AU640720B2 - Synergistic composition for regulating plant growth - Google Patents

Description

640720 S F Ref: 145735 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: Priority: oo Related Art: *to Name and Address 9 5 9 9* 9., 6 9o..

4 9 eo 09.

S

9 of Applicant: Ciba-Geigy AG Klybeckstrasse 141 4002 Basel

SWITZERLAND

Address for Service: Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: Synergistic Composition for Regulating Plant Growth The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 PS /5-17876/= Synergistic C omposition for Regulating Plant Growth Abstract of the Disclosure The inventions relates to a synergistically acting compotistion and to a method for regulating plant growth, which contains as active compound of formula I, the ethylester of 4-cyclopropyl-3,5-,cyclohexanedione- 1 -carbonic acid of the formula I 0 *090 .50 0 @0 0 9 00

OS

0 9 5950 0 000* **50 0* 00 0

S

o 0 *5

S

000009 0 00 S 5 0 00 909995 0 0 0 together with a synergistically active amount of a phenolether of the formula HI

OR

1

R

2 I R o a cliloroacetanilide of the formula III 0 11 C1CH 2 C 'N R

C

2

H

5

'J

or a dinitroaniline of the formula IV 0 2 N

NO

2 or the ethylester of N-benzoyl-N-(3,4-dichlorophenyl)-DL-alanine, or of 1,1-dime rhylpyridine-chloride, 2-chil'oroethyl-N,N-trimethylammonium chloride, 2-chiorethylphosphonic acid, 1-phenyl-4,4-dimethyl-2-(1H- 1,2,4-triazole- 1-yl)-pent-l1-en-3 -ol, *Goes 1 -(4-chlorophenyl)-3,3-dimethyl- 1-(1H- 1,2,4-triazole- 1-yl)-butan-2-ol or of s thiocyclopropan- 1-yl)-[(trans-2-chlorallyloximino)-propionyl]-cyclohexane-1, 3-dione.

.In the formulae HI to IV, R, to RO have the meaning given in the description. The com- 9 to position serves to regulate plant growth, especially inhibiting the growth of cereal and *grass and is used preferably in post-emergent application.

-1B- PS/5-17876/= Synergistic Composition for Regulating Plant Growth The present invention relates to synergistic compositions containing plant growth regulating combinations of active compounds. The compositions according to this invention are suitable for regulating, especi ly inhibiting the growth of cultures of crop plants.

The invention relates furti -r to a method for regulating, especially inhibiting the growth of crop plants, especially of cereal, grass and other cultures and to the use of the new compositions.

Form the European Patent No. 126,713 respectively the US Patent No. 4,693,475 the ethyl ester of 4-cyclopropionyl-3,5-cyclohexanedione-1-carboxylic acid of formula O O

C

2

H

5 O- C 0 has been known. This active compound has good plant growth regulating, especially plant growth inhibiting properties.

S. Surprisingly the plant growth regulating property of this compound can be enhanced in a synergistic manner, by adding to it certain active compounds chosen from the group consisting of a) phenol ether, b) chloroacetanilide, c) dinitroaniline d) the ethyl ester of N-benzoyl-N-(3,4-diphenyl)-DL-alanine, e) quaternary ammonium salts f) 2-chloroethylphosphonic acid g) triazole derivatives and h) 5-(1-methyithiocycloprop-1-yl)-2-[1-(trans-3-chlorallyloximino)-propionyl]-cyclohexane-1,3-dicne.

-2- Object of the invention are therefore synergistic compositions for regulating plant growth, which contain, bosides inert carriers, auxiliaries and adjuvants, as active compound 4-cyclopropionyl-3,5-cyclohexanedione- 1 -carboxylic-acid ethyl ester of the formula I 0 0 0()

C

2

H

5 0- C 0 and additionally a synergistically active amount of another active compound selected from among egg a) phenol ethers of the formula IEI goes*

OR,

R

2 R4~

R

3 wherein R, is an acid or the C 1

-C

4 alkyI ester of a radical -CH 2 CO'OH, -CH(CH 3

)COO,,

goes~ -(CH 2 3 COOH or the nitrobenzoic-5-yl radical, R is chlorine or methyl, R, is chlorine and :RI is hydrogen, chlorine or m~ethyl; or b) chloracetanilides of formula II 0* 0 0

CICH

2 C N R

CA

5

R

6 (Ml) Wherein Rr)is methyl or ethyl and R, is methoxymethyl or 2-methoxy-l-methylethyl; or c) dinitroanilines of the formula IV Rg--N-R 7 0 2 N N2 R o v) Rio wherein

