CS202520B2 - Herbicide means - Google Patents

Abstract

Novel chloracetanilides of the formula I <IMAGE> (wherein R1, R2 and R3 each represents H, C1-4-alkyl, halogen or F3C, R4 represents C1-6-alkyl and n is 1, 2 or 3) and their manufacture from chloroacetyl chloride and the appropriate sec-amine. The novel compounds of the formula I have both a herbicidal and a growth-regulating action, and accordingly may be made up with suitable carriers into herbicidal preparations and may be used for treating living plants and areas of land.

Description

The invention relates to a herbicidal composition comprising as active ingredient at least one chloroacetanilide derivative and a process for the preparation of these derivatives.

Haloacetanilide derivatives having herbicidal activity are already known, for example from U.S. Pat. No. 3,547,620. However, these compounds have only a narrow spectrum of activity and their effect is greatly influenced by the nature of the soil.

It is therefore an object of the invention to provide a herbicide which has a broad spectrum of activity and whose effect is not dependent on the nature of the soil.

This object is achieved by a herbicidal composition which comprises at least one compound of the formula I

снасн ^ оснаснз ^ ойа ^ ccHaCi

A r ₂ o (i) wherein R p R ₂ and R 6 are alkyl of 1 to the same or different and each independently of the other is hydrogen, 4 carbon atoms, halogen or trifluoromethyl,

R 1 represents an alkyl group having 1 to 6 carbon atoms and n represents 1, 2 or 3;

These compounds are characterized by a wide soil. herbicic effect. They can be used against monocotyledonous and dicotyledonous weeds.

These compounds are used in the pre-emergence stage against weeds such as garlic, aubergine, ragwort, chamomile, bedstraw, cotton, clover, Eschootzia, foxglove, tassel, sorghum, hedgehog, dew, rosette, sedge, lipstick, distemper, brome, - rye, timothy, roe, fescue, etc.

In general, weights of from 0.5 kg / ha to 5 kg / ha are used to combat weeds. Surprisingly, these active substances also prove to be selectively effective in crops of useful plants, such as cotton, peanuts, rape, curly kale, cauliflower, soybean, peas, sugar beet, spinach and lettuce.

In addition, the active ingredients were equally characterized by growth-regulating properties.

Another of the technically valuable changes in plant development caused by the composition of the present invention are, for example, the inhibition of vertical growth, the reduction of root development, and support. deploying buds or shoots to form a strain, intensifying the formation of dyes. and improving the ability to store the substances contained in the plants.

The compounds contained in the herbicidal composition according to the invention can be used either alone, in admixture with one another or in admixture with other active substances. Alternatively, other plant protection or pest control agents may be added as desired.

Other herbicides may also be added to enhance spectrum efficiency. Suitable herbicidally active ingredients for admixture with the herbicidal composition according to the invention are, for example, compounds from the group consisting of triazirins, aninrotiazoles, amides, diazines, uracils, aliphatic carboxylic acids and halogenated acids. substituted benzoic acids and aryloxycarbonyl acids, hydrides, amides, ritriles or esters of such carboxylic acids, esters of carbanic acid and thiocarbamic acid. eoUuuirn ^г l ^ o-trichlorbenzyloxypropaari means ubssaožjcí rhodanine and the like. Other additives are, for example and nefytotoxické- additives which in herbicides vyωUávaaí synergistic increase in effect, "such as network Áč ^ ^ and, emulators, solvents and oily additives.

Suitably, the active compounds or their use are in the form of preparations such as dusts, sprinkles, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers, for example diluents and, if appropriate, emulsifiers, adhesives and / or dispersing agents.

Suitable liquid carriers are, for example, water, aliphatic and aroeight hydrocarbons such as benzene, toluene, xylene, cyclohexanone, dihydrofuxide, diethyl urea and mineral oil fractions.

Suitable solid carriers are mineral clays, for example tond, silica gel, maatek, kacr, attaclay, limestone. silica and rostl.rrn ^ é _l prudukky e.g. flours ·

Examples of surfactants include calcium lignosulfate, pulyuxylthyl-alkylphthalene, naphthalenesulfonic acids and their salts, phthalic acid and their salts, furealdehyde condensates, fatty alcohol surfactants and substituted sulfonic acid sulfonates. and theirscoi.

The active compound (s) in the various preparations can vary within wide limits, for example, the composition according to the invention contains approximately 5 to 95% by weight of active compound, approximately 95 to 5% by weight of liquid or solid carrier, and optionally up to 20% by weight of surfactants.

