Cyclohexanedione-carboxylic-acid derivatives having a herbicidal and plant growth regulating activity.

'The invention relates'; to a liquid herbicidal composition and / or to regulate plant growth.

A herbicidal composition with a synergistic effect consisting of 20 parts is known consisting of the general formula:

θ NH — OR₂ wherein R 1 is H, 1-4 alkyl carbonyl, phenyl; R₂ is 1-4 alkyl carbon, alkenyl, alkoxy-alkyl, alkoxycarbonyl; X is alkyl, alkoxycarbonyl cyano, phenyl, methyl, irtetoxy, news, phenyl, thienyl, 5-5-pentamethylen, 4,5-tetramethylene, n = or an integer from 1-6 or a hydrate or a salt. metal of such a compound, 20 parts by weight 3-methoxy-carbonylaminophenyl-N- (3'-methylphenyl) -carbonate, 35 parts xylene as filler, 15 parts by weight dimethylformamide, 10 parts by weight etherpolioxyethylphenyl dispersion agent conditioned in the form of emulsifiable concentrate.

The object of the present invention is to expand the range of herbicidal compositions.

The problem solved by the invention is to determine the active substance and the optimal ratios.

The composition according to the invention consists in the fact that it is composed of 0.1 ... 5% active substance consisting of a cyclohexandioncarboxylic acid derivative corresponding to the general formula I:

<img file="RO92510A_D0001.tif" />

wherein A represents the radical -QR₂ or -NR₃R₄, B is hydroxyl, a -NHORj residue or a metal or ammonium salt thereof, R is C 1 -C 9 alkyl or C₃-Cg-cycloalkyl, substituted or substituted by halogen, Cp -C₄-alkoxy or C 1 -C 6 alkylthio, R₄ represents C 1 -C 6 alkyl, C 1 -C 6 halogenalkyl, C 1-6₃-C₆-alkenyl, C₃-C₆-haloalkenyl or C₃-C₆-alkynyl, R₂, R₃ and R₄ represents independently of each other hydrogen; Cj-Ce-alkyl, C₄-C₆haloalkyl; C₂-C₁₀-alkoxyalkyl, C₂-C₁₀-alchiltioalchil; C₃-C_e-alkenyl, unsubstituted or substituted by halogen, C 1 -C₄-alkoxy or Cj, -C₄-alkylthio; C₃What alkynyl; phenyl, wherein the phenyl ring is unsubstituted or substituted by halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C₄-C₄-halogenalkyl, nitro or cyan; R₃ and R₄together with the dc nitrogen atom which they are linked to, they also form a 5, 6 membered heterocycle, which may also contain an oxygen or sulfur atom in the ring; from 3 ... 10% by weight surface active agent, selected from octyl - or nonylphenolpolyethylene glycol ether, Ca dodecylbenzenesulphonate and 10 ... 92% solvent selected from cyclohexane, isopropylamine and water, possibly in the presence of adhesives and regulators of yiSeosity.

The following are examples of embodiments of the invention.

Example 1. It refers to active substances

<td>of formula I (% = percentage in</td><td colspan="2">weight).</td>

<td>Emulsion concentrate (in%)</td><td>a)</td><td>b)</td>

<td>- active substance of general formula I;</td><td> 10</td><td> '1;</td>

<td>- octylphenolpolyethylene glycol ether (4 - 5 mol ethylene oxide)</td><td> 3</td><td> 3;</td>

<td>- calcium dodecylbenzenesulfonate</td><td> 3</td><td> 3;</td>

<td>- castor oil polyglycol ether (36 mol% ethylene oxide)</td><td> 4</td><td> 4;</td>

<td>- cyclohexane</td><td> 30</td><td>I0;</td>

<td>- Chilean mixture</td><td> 50</td><td> 79.</td>

<td colspan="3">From this concentrate by dilution with water</td>

<td>emulsions can be prepared with anything</td><td colspan="2">focus-</td>

<td>you want. Example 2 Suspension concentrate (in%)</td><td>a)</td><td>b)</td>

<td>- the active substance with the general formula I</td><td> 40</td><td> 5;</td>