R

7 is hydrogen or C 1

-C

4 alkyl,

R

8 is C 1

-C

4 alkyl, benzyl or halobenzyl,

R

9 is hydrogen, methyl or halogen and

RI

1 is methyl, trihalomethyl or chlorine; or d) N-benzoyl-N-(3,4-dichlorophenyl)-DL-alanine acid ethyl ester or e) a quaternary ammonium salt selected from among 1,1-dimethylpiperidine chloride (VIa) and 2-chloro-N,N,N-trimethylethylammonium chloride (VIb);or f) 2-chloroethylphosphonic acid (VII); or g) l-phenyl-4,4-dimethyl-2(1H-1,2,4-triazol-l-yl)-pent-l-en-3-ol (VIII); or h) 5-(1-methylthioxycyclopropan-1-yl)-2-(trans-3-chloroallyloximino)-propionylcyclohexane-1,3-dione (IX).

15 The invention also relates to the use of the plant growth regulating compositions, S which contain an active compound of the formula I, together with a synergistically acting e: amount of a compound of the formulae II to IX, e.g. for inhibiting the growth of plants.

Accordingly, there is also provided according to the invention a method of regulating plant growth, which is characterized in that one applies to the plants or their locus an active amount of the composition of the invention, respectively a tank mix containing the active compound of the formula I and a mixing partner of formulae II to

IX.

There is further provided according to the invention a method of inhibiting plant growth in field cultures of useful plants and grasses which is characterized in that one 25 applies to the plants post-emergently an active amount of a composition according to the invention.

The compounds of the formulae I to IX are known.

Ethyl-4-cyclopropyl-3,5-cyclohexanedionecarboxylate of formula I is e.g. prepared as follows: 30 ml of cyclopropanoyl chloride are added dropwise to a solution of 60g of cyclo- S(G:\WPUSER\LIBFFIOOO16:EAR 1 of 2 71~V hexanedionecarboxylate and 25 ml of pyridine in 400 ml of dichloroethane. When everything is added, the mixture is stirred for a further 15 hours at room temperature. The reaction solution is then filtered and the filtrate is washed with 1N hydrochloric acid, dried and concentrated. The O-acylated intermediary product so obtained, is taiken up in 200 ml of dichloroethane, 4 g of 4-dimethylaminopyridine are added and the reaction mixture is refluxed for 4 hours. The cooled reaction solution is then washed with 1N hydrochloric acid, dried, concentrated, and the residue is chromatographed for purification over a small amount of silica gel. After evaporation of the solvent, one obtains the ethyl 4-cycloas a pale oil with a refractive index of n3 0 1.5350.

The following compounds of the formulae II to IX are to be mentioned: Phenol ethers of the formula II: HIIa) the methylester 2-nitro-5-(2,4-dichlorophenoxy)benzoic acid, common name "Bifenox", known from aus USP 3 776 715, see also The Pesticide Index 7th Ed. by R.

Worthing and S.B. Walker, published by the British Crop Protection Council, Lavenham Press Ltd. 1983.

lib) 2-(4-chloro-2-methylphenoxy)-propionic acid, common name "Mecoprop" or "MCPP", known from GBP 820 180, see also "The Pesticide Manual 7th Ed. 1983 7860".

IIc) 2-(2,4-dichlorophenoxy)acetic acid common name "2,4 see "The Pesticide Manual 7th Ed. 1983 3780".

IId) 2-(4-chloro-2-methylphenoxy)acetic acid, common name "MCPA", see "The Pesticide Manual 7th Ed. 1983 7790".

He) 4-(4-chloro-2-methylphenoxy)butyric acid common name "MCPB", see "The Pesticide Manual 7th Ed. 1983 7810".

-Chloroacetanilides of the formula III: rra) 2-chloro-2'-ethyl-6'-methyl-N-(2-methoxy-l-methylethyl)-acetanilide; common name "Metolachior"; (described in "The Pesticide Manual", 8th ed. (1987), p. 568, Ed. C.R.

Worthing; The British Crop Protection Council, Thornton Heath, GB).

Illb) 2-chloro-2',6'-dliethyl-N-methoxymethyl-acetanilide; common name "Alachior"; (described in "The Pesticide Manual", 8th ed. (1987), p. 5, Ed. C.R. Worthing; The British Crop Protection Councl'. Thornton Heath, GB).

111c) 2-chloro-N-ethoxymethyl-6'-ethyl-acet-o-toluidide; common name "Acetochior"; (described in "The Pesticide Manual", 8th Ed. (1987) p. 2, C.R. Worthing; The British Crop Protection Council, Thorntoxi I Ath, GB).

