WO2008073369A1 - Herbicidal mixtures - Google Patents

Abstract

Disclosed is a herbicidal mixture comprising (a) at least one herbicidal compound selected from pyrimidines of Formula 1, N-oxides, and salts thereof: (I) here wherein R1 is cyclopropyl, 4-Br-phenyl or 4-Cl-phenyl; X is Cl or Br; R2 is H, C1 -C14- alkyl, C2- C14 alkoxyalkyl, C3-C14 alkoxyalkoxyalkyl, C2- C14 hydroxyalkyl or benzyl; and (b) at least one additional herbicidal compound selected from compounds of Formula 2, N-oxides, and salts thereof (II) wherein R3, R4, W and G are as defined in the disclosure. Also disclosed is a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a composition comprising a mixture of the invention and optionally further comprising at least one other herbicide.

Description

TITLE HERBICIDAL MIXTURES

FIELD OF THE INVENTION

This invention relates to herbicidal mixtures of certain pyrrolidine derivatives, their jV-oxides and salts, and to compositions comprising such mixtures, and methods for controlling undesirable vegetation.

BACKGROUND OF THE INVENTION

The control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beets, corn (maize), potatoes, wheat, barley, tomatoes, sugarcane and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumers. The control of undesired vegetation in noncrop areas is also important. Combinations of herbicides are typically used to broaden the spectrum of plant control or enhance the level of control of any given species through additive effect. Certain rare combinations surprisingly give a greater-than-additive or synergistic effect. Additionally, certain rare combinations surprisingly give a less than additive or safening effect on useful crops. Such valuable combinations have now been discovered. PCT Patent Publication WO 2005/063721 discloses herbicidally active 4-pyrimidine carboxylic acids of Formula i

wherein R¹ is cyclopropyl optionally substituted with 1-5 R⁵, or phenyl optionally substituted with 1-3 R⁷; R² is ((O)_jC(R¹⁵)(R¹⁶))_kR; R is CO₂H or a herbicidally effective derivative of CO₂H; R³ is halogen, cyano, nitro; R⁴ is -N(R²⁴)R²⁵ or -NO₂; j is 0 or 1; and k is 0 or 1; provided that when k is 0, then j is 0; and R⁵, R⁷, R¹⁵, R¹⁶, R²⁴ and R²⁵ are as defined in the disclosure. However, this publication does not disclose the mixtures of the present invention or their surprising synergistic utility. SUMMARY OF THE INVENTION

This invention is directed to a herbicidal mixture comprising (a) at least one herbicidal compound selected from pyrimidines of Formula 1 (including all geometric and stereoisomers), N-oxides, and salts thereof:

wherein

R¹ is cyclopropyl, 4-Br-phenyl or 4-Cl-phenyl; X is Cl or Br; and

R² is H, C₁-C₁₄ alkyl, C2-C1₄ alkoxyalkyl, C₃-C₁₄ alkoxyalkoxyalkyl, C₂-C₁₄ hydroxyalkyl or benzyl; and

(b) at least one additional herbicidal compound selected from compounds of Formula 2 (including all geometric and stereoisomers), N-oxides, and salts thereof:

wherein

R³ is H, halogen, C₁-C₆ alkyl, C₂-C₆ alkoxyalkyl, C₃-C₆ cycloalkyl or C₃-C₈ cycloalkylalkyl;

R⁴ is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyloxy, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ hydroxyalkyl, phenoxycarbonyl or benzyloxycarbonyl; W is O or NR⁵; R⁵ is H, halogen, CN, C₁-C₆ alkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ haloalkylcarbonyl,

C₂-C₆ alkoxycarbonyl or C₁-C₆ alkylsulfonyl; G is a phenyl ring or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with from 1 to 4 substiruents independently selected from R⁶; R⁶ is halogen, cyano, hydroxy, amino, nitro, -CHO, -C(=O)OH, -C(=O)NH₂, -SO₂NH₂, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, C₁-C₁₀ haloalkyl, C₂-C₁₀ alkylcarbonyl, C₂-C10 haloalkylcarbonyl, C₂-C₁₀ alkoxycarbonyl, C₄-C₁₀ cycloalkoxycarbonyl, C5-C₁₀ cycloalkylalkoxycarbonyl, C₂-C₁₀ alkylaminocarbonyl, C₃-C₁₀ dialkylaminocarbonyl, C₁-C₁₀ alkoxy, C₁-C₁₀ haloalkoxy, C₂-C₁₀ alkylcarbonyloxy, C₁-C₁₀ alkylthio, C₁-C₁₀ haloalkylthio,

C₁-C₁₀ alkylsulfinyl, C₁-C₁₀ haloalkylsulfinyl, C₁-C₁₀ alkylsulfonyl, C₁-C₁₀ haloalkylsulfonyl, C₁-C₁₀ alkylaminosulfonyl, C₂-C₁₀ dialkylaminosulfonyl, C₃-C₁₀ trialkylsilyl, C₁-C₁₀ alkylamino, C₂-C₁₀ dialkylamino, C₂-C₁₀ alkylcarbonylamino, C₁-C₁₀ alkylsulfonylamino, phenyl, pyridinyl or thienyl. This invention also relates to a herbicidal composition comprising a herbicidally effective amount of a mixture of the invention and at least one of a surfactant, a solid diluent or a liquid diluent.

This invention further relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a mixture of the invention (e.g., as a composition described herein).

DETAILS OF THE INVENTION

As used herein, the terms "comprises," "comprising," "includes," "including," "has,"

"having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Also, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore "a" or "an" should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

Numeric ranges are inclusive of each and every integer value defining the range. ^v

In the above recitations, the term "alkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, z-propyl, or the different butyl, pentyl or hexyl isomers.

"Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ and

CH₃CH₂OCH₂CH₂. "Alkoxyalkoxy" denotes alkoxy substitution on alkoxy.

"Alkoxyalkoxyalkyl" denotes alkoxyalkoxy substitution on alkyl. Examples of

"alkoxyalkoxyalkyl" include CH₃OCH₃OCH₂, CH₃OCH₃OCH₂CH₂, CH₃CH₂OCH₃OCH₂ and CH₃OCH₃CH₂OCH₂CH₂. "Hydroxyalkyl" denotes hydroxy substitution on alkyl. Examples of "hydroxyalkyl" include HOCH₂CH₂ and HOCH₂CH₂CH₂CH₂.

Compounds in the mixtures of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.

Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.

One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of the compounds of Formula 1 and Formula 2 are useful for control of undesired vegetation (i.e. are agriculturally suitable). The salts of the compounds in the mixtures of this invention including Formula 1 and Formula 2 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. When a compound of Formula 1 and Formula 2 contains an acidic moiety such as a carboxylic acid or phenol, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. In these salts formed from bases, the salt cation is derived from the base. Examples of salt cations derived from the aforementioned bases are respectively: pyridinium (C₅HgN*), triethylammonium (HN^φ(Et)₃), ammonium (H₄N^Θ), sodium (Na^φ), potassium (K^φ), lithium (Li^φ), calcium (Ca^2Φ), magnesium (Mg^2φ) and barium (Ba^2θ). Accordingly, the present invention compromises compounds selected from Formula 1, TV-oxides and agriculturally suitable salts thereof and compounds selected from Formula 2, TV-oxides and agriculturally suitable salts thereof.

