CS244143B2 - Herbicide and efficient substance production method - Google Patents

Description

The present invention relates to a herbicidal composition comprising as active ingredient new cyclohexenone derivatives. The invention further relates to a process for the preparation of these novel cyclohexenone derivatives.

It is known that cyclohexane-1,3-dione derivatives with hetarocyclicyl substituents at the e-position with helogenelkenyloaluminophenylddenyl residues at the 2 'position are herbicidally active (cf. EP-OS 00 71 707). 5-Tetrelyrdrothiopyranylcycoohexenedione derivatives with helogenalkenyloty. residues such as oxime substituents have not yet been disclosed.

It has now been found that herbicidal compositions which occupy cyclohexenone derivatives of formula X

(I) in which? is alkyl of 1 to 4 carbon atoms and ¹² is chloro-alkenyl of 3 to 5 carbon atoms, or salts thereof are excellent herbicidally effective.

Compounds of formula X may exist in tautomeric forms, all of which are within the scope of this invention:

In the general formula X, the general symbols have the following meanings:

and

R 'represents a methyl group, a stylish group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a target, a butyl group or an isobutyl group and

R ² represents alkenytovou group 3 ^and 5 atoms in ^ TKU which otaataje ^{1 and 3} chlorine atoms, such as cis-3-chlooelly0ovoj group, trans-3-chlirellylovou group, cis-3-chloro-2-methylchloroformamidium nominal group, trans-1-chlorobut-4-enyl, 2-chloro-butyl or 2,3,3-O-chloroprop-2-yl.

Preferred cyclohexenone derivatives of the formula X are those in which R declared unto ^3-chloro-l oo ^{r r} ro-2-enyl. Preferred sta ^ ^{us, R1} is methyl, ethyl, n-propyl, preferred style, and n-poopylová group. .

Suitable salts of the compounds of the formula (X) are, for example, alkali metal salts, in particular potassium or sodium salts, alkaline earth metal salts, in particular calcium salts, magnesium salts or barium salts as well as copper salts, copper salts, copper salts. , zinc salts or iron salts as well as ammonium salts and phosphonium salts, for example alkylammonium salts, dialtylammonium salts, trielkylenionium salts or tetrealtylanionium salts, benzyltrialkylemmonium salts, triphenylphosphonium salts. i, triallylsulfonium salts or trislylsulfoxonium salts.

Accordingly, the present invention provides a herbicidal composition, characterized in that it contains at least one cyclohexenone derivative of the aforementioned and defined formula I or a salt thereof as an active ingredient.

According to the invention, the compounds of formula (I) as defined above are prepared by reacting compounds of formula (II)

wherein ^h has ora hereinbefore defined, with hydroxylamine of the formula and j-NH in which

B is as hereinbefore defined, which is optionally present in the form of an aqueous solution in inert diluents at a temperature between 0 ° C and 70 ° C.

Aqueous solvents for this reaction are, for example, alcohols, such as methanol, ethanol, isopropanol, cyclohexanol, and optionally chlorinated hydrocarbons such as hexane, methylene chloride, toluene, dichloro, esters, such as triethyls, cyclic ethers, as tetrahydrofurlo ·

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

Other metal salts, such as. salts of maten, copper, iron, calcium, magnesium and barium can be prepared from sodium salts by reaction with the corresponding metal chlorides in aqueous solution. The ammonium and phosphorus salts may be prepared by reacting the compounds of formula I with ammonium, phosphonium, sulfonium, or sulfonium (III) salts, optionally in aqueous solution.

Compounds of formula II may be prepared from cyclohexane-1,3-οοϋ of formula IV,

which may also be present in the tautomeric form of formula IVa . OH / - \ O (IV) (IVa) ^O

by methods known from literature (Tetrahedron Letters, 29, 2,491 (1975)) ·

It is also possible to produce compounds of formula II via intermediate enol esters which are reacted in the reaction of compounds of formula IV and which are redirected in the presence of iBL -dezole or pyridine derivatives (cf. JP-OS 79/063052).

The compounds of formula (IV) are obtained by procedures known from the lieerature, as shown in the following scheme:

ch ₃ oh ch ₂ (cooch ₃ ) ₂

CH ₃ ONa

HoCOOC

C-CH ₂ - COOCH3 / CH3ON ·

_CH2 (COOH) pyridine

CH = CH-C-OH

in

CH-CH-COOCH 3

1) KOH

2) HCl

The following example illustrates the preparation of cyclohexenone derivatives of formula (I). The parts by weight and parts by volume are relative to each other as kilogram to liter.

