CA1283553C - Plant growth regulating composition - Google Patents

Abstract

Plant growth regulating composition Abstract of the Disclosure A plant growth regulating synergistic mixture is described which consists of a) a cyclohexanedionecarboxylic acid derivative of formula I

(I) wherein A is the hydroxyl group, an ester or an amide radical, B is the hydroxyl group, an -NHOR1 radical or a metal salt or ammonium salt thereof, R is Cl-C6alkyl or C3-C6cycloalkyl, R1 is C1-C6alkyl, Cl-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl or C3-C6alkynyl, and b) a sulfonylurea of formula II

Z-SO2-NH-CO-NH- (II) wherein E is N or CH, Z is an unsubstituted or substituted phenyl, pyridyl, thienyl or 3,3-dioxobenzothioxine radical, X is methyl, difluoromethoxy, ethoxy, methoxy or cyclopropyl and Y is chlorine, methyl, methoxy, difluoromethoxy, methylamino, dimethylamino or ethoxy.

The mixture is suitable above all for inhibiting the growth of grasses and weeds.

Description

~LV~33~53 2148g-7025 Plant crrowth r~u_a~ com~osit.~oll The present invention relates to a plant growth inhibiting or suppressiny synergistic mlxture consistlng of t~o active components, to a composition con~aininy said mixture, and to the use of this composition for regulating, in particular inhibiting, plant gro~th.
The composition of the present inven-tion consists of a mixture of two active components which are known per se. The first component helongs to that class of herbicidal and plant growth regula-tincJ ~yclohexanedionecarboxylic acid derivatives clescribed in published European patent application A 126 713. The second component is a sulfonylurea to which, above all, strongly ; herbicidal proper~.ies have hitherto been attribut~d.
Such sufonylureas, some of which are commercially avallable, are des~ribed in great number in the literature.
Active components which are employed in accordance with the present invention are described for example in the following publications: German Offenlegungsschrif~ 2 715 786 and published European patent applications 4 163, 7 687, 13 480, 23 141, 23 422, 30 139, 30 142, 35 893, 44 209, 44 211, 44 212, 44 213, 44 807, 44 808, ~4 ~09, 48 1~3, 51 466, 57 546, 70 ~02, 72 347, 73 562, 79 683, 82 108, 83 975, 84 020, 84 224, 85 028, 85 476, 87 780, 95 925, 96 002, 96 593, 99 339, 102 925, 107 979, 117 014, 108 708 and 120 814.
Surprisingly, the plant growth regulating or inhibiting activity of the cyclohexanedionecarboxylic acid derivatlve can be changed and improved by the addition of the sulfonylurea.
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~33~;5i3 The plant grow~h inhibitiny or supressing composition of the present inventlon contains as active components a) a growth inhibltlng or suppressing effective amount of a cyclohexanedionecarboxlic acid derivative of formula I

Q ~ R
A & ~-f ~ (I) whereln A is an OR~ or NR3R4 radical, B is hydroxy, an -NHORl radical or a metal salt or ammonium salt thereof, R is Cl-C6alkyl or C3-C6cycloalkyl, each unsubstituted or substituted by halogen, Cl-C4alkoxy or Cl-C4alkythio, Rl is Cl-C6alkyl, Cl-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl or C3-C6alkynYl, R2, R3 and R4 are each independently hydrogen; Cl-C6alkyl, Cl-C6-haloalkyl, C2-Cl0alkoxyalkyl~ C2-C10alkylthioalkyl; C3-C6alkenyl which is unsubstituted or substituted by halogen, Cl-C~alkoxy or Cl-C4alkylthio; C3-C6alkynyl; phenyl or aryl-(Cl-C6~-alkyl, the phenyl nucleus being unsubstituted or substitutad by halogen, Cl-C~alkyl, Cl-C4alkoxy, Cl-C4haloalkyl, nitro or cyano, one of R3 and R4 is also methoxy or R3 and R4, together with ~he nitrogen atom to which they are attached, also form a 5- or 6-membered saturated heterocycle , J

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~J~3~i3 2a 21489-7025 which may contaln an oxygen atom or a further nitrogen atom in the ring, and b) a synergistically active amount of a sulfonylurea of formula Z-S02-NH C0-NH-~
N~

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~2~33~53 or a salt thereof~ wherein Z i9 a radical ~ (CH2)n- , t il , ~ ~ or ~ 2\, CH
Q ~ L S \. ~ \ , /
1l ~,/

L is halogen, nltro, -S02N(CH3)~, Cl~Csalkoxycarbonyl, Cl-Csalkyl, Cl-C5alkoxy, Cl-Csalkylthio os l-Csall~ylsulfonyl, Q is halog~n, nitro9 -SOzN(CH3)2, -C0-Rl, -(A) -R2~ phenyl, phenoxy, Cl-Csalkyl, halophenyl, halophenoxy, C~-Cshaloalko~y, Cl-Cshaloalkylthio or Cl-Cshaloalkyl, n is 0 or l, E ig N or CH, X i~ methyl, methoxy, ethoxy, dlfluoromethoxy or cyclapropyl and Y is chlorine, methyl, methoxy, difluoromethoxy, methylamino, dlmethylamino or ethoxy~ and Rl i~ hydrogen, Cl-Csalkyl, C1-Csalkoxy~ C3-Csalkenyloxy or C~-Csalkynyloxy, A i~ oxygen, ~ulur, -S0-, -S02- or -0-S02-, m is 0 or 1 and R2 i9 Cl-C5alkyl, C2-C511kenyl, C2-C5alkynyl, Cl-Cshaloalkyl, C2-C7alkoxyalkyl, C2-Cshaloalkenyl or C2-Cshaloalkynyl, together with inert ad~uYants.

