CA1239410A - Cyclohexenone derivatives, their preparation and their use for controlling undesirable plant growth - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE:

The invention relates to new cyclohexenone derivatives of the formula:

Description

I

- I 0050/3728~
Cyclohexenone derivatives, their preparation and their use for controlling undesirable plant growth The present invention relates to cyclohexenone derivatives, processes for their manufacture herbicides which contain these compounds as active ingredients, and a method for controlling undesirable plant growth It has been disclosed that cyclohexenone derive-toes can be used for controlling undesirable grasses in broad-leaved crops (DE-A-2 439 104). Moreover, DE-A-3 032 973 discloses derivatives Shea are cycloatkeny~-substituted in the 5-position and which likewise possess herb;cidal activity.
We have found that cyclohexenone derivatives of the formula I

OH

A ~-~R3 I
Al D

where A is a cycloaLkyl radical of 5 to 12 rung members which us fused with one or two ox;rane or thrown rungs, is unsubstituted or substituted my not more than four methyl groups and is bridged with an alkaline chain of not more than 3 carbon atoms, R1 is hydrogen, moth-oxycarbonyl or cyan, preferably hydrogen, R2 is alkyd of 1 to carbon atoms and R3 us alkyd of 1 to 3 carbon atoms alkenyl of 3 or 4 carbon atoms, haloalkenyl of 3 or 4 carbon atoms Shea has 1, Z or 3 halogen substitu-entice or propargyl, and salts of these compounds have a good herb;c;dal action preferably against species from the grass foamily (Grumman). They have a selective action in broad-leaved crops and in monocotyledon crops which do not belong to the Rumania The compounds of the formula I can occur in a ,; -`' , .`

- 2 - O . Z . SUE
plurality of forms all of which are embraced by the c lams:

Jo Nut DRY Jo N O R 3 A {I= A
R I/ \ R R 1 D

A -.~ C A C

Al DO

In formula I, A is a cycloalkyl radical having S
to 12, preferably 5 to 8, rung members which is Fused with one or two oxirane or thrown rings, is unsub-statewide or substituted by not more than four methyl groups and is bridged with an alkaline chain Do not more than 3 carbon atoms, ego epoxycyclopentyl, epoxycyclo-Huxley, epoxycycluheptyl, epoxycycLooctyl, epoxycyclo-dodecyl, d;epoxycyclododecyl, epoxymethylcyclopentyl, d;methylepoxycyclopentyl, epoxymethylcyclohexyl, dimethylepoxycyclohexyl, epoxytr;methylcyclohexyl, epoxytetramethylcyclohexyl, epoxybicycloheptyl, diepoxy-trimethylcyclohexyl, epoxydimethylbicycloheptyl, en;-thiocyclopentyl~ epith;ocyclohexyl or epithiobicyclo-hotly. 3,4 Epoxycyclopentyl is particularly preferred.
In formula It I is striation or branched ~lkyl of 1 to 4, preferably 2 or 3, carbon atoms, to.
methyl, ethyl, nopropyl~ isopropyl, n-butyl, sec.-butyl, i sobuty l or left buy l .
In formula I, R3 is propargyl, alkyd of 1 to 3 carbon atoms alkenyl of 3 or 4 carbon atoms or halo-alkenyl of 3 or 4 carbon atoms which may contain not I

- 3 - OOZE. 0~50/3728~
more than three halogen substituents, ego methyl ethyl, n-propyl~ isopropyl, n-butyl~ sec. bottle, isobutyl, tert~-butyl, allele 3 chloroprop-2-enyl, 2-chloroprop~
2-enyl, 1,3-dichloroprop 2~enyl or 2,3,3-trichloroprop-2-enyl.
Suitable salts of the compounds of the formula I
are those which can be used in agriculture for example the alkali metal salts, in particular the potassium or sodium salts, alkaline earth metal salts, in particular calcium, magnesium or barium salts, manganese, copper, zinc and iron salts, and ammonium, sulfonium and pros-phoneme salts.
The compounds of the formula I can be obtained by reacting a tricarbonyl compound of the formula II
o O
\ C
A r \ R2 IT

