HU177166B - Herbicide composition containing isoxasolyl-methyl-thiocarbamates and process for producing isoxasolyl-methyl-thiolcarbamates - Google Patents

Abstract

Novel isoxazolylmethyl thiocarbamates of the formula I are used for controlling undesired plant growth either by themselves or together with a carrier. The symbols in formula I have the meaning given in Patent Claim 1. <IMAGE>

Description

FIELD OF THE INVENTION The present invention relates to herbicides containing isoxazolylmethylthiolcarbamates and to a process for the preparation of novel isoxazolylmethylthiolcarbamates.

It is known from French Patent No. 2,205,514 that the thiolcarbamic acid ester of imidazole is useful as an herbicide. Nothing is said about the nature of the herbicide, such as selectivity or tolerance of the crop, and the amount to be used, and the herbicidal effect is low.

Many thiolcarbamate derivatives are used as herbicides. Some of these are of great importance in agricultural and horticultural practice for controlling unwanted plants. These agents generally have good activity against weeds. However, their effects are different for some species of this plant family. Thus, helix oat can be excreted with an agent containing N, N-dipropyl-S-ethylthiolcarbamate (German Patent Publication No. 1,031,571), whereas the agent containing N, N-dipropyl-S-propylthiolcarbamate is not recommended by this manufacturer. disinfected. The NJM-dipropyl-S-ethyl-thiolcarbamate agent is a good agent for Setaria spp. but is ineffective in containing N, N-di (isopropyl) -S- (2,3-dichloroallyl) -thiolcarbamate (German Patent Publication No. 1,142-464). In addition to weeds, this group of agents can kill Cyperaceae species and some broadleaf weeds. For example, grains containing N, N-dipropyl-S-propyl-thiolcarbamate contain Cyperus spp. has excellent activity, but the agent containing 5 N, N-di (isopropyl) -S- (2,3-dichloroallyl) thiolcarbamate is practically inactive against this species. An important condition for the use of a herbicide containing said compounds is the difference in the selectivity of each crop plant 10. For example, the agent containing N-ethyl-N-cyclohexyl-S-ethyl-thiolcarbamate is mainly used in beet plantations (British Patent No. 995,316). The most important use of the N, N-di (isobutyl) -S-ethylthiolcarbamate-containing agent is in weed control of maize (German Patent Publication No. 1031 571). N, N-di (isopropyl) -S- (2,3-dichloroallyl) -thiolcarbamate and N, N-di (isopropyl) -S- (2,3,3-trichloroallyl) are extremely surprising. difference between an agent containing thiol-carba20 (German Patent Publication No. 1,142,464). Both agents can be used without difficulty in broadleaf plantations such as beet and rape weeds. However, for cereals, only an agent containing N, N-di (isopropyl) -S- (2,3,3-trichloroallyl) thiolcarbamate is recommended as it is less aggressive.

Known thiol carbamates generally have high vapor pressures, as shown in the following table:

agent Vapor pressure, Pa C N, N-dipropyl-S-ethyl-thiolcarbamate 4.53 25 N, N-di (isobutyl) -S-ethylthiol carbamate 1.73 25 N, N-dipropyl-S-propyl-thiolcarbamate 1.39 25 N-ethyl-N-cyclohexyl-S-ethylthiol carbamate 0.83 25 N, N -di (isopropyl) -S- (2,3-dichloroallyl) thiolcarbamate 0.20 25 N -di (isopropyl) -S- (2,3,3-trichloroallyl) thiolcarbamate 0.16 25 Hexahydro-lH-azepine-1-thiourea-acid S-ethyl ester 0.75 25

(German Patent No. 1,300,947).

All these active ingredients must be well incorporated into the soil to avoid evaporation losses. For the last compound, in addition to good incorporation, the water in the paddy fields also needs to be swelled.

Although the use of herbicides is generally considered to be advantageous for a number of reasons, there are significant drawbacks to this application. Such drawbacks include labor-intensive work and the purchase of special machinery for work. This is particularly detrimental to less mechanized farms. The soil in the seedbed is loosened too much, which makes it difficult for some seeds to hatch in the event of drought. In areas with a high risk of thunderstorms, excessive soil preparation increases the risk of erosion. In windy and dry areas, loosened soil is carried away by the wind. For these reasons, efforts are being made to reduce tillage to a minimum.

Therefore, they are looking for pesticides with different uses. Because of their specific properties, they have not yet been found in the field of lolycarbanates with the exception of the S-ethyl ester of hexahydro-1H-azepine-1-thiocarbamic acid in rice and S- (4-chlorobenzyl) -N, N-diethylthiolcarbamate. Recently, research has focused on the production of thiolcarbamate sulfoxides.

We have found that herbicides containing isoxazolylmethylthiolcarbamates of the formula I have potent herbicidal activity and are selective. In the formula (I), R ^{1 is a C} 1-6 alkyl group,

R ^{2 is} hydrogen or halogen,

R ^{3 and} R ^{4 are} hydrogen or C 1-4 alkyl; and

R ^s or R ⁶ are independently C 1-6 alkyl, C 3-7 cycloalkyl, (1-4C) alkoxy (Cl-C4) -alkyl residues, or ^R5 and ^R6 together are no more than three, one C3-6 alkylene substituted with C4 alkyl.

The process of the invention also relates to the preparation of compounds of formula I wherein, in addition to the above, R ^{1 is} hydrogen or phenyl optionally substituted with up to 5 halogen atoms, R ⁵ and R ^{6 are C} 2 -C ⁶ alkenyl.

Some examples of isoxazolylmethylthiolcarbamates of formula (I) include:

^R1 is hydrogen, up to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl, izobu15 butyl, tert-butyl, η-pentyl, 2- pentyl, 3-pentyl, n-hexyl or optionally substituted ^1- phenyl such as chlorophenyl, fluorophenyl, dichlorophenyl,

2o R ^{2 is a} hydrogen atom or a halogen atom such as chlorine, bromine or iodine,

R ^{3 and} R ^{4 are} hydrogen or C 1-4 alkyl, especially methyl,

R ^s and R ⁶ are independently selected from up to 6 szén25 alkyl group such as methyl, ethyl, η-propyl, isopropyl, η-butyl, sec-butyl, isobutyl, η-pentyl, 2- pentyl,

3-pentyl, n-hexyl, alkenyl of up to 6 carbon atoms, for example allyl, methyl, but-2-en-1-yl, but-4-en-1-yl-

C3-7-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkoxyalkyl groups having up to 8 carbon atoms, such as 2-methoxyethyl, 2-ethoxyethyl, .

methoxy-2-propyl, 3-methoxy-propyl, or ^R5 and ^R6 taken together with the nitrogen atom optionally substituted by lower alkyl, leg40 total of up to 10 carbon atoms, a heterocyclic group, such as azetidino, 2-methyl-azetidinone -, 2,4-Dimethyl-azetidino, 2,4,4-trimethyl-azetidino, pyrrolidino, 2-methylpyrrolidino, 2-ethylpyrrolidino, 2,5-dimethylpyrrolidino, piperidine -, 2-methylpiperidino,

2-ethyl-piperidino, 2-methyl-5-ethyl-piperidino, beaxahydro-azepino, 2-methylhexahydro-azepino, 2,3-dimethylhexahydro-azepino, leptamethylenimino, bicyclo [3 , 2,2] -3-azanone-50.

Compounds of formula (I) may be prepared using process variants (a), (b), and (c) as illustrated in Schemes [A], [B] or [C].

₅₅ According to the method alternative a) (II) isoxazolyl-methyl-halide or methyl-alkanesulfonates · reacted formula (III) thiolcarbamate salt thereof. In these formulas, R '-R ⁶ are as defined above, X is a halogen or alkanesulfonate group and M is an alkali metal atom or an ammonium group optionally substituted with 2 or 3 alkyl groups. The starting compounds of formula (II) are known or may be prepared by reaction of nitrile oxides with acetylene halides. Examples of such compounds are 5- (chloromethyl) -3-methylisoxazole,

5- (bromomethyl) -3-ethylisoxazole, 5- (chloromethyl) -3-isopropylisoxazole, 5- (bromomethyl) -3-tert-butylisoxazole, 5- (chloromethyl) ) -3,4-dimethylisoxazole, 5- (1'-chloroethyl) -3-methylisoxazole, 5- (bromomethyl) -3-phenylisoxazole,

5- (chloromethyl) -3- (3 ', 4'-dichlorophenyl) isoxazole,

5- (bromo-methyl) -3-cyclohexyl-isoxazole. 5- (Chloromethyl) -isoxazole and 5- (bromomethyl) -3-methyl-4-chloro (or 4-bromo) -isoxazole are known in the art (Kocsetkov et al., 1953, Chemical Abstracts 47, 2167). , Khim. Geterotsikl. Soedin 1974, 602], The corresponding isoxazolylmethyl alkanesulfonates from the known isoxazolyl methanols [Gazz. chim. drink. 69, 536 (1939)] may be prepared by reaction with alkanesulfonic acid chlorides in the presence of a hydrochloric acid binding agent such as pyridine. The preparation of isoxazolylmethyl halides is described in detail in the Examples.

The compounds represented by formula (III) are salts of thiolcarbamic acids. Representative examples include Ν, Ν-dimethylthiolcarbamic acid, Ν, Ν-diethylthiolcarbamic acid, N, N-diisopropylthiolcarbamic acid, N, N-di (n-propyl) thiolcarbamic acid, N3S / -di ( n-butyl) thiolcarbamic acid, N, N-di (isobutyl) thiolcarbamic acid, N-ethyl-N- (n-butyl) thiolcarbamic acid, N-ethyl-N-isopropylthiolcarbamic acid, N-ethyl-N-cyclohexylthiolcarbamic acid , N, N-diallylthiolcarbamic acid, and also the sodium salts of Ν-azetidyl, N-pyrrolidyl, Ν-piperidyl, N-hexahydroazepylthiolcarbamic acid, and their derivatives substituted with 1-3 methyl and / or ethyl groups and optionally one or two alkyl substituted ammonium salts. These compounds can be prepared in known manner.

The reaction may be carried out in any inert organic solvent. For example, hydrocarbons such as cyclohexane, benzene, toluene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chloroform, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether, alcohols or ketones, such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, cyclohexanone, or nithiles such as acetonitrile or water can be used. Mixtures of the solvents mentioned may also be used.

This method is particularly suitable for the preparation of compounds of formula (I).

The isoxazolylmethylthiolcarbamates of formula (I) may also be prepared by reaction of method (b) with an isoxazolylmethyl mercaptan of formula (IV) or a salt thereof with a urea chloride of formula (V).

In these two formulas, R ¹ -R ^{6 are} as defined above, and Y is hydrogen, an alkali metal, or an ammonium group optionally substituted with two or three alkyl groups.

The starting compounds of formula (IV) may be prepared from the isoxazolylmethyl halides of formula (II) using hydrogen sulfide or a salt thereof (Houben-Weyl Methoden der Organischen Chemie, Vol. IX, 1-18). The following mercaptans of general formula IV may be mentioned: 3-methylisoxazol-5-ylmethylmercaptan, 3-ethylisoxazol-5-ylmethylmercaptan, 3-ferulisoxazol-5-ylmethyl- mercaplan, 3-methylisoxazole-5-yl (r-ethyl) mercaptan.

Examples of carbamoyl chlorides of formula (V) include dimethylamine, diethylamine, di (n-propyl) amine, diisopropylamine, di (n-butyl) amine, ethyl (n-butyl), amine, ethyl (n-isopropyl) amine, azetidine, pyrrolidine, piperidine, hexahydroazepine, and carbamoyl chlorides derived from their ring-substituted 1-3-methyl and / or ethyl derivatives.