The vegetative growth of grasses, mixed vegetation and weeds can be inhibited with the compositlons of thls invention Whereas the total destruction of plants pro~otes erosion of the soil by wind and rainfall, the application of the compositions of thi~ invention results in a ~ubstantial reduction of growth, thereby ensuring the formati.on or maintcnance of a unifor~, low plant cover and so preventing soil erosion. Falling within this field of application is, in psrticular, the reduction of grass growth for the maintenance of gras~ areas such as in parks and orchards, on airfields and .. . .

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~283~Si3 ~ 4 --industrial ~ites, beside roads, on railway embankments or on the sloping banks of river~ and lakes. In all of the~e cases it is normally necessary to cut the gra~s periodically. This not only require~ a great deal of labour and machinery, but on road~ al~o involves a considerable amount of danger both to the workers con-cerned and to road u~ers.

Therefore, ln particular in the above-mentioned areas, there is a great need on the one hand to pr~serve and tend the sward necessary for the maintenance and solidiEicatlon of the soil and an the other hand to keep the growth of the plants at an average level by simple measures during the entire vegetation period.

Surprlsingly, it has been found that the compositions of this invention are particularly suitable for inhibiting the growth of grasse~ and al~o o~ weed~. Even under variable environmental condi-tions, the compositions exhibit their activity extremely quickly and also remain effective over a long period of time. Thus the composi-tions are superior to the individual components. Further advantages of the compositions reside in the fact that they are used at lower rates of application, which ha~ a favourable influence on the phytotoxicity, and that they have a better total action and a broader activity spectrum. The compositions are effective again~t both dicots and monocot3.

In the compositionfl of thi~ invention, the ratio of cyclohexane-dionecarboxylic acid derivative (active component of formula I) to sulfonylurea (active component of formula II) is generally in the range from 200:1 to 1:1, preferably from 100:1 to 10:1.

As a rule, rates of application corresponding to the following are employed:
0.1 to 5 g of active sub~tance per hectare, preferably 0.1 to 2 kg, i.e. 100 g to 4 kg/ha of the active component of formula I and 1 to 500 g/ha of the active component of formuls II.

' ,.. -~835~;3 Preferred cyclohexanedionecarboxyllc acid derivatives of formula I
are those which correspond to the formula Ia ,Q ~-R R ~ R
A~ A~ (Ia) wherein A and R are as defined for formula I, in particular those wherein A is the acid radical -OH or an ester radical -OR2 and R is a C3-C6cycloalkyl radical and, above all, the compounds 1.1 ethyl 4-(cyclopropylcarbonyl)-cyclohexane-3,5-dione-1 carbo~y-late, 1.2 4-(cyclopropylcarbonyl)-cyclohexane-3,5-dione-1-carboxylic acid, 1.3 methyl 4-(cyclopropylcarbonyl)-cyclohexane-3,5-dione-1-carboxy-late, 1.4 4-(cyclobutylcarbonyl)-cyclohexane-3,5~dione-1-carboxylic acid.

The preparation of these cyclohexanedionecarboxylic acid derivatives does not con8 titute an obJect oE the present invention. Their preparation and the u3e thereof a3 herbicides and plant growth regulators are described in published European patent applica-tion 126 713.

Preferred sulfonylureas of formula II are phenylsulfonylureas which correspond to the formula IIa /x ~.\ /SOz-NH-CO-NH~ (Ila) ~ CH3 wherein E is N or CH, X i~ methyl, methoxy or cyclopropyl, Q is halogen or an -SO2N(CH3)2, -CO-R1 or -(A~mR2 radical, , .

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3~2~3~s3 Rl ls hydrogen, C1-Csalkyl, C1-Csalkoxy, C3-Csalkenyloxy or C3-Cs-alkynyloxy, A is oxygen, sulfur, SO-, -SO2- or -OSO2-, m is O or 1, R2 is Cl-Csalkyl, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl, C1-C5haloalkyl, C2-C7alkoxyalkyl, C2-Cshaloalkenyl or Cz-Cshaloalkynyl, ln particular those wherein E is N and ~ i9 a9 defined above, or the compounds o formula IIb i~ D ~= ~ (IIb) ~,~ 2 ~H3 wherein X i~ as defined above.

Particularly ~uitable sulfonylureas are:

2.1 N-(2-~chloroethoxyphenylsul~onyl)-N'-(4-methoxy-6-methyl-1,3,5 triazin-2-yl)urea, 2.2 N-(2-methoxyethoxyphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, 2.3 N-(2-methoxycarbonylphenyl~ulfonyl)-N'-(4,6-bis-difluorometh-oxypyrimidin-2-yl)urea, 2.4 N-[2-(2-methoxyethoxy)phenylsulfonyl~-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)urea, 2.5 N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-cyclopropyl-6-methyl-pyrimidin 2-yl)urea9 2.6 N-(2,2-dloxo-3-methyl-1,2-benzothioxin-2-ylsulfonyl)-N'-(4-me-thoxy-6-~ethylpyrimidin-2-yl~urea, 2.7 N-(2-chlorophenylsulfonyl)-N'-~4-~ethoxy-6-methyl-1,3,5-tria-zin-2-yl)urea, 2.8 N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5~triAzin-2-yl)urea, ' ' ' ' ' ' , ~

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~2~33~53 2.9 N-(2-~ethoxycarbonylphenylsulfonyl)-N'-(4,6-dimethylpyrimidin-2-yl)urea, 2.l0 N-(2-methoxycarbonylthien-3-yl 9 U lfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, 2.11 N~(2-ethoxycarbonylphenyl sul fonyl)-N'-(4-chloro-6-methoxypyri-midin-2-yl)urea, and 2.l2 N-(2-methoxycarbonylphenylsulfonyl)-N'-~4,6-dimethoxypyri-midin-2-yl)urea.

