of the same or different halogen atoms, the halogen being especially fluorine and chlorine, for example a trifluoromethyl group; further preferably an alkylthio group and an alkylsulfonyl group having from 1 to 4 carbon atoms in the alkyl moiety, as well as an aminosulfonyl group, a cyano group and a nitro group. R ¹ ·. and R ² are the same or different and are preferably hydrogen, a straight or branched (C 1 -C 4) alkyl group, halogen, in particular fluorine, chlorine and bromine, a haloalkyl group of up to 3 carbon atoms and up to 5 identical or different halogen atoms, wherein halogens are, in particular, fluorine and chlorine; and preferably optionally substituted once or several times -phenyl, such as · substitueinty preferably include the radicals given for R. R ³ preferably represents a straight or branched .alkyldvou group having 1 to 6 carbon atoms, especially with 1 to 4 carbon atoms and optionally substituted one or more times a phenyl group, the substituents which are preferably those already mentioned for R and the phenyl group and the phenoxy group, which may also be substituted by the radicals R, are suitable.

N-Acylmethylanilines of formula II are known [cf. except; another Blschler; Chem. Ber. 25, 286-5 (1892) and Crowther, Marni, purdle, Chem. Soc. 1943, 63) or can be produced according to known methods. Thus they are obtained, for example, by introducing anilines in the re? action with α-haloketones in the presence of an organic solvent, such as ethanoate (cf. also examples describing the method of manufacture of the active ingredients).

Suitable diluents for the reaction according to the invention are preferably inert organic solvents. These preferably include ketones such as diethyl ketone, especially acetone and methyl ethyl ketone. Nitrile, such as propionyltril, especially acetonitrile. Furthermore, ethers such as tetrahydrofuran or dioxane, aliphatic and aromatic hydrocarbons such as petroleum ether, benzene, toluene or xylene, halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene and esters such as ethyl acetate.

The reaction temperatures can be varied within a wide range when carrying out the process according to the invention. In general, the reaction is carried out at temperatures between 0 and 120 ° C, preferably between 20 and 100 ° C.

In the process according to the invention, preferably 1 to 3 moles of the compound of formula (II) is 1 to 3 moles of chloroacetyl chloride. The isolation of the compounds of formula I is carried out in a conventional manner.

The active compounds according to the invention influence plant growth and can therefore be used as defoíiační, desiccants, agents к weed control _agents germination inhibitors and, especially, as weed control к. Weed, in the broadest sense, means all plants that grow where they are undesirable. Whether the compounds of the invention act as total or selective herbicides depends essentially on the amount used.

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

dicotyledonous weeds of genera:

mustard (Sinapis), watercress (Lepidium), bedstraw (Galium), chickweed (Stellaria), chamomile (Matric.aria), yard ^: (Anthemis), 5''our • (Galinsoga), · goosefoot (Chenopodium), nettle ( Urticaj, Tentacle (Senecio), Amaranthus, Portulaca, Xahthium, Convolyulus, Ipomoea, Polygonum, Sesbania, -ambrosia . (Ambrosia), Thistle (Girsium), Thistle (Cárduus), Milk (Sonchps), Eggplant (Solanum), Mustard (Roríppa), Roitala, .Lindernia, Lamella, Speedwell (Veronica), Abutilon (Abutilon), Emex, Durman (Datura), Violet (Viola), Hemp (Galeopsis), Poppy (Papaver), Cornflower (Centaurea).

dicotyledonous plants of the genera :.

cotton (Gossypium), soybean (Glycine), beet (Beta), carcass (Daucus), bean (Phaseolus), peas (Pisum), potatoes (Solarium), flax (Linen), mulch (Ipomoea), wolf (Vicia), tobacco (Nicotiana), tomatoes (Lycopersioon), peanuts (Aracihis), cucumbers (Brassíca), lettuce (Lactuca), cucumber (Cucumis), gourd (Cucurbita).

monocotyledonous weeds of genera:

hedgehog (Echlnpchloa), shear (Setaria), millet (Panicům), sundew (Digitaria), timothy (Phleum), lupine (Poa), fescue (Festuca), eleusine (Eleusine), Brachlaria, Rye (Lolium), brome (Bromus) ), oats (Avena), flathead (Cyperus), sorghum (Sorghum), wheatgrass (Agropyiron), wreckage (Cynodon), Monochari.a, Fimbristylis, arrowhead (Sagittaria), Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenocléa, Dactyloctléa distemper (Agrostis), feather-tail (Alopecurus), chundelka (Apera).