1ild) 2-chloro-N-(methoxycarbonylaminomethyl)-2',6'-diethyl-acetanilide, common name "Amidochlor".

-2,6-Dinitroanilines of the formula IV:

R

8 R 7

N

0 2 N 14p N0 2 (IV) zzN

R

9

R

10 o V*00 0 wherein to. R 7 is hydrogen or Cj-C 4 alkyl,

R

8 is C-akybe yl or halobenzyl, 0 o eq R 9 i ydrUge or halolen,

R

10 is methyl, trihalomethyl or chlorine.

SAmong the compounds of formula IV the following individual compounds are especially active: IVa) N-(l-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline, common name "Pendimethalin" known from USP 4 199 669, see the "The Pesticide Manual, 7th Ed. 1983 p. 9390".

l~b) N-ethyl-N(2'-chloro-6'-fluorobenzyl)-2,6-dinitro-4-trifluoromethylaniline, common name "Flumetralin" known from USP 4 169 721, see "The Pesticide Manual, 7th Ed, -6- 1983 p. 6480".

TVc) N 1 ,Nl-diethyl-2,6-dinitro-4-tifluormethyi-1,3-phenyldiamine, common name "Dinitramine", known from USP 3 617 252, see "The Pesticide Manual 7th Ed. 1983 5070.

The ethylester of N-benzoyl-N-(3,4-dichlorophenyl)-DL alanine of the formula V C -N CH- COC 2

H

'N C1 C1 common name "Benzoylprop-ethyl", known from the GIBP 1164 160, see "The Pesticide Manual 7th Ed. 1983 850".

-Quatemnary ammonium salts of the formula VI: VIa) The chloride of 1, 1 -dimethylpiperidine CS SOCH 3

CH

3 C1 :common name "Mequipat", known from DR-A 2 207 575, see "The Pesticide Manual 7th Ed. 1983 7920.

VIb) The chloride of 2-chloroethyl-N,N,N-trimethylammonium ClCH 2

CH

2

N(CH

3 3 D C common name "Chiomequat", known from GBP 944 807, see "The Pesticide Manual 7th Ed. 1983 5680".

-7- 2-Chioroethyiphosphonic acid of the formula VII: 0 C1CH 2

CH

2 P(0H) 2

(VII)

common name "Ethephon", known from USP 3 879 188, see "The Pesticide Manual 7th Ed. 1983 5680".

1-Phenyl-4,4-di .iethyl-2(1H-1,2,4-triazole-1-yl)-pent-1-en-3- ol of the formula VIII

C

3

OH

0:0H H I C- 0O** 3 C-C-CH-CdH

CH

3 N

(VIII)

N N bee

'-N

I. SO common name "Triapenthenol" known from "The British Crop Protection Conference" VIS Weeds Vol. 1 p. 113-128 1985.

1-Methylthiocyclopropan- l-yl)-2- [1-(trans-3-chloroallyloximidno)-propionyljcyclohexane- 1 ,3-dione of the formula IX

HCCI

Cs *0 NOCH 2

CH

S CCH 2

CH

3

(X

trans (X

H

3 C -S-C \A 0

H

2 C -CH 2 known from EP-A 243 313 or USP 4,909,835.

On the other hand other compounds with herbicidal or plant growdtiegulating properties, that were tested, showed surprisingly no synergistic enhancement of activity at all bi combination with the active compound of formula 1.

Plant growth regulators are substances which cause agronomically desired biochemical and/or physiological and/or morphological alterations in/on the plant.

The active substances contained in the compositions according to the invention have various effects on the plant growth, depending on the point in time of application, the dosage, the type of application and the environmental conditions. For example, the plant growth regulating combinations of this invention can inhibit the vegetative growth of plants. This type of action is interesting on lawns, in the production of ornamental plants, in orchards, on verges, on sports grounds and industrial terrain, but also in the targeted inhibition of secondary shoots, such as in tobacco. In arable farming, inhibition of the vegetative growth in cereals by means of thickened stems results in reduced lodging, and similar agronomical effects are achieved in oil seed rape, sunflowers, maize and other crop plants. Moreover, inhibition of the vegetative growth makes it possible to increase the number of plants per unit area. Another field of application of growth inhibitors is the selective control of ground-cover plants in plantations or crops with substantial distances S between the rows by powerful inhibition of growth without killing these ground-cover 0* plants, which results in the elimination of competition with the main crop but S agronomically positive effects, such as prevention of erosion, nitrogen fixation and loosening of the soil, are retained.

