HU193703B - Herbicide compositions containing cyclohexenone derivatives and process for producing the active agents - Google Patents

Abstract

The present invention relates to herbicidal compositions which contain, in addition to inert additives, new cyclohexenone derivatives or their salts as active ingredients. The compounds have the formula in which R1 and R2 have the meanings given in the description. The herbicidal compositions containing 0.1 to 95 wt .-% active ingredient are suitable for combating undesirable plant growth, especially of gramineae. formula

Description

The present invention relates to herbicides containing cyclohexenone derivatives as an active ingredient, and to a process for the preparation of new cyclohexenone derivatives.

Cyclohexane-1,3-dione derivatives substituted at the 5-position with a heterocyclic group and at the 2-position with a haloalkenyloxyaminoalkylidene are known to have herbicidal activity (European Patent Application Publication No. 0071707). 5-Tetrahydro-thiopyranyl-cyclohexanedione substituted with a haloalkenyl group on the oxime ether substituent is not known in the art.

"- · We have found that the compounds containing the cyclohexenone derivatives of the formula I have excellent herbicidal activity. In the formula

R ^{1 is C} 1-4 alkyl and

R ^{2 is C} 3 -C 5 chloroalkenyl.

The compounds of formula (I) may exist in tautomeric forms (Ia), (Ib) and (Ic); the formula (I) includes all tautomeric forms.

In the formula (i), R ^{1 is} methyl, ethyl, η-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or isobutyl and

R ^{2 is C} 3 -C 5 alkenyl containing 1 to 3 chlorine atoms, such as cis-3-chloroallyl; trans-3-chloro-a11, cis-3-chlorobut-2-enyl, trans-3-chlorobut-2-enyl, 2-chloroallyl or 2,3,3- trichloro-prop-2-enyl.

Preferred cyclohexenone derivatives are those wherein R ^{2 is} 3-chloroprop-2-enyl. R ¹ is preferably methyl, ethyl or n-propyl, especially ethyl or n-propyl.

Salts of compounds of formula I include, for example, their alkali metal salts, such as potassium or sodium salts; alkaline earth metal salts such as calcium, magnesium or barium salts and their manganese, copper, zinc or iron salts and ammonium and phosphonium salts such as alkylammonium, dialkylammonium, trialkyl or tetraalkylammonium salts, their ammonium salts, triphenylphosphonium salts, trialkylsulfonium salts or triacylsulfoxonium salts.

Compounds of formula (I) may be prepared by reacting a compound of formula (II), R ¹ as defined above, with a hydroxylamine derivative of formula R ² O-NH ₃ Y, R ² as defined above, and Y anion.

The reaction is conveniently carried out in a heterogeneous phase in the presence of an inert diluent at 0 to 80 ° C or at 0 to the boiling point of the reaction mixture in the presence of a base. Suitable bases are, for example, alkali or alkaline earth metals such as sodium, potassium, magnesium or calcium carbonate, bicarbonate, acetate, alcohol 1, hydroxide or oxide.

Organic bases such as pyridine or tertiary amine may also be used.

The reaction is carried out particularly well at pHs of 2 to 9, in particular 4.5 to 5.5. The pH adjustment may conveniently be carried out with an acetate such as an alkali metal acetate such as sodium or potassium acetate or a mixture thereof. For example, the alkali metal acetate is added in an amount of 0.5 to ² moles relative to the ammonium compound R ² O-NH ₃ Y.

Examples of the solvent include dimethylsulfoxide, an alcohol such as methanol, ethanol, isopropanol, benzene, optionally a chlorinated hydrocarbon such as chloroform, dichloroethane; hexane, cyclohexane, esters such as ethyl acetate; an ether such as dioxane, tetrahydrofuran may be used.

The reaction is complete within a few hours and the reaction product can be isolated by evaporation of the mixture, addition of water and extraction with an apolar solvent such as methylene chloride and distillation of the solvent under reduced pressure.

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

Other metal salts, such as manganese, copper, zinc, iron, calcium, magnesium and barium, may be prepared from the sodium salt by reaction with the appropriate dimethyl chloride in aqueous solution. The ammonium and phosphonium salts may be prepared by reacting the compounds of formula (I) with ammonium and phosphonium hydroxide, optionally in aqueous solution. Similarly, the sulfonium and sulfoxonium salts are obtained.

Compounds of formula (II) may be prepared from cyclohexane-1,3-dione derivatives of formula (IV), which may exist in tautomeric form (IVa), by methods known in the art (Tetrahedron Letters, 29, 2491 (1975)).

