DE2435747A1 - STABLE LIQUID PREPARATION WITH HERBICIDAL EFFECT AND METHOD FOR MANUFACTURING IT - Google Patents

Description

T V) 561

Note : Lilly Industries Limited

Henrietta House, Henrietta Place, London, W.1.,

England

Stable liquid preparation with herbicidal action and process for its production

The invention relates to a new stable liquid preparation with herbicidal action (hereinafter referred to as herbicidal preparation), in particular a liquid, emulsifiable, concentrated preparation, which contains a mixture of herbicidal compounds, and a method for their production.

To control or remove weeds from agricultural land on which economically To grow valuable fruits and plants, more than one herbicide must often be applied achieve a sufficient weed killing effect see below. This may be due to the fact that the

509807/1139

various weeds are present, so that no a single herbicide gives sufficient control or gives such control only at dosage rates too high to cause possible damage to prevent the valuable fruits and plants. Accordingly, this is the solution to this Problem, many combinations of herbicides have already been suggested in the literature, with one in particular valuable combination that from a dinitroaniline herbicide and an N-aryl-N'-alkoxyurea herbicide is. In the information about the Braophbar-

° either

ability of the last-mentioned combination sina / none specific Contain details regarding the composition (see e.g. the German Offenlegungsschrift 2,037,265) or the required mixture of active ingredients is obtained by simply mixing the individual components in a container immediately prior to use, or both components are applied separately (see, for example, "Report of the Canadian National Weed Committee (Eastern Section), November 1968 and Report of the United States Southern Weed Conference, January 1969)

Although the successful application of dinitroaniline and urea herbicides or applying one immediately A workable suggestion for a mixture of these ingredients prepared before use May be research purposes, it is clear that if such procedures are to be used technically, the time and labor factors involved make the process uneconomical and possibly also render ineffective due to the inevitable Inaccuracies in relation to the dosage,

509807/1139

which result from the components being applied separately on a large scale under field conditions or mixtures of the constituents can be prepared.

In order to make the use of the combination of dinitroaniline and urea herbicides practicable, a concentrated preparation must be prepared which contains these two active ingredients, which is both chemically and physically stable UDd in which the proportions of the active ingredients are precisely controlled and which before Use can be diluted easily and cheaply to produce a herbic.id effective concentration of the active ingredients. Due to the physical nature of the dinitroaniline herbicides, it is expedient that such a concentrated preparation should be in liquid form, although it has been found that, in contrast to the dinitroanilines, the N-aryl-N'-alkoxyureas intended for the use according to the invention are in the herbicidal Formulations commonly used non-phytotoxic solvents are not sufficiently soluble to obtain the desired concentrations, which is the case in particular at temperatures in the vicinity of O ⁰ C, at which the preparations are often stored and occasionally even used. It has also been found that unless certain precautions are taken with respect to the selection of emulsifiers to be used in the desired concentrated formulations, the urea herbicide is chemically unstable.

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The object of the invention is therefore to provide a solvent and to specify an emulsifier system in which the dinitroaniline and urea herbicides are converted into the desired Concentrations can be dissolved; The object of the invention is in particular, liquid concentrated To indicate preparations of dinitroaniline and urea herbicides, which under the conditions under which they are normally transported, stored and used, physically and chemically resistant are.

This object is achieved with a liquid herbicidal preparation which is characterized in that it contains a dinitroaniline herbicide and an N-aryl-N ¹ -alkoxyurea herbicide, dissolved in a non-phytotoxic alicyclic ketone, the ratio of dinitroaniline to urea in the The order of magnitude is from 4: 1 to 1: 4, preferably from 2: 1 to 1: 2.

The term "non-phytotoxic" used here in connection with the alicyclic ketone includes not only those ketones which do not in themselves damage fruits and plants, but also those ketones which, although they have a certain phytotoxicity, at the dosage in which the preparation is used to control weed growth but is not phytotoxic. The ketone can be used as the only solvent in the preparations according to the invention, but for economic and practical reasons the amount of ketone only needs to be sufficient to ^{solubilize the urea herbicide at temperatures from 0} ° C. upwards. Ever

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depending on the particular urea used, the ketone can therefore make up 15 to 100% by volume of the total solvent concentration, with the remainder consisting of a non-phytotoxic solvent or a solvent mixture that is compatible with the ketone and can solubilize the dinitroaniline content of the preparation. These other solvents are known per se and include in particular aromatic hydrocarbon solvents such as alkylbenzenes and haloalkylbenzenes such as toluene, halotoluenes, xylenes and mixtures thereof, alkylbenzene mixtures, e.g. B. those as sold under the trade names Solvesso and Shellsol, other petroleum distillates, such as. B. the heavy aromatic naphthalene solvents and various solvent mixtures derived from the petroleum industry and containing 60 to 100% aromatic hydrocarbons, the remainder being aliphatic and alicyclic hydrocarbons.

The alicyclic ketones which have proven to be particularly suitable according to the invention include cycloalkyl or cycloalkenyl ketones, in particular cyclohexanone, cyclohexenone and their C ^^ alkyl derivatives such as 2-methylcyclohexanone, 3-methylcyclohexanone, 3-methylcyclohex-2-en-1- one, I ^ -Dimethylcyclohex ^ - en-1-one, 2,6-Mmethylcyclohexanone, 2,2,6-Trimothylcyclohexanone, 3,3 »5» 5-tetramethylcyclohexanone and, preferably, 3,5 »5-1 ^l rimethylcyclohex-2-en-'l-one.