Monocotyledonous plants of genera:

rice (Oryza), maize (Zea), wheat (Market ticum), barley (Hordeum), oats (Avena), rye (Secale), sorghum (Sorghum), millet (Panicum), sugarcane (Saccharum), pineapple ( Pineapple), Asparagus (Asparagus), Garlic (Allium).

However, the use of the active compounds according to the invention is in no way limited to these genera but is withdrawn in the same manner. to other plants. . .

The compounds according to the invention are suitable, depending on concentrations, 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 for weed control in long-term crops such as forest crops, ornamental trees, fruit trees, vineyards, citrus, butternut, banana, coffee, teas, coconut, cocoa and other crops. plants, with berries and on hop gardens, and for selective control of weeds in annual crops.

The active compounds according to the invention can be used advantageously for the selective control of weeds and in particular for the control of grassy weeds in various crop plants. With the active compounds according to the invention, in contrast to chloroacetenilides, which are already known as herbicides already successfully succumbed to dicotyledonous plants such as fowl (Galinsoga) and mustard (Sinapis), weeds which are difficult to control are oat (Avena. Fatua) or, common foxtail (Alopecurus myosuroides) together with other grassy weeds such as the crabgrass (Digitaria), the hedgehog (Echlnochloa), millet (Panicum) and / or shear (Setaria) in crops such as sugar beet, soybeans , beans, cotton, canola, peanuts, various vegetables, corn and rice.

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 manner known per se, 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 alkyl naphthalenes, 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 dimethylforiamide and dimethylsulfoxide, as well as 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; Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or quartz, and synthetic stone meal, such as highly disperse silica, alumina and silicates. They come as emulsifiers. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkylsulfonates, alkylstilphates, arylsulfonates, and hydrolysates of proteins and, for example, dispersants and disintegrants, for example lignin, are present. ‘

The active compounds according to the invention can be used as such or can be combined in the intended use with other herbicidally active compounds in the compositions for enhancing and supplementing the spectrum of action, with the addition of these additives to the finished compositions, or added immediately before use.

The compositions generally contain from 0.1 to 95% by weight of the substance, preferably from 0.5 to 95% by weight. 90% by weight of the active ingredient.

The active substances - can - be used as such, in the form of concentrates or - in the form of application preparations prepared from these concentrates, such as - solutions, emulsions, - suspensions, - powders, pastes and granules are ready for use. The application is carried out in the usual manner, for example by spraying, dusting, spreading and watering. .

The active compounds according to the invention can be:. apply both - emergence and 1 especially before emergence: plants. They can also be worked before sowing.

The application rate of the active ingredient can vary within wide limits. Essentially, it depends on the type of effect desired. In general, the application rate is from 0.1 to 10 kg of active substance per ha, preferably from 0.3 to 5 kg / ha. ^:

The good herbicidal effects of the active compounds according to the invention and the possibilities for their selective use are evident from the following examples. · · '

The active compounds according to the invention can also be mixed with other herbicides, such as, for example, Metamitron pro. sugar beet, with sinteredbean for soybeans, with - atrazine for maize and with diuron or fluomethuron. Example B

Preemergentnl test

Solvent:

parts by weight of acetone.

Emulsifier:

- part by weight of alkylaryl polyglycol ether. '

The active agent is prepared so that it is. by mixing one part by weight of the active compound with the indicated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted to the desired concentration with water.

The seeds of the test plants are sown in normal soil and after 24 hours are poured with the active agent. The amount of water per unit area is expediently constant. The concentration of the active substance in the composition is not important, only the consumption of active substance per unit area is decisive. After three weeks, the degree of damage to the test plants is determined, expressed as a percentage compared to the development of untreated control plants. . - 0% means no effect (as in the case of untreated control plants) and 100% total destruction of the plants. , · ·

The active substances, - consumption and results obtained are shown in the following table.