Plant growth regulators can stimulate crop yield in a quantitative way flow of latex) or a qualitative way sugar content), the apical dominance can be broken and the for- S" ming of side-shoots promoted in ornamental plants), the drop of fruit and flowers can be promoted thinning out in fruit trees in order to break the alterw~ance, fruit S abscission in olives, making possible mechanical harvesting), the ripening of fruits can be harnonised, sped up or delayed by means of growth regulators opening of the S: capsules in cotton, ripening of tomatoes or bananas).

A method for inhibiting plant growth is taken to mean that man interferes with the natural development of the plant without altering, in the sense of a mutation, the life cycle of the plant, which is determined by the genetic make-up. The method of growth regulation is applied at a point in time of development of the plant to be determined in the individual case. The active substances of the formula I can be applied before or after' emergence of the plants, for example as early as in the seed stage, or to the seedlings, to roots, tubers, stalks, leaves, flowers or other parts of the plant. This can be effected for example by applying the mixture of active substances of this invention itself or in the form of an agent to the plants and/or by treating the culture substrate of the plant (soil).

Plants can be made more resistant to environmental stress such as draught, cold or salt content in the soil with plant growth regulators. The defoliation of culture plants can be induced at a fixed time so that mechanical harvesting of crops like cotten, potatoes or vines becomes facilitated respectively made possible.

The synergistic compositions according to this invention (crop plant growth inhibitors are preferably used for growth inhibition in monocotyledonous cultures, such as cereal, grasses but also in dicotyledonous cultures with post-emergent application.

The synergistic mixtures according to this invention are used in general in application rates of 50 g/ha to 5000 g/ha. The proportion between the amount of compound of the 0:0, formula I and the synergistically active amount of the compound of formula II to IX can vary in wide ranges. As a rule the amount of compound of the formula I to the synergistically active amount of mixing partner of the formula II to IX lies between 100:1 to 1:20, preferably between 1:1 to 1:10.

The present invention includes also the preparation of agrochemical compositions, which is characterised by intimely mixing the active substances with one or several of the substances or groups of substances described herein. Included is also a method for treating plants, which is distinguished by the application of the compositions according to this invention.

Mixtures of the active compounds of the formula I and II to IX are generally used in the form of combinations and can be applied to the plants or the area to be treated simultaneously or successively.

Suitable carriers and adjuvants may be solid or liquid and correspond to appropriate substances used in the technique of formulation, such as e.g. natural or regenerated mineral material, solvents, dispergents, wetting agents, adhesifs, thickeners, binding agent, or fertilizers.

The compositions according to the invention are used in the unchanged form or preferably together with adjuvants usual in formulation technique and are used therefore e.g. as emulsion concentrates or solutions which can be sprayed directly or after dilution, diluted emulsions, meltable powders, dusts, granulates, or they are worked up e.g. by capsulation e.g. in polymeric material in the known way. According to the pursued goal and the given circumstances, applications like spraying, atomizing, dusting, scattering, spreading or powdering are selected as well as the appropriate kind of formulation. Favorable application rates are in general 10 to 5 kg of active substance (AS) per ha; preferably 100 g to 2 kg AS/ha.

The formulations, i.e. the compositions, containing the compound of formula I with a compound of the formulae II to IX and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

**o Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 000** 12 carbon atoms, e.g. xylene mixtures or substituted naphthalene, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or S0 S paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, .t ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverisedplant residues e.g. cork powder or sawdust. Especially suitable adjuvants are further phospholipides.

Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifiying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

-11- Both so-called water-soluble soaps and also water-soluble synthetic surface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C 10

C

22 e.g. the sodium cr 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 acid methyllaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

**ee The fatty sulfonates of sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a Cs-C 22 alkaly S radical which also includes ihe alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate of of a mixture of fatty alcohol sulfates S obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.

Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.

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

Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

-12- Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C 8

-C

22 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower'alkyl radicals. The salts are preferably S in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described, inter alia, in the following publications: "1985 International Mc Cutcheon's Emulsifiers Detergents", Glen Rock NJ USA, 1985, M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980.

The agrochemical compositions usually contain 0.1 to 99 preferably Gb1 to 95 of the mixture accord ig to the invention and 1 to 99.9 especially 99.8 to 5 of solid or liquid adjuvants, whereof 0 to 25 preferably 0.1 to 25 of a surfactant. While commercial ware is rather in the form of concentrates the end user prefers as a rule diluted COrCTO.7L,-lnS.

