Herbicide and method of its efficient substances production

The present invention relates to a herbicidal composition comprising as active ingredient novel cyclohexenone derivatives. The invention further relates to a process for the production of these novel cyclohexenone derivatives and to their use for preventing undesirable plant growth.

It is already known to use cyiclohexenone derivatives to combat undesirable monocotyledonous plants in dicotyledonous crop plants (cf. DE-A No. 2,439,104). Further, DE-A No. 3,121,355, DE-A No. 3,123,312 and DE-A No. 3,239,071 disclose heterocyclic substituted derivatives.

We have now found novel cyclohexenone derivatives of the general formula I

<img file="CS255000B2_D0001.tif" />

in which

R¹ represents 2-fluoroethyl or but-2-en-2-yl,

R² represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 2 or 3 carbon atoms,

R³ means:

2-isopropyl-1,3-dioxepan-5-yl, tetrahydrothiopyran-3-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl,

3-methyl-tetrahydropyran-4-yl, pyrid-3-yl or 4a, 7,8,8a-tetrahydro-2H, 5H-pyrano [4,3-b] pyran-3-yl, as well as and salts of these compounds useful for agricultural purposes, such as alkali metal salts, alkaline earth metal salts, manganese, copper, zinc or iron salts, as well as ammonium, sulfonium and phosphonium salts. These novel cyclohexenone derivatives have good herbicidal activity, preferably against grass species (Gramineae).

The compounds of formula I may exist in several tautomeric forms, all of which are within the scope of the present invention. Thus, for example, the compounds may exist in the following tautomeric forms:

<img file="CS255000B2_D0002.tif" />

<img file="CS255000B2_D0003.tif" />

<img file="CS255000B2_D0004.tif" />

In case R¹ is but-2-en-2-yl, then both E- and Z-isomers are meant by the respective compounds.

R² in formula (I), for example, means: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

Suitable salts of the compounds of the formula I are those suitable for agriculture, such as, for example, alkali metal salts, in particular potassium or sodium salts, alkaline earth metal salts, in particular calcium and magnesium salts, manganese, copper, zinc or iron salts as well as ammonium, sulfonium and phosphonium salts.

Accordingly, the present invention provides a herbicidal composition which comprises as active ingredient at least one cyclohexenone derivative of the formula I as defined above or a salt thereof useful for agricultural purposes, such as:

an alkali metal salt, an alkaline earth metal salt, a manganese, copper, zinc or iron salt, or an ammonium, sulfonium or phosphonium salt.

The novel compounds of the formula I are prepared according to the invention by reacting the tricarbonyl compounds of the formula II

<img file="CS255000B2_D0005.tif" />

<img file="CS255000B2_D0006.tif" />

in which

R² and R³ are as defined above, with an ammonium compound of the general formula

R 1 = NH 3 Y, wherein

R¹ is as defined above and

Y represents an anion, for example a halide such as:

a fluoride, chloride, bromide or iodide anion, a carbonate or sulfate anion, optionally in the presence of an inert solvent.

The reaction with the ammonium compound is conveniently carried out in a heterogeneous phase in an inert diluent at a temperature between 0 and 80 ° C or at a temperature between 0 ° C and the boiling point of the reaction mixture in the presence of a base. Examples of suitable bases are:

alkali metal or alkaline earth metal carbonates, bicarbonates, acetates, alkoxides, hydroxides or oxides, in particular sodium, potassium, magnesium or calcium;

organic bases such as pyridine or tertiary amines can also be used. Suitable inert diluents for this reaction step are, for example, dimethylsulfoxide, alcohols such as methanol, ethanol or isopropanol, benzene and optionally chlorinated hydrocarbons such as chloroform, dichloromethane, hexane or cyclohexane; carboxylic acid esters such as ethyl acetate; or ethers such as dioxane or tetrahydrofuran.

The reaction is complete after several hours. The reaction product can then be isolated by concentrating the reaction mixture, adding water and extracting with a non-polar solvent such as methylene chloride and distilling off the solvent under reduced pressure.

Instead of the ammonium compound, the tricarbonyl compounds of the formula II can also be reacted with a hydroxylamine of the formula

R¹O — NH2 in which

R¹ is as defined above, in inert diluents at a temperature between 0 ⁹And the boiling point of the reaction mixture, especially at a temperature between 15 and 70 ° C. The hydroxylamine can optionally also be used in the form of an aqueous solution.

Suitable solvents for this reaction are, for example, -alcohols such as methanol, ethanol, isopropyl alcohol or cyclohexanol, or chlorinated hydrocarbons such as hexane, cyclohexane, methylene chloride, toluene or dichloroethane, carboxylic acid esters such as ethyl acetate, nitriles such as acetonitrile or cyclic ethers , such as tetrahydrofuran.

The above alkali metal salts of the cyclohexenone derivative of the formula I can be obtained by reacting the compounds with sodium or potassium hydroxide in an aqueous solution or in an organic solvent such as methanol, ethanol or acetone. Sodium alkoxides and potassium alkoxides can also serve as bases.

