NO781931L - DIURETANE WITH HERBICID EFFECT - Google Patents

Abstract

"Diuretic with herbicidal effect"

Description

The present invention relates to new valuable sulphur-containing diurethanes with excellent herbicidal action, which can be used to combat unwanted plant growth.

It is known to use methyl N- (3-(N1 - (3 '-methylphenyl-carbamoyloxy))phenyl)-carbamate, ethyl-N-(3-(N1-phenylcarbamoyloxy)phenyl)-carbamate, methyl-N -(3-(N'-methyl-N<1->phenylcarbamoyloxy)-phenyl)-

carbamate (DT-AS 15 67 151) or 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide (DT-AS 15 42 836) as herbicides.

It has now been found that the new diurethanes with it

general formula

where

Z means the rest

and Y means the rest

since Z is always different from Y,

etc. c2

and R and R

is independent of

each other hydrogen, alkyl (e.g. methyl, ethyl, isopropyl), alkoxyalkyl (e.g. methoxymethyl, 2-methoxyethyl), alkoxycarbonylalkyl (e.g. methoxycarbonylmethyl), haloalkyl (e.g. chloromethyl) or optionally with alkyl or halogen substituted benzyl, R 3 and R 4 are independently unsubstituted alkyl or med

halogen or alkoxy or alkoxycarbonyl or substituted or unsubstituted aryl substituted alkyl (e.g. methyl, ethyl, 2-chloroethyl, 2-methoxyethyl, methoxycarbonylmethyl, benzyl, isopropyl, n-propyl, 4-chlorobenzyl, n-butyl, sec.butyl , tert.butyl, isobutyl, 2,4-dichlorobenzyl, 2-ethylhexyl, n-decyl, 2-phenylethyl), or optionally with halogen-substituted alkenyl (e.g. allyl, 2-chloro-propen(l)yl(3), buten (1) yl ( 3 ), 2,3-dichloroallyl, 3,3-dichloro-2-methyl-allyl), or optionally with halogen or alkoxy substituted alkynyl (e.g. propargyl, butyn(1)yl (3 ), 1-chlorobutyn (2)yl (4))

or optionally with alkyl substituted cycloalkyl (e.g. cyclopentyl, cyclohexyl, 3-methylcyclohexyl, 2,6-dimethylcyclohexyl, cycloheptyl, 4-tert.butylcyclohexyl, cyclooctyl, cyclododecyl, 3.5-dimethylcyclohexyl) or bicycloalkyl (e.g. norbornyl)

or tricycloalkyl (e.g. tricyclo(4,3,1, ' 0 ' )-decyl),

a phenyl radical with a condensed ring system (e.g. naphthyl or indyl), phenyl or a singly or polysubstituted phenyl radical with the substituents alkyl, haloalkyl, alkoxyalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkoxycarbonyl-alkoxy, nitro, amino, aryl, aryloxy , thiocyanato, cyano,

(e.g. phenyl, 4-fluorophenyl, 2-methoxyphenyl, 3-methylphenyl, 2-fluorophenyl, 3-methyl-5-isopropylphenyl, 3-ethylphenyl, 3-chlorophenyl, 2,4,6-trimethylphenyl, 3-fluorophenyl , 3-chloro-4-fluorophenyl, 3,4-dimethylphenyl, 3-trifluoromethylphenyl, 4-methylphenyl, 3,4-difluorophenyl, 3-chloro-4-methylphenyl, 3-bromophenyl, 4-iodophenyl, 4-chlorophenyl, 2 -chlorophenyl, 3-N,N-dimethylaminophenyl, 2-chloro-4-fluorophenyl, 3-isopropylphenyl, 4-ethylphenyl, 3-methoxycarbonylaminophenyl, 4-ethoxyphenyl, 2-methylphenyl, 3-methoxyphenyl, 4-cyanophenyl, 2,6 -dimethylphenyl, 2,4-dichlorophenyl, 3-methyl-4-chlorophenyl, 2-trifluoromethylphenyl, 2,4-dibromophenyl1, 4-trifluoromethylphenyl, 4-methoxyphenyl, 3-(l<1->ethoxycarbonylethoxy)-phenyl), 2 . 2,3-dimethylphenyl, 2-methyl-4-chlorophenyl, 2,4,5-trichlorophenyl, 2,3,6-trichlorophenyl, 5 6 . p-chlorophenoxy-phenyl), where R and R independently of each other mean hydrogen or a possibly single or polysubstituted aryl radical,