Process variant b) is conveniently carried out in the presence of a hydrochloric acid killer binding agent. For this purpose, inorganic bases, such as alkali metal bicarbonates, carbonates or hydroxides, or organic bases, such as alkali metal alcoholates such as sodium methylate or tertiary amines such as triethylamine, Ν, Ν- dimethylcyclohexylamine or saturated or unsaturated nitrogen containing heterocyclic compounds such as N-methylpiperidine, pyridine or quinoline. The process may conveniently be carried out in the solvents or mixtures thereof mentioned in Process variant a).

In process variant (c), the isoxazolylmethylthiolcarbamates of formula (I) may be prepared by reacting an isoxazolylmethylthiocarbonyl chloride of formula (VI) with a secondary amine of formula (VII). In these formulas, R ¹ to R ^{6 are} as defined above.

The thiocarbonyl chloride of formula (VI) may be prepared from isoxazolylmethylmercaptans of formula (IV) 30 (Y = hydrogen) and phosgene in known manner. Examples of compounds of formula (VI) include 3-methylisoxazol-5-ylmethylthio-carbonyl chloride, 3-ethylisoxazol-5-yl (methylthio) carbonyl chloride. , 3-phenylisoxazol-5-yl-35- (methylthio) carbonyl chloride. Particularly useful secondary amines of the formula (VII) are those mentioned in the process variant (b) as a component of the urea chloride. Process variant c) may be carried out in the presence of inert solvents less alcohol and water as listed in process variant a) and optionally in the presence of hydrochloric acid binding agents used in process variant b).

Process variant (a) may be carried out in detail in the following 45 ways.

To a solution or suspension of at least 1 mol of the thiolcarbamate of formula (III), optionally 1 mol of isoxazolymethyl halide (II) or alkanesulfonate (II) is added dropwise at -20 to + 50 ° C in the above solvent. The reaction is stirred for 3-12 hours at 0-80 ° C. After completion of the reaction, it is poured into water, the product is extracted with an organic solvent immiscible with water, if appropriate, and then isolated by distillation or crystallization.

For example, process variant b) is carried out as follows.

One mole of isoxazolylmethyl60-mercaptan of formula IV is reacted with at least 1 mole of the aforementioned organic or inorganic base in a solvent in the presence of at least 1 mole of the aforementioned organic or inorganic base for a period of from 1 to 12 hours. The isolation of the thiolcarbamate of formula (I) is carried out as described above.

For example, process variant c) is carried out as follows:

A solution of one mole of thiocarbonyl chloride (VI) in an inert organic solvent is reacted with at least 1 mole of an amine (VII) and at least 1 mole of an inorganic or organic base as in acid variant (b) can be used. The reaction temperature is -10 to + 80 ° C and the reaction time is 1 to 12 hours, depending on the reaction partners, the base and the solvent. Isolation of thiol carbamate 10 is carried out as described above.

The isoxazolylmethyl halides used as starting material in process variant a) may be prepared, for example, as follows:

WHO. example

Propargyl bromide (238 g), phenyl isocyanate (476 g) and nitroethane (208 g) and toluene (158 g) were dissolved in toluene (1500 ml) and triethylamine (1 ml) was added at 15-20 ° C to activate the phenyl isocyanate. The temperature was maintained at 15-30 ° C for 3 hours and 1 ml of triethylamine (4 ml total) was added every hour. The mixture was stirred at 70 ° C for 1 hour and cooled. The precipitate is suctioned off and the residue is washed with 1 liter of toluene. The combined filtrates were evaporated and the residue was distilled in an oil pump vacuum. 2.67 · 10 ^-1 mbar at 30 pressures and 59-61v 310g (88%)

3- (Bromomethyl) -5-methylisoxazole is distilled over.

no = 1.5168. 60MHz NMR (in δ-values in deuterochloroform): 2.3 (3H, s), 4.44 (2H, s),

6.15 (1H, s), ¹³ C-NMR (in deuterochloroform form, ppm values relative to TMS): 167.2 (C), 160.1 (C), 104.5 (CH), 18.8 (CH ₂ ) 11.3 (CH ₃ ).

K2. Example 40

93.5 g of aceto-hydroxymoyl chloride [Bér. dtsch. Chem. Ges. 40, 1677 (1907) and 90 g of isobutynyl chloride in 1500 ml of benzene are added dropwise at 105-20C and 105 g of triethylamine are added dropwise. For 1 hour, then 45 stirred at 20-25 ° C and 1 h at 70 ^u C. After cooling, it is filtered and the filtrate is evaporated. The resulting residue was distilled under an oil pump vacuum. There was obtained 133 g (92%) of 5- (1'-chloroethyl) -3-methylisoxazole. Boiling point 50

6,67 · 10 ³ mbar at 48-50 ° C.

np ^S = 1.4740. 60 MHz-NMR (δ-values in deuterochloroform): 1.78 (3H, d), 2.3 (3H6), 5.05 (1H, 9), 6.09 (1H, s). ¹³ C-NMR spectrum (in deuterochloroform, ppm values relative to TMS): 171.5 (C), 159.8 (C), 102.5 (CH), 47.4 (CH), 23, 3 (CH ₃ ), 11.5 (CH ₃ ).

K3. example

Propargyl bromide (119 g), 1-nitropropane (95 g) and triethylamine (440 g) were dissolved in chloroform (1200 ml) and phosphoryl chloride (155 g) was added dropwise at 0 ° C. It is then refluxed for 30 minutes at 20 ° C and for 2 hours. After cooling, the mixture is filtered, concentrated and the residue is dissolved in water. The aqueous layer was extracted with toluene and the combined toluene layer was washed with water and dried over sodium sulfate. It is separated from the sodium sulfate and the filtrate is evaporated and the residue is distilled under an oil pump vacuum. 150 g of 5-bromomethyl-3-ethylisoxazole are obtained. Boiling point 78-79 ° C at 1.33 · 10 ^-1 mbar. ηθ ⁵ = 1.5108.

5- (1-Chloroethyl) -3-methylisoxazole ( ⁵ = 1.4806), 5- (1-iodoethyl) -3-methylisoxazole (ηθ = 1.5500) can be prepared analogously ), 5- (1-bromoethyl) -3-ethylisoxazole, 5- (1-bromopropyl) -3-isopropylisoxazole, 5- (1-bromoethyl) -3- ( isopropylthiomethyl) isoxazole, 5- (1-chloroethyl) -3-isopropyl isoxazole and 5- (chloromethyl) -3- (methoxymethyl) isoxazole.

The following examples illustrate the preparation of isoxazolylmethylthiolcarbamates of formula (I). Temperature data is given in degrees Celsius and amounts are by weight.

Example 1

102 sr. N-ethylcyclohexylamine, 80.8 sr. triethylamine and 700 sr. of methylene chloride at 0 °, 0.0, sr. carbon dioxide sulfide gas was passed and stirred for 2 hours at room temperature. Then, at 0 [deg.] C., 105.3 sr was added dropwise for 1 hour. 3-Methyl-5- (chloromethyl) -isoxazole was stirred at room temperature for 10 hours. After suctioning off the resulting salt, the filtrate was washed with water, 1N hydrochloric acid and water and dried. Removal of the solvent and distillation of the residue gave 194.2 sr. 3-Methyl-5-isoxazolylmethyl-N-ethyl-N-cyclohexylthiolcarbamate is obtained. It has a boiling point of 176-179 ° at 2.67 · 10 ^-1 mbar. 60-62 °,

Example 2

21.2 sr. diisopropylamine 100 sr. to a mixture of tulle at 0 ° 8.0 sr. carbon dioxide sulfide gas was passed and stirred at 0 ° C for 0.5 hour and at room temperature for 1 hour. Thereafter, 19.0 sr was added dropwise over 15 minutes. 3-ethyl-5- (bromomethyl) -isoxazole was stirred for 3 hours at room temperature. Processed according to Example 1, 21.8 sr. 3-ethyl-5-isoxazolylmethyl-Nhl-diisopropylthiolcarbamate is obtained. Boiling point 154-156 ° at 4'10 ^l mbar. n ^ ⁵ = 1.5089.

Example 3

25.8 sr. To a mixture of 3-methyl- (isoxazol-5-ylmethylmercaptan in 100 l ether and 50 l pyridine) was added 29.8 l Ν, Ν-diethylcarbamic acid chloride under cooling while refluxing for 3 hours. Work up as in Example 1 to obtain 35.8 parts of (3-methyl-5-isoxazolylmethyl) -N 4 -diethylthiolcarbamate.

6,67 · 10 at ² mbar 136-138 °.

By analogy with the preceding examples, the isoxazolylmethylthiolcarbamates listed in the following Table I can be prepared.

Table I

number R ¹ R ² R ³ R ⁴ R ^s R ⁶ Physical data (Fp./mbar, Op., N25 Third ch ₃ H H H c ₂ h ₅ c ₂ h ₅ Example 3 4th ch ₃ H H H iC ₃ H ₇ -C ₃ H ₇ 143 / 6.67 · 10 ^"2 (68 ° C) 5th ch ₃ H H H - (ch ₂ ) ₆ - n25 = 1.5435 6th ch ₃ H ch ₃ H c ₂ h ₅ c ₂ h ₅ 124 / 6.67 · ΙΟ ' ² 7th ch ₃ H ch ₃ H i-C ₃ H ₇ i-C ₃ H ₇ 132 / 6.67 · 10 ² 8th ch ₃ H ch ₃ H - (CH ₂ ) ₆ - 160 / 2.67 · 10 ¹ 9th ch ₃ H H H n-C ₃ H ₇ n-C ₃ H ₇ 139 / 6.67 · 10 ² Second c ₂ h ₅ H H H -C ₃ H ₇ i-C ₃ H ₇ Example 2 10th ch ₃ H H H CH ₂ -CH (CH ₃ ) ₂ CH ₂ -CH (CH ₃ ) ₂ 143 / 6.67 · 10 ² 11th ch ₃ H H H n-C4H9 I1-C4H9 ' 164 / 2.67 · 10 ' ¹ 12th ch ₃ H H H CH ₂ -CH = CH ₂ x ch ₂ -ch = ch ₂ 144 / 2.67 · 10 ¹ First ch ₃ H H H c ₂ h _s cyclo-C ₆ Hi 1 Example 1 13th ch ₃ H H H c ₂ h ₅ n-C4 H9 147 / 4.00 · 10 ^_1 14th ch ₃ H H H - (CH ₂ ) s -CH (CH ₃ ) - 170 / 5.33 · ΙΟ ⁻¹ 15th ch ₃ H H H - (ch ₂ ) ₃ Mp 72-73 ° C * 16th ch ₃ H H H C'H (CH 3) -CH ₂ -C (CH ₃ ) ₂ - 148 / 2.67 · 10 ¹ 17th ch ₃ H H H -CH (CH ₃ ) -CH (CH ₃ ) - (CH ₂ ) ₄ - 184 / 5.33 · 10 ' ¹ 18th ^α Ό > H H H C ₂ H ₅ C ₂ H _S. Mp 88-90 ° C cl 19th c.p H H H i-C ₃ H ₇ i-C ₃ H ₇ 99-101 ° 20th □ c ₂ h ₅ H H H c ₂ h _s c ₂ h ₅ 144 / 1.33 · 10 ¹ 21st c ₂ h _s H H H n-C ₃ H ₇ n-C ₃ H ₇ 152 / 2.67 · 10 ¹ 22nd c ₂ h ₅ H H H - (CH ₂ ) ₆ - 180 / 4.00 · 10 ¹ 23rd c ₂ h ₅ H H H -CH (CH ₃ ) - (CH ₂ ) ₅ - 184 / 4.00 · 10 ¹ 24th c ₂ h _s H H H -CH (CH ₃ ) -CH (CH ₃ ) - (CH ₂ ) ₄ - 190 / 2.67 · 10 ' ¹ 25th c ₂ h ₅ H H H n-C ₄ H ₉ nC ₄ H ₉ 168 / 1.33 · IQ ' ¹