Example 1

14.1 parts by weight of 2- (n-butyryl) -5- (tetropyridinopyridan-3-yl) cyclohexan-1-ol, dissolved in 100 parts by volume of methylene chloride, 7.9 was added to the obtained solution. and about 4.6 parts by weight of sodium bicarbonate and 4.6 parts by weight of sodium bicarbonate. the mixture is stirred for several hours at eíítnosti · Then the reaction mixture zehuusí, taken eθeylenchloridee, promotes the water again zahiiusí · A residue of 16 ^{1 d} clay U · of ^the SAFETY ^h with oil of IIDEX refractive ng ² я Ц5 ⁶ 6 ⁹ (Compound No. ¹⁾ .

(AND)

The following compounds of formula I can be prepared in an analogous manner:

Compound number R ¹ R ² Пр, melting point (° C), data of the @ 1 H NMR spectrum (in ppm relative to tetramethylsilane) 1 C3H7 trans-CH ₂ CH »CHCl 1,567 9 (22 ° C) 2 С _Л cis-CH 2 CH 2 CHCl 1,566.1 (22 ° C) 3 ^C 2 «5 trans-CH ₂ CH ₂ CHCl 1,572 0 (22 ° C) 4 ^C 2 ^H 5 cis-CH ₂ CH · CHCl 1.571 5 (22 ° C) 5 ch ₃ trans-CH ₂ CH-CHCl m.p. Mp 57-64 ° C 6 CHj cis-CH3HxCHCl m.p. Mp 48-50 ° C 7 ι »-0 ₃ Ηγ CHgCClsCHg Sm 1.0 (t), 4.6 (.), 5.5 (a) 8 CjHj CHgCClnCHg 2.05 (), 2.9 (t), 4.6 (a) 13 п-С _Л CHgCClaCClg 1.570 4 (25 ° C)

The herbicidal compositions according to the invention can be applied, for example, in the form of direct sprayable solutions, powders, suspensions, even of higher percentage aqueous, oily or other suspensions or dispersions, emulsions, oily dispersions, pastes, foregrounds, gritings or granules by spraying, fogging, by dusting, sprinkling or watering.

The dosage forms of these compositions are entirely within the scope of the intended use. In any case, they are intended to ensure the best possible distribution of the compositions according to the invention.

Mineral oil fractions of medium to high boiling point, 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 and oil dispersions. hydrocarbons such as benzenes toluene, xylene, paraffin, tetrahydronaphthalone, alkyl naphthalones or derivatives thereof such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclooxanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents such as dimethylformamide, dimethylsulfide -methylpyrrolidone, water.

Aqueous use forms can be prepared with emulsion concentrates, pastes or wettable powders or oil dispersions by the addition of water. For the preparation of emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized using wetting agents, adhesives, dispersing agents or emulsifiers in water. However, concentrates consisting of the active ingredient, wetting agent, adhesive, dispersant or emulsifier and, optionally, solvent or oil, which are suitable for dilution with water, may also be prepared.

Suitable surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, corresponding naphthalenesulfonic acid, phenolsulfonic, alkylerylsulfonates, alkylsulfates, alkylsulfonates, alkali metal and alkaline earth metal dibutylnaphthalenesulfonic acid salts, lauryl * · ether sulphate, sulphated fatty alcohols, as well as salts of matt thyelin and alkali metals and alkaline earth metals, salts of sulphated hexadecanols, heptedecanols, octadetaine> 1, aoli sulphated glycol ethers of fatty alcohols, condensation products foímaldehydem with phenol and p> lyooyetylenootylfenoletery, etoxylovený octylphenol noryyfenol, elkylfenolpolyglykoletery, tributylfemyLpc ^] ^; ^^^] ^; ^ l ^ C ^ ^ ^ol, esters, eltllerllpolletereltoholy, Isot ^^ ^^ e ^ Ho) !, kon DETERMINATION PRODUCTS Matte alcohols with ethylene oxide, ethoxylated castor oil, polysiloxyl]] mllkfl · grsrl, ethoxylated polyoxypropylene, leurlleltoholpolygllkoleererel4 sorbitol esters, lignin, eulfite waste liquors and meety.cellul.