The amount of in the preparations according to the invention active ingredients present depends on the desired use of the preparation, usually

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However, the two ingredients are contained in as high a concentration as possible in order to make the use of solvents and the transport and storage costs for the preparations economical. From the point of view of the solubility of the dinitroaniline and urea herbicides used in the present invention, the upper limit of the concentration of the active ingredients is of the order of 60 w / v. % and in order to make the preparations as economical as possible, the lower limit of the concentration is normally not below 10% w / v.

Since a preferred feature of the invention is to provide a liquid concentrated preparation, which can be diluted with water to the desired concentration before use the preparations according to the invention are expedient an emulsifier or an emulsifier mixture, usually in an amount of 4 to 15% w / v% stated above, careful selection of the type of emulsifier must be made, as it has been found that certain commercial emulsifiers can chemically break down the urea herbicide. It was found that this problem was with the alcohol content

of the emulsifier, which is a consequence of Heriss

Positional method / or more often on the solvent can be recycled in which the emulsifier is supplied, and it is therefore necessary that according to the invention only those emulsifiers are used, which have practically no content of free alcohols or polyalcohols. The presence or Absence of free alcohol can be confirmed by analysis

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can be easily determined, so that it is superfluous here to list suitable emulsifiers.

The emulsifiers used according to the invention can be anionic or non-ionic, or a mixture thereof is preferably used. Examples suitable anionic emulsifiers are the alkyl and aryl sulfonates, sulfates and sulfosuccinates, such as Isopropylnaththalinsulfonate, Dodecylbenzenesulfonate, Dioctyl esters of sulfosuccinic acids, dinonyl sulfosuccinates, Lauryl polyglycol ether sulfosuccinate, lauryl sulfate and cetostearyl sulfate. examples for suitable non-ionic emulsifiers are polyoxyethylene sorbitan esters of mixed fatty and resin acids, such as polyoxyethylene sorbitan monolaurate, monopalmitate, monostearate, monooleate, tristearate and trioleates, alkylaryl polyethoxyethanols, such as nonyl and isooctylphenylpolyethoxyethanols, glyceride esters, such as diglyceryl monooleate, glyceryl dioleate and glyceryl dilaurate and ethoxylated alkylphenols and Cresols such as ethoxylated octylphenol, ethoxylated nonylphenol and ethoxylated octylcresol.

In the case of those used in the preparations according to the invention Dinitroaniline herbicides are a class of herbicides that have been around for many Years are known. The most suitable representatives of this class have the structural formula

(I)

- 8 509807/1 139

where mean:

E is hydrogen, C. _K -alkoxy, C ₁ ,, - alkyl thio or

ρ ζ '- ^ ' - ^ "-NETT,

2 3 4 5
E, E, E and E ^ individually each hydrogen or an aliphatic hydrocarbon radical or C ^ /, - acyloxy, optionally substituted by halogen, hydroxy, azido, cyano, C - ^ - alkoxy, CL _ ^ - alkylthio, -sulphinyl or -sulphonyl, with the proviso,

2 5 4 5 that at least one of the best B, B, B and E ^ is not hydrogen, or and E or E and B ^ together m th nitrogen atom a heterocyclic ring and

E and E or E and B ^ together with the adjacent E ⁶ hydrogen, C _1-4 alkyl. C ^^ alkoxy, C _1- ^ -alkylthio, -sulfinyl or -sulfonyl, C ₁ ,, - haloalkyl,

"~ 7 8 halogen, cyano, thiocyano or -SO ₀ NB'B, where E 'and E individually are each hydrogen, C ₁ ^ ₄ -alkyl,

-Alkenyl or Cv_g-Cycloalkyl or together together with the neighboring nitrogen atom represent a heterocyclic ring.

If E, E, E or B ^ is an aliphatic hydrocarbon radical, may be alkyl in this order C _1-6 -alkyl, C _2-6 -alkenyl, C ₂ _ ₆ alkynyl, C, ₆ -cycloalkyl, C , -_ g-Cycloalkenyl and C ₄ _ "- cycloalkylalkyl, each of these best may optionally be substituted as indicated above. If the groups -NE ² E ⁵ , -NB ⁴ E ^ or -NB ^ B ⁸ mean a heterocyclic input , this can be a saturated input of the structure -NZ, where Z is an alkylene group having 2 to 6 carbon atoms one of which can optionally be replaced by an oxygen or nitrogen atom.

509807/1139 - 9 -

Examples of C 1-4 alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, amyl, isoamyl, see-amyl, hexyl and sec-hexyl. Examples of Cp_ £ -alkenyl and Cp, - alkynyl groups are ethenyl, allyl (2-propenyl), isopropenyl, propargyl (2-propynyl), 2-butenyl, 3-butenyl, 2-methylallyl, 2-butynyl, 2 -Pentenyl, 4-pentenyl, 3-pentynyl, 2-methyl-2-butenyl, 2-methyl-2-pentenyl, 2-hexenyl and 1-ethyl-2-propenyl.Beispiele for C, _ ₆ cycloalkyl groups are cyclopropyl, Cyclobutyl, cyclopentyl and cyclohexyl and examples of C ^^ - cycloalkylalkyl groups are cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopentylmethyl, cyclobutylethyl, 2-methylcyclopropyl and 2-methylcyclohexyl. Examples of C 1-6 cycloalkenyl groups are 2-cyclopentenyl, 3-cyclopentenyl, 2-cyclohexenyl and 2-cyclooctenyl.

Examples of the above-mentioned hydrocarbon radicals which are substituted by halogen, hydroxy, azido, cyano, C, - ^ - alkoxy, C - ^ - alkylthio, -sulphinyl or -sulphonyl, or for Cp _- /, - acyloxy groups are 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, trifluoromethyl, pentafluoroethyl, 3-chloropropyl, 2-chloroallyl, 2-chloromethylallyl, 3-chloropropargyl, 2-hydroxyethyl, 2-azidoethyl, 2-cyanoethyl, 3-hydroxypropyl, 4-hydroxy -2-butenyl, 4-cyanobutyl, 2-isopropoxypropyl, 4-azidobutyl, 2-methylthipethyl, 2-methylsulfonylethyl, 2-t-butylthioethyl, 3-methylsulfinylpropyl, 2-acetyloxyethyl, 3-acetyloxypropyl, 2-propionyloxyethyl -Butyryloxyethyl.