I

where A, R1 and R2 have the above meanings, with a hydroxylam;ne derivative R30-NH3Y, where R3 has the above meaning an Y is an anion.
The reaction is advantageously carried out in the heterogeneous phase in an inert delineate at From û Jo B0C or from 0C to the boiling point of the reaction mixture in the presence of a base. Examples of suit able bases are carbonates, bicarbonates, acetates, Alcoa hilts, hydroxides or oxides of alkali metals or Z5 alkaline earth metal, in particular those of sodium, potassium, magnesium and calcium. It is also possible to use organic bases, such as pardon or tertiary ammonias Examples of suitable delineates are dim ethyl sulk oxide, alcohols, such as methanol, ethanol or I

- 4 - OOZE. 0050/37Z80 isopropanol~ Bunsen, hydrocarbons and chLorohydro-carbons, such as chloroform, dichloroethane, hexane or cyclohexane, esters, such as ethyl acetate, and cyclic ethers, such as Dixon or tetrahydrofuran. Mixtures of these delineates may also be used.
The reaction is complete after a few hours, and the product can then be isolated by evaporating down the mixture, adding water and extracting with a non-polar solvent, such as ethylene chloride, and distilling off the solvent under reduced pressure.
The compounds of the formula I may furthermore be obtained by reacting a compound of the formula II with a hydroxylamine of the formula Ryan where R3 has the above meanings, on an inert delineate at from 0C to the boiling point of the reaction mixture, in particular from 15 to kiwi If necessary, the hydroxylamine can be employed in aqueous solution.
Examples of suitable delineates for this reaction are alcohols such as methanol, ethanol, ;sopropanol or I cyclohexanol, hydrocarbons and chlorohydrocarbons, such as hexane, cyclohexane, ethylene chloride, Tulane or dichloroethane, esters, such as ethyl acetate, nitrites, such as acetonitrile, and cyclic ethers, such as twitter hydrofuran.
The alkali metal salts of the compounds of the formula I can be obtained by treating these compounds with sodium hydroxide or potassium hydroxide in aqueous solution or in an organic solvent such as methanol, ethanol or acetone Sodium alcoholates and potassium alcoholates may also serve as bases.
The other metal salts, for example the mange-; nose, copper, zinc, iron calcium, magnum and barium salts, can be prepared from the sodium salts by reaction with the corresponding metal chlorides in aqueous soul-Sheehan kmmonium, sulfonium and phosphonium salts can be obtained by reacting compounds of the formula I with ammonium, suLfonium or phosphonium hydroxides, of Lo

5 w Z 0050/3~2~0 necessary in aqueous solution.
he tricarbonyl compounds of the formula II are novel. They can be prepared by conventional methods tetrahedron Lotte 29 t1975~, 2491) from cyclohexane~
Dennis of the formula III, which may also occur in the tautomeric forms IIIa and IIIb I

-A A

R 0 Al OH Al (III) (IIIa) (IIIb) It us also possible to prepare the novel come pounds of the formula II via the enlister inter-mediates which are obtained, possibly as an isomer mixture, in the reaction of compounds of the formula : III, and undergo rearrangement in the presence of an imidazole or porn derivative (JP-A-63052/1979).
As is evident from the statements above, the in-carbonyl compounds of the formula II are useful inter-mediates in the preparation of herbicidal cyclohexenone derivatives of the formula I.
The compounds of the formula XII can be obtained by methods which are known from the literature, as is evident from the scheme below:

Lo

- 6 - OOZE. 0050/37280 O f I ( ) 2 base / \ p,vridine C~$3 '\ 1 c~3-~
I ( CCX3 ) 2 C~-3QNa A Cal Croci 5 SEIKO C~OC~3/C~3 0 '. ' COG Ox 1 ) Clue ,: 2) clue ~~~ .
A< .
.
O