or one of the two substituents has the meanings given for R, X means hydrogen, alkyl (e.g. methyl), haloalkyl (e.g. trifluoromethyl), alkoxy (e.g. methoxy), halogen (e.g. e.g. fluorine, chlorine, bromine or iodine), nitro or amino, n means the numbers 1 to 4, and A, B, D and E independently mean oxygen or sulphur, not all the residues A, B, D and E at the same time can mean oxygen,

and at least one of these residues always means sulphur,

has a good herbicidal effect against numerous important unwanted plants and at the same time a good compatibility with many cultivated plants. These effects are better than the effects of the known active substances.

The new connections can e.g. are prepared by the following methods, where the residues A, B, D, E, R, R 1 , R , R , R 4 , X and n have the meanings given above. When in the following reference is made to urethanes and chloroformic acid esters, these two collective terms shall also be understood to include thiono-, thio- and dithio-urethanes in addition to chloroformic acid thioesters, chloroformic acid thioesters and chloroformic acid redithioesters.

The reaction scheme clearly shows the mutual dependence between the starting substances. Furthermore, it is clear that depending on the nature of the substituents A, B, D, E, R , R , R 3 , R

and X and the availability of the relevant reaction components,

can be beneficial one way or the other. The turnover from F to H is preferred.

Starting from known meta-nitranilines (A), meta-nitrophenyliso(thio)cyanates (1) can be prepared (W. Siefken,

J. Liebigs Annalen der Chemie, 562, 75 ff, (1949)), which in turn react smoothly with the components R 3-BH to the nitro(thio)urethanes ( Q)

(S. Petersen in Methoden der Organ. Chemie, volume VIII, page 131, Georg, Thieme-Verlag, Stuttgart, 4th edition (1952)), which can of course also be prepared directly from the meta-nitranilines (A) with chloroformate esters (R 3 B-CA-C1) (DT-OS 16 4 3 763) or with carbon disulfide or carbonoxysulfide, base and alkylating agent

(Methoden der Organischen Chemie, volume IX, page 831 ff, Georg Thieme-Verlag, Stuttgart, 4th edition, 1955). Subsequent reduction leads to the amino compounds (F, R 2=H) (S. Schroter in Methoden

der Organischen Chemie, volume XI/1, page 360 ff., Georg Thieme-Verlag, Stuttgart, 4th edition, 1957), as either directly or

after subsequent conversion to the product which is monosubstituted

on the amino nitrogen (F, R 2=H) (Methoden der Organischen Chemie,

volume XI/1, page 24 ff., Georg, Thieme-Verlag, Stuttgart, 4th edition 1957), react with chloroformic acid esters (R<4>D-CE-C1) (DT-OS 16 43 763) or with carbon disulphide resp. . carbonoxysulfide, base and alkylating agent; (Methoden der Organischen Chemie, volume IX, page 831 ff, Georg-Thieme-Verlag, Stuttgart, 4th edition, 1955) to the desired diuretans (g) . However, the aminourethanes F_ can also be prepared by reacting meta-phenylenediamines (p) with chloroformate esters.

A further synthesis option consists in reacting aryl-1,3-diiso(thio)cyanates (E) with only one mole of the component R 3-BH,

leading to the iso (thio)cyanatoureethanes ( Q) (J.A. Parker, J.J. Thomas and CL. Zeise, J. Org. Chem. 22y 594 to 596 (1957)), which also

can be prepared by (thio)phosgenation of the aminourethanes (F_)

(DT-OS 19 14 270, page 5, example 8). Subsequent turnover with the components R 4DH leads to the desired end products. In principle, it should be noted that the order of -CABR<3>resp. -CEDR<4->groupings are arbitrary.