Examples of the above-mentioned C 1-4 alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy and

- 10 -

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t-butoxy. Examples of C ^^ j ^ alkylthio, sulfinyl and sulfonyl groups are methylthio, methylsulfinyl, methylsulfonyl, ethylthio, ethylsulfonyl, propylthio, isopropylsulfonyl, butylsulfyl, sec-butylsulfony] and t-butylthio. Examples of C ₂ _ ^ - acyloxy groups are acetyloxy, propionyloxy, isopropionyloxy and butyryloxy, and examples of the above-mentioned heterocyclic rings are aziridino, pyrrolidino, morpholino, piperazino, piperidino and homopiperidino.

Examples of specific compounds falling under the definition given above are the following: N, N-di-n-butyl-4-chloro-2,6-dinitroaniline Kn-propyl-N-2-methylallyl-4-t-butyl -2,6-dinitroaniline K, N-di-isobutyl-4- trifluoromethyl-2,6-dinitroaniline N-ethyl-N-2-methylallyl-4-isopropyl-2,6-dinitroaniline N, N-di-sec. butyl-4-trifluoromethyl-2,6-dinitroaniline, N-allyl-N-2-methylallyl-4-t-butyl-2,6-dinitroaniline, N-methyl-Nn-amyl-1- trifluoromethyl-2,6 -dinitroan \ lin N _> N-dipropyl-4-sulfamoyl-2,6-dinitroaniline N-methyl-Nn-butyl-4-trifluoroniethyl-2,6-dinitroaniline K _i N-dipropyl-4- (N-methylsulfamoyl) - 2,6-dinitroaniline N-ethyl-Nn-butyl-4-trifluoromethyl-2,6-dinitroaniline K, N-dipropyl-4- (N, N-dimethylsulfanioyl) -2,6-dinitroaniline N-ethyl-Nn-propyl -4-trifluoromethyl-2,6-dinitroaniline NjN-dipropyl - ^ - (N-allylsulfamoyl) -2,6-dinitroaniline N-ethyl-Nn-propy1-2 _v 6-dinitroaniline N, N-dipropyl-4- - (il-propylsulfamoyl) -2,6-dinitroan'iline Nn-butyl-Nn-propyl-2,6-dinitroaniline N, N-dipropyl-4- (N-ethylsulfamoyl) -2,6-dinitroaniline N-methyl-Nn-propyl-2,6-dinitroaniline N, N "-diallyl-4- (N-cyclopropylsulfamoyl) -2,6-dinitroaniline

509807/1139 - 11 -

N-ithyl-N-n-butyl-2,6-dinitol.ro-p-toluidine N, N-dipropyl-4- (N-cyclopropy1-N-ethylsulfamoyl) -2,6-dinitroaniline

Nn-Propyl-Nt-butyl-2,6-dinitro-p-toluidine N, N-Dimethylallyl-4-sulfamoyl-2,6-dinitroaniline H, N-Dimethy1-4- trifluoromethyl-2,6-dinitroaniline N- ( 2-hexyl) -4-piperidinosulfonyl-2,6-dinitroaniline N _i N-dimethyl-4 - chloro-2,6-dinitroaniline N-cyclopentyl - ^ - ^ J morpholino--dinitrobenzolsulf onamid

N, N-dimethyl-2,6-dinitro-p-toluidine I- (1-Ethylpropyl) -4- (N, N-dimethylsulfamoyl) -2,6-dinitroaniline

N, N-Di-n-propyl-2,6-dinitroanilia N-ethyl-N-2-methylallyl-4-trifluoromethyl-2 ₁ 6-dinitroaniline

N, N-di-n.-propyl-4-trifluoromethyl-2,6-dinitroaniline N-propyl-K-2-chloroethyl-4-difluoromethyl-2,6-dinitroaniline

NjN-Di-n-propyl - ^ - cyano-2,6-dinitroaniline N-Propyi-N-2-azidoethyl-4-ctilor-2 _> 6-dinitroaniline N, N-Di-n-propyl-4-chloro- 2,6-dinitroaniline, N-propyl-N-2-cyanoethyl-4-trifluoromethyl-2,6-dinitroaniline

N, N-di-n-propyl-2,6-dinitro-p-toluidine N, N-Dipropyl-4- (2-chloroethyl) -2,6-dinitroaniline N, N-di-n-propyl-2,6-dinitro-p-anisidine. N, N-Dipropyl-4-methylsulfonyl-2,6-dinitroanilia H, N-di-n-propyl-2,6-dinitro-m-toluidine. N-ethyl-N-2-methylallyl-4-methylsulfQαyl-2,6-'dinitro-

aniline.

