WO1988002598A1

WO1988002598A1 - Herbicidal mixtures

Info

Publication number: WO1988002598A1
Application number: PCT/US1987/002558
Authority: WO
Inventors: Timothy T. Obrigawitch; Kent M. Reasons
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1986-10-10
Filing date: 1987-10-09
Publication date: 1988-04-21
Also published as: KR880701525A

Abstract

Herbicidal mixtures comprising an oxabicycloheptane compound.

Description

Title HERBICIDAL MIXTURES Background of the Invention

The present invention relates to herbicidal mixtures for crop plants that more effectively control weeds. These mixtures permit lower use rates or reduce phytotoxicity to the crop plants. The control of undesired vegetation is extremely important in achieving high crop efficiency. The selective control of the growth of weeds in such useful crops as rice, soybeans, sugarbeets, peanuts or cotton, to name a few is a desirable achievement. Unchecked weed growth in such useful crops can cause significant losses, reduction of profits to farmers and increasing costs to consumers. There are many products commercially available for these purposes but the search continues for products which are more effective, less costly and safe.

U.S. 4,420,325 discloses herbicidal sulfonylureas, including Compound 3.

Japanese Application 59-122488, laid open July 14, 1984, discloses herbicidal sulfonylureas, including Compound 4.

Japanese Application 60-193983. published October 2, 1985, discloses herbicidal sulfonylureas. including Compound 6.

Japanese Application 60-197676, published October 7, 1985, discloses herbicidal sulfonylureas, including Compound 5.

U.S. 4,487,945 teaches the process of preparing a cineole intermediate of Compounds 1 and 2, whose total synthesis is taught in EP-A 81,893, published on June 22, 1983.

GB-A-2,042.639 discloses herbicidal quinoxylines, including Compound 7. GB-A-2,134,391, published August 15, 1984 discloses mixtures of Compound 1 with either metr ibuzin or cyanazine.

U.S. 4,481,029 discloses herbicidal sulfonylureas which include Compound 19 of the present invention but not the mixtures of the invention.

The mixtures of the present invention are not disclosed in the above references.

Summary of the Invention The invention relates to herbicidal mixtures comprising 2-exo-(2-methylbenzyloxy)-1-methyl-4-(1- methylethyl)-7-oxabicyclo[2.2.1]heptane. Compound 1; or 2-exo-)2-bromobenzyloxy)-1-methyl-4-isopropyl-7-oxabicyclo[2.2.1]heptane. Compound 2, with another herbicide. The invention includes herbicidal mixtures of 1-methyl-4-(1-methylethyl)-2-exo-[(2-methylphenyl)- methoxy]-7-oxabicyclo[2.2.1]heptane, Compound 1; or 1-methyl-4-(1-methylethyl)-2-exo-[(2-bromophenyl)- methoxy]-7-oxabicyclo[2.2.1]heptane, Compound 2, with herbicidal compounds selected from (a) 2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]- aminosulfonylmethyl]benzoic acid, methyl ester. Compound 3; (b) 5-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]- aminosulfonyl]-1-methylpyrazole-4-carboxylic acid, ethyl ester. Compound 4; (c) N-[((4,6-dimethoxy-2-pyrimidinyl)aminocarbonyl)]- 3-(pentafluoro-1-propenyl)-2-thiophenesulfonamide. Compound 5;

(d) 3-(2-chloro-1.2-difluoroethenyl)-N-[(4,6- dimethoxy-2-pyrimidinyl)aminocarbonyl]-2- thiophenesulfonamide. Compound 6; or

(e) ethyl 2-[4-(6-chloro-2-quinoxalinyloxy)phenoxy]- propionate. Compound 7; (f) sethoxydin : 2-[(1-ethoxyimino)butyl]-5-[2- (ethylthio)propyl]-3-hydroxy- 2-cyclohexen-1-one, Compound 8;

(g) fluazifop-butyl : (±)-butyl-2-[4-[(5-trifluoromethyl)-2-pyridinyl)oxy]phenoxy]propanoate. Compound 9;

(h) fluazifop-P-butyl : butyl(R)-2-[4-[(5-trifluoromethyl)-2-pyridinyl)oxy]phenoxy]propanoate. Compound 10;

(i) haloxyfop-methyl : Methyl 2-(4-((3-chloro-5- trifluoromethyl)-2-pyridinyl)oxy)phenoxy)-propanoate. Compound 11;

(j) cycloxydim : 2-[1-(ethoxyimino)butyo]-3-

(BASF 517H) hydroxy-5-[2(H)-tetrahydrothiopyran-3-yl]-2-cyclohexen- 1-one, Compound 12; (k) acifluorfen : 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid. Compound 13;

(l) sodium salt of : sodium 5-[2-chloro-4-(triacifluorfen fluoromethyl)phenoxy]-2-nitrobenzoate. Compound 14;

(m) bentazon : 3-isopropyl-1H-2.1.3-benzothiadiazin-4(3H)-one 2.2-dioxide, Compound 15;

(n) linuron : 3-(3,4-dichlorophenyl)-1- methoxy-1-methylurea. Compound 16;

(o) Harmony ^TM : 3-[[(4-methoxy-6-methyl-1,3.5- triazin-2-yl)-aminocarbonyl]- aminosulfonyl]-2-thiophenecarboxylic acid, methyl ester. Compound 17;

(P) atrazine (propylamino ) -s-triazine , Compound 18 ; (q) alachlor : 2-chloro-2',6'-diethyl-N-

(methoxymethyl)-acetanilide, Compound 19;

(r) metolachlor : 2-chloro-N-(2-ethyl-6-me thylphenyl)-N-(2-methoxy-1-methylethyl)acetamide. Compound 20; and their agriculturally suitable salts. The mixtures of compounds 1 or 2 with compounds (e), (f), (g), (h), (i) or (j) are excellent grass killers.