In the following, the preferred synthesis routes will be described in more detail:

a) The turnover of 3-nitrophenyliso(thio)cyanatene (B)

occurs with or without a catalyst suitable for iso(thio)cyanate reactions, e.g. tertiary amines (triethylamine, 1,4-diaza-bicyclo[2.2.2]octane), nitrogen-containing heterocyclic compounds (pyridine, 1,2-dimethylimidazole) or organic tin compounds (dibutyltin diacetate, dimethyltin dichloride), optionally in a solvent that is inert under the reaction conditions, e.g. hydrocarbons (naphtha, petrol, toluene, pentane, cyclohexane), halogenated hydrocarbons (methylene chloride, chloroform, dichloroethane, chlorobenzene, o-, m- or p-dichlorobenzene), nitrohydrocarbons (nitrobenzene, nitromethane), nitriles (acetonitrile, butyronitrile, benzonitrile), ethers (diethyl ether, tetrahydrofuran, dioxane),

esters (acetic acid ethyl ester, propionic acid methyl ester), ketones (acetone, methyl ethyl ketone) or amides (dimethylformamide, formamide)

(DT-OS 15 68 138) at temperatures in the range from 0 to 150°C, preferably in the range from 40 to 100°C.

b) 3-nitranilines (A) are reacted with chloroformate esters in a suitable solvent, e.g. water, alcohols (methanol, ethanol, isopropanol) or as stated under a), with the addition of a common acid-binding agent, e.g. alkali hydroxides, carbonates, hydrogen carbonates, alkaline earth oxides, hydroxides,

-carbonates, -hydrogen carbonates, tertiary organic bases

(e.g. triethylamine, pyridine, N,N-dimethylaniline, N,N-dimethylcyclohexylamine, quinoline, tributylamine) or the starting product 3-nitraniline, at temperatures from -20 to 150°C, preferably in the range from 20 to 80 °C.

c) The reduction of the nitrourethanes (C) can be carried out according to a known method, e.g. by catalytic

hydrogenation, using a metal-acid combination, e.g. an iron-acid combination, using a metal-alcohol combination, e.g. zinc dust-aqueous alcohol, iron-aqueous alcohol.

d) For the turnover of m-phenylenediamines (D) similar conditions apply as for b), although it may, however, be

advantageous to work with an excess of m-phenylenediamines.

e) The reaction of the aminourethanes F with chloroformate esters is carried out analogously to b), as one can also use directly the solution obtained, e.g. by catalytic hydrogenation of the nitrourethanes C without further purification.

The following examples shall illustrate the preparation

of the new diurethanes and their precursors:

I. Nitrourethanes

Example A

A resolution of. 64.3 parts by weight of 4-chlorophenol and 3 parts by weight of triethylamine in 4 30 parts by weight of toluene (absolute) were added with stirring at 20 to 25°C to a mixture of 85 parts by weight of 3-nitrophenyl isocyanate and 43 parts by weight of toluene (absolute).

To complete the reaction, stirring was continued for 1 hour at room temperature. After cooling to 0°C, the reaction product was filtered off: mp. 137-138°C.

The compound has the following structural formula:

Example B

87 parts by weight of sodium bicarbonate are added to 138 parts by weight of m-nitraniline in 500 parts by weight of tetrahydrofuran (THF). While stirring, 120 parts by weight of chloroformic acid thiomethyl ester are added dropwise at room temperature, stirred for 16 hours at room temperature, filtered, the solvent is distilled off on a rotary evaporator and the resulting oil is stirred into toluene. The separated crystals are suctioned off and dried: mp. 137-138°C.

The compound has the following structural formula:

Example C

17.4 parts by weight of sodium bicarbonate are added to 26 parts by weight of 3-nitro-N-methylaniline in 320 parts by weight of acetic acid ethyl ester. While stirring, 3 parts by weight of chloroformic acid-m-tolyl ester are slowly added, stirred for 20 hours at room temperature, filtered, the solvent is evaporated in vacuo and the remaining residue is recrystallized from toluene/cyclohexane.

M.p..114-116°C.

The compound has the following structural formula:

By similar methods, the following nitrourethanes (C) can be produced:

II. Aminourethanes

Example D

A solution of 135 parts by weight of N-(3-nitrophenyl)carbamic acid-4-chlorophenyl ester in 900 parts by weight of tetrahydrofuran (absolute) was added with 3 parts of hydrogenation catalyst (palladium-on-bone charcoal, 10%) and hydrogenated at room temperature and 0.02 bar t^ pressure to constant pressure. For work-up, the solution, which had been freed of catalyst and dried with MgSO 4 , was freed of so much solvent that the crystalline reaction product could be well filtered off: 186-187°C.

Structure:

Example E

To a solution of 108 parts by weight of m-phenylenediamine

in 1000 parts by weight of water, 25.2 parts by weight of chloroformic acid phenyl ester were added drop by drop very slowly under intense stirring. After completion of the reaction, the reaction mixture was subjected to suction, the solid was washed several times with dilute hydrochloric acid, the combined acidic solutions were neutralized with ammonia and suctioned off. The dried product thus obtained melts at 178 to 180°C during decomposition.

