NO744703L - - Google Patents

Description

The present invention relates to new substituted butynyl carbamates with herbicidal action, as well as herbicides containing these compounds, and their use as herbicides.

The use of 4-chlorobutyn-2-yl-N-(3-chlorophenyl)-carbamate as a herbicide is known (DT-AS 1 137 255). However, its effect is small.

It was now found that butynyl carbamates of the formula Is

where R1 means an aryl residue which is optionally substituted in a single or mixed manner with one or more halogen atoms, nitro groups, alkyl groups, alkoxy groups, haloalkyl residues, R means hydrogen or an alkyl residue (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.butyl) or a haloalkyl residue (B-chloroethyl), • has a good herbicidal effect. The new substituted butynyl carbamates of the formula I can be prepared by reacting a 4-hydroxybutyn-2-yl carbamate of the general formula II where R<1> has the same meaning as above, with an aminosulfonyl halide of the general formula III where R 2 has the same meaning as above, and where x is halogen (for example chlorine or bromine). This manufacturing method is preferred. Likewise, the new butynylcarbamates of the general formula I can be prepared by reacting a compound of the general formula IV

where R 2 has the same meaning as above, with an isocyanate with it

general formula V where R<1> has the same meaning as above, or with a phosgene and an amine of the general formula VI

where R1 has the meaning given above.

The compounds with the general formulas II, III and IV are generally known or can be prepared as follows: Compounds with the general purpose II can be prepared by reacting a 1,4-butynediol and an isocyanate of the formula V, or phosgene and an amine with formula VI. Compounds with the formula III can, among other things, be prepared according to the methods described in Liebig's Ann. Chem. 729 40-51 (1969). Compounds of the formula IV can be prepared by reacting a 1,4-butynediol and a compound of the formula III R NHSOjX, where x is halogen.

The following examples will further illustrate the invention.

Example 1

To a solution of 23.95 parts by weight of 4-hydroxy-butyn-2-yl-N-(3-chlorophenyl)-carbamate in 650 parts by weight of methylene chloride, 20.8 parts by weight of methyl- aminosulfonyl chloride (approx. 90%) and 16.6 parts by weight of triethylamine. 30 minutes after the reaction was complete, the reaction mixture was treated with ice water, dilute aqueous hydrochloric acid, water, sodium bicarbonate solution and finally again with water. After evaporation of the magnesium sulfate-dried methylene chloride solution, 33 parts of crude product were obtained, m.p. 99-102°C.

After recrystallization from 1,2-dichloroethane/benzene, the compound melts at 103-105°c.

The compound 4-methylaminosulfonyloxy-butyn-1-yl-N-(3-chloro-phenyl)-carbamate has the following formula

The following compounds with the general formula I were prepared analogously to the method described in example 1, starting from the corresponding 4-hydroxy-butyn-2-yl-substituted carbamate and a corresponding aminosulfonyl chloride.

The active substances have a strong herbicidal effect and can therefore be used as weed killers or to combat unwanted plant growth. Whether the agents are used as total or selective agents mainly depends on the amount of active substance used per surface unit.

Food weeds or unwanted plant growth means all monocotyledonous and dicotyledonous plants which grow in places where they are not wanted.

Thus, for example, the following plants can be combated with the means according to the invention

Plants of the grass family, such as

The herbicides according to the invention are used in cereal cultures, such as and in cultures of dicotyledonous plants, such as

The amounts used of the agents according to the invention may vary. The amount depends mainly on the nature of the Desired

effect.

The amount used is usually between 0.1 and

15 kg or more, preferably between 0.2 and 6 kg, active substance per hectares. v

The agents according to the invention can be used, among other things, before planting, after planting, before sowing, before the plants emerge from the soil, after the plants have emerged from the soil or while cultivated or unwanted plants are about to emerge from the soil, and the funds can be used one or more times.

The application takes place, for example, in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusty agents, flow agents, granules, by spraying, atomizing, spreading or spreading. The forms used depend entirely on the purpose of use, one always aims to achieve the best possible distribution of the active substances according to the invention.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, mineral oil fractions with medium to high boiling points can be used, such as kerosene or diesel oil, further coal tar oils etc., as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, for example methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water etc.

Aqueous forms of use can be prepared from emulsion concentrates, pastes or wettable powders (spray powders) or oil dispersions by adding water. in the production of emulsions, pastes or oil dispersions, the substances as such or dissolved in oil or solvent can be homogenised in water using wetting, adhesive, dispersing or emulsifying agents. However, it is also possible to prepare concentrates consisting of active substance, wetting, adhesive, dispersing or emulsifying agent and any solvent or oil, which concentrates are suitable for diluting with water.

Among surfactants, Neveess can mention alkali, alkaline earth, ammonium salts of ligninsulfonic acid, naphthalene sulfonic acids, phenolsulfonic acids, alkylarylsulfonates, alkyl sulfates, alkylsulfonates. alkali and alkaline earth salts ay dibutyl naphthalene sulphonic acid, lauryl ether sulphate, fatty alcohol sulphates, alkaline and earth fatty acids

alkali salts; salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulfated fatty alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil. polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester,

lignin, sulphite liquors and methyl cellulose.

Powders, stiffeners and dust-form preparations can be produced by mixing or grinding together the active substances with a solid carrier material.