The compounds of formula (II) may also be prepared from the enol esters formed in the preparation of compounds of formula (IV) and rearranged in the presence of imidazole or pyridine derivatives (Japanese Patent Application Publication No. 79/063052).

Compounds of formula (IV) may be prepared by methods known in the art, for example, as shown in Scheme [A].

The preparation of cyclohexenone derivatives of formula (1) is illustrated in the following example. The parts by weight are related to parts by volume as kg per liter

Example 1

14.1 parts by weight of 2- (n-butyryl) -5- (tetrahydrothiopyran-3-yl) -cyclohexane-1,3-dione are dissolved

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100 volumes of methanol followed by addition of 7.9 parts of O- (trans-3-chloroallyl) -hydroxylamine hydrochloride and 4.6 parts of sodium bicarbonate. The mixture was stirred at room temperature for several hours, then concentrated, taken up in methylene chloride, washed with water and evaporated again. 16.1 parts by weight of oil are obtained; n £ ² = 1.5669 (active ingredient 1).

In an analogous manner, the compounds of formula (I) listed below can be prepared.

Compound number R ¹ R ^{2 n} D / Mp. (° C) 1. -C ₃ H ₇ trans-CH ₂ CH = CHCl 1.5669 (22 C) Second -C ₃ H ₇ cis-CH ₂ CH = CHCl 1.5661 (22 C) Third -c ₂ h ₅ trans-CH ₂ CH = CHCl 1, 5730 (22 C) 4th -c ₂ h ₅ cis-CH ₂ CH = CHCl 1.5715 (22 C) 5th -ch ₃ trans-CH ₂ CH = CBCl 57-64 6th -ch ₃ cis-CH ₂ CH = CHCl 48-50 7th -nC ₃ H ₇ -ch ₂ cci = ch ₂ 8th -C ₂ H ₅ -ch ₂ cci = ch ₂ 9th -nC ₃ H ₇ trans z-CH ₂ CH = CC ₁ CH ₃ 10th -nC ₃ H ₇ title-CH ₂ CH = CC ₁ CH ₃ 1 1 -c ₂ h ₅ trans-CH ₂ CH = CClCH ₃ 12th -nC ₃ H ₇ title-CH ₂ CH = CC ₁ CH ₃ 13th ^- nC ₃ H ₇ -ch ₂ cci = cci ₂ 1.5704 (24 ' ° C)

The herbicidal compositions containing the cyclohexenone derivatives of the formula I or their salts are, for example, directly sprayable solutions, as well as powders, suspensions, also in aqueous, oily or other suspensions with high content, dispersions, emulsions, oily dispersions, pastes, dusts, granulates spraying, spraying, spraying, dusting or spraying. The forms of application shall be adapted to the particular purpose of use and in all cases shall be such as to distribute the active substances as evenly as possible.

Medium to high boiling petroleum fractions such as kerosene or gas oil, coal tar oil, vegetable or animal oils, aliphatic, cyclic and aromatic hydrocarbons and their derivatives, e.g. paraffin, tetrahydronaphthalene, alkylated naphthalene, methanol, ethanol, propanol, butanol, chloroform, sulfur tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone; a highly polar solvent such as dimethylformamide; dimethyl sulfoxide, N-methylpyrrolidone, water and the like. can be used.

Aqueous agents which can be used directly can be prepared from emulsion concentrates, pastes or wettable powders and oil dispersions by the addition of water. For preparing emulsions, pastes or oil dispersions, the active compounds, optionally dissolved in an oil or solvent, are homogenized in water in the presence of a surfactant such as a wetting agent, tackifier, dispersant or emulsifier. Concentrates of the active ingredient and of the surfactant additive, such as wetting agents, tackifiers, dispersants or emulsifiers and optionally solvents or oils, may be prepared which may be diluted with water.

As the surfactant, the alkali metal, alkaline earth metal and ammonium salts of lignin sulfone ⁴ θ acid, naphthalene sulfonic acid, phenol sulfonic acid, alkyl aryl sulfonate, alkyl sulfate, alkyl sulfonate, dibutyl naphthalene sulfonic acid, alkali metal, lauryl ether sulfate, fatty alcohol 45 sulfate, fatty acid alkali and alkaline earth metal salts, sulfated hexadecanol, heptadecanol and octadecanol salts, sulfated fatty alcohol glycol ether salts, naphthalene and naphthalene derivatives, sulfonated naphthalene and naphthalene derivatives, condensation products of sulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl poly (glycol 55-ether), tributylphenyl poly (glycol ether), alkyl acrylic poly (ether alcohol), isotriediol alcohol, fatty alcohol and ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl er, ethoxylated polyoxypropylene, lauryl 60-alcohol-polyglycol ether-acetal, sorbitol ester, lignin, sulphite impurities and methylcellulose.