Structure:

Example F

To 51 parts by weight of 2,4-diaminonitrobenzene and 43 parts by weight of sodium hydrogen carbonate in 600 parts by weight of tetrahydrofuran, 52.1 parts by weight of chloroformic acid phenyl ester are slowly added dropwise under intense stirring. After 14 hours of stirring, filtration and post-washing with tetrahydrofuran is carried out. The solution is freed from so much solvent that the crystalline crude product can be easily suctioned off, and after washing with diethyl ether and drying, the product melts at 223-225°C. According to the NMR spectrum and elemental analysis, it has the following structure:

Example G

To a mixture heated to 80°C of 33 parts by weight of iron powder, 75 parts by weight of alcohol, 60 parts by weight of water and 3 parts by weight of concentrated hydrochloric acid, 40 parts by weight of 3-(S-methylthiocarbamoyl)-nitrobenzene are added under intense stirring in such portions that the temperature without further heating is maintained at 80°C. It is then boiled for a further 1 hour under reflux, the reaction mixture is filtered off while still hot, the residue and the filtrate are washed with approx. 1000 parts by weight of methylene chloride, dry over sodium sulphate, evaporate and recrystallize from toluene, m.p. 101-103°C. Structure:

According to corresponding methods, the following aminourethanes (g) can be prepared:

III. Diurethans

Example 1

To a solution of 22.8 parts by weight of N-(3-aminophenyl)carbamic acid phenyl ester in 200 parts by weight of tetrahydrofuran (absolute) was added 11 parts by weight of sodium bicarbonate and then at 20 to 25°C under cooling added 13.3 parts by weight of chloroformate thiomethyl ester.

To complete the reaction, stirring was carried out for 1 hour at room temperature. The reaction mixture was then filtered, and the filtrate evaporated in vacuo. The oily residue was brought to crystallisation by the addition of toluene.

Sm.p. 155-157°C (No. 1). The connection has the following structure:

Example 2

A mixture of 20 parts by weight of N-(3-isothiocyanatophenyl)-O-methylcarbamate (which can be prepared from N-(3-aminophenyl)-O-methyl-carbamate and thiophosgeh, m.p. 99-100°C), 20 parts by weight methanol, 3 parts by weight of triethylamine and 150 parts by weight of toluene are heated for 6 hours to boiling. After evaporation, it is recrystallized from toluene: mp. 147-149°C (No. 2).

The compound has the following structural formula:

Example 3

To a solution of 16.6 parts by weight of N-(3-aminophenyl)-0-methylurethane and 10.1 parts by weight of triethylamine in 300 parts by weight of diethyl ether, 10 parts by weight of carbon disulfide are added dropwise at room temperature. After stirring for 20 hours, suction is carried out, the residue is suspended in 120 parts by weight of water and 9.1 parts by volume of diethyl sulphate are added while stirring. After stirring for 20 hours, suction is carried out, washing with water and drying in air: mp. 122-124°C (No. 3) .

The compound has the following structural formula:

For the following experiments, known herbicidal substances were used as a comparison. Methyl N-(3-(N<1->(3<1->methylphenyl-carbamoyloxy)-phenyl)-carbamate and ethyl-N-(3-(N'-phenylcarbamoyloxy)-phenyl)-carbamate ( DT-AS 15 67 151) is distinguished by its, albeit different, action against broad-leaved unwanted plants with a significant degree of compatibility with sugar beet. Here, however, there are, as is known, differences, as methyl-N-(3-(N1 - (3 '-methylphenylcarbamoyloxy)phenyl)-carbamate exhibits a more favorable selectivity in this culture than the other above-mentioned compound of this type. A completely different area of application has 3 -isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide (DT-AS 15 42 836).

With this compound, various broad-leaved weeds are combated

in soybeans, peanuts, grains, corn and some vegetables.

Here, however, there are also missing effects. Methyl-N-(3-(N'— methyl-N'-phenyl-carbamoyloxy)-phenyl)-carbamate, with a good herbicidal effect for its class, shows hardly any crop plant selectivity, which is why the compound e.g. for soy is only recommended for underleaf spraying (Arndt, F. and G. Boroschewsky: New Selective Herbicides VIII International Plant Protection Congress, Reports. and Information, Section III Chemical Control, Part I, Moscow 19 75,

pp. 42-49). Below this, the young shoots and leaves of the cultivated plants must not be hit by the spray liquid, but only unwanted plants that are located below them.