<td>- ethylene glycol</td><td> 10</td><td> 10;</td>

<td>- nonylphenolpolyethylene glycol (15 mol ethylene oxide)</td><td> 6</td><td> 1;</td>

<td>- sodium lignin sulphonate</td><td> 10</td><td> 5;</td>

<td>- Carboxymethylcellulose</td><td> 1</td><td> 1;</td>

<td>- 37% aqueous solution of formaldehyde</td><td> 0,2</td><td> 0,2;</td>

<td colspan="2">- silicone oil in the form of a</td><td></td>

<td>75% aqueous emulsions</td><td> 0,8</td><td> 0,8;</td>

<td>- the water</td><td> 32</td><td> 77.</td>

The finely ground active substance is intimately mixed with the additives, thus obtaining a suspension concentrate, from which by diluting with water the suspensions can be prepared with any desired concentration.

Example 3

Salt solution (in%) a) - active substance of general formula I 5 - isopropylamine 1 - octylphenolpolyethylene glycol (78 mol. Ethylene oxide) 3 - water 91

The mode of application of the above compositions is shown in the following examples:

a) Herbicidal action before emergent plants in the greenhouse sow the seeds of plants in flower pots with a diameter of 11 cm. Immediately thereafter, the earth surface is treated with an aqueous emulsion of the active substances. Use a concentration of 4 kg of active substance used per ha. Then the pots are kept in a greenhouse at a temperature of 22 ... 25 ° C and a relative atmospheric humidity of 50 ... 70%. After 3 weeks the test is interpreted and the action on the experience plants is noted according to the following scale: 1 - the plant has not sprouted or completely dead; 2—3 - very strong action; 4–6 - average action; 7-8 - weak action; 9 - without any action (like untreated control).

The results are as follows (table 1):

Table 1

<td>The plant</td><td>Alien satin</td><td>Setaria italica</td><td>Sinapis alba</td><td>Stellar average</td>

<td>Active substance: 2.37</td><td> 1</td><td> 1</td><td> 9</td><td> 9</td>

<td> 2.47</td><td> 1</td><td> 1</td><td> 9</td><td> 9</td>

<td> 2.61</td><td> 1</td><td> 1</td><td> 9</td><td> 9</td>

<td> 2.63</td><td> 3</td><td> 1</td><td> 9</td><td> 9</td>

<td> 2.64</td><td> 1</td><td> 2</td><td> 8</td><td> 8</td>

<td colspan="5"></td>

b) Herbicidal action when applying active substances after the emergence of plants

Different crops and weeds are grown from seeds in pots, in the greenhouse until they reach the stage of 4 to 6 leaves. Then the plants 30 are sprayed with aqueous emulsions of the active substance (obtained from the 25% emulsion concentrate) in a dosage of 4 kg / ha. The treated plants are then kept under optimal conditions of light, regular watering, temperature

22 ... 25 ° C and relative atmospheric humidity of 50 ... 70%. The interpretation of the test is done 15 days after the treatment according to the above scoring scheme with the following results (table 2):

Table 2

<td rowspan="2">The plant</td><td>Avena</td><td>Setaria</td><td>Lolium</td><td rowspan="2">Solanum (ycopersi- How</td><td>sinapis</td><td>Stellaria</td><td>Phaseolus</td>

<td>saliva</td><td>Italic</td><td>Perennial</td><td>white</td><td>mediate</td><td>vulgaris</td>

<td>Active substance: 2.37</td><td> 1</td><td> 2</td><td> 2</td><td> 9</td><td> 8</td><td> 8</td><td> 7</td>

<td> 2.47</td><td> 2</td><td> 4</td><td> 2</td><td> 4</td><td> 6</td><td> 8</td><td> 9</td>

<td> 2.61</td><td> 1</td><td> 2</td><td> 2</td><td> 7</td><td> 7</td><td> 8</td><td> 9</td>