Powders, dusts and dusts can be prepared by mixing or co-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 ingredients to a solid carrier. Solid carriers are, for example, mineral clays such as β1111ο <ο1, silicic acids, silicates, mothers, kaolin, calcium, limestone, lime, chalk, bolus, loess, clay, dolomite, quartz, calcium sulfate, magnesium sulfate, ground urn, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal meal, tree bark meal, wood meal and nut shell meal, powdered cellulose and other solid carriers.

The herbicidal compositions or preparations contain from 0.1 to 95% by weight of the active ingredient, preferably from 0.5 to 90% by weight. .

V follows! Examples of compositions and preparations according to the invention are given.

I. 90 parts of the hmoonoot active substance No. 13 are mixed with 10 parts of the hmoonothymaltic-.alpha.-pyrrolidone to give a solution which is suitable for use as ilimination drops.

II. 20 parts of the mono-active substance No. 2 are dissolved in a solution consisting of 80 parts of the mono (ootintch xylene, 10 parts of the editorial product 8 to 10 moles of ethoxylate with 1 mol of N-minototnolamiil oleic acid, 5 parts of the monomeric of dodecylbenzhaulfonic acid salt and 5 parts by weight of the editorial product of 40 grams with 1 mole of essential oil, and by dispersing the solution gently in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient. J

III. 20 parts by weight of the active substance No. 4 are dissolved in a mixture consisting of 40 parts by weight of mono-cyclohexene, 30 parts by weight of isoblteol, 20 parts by weight of the editorial product 7 mol% with 1 mol of 18-ethyltylphenol and 10 parts by weight. The starting product was 40 liters with 1 mol of castor oil. Layering and finely distributing this solution in 100,000 parts by weight of water gives an aqueous dispersion having a content of 0.02% by weight of the hormone-active substance.

IV. 20 parts by weight of the active substance No. 1 are dissolved in a cobweb comprising 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a temperature of 210 to 280 ° C and 10 parts by weight 40 mol of ethyl ethylxiil with 1 mol of castor oil. tyUím and finely distributing the solution into 100,000 parts by hmotněních ^dy is obtained as v ^ ^{and i t} is ersion ^wich are ^^ sehlfte ^{0.02% in} C ^Inn é substance. ^{iek k} . linhyd

V. 20 parts of the humorous active substance No. 3 ° well with 3 parts by weight of the sodium salt of II-isoiltylphthyl-tert-butylphosphate, 17 parts by weight of the sodium salt &gt;

The sulfonic acids from the sulphite waste liquors and 60 parts by weight of the powdered powder are ground to a hammer mill. By finely distributing the mixture in 20,000 parts of water, a spray suspension is obtained containing 0.1% of the mono-mono-active substance.

VI. 3 parts by weight of active substance No. 3 are mixed with 97 parts by weight of finely dispersed kaolin. In this way, a dust is obtained which contains 3% of a Umo-active substance.

VII. 30 parts of the mono-active substance No. 6 are intimately mixed with a mixture of 92 parts by weight of siliceous silica and 8 parts of non-mono-paraffin-oil-free paraffin oil. In this way, an effective formulation with good adhesion is obtained.

VIII. 20 parts of the active ingredient No. 5 are intimately mixed with 2 parts of calcium salt of dodecylbutyric acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of the condensation product of phenol, urea and formaldehyde and 68 parts of paralinic mineral oil. A stable oil dispersion is obtained.

Application of the compositions of the invention may be pre-emergence or post-emergence.

Certain crop plants are less tolerant of the active ingredients. application methods in which the herbicidal compositions are sprayed in such a way that the leaves of the susceptible crop plants remain unsprayed by the moonoosum, can be applied to the leaves of undesirable plants which grow under the crop plants or on the opaque surface soil (post directed, ley-ty).

Depending on the season of the plants to be treated and the growth stage, the active ingredient used is 0.01 to 3 kg / ha, preferably 0.025 to 0.5 kg / ha.

The effect of herbicidal compositions containing cyclohexenone derivatives of the formula I on the growth of plants from the grass family (Gramioeae) and dicotyledonous crop plants is illustrated by the following experiments carried out in a greenhouse.

As a culture container there are 300 ml plastic pots filled with Jefovifso soil with a dog content of 1.5% humus. The seeds of the test plants are sown separately by species.