Other metal salts, for example:

manganese salts, copper salts, zinc salts, iron salts, calcium salts and magnesium salts can be prepared from sodium salts by reaction with the appropriate metal chlorides in aqueous solution. The ammonium, sulfonium and phosphonium salts can be prepared from the novel compounds of formula I by treatment with ammonium hydroxide or phosphonium hydroxide, optionally in aqueous solution.

The tricarbonyl compounds of formula II may be prepared from cyclohexenones of formula III, which may also exist in the tautomeric form of formula ГПа,

<img file="CS255000B2_D0007.tif" />

<img file="CS255000B2_D0008.tif" />

according to methods known from the literature by reaction with carboxylic acid anhydrides (Tetrahedron Letters, 29, 2,491 (1975)).

It is also possible to prepare the tricarbonyl compounds of formula II via the intermediate stage of the enol esters. These compounds are formed in the reaction of cyclohexenones of formula III (optionally as mixtures of isomers) and can be rearranged in the presence of imidazole or pyridine derivatives (JP-A-36 052/1979).

The compounds of formula (III) can also be obtained by methods known from the literature, as shown in the following reaction scheme:

O

II

СНз — С — СНз base

O

II

R³—CH —CH — С — СНз

<img file="CS255000B2_D0009.tif" />

CH 2 (COOH) 2 pyridine o

. ¹¹

R³—СИ = СН — C — OH

<img file="CS255000B2_D0010.tif" />

СНз — OH

<img file="CS255000B2_D0011.tif" />

<img file="CS255000B2_D0012.tif" />

Aldehydes of the general formula R³The CHOs shown in the above scheme are available by methods known in the literature, for example by oxidation of the corresponding alcohols, reduction of carboxylic acid derivatives or hydroformylation of olefins.

The following examples illustrate the preparation of the novel cyclobexenone derivatives. In the examples, the parts by weight are relative to the parts by volume in a ratio as kilogram per liter.

¹The H-NM.R spectra were performed in deuterochloroform as solvent using tetramethylsilane as internal standard. ¹H-chemical shifts are reported in 6 '[ppm]. The following abbreviations are used for signal structure:

s = singlct d = doublet t = triplet q = quartet m = multiplet, ie the strongest signal.

In the examples, the but-2-en-2-yl group is abbreviated as "2-butenyl". The isomeric form is always indicated.

Example 1

7.3 parts by weight of 2-acetyl-5- (3-tetrahydrothiopyranyl) cyclohexane-1,3-dione, 3.6 parts by weight of 2-butenyloxyammonium chloride and 2.4 parts by weight of sodium bicarbonate were stirred in 100 parts by volume of methanol for 16 hours at room temperature. The solvent was distilled off under reduced pressure, the residue was stirred with a mixture of 50 parts by volume of water and 50 parts by volume of dichloromethane and the aqueous phase was extracted once with 50 parts by volume of dichloromethane. The combined organic phases were washed with water, dried over sodium sulfate and the solvent was distilled off under reduced pressure. 2- [1- (2-Butenyloxyimino) ethyl] -3-hydroxy-5- (3-tetrahydrothiopyranyl) cyclohex-2-en-1-one is obtained as a solid, m.p. 65 C (Compound No. 2). ).

Example 2 parts by weight of 2-butyryl-5- (3-tetrahydrothioipyranyl) cyclohexane-1,3-dione and 2.6 parts by weight of 2-butenyloxyamine are stirred for 16 hours at room temperature in dichloromethane. The resulting solution was washed with 5% (w / w) hydrochloric acid and water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. 2- [1- (2-Butenyloxyimino) butyl] -3-hydroxy-5- (3-tetrahydrothiopyranyl) cyclohex-2-en-1-one was obtained as an oil (Compound No. 14).

Example 3 parts by weight of 2-butyryl-5- (tetrahydrothiopyran-3-yl) cyclohexane-1,3-dione, 2.31 parts by weight of 2-fluoroethyloxyammonium chloride and 1.68 parts by weight of sodium bicarbonate are stirred in 100 parts by volume of methanol. at room temperature for 16 hours. The solvent was distilled off under reduced pressure, the residue was taken up in dichloromethane and water 1: 1 was added. The aqueous phase was separated and extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated under reduced pressure. 5.3 parts (85%) of 2- [1- (2-fluoroethyloxyimino) butyl] -3-hydroxy-5- (tetrahydrothiopyran-3-yl) cyclohexen-2-en-1-one are obtained in the form of light yellow oil (Compound No. 13).

Other cyclohexenone derivatives are listed in Table 1. These compounds are prepared in an analogous manner.

Table 1

Slouče- R³ nina č.