Continuation of Table I

number R ¹ R ² R ³ R ⁴ R ^{5 R} Physical data (Fp./mbar. Op., N * / 26th C ₂ H _s H H H -CH (CH ₃ ) -CH ₂ -C (CH ₃ ) ₂ - 139 / 6.67 · 10 ' ² 27th c ₂ h _s H H H C ₂ H $ n - C ₄ H 9 154 / 1.33 · 10 ' ¹ 28th c ₂ h ₅ H H H - CH (C ₂ H ₅ ) - (CH ₂ ) ₄ - 170 / 1.33 · 10 ' ¹ 29th c ₂ h _s H H H -CH (CH ₃ ) - (CH ₂ ) ₄ 165 / 2.67 · 10 ^-1 30th c ₂ h ₅ H H H -CH (CH ₃ ) - (CH ₂ ) ₃ - 166 / 1.33 · 10 ¹ 31st c ₂ h _s H H H C ₂ Hj cyclo-CgHj 1 180 / 1.33 · 10 ^_1 32nd ch ₃ H H H c ₂ h _s -C ₃ H ₇ 124 / 5.33 · 10 ^-2 33rd ch ₃ H H H ch ₂ ch ₂ och ₃ ch ₂ ch ₂ och ₃ 200 / 5.33 · 10 ' ¹ 34th ch ₃ H ch ₃ H -CH (CH ₃ ) -CH ₂ -C (CH ₃ ) ₂ - 136 / 1.33 · 10 ′ ² 35th ch ₃ H ch ₃ H CH (CH ₃ ) (CH ₂ ) _s - 167 / 1.33 · 10 ″ ² 36th ch ₃ H ch ₃ - H -CH (CH ₃ ) -CH (CH ₃ ) - (CH ₂ ) ₄ - 157 / 1.33 · 10 ′ ² 37th ch ₃ H H H - (CH ₂ ) ₂ -0- (CH ₂ ) ₂ - 74-76 ° C

38th ch ₃ H H H CH ₂ -CH (CH ₃ ) ₂ ch-ch ₂ -ch ₃ 1 ch ₃ 152 / 2.67 - ΙΟ ' ¹ 39th ch ₃ cl H H CH (CH ₃ ) ₂ ch (ch ₃ ) ₂ 148 / 2.67 · 10 ^_1 40th CH (CH ₃ ) ₂ H H H CH (CH ₃ ) ₂ CH (CH ₃ ) ₂ 148 / 2.67 · 10 ^-1 41st c ₂ h ₅ H H H ch ₂ ch = ch ₂ cyclo-C _e Hi 1 187 / 1.33 · 10 ^_1 42nd c ₂ h ₅ H H H CH (CH ₃ ) ₂ CH ₂ CH (CH ₃ ) ₂ 153 / 1.33 · 10 ¹ 43rd c (ch ₃ ) ₃ H H H CH (CH ₃ ) ₂ CH (CH ₃ ) ₂ 144 / 2.67 · 10 * ¹ 44th C (CH ₃ ) ₃ H H H c ₂ h _s cyclo-C ₆ Hi j 168 / 1.33 · 10 ” ¹ 45th c (ch ₃ ) ₃ H H H -CH (CH ₃ ) CH ₂ C (CH ₃ ) ₂ - 142 / 1.33 · 10 ^_1 46th c (ch ₃ ) ₃ H H H c ₂ h _s n-C ₄ H ₉ 152/133 · 10 ^_1 47th ch ₃ the H H c ₂ h _s dklo-C ₆ Hi 1 178 / 2.67 · 10 ^-1 48th ch ₃ cl H H c ₂ h _s nC ₄ H ₉ 157 / 2.67 · 10 ' ¹ 49th ch ₃ cl H H -CH (CH ₃ ) -CH ₂ -C (CH ₃ ) ₂ - 147 / 2.67 · 10 ^_1 50th ch ₃ cl H · H -CH (CH ₃ ) -CH (CH ₃ HCH _a ) ₄ - 180 / 2.67 · 10 ^_1 51st ch ₃ H ch ₃ H nC ₃ H ₇ nC ₃ H ₇ 156 / 1.33 · 10 ¹ 52nd ch ₃ H ch ₃ H CH ₂ CH (CH ₃ ) ₂ CH ₂ -CH (CH ₃ ) ₂ 157 / 2.67 · 10 ^_1 53rd ch ₃ H ch ₃ H ch ₂ -ch = ch ₂ CH ₂ -CH = CH ₂ 150 / 1.33 · 10 ^_1

Continuation of Table I

number R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ Physical data (Fp./mbar. Ορ., Ηο ⁵ 54th ch ₃ H ch ₃ H c ₂ h ₅ Π — C4 H9 148 / 1.33 · 10 ^-1 55th ch ₃ H ch ₃ H CH (CH ₃ ) ₂ CH ₂ -CH (CH ₃ ) ₂ 142 / 1.33 · 10 ^-1 56th c ₂ h ₅ H ch ₃ H CH (CH ₃ ) ₂ CH (CH ₃ ) ₂ 148/133 · 10 ^-1 57th c ₂ h _s H ch ₃ H c ₂ h ₅ cyclo-C ₆ H ₁ ! 170 / 1.33 · 10 ^-1 58th c ₂ h ₅ H ch ₃ H c ₂ h ₅ nC ₄ H ₉ 143 / 1.33 · 10 ^-1 59th c ₂ h ₅ H ch ₃ H CH (CH ₃ ) ₂ CH ₂ -CH (CH ₃ ) ₂ 146 / 1.33 · 10 ¹ 60th C ₂ H _s H ch ₃ H CTI ₂ - CH (CH ₃ ) ₂ CH (CH ₃ ) -CH ₂ -CH _: j 142 / 1.08 · 10 „ ^J 61st CH (CH ₃ ) ₂ H ch ₃ H C ₂ H _s cyclo-C ₆ Hi 1 184 / 1.33 · 10 ^-1 62nd CH (CH ₃ ) ₂ H ch ₃ H CH (CH ₃ ) 2 CH (CH ₃ ) ₂ oil 63rd C (CH ₃ ) ₃ H ch ₃ H CH (CH ₃ ) ₂ CH (CH ₃ ) ₂ 90 ° 64th H H H CH (CH ₃ ) ₂ CH (CH ₃ ) ₂ 104 ° 65th CH (CH ₃ ) ₂ H ch ₃ H c ₂ h ₅ nC ₄ H ₉ 164 / 1.33 · 10 ' ¹ 66th C (CH ₃ ) ₃ H ch ₃ H c ₂ h _s nC ₄ H ₉ 165 / 2.67 · 10 ^-1 67th C (CH ₃ ) ₃ H ch ₃ H C ₂ H _s cyclo-C ₆ Hi 1 73 ° C 68th c (ch ₃ ) ₃ H ch ₃ H CH ₂ -CH (CH ₃ ) ₂ CH (CH ₃ ) -CH ₂ -CH ₃ , 172/133 · 10 ^-1 69th ch ₃ H ch ₃ H -ch ₂ -ch ₂ -ch ₂ -CH ₂ -CH (CH ₃ ) - 76 ° 70th ch ₃ H ch ₃ H -ch ₂ -ch ₂ -CH ₂ -CH (CH ₃ ) - 140 / 1.33, -, 10 ^-2 71st ch ₃ H ch ₃ H -ch ₂ -ch ₂ -ch ₂ -CH ₂ -CH (C ₂ H ₅ ) - 1 · 5297 72nd C ₂ H _s H ch ₃ H -CH (CH ₃ ) -CH ₂ -C (CH ₃ ) ₂ - 1 · 5129 73rd ch ₃ H ch ₃ H -ch ₂ -ch ₂ -ch = ch-ch ₂ - 46-47 °

New herbicides containing isoxazolylmethylthiolcarbamates

At the beginning of this description, experiments were conducted to verify the properties of the active ingredients. These experiments essentially involved three groups.

Greenhouse experiments

200 ml paraffin woven paper bags were used as the culture flasks and filled with clay sand containing 1.5% by weight of humus. Seeds of the test plants were planted in the soil flat by variety. Immediately thereafter, the compounds were treated with the active substances suspended or emulsified in water and a fine spray at the soil surface (pre-emergence treatment). Before the treatment, the dishes were slightly watered so that the product came into contact with wet soil. After application, the pots were covered with a transparent plastic lid until the plants had grown. This coverage prevented evaporation of water and volatile substances. At the same time, it assured the uniform development of the tested plants, if not influenced by the agent. In the post-emergence treatment, the plants were allowed to grow to a height of 3-10 cm, depending on the form of development, and then treated. No coverage was applied. Depending on the temperature requirements of the plants tested, the experiments were carried out in cooler (10-20 °) or warmer (18-30 °) places of the greenhouse. The experimental period was 2.5 to 6 weeks. During this time, the plants were cultivated and their behavior evaluated against various treatments. The test substances, the amount of active substance in kg / ha and the test plants are given in the table. The evaluation was carried out on a scale from 0 to 100. A value of 0 means total damage and normal development, and a value of 100 means complete destruction or failure to hatch.

Field experiments

These experiments were performed on plots of different sizes. The soil was clayey sand with a pH of 5-6 and a humus content of 1-1.5%. The treatment date was early and late morning and early and late spring, according to the sowing time of the crop plants. The active compounds were emulsified or suspended in water and applied by means of a motor-driven mobile spraying device. The most common application was pre-sowing and pre-emergence treatment. In some experiments, the effects of the agents on the development of crops and weeds, as well as some true leaves, were studied at an early age. All experiments lasted several months, during which time intervals were evaluated on a 0-100 scale.

Vapor phase weed control

The agents containing the isoxazolylmethylthiolcarbamates of the present invention have a significant herbicidal activity, even when unlike the known thiolcarbamates, have been shown to have a low evaporation loss due to evaporation. For this statement. the following experiment was performed to verify it in a greenhouse.

Sensitive oats were sown as described in the greenhouse experiments and treated with herbicides containing various active ingredients. Thereafter, the pots were not covered with plastic lids, but were evenly placed in 5 liter glass cylinders. Each pair consisted of one treated and one untreated vessel. Control rollers containing untreated vessels were also used. With ambient air. In order to prevent the horse from changing gas, the edges of the cylinders were lubricated with petroleum jelly and the opening was covered with a glass plate. Thus, from the surface of the soil of the treated pots, the volatile materials could enter the inside of the roller and influence the germination and development of the test plants in the originally drug-free pots. Temperature in the glass cylinder ranged from 11 ° C in the morning to 30 ° C in the sunny day. After the plants were 13-15 cm tall in the control rolls at 14 days of age and the effects of each treatment were well on their way, the experiment was evaluated. In addition to the visual examination, the weight of oat sprouts in each vessel was also determined. The results are shown in Table XI. is illustrated in Table.

evaluation

The conclusions drawn from the various experiments and their results are mosaic-like:

The introduction of the isoxazolylmethyl group into the thiol carbamates resulted in a shift in the effect, especially a broader effect than the known thiol carbamates. For example, some compounds had activity that included Ν, Ν-diisopropyl-S- (2,3-dichloroallyl) thiolcalbamate and Ν, Ν-diisopropyl-S- (2,3,3-trichloroallyl). ) -thiolcarbamate and the effect of Ν, Ν-dipropyl-S-ethylthiolcarbamate (see II,

III. and IV. table). In other cases, a similar, although slightly weaker, herbicidal effect was observed than with N-ethyl-N-cyclohexyl-S-ethylthio-carbamate. The range of selectivity for crop plants was incomparably larger (see Table VI).