~Z3~

- 7 - 0 Z. 0050/3728D
Aldehydes of the general formula A SHEA can be obtained from the corresponding unsaturated aldehydes by a conventional method; it may be necessary to protect the alluded function.
The oxirane derivatives can be obtained in a conventional manner by reacting the corresponding unsaturated aldehydes or alluded derivatives with a proxy compound such as hydrogen peroxide, tert.-butyl hydroperoxide, per formic acid or m-chloroperben~o;~
acid, or with atmospheric oxygen.
The epox;de structure car, also be synthesized by elimination of hydrogen halide from 1,2-halohydrins.
The thrown compounds can be prepared either by reacting the corresponding epoxies with thiocyanates or Thor, as described in, for example, J. Chum. Sock 1946, 1050, or by reacting the corresponding unsaturated derivatives with sulfur transfer reagents, such as aureole thiosulfenyl chlorides chemistry of Heterocyclic Compounds, Al 42~ page 340). The transformation methods described above can, if desired, be carried out at any stage of synthesis.
The Examples which follow illustrate the pro-parathion of the cyclohexenone derivatives of the formula I. Parts by weight bear the same relation to parts by Z5 volume as thaw of the kilogram to the liter.
The ~H-NMR spectra were recorded on solutions in deuterochloroform as a solvent using tetramethylsilane as an internal standard. The OH chemical shifts are each stated in Pam The following abbreviations were used to describe the signal structure:
s = singlet, d doublet, t - triplet, q = quartet and m = multi pet strongest signal 3.5 parts by weight of bitterly 5-(3~4-epcxy-cyclohexyl)-cyclohexane-1~3-dione, 1.5 parts by weight of allylDxyammonium chloride and 1.2 parts by weight of sodium bicarbonate on 50 parts by volume of methanol

8 - I 0050/37~0 were stirred for 16 hours at room temperature. The sol-vent was distilled off under reduced pressure, the residue was stirred with So parts by volume of water and 50 parts by volume of dichLoromethane, the organic phase was separated off, the aqueous phase was extracted once With 50 parts by volume of dichloromethane, the combined organic phases were dried over sodium sulfate and the solvent was distilled off under reduced pressure.
I Allyloxyiminobutyl)-5 t3,4-epoxycyclohexyl)-3-hydroxycyclohex-2-en-1-one (active ingredient No. 1) was obtained.
H-NMR spectrum: 0.95 (t), 2.9 (q), 5.3 em).
Example 2 3.5 parts by weight of Z-butyryl-5-(3,4-epoxy-cyclohexyl) cyclohexane-1,3-dione and 0.8 part by weight of ethoxyamine in 100 parts by volume of methanol were stirred for 16 hours at room temperature. The solvent was distilled off under reduced pressure, the residue was dissolved in dichloromethane, the solution was washed with 5% strength by weight hydrochloric arid and water and tried over sodium sulfate, and the solvent was distilled off under reduced pressure I Ethics-iminobutyl)-5-~3,4-epoxycyclohexyl)-3-hydroxycycloohex~2-en~1-one active ingredient No. 2) was obtained.
Z5 1H-NMR spectrum: 1.3 it), 3.2 my 4.1 I

9 parts by weight of 2-~1-propoxyiminobutyl)~
5-(cyclohex~3-enyl)-3-hydroxycyclohex-2-en-1-one were dissolve in 100 parts by weight of dichloromethane~ and So parts by weight of m-chloroperbenzoic acid about 80%) in 100 parts by volume of dichloromethane were added drops at 5 - kiwi Tory one hour the course of the reaction was checked by means of thin layer chromatography using a precoated silica gel 60 TLC plate and 1 : 1 cyclohexane/ethyl acetate as the mobile phase.
Further m-chLoroperbenzn;c acid was added drops until I

- g - OOZE. ~050/37280 conversion was complete. Excess pursued was destroyed by shaking with sodium thiosulfate solution. There-after the mixture was extracted twice with semi-saturated sodium bicarbonate solution and once with water, the organic phase was dried over sodium sulfate and the solvent was distilled off under reduced pros-sure. I Propoxyiminobut yule (3,4-epoxycyclo-- hexyl)-3-hydroxycyclohex-Z-en 1-one active ingredient No 3) was obtained.
1H~NMR spectrum: 2.2 to), 3.1 (m), 4.0 (q).
The compounds below were obtained by methods similar to those described on the Examples.