An advantageous plant growth regulating composition of this inven-tion is one which contains as active components a) a cyclohexanedionecarboxylic acid derlvative of the above formula Ia and b) a phenylsulfonylurea of formula IIa, together with inert adjuvants.

Particularly effectlve compositions of this invention are those which contain, together with inert adJuvants, a cyclohexanedione-carboxylic acid derivative of formula Ia, wherein A is the acid radical -OH or an ester radical -OR2 and R is a C3-Cccycloalkyl radical, and a phenylsulfonylurea of the formula IIa, wherein E is nitrogen and Q i9 as defined above, or a phenylsulfonylurea of formula IIb~ wherein E and X are as defined above.

In practice, mixtures of one of the above specifically named cyclohexanedionecarboxylic acid derivatives and one of the above specifically named phenylsulfonylureas show very good activity, in particular the combination ethyl 4-(cyclopropylcarbonyl)-cyclo-hexane-3,5-dione-1-carboxylate and N-(2-~-chloroethoxyphenyl-sulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl3urea (combi-nation of compound l.l ~ith compound 2.1).

Surprisingly, it has now been found that compositions containing these active components are characterised in particular by their selec~ive in~luen~e on plant metabolism. This selective influence on the phy~iological processes of plant development makes it possible .

~83SS3 to u~e the compositions of this invention for different purposes, especlally for those in connection with increasing the yield of u~eful plants, with facilitatlng harvesting, and with labour-saving in measures taken in crops of cultlvated plants.

Prevlous experience with plant growth regula-tor3 has shown that they are able to induce one or more dlf~erent responses in the plants.
These different responses depend substantially on the -time of application, based on the state of development of the seed or plant, as well as on the concentrations of active substance applied to the plants or to the locus thereof and on the nature of application.
Growth regulators should at all events induce positive responses in the cultivated plants in the desired manner.

Plant growth regulators may be used e.g. for inhibiting vegetative plant growth. Such a growth inhibition is of economic interest, inter alia, in respect of gra~ses, as the frequency of cutting in flower gardens, parks, sports fields or road 3houlders can thereby be reduced. Of importance too i8 the inhibition of growth of herbaceous and ligneous plants on road shoulder~ and near trans-mission lines, or generally in areas in which strong growth is undesirable.

The u~e of growth regulators for inhibiting the growth ln height of cereals is alao important, as shortening the stalks dimini~hes or completely eliminates the danger of lodging before harve3ting. In addition, growth regulators are able to bring about a strengthening of the stalks in crops of cereals, thereby also counteracting lodging.

Inhibition of the vegetative growth of many cultivated plants per~its more plant~ to be sown in a crop area, so that a higher yield may be obtained per unit of area. A further mechanism of yield increase using growth regulators re~ide~ in the fact that nutrients are able lncreasingly to promote flower formation and fruiting, wherea3 vegetative growth i3 lnhibited.

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~283~i3 Growth regulators are also frequently able to promote vegetative growth. This i9 very beneficial when the vegetative parts of plants are to be harvested. However, promotion of ~egetative growth can also result simultaneously in promotion of generative growth, so tha~ e.g. more or larger fruit is formed~

Yield increases may also often be obtained by influencing the plant metabolism without any visible cbanges in vege~ative growth. Growth regulators can also induce a change in the composition of plants, so that the quality of the harvest produce i9 lmproved. For example, it i8 possible to increase the sugar content of sugar beet, sugar cane, pineapples and citrus fruit, or to increase the protein content of soybeans or cereals.

The use of growth regulators can lead to the formation of partheno-carpic fruit. The sex of blossoms can also be influenced. The production or flow oE secondsry plant substances can also be positively influenced by growth regulators, for example the stimu-lation o~ the flow of latex in rubber tr0es.

During plant growth, the development of side-shoots can also be promoted by the chemical interruption of apical do~inance using growth regulators. This i8 of interest e.g. in the propagation of plant cuttings. However, it is also possible to inhibit the growth of side-shoots, e.g. in tobacco plants aEter decapitatlon in order to prevent the formation of side-shoots, and thus to promote leaf growth.

Influenced by growth regulators, the foliage of plant~ can be regulated in such a way that defoliation of the plants is achieved at a desired time. Such defoliation is useful for facilitating ~echanical har~esting e.g. in vines or cotton, or for diminiæhing tranæpirat~on at a time when it iæ i8 desir~d to transplant the plants.

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Premature fruit drop can be prevented by the use of growth regula-tors. However, it is also possible to promote fruit drop - e.g. ln fruit crops - by means of chemlcal thlnning up to a specific degree.
Growth regulators can also be used for reducing the force necessary for detaching fruit at harvesting, ~o making po~slble mechanical harvesting of plants or facilitating manual harvesting.