This invention also includes mixtures of 2-exp-(2-methylbenzyloxy)-1-methyl-4-(1-methylethyl)- 7-oxabicyclo[2.2.1]heptane, Compound 1; or

2-exo-)2-bromobenzyloxy)-1-methyl-4-isopropyl-7-oxabicyclo[2.2.1]heptane. Compound 2, with

(a) 2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]- aminosulfonylmethyl]benzoic acid, methyl ester, Compound 3;

(b) 5-[ [ (4 , 6-dimethoxypyrimidin-2-yl ) aminocarbonyl ] - aminosulf onyl] -1-methylpyrazole-4-carboxylic acid , ethyl ester . Compound 4;

( c) N-[ (4 , 6-dimethoxy-2-pyrimidinyl ) aminocarbonyl ] -3- (pentafluoro-1-propenyl ) -2-thiophenesuIfonamide .

Compound 5 ;

(d) 3-(1-chloro-2,2-difluoroethenyl-N-[(4.6-dimethoxy- 2-pyrimidinyl)aminocarbonyl]-2-thiophenesulfonamide. Compound 6; or (e) ethyl 2-[4-(6-chloro-2-quinoxalinyloxy)phenoxy]- propionate. Compound 7. Accordingly the invention includes mixtures of

Compound 7

Preferred for their improved crop safety, reduced use rates or superior weed control are:

1. The mixture of Compound 1 and Compound 3.

2. The mixture of Compound 1 and Compound 4.

3. The mixture of Compound 1 and Compound 5.

4. The mixture of Compound 1 and Compound 6. 5. The mixture of Compound 1 and Compound 7.

6. The mixture of Compound 1 and Compound 8.

7. The mixture of Compound 1 and Compound 9.

8. The mixture of Compound 1 and Compound 10.

9. The mixture of Compound 1 and Compound 11. 10. The mixture of Compound 1 and Compound 12.

11. The mixture of Compound 1 and Compound 13.

12. The mixture of Compound 1 and Compound 14.

13. The mixture of Compound 1 and Compound 15.

14. The mixture of Compound 1 and Compound 16. 15. The mixture of Compound 1 and Compound 17.

16. The mixture of Compound 1 and Compound 18.

17. The mixture of Compound 1 and Compound 19.

18. The mixture of Compound 1 and Compound 20.

19. The mixture of Compound 2 and Compound 3. 20. The mixture of Compound 2 and Compound 4.

21. The mixture of Compound 2 and Compound 5.

22. The mixture of Compound 2 and Compound 6.

23. The mixture of Compound 2 and Compound 7.

The invention includes compositions of the above mixtures. Preferred for their crop safety, reduced use rates or superior weed control are:

24. The composition comprising Compound 1 and Compound 3. 25. The composition comprising Compound 1 and

Compound 4.

26. The composition comprising Compound 1 and Compound 5. 27. The composition comprising Compound 1 and Compound 6. 28. The composition comprising Compound 1 and Compound 7.

29. The composition comprising Compound 1 and Compound 8.

30. The composition comprising Compound 1 and Compound 9.

31. The composition comprising Compound 1 and Compound 10.

32. The composition comprising Compound 1 and Compound 11. 33. The composition comprising Compound 1 and

Compound 12.

34. The composition comprising Compound 1 and Compound 13.

35. The composition comprising Compound 1 and Compound 14.

36. The composition comprising Compound 1 and Compound 15 .

37. The compos ition compr is ing Compound 1 and Compound 16. 38. The composition comprising Compound 1 and

Compound 17.

39. The composition comprising Compound 1 and Compound 18.

40. The composition comprising Compound 1 and Compound 19.

41. The composition comprising Compound 1 and Compound 20.

42. The composition comprising Compound 2 and Compound 3. 43. The composition comprising Compound 2 and

Compound 4. 44. The composition comprising Compound 2 and Compound 5. 45. The composition comprising Compound 2 and Compound 6.

46. The composition comprising Compound 2 and Compound 7.

The invention includes the method of controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected mixtures of Compound 1 or 2 with certain other herbicides to provide improved spectrum of control or control at lower use rates with reduced crop injury. Preferred for their crop safety, reduced use rates or superior weed control are:

47. The mixture of Preferred 1 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

48. The mixture of Preferred 2 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

49. The mixture of Preferred 3 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

50. The mixture of Preferred 4 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled. 51. The mixture of Preferred 5 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

52. The mixture of Preferred 6 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

53. The mixture of Preferred 7 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

54. The mixture of Preferred 8 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undes ired vegetation to be controlled.