It is emphasized that the known thiolcarbamates were selected for comparison only because of their herbicidal activity. No structurally similar compounds of the present invention are known. The effect of a known thiolcarbamate containing a heterocyclic ring was negligible (see Table III). The corresponding dithiocarbamate was completely ineffective. The herbicidal activity of agents containing the compounds of the present invention as an active ingredient is illustrated in Table IV. spreadsheet.

2. In addition to the inherent phytotoxicity of the active ingredient and the incorporation of herbicides for known herbicides, the known thiolcarbamate agents also raise the issue of eradicable weeds and crop plants (e.g. broadleaf species), with increased and broader selectivity for a significant proportion of novel compounds. , V.,

VI. and VII. table). The selectivity of the agents according to the invention can also be explained in terms of plant physiology and the method of application. The latter means that stationary agents distributed on the soil surface do not contact phytotoxic amounts of the seeds and roots of the crop plants, which are slightly deeper. This selectivity is distinguished by agents that can be left on the soil surface after application. However, this does not apply if the agents have to be incorporated into the soil due to high vapor pressure of the active ingredient or for other reasons to reduce evaporation losses.

3. Agents containing the new compounds are as effective as the compounds containing the known active compounds before sowing. Used without incorporation, they outperformed known thiolcarbamate-containing agents for use in this plantation (see Table VIII). It is noteworthy that, for example, 3-methyl-5-isoxazolylmethyl-Ν, di-diisopropylthiolcarbamate, when applied pre-emergent in maize, was as well controlled by undesired plants as significant known other pre-emergence herbicides of other structures (see Table EX). The control of unwanted plants during and after hatching was successful and the crop plants remained intact (see Tables VIII and X).

4. The phytotoxicity of Ν, Ν-diisopropyl-S (2,3,3-trichloroallyl) thiolcarbamate vapor is known to be more subtle. Our model experiments have confirmed this phenomenon. With respect to the new compounds, it was found that 3-methyl-5-isoxazolylmethyl-N, N-diisopropylthiolcarbamate was as aggressive as N, N-diisopropyl-S- (2,3- dichloroallyl) thiolcarbamate or N, N-diisopropyl-S- (2,3,3-trichloroallyl) thiolcarbamate. Untreated plants in pots in the same glass cylinder 1 were not damaged by the new compound, while growth of oats was more or less inhibited by the comparator (see Table XI). This means that less active ingredient was evaporated from the pots treated with the agent containing the new compound than would be necessary to damage neighboring plants through the gas phase. The (3-methyl-4-isoxazolyl) methyl-Ν, Ν vapor pressure actually measured diisopropylthiolcarbamate 20 ° C for l, 3xl0 ~ ^s mbar and j same at this temperature, N, N-diisopropyl-SC, 3-dichloroallyl) thiolcarbamate 3.7 x 10 ⁴ mbar.

Of course, the experimental results reported here are only examples of the behavior of many undesirable and 2 crop plants from a variety of botanical families. The quantities used may also vary. This is primarily dependent on the intended use and also depends on local conditions and the degree of development and size of the plants, for example 0.1 to 10 kg per hectare. 3

This new class of isoxazolylmethyl-thiolcarbamates is characterized in particular by the flexibility of the applications, in contrast to known thiolcarbamates.

The following weeds and crop plants were used for the experiments. Their Hungarian name is described in Ujvárossi M., Weeds, Agricultural Publisher, Budapest, 1974. We also provide the abbreviation used here.

Alopecurus myosuroides Alopec. myosur. Amaranthus retroflexus Amar. retro. Avena fatua Avena tree. Beta vulgar Beta Vulg. Brassica napus Chenopodium album Cynodon dactylon Cynon. Dactyl. Cyperus esculentus Cypern. esculentus. Echinochloa crus galli Echia. c.g. Eleusine indica Eleus. ind. Euphorbia. geniculata Euph. genic. Glycine max Gossypium hirsutum Gossypii. Hirst. Hordeum vulgare Lolium multiflorum Lolium multifl. Matricaria spp. Matric. spp. Poa annua Setaria faberii Set. fab. Setaria spp. Solanum nigrum Sorghum halepense Sorghi. Halep. Stellaria media Triticum aestivum Tritici. AEST.

Zea mays

II. spreadsheet

Effect against major weeds in the greenhouse by pre-emergence treatment

Formula (Ia) R ³ Number of active ingredient Application rate kg / ha % Of plants tested and their damage R ¹ R ² Alopecurus myosuroides Avena fatua Echinochloa crus galli 6 0.75 60 _ 80 1.5 90 - 90 3.0 100 - 90 3 0.75 95 0 60 1.5 100 80 70 3.0 100 80 75 4 0.75 90 65 85 1.5 95 95 90 3.0 95 100 95 0.75 90 0 95 ethyl ethyl 4-chlorobenzyl known 1.5 95 80 95 3.0 95 80 95 0.75 40 80 0 i-propyl i-propyl ethyl known 1.5 90 90 20 3.0 95 95 70

* no damage,

100 ^is total destruction

II. Table (continued)

Number of active ingredient Application rate kg / ha % Of plants tested and their damage Alopec. myosur. Avena fatua Echinochloa crus galli 34 2.0 94 98 94 39 2.0 95 92 80 4.0 100 100 78 40 1.0 80 95 90 2.0 90 95 95 23 2.0 80 80 90 4.0 100 100 95 24 2.0 90 60 85 4.0 100 100 90

= no damage,

100 = total destruction

III. spreadsheet

Destruction of unwanted plants and tolerance of crop plants to thiolcarbamates in a greenhouse with pre-emergence treatment

R ¹ Formula la R ² R ³ Number of active ingredient Uses-% of plants tested and their damage how- .g «2 GossyZea g g «Sky g | § · ο kg / ha «ö Ο E hirs. may.s <g. Amar. retro. i-propyl i-propyl l-methyl-5- (2,205 51 4 Fr ^ z.) nitro-imide S- 1.0 0 20 - 0 0 0 azole-methyl because. 4.0 0 90 - 25 90 20 (THE) 1.0 0 0 10 0 100 100 4 2.0 0 5 20 10 100 100 4.0 0 15 27 10 100 100 1.0 0 0 0 0 100 100 2 2.0 0 5 0 0 100 100 4.0 0 15 5 - 100 100 1.0 0 0 20 0 80 100 9 2.0 0 0 25 0 100 100 4.0 0 5 45 0 100 100 1.0 0 0 0 0 60 100 10 2.0 0 0 0 0 70 100 4.0 0 5 15 0 100 100 13 1.0 0 0 0 0 60 100 2.0 0 0 10 20 80 100 4.0 0 0 12 20 80 100 1.0 0 10 0 0 0 90 27 2.0 0 10 0 0 10 95 4.0 0 10 10 10 90 100

III. Resume table

f- " la is the general formula Number of active ingredient Application rate kg / ha % Of plants tested and their damage Brassica napus Glycine max Gossy hirs. Zea mays Alopec. myosur. Amar. retro. R ¹ R ² R ³ 1.0 0 0 0 0 90 0 7 2.0 0 0 0 0 90 0 4.0 0 0 0 20 - 90 1.0 0 0 0 0 60 95 20 2.0 0 0 0 0 100 - 4.0 0 0 20 10 100 95 1.0 0 0 0 0 90 90 21 2.0 0 0 10 0 100 95 4.0 0 10 20 0 100 100

III. table .continue, other plants)

authorities Used % Of plants tested and their damage material quantity Cyperus Echia Eleus. Euph. Poa Setaria Solanum Sorgh. Stellaria number kg / ha esculentus. c-g- ind. genic. annua spp. nigrum halep. media

known 1.0 - - - 0 0 - 0 - 0 (THE) 4.0 - - - 10 80 - 10 - 0 1.0 42 90 10o 100 100 90 90 82 20 4 2.0 85 95 100 100 100 100 90 95 30 4.0 85 95 100 100 100 100 100 97 60 1.0 60 95 100 60 100 100 100 72 0 2 2.0 60 95 100 95 100 100 100 95 30 4.0 82 95 100 95 100 100 100 95 70 L0 30 57 85 60 70 0 70 45 10 9 2.0 55 92 100 60 100 15 70 75 80 4.0 55 95 100 90 100 40 100 90 80 1.0 10 55 22 50 0 30 90 15 70 10 2.0 32 80 85 50 0 45 90 20 80 4.0 32 80 95 95 0 65 100 50 80 1.0 10 20 52 20 80 0 90 15 0 13 2.0 40 85 95 20 90 0 90 45 0 4.0 70 95 100 70 90 55 100 67 0 1.0 60 50 _ 90 10 25 10 0 27 2.0 _ 95 90 - 100 80 60 60 0 4.0 - 95 90 - 100 85 90 70 0 1.0 90 40 0 90 - 0 7 2.0 _ - - 90 90 - 90 - 0 4.0 - - - 90 100 - 100 - 0 1.0 60 80 30 90 20 30 10 0 20 2.0 _ 90 95 30 100 75 30 65 0 4.0 - 95 95 70 100 95 70 95 0 1.0 85 90 100 100 55 70 60 0 21 2.0 _ 95 95 100 100 85 80 60 0 4.0 - 95 100 100 100 95 100 70 0

III. Table (continued)

177 156

la is the general formula Number of active ingredient Application rate kg / ha R ¹ R ² R ³ 14 1.0 2.0 4.0 17 1.0 2.0 '4.0 • 5 1.0 2.0 4.0 -c ₆ h ₁₂ - ethyl known (B) 1.0 2.0 4.0 n-butyl ethyl n-propyl known (C) A solution of 1.0 2.0 4.0 j-propyl i-propyl -ch ₂ Cl Cl 1 1 C = CH known (D) 1.0 2.0 4.0 n-propyl n-propyl ethyl known (E) 1.0 2.0 4.0 ethyl ethyl 4-chlorobenzyl known (F) 1.0 2.0 4.0

% Of plants tested and their damage Brassica napus Glycine max Gossy Zea Alopec. myosur. Amar. retro. Hirs. mays 0 0 5 0 100 90 0 0 12 10 100 90 0 0 12 10 100 100 0 0 10 0 60 100 0 0 17 0 100 100 0 5 32 0 100 100 0 0 0 0 90 90 0 0 2 0 90 90 0 5 5 40 100 100 0 - 60 _ 100 0 - 92 - 100 -> 0 - 92 - 100 - - 5 0 0 _ 30 - 5 10 0 - 70 - 25 20 10 - 95 0 0 5 0 100 40 0 15 17 0 100 40 0 35 22 15 100 90 0 5 5 0 70 20 0 5 10 0 90 20 0 25 15 20 100 100 0 0 0 10 100 95 0 0 7 20 100 95 0 10 7 20 100 100

= no damage,

100 = total destruction

III. Table (continued, additional plants)

Effect- Used% of plants tested and their damage

material quantity Cyperus Echia Eleus. Euph. Poa Setaria Solanum Sorgh. Stellaria number kg / ha esculentus. c.g. ind. genic. annua spp. nigrum halep. media

1.0 20 80 85 30 90 40 90 45 0 14 2.0 50 95 97 70 100 95 90 85 0 4.0 77 97 100 100 100 100 80 90 0 1.0 15 85 85 90 100 35 100 47 100 17 2.0 30 95 100 100 100 65 100 92 100 4.0 42 97 100 100 100 100 100 92 100 1.0 35 55 60 45 80 5 30 15 0 5 2.0 40 92 97 45 90 20 30 40 0 4.0 50 95 100 80 100 60 90 55 60

III. Table (continued, additional plants)

Effect- Used% of plants tested and their damage

material quantity Cyperus Echin Eleus. Euph. Poa Setaria Solanum Sorgh. Stellaria number kg / ha esculentus. c.g. ind. genic. annua spp. nigrum halep. media

'1.0 10 67 82 - 0 65 - 10 0 known 2.0 40 80 92 - 30 100 - 50 20 (B) 4.0 65 92 92 - 90 100 - 70 ²⁰ 1.0 _ 20 60 20 _ 20 0 30 known 2.0 - 60 90 20 - 60 0 70 - (C) 4.0 - 70 90 90 - 80 30 90 - 1.0 0 15 92 80 100 90 50 67 0 known 2.0 10 75 95 80 100 95 80 85 0 (D) 4.0 40 87 100 80 100 100 80 90 0 1.0 55 JU 72 30 90 65 0 40 40 known 2.0 75 50 95 30 90 95 0 57 40 (E) 4.0 75 60 95 100 100 100 30 70 50 - 1.0 30 80 100 90 100 80 50 90 0 known 2.0 40 95 100 90 100 100 70 90 0 (F) 4.0 40 95 100 100 100 100 90 95 0

ARC. spreadsheet

Pre-emergence and post-emergence herbicides in new isoxazolyl-alkyl thiolcarbamates

authorities material number Application rate kg / ha Method of application Cyperu escul. Plants tested and their effect,% _s Echinochloa crus-galli Lolium multifl 26 3.0 3.0 KE KU 90 90 90 90 90 28 3.0 3.0 KE KU 90 90 90 70 90 29 3.0 3.0 KE KU 70 90 90 90 50 33 3.0 3.0 KE KU 0 0 90 0 50 38 3.0 3.0 KE KU 90 90 90 30 90

KE = pre-emergence treatment Kü = post-emergence treatment 0 = no damage

100 = total destruction

Table V.