R²

R¹ Data ^rH-NMR spectra 'melting point (° C)

<td> 1</td><td>tetrahydrothiopyran-3-yl</td><td>methyl</td><td>2-fluoroethyl</td>

<td> 2</td><td>tetrahydrothiopyran-3-yl</td><td>methyl</td><td>2-butenyl (E) 2.3 (s), 4.45 (d), 5.65 (m)</td>

<td> 3</td><td>tetrahydrothiopyran-3-yl</td><td>methyl</td><td>3-Butenyl (Z)</td>

<td> 7</td><td>tetrahydrothlopyran-3-yl</td><td>ethyl</td><td>2-fluoroethyl</td>

<td> 8</td><td>tetrahydrothlopyran-3-yl</td><td>ethyl</td><td>2-butenyl (E) 1.1 (t), 1.75 (d), 4.5 (d)</td>

<td> 9</td><td>tetrahydrothiopyran-3-yl</td><td>ethyl</td><td>2-Butenyl (Z)</td>

<td> 13</td><td>tetrahydrothiopyran-3-yl</td><td>n-propyl</td><td>2-fluoroethyl 1.0 (t), 2.9 (m), 4.6 (t), 4.75 (t)</td>

<td> 14</td><td>tetrahydrothlopyran-3-yl</td><td>n-propyl</td><td>2-butenyl (E) 1.75 (d), 2.35 (s), 4.40 (d)</td>

<td> 15</td><td>tetrahydrothiopyran-3-yl</td><td>n-propyl</td><td>2-Butenyl (Z)</td>

<td> 19</td><td>tetrahydropyran-4-yl</td><td>methyl</td><td>2-fluoroethyl</td>

<td> 20</td><td>tetrahydropyran-4-yl</td><td>methyl</td><td>2-Butenyl (E)</td>

<td> 21</td><td>tetrahydropyran-4-yl</td><td>methyl</td><td>2-Butenyl (Z)</td>

<td> 25</td><td>tetrahydropyran-4-yl</td><td>ethyl</td><td>2-fluoroethyl</td>

<td> 26</td><td>tetrahydropyran-4-yl</td><td>ethyl</td><td>2-butenyl (E) 1.1 (t), 1.8 (d), . 3.35 (t)</td>

<td> 27</td><td>tetrahydropyran-4-yl</td><td>ethyl</td><td>2-Butenyl (Z)</td>

<td> 31</td><td>tetrahydropyran-4-yl</td><td>n-propyl</td><td>2-fluoroethyl</td>

<td> 32</td><td>tetrahydropyran-4-yl</td><td>n-propyl</td><td>2-butenyl (E) 0.95 (t), 2.9 (d), 4.5 (d)</td>

<td> 33</td><td>tetrahydropyran-4-yl</td><td>n-propyl</td><td>2-Butenyl (Z)</td>

<td> 37</td><td>tetrahydropyran-3-yl</td><td>methyl</td><td>2-fluoroethyl </td>

<td> 38</td><td>tetrahydropyran-3-yl</td><td>methyl</td><td>2-Butenyl (E)</td>

<td> 39</td><td>tetrahydropyran-3-yl</td><td>methyl</td><td>2-Butenyl (Z)</td>

<td> 43</td><td>tetrahydropyran-3-yl</td><td>ethyl</td><td>2-fluoroethyl</td>

<td> 44</td><td>tetrahydropyran-3-yl</td><td>ethyl</td><td>2-butenyl (El</td>

<td> 45</td><td>tetrahydropyran-3-yl</td><td>ethyl</td><td>2-Butenyl (Z)</td>

<td> 49</td><td>tetrahydropyran-3-yl</td><td>n-propyl</td><td>2-fluoroethyl 0.95 (t), 3.95 (m), 4.6 (t), 4.75 (t)</td>

<td> 50</td><td>tetrahydropyran-3-yl</td><td>n-propyl</td><td>2-butenyl (E) 0.95 (t), 3.2 (t), 4.45 (d)</td>

<td> 51</td><td>tetrahydropyran-3-yl</td><td>n-propyl</td><td>2-Butenyl (Z)</td>

<td> 55</td><td>3-methyltetrahydropyran-4-yl</td><td>methyl</td><td>2-fluoroethyl</td>

<td> 56</td><td>3-methyltetrahydropyran-4-yl</td><td>methyl</td><td>2-Butenyl (E)</td>

<td> 57</td><td>3-methyltetrahydropyran-4-yl</td><td>methyl</td><td>2-Butenyl (Z)</td>

<td> 61</td><td>3-methyltetrahydropyran-4-yl</td><td>ethyl</td><td>2-fluoroethyl</td>

<td> 62</td><td>3-methyltetrahydropyran-4-yl</td><td>ethyl</td><td>2-butenyl (E) 0.80 (d), 1.75 (d), 4.5 (d)</td>

<td> 63</td><td>3-methyltetrahydropyran-4-yl</td><td>ethyl</td><td>2-Butenyl (Z)</td>

<td> 67</td><td>3-methyltetrahydropyran-4-yl</td><td>n-propyl</td><td>2-fluoroethyl</td>

<td> 68</td><td>3-methyltetrahydropyran-4-yl</td><td>n-propy]</td><td>2-Butenyl (E)</td>

<td> 69</td><td>3-methyltetrahydropyran-4-y]</td><td>n-propyl</td><td>2-Butenyl (Z)</td>

<td> 91</td><td>pyrid-3-yl</td><td>methyl</td><td>2-fluoroethyl</td>

<td> 92</td><td>pyrid-3-yl</td><td>methyl</td><td>2-Butenyl (E)</td>

<td> 93</td><td>pyrld-3-yl</td><td>methyl</td><td>2-Butenyl (Z)</td>

<td> 97</td><td>pyrld-3-yl</td><td>ethyl</td><td>2-fluoroethyl</td>

<td> 98</td><td>pyrld-3-yl</td><td>ethyl</td><td>2-Butenyl (E)</td>

<td> 99</td><td>pyrid-3-yl</td><td>ethyl</td><td>2-Butenyl (Z)</td>

<td> 103</td><td>pyrid-3-yl</td><td>n-propyl</td><td>2-fluoroethyl 85-87</td>

<td> 104</td><td>pyrid-3-yl</td><td>n-propyl</td><td>2-butenyl (E) 0.95 (t), 1.7 (d), 8.5 (inter alia)</td>

