NZ197643A - Synergistic herbicidal compositions containing 4-(3',5'-dichloropyridl-2'-oxy-alpha-phenoxypropionic acid derivatives - Google Patents

Abstract

1. A synergistic composition for selectively controlling weeds, which composition comprises, on the one hand, a 4-(3',5'-dichloropyridyl-2'oxy)-alpha-phenoxypropionic acid propargyl ester of the formula I see diagramm : EP0043802,P15,F1 wherein Z is oxygen or sulfur, and, on the other, one of 3-(3'-chloro-4'-methylphenyl)1,1-dimethylurea (IIa), 3-(3'-chloro-4'-methoxyphenyl)-1,1-dimethylurea (IIb), 3-(4'-isopropylphenyl)-1,1-dimethylurea (IIc), 1-benzothiazol-2-yl-1,3-dimethylurea (IId), 4-hydroxy-3,5-diiodobenzonitrile (IIe) or 3,5-dibromo-4-hydroxybenzaldehyde-O-(2',4' -dinitrophenyl)-oxime (IIf), together whith carriers and/or other adjuvants.

Description

New Zealand Paient Spedficaiion for Paient Number 1 97643 197643 Priority Dasc(s): . 5.".1......... <2 —t , Oj CompSetG Specification FHad: ftoi-OH-T\Z°> Clsss; o Publication Date: .. . ."T.V. SEP .1 P.O. Journal Mo: .....

Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION M.w,TCNTO(m -8 JULlttt "Synergistic composition and method of selectively controlling weeds, especially in cereals" -1/WE CIBA-GEIGY AG of Klybeckstrasse 141, 4002 Basle, Switzerland, a Swiss Corporation hereby declare the invention, for which -I/we pray that a patent may Ipe granted to -me/us, and the method by which it is to be performed, to be particularly described in and by the following statement (followed by page I A.) - let- 197643 Case 5-12951/=- Synergistic composition and method of selectively controlling weeds, especially in cereals The present invention relates to a synergistic composition comprising a combination of herbicides and which is most suitable for selectively controlling weeds in cereals. The invention also relates to a method of controlling weeds which comprises the use of the novel composition, especially in cereals. weeds at the present time in cereals are species of the genera Sinapis (mustard) and Chryset^theimn(corn marigold), and certain Avena species (wild oats).

Excellent postemergence selective herbicides against monocot weeds are 4-(3',5'-dichloropyridyl-21-oxy)-a-phenoxyproplonic acid propargyl ester of the formula I a. and 4- (3' »5 ' -dichloropyridyl-2' -oxy) -oc -phenoxythiopropionic acid prop. " " " The two compounds of formula I, viz. 4-(3',5*-dichloro-pyridyl-21-oxy)-a-phenoxypropionic acid propargyl ester (la) and 4-(3' ,5' -dichloropyridyl-2' -oxy)-a-phenoxy thiopropionic acid propargyl ester (lb), processes for the production thereof and the use thereof as selective herbicides, are described in the New Zealand Patent Specification 189414.

The most frequently encountered and most important CI— o-ch-co-o-ch2-csch (Icl) , CI— It is known that dicot weeds, and also a number of mono-cots, can often be successfully controlled postemergence in cereals with 3-(3'-chloro-4'-methylphenyl)-l,l-diniethylurea (Chlortoluron) of the formula Ila H3C—^ iNH-CO-N(CH ) (Ila) • ta • / ci or with 3-(3,-chloro-4'-methoxyphenyl)-l,l-dimethylurea (Metoxuron) of the formula lib H3C-0—^ NH-CO-N(CH3>2 (lib) •a • / Cl or with 3-(4'-isopropylphenyl)-l,l-dimethylurea (Isoproturon) of the formula lie i-H7C3—^ NH-CO-N(CH3)2 (He) or with l-benzothiazol-2-yl-l,3-dimethylurea (Methabenzthiazuron) of the formula lid M ?3 N-CO-NH-CH, did) V \/ or with 4-hydroxy-3,5-diiodobenzonitrile (loxynil) of the formula lie 1976 43 I i ✓ \ y°H r. Y (IIe) or with 3,5-dibromo-4-hydroxybenzaldehyde-0-(21,4'-dinitrophenyl)-oxime (Bromophenoxime) of the formula Ilf Br L. X.-.N HO—^ CH»N-0—^ /*"n02 (IIf) •a* I I Br N02 The compounds of the formulae Ila to Ilf and their herbicidal activity are described e.g. in the following publications: Chlortoluron (compound Ila) in C.r. 5 Conf. Com. franc.: Mauvaises Herbes (COLUMA), 1969, II, 349, Metoxuron (compound lib) in Z. Pflkrankh., PflPath., PflSchutz, 1968, 75, 233, Isoproturon (compound lie) in German Offenlegungsschrift 2 107 774, Methabenzthiazuron (compound lid) in PflSchutz-Nachr. Bayer, 1969, 22, 314, loxynil (compound lie) in Nature, Lond., 1963, 200, 28, and Bromofenoxime (compound Ilf) in Proc, 3rd EWRC Symp. "New Herbicides", Paris, 1968, S. 177.