Powders, dusts, and sprays may be prepared by mixing and / or grinding the active ingredient with a solid carrier.

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Granules, such as coated, impregnated and homogeneous granules, may be prepared by binding the active ingredient to a solid carrier. Solid carriers include natural or artificial minerals such as silica gel, silicic acid, colorants, talc, kaolin, attapulgite, limestone, lime, chalk, bolus, loose, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, , fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and plant products such as corn flour, bark, wood and bone meal, cellulose powder, etc. can be used.

The agents according to the invention contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of the active ingredient.

The following examples serve to illustrate the agents of the present invention.

Example I Tr 13 is mixed with 10 tr N-methyl-alpha-pyrrolidone to give a 90% by weight mixture of the active ingredient in the form of small droplets.

II. Example 2 Tr is dissolved in 80 tr of xylene, 8-10 moles of ethylene oxide and 1 mole of N-monoethanolamide oleic acid in 10 parts by weight of a solution of 5 tr of dodecylbenzenesulfonic acid calcium salt, 40 moles of ethylene oxide and 1 mole castor oil derived from its 5 parts by weight additive. The mixture was poured into 100,000 tr of water and uniformly distributed to give an aqueous dispersion of 0.02% active ingredient.

III. EXAMPLE 1b The active ingredient tr 4 is dissolved in 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 7 parts by weight of ethylene oxide and 1 mole of isooctylphenol in 20 parts by weight, and 40 parts by weight of ethylene oxide and 1 mole of castor oil. The solution was poured into 100,000 tr of water and uniformly distributed to give an aqueous dispersion containing 0.02% by weight of active ingredient.

ARC. EXAMPLE 1b The active ingredient tr 1 was dissolved in 25 tr of cyclohexanol, 65 tr of a petroleum fraction boiling in the range of 210-280 ° C, and 40 parts of ethylene oxide and 1 mole of castor oil in 10 parts by weight. The solution was poured into 100,000 tr of water and uniformly distributed to give an aqueous dispersion containing 0.02% by weight of active ingredient.

Example V The active ingredient tr 3 is mixed thoroughly with 3 tr sodium diisobutylnaphthalene-α-sulfonic acid, 7 tr l of lignin sulfonic acid sodium salt from a sulphite slurry and 4 tr of powdered silica gel and ground in a hammer mill. The mixture was uniformly distributed in 20,000 tr of water to give a spray solution containing 0.1% active ingredient.

VI. Example 3b Tr 3 is mixed with 97 tr of powdered kaolin. A powder containing 3% by weight of active ingredient is obtained.

VII. Example 6b Tr 6 is intimately mixed with 92 tr of powdered silica gel and 8 tr of paraffin oil sprayed on the silica gel. A good adhesive is obtained.

VIII. EXAMPLE EXAMPLE 2 [0125] The active ingredient tr5 is thoroughly mixed with 2 trodecalcium benzoulfonic acid calcium salt, 8 trr of fatty alcohol poly (glycol ether), 2 tr of phenol, urea and formaldehyde condensate sodium and 68 tr of paraffinic mineral oil. A stable, oily dispersion is obtained.

The herbicides according to the invention may be applied before or after emergence. If some crop plants are less tolerant to the active ingredients, a spraying method may be used so that the sprayed herbicide does not touch the leaves of the sensitive crop, only the harmful plants underneath them or the soil surface.

The application rate of the agents according to the invention is 0.01 to 3.0 kg / ha, preferably 0.025 to 0.5 kg / ha, depending on the season, the plants and their level of development.

The effect of the compounds containing the cyclohexenone derivatives of the formula I on the development of grasses (Gramineae) and broadleaf crops was investigated in a greenhouse.

300 ml plastic flower pots filled with clay sand containing about 1.5% by weight of humus were used as breeding pots. Seeds of experimental plants were sown shallowly by species.

In the case of pre-emergence treatment, the herbicides to be tested were applied to the soil immediately after sowing. II-IV. Formulations analogous to any one of Examples 1 to 4 were emulsified in water and sprayed with a fine spray syringe. The application rate is 3.0 kg / ha.