Effect of selective weed control agents on various fields of thiolcarbamates applied before sowing

Formula (Ia) agent Application rate kg / ha % Of plants tested and damage R ¹ R ² R ³ Beta vulgar Alopecurus myosuroides 2 2.0 5 95 16 2.0 0 75 3 2.0 5 80 10 4.0 0 65 13 4.0 0 50 9 4.0 50 70 14 4.0 50 90 i-propyl i-propyl known 2.0. 0 30 Cl Cl | | ch ₂ -C = c-ci 4.0 0 80 n-propyl n-propyl ethyl known 2.0 10 80 4.0 30 95 0 = no damage 100 - complete destruction

VI. spreadsheet

Herbicidal Effect of Some Thiol Carbamate-Contained Products and Pre-emergence in Crop Greenhouse

Formula (Ia) R ¹ R ² R ³ Number of active ingredient Application rate kg / ha Beta Vulg. Plants tested,% damage Echia. c-g- Brassica Gossyp. Tritici. aestiva. Amar. retr. Cynon. Dactyl. napus Hirs. 1 2.0 0 0 5 0 90 75 . 87 4.0 0 0 10 0 100 95 92 ethyl cyclohexyl ethyl known 2.0 0 30 20 100 85 97 92 4.0 10 40 40 100 92 97 93 31 2.0 0 0 0 0 95 95 4.0 0 0 10 10 100 - 95

= no damage

100 = total destruction

R ¹ 29 1/7166 30 (Ia) wherein R 2 _R 3z Number of active ingredient User. quantity kg / ha Setaria spp. Solanum nigrum Soighum halepense 1 20 50 95 70 40 65 95 75 ethyl cyclohexyl ethyl known 20 95 30 90 40 95 90 95 31 20 85 80 60 40 90 90 60

VII. spreadsheet

In the case of thiolcarbamate-containing products, the tolerance of rape and summer wheat in the open air before sowing

Formula (Ia) Number of active ingredient Application rate kg / ha % Of plants tested and their damage R ¹ R ² R ³ Brassica napus Triticum aestivum ⁺ Alopecurus myosuroides * 4 2.0 0 0 82 4.0 0 5 95 Cl, Cl | '| i-propyl i-propyl CH ₂ -C = CH known 2.0 0 - 86 4.0 0 - 100 Cl Cl 1 I i-propyl i-propyl 1 1 CH ₂ C = C-C 1 known 2.0 0 2 58 4.0 0 8 92 i-butyl i-Butyl ethyl known 1.5 0 15 30 3.0 0 82 75 n-propyl n-propyl ethyl known 1.5 0 12 25 3.0 10 88 82

= no damage

100 = total destruction + = summer wheat ++ = weed to control herbicide

VIII. spreadsheet

Depending on the method of application, some thiolkaTbamate-containing agents have an effect on free-grained cereals

Plants and their percentage of damage is of formula (Ia)

R ¹ R ² R ³

spp.

Cl Cl 4 2.0 2.0 2.0 2.0 VE VU KS KU 2.5 0 0 0 0 1.2 0 68 85 93 72 9 54 65 20 i-propyl i-propyl ch ₂ -c = c known 2.0 VE 0 2.5 70 6 1 2.0 VU 0 0 51 23 cl 2.0 KS 0 0 42 20 2.0 KU - - 65 5 ethyl ethyl 4-chlorobenzyl known 2.0 VE 2.5 0 57 0 2.0 VU 0 0 64 30 2.0 KS 0 5 65 65 2.0 KU 8 - 59 6

1) Method of application: VE = before sowing

VU = after sowing, before emergence KS = spraying during emergence KU = post-emergence treatment 0 = no damage

100 = total destruction

2) winter barley

3) winter wheat

IX. spreadsheet

Effect of an agent containing 3-methyl-5-isoxazolylmethyl-NJSJ-diisopropylthiolcarbamate on field application prior to hatching compared to known active substances

Substances tested Application rate kg / ha % Of plants tested and their damage Echinochloa crus gallí Zea mays Chenopodium album 4 2.0 80 0 25 4.0 95 0 60 N, N -diisopropyl-thiolcarbamic acid-2,3- 2.0 49 15 - (dichloroallyl) ester (known) 4.0 85 - 35 N- (methoxymethyl) -2,6-diethyl- 2.0 65 0 20 -α-chloroacetanilide (known) 4.0 95 0 70 N-isopropyl-α-chloroacetanilide (known) 2.0 55 0 62 4.0 70 0 75

= no damage

100 = total destruction

Table X.

Herbicidal Effects of Some Thiol Carbamate Containers and Habitat Tolerance of Crop Plants after Hatching

% Of plants tested and their damage

Effective-

Formula (Ia) material number heaven, kg / ha Beta. VULGO. ' SHE, &. d, x c «S O & X> Í 5 & Q Echia c.g. Eleus. Indic. · * - »_D 0) R ¹ R ² R ³ 4 1.0 0 0 80 75 65 78 20 55 2.0 0 0 90 88 65 78 60 70 Cl Cl i-propyl i-propyl | | CH ₂ -C = CH known 1.0 0 - 50 70 ________, 2.0 0 - 90 70 - - - - ethyl ethyl 4-chlorobenzyl known 1.0 _ 0 20 10 45 10 55 2.0 - 5 60 30 48 50 55

= no damage,

100 = total destruction

XI. spreadsheet

Phytotoxicity of some thiol carbamate vapors against oat in a model experiment

(la) ' authorities Used Avena sativa weight, g material quantity Directly Untreated R ¹ r2 _r3 number kg / ha handled

Cl Cl I 1 i-propyl i-propyl 1 1 ch ₂ -c = ch 1.0 2.0 13 CDE 0.6 ABC 2.7 FG 13 EF 4.0 0.2 AB 1.1 BCDE Cl Cl i-propyl i-propyl 1 1 CH ₂ -C = C 1 1.0 2.0 1.8 DEF 1.0 BCDE 2.7 FG 1.5 CDE cl 4.0 0.82 ABCD 1.7 DEF 4 1.0 13 CDE 3.7 H 2.0 0.8 ABCD 3.6 GH 4.0 0.2 AB 3.5 GH

Untreated control

3.7 H

Values containing a common letter do not differ significantly (Duncan's new multiple rank test, level 0.05)

Steel, R.G.D. and Torrie, J.H. - Prindples and Procedures of Statistics, New York, Toronto, London, 1960, 481. '

XII. spreadsheet

1/7166

Selective herbicide applied in rice before hatching in a greenhouse

Number of active ingredient Application rate kg / ha Oryza sativa % Of plants tested and their damage Setaria SPP · Echinochloa crus galli Cynodon dactylon 34 0.5 13 79 75 72 1.0 19 86 95 92

= no damage

100 = total destruction

In terms of use, the agents of the invention and mixtures thereof can be used in a number of plantations to control undesired plants in addition to the crop plants mentioned above. The application rate may be between 0.1 and 15 kg / ha or more, depending on the intended use. We also mention the following crop plants:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vul- garis spp. altissima, Beta vulgaris spp. rapa, Beta vulgaris spp. esGulenta, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica napus var. rapa, Brassica rapa var. silvestris, Camellia sinensis, Citrus limon, Citrus maxima, Carthamus 30 tinctorius, Citrus reticulata, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis melo, Cucumis sativus, Cynodon dactylon, Daucus carota, Glycine max, Gossypium hirsutum (Gossypium arborea, Gossypium herbaceum, Gossypium viti'folium), Helianthus annuus, Helianthus tuberosus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Lactucea, Lactucea - 40 sicum, Malus spp. Manihot esculenta, Medicago sativa, Mentha piperita, Musa spp., Nicotiana tabacum (N. rustica), Olea europaea, Panicum miliaceum, Phaseolus lunatus, Phaseolus mungo, Phaseolus vulgaris, Pennisetum glaucum, Petroselinum cris- 45, p. tuberosum, Picea abies, Abies alba, Pinus spp., Pisum sativum, Prunus avium, Prunus domestica, Prunus persica, Pyrus communis, Ribes sylvestre, Ribes uva-crispa, Ricinus communis, Saccharum officinarum, Secale cereale, Sesamum 50 indicum, , Sorghum bicolor (s. Vulgare), Sorghum dochna, Spinacia oleracea, Theobroma cacao, Trifolium pratense, Triticum aestivum, Vaccinium corymbosum, Vaccinium vitis, idaea, Vicia faba, Vigna sinensis (V. unguiculata), Vi- mays.

The new isoxazolylalkylthiolcarbamates may contain other herbicides. These combinations increase the spectrum of action and also produce synergistic effects. By way of example, the following active substances may be mentioned:

5-amino-4-chloro-2-phenyl-3 (2H) -pyridazinone,

5-amino-4-bromo-2-phenyl-3 (2H) -pyridazinone, 65

5-amino-4-chloro-2-cyclohexyl-3 (2H) -pyridazinone,

5-amino-4-bromo-2-cyclohexyl-3 (2H) -pyridazinone,

5- (methylamino) -4-chloro-2- (3-trifluoromethylphenyl) -3 (2H) -pyridazinone,

5- (methylamino) -4-chloro-2- (3- (trans) -tetrafluoroethoxy) phenyl] -3 (2H) -pyridazinone,

5- (dimethylamino) -4-chloro-2-phenyl-3 (2H) -pyridazinone,

4.5-dimethoxy-2-phenyl-3 (2H) -pyridazinone,

4.5-dimethoxy-2-cyclohexyl-3 (2H) -pyridazinone,

4.5-dimethoxy-2- (3-trifluoromethyl-phenyl) -3 (2H) -pyridazinone,

5-methoxy-4-chloro-2- (3-trifluoromethylphenyl) -3 (2H) -pyridazinone,

5-amino-4-bromo-2- (3-methylphenyl) -3 (2H) -pyridazinone,

- (1-methyl-ethyl) -1H-2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide and its salts,

3- (1-methylethyl) -8-chloro-1H-2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide and its salts,

3- (1-methylethyl) -8-fluoro-1H-2,1,3-benzothiadiazin-3 (3H) -one-2,2-dioxide and its salts,

3- (1-Methylethyl) -8-methyl-1H-2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide and its salts, 1- (methoxymethyl) -3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide,

- (methoxymethyl) -8-chloro-3- (1-methyl-ethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide,