<td> 105</td><td>pyrid-3-yl</td><td>n-propy]</td><td>2-Butenyl (Z)</td>

<td> 109</td><td>4a, 7,8,9a-Tetrahydro-2H-5H-pyrano [4,3-b] pyran-3-yl</td><td>methyl</td><td>2-fluoroethyl</td>

<td> 110</td><td>4a, 7,8,8a-Tetrahydro-2H-5H-pyrano [4,3-b] pyran-3-yl</td><td>methyl</td><td>2-Butenyl (E)</td>

<td> 111</td><td>4a, 7,8,8a-tetrahydro-2H-5H-</td><td>methyl</td><td>2-Butenyl (Z)</td>

-pyrano [4,3-b] -pyran-3-yl

255090

<td>Compound No.</td><td>R³</td><td>R^of</td><td>R¹</td><td>Data ^JH-NMR spectra melting point (° C)</td>

<td> 115</td><td>4a, 7,8,8a-tetrahydro-2H-5II- -pyrano [4,3-b] -pyran-3-yl</td><td>ethyl</td><td>2-fluoroethyl</td><td></td>

<td> 116</td><td>4a, 7,8,8a-tetrahydro-2H-5H- -pyrano [4,3-b] -pyran-3-yl</td><td>ethyl</td><td>2-Butenyl (E)</td><td></td>

<td> 117</td><td>4a, 7,8,8a-tetrahydro-2H-5H- -pyrano [4,3-b] -pyran-3-yl</td><td>ethyl</td><td>2-Butenyl (Z)</td><td></td>

<td> 121</td><td>4a, 7,8,8a-tetrahydro-2H-5H- -pyrano [4,3-b] -pyran-3-yl</td><td>n-propyl</td><td>2 fluoroethyl</td><td>0.95 (t), 2.9 (m), 4.6 (t), 4.75 (t)</td>

<td> 122</td><td>4a, 7,8,8a-tetrahydro-2H-5H- -pyrano [4,3-b] -pyran-3-yl</td><td>n-propyl</td><td>2-Butenyl (E)</td><td>1.75 (d), 2.9 (m), 5.6 (m)</td>

<td> 123</td><td>4a, 7,8,8a-tetrahydro-2H-5H-</td><td>n-propyl</td><td>2-Butenyl (Z)</td><td></td>

<td></td><td>-pyrano [4,3-b] -pyran-3-yl</td><td> ....</td><td>^r'' í ^;.:^г ·</td><td></td>

<td> 127</td><td>2-isopropyl-1,3-dioxepan-5-yl</td><td>methyl</td><td>2-fluoroethyl</td><td></td>

<td> 128</td><td>2-isopropyl-1,3-dioxepan-5-yl</td><td>methyl</td><td>2-Butenyl (E)</td><td></td>

<td> 129</td><td>2-Isopropyl-1,3-dioxepan-5-yl</td><td>methyl</td><td>2-Butenyl (Z)</td><td></td>

<td> 133</td><td>2-Isoproipyl-1,3-dioxepan-5-yl</td><td>ethyl</td><td>2-fluoroethyl</td><td></td>

<td> 134</td><td>2-Isoproipyl-1,3-dioxepan-5-yl</td><td>ethyl</td><td>2-Butenyl (E)</td><td>0.9 (m), 1.115 (t)_;4.45 (d)</td>

<td> 135</td><td>2-Isopropyl-1,3-dioxepan-5-yl</td><td>ethyl</td><td>2-Butenyl (Z)</td><td></td>

<td> 139</td><td>2-isoproipyl-1,3-dloxepan-5-yl</td><td>n-propyl</td><td>2-fluoroethyl</td><td></td>

<td> 140</td><td>2-Isopropyl-1,3-dioxepan-5-yl</td><td>n-propyl</td><td>2-Butenyl (E)</td><td></td>

The novel herbicidal compositions containing the cyclohexenone derivatives of the formula I as active ingredient can be used, for example, in the form of directly sprayable solutions, powders, suspensions, even highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts · Granulates and applied by spraying, fogging, dusting, sprinkling or watering. The application forms are entirely governed by the purpose of application. In any case, they are intended to ensure the finest possible distribution of the active compounds according to the invention.

Medium to high boiling mineral oil fractions, such as kerosene or diesel oil, tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic, are suitable for the production of directly sprayable solutions, emulsions, pastes or oil dispersions. hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly ipolar solvents such as dimethylsulfoxide, dimethylformamide, N-methylpyrrolidoin and water.

Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by the addition of water. To produce emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized with a wetting agent, adhesive, dispersant or emulsifier in water. However, concentrates consisting of the active ingredient, wetting agent, adhesive, dispersant or emulsifier and optionally a solvent or oil which are suitable for dilution with water may also be prepared.