Tile compositions can also contain further additives, like stabilizers, anti-foaming agents, regulators of viscosity, binding agents, adhesifs as well as fertilizers and/or different active agent in order to achieve specific effects.

Agrochemical compositions of this kind are also a part of the present invention.

Active compounds or compositions with different biocidal properties can also be admixed to the compositions of this invention. Thus the new composition can contain besides the 13 compounds of the formula I and of the formulae II to IX e.g. also insecticides, fungicides, bactericides, fungistatics, bacteriostatics or nematocides.

The compositions according to the invention can generally be formulated, in detail, in accordance with the following Examples: Sos 00O *4 4*.

9666 0 9 0..

-14- Formulation Examples Example Fl: Formulation Examples for synergistic active ingredient mixtures of the formulae I and II, III, IV, V, VI, VII, VIII or DI (throughout, percentages are by weight) a) Wettable powders a) b) c) compound I and one of the compounds II to IX 25 50 75 sodium lignosulfonate 5 5 sodium lauryl sulfate 3 5 sodium diisobutylnaph- Sthalenesulfonate 6% octylphenol polyethylene glycol ether (7-8 moles of S ethylene oxide) 2% highly dispersed silicic acid 5% 10% kaolin 62 27 The active ingredient mixture is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

b) Emulsifiable concentrate compound I and one of the compounds II to IX 10 octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3% calcium dodecylbenzenesulfonate 3 castor oil polyglycol ether (36 moles of ethylene oxide) 4 cyclohexanone 30 xylene mixture 50 Emulsion of any required concentration can be obtained from this concentrate by dilution with water.

S o c) Dusts a) b) S, compound I and one of the compounds II to IX 5 8 talcum 95 kaolin 92 Ready-for-use dusts are obtained by mixing the active ingredient mixture with the carrier and grinding the mixture in a suitable mill.

d) Extruder granulate S compound I and one of the compound II to IX sodium lignosulfonate 2 carboxymethylcellulose 1% kaolin 87 The active ingredient mixture is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.

-16e) Coated granulate compound I and one of the compound II to IX 3% polyethylene glycol (mol.

wt. 200) 3% kaolin 94 The finely ground active ingredient mixture is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

f) Suspension concentrate compound I and ona of the com- S pound II to IX 40 S polyethylene glycol 10 nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% sodium lignosulfonate 10 carboxymethylcellulose 1 silicone oil in the form of a 75 aqueous emulsion 1% water 32 The finely ground active ingredient mixture is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Often it is more convenient to formulate the active substance of the formula I as well as the mixing partner of formulae II to IX individually, in order to mix them in the desired proportions shortly before the treatment in the applicator and to combine them with water as "tank mix".

-17- A synergistic effect is always present in the case of herbicides, when the herbicidal action of the combination of compounds I and II, III, IV, V, VI, VII, VIII or IX is greater than the expected action of the active ingredients applied individually, when calculated according to "Colby".

The expected herbicidal action Ae for a given combination of two compounds can be calculated as follows (cf. COLBY, "Calculating synergistic and antagonistic response of herbicide combinations", Weeds 15, pages 20-22, 1967): Y. (100-X) Ae=X 100 in which: S. X percentage inhibition of growth in the case of treatment with a herbicide I at a rate of application of p kg per hectare in comparison with the untreated control 0 Y percen' .ge inhibition of growth in the case of treatment with a herbicide II, m, IV, V, VI, VII, VIII or IX at a rate of application of q kg per hectare in comparison with the untreated control Ae expected herbicidal action (percentage inhibition of growth in comparison with the untreated control) after treatment with herbicide mixture I and II, III, IV, V, VI, VII, VIII or IX at a rate of application of p q kg active ingredient per hectare.

If the action actually observed is greater than the expected value Ae then synergism has been achieved.

The synergistic effect of the combinations of compounds I and II, III, IV, V, VI, VII, VIII or IX is demonstrated in the following Examples.

-18- Biological Examples Example 1: Growth inhibition of cereal Summer barley of the type "Iban" is sown in plastic beakers of 15 cm diameter filled with sterilized soil and raised in a climatized room at a day temperature of 10 to 15 0 C and a night temperature of 5 to 10 0 C. The light period was 13.5 hours daily at an intensity of about 25000 Lux.

Abour 34 days after sowing and thinning out to 4 plants per pot, the active substance or mixture was sprayed as an aqueous broth in the application rate given in the table of results. The amount of water used corresponds to about 500 I/ha. After the application, the plants are kept in the greenhouse at a day temperature of at least 10 0 C. The light period S was at least 13.5 hours daily.