55. The mixture of Preferred 9 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

56. The mixture of Preferred 10 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

57. The mixture of Preferred 11 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled. 58. The mixture of Preferred 12 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

59. The mixture of Preferred 13 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

60. The mixture of Preferred 14 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

61. The mixture of Preferred 15 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

62. The mixture of Preferred 16 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

63. The mixture of Preferred 17 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

64. The mixture of Preferred 18 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled. 65. The mixture of Preferred 19 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undes ired vegetation to be controlled .

66. The mixture of Preferred 20 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

67. The mixture of Preferred 21 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

68. The mixture of Preferred 22 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

69. The mixture of Preferred 23 where it is applied postemergence with respect to the crop and either postemergence or preemergence with respect to the undesired vegetation to be controlled.

70. A method of use for selectively preventing or killing a weed of a paddy rice crop comprising applying a mixture of compounds

one of the following compounds:

Compound 5 or Compound 6

71. A method of Preferred 70 wherein the crop is transplanted paddy rice.

72. A method of Preferred 51 wherein the crop is a broadleaf crop such as soybeans. sugarbeets, peanuts or cotton.

73 A method of use comprising selectively killing or preventing a grass weed in a broadleaf crop by applying a mixture of

Compound 1 with a compound selected from

Compounds 8 to 12.

74, A method of use comprising selectively killing or preventing a weed in a broadleaf crop such as soybeans by applying a mixture of Compound 1 with a compound selected from

Compounds 13 to 16. 75 . A method of use f or select ively ki l l ing or preventing a weed in a crop such as corn comprising applying a mixture of Compound 1 with one of Compounds 16 to 20. The instant mixtures when applied postemergent to the crop and either pre- or postemergent to the undesired vegetation provide improved crop safety, reduced rates or superior weed control, than the individual components alone.

The mixtures of the invention provide both the control of existing vegetation and newly germinating weeds. By using these mixtures, the amount of each herbicide may be reduced or the spectrum and length of control improved. In other instances, the mixture may provide the needed weed control while reducing or eliminating phytotoxicity to the crop.

DETAILED DESCRIPTION OF THE INVENTION The compounds within the mixtures of the present invention are known herbicidal compounds and the method for their production is already well known.

Compounds 1 and 2 can be prepared by the methods described in U.S. 4,487.945. and EP-A 81.893. published on June 22, 1983. As discussed in these references, their various stereoisomers; their endo and exo forms, and mixtures thereof are incorporated herein.

Compound 3 can be prepared by the method described in U.S. 4,420,325. Compound 4 can be prepared by the method described in laid open Japanese Application 59-122488, laid open July 14, 1984.

Compound 5 can be prepared by the method described in laid open Japanese Application 60-197676, published October 7. 1985.

Compound 6 can be prepared by the method described in laid open Japanese Application 60-193983, published October 2, 1985. Compound 7 can be prepared by the method described in GB-A-2.042, 639 (Nissan).

Formulations

Useful formulations of the mixture of Compounds 1 or 2 with Compounds 3 to 20 can be prepared in conventional ways . They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of the active ingredient mixture and at least one of (a) about 0.1% to 20% surfactant (s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). The active ingredient mixture comprises either Compound 1 or 2 and one of Compound 3 to 20 and usage of the combination in a ratio from about 1:0.1 to 1:100 provides a synergistic effect. Proportions in which to use the mixtures of compounds of the present invention may optionally be selected within the range substantially not impairing excellent field weed control effect and phytotoxicity reducing effect with the herbicidal mixture of the present invention. More specifically, they will contain these ingredients in the following approximate proportions:

Active Weight Percent* Ingredient Mixture Diluent(s) Surfactant (s)

Wettable Powders 20-90 0-74 1-10

Oil Suspensions, 3-50 40-95 0-15

Emulsions, Solutions, (including Emulsifiable Concentrates) Aqueous Suspension 10-50 40-84 1-20

Dusts 1-25 70-99 0-5

Granules and Pellets 0 . 1-95 5-99 . 9 0-15

High Strength 90-99 0-10 0-2 Compositions * Active ingredient mixture plus at least one of a

Surfactant or a Diluent equals 100 weight percent. Lower or higher levels of the active ingredient mixture can. of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden. "Solvents Guide." 2nd Ed., Interscience, New Yorle. 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and

Eraulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents". Chemical Publishing Co.. Inc.. New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of addit ives to r educe f oaming , caking , corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example. Littler, U.S. Patent 3,060.084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering. December 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Patent 3,309,192, March 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15. 39. 41, 52. 53. 58. 132. 138-140, 162-164, 166, 167 and 169-182; H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford. 1968, pp. 101-103. In the following Examples, all parts are by weight unless otherwise indicated. Example 1

Wettable Powder

Compound 1 and Compound 3 (weight ratio 2:1) 80% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 13%

The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged. Example 2

Wettable Powder

Compound 1 and Compound 4 (weight ratio 3:1) 50% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46%

The ingredients are blended, coarsely hammermilled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging. Example 3

Granule

Wettable Powder of Example 2 5% attapulgite granules 95%

(U.S.S. 20 to 40 mesh; 0.84-0.42 mm) A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged. Example 4 Extruded Pellet Compound 1 and Compound 5 (weight ratio 1:1) 25% anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium a lkylnaphthalenesulfonate 1%. calcium/magnesium bentonite 59% The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

Example 5 Low Strength Granule

Compound 1 and Compound 6 (weight ratio 3:1) 0.1% attapulgite granules 99.9%

(U.S.S. 20 to 40 mesh) The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged. Example 6

Granule

Compound 1 and Compound 7 (weight ratio 7:1) 80% wetting agent 1% crude ligninsulfonate salt (containing 10% 5 to 20% of the natural sugars) attapulgite clay _9%

The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14 to 100 mesh (1410 to 149 microns), and packaged for use.