Suitable surfactants are the alkali metal, alkaline earth metal or ammonium salts of ligninsulphonic acid, naphthalenesulphonic acid or phenol sulphonic acid, furthermore alkylarylsulphonates, alkyl sulphates, alkyl sulphonates, alkali metal dibutylnaphthalenesulphonic acid salts and alkaline-earth metal salts, lauryl ether sulphate, sulphate, sulphate alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulfated glyikoletherů fatty alcohols, condensation products of sulfated naftaleriu and derivatives of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol tributylfenýlpolyglvkolethery, alkylaryl polyether alcohols, isotridecyl alcohol, condensation products of fatty alcohols with ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulphite waste liquors or methylcellulose.

Powders, dusts and dusts can be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredient to solid carriers. Solid carriers are mineral clays such as silica, silica, silica, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomite, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastics, fertilizers , for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and plant products such as cereal meal, ground tree bark, wood meal and ground nut shells, powdered cellulose and other solid carriers.

The compositions according to the invention contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient.

Examples of compositions according to the invention:

Example I parts by weight of Compound No. 134 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone to give a solution which is suitable as minimal drops for application.

Example II parts of compound No. 50 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of an adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of dodecylbenzenesulfonic acid calcium salt and 5 parts by weight addition product, 40 moles of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it results in an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example III parts by weight of Compound No. 2 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mole. castor oil. Pouring this solution into 100,000% water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example IV parts by weight of active ingredient No. 104 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol. 65 parts by weight of a mineral oil fraction boiling at 210 to 280 ° C and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it yields an aqueous dispersion containing 0.02% by weight of the active ingredient.

EXAMPLE In parts by weight of active ingredient No. 14, it is well mixed with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of lignin sulphonic acid sodium salt from sulphite waste liquors and 60 parts by weight of powdered silica gel and grind well. mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

Example VI parts by weight of active ingredient No. 122 are mixed with 97 parts by weight of finely dispersed kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

Example VII parts by weight of active ingredient No. 2 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, a formulation with good adhesion is obtained.

Example VIII parts of active substance No. 50 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of phenol, urea and formaldehyde condensation product and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained.

Example IX parts by weight of active substance No. 2 are dissolved in a mixture consisting of 93% by weight of xylene and 7% by weight of an adduct of 8 moles of ethylene oxide with 1 mole of nonylphenol. A solution is obtained containing 40% by weight of the active ingredient.

The novel herbicides have good herbicidal activity, preferably against grass species (Gramineae). They are well tolerated and are therefore selective in dicotyledonous plants, as well as in monocotyledonous plants, which do not count as grasses. Among them are also active substances which additionally have a herbicidal action against dicotyledons and also those which are suitable for non-selective control or suppression of undesirable vegetation.

Application of the compositions according to the invention can be carried out either indirectly or post-emergently. If the active substances are less well tolerated by some crop plants, application methods can also be used in which the herbicidal compositions are sprayed by spraying in such a way that the leaves of the susceptible crop plants remain undamaged, if possible, while the active substances undermine the leaves. plants under them or the uncovered soil surface (post-directed, lay-by).

The application rate of the active ingredient is from 0.015 to 3 kg of active ingredient per ha, preferably 0.05 kg of active ingredient per ha, according to the season, the type of target plants and the growth stage.

The novel herbicidal compositions containing the cyclohexenone derivatives of formula I as active ingredient for plant growth can be illustrated by the following greenhouse experiments:

300 ml of plastic pots are used as containers for cultivation of crops, and they are filled with clay sandy soil containing about 3.0% humus as a substrate. The seeds of the test plants are sown separately by species. In the pre-emergence treatment, the active compounds are immediately applied to the soil surface. The active compounds are suspended or emulsified in water as a dispersing medium and sprayed by means of fine nozzles. The application rate is 3.0 kg of active substance per ha.

After application of the compositions, the containers are gently sprayed with water to accelerate germination and growth. The containers are then covered with a transparent plastic sheet until the plants have grown. This covering allows for a uniform growth of the test plants, if not already influenced by the active substances.

For the purposes of post-emergence treatment, the test plants are grown according to the form of growth up to a height of 3 to 15 cm before the test plants are treated. Soybean plants are grown in peat-enriched soil as a substrate. For the purposes of post-emergence treatment, either directly sown and grown plants in the same vessel are selected, or plants which have been first grown separately and transplanted a few days before treatment are used. The application rate for post-emergence treatment is 0.015 to 3.0 kg of active ingredient per ha. In post-merger treatment, no covering is performed.

The containers of the test plants are placed in a greenhouse, with warmer parts of the greenhouse (20-35 ° C) being chosen for the more thermophilous plant species and colder parts (10-25 ° C) for the plants with a milder climate. The experiment takes 2 to 4 weeks. During this time, the plants are treated and their response to the individual treatments evaluated. The evaluation is carried out on a scale from 0 to 100. 100 ALIGN! it means that the plants do not occur or completely destroy at least the above-ground parts of the plants.