The evaluation takes place 14 to 35 days after the treatment (the duration is given in the tables). The activity is measured and expressed in percent of the new growth, compared to not treated tables (plants is meant). 0 stands for no inhibitory action (same growth as with not treated plants), 100 means complete growth stop. The height of the new growth is represented in of the average of that of not treated control plants.

The results of growth inhibition are summarized in the following table 1. The combinations according to this invention that were tested show a clear synergistic increase in activity.

-19- Table 1: Compund/appli- Time of evaluation growth inhibition cation rate gjha Days after application measured expected I Ha 34 days (calculated according to Colby) 250 12 500 20 1000 0 2000 0 250 1000 57 12 250 2000 59 12 500 1000 71 500 2000 69 6.00 I00 1 Ib 34 days 250 12- 500 26- 1000 8- 5 2000 12 250+ 1000 82 19 250 2000 86 23 500 1000 91 32 500 2000 91 I hic 34 days 250 12 500 26 SS 500 10 1000 12 250-4+ 500 35 21 *250 1000 42 23 500 500 60 33 500 1000 64 S I M~a 35 days 1250 -8 500o 23 1000 2 2000 2 250 1000 '17 250 2000 29 500 1000 32 500 2000 46 20 0 *se.

S

*0 5 9 *0

S.

S

0006 Table 1 (continuation): Compund/appli- Time of evaluation growth inhibition cation rate g/ha Days after application measured expected I lid 32 days (calculated according to Colby) 125 -3 250 8 250 7 500 12 1000 12 125 250 30 125 500 48 14 125 1000 53 23 250 250 41 14 250 250 58 19 250 250 69 28 1 IVa 35 days 250 12 500 23 1000 0 2000 0 250 1000 27 12 250 2000 31 12 500 1000 27 23 500 2000 60 23 I IVc 19 days 250 8 500 23 1500 2 3000 2 250 1500 38 250 3000 49 500 1500 47 500 3000 74 I V 35 250 8 500 23 500 8- 1000 12 250 500 36 250 1000 66 19 500 500 61 29 500 1000 68 32 60 0 S S .5

U

0 0S S 0 05

S

.550.0

S

0 -21 0 *006* 0014 0*40 osoV.

*G

Table 1 (continuation): Compound/appli- Time of evaluation growth inhibition cation rate g/ha Days after application measured expected I VIa, 35 days (calculated according to Colby) 250 8 500 23 1000 8 2000 250 1000 27 250 2000 41 17 500 1000 47 29 500 2000 48 31, I VIb 35 days 250 8 500 23 1000 8 2000 6 250 1000 29 250 2000 32 14 500 1000 38 29 500 2000 55 28 1 VII 34 days 250 500 12 500 1 1000 3 250 500 15 6 250 1000 19 8 500 500 30 13 500 1000 49 13 I VIII 35 days 125 3 250 8 60 8 125 14 250 41 125 60 36 11 125 125 40 17 125 250 70 43 250 60 53 250 125 75 21 250 250 84 46 -22- Example 2: Growth inhibition of grasses A mixture of the grasses Poa, Festuca, Lolium, Bromus and Cynodon is sown into plastic dishes of 15 cm diameter that were filled with sterile soil and raised in the greenhouse at a day temperature of 21 0 C and a night temperature of 17 0 C. The light period is 13.5 hours per day at a light intensity of minimum 7000 Lux.

After emerging the grasses were cut back every week to about 6 cm height. About 42 days after sowing and 1 day after the last cut, the grass was treated with the amount of active substance or combination of active substances in the application rate in g/ha given in the tables of results, in the form of an aqirous broth. The amount of water used was about *9@O 500 1/ha. The test was evaluated 20 days after the treatment. The height of the new growth was measured and is expressed as inhibition as compared to the average of the new e growth of the not treated control plants.

