CS242883B2 - Herbicide and method of its efficient component production - Google Patents

Abstract

Die Erfindung betrifft Aryloxyalkylamine der Formel in der Y, m. n. R¹ und R² die in der Beschreibung genannten Bedeutungen haben. Verfahren zu ihrer Herstellung und ihre Verwendung zur Bekämpfung unerwünschten Pflanzenwuchses.

Description

(54) A herbicidal composition and a process for the manufacture of an active ingredient

A herbicidal composition comprising as active ingredient at least one aryloxyalkylamine of the formula I

Y is halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or phenoxy, m is 1, 2 n (b > 3, n is <5) to 1 ,,

R ¹ and R ² are each independently hydrogen or C 1 -C 4 alkyl or R 1 and R 2 together are optionally C 1 -C 4 alkyl substituted by C 4 -C 6 alkylene or R 1 and R 2 together with the nitrogen atom of which they are substituted is optionally a halogen or a C1-C4 alkyl group substituted by a pyridine residue, or a salt of such aryloxyalkylamine.

Further, a process for the preparation of an active ingredient is described.

The present invention relates to a herbicidal composition comprising aryloxylalkylamines as active ingredient. The invention further relates to a process for the preparation of these active aryloxyalkylamines and their use in preventing undesirable plant growth.

N - (N, N-dialkylamino) alkyl halophenyl ethers are known to be herbicidally active (cf. DE-OS 19 28 606). In addition, phenoxyalkylpiperidines are known which are used as antioxidants (cf. C. A.82, 16022 n (1975)).

It has now been found that a herbicidal composition comprising as active ingredient at least one aryloxyalkylamine of the formula I

(I) in which:

Y is halogen, C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or phenoxy, m is 1, 2 or 3, n is an integer from 5 to 12 and

2

R @ 1 and R @ 2 independently represent hydrogen or (C1 -C4) alkyl, 12 or R @ 1 and R @ 2 together represent optionally C1 -C4 alkyl; with a nitrogen atom of which the substituents are optionally substituted by a halogen or a C1 -C4 alkyl group, or a salt of such aryloxyalkylamines, is selectively herbicidally active in both preemergence and postemergence applications.

The subject of the present invention is a herbicidal composition, characterized in that it contains at least one aryloxyalkylamine as defined above or a salt of such aryloxyalkylamines as the active ingredient.

For example, the substituents of Formula I may have the following meanings:

Y represents halogen, such as fluorine, chlorine, bromine, iodine, C 1 -C 6 alkyl, such as methyl, ethyl, tert-butyl, n-hexyl, sec. Hexyl, haloalkyl of 1 to 4 atoms carbon, such as trifluoromethyl, difluoromethyl, 1,2,2-trifluoroethyl, C 1 -C 4 alkoxy, such as methoxy, n-propoxy, t-butoxy or phenoxy, m is 1, 2 or 3, wherein the substituents Y may be the same or different from each other if m is a number or 3, n is an integer from 5 to 12, preferably from 6 to 10,

2

R @ 1 and R @ 2 are each independently hydrogen or (C1 -C4) -alkyl such as methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, tert-butyl, isobutyl; or R and R may also together represent optionally C1-C4 alkyl substituted C4-C7 alkylene in the chain, such as tetramethylene, pentamethylene, hexamethylene, 1,4-dimethyltetramethylene or R and R together with the nitrogen atom of which they are substituted may optionally be a halogen such as chlorine or an alkyl group of 1 to 4 carbon atoms such as a methyl group, an ethyl group, a tert-butyl group, a substituted pyridinium radical, e.g. chloropyridinium, 4-meetylpyridinium or 4-tert-butylpyridinium.

AryPoxy and alkylamines of general formula

in which n

R ¹

R ² is halogen, C 1 -C 4 alkyl, or lower alkoxy. number 1, 2 or 3, the whole cell Р! from 2 to 12, which is hydrogen or hydrogen;

2 or R and R have up to 6 carbon atoms, haloalkyl of 1-4 carbon atoms or phenoxy, alkyl, -C 4 alkyl substituted ⁱⁿ the formula --NR aUytenovou group having from ⁴ to ⁷ and ^t ^ c ^ m ^s uhlíb in řetiězci No ^b of R ¹ a _vvzvz vzw

R is taken together with the nitrogen atom of which the pyridines are optionally substituted by a halogen or a C1 -C4 -alkyl group, with the proviso that n is not 6 if Y is teic. butyl groups 12 and R and R denote a common pentamethylene group, and, in particular, these arrloxalkalkylamines are novel compounds. an alkyl group having 1 to 1 is optionally a 1-alkyl group

Preferred aryloxyalkylaines of formula (I) are those in which:

Y is halogen, such as chlorine or bromine, m is 1, n is an integer from 6 to X 2 to 10, and R 2 and R are attenuated! independently of the salt, a (C 1 -C 4) -alkyl group, such as ethyl or isopropyl, as well as acid addition salts thereof.