Immediately thereafter, pre-emergence treatments are applied. herbicidal agents for soil surface. To this end, the herbicidal compositions are suspended in water as a dispersing medium and sprayed using fine scattering nozzles. The application rates are 3.0 kg of active ingredient per hectare.

After application of the herbicidal compositions, the containers are slightly irrigated for germination to grow. The containers are then covered with a transparent plastic sheet until the plants start growing. This covering results in a uniform germination of the test plants when these plants are still affected by the active substances.

Depending on the form of growth, the test plants are grown up to a height of from 3 to 15 cm, after which they are treated with herbicidal agents. Ко ^ Иоу soy with pS ^ uu! in which it is enriched with peat. For the purpose of pre-emergence treatment, the plants are either directly sown and grown in the same containers, or plants which are first segregated as seedlings in seeding pans and transferred to the test containers before treatment. The applied coatings for the treatment of PDO allergens are 0.015 and 3.0 kg of active ingredient (ha).

Both the preemargent and post emergence treatments are attempted in the greenhouse. ·

Experimental vessels ae are directed to the greenhouse, with temperatures of from 10 to 20 ° C being preferred for thermophilic species ae choosing warmer cities (at a temperature of 20 to 35 ° C) and for those plant species that thrive in a milder climate zone. The experiment time is 2 to 4. weeks. During this time, the plants are treated and evaluated and their reactions to the individual treatments. The evaluation is carried out on a scale of 0 to 100. In this case, a value of 100 means that the plants did not grow up or that at least the aerial parts of the plants were completely destroyed.

Plants of the following species were selected for the greenhouse experiments:

Common oat (Avena setlva), hedgehog (Echinochloa oruu-galli), soybean (Glycine mx <), jetaen (Hordeum vulgare), ryegrass (Lolium ^ ΙΗίΊοπϋ), walnut (Sataria italap), white mustard (white mustard) ), Sorghum bicolor, Sorahum halapeiue, Tritiuum eestivum, Zea mayy, Centraurea cyu ^^, Cyperus asculantus, Galium aparine, Ipomoea spec., Merrirrilis annua.

Herbicidal compositions which contain compounds known from EP-OS 00 71 707 of the general formula

Compound čiIo ”--R ---- X Ϊ OF AND ^C 2 «5 with H H II n-CjHy 0 CH3 Cl III η-Ο ₃ Ηγ 0 H Cl

Praemergehtm application:

For example, herbicidal compositions containing, as active ingredients, compounds No. 1, 2 or 4, when applied to the composition

3.0 kg of active substance / ha, against plants from the grass family (Graminnaa). White mustard (Sinapie alba) remains undamaged as a dicotyledonous test plant.

Postamergant treatment:

In the sterile treatment, the herbicidal compositions containing Compound No. 1 exhibit, at an application rate, an amount of Compound No. 1. 0.06 kg / ha and a significantly higher herbicidal effect compared to comparative composition II at an application rate of 0.125 kg / ha and comparative composition III 'to the herbaceous plant (Grandma), no damage to soybean.

Compositions No. 3 at an application rate of 0.015 kg are more effective than comparative compositions against grasses, such as the hedgehog (Echinochloa i: ιrιjsjsglli) or sorghum (Sor im im bicolor). In post emergence application at 0.125 kg active ingredient / ha, the compositions with this compound exhibit much more potent activity against the song (which may also occur as undesirable grass) than comparative formulation I in the soybean sensibility.

On the other hand, herbicidal compositions containing compounds 2 or 4, when applied with 0.06 kg of active substance / he wheat (Triticum aestivum, Vuka species), are only negligible and must be considered selective for this crop plant, while comparative agents III cause considerable damage. Also dicotyledonous crop plants tolerate treatment with said compounds.

At an application rate of 3.0 kg / ha, herbicidal compositions containing compounds No. 5, 6 or 13 as active ingredients have excellent activity against grass species. In addition, the compositions of compounds 5 or 6 have a remarkable action against Cyperus esculentus and dicotyledonous weeds, which have been selected by way of example.