After application, the pots were slightly watered to promote germination and development of the seeds. The pots were then covered with a transparent plastic cover until the plants were sprouted. Covering promoted uniform germination of seeds, as long as it was not affected by the active ingredients.

For post-emergence treatment, the plants were first allowed to grow to a height of 3 to 15 cm, according to their developmental nature, and then treated. Soy enriched with peat

-4193703 in soil. Post-emergence treatment was carried out on plants directly sown and sprouted in the same pot, or the seeds of the plants were first germinated and transplanted into experimental vessels a few days before treatment. Post-emergence treatment was carried out with 0.015-3 kg / ha of active compound. No cover was used for post-emergence treatment.

During both pre-emergence and post-emergence treatment, the test vessels were kept in a greenhouse; warm-loving plants at 20-35 ° C, and warmer plants at 10-25 ° C. The experimental period was 2-4 weeks. During this time, the plants were nurtured and their behavioral response was evaluated. The evaluation was carried out on a scale of 0 to 100. 100 means that the seeds are not boiled or at least the above-ground parts of the plant are completely destroyed.

Greenhouse tests were performed on the following plant species:

Avena sativa (oat), Echinochloa crus-galli, Glycine max (soybean), Hordeum vulgare (barley), Lolium multifíorum, Setaria italica, Sinapis alba, Sorghum bicolor (sorghum), Sorg ¹⁰ um halepense, Triticum aestivum (buh) Zea mays (corn), Centaurea cyanus, Cyperus esculontus, Galium aparine, Ipomoea spp., Mercurialis annua.

Compounds containing active compounds of the general formula (V) known from European Patent Application Publication No. 00 71 707 were used as comparator. These agents contained the following active substances:

Compound sign R ¹ X Y Z I ethyl S H H II n-propyl 0 methyl chlorine III n-propyl 0 H chlorine

Pre-emergence treatment

For example, during pre-emergence treatment, the herbicides containing 3.0 kg / ha of active ingredients 1, 2 or 4 had a herbicidal effect on broadleaf Sinapis alba.

Post-emergence treatment

In the post-emergence treatment, agent 1 containing 0.06 kg / ha of active ingredient II and 0.125 kg / ha of agent III significantly outweighed the herbicidal activity of the agent III. Soybean plants are not damaged. The active ingredient-containing agent at 0.015 kg / ha was more effective than the active ingredient-containing agent at grasses such as Echinochloa crus-galli or Sorghum bicolor ("shattercane"). Using the latter active ingredient at a rate of 0.125 kg / ha, wheat, which is an undesirable plant here, was significantly more effective than the known agent containing active ingredient I and was well tolerated by soy.

Contrary to the above, wheat ("Vuka") at a rate of 0.06 kg / ha of active ingredient only slightly affected the wheat ("Vuka" variety) and can be considered selective in this crop plantation, whereas has caused significant damage. The agents were well tolerated by broadleaf crop plants.

Agents containing 5, 6 or 13 active compounds at 3.0 kg / ha proved to be excellent against plants of the grass family; the agents containing active ingredients 5 or 6 still had excellent activity against Cyperus esculentus and some arbitrarily selected broadleaf weeds.

Due to the versatility of the methods of application, the agents of the present invention can be used in a variety of crop plants against harmful wild grasses and herbaceous crop plants considered to be harmful in the circumstances. The agents according to the invention can be used, for example, for weed control of the following crop plants.

50 Allium cepa Pineapple comosus Arachis hypogaea Asparagus officinalis Beta vulgar spp. altissima onion pineapple peanuts asparagus sugar beet 55 Beta vulgar spp. rapa beets Beta vulgar spp. eseulenta beetroot Brassica napus var.napus Brassica napus var napo- rape brassica beetroot SALT Brassica napus var.rapa turnip Brassica rapa can silvester carrot Camellia sinensis Tea Tree Carthamus tinctorius safflower Carya illinoinensis hikordiófa 65 Citrus limon citron Citrus maxima grapefruit