The herbicidally well-effective salts of the arrloxralkylalanes of the general formula (I) in which the group I

is represented by a pyridinium radical, are salts of those compounds of formula I wherein Y is halogen, such as chlorine, or a C 1 -C 4 alkyl group, such as

2 is methyl, m is 2, n is an integer from 6 to 10, and R and R together with the nitrogen atom, which is a nitrite, optionally or halogen, such as chlorine or bromine, or an alkyl group of 1 to 4 carbon atoms, such as an acetyloalkyl group, a substituted pyridyl moiety.

According to the invention, the arrloxylpropyl chloride of the formula (I) is prepared in a manner known per se by reacting the alkoxyalkyl halides of the formula (II)

O- (CH3) -Hal n

in which ^Ym

Y, m and n have the above meanings and

Hal represents halogen, in particular chlorine or bromine,

(II) with amines of formula III

in which

R ^1, R ^{2 and} n

Hal np abovementioned meaning and represents halogen, at temperatures of ^50-2 00 ° C, and optionally in the presence of an inert solvent.

This reaction is preferably carried out at a temperature of from 60 to 120 ° C.

Suitably, this reaction is carried out in an inert solvent. The reactants are heated in the presence of a solvent and the reaction product is then separated by distillation or separated by forming an acid addition salt. ·

Suitable solvents are alcohols, such as methanol, ethanol, and sopropanoo, tert. butanoo, lithium and aromatic hydrocarbons such as n-hexane, toluene, xylenes, decaine, 1,2,3,4-tetrahydronaphthalene, amides such as dimethyioormamide, dimethylacetamide, cyclic and acyclic ethers such as diethyl ether, methylthi-tert-butyl ether, dioxane, uranium, as well as N-deadlyprididone.

The solvent, based on the phenoxyalkyl peroxide of the formula II, is 10 to 80% by weight.

This process can also be carried out by heating the substituted phenoxyacetylogenide with an excess of the appropriate amine in the reaction vessel. Isolation of the product from the reaction networks is then carried out in the form of the free base or in the form of the acid-substituted substituted phenoxyalkylamine obtained.

The compounds of formula (I) may also be prepared by reacting an amino alkyl halide of formula (IV)

A. ^ H-CH ²⁾ -NR ¹ R ² n

(IV) in o

Hal

R, R and R are as defined above and

The halogen is halogen, in particular chlorine or bromine, of the phenol salt of formula (V)

OH (V) in which they have the meanings given above, with an alkali metal. This reaction is carried out in an inert solvent příSornosti at OZM vr ^ ^; ^ L of ^50-2 00 ° C above the date ^{y lp} s te ^pl with ^thickness from ⁶⁰ to ¹⁴⁰ ° C. '

Suitable solvents are alcohols such as rehaan, ethanol, isopropanol, acyclic and cyclic ethers, such as tert-butyl tert-butyl, dioxane, tetrahydrofuran, aromatic hydrocarbons, such as toluene, xylenes, chloro enzene, and water. The amount of solvent, based on the phenoxide, is 10 to 80% by weight.

Substituted phenols, aminoalkyl halides, phthalicyl-phenyl-amines and amines which are used as starting materials for the synthesis of the compounds of formula (I) are conventional. on the market. These compounds can be shipped by conventional methods known in the art.

The halogens of formula II may be prepared by the method described in J. Med. Chem. 14, 133 (19711-) To synthesize, for example, 1- (4-oethylphenyl) 11O-boom-n-decane, heat a solution of 4-methyl-phthololb, potassium hydroxide and 1,10-dibonocecan in oothanolb at reflux overnight. The reaction mixture was then cooled and thickened, and then the filtrate was concentrated under reduced pressure to remove the solvent. The solution was dissolved in ether and the resulting ether solution was washed with a dilute aqueous solution of sodium hydroxide and water until the wash liquid was a non-natural reaction.

OrganickS layer which přioom formed was then dried over a suitable desiccant poouití nappíklad sodium sulfate, filtered and the de filtrSt ^^ U is under reduced pressure, whose ^MZ at t ^ ture of about ¹⁶⁵ ° C under ²⁵ Pa UBATT comes ^to The product can ^be identified as 1- (4-methylphenoxy) -1d-boom-n-decane.

