FI64362C - 2- (DIMETHYLCARBAMOYLIMINO) -1,3,4-THIADIAZOLIN-3-ID-SALTER FOR HERBICIDES - Google Patents

Description

1 Λ ^ „. r, ADVERTISING PUBLICATION £ 4362 flSjgA lBJ (11> UTLÄGGNINGSSKRIFT 0 * ° ° Ζ (45) Falr-nt c,: - Jdolat (51) Ky.ik. ^ int.a.3 C 07 D 285 / ^ 2 FINLAND —FINLAND (21) P * t * "ttlh» k «mu« —Pit * nt * n * 8knlnj 771323 (22) H »k * ml * pllr | - Ansöknlnpdij 26.0U.77 (23) AlkupUvl— Glltt | het» d »J 26.OU.77 (41) Become Public - Bllvlt offsntllg 25.11.77

Patent · And racket board Nihtwucp ** »j. Date of revision: oo'07 3 '

Patent · och registrstyrelsen Arabian utltgd oeh uil.skrKten publlcerad 1 '“(32) (33) (31) Pyydetty etuoikeus — Bejird prlorltet 2U. 05 · 76

Federal Republic of Germany-Förbundsrepubliken

Tyskland (DE) P 2623657-7 (71) Schering Aktiengesellschaft, Berlin / Bergkamen, DE; Mullerstrasse 170-178, 1 Berlin 65, Federal Republic of Germany-Förbundsrepubliken iy ski and (DE) (72) Ludwig Nusslein, Berlin, Friedrich Arndt, Berlin, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (7U) Oy Kolater Ab (5U) ) 2- (Dimethylcarbamoylamino) -1,3,5-thia-diazolin-3-yl salts - 2- (dimethylcarbamoyl-amino) -1,3,3-thiadiazolin-3-yl salts for use in herbicides for use in herbicides

The invention relates to novel 2- (dimethylcarbamoylamino) -1,3,10-thiadiazole-3-ici salts for use in herbicides, having the formula N - N (_) 0

I M. C-I

, J t 3 \ ch3 B (t> where R is C 1-6 alkyl and B is an alkali metal atom, preferably a lithium, sodium or potassium atom.

1- (1,3, U-thiadiazol-2-yl) urea derivatives, 64362 oz with herbicidal activity, are known from DE-A-1 316 696, 1 901 672 and 2 118 520. However, these compounds have an unsatisfactory effect against the growth of unwanted plants by planting crops.

It has now been found that the compounds of the formula I have an excellent effect on weeds as well as a broad selectivity spectrum for crops.

The compounds of the invention have a broad herbicidal action on soil and leaves. They can be used to control monocotyledonous and dicotyledonous weeds.

The compounds are used to control field weeds before germination and also after germination. Suitable weeds are, for example, Sinapis ssp., Stellaria media, Senecio vulgaris, Matricaria chamomilla, Ipomoea purpurea, Chrysanthemum segetum, Eamium amplexicaule, Centaurea cyanus, Amarantnus retro-flexus, Alopecurus myosuroides, Echinochlo perennials and other weeds.

In general, 0.5 kg to 5 kg of active substance / ha are used for controlling seed weeds, in which case the compounds according to the invention have proved to be selective in crops such as shrub bean, peanut, potato, pea, rice, Sorghum and soybean.

In higher applications, the compounds are also suitable as total herbicides for killing or suppressing wild vegetation during the growth phase of plants.

The compounds of the invention may be used either alone, in admixture with each other or with other active ingredients.

