NZ210226A - Synergistic herbicidal combinations of phenoxyethers with phenylisocyanates or halopyridines - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £10226 2 102 Priority Date(s): ..

ZJ.T.fcr.&V:.

Complete Specification Filed: 'MM c»ss: /& AGMUrS/Z&rMS: 2 9 APR 1988 pi.;b!ij.?!.icn Date: P.O. Vernal, No: ..... /.3f?7.

TENT OFFICE 16 NOV 1984 RECEfVtD N. Z .No.

NEW ZEALAND Patents Act, 1953 COMPLETE SPECIFICATION "HERBICIDAL AGENTS" We, HOECHST AKTIENGESELLSCHAFT, a corporation organized under the laws of the Federal Republic of Germany, of D-6230 Frankfurt/ Main 80. Federal Republic of Germany, do hejreby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - 1 u ^ c I © The present invention relates to herbicidaL agents containing a compound of the formula (A) R-O- ?H3 -O-CH-COOR 1 (A) in whi ch R denotes N CI V / ci or Cl in which R-j = Hy. ( C-|-C4)-a I ky I, (C2-C4)-a IkinyI or one 10 equivalent of a cation, in synergistic combination with a cor.;pound of the formula (B) R, N (B) in which ^2 R2 denotes bromine or iodine and R3 denotes H, NH4, an alkali metal cation or (C-j-Cg)-15 a Ikyly or with a compound of the formula Cc) o CI & (C) OCK2COOR4 in which R4 denotes H, C -Cg)-a I ky I or one equivalent of a cation.

E N © \ \ '-C \ 24 FEB 198* 'OJ 'Pr.. 3 By one equivalent of a cation there is to be understood, in each case, one equivalent of a metal cation, such as, for example, an alkali metal or alkaline earth metal cation, cr of an optionally (C1-C4)-a I ky l-substi-tuted ammonium ion.

Since the compounds of the formula (A) have a center of asymmetry in the propionic acid part, they can be in the form of pure sterioisoraers or in the form of sterioisomer mixtures.

The compounds of the formula (A) are particularly active against monocoty ledonous harmful plants, such as, for example, Alopecurus. wyosuroides and Avena fatua (c. f New Zealand Patent Specification No. 185135 and U.S. Patent No. 3,954,442).

R1 particularly denotes (C.,-C2)-a I ky I. Compounds of the formula (A) which are of particular interest are ethyl oc "*C4- (6-clilorobenzoxazolylo^y)-phenoxy]-propionate (A^), and prop-2-inyl o-C4-(3,5-dichloro-pyrid-2-yloxy5-phenoxyD-propionate, and component (A-j) is particularly preferred.

Preferred compounds of the formula (B) are those where Rj = octyl, common names: bromoxynil octyl ester for R2 = bromine (compound and ioxynil octyl ester for R 2 = iodine (compound B 2 ^ • Both conipounds are known as agents for combating weeds in cereals from GB -A 1,106,123.

The preferred compound of the formula (C) is that in which R = octyl (C^). This compound is described in reques- Weed Research Organization, Technical Report No. 63 (available uponl The compounds of the formulae (B) and (C) are dis~ tinguished by a good activity against dicotyledonous harmful plants, such as Stellaria media and Chenopodium album.

Surprisingly striking syne rg i s t i c >e f f ect s were found when the compounds of the formula (A) were combing ■ ■' " ' '0 ' with compounds of the forriula (3) or (C). 24 FEB m - 4 - ^ u d d r s ) The active substance combinations according to the invention can be used for combating undesirable species of plants, such as, for example, Alopecurus myosuroides, Avena fatua, Stellaria media, Chenopodium alburn, Setaria 5 viridis, Phalaris sp., Galium aparine, Matricaria sp., Sinapis arvense and Miosotis arvense in crops of useful plants, in particular in cereal crops, such as wheat and barley, preferably wheat.

The mixing ratios of the components of the formu-10 lae (A) and (B) or (C) can vary within wide limits. Thus, V- the ratio of components A to B (or C) is in the range from 1:10 to 15:1; the range from 1:5 to 5:1 is preferred if R in formula (A) denotes 6-chlorobenzoxazolyl, The combinations according to the invention can be used as tank mixes, in which the individual active substance components are mixed with one another only directly before application, or as finished formulations.