The experimental plants used in the table are indicated by letters with the following meanings:

A = Setaria.

B = Sinapis.

C = Maticaria

D = Galinsoga E = Stellaria

F = LoliumG = Echinochloa

H = Cyperus I = wheat J - = oats

K = Cotton L = Corn M - = Beet.

it

W

CQ

Active Substances The amount of active substance used is honored

196431 38 O O 38 O © CM o Φ © © © © oo ^x OO ТГ O O тГ Ί 1 ss rH OO CD QD §§ Q'O CQ 00 o o 00 0O © Q CM CM © About CD 00. 38 й тН © © 00 QQ © ⁰ co cp 8 ° 88 38 §with it. to cm - it to cm

190431

Examples illustrating a process for the preparation of active substances. ·

Example 1 'сНхСО-С

9 ^Н Ъ гл

Xco-CH, ct

To a solution of 18.5 g (0.068 mol) of 2,6-dimethyl-N- (4-chlorobenzoylmethyl) aniline in 160 ml of benzene was added dropwise 16 ml (0.2 mol) of chloroacetyl chloride. The mixture was then left under stirring for 15 hours under reflux and concentrated by distilling off the solvent and excess chloroacetyl chloride in vacuo. The residue was triturated with a 1: 3 mixture of ether and petroleum ether, the resulting crystalline residue was filtered off and dried. It is obtained

17.7 g (75% of theory) of 2,6-dimethyl-N- (4-chlorobenzoylmethyl) chloroacetanilide, m.p. 128 DEG.

Production of starting material

(^ y_ _N ' ^C ^ ^C0 XJA -

CMj

46.7 g (0.2 mol) of n-bromo-α-chloroacetophenone in 40 ml of ethanol are added to 48.4 g (0.4 mol) of 2,6-dimethylaniline in 40 ml of ethanol and the mixture is heated 20 minutes to 50 ° C. The mixture is then cooled to 0 ° C, the crystals formed are filtered off and washed with a small amount of ethanol. 30 g (55 percent of theory) are obtained. 2,6-Dimethyl-N- (4-chlorobenzoylmethyl) aniline, m.p.

23.3 g (0.1 mol) of 2-methyl-6-methylpyridyl valoylmethylaniline are dissolved in 100 ml of benzene and 24 ml (0.3 mol) of chloroacetyl chloride are added. The reaction mixture was then stirred at reflux for 15 hours and concentrated by distilling off the solvent and excess chloroacetyl chloride in vacuo. The oily residue was. Stir with petroleum ether, decant, stir with charcoal, filter, and concentrate the filtrate in vacuo. The residue was stirred with n-hexane and the resulting solid was filtered off and dried. 13.7 g (45% of theory) of 2-ethyl-6-methyl-N-rivoylmethyl-chloroacetanilide, m.p. 86 DEG C., are obtained.

Preparation of the starting material ^J ccco _7-Acha <25th

108 g (0.8 mol) of 2-ethyl-6-methylaniline and 53.8 g (0.4 mol) of mono-chlorpinpinol are heated in 300 ml of toluene for 25 hours. to 1'10 ° Celsius. It is then allowed to cool, filtered, and the filtrate is filtered. It is washed with water, dried over sodium sulphate and concentrated. by distilling off the solvent in. vacuum. The residue was subjected to fractional distillation. 24.1 g (26% of theory) of 2-ethyl-3-methyl-N-plvaloyl-methylaniline having a boiling point of 138-150 DEG C./93 Pa are obtained, with a refractive index n _D20 = 1.5 168.

It is produced in an analogous manner. compounds listed in Table 1 below:

TABLE 1

....... R ¹ . VCO-R ³ _R ^^ ^N \ CO-CH _of Cl

Example # Rn Ri R ² R3 Melting point (° C) or refractive index 3 , Λ 2-CH3 H. ' H © 138 4 2-CH3 H .. H . 140 5 2,6 - (C2H5) 2 H H ^- - ^C 134 6 2,6- (C2 H5) 2 H H © 116 7 2-C1 H H 124 8 2,8- (CH 3) 2 H . H © 100 ALIGN! 9 4-C1 H H 114 10 2,6- (CH 3) 2 CH3 H 'UH3 . 104. 11. 2,6- (bC 3 H 7) 2 H . H <Q> 200 12 2 (6- (C 2 H 5) 2, 4-CH 3) H H 112 13 2,6- (1-C 3 H 7 ') 2 H. H © -УоУ-ск 140 14 . 2,6- (CH 3) 2 H H \ / 5 90 15 Dec 2Ч2ЙЙ, 6-CHs H , H 70 16 2,6- (CH 3) 2 H H OCH ₃ 114 17 2-C2H5, 4,6- (CH3) 2 H H W n _D 20 = 1.5680