Depending on the intended use, there are, for example, the following herbicidally active substances which can also be added to the compounds according to the invention immediately before use: substituted anilines, substituted aryloxycarboxylic acids and their salts, esters and amides, substituted ethers, 3 64362 substituted arsonic acids and their salts , substituted benzimidazoles, substituted benzisothiazoles, substituted -bentstiadiatsinonidioksidit, substituted benzoxazines, substituted benzoxazinones, substituted benzothiazole, substituted bentstiadiatsolit, substituted biurets, substituted quinolines, substituted carbamates, substituted aliphatic carboxylic acids and their salts, esters and amides substituted aromatic carboxylic acids and their salts, esters and amides, substituted carbamoylalkylthio or dithiophosphates, substituted quinazolines, substituted cycloalkylamidocarbars hydroxythiolic acids and their salts, esters and amides, substituted cycloalkylcarboxamido-thiazoles, substituted dicarboxylic acids and their salts, esters and amides, substituted dihydrobenzofuranyl sulfonates, substituted disulfides, substituted disulfides, substituted dipyridyls, Science, substituted hexahydro-lH-carbothioate, substituted hydantionit, substituted hydrazides, substituted hydratsoniumsuolat, substituted isoksatsolipyrimidonit, substituted imidazoles, substituted isotiatsolipyrimidonit, substituted ketones, substituted naphthoquinones 64362, substituted aliphatic nitriles, substituted aromatic nitriles, substituted oxadiazoles, substituted oksadiatsinonit, substituted oxadiazolidinediones, substituted oxadiazinediones, substituted phenols and their salts and esters, substituted phosphonic acid and their salts, esters and amides, substituted phosphonium chlorides, substituted phosphonoalkylglycines, substituted phosphites, substituted phosphonic acids and their salts, esters and amides, substituted piperidines, substituted pyrrolidates, substituted pyrazoles, substituted pyrazole acids and their pyrazole alkylcarboxylates pyratsoliumalkyylisulfaatit, substituted pyridazines, substituted pyrimidines, substituted pyrrolidones, substituted pyridazones, substituted pyridine carboxylic acid and their salts, esters and amides, substituted pyridines, substituted pyridiniumkarboksilaatit, substituted pyridinone, substituted pyrimidones, substituted pyrrolidine carboxylic acid and their salts, esters and amides, substituted pyrrolidines, substituted arylsulfonic acids and their salts, esters and amides, substituted styrenes, substituted tetrahydrooxadiazinediones, substituted tetrahydromethanoindenes,

II

6AZ62-Substituted tetrahydro-diazolithiones, substituted tetrahydro-thiadiazine-1: ions, substituted tetrahydro-thiadiazolidione ions, substituted thiadiazoles, substituted aromatic thiol carboxylic acid amides, substituted thiocarboxylic acid amides, substituted thiocarboxylic acids and their thiocarboxylic acids and their , esters and amides, substituted triazines, substituted triazoles, substituted tetrahydrooxadiazolidionions, substituted thioureas, substituted uracils and substituted uretidinediones.

In addition, other additives can be used, e.g. non-herbicidal additives, which have a synergistic effect with herbicides. Such substances include wetting agents, emulsifiers, solvents and oily additives.

The compounds according to the invention or mixtures thereof are expediently used as preparations, such as powders, dispersants, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and, if appropriate, wetting, fixing, emulsifying and / or dispersing agents. excipients.

Suitable liquid carriers include, for example, water, aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, isophorone, dimethyl sulfoxide, dimethylformamide and mineral oil fractions.

Suitable solid carriers are mineral soils, e.g. tonsil, silica gel, talc, kaolin, attaclay, limestone, silicic acid and vegetable products, e.g. flour.

Surfactants which may be mentioned are, for example, calcium lignin sulfonic acid, polyoctylene, ethylene and phenyl, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts. , formaldehyde condensate, fatty alcohol sulphates and substituted benzene sulphonic acids and their salts.

6 64362

The proportion of active compound or compounds in different preparations can vary widely. The substances may, for example, contain from about 10 to 80% by weight of active compounds, from about 90 to 20% by weight of liquid or solid carriers and possibly up to 20% by weight of surfactants.

The application of the substances can take place in a conventional manner, e.g. using water as a carrier at spray rates of about 10 ° C / liter. The use of the substances by the so-called "low-volume" and "ultra-low-volume methods" is as possible as their use in the form of so-called microgranules.

The substituent R in formula I may be, for example, methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, 1-methylbutyl, 1- ethylpropyl, n-hexyl, isohexyl or 1,1-dimethylbutyl.

The compounds of the invention are salts which occur as ions, corresponding to the following polar boundary formulas, I — f <_> z ™ 3 li — I'd dk R ll J1n-C0-N ^ B (+) <—> 'XS "" VS \ h3 N_N | öl (_). <Li-, /. <·> XS / \ 0 ^ 3

The compounds according to the invention can be prepared, for example, by a) dimethylcarbamoyl chloride of the formula

H3C

N-C0-C1 II

H 3 Cl 2 is reacted with 1,3,3-thiadiazol-2-amine of formula RC-C 7 NH 4 S / 2 in the presence of an acid scavenger to give 2- (dimethylcarbamoylamino) - 1,3,4-Thiadiazoline-3-carboxylic acid dimethylamide derivative of the formula 7 64362 / ™ 3, co-n / rY z RC C> ri3 \ δ // ^ N-CO-N ^ \ oi3 optionally dissolved in a solvent, after which the resulting compound is cleaved with a metal compound of the formula

V

b) 1- (1,3, H-thiadiazol-2-yl) -3,3-dimethylethyl derivative of the formula N-N m

Il il / ®3

R-Q „C-NH-CO-N \ VI

\ ch3 is treated with a metal compound of formula

g (+) y (~) V

optionally using a solvent, wherein R and B in the above formulas have the same meaning as above and Y is hydrogen, hydroxyl, lower alkoxy or an amino group.

