Safened herbicidal compositions including 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid or a derivative thereof for use in rice

Abstract

A safened herbicidal composition for use in rice comprising a herbicidally effective amount of (a) a compound of formula (I): ##STR00001##
or an agriculturally acceptable salt or ester thereof and (b) a safener or a compatible herbicide capable of safening such as a chemical from the quinolinyloxyacetate family of chemicals, dicyclonon, daimuron, dimepiperate, fenclorim, furilazole, halosulfuron, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (NA), or agriculturally acceptable salts, esters, or mixtures thereof, for use in direct-seeded, water-seeded or transplanted rice.

Claims

1. A safened herbicidal composition for use in rice comprising a herbicidally effective amount of (a) benzyl ester of a compound of the formula (I) ##STR00030## or an agriculturally acceptable salt or ester thereof and (b) a safener or a compatible herbicide capable of safening, wherein the compatible herbicide capable of safening is bispyribac-sodium, carfentrazone-ethyl, cyhalofop-butyl, diamuron, dimepiperate, halosulfuron-methyl, norflurazon, pyriclor, or sulcotrione.

2. The composition of claim 1, wherein (b) is a chemical from the quinolinyloxyacetate family of chemicals, dicyclonon, dichlormid, fenclorim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (NA), or agriculturally acceptable salts, esters, or mixtures thereof.

3. The composition of claim 2, wherein the chemical from the quinolinyloxyacetate family of chemicals is cloquintocet acid, cloquintocet mexyl, cloquintocet triisopropylamine, or cloquintocet dimethylamine.

4. The composition of claim 2, wherein the chemical from the quinolinyloxyacetate family of chemicals is cloquintocet mexyl.

5. The composition of claim 1, wherein the weight ratio of (a) to (b) is from 2:1 to 1:32.

6. The composition of claim 1, wherein the weight ratio of (a) to (b) is from 1:1 to 1:4.

7. The composition of claim 1, further comprising an agriculturally acceptable adjuvant or carrier.

8. The composition of claim 1, wherein the rice is direct-seeded, water-seeded, or transplanted paddy.

9. The composition of claim 1, wherein the rice is a glyphosate, glufosinate, dicamba, phenoxy auxin, pyridyloxy auxin, aryloxyphenoxypropionate, acetyl CoA carboxylase (ACCase) inhibitor, imidazolinone, acetolactate synthase (ALS) inhibitor, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitor, protoporphyrinogen oxidase (PPO) inhibitor, triazine, or bromoxynil tolerant rice possessing multiple or stacked traits conferring tolerance to multiple chemistries and/or multiple modes of action.

10. A method of controlling undesirable vegetation in rice comprising contacting the vegetation or applying to the soil or water adjacent thereto with a safened herbicidal composition comprising a herbicidally effective amount of (a) benzyl ester of a compound of the formula (I) ##STR00031## or an agriculturally acceptable salt or ester thereof and (b) a safener or a compatible herbicide capable of safening, wherein the compatible herbicide capable of safening is bispyribac-sodium, carfentrazone-ethyl, cyhalofop-butyl, diamuron, dimepiperate, halosulfuron-methyl, norflurazon, pyriclor, or sulcotrione.

11. The method of claim 10, wherein (b) is a chemical from the quinolinyloxyacetate family of chemicals, dicyclonon, dichlormid, fenclorim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (NA), or agriculturally acceptable salts, esters, or mixtures thereof.

12. The method of claim 11, wherein the chemical from the quinolinyloxyacetate family of chemicals is cloquintocet acid, cloquintocet mexyl, cloquintocet triisopropylamine, or cloquintocet dimethylamine.

13. The method of claim 11, wherein the chemical from the quinolinyloxyacetate family of chemicals is cloquintocet mexyl.

14. The method of claim 10, wherein the weight ratio of (a) to (b) is from 2:1 to 1:32.

15. The method of claim 10, wherein the weight ratio of (a) to (b) is from 1:1 to 1:4.

16. The method of claim 10, further comprising an agriculturally acceptable adjuvant or carrier.

17. The method of claim 10, wherein the rice is direct-seeded, water-seeded, or transplanted rice.

18. The method of claim 10, wherein the undesirable vegetation is immature.

19. The method of claim 10, wherein the (a) and (b) are applied to water.

20. The method of claim 19, wherein the water is part of a flooded rice paddy.

21. The method of claim 10, wherein the (a) and (b) are applied pre-emergently to the weed or the crop.

22. The method of claim 10, wherein the (a) and (b) are applied post-emergently to the weed or the crop.

23. The method of claim 10, wherein the rice is glyphosate, glufosinate, dicamba, phenoxy auxin, pyridyloxy auxin, aryloxyphenoxypropionate, acetyl CoA carboxylase (ACCase) inhibitor, imidazolinone, acetolactate synthase (ALS) inhibitor, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitor, protoporphyrinogen oxidase (PPO) inhibitor, triazine, or bromoxynil tolerant.