19 В 432 Example # R _n R1 R2 R ⁵ Melting point (° C), optionally index of llama 18 2,6- (СНз) 2 н Н 104 19 Dec 2,4,6 - (. СНз) з н н <134 20 May 2,4,6- (СНз) з н н η _υ ²⁰ · = 1.5610 21 2,6- (СНз) 2 н 149 22nd 2,6- (СНз) 2 н СНз '84

In a similar manner, the compounds listed in the following Table 2 can be obtained:

TABLE 2

Example # ^R n R ¹ R ² R ³ 23 3,5- (CF 3) 2. . Н Н 24 2,6- (СНз) 2 Н Н 25 2,6- (СНз) 2 Н н 26 2,6- (СНз) 2 Н н 27 Mar: 2,6- (N 2 O) 2,4-SO 2 NH 2 Н н 28 2-CI Н н - @ - Cl 29 2.-С2Н5,6-СНз СНз СНз © 30 2-С2Н5,6-СНз СНз 'СНз 31 2-С2Н5,6-СНз СНз СНз 32 2-С2Н5,6-СНз СНз СНз 33 2-С2Н5,6-СНз СНз СНз - <0 ^ 0! 34 2-С2Н5,6-СНз Н СНз 35 2-N2H5, 6-NN Н 'СНз - <о ^ -ХоУ

. . - -. 12

Example # . ^R n R ¹ R2 R3 36. 2,6- (CH 3) 2 H ~ © ~ = i 37 2,6- (CH 3) 2 . H 38 2,6- (CH 3) 2 © 39 2,6- (CH 3) 2 '. . H © © 40. 2,6- (CH 3) 2 H ~ © -ci © 41 2,6- (CH 3) 2 H CH3. —ŤoYci

OBJECT OF THE INVENTION

Claims (2)

What is claimed is: 1. A herbicidal composition comprising, as active ingredient, at least one N-acylmethylchloroacetanilide of the formula I having an ^R @ ^{1 of R} @ ^1. * ^М \ С0СНдС1 Rn. (I) in which:. R represents an alkyl group having 1 to 6 carbon atoms, fluorine, chlorine, bromine, a haloalkyl group having up to 3 carbon atoms and up to 5 identical or different halogen atoms, furthermore an alkylthio group and an alkylsulfonyl group having 1 to 4 carbon atoms each an aminosulfonyl, cyano or nitro group, R1 and R2 are the same or different and represent hydrogen, C1-C4alkyl, fluorine, chlorine, bromine, haloalkyl of up to 3 carbon atoms and up to 5 of the same or different halogen atoms and optionally fluorine C1-C6 alkyl, C1-C6 haloalkyl, C3-C3 haloalkyl, C1-C4 alkylthio, C1-C4 alkylthio, C1-C4 alkylthio carbon atoms, aminosulfonyl, cyano and / or nitro substituted phenyl, and R 3 represents an alkyl group having 1 to 6 carbon atoms and optionally fluorine. chlorine, bromine, C1-C6-alkyl, haloalkyl of up to 3 carbon atoms and up to 5 identical or different halogen atoms, C1-C4 alkylthio. C 1 -C 4 alkylsulfonyloxy, aminosulfonyl, phenyl, chlorophenyl, phenoxy, C 1 -C 4 alkoxy, cyano and / or nitro substituted phenyl and n are integers of 0 to 3.. 2. A process for the preparation of an active ingredient according to claim 1, characterized in that the N-acylmethylanilines of the formula II are: R ¹ , R ¹ , R 2, R 3 and n are as defined above, in reaction with chloroacetyl chloride in the presence of a diluent.