As finished mixtures, they can be formulated, for example, in the form of wettable powders, emulsifiable concentrates, solutions, dispersions, dusting agents or granules, and thc-n contain, if appropriate, the customary formulation auxiliaries, such as wetting agents, tacki-fiers, emulsifiers, dispersing agents, solid or liquid inert substances, grinding auxiliaries and solvents.

Wettable powders are products which are uniformly dispersable in water and which, in addition to the active '\^J substance and apart from diluents or inert substances, if appropriate, can also contain wetting agents, for example polyoxyethy1 ated a IkyIpheno1s, polyoxyethylated oleyl-amines or stearyI amines or alkyl- or a IkyIpheny I-su I fo-_ nates, and dispersing agents, for example sodium lignin- sulfonate, sodium 2 , 2 '-d i nap h t hy l-iiiet h a ne-6,6 '-d i su I f o-nate, sodium dibuty Inaphthalene sulfonate or sodium oleyl-methyl-tauride.

Jur x Emulsifiable concentrates can. be prepared, for j(N ^ |Z24 FEB 1983^'' V-* . *<?/ 2 1 ? example, by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethyl-formamide, xylene, i sophorone or highei—boiling aromatics, with the addition of one or more emulsifiers. Examples 5 of emulsifiers which can be used are: calcium alkylaryl-sulfonates, fatty acid polyglycol esters, alkylaryl poly-glycol ethers, fatty alcohol polyglycol ethers, polyoxy-ethylated oleylamines or steary I amines, propylene oxide/ ethylene oxide condensation products, alkyl polyethers, 10 sorbitan fatty acid esters, a I ky la r y I/p ropy lene oxide/ ethylene oxide condensation products and the like.

Dusting agents are obtained by grinding the active substance with finely divided, solid substances, for example talc or naturally occurring clays, such as kaolin, 15 bentonite, pyrophillite or diatomaceous earth.

J Granules can be prepared either by spraying a so lution of the active substance onto an adsorbent granular inert material, or by applying active substance concentrates to the surface of carriers, such as sand or kaoli-20 nites, or a granular inert material by means of a binder, for example polyvinyl alcohol, sodium acrylate, methylhy-droxyethyl cellulose or mineral oils. Suitable formulations of active substance can also be prepared in the manner customary for the preparation of fertilizer granules 25 - if desired as a mixture with fertilizers.

The synergistic active substance mixtures according to the invention of compounds of the formulae A and B or C can be formulated in the form of usual formulations, in particular as wettable powders, emulsifiable I ^ concentrates, solutions, dispersions, dusting agents or granules. The total content of active substance in the multiple formulations is then about 2 to 95% by weight, preferably 10 to 70% by weight, the remainder to make up to 100% by weight consisting of the usual formulation ^ 35 auxili aries, such as tackifiers, wetting agents, emulsifiers, dispersing agents, fillers, solvents and carriers.

The total concentration of active substance in wettable powders varies in the range from about 10 to 80% b y w e i g h t. 210226 In emulsifiable concentrates, the total concentration of active substance is in the range from about 10 to 70% by weight. In granules, it is about 2 to 10% by weight. Dust-like .formulations contain about 5 to 20% by 5 weight of active substance mixture.

The invention thus also relates to herbicidal agents containing 2 to 95% by weight, preferably 10 to 70% by weight, of an active substance combination of compounds of the formulae A and B or C, the remainder to 10 make up to 100% by weight consisting of the usual formu-I at ion aux i I i ari es.

For use, the concentrates mentioned are diluted, if appropriate, in the customary manner, for example by means of water in the case of wettable powders, emulsi-15 fiable concentrates and dispersions. Dust-like and gran-J ular formulations and solutions which can be sprayed are in general not further diluted with additional inert substances before use. The application amount of the agents according to the invention also varies according to e x -20 terne I conditions, such as temperature, humidity and the like. It can vary within wide limits, and is in general between 0.2 and 10 kg of active substance combination/ha, preferably 0.3-2.0 kg/ha.

The invention is illustrated by the following 25 examples.

Formulation Examples General instructions: vj An active substance was dissolved in the solvent mixture in question at 50-60°C/ and the second active substance, if appropriate in the form of a melt, was then added. The individual emulsifiable components were added, 30 with thorough stirring, and the mixture was allowed to cool. The resulting emulsifiable concentrates are slightly to moderately browrt- colored.