- (methoxymethyl) -8-fluoro-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide, 1-cyano-8-chloro- 3- (l-methyl-ethyl) -2, l, 3-benzothiadiazine-4 (3H) -one-2,2-dioxide,

cyano-8-fluoro-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide, 1-cyano-8-methyl-3- (1 methylethyl) -2, l, 3-

benzothiadiazin-4 (3H) -one-2,2-dioxide,

- cyano-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide,

- (azidomethyl) -3 (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide,

3- (1-methylethyl) -1H-pyridino- [3,2-e] -2,1,3-thiadiazin (4) -one-2,2-dioxide,

N- (1-ethyl-propyl) -2,6-dinitro-3,4-dimethylaniline,

N- (1-methylethyl) -N-ethyl-2,6-dinitro-4-trifluoromethylaniline,

N-n-propyl-N- (β-chloroethyl) -2,6-dinitro-4-trifluoromethylaniline,

N-n-propyl-N- (cyclopropylmethyl) -2,6-dinitro-

4-trifluoromethylaniline,

N-bis (n-propyl) -2,6-dinitro-3-amino-4-trifluoromethylaniline,

N-bis (n-propyl) -2,6-dinitro4-methylaniline,

N-bis (n-propyl) -2,6-dinitro4-methylsulfonyl aniline,

N-bis (n-propyl) -2,6-dinitro-4-aminosulfonylaniline, bis - (3-chloroethyl) -2,6-dinitro4-methylaniline,

N-ethyl-N- (2-methylallyl) -2,6-dinitro-4-trifluoromethylaniline,

N-methylcarbamic acid (3,4-dichlorobenzyl) ester, N-methylcarbamic acid 2,6-di-tert-butyl (4-methylphenyl) ester,

N-phenylcarbamic acid isopropyl ester, N- (3-fluorophenyl) carbamic acid 3-methoxypropyl-2-ester,

N- (3-chloro-phenyl) -carbamic acid isopropyl ester,

N-(3-chlorophenyl) -carbamic acid butin-1-yl-3-ester,

N- (3-chlorophenyl) -karbamidsav4-chloro-2-butyn-1-yl ester,

N- (3,4-dichloro-phenyl) -carbamic acid methyl ester,

N- (4-amino-benzenesulfonyl) -carbamic acid methyl ester,

0- (N-phenylcarbamoyl) propanone oxime,

N-ethyl-2- (phenylmethyl karbainoil) -oxipropionsav amide,

3'-N-isopropylcarbamoyloxypropionic anilide, ethyl N- [3- (N '-phenylcarbamoyloxy) -.

-phenylcarbamate, methyl-N- [3- (N'-methyl-N'-phenylcarbamoyloxy) -phenyl] -carbamate, isopropyl-Np-CN'-methyl-N'-phenylcarbamoyloxy) -phenyl] - carbamate, methyl N- [3- (N'-3-methylphenylcarbamoyloxy) phenyl] carbamate, methyl N- (3- (N'4-fluorophenylcarbamoyloxy) phenyl) carbamate, methyl -N- [3- (N'-3-chloro-4-fluorophenylcarbamoyloxy) phenyl] carbamate, ethyl N- [3- (N '-3-chloro-4-fluorophenylcarbamoyloxy) ) -phenyl] -carbamate, ethyl N- [3- (N'-3,4-difluorophenylcarbamoyloxy) -phenyl] -carbamate, methyl N- [3- (N'-3,4-difluorophenyl) carbamoyloxy) -phenyl] -carbamate,

N-3 - [(4-fluorophenoxy) carbonylamino] phenyl-carbamic acid methyl ester,

N-3 - [(2-methylphenoxy) carbonylamino] phenyl-carbamic acid ethyl ester,

N-3 - [(4-fluorophenoxy) carbonylamino] phenyl tiolkarbamidsav methyl ester,

N-3 - [(2,4,5-trimethyl-phenoxy) -carbonylamino] -phenyl-thiolcarbamic acid methyl ester,

N-3- (Phenoxycarbonylamino) -phenylthiolcarbamic acid methyl ester, N, N-diethylthiolcarbamic acid (p-chlorobenzyl) ester,

N, N-di- (n-propyl) -thiolcarbamic acid ethyl ester, N, N-di- (n-propyl) -thiolcarbamic acid n-propyl ester,

N, N-di (isopropyl) thiolcarbamide (2,3-dichloroallyl) ester,

N, N-Di- (isopropyl) thiolcarbamic acid (2,3,3-trichloroallyl) ester, N, N-di- (isopropyl) thiolcarbamic acid (3-methyl-5-isoxazolylmethyl) -ester,

N, N-di (isopropyl) thiolcarbamic acid (3-ethyl-5-isoxazolylmethyl) ester, N, N-di (sec-butyl) thiolcarbamic acid ethyl ester,

N, N-Di- (sec-butyl) -thiolcarbamic acid benzyl10-ester, N-ethyl-N-cyclohexylthiolcarbamic acid ethyl ester, N-ethyl-N-bicyclo [2.2.1] heptylthiolcarbamic acid- ethyl ester,

S- (2,3-dichloro-allyl) - (2,2,4-trimethyl-azetidin) -1-carbothiolate,

S- (2,3,3-trichloroallyl) - (2,2,4-trimethyl-azetidine) -! -karbotiolát,

S-ethylhexahydro-1-H-azepine-1-carbothiolate,

2Q S-benzyl-3-methylhexahydro-1-H-azepine-1 · carbothiolate,

S-benzyl-2,3-dimethylhexahydro-1-H-azepine-1-carbothiolate,

S-ethyl-3-methylhexahydro-1-H-azepine-125-carbothiolate, N-ethyl-N-n-butylthiolcarbamic acid n-propyl ester,

N-dimethyldithiocarbamic acid (2-chloroallyl) ester,

3θ Sodium salt of N-methyldithiocarbamic acid, sodium salt of trichloroacetic acid, sodium salt of α, α-dichloropropionic acid, sodium salt of α, α-dichlorobutyric acid, β-β3-tetrafluoropropionic acid,

3 _{5-methyl-AJ3-dichloro-propionic} acid sodium salt, alpha-chloro - /? - (4-chlorophenyl) -propionic acid methyl ester, AJ3-dichloro-0-phenyl-propionic acid methyl ester, benzamido oxy-acetic acid,

2,3,5-triiodobenzoic acid, its salts, esters, · amides,

2.3.6-Trichlorobenzoic acid, its salts, esters, amides,

2.3.5.6- tetrachlorobenzoic acid, its salts, esters, amides,

2-methoxy-3,6-dichlorobenzoic acid, its salts, esters, amides,

2-methoxy-3,5,6-trichlorobenzoic acid, its salts, esters, amides,

3-amino-2,5,6-trichlorobenzoic acid, its salts, esters, amides,

O, S-dimethyl-tetrachlorothiothephthalate, dimethyl-2,3,5,6-tetrachloro-terephthalate, disodium 3,6-endoxohexahydrophthalate,

4-amino-3,5,6-trichloro-picolinic acid and its salts,

2-cyano-3- (N-methyl-N-phenyl) amino-acrylic acid ethyl ester,

2- (4- (4'-chlorophenoxy) -phenoxy] -propionic acid isobutyl ester,

2- [4- (2 ', 4'-dichlorophenoxy) -phenoxy] -propionic acid methyl ester,

2- [4- (4'-trifluoromethylphenoxy) phenoxy] propionic acid methyl ester,

Sodium salt of 2- (4- (2 '-chloro-4' -trifluorophenoxy) phenoxy] 65-propionic acid,

2- [4 <3 ', 5'-Dichloro-benzyloxy-2-pyridyl) phenoxy] propionic acid,

2- [N-benzoyl- (3,4-dichlorophenyl) amino] -propionic acid ethyl ester,

2- [N-benzoyl / 3-chloro-4-fluorophenyl) -amho] -propionic acid methyl ester,

2- [N-benzoyl- (3-chloro-4-fluorophenyl) -amino] -propionic acid isopropyl ester,

2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine,

2-chloro-4-ethylamino-6 <amino-2'-propionitrile) 1,3,5-triazine,

2-chloro-4-ethylamino-6-2-methoxy-propyl-2-amino-1,3,5-triazine,

2-chloro-4-ethylamino-6-butin-1-yl-2-amino-1,3,5-triazine,

2-chloro-4,64) -is (ethylamino) -1,3,5-triazine, 2-chloro-4,6-bis (isopropylamino) -1,3,5-triazine, 2-chloro- 4-isopropyl-amino) -6-cyclopropylamino-1,3,5-triazine,

2-azido-4- (methylamino) -6-isopropylamino) -1,3,5-triazine,

2-methylthio-4- (ethylamino) -6- (isopropylamino) -1,3,5-triazine,

2-methylthio-4- (ethyl-AMIA) -6- (tert-butylamino) -1,3,5-triazine,

2-methylthio-4,6-his (ethylamino) -1,3,5-triazine, 2-methylthio-4,6-bis (isopropylamino) -1,3,5-triazine,

2-methoxy-4- (ethylamino) -6- (isopropylamino) -

1,3,5-triazine, 2-methoxy-4,6-bis (ethylamino) -1,3,5-triazine,

2-methoxy-4,6-bis (isopropylamino) -1,3,5-triazine,

4-amino-6-tert-butyl-3-metiltio4,5-dihydro-l, 2,4-triazin-5-one,

4-amino-6-phenyl-3-methyl-4,5-dihydro-l, 2,4-triazin-5-one,

4- (isobutylidene-amino) -6-tert-butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one,

-methyl-3- cyclohexyl- (6-dimethylamino) -1,3,5-triazine-2,4-dione,

3-tert-butyl-5-chloro-6-methyluracil,

3-ter c-b 1-5-bromo-6-methyluracil,

3-isopropyl-5-bromo-6-methyl-uracil

3-sec-b util-5-bromo-6-me tiluracil,

3- (2-tetrahydropyranyl) -5-chloro-6-methyluracil, 3- (2-tetrahydropyranyl) -5,6-trimethyleneuracil, 3-cyclohexyl-5,6-trimethyluracil, 2-methyl- 4- (3'-trifluoromethylphenyl) tetrahydro-

1,2,4-oxadiazine-3,5-dione,

2-methyl-4- (4'-fluorophenyl) -tetrahydro-1,2,4-

-oxadiazine-3,5-diol,

3-amino-1,2,4-triazole,

allyloxy-1- (4-bromophenyl) -2- [1 ', 2', 4'-triazolyl (r)] - ethane and its salts, <4-chlorophenoxy) -3,3-dimethyl -1- (1H-1,2,4-triazol-1-yl) -2-butanone,

N / N-diallyl chloroacetamide,

N-isopropyl-2-chloroacetanilide,

N- (1-methylpropyn-2-yl) -2-chloroacetanilide,

2-methyl-6-ethyl-N- (propargyl) -2-chloro acetanilide •,

2-methyl-6-ethyl-N- (ethoxymethyl) -2-chloroacetanilide,

2-methyl-6-ethyl-N- (2-methoxy-1-methylethyl) -2-chloroacetanilide,

2-methyl-6-ethyl-N- (isopropoxycarbonyl-ethyl) -2-chloroacetanilide,

2-methyl-6-ethyl-N- (4-methoxypyrazol-1-ylmethyl) -2-chloroacetanilide,

2-methyl-6-ethyl-N- (pyrazol-l-yl) -2-chloroacetanilide,

2,6-dimethyl-N- (pyrazol-1-ylmethyl) -2-chloro-

acetanilide;