Surprisingly, it has now been found that a combination of both classes of compound I and II, in a ratio varing within specific limits, exerts a specific synergistic action which is able to control the majority of all weeds in cereals without damaging these latter. The principal 1 976 43 weeds in cereals, such as species of the dicot genera Chrysenthemum and Sinapis as well as certain Avena (wild oat) species, are selectively destroyed in the emergent crops.

It is surprising that the combination of a compound of the formula I with a compound of the formula II not only brings about an expected additive enhancement of the activity spectrum against the customary weeds associated with cereals and soybeans, but gives rise to a synergistic effect which potentiates the action of both components from two points of view.

On the one hand, the rates of application of the single compounds I and II are distinctly reduced while the same good action is retained. On the other hand, the combination also achieves a high degree of weed control where both single compounds have become totally ineffective at too low rates of application. The consequence is a substantial broadening of the activity spectrum against weeds and an additional increase in the safety margin on application to crops of cereals and soybeans, as is necessary and desirable in the event of unintentional overapplication.

In addition to being used in crops of soybeans and cereals such as barley, rye and, in particular, wheat, the composition of this invention can also be used for selectively controlling weeds in crops of other monocot plants having similar sensitivity to herbicides and similar weed infestation, e.g. in maize and rice.

The herbicidal combination employed in the practice of this invention will contain a compound of the formula I and a compound of the formula II in any ratio, usually with 197643 an excess of the one over the other. The preferred ratio of component I to component II is 1:1 to 1:25, with the most preferred ratio being from 1:1 to 1:10.

The herblcidal combination has an excellent action against weeds without having any noticeable effects in crops of cereals when used in the conventional rates of application of 0.2 to 4 kg/ha, preferably 0.5 to 3 kg/ha.

The following combinations have proved particularly effective synergistic herblcidal mixtures: a) 4- (31,5'-dlchloropyridyl-2,-oxy)-a-phenoxypropionic acid propargyl ester (la) and 3-(3'-chloro-4l-methylphenyl)-l,1-dimethylurea (Ila), b) 4- (3*, 5,-dichloropyridyl-2*-oxy)-a-phenoxy thiopropionic acid propargyl ester (lb) and 3-(4f-chloro-41 -methylphenyl)-l, 1-dimethylurea (Ila), c) 4- (31,5'-dichloropyridyl-21-oxy)-a-phenoxypropionic acid propargyl ester (la) and 3-(4'-isopropylphenyl)- • 1,1-dimethylurea (lie), and d) 4- (31,5'-dichloropyridyl-2'-oxy)-a-phenoxythiopropionic acid propargyl ester (lb) and 3-(4'-isopro-pylphenyl)-l, 1-dimethylurea (lie).

The present invention also relates to the use of the composition, i.e. to a method of selectively controlling grasses and weeds postemergence in cereals.

In addition to the novel combination o£ active Ingredients, the composition o£ this invention also contains suitable carriers and/or other adjuvants* These can be solid or liquid and correspond to the substances conventionally employed In the art of formulation, e.g. natural or ^ regenerated mineral substances, solvents, dispersants,y ^ r 1 976 43 wetting agents, tackifiers, thickeners, binders or fertilisers. Suitable formulations are therefore e.g. emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. The methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances, just like the nature of the compositions.

The formulations, i.e. the compositions or preparations containing the herbicidal combination of the invention 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).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water. 1 976 4 3 > 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 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 dolimite or pulverised plant residues.