The plants used for the greenhouse experiments were selected from the following species:

field fox (Alopecuriis myosuroides), Deaf oat (Avena fatua), sugar beet (Beta vulgaris), cornflower bluebell (Centaurea cyanus), bloody dew (Digitaria sanguinalis], hedgehog corn (Echinochloa crus-galli), soybean (Glycine) , barley (Hordeum vulgare), moth (Ipomoea spec.), annual pheasant (Mercurialis annua), rice (Oryza sativa), walnut (Setaria-italica), white mustard (Sinapis alba), sorghum (Sorghum bicolor), wheat (Triticum aestivum), corn (Zeamays).

Example В 1

Test for control of undesirable monocotyledonous plants in post-emergence treatment in a greenhouse

The herbicidal action of the active compounds No. 134, 122, 50 and 104, selected as an example, against widespread monocotyledonous weeds and plants growing from accidentally fallen seeds clearly outweighs the effect of chemically closely related derivatives. Herbicides which contained as active substances known from DE-A-1. 3 340 2'65, DE-A No. 3 239 071, DE-A No. 3 123 312 and DE-A No. 3 121 355.

The results of this test are summarized in Tables 1-4 below.

Table 1 (Control of undesirable monocotyledonous plants in post-emergence treatment in a greenhouse

<img file="CS255000B2_D0013.tif" />

sN-OR¹ '7 c

C_? Hg

<td>Example</td><td>R¹</td><td>kg / ha</td><td>Sorghum</td><td>Trial plants and% damage</td>

<td>number</td><td></td><td></td><td>bicolor *</td><td>Zea m-ays Triticum Digitaria aestive * sanguinalis</td>

0,015

0,015

1134 but-2-en-2-yl ** allyl * cultures resulting from fallen seeds

100

95

68 ** Comparative Example 17 of EP 142 741

Table 2

Control of undesirable monocotyledonous plants in post-emergence treatment in a greenhouse

<td colspan="2">O-\</td><td rowspan="2">OH / 7 ~^λο</td><td colspan="2" rowspan="2">NORWEGIAN¹ //</td>

<td></td><td>W О- /</td>

<td>Example</td><td>R¹</td><td>kg / ha</td><td colspan="2">Trial plants and% damage</td>

<td>number</td><td></td><td></td><td>Echinochloa crus galii</td><td>Digitaria sanguinalis</td>

<td> 122</td><td>but-2-en-2-yl</td><td> 0,06</td><td> 100</td><td> 90</td>

<td> * *</td><td>allyl</td><td> 0,06</td><td> 75</td><td> 75</td>

· Comparative No. 124 of EP 107 156

Table 3

Control of undesirable monocotyledonous plants in post-emergence treatment in a greenhouse

Example R¹ number

<img file="CS255000B2_D0014.tif" />

y^{, CR1}^XcH2.^CH2^CH3

Trial plants and% damage

Oryza sativa *

Echinochloa * fallen seed culture * · comparative (Compound No. 79 of EP 70 370) crus galii

0,12'5

0,125

100 ALIGN! but-2-en-2-yl allyl

Table 4

Control of undesirable monocotyledonous plants in post-emergence treatment in a greenhouse

<img file="CS255000B2_D0015.tif" />

<td rowspan="2">Example number</td><td rowspan="2">R¹</td><td rowspan="2">kg / ha</td><td colspan="3">Trial plants and% damage</td>

<td>Triticum aestlvum *</td><td>Zea mays</td><td>Avena fatua</td>

<td> 104</td><td>but-2-en-2-yl</td><td> 0.125</td><td> 100</td><td> 100</td><td> 100</td>

<td> * * .</td><td>allyl</td><td> 0 125</td><td> 59</td><td> 80</td><td> . 75</td>

<td>* culture</td><td>arose from fallen out</td><td>seeds</td><td></td><td></td><td></td>

** Comparative (Compound No. 2 of EP 66 195)

Example 2

For example, active substances Nos. 2 and 14 at a concentration of 3 kg / ha are suitable for controlling undesirable monocotyledonous plants in post-emergence treatment in a greenhouse, as shown in our tables 5 and 6, for controlling undesirable vegetation in dicotyledonous crops such as soya and sugar beet. without affecting their growth in any remarkable way. They have a higher herbicidal activity than the known comparative agents which are known from No. 3,121,355.

The test results are shown in Tables 5 and 6 below.

Table 5

Controlling undesirable monocotyledonous vegetation during post-emergence treatment in a greenhouse.

<img file="CS255000B2_D0016.tif" />

<td>Example</td><td>R¹</td><td>kg / ha</td><td colspan="2">Trial plants and% damage</td><td></td>

<td>number</td><td></td><td>Glycine</td><td>Hordeum</td><td>Alopecurus</td><td>Echinochloa</td>

<td></td><td></td><td>max</td><td>vulgare *</td><td>myosuroides</td><td>crus galii</td>

but-2-en-2-yl 0.03 10 98 ** allyl. - 0,03. 5 64 * fallen seed culture Comparative: (Compound No. 88 of EP 70 370)

98

78

T abu 1 к а 6

Controlling undesirable vegetation of monocotyledons in post-emergence treatment in a greenhouse

<img file="CS255000B2_D0017.tif" />

<td rowspan="2">Example number</td><td rowspan="2">R¹</td><td rowspan="2">R²</td><td rowspan="2">kg / ha</td><td colspan="4">Trial plants and% damage</td><td rowspan="2">Echinochloa crus galii</td>