N, N-diethyL-2,6-dinitroaailin N, N-bis (2-chloroethyl) -2,6-dinitro-p-toluidine

509807/1139 / _; ·; " ¹² ~

N-Cyclopropylmethyl-N-propyl-2,6-dinitro-p-toluide, in N, N-diethyl-2,6-dinitro-p-tuoluidine N- (2-cyclohexenyl) -N-ethyl-4-trifluoromethyl-2,6-dinitroaniline

N, N-diethyl-2,6-dinitro-p-anisidine, N-cyclopropyl-fl-ethyl-4-chloro-2,6-dinitroaniline N, N-ethyl-2,6-dinitro-4-trifluoromethylaniline N-2-methylcyclohexyl ~ 4-trifluoromethyl-2,6-dinitroaniline

N, N-di-n-butyl-2,6-dinitroaniline N- (2-pentyl) -4-trifluoromethyl-2,6-dinitroaniline N, N-di-n-butyl-2,6-dinitro-p-toluidine N-sec-butyl-4-trifluoromethyl-2,6-dinitroaniline Ν, Ν-di-n-butyl-A-trifluoromettiyl-2,6-dinitroaniline N- (3-hexyl) -A- trifluoromethyl-2,6-dinitroaniline N-Allyl-N-methyl-4-trifluoromethyl-2,6-dinitroaniline N- (2-chloroethyl) -N-propyl-4-sulfamoyl-2,6r-dinitroaniline

N-allyl-N-ethyl-4-trifluoromethyl-2,6-dinitroaniline N, N-Dipropyl-4-aziridinosulfonyl-2,6-dinitroaniline N-allyl-N-ethyl-2,6-dinitro-p-toluidine N-ethyl-N ^ -methylallyl - ^ - sulfamoyl ^, 6-dinitroaniline K, N-diallyl-2,6-dinitroaniline

N, N-diallyl-4-trifluoromethyl-2,6-dinitroaniline N, N-diallyl-4-methyl-2,6-dinitroaniline N-Methyl-N-J-chlorallyl - ^ - trifluoromethyl-2,6-dinitroaniline

H, N-Dipropargyl-4-trifluoromethyl-2,6-dinitroaniline N- (2,6-Dinitrophenyl) pyrrolidine, N- (4-Trifluoromethyl-2,6-dinitrophenyl) pyrrolidine N- (A - chloro-2,6-dinitrophenyl) pyrrolidine N- (4 ~ methyl-2,6-dinitrophenylpyrrolidine

- 13 -509807/1139

N- (2,6-Dinitrophenyl) piperidine

N- (4-trifluoromethyl-2,6-dinitrophenyl) piperidine N-methyl-N- (2,2-dimethoxyethyl) -4-trifluoromethyl-2,6-

dinitroaniline
N-ethyl-N- (2-methoxyethyl) -4-trifluoromethyl-2,6-di-

nitroaniline
Nn-Propy1-N- (3-methoxypropyl) -4-trifluoromethyl-2,6-

dinitroaniline
Nn-propyl-N- (2,2-diethoxyethyl) -4 - trifluoromethyl-2,6-

dinitroaniline
N ⁵ -sec.-Butyl ^ N ¹ , N ¹ -dimethyl-2,6-dinitro-4-trifluoro-

methyl-1,3-phenylenediamine
N ¹ -ätnyl-N ¹ -2-methylallyl-4-trifluoromethyl-2,6-di-

nitro-1,3-phenylenediamine
N ⁵ -Ethyl-N ¹ , N ¹ -diethyl-2,6-dinitro-4-trifluoromethyl-

1,3-phenylenediamine
N ^ -Methyl-N ¹ -sec.-butyl-2,6-dinitro-4-trifluoromethyl-

1,3-phenylenediamine

5 ·· 1

N -Athyl-N -see.-butyl-2,6-dinitro-4-trifluermethyl-

1,3-phenylenediamine
N ⁵ -Methyl-N ¹ , N ¹ -di-n-propyl-2,6-dinitro - 4-trifluoro-

methyl-1,3-phenylenediamine
N ¹ y N ¹ -Di-n-propyl-2,6-dinitro-4-trifluoromethyl-1,3-

phenylenediamine
N ³ -Methyl-N ¹ , N ¹ -diethyl-2,6-dinitro-4-trifli; ormetliyl-

1,3-phenylenediamine
N ⁵ -n-propyl-N ¹ , N ¹ -diethyl-2,6-dinitro-4-trifluoro-

methyl-1,3-phenylenediamine
N ^ -sec.-Pentyl-N ¹ , N ¹ -dimethyl-2,6-dinitro-4-trifluoro-

methyl-1,3-phenylenediamine
N ¹ , N ¹ -Diet hyl-2,6-dinitro-4 - trifluoromethyl-1,3-

phenylenediamine
N - (3-pentyl) -r, 6-dinitro-4-trifluoromethyl-1,3-phenylenediamine

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N ¹ -sec-butyl-2,6-dinitro-4-trifluoromethyl-1,3-

pheny1endiamiη N ¹ - (1-methyl-2-methoxyethyl) -2,6-dinitro-4-trifluoro-

methyl-1,5-piienylenediamine N ⁵ -ethyl-N ¹ , N ¹ -diethyl-2,6-dinitro-4-bromo ~ 1,3-

phenylenediamine N ⁵ ^ methyl-N ¹ -sec.-butyl-2,6-dinitro-4-chloro-1,3-

phenylenediamine N ⁵ -ethyl-N ¹ -sec.-butyl-2,6-dinitro-4-bromo ~ 1,3-

phenylenediamine N ⁵ -Methyl-N ¹ , N ¹ -di-n-propyl-2,6-dinitro-4-ctilor-1,3-

phenylenediamine N, N -Di-n-propyl-2,6-dinitro- ^z i - chloro-1,3-phenylenedi-

amine
N ⁵ -Methyl-N ¹ , N ¹ -dietiiyl-2,6-dinitro-4-chloro-1,3-

phenylenediamine

N ^yl ₁ N ¹ -diethyl-2,6-dinitro-4-bromo-1,3-phenylenediamine N ^ -sec.-pentyl-N ¹ , N ¹ -dimethy1-2, e-dinitro - ^ - chloro-i , 3-