In view of the compatibility of the application methods, the herbicidal compositions according to the invention can be used in a number of other species of crop plants to remove undesired wild grasses or grass-type crop plants if these are undesirable in certain places where they grow. For example, the following types of crop plants are suitable:

Botanical name

Allium сера

Pineapple comosus Arechis hypogoea Aspereguβ officinalis Bete vulgeris spec, Biss vulgeris spec.

esculenta

Bassica nepus var. napus Bressice napus var. napobressica

Bressice nepus ver, beet Bressice rape var. Silvestris Cemellie sinensis

Carthemus tinctorius Carya illinoinensis Citrus limon Citrus maxima · Citrus reticulata Citrus sinensis Coffea erebice (Coffea canephora, Cofea liberice) Cucumis melo Cucumis sativus Cynodon dactylon

Deucus cerote Eleeis guineensis Gossypium hirsutum (Gossypium arboreum Gossypium herbeceum Gossypium vitifolim) Helianthus teberosus Hevea bresiliensis

Sesame name onion pineapple peanut asparagus sugar beet fodder beet red beet rape turnip white beet rape oilse teasel safflower dye peanut lemon lemon tangerine orange coffee tree melon cucumber finger tart carrot coconut palm strawberry cotton tree cotton sow cottoncup cucumber cotton soybean cottonhead soybean cottonhead soya cottonwood

244U3

Botanical name

Humulus lupulue Ipomoea batatas Juglans regia Lactuca sativa Lens culinaris Linus usitatissimum Lycopersicon lycopersicum Melus spec.

Monothy esculenta Medicago sativa Mentha piperita Goose spec. · Nicotiana tabacum (N. rustica) Olea europasa

Oryza sativa Phaseolus lunatus Phaseolus mungo Phaseolus vulgaris Petroselium crispum spec · tuberoeum Picea abies

Abies alba Pinus spec. Pisum eativum Prunus avium Prunus donestica Prunus sulcis Prunus persica Pyrus communis Ribes sylvestre Ribes uva-crispa Ricinus communis Saccharum oxxicinarum Secale cereale Sesamum indicum Solanum tuberosum Sorghum bicolor faba Vigna sinenai (V. unguiculata) Vitia vinifera Zeemays

Saxon name hops sweet potato walnut salad lentils flax tomato apple apple tree tapioca alfalfa.

peppermint banana tree olive olive millet bean bush bean parsley spruce fir silver pine peas cherry plum almond peach pear pear currant red gooseberry castor sugar cane rye sesame potatoes sorghum bicolour spinach cocoa clover wheat blueberries cranberry bean cranberries bobberry

In order to broaden the spectrum of action and to achieve synergistic effects, the compositions of the invention may be mixed with a number of other herbicidally active compounds or groups of substances that regulate plant growth, and then the mixtures may be applied together. Diazines, 4H-3,1-benzoxazine derivatives, benzooiadiezinones, 2,6-dinitxoenilines, N-phenylcarbemates, thiolkerbamates, halocarboxylic acids, triains, amides, ureas diphenylethers, traaznones, uracils, benzofurene derivatives are suitable as components of such mixtures, cyHohexenone derivatives Other structures and longer herbicidally active substances.

In addition, it may be useful to mix the herbicidal compositions of the invention, alone or in combination with other herbicides, with longer compositions for protecting saliva and then to apply these mixtures together, e.g. Also of interest is the miscibility with mineral salt solutions. Such mixtures can be used to eliminate nutrient deficiencies and trace elements. Non-phytotoxic oils and olefin lonenates may also be added.

Claims (4)

A herbicidal composition, characterized in that it contains one cyHohexenone derivative of the general formula I, characterized in that it comprises at least R ¹ R ² represents an alkyl group having 1 to 4 carbon - atoms and represents chlorelkentylovou Sapin 3 to ⁵ carbon phorous ^ ^y ^ or a salt · 2. A composition according to claim 1, at least the ^d vyznaačuJcí en cyclohexenone derivative of general means and chlorpTop .l-S-enyl. The method according to claim 1, characterized in that it contains the formula ^I as active ingredient in which ^r 'has the meaning given in 1 5. A composition according to claim 1, characterized in that it is tren-S-chloroprop-cyclohex-2-en-1-or. It is characterized in that it is present as an active ingredient -eryyy _{OX (} emirG) buylyl] - 3 ^ hydгoxy ^^ 5 “´ ((© (гат ^ уйги ^ сруг ^ ш-З-у!) II 4. A process for the preparation of an active ingredient according to claim 1, which comprises reacting a compound of the formula: R is as defined in (1) (II) with a hydroxylamine derivative of the general formula H ² O-NH ₂ wherein. ^r2 has the appearance mentioned in item 1, which is optionally present in an aqueous solution, at temperatures between 0 and 70 ° C and optionally in the presence of an inert solvent.