Example 7 Low Strength Granule

Compound 2 and Compound 3 (weight ratio 3:1) 1% N,N-dimethylformamide 9% attapulgite granules 90%

(U.S.S. 20 to 40 sieve) The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged. Example 8

Aqueous Suspension

Compound 2 and Compound 4 (weight ratio 2:1) 40% polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol ether 0.5% disodium phosphate 1% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7%

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size. Example 9

Solution Compound 2 and Compound 5 (weight ratio 4:1) 5% water 95%

The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use. Example 10

High Strength Concentrate

Compound 2 and Compound 6 (weight ratio 3:1) 99% silica aerogel 0.5% synthetic amorphous silica 0.5% The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

Example 11 Wettable Powder

Compound 2 and Compound 7 (weight ratio 1:6) 90% dioctyl sodium sulfosuccinate 0.1% synthetic fine silica 9.9%

The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.

Example 12 Wettable Powder Compound 1 and Compound 3 (weight ratio 3:1) 40% sodium ligninsulfonate 20% montmorillonite clay 40%

The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged. Example 13 Oil Suspension Compound 1 and Compound 3 (weight ratio 4:1) 35% blend of polyalcohol carboxylic 6% esters and oil soluble petroleum sulfonates xylene 59% The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

Example 14 Dust

Compound 1 and Compound 7 (weight ratio 1:8) 10% attapulgite 10%

Pyrophyllite 80%

The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.

Example 15 Oil Suspension

Compound 1 and Compound 3 (weight ratio 3:1) 25% polyoxyethylene sorbitol hexaoleate 5% highly aliphatic hydrocarbon oil 70%

The ingredients are ground together in. a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water. Example 16 Wettable Powder Compound 1 and Compound 7 (weight ratio 1:7) 20% sodium alkylnaphthalenesulfonate 4% sodium ligninsulfonate 4% low viscosity methyl cellulose 3% attapulgite 69% The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

Utility

The application of Compound 7, ethyl 2-[4-(6- chloro-2-quinoxalinyloxy)phenoxy]propionate. Compound 1. 2-exo-(2-methylbenzyloxy)-1-methyl-4-(1-methylethyl)-7-oxabicyclo[2.2.1]heptane or Compound 2 of this invention, postemergence to the crop and weeds provides season long grass weed control in soybeans, cotton, sugarbeets, peanuts, sunflower, dry and snap beans, potatoes, tobacco, transplanted tomatoes, Brassica species, peas, alfalfa and other crops. When this mixture is applied as described, it will control the existing gramineous weeds and prevent the development of grass weeds for the remainder of the crop season. The application is made after crop and initial grass weed emergence.

Combinations of Compound 1 with Compound 7 provide unexpectedly good control of weeds such as giant foxtail, johnsongrass. crabgrass and barnyardgrass. And combinations of Compound 1 with Compound 8 provide unexpectedly good control of weeds such as barnyardgrass and giant foxtail. The range of rates for Compound 7 is from 2 to 220 g/ha and for Compound 1 is from 50 to 1500 g/ha. The exact ratio of the two ingredients will depend on the weed species to be controlled and soil type. One with ordinary skill in the art can select the proper ratio.

The range of rates of Compound 8 is from 8 to 800 g/ha and for Compound 1. is from 50 to 1500 g/ha.

The exact ratio of the two ingredients will depend on the weed species to be controlled and soil type. One with ordinary skill in the art can select the proper ratio. The other mixtures of the present invention may be used to provide weed control in crops such as rice, corn, soybeans, cotton, etc. The range of ratios for the individual compounds is bounded by their synergistic utility and rates can be determined by one skilled in the art based on temperature, rainfall and soil type of the area where mixture is to be used.

The range of rates of Compound 9 is from 100 to

500 g/ha and for Compound 1. is from 50 to 1500 g/ha.

The exact ratio of the two ingredients will depend on the weed species to be controlled and soil type. One with ordinary skill in the art can select the proper ratio.

The range of rates of Compound 10 is from 50 to

400 g/ha and for Compound 1. is from 50 to 1500 g/ha. The exact ratio of the two ingredients will depend on the weed species to be controlled and soil type. One with ordinary skill in the art can select the proper ratio.

The range of rates of Compound 11 is from 50 to 500 g/ha and for Compound 1. is from 50 to 1500 g/ha.

The range of rates of Compound 12 is from 50 to

800 g/ha and for Compound 1, is from 50 to 1500 g/ha.

The range of rates of Compound 13 is from 50 to

400 g/ha and for Compound 1, is from 50 to 1500 g/ha.