24. The method of claim 23, wherein the rice possesses multiple or stacked traits conferring tolerance to multiple chemistries and/or multiple modes of action.

Description

EXAMPLES

Example I: Evaluation of Postemergence Foliar-Applied Herbicides and Safeners in Direct-Seeded Rice

(1) Seeds or nutlets of the desired test plant species were planted in a soil matrix prepared by mixing a loam or sandy loam soil (e.g., 28.6 percent silt, 18.8 percent clay, and 52.6 percent sand, with a pH of about 5.8 and an organic matter content of about 1.8 percent) and calcareous grit in an 80 to 20 ratio. The soil matrix was contained in plastic pots with a surface area of 84.6 square centimeters (cm.sup.2). When required to ensure good germination and healthy plants, a fungicide treatment and/or other chemical or physical treatment was applied. The plants were grown for 8-22 days in a greenhouse with an approximate 14 hr photoperiod which was maintained at about 29 C. during the day and 26 C. during the night. Nutrients (Peters Excel 15-5-15 5-Ca 2-Mg and iron chelate) were applied in the irrigation solution as needed and water was added on a regular basis. Supplemental lighting was provided with overhead metal halide 1000-Watt lamps as necessary. The plants were employed for testing when they reached the second or third true leaf stage.

(2) Treatments consisted of the acid or esters of 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)pyridine-2-carboxylic acid (compound A) and various safener components alone and in combination. Forms of compound A were applied on an acid equivalent basis. Safener components were applied on an active ingredient or acid equivalent basis depending on the compound.

(3) Forms of compound A (compound of formula I) tested include:

(4) ##STR00028##

(5) Treatment requirements were calculated based upon the rates being tested, the concentration of active ingredient or acid equivalent in the formulation, and a 12 mL application volume at a rate of 187 L/ha.

(6) For treatments comprised of formulated compounds, measured amounts of compounds were placed individually in 25 mL glass vials and diluted in a volume of 1.25% (v/v) Agri-dex crop oil concentrated to obtain 12 stock solutions. If a test compound did not dissolve readily, the mixture was warmed and/or sonicated. Application solutions were prepared by adding an appropriate amount of each stock solution (e.g., 1 mL) and diluted to the appropriate final concentrations with the addition of 10 mL of an aqueous mixture of 1.25% (v/v) Agri-dex crop oil concentrate so that the final spray solutions contained 1.25% (v/v) Agri-dex crop oil concentrate.

(7) For treatments comprised of technical compounds, weighed amounts were placed individually in 25 mL glass vials and dissolved in a volume of 97:3 v/v acetone/DMSO to obtain 12 stock solutions. If a test compound did not dissolve readily, the mixture was warmed and/or sonicated. Application solutions were prepared by adding an appropriate amount of each stock solution (e.g., 1 mL) and diluted to the appropriate final concentrations with the addition of 10 mL of an aqueous mixture of 1.5% (v/v) Agri-dex crop oil concentrate so that the final spray solutions contained 1.25% (v/v) Agri-dex crop oil concentrate. When technical materials were used, the concentrated stock solutions were added to the spray solutions so that the final acetone and DMSO concentrations of the application solutions were 16.2% and 0.5%, respectively.

(8) For treatments comprised of formulated and technical compounds, weighed amounts of the technical materials were placed individually in 25 mL glass vials and dissolved in a volume of 97:3 v/v acetone/DMSO to obtain 12 stock solutions, and measured amounts of the formulated compounds were placed individually in 25 mL glass vials and diluted in a volume of 1.5% (v/v) Agri-dex crop oil concentrate or water to obtain 12 stock solutions. If a test compound did not dissolve readily, the mixture was warmed and/or sonicated. Application solutions were prepared by adding an appropriate amount of each stock solution (e.g., 1 mL) and diluted to the appropriate final concentrations with the addition of an appropriate amount of an aqueous mixture of 1.5% (v/v) Agri-dex crop oil concentrate so that the final spray solutions contained 1.25% (v/v) Agri-dex crop oil concentrate. When required, additional water and/or 97:3 v/v acetone/DMSO was added to individual application solutions so that the final acetone and DMSO concentrations of the application solutions being compared were 8.1% and 0.25%, respectively.