In order to prepare the halogenated halides of the formula IV, the aminoalcohol is reacted with a halogenating agent such as a thionyl chloride or phosphorus oxybromide in a suitable solvent, and then the desired halogenated halide is isolated (cf.

J. Med. Chem. 14, 133/19711).

2

The acid addition salts of the compounds of formula I in which the -NR R group is not a pyridinium radical are carried out using an acidity such that the amino group of the compound in question reacts. Acids suitable for this purpose are hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid (methanesulphonic acid, p-butylene sulphonic acid).

is carried out in a manner known per se.

avelic acid,

Production of acid addition salts

The pyridinium compounds of formula (I) may be prepared by reaction with the correspondingly substituted pyridine. Chlorides and iodides are considered.

The aryloxialkylamines of the formula II are preferably bromides,

The following examples illustrate the preparation of aryloxyalkylamines of formula (I).

Example 1

1- (4-methylphenoxy) -10- (N, N-diethylamino) decane (Compound No. 1)

A mixture of 36.6 g of diethylamine and 14.6 g of 1- (4-methylphenoxy) -10-bromo-n-decane was heated in an oil bath overnight at reflux. After cooling, the reaction mixture was taken up in ether and 20% sodium hydroxide solution. The mixture was extracted with ether and the collected organic phases were dried over sodium sulfate. Evaporation of the solvent left 14.1 g of an oil which was chromatographed on a silica gel column (60 ml); particle size (63 to 2 mm), eluting with methyl chloride and methanol (9: 1). ZískS 5 g of 1- (4-methylftnrxy) -10- (N, N-dittУylaminr) decane, which idennifikuje using with ^p ektra and IR spectra.

1 H-NMR spectrum (100

6.85

3.88

2.25

1.15-1.95

1.0 ppm (6 t)

MHz, ppm ppm ppm deuterated chloroform; tetramethyysilane) (AA ', BB', p-aromatic residue) (2H, (6H, ppm t, CH 2 - on phenoxy) mc) (o)

IR spectrum (chloroform, cm ^-1)

970, 2 930, 2 860, 2 800, 1 512, 1 470, 1 385, 1 295, 1 245, 1 170,

800, 820

Example 2

1- (4-chlorophenoxy) -10-pipcrim.ny tk _<and n (^ compound No. 2)

A mixture of piperidine (24.7 g) and 4-chlorophenoxy-n-decyl bromide (10.1 g) was heated to reflux in an oil bath overnight. After cooling, the reaction mixture was taken up in ether and 20% sodium hydroxide solution. The mixture is extracted with ether and the isolated organic phases are dried over sodium sulfate.

^p o scalding ^ka the solvent in vacuo ^{9.5 g} of an oil which was ^ entúíukován using ¹H-NMR spectrum and IR spectrum as 1- (4-chlorophenoxy) -10-piperidinyl] n - decane.

NMR spectrum (100 MHz, deuterated chloroform, tetrameehlsilane)

6.88 ppm (4 AA ', BB') 3.82 ppm (2 t, CH2 on phenoxy) 2.35 ppm (7 mc) 1,0-2, 1.0-2.0 ppm (m)

IR spectrum (chloroform, cm ^-1 )

930, 2,854, 1,493, 1,469, 1,286, 1,245, 1,169, 1,102, 1,092, 823

Example 3

N- [6 ^- (2 ^- meehyl ^-4 -chlof ^e ENOX ^yl) -N- ^H ex 2 ^{y 4- methylthiophenyl} lp ^ id ^ ^ iumbrom (Compound ^no. 91)

A solution of 185.2 g of 2-methyl-4-chlorophenol, 57 g of potassium hydroxide and 388.4 g of 1,6-dibromo-n-hexane in 600 ml of methanol is heated at reflux for 48 hours. The reaction mixture was then cooled, filtered and the filtrate was concentrated under reduced pressure.

Then zb ^y Tek taken up in water and extracted twice with dietlleelherem (500 mL). The ether phase is washed again with 10% sodium hydroxide solution and dried over sodium sulfate. R ^ 2 ^ a ^ ^c ^ ^v ^ u ^t ^ '^ ^{<^;} l ^o odcdesiluje residue under reduced fractionally deestluje hook, přčeemž product is obtained boiling ^p s 162 and ^from 163 ° C at a pressure ^{of 13} Pa.