<td> 2.63</td><td> 1</td><td> 1</td><td> 2</td><td> 8</td><td> 5</td><td> 8</td><td> 5</td>

<td> 2.64</td><td> 1</td><td> 1</td><td> 2</td><td> 4</td><td> 7</td><td> 8</td><td> 9</td>

c) Inhibition of growth in tropical legume cover crops (covcr erops)

Experimental plants (Centrosema piu- 50 lambs and Controsema pubescens) are cultivated until the complete development stage and then shortened by cutting to a height of 60 cm. After 7 days, the active substance is sprayed with aqueous emulsion. The 55 experimental plants are kept at a relative atmospheric humidity of 70% and 6 000 lux artificial light, 14 hours a day, at a temperature of 27 ° C during the day and 21 ° C during the night.

weeks after application the test is interpreted. For this, the growth again is compared to the control and the phytotoxicity is weighed and noted. in that. test-, the plants treated with the active substances of formula I show a marked reduction of the growth again (less than 20% growth again in the untreated control plants), without this being attacked the experimental plants.

d) Adjusting the growth of soy beans in plastic vessels with a soil-peat-sand mixture in a ratio of 6: 3: 1 soybean seeds are sown and kept in a climate-controlled room. By optimum choice of temperature, lighting, fertilizer and watering addition, the plants develop after about 5 weeks until the stage of

5 ... 6 trifolia leaves. At this point, the plants are sprayed with an aqueous solution of an active substance of formula I until well watered. The concentration of active substance reaches up to 100 g AS / ha, the interpretation is done about 5 weeks after the application of the aclhe substance. In combination with the dc coneentralc planes, the active substances of formula I, according to the invention of the oil, determine a 'remarkable size of the number and weight of the pods at the main stem.

e) Inhibition of the ridge in cereals in pots of matter! plastic with sterilized earth kept in the greenhouse resembles the sorts of Hordeum vulgare (spring barley) and Secale (spring rye) cereals and watered as needed. The seedlings are sprinkled about 21 days after sowing with the aqueous spray solution of an active substance of formula I. The amount of active substance is up to 100 g of active substance per hectare. 21 days after application the growth of cereal is noted. The treated plants show in comparison with the untreated controls a growth movement again (60 ... 90% of the control), as well as in part an increase of the diameter of the stem.

f) Inhibition of the growth of grasses in plastic capsules with soil-peat-sand mixture (6: 3: 1) kept in the greenhouse, sow the herbs Lolium perenne, Pqu pratensis, Festuca ovina, Dactglis glomerate and Cynodon dactylon and water after need. The emergent herbs are cut weekly to a height of 4 cm and about 50 days after sowing and 1 day after the last cutting they are sprayed with the aqueous spray solution of an active substance of formula I. The amount of active substance is recalculated up to 100 g of active substance per ha. 21 days after application, weed growth is estimated. The investigated compounds cause a reduction in growth again of 10 ... 30% compared to the untreated control.

When using small amounts applied, the compounds of formula I are characterized by good selective properties of growth inhibition and selectively - herbicides that make them ideally suitable for use in useful plant crops, especially sugar cane, cereals, cotton, soy, corn and rice. In this case, weeds are attacked, which until now could only be attacked with total herbicides.

The mode of action of these active substances is unusual. Many of them are translocated, meaning they are taken by the plant and transported to other places where they begin to act. Thus, for example, it is possible to attack perennial weeds up to the roots by surface treatment. The compounds of formula I already work in very small quantities compared to other herbicidal compounds and growth regulators.

In addition, the compounds of formula I have strong regulatory properties for the growth of plants that can be evidenced by an increase of the crop to the grape plants or cereals. Many compounds of formula I also present an action to prevent the growth of plants depending on the concentration. They are affected in their growth both monocotyledons and dicotylcdones.

Thus, for example, legumes grown in agriculture in tropical regions are often selectively inhibited in their growth of compounds of formula I, so that soil erosion is actually prevented between crop plants, without competing with the crop.