Embodiments of the present invention include: Embodiment Al. A mixture as described in the Summary of the Invention comprising a herbicidal compound of Formula 1 wherein R² is H, salt cation, CJ-CJ_Q alkyl, C2-C₁0 alkoxyalkyl, C₃-C₁₀ alkoxyalkoxyalkyl, C2-C₁0 hydroxyalkyl or benzyl.

Embodiment A2. The mixture of Embodiment Al wherein R² is H, salt cation, Cj- C4 alkyl, C₂-C4 alkoxyalkyl, C₃-C₄ alkoxyalkoxyalkyl, C₂-C₄ hydroxyalkyl or benzyl. Embodiment A3. The mixture of Embodiment A2 wherein R² is H, salt cation or C₁-

C₂ alkyl.

Embodiment A4. The mixture of Embodiment Al wherein R² is C₅-C₁O alkyl C₅-C₁₀ alkoxyalkyl, C₅-C_j0 alkoxyalkoxyalkyl or C₅-C_j0 hydroxyalkyl.

Embodiment A5. The mixture of Embodiment A4 wherein R² is C₅-Cg alkyl, C₅-Cg alkoxyalkyl or C₅-Cg alkoxyalkoxyalkyl.

Embodiment A6. A mixture as described in the Summary of the Invention comprising a herbicidal compound of Formula 1 wherein R¹ is cyclopropyl.

Embodiment A7. A mixture as described in the Summary of the Invention comprising a herbicidal compound of Formula 1 wherein X is Cl. Embodiment A8. A mixture as described in the Summary of the Invention comprising a herbicidal compound of Formula 1 wherein X is Br.

Embodiment Bl. A mixture as described in the Summary of the Invention comprising 3 -(((5 -(difluoromethoxy)- 1 -methyl-3 -(trifluoromethyl)- lH-pyrazol-4- yl)methyl)sulfonyl)-4,5-dihydro-5,5-dimethylisoxazole (pyroxasulfone, Compound 27, Formula 2 wherein R³ is CH₃, R⁴ is H, W is O and G is 5-

(difluoromethoxy)- 1 -methyl-3-(trifluoromethyl)- lH-pyrazol-4-yl). Specific embodiments include a mixture wherein component (a) is selected from the group consisting of

6-amino-5-chloro-2-cyclopropyl-4-pyrrmidinecarboxylic acid (Compound 1), methyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 2), ethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 3), 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylic acid (Compound 4), methyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 5), ethyl 6-ammo-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 6), 6-ammo-5-chloro-2-(4-cMorophenyl)-4-pyrimidinecarboxylic acid (Compound 7), methyl 6-ammo-5-cMoro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate (Compound 8), ethyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate (Compound 9), phenylmethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate

(Compound 10),

6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt

(Compound 11), phenylmethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate

(Compound 12),

6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt

(Compound 13), ethyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate (Compound 14), methyl 6-amino-2-(4-bromophenyl)-5 -chloro-4-pyrimidinecarboxylate (Compound

15),

6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylic acid (Compound 16),

1 -methyl ethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 17), butyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 18),

3-hydroxypropyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate

(Compound 19), propyl 6-ammo-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 20), 1-methylheptyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate

(Compound 21),

2-(2-methoxyethoxy)ethyl 6-amino-5-chloro-2-cyclopropyl-4- pyrimidinecarboxylate (Compound 22), octyl 6-ammo-5-ctøoro-2-cyclopropyl-4-pyiiniidinecarboxylate (Compound 23), 2-butoxyethyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate

(Compound 24),

2-ethylhexyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate (Compound

25), and

2-butoxy- 1 -methylethyl 6-amino-5 -chloro-2-cyclopropyl-4-pyrimidinecarboxylate (Compound 26).

Also noteworthy as embodiments are herbicidal compositions of the present invention comprising the mixtures of embodiments described above. Compounds of the invention are particularly useful for selective control of weeds in corn, wheat, barley, pasture, rangeland, sugarcane, plantation crops and also for total vegetation management. This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the mixtures of the invention (e.g., as a composition described herein). Of note as embodiments relating to methods of use are those involving the mixtures of embodiments described above. Compounds of Formula 1 can be prepared by one or more of the methods and variations thereof as described in PCT Patent Publication WO 2005/063721, which is hereby incorporated by reference in its entirety. For example, compounds 1, 2, 5, 6, 7 and 9 as identified in Table A can be prepared by the method described in Example 2 (page 29), Example 3 (page 31), Example 1 (page 27), Example 1 (page 27), Example 4 (page 32), and Example 5 (page 33) of WO 2005/063721 respectively.

3-(((5-(Difluoromethoxy)- 1 -methyl-3-(trifluoromethyl)- lH-pyrazol-4- yl)methyl)sulfonyl)-4,5-dihydro-5,5-dimethyl-isoxazole (pyroxasulfone (Compound 27), a compound of Formula 2) and its preparation is known from US 2004/110749; mixtures of this compound with other herbicides is known from US 2005/256004.

By the procedures described in pages 22-33 of PCT Patent Publication WO 2005/063721 together with methods known in the art, the following compounds in Tables A and B, which exemplify compounds of Formula 1 in the present mixtures, can be prepared. The following abbreviations are used in the Tables A-C which follow: t means tertiary, / means iso, Me means methyl, Et means ethyl, Pr means propyl (i.e. n-propyl), /-Pr means isopropyl, Bu means butyl (i.e. w-butyl), *-Bu means tert-butyl, "^θ" means negative formal charge, and "^®" means positive formal charge. The compound numbers of Tables A, B and C refer to compounds listed as Embodiments or Specific Embodiments in the Details of the Invention. TABLE A

Compd Compd

R* X No. R² X Rl R2 No.

1 cyclopropyl H Cl 22 cyclopropyl CH₃O(CH₂)₂OCH₂CH₂ Cl

2 cyclopropyl Me Cl 23 cyclopropyl CH₃(CH₂)₆CH₂ Cl

3 cyclopropyl Et Cl 24 cyclopropyl CH₃(CH₂)₃OCH₂CH₂ Cl

20 cyclopropyl Pr Cl 25 cyclopropyl CH₃(CH₂)₃CH(Et)CH₂ Cl

17 cyclopropyl i-Pr Cl 26 cyclopropyl CH₃(CH₂)₃ OCH₂CHMe Cl cyclopropyl /-Bu Cl 4 cyclopropyl H Br