2,6-dimethyl-N- (4-methylpyrazol-1-ylmethyl) -2-chloroacetanilide,

2,6-dimethyl-N- (1,2,4-triazol-1-ylmethyl) -2-chloroacetanilide,

2,6-dimethyl-N- (3,5-dimethylpyrazol-1-ylmethyl) -2-chloroacetanilide,

2,6-dimethyl-N- (1,3-dioxolan-2-ylmethyl) -2-chloroacetanilide,

2.6-dimethyl-N- (2-methoxyethyl) -2-chloro ·

acetanilide;

2.6-dimethyl-N- (isobutoxymethyl) -2-chloroacetanilide,

2.6-diethyl-N- (methoxymethyl) -2-chloroacetanilide,

2.6-Diethyl-N- (n-butoxymethyl) -2-chloro ·

acetanilide;

2.6-diethyl-N '- (ethoxycarbonylmethyl) -2-chloroacetanilide,

2.3.6-Trimethyl-N- (pyrazol-1-ylmethyl) -2-chloroacetanilide,

2,3-dimethyl-N- (isopropyl) -2-chloroacetanilide,

2.6-diethyl-N- (2-n-propoxyethyl) -2-chloroacetanilide,

2- (2-methyl-4-chlorophenoxy) -N-methoxyacetamide, 2- (α-naphthoxy) -N, N-diethylpropionamide,

2,2-diphenyl-N, N-dimethylacetamide, α- (3,4,5-trifluoropyrazol-1-yl) -N, N-dimethylpropionamide,

N- (1,1-dimethylpropynyl) -3,5-dichlorobenzamide, N1-naphthylphthalamic acid, propionic acid 3,4-dichloroanilide, cyclopropanecarboxylic acid 3,4-dichloroanilide, methacrylic acid 3, 4-dichloroanilide, 2-methylpentanecarboxylic acid 3,4-dichloroanilide,

5-acetamido-2,4-dimethyl-trifluoromethane-

-szulfonanilid,

5-Acetamido-4-methyltrifluoromethane, sulfonanilide, 2-propionylamino-4-methyl-5-chlorothiazole, O- (methylsulfonyl) glycolic acid N-ethoxymethyl-

-2,6-dimethylanilide, O- (methylaminosulfonyl) glycolic acid-N-isopropylanilide, O- (i-propylaminosulfonyl) glycolic acid-N-butin-1-yl-3 anilide,

O- (methyl-aminosulfonyl) hexametilénimid-glycolic acid,

2.6-dichlorothiobenzamide,

2.6-dichlorobenzonitrile,

3.5-dibromo-4-hydroxybenzonitrile and its salts,

3,5-Dichloro-4-hydroxybenzonitrile and its salts,

3,5-dibromo-4-hydroxy-O- (2,4-dinitrophenyl) -benzaldoxime and its salts,

3,5-dibromo-4-hydroxy-O-2-cyano-4-nitrophenylbenzaldoxime and its salts, pentachlorophenol sodium salt,

177'66 (2,4-dichlorophenyl) - (4'-nitrophenyl) ether, (2,4,6-trichlorophenyl) - (4'-nitrophenyl) ether, (2- fluoro-4,6-dichlorophenyl) - (4'-nitrophenyl) ether, (2-chloro-4-trifluoromethylphenyl) - (4'-nitrophenyl) ether,

2,4'-dinitrotrifluoromethyl diphenyl ether, (2,4-dichlorophenyl) (3'-methoxy-4'-nitrophenyl) ether, (2-chloro-4-trifluoromethylphenyl) - ( 3'-ethoxy-4'-nitrophenyl) ether, (24doro-4-trifluoromethylphenyl) (3'-carboxy-4'-nitrophenyl) ether and its salts, (2,4-dichloro) phenyl) -3 '- (methoxycarbonyl-4-nitrophenyl) ether,

2- (3,4-dichlorophenyl) -4-methyl-1,2,4-oxadiazolidine-3,5-dione,

2- (3-tert-butylcarbamoyloxyphenyl) -4-methyl-1,2,4-oxadiazolidine-3,5-dione,

2- (3-isopropyl-carbamoyl-phenyl) -4-methyl-1,2,4-oxadiazolin-3,5-dione,

2-phenyl-3,1 -benzoxazinon- (4), (4-bromophenyl) -3,4,5,9,10-pentaaza-tetracyclo [5,4, l, 0 ^{2, 6,} 0, ® , 11l] -dodeca-3,9-diene,

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl methanesulfonate,

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl-dimethylaxninosulfonate,

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl (N-methyl-N-acetyl) aminosulfonate,

3,4-Dichloro-1,2-benzisothiazole, N- (4-chlorophenyl) allyl succinic acid, 2-methyl-4,6-dinitrophenol, salts and esters thereof, 2-sec-butyl- 4,6-dinitrophenol and its salts, 2-sec-butyl-4,6-dinitrophenol acetate, 2-tert-butyl-4,6-dinitrophenol acetate, 2-tert-butyl-4, 6-dinitrophenol and its salts, 2-tert-butyl-5-methyl-4,6-dinitrophenol and its salts, 2-tert-butyl-5-methyl-4,6-dinitrophenol acetate, 2- secamyl-4,6-dinitrophenol, salts and esters thereof, 1- (α, α-dimethylbenzyl) -3- (4-methylphenol) urea, 1-phenyl-3- (2-methyl) cyclohexyl) -urea,

phenyl-1-benzoyl-3,3-dimethylurea, 1- (4-chlorophenyl) -1-benzoyl-3,3-dimethylurea,

- (4-chlorophenyl) -3,3-dimethylcarbamide,

- (4-Chloro-phenyl) -3-methyl-3-butyn-1-yl-urea, 1- (3,4-dichloro-phenyl) -3,3-dimethyl-urea, 1- (3, 4-dichlorophenyl) -1-benzoyl-3,3-dimethylurea, 1- (3,4-dichlorophenyl) -3-methyl-3-n-butylurea, 1- (4-i- propylphenyl) -3,3-dimethylurea, 1- (3-trifluoromethylphenyl) -3,3-dimethylurea,

- [3- (α, α β-β-tetrafluoroethoxy) phenyl] -3,3-dimethylurea, 1- (3-tert-butylcarbamoyloxyphenyl) -3,3-dimethylurea,

- (3-chloro-4-methylphenyl) -3,3-dimethylurea, 1- (3-chloro-4-methoxyphenyl) -3,3-dimethylurea,

- (3,5-Dichloro-4-methoxyphenyl) -3,3-dimethylurea, 1- [4- (4'-chlorophenoxy) -phem] -3,3-dimethylurea, 1- [4- (4'-Methoxy-phenoxy) -phenyl] -3,3-dimethyl-urea,

cyclooctyl-3,3-dimethylurea,

1- (hexahydro-4,7-methane-indan-5-yl) -3,3-dimethylurea,

1- [1- or 2- (3a, 4,5,7,7a-hexahydro) -4,7-methanoindanyl] -3,3-dimethylurea, 1- (4-fluorophenyl) -3-carboxy -methoxy-3-methyl15-urea,

phenyl-3-methyl-3-methoxy-urea, 1- (4-chlorophenyl) -3-methyl-3-methoxy-urea, 1- (4-bromophenyl) -3-methyl-3-methoxy urea, 1- (3,4-dichlorophenyl) -3-methyl-3-methoxy-20-urea, 1- (3-chloro-4-bromophenyl) -3-methyl-3-methoxyurea, - (3-chloro-4-isopropyl-phenyl) -3-methyl-3-methoxy-urea,

1- (3-chloro-4-methoxy-phenyl) -3-methyl-3-methoxy-urea, 1- (3-tert-butyl-phenyl) -3-methyl-3-methoxy-urea,

- (2-benzothiazolyl) -1,3-dimethylurea,

- (2-benzothiazolyl) -3-methyl-urea,

1- (5-trifluoromethyl-1,3,4-thiadiazolyl) -1,3-dimethylurea, imidazolidin-2-one-1-carboxylic acid isobutylamide,

1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate,

1,2,4-trimethyl-3 β-diphenylpyrazolium-

-metilszulfát,

1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium methyl sulfate,

1,3-dimethyl-4- (3,4-dichlorobenzoyl) -5 -: [(4-methylphenyl) sulfonyl-oxy] -pyrazole,

2,3,5-trichloro-pyridinol (4);

1-methyl-3-phenyl-5- (3'-trifluoromethyl-phenyl) -pyridone (4),

methyl-4-phenyl pyridinium chloride,

1,1-dimethylpyridinium chloride,

3-phenyl-4-hydroxy-6-chloro-pyridazine,

1,1 '-dimethyl-4,4'-dipyridylium di- (methylsulfate),

1,1 '-di- (3,5-dimethylmorpholine carbonylmethyl) -4,4'-dipyridylium dichloride,

1,1 '-ethylene-2,2' -dipyridylium dibromide,

3- [1- (N-ethoxyamino) -propylidene] -6-ethyl-3,4-dihydro-2-H-pyran-2,4-dione,

3- [1- (N-Allyloxyamino) -propylidene] -6-ethyl-3,4-dihydro-2-H-pyran-2,4-dione,

2- [1- (N-Allyloxyamino) propylidene] -5,5-dimethylcyclohexane-1,3-dione and its salts,

2- [1- (N-Allyloxyamino) butylidene] -5,5-dimethylcyclohexane-1,3-dione and its salts,

2- [1- (N-Allyloxyamino) butylidene] -5,5-60-dimethyl-4-methoxycarbonyl-cyclohexane-1,3-dione and its salts, (2-chlorophenoxy) -acetic acid, salts , esters and amides, (4-chlorophenoxy) acetic acid, and its salts, esters, amides, (2,4-dichlorophenoxy) acetic acid, and its salts, esters, amides, (2,4,5-trichloro), phenoxy) acetic acid and its salts, esters, amides, (2-methyl-4-chlorophenoxy) acetic acid and its salts, esters, amides,

3,5,6-trichloro-2-pyridinyloxyacetic acid and its salts, esters, amides, methyl α-naphthoxyacetic acid, 2- (2-methylphenoxy) propionic acid, and its salts, esters, amides,

2- (4-chlorophenoxy) propionic acid and its salts, esters, amides, 2- (2,4-dichlorophenoxy) propionic acid and its salts, esters, amides,

2- (2,4,5-trichlorophenoxy) -propionic acid and its salts, esters, amides, 2- (2-methyl-4-chlorophenoxy) -propionic acid and its salts, esters, amides,

4- (2,4-dichlorophenoxy) butyric acid and its salts, esters, amides,

4- (2-methyl-4-chlorophenoxy) -butyric acid and its salts, esters, amides, cyclohexyl-3- (2,4-dichlorophenoxy) -acrylate, 9-hydroxy-fluorenecarboxylic acid (9), and salts, esters, (2,3,6-trichlorophenyl) acetic acid, and its salts, esters,

4-Chloro-2-oxo-benzothiazolin-3-yl-acetic acid and its salts, esters, gibelleric acid and its salts, disodium methylsilonate, monosodium salt of methylsilone, N-phosphonomethylglycine and its salts, N / N-bis (phosphone) methyl methylglycine and its salts, 2-chloroethane phosphonic acid (2-chloroethyl) ester, ammonium ethylcarbamoylphosphonate, di-n-butyl-1- (n-butylamino) -cyclohexyl-

-phosphonate, trithiobutylphosphite, 0,0-diisopropyl-5- (2-benzosulfonylaminoethyl) -phosphonate. ^c zfordithio,

2,3-dihydro-5,6-dimethyl-1,4-dithine-1,4,4,4-tetraoxide,

5-tert-Butyl-3- (2,4-dichloro-5-isopropoxy)

-phenyl) -1,3.4-oxadiazolin- (2);

4,5-dichloro-2-trifluoromethylbenzimidazole and its salts,

1,2,3,6-Tetrahydropyridazine-3,6-dione and its salts, succinic mono-N-dimethylhydrazide and its salts, (2-chloroethyl) trimethylammonium chloride, (2-methyl-4-phenyl) sulfonyl) -trifluormetán-