The range of rates of Compound 14 is from 50 to 400 g/ha and for Compound 1, is from 50 to 1500 g/ha. The exact ratio of the two ingredients will depend on the weed species to be controlled and soil type. One with ordinary skill in the art can select the proper ratio.

The range of rates of Compound 15 is from 200 to 1200 g/ha and for Compound 1. is from 50 to 1500 g/ha. The exact ratio of the two ingredients will depend on the weed species to be controlled and soil type. One with ordinary skill in the art can select the proper ratio. The range of rates of Compound 16 is from 50 to 800 g/ha and for Compound 1. is from 50 to 1500 g/ha. The exact ratio of the two ingredients will depend on the weed species to be controlled and soil type. One with ordinary skill in the art can select the proper ratio.

The range of rates of Compound 17 is from 50 to 1000 g/ha and for Compound 1. is from 50 to 1500 g/ha. The exact ratio of the two ingredients will depend on the weed species to be controlled and soil type. One with ordinary skill in the art can select the proper ratio.

The range of rates of Compound 18 is from 1 to 280 g/ha and for Compound 1, is from 50 to 1500 g/ha. The exact ratio of the two ingredients will depend on the weed species to be controlled and soil type. One with ordinary skill in the art can select the proper ratio.

The range of rates of Compound 19 is from 100 to 2500 g/ha and for Compound 1, is from 50 to 1500 g/ha. The exact ratio of the two ingredients will depend on the weed species to be controlled and soil type. One with ordinary skill in the art can select the proper ratio.

The range of rates of Compound 20 is from 250 to 6000 g/ha and for Compound 1, is from 50 to 1500 g/ha. The exact ratio of the two ingredients will depend on the weed species to be controlled and soil type. One with ordinary skill in the art can. select the proper ratio. Additionally, mixtures of Compound 1 or Compound 2 with one of Compounds 8, 9, 10. 11 or 12 will have the same utility as mixtures of Compounds 1 and 7.

The utility of this invention also includes the ability of Compound 1 or 2 to reduce the crop injury normally observed with Compounds 3 to 6 when applied to rice. While Compounds 3-6 generally provide good control of broadleaf and sedge weeds, crop injury can be observed. Preparing a mixture of Compound 1 or 2 with any of the other compounds (3-6) not only reduces the injury caused by Compounds 3-6 but also controls barnyardgrass. an important weed species in rice. Notably, mixtures of Compound 1 or 2 with Compounds 3-6 result in reducing the rates of all compounds required for effective weed control below those required for each individual compound alone. In particular, these mixtures provide unexpectedly effective control of water chestnut. Mixtures involving Compound 1 with Compound 3 or 4 are especially effective. Effective rates of Compounds 3 or 4 with Compound 1 range from 10-500 g/ha

(preferably 10-250 g/ha) of Compound 1 with 5-50 g/ha (preferably 5-40 g/ha) of Compounds 3 or 1-20 g/ha (preferably 1-10 g/ha) of Compound 4.

Example 17

Compound 7 at 35 or 70 g/ha in combination with Compound 1 at 240 or 480 g/ha was applied to a Matapeake silt loam (pH 6.8, O.M. 1%).

The treatments were postemergence to seedling johnsongrass, crabgrass, barnyardgrass. green foxtail, giant foxtail and shattercane at between the zero and six leaf stage. There was a reservoir of grass weed seeds in the soil which germinated after application. The mixture was applied with 0.25% (v/v) of x-77 surfactant. Nineteen days later the data in Table 1 was collected. Thirty-four days after application a combined grass rating was taken and is shown in Table 2. The data observed in Tables 1-10 of weed control was determined visually with 0 denoting no effect and 100 denoting complete kill.

These results demonstrate the ability of these combinations to provide long term weed control.

Example 18 Use of Colby's Equation to Determine Synergism In pesticide science, synergism can be defined as the greater-than-expected, or greater-than-additive effect of two compounds when applied in combination as a mixture. To test for synergism between two compounds, the effects of each compound when applied singly against a given pest are determined, as well as the effects of the two compounds applied in combination as a mixture. Based on the effects of each compound applied singly, Colby's equation is used to calculate the effect that would result from an application of the combination of the two if they acted together as expected, or additively. Colby's equation is:

(X Y

E = (X + Y) -

where E = the expected effect, and X and Y are the measured (or observed) effects of each compound applied singly, commonly expressed as percent kill or percent control. For example, if each compound applied singly produced 50% kill, the expected result from a combination of the two would be 75%:

E = (50 + 50) - = 75

The explanation for this is that the first compound is capable of removing 50% of the pest population, and the second compound is capable of removing 50% of the remaining population, so a total of 75% of the population is expected to be removed by the combination. If the measured or observed effect of the combination exceeds the value predicted by

Colby's equation, the effect is greater than expected

(greater than additive) or synergistic. Experimental Protocol

Johnsongrass (Sorghum halepense), barnyardgrass (Echinochloa crus-galli). giant foxtail (Setaria faberii). and large crabgrass (Diqitaria sanguinalis) were grown in 6-inch pots of Sassafras soil in the greenhouse. Each pot contained all four species, one in each quadrant. When the grasses had reached the 2-3 leaf stage of growth, they were treated using a traveling-belt laboratory sprayer operated at 40 psi, delivering 374 liters per hectare. For the Compound 1 and Compound 7 interactions, treatments involved the technical ingredients dissolved in a nonphytotoxic solvent system containing acetone, glycerin, water and surfactant. The study of Compound 1 and Compound 8 interactions involved formulated materials mixed with water with 0.25% surfactant. Each study was conducted in randomized complete block design with three replications.