With growth regulators it i8 also possible to speed up or delay the ripening of harvest products before or after harvesting. This is particularly advantageous, because a best possible accommodation to ~arket requirements can thereby be achieved. In addition, growth regulators can often improve the colour of fr~it. With the aid of growth regulators it is also possible to concentrate ripening at a particular time. The conditions are thus created for a complete mechanical harvesting of e.g. tobacco, tomatoes or coffee, or for manual harvesting, in only one single operation.

The application of growth regulators can also make it possible to influence the dormancy of seeds and buds of plants, i.e. the endogenic annual rhythm, so that plants, e.g. pineapples, or ornamentals in nurseries, germinate, sprout or blossom at a time when they would normally not tend to do so.

With growth regulators it ls also possible to delay budding or the germination of seeds, e.g. in order to avoid damage by late frosts in areas endangered thereby. Conversely, root growth and/or the formation of shoots can be stimulated, so that growth may be restricted to a shorter period.

Growth regulators can also impart halophilic properties to cultl-vated plants. The condit~ons are thus created for cultivating plants in salty soil. Growth regulators can al~o induce re~igtance to frost and drought ln plants.

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~2~3~i3 Under the influence of growth regulators, the ageing (senescence) of plants or parts of plants can be inhiblted or delayed. Such an action can be of great economic importance, as the storability of treated parts of plants or whole plants such as fruit, berries, vegetables, salads or ornamentals can be improved or prolonged after harve3tingO Likewise, a substantial yield increase can be obtained by treating cultivated plants by prolonging the phase of photo~ynthe-tlc activity.

A further important fleld of use for growth regulators is the inhibition of excessive growth of tropical cover crops. In ~ropical and subtropical monocultures, e.g. in palm tree plantations, cctton and maize fields etc., cover crops, especially species of legumino-sae, are often planted together with the actual cultivated plants with the ob~ect of maintaining or improving the quality of the soil (prevention of desiccation, supplying nitrogen) and for preventing erosion. By applying the campounds of this invention it 1s possible to control the growth of thèse cover crops and so to keep the growth in height of these plsnts at a low level, thus ensuring healthy growth of the cultivated plants and the maintenance of favourable soil conditions.

Within the scope of the present invention, cultivated orops shall be understood as me~ning all plants which produce in some form or other harvestable goods such a9 seeds, roots, stems, tubers, leaves and blossoms, and also metabolite~ such as oils~ sugar, starch, protein etc. and which are cultivated for this purpose. Such plants comprise e.g. all species Df cereals such a3 wheat, ~ye, bsrley and oats, as well as, in particular, rice, cultivated sorghum, maize, cotton, sugar beet, sugar cane, soybeans, beans and peas.

The mixtures ~f artive components of thi3 invention are used ln unmodified form or, preferably, together with the adjuvants c~nven-tionally employed in the art of formulation, and are therefore formulated in known manner to emulsiflable concentrates, directly sprayable or dilutable solutions, dilute emulsions~ wettable 12 ' ~33~i~3 powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. Ag with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixtures containing the active components of formulae I and II and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by intimately mixing and/or grinding the active components with extenders, e.g. with solvents, sol~d carriers, and optionally surface-active compounds (surfactants3.

Sui~able solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dlbutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffin~, alcohols and glycols and their ethers and esters, such as ethanol, ethylene g~ycol, ethylene glycol monomethyl or monoethyl ether, ketone~ such as cyclohexanone, strongly polar solvents such a~ N-methyl-2-pyrrolidone, dlmethyl sulfoxide or dimethylformamide, as well as vegetabl0 oil5 or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; o~ water.

The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, tslcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it i~ also possible to add highly disperced silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorp-tive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant re~idues.

'; ' -' ' ' , - 13 - ~83~S3 Depending on the nature of the mixture of actlve components to be formulated, suitable gurface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dlsperslng and wetting properties. The term "surfactants" wlll also be understood as comprislng mixtures of surfactants.

Suitable anionic surfactants can be both water-~oluble soaps and water-soluble 3ynthetic surface-active compounds.

Su$table soaps are e.g. the alkali metal salts, alkaline earth metal salts or unsubstltuted or substituted ammonium salts of higher fatty acid~ (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acld methyltaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated ben~imid-azole derivative~ or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substi-tuted ammonium salts and contain a CB-C22alkyl radical whlch al90 includes the alkyl moiety of acyl radlcals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
These compounds also comprise the salts of sulfuric acid esters and sulEonic acids of fatty alcohol/ethylene oxide adducts. The sulfona-ted benzl~idazole derivatives preferably contain 2 sulfonic acld groups and one fatty acld radical containing 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri-ethanoIamine salts of dodecylbenzenesulfonic acid, dibutylnaph-thalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensatlon product. Also suitable are corresponding phosphates, e.g. salts of ~he phosphoric acid ester of an adduct of p-nonyl-phenol with 4 to 14 moles of ethylene oxide, or phospholipids.

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Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatlves containing 3 to 30 glycol ether groups and 8 to 20 carbon atom~ in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surEacta~ts are ~he water-soluble adduct~
of polyethylene oxide wi~h polypropylene glycol, ethylenediamlno-propylene glycol and allcylpolypropylene glycol containing 1 to 10 carbDn atoms in the alkyl chainl whlch adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These ~ompounds usually contain 1 to S ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenol-polye~hoxyethanols, castor oil polyglycol ethers, polypropylene/-polyethylene oxide adducts, trihutylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polynxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactant~.