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

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (ci0~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 acid methyltaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkyl-arylsulfonates. 1 97 6 43 The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a ^8~^22a^k^" rac*^cal which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of ligno-sulfonic 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 sulfonic acids of adducts of fatty alcohols and ethylene oxide. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulf-onates are the sodium, calcium or triethanolamine salts of docecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. 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, or 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, ethylenediaminepolypropylene 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 1976 43 groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributyl-phenoxypolyethoxyethanol, polyethylene glycol and octyl-phenoxypolyethoxyethanol. Fatty acid esters of polyoxy-ethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one polyglycol ether or Cg-G22alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxylalkyl radicals . The salts are preferably 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 e.g. in the following publications: "McCutcheon1s Detergents and Eraulsifiers Annual", MC Publishing Corp., Ringwood, New Jersey, 1979; Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co. Inc., New York, 1964.

The concentration of active ingredient in commercial compositions is from 0.1 to 95 % by weight, preferably from 1 to 80 70 by weight. 197641 Preferred formulations are composed in particular of the following constituents (% « percentage by weight): Solutions. active ingredient: 5 solvent: 95 surfactant: 1 to 95%, preferably 10 to 80% to 57o, preferably 90 to 0% to 30%, preferably 2 to 20% Emulsifiable concentrates active ingredient: surfactant: liquid carrier: % to 50%, preferably 10 to 40% 5% to 40%, preferably 10 to 20% 20% to 95%, preferably 40 to 80% Dusts active ingredient: solid carrier: 0.5 to 10%, preferably 2 to 8% 99.5 to 90%, preferably 98 to 2% Suspension concentrates active ingredient: water: surfactant: to 757o, preferably 10 to 507o 94 to 25%, preferably 90 to 30% 1 to 40%, preferably 2 to 30% Wettable powders active ingredient: surfactant: solid carrier: to 90%, preferably 10 to 80% and, most preferably, 20 to 60% 0.5 to 20%, preferably 1 to 15% 5 to 90%, preferably 30 to 70% Granulates active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%. \ 976 4 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%.

The compositions of the invention can be mixed with other biocidal compounds or compositions. Accordingly, in addition to containing the compounds of the general formula I and formula II, the compositions of the invention can also contain e.g. insecticides, fungicides, bactericides, fungistats, bacteriostats, or nematocides, in order to broaden the activity spectrum.

Herbicides always have a synergistic effect if the herbicidal action of the combination of I + II is greater than the sum of the action of the individual active ingredients.

The expected plant growth E for a given combination of two herbicides can be calculated as follows (cf. COLBY, S.R., "Calculating synergistic and antagonistic responses of herbicide compositions", Weeds 15, pages 20-22,1967): X • Y E - wherein 100 X « the percentage growth (compared with untreated plants) after treatment with a herbicide I at a rate of application of p kg per hectare, Y =» the percentage growth after treatment with a herbicide II at a rate of application of q kg per hectare, and E » the expected percentage growth (compared with the control plants) after treatment with the herbicidal mixture of I + II at a rate of application of p + q kg of active ingredient per hectare. 1 976 43 If the actually observed value is lower than the expected value E, then there is synergism.

The synergistic effect of the combinations of compounds I and II is demonstrated in the following Examples. 4 97 6 4 Example 1: The test plants are sown, in a greenhouse, in plastic containers filled with 30 litres of sterilised garden soil. The plants are then sprayed postemergence in the 2- to 3-leaf stage with an aqueous dispersion of the combination of herbicides. The rate of application of the dispersion is 50 ml/m . Evaluation is made after 20 days at 18°-20°C and a relative humidity of 60-70%, and daily watering of the containers. The degree of damage to the plants is assessed linearly in accordance with the following rating: 1 - plants withered 5 - medium damage 9 - normal state.