27.5 g of the thus obtained 6- (2-meth ^yl --- cllofennoxy) 1lbbrum-nlhexanu and 8.4 g ^{of di} --mettlllpcli Nu zahř.vá eJkvimoiárním ratio in ²⁰⁰ ml ιοθ π ^ ^- te ^p ttilu m.p. 82 ° C. The end of the reaction was detected by thin-layer chromuroggarf control. After distillation of the solvent, the resulting crystalline slurry was stirred with diethyl ether and the product was recrystallized from methanol. Isolated ^é ^ Cr ¹¹ obstructs the pulsation of the ^{T d 63 d 65} ° C. ^Also with above ^{and 29.1 g.}

O ^{d d} dcví dlícím way as described in previous cříkla ^d scl may be obtained náásecliUící rrlloxlrlkllaminl Formula I.

Abbreviations used in the table have the following meaning:

+ = 100 MHz ! ++ = 270 MHz +++ = 200 MHz d = duplet

t = triplet mc = multiplet with a center (if simulated) or with the highest peak (if it cannot be characterized in detail);

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5-4 "- {cn number _m Y n R к data ^of H-NMR 80 MHz; deuterated chloroform, tetramethylsilane, ppm

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гЧ ÍX r4 r-4 r4 řx rH 0 > 1 > 1 > 1 X > 1 μ X3 x P X and. -P P P 0 P 1 0 0 φ E 0 and

r4 rH r4 r4 f-4 rH > 1 > 4 > 1 > 1 > 1 > 1 x X! X X x x P P -P -P P • P 0 0 φ 0 ω φ E E E

Ld 40 40 o CN> N d

Ol

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CN cn CN

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UJ 40

CN CN

-Cl 8 methyl ethyl 7.05 (4 a '), 3.95 (2 t), 2.2 (7 mc), 1.2-

2.0 (m), 1.05 (3 t)

-Cl 8 methyl n-propyl 7.0 (4 a '), 3.9 (2 t), 2.28 (4 mc), 2.2 (3 s)

1.1-1.9 (m), 0.85 (3t) ⁺

ГCN

CN

Ή

Й

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X Д rt

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CN (Z

o r-l (Л Ή> υ

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γΗ rd <~ Η r — t φ- < • -Ч Г — 1 г-1 Г-Ч no ο at at at AT O ο υ * φ ’Φ • φ • φ , φ 'φ -φ , φ 'Φ

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σ O r-l (M (O -Φ in v © 1- oo O O cc in Ю r * cm cc OC (O O cc cc cc <c-) cc cc * φ * φ * φ

porakávání

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Γ-

гЧ ’ гЧ .4 гЧ гЧ no О no no no со сч 1 AND 1 1 1 ’У чу чУ чу чу Я со сч (Ν ко Я со ч ч гЧ ч гЧ ч ч и ¹ no СО Я со со со О со со О СО со со со со Я о Я Я я 1 я Я 1 Я Я ь • гЧ ь 1 Я гЧ no о no no no ну no я О чу no no no * č no ко О О 1 1 1 1 1 1 1 1 Ф 1 1 1 1 чУ чу ГЧ сч чу со сч чГ CN со сч сч чу (Л чу чу сч чу чу

χσΊΟΗίΝΠ’τιη ^ ^^ ιηΐΛΐηιηΐπίΛΐη> οοσιθΗ ^ ω> ЩиКиОКОкОКОГ-Г ^. 00 ок \> г-

1Л AT) ш ш я Я со Я я ГЧ сч Я сч ГЧ О О О no no

ΟΟ о о

ο r-t cn со м ·

00 00 00 со

number Y m n R ^t e ^pl OTA mp (° C) 85 2-CH3, 4-C1 6 4-t-C 4 ^H ₉ 150 to 153 86 2-CH3, 4-C1 7 H 109 to 112 87 ’ 2-CHg, 4-C1 8 H 62 to 65 88 _4-CH3 6 ^2-СНз 96 to 98 89 2-CH3, 4-C1 10 4-CH 3 paste 90 2-CH3 4-C1 12 4-CH3 ' paste 91 2-CH _3, 4-C1 6 4 “ ^C H3 63 to 65 92 2-CH3, 4-C1 8 4-CH, 68 to 70. 93 2-CH3, 4-C1 9 4- ^ch3 75 to 77 94 2-CH3, 4-C1 5 4-CH3 100 to 105 95 2-CH3, 4-C1 7 4-CH3 77 to 79 96 2-CH3, 4-C1 6 H 81 to 84 97 2-CH3, 4-C1 5 3-Cl 130 to 132 98 2-CHg, 4-C1 9 H 100 to 104 99 2-CH3, 4-C1 5 2-CH3 98 to 100 100 ALIGN! 2-CH3, 4-C1 6 2-CH3 146 to 148