12 cyclopropyl PhCH₂ Cl 5 cyclopropyl Me Br

18 cyclopropyl Bu Cl 6 cyclopropyl Et Br

19 cyclopropyl (HO)CH₂CH₂CH₂ Cl cyclopropyl Pr Br

21 cyclopropyl CH₃(CH₂)₅CHMe Cl cyclopropyl ι-Fi Br Compd R2 Compd

Rl X Rl R2 X No. No. cyclopropyl t-Bu Br 4-Cl-Ph CH₃O(CH₂)₂OCH₂CH₂ Br

10 cyclopropyl PhCH₂ Br 4-Cl-Ph CH₃(CH₂)₆CH₂ Br cyclopropyl Bu Br 4-Cl-Ph CH₃(CH₂)₃OCH₂CH₂ Br cyclopropyl (HO)CH₂CH₂CH₂ Br 4-Cl-Ph CH₃(CH₂)₃CH(Et)CH₂ Br cyclopropyl CH₃(CH₂)₅CHMe Br 4-Cl-Ph CH₃(CH₂)₃OCH₂CHMe Br cyclopropyl CH₃O(CH₂)₂OCH₂CH₂ Br 16 4-Br-Ph H Cl cyclopropyl CH₃(CH₂)₆CH₂ Br 15 4-Br-Ph Me Cl cyclopropyl CH₃(CH₂)₃OCH₂CH₂ Br 14 4-Br-Ph Et Cl cyclopropyl CH₃(CH₂)₃CH(Et)CH₂ Br 4-Br-Ph Pr Cl cyclopropyl CH₃(CH₂)₃OCH₂CHMe Br 4-Br-Ph j-Pr Cl

7 4-Cl-Ph H Cl 4-Br-Ph t-Bu Cl

8 4-Cl-Ph Me Cl 4-Br-Ph PhCH₂ Cl

9 4-Cl-Ph Et Cl 4-Br-Ph Bu Cl

4-Cl-Ph Pr Cl 4-Br-Ph (HO)CH₂CH₂CH₂ Cl

4-Cl-Ph /-Pr Cl 4-Br-Ph CH₃(CH₂)₅CHMe Cl

4-Cl-Ph t-Bu Cl 4-Br-Ph ^' CH₃O(CH₂)₂OCH₂CH₂ Cl

4-Cl-Ph PhCH₂ Cl 4-Br-Ph CH₃(CH₂)₆CH₂ Cl

4-Cl-Ph Bu Cl 4-Br-Ph CH₃(CH₂)₃OCH₂CH₂ Cl

4-Cl-Ph (HO)CH₂CH₂CH₂ Cl 4-Br-Ph CH₃(CH₂)₃CH(Et)CH₂ Cl

4-Cl-Ph CH₃(CH₂)₅CHMe Cl 4-Br-Ph CH₃(CH₂)₃OCH₂CHMe Cl

4-Cl-Ph CH₃O(CH₂)₂OCH₂CH₂ Cl 4-Br-Ph H Br

4-Cl-Ph CH₃(CH₂)₆CH₂ Cl 4-Br-Ph Me Br

4-Cl-Ph CH₃(CH₂)₃OCH₂CH₂ Cl 4-Br-Ph Et Br

4-Cl-Ph CH₃(CH₂)₃CH(Et)CH₂ Cl 4-Br-Ph Pr Br

4-Cl-Ph CH₃(CH₂)₃OCH₂CHMe Cl 4-Br-Ph z-Pr Br

4-Cl-Ph H Br 4-Br-Ph t-Bu Br

4-Cl-Ph Me Br 4-Br-Ph PhCH₂ Br

4-Cl-Ph Et Br 4-Br-Ph Bu Br

4-Cl-Ph Pr Br 4-Br-Ph (HO)CH₂CH₂CH₂ Br

4-Cl-Ph /-Pr Br 4-Br-Ph CH₃(CH₂)₅CHMe Br

4-Cl-Ph t-Bu Br 4-Br-Ph CH₃O(CH₂)₂OCH₂CH₂ Br

4-Cl-Ph PhCH₂ Br 4-Br-Ph CH₃(CH₂)₆CH₂ Br

4-Cl-Ph Bu Br 4-Br-Ph CH₃(CH₂)₃OCH₂CH₂ Br

4-Cl-Ph (HO)CH₂CH₂CH₂ Br 4-Br-Ph CH₃(CH₂)₃CH(Et)CH₂ Br

4-Cl-Ph CH₃(CH₂)₅CHMe Br 4-Br-Ph CH₃(CH₂)₃OCH₂CHMe Br

TABLE C

Compd

W R' G No.

27 O H 5-(difluoromethoxy)- 1 -methyl-3-(trifluoromethyl)- l/f-pyrazol-4-yl

O H l-methyl-3-(trifluoromethyl)-l#-pyraz^"ol-4-yl

O H 2 ,3 -diclhoro-6-ethoxyphenyl

O H 2,5-dichloro-4-ethoxyphenyl

O H 5-chloro-2-nitrophenyl ompd

O H 2,6-dlfluorophenyl

O H 5-chloro-2-(difluoromethoxy)phenyl

O F 5-(difluoromemoxy)-l-memyl-3-(trifluoromemyl)-li7-pyrazol-4-yl

O F 1 -methyl-3-(trifluoromethyl)- l.ff-pyrazol-4-yl

O F 2,3-diclhoro-6-ethoxyphenyl

O F 2,5-dichloro-4-ethoxyphenyl

CL F 5-chIoro-2riiiQOphenyJL__.

O • F 2,6-dlfluorophenyl

O F 5-chloro-2-(difluoroinethoxy)phenyl

NH H 5 -(difluoromethoxy)- 1 -methyl-3 -(trifluoromethyl)- lif-pyrazol-4-yl

NH H 1 -methyl-3-(trifluoromethyl)- liϊ-pyrazol-4-yl

NH H 2,3-diclhoro-6-ethoxyphenyl

NH H 2 , 5 -dichloro-4 -ethoxyphenyl

NH H 5-chloro-2-nitrophenyl

NH H 2,6-dlfluorophenyl

NH H 5-chloro-2-(difluoromethoxy)phenyl

NH F 5-(difluoromethoxy)-l-methyl-3-(trifluoromethyl)-l/f-pyrazol-4-yl

NH F 1 -methyl-3-(trifluoromethyl)- liϊ-pyrazol-4-yl

NH F ^' 2,3-diclhoro-6-ethoxyphenyl

NH F 2,5-dichloro-4-ethoxyphenyl

NH F 5-chloro-2-nitrophenyl

NH F 2,6-dlfluorophenyl

NH F 5-chloro-2-(difluoromethoxy)phenyl

NMe H 5 -(difluoromethoxy)- 1 -methyl-3 -(trifluoromethyl)- 1 ΛT-pyrazol-4-yl

NMe H 1 -methyl-3-(trifluoromethyl)- l/f-pyrazol-4-yl

NMe H 2 ,3 -diclhoro-6-ethoxyphenyl

NMe H 2,5-dichloro-4-ethoxyphenyl

NMe H 5-chloro-2-nitrophenyl

NMe H 2,6-dlfluorophenyl

NMe H 5-chloro-2-(difluoromethoxy)phenyl

NMe F 5-(difluoromethoxy)- 1 -methyl-3-(trifluoromethyl)- l/f-pyrazol-4-yl

NMe F l-methyl-3-(trifluoromethyl)-l/f-pyrazol-4-yl

NMe F 2 ,3 -diclhoro-6-ethoxyphenyl

NMe F 2,5-dichloro-4-ethoxyphenyl

NMe F 5-chloro-2-nitrophenyl

NMe F 2,6-dlfluorophenyl Compel

W R⁴ No.

NMe 5-chloro-2-(difluoromethoxy)phenyl

Formulation/Utility

Mixtures of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the_ physical. properties_of _the_ active, ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films (including seed coatings), and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.