The reaction between the reaction components takes place at a temperature of 0 to 100 ° C, but generally at room temperature.

For the synthesis of the compounds of the invention, the reaction components are used in approximately equimolar amounts. Suitable reaction media are polar organic solvents, alone or in admixture with water. Their choice depends on the metal compound used. As solvents or suspending agents, mention may be made of: acid amides, such as dimethylformamide, acid nitriles, such as acetonitrile, alcohols, such as methanol or ethanol, ethers, such as tetrahydrofuran, etc.

8 64362

In the synthesis of the compounds of general formula IV, any conventional acid-binding agent can be used, such as an organic base, suitably a tert-amine, e.g. triethylthiamine, N, N-dimethylaniline or a pyridine derivative, or an inorganic base, e.g. an alkali or an alkaline earth metal oxide, hydroxide, carbonate or alkanoic acid salt, whereby liquid acid scavengers can simultaneously act as solvents.

The compounds of the invention are finally isolated by distilling off the solvents used under normal or reduced pressure or by coupling with less polar organic solvents, e.g. ketones such as acetone or ethers such as diisopropyl ether.

The following examples illustrate the preparation of the compounds of the invention.

Example 1 27.1 g of 5-ethyl-2- (dimethylcarbamoylamino) -1,3,4-thia-diazoline-3-carboxylic acid dimethylamide, m.p. at 13 ° C is suspended in 150 ml of methanol. A solution of 4 g of sodium hydroxide in 100 ml of methanol is added dropwise with stirring at room temperature. After 3 hours, a clear solution is obtained, from which methanol is then distilled off in vacuo. The residual residue is digested with acetonitrile, filtered off with detergent and k.u 'whale at 80 ° C under vacuum.

Yield: 15.5 g (69.8% of theory) of the sodium salt of 5-ethyl-2- (dimethylcarbamoyl-imino) -1,3,10-thiadiazole-3-yl.

M.p .:> 25 ° C

C 7 H 11 N 4 NaO 5 Mp: 222> 26 Analysis calculated C 37.83% H 4.99% N 25.21% Na 10.34% found C 37.70% H 5.05% N 24.95% Na 10.76%.

Example 2 8.1 g of 1- (5-tert-butyl-1,3,4-thiadiazol-2-yl-3,3-dimethylurea) at 121 ° C are dissolved together in 0.852 g jug 1 iti umhydrok r.id ia to 70 ml me tanol After the solution I ijvi:; t <· this r · assured i ·: · ;.), '] rules; i e h ί err'’I au ti d i - i sopropvy 1 t <'>'! * <'r · s -

II

9 64362 with isopropanol, suction filtered and washed with diethyl ether. After drying in vacuo at 120 [deg.] C., 7.8 g (93.8% of theory) of 5-tert-butyl-2- (dimethylcarbamoyl-imino-1,3,4-thiadiazolin-3-yl) are obtained. liters of salt having a mp> 250 ° C.

CnH, CLiN, .OS Mp: 231.26 y _i o h-

Analysis calculated for C 46.15% H 6.45% N 23.92% Li 2.96% Found C 46.04% H 6.33% N 23.73% Li 2.68%.