An inhibition of vegetative growth allows for many crop plants a denser cultivation of the crop so that a larger crop can be obtained relative to the soil surface. Another mechanism of crop growth with growth inhibitors is based on the fact that nutrients to a greater extent help flower and fruit formation, while vegetative growth is limited.

In monocotyledons, for example, herbs or also cereal crops, it is sometimes desirable and advantageous to inhibit vegetative growth. Such growth inhibition is among others of economic interest in grasses, because, for example, it is possible to reduce the frequency of grass clippings in gardens, parks and sports fields or roadside. Important is also the inhibition of growth in plants of the cabbage category and in woody plants on the roadside and near the electricity transmission lines or at all, generally in regions where strong growth is undesirable.

Important is the use of growth regulators to inhibit the growth in length in cereals, because by shortening the straw reduces or completely eliminates the danger of crushing plants before harvesting. In addition to this, the growth regulator can cause the grain to strengthen the straw, which also opposes breaking. Also, the compounds of formula I can be successfully used to prevent the potato sprouting from the stock. In potatoes it often develops in storage during winter sprouts that result in wrinkling, weight loss and rot.

In the case of larger application quantities, all the tested plants are stored in their development to the extent that they are damaged.

The present invention relates to herbicidal and plant growth regulators containing an active substance of formula I as well as to processes for pre-emergent and post-emergent weed control and for inhibiting plant growth and monocotyledons and dicotyledons, especially tropical grasses, soil and tobacco branches.

The compounds of formula ί are used in the unmodified form or, preferably, as agents together with the usual auxiliary substances in the formulation technique and for this purpose are processed, in a known manner, for example, as emulsion concentrates, directly sprayable or dilutable solutions, emulsions. , diluted, spray powders, soluble powders, powdering agents, granules, as well as encapsulations in, for example, polymeric substances. The methods of application such as spraying, blurring, powdering, spreading or pouring are suitably chosen, as well as the type of agents, the goals pursued and the conditions given.

Formulations, that is, agents containing the active substance of formula I and, possibly, a solid or liquid additive, the preparations or compositions are prepared in the known manner, for example by intimately mixing and / or milling the active substances with diluting agents such as, for example, with solvents, solid support materials and possibly surfactants.

Solvents can be considered: aromatic hydrocarbons, preferably, fractions C₈ the C₁₂ such as, for example, substituted xylene or naphthalene mixtures, Italic acid esters such as dibutyl - or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane, or paraffins, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycolmonomethyl etherone, ethylene glycol, ethylene glycol or ethylene glycol. such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and possibly epoxidized vegetable oils such as epoxidized coconut oil or soybean oil or water.

As solid support materials, for example, for powdering agents and dispersible powders, natural rock flour such as talc, calcite, kaolin, montmorilonite or attapulgite are commonly used. Highly dispersed silica or highly dispersed polymer absorbent silica can be added to improve the physical properties. As adsorbed granular support materials, porous types such as pumice stone, bricks crack, sepiolite or bentonite can be considered as non-absorbent support materials, for example, calcite or sand, in addition a multiple can be used. of prepranulated materials of an inorganic or organic nature, in particular dolomite or milled residues of plants.

As surfactant compounds, depending on the type of active substance of formula I to be formulated, non-ionic surfactants, cations and / or anions with good emulsifying, dispersing and wetting properties are considered. By tensides we will also mean mixtures of tensides. Polar anionic tensidides vi po! be so-called water-soluble soaps as well as water-soluble synthetic surfactants. As soaps can be mentioned its alkaline, alkaline-earthy salts of ammonium, possibly substituted by higher fatty acids (C₁₀-C₂₃) as, for example, sodium or potassium salts of oleic or stearic acid, or dc. mixtures of natural fatty acids which can be obtained, for example, from coconut oil or soybean oil. Fatty acid metiltaurin salts can also be mentioned. However, so-called synthetic surfactants, especially fatty sulphonates, fatty sulphates, benzimidazole sulphonates or alkylaryl sulphonates, are often used. Sulfonates or fatty sulphates are usually found with alkali, âlcaϋηό-earthy or ammonium salts, possibly substituted and have an alkyl radical of 8 to 22 carbon atoms, in which case alkyl also includes the alkyl part of acyl radicals, for example, sodium or calcium salt of ligninsulfonic acid, dodecylsulfuric acid ester or a mixture of_; fatty alcohol made from natural fatty acids. These include the salts of sulfuric acid esters and sulfonic acids of fatty alcohol and ethylene oxide adducts. derivatives; Benzimidazole sulfonates preferably contain 2-sulfonic acid groups and a fatty acid radical of 8 to 12 carbon atoms. Alkylarylsulfonates are, for example, the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a condensation product of meta-thalinsulfonic acid and formaldehyde.