phenylenediamine N ⁵ -ethyl-N ¹ , N ¹ -diallyl-2,6-dinitro-4-methyl-1,3-

pJienylenediamine N ^ -Methyl-N ¹ -sec.-butyl-2,6-dinitro-4-cyano-1,3-

phenylenediamine

N ⁵ -ethyl-N ¹ -ssc.-butyl-2,6-dinitro-4-methyl-1 _t 3-

phenylenediamine N ^ -Methyl-N ¹ , N ¹ -di-n-propyl-2, e-dinitro ^ -isopropyl-

1,3-ptienylenediamine N, N-di-n-propyl-2, ö-dinitro - ^ - methyl-i _t 3-phenylene-

diamine
N ⁵ -Methyl-N ¹ , N ¹ -diethyl-2,6-di.nitro-4-cyano-1,3-

phenylenediamine

N ¹ , N ¹ -diethyl-2,6-dinitro-4-ethyl-1 »3-ptienylenediamine in N - (3-pentyl) -2,6-dinitro-4-cyano-1,3-phenylenediamine

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N ^ -Methyl-N ¹ - (1-methyl-2-methoxyethyl) -2,6-dinitro-4--

methyl-1,3-phenylenediamine
N ⁵ -Methyl-N ¹ -cyclopropyl-2,6-dinitro-4-ethyl-1,3-

phenylenediamine
N ⁵ -sec. -Pentyl-N ¹ , N ¹ -dimethyl-2,6-dinitro - 4 - methyl-

1,3-phenylenediamine
N -0-chloro-n-propyl) -2,6-dinitro-4-methyl-1,3-phenylene-

diamine
N - (4-heptyl) -2,6-dinitro-4-methyl-1,3-plienylenediamine

K ¹ _ (4-chloro-2-butenyl) -2,6-dinitro-4-methyl-1 _i 3-

phenyl ndiamin
N -sec. Butyl-2,6-dinitro-4-methyl-1,3-piienyleadiamine.

In view of their excellent herbicidal action, dinitroanilines are used in the invention

Preparations preferably used in which R is hydrogen or -NH ^, R is halogen, cyano, sulfamoyl, C ^ _ ^ -alkoxy, C. ^ - haloalkyl or C - ^ - alkylsulfonyl, R and R ^ individually each hydrogen - C ₁ , - alkyl, C ₃ . , - alkenyl, C *, - alkynyl, C., - haloalkyl, C ₀ , -

y-OP DI -Ö el- D

Alkoxyalkyl, C ^^^ - haloalkenyl or C ^ _g-cycloalkylalkyl, where at least one of the radicals R and Ir has a meaning other than that of hydrogen, j or H and Έ. together with the neighboring nitrogen atom are pyrrolidino or piperidino.

Also those used in the preparations according to the invention N-aryl-N'-alkoxyureas represent a known class of herbicides. The most suitable Representatives of this class have the structure:

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where mean:

r "hydrogen, C _1-4 -alkyl, C ₂ ^ -alkoxyalkyl, CUg-cycloalkyl, C ^ D-cycloalkenyl or C _4- ^ -CyCloalkylalkyl,

R ¹⁰ C _1-4 alkyl or C _2-4 alkenyl,

R ¹¹ C ..- alkyl and

R one to three representatives of the same or different radicals selected from the group consisting of hydrogen, halogen, C./I, - alkoxy, C ₁ , - haloalkyl, C 1, - haloalkoxy, C _{1-4 -alkylthio, C 1 -4} haloalkylthio, C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _2-4 alkenyloxy or Cp ^ alkynyloxy.

Examples of groups included under the expressions alkoxy, C _1-4 haloalkyl, C _1-4 alkylthio, C _1-2 C ₀ /. Alkenyl, C ₀ , - alkynyl, O, V-cycloalkyl, C ^ _β- Cycloalkenyl and C ₄ ^ -CyCloalkylalkyl are indicated above. Examples of C _1-4 -haloalkyloxy and C _1-4 -haloalkylthio are chloromethoxy, dichloromethoxy, trifluoromethoxy, difluorochloromethoxy, pentafluoroethoxy, 2-bromoethoxy, 3-chloropropoxy, 4-fluorobutoxy, 2-chlorineethylthio, 2- chloroethylthio, trifluoromethylthio, 2-chloroethylthio, trifluoromethylthio, 2-chloroethylthio, 2-chloroethylthio Bromoethylthio, and 4-chlorobutylthio. Examples of C _2-4 -alkenyloxy and C _2-4 -alkinyloxy are allyloxy, isopropenyloxy, propargyloxy, 2-butenyloxy, 3-butenyloxy, 2-isobutenyloxy and 2-butinyloxy. Examples of alkoxyalkyl are methoxyinethyl, ethoxymethyl,

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- 17 -

Isopropoxymethyl, methoxyethyl, 2,2-dimethoxymethyl and ethoxyethyl.

Examples of the above compounds are as follows:

N- (4-chlorophenyl) -N'-diethyl-N-methoxyurea N- (4-bromopheny1) -N'-methyl-N'-methoxyureaff N- (3,4-dichlorophenyI) -N '-methyl-N'-methoxyurea N- (2 ₁ 4,5-trichlorophenyl) -N ^l -methyl-N'-methoxyurea-

substance N- (3-trifluoromethylphenyl) -N'-methyl-N ¹ -methoxy urine-

substance N- (2-methyl-4-chlorophenyl) -N'-methyl-N'-methoxyurea

N- (4-Chlorphe ny1) -N'-ethyl ~ N'-me tb oxyharns bo ff N-phenyl-N'-ethyl-N'-methoxyurea N- (3 » ^/ <- dichlorophenyl) -N ^l - isopropyl-N'-methoxyurea