<td>Beta vulgaris</td><td>Sorghum bicolor *</td><td>Zeá inays' </td><td>Alopecurus myosuroides</td>

<td> 2</td><td>but-2-en- -2-yl</td><td>methyl</td><td> 0,03</td><td> 0</td><td> 99</td><td> 99</td><td> 90</td><td> 97</td>

<td> # *</td><td>allyl</td><td>ethyl</td><td> 0,03</td><td> 0</td><td> .......80</td><td> 77......</td><td> 60 '</td><td> 77</td>

* fallen seed culture ** comparative (Compound No. 90 of EP 70 370)

Example В 3

Test for suppression of undesirable vegetation in pre-emergence or post-emergence treatment in a greenhouse

As can be seen from Table 7 below, the novel compounds of the invention can also be used to control undesirable dicotyledonous vegetation. In pre-emergence and post-emergence application, for example, the compound of Example 2 shows a significantly better herbicidal effect than the known active compounds.

The test results are shown in Table 7 below.

Ta b u1 k a 7

Suppression of undesirable vegetation in pre-emergence or post-emergence treatment in a greenhouse

<img file="CS255000B2_D0018.tif" />

<img file="CS255000B2_D0019.tif" />

<td rowspan="3">Example number</td><td rowspan="3">R¹</td><td rowspan="3">'R²</td><td rowspan="3">kg / ha</td><td colspan="4">Experimental plants and% damage</td>

<td rowspan="2">pre-emergence treatment of Sinapis alba</td><td colspan="3">post-emergence treatment</td>

<td>Ipamoea spec.</td><td>Centaurea cyanus</td><td>Mercurlalis annuai</td>

<td> 2</td><td>but-2-en-1-yl</td><td>methyl</td><td> 3,0</td><td> 100</td><td> 80</td><td> 85</td><td> 95</td>

<td> # *</td><td>allyl</td><td>ethyl</td><td> 3,0</td><td> 30</td><td>⁰</td><td> 120</td><td> 0</td>

<td colspan="2">·· comparative</td><td colspan="3">(compound 6. 90 of EP 70 370)</td><td></td><td></td><td></td>

2 5 5 О О О

Example В 4

Herbicidal action against undesirable monocotyledonous species and tolerance by dicotyledonous crop plant in post-emergence treatment in a greenhouse

For example, as shown in Table 8, the active ingredient of Example 49 is more herbicidally effective at undesirable monocotyledonous plants and fallen seed wheat at lower and more cropped rates with very good soybean tolerance than the compounds known from British Patent No. 2,137,200 and European Patent Specification No. 125,094.

The results are shown in Table 8 below.

<img file="CS255000B2_D0020.tif" />

Table 8

Herbicidal action against undesirable monocotyledonous plants and tolerance by dicotyledonous crop plants during post-emergence treatment in a greenhouse

<img file="CS255000B2_D0021.tif" />

\\ /

L)

<img file="CS255000B2_D0022.tif" />

<img file="CS255000B2_D0023.tif" />

<img file="CS255000B2_D0024.tif" />

x c e φ &gt;&gt;

cd bo 'bo

<img file="CS255000B2_D0025.tif" />

O o σ&gt;

ooo co r4 oo cn см

<img file="CS255000B2_D0026.tif" />

<img file="CS255000B2_D0027.tif" />

<img file="CS255000B2_D0028.tif" />

<img file="CS255000B2_D0029.tif" />

CQ

Example В 5

Test for suppression of undesirable vegetation of monocotyledons in post-emergence treatment in a greenhouse

As can be seen from Table 9 below, even at low applied concentrations of active substances Nos. 8, 26 &amp; lt; and 62, they are suitable for combating a broad spectrum of undesirable monocotyledonous plants without damaging soy as a crop plant.

The test results are shown in Table 9 below.

<img file="CS255000B2_D0030.tif" />

oo co

02 05

Table 9

Suppression of undesirable monocotyledonous vegetation in post-emergence treatment in a greenhouse

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rH

OO

O 05 O

CD

<img file="CS255000B2_D0032.tif" />

<img file="CS255000B2_D0033.tif" />

00 00

CD CD

Г - O CD O&gt; O

ООО

CO O CO OO CD O '(OO

<img file="CS255000B2_D0034.tif" />

<td>p4</td><td>opyran-4-yl ethyl an-4-yl ethyl yran-3-yl ethyl</td>

<td>Ю</td><td>3-methyltetrahydr tetrahydropyr tetrahydrothiop</td>

<td>Example number</td><td>cm to oo CO CM</td>

26

Taking into account the efficacy spectrum for weed control, crop tolerance or undesirable growth of these plants, as well as a large number of application methods, the compounds of the invention may be used in a large number of crop plants.