Catlonic ~urPactant~ are preferably quaternary ammoniuM salts which contain, as N-~ubstituent, at lea~t one Ca-C22alkyl radical and, as further sub~tituents, unsubstituted or halogenated lower allcyl, benæyl or hydroxy-lower alkyl radicals. The salt~ are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyl-trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described e.g. in the following publications-.

': , -- 15 ~2~S3 "McCutcheon' 8 Detergents and Emulsiflers Annual", MC Publishing Corp., Ridgewood, ~ew Jersey, 1979; Sisley and Wood, "Encyclopedia of Surface Actlve Agents", Chemical Publishing Co. Inc., New York, 1980-81; Dr. Helmut S~ache, "Tensid Taschenbuch" (Handbook of Surfactants), 2nd editlon, Carl Hanser Verlag, Munich/Vienna 1981.

The formulations oE this invention usually contain 0.1 to 95 %, pre-ferably 0.1 to 80 %, of a mixture of active components, 1 to 99.9 %, of a solid or liquid adjuvant, and/or 0 to 25 %, preferably 0~1 to 25 %, of a surfactant.

Preferred formulations are composed in particular of the following con~tituents (% ~ percentage by weight):

Emulsifiable concentrates mixture oE active components: 1 to 20 %, preferably 5 to 10 %
surfactant:5 to 30 %, preferably 10 to 20 %
liquid carrier:50 to 94 %, preferably 70 to 85 %

Dusts mixturè of ac~ive components: 0.1 to 10 %, preferably 0.1 to 1 %
solid carrier:99.9 to 90 %, preferably 99.9 to 90 %

Suspension concentrates __ mixture of active components: 5 to 75 %, preferably 10 to 50 %
watar: 94 to 25 %, preferably 90 to 30 %
surfactant:1 to 40 %, preferably 2 to 30 %

Wettable powders mixture of active components: 0.5 to 90 YO~ preferably 1 to 80 %
surfactant:0.5 to 20 %, preferably 10 to 20 %
solid carrier:5 to 95 %, preferably lS to 90 %

Granulates mixture of active components: 0.5 to 30 %, preferably 3 to 15 %
solid carrier:99.5 to 70 %, preferably 99 to 85 %.

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16 ~Z~33~;~;3 Whereas commercial products will be preferably formulated as concentrates, the end user will normally employ dilute formulations.
The formulations can be diluted to a concentration as low as 0.001 %
of act;ve substance. The rates of application are usually 0.01 to 10 kg a.s./ha, preferably 0.025 to 5 kg a.s./ha.

The compositlons may also contain further ingredients such a~
stabilisers, sntifoams~ viscosity regulators, binders, tackifiers, as well as fertilisers and other compounds for obtaining special effects.

xample 1:

Formulation examples for the composition of this invention ~throughout, percentages are by weight) a~ Wettable powder~ a) b) c) mixture consisting of 1000 parts of compound 1.1 and 10 parts of com pound 2.1 or 50 parts of compound 2.4 20 % 60 % 0.5 %
sodium lignoaulfonate 5 % 5 % 5 %
sodium lauryl sulfate 3 % - -sodium diisobutylnaphthalenesulfona~e - 6 % 5 %
octylphenol polyethylerle glycol ether (7-8 moles of ethylene oxide) - 2 % 2 %
highly dispersed 9ilicic acid 5 % 27 % 27 %
kaolin 67 %
sodium chloride - - 60.5 %

The mixture of active components is thoroughly mixed wlth the ad~uvants, and the mixture thus obtained is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

;~: ' ~ ' . ' ' 17 ~2~33~;~;3 b) Emul&ifiable concentrates a) b) mixture consisting of 1000 parts of compound 1.1 and 10 parts of com-pound 2.1 or 50 parts of compound 2.4 10 % 1 %
octylphenol polyethlene glycol ether (4-5 moles of ethylene oxide) 3 % 3 %
calcium dodecylbenzenesulfonate 3 % 3 %
castor oil polyglycol ether (36 moles of ethylene oxide) 4 % 4 %
cyclohexanone 30 % 10 %
xylene mlxture 50 % 79 %

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Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

c) Dus~s a) b) mixture consisting of 1000 parts of compound 1.1 and 10 parts of compound 2.1 or 50 parts of compound 2.4 0.1 % 1 %
talcum 99.9 %
kaolin ~ 99 %

~eady-for-use du3ts are obtained by mixing the mixture of active components with the carrier, and grinding the mixture thus obtained in a suitsble mill.

d) Extruder ~ranulates a) b) mixture consisting of 1000 parts of compound 1.1 and 10 parts of compound 2.1 or 50 parts of com-pound 2.4 10 % 1 %
~odium lignosulfonate 2 % 2 %
carboxymethylcellulose 1 % 1 %
kaolin 87 % 96 %

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~83~3 The mixture of active components is mixed and ground with the acl~uvants, and the mixture thus obta~ned is subsequently moistened with water. This mixture i9 extruded and then dried in a ~tream of air.

e) Coated granulate mixture conslsting of 1000 parts of compound 1.1 and 10 parts of compound 2.1 or 50 parts of com-pound 2.4 3 %
polyethylene glycol 200 3 %
kaolin 94 %

The finely ground mixture oE active component3 i5 uniformly applied, in a mixer, to the kaolin moistened with polyethlene glycol.
Non-dusty coated granulates are obtained in this manner.

f) Suspension concentrates a) b) mixture consisting of 1000 parts of compound 1.1 and 10 parts o~ com-pound 2.1 or 50 parts of compound 2.4 40 % 5 %
ethylene glycol 10 % 10 %
nonylphenol polyethylene glycol (15 moles of ethylene oxide~ 6 % 1 %
sodium lignosulonate 10 % 5 %
carboxymethylcellulose 1 % 1 %
37 % aqueous formaldehyde solution 0.2 % 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 0.8 %
water 32 % 77 %

The finely ground mixture of active components is intimately mixed with the ad~uvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

~, ' '' , , ' , ~ .
,~ . - , - .