After spraying, the plants were maintained in the greenhouse for six days, when phytotoxicity was visually evaluated on a 0 to 100% scale, where 0 indicates no effect and 100 indicates complete control.

Results

The mean effects of each treatment were calculated, and Colby's equation was used to calculate expected effects for combinations. The results are listed in Tables 3 to 10. Synergism between Compound 1 and Compound 7 was most apparent against giant foxtail (Table 3). Out of sixteen treatments involving combinations of various rates of he two herbicides, eleven resulted in effects substantially greater than predicted by Colby's equation. For example. Compound 1 alone at 62 g ai/ha produced 35% control of giant foxtail and Compound 7 alone at 4 g ai/ha produced 55% control. Colby's equation predicts that the combination of these rates of the two herbicides would produce 70.8% control, while the observed control was 90%.

Synergism was also readily observed against johnsongrass (Table 4). For example. Compound 1 alone at 125 g ai/ha produced only 10% control, while Compound 7 alone at 4 g ai/ha produced 55% control. The combination of these two rates of the herbicides produced 93.3% control, while Colby ' s equation predicted only 59.5% control. Synergism between Compound 1 and Compound 7 also occurred against crabgrass and barnyardgrass (Tables 5 and 6).

Finally, synergism was also observed to occur between Compound 1 and Compound 8 in controlling barnyardgrass and giant foxtail at some application rates (Tables 7 and 8).

1. Results are the means of three replications

2. Based on Colby's equation

3. Values marked * indicate treatments where observed effect substantially exceeded expected effect.

1. Results are the means of three replications

2. Based on Colby's equation

1. Results are the means of three replications

2. Based on Colby's equation

1. Results are the means of three replications

2. Based on Colby's equation

1. Resu ts are the means o three replications

2. Based on Colby's equation

1. Results are the means of three replications

2. Based on Colby's equation

1. Results are the means of three replications

2. Based on Colby's equation

1. Results are the means of three replications

2. Based on Colby's equation Example 19 Concrete pot tests were conducted outdoors in 50 x 50 cm pots at Ushiku, Japan. The pots were filled with 6 cm of gravel, 3 cm of sand, and 16 cm of paddy soil (Fujishiro light clay). Weed seeds and tubers were incorporated into the top 2-3 cm of soil. After flooding, Nipponbare rice plants at the 2-leaf stage were transplanted into the pots using three plants per hill and six hills per pot. After transplanting, the water level was maintained at a depth of 3 to 4 cm. Chemicals were formulated in granules so that 30 kg/ha of granules gave the desired dosage. These were spread over the surface of the pots. Applications were made at the 0.5-1 (11 days after transplanting (DAT). Trial 1) and 2-2.5 (18 DAT. Trial 2) leaf stage (Ls) of barnyardgrass. Each treatment consisted of two replications. Evaluations of rice tolerance and weed control efficacy were made 28 (Trial 1) and 21 (Trial 2) days following treatment. Weed control ratings were on a 0 to 10 scale; 0 = no effect, 10 = complete kill. The results are summarized in Table 11. Weeds

Scientific Name Common Name Code

Cyperus serotinus flatsedge CYPSE

Echinochloa crus-galli barnyardgrass ECHCG

Monochoria vaginalis Monochoria MOOVA

Scripus juncoides bulrush SPCJU

1. Application rate in grams active ingredient per hectare.

2. Percent of Corresponding Untreated Check Values.

3. Numbers in parenthesis are the size of plants in the control at the time evaluations were made. Example 20

These tests were conducted in a greenhouse at Ushiku, Japan. Wagner pots of either 100 (barnyardgrass, Echinochloa crus-galli) or 200 cm

(rice) surface area were partially filled with

Fujishiro light clay soil. Barnyardgrass seeds were incorporated into the surface soil to a depth of 2-3 cm for grass efficacy tests. In rice tolerance tests, two stands of three rice seedlings (Nihonbare variety) at the 2-2.5 leaf stage were transplanted to each pot. Before treatment the pots were flooded to a depth of 3-4 cm of water and maintained at this level throughout the tests. Technical samples of the chemicals were dissolved in acetone and then added to the water in each pot to give the desired rates. Each treatment was replicated twice in the case of barnyardgrass and three times for rice. Visual ratings of crop injury and weed control efficacy were made 3-4 weeks following treatment on a 0 to 10 scale; 0 = no effect, 10 = complete kill. The results are summarized in Tables 12-15.