The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.

Weight Percent

Active Inεredient Diluent Surfactant

Water-Dispersible and Water-soluble 0.001-90 0-99.999 0-15 Granules, Tablets and Powders.

Suspensions, Emulsions, Solutions 1-50 40-99 0-50 (including Emulsifiable Concentrates)

Dusts 1-25 70-99 0-5

Granules and Pellets 0.001-99 5-99.999 0-15

High Strength Compositions 90-99 0-10 0-2

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity. Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, NJV-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, glycerol esters, poly- oxyetKylelie/polybxyplOpylene block ^"cδpl)ly^rϊers7 and ^{^}alkylpolyglycosides^{" "}where^"" the^~ number of glucose units, referred to as degree of polymerization (D.P.), can range from 1 to 3 and the alkyl units can range from Cg to C_J4 (see Pure and Applied Chemistry 72, 1255- 1264). Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N//-dimethylformamide, dimethyl sulfoxide, 7V-alkylpyrrolidone, ethylene glycol, polypropylene glycol, propylene carbonate, dibasic esters, paraffins, alkylbenzenes, alkylnaphthalenes, glycerine, triacetine, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as hexyl acetate, heptyl acetate and octyl acetate, and alcohols such as methanol, cyclohexanol, decanol, benzyl and tetrahydrofurfuryl alcohol.

Useful formulations of this invention may also contain materials well known to those skilled in the art as formulation aids such as antifoams, film formers and dyes. Antifoams can include water dispersible liquids comprising polyorganosiloxanes like Rhodorsil® 416. The film formers can include polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Dyes can include water dispersible liquid colorant compositions like Pro-lzed® Colorant Red. One skilled in the art will appreciate that this is a non-exhaustive list of formulation aids. Suitable examples of formulation aids include those listed herein and those listed in McCutcheon 's 2001, Volume 2: Functional Materials published by MC Publishing Company and PCT Publication WO 03/024222.

Solutions, including emulsifϊable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described Ln U.S. 4,172,714.

Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050,

U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S.

5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

For further information regarding the art of formulation, see T. S. Woods, "The

Formulator's Toolbox - Product Forms for Modern Agriculture" in Pesticide Chemistry and

Bioscience, The Food— Environment Challenge, T. Brooks and T. R. Roberts, Eds.,

^"Tfoceedings^~6f the 9th International Congress on Pesticide Chemistry;

of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through

Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, 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;

U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1^4; Klingman, Weed

Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and

Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Tables A and B.

While specific compounds are exemplified in the formulation Examples below, the ordinarily skilled artisan recognizes that all compounds of the invention would be amenable to substantially similar formulations.

Example A High Strength Concentrate

Compound 2 48.5% Compound 27 (pyroxasulfone) 50.0% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.

Example B Wettable Powder Compound 2 30.0%

Compound 27 (pyroxasulfone) 35.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%. Example C Granule

Compound 3 4.0%

Compound 27 (pyroxasulfone) 6.0% attapulgite granules (low volatile matter,

0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.

Example D Aqueous Suspension

Compound 2 10.0% Compound 27 (pyroxasulfone) 15.0% hydrated attapulgite 3.0% crude calcium ligninsulfonate 10.0% sodium dihydrogen phosphate 0.5% water 61.5%. Example E

Extruded Pellet

Compound 1 12.5%

Compound 27 (pyroxasulfone) 12.5% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.

Example F Microemulsion Compound 6 0.5%

Compound 27 (pyroxasulfone) 0.5% triacetine ^' 30.0%

C₈-C₁₀ alkylpolyglycoside 30.0% glyceryl monooleate 19.0% water 20.0%.

Test results indicate that the mixtures of the present invention are highly active preemergent and/or postemergent herbicides and/or plant growth regulants. Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, air fields, river banks, irrigation and other waterways, around billboards and highway and railroad structures. Many of the mixtures of this invention, by virtue of selective metabolism in crops versus weeds, or by selective activity at the locus of physiological inhibition in crops and weeds, or by selective placement on or within the environment of a mixture of crops and weeds, are useful for the selective control of grass and broadleaf weeds within a crop/weed mixture. One skilled in the art will recognize that the preferred combination of these selectivity factors within mixtures can readily be determined by performing routine biological and/or biochemical assays. Mixtures of this invention may show tolerance to important agronomic crops including, but not limited to, alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa7^~oirp^~alm, fubT>er7 sugarcarϊe7 citrusV gfapesT fruit^" trees, nut^~tfees7^~banana7 plantain; pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Mixtures of this invention can be used in crops genetically transformed or bred to incorporate resistance to herbicides, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin), and/or express other useful traits. Those skilled in the art will appreciate that not all mixtures are equally effective against all weeds. Alternatively, the subject mixtures are useful to modify plant growth.

As the mixtures of the invention have preemergent and/or postemergent herbicidal activity, to control undesired vegetation by killing or injuring the vegetation or reducing its growth, the mixtures can be usefully applied by a variety of methods involving contacting a herbicidally effective amount of a mixture of the invention, or a composition comprising said mixture and at least one of a surfactant, a solid diluent or a liquid diluent, to the foliage or other part of the undesired vegetation or to the environment of the undesired vegetation such as the soil or water in which the undesired vegetation is growing or which surrounds the seed or other propagule of the undesired vegetation. , A herbicidally effective amount of the mixtures of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of mixtures of this invention is about 0.001 to 20 kg/ha with a preferred range of about 0.004 to 7 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.

The weight ratios of component (a) (e.g., methyl 6-amino-5-chloro-2-cyclopropyl-4- pyrimidinecarboxylate, Compound 2) and component (b) (e.g., pyroxasulfone, Compound 27) of this invention typically are between about 500:1 and about 1:500, preferably between about 200:1 and about 1:500, more preferably between about 5:1 and about 1:50, and most preferably between about 1 : 1 and about 1 :20.