~ 2 ~ 3 ~35 3 Biological Examples.

le l: Growth inhibition test in a ~reenhouse In a greenhouse, the plants Avena sative, Lolium perenne, Solsnum lycopersicum, Sinapis alba, Stellaria media and Phaseolus vulgaris are sown in plastic pots (dlameter: 12 cm) which have been filled with sieved sterllised country soil. The plants are kept under the conditions of light, temperature, humidity and watering essential for good growth. 11 to 14 days after sowing, the young plant~ are then sprayed with the test substance. Application i~ made at a concentration corresponding to 500 l of water and 4 kg of the mixture of active components per hectare. The plants are kept ln the greenhouse and observed. The test i8 evaluated 14 days after treatment and the plants are examin0d for growth in comparison with untreated plants (~ lOO % growth), verdancy, chlorosis, necrosis and tillering.

The test mixtures exhibit marked growth inhibiting action.

~xample 2: Growth inhibition of cereals Summer barley (Hordeum vulgare) and summer wheat (Triticum~ are sown in sterilised soil in plastic pots in a greenhouse and watered as required. The cereal shoots are sprayed about 21 days after sowing with an aqueous spray formulation of the mixture of active compo-nents. The concentration corresponds to up to 3 kg of active substance per hectare. Evaluation of the growth of the cereals is made 28 days after application. A comparison with untreated con~rols shows that the growth of cereal plants treated with the mixture of active components of ~bis invention i~ significantly reduced. The growth rate is reduced to less than lO %.

Example 3: Growth inhibition of grasses and clover Seeds of the gra~ses Lolium perenne, Poa pratensis, Festuca ovina9 Dactylis glomerata, Festuea rubra, Agropyron repens, B~omus lnermis, Cynosurus cristatus, and two species of clover are sown in plastic di~hes filled with an earth/peat/sand mixture (6:3:1)3 in a green-~2a~35~3 house, and wa~ered a~ required. The emergent grasses are cut back weekly to a height of about 4 cm, and about 40 daya after sowlng and 1 day after the last cut are sprayed with an aqueou~ spray mixture of the compo~ent of formula I, of the component of formula II, and of a mixture of both compon~ntg. The concentration corresponds to 1000 g of the component of ~ormula I, 10 g or 50 g of the component of formula II, and 1000 + 10 g or 1000 + 50 g of the mixture per hectare. The growth of the grasses is evaluated 14 to 49 days after application. The tes~ shows tha~ the components and combinatlons of the invention effect a marked growth inhibition. Particularly ~arked inhibition is effected by the mixtures. The inhibiting ac~ion of compounds 1.1 and 2.1 individually and in admixture is compared below.

A synergistic effect has been achieved if the growth inhibiting action of the combination of active componen~s I + II is greater than the sum of the action of the individually applied components.

The expected plant growth E for u glven combination of two herbi-cides can be calculated as follows (q.v. COLBY, S.R., "Calculating ~ynergistlc and antagoni3tic respon~e of herbicide combinations", Weed~ 15, pp. 20-22, 1967):

E X ~ loo in which formula X ~ the percentage growth inhibition, compared with untreated controls, after treatment with a product I at a ratc of applica-tion of p kg per hectare y 8 the percentage growth inhibi~ion, compared with untreated conrols, after treatment with a product II at a rate of application of q kg per hectare .:, ~283~i~3 E ~ the percentage growth inhibition, compared with untreated control~, expected aftsr treatmant wlth the mlxture I ~ II at a rate of application of p + q kg of active substance per hectare.

If the actually observed ~alue is higher than the expected value E, then there is synerglsm.

The synergi~tic effect of the combinati~n of compoDents I a~d II is demon~trated in the following Tables.

The growth i~hibiting action ln comparison with untreated plants (0 %) lg as follow~:

Evaluation, Compound Compound Mixture Expected value number of 1.1 (X) 2.1 (Y) 1.1+2.1 (E) computed in days after rate of rata of rate of accordance with applicat~on application application application the Colby 1000 glha 10 g/ha 1000~10 glha formula 14 58 % 42 % 81 % 76 %
21 56 % 31 % 81 % 70 %
29 29 % 32 % 76 % 52 %
20 % 24 % 56 % 39 %
42 12 % 16 % 40 % 26 ~0 49 0 % 13 % 27 % 13 %

Evaluation, Compound Compound Mixture Expected value number of 1.1 (X)2.4 tY) 1.1+2.4 (E~ computed in day~ after rate ofrate of rate of accordance ~ith application application application application the Colby 1000 g/ha 50 g/ha 1000~50 g/ha form~la .
14 59 % 37 % 73 % 74 %
21 ~9 % 28 % 78 % 71 %
2~ 24 % 0 % 53 % 24 %

, . .
' ~ , i ' Example 4: Growth inhibition of tropical cover crops Test plants of the varieties Psophocarpus palustris, Centrosema plumieri and Centro~ema pubescens are reared from cuttings in plastic pots filled with an earth/turf mixture (1:3) and watered as required. After they have grown roots, the plants are transplanted into 11 cm pots. For further growth the plants are then kept in a greenhouse at a day temperature of 27C and a night temperature of 21C. The average light exposure i9 14 hours (6000 lux) and the humidity is 70 %. The plants are cut back to a height of about 15 cm and sprayed 7 days later with a spray formulation of the mixture of active components of this invention (corresponding to a concentra-tion of 0.3 and 3 kg a.s./ha respectively~. Four weeks after application the growth of the treated plants is compared wi~h that of untreated control plants which have been cut back. The test shows that mixtures of compounds 1.1 to 1.4 and 2.1 to 2.12 effect a marked inhibition of the growth of cover crops.

