FI57754C - SAOSOM SELECTIVE HERBICIDER ANVAENDBARA 1,3,4-THIADIAZOLE-2-YLUREOR - Google Patents

Description

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Patent · och refiatentyrelMft 7 AimMcm uti «* d och utiakrNtM puwieood 30.06.80 ^ (32) (33) (31) Pyri *« y muoHtme — Wj * H prior * · * 05.10.73

Federal Republic of Germany-Förbundsrepubliken Tyskländ (DE) P 2350709-7 ^ (71) Schering Aktiengesellschaft, Berlin / Bergkaxnen, DE; Miillerstrasse 170-172,

Berlin, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) Friedrich Arndt, Berlin, Ludwig Nfisslein, Berlin, Federal Republic of Germany-Förbundsrepubliken! Fyskland (DE) (7 * 0 Oy Kolster Ab (5 ^) For use as selective herbicides l ^^ - thiadiazol-4-yl ureas -S & som selective herbicide användbara 1,3, U-thiadiazol-2-ylureor

The invention relates to novel 1,3,3-thiadiazol-2-yl ureas.

Today, herbicidally active thiadiazolyl ureas are already known (German Patents Nos. 18 16,696 and 20 M M2), but these substances do not have a selective herbicidal activity.

CH Patent Publication No. 513,585 also discloses thiadiazolyl ureas for use as herbicides, which, however, do not have the same selective herbicidal activity as the compounds of the present invention.

. ....... . .

The invention relates to 1,3,3 * t-thiadiazol-2-ureas of the general formula S ff / R2 Ει-3 (0) η for use as selective herbicides. 1-.-00-1./ (I) having alkyl, allyl or butenyl having 1 to 8 carbon atoms, is hydrogen or methyl, R 1 is allyl, methoxy or, if allyl or butenyl, also methyl, and n is 1 or 2.

2 57754

The compounds according to the invention can be used as herbicides both in the soil and when applied to the leaves of plants, and are suitable for controlling monocotyledonous and dicotyledonous weeds among useful plants.

Useful crops include peanuts, potatoes, peas, maize and millet.

The compounds according to the invention control, for example, field-rich plants such as Stellaria media, Senecio vulgaris, Matricaria Chamomilla, Lamium amplexicaule,

Galium aparine, Chrysanthemum segetum, Ipomea purpurea, Sinapis sp., Solanum sp., Setaria italics, Setaria feberi and Poa annua.

Depending on the compound and the intended use, about 0.5-5 kg of active ingredient / ha is usually used for weed control. Use can take place before or after plant development.

The active ingredients according to the invention can be used as such or mixed with other active ingredients. Other plant protection and pest control agents may also be added, e.g. fungicides, nasicides or other agents depending on the intended use. It is also possible to add fertilizers.

Other herbicides may be added to broaden the spectrum of action or to destroy desert vegetation. Examples of herbicidal admixtures are triazines, aminotriazoles, anilides, diazines, uracils, aliphatic carboxylic acids and halocarboxylic acids, halogenated benzoic acids and phenylacetic acids and carboxylic acid esters, carboxylic acids, nitric oxides, nitric acids, hydrazides, amides, amides, 3,6-Trichlorobenzyloxypropanol and rhodan-containing substances. Other additives which may also be mentioned are non-toxic substances which enhance the herbicidal activity, e.g. wetting agents, alligators, solvents and oils.

Preferably, the active ingredients are used in the form of powders, spreads, granules, solutions, emulsions or suspensions with liquid and / or solid carriers or diluents and, if appropriate, wetting, tackifying, emulsifying and / or dispersing agents.

Suitable liquid carriers include, for example, water, aliphatic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, cyclohexanone, isophorone and in addition petroleum fractions.

Suitable solid carriers are minerals, e.g. aluminosilicate, silica gel, talc, kaolin, atta clay, limestone, silicic acid and vegetable products, e.g. flour.

Surfactants which may be mentioned are, for example, calcium lignin sulphonate, polyoxyethylene octylphenol ether, naphthalenesulphonic acids, phenolsulphonic acids, formaldehyde condensates, fatty alcohol sulphates and alkali and earth salts of fatty acids.

The active ingredient content of the preparations can vary within wide limits. Formulations 3,5754 contain, for example, about 20-80% by weight of active ingredients, about 80-20% by weight of liquid or solid carriers and up to 20% by weight of surfactants.