· 3 '202520

Application of the composition of the invention is carried out in a conventional manner, for example with water _; as carrier in sprayers, used in an amount of about -100 to about 1,000 liters / ha. It is also possible to use the compositions according to the invention in the so-called low-volume and in the low-volume applications or in the form of the so-called milk granules. '

R, Rg and represented by formula (I) are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, isobutyl, tert-butyl, fluorine, chlorine, bromine, iodine, trifluoromethyl}. yiovsu group i.

R @ 1 can be, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl and the like.

Of the compounds of the present invention, those having the formula (I) and wherein R 1 and R 8, which are the same or different, are C 1 -C 4 alkyl, are particularly effective. - represents hydrogen, R- represents an alkyl group having 1 to 4 carbon atoms and o represents 1 or 2. '

These hitherto unwritten compounds can be prepared, for example, by reacting the anilines of formula II.

1 ¹ ^^ - ^мн а (II)

where

R, Rg, and R- are as defined above, reacted with compounds of formula III

X - CHgCHg - (OCHgCHg ^ - OR ₄ - (III) where ·

R 4 is as defined above, o is 1 or 2 and

X represents a hydroxyl group, a halogen or a group of the formula CHyCCH H -SO-gO-, va-.

in the molar mass ratio preferably in the range of 2: 1 to 3: 1, wherein the reaction in when X is a hydroxyl group, it is carried out at a temperature of 50 to 250 ° C at a pressure of 1 to 40 bar and optionally with the addition of water and a catalyst, preferably a nickel-based catalyst, and when X is halogen or the group CHyCgHySOg-O-, the reaction is carried out at temperatures between 20 and 200 ° C, optionally using an inert solvent, for example an organic solvent such as toluene or xylene, and the resulting reaction products of the general formula IV

CH ₂ CH ₂ - (OCH ₂ CH ₂ ) _n ^K H ^(IV) "and where

R, Rg, R 1, R 2, and as defined above, are reacted with the chloromethyl chloride in an equimolar weight ratio, preferably with an excess of chloroacetyl chloride, in the presence of an acid binding agent, for example an organic base; or such as inorganic bases, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or magnesium oxide, and optionally in the presence of an organic solvent at temperatures ranging from -10 ° C to +105 ° C to form compounds of Formula I; 'where R, R _2, R, R. An owner výěe defined hereinbefore, which compounds - - then in known manner isolated.

The following example illustrates the preparation of the active compounds contained in the herbicidal compositions according to the invention.

Example 1.

Chloroacetic acid [N- (3,6-ditxahlethyl) -2 / 6-dimethananilide]

A solution of 60.5 g (0.5 mile) of 2,6-dm-2-lmol and 68.5 g (0.25 mole) of (1,4 mole) - (1,4 The 7-methyl-octyl-octyl in 100 ml of toluene was heated at reflux for 20 hours, and after cooling, water and 25 ml of concentrated sodium hydroxide solution were added to the solution. and the organic phase is separated after dilution with thylaottate, washed with water until near neutral, dried with magnesium sulphate and concentrated to dryness under reduced pressure, and the residue is de-concentrated under reduced pressure, and in the distillation range 119-131 ° C (under pressure). 53.33 Pa) gave the desired N- (3,6-methoxyhexyl) -2,6-dimethylhylanine in a yield of 32.44 g (58.1% of theory).

To a solution of 11.15 g (0.05 mol) of N- (3,6-ěitxlhlttyУ) -2,6-ěimetlhУLali ^y yne in 50 ml of ethyl acetate 13.82 - g (0.1 mole) of anhydrous potassium carbonate. To the suspension under stirring at a temperature between 25-30 ° C under ice-cooling - was added 11.29 g (0.1 mol) ^y -clh.trlcety chltriěu and the reaction mixture stirred for another hour. The mixture was then allowed to continue někooik hours at room temperature was added water and the mixture někooikrát _Shake AoAt ethyl acetate. The combined ethyl acetate extracts were dried over magnesium sulphate and concentrated under reduced pressure after filtering.

After drying under high vacuum at room temperature, an almost colorless oil is obtained in a yield of 12.23 g (81.6% of theory).