N- (4-bromophenyl) -N'-n-butyl-N ¹ -methoxyurea N- (4-methoxyphenyl) -N'-allyl-N'-methoxyurea N- (4-methylphenyl) -N'-methyl- N ¹ -isoprop'oxyurea N- (4-isopropylphenyl) -N'-methyl-N'-methoxyurea N- (4-methylthiophenyl) -N'-methyl-N'-methoxyurea N- (4-n-butylpheny1) -N'-methyl-N'-methoxyurea, N- (4-t-butylphenyl) -N'-methyl-N'-methoxyurea! N- (3-trifluoromethylphenyl) -N'-methylallyl-N'-methoxyurea

N- (4-trichloromethylphenyl) -N'-methyl-N'-methoxyurea

N- (3-chloro-4-ethoxyphenyl) -N'-methyl-N'-methoxyurea

N-f3- (difluorochloromethoxy) ph3nyl] -N'-methyl-N ¹ -methoxyurea

- 18 509807/1139

N- £ 3-chloro-4- (difluorochloromethoxy) pnenyl] -N ¹ -methyl-

N'-mettioxyurea
N - (_ 3-chloro-4- (difluorochloromethylthio) phenyl3-N '-methyl-

N'-methoxyurea
N- (4-trifluoromethoxyphenyl) -N'-methyl-N'-methoxy urine

material
N- (3-chloro-4-methylthiiophenyl) -N ^l -methyl-N'-methoxy-

urea
N- (4-bromomethylthiophenyl) -N'-methyl-N'-methoxyiiarn-

material
N- (3-chloro-4-isopropoxyphenyl) -N'-methyl-N ¹ -methoxyurea

N- (4-Allylphenyl) -N'-methyl-N ¹ -methoxyurea N- (4-allyloxyphenyl) -N ¹ -meühyl-N'-methoxyurestbff N- (3-Pi * opargylphe ny 1) -N '-me ethyl -N '-me thoxyhar ns t off N- (3-trifluoromethylphenyl) -N'-butyl-N'-butoxyurea

N- (4-Bromophenyl) -N'-methyl-N ¹ -ethoxyurea N- (3,4-Mchlorphenyl) -N'-methyl-N ¹ -t-butoxyurea NC 1 -ChlorhenyD-N 1 -dimethyl-N ^1- methoxyurea N- (3-trifluoromethylphenyl) -N-methoxymethyl-N ¹ -methyl-

N ¹ methoxyurea
N- (3-difluorochloromethoxyphenyl) -N-cyclopropyl-N'-

methyl-N'-methoxy urine off
N- (3 » ^/ <-Dichlorophenyl) -N-cyclopropylmethyl-N'-methyl-

N ¹ methoxyurea
N- (3,4-Dichlorphe ny1) -N-cyclohex-1-e nyl-N'-methyl-N'-

methoxyurea
N- (3-methylthio-4-chlorophenyl) -N-ethoxymethyl-N · -

allyl N ¹ methoxyurea
N- (3-chloro-4-methoxyphenyl) -Nn-propyl-N'-methyl-N ¹ -

methoxy urine off
N- (4-isopropylphenyl) -N, N'-diethyl-N'-methoxyurea ff

- 19 -509807/1139

N-O-Pentafluoräthoxypheny ^ -N'-methyl-N'-methoxy-

urea
NO-trifluoromethylthiophenyO-N'-methyl-N'-methoxy-

urea
N- (4-bromophenyl) -Nn-butyl-K'-methyl-N ¹ -methoxy urine-

material
N- (4-t-Butylphenyl) -N-cyclopropylmethyl-N'-iae thyl-N'-

metho'xyurea
N- (2-methyl-4-chlorophenyl) -N-ethyl-N'-methyl-N · -

methoxytia agent
N- (3-Allyl-4-chlorophenyl) -N ^l -allyl-N'-mettioxyliarn-

material
N_ (4-propargylphenyl) -N-propy1-N'-methyl-N'-methoxy-

urea
N- (3, ^ - dichlorophenyl) -N'-isopropenyl-N'-iaethoxyliarn-

material
N- (4-Tr if luormeth.oxyphenyl) -N-methoxyiiie thyl-N'-methyl-

N'-methoxyurea
N- (3-chloro-4 ~ isopropylphenyl) -N, N'-diethyl-N ■ -methoxyurea

N- (4-chlorophenyl) -N'-methyl-N ¹ -ethoxyurea N- (4-chlorophenyl) -N '-methyl -N ¹ -n-propoxyurea N- (4-chlorophenyl) -N'-methyl- N ¹ -n-butoxyurea N- (3,4-D ichlorp.'ae nyl) -N'-methyl -N'-ethoxyurea f N- (3> ^ - dichlorophenyl) -N ¹ -methyl-N ¹ -n-propoxyurea
N- (3, ^ - dichlorophenyl) -N'-methylallyl-N ^I -methoxyurea

N- (4-bromophenyl) -N ^l -allyl-N'-methoxyurea N- (4-bromophenyl) -N'-isopropenyl-N'-methoxyurea N-jf3-chloro-4- (difluorochloromethylthio) phenyl] -N ^I -allyl-

N ¹ methoxyurea
N - ["3-Chloro-4- (aifluorochloromethoxy) phenyl] -N'-allyl-N * -methoxyurea.

- 20 509 807/1139

2A357A7

With regard to their spectra of herbicidal activity and their effectiveness in combination with the dinitroaniline herbicides, the ureas preferably used according to the invention have the formula

10 11 15

wherein R and R are as defined above and R ^ and

14 ·
R individually in each case hydrogen, halogen, C.. -Alkyl,

G * _j ± alkoxy, halomethyl, halomethoxy or halomethylthio mean.