Previously unknown active ingredients of formula (i) can be prepared, for example, by reacting the general formula | - a compound of the formula K - H (II) is3 to react when Rg is hydrogen, a) with an isocyanate of the general formula R3 - N - C = O (III) dissolved in an organic solvent or, when R_ is methyl, db) with an inert solvent , general formula / CH-

With a carbamoyl halide according to Hal - Co - NJ (IV) ^ S3 in the presence of an acid scavenger, or c) reacting with a carbonic acid ester halide, preferably carbonic acid phenyl ester chloride or thioic acid S-phenyl ester chloride or phosgene, in the presence of an acid scavenger, in the presence of an acid scavenger / 0¾ m (v)

\ R

With the amine of R 3 and the reaction product obtained is optionally treated in a solvent with an oxidant, preferably an organic hydroperoxide, peracid or an inorganic oxidant, preferably an organic hydroperoxide, peracid or an inorganic oxidant, wherein R 1 and n are as defined above and Hal is a halogen atom.

The kind! for the preparation of compounds of formula (i) in which n is 2, in addition to the oxygenates already mentioned, inorganic oxygen-free, e.g. chlorine or potassium permanganate, chromic acid or its salts or nitric acid can be used at a temperature of 0 to 120 ° C.

In this case, four oxidation equivalents or, if desired, an excess of at least twice the amount used in the sulfoxidation described above are preferably used per mole of the thio compound in the preparation of compounds in which n 11 57754 is 1.

Compounds in which R 1 is methoxy can be prepared from the general formula “3 / * 2

R - S (O) -I J- N - CO - N

\ 0H

by methylation, e.g. with methyl iodide or dimethyl sulphate, optionally with organic bases, e.g. triethyl sulphate, optionally with organic bases, e.g. triethylamine, dimethylaniline or inorganic bases, e.g. sodium or potassium hydroxide.

As the reaction precursor, organic solvents such as carboxylic acids, e.g. acetic acid, ethers, e.g. dioxane, ketones, e.g. acetone, acid amides, e.g. dimethylformamide, nitriles, e.g. acetonitrile and the like, alone or in aqueous mixtures, can be suitably used.

As the carbonic acid ester halides, carbonic acid phenyl ester chloride and thioic acid S-phenyl ester chloride are preferably used to give, e.g. with an amine, e.g. dimethylamine.

In the process in which hydrohalic acid is formed, organic bases which bind it are added, such as tertiary amines, e.g. triethylamine or dimethylaniline, pyridine bases or suitable inorganic bases, e.g. alkali and alkaline earth metal oxides and hydroxides.

The reaction with carbonic chlorides takes place at a temperature of about -10 ° to 150 ° C and the subsequent reaction with a dimethylamine of formula (V) at a temperature of about -10 ° to 100 ° C, but generally at room temperature.

Suitable reactants are solvents which do not react with the reactants. These include aliphatic and aromatic hydrocarbons and halogenated hydrocarbons, e.g. benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, ketones, ether compounds, K, N-dialkylated amides and nitriles.

The starting materials for carrying out the described methods are known or can be prepared by known methods.

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

1-Allyl-3-methyl-3- (5-ethylsulfinyl-1,3H-thiadiazol-2-yl) -urea

28.6 g of 2-ethylsulfinyl-5-methylamino-1,3,3 + -diadiazol are dissolved, m.p. 76 ° C, to 100 ml of tetrahydrofuran and 200 ml of acetonitrile and 8.5 g of allyl isocyanate are added with stirring. After standing overnight, the solvents are removed by distillation in vacuo. The remaining precipitate is recrystallized from 75 ml of methyl isobutyl ketone. 17.5 g (6% of theory) of 1-allyl-3-methyl-3- (5-ethylsulphonyl-1,3,1 * -thiadiazol-2-yl) urea are obtained, m.p. At 88 ° C.

5 57754 Starting steps sol are prepared by alkylation of 2-thione diethyl sulfate α-2-ethylthio-5-methylamino-1,3,3-thiadiazole, m.p. 61 ° C and then oxidizing with hydrogen peroxide.

1,3-Dimethyl-1-methoxy-3- (5-methylsulfonyl-1,3,3-thiadiazol-2-yl) -urea

To a mixture of U, 88 g of Ν, Ο-dimethylhydroxylamine hydrochloride, 25 ml of water and 100 ml of dioxane are added 11 + ml of triethylamine. 11.15 g of N-methyl-N- (5'-ethylthio-1,3,1-thiadiazol-2-yl) urea acid chloride are added with stirring at 5 [deg.] C., m.p. T8 ° C. The reaction mixture is allowed to stand overnight, then methylene chloride and water are added, the organic phase is isolated, dried over magnesium sulfate and the solvent is removed by distillation. The residue is recrystallized from isopropyl ether to give 9.2 g of theoretical) 1,3-dimethyl-1-methoxy-3- (5-methylthio-1,3,1 + -thiadiazol-2-yl) urea, m.p. . 85 ° C.

Urea acid chloride is prepared by phosgenation of 2-methylamino-5-methyl-thio-1,3, h-thiadiazole.