Specifically preferred mixtures (compound numbers refer to compounds in Tables A, B and C) are selected from the group: compound 1 and pyroxasulfone (compound 27); compound 2 and pyroxasulfone (compound 27); compound 3 and pyroxasulfone (compound 27); compound 4 and pyroxasulfone (compound 27); compound 5 and pyroxasulfone (compound 27); compound 6 and pyroxasulfone (compound 27); compound 7 and pyroxasulfone (compound 27); compound 8 and pyroxasulfone (compound 27); compound 9 and pyroxasulfone (compound 27); compound 10 and pyroxasulfone (compound 27); compound 11 and pyroxasulfone (compound 27); compound 12 and pyroxasulfone (compound 27); compound 13 and pyroxasulfone (compound 27); compound 14 and pyroxasulfone (compound 27); compound 15 and pyroxasulfone (compound 27); compound 16 and pyroxasulfone (compound 27); compound 17 and pyroxasulfone (compound 27); compound^{^} 18^" uncT pyroxasulfone^" (compound 27)^"; cόϊnpoufid 19 ^"and^" pyroxasulfone (compound 27); compound 20 and pyroxasulfone (compound 27); compound 21 and pyroxasulfone (compound 27); compound 22 and pyroxasulfone (compound 27); compound 23 and pyroxasulfone (compound 27); compound 24 and pyroxasulfone (compound 27); compound 25 and pyroxasulfone (compound 27); and compound 26 and pyroxasulfone (compound 27). Of note are combinations of a compound of Formula 1 (component (a)) and a compound of Formula 2 (component (b)) with at least one other herbicide. In certain instances, combinations with other herbicides having a different site of action will be particularly advantageous for resistance management (especially if the other herbicide also has a similar spectrum of control). Of particular note are compositions which in addition to component (a) and component (b) include (c) at least one compound selected from the group consisting of: (cl) ACCase (acetyl-coenzyme A carboxylase) inhibitors; (c2) AHAS (acetohydroxy acid synthase) inhibitors; (c3) photosystem II inhibitors; (c4) photosystem I electron diverters; (c5) PPO (protoporphyrinogen oxidase) inhibitors; (c6) EPSP (5-enol- pyruvylshikimate-3 -phosphate) synthase inhibitors; (c7) GS (glutamine synthetase) inhibitors; (c8) VLCFA (very long chain fatty acid) elongase inhibitors; (c9) auxin mimics; (clO) auxin transport inhibitors; (el l) other herbicides selected from the group consisting of fiamprop-M-methyl, flamprop-M-isopropyl, difenzoquat, DSMA, MSMA, bromobutide, flurenol, cinmethylin, cumyluron, dazomet, dymron, methyldymron, etobenzanid, fosamine- ammonium, metam, oxaziclomefone, oleic acid, pelargonic acid and pyributicarb; and salts of compounds of (cl) through (cl 1).

Further descriptions of (c) groups corresponding to classes of herbicidal compounds are provided below.

"Acetyl-coenzyme A carboxylase (ACCase) inhibitors (cl)" are chemical compounds that inhibit the acetyl-CoA carboxylase enzyme, which is responsible for catalyzing an early step in lipids and fatty acid synthesis in plants. Lipids are essential components of cell

^"membranes, and without them, new cells cannot be produced. The inhibition of acetyl CoA carboxylase and the subsequent lack of lipid production leads to losses in cell membrane integrity, especially in regions of active growth such as meristems. Eventually shoot and rhizome growth ceases, and shoot meristems and rhizome buds begin to die back. ACCase inhibitors include compounds such as clodinafop, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, propaquizafop, quizalofop, alloxydim, butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim and tralkoxydim, including resolved forms such as fenoxaprop-P, fluazifop-P, haloxyfop-P and quizalofop-P and ester forms such as clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl and fenoxaprop-P-ethyl.

"Acetohydroxy acid synthase (AHAS) inhibitors (c2)" are chemical compounds that inhibit acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS), and thύ¥ kill^" plants^" by ihhib^"iting^"the^~productionTof the bTanch^^Min^~aliphatic^"amino acids such^" as valine, leucine and isoleucine, which are required for protein synthesis and cell growth. AHAS inhibitors include compounds such as amidosulfuron, azimsulfuron, bensulfuron- methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron- methyl, ethoxysulfuron, flazasulfuron, flupyrsulfuron-methyl (including sodium salt), foramsulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron-methyl (including sodium salt), mesosulfuron-methyl, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron- methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, trifioxysulfuron (including sodium salt), triflusulfuron-methyl, tritosulfuron, imazapic, imazamethabenz-methyl, imazamox, imazapyr, imazaquin, imazethapyr, cloransulam-methyl, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam, bispyribac-sodium, pyribenzoxim, pyriftalid, pyrithiobac-sodium, pyriminobac-methyl, flucarbazone-sodium and propoxycarbazone- sodium.

"Photosystem II inhibitors (c3)" are chemical compounds that bind to the D-I protein at the QB -binding niche and thus block electron transport from Q_A to Qg in the chloroplast thylakoid membranes. The electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds that disrupt cell membranes and cause chloroplast swelling, membrane leakage, and ultimately cellular destruction. The Qjg-binding niche has three different binding sites: binding site A binds the triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil, binding site B binds the phenylureas such as diuron, and binding site C binds benzothiadiazoles such as bentazon, nitriles such as bromoxynil and phenyl-pyridazines such as pyridate. Other photosystem II inhibitors include compounds such as ametryn, cyanazine, desmetryne, dimethametryn, prometon, prometryne, propazine, simazine, simetryn, terbumeton, terbuthylazine, terbutryne, trietazine, metamitron, metribuzin, amicarbazone, lenacil, terbacil, chloridazon, desmedipham, phenmedipham, chlorobromuron, chlorotoluron, chloroxuron, ^"dimefuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, metobromuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron, propanil, pentanochlor, bromofenoxim, ioxynil and pyridafol. "Photosystem I electron diverters (c4)" are chemical compounds that accept electrons from Photosystem I, and after several cycles, generate hydroxyl radicals. These radicals are extremely reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This destroys cell membrane integrity, so that cells arid organelles "leak", leading to rapid leaf wilting and desiccation, and eventually to plant death. Paraquat and diquat are examples of this second type of photosynthesis inhibitor.

"Protoporphyrinogen oxidase (PPO) inhibitors (c5)" are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, quickly resulting in formation of highly reactive compounds^" m^lants that rupture cell membranes, causing^{^} cell^" fluids^" to leak^~out. PPO inhibitors include compounds such as acifluorfen-sodium, bifenox, chlomethoxyfen, fluoroglycofen-ethyl, fomesafen, halosafen, lactofen, oxyfluorfen, fluazolate, pyrafiufen- ethyl, cinidon-ethyl, flumioxazin, flumiclorac-pentyl, fluthiacet-methyl, thidiazimin, oxadiazon, oxadiargyl, azafenidin, carfentrazone-ethyl, sulfentrazone, pentoxazone, benzfendizone, butafenacil, pyraclonil, profluazol and flufenpyr-ethyl. "5-Enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitors (c6)" are chemical compounds that inhibit the enzyme, 5 -enol-pyruvylshikimate-3 -phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan and phenylalanine. EPSP inhibitor herbicides are absorbed through plant foliage and translocated in the phloem to the growing points. Glyphosate is a relatively nonselective postemergence herbicide that belongs to this group. Glyphosate includes its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate). EPSP synthase inhibitors also include compounds such as sulfosate.

"Glutamine synthetase (GS) inhibitors (c7)" are chemical compounds that inhibit the activity of the glutamine synthetase enzyme, which plants use to convert ammonia into glutamine. Consequently, ammonia accumulates and glutamine levels decrease. Plant damage probably occurs due to the combined effects of ammonia toxicity and deficiency of amino acids required for other metabolic processes. The GS inhibitor glufosinate is a broad- spectrum postemergence herbicide that has no soil activity. GS inhibitors include compounds such as glufosinate, glufosinate-ammonium and bilanaphos.

Elongase is one of the enzymes located in or near chloroplasts which are involved in biosynthesis of very-long-chain fatty acids (VLCFAs). In plants, very-long-chain fatty acids are the main constituents of hydrophobic polymers that prevent desiccation at the leaf surface and provide stability to pollen grains. "Very long chain fatty acid (VLCFA) elongase inhibitors (c8)" include herbicides having a wide variety of chemical structures, such as acetochlor, alachlor, butachlor, dimethachlor, dimethanamid, metazachlor, metolachlor, pethoxamid, pretilachlor, propachlor, propisochlor, thenylchlor, diphenamid, napropamide, naproanilide, flufenacet, indanofan, mefenacet, fentrazamide, anilofos, cafenstrole and piperophos, including resolved forms such as S-metolachlor.