In a similar manner, the following compounds of the invention were prepared:

Name of the compound Physical Constants

2- (dimethylcarbamoylamino) -5-isopropyl-M.p .: 288 ° C

1.3.4-Thiadiazolin-3-yl, sodium salt (decomposed)

5-tert-butyl-2- (dimethylcarbairoylamino) - m.p .: 306 ° C

1.3.4-Thiadiazolin-3-yl, sodium salt (decomposed)

5-ethyl-2- (dimethylcarbamoylamino) -p .: 250 ° C

1.3.4-Thiadiazolin-3-yl, potassium salt

5-ethyl-2- (dimethylcarbamoylamino) -p .: 250 ° C

1.3.4-Thiadiazolin-3-yl, lithium salt

2- (dimethylcarbamoylamino) -5-propyl-M.p .: 250 ° C

1.3.4-Thiadiazolin-3-yl, sodium salt

5-isobutyl-2- (dimethylcarbamoylimino) - m.p .: 250 ° C

1.3.4-Thiadiazolin-3-yl, sodium salt

2- (dimethylcarbamoylamino) -5-isopropyl-Jp .: 250 ° C

1.3.4-Thiadiazolin-3-yl, lithium salt

2- (dLmethyl) carbamoylimino) -5-methyl- Jp .: 25GUC

1.3.4-Thiadiazolin-3-yl, sodium salt

5- (1,1-dimethylbutyl) -2- (dimethyl-Jp .: 250 ° C

carbanoylimino) -1,3,4-thiadiazolin-3-yl, lithium salt

5-butyl-2- (dimethylcarbamoylimino) - m.p .: 250 ° C

1.3.4-Thiadiazolin-3-yl, sodium salt

5-butyl-2- (dimethylcarbamoylimino) - m.p .: 230 ° C

1.3.4-Thiadiazolin-3-yl, lithium salt 10 64362

The compounds according to the invention are colorless and odorless crystalline substances which are excellently soluble in water and in highly polar organic solvents such as carboxylic acid amides, e.g. dimethylformamide, sulfoxides, e.g. dimethyl sulfoxide, lower alcohols, e.g. methanol and ethanol, acetyls, carboxyls. they are less soluble and do not dissolve at all in hydrocarbons, halogenated hydrocarbons, ethers and ketones.

The following examples illustrate the effect of the 2- (dimethylcarbamoylamino) -1,3,4-thiadiazolin-3-idi derivatives of the invention.

Example A

In the greenhouse, the compounds according to the invention shown in the table were sprayed at a rate of application of 5 kg of active substance / ha, dissolved in 500 liters of water / ha of Sinapis sp. and Solanum sp. related plants, acting as test plants under pre-emergence and post-emergence treatments. At 3 weeks after treatment, the result of the treatment was evaluated, where 0 = no effect and 4 = destruction of plants

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

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13 64362

Example B

The plants presented were treated in the greenhouse before they emerged with the said substances using the indicated application rate. The substances were applied for this purpose as an aqueous solution with an application rate of 1 kg of active substance / ha and 50 Q liters of water / ha evenly in the soil. The results show that the compounds of the invention have a better effect than the known substance.

14 64362

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Example C

In the greenhouse, the plants shown were treated after germination with said substances at an application rate of 1 kg of active substance / ha. For this purpose, the substances were sprayed evenly on the plants. Also in this case, 3 weeks after the treatment with the substances according to the invention, there is a good selectivity, the effect on weeds being excellent. The reference substance did not have this good effect.

16 64362

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In the following, the herbicidal properties of the compounds according to the invention have been compared with those of the compounds known from DE-A-2 002 764. The plants were treated in a greenhouse. compounds.

Herbicide test before germination 1. Plant cultivation

The plants were planted in plastic pots containing pot soil with a large amount of organic material with strong adsorption capacity (high humus soil). Six seeds per plant were planted so that the depth was the same as the diameter of the seed. Immediately after planting, the pots were watered by spraying. The plants were planted the day before treatment with Herbi-s ideas.

2. Processing

The test compound was applied at 1 kg / ha with a spray volume of 500 l / ha. Spraying device used, ie as follows:

Nozzle speed: 3.7 - 3.8 m / s

Air pressure: 2.5 atm overpressure

Nozzle Type: Teejed No. SS 8002 E

Nozzle discharge rate: 100 ml / 8.2 s Compositions were prepared from the following components: 200 mg test compound (1 kg / ha) 1.2 g Tonsil®, Zellpech Arkcpon ®

The components were triturated by hand and suspended in 100 ml of water. Spraying was performed with a device with a removable nozzle. The pots were placed in wooden containers and after spraying they were transferred to the greenhouse. During the observation period, irrigation took place from inside the pots.

3. Results

Three weeks after treatment, the effect of the test compounds on the plants was evaluated visually. The herbicidal effect was expressed as numbers 0-10, where 0 meant that the plant had been completely eradicated and 10 meant that there was no noticeable damage to the plant. The results are shown in the following tables and show that the compounds of the invention are considerably more potent than the compounds in question. known compounds.

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