Dissolve 9.2 g of 1,3-dimethyl-1-methoxy-3- (5-methylthio-1,3,1 * -thiadiazol-2-yl) -urea in 100 ml of glacial acetic acid and * 0 ml of water. To this mixture, 15 g of finely divided potassium permanganate are added with stirring at 100 ° C, bringing the temperature to 70 ° C. After stirring for a further 30 minutes, the precipitated runestone is reduced at 10 [deg.] C. by dropwise addition of 9 g of sodium metabisulphite in 100 ml of water and the reaction product is precipitated in 100 ml of ice water.

Bisted 1,3-dimethyl-1-methoxy-3- (5-methylsulfonyl-1,3,1-thiadiazol-2-yl) urea melts after recrystallization from isopropanol (7.5 g = 72% theoretical) at 117 ° C.

In analogy to the above methods, the following compounds were prepared.

Compound Physical Constants 1,3-Dimethyl-1-methoxy-3- (5-ethylsulfonyl-1,3,3-thiadiazol-2-yl) -urea m.p. 72

N-allyl-3-methyl-3- (5-methyl-Q

sulfinyl-1,3,3-thiadiazol-2-yl) urea m.p. 121 C

1-allyl-3-methyl-3- (5-ethyl-

sulfonyl-1S (4-thiadiazol-4-yl) -urea m.p. 166 C

1,3-dimethyl-3- (5-allylsulfonyl-Q

1S (trans-thiadiazol-5-yl) -urea m.p. 130 C

1,3-dimethyl-3- (5-2-butenylsulfonyl) -Q

1,3,6-adiathol-2-yl) -urea m.p. 1 ^ 5 C

1-allyl-3-methyl-3- (5-methyl-Q

sulfonyl-1,3,3-thiadiazol-2-yl-urea m.p. 109 C

1,3-dimethyl-1-netoxy-3- (5'-iso pentyl-20-sulfonyl-1,3,3-thiadiazol-2-yl) -urea nQ = 1.5 ^ 05

-allyl-3-methyl--3- (5-iobutyl) -Q

sulfonyl-1,3,3-thiadiazol-2-yl) -urea m.p. 122 C

6 57754

Compound Physical Constants 1,3 "dimethyl-1-methoxy-3- (5", 1'-ethylpentylsulfonyl-1H-thiadiazol-4-yl) -1α = 1,5372 1,3-dimethyl-1-methoxy-3 - (5-methyl-

sulfinyl-1,3 (k-thiadiazol-2-yl) -urea m.p. ^ 7 ° C

1,3-dimethyl-1-methoxy-3- (5-ethyl-

sulfinyl-1,3,1-thiadiazol-2-yl) -urea m.p. 63 ° C

The compounds according to the invention are colorless, odorless, oily or crystalline substances which are sparingly soluble in water but very soluble in organic solvents, e.g. acetone, methylene chloride, tetrahydrofuran, dimethylformamide, cyclohexanone and isophorone.

The following examples illustrate the herbicidal and selective-herbicidal properties of the compounds of the invention compared to known substances. Example 1

In the greenhouse experiment, the mentioned plants were treated with substances using 1 kg of active ingredient / ha before they came to the surface.

The substances were sprayed evenly on the ground as aqueous suspensions at 500 l of water / ha. The results three weeks after treatment showed that when the substances according to the invention were very effective against weeds, they were tolerated by similarly treated crops. Instead, the reference substances damaged the crops.

Poa annua * - · · = * * “· · 7 57754

Polygonum lapathifoliurr o O cvi I m

Ipomea purpurea W I KN O

Chrysanthemum segetum h O 'o

Galium aparine Ο · K \ O .1

Amaranth retroflexus q cj h rH I

Centaurea cyanus η ι ιτν ι O

Matricaria chamomilla O O O O O

Senecio vulgaris Of h'O O

Stellaria Madia Hl KN h O

Medicago sp. O rH O o O

Allium sp. «-» c \ h ι ι I

^ Datrpus oarota cvj I O O

Solanum sp. η ι. ι O O

Sinapis sp. ο Ο K \ O O

Sowing millet η «η · η h h O Q o o o

Maize ι-ι ή rH h O o

Pea * H 1 * "·. 1 o o o O o

Deruna h r- <h h

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tDO E O 0) 0 l-P l-P

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(0 · Η · γ-Ι · Η · Η · Η Ή -Ρ ι 4-1 I

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Poa annua O O 5 7754 8

Polygonum lapathif oliur 'Λ _ o 3

Ipomea porpurea 0 o

Chrysanthemum segetur. O o

H

Galium aparine 0 0

Amarantus retroflexus O o

B

Centaurea cyanus O O

Matricaria chamomilla ^ o o

Senecio vulgaris 0 H

o # Ή

Stellaria media O

Medicago sp. o Q

Allium sp. O o

B

Oaucus carota O o r-4

Solanum sp. O o r-i

Sinapis sp. 0 0

Sowing Millet cm o r

Corn ** · Q

Herne w ®

Potato ... O

H

Peanut O

I I

B

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in cm

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9 57754

Example 2

In the greenhouse, after rising to the surface, said plants were treated with substances using 3 kg of active ingredient / ha. The substances were sprayed evenly on the plants as aqueous suspensions at 500 l / water / ha. As can be seen from the table, the substances according to the invention achieved better selectivity than the reference substance.