¢ 1 (3, ⁶ -ěitxlhe tyУ ^{t) -2, 6} - ^di met ^hy ^ ⁿ .lid] carbamic acid cřiloroctové n. ° = ^{1, 52} 5 ⁰

The following compounds, which are active ingredients in the compositions of the invention, can be prepared in an analogous manner:

Title compound ^{[32 N,} 6- ^of itxltktyl) - ^{2-methylbenzyl г} llni ^y id] tyseliny cihloroctové ^[N- (3 ioxah ^^ ^ ^ the ^ -ai iDJ acidulous cis oroctové ^{[2, 6} - ^{d ly} ITT l N- (3,6-ďitxl ^h e ^{e y} ones) -aíli ^l id] kyee ^y ins chloroacetic [N- (3,6-dioxlhtpty ^{yl) -2-y} or ^y mtthy ED] KYSE ins ^y ch ^y _ oroctové IFN- ^{(3, 6} - ^E ioxlokty ^yl) - ^2, 6-dimtth ^гy an ^nyiě J cWLoroctové acid ^[2, 6-ěitthyl-N- (3,6-ěioxlottyУ) -l'lnlid] chloroacetic acid ^[2 -clltr N- (3,6-ěitxlhθptyУ) -6-methyl) hУL- ^ n ^y IE] £ chloroacetic acid 2-t-H, OR-N- (3,6-ěioxlheptyl) -6-mθtlhУ LNI ^y-EDJ chloroacetic acid [N - ( ^{'3, 6} - ^E ioxltktyl) - ^2L mttlWlan ⁿ d l ^{i] for i} ny Yssel cWoroctové f ^{2, 6} -ěime hh ^{y t} - ^- - _(3.6> ^9-yl ttitXl ^of θty Lie -lH ^n] c acid amide ^hy oroctov ^s E ^{2, 6-hydroxy-děθt} -N- (3, ^6, 9-trimethyl ^about oxlěθcy ^yl -ani ^l i ^e] kyseMny DH-orocto -meUihL ^ ^ N- ( 3,6,9-tt ⁱ txlděty ^s) -ιal ⁿ l ⁱ d] carbamic acid cis oroctové

Physical constant

-20 ^nD 3 1,5108 '20 ⁿ D 3 1.5260 -20 ^nD TO 1.5214 n ^{20 n} D 3 1.5212 '20 ⁿ D with 1,5200 “20 HD « 1,5176 '20 ⁿ D 3 1,5252 '20 ⁿ D = 1.5315 20 ⁿ D = ' 1,5092 '20 ⁿ D = 1,5208 '20 ⁿ D * 1,5190 -20 nD WITH 1,5200

2025.20

Name - compounds

[2,6-dimethyl-N- (3,6,19,12-tetraoxytetradecyl) -anilino] chloroacetic acid physical constant [2,6-dimethyl-N- (3 _with 6,9-trioxauncldeyl) -anilide chloroacetic acid [2 -ethyl-6-methyl-N- (3,6-dioxaacetyl) -amino] - chloroacetic acid

_n 20 = ⁿ 1,5104 _n 20 = ^η 2 ^- · 1, 5140 _n ⁿ D = D0 ^- 1.5225

The compounds produced by the process of the invention are generally almost colorless, odorless, difficult to move liquids that are well soluble in polar organic solvents such as acetone, dimethylformamide and diethylsulfoxide, but almost insoluble in water and gasoline. .

The following examples illustrate the possibilities of using the compounds produced by the process of the invention and demonstrate their superior effect. .

Example 2.

In the greenhouse, in the pre-emergence stage, the houseweed and the hedgehog kw ⁴ were treated as test plants. foot sprayed at a rate of 500 liters - water / ha containing 3 kg of active substance / ha. After 3 weeks of treatment, the result is detected, indicating no effect and indicating the destruction of the plants.

As shown in the table, destruction of the test plants is achieved.

Compound contained as an active ingredient in the compositions of the invention [N- (3,6-dimethoxyphenyl) -2,6-dimethylphenyl] -2-chloroacetic acid [N- (3,6-dimethoxyphenyl) -2,6-dimethylpyridine] chloroacetic acid (3,6-disxaoSlyl) -2,6-dimeeУhlltf 01idJ-chloroacetic acid [2,6-diethyl-N- (3,6-disxtaleetyl) -лilidJ acid chlorite [2,6-diethyl-N - ((3 _i 2-chloroacetic acid 6-disoxaolyl) -ananilide] -2-chloro-N- (3,6-disoxaolyl) -6-methyl-C22-yllo- (N (з ₎ 6- (oxoxheetyl) -6- meeУhlaa01idJ chloroacetic acid [N- (3,66-čosxoklyl) -2-meehhl - al01idJ chloroacetic acid [2,6-dimethyl-l H ^{R '(I} - (3,6,9-trisxadeeyl) -anilidJ chloroacetic acid [ Chloroacetic acid 2,6-diethyl-N- (3,6,9-oxisadecyl) -anilic acid [2,6-dimethyl-N-] - [2-methyl-N-3 (6,9-trioxadecyl) -anilic acid] Chloroacetic acid ((3,6,9,12-trans-oxate-radecyl) -anilide)

C2,6-Dimethyl-N- (3,6,9-trisoxa-10-yey)) (Chloroacetic acid id01ID) [2-ethyl-6-methyl-N- (3,6-disxaheetyl)] - Chloroacetic acid anionide • Untreated

Rosaceae Bloody kiu ^ í - foot

4

44 '’0

Example ^ d 3.