The herbicidal compositions according to the invention can be used, for example, in the form of directly sprayable solutions, powders, suspensions, as well as high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scatters or granulates and sprayed, misted, sprayed , sprinkling or watering. The use forms depend entirely on the intended use. These dosage forms are in any case intended to ensure the finest possible distribution of the compositions.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, suitable fractions of mineral oil of medium to high boiling points, such as kerosene or diesel oil, as well as tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N -methylpyrrolidone, water.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders or oil dispersions by the addition of water. For the preparation of emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent may be homogenized with wetting agents, adhesives, dispersing agents or emulsifiers in water. However, concentrates consisting of a tor or an emulsifier and optionally solvents with water may also be prepared.

an active ingredient, a wetting agent, an adhesive, a dispersant or an oil which is suitable for dilution

Surfactants include:

alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, corresponding salts of naphthalenesulfonic acid, phenolsulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, alkali metal dibutylnaphthalenesulfonic acid salts, alkaline earth metal salts, lauryl ether sulfates, sulfated fatty alcohols, alkali metals and alkaline earth metals, sodium sulfides, hexadecanols, heptadecanols, octadecanols, soh sulfated glycol ethers of molar alcohols, condensation products of sultonated naphthalene and naphthalene derivatives with trimethyl aldehyde, codensation products of ruthenealdehyde ally, optionally naphthylsulphonic acids with phenol and triethyldehyde, ethylene ethers, ethylene glycol alkylsilyl, ethyl glycol allyl, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol, ethyl glycol. , condensation products of alcohols with ethylene oxide, ethoxyl Pure oil, polytxyelhenyl ether _; ethanol, polysilkylene, isilyl lactol, glycyl glycol, cellulose, sorbitol esters, lignin, sulfite waste liquors, and ethylcellulose.

Powders, dusts and dusts can be prepared by mixing or jointly spreading the active ingredients with a solid carrier.

Graadates, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solids such as silica, such as silica gel, silicas, silicates, molasses, kaofio, silicates, limestone, lime, chalk, bolus, crack, clay dolomite, quartz, calcium sulphate and magnesium sulphate, magnesium oxide, ground plastics, fertilizers such as ammonium phosphate, ammonium nitrate, motovioa and plant products such as cereal meal, tree bark meal, wood meal and nut shell meal, powdered cellulose and other solid carriers.

The herbicidal compositions comprise between 0.1 and 95% by weight of the active ingredient, preferably between 5 and 90% by weight.

The following are examples of compositions and preparations of the compositions of the present invention.

I. 90 parts of hootnootic active substance No. 21 are mixed with 10 parts of N-methyl-V

pyrrolidine to give a solution which is suitable for use in the form of minimal drops.

II. 20 parts of the potency active substance No. 33 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8-10 oot of ethylene oxide with 1 mole of N-mono-oleohanol oleic acid, 5 parts by weight of calcium calcium salt and iodecylbenzenesulfonate. 40 mole of ethyl acetate with 1 mole of ethyl acetate oil. By pouring and finely distributing this solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% of the mono-active substance.

III. 20 parts by weight of the active ingredient No. 25 are dispersed in a mixture consisting of 40 parts by weight of cyclohexane, 30 parts by weight of ittiutanol, 20 parts by weight of the addition product of 7 ool / ml and 1 ool / ml. 10 parts by weight of the addition product of 40 ool of ethylene oxide with 1 ool of ricotta oil. By pouring and dispersing the solvent in 100,000 parts of hot water, an aqueous dispersion is obtained which contains 0.02% of hot water.

IV. 20 parts by weight of the active ingredient No. 29 is dissolved in a mixture consisting of 25 parts by weight of cyclotexanol, 65 parts by weight of mineral oil fraction and a boiling point of 210 DEG-280 DEG C. and 10 parts by weight of 40 ool of ethylene oxide. with 1 mol of castor oil. By pouring and dispersing this solution in 100,000 parts of water, a water dispersion is obtained which contains 0.02% by weight of the active ingredient.

V. 20 parts by weight of the active substance No. 37 are well mixed with 3 parts by weight of diisobutylo-naphthalene-phthalic acid sodium salt, 17 parts by weight of ligninsultonic acid sodium salt from the waste liquors and 60 parts by weight. The mixture was mixed with 20,000 parts by weight of water by gently dispersing it to give a spray suspension containing 0.1% by weight of the active ingredient.

VI.

parts by weight of active ingredient no. 18 are mixed with 97 parts by weight of finely dispersed kaolin. In this way, a dust is obtained which contains 3% of active ingredient.

VI.