The following results are obtained with different mixture ratios and total amounts of active ingredient: a) Table l:Tolerance and activity of 4-(3',5*-dichloro-pyridyl-21-oxy)-a-phenoxypropionic acid propargyl ester (compound la) and compounds Ila to Ilf, and mixtures thereof, when applied post-emergence: Test ( plant "Colib ri" wheat Avena fatua Sinapis arvensis Chrysanthemum segetum Comp^-la ikg ajjffa 0 0.5 0.2! ( ) 0.5 0.25 0 0.5 0.25 0 0.5 0.25 Co-component kg aijbE 1.0 0.5 0 1.0 0.5 0 1.0 0.5 1.0 0.5 0 1.0 0.5 0 1.0 0.5 1.0 0.5 0 1.0 0.5 0 1.0 0.5 1.0 0.5 0 1.0 0.5 0 1.0 0.5 Cotnp. Ha 9 9 6 7 7 7 7 8 9 9 2 2 2 2 2 2 3 6 9 2 3 9 2 3 6 6 9 3 4 9 4 6 Comp. lib 9 9 6 6 9 7 9 9 9 9 2 2 2 2 2 2 2 3 9 2 3 9 1 2 2 6 9 2 2 9 2 3 Compile 9 9 6 6 6 7 9 9 7 9 2 2 2 2 2 2 1 1 9 1 1 9 1 1 4 9 2 3 9 2 3 Canp.IId 9 9 6 7 7 7 9 9 9 9 2 2 2 2 2 2 2 3 9 1 2 9 1 2 9 9 9 4 4 9 3 4 Comp.IIe 9 9 6 8 8 7 9 9 9 9 2 2 2 2 2 2 1 2 9 1 2 9 1 2 2 4 9 2 3 9 1 3 Comp. Ilf 9 9 6 9 9 7 9 9 9 9 2 2 2 2 2 2 2 3 9 1 1 9 I 2 1 3 9 1 3 9 1 3 * 0s 1 976 If the values relating to the additive action calculated by the method of Colby are compared with the results reported in Table 1, then it is evident that the observed growth figures given for Sinapis arvensis and Chrysanthemum are lower than those calculated. The synergistic effect of the combination of 4-(3',5'-dichloro pyridyl-2'-oxy)-a-phenoxypropionic acid propargyl ester and compounds Ila to Ilf is thus demonstrated (cf. Table 2).

Table 2: Values calculated by the method of Colby for demonstrating the synergism of 4-(3',5r-dichloropyridyl-2'-oxy)-ct-phenoxypropionic . acid propargyl ester (compound la) and compounds Ila to Ilf. -rr o >§ • M O O 3 X) • M O O 5 T3 • W n o 3 T3 • o o 3 "V • M O O 3 • w Co-component kga.i./ha M ^.

Test plant ct> a.