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OOZE. 0050/37280 The cyclohexenone derivatives of the formula I may be applied for instance in the form of directly spray able solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, Emil-05 sons, oil dispersions, pastes, dusts, broaacastingagents, or granules by spraying, atomizing, dusting broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, buy they must ensure as fine a distribution of the active ingredient according to the invention as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil free-lions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydra carbons such as Bunsen, Tulane, zillion, paraffin, twitter-hydronaphthalene, alkylated naphthalenes and their derivatives such as methanol ethanol, propanol, buttonhole, chloroform, carbon tetrachloride, cyclohexanol, cycle-hexanone, chloroben7ene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dim ethyl sulfa oxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil disk pensions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with waxer may be prepared from active ingredient wetting agent, adherent, emulsify-in or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyd sulfates, and alkyd sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalene-I
- 15 - OOZE. 0050/3728 sulfonic acid, laurel ether sulfate, fatty alcohol sup fates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, Hyatt-decanols, and octadecanols, salts of sulfated fatty Alcoa 05 hot glycol ethers, condensation products of sulfonatednaphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesul-ionic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, elk-lo oxylated octylphenol and ethoxylated nonylphenol, alkyd-phenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyd ethers, ethoxylated polyp oxypropylene, laurel alcohol polyglycol ether acetal,sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active inure-dints to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loss, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and urea, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders etc.
The formulations contain from 0.1 to 95, and prefer-ably 0.5 to 90, Jo by weight of active ingredient.
Examples of formulations are given below Lo - 16 - OOZE. 0050~37280 X. Jo parts by weight of compound no. 1 is mixed with 10 parts by weight of N-methyl~alpha-pyrrolidone. A
mixture is obtained which is suitable for application in the form of very fine drops.
05 II. 20 parts by weight of compound no. 2 is dls-solved in a mixture consisting of 80 parts by weight of zillion, 10 parts by weight of the adduce of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanol aside, 5 parts by weight of the calcium salt of dodecyl-benzenesulfonic acid, and 5 parts by weight of the adduce of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispel-soon is obtained containing 0.02~ by weight of the active ingredient.
III. I parts by weight of compound no. 1 is disk solved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduce of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduce of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02~, by weight of the active ingredient.
IV. 20 parts by weight of compound no. 4 is disk solved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C! and 10 parts by weight of the adduce of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02~ by weight of the active ingredient.
V. 20 parts by weight of compound no. 6 is well mixed with 3 parts by weight of the sodium salt of dliso-- 17 I ~050/37280 butylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly 05 distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1~; by weight of the active ingredient.
VI. 3 parts by weight of compound no. 13 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing I by weight of the active ingredient.
VII. 30 parts by weight of compound no. 11 is intimately mixed with a mixture consisting 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. A formulation of the active ingredient is obtained having good adherence.
VIII. 20 parts of compound no. 1 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea form-alluded condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
The active ingredients, or agents containing them, may be applied pro- or postemergnece. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post--directed, lay-by treatment).
Thy amount of active ingredient applied depends on the time of the year, the plants to be combated and their growth stage, and varies from 0.025 to 3 kg/ha, but is preferably from 0.05 to 0.5 kg/ha.

~L23~

The action of the cyelohexenone derivatives of the formula I on plant growth is demonstrated in greenhouse experiments.
The vessels employed were plastic flowerpots having a 05 volume of 300 cm3, and wisher filled with a sandy loam containing about 3.0~j humus. The seeds of the test plants were sown shallow, and separately, according to species.
For the reemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 3.0 kg of active ingredient per Hector. After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensure uniform germination of the plants, insofar as this was not impaired by the active inure-dints.
For the post emergence treatment, the plants were first grown in the vessels to a height of from 3 to 15 cm, depending on growth form, before being treated. The soy-bean plants were grown in a peat-enriched substrate. For this treatment, either plants which had been sown directly in the pots and grown there were selected, or plants which had been grown from seedlings and were transplanted to the pots a few days before treatment. The application rates for post emergence treatment were 0.06 to 0.125 kg of active ingredient per Hector. No covers were placed on the vessels in this method.
The pots were set up in the greenhouse - species from warmer areas at from 20 to 35C, and species from moderate climates at 10 to 25~C. The experiments were run for 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed The scale used for assessment was 0 to 100, 0 denoting no I