Poa annua cu ι ι ο i 10 57754

Setaria italica t ι ι

O I

Polygonum lapathifolium O o o O o

Ipomea purpurea Ο ι O O O

Chrysanthemum segetum ι ι I O O

Amaranth retroflexus O o o o o

Centaurea cyanus - ^, l O O

Lamium amplexicaule

o CM «H O O

Matricaria chamomilla Ο ι ι ο ι

Senecio vulgaris Ο γη o O o

Stellaria media Ο ι o O o

Medicago sp. o rH w ο κλ

Caucus carota rH ι O O

Solanum sp. Ο ι ι o o

Sinapis sd. O rH rH

o o o o

Sowing millet h r-π σ \ O o

Rice 3 3 ι co.

Maize 3 3 3 3 00

Peruna 3 3 3 S 3

Peanut 3 3 ι 3 3 t

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11

Poa annua o o ^ i lt \ 57754

Setaria italica O o h h!

Polygonum lapathlfolium O O cvj O O

Ipomea purpurea O Oh O t

Chrysanthemum segetum h i in cm

Amaranth retroflexus o o h h O

Centaurea cyanus o o -st · ο i

Lamium amplexicaule - O O H H h

Matricaria chamomilla Ο ο ι O O

Senccio vulgaris o o h o h

Stellaria media o O O O h

Medicago sp. ο ο ο ο i

Caucus oarota ι ι h O i

Solanum sp. Ο Ο ι ι. ι

Sinapis sp. O o O O h

Seed millet ι co co h h o o

Rice ι ι r H r-i

Maize ι ι ι O O

rH rH

„O O CO

Peruna h h O o

H H

Peanut oo qq o ö o o

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Poa Annua i · - * 5 7754

Satarta italica m h o

Polygonum lapathifollum. h o o • Ipomea purpurea O o o

Chrysanthemum segetum. ι O o

Amaranth retroflexus αι O o

Centaurea cyanus h o o

Lamlum amplexicaule cu ή o

Matricaria chamomilla moo

Senecio vulgaris r-t o o

Stellaria media O o o

Medicago sp. ι O o

riaucus carota 'W O O

Solanum sp. ι o O

Sinapissp. o o o Ο ο ι

Sowing logs »h γη o. . . O ι on

Rice i-o o

Maize r-ι ή oo „o o ι

Peruna h .n „o o <J \

Peanut ή I * I in n in ι in - · ·> w nj w ι I H I · Η I (0 mi m -p m -h

I · ιΗ I I | - | J

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C -P C o -P 3 (M -P H CM

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C E CL "P E Ή I — I £ 0) rH

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• H O rH «H □> i 10 OH U)

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Poa annua ° S 5,775 4

Setaria italica ° S

Polygonum lapathlfollum © 9, o o iDomea purpurea, η

Chrysanthemum segetum © S

Amarantus retroflexus O O

B

Centaurea cyanus O S

, o o

Lamium amplexicaule h

_ Matricaria chamomilla O S

Senecio vulgaris © S

Stellaria media ° 2

- Medicago sp. ° S

o o

Caucus carota iH

Solanum sp. O Q

e .. oo

Sinapis sp. r-s

Seed millet ^ S

Rice ^ 8

Maize W H

_ OJ o

Peruna «π

Peanut ^^

F-I

D I

tn cm • H I ι-H rH> 1 O >> (0

- -P

ffl ID I * rl

in XJ C

w ID O

I -H -p

'-I -P ID

lie E

- -n: o U

03 I — I »-μι o 4-} c> im« ο .π · η * rl >> «id E o o ID 4-) rH CD m -P -rl 3 ω I Li rH in Li

rH ε · | Η 3 03> 1 D

• rl "H H I -P: iD ID

ID O -P (-> 4-) I * γΗ

Li m ch tn n n ω ·> o> ι: <d> r-I L | _>, O □

B

57754 lb

Comparative Test

In the greenhouses, the plants listed in the following table were treated after their application to the surface at an application rate of 3 kg active ingredient / ha. The substances were sprayed evenly on the plants as aqueous suspensions (500 l of water / ha). As can be seen from the table, the substances according to the invention gave a better selectivity than the blood fin.

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