C to B fl» § 00 Ln ON ro ON ro Ln determined value h-» • o o i—* ON to o> ro ON ro ON ro ON ro ON ro expected value o o Ln 00 Ln ON ro ■vj Ln determined value o i-" cr hi OH N9 ON ro ON ro ON ro ON ro On ro expected value Ln t-^ § § § § § Ln detErmined value X XT —ST" Ln «^j Ln «*4 Ln Ln Ln vj Ln expected value O © ft> P3 t—• O o g 8 >-» 8 00 determined value o • ro Ln rr Ln •NJ Ln Ln «NJ Ln Ln •NJ Ln expected value Ln to M ro ro to M ro M ro detBr mined value t—1 h- to to i-- ro to to ro expected value O O • % I—» tO f—• ro ro t-» ro i—» ro h-» ro determined value o 9 P> ro ** ro «—» ro h-» to ro ♦—» ro expected value • Ln i-h M ro t—■ ro 1—» ro t-» ro ♦—» ro ro determined value (-• C to i-^ ro i—• ro vo i—• ro »-» ro expected value O o » K? f—» ro c-• ro i-» to ro i-* ro determined \alue o Ln »-* N> h- IO *-* ro >—» ro i-* ro c expected value Ln t-» 1—» h-1 f—• ro ♦—» ro determined value >-* • cn *-* ro f-» I—* ro »-» h- to ro Ln expected value o o • Ln 9 D3 H-» ro t—' ro i—> ro ro Ln ro Ln determined value o CD ro LA i-* ro ro Ln ♦—» ro Ln ON ro expected value kn 03 r< *-» »—» I-* i—' ♦—* ro determined value <t> h- JO ro l-4 ro ro Ln expected value O O CD 1—» ro f—• ro ro *-» to ro Ln determined value o ro Ln ro Ln ** ro to Ln ro Ln On ro expected value Ln i—« ro Ud »-* ro t-4 ro ro Ln determined value »-» ro *-» o o U3 •nj ♦—» ro ON ro expected value O O • Ln n V< CD ro Ln u? •»%j u> ro Ln *-* ro L^ determined value O • 03 9 rr s* ro Ln U> § Ln O ON to On ro expected value n> 3 H- ♦-» ro Ln t—» ' ro r- ro u> •vj determined value 3 »—» ro g UJ ro ON ro expected value o O ro a 09 (D ro Ln ro Ln Lti ro tn ro Ln ON ro detErmined value © Ln rT C B ro Ln u> I-1 o o O On ro o* ro expected value Ln 9 Z 6 I I 97643 b) Table 3;Tolerance and activity of 4-(3',5'-dichloro-pyridyl-21 -oxy)-a-phenoxythiopropionic acid propargyl ester (compound Ih) and compounds Ila to Ilf, and mixtures thereof, when applied post-emergence: Test plant "Collbri" wheat Avena fatua Sinapis arvensis Chrysanthemum segetum Comp. Ib ai./ha 0 0.5 0.25 0 0.5 0.25 0 0.5 0.25 0 0.5 0.25 Co-component jkg ai./ha 1.0 0.5 0 1.0 0.5 0 1.0 0.5 1.0 0.5 0 1.0 0.5 0 1.0 0.5 1.0 0.5 0 1.0 0.5 0 1.0 0.5 1.0 0.5 0 1.0 0.5 0 1.0 O.t Comp J la 9 9 7 7 7 7 9 9 9 9 2 2 2 2 2 2 3 6 9 2 4 9 2 3 6 6 9 2 4 9 4 4 Conp.IIb 9 9 7 9 9 7 9 9 9 9 2 2 2 2 2 2 2 3 9 2 3 9 3 3 2 6 9 2 3 9 1 2 Compjic 9 9 7 8 8 7 9 9 7 9 2 2 2 2 2 2 1 1 9 1 1 9 1 1 4 9 2 2 9 3 3 Coitpjid 9 9 7 9 9 7 8 8 9 9 2 2 2 2 2 2 2 3 9 1 2 9 1 2 9 9 9 6 6 9 6 9 Compile 9 9 7 9 9 7 9 9 9 9 2 2 2 2 2 2 1 2 9 1 2 9 1 1 2 4 9 2 2 9 2 3 Compjif 9 9 7 9 9 7 9 9 9 9 2 2 2 2 2 2 2 3 9 2 2 9 - - 1 3 9 I 3 9 1 3 « ^ C" 04 1 97643 If the values relating to the additive action calculated by the method of Colby are compared with the results reported in Table 3, then it is evident that the observed growth figures given for Sinapis arvensis and Chrysanthmum segetum are lower than those calculated. The synergistic effect of the combination of 4-(3*,5'-dichloro-pyridyl-2'-oxy)-a-phenoxythiopropionic acid ester (compound lb) and compounds Ila to Ilf is thus demonstrated (cf. Table 4).

Table 4: Values calculated by the method of Colby for demonstrating the synergism of 4-(3',51-dichloropyridyl-2'-oxy)-a-phenoxypropionic acid propargyl ester (compound la) and compounds Ila to Ilf.