damage or normal emergence, and 100 denoting non emergence or complete destruction of at least the visible plant parts.
The plants used in the experiments were Alopecurus myosuxoides, Arena fish, Arena saliva, Digit aria swung 05 nails, Echinochloa crus-galli, Gleason max., Lolium multi-forum, Satyr italic, Synapse alga, Sorghum halepense, Sorghum buckler, and Zeta may.
The compounds used for comparison purposes were I allyloxyamino-n-butyl)~5-(cyclohex-l~en-4 yule--hydroxycyclohex-2-en-1-one (A) and I ethoximino-n--butyl)-5-(cyclohex-1-en-4-yl)-3-hydroxycyclohex-~~-en-1-one (B) disclosed in German DE-A-3 032 973, and ethics-amino-nbutyl)-5-(cyclooct-1-en-5-yl)-3-hydroxycyclohex-2--en-l-one (C) disclosed in German DE-A-3 219 490, and herbicidal agents containing these compounds.
On preemer~ence application, compounds nos. 4, 6, 11 and 13, for instance, had a herbicidal action on plants from the grasses family, whereas Synapse alga, as a dicotyledonous representative, remained completely undamaged.
or example compounds nos. 4 and 6, applied post-emergence at a rate of 0.125 kg/ha, had a strong herbicidal action on a broad spectrum of grassy weeds;
soybeans, as dicotyledonous crop plants, suffered no damage whatsoever.
Unwanted grass species were combated well by, for example, compounds nos. 26, 28, 52, 53, 55 and 61, whereas the broad leaved crop plant alfalfa remained completely undamaged.
Compound no. 8, for example, was suitable at low application rates for controlling undesirable grass species, and was tolerated by wheat.
Compounds nos. 1 and 2 selected by way of example control problem grasses much better than prior art comparative agents A and B, and are fully tolerated by soybeans.

I

- 20 OOZE. 0050/37280 Compared with prior art agent C, the degree of herbicidal action of, for instance, compound no. 50 is significantly higher, without compatibility for alfalfa being influenced.
05 In view of the spectrum of weeds which can be come batted, the tolerance of the active ingredients according to the invention by crop plants, the desired influence on the growth of crop plants, and in view of the numerous application methods possible, the compounds according to may be used in a large number of crop plants.
The following may be mentioned by way of example:
Botanical name Common name Allele cope onions 15 Bananas comosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus officinalis asparagus Arena saliva oats Beta vulgarism sup. altissima sugar beets 20 Beta vulgarism 5pp. nape fodder beets Beta vulgarism sup. esculenta table beets, red beets Brusque naps var. naps rhapsody Brusque naps var. napobrassica suedes Brusque naps var. nape turnips 25 Brusque nape var. silvestris Camellia sinensis tea plants Carthamus tinctures safflower Carve illinoinensis pecan trees Citrus lion lemons 30 Citrus maxima grapefruits Citrus reticulate mandarins Citrus sinensis orange trees Coffee Arabic (Coffee conifer, Coffee Liberia) coffee plants 35 Cucumis memo melons Cucumis sativus cucumbers ~23~

- 21 - OOZE. 0050/37280 Botanical name Common name Sundown dactyl on Bermuda grass in turf and lawns 05 Caucus karat carrots flats guineensis oil palms Fragaria vesca strawberries-Gleason Max soybeans Gossypium hirsutum 10 ~Gossypium arboretum cotton Gossypium herbaceum Gossypium vitifolium) Helianthus annuls sunflowers Helianthus tuberosus Jerusalem artichoke 15 Hove brasiliensis rubber plants Hordeum vulgar barley Cumulus lapels hops Ipomoea batatas sweet potatoes Juglans Regina walnut trees 20 Lactic saliva lettuce yens culinaris lentils Linus usitatissimum flax Lycopersicon lycopersicum tomatoes Mauls sup. apple trees 25 Monet esculenta cohesive Medic ago saliva alfalfa (Lucerne) Month paperweight peppermint Muse sup. banana plants Nicothiana tabacum tobacco 30 ON. rustic) : Olga europaea olive trees Ours saliva rice Panicum miliaceum millet Fossils lunatus lima beans 35 Fossils mango mungbeans Fossils vulgarism snap beans, green beans, dry beans 123~