The following examples are intended to illustrate the herbicidal preparations of the invention, but without them to limit it. In each case the formulation was prepared by dissolving the necessary Amounts of aniline and urea in the cyclic ketone and, if used, most of the aromatic Solvent. The solution was then filtered and the emulsifiers previously examined to ensure the absence of free alcohol were stirred in. The rest of the aromatic Solvent was added and the solution was filtered and packaged.

509807/1139 -21-

Tabel

Example no.

W / v%

Dinitro aniline

urea

anionic emulsifier

non-ionic emulsifier

alicycli-

sches

Ketone

aromatic

solvent

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 10 19

A - 407. * - 127. C - 247. E - 257 "H - 367. I - 247. F - 24% A - 247" D - 18% G - 247. B - 12% E - 127. G H - 187. G - 24% H - 247. C - 187o F - 18% A - 24%

J L -K N K M R

K P K

L J P N J L J L

107.

18 ?;

127, 157, 127, 127. 12% 127o 187, 127, 127, 187, 127. 127, 187, 127, 187, 127, 67.

Y - 57.

Y - 6.57.

Y - 2.57.

Y - 47.

Y - 37.

Y - 37.

Y - 37.

Y - 47.

Y - 37.

Y - 37.

Y - 57.

Y - 47.

Y - 37.

Y - 67.

Y - 1> 7.

Y - 47.

Y - 47.

Y - 37,

Y - 37.

Z - 37.

2 Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z

4.57.

47.

3%

47.

47.

47.

37.

37.

37.

47.

37.

17th

37..

47.

4%

5%

3%

Q - 157,
R -to 100%
S - 207.
S - 357.
S - to 1007.
R - 207.
S - 207.
S - 207.
S - 257.
S - 207.
Q - 257.
S - 157.
S - 157.
Q -b »* s 1007.
S - 25%
S - 20%
R - 25%
Q - Ils 100%

S - 10%

T-lis 1007.

U - Us 100%

V - "100%

X - "to 1007.

X - "1007.

U - "1007.

V - ^H 1007.

T -

1007

U - "1007. U -" 100%

V - "1007.

T - tis 1007.

V - "·. 100% T -" 100%

U-Us 100%

50980771 139

- 22 -

Table continued

example
No.

Weight AoI.

Di-

nitro-

aniline

urea

anionic emulsifier

not -

more ionic

Emulsifier

alicycli-

sches

Ketone

aromatic

Solution

nittel

20 21 22 23 24 25 26 27 21

C - 127. - - 247. D - 187. F - 127. B - 18% E - 367. I - 247. G - 247. A - 247.

J - 127.

K - 127o

J -

L - 127.

K - 12%

K - 127.

K - 12%

L - 12%

N - 12%

Y - 4%

Y - 2.5%

Y - 5%

Y -

Y - 4%

Y -

Y - 3%

Y - 4%

Y - 4%

Z - 4% Z - 4.5% Z Z - 3% Z Z - 5% Z - 3% Z - 3% Z - 4%

S - 15% S - 20% R - 20% S - 15% S - 207. Q - 25% S - 20% S - 20% S - 20%

V - "US 100% U - "100% X -" 10U7.

V - "100% T -" 100% X - "100% X - "100% T -" 100% T - π 100%

A »N, N-Dipropyl-4-trifluoromethyl-2,6-dinitroaniline B« N-Ethyl-N-butyl-4-trifluoromethyl-2,6-dinitroaniline C »N, N-DipropyJ.-4-isopropyl -2,6-dinitroaniline D «NjN-Dipropyl-4-methylsalfonyl-2 _t 6-dinitroaniline E * N, K-Dipropyl-4-sulfamoyl-2,6-dinitroaniline F» NjU-diethyl - ^ - triiluorraethyl-i: , 3-phenylenediamine G - N-ethyl-I ^ -methylallyl - ^ - trifluoromethyl ^ e-di-

nitroaniline H - M

aniline

N, N-di (2,2-dichloroethyl) -2,6-dinitro-p-toluidine N- (4-chlorophenyl) -N * -methyl-N'-methoxyharnsiaff

509807/1139 COPY

K = li - ($ ₁ 4-dichlorophenyl) -N'-methyl-N ^I -mettioxyur-

material
L = NC ^ -E ^ omphenyO-N'-methyl-N'-methoxyurea M = N- (3-trifluoromethylphenyl) -N'-methyl-N'-methoxy-

urea
N = N- (3-chloro-4-difluorochloromethoxyph .enyl) -N ^I -

methyl-N'-methoxyurea
P = N- (3, ^ - I ⁾ chlorophenyl) -l ( ¹ -2-niethylallyl-N ^I -

methoxyurea
Q = cyclohexanone
R = 3-methylcyclohexanone
S = ■ 3,5,5-triniethylcyclohex-2-en-1-one T = mixture of alkylbenzenes, sold under

Trade name Solvesso
U = xylene

V = o-chlorotoluene

X «heavy aromatic naphtha

Y - alkyl aryl sulfonate

Z - polyoxyethylene sorbitan ester of mixed fatty and resin acids.

Any of the above formulations or The preparation is physically and chemically stable and can be easily diluted with water before use will. The dilution amounts are generally in the order of ■ 1 liter of that given above emulsifiable concentrate in 150 to 500 liters of water and the diluted solution is usually applied in an amount of 1 to 10 1 concentrate per hectare, it however, quantities outside this range can also be used, depending on the fruit to be protected, the type of soil, the type of weeds to be controlled, and the particular one used

509807/1139
COPY

active ingredient.

It has been found that the herbicidal preparations of the invention are particularly useful for application to the soil surface before emergence (ie before the weeds emerge, but before
or after the fruits have risen) for grain,
Peas, beans, alfalfa, clover, potatoes, tomatoes, pepper, artichokes, asparagus, carrots, parsnips and similar fruits. The preparations are also suitable as herbicides for the abovementioned fruits, except for cereals and nightshades, which are incorporated into the soil before the plant.