Comp. ilf Comp. lie Comp.IId Comp. lie Comp.lib ft" 0 -1 % fH M P Co-component kg ai./haj ?r o OQ o F* f? Test plant | g § 00 § Di determined value f o o • Ln "Collbri" wheat •vj Ln Ln Ln •Nl Ln -J Ln 3 expected value § | § 00 -sj g Ln determined! value © • Ln Ln *0 Ln •NJ Ln -J L/I Ln Ln expected value i—» O O i—' O o 00 •o h-» O O I-* O o H- o o determined value *-* » O 0.25 •sj Ln Ln Ln •O Ln •o Ln Ln expected value ** 8 8 00 i—» O o g 1—1 O o determined value O • Ln Ln Ln Ln Ln Ln Ln expected value N? *-» ro <r* to i-* ro t-* ro i—1 ro determined value »-* o • Avena fatua ♦—> ro *-* ro ♦-» ro vo h-» to »-» ro expected value © tO ro ♦-* ro t-* to h* to »—• to determined value © • Ln h- ro i—* ro r-» to «—1 ro t—» to »—1 ro expected value >—• ro ro h- ro h* to *-» ro »—• ro determined value I-* • o 0.25 ro ro r-* ro VD t-» ro to expected value ro ro t—* ro to h-» to ♦—* ro determined value o • Ln ro »-* ro t-* to fO h-» to t—' to expected value *-• ro t—» r* f* ro t—» ro determined \Ettae • © o • Sinapis arvensis i—» ro t—» f—> ro ro ro Ln expected value ro ro i-» ro ro Ln u> determined value © • Ln ro LSI «—• ro ro Ln 1—1 to Ln ON ro expected viue I h— ro Ln t-- ro determined value • © 0.25 1 *—» to ro ro Ln expected value l f* *-» ro c ro Ln ro Ln deternined value © Ln l ro Ln h* ro Ln 0\ ro expected value ♦—> *-* ro a* ro M to t—* ro ro determined value *-■ • o © • Ln Chrysanthemum segetum i—1 *■* to »—* 8 w NJ <-* ro ro expected value ro Ln »—1 ro o* fO M to ro Ln LO determined value o • Ln ro Ln u> •sj s o Ln O O ro cr ro expected value ro ro ro Ln ♦—» •sj detEnnined vd.ue • o 0.25 i—* t—• ro § w xj hi ro expected value ro Ln ro Ln 6 o ro ui r-- ro us H rt-pirmined value o • Ln ro Ln t-' g un O ro to expected vailue - oz - Ct? 9 Lb t t 97643 Example 2: Field tests in wheat fields yielded the following results. The growth figures are reported as percentages compared with the untreated control field. a) Field test in Cisse/France.

Application on March 18, 1980.

Evaluation 85 days after application (June 10, 1980).

Compound Growth of AVENA FATUA Growth of rate of appli observed expected accord WHEAT cation in g/ha ing to COLBY la : 150 50 - 100 lb : 200 55 - 100 Ila: 2000 60 - 100 lie: 1250 90 - 100 la + Ila: (150 + 2000) 12 100 la + lie: (150 + 1250) 6 45 100 lb + Ila: (200 + 2000) 12 33 100 lb + lie: (200 + 1250) 50 100 b) Field test in Pouant/France.

Application on March 19, 1980.

Evaluation 84 days after application (June 10, 1980).

Compound rate of application in 2/ha Growth of observed AVENA FATUA expected according to COLBY Growth of WHEAT la: 150 - 100 lb: 200 - 100 Ila: 2000 80 - 100 lie: 1250 70 - 100 la + Ila: (150 + 2000) 2 12 100 la + lie: (150 + 1250) 0 ,5 100 lb + Ila: (200 + 2000) 3 16 100 lb + lie: (200 + 1250) 2 12 100 t1 97643 Formulation Examples Example 3 Formulation examples for synergistic mixtures of compounds of the formulae I and II (throughout, percentages are by weight) Wettable powders a) b) c) d) compound la or lb % 7o % ■% one of compounds Ila to Ilf 7o 40 7c 7o % sodium lignosulfonate 7o 7o % 7o sodium laurylsulfate 3 % - 3 7o - sodium diisobutylnaphthalene-sulfonate .. 6 7o 6 7> octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) 2 7o 2 7, highly dispersed silicic acid 7o 27 % % 27 % kaolin 67 % - 67 % - 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.

Emulsifiable concentrates a) b) c) compound la or lb 7o 7o 12 7o one of compounds Ila to Ilf 7o 7o 13 7o octylphenol polyethylene glycol (4-5 moles of ethylene oxide) ether 3 7> 3 7o 3 70 calcium dodecylbenzenesulfonate 3 7, 3 7, 3 7o castor oil polyglycol ether (36 moles of ethylene oxide) 4 7o 4 7o 4 7o cyclohexanone 7o 7, 7o xylene mixture 50 7o 7o 7, Emulsions of any required concentration can be obtained from these concentrates by dilution with water. 197643 c) Dusts a) b) c) d) compound la or lb 2 % 4 7o 2 7o 4 one of compounds Ila to Ilf 3 % 4 7o 4 7o 8 talcum 95 % - 94 7o - kaolin — 92 7o - 88 Dusts which are ready for use are obtained by mixing the active ingredient mixture with the carriers, and grinding the mixture in a suitable mill.