Granules, for example encasing, impregnation and homogenous granules, can be produced by binding the active substances to solid carrier materials. Solid carrier materials are, for example, mineral materials such as silica gel, silicic acids, silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess,

clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground resins, fertilizers such as ammonium sulphate, ammonium phosphate, aluminum nitrate, urea and vegetable products such as grain flour, bark, tree nut shells, cellulose powder and other solid carrier materials.

The preparations contain between 0.1 and 95% by weight of active ingredients

substance, preferably between 0.5 and 90% by weight.v

Oils of different types, herbicides, fungicides, nematocides,

insecticides, bactericides, trace elements, fertilisers, anti-foaming agents (for example silicones), growth promoters, iaot poisons or other herbicidally active compounds, such as for example

substituted anilines

substituted aryloxycarboxylase and their salts, esters and amides,

substituted ethers

substituted arsonic acids and their salts, esters and amides substituted benziroidazoles

substituted benzisothiazoles

substituted isoxazolepyrimidones

substituted imidaeols

substituted isothiazolepyrimidones

substituted ketones

substituted naphthoquinones

substituted aliphatic nitriles

substituted aromatic nitriles

substituted oxadiaeols

substituted oxadiazinones

substituted oxadiazolidinediones

substituted oxadiazinediones

substituted phenols and their salts and esters substituted phosphoric acids and their salts, esters and amides substituted phosphonium chlorides

substituted phosphonalkylglycines

substituted phosphites

substituted phosphoric acids and their salts, esters and amides substituted piperidines

substituted pyrazoles

substituted pyrazolealkylcarboxylic acids and their salts, esters and amides

substituted pyrazolium salts

substituted pyrazolium alkyl sulfates

substituted pyridazines, substituted pyridazones

substituted pyridine carboxylic acids and their salts, esters and amides

substituted benzthiadiazine dioxides

substituted benzoxazines

substituted benzoxazinones substituted benzthiadiazoles

substituted blurs

substituted quinolines

substituted carbamates

substituted aliphatic carboxylic acids and their salts, esters and amides

substituted aromatic carboxylic acids and their salts/esters

pg, amides substituted carbamoylalkyl thiols dithiophosphates substituted quinaisolines

substituted cycloalkylamide carbonthiolic acids and their salts, ©ster© and amides substituted cycloalRylcarbonaiaido-thiaEolQr

substituted dicarboxylic acids and salts, esters© and amides substituted© dihydrobenzofurany1sulfonates

substituted© disulfides

substituted© dipyridyltumsoltsr

substituted ditlocarbamator

unsubstituted dithiophosphoric acids and their salts, substituted sters and amides

substituted ©hexabydrb-1-H-knrbutioates substituted hydantc-ones substituted hydrazides

substituted© hydrazonium salts

substituted© pyridines substituted pyridine carboxylates 1 ■ substituted© pyridinones esubstituted© pyrimidines s substituted© pyrimldones

substituted© pyrrolidine carboxylic acid© and its salts, ©esters© and amides substituted©pyrrolidines

substituted pyrrolidones. tetrahydro-thiadiaBin-tions substituted©tetrahydro-thiadiasol ions

substituted© aromatic thiocarboic acid amides

substituted© thiocarboxylic acids and their salts, esters and amides substituted®; thiol carbamates ' substituted© thioureas©r substituted thiophosphoric acids and their salts, esters© and amides.

substituted triazines

sug substituted triazoles

substituted uracils

substituted uretidine diones.

The latter herbicidal compounds can be used before or after the active single substances or mixtures according to the invention.

The addition of these agents to the herbicides according to the invention can take place in a weight ratio of 1:10 to 10:1. The same applies to oils, fungicides/nematocides, insecticides, bactericides, antivenoms and growth regulators.

Example 2

In a greenhouse, different plants at a growth height of 2-18 cm were treated with the active substances

4-methylaminosulfonyloxy-butyn-2-yl-N-(3-chlorophenyl)-carbamate (I)

4-ethylarainosulfonyloxy-butyn-2-yl-N~(3-chlorophenyl)-carbamate (II)

and the active comparator substance

4-Chloro-butyn-2-yl-N-(3-chlorophenyl)-carbamate (III).

The amounts used were in each case 0.5 kg of active substance per hectare and was in each case dispersed or emulsified in 500 liters of water per hectares.

After 2-3 weeks, it was established that the active substances

I and II showed a better herbicidal effect at the same compatibility with the cultivated plants than the active substance III.

The test result will appear in the following table.

Example 3

In a greenhouse, loamy sandy soil was filled in experimental boxes, and seeds of various plants were sown. Treatment followed immediately afterwards

4-Methylarainosulfonyloxy-butyn-2-yl-N-(3-chlorophenyl)-carbamate (I)

4-ethylaminosulfonyl, alkylbutyn-2-yl-N-(3-chlorophenyl)-carbamate (II)

and in comparison with

4-chloro-butyn-2-yl-N-(chlorophenyl)-carbamate (III),

in each case with an applied quantity of 2 kg of active substance per hectare, dispersed or emulsified in 500 liters of water per hectares.

After 3-4 weeks, it was established that the active substances I and II showed a better herbicidal effect at the same compatibility with the cultivated plants than the comparative agent III.

The result will appear in the following table.

Claims (1)

Herbicide, characterized in that it contains a butynylcarbamate with the formula 1 where R means an aryl radical which is optionally uniformly or mixed substituted with one or more halogen atoms, nitro groups, alkyl groups, alkoxy groups, haloalkyl radicals, and where R 2 means hydrogen or an alkyl radical or a haloalkyl radical.