0* The results of growth inhibition of grasses are summarized in the following table 2. The mixtures tested show a clearly synergistic activity.

a* C o *o 0 -23 Table 2: Comnpound/appli- Time of evaluation growth inhibition cation rate g/ha Days after application measured expected I Ha 20 days (calculated according to Colby) 250 500 33 1500 4 3000 8 250 1500 38 18 250 3000 38 22 500 1500 49 36 500 3000 49 38 06 1 11d 20 days 250 500 33 1000 O 2000 o 250 1000 66 250 2000 86 66 500 1000 79 56 500 2000 83 73 I Via 20 days 250 -11 500 31 eele 1000 18 2000 21 250+ 1000 49 27 250 2000 52 500 1000 55 43 500+ 2000 59 6 24 Table 2: (continuation) Compound/appli- Time of evaluation growth inhibition cation rate g/ha Days after application measured expected I VIb 20 days (calculated according to Colby) 250 11 500 31 1000 1 2000 8 250 1000 35 12 250 2000 37 18 500 1000 52 32 500 2000 52 37 I VII 20 days 500 39 1000 46 500 9 1000 9 2000 13 500+ 500 56 44 500+ 1000 65 44 500+ 2000 73 47 1000+ 500 79 44 1000 1000 01 51 1000+ 2000 87 53 *I IX 20 days 500 33 750 52 0 15 500 5 48 3 500 15 91 750 5 76 52 750 15 97 78

Claims (3)

1. A synergistically acting composition for regulating plant growth, which is characterized that it contains besides inert carriers, auxiliaries and adjuvants, as active component

4-cyclopropionyl-3,5-cyclohexanedione- 1-carboxylic acid of formula I 0 0 0. 11(M C 2 H 5 C 0 besides a synergistically active amount of a further active compound selected from among phenolethers of the formula 11 OR, goes R 2 -R 4 00 R 3 wherein R, is an acid the C 1 -C 4 a~kyl ester of a radical -CH 2 COOH, -CH(CH 3 )COOH, -(CH 2 3 COOH or the nitrobenzoic-5-yl radical, 6 R 2 is chlorine or methyl, R 3 is chlorine and *~R 4 is hydrogen, chlorit~e or methyl; or b) chloracetanilides of the formula Ill S. S 0 CIC)i 2 C N R CAH R 6 (UT) wherein R 5 is methyl or ethyl and R 6 is methoxymethyl, ethoxymethyl or 2-methoxy-,1-methyilethyl; or 26 c) dinitroanilines of the formula IV R 8 N R 02N -~NO 2 wherein R 7 is hydrogen or C 1 -C 4 alkyl, R 8 is Cl-C 4 alkyl, be zy or halobenzyl, SR 9 is hydrogen/or alolen and Rio is methyl, trhalomethyl or chlorine; or s d) N-benzoyl-N-(3,4-dichlorophenyl)-DL-alanine acid ethyl ester; or 0.. e) a quaternary ammonium salt selected from among 1, 1-dimethylpiperidine chloride and 2-chloro-N,N,N-trimethylethylamnmonium chloride; or f) 2-chloroethylphosphonic acid; or g) 1-phenyl-4,4-dimethyl-2(lH-1,2,4-triazol-l-yl)-pent-l-en-3 -ol; or S h) 5-(l -methyithioxycyclopropane- 1-yl)- 2-(trans-3-chloroallylo ximino)-propionyl- cyclohexane-l1,3-dione, 2. A composition for regulating plant growth according to claim 1, which is characterized that it contains, besides inert adjuvants and the active compound of formula I, a synergistically active amount of a phenol ether of formula 11 OR, R 2 wherein 27 R, is an acid or the Cl-C 4 alkyl ester~of a radical -CH 2 COORl, -CH(CH 3 )COOH, -(CH 2 3 COOH or the nitrobenzoic-5-yl radical, R 2 is chlorine or methyl, R 3 is chlorine and R 4 is hydrogen, chlorine or methyl, or in the proportion active compound of formula I to active compound of formula 1E1 of 10: 1 to 1: 3. A composition for regulating plant growth according to claim 1, which is characterized that it contains a synergistically active amount of a compound selected from among 2-ni~tro-5-(2^,4-dichloro.phenoxy)-benzoic acid, 2-(4-chlolro-2-methyl-phenoxy-)- prop onic-ac~d, 2-(2,4-dichlorophenoxy)acetic-acid, 2-(4-chloro-2-methyl-phenoxy)- 0 e~g~-4 n4 1