Extruder granulates a) b) c) compound la or lb 7o 3 7o 7o one of compounds Ila to Ilf 5 7o 7 7o % sodium lignosulfonate 2 70 2 7o 2 7o carboxyme thyleellulo s e 1 7o 1 7o 1 7o kaolin 87 7o 87 7o 77 7o 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.

Coated granulates a) b) compound la or lb 1.5 % ' 3 7o one of compounds Ila to Ilf 1.5 % ' 5 7o polyethylene glycol 200 3.0 7o 3 7o kaolin 94.0 7o 89 7o 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.

Claims (10)

197643 - 24 - Suspension concentrates a) b) compound la or lb 20 % 20 7o one of compounds Ila to Ilf 20 % 40 7o ethylene glycol 10 % 10 7a nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 7, 6 70 sodium lignosulfonate 10 % 10.0 7o carboxymethy1ce11ulose 1 % 1.0 7o 37 % aqueous formaldehyde solution 0.2 % 0.2 7o silicone oil in the form of a 75 % aqueous emulsion 0.8 7o 0.8 7> water 32.0 7o 12.0 7o 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. - 25 - 1 97643 WHAT//WE CLAIM IS:-Whati we olftim ioi

1. A synergistic composition for selectively controlling weeds, which composition comprises, on the one hand, 4- (3» ^s'-dichloropyridyl-Z'-oxyJ-a-phenoxypropionic acid propargyl ester of the formula I cl. Z1 fa Cl-J 0-CH-C0-0-CH2-C=CH (IQ)» N—^ — or 4_(3»,5'-dichloropyridyl-2'-oxy)-OC-phenoxythiopropionic acid propargyl ester of the formula lb _/1 ^ Cl—^ y-o—\ )--O-CH-CO-5-CH2-C=CH (lb) - •-M and, on the other, one of 3-O'-chloro-V-methylphenyl)-!, 1-dimethylurea (Ila), 3- (S'-chloro-V-methoxyphenyl)-!, 1-dimethylurea (lib), 3-(4'-isopropylphenyl)-1,1-dimethylurea (lie), 1-benzothiazol-2-yl-l,3-dimethylurea (lid), 4-hydroxy-3,5-diiodobenzo-nitrile (lie) or 3,5-dibromo-4-hydroxybenzaldehyde-0-(21,4'-dinitrophenyl)-oxime (Ilf), together with carriers and/or other adjuvants.

2. A composition according to claim 1 which comprises 4-(3' ,5'-dichloropyridyl-21-oxy)-a-phenoxypropionic acid propargyl ester (la) and 3-(3'-chloro-4'-methylphenyl)- 1,1-dimethylurea (Ila).

3. A composition according to claim 1 which comprises 4-(3',5,-dichlorop3rridyl-2,-oxy)-a-phenoxythiopropionic acid propargyl ester (lb) and 3-(4,-chloro-4'-methylphenyl)^ 1,1-dimethylurea (Ila).

4. A composition according to claim 1 which comprises 4-(31,5*-dichloropyridyl-21-oxy)-a-phenoxypropionic acid;>•* o&, dimethylurea (lie). . propargyl ester (la) and 3-(4,-isopropylphenyl)-l,l- / 19/643 - 26 -

5. A composition according to claim 1 which comprises 4-(3',5'-dichloropyridyl-2'-oxy)-a-phenoxythiopropionic acid propargyl ester (lb) and 3-(4'-isopropylphenyl)-1,1-dimethylurea (He).

6. A composition according to any one of claims 1 to 5, said composition containing component (II) in frppgoicimafcelyl equal amount to, or in excess of, component (I).

7. A composition according to claim 6, wherein the ratio of component (I) to component (II) is 1:1 to 1:25, /preferably 1:1 Lu 1.10,1

8. A method of selectively controlling weeds in cereals, which method cooprises treating weed-infested cereal crops postemergence with a herbicidally effective amount of a composition according to any one of claims 1 to 7.

9. A method according to claim 8, wherein the weeds to be controlled are dicot weeds of the genera Chrysanthemum and Sinapis and Avena species.

10. A method according to either of claims 8 and 9, which method comprises treating the cereals crops at rates of application corresponding to 0.2 to 4 kgf preferably 0.5 to ■3 Kg,/ of total active ingredient per hectare. BALDWIN, SON & CAREY