The active substances and formulation auxiliaries shown in Examples 1-12 of the following Table are mixed 35 with one another by this procedure. The numerical data in the Table correspond to parts by weig.ht.

I S VIt f V ■ <U (1? O C) Constituents of the formulations Example Mo. 1 2 3 4 5 6 7 8 9 10 11 12 Active substance (A^), techn. 10.1 3.6 16.6 10.1 3.6 16.6 10.1 3.6 16.'6 Bromoxynil octyl ester techn. 14.3 22.5 5.1 Ioxynil octyl ester (B^), techn. " 13.5 22.2 4.7 Active substance (C^), techn. 13.8 22.7 4.9 12.0 5.0 2.5 ?fc * ^ ~n - , n m r - OJ z; 2 y i Xylene 33.0 42.3 36.3 34.0 32.3 36.7 28.1 28.7 33.5 42.0 50.0 50.0 Isophorone 15.0 15.0 20.0 Cyclohexanone 5.6 15.4 20.0 10.0 10.0 Dimethylformamide 15.6 1.50 15.0 15.0 Calcium dodecyIbenzenesulfonate 6.0 5.0 5.0 7.0 7.0 5.0 5.0 5.0 5.0 4.0 5.0 4.0 » Ethoxylated castor oil (40 mole's * '■ of ethylene oxide) 6.0 5.0 8.0 8.0 8.0 7.0 6.0 Ethoxylated nonylphenol (10 moles ot ethylene oxide) 7.0 15.0 15.0 15.0 15.0 Ethoxylated tributy IphencldO moles of ethylene oxide) 6.0 7.0 3.0 5.0 Ethoxylated oleyl alcohol (15 moles of ethylene oxide) 5.0 2.0 2.0 2.5 Ethoxylated tridecyl alcohol (8 moles of ethylene oxide) 15.0 15.0 15.0 15.0 15.0 r— o Jv. r<: 2 10226 • " Biological Examples: In the following use Examples, the test plants were grown i n pots in a greenhouse. The concentrates, diluted in water, were applied when the monocotyledonous plants - ALopecurus myosuroides, Avena fatua and Triticum aestivum - had reached the 3-4 leaf stage and the dicoty-ledenous plants - Stellaria media and Chenopodium album - had grown to a height of 5-10 cm.

After 4 weeks, the action (damage) was rated. The degree of action found is compared with the oxpcctcd degree of action in the Tables.

The expected degree of action was calculated from ^ the formula of S.R. Colby, Calculating synergistic and antagonistic response of herbicide combinations (Weeds pages 20-22, 1 967) .

The Colby formula is: O E = X + Y - in which x 100 X = % damage by herbicide A applied in an amount of x kg/ha, Y = % damage by herbicide B applied in an amount of y kg / h a E = the expected damage of herbicides A + B applied in an amount of x + y kg/ha.

If the actual damage is greater than the calculated damage, the action of the combination is more than additive, i.e. a synergistic effect exists. In the case of treatment with the combinations, the action calculated from the above formula is given in parentheses. o © o © Combating of monocotyledonous and dicotyledonous weeds in wheat (Triticum aestivum) Table 2) Damage in % to Active ^ Dose Alopecurus Avena Stellaria Chenopodium Triticum substance g of AS/ha myosuroides fatua media alburn aestivum 7.5 0 0 0 0 0 0 11 0 0 0 22.5 0 33 0 0 0 27 45 0 0 0 .'7.5 41 58 0 0 0 45 52 63 0 0 0 75 65 88 0 0 0 150 87 96 0 0 0 X It mi.. (.