44-(4chloro-2-methylphenoxy)-butyic-acid. sue* 4. A composition for regulating plant growth according to claim 1, which is characterized that it contains besides inert adjuvants and the active compound of formula I, a syner- O gistically active amount of a chloro acetanilide of the formula Ill CICH 2 R 000 2 H 5 R6 OI) wherein *~R 5 is methyl or ethyl and R 6 iA. methoxymethyl, ethoxymethyl or 2-methoxy-l1-methylethyl, in the proportion of active compound of the formula I to active compound of the formula III of 10: 1 to 1: g~ept: 5. A composition for regulating plant growth according to claim 1, which is characterized, that it contains a synergistically active amount of a compound selected from among 2-chloro-2'-ethyl-6'-methyl-N-(2-methoxy- 1-methylethyl)acetanilide, 2-chloro- 2',6'-diethyl-N-methoxymethylacetanilide, 2'-chloro-N-ethoxymethyl-6'-ethylacet-o- toluidide and 2-chloro-N-(methoxycarbonylaminomethyl)-2,6'-diethylacetanilide. 6. A composition for regulating plant growth according to claim 1, which is characterized that it contains, besidf,. inert adjuvants and the active compound of formula I, a syner- _gistically active amount of a 2,6-dinitroanilide of the formula IV 28 Ra- N -R 7 0 2 N NOp R 9 wherein R 7 is hydrogen or Cl-C 4 alkyl, Rg is Cl-C 4 allcyl, benzyl or halobenzyl, R 9 is hydroge orhaogn and RIO is methyl, trhalomethyk or chlorine, in the proportion of active compound of the :~'formula I to active compound of the formula IV of 10: 1 to 1: 7 A composition for regulating plant growth according to ;I1aimn 1, which is characterized that it contains a synergistically active amount of a compound selected from among N-(1-ethylpropyi)-3,4-dirniethyl-2,6-dinitroaniline, N-ethyl-N-(2'-chloro-6'-fluorobenzyl)- 2,6-dinitro4-trifluoromethylaniline and N 1 ,Nl-diethyl-2,6-dinitro-4-trifluoro- methyl-i ,3-phenyldiamine. 8. A composition for regulating plant growth,which is characterized that it contains besides inert adjuvants and the active compound of formula I, a synergistically active sels amount of the ethyl ester of N-ben zoyl-N-3,4-dichlorophenyl)-DL-alanine of the for- mulaYV C. CH3 km C-N-CH-COCH 0M C] in the proportion active compound of formula I to active compound of formula V of 10: 1 to 1:10. 9. A composition for regulating plant growth according to claim 1, which is characterized that it contains besides inert adjuvants and the active compound of formula I, a syner- -29- gistically active amount of a quaternary ammonium salt, which is selected from among 1,1-dimethylpiperidine chloride and 2-chloroethyl-N,N,N-trimethylammoniumchloride, in the proportion of active compound of the formula I to ammonium salt of 10:1 to 1:10. A composition for regulating plant growth according to claim 1 which is characterized that it contains besides inert adjuvants and the active compound of formula I, a syner- gistically active amount of 2-chloroethylphosphonic acid, in the proportion of active compound of the formula I to 2-chloroethylphosphonic acid of 10:1 to 1:10. 11. A composition for regulating plant growth, which is characterized that it contains besides inert adjuvants and the active compound of formula I, a synergistically active amount of 1-phenyl-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-l-en-3-ol, of the formula VIII &see *ee CH 3 OH H 3 C-C-CH-C=CH ,Go" CH 3 N (VImI), N N in the proportions of active compound of the formula I to compound of the formula VIII of 10:1 to 1:10. 12. A composition for regulating plant growth, which is characterized that it contains besides inert adjuvants and the active compound of formula I, a synergistically active amount of 5-(1-methylthiocyclopropane-1-yl)-2-[1-(trans-3-chloroallyloximino)-propio- nyl]-cyclohexane-1,3-dione of the formula IX r HCCI II O NOCH 2 CH It CCH 2 CH 3 a tans (IX) H 3 C-S C- H 2 C C,2 in the proportion of active compound of tf e formula I to active compound of the formula IX of 100:1 to 1:10. 13. A composition for regulating plant growth according to claim 1, which is characterized that it contains besides 09.9 to 5% solid or liquid inert adjuvants, among them 0.1 to 25% of a surfactant, 0.1 tk 95% of a combination of active compounds of the compound of formula I with a compound of one of the formulae II to IX in the proposition of 100:1 to 1:10. 14. A synergistically acting composition for regulating plant growth, substantially as hereinbefore described with reference to any one of Formulation Examples F1(a) to A method of regulating plant growth, which is characterized in that one applies to the plant, or their locus an active amount of a composition according to any one of claims 1 to 14, respectively a tank mix containing the active compound of the formula I and a mixing partner of formulae II to IX. 16. A method of inhibiting plant growth in field cultures of useful plants and grasses which is characterized in that one applies to the plants post-emergently an active amount of a composition according to any one of claims 1 to 14. Dated 20 May, 1993 Ciba-Geigy AG Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON *S S S S. So S S 0 IG:\WPUSER\LIBFF10001 :EAR 2 o 2