Auxin is a plant hormone that regulates growth in many plant tissues. "Auxin mimics (c9)" are chemical compounds mimicking the plant growth hormone auxin, thus causing uncontrolled and disorganized growth leading to plant death in susceptible species. Auxin mimics include compounds such as clomeprop, 2,4-D, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, chloramben, dicamba, TBA, clopyralid, fluroxypyr, picloram, triclopyr, quinclorac, quinmerac and benazolin-ethyl.

"Auxin transport inhibitors (clO)" are chemical substances that inhibit auxin transport in plants, such as by binding with an auxin-carrier protein. Examples of auxin transport inhibitors include naptalam (also known as N-(l-naphthyl)phthalamic acid and 2-[(l- naphthalenylamino)carbonyl]benzoic acid) and diflufenzopyr.

Of note are mixtures combining component (a) (e.g., methyl 6-amino-5-chloro-2- cyclopropyl-4-pyrimidinecarboxylate, Compound 2) and component (b) (e.g., pyroxasulfone, Compound 27) with component (c) selected from rimsulfuron, nicosulfuron, thifensulfuron- methyl, tribenuron-methyl, chlorimuron-ethyl, metsulfuron-methyl, chlorsulfuron, sulfometuron-methyl, bensulfuron-methyl, pyrithiobac-sodium, atrazine, bentazon, bromoxynil, mesotrione, topramezone, tembotrione, isoxaflutole, imazethapyr, imazapyr, imazaquin, fiumetsulam, cloransulam-methyl, foramsulfuron, iodosulfuron-methyl (including sodium salt), trifloxysulfuron, primisulfuron-methyl, prosulfuron, halosulfuron- methyl, quizalofop, clethodim, sethoxydim, carfentrazone-ethyl, 2,4-D, 2,4-DB, dicamba, clopyralid, triclopyr, fluroxypyr, picloram, diflufenzopyr, quinclorac, flumioxazin, oxadiazon, sulfentrazone, fomesafen, acifluorfen-sodium, oxyfluorfen, flumiclorac-pentyl, glyphosate, glufosinate, paraquat, pendimethalin, prodiamine, ethalfluralin, txifluralin, oryzalin, clomazone, simazine, ametryn, asulam, hexazinone, diuron, linuron, terbacil, fluometuron, metribuzin, bromacil, MSMA, isoxaben, norflurazon and amitrole.

Preferred for better control of undesired vegetation or resistance management are mixtures of component (a) (e.g., methyl 6-amino-5-chloro-2-cyclopropyl-4- pyrimidinecarboxylate, Compound 2) and component (b) (e.g., pyroxasulfone, Compound 27) with component (c) selected from the group consisting of rimsulfuron, nicosulfuron, thifensulfuron-methyl, tribenuron-methyl, chlorimuron-ethyl, metsulfuron-methyl, atrazine, mesotrione, topramezone, tembotrione, isoxaflutole, imazapyr, fiumetsulam, cloransulam- methyl, foramsulfuron, iodosulfuron-methyl (including sodium salt), halosulfuron-methyl, quizalofop, clethodim, sethoxydim, carfentrazone-ethyl, 2,4-D, dicamba, clopyralid, fluroxypyr, diflufenzopyr, flumioxazin, sulfentrazone, fomesafen, oxyfluorfen, glyphosate, glufosinate, paraquat, pendimethalin, oryzalin, simazine, ametryn, asulam, hexazinone, diuron, terbacil, fluometuron, metribuzin, bromacil, isoxaben and norflurazon. Mixtures of this invention can be mixed with one or more insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of such agricultural protectants with which mixtures of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chlorantraniliprole, chlorpyrifos, chlorpyrifos-methyl, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhaldthrin, deltamethrin, diafeήthiurόh^", diazinδn, diflϋbeήzurδn, dimefluthrin, dimethoate, dinotefuran, esfenvalerate, fenoxycarb, fenpropathrin, fen valerate, fipronil, flonicamid, flubendiamide, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, indoxacarb, isofenphos, malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, pyrafluprole, pyridalyl, pyrifluquinazon, pyriprole, rotenone, spinetoram, spirodiclofen, spiromesifen, spirotetramat, sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiamethoxam, thiodicarb, tralomethrin, trichlorfon and triflumuron; fungicides such as acibenzolar-S-methyl, aldimoφh, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl, benalaxyl-M, benodanil, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), boscalid, bromuconazole, bupirimate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper oxychloride, copper salts such as copper sulfate and copper hydroxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomoφh, dimoxystrobin, diniconazole, diniconazole-M, dinocap, ditbianon, dodemorph, dodine, edifenphos, enestroburin, epoxiconazole, ethaboxam, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimoφh, fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furametpyr, hexaconazole, hymexazol, guazatine, imazalil, imibenconazole, iminoctadine, iodocarb, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isotianil, kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, maneb, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole, methasulfocarb, metiram, metominostrobin, mepanipyrim, metrafenone, myclobutanil, naftifine, neo-asozin (ferric methanearsonate), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron, penthiopyrad, pefurazoate, phosphorous acid and salts, phthalide, picobenzamid, picoxystrobin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propamocarb-liydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pryazophos, pyribencarb, pyrifenox, pyrimethanil, pyrohiitrine, pyroquilon, quinomethionate, quinoxyfen, quintozene, silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tecloftalam, tecnazene, terbinafϊne, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos- methyl, tolyfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, triflumizole, tiricyclazole, trifloxystrobin, trifofine, triticόnazole, uniconazole, validamycin, valiphenal, vinclozolin, zineb, ziram, zoxamide, 5-chloro-6-(2,4,6-trifluorophenyl)-7-(4- methylpiperidin-l-yl)[l,2,4]triazolo[l,5-α]pyrimidine (BAS600), _V-[2-(l,3- dimethylbutyl)phenyl] -5 -fluoro- 1 , 3 -dimethyl- 1 H-pyrazol-4-carboxamide, JV- [2- [4- [ [3 -(4- chlorophenyl)-2-propyn- 1 -yl] oxy] -3 -methoxyphenyl] ethyl] -3 -methyl-2-[(methylsulfonyl)- aminojbutanamide, iV-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3-methoxyphenyl]- ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide, 2-butoxy-6-iodo-3-propyl-4H-l- benzopyran-4-one, 3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine, A- fluorophenyl N-[ 1 -[[[ 1 -(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate, N-[[(cyclo- propyhnethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]- benzeneacetamide, α-[methoxyimino]-N-methyl-2-[[[l-[3-(trifluoromethyl)phenyl]-ethoxy]- imino]methyl]benzeneacetamide, iV-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5- dmiethylphenyl]-N-ethyl-N-memymiemanimidamide, 2-[[2-fluoro-5-(trifluoromethyl)- phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazolidinylidene]acetonitrile, N-[2-(lS,2R)-[ 1,1'- bicyclopropyl] -2-ylphenyl] -3 -(difluoromethyl)- 1 -methyl- lif-p yrazole-4-carboxamide, and 7V-(4-chloro-2-nitrophenyl)-iV-ethyl-4-methylbenzenesulfonamide; nematocides such as aldoxycarb, imicyafos, oxamyl and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.