Claims (23)

1. A plant growth inhibiting or suppressing composition, which contains as active component a) a growth inhibiting or suppressing effective amount of a cyclohexanedionecarboxylic acid derivative of formula I

(I) wherein A is an OR2 or NR3R4 radical, B is hydroxy, an -NHOR1 radical or a metal salt or ammonium salt thereof, R is C1-C6alkyl or C3-C6cycloalkyl, each unsubstituted or substituted by halogen, C1-C4alkoxy or C1-C4alkythio, R1 is C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl or C3-C6alkynyl, R2, R3 and R4 are each independently hydrogen; C1-C6alkyl, C1-C6-haloalkyl, C2-C10alkoxyalkyl, C2-C10alkylthioalkyl; C3-C6alkenyl which is unsubstituted or substituted by halogen, C1-C4alkoxy or C1-C4alkylthio; C3-C6alkynyl; phenyl or aryl-(C1-C6)-alkyl, the phenyl nucleus being unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, nitro or cyano, one of R3 and R4 is also methoxy or R3 and R4, together with the nitrogen atom to which they are attached, also form a 5- or 6-membered saturated heterocycle which may contain an oxygen atom or a further nitrogen atom in the ring, and b) a synergistically active amount of a sulfonylurea of formula II

(II) or a salt thereof, wherein Z is a radical , , or L is halogen, nitro, -SO2N(CH3)2, C1-C5alkoxycarbonyl, C1-C5alkyl, C1-C5alkoxy, C1-C5alkylthio or C1-C5alkylsulfonyl, Q is halogen, nitro, -SO2N(CH3)2, -CO-R1, -(A)m -R2, phenyl, phenoxy, C1-C5alkyl, halophenyl, halophenoxy, C1-C5haloalkoxy, C1-C5haloalkylthio or C1-C5haloalkyl, n is 0 or 1, E is N or CH, X is methyl, methoxy, ethoxy, difluoromethoxy or cyclopropyl and 24a 21439-7025 Y is chlorine, methyl, methoxy, difluoromethoxy, methylamino, dimethylamino or ethoxy, and R1 is hydroyen, C1-C5alkyl, C1-C5alkoxy, C3-C5alkenyloxy or C3-C-5alkynyloxy, A is oxyyen, sulfur, -SO-, -SO2- or -O-SO2-, m is 0 or 1 and R2 is C1-C5alkyl, C2-C5alkenyl, C2-C5alkynyl, C1-C5haloalkyl, C2-C7alkoxyalkyl, C2-C5haloalkenyl or C2-C5haloalkynyl, together with an inert adjuvant.

2. A composition according to claim 1, which contains a cyclo-hexanedionecarboxylic acid derivative of formula Ia (Ia) wherein A and R are as defined in claim 1.

3. A composition according to claim 1, which contains a cyclo-hexanedioncearboxylic acid derivative of formula Ia (Ia) wherein A is the acid radical -OH or an ester radical -OR2 and R2 is as defined in claim 1 and R is a C3-C6cycloalkyl radical.

4. A composition according to claim 1, which contains a phenyl-sulfonylurea of formula IIa (IIa) wherein E is N or CH, X is methyl, methoxy or cyclopropyl, Q is halogen, -SO2N(CH3)2, or a -CO-R1 or -(A)mR2 radical, R1 is hydrogen, C1-C5alkyl, C1-C5alkoxy, C3-C5alkenyloxy or C3-C5-alkynyloxy, A is oxygen, sulfur, -SO-, -SO2- or -OSO2-, m is 0 or 1, R2 is C1-C5alkyl, C2-C5alkenyl, C2-C5alkynyl, C1-C5haloalkyl, C2-C7alkoxyalkyl, C2-C5haloalkenyl or C2-C5haloalkynyl.

5. A composition according to claim 1, which contains a sulfonylurea of formula IIa (IIa) wherein E is N and X is methyl, methoxy or the cyclopropyl group, Q is halogen, dimethylsulfamoyl -SO2N(CH3)2, or a -CO-R1, -(A)mR2, radical, R1 is hydrogen, C1-C5alkyl, C1-C5alkoxy, C3-C5alkenyloxy or C3-C5alkynyloxy, m is 0 or 1, R2 is C1-C5alkyl, C2-C5alkenyl, C2-C5alkynyl, C1-C5haloalkyl, C2-C7alkoxyalkyl, C2-C5haloalkenyl or C2-C5haloalkynyl.

6. A composition according to claim 1, wherein the sulfonylurea is of formula IIb (IIb).
wherein E and X are as defined in claim 1.