19 parts by weight of the active ingredient are thoroughly mixed with a network of 92 parts by weight of powdered silica and 8 parts by weight of oil which has been sprayed onto the surface with good adhesion.

si.lk-agel. In this way, an effective preparation with a

VII. 20 parts of active ingredient No. 87 sulfonic acid, 8 parts of the condensation product of phenol, motor oil and fluorine, and 68 parts of paraffinic mineral oil. A white oil dispersion is obtained.

is thoroughly mixed with 2 parts of calcium salt of Uodecylbenzkn polyglycol ether of fatty alcohol, 2 parts of sodium

Application of the particles can be carried out pre-emergence or post-emergence. If the active ingredients are less seeded with crop plants, then application techniques can be used in which the herbicidal compositions are sprayed by spraying so that the leaves of the susceptible crop plants are directed to undesirable plants, the soil surface (e.g. -UirlctlU, lay-by).

they remain unpainted, if possible, while active which grow below them or mix and uncoated

The application of the control and preferably 0.25 to 5 kg of active ingredient according to the growth stage and the soil type is 0.1 to 5 kg of active compound and 13 kg / ha.

in the lorma of the kit, by season, by ha or more,

In greenhouse:

the effect of the composition according to the invention is even the following experiments carried out

The pots of 300 ml plastic filled with sandy clay soil with about 1.5% humicum serve as pots for growing rossicles. Seeds of test rossicles are sown in the soil separately by species. Immediately thereafter, the pre-emergence focus is divided by the active ingredient onto the soil surface. The active substances are present in the water as a peroxygen medium and I will! with spray nozzles.

suspended or emulsified by suturing the substance o and seeds and mortars until experimental rosslic

In this method of application, a variety of 2.0 or more are used

3.0 kg effective 1 ha. After application of the compositions, the pots were slightly watered to start germination to begin to grow. Then the pots are covered with a transparent plastic foil when the plants start growing. This covering results in uniform germination, if not yet affected by the active ingredients.

For the purposes of post-emergence treatment, the test plants are aypsified up to a height of 3 to 15 cm, depending on the form of growth, before the treatment is carried out. For post-emergence treatment, either directly sown and grown pots are used in the same pots, or such pots are first grown separately as a germinating plant and transplanted into experimental pots a few days prior to treatment. The application rate varies depending on the active ingredient in the case of a tissue allergen treatment. This onset of 0.05, 2.0 or 3.0 kg of active ingredient / ha. In post-emergence treatment, the plants are cloaked.

The test vessel was placed in a greenhouse, wherein the thermophilic plant species selected warmer ^ STI tk ^l cs ^I to ^(20-35 ° C) and ^p ro ro ^ t ¹ ^, ^the esters ye ^H <ovuje milder ^SK lima is Voh te ^p lot ^yk ol ¹⁵ to ²⁵ ° C,

The experiment time is 2 to 4 weeks. During this time, the roots are treated and their response to single treatments is evaluated. Evaluation is carried out on a scale of 0 to 100. At the same time, 0 means no treatment or normal growth and 100 means that the plants are not capable of being destroyed, or the complete destruction of at least the above-ground parts of the plant.

The following types of growth are used in experiments: lin:

Pigweed (Anmranthus spp.), Common oat (Avena saaiva), Cassia Torah, Blue cornflower (Centaurea cyanuss, White album), Eupporbia gennculata, Bedstraw (Galium apaaine), Cotton (Gossypium hirsutum), povea ^ nice .), white mustard (Sinapis alba), black aubergine (Solanum nigrum), violet (Viola spp.), triola (Viola tri ^ irLr ^).

As the comparator means is used to herbicidal compositions which obsahtuí as active ingredient 3- (4-c01lrfenoxy) ^-1-yl diehУ Limin n-poopan (cf. DE-OS 19 28 606), hereinafter referred to as Units A ^o or L- (4-i ⁰ lorfeoox ^yl) -1- ^d iehh lamirlo ^y-o-BSTA (cf. DE-SO ^{2 9} 1 8606), which is referred to hereinafter as ingredient B.

For example, herbicidal compositions which contain compounds No. 21, 29 or 37 exhibit a better herbicidal effect when compared to Comparative Formulations A and B (cf. Table 1).

Herbicidal compositions which contain the active ingredient of Compound Nos. 2, 15, 18, 26, 28, 36 and 31 have been shown to be effective in oats at a low rate of application. 3.0 kg of active substance per ha (cf. Table 4).

In post-emergence treatment, the herbicidal activity, for example, of herbicidal compositions which contain Compound No. 25, 29, 33 or 37 as the active ingredient is more intense than that of the comparative compositions (cf. Table 2).

Compositions with Compounds No. 25, 29 or 33 as active ingredients. they also have good teleecivity (cf. Table 3).