G O Continuation of Table Act ive substance 1) Dose 2) Alopecurus Avena Damage in % to Stellaria Chenopodium Triticum of AS/ha myosuroides fatua media album aestivum 7.5 0 0 0 0 0 0 0 0 7 0 22.5 0 0 0 22 0 0 0 0 38 0 37.5 0 0 0 51 0 45 0 0 7 67 0 75 0 13 80 0 150 33 0 92 0 7.5 0 0 0 0 0 0 0 0 22.5 0 0 27 0 0 0 31 40 0 37.5 0 0 37 45 0 45 0 0 42 52 0 75 0 0 53 65 0 150 0 0 55 73 0 i 0 1 ' N> O K> NJ O* Continuation of Table Active ^ substance C1 Dose2) Damage in 'A to Alopecurus Avena Stellaria Chenopodium Triticum g of AS/ha myosuroides fatua media album aestivum 7.5 0 0 0 0 0 0 40 0 0 22.5 0 0 52 0 0 0 0 60 0 0 37.5 0 0 70 0 0 45 0 0 75 0 0 75 14 7 86 27 0 15C 24 7 100 40 0 1) for the meanings of A^, B^, and C^, see .the descriptive section, page 3 2) AS = Active Substance M. M < •U ft1 0 Continuation of Table Active substar combination g of AS/ha myosuroides fatua substance Dose25 Alopecurus Avena A1 + C1 22.5 + 22.5 45 + 45 87 (52) 82 (63) 7.5 + 37.5 15+75 + 150 72 (45) 75 (49) 37.5 + 7.5 78 (41) 82 (58) 75 + 15 90 (65) 95 (88) 150 + 30 99 (87) O 9 Damage in V. to Stellaria media Chenopodium album 82 (52) 90 (75) 87 (70) 99 (86) 68 (20) 77 (40) 85 (60) 68 (40) Triticum aestivum 0 0 •0 0 0 0 0 0 r\> i O M. >V! lt .* / /;C>-;U ■ &;Continuation of Table;A1 +B1;A1 + B2;Damage in % to;Active substar combination g of AS/ha myosuroides fatua media album aestivum;2);substance Dose Alopecurus Avena Stellaria Chenopodium Triticum;22.5;+;22.5;59;(22);0;45;+;45;70;(52);80;(63);91;(67);0;7.5;+;37.5;-;83;(61);0;15;+;75;-;100;(80);0;30;+;150;69;(52);78;(45);.100;(92);0;■37.5;+;7.5;65;(41);89;(58);0;75;+;15;87;(65);93;(88);0;150;+;30;95;(87);78;(38);0;22.5;+;22.5;64;(25);0;45;+;45;73;(52);87;(63);53;(42);82;(52);0;7.5;+;37.5;80;(45);0;15;+;75;99;(65);0;30;+;150;65;(27);78;(45);79;(55);100;(78);0;37.5;+;7.5;67;(41);85;(58);0;75;+;15;80;(65);93;(88);0;150;+;30;92;(87);82;(40);0;#;I;hJ;O N> N);O* >

Claims (8)

WHAT WE CLAIM IS:

1. A herbicidaL agent containing a compound of the formula (A) J O J in whi ch R denotes CI R-0- or CI CH, I J -O-CH-COOR. CA) in which m O R-j = Vt, ( C-j-C^J-a Lky L, ( Cj-C/^)-a L k i ny I or one equivaLent of a cation, in synergistic combination with a compound of the formula (E) C = N (B) in which R2 denotes bromine or iodine and R3 denotes H, NH4, an aLkaLi metal cation or (C-j-Cg)-a lky I, or with a compound of the formula (C) NH. <0 . OCH2COOR4 in whi ch R4 denotes H, (C-j-Cg)-a Ikyl or one equivalent of a/ /'' cation. , '"%V p

2. A herbicidaL agent as claimed in claim 1, containing ethyl a-C4- (6-ch lorobenzoxazo lytoxy)-phenoxy]- propionate as the compound of the formula (A).

3. A herbicidal agent as claimed in claim 1, in which R^ in formula (B) denotes octyl.

4. A herbicidal agent as claimed in claim 1, in which in formula (C) denotes octyl.

5. A herbicidal agent as claimed in claim 1, in which the mixing ratio of the component of the formula (A) to the component of the formula (B) or (C) varies in the range from 1 : 10 to 15 : 1.

6. A herbicidal agent as claimed in claim 1, in v/hich the mixing ratio of the component of the formula (A), in which R denotes 6-chlorobenzoxazolyl, to the component of the formula. (B) or (C) varies within the range from 1 : 5 to 5 : 1 .

7. The use of a herbicidal agent as claimed in claim 1 for combating undesirable plant growths in crops of useful plants.

8. A method of combating harmful plants in crops of useful plants, which comprises applying an agent as-claimed in claim 1 to these plants or to the cultivated areas. HOECHST AKTIENGESELLSCHAFT By Their Attorneys HEliRY HUGHES LIMITED "f/vLlij ' !N