In the greenhouse, two different types of soil are treated with the above-mentioned compositions at low levels (> 1 kg of active substance / ha) after sowing and before emergence of the above-mentioned plants. To this end, the compositions are applied by spraying evenly on said plants. It will be appreciated that the compositions of the present invention will be found to be effective. a surprisingly high selectivity to weeds while excelling the effect and minimal dependence on the soil type. The comparative composition exhibits a much smaller effect compared to the compositions according to the invention, which is moreover more dependent on the type of soil.

202520 б

Compositions of the Invention 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Dec 16 17 18 19 20 21 22 Chloroacetic acid [N- (3,6-dioxaheptyl) -2,6-dimethylanilide] humus soil 10 10 ¹⁰ 10 10 10 10 10 10 10 3 2 2 0 0 0 0 0 0 0 0 0 soil containing 10 little humus 10 10 10 10 10 10 10 10 10 2 1 1 0 0 0 0 0 0 0 0 0

US Patent No. 3,547,620 (2,6-diethyl-N- (methoxymethyl) enilide) chloroacetic acid

humus-like soil 10 10 10 io 10 10 10 10 10 8 10 8 8 2 6 10 3 10 0 0 0 0 soil containing little humus 10 10 10 7 8 6 6 4 8 3 8 4 4 0 5 4 0 2 0 0 0 0 N / A humus-like soil 10 ÍO 10 10 10 10 10 10 10 10 10 ÍO 10 10 10 10 10 10 10 10 10 10 soil containing little humus 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Ϊ0 10 10 10 10 10 10

= soya; 2 = cotton; 3 = groundnut; 4 = rape; 5 = curly kale; 6 «cauliflower; 7 «sugar beet; 8 »· Spinach; 9 = peas; 10 = salad; 11 = maize; 12 pSenice; 13 = barley; 14 = garlic; 15 = aubergine; 16 = ragwort; 17 ^я deaf; 18 = trouble;

= hedgehog; 20 = dew; 21 = Sachor; 22 »Sorghum

Claims (2)

1 · herbicidal composition characterized in that it contains as active ingredient at least one chloroacetanilide derivative of the formula I _N _-- ^{сн с На-} 2 _<2 осн сн _{2) п -ой4} ^ ₂ or XCN ₂ R 6 (I) wherein. each of R 1, R g and R j, which may be the same or different, represents hydrogen, (C 1 -C 4) alkyl, halogen or trifluoromethyl, R ₄ represents an alkyl group having 1 to 6 carbon atoms and n represents 1, 2 or 3, in admixture with a carrier and / or excipients. 2. A process for the preparation of the chloroacetanilide derivatives of the formula I used as active ingredient in the compositions according to claim 1, characterized in that the aniline derivative of the formula II '(II) wherein: R p R ₂ and R ₃ are as defined in 1, reacted with a compound of formula III X - CHgCHg - (OCHgCHg) _n - or ₄ (III) wherein R ₄ is as defined in point 1 X represents a hydroxyl group, a halogen or a group of the formula CH ^-G ^H ^ in SOg-O-, bonded at the 4-position, in a molar mass ratio ranging preferably from 2: 1 to 3: 1, wherein the reaction when X is hydroxyl The reaction is carried out at a temperature of from 50 to 250 ° C at a pressure of from 1 to 40 bar, optionally with the addition of water and a catalyst, preferably a nickel-based catalyst, and in the case where X is halogen or CH skupinuC ^H ^. The SOg-O- bonded at the 4-position is carried out at a temperature in the range of 20 to 200 ° C, optionally using an inert solvent, whereupon the resulting reaction product of formula IV is formed CH ₂ CH ₂ - (OCH ₂ CH ₂ ) n -OR ₄ * 3 (IV) wherein R p R g, R j, R g and n are as defined above, reacted with chloroacetyl chloride in an equimolar mass amount, preferably with an excess of chloroacetyl chloride, in the presence of an acid binding agent and optionally in the presence of an organic solvent at temperatures ranging from -10 to +105 ° C to form a compound of formula I wherein R ₁ , R 8, R 6, R 6a and n are as defined above, which is then isolated. .