- 22 - OOZE. 0050/37280 Botanical name Common name Pennisetum glaucoma pearl millet Petroselinum crispum parsley 05 sup- tuberosum Pica abides Norway spruce Abides alga fir trees Pious sup. pine trees Possum sativum English peas 10 Prunes avium cherry trees Prunes domestic plum trees Prunes dualizes almond trees Prunes Persia peach trees Pyres communist pear trees 15 Robes Sylvester redcurrants Robes uva-crispa gooseberries Rosins communist castor-oil plants Saccharum officinarum sugar cane Scale cereal rye on Sesamum indicum sesame Selenium tuberosum Irish potatoes Sorghum buckler (s. vulgar) sorghum Sorghum dochna forgo Spanish oilers spinach Theobroma cacao cacao plants Trifolium pretense red clover Triticum aestivum wheat Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries 30 Viola phoebe tick beans Vegan sinensis (V. unguiculata) cow peas Votes veneerer grapes Zeta may Indian corn, sweet corn maize I (post-directed) To increase the spectrum of action and to achieve synergistic effects, the novel substituted cyclohexenone derivatives may be mixed and applied together with numerous representatives of other herbicidal or growth--regulating active ingredient groups. Examples of suitable mixture components are Dennis, 4H-3,1-benzoxazine OX derivatives r benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, treasons, asides, ureas/ diphenyl ethers, triazinones, uracils, benzofuran derivatives, quinolinecarboxylic acid derivatives, etc.
It may also be useful to apply the cyclohe~enone derivatives of the formula I, either alone or in comb-nation with other herbicides in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
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Claims (10)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. A cyclohexenone derivative of the formula (I), where A is a cycloalkyl radical of 5 to 12 ring members which is fused with one or two oxirane or thiirane rings, is unsubstituted or substituted by not more than four methyl groups and is bridged with an alkylene chain of not more than 3 carbon atoms, R1 is hydrogen, methoxycarbonyl or cyano, R2 is alkyl of 1 to 4 carbon atoms and R3 is alkyl of 1 to 3 carbon atoms, alkenyl of 3 or 4 carbon atoms, haloalkenyl of 3 or 4 carbon atoms which has 1, 2 or 3 halogen substituents, or propargyl, or a salt thereof.

2. A cyclohexenone derivative of the formula I as set forth in claim 1, where R1 is hydrogen.

3. A cyclohexenone derivative of the formula I as set forth in claim 1, where A is cycloalkyl of from 5 to 8 ring members which is fused with one or two oxirane or thiirane rings, is unsubstituted or substituted by not more than four methyl groups, and is bridged with an alkylene chain of not more than 3 carbon atoms.

4. A cyclohexenone derivative of the formula I as set forth in claim 1, where A is 3,4-epoxycyclopentyl.

5. A cyclohexenone derivative of the formula I as set forth in claim 1, where R2 is alkyl of 2 or 3 carbon atoms.

6. A process for the manufacture of a cyclohexenone derivative of the formula I as set forth in claim 1, wherein a compound of the formula (II), where A, R1 and R2 have the meanings given in claim 1, is reacted with a) an ammonium compound of the formula R3O-NH3Y, where R3 has the meanings given in claim 1 and Y is an anion, in an inert diluent, in the presence or absence of water, at from O° to 80°C and in the presence of a base, or b) a hydroxylamine - if desired, in aqueous solu-tion - of the formula R3O-NH2, where R3 has the meanings given in claim 1, in an inert solvent.

7. A herbicide containing inert additives and from 0.1 to 95 wt% of a cyclohexenone derivative of the formula I as set forth in claim 1.

8. A herbicide as set forth in claim 7, containing a cyclohexenone derivative of the formula I where A is cycloalkyl of from 5 to 8 ring members which is fused with one or two oxirane or thiirane rings, is unsubstituted or substituted by not more than four methyl groups, and is bridged with an alkylene chain of not more than 3 carbon atoms.

9. A herbicide as set forth in claim 7, where R1 in the cyclohexenone derivative of the formula I is hydrogen.

10. A process for combatting the growth of unwanted plants, wherein the unwanted plants or the areas to be kept free from unwanted plant growth are treated with a herbicidally effective amount of a cyclohexenone derivative of the formula I as set forth in claim 1.