Also suitable sulfates, for example, phosphoric acid ester salts of a p-nonylphenol- (4-14) -ethylene oxide and phospholipid adducts may be considered.

As nonionic surfactants, one can consider, first of all, derivatives of polyglycols of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and phenolic alkyls which may contain 3 to 30 groups of glycoleters and 8 to 20 carbon atoms in the radical. hydrocarbon (aliphatic) and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Other suitable nonionic surfactants are polyethylene oxide soluble in water soluble polypropylene glycol containing 20 to 250 groups of ethylene glycol and 10 to 100 groups of propylene glycol, ethylenediamine polypropylene glycol and alkyl polypropylene glycol and 1 to 10 carbon atoms in the chain carbon atoms. Said compounds usually contain per unit of propylene glycol 1 to 5 units of ethylene glycol.

Examples of nonionic surfactants may be mentioned nonylphenylpolyethoxyethanol, castor oil polyglycols, polypropylene polyethylene oxide adducts, tributylphenoxypoly 92510 ethanol, polyethylene glycol and cetylphenoxypolyethoxyethanol. Also, polyoxyethylensorbitan fatty acid esters such as polyoxyethylensorbitan triolate may be considered.

In cationic tensides, it is mainly quaternary ammonium salts which contain at least one N-substituent alkyl radical of 8 to 22 carbon atoms and as other substituents have lower hydroxyalkyl radicals, lower alkyl, benzyl or hydroxyalkyl radicals, optionally halogenated. . The salts are preferably found as halides, methylsulphates or ethylsulphates, for example, stearyltrimethylammonium chloride or benzyl- (2-) bromide._tchloroethyl) ethylammonium. The tensides used in the formulation technique are described, among others, in the following publications: "Mc Cutcheon's Detergents and Emulsifiers Annual MC Publishing Corp., Ridgewood, New Jersey, 1979; J. and M. Ash., "Encyclopedia of Surfactants you. I — III, Chemical Publishing Co., Inc. New York, 1980/81.

Preparations of the active substance usually contain 0.1 to 95%, in particular 0.1 to 80%, active substance of formula I, 1 to 99.9% of a solid or liquid additive and 0 to 25%, especially 0, 1 to 25% of a surfactant.

In particular, the preferred formulations have the following composition: (% = weight percent).

Emulsifiable concentrates - active substance ......... 1 to 20%, preferably 5 to 10%;

- surfactant ........, 5 to 30%, preferably 10 to 20%;

- liquid support material ...... 50 la

94%, preferably 70 to 85%;

Suspension concentrate - active substance ......... 5 to 75%, preferably 10 to 50%;

- water ........................... 94 to 25%, preferably 90 to 30%;

- surfactant ......... 1 to 40%, preferably 2 to 30%.

While as &lt;commercial values ​​sc prefers more concentrated agent, the final consumer usually uses dilute agents. The forms of: application can be diluted up to 0.001% active substance. The applied quantities usually include 0.001 at 10 kg / ha, preferably 0.025 at 5 kg / ha.

Agents may also contain other additions such as stabilizers, foams, the rule of the chair of the Examiner's committee: ing. Viscosity beads, binders, adhesion agents as well as fertilizers or other active substances for obtaining special effects.

The invention has the advantage of leading to the obtaining of herbicidal compositions which have at the same time strong regulatory properties of plant growth, which leads to the increase of the crops of the plants. culture.