Mixtures of this invention can also be used in combination with herbicide safeners such as benoxacor, BCS (l-bromo-4-[(chloromethyl)sulfonyl]benzene), cloquintocet-mexyl, cyometrinil, dichlormid, 2-(dichloromethyl)-2-methyl-l,3-dioxolane (MG 191), fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr- ethyl, methoxyphenone ((4-methoxy-3-methylphenyl)(3-methylphenyl)methanone), naphthalic anhydride (1,8-naphthalic anhydride) and oxabetrinil to increase safety to certain crops. Antidotally effective amounts of the herbicide safeners can be applied at the same time as the mixtures of this invention, or applied as seed treatments. Therefore an aspect of the present invention relates to a herbicidal mixture comprising a mixture of this invention and an antidotally effective amount of a herbicide safener. Seed treatment is particularly useful for selective weed control, because it physically restricts antidoting to the crop plants. Therefore a particularly useful embodiment of the present invention is a method for selectively controlling the growth of undesired vegetation in a crop comprising contacting the locus of the crop with a herbicidally effective amount of a mixture of this invention wherein seed from which the crop is grown is treated with an antidotally effective amount of safener. Antidotally effective amounts of safeners can be easily determined by one skilled in the art through simple experimentation. Mixtures of this invention can also be used in combination with plant growth regulators such as aviglycine, 7V-(phenyknethyl)-lH-purin-6-amine, epocholeone, gibberellic acid, gibberellin A₄ and A₇, harpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl, and plant growth modifying organisms such as Bacillus cereus strain BPOl. Mixtures of this invention typically provide a broader spectrum of control of undesired vegetation than provided by each active herbicide ingredient separately. Furthermore mixtures of herbicides having a similar spectrum of control but different sites of action can be particularly advantageous in certain situations for preventing the development of resistant weed populations. Particularly surprisingly, many of the mixtures of this invention have been discovered to provide a greater-than-additive (i.e. synergistic) effect on weeds and/or a less-than-additive (i.e. safening) effect on crops or other desirable plants compared to the control expected based on the effects of the individual components. Herbicidally effective amounts of the herbicidal active ingredients in the mixtures of this invention, including amounts to achieve synergism (i.e. synergistically effective amounts) or safening (i.e. safening effective amounts), to achieve the desired spectrum of weed control and safety to desired vegetation can be easily determined by one skilled in the art through simple experimentation.

The following Tests demonstrate the control efficacy of the mixtures of this invention against specific weeds and/or on crops including other desirable plants. The control afforded by the mixtures are not limited, however, to these species.

BIOLOGICAL EXAMPLES OF THE INVENTION

TEST l

A greenhouse test was conducted to evaluate the effects on corn (ZEAMD, Zea mays ssp. indentata) and several weed species, of mixtures of Compound 2 (i.e. the compound listed as Specific Embodiments in the Details of the Invention) with pyroxasulfone

(Compound 27). Seeds were planted in individual 6.35 cm square pots in a silt loam soil having 3 % organic matter, and they were grown until they achieved the desired stage of growth for application. Weeds in the test included velvetleaf (ABUTH, Abutilon theophrasti Medik.), redroot pigweed (AMARE, Amaranthus retroβexus L.), common waterhemp (AMATA, Amaranthus rudis Sauer), common ragweed (AMBEL, Ambrosia artemisiifolia L.), common lambsquarters (CHEAL, Chenopodium album L.), large crabgrass (DIGSA, Digitaria sanguinalis (L.) Scop.), woolly cupgrass (ERBVI, Eriochloa villosa (Thunb.) Kunth), ivyleaf morningglory (IPOHE, Ipomoea hederacea (L.) Jacquin), wild proso millet (PANMI, Panicum miliaceum L.), ladysthumb smartweed (POLPE, Polygonum persicaria L.), giant foxtail (SETFA, Setaria faberi Herrm.), yellow foxtail (SETLU, Setaria glauca (L.) -P_^ Beauv.), green foxtail- (SETVI, Setaria viridis (L.) P. Beauv.)_r Eastern black nightshade (SOLPT, Solarium ptycanthum Dunal), and common cocklebur (XANST, Xanthium strumarium ssp. strumarium L.). Plants were treated preemergence, and each treatment was replicated three times. Treatments were applied using a belt sprayer that delivered a spray volume of 457 L/ha using a pressure of 262 kPa. Treatments consisted of Compound 2 and pyroxasulfone (Compound 27) alone and in combination, dissolved or suspended in water. After treatment, the plants were returned to a greenhouse where balanced supplemental lighting was used to maintain a 16-hour photoperiod and the daytime and nighttime temperatures were about 25 °C and 19 °C, respectively. Plants were watered and fertilized as needed to maintain optimal vigor. The effects on the treated plants and untreated controls were recorded approximately 21 days after application. Plants were visually evaluated compared to controls for response to the treatments using a scale of 0 to 100 where 0 is no effect and 100 is complete control. Results are summarized in Table 1 and are the means of the three replicates. Colby's Equation was used to determine the herbicidal effects expected from the mixtures. Colby's Equation (Colby, S. R. "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-22 (1967)) calculates the expected additive effect of herbicidal mixtures, and for two active ingredients is of the form:

P_a+b = P_a + P_b - (P_aP_b / 100) wherein P_a+b is the percentage effect of the mixture expected from additive contribution of the individual components, P_a is the observed percentage effect of the first active ingredient at the same use rate as in the mixture, and

P_b is the observed percentage effect of the second active ingredient at the same use rate as in the mixture.

The results and additive effects expected from Colby's Equation are listed in Table 1. Columns labeled "Obs" contain the observed effects, and the values are the means of the replicates in the test. Columns labeled "Exp" contain the values for the expected additive effects of treatment mixtures calculated from Colby's Equation. A dash (-) in columns under the "Application Rate" heading means no compound. The results are based on visual comparison of treated plants to control plants for response to treatments using a scale of 0 to 100 where 0 is no effect and 100 is complete control. An observed effect for a weed that is greater than the expected effect is indicated with an asterisk (*). An observed effect for a crop that is less than the expected effect is indicated with a pound sign (#).

Table 1 - Observed and Expected Results from Compound 2 Alone and in Combination with Pyroxasulfone (Compound 27).

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

Table 1 (Continued)

As can be seen from the results in Table 1, many of the observed results for the mixtures of Compound 2 and pyroxasulfone (Compound 27) on weeds were greater than expected from the Colby Equation, which indicates synergistic activity of these mixtures. Synergy was especially apparent for velvetleaf, redroot pigweed, common waterhemp, large crabgrass, woolly cupgrass, wild proso millet, ladysthumb smartweed, yellow foxtail and Eastern black nightshade control. In test species or at rate combinations where a greater than additive response was less apparent, it was typically because the expected effect was already near 100 %. In addition, some of the observed results for the mixtures on corn were less than expected from the Colby Equation, which indicates safening activity of these mixtures. Although in most cases the expected effect on corn was 0 %, at the highest rate of Compound 2 and the three lowest rates of pyroxasulfone (Compound 27), where a slight effect on corn was expected, the mixtures resulted in apparent safening.