1. Application rate in grams active ingredient per hectare.

2. DAT = treatment time (days after transplanting rice).

3. Leaf stage at time of treatment.

1. Application was 14 days after seeding, and rating was 28 days after application.

2. Application rates in units of grams, active ingredient per hectare.

1. Evaluations made 21 days after treatment.

2. Applications rate in grams active ingredient per hectare.

1. Application rate in grams active ingredient per hectare.

2. Barnyardgrass treated at 1, 2, and 3-leaf stages

1. Application rate in grams active ingredient per hectare.

2. Barnyardgrass treated at 1, 2, and 3-leaf stages.

Example 21 These tests were conducted on direct-seeded rice in the field in California in 1987. Treatments were made at the 2-leaf stage of rice as either a foliar spray or granules spread by hand. Granules (G) of Compound 1 and Compound 3 contained 0.5% and 0.32% active ingredient, respectively. The formulation of Compound 1 used for spraying was an emulsifiable concentrate (EC) containing 7 lbs/gallon active ingredient. The formulation of Compound 3 used for spraying was a dry flowable (DF) containing 60 weight % active ingredient. Plots contained 9.0 X 20.0 ft of direct water seeded rice in a water depth of 4 to 6 inches. Evaluations were made 38 days after application and represent an average of four replications. The results are summarized in Table 16.

Weeds

Scientific Name Common Name Code

Ammannia auriculata Ammannia, redstem AMMAU Ammannia coccinea Ammannia, purple AMMCO Bacopa bisenii Waterhyssop, Carolina BAOEI Bacopa rotundifolia Waterhyssop, roundleaf BACRO Cyperus difformis Umbrellaplant, CYPDI smallflower

Echinochloa crus-galli Barnyardgrass. common ECHCG

Eleocharis obtusa Spikebrush. blunt ELOOB

Heteranthera limosa Ducksalad HETLI

Leptochloa fascicularis Sprangletop, bearded LEFFA

Najas guadalupensis Southern naiad NAIGU

Sagittaria montevidensis Arrowhead. California SAGMO Scirpus mucronatus Bulrush, roughseed SCPMU

In Table 16. the weed control was determined visually with 0 being no effect and 100 being a complete kill.

Example 22 Airlite plastic pots (16 cm diameter) were partially filled with Tama silt loam soil and the soil was saturated with water. Japonica (cv. M101) and Indica (cv. Lemont) rice seedlings at the 2.0 to 2.5 leaf stage were transplanted into one-third of the pots. Into another third of the pots were transplanted seedling or sprouted tubers of water plantain (Alisma trivale). Scripus (Scirpus paludosus). Cyperus (Cyperus esculentus), and arrowhead (Sagittaria spp.). The remaining pots were planted with barnyardgrass (Echinochloa crus-galli) seeds and sprouted tubers of water chestnut (Eleocharis spp.). These weeds all represent major rice weeds or genera of weeds important in rice .

Three to four days after planting, the water level was raised to 3 cm (about 1200 ml/pot) and maintained at this level throughout the test.

Chemical treatments were applied directly to the paddywater, within 24 hours of raising the water, after being formulated in a non-phytotoxic solvent. The. pots were maintained in the greenhouse. Each treatment was replicated three times in a completely randomized block design. Rates of application and plant response ratings made 21 days after treatment are summarized in Table 17.

Expected effects were then calculated using Colby's equation as described in Example 18. The expected and observed activities are tabulated in Tables 18 and 19 for combinations of Compound 1 with Compounds 3 and 4, respectively. As can be from from Table 18, combinations of 16 or 250 g/ha of Compound 1 with 8 or 32 g/ha of Compound 3 or 64 g/ha of Compound 1 with 8 g/ha of Compound 3 were unexpectedly less phytotoxic to both the Japonica and Indica varieties of rice. Moreover, combinations of 16 g/ha of Compound 1 with 8 g/ha of Compound 3 or 64 g/ha of Compound 1 with 8 or 32 g/ha of Compound 3 gave unexpectedly better control of water chestnut (ELESS), thus indicating a synergistic effect on this weed species.

As can be seen from Table 19, combinations of 16 or 64 g/ha of Compound 1 with 2 or 8 g/ha of Compound 4 were unexpectedly less phytotoxic to the Japonica variety of rice. Moreover, combinations of 16 or 64 g/ha of Compound 1 with 2 g/ha of Compound 4 gave unexpectedly better control of water chestnut (ELESS), thus indicating a synergistic effect on this weed species.

Weeds

Scientific Name Common Name Code

Alisma trivale Water plantain ALSPA Cyperus esculentus Cyperus CYPSS Echinochloa crus-galli Barnyardgrass ECHCG Eleocharis spp. Water chestnut ELESS Sagittaria spp. Arrowhead SAGSS Scirpus paludosus Scripus SCPSS

In Tables 17, 18 and 19, the weed was determined visually with 0 being no effect and 100 being complete kill.

1. Expected values calculated using Colby's equation.

Substantially less than expected injury to rice.

*Substantially better than expected weed control.

1. Expected values calculated using Colby's equation.

Substantially less than expected injury to rice.

*Substantially better than expected weed control.