Examples of herbicidal action of new sulphur-containing diurethans

Numerous experimental results prove the good herbicidal properties of the new compounds. They are classified with regard to their herbicidal activity and their selectivity towards cultivated plants on the basis of the biological effect in the following tests:

Greenhouse experiment

Plastic flowerpots with a content of 300 cm 3 were filled with clayey sand, and the experimental plants were placed in these separated by species. This is mainly about sowing seeds or also about planting in the case of species that reproduce vegetatively.

The active substances were suspended or emulsified in water as a distribution agent and were sprayed with the aid of fine-distributing nozzles in increasing amounts on the leaves of the test plants or only on the bare soil surface. For the leaf treatment, the plants were used as appropriate

growth form in the experimental containers only when they had reached a height

of 3-10 cm, and then treated them. The temperature requirements of the trial plants were naturally met by placing them in colder or warmer parts of the greenhouse facilities. The trial period lasted

2-4 weeks. During this time, the plants were cared for, and their reaction to the individual treatments was assessed. The amounts of the test compounds used are indicated as kg/ha of active substance. For the assessment, a grading scale from 0 to 100 was used. Here 0 means: no damage, 100: the plants died.

Results

The figures in the following tables illustrate the effect of the active substances in foliar treatment after germination of cultivated plants and unwanted plants (tables 2 to 12). It should be noted here that the new compounds with regard to herbicidal activity

and spectrum of action approaches the diurethanes used as comparators. However, the focal points in the selectivity for cultivated plants are different. It is possible, e.g. well illustrated on soybeans and cereals. On these cultures, degrees of compatibility are obtained which are equivalent to what is obtained with the 3-isopropyl-2,1,3-benzothiadiazinone(4)-2,2-dioxide known for the same purpose (tables 5, 6). In addition, a number of cultivated plants exist which have an excellent tolerance towards the new compounds, while the investigated comparative agents are unsuitable (tables 2, 4, 5).

Introduction can be used as an application method

in the soil or treatment of the soil surface, but treatment of plants that have emerged is preferred. Special applications such as underleaf spraying (post directed, lay-by) are also considered. Below this, the spray jet is directed so that the leaves of sensitive cultivated plants that have come up are not hit as far as possible, while the agent, on the other hand, hits the underlying soil surface and the unwanted plants that grow there.

Considering all the possible application methods can

the new compounds and mixtures containing these, besides on

the useful plants indicated in the table are also used on a number of other cultures to combat unwanted plant growth. The application concentrations can be from 0.1 to 15 kg/ha and more, depending on the object being combated.

The following beneficial plants must be mentioned separately:

To further expand the spectrum of action of the new individual compounds, to achieve a synergistic effect or to improve the remaining effect on the soil, the new compounds can be mixed with each other, or numerous other herbicides or growth-regulating compounds can be used as mixing and combination partners. Depending on the area of application and control plan, the following compounds or chemically similar derivatives can be used as partners:

Moreover, it is possible to use the new compounds alone or in combination with other herbicides and also with other plant protection agents. It is relevant here to use agents for combating harmful organisms or phytopathogenic fungi or bacteria. Also of interest is the mixability with mineral salt solutions, which can be used to remedy nutritional and trace element deficiencies.

To activate the herbicidal effect, wetting agents and adhesives as well as non-phytotoxic oils can be used.

The application takes place e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusting agents, streamers, granules, by spraying, fogging, atomizing, scattering or pouring. The forms of application depend entirely on the purpose, but they should in any case lead to as fine a distribution of the new compounds as possible.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, e.g. mineral oil fractions with medium to high boiling points, such as kerosene or diesel oil, are used. also coal tar oils, etc., oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydro-naphthalene, alkylated naphthalenes or derivatives thereof, e.g.

methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., strongly polar solvents, e.g. dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc.

Aqueous application forms can. prepared from emulsion concentrates, pastes or wettable powders (spray powders),

and oil dispersions by adding water. For the production of emulsions, pastes or oil dispersions, the compounds as such or dissolved in an oil or a solvent can be homogenised with the aid of wetting, binding, dispersing or emulsifying agents in water. However, it is also possible to prepare concentrates consisting of active substance, wetting, binding, dispersing or emulsifying agents and possibly solvents or oil, which are suitable for dilution with water.