Claims

CLAIMS What is claimed is:

1. A mixture comprising (a) at least one herbicidal compound selected from pyrimidines of Formula 1, N-oxides, and salts thereof:

wherein

R¹ is cyclopropyl, 4-Br-phenyl or 4-Cl-phenyl; X is Cl or Br; and

R² is H, C₁-C₁₄ alkyl, C2-C1₄ alkoxyalkyl, C3-C₁₄ alkoxyalkoxyalkyl, C₂-C₁₄ hydroxyalkyl or benzyl; and

(b) at least one additional herbicidal compound selected from compounds of Formula 2, N- oxides, and salts thereof:

2 wherein

R³ is H, halogen, C₁-C6 alkyl C2-C6 alkoxyalkyl, C₃-C₆ cycloalkyl or C₃-Cg cycloalkylalkyl; R⁴ is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyloxy, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ hydroxyalkyl, phenoxycarbonyl or benzyloxycarbonyl; W is O or NR5;

R⁵ is H, halogen, CN, C₁-C₆ alkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ haloalkylcarbonyl, C₂-C₆ alkoxycarbonyl or C₁-C₆ alkylsulfonyl;

G is a phenyl ring or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with from 1 to 4 substituents independently selected from R⁶; R⁶ is halogen, cyano, hydroxy, amino, nitro, -CHO, -C(=O)OH, -C(=0)NH₂, -SO₂NH₂, C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, C₁-C₁₀ haloalkyl, C₂-C₁₀ alkylcarbonyl, C₂-C₁₀ haloalkylcarbonyl, C₂-C₁₀ alkoxycarbonyl, C₄-C₁₀ cycloalkoxycarbonyl, C₅-C₁₀ cycloalkylalkoxycarbonyl, C₂-C₁₀ alkylaminocarbonyl, C3-C₁₀ dialkylaminocarbonyl, C₁-C₁₀ alkoxy, C₁-C₁₀ haloalkoxy, C₂-C₁₀ alkylcarbonyloxy, C₁-C₁₀ alkylthio, C₁-C₁₀ haloalkylthio,

C₁-C₁₀ alkylsulfinyl, C₁-C₁₀ haloalkylsulfinyl, C₁-C₁₀ alkylsulfonyl, C₁-C₁₀ haloalkylsulfonyl, C₁-C₁₀ alkylaminosulfonyl, C₂-C₁₀ dialkylaminosulfonyl, C3-C₁0 trialkylsilyl, C₁-C₁₀ alkylamino, C₂-C₁₀ dialkylamino, C₂-C₁₀ alkylcarbonylamino, C₁-C₁₀ alkylsulfonylamino, phenyl, pyridinyl or thienyl. 2. The mixture of Claim 1 wherein

R¹ is cyclopropyl, 4-Br-phenyl or 4-Cl-phenyl; X is Cl or Br; and

R² is H, salt cation, C₁-C₁₀ alkyl, C₂-C₁₀ alkoxyalkyl, C3~C₁₀ alkoxyalkoxyalkyl, C₂-C₁₀ hydroxyalkyl or benzyl.

3. The mixture of Claim 2 wherein

R² is H, salt cation or C₁-C₂ alkyl.

4. The mixture of Claim 2 wherein

R² is C₅-Cg alkyl, C₅-Cg alkoxyalkyl, C₅-Cg alkoxyalkoxyalkyl or C₅-Cg hydroxyalkyl.

5. The mixture of Claim 1 wherein the pyrimidine compound of Formula 1 is selected from the group consisting of:

6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid, methyl 6-amino-5-chloro-2-cyclopropyl-4-pyrirnidinecarboxylate, ethyl 6-ammo-5-chloro-2-cyclopropyl-4-pyrirnidinecarboxylate, 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylic acid, methyl 6-arnino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate, ethyl 6-amino-5 -bromo^-cyclopropyM-pyrirnidinecarboxylate, 6-amino-5 -chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylic acid, methyl 6-amino-5 -chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate, ethyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate, phenylmethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate, 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt, phenylmethyl 6-ammo-5-chloro-2-cyclopropyl-4-pyrirnidinecarboxylate, 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid monosodium salt, ethyl 6-arnjLno-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate, methyl 6-arnino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate, 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidrnecarboxylic acid, 1 -methyl ethyl 6-amino-5-chloro-2-cyclopropyl-4-pyriinidinecarboxylate, butyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate, 3-hydroxypropyl 6-amrno-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate, propyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate, 1-methylheptyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate,

2-(2-methoxyethoxy)ethyl 6-amino-5-chloro-2-cyclopropyl-4- pyrimidinecarboxylate, octyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate, 2-butoxyethyl 6-ammo-5 -cMoro^-cyclopropyM-pyrimidinecarboxylate, 2-ethylhexyl 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylate, and

2-butoxy- 1 -methylethyl 6-amino-5 -chloro^-cyclopropyl^-pyrimidinecarboxylate.

6. The mixture of any one of Claims 1 through 5 wherein component (b) comprises 3-(((5-(difluoromethoxy)- 1 -methyl-3-(trifluoromethyl)- lH-pyrazol-4-yl)methyl)sulfonyl)- 4,5-dihydro-5,5-dimethylisoxazole.

7. The mixture of Claim 1 wherein component (a) and component (b) are in a ratio ranging from about 5: 1 to about 1 : 50 by weight.

8. The mixture Claim 7 wherein component (a) and component (b) are in a ratio ranging from about 1 : 1 to about 1 : 20 by weight.

9. The mixture of Claim 1 wherein the mixture further comprises a herbicidal compound in addition to components (a) and (b) selected from rimsulfuron, nicosulfuron, thifensulfuron-methyl, tribenuron-methyl, chlorimuron-ethyl, metsulfuron-methyl, chlorsulfuron, sulfometuron-methyl, bensulfuron-methyl, pyrithiobac-sodium, atrazine, bentazon, bromoxynil, mesotrione, topramezone, tembotrione, isoxaflutole, imazethapyr, imazapyr, imazaquin, flumetsulam, cloransulam-methyl, foramsulfuron, iodosulfuron-methyl (including sodium salt), trifloxysulfuron, primisulfuron-methyl, prosulfuron, halosulfuron- methyl, quizalofop, clethodim, sethoxydim, carfentrazone-ethyl, 2,4-D, 2,4-DB, dicamba, clopyralid, triclopyr, fluroxypyr, picloram, diflufenzopyr, quinclorac, flumioxazin, oxadiazon, sulfentrazone, fomesafen, acifluorfen-sodium, oxyfluorfen, flumiclorac-pentyl, glyphosate, glufosinate, paraquat, pendimethalin, prodiamine, ethalfluralin, trifluralin, oryzalin, clomazone, simazine, ametryn, asulam, hexazinone, diuron, linuron, terbacil, fluometuron, metribuzin, bromacil, MSMA, isoxaben, norflurazon and amitrole.

10. A herbicidal composition comprising a herbicidally effective amount of the mixture of Claim 1 and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent.

11. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of the mixture of Claim 1.