Claims

WHAT IS CLAIMED IS:

1. A herbicidal mixture of

1-methyl-4-(1-methylethyl)-2-exo-[(2-methylphenyl)- methoxy]-7-oxabicyclo[2.2.1]heptane. Compound 1; or 1-methyl-4-(1-methylethyl)-2-exp-[(2-bromophenyl)- methoxy]-7-oxabicyclo[2.2.1]heptane. Compound 2, with herbicidal compounds selected from

(a) 2-[[(4.6-dimethoxypyrimidin-2-yl)aminocarbonyl]- aminosulfonylmethyl]benzoic acid, methyl ester. Compound 3;

(b) 5-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]- aminosulfonyl]-1-methylpyrazole-4-carboxylie acid, ethyl ester. Compound 4;

(c) N-[((4,6-dimethoxy-2-pyrimidinyl)aminocarbonyl)]- 3-(pentafluoro-1-propeny1)-2-thiophenesulfonamide. Compound 5; (d) 3-(2-chloro-1.2-difluoroethenyl)-N-[(4,6- dimethoxy-2-pyrimidinyl) aminocarbonyl]-2- thiophenesulfonamide. Compound 6; or (e) ethyl 2-[4-(6-chloro-2-quinoxalinyloxy)phenoxy]- propionate. Compound 7; (f) 2-[(1-ethoxyimino)butyl]-5-[2-(ethylthio)propyl]- 3-hydroxy-2-cyclohexen-1-one, Compound 8; (g) (±)-butyl-2-[4-[(5-trifluoromethyl)-2-pyridinyl)- oxy]phenoxy]propanoate. Compound 9; (h) butyl(R)-2-[4-[(5-trifluoromethyl)-2-pyridinyl)- oxyjphenoxyjpropanoate. Compound 10;

(i) methyl 2-(4-((3-chloro-5-trifluoromethyl)-2- pyridinyl)oxy)phenoxy)-propanoate. Compound 11; (j) 2-[1-(ethoxyimino)butyo]-3-hydroxy-5-[2(H)- tetrahydrothiopyran-3-yl]-2-cyclohexen-1-one, Compound 12;

(k) 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2- nitrobenzoic acid. Compound 13; (l) sodium 5-[2-chloro-4-(trifluoromethyl)ρhenoxy]- 2-nitrobenzoate, Compound 14; (m) 3-isopropyl-1H-2.1.3-benzothiadiazin-4(3H)-one 2.2-dioxide, Compound 15; (n) 3-(3.4-dichlorophenyl)-1-methoxy-1-methylurea, Compound 16; (o) 3- [[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)- aminocarbonyl]aminosulfonyl]-2-thiophenecar- boxylic acid, methyl ester. Compound 17;

(P) (propylamino)-s-triazine. Compound 18; (q) 2-chloro-2',6'-diethyl-N-(methoxymethyl)- acetanilide. Compound 19; or (r) 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2- methoxy-1-methylethyl)acetamide. Compound 20; and their agriculturally suitable salts.

2. A mixture of compounds of the Formula I or II

Compound 7

3. The mixture of Claim 2 which is the compound of Formula I and Compound 3.

4. The mixture of Claim 2 which is the compound of Formula I and Compound 4.

5. The mixture of Claim 2 which is the compound of Formula I and Compound 5 .

6. The mixture of Claim 2 which is the compound of Formula I and Compound 6.

7. The mixture of Claim 2 which is the compound of Formula I and Compound 7.

8. The mixture of Claim 2 which is the compound of Formula II and Compound 3.

9. The mixture of Claim 2 which is the compound of Formula II and Compound 4.

10. The mixture of Claim 2 which is the compound of Formula II and Compound 5.

11. The mixture of Claim 2 which is the compound of Formula II and Compound 6.

12. The mixture of Claim 2 which is the compound of Formula II and Compound 7.

13. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

1 and at least one of the following: surfactant, solid or liquid diluent.

14. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

2 and at least one of the following: surfactant, solid or liquid diluent.

15. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

3 and at least one of the following: surfactant, solid or liquid diluent.

16. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

4 and at least one of the following: surfactant, solid or liquid diluent.

17. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

5 and at least one of the following: surfactant, solid or liquid diluent.

18. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

6 and at least one of the following: surfactant, solid or liquid diluent.

19. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

7 and at least one of the following: surfactant, solid or liquid diluent.

20. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

8 and at least one of the following: surfactant, solid or liquid diluent.

21. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

9 and at least one of the following: surfactant, solid or liquid diluent.

22. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

10 and at least one of the following: surfactant, solid or liquid diluent.

23. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

11 and at least one of the following: surfactant, solid or liquid diluent.

24. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of a compound of Claim

12 and at least one of the following: surfactant, solid or liquid diluent.

25. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 1.

26. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 2.

27. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 3.

28. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 4.

29. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 5.

30. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 6.

31. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 7.

32. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 8.

33. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 9.

34. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 10.

35. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 11.

36. A method for controlling the growth of undesired vegetation which comprises applying to the locus of the crop to be protected postemergence to the crop and either postemergence or preemergence to the undesired vegetation an effective amount of the mixture of Claim 12.

37. A method for controlling the growth of undesired vegetation which comprises applying to the locus of a paddy rice crop postemergence to the rice an effective amount of the mixture of Claim 1 wherein the herbicidal compounds are selected from Compound 3, 4, 5 or 6.

38. A method for controlling the growth of undesired vegetation which comprises applying to the locus of a broadleaf crop selected from soybeans, sugarbeets. peanuts or cotton postemergence to the crop an effective amount of the mixture of Claim 6.