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Citrus reticulata Mandarin Citrus sinensis orange Coffea arabica (Coffea can- aphora, Coffea liberica) coffee Cucumis job melon Cucumis sativus cucumber Cynodon dactylon bermudagrass Daucus carota carrots Elaeis guineensis oil palm Fragaria vesca strawberry Glycine max soy-bean Gossypium hirsutum (Gossypium arboreum, Gossypium herbeceum, Gossypium vitifolium) cotton Helianthus annuus sunflower Helianthus tuberosus sweet potato Hevea brasiliensis seringa Humulus lupulus hop Ipomoea batat sweet potatoes Juglans regia walnut Lactua sativa lettuce Lens culinaris lens Linum usitatissimum hemp Lycopersiocon lycopersicum tomato Malus spp. Apple Manihot esculenta cassava Medicago sativa alfalfa Mentha piperita peppermint Musa spp. banana Nicotiana tabacum (N.rustica) tobacco Olea europaea olive tree Oryza sativa rice Panicum miliaceum bound Phaseolus lunatus holdbab, limabab Phaseolus mungo ground beans Phaseolus vulgaris bean Petroselinum crispum spp. tuberosum parsley Picea abies larch Abies alba fir Pinus spp. fir tree Pisum sativum pea Prunus avium cherry Prunus domestica plum Prunus dulcis almond Prunus persica peach Pyrus communis pear Ribes sylvestre red currant Ribes uva-crispa gooseberry Ricinus communis castor Saccharum officinarum sugar cane Secale cereale rye Sesamum indicum til Solanum tuberosum potato Sorghum bicolor (S.vulgare) sorghum Sorghum dochna sweet sorghum Spinacia oleracea spinach Theobroma cacao cacao tree Trifolium pratense clover Triticum aestivum wheat Vaccinium corymbosum Blueberries Vaccinium vitis-idaea cranberries Vicia faba horsebean

Vigna sinensis 6 (V.unguiculata) cow pea

Vitis vinifera grapes

Zea mays corn

Many other herbicides or growth regulators may be mixed with the agents of the invention or the agents of the invention may be used in conjunction with agents containing these agents. For example, the following compounds may be used as further active ingredients: diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dimethylanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl-. ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives and the like.

It may be useful to administer the compounds of the present invention or combinations thereof with other herbicides in admixture with other plant protection agents, for example, pesticides, fungicides, or bactericides. The agents of the present invention may also be mixed with mineral saline solutions to aid metabolism and eliminate trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added to the agents of the invention.

Table I

Pre-emergence treatment authorities material number Damage's, Z Echinochloa Setaria Sorghum hale- pense crus-galli italica First 100 100 100 Second 100 100 100 4th 100 100 100

II. spreadsheet Post-emergence treatment Impact Damage, Z substance Echinochloa number crus-galli Setaria Sorg- italica hum hale- pense First (trans) 98 III (is- 98 90 because) 45 85 70

III. spreadsheet hatching post treatment authorities Damage, Z material Echinochloa crus-galli sama 1st (trans) 95 II (known) 50

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ARC. Table 1 Post - emergence treatment

Impact Damage, 7 " substance Echinochloa crus- Triticum sam-galli eastivum I. (known) 40 60 Third (Trans) 90 90

V spreadsheet After Kikele's kezelás authorities Damage, % substance Triticum Setaria number of aestivum italica III. (known) 80 60 2. (cis) 10 90 4. (cis) 10 90

Claims (4)

CLAIMS 1. An herbicide comprising from 0.1 to 95% by weight of a cyclohexenone derivative of the formula (I) as an active ingredient. 5 - in the formula R ^{1 is C} 1 -C 4 alkyl and R ^{2 is C} 3 -C 5 chloroalkenyl - solid or liquid carrier or ¹ θ diluent - preferably natural or artificial mineral ground, aliphatic, aromatic or cyclic hydrocarbon, inorganic or organic base , mineral oil fraction - and surfactant additive - preferably dispersant, 15 emulsifiers, wetting agents, and at least one. 2. A herbicide composition as claimed in claim 1, characterized in that it comprises (I) active compound of formula I, where θ ² R ² 3-chloro-prop-2-enyl. The herbicide according to claim 1, characterized in that the active ingredient is 2- [1- (trans-3-chloroprop-2-enyloxyamine) butane] -3-hydroxy-5- (tetrahydro). -thiopyran-3-yl) -26-cyclohex-2-en-1-one. 4. A process for the preparation of cyclohexenone derivatives of the formula I, characterized in that the compound of the formula II - R ^{1 has} the meaning given above - R ² ONH ₃ Y 30 ammonium compound of the formula - R ² has the above meanings and Y is an anion, preferably a halogen atom - in an inert solvent, 0 to 80 ° C are reacted in the presence of an auxiliary base. 3 sheets with drawing formulas