For example, the following types of crop plants are suitable:

<td>Botanical name</td><td>Czech name</td>

<td>Allium сера</td><td>onion</td>

<td>Pineapple comosus</td><td>pineapple</td>

<td>Arachls hypogaea</td><td>peanuts</td>

<td>Asparagus officlnalis</td><td>oil asparagus</td>

<td>Beta vulgaris</td><td>cukrová</td>

<td>sipp. altissima</td><td>beet</td>

<td>Beta vulgaris spp. rapa</td><td>fodder beet</td>

<td>Beta vulgaris</td><td>beetroot</td>

<td>spp. esculenta Brassica napus var. napus</td><td>rape</td>

<td>Brassica napus</td><td>turnip</td>

<td>var. napobrassica Brassica napus var. rapa</td><td>white beets</td>

<td>Brassica rapa</td><td>oilseed rape</td>

<td>var. Camellia sinensis</td><td>tea</td>

<td>Cart-hamus tinctorius</td><td>flare</td>

<td>Carya illinoinensis</td><td>dyeing walnut</td>

<td>Citrus limon</td><td>pecan lemon</td>

<td>Citrus maxima</td><td>lemon tree</td>

<td>Citrus reticulata</td><td>biggest tangerine</td>

<td>Citrus sinensis</td><td>orange-</td>

<td>Coffea arabica</td><td>English Translation:</td>

<td>(Coffea canephora) Cucumis melo</td><td>melon</td>

<td>Cucumis sativus</td><td>cucumber</td>

<td>Cynodon dactylon</td><td>trosku t</td>

<td>Daucus carota</td><td>carrot</td>

<td>Elais guineensis</td><td>coconut</td>

<td>Fragarla vesca</td><td>palm tree strawberry</td>

<td>Glycine max</td><td>general soya</td>

<td>Gossypium hirsutum</td><td>cotton</td>

<td>(Gossypium arboreum Gossypium herbaceum) Helianthus annuus</td><td>sunflower</td>

<td>Helianthus tuberosus</td><td>Jerusalem artichoke</td>

<td>Hevea brasiliensis</td><td>rubber culprit</td>

<td>Humulus lupulus</td><td>hop</td>

<td>Ipomoea batatas</td><td>sweet</td>

<td>Juglans regia</td><td>potato walnut</td>

<td>Lactuca sativa</td><td>walnut</td>

<td>Lens culinaris</td><td>salad edible lentils</td>

<td>Botanical name</td><td>Czech name</td>

<td>Linum usitatissimum</td><td>only</td>

<td>Lycopersicoin lycoper-</td><td>paradise</td>

<td>sicum</td><td>apple</td>

<td>Malus spp.</td><td>apple tree</td>

<td>Manihot esculenta</td><td>tapioca</td>

<td>Medicago sativa</td><td>lucerne</td>

<td>Metha piperita</td><td>peppermint</td>

<td>Musa spp.</td><td>banana tree</td>

<td>Nicotiana tabacum (N. rustica)</td><td>tobacco</td>

<td>Olea europaea</td><td>olive</td>

<td>Phaseolus lunatus</td><td>bean</td>

<td>Phaseolus mungo</td><td>bean</td>

<td>Phaseolus vulgaris</td><td>shrimp beans</td>

<td>Petroselin-erispum spp. tuberosum</td><td>parsley</td>

<td>Picea abies</td><td>spruce</td>

<td>Abies alba</td><td>Fir</td>

<td>Pinus spp.</td><td>pine</td>

<td>Pisum sativu / m</td><td>pea</td>

<td>Prunus avium</td><td>cherry</td>

<td>Prunus domestica</td><td>plum</td>

<td>Primus dulcis</td><td>almond tree</td>

<td>Prunus persica</td><td>peach</td>

<td>Pyrus communis</td><td>pear</td>

<td>Ribes sylvestre</td><td>redcurrant</td>

<td>Ribes uva-erispa</td><td>gooseberry</td>

<td>Ricinus communis</td><td>castor</td>

<td>Saccharum officlnarum</td><td>sugarcane</td>

<td>Secale cereale</td><td>rye</td>

<td>Sesanum indicum</td><td>sesame</td>

<td>Solanum tuberosum</td><td>potatoes</td>

<td>Spinacia oleracea</td><td>spinach</td>

<td>Theobroma cacao</td><td>cacao tree</td>

<td>Trifolium pratense</td><td>Clover</td>

<td>Triticum aestivum</td><td>wheat</td>

<td>Vaccinium corymbosum</td><td>blueberries</td>

<td>Vaccinium vitis-idaea</td><td>cranberries</td>

<td>Vicia faba</td><td>bob horse</td>

<td>Vigna sinensis Vigna unguiculata</td><td>bean</td>

<td>Vitis vinifera</td><td>Grapevine</td>

<td>Zea mays</td><td>maize</td>

In order to extend the spectrum of action and to achieve synergistic effects, the novel substituted cyclohexenone derivatives of the formula I can be mixed with numerous representatives of other herbicidally active or growth-regulating groups of active substances and then applied together. For example, Talk is a component of the mix for this purpose:

diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones,

2,6-dinitroanilines,

N-phenylcarbamates, halocarboxylic acids, triazines, amides,

5 5'D'ffff ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, quinolinecarboxylic acids and others.

In addition, it may be useful to apply the new herbicidal compositions alone or in combination with other herbicides also with other agents (plant protection agents, for example, pest control agents or phytopathogenic fungi or bacteria). They are also used to eliminate nutrient and trace element deficiencies, and non-phytotoxic oils and oil concentrates may also be added.