Viscous herbicidal activity in oats is shown by applied mash. 3.0 kg of active ingredient per hectare, as well as an oecidal composition comprising as active ingredients of compound 7, 22, 77, 81, 84 or 87 (cf. Table 5).

Remarkably effective for broad-spectrum undesirable plants are also oeebidial agents which contain as active ingredients compounds 18, 19, 38, 39 or 76 at an application rate of 3.0 kg of active substance per ha (cf. Table 6).

Tables 1 to 6 are listed below.

Table 1

Combating unwanted plants with a pre-emergence application of 2.0 kg of active ingredient per hectare in a greenhouse

Active substance no. Test plants and percent damage Gossypium hirsutum Amranthut spec. AND 0 0 (B) 0 20 May 21 0 80 29 0 90 37 0 80

Table 2

Combating undesirable plants with a potential application of 2.0 kg of active substance per ha (greenhouse fines)

Active substance no. Chenopodium album Fine plants and percent damage Galium aparine Solanum nigrum Viola tpec. AND 40 40 30 60 (B) 30 10 35 60 25 95 90 100 ALIGN! 95 29 95 90 100 ALIGN! 95 33 100 ALIGN! 70 100 ALIGN! 95 37 100 ALIGN! 80 100 ALIGN! 95

Table 3

Ss-minic control of Euphotbia gennculata in cotton under pottemergent treatment (greenhouse fines)

Active substance no. Amount of active substance kg / ha Fine plants and percent damage Gassypium h ^ su ^ m Eupphrbia gennculata AND 2,0 0 30 (B) 2,0 0 25 25 2,0 0 95 29 0.5 10 90 33 0.5 0 100 ALIGN!

Table 4

Oat selectivity test with pre-emergence application of 3.0 kg of active substance per ha (greenhouse experiment)

Active substance no.

Experimental results and percent damage to Avena sativa Sinapis alba

15 Dec 0 90 36 0 100 ALIGN! 28 0 100 ALIGN! 31 0 95 26 0 100 ALIGN! 2 0 100 ALIGN! 18 0 100 ALIGN!

Table 5

Selertive control of unwanted rosslin in post-haemegetic application using 3.0 kg of active ingredient per 1 ha in cereals (greenhouse experiment)

Active substance no.

Test plants and percent damage

Avena sativa Viola iricolor

87 0 80 80 77 0 80 95 84 10 100 ALIGN! 100 ALIGN! 81 0 100 ALIGN! 100 ALIGN! 7 0 100 ALIGN! - 22nd 10 100 ALIGN! -

Table 6

Control of undesirable rosslins in pustrmergent application of 3.0 kg of active substance per ha (greenhouse experiment)

Active substance no. Experimental ro ^ t ^ Hn ^ y and percent damaged! Anaranthus spec. Cassia Torah CenSaurea cyanus Ipomura spec. 76 100 ALIGN! 100 ALIGN! 100 ALIGN! 85 39 80 95 90 90 18 90 100 ALIGN! 80 100 ALIGN! 38 80 100 ALIGN! 100 ALIGN! 100 ALIGN! 19 Dec 80 100 ALIGN! 100 ALIGN! 95

In view of the good removability of the active compounds and the numerous application methods, the herbicidal compositions according to the invention can be used in addition to the commercial rossins which have been tested in greenhouse experiments, in a large number of cultural rossins to prevent unwanted growth of the rossins.

For example, the following cultural features are considered:

Botanical name Czech name AilUum cepa onion Pineapple comoiui pineapple Arachis hypogoea peanut Aiparagui officinalii asparagus Avena lativa oats Beta vulgaria ipec. altliiima sugar beet Beta vulgaria ipec. rapa fodder beet Beta vu ^ g ^ i ^: Liipec. eiculenta beetroot Brassica napus var. napui rape Brassica napui var. napobrassica turnip Brassica napui var. rapa white beets Braisica rapa var. lilveitrii oilseed rape Caamllia iinensii tea Carthamus tinctoriui ivvtlice dye Carya illinoieensii walnut pecan Citrus limon lemon tree Citrus maxima citroník neevětší Citrus reticulata · maaduainka Citrui iinensii orange Coffea ambica (Coffea canephora) coffee tree Cucuiíís melo melon Cucumis lativui cucumber Cynodon dactylon troikut pritnaté Daucus carota carrot Elaeis guineensis coconut tree Fragaria vesca Strawberry Glycine max soya Gossypium hirsuuum cotton (Gossypium arboreum cotton Gossypium herbaceum cotton Gossypium vitfoouuum) cotton Heeianthui annuus. sunflower Heeianthui teberosui topnnambur Hevea brasllieniii rubber tree Hummuus lupulus hop Ipomoea batatas sweet potato Juglans regia Walnut Lactuca lativa salad Lens culinarii edible lentils Linum usitaiissiuum only Lycopersicon Oycořersiuum tomato Malus spec. apple tree Mannhot et al tapioca Medicago lativa vojttška Mentha pipe peppermint Musa spec. banana tree Nicotiana tabacum (N. rusti) tobacco Olea europaea olive Oryza sativa rice Panicům milňcceum millet 5