The following can be mentioned as surfactants:

Alkali, alkaline earth, ammonium salts of ligninsulfonic acid, naphthalenesulfonic acid, phenolsulfonic acids, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, alkali and alkaline earth salts of dibutyl naphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, fatty acid alkali and alkaline earth salts, salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulphated fatty alcohol-glycol ether, condensation products of sulphonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene resp. naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl glycol ether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulphite liquor and methyl cellulose.

Powders, dusting and dusting agents can be produced by mixing or by grinding the active substances together with a solid carrier.

Granules, e.g. coating, impregnation and homogeneous granules, can be produced by binding the active substances to solid carriers. Solid carriers are e.g. mineral soil such as silica gel, silicic acid, silica gels, silicates, talc, kaolin, attapulgite clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground synthetic substances, fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea and plant products such as grain flour, bark, tree and nut shell flour, cellulose powder and other solid carriers.

The preparations contain between 0.1 and 95% by weight of active substance, preferably between 0.5 and 90% by weight.

Example 4

90 parts by weight of compound 2 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a solution is obtained which is suitable for use in the form of the smallest droplets.

Example 5

20 parts by weight of compound 8 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight

of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

Example 6

20 parts by weight of compound 13 are dissolved in a mixture consisting of 40 parts by weight cyclohexanone, 30 parts by weight isobutanol,

20 parts by weight of the addition product of 7 moles of ethylene oxide to

1 mole of isooctylphenol, and 10 parts by weight of the addition product of

40 mol ethylene oxide to 1 mol castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

Example 7

20 parts by weight of compound 2 3 are dissolved in a mixture

which consists of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280°C, and 10 parts by weight

of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water

an aqueous dispersion containing 0.02% by weight of the active substance is obtained.

Example 8

20 parts by weight of compound 7 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid from a sulphite leachate, and 60 parts by weight of powdered silicic acid rule, and the whole is ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquid containing 0.1% by weight of the active substance is obtained.

Example 9

3 parts by weight of compound 46 are mixed well with 9 7 parts by weight of finely divided kaolin. In this way, a dusting agent is obtained which contains 3% by weight of the active substance.

Example 10

30 parts by weight of compound 2 are mixed well with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, a preparation of the active substance with good adhesion is obtained.

Example 11

40 parts by weight of compound 7 are mixed well with 10 parts sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts silica gel and 48 parts water. A stable, aqueous dispersion is obtained. When diluted with 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.04% by weight of active substance.

Example 12

20 parts of compound 8 are mixed well with 2 parts calcium salt of dodecylbenzenesulfonic acid, 8 parts fatty alcohol-polyglycol ether, 2 parts sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable, oily dispersion is obtained.

Claims (1)

Diurethane with herbicidal effect, characterized in that it has the formula: where Z means the remainder ■ and Y means the residue where Z is always different from Y, and R and R2 are independently of each other hydrogen, alkyl, alkoxyalkyl, alkoxycarbonylalkyl, haloalkyl, optionally with alkyl or halogen substituted benzyl, 3 4 R and R are independently of one another unsubstituted alkyl or with halogen or alkoxy or substituted or unsubstituted aryl substituted alkyl; optionally halogen-substituted alkenyl, optionally halogen- or alkoxy-substituted alkynyl; optionally with alkyl substituted cycloalkyl; bicycloalkyl; tricycloalkyl; a phenyl ring with a fused ring system, phenyl, mono- or polysubstituted phenyl, with the substituents alkyl, haloalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkyloxy, cycloalkyl, halogen, alkoxy, haloalkoxy, nitro, amino, aryl, aryloxy, thiocyanato, cyano, NH-COR5, NHCOOR <5> , NHCONR5R6, COOR <5> , CONR5R6, SR5, S02 R <5> , OSC^ R <5> , COR <5> , S02 NR <5> R <6> , where R5 and R6 independently of each other means hydrogen or an optionally singly or polysubstituted aryl residue, or one of the two substituents has the meanings indicated for R" <*> "; and X means hydrogen, alkyl, haloalkyl, alkoxy, halogen, nitro or amino, n means the numbers 1 to 4, and A, B, D and E independently mean oxygen or sulphur, not all the residues A, B, D and E at the same time means oxygen, and at least one of these residues always means sulphur,