26a 21489-7025

7. A composition according to claim 1, which contains as active components a) a cyclohexanedionecarboxylic acid derivative of formula Ia (Ia) wherein A and R are as defined in claim 1 and b) a sulfonylurea of formula IIa (IIa) wherein E is N or CH, X is methyl, methoxy or cyclopropyl, Q is halogen, -SO2N(CH3)2, or a -CO-R1 or -(A)mR2 radical, R1 is hydrogen, C1-C5alkyl, C1-C5alkoxy, C3-C5alkenyloxy or C3-C5-alkynyloxy, A is oxygen, sulfur, -SO-, -SO2- or -OSO2-, m is 0 or 1, R2 is C1-C5alkyl, C2-C5alkenyl, C2-C5alkynyl, C1-C5haloalkyl, C2-C7alkoxyalkyl, C2-C5haloalkenyl or C2-C5haloalkynyl, together with an inert adjuvant.

8. A composition according to claim 1, which contains as active components a) a cyclohexanedionecarboxylic acid derivative of formula Ia (Ia) wherein A is the acid radical -OH or an ester radical -OR2, in which R2 is as defined in claim 1, and R is a C3-C6cycloalkyl radical and b) a sulfonylurea of formula IIa (IIa) wherein E is N, X is methyl, methoxy or cyclopropyl, Q is halogen, -SO2N(CH3)2, or a-CO-R1 or -(A)mR2 radical, R1 is hydrogen, C1-C5alkyl, C1-C5alkoxy, C3-C5alkenyloxy or C3-C5alkynyloxy, A is oxygen, sulfur, -SO-, -SO2- or -OSO2-, m is 0 or 1 and R2 is C1-C5alkyl C2-C5alkenyl C2-C5alkynyl C1-C5haloalkyl C2-C7alkoxyalkyl, C2-C5haloalkenyl or C2-C5haloalkynyl, together with an inert adjuvant.

9. A composition according to claim 1, which contains as active component a) a cyclohexanedionecarboxylic acid derivative of formula Ia (Ia) wherein A is the acid radical -OH or an ester radical -OR2, in which R2 is as defined in claim 1, and R is C3-C6cycloalkyl radical, and b) a sulfonylurea of formula IIb (IIb) wherein E and X are as defined in claim 1, together with an inert adjuvant.

10. A composition according to claim 1, which contains as active components a) one of the cyclohexanedionecarboxylic acid derivatives ethyl 4-(cyclopropylcarbonyl)-cyclohexane-3,5-dione-1-carboxylate, 4-(cyclopropylcarbonyl)-cyclohexane-3,5-dione-1-carboxylic acid, methyl 4-(cyclopropylcarbonyl)-cyclohexane-3,5-dione-1-carboxylate or 4-(cyclobutylcarbonyl)-cyclohexane-3,5-dione-1-carboxylic acid and b) one of the phenylureas N-(2-.beta.-chloroethoxyphenylsulfonyl)-N'(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, N-[2-(2 methoxyethoxy)phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-bis-difluoromethoxy-pyrimidin-2-yl)urea, N-[2-(2-methoxyethoxy)phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-cyclopropyl-6-methyl-pyrimidin-2-yl)urea, N-(2,2-dioxo-3-methyl-1,2-benzothioxin-8-ylsulfonyl)-N'-(4-me-thoxy-6-methylpyrimidin-2-yl)urea, N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-tria-zin-2-yl)urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-methoxy 6-methyl-1,3,5-triazin-2-yl)urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-dimethylpyrimidin-2-yl)urea, N-(2-methoxycarbonylthien-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, N-(2-ethoxycarbonylphenylsulfonyl)-N'-(4-chloro-6-methoxypyri-midin-2-yl)urea, or N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl) urea, together with an inert adjuvant.

11. A composition according to claim 1, which contains as active components a) ethyl 4-(cyclopropylcarbonyl)-cyclohexane-3,5-dione 1-carboxylate and b) N-(2-.beta. chloroethoxyphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, together with an inert adjuvant.

12. A composition according to claim 1, which contains as active components a) ethyl 4-(cyclopropylcarbonyl)-cyclohexane-3,5-dione-1-carboxylate and b) N-[2-(2-methoxyethoxy) phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)urea, toyether with an inert adjuvant.

13. A composition according to any one of claim 1 to 12, which contains the active components I and II in a ratio in the range from 200:1 to 1:1.

14. A composition according to claim 13 which contains the active components I and II in a ratio in tha range from 100:1 to 10:1.

15. A method of inhibiting or supressing plant growth, which method comprises treating plants, parts of plants, or seeds with an effective amount of a composition according to any one of claim 1 to claim 12 or claim 14.

16. A method of inhibiting the growth of grasses, mixed vegetation and weeds, which method comprises applying to an area covered in grass or weeds an effective amount of a composition according to any one of claim 1 to claim 12 or claim 14.

17. A method of suppressing the growth of plants beyond the 2-leaf stage, which method comprises applying to plants a composition according to any one of claim 1 to claim 12 or claim 14 reemergence.

18. A method according to claim 15, wherein the composition is applied to crops of sugar cane, cereals, maize, soybeans, rice and cotton.

19. A method according to claim 18, wherein the composition is applied to crops of soybeans.

20. A method according to claim 15, wherein the composition is applied to crops of fruit.

21. A method according to claim 15, wherein the composition is applied to leguminous cover crops.

22. A method of inhibiting growth in order to increase resistance to lodging and shorten the stalks in crops of cereals, which method comprises applying a composition according to any one of claim 1 to claim 12 or claim 14 to said cereals or a locus of said cereals.

23. A method according to claim 22, wherein the crops of cereals are oats, wheat, barley, or rye.