Botanical name Czech name Phaseolus lunatus bean Phaseolus mungo - Phaseolus vulgaris shrimp beans Pennisetum glaucum - P ^ ttrose ^ linum cripppum spec. parsley root tuberosum Picea abies spruce Abies alba silver fir Pinus spec. pine Pisum sativum pea Prunus avium cherry Prunus domestica plum Prunus dulcis \ almond Prunus persica \ peach Pyrus communis pear ^Rib es syKestre 1 redcurrant Ribes uva-crispa gooseberry Ricinus communis castor Saccharum officinarum sugarcane Secale cereale rye Sesamum indicum sesam Solanum tuberosum potatoes Sorghum bicolor (p. Vulgare) sorghum Sorghum dochna sorghum Spinacia oleracea spinach Theobroma cacao cacao tree Trifolium pratense Clover Triticum aestivum wheat Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vica faba bob horse Vigna sinensis (V. unguiculata) bean Vitis vinifera Grapevine Zea mays maize

To extend the efficiency. The compositions according to the invention can be mixed with numerous representatives of other herbicidally active substances or with groups of substances which regulate the growth of plants, and then the mixtures can be applied together. Suitable components of such mixtures are, for example, diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, and others.

In addition, it may be useful to mix the herbicidal compositions of the invention alone or in combination with other herbicides with other plant protection agents and to apply these mixtures together, e.g. Also of interest is the miscibility with mineral salt solutions. Such mixtures can be used to eliminate nutrient and trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.

Claims (6)

SUBJECT OF THE INVENTION CLAIMS 1. A composition according to claim 1 comprising at least one active ingredient as active ingredient. R ^{1 -ZP} R (I) in which the alkyl group has 1 to 6 carbon atoms, haloalkyl carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 2 or 3, n R ¹ R ² is halogen, a group having 1 to 4 phenoxy is cis! 1, denoted by an integer from 2 to 12, denoted! independently of one another hydrogen atom or alkyl group having 1 to 4 atoms Or R @ 2 and R @ 2 denote: together with an alkyl group having from 1 to 12 carbon atoms; 4 carbon atoms substituted with an alkylene group having 4 to 7 carbon atoms; optionally a halogen or asylum substituted pyridinium moiety, together with a nitrogen atom of which it is a substituent, having from 1 to 4 carbon atoms or such aryloxyalkylamine. 2. A composition according to claim 1 comprising at least one of formula (I), wherein Y, m, n &lt; 12 &gt; in point 1 and R and R and m are carbon; or R @ ^{1 is a} carbon tetrachloride chain of 4 to 7 carbon atoms in the chain, or a salt of such an aryloxyalkyl amine. independently of one another hydrogen or an alkyl group having 2 and R together and optionally an alkyl group having 1 to a component of said 1-4 carbon atoms 3. A composition according to claim 1, wherein the active ingredient is at least one aryl-oxyalkyloxy of formula I wherein Y is halogen, m is 1 in 12, n is 1, n is an integer of from 6 to 10 and R and R are independently C 1 -C 4 alkyl, or an acid addition salt of such aryloxyalkylamine. 4. A composition according to claim 1, wherein one salt of the aryl-oxyalkylamino group of formula (I) wherein Y is C1-C4, m is 2, n is an integer from 6 to 10 a R @ 1 and R @ 2 denote a substituted pyridine moiety together with the nitrogen of which the substituents are optionally halogen or C1 -C4 alkyl. as active ingredient it comprises at least a halogen or an alkyl that is present in the composition 5. A method for producing an active ingredient according to claim 1 of formula I, U ^ significance in females (lxyalkylhalogenid formula II _{^(CH2) n} ^'-Hal (II) wherein Y, m and Hal, as defined in 1, and represents halogen, acts by an amine of formula III (III) wherein: 1 2 R and R have the meanings given in point 1, at a temperature ranging from 50 to 200 ° C, optionally in the presence of an inert solvent. 6. A process according to claim 2, wherein the phenoxyalkyl halide of formula (II) wherein Y, m and n are as defined in (1). 1 and Hal is halogen, reacts with an amine of the formula III in which R and R have the meanings given in point 2, at a temperature in the range from 50 to 200 ° C and optionally in the presence of an inert solvent.