-szulfonanilid,

1,1-dimethyl-4,6-diisopropyl-5-indanylethylketone, sodium chlorate, ammonium rhodanide, calcium cyanamide, 2-chloro-4-trifluoromethyl- (3'-ethoxycarbonyl),

-4 '-nitrophenyl) ether,

1- (4-benzyloxy-phenyl) -3-methyl-3-methoxy-urea,

2- [1 <2,5-dimethylphenyl) ethylsulfonyl]

pyridine N-oxide, 1-acetyl-3-anilino-4-methoxycarbonyl-5-methylpyrazole,

3-Anilino-4-methoxycarbonyl-5-methylpyrazole, 3-tert-butylamino-4-methoxycarbonyl-5

methyl-pyrazole,

N-benzyl-N-isopropyl-trimethyl-acetamide,

2- (4- (4'-chlorophenoxy-methyl) -phenoxy-propionic acid methyl ester,

2- (4- (5 '-Bromopyridyl-2-oxy) -phenoxy] -propionic acid 5-methyl ester, 2 [4 <5'-iodo-pyridyl-2-oxy) -phenoxy] -propionic acid methyl ester,

2- (4- (5'-Iodo-pyridyl-2-oxy) -phenoxy] -propionic acid n-butyl ester, (2-chloro-4-trifluoromethyl-phenyl) - [3 '- (2-fluoro-ethoxy) -4'-nitrophenyl] ether, (2-chloro-4-trifluoromethylphenyl) [3- (ethoxycarbonyl) methylthio-4-nitrophenyl] ether, (2,4,6- trichlorophenyl) [3- (ethoxycarbonyl) 15-methylthio-4-nitrophenyl] ether,

2- [1- (N-ethoxyamino) butylidene] -5- (2-ethylthiopropyl) -3-hydroxycyclohexen-2-one-1 and its salts,

2- (1- (N-ethoxyamino) butylidene] -5- (2-phenylthio20-propyl) -3-hydroxycyclohexen-2-one-1 and its salts,

4- [4- (4'-Trifluoromethyl) -phenoxy] -pentene-2-carboxylic acid ethyl ester, (2,4-dichlorophenyl) - (3'-carboxy-4'-nitrophenyl) 25- ether and its salts,

4,5-Dimethoxy-2- (3-a, 3'-trifluoro; 0-bromoethoxyphenyl) -3- (2H) -pyridazinone, (2,4-dichlorophenyl) - (3'-ethoxy) ethoxyethoxy-4'-nitrophenyl) ether,

2,3-dihydro-3,3-dimethyl-5-benzofuran ethanesulfonate,

N- [4-methoxy-6-methyl-1,3,5-triazin-2-ylaminocarbonyl] - (2-chlorobenzene) sulfonamide,

- (3-chloro-4-ethoxyphenyl) -3,3-dimethylurea, (2-methyl-4-chlorophenoxy) thioacetic acid ethyl ester,

4-Dor-3,5-diiodo-4-acetoxypyridine, 1- (4- [2- (4-methylphenyl) ethoxy] phenyl) -3-methyl-

-3-methoxy-urea.

It may be useful if the agents containing the active compounds according to the invention are optionally used in combination with other active compounds in admixture with other pesticides. These may be pesticides, phytopathogenic fungicides or growth regulators. It is worth mentioning the miscibility of the agents with mineral fertilizer solutions, which are suitable for the elimination of nutrient and trace element deficiencies.

The agents of the present invention may be used, for example, in the form of directly sprayable solutions, powders, suspensions or high concentration aqueous, oily or other dispersions or suspensions, emulsions, oily dispersions, pastes, dusts, sprays, granules by spraying, spraying, spraying or spraying. The application forms are adapted to the intended use and must in all cases ensure a uniform distribution of the active ingredients.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, medium and high boiling petroleum fractions such as kerosene or gas oil, coal tar oils, vegetable and animal oils, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, naphthalenes and their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., highly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like. They can be used.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders, oil dispersions by the addition of water. For the preparation of emulsions, pastes or oil dispersions, the active compounds are homogenized in oil or solvent in the presence of wetting, tackifying, dispersing or emulsifying agents in water. Concentrates of the active ingredient, wetting agent, tackifier, dispersant or emulsifier, and optionally oil or solvent, can be prepared in water-dilutable concentrates.

Surfactant additives include the alkali, alkaline earth and ammonium salts of lignin sulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylarylsulfonates, alkylsulfates, alkylsulfonates, dibutylnaphthalenesulfonic acids and the like; káliföldfémsóit, lauriléterszulfátot, fatty alcohol sulfates, fatty acid alkali and alkaline earth metal salts, sulfated hexadecanols, heptadecanols, octadecanols, salts of sulfated fatty alcohol glikolétersókat, consisting of sulfonated naphthalene and naphthalene derivatives .3 formaldehyde condensation products consisting of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, condensation products , polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol 3, choleters, tributylphenol polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, 4 (sorbitol ester, lignin, sulphite impurities.

Powders, dusts and dusts may be prepared by mixing and / or grinding the active ingredient with a solid carrier. 45

Granules, such as coated, impregnated and homogeneous granules, may be prepared by binding the active ingredient to a solid carrier. Solid carriers include, for example, mineral soils such as silica gel, silica, silicates, 50 talc, kaolin, attapulgite, limestone, lime, chalk, bolus, clay, loess, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, magnesium oxide, such as ammonium phosphate, ammonium nitrate, urea and plant products such as cereal flour, wood, cinnamon and bone meal, cellulose powder and other solid carriers.

The compositions may contain from 0.1 to 95% by weight, preferably from 0.5 to 60% by weight, of the active ingredient.

Various oils, trace elements, tackifiers and wetting agents, antifoams such as silicone, growth regulators, protective agents and the like are used in the herbicidal compositions of the present invention. We can mix.

These agents and the other herbicides mentioned above may be added to the agent of the invention immediately before use, or the herbicides may be applied before or after the agent of the invention.

Said agents and additives may be mixed with the herbicide according to the invention in a ratio of 1: 10 to 10: 1.

The following examples illustrate the preparation and composition of some formulations without limiting the invention.

Example 4 sr. 3-Methyl-5-isoxazolylmethyl-N-ethyl-N-cyclohexylthiolcarbamate was mixed with 10 µl. N-methyl-α-pyrrolidone and thus a solution containing 90% by weight of active ingredient can be used in the form of small droplets.

Example 5 sr. 3-Ethyl-5-isoxazolylmethyl-N, N-diisopropylthiolcarbamate was dissolved in 80 µl. xylene, 8-10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide in 10 v / v. addition product, 5 sr. calcium salt of dodecylbenzenesulfonic acid and 40 mol of ethylene oxide and 1 mol of castor oil in 5 sr. of its additive product. The solution was diluted 100,000. poured into water and uniformly distributed to give an aqueous dispersion containing 0.02% by weight of active ingredient.

Example 6 sr. 3-methyl-5-isoxazolylmethyl-N, N-diethyl-thiolcarbamate was dissolved in 40 µl. cyclohexanone, 30 sr. isobutanol, 7 moles of ethylene oxide and 1 mole of isooctylphenol in 20 sr. and 40 mol of ethylene oxide and 1 mol of castor oil in 10 volumes. of its additive product. The solution was diluted 100,000. poured into water and uniformly distributed to give an aqueous dispersion of 0.02% by weight of active ingredient.

Example 7 sr. 3-Methyl-5-isoxazolylmethyl-N, N-diisopropylthiolcarbamate was dissolved in 25 µl. cyclohexanol, 65 lbs., petroleum fractions boiling in the range of 210-280 ° C, and 40 moles ethylene oxide and 1 mole castor oil in 10 l. of its additive product. The solution was diluted 100,000. poured into water and uniformly distributed to give an aqueous dispersion containing 0.02% by weight of active ingredient.

Example 8 sr. 3-Methyl-5-isoxazolylmethyl-N, 4-diisopropylthiolcarbamate is thoroughly mixed with 3 sr. diisobutylnaphthalene-α-sulfonic acid, sodium salt, 17 sr. lignin sulfonic acid sodium salt and 60 sr. powdered silica gel and hammer mill. The mixture was added at 20,000 sr. uniformly distributed in water to give a spray solution containing 0.1% by weight of active ingredient. 5

Example 9 sr. 3-Methyl-5-isoxazolylmethyl-N, N-diisopropylthio olcarbamate is thoroughly mixed with 97 parts by weight. powdered kaolin. A powder containing 3% by weight of active ingredient is thus obtained.

Example 10 sr. 3-Methyl-5-isoxazolylmethyl-N, N-diisopropylthiolcarbamate is thoroughly mixed with 92. powdered silica gel and sprayed on silica gel 20 8 sr. paraffin oil to give a good adhesive composition.

Example 11 25 sr of 3-methyl-5-isoxazolylmethylhexahydroazepinethiolcarbamate was thoroughly mixed with 10 µl. fen ο l sulfonic acid-urea-formaldehyde condensate with sodium salt, 2 sr, co-iron and 48 sr. water to give 30 stable aqueous dispersions of 100,000 sr. diluted with water to give an aqueous dispersion of 0.04% w / w.

Example 12 sr, 3-methyl-S-isoxazolylmethyl-N, N-diethylthiolcarbamate was mixed with 2 sr. calcium salt of dodecylbenzenesulfonic acid, 8 sr. with fatty alcohol polyglycol ether, 40 2 sr. phenol sulfonic acid urea formaldehyde condensate · sodium salt and 68 sr. with paraffinic mineral oil. A stable oily dispersion is obtained,

Claims (2)

Patent claims: CLAIMS 1. An herbicide comprising from 0.1% to 95% by weight of an isoxazolylmethylthiolcarbamate of general formula (I) as an active ingredient. R * is C 1-6 alkyl, R is hydrogen or halogen, 55 R ^{3 and} R ^{4 are} hydrogen or C 1-4 alkyl; and R ^s or R ⁶ are independently C 1-6 alkyl, C 3-7 cycloalkyl, (1-4C) alkoxy- (1-4C) -alkyl residues, or ^R5 and ^R6 together are no more than three of 1- C 3 -C 6 alkylene substituted with C 4 alkyl, together with at least one of a solid and liquid carrier, preferably an artificial and natural mineral hydrocarbon derivative, and a surfactant, preferably a dispersant, emulsifier, wetting agent. 2. Process for the preparation of isoxazolylmethyl-thiolcarbamates of the formula (I) R ^{1 is} hydrogen, C 1-6 alkyl or phenyl optionally substituted with up to two halogens, R ^{2 is} hydrogen or halogen, R ^{3 and} R ^{4 are} hydrogen or C 1-4 alkyl; and R ^f or R ⁶ are independently C 1-6 alkyl or C 2-6 alkenyl, C 3-7 cycloalkyl means (1-4C) alkoxy (Cl-C4) -alkyl residues, or R ^s and R ⁶ together represent up to three C3-C6 alkylene groups optionally substituted with up to three C1-C4 alkyl groups, characterized in that a) an isoxazolylmethyl halide or methyl alkanesulfonate of formula II wherein R *, R ² , R ³ and R ^{4 are} as defined above, X is a halogen or alkanesulfonate group; reacting thiolcarbamate salt of formula - is of the formula: wherein R ^s and R ⁶ are as hereinbefore defined and M is an alkali metal atom or an optionally substituted 2-3 -alkyl-ammonium group -, or b) an isoxazolylmethylmercaptan of formula (IV) wherein R ¹ , R ² , R ³ , and R ^{4 are} as defined above, Y is hydrogen, an alkali metal or an ammonium group optionally substituted with 2 to 3 alkyl groups; V) with a carbamic acid chloride of the formula - R ^s and R ⁶ in the formula is as defined above -.