509807/1139 -25

Claims (1)

Claims rf) Stable, liquid preparation with herbicidal effect, characterized in that it contains a dinitroaniline herbicide and an N-aryl-N'-alkoxyurea herbicide, dissolved in a non-phytotoxic alicyclic ketone, containing the ratio from dinitroaniline to urea is 4: 1 to 1: 4. 2. Preparation according to claim 1, characterized in that that it also contains a nonionic or anionic emulsifier. 3. Preparation according to claim 1 or 2, characterized in that it is used as a dinitroaniline herbicide contains a compound of the formula (D wherein R is hydrogen or -NHp »R Halogen, cyano, Sulfamoyl, C. _1. -Alkoxy, C., -haloalkyl or ι - ^ ^ '5
onyl, R and R singly each represents hydrogen, Cj ^ alkyl, C ₆ alkenyl, Cg alkynyl, C ^ _ ^ - haloalkyl, C _2- ^ alkoxyalkyl, C, - C ^ ^ Haiοgenalkenyl or cycloalkylalkyl mean, where 4 pp 4th
at least one of the radicals R and another Has meaning as that of hydrogen, or 509807/1 139 - 26 - / J. C. R and R ^ together with the neighboring nitrogen atom mean pyrrolidino or piperidino . 4. Preparation according to claim 3, characterized in that it is used as dinitroaniline herbicide N.N-dipropyl-4-trifluoromethyl-2,6-dinitroaniline, N-ethyl-N-2-methylallyl-4-trifluoromethyl-2,6-dinitroaniline or contains N, N-dipropyl-4-sulf-amoyl-2,6-dinitroaniline. 5. Preparation according to one of claims 1 to 4, characterized in that it is used as a urea herbicide an N-aryl-N'-alkoxyurea of the formula contains R ¹⁰ wherein R ^IU 0 _Λ , .- alkyl or C _0. -alkenyl, R ¹ 'C ₁ .- Λ% 14
Alkyl and R '■ -' and R individually each hydrogen, Halogen, C ^ _ ^ - alkyl, G ^ _ ^ - alkoxy, halomethyl, Mean halomethoxy or halomethylthio. 6. Preparation according to A.is claim 5 »characterized in that it contains as urea herbicide N-0,4-dichlorophenyl) -N'-methyl-N ^< -methoxyurea. 7. Stable liquid preparation with herbicizing effect, characterized in that it contains N, N-dipropyl 4-trifluoromethyl-2,6-jinitroaniline and the like 509807/1139 -27- N- (3,4-dichlorophenyl) -N'-methyl-N'-methoxyurea, dissolved in J ^^ - trimethylcyclohex-a-en-ion, contains, wherein the ratio of dinitroaniline to urea is 4: 1 to 1: 4-, and that it also contains an emulsifier, which is a mixture of polyoxyethylene sorbitan esters of mixed fatty and resin acids and an alkylarylsulfonate, in which the emulsifier is practically free of alcohol or polyalcohol contamination. 8. A process for the production of a stable, liquid preparation with herbicidal action according to claims 1 to 7 »characterized in that one dinitroaniline herbicide and an N-aryl-N ¹ -alkoxyurea herbicide in a non-phytotoxic alicyclic ketone in a ratio of dinitroaniline to Dissolves urea from 4: 1 to 1: 4-. 9. The method according to claim 8, characterized in that the active ingredients in the liquid herbicidal preparation used in a concentration of 10 to 60% w / v. 10. The method according to claim 8 or 9 »characterized in that in the mixture of" the Herbiciden and deii ketone also uses a nonionic or anionic emulsifier, free
which is practically free from / alcohol or polye alcohol. is. 11. The method according to claims 8 to 10, characterized in that there is a dinitroniline herbicide 509807/1139 the formula used (D 16 4- 5 wherein R ₁ B ₁ R and R- ^ have the meanings given in claim 3. 12. The method according to claim 11, characterized in that as dinitioaniline herbicide N ₁ N-dipropyl-4-trifluoromethyl-2,6-dinitroaniline, N-ethyl-N ^ -methylallyl ^ -trifluoromethyl ^^ - dinitroaniline or NjN-dipropyl- 4 · -sulfamoyl-2,6-dinitroaniline used. 13-. Process according to one of Claims 8 to 12, characterized in that the urea herbicide used is an N-aryl-N'-alkoxyurea of the formula
Used (III) 1Γ) 11 1 ^ 1/1 wherein R ₁ R ¹¹ , R ^{i ;?} and R ¹ ^ have the meanings given in claim 5. Process according to Claim 13, characterized in that the N-aryl-N'-alkoxyurea . - 29 - 50 9 807/1 139 N- (3,4-dichlorophenyl) -N'-methy 1-N'-methoxyurea used. 15. The method according to any one of claims 8 to 14, characterized characterized in that a cycloalkyl or cycloalkenyl ketone is used as the alicyclisch.es ketone. 16. The method according to claim 15 »characterized in that that the alicyclic ketone used is cyclohexanone or 3,5 »5-trimethylcyclohex-2-en-1-one. 17. Process for the production of a stable, liquid preparation with herbicidal action, characterized in that N, N-dipropyl-4-trifluoromethyl-2,6-dinitroaniline and N- (3,4-dichbrphenyl) -N'-methyl- Dissolves N'-methoxyurea in a ratio of dinitroaniline to urea of 4: 1 to 1: 4 in 3 ₁ 5 »5-trimethylcyclohex-2-en-1 ^ one and uses an emulsifier which is a mixture of polyoxyethylene sorbitan esters of mixed fat and represents resin acids and an alkylaryl sulfate which is substantially free of alcohol or polyalcohol impurities. 509807/1139