(9) All stock solutions and applications solutions were visually inspected for compound compatibility prior to application. Spray solutions were applied to the plant material with an overhead Mandel track sprayer equipped with a 8002E nozzles calibrated to deliver 187 L/ha over an application area of 0.503 m.sup.2 at a spray height of 18 to 20 inches (46 to 50 cm) above average plant canopy height. Control plants were sprayed in the same manner with the solvent blank.

(10) The treated plants and control plants were placed in a greenhouse as described above and watered by sub-irrigation to prevent wash-off of the test compounds. After approximately 3 weeks, the condition of the test plants as compared with that of the untreated plants was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury or growth inhibition and 100 corresponds to complete kill.

(11) Some of the safener-herbicide combinations tested, application rates and ratios employed, plant species tested, and results are given in Tables 1-15. The results demonstrate the utility of Compound I acid and benzyl ester as post-emergence treatments in seeded rice, with increased tolerance of rice to Compound I benzyl ester in comparison to Compound I acid, and significant ECHCG weed control activity at rates safe to rice. In the Tables, DAA=Days After Application; ECHCG=Echinochloa crus-galli; NT=not tested; and ORYSA=Orysa sativa, Rice.

(12) TABLE-US-00001 TABLE 1 Safening Activity in Rice (Cloquintocet-mexyl) Visual Injury (%) - 21 DAA Cloquintocet- ORYSA- ORYSA- ORYSA- Compound A mexyl Herbicide to Neptune Wells Clearfield 171 g ae/ha g ai/ha safener ratio Obs Exp Obs Exp Obs Exp Acid - 70 0 40 12 22 Benzyl - 70 0 5 0 0 0 70 0 0 0 0 140 0 0 0 0 280 0 0 Acid -70 70 1 to 1 17 40 3 12 8 22 Acid - 70 140 1 to 2 17 40 0 12 3 22 Acid - 70 280 1 to 4 10 40 0 12 3 22 Benzyl -70 70 1 to 1 3 5 0 0 0 0 Benzyl -70 140 1 to 2 3 5 0 0 0 0 Benzyl -70 280 1 to 4 0 5 0 0 0 0

(13) TABLE-US-00002 TABLE 2 Safening Activity in Rice (Daimuron) Visual Injury (%) - 21 DAA ORYSA- ORYSA- ORYSA- Compound A Daimuron Herbicide to Neptune Wells Clearfield 171 g ae/ha g ai/ha safener ratio Obs Exp Obs Exp Obs Exp Acid - 70 0 40 12 22 Benzyl -70 0 5 0 0 0 70 0 0 0 0 140 0 0 0 0 280 0 0 Acid - 70 70 1 to 1 35 40 3 12 17 22 Acid - 70 140 1 to 2 37 40 3 12 15 22 Acid - 70 280 1 to 4 22 40 7 12 20 22 Benzyl - 70 70 1 to 1 8 5 3 0 0 0 Benzyl - 70 140 1 to 2 20 5 0 0 0 0 Benzyl - 70 280 1 to 4 15 5 0 0 0 0

(14) TABLE-US-00003 TABLE 3 Safening Activity in Rice (Diclormid) Visual Injury (%) - 20 DAA Compound Herbicide ORYSA- A Dichlormid to safener Clearfield 171 ECHCG g ae/ha g ai/ha ratio Obs Exp Obs Exp Acid - 140 0 43 98 Benzyl - 140 0 13 98 0 140 0 NT 0 280 0 0 Acid - 140 140 1 to 1 63 43 99 NT Acid - 140 280 1 to 2 55 43 99 98 Benzyl - 140 140 1 to 1 12 13 99 NT Benzyl - 140 280 1 to 2 8 13 98 98

(15) TABLE-US-00004 TABLE 4 Safening Activity in Rice (Dimepiperate) Visual Injury (%) - 20 DAA Compound Herbicide ORYSA- A Dimepiperate to safener Clearfield 171 ECHCG g ae/ha g ai/ha ratio Obs Exp Obs Exp Acid - 140 0 43 98 Benzyl - 140 0 13 98 0 140 7 0 0 280 3 0 Acid - 140 140 1 to 1 60 47 98 98 Acid - 140 280 1 to 2 65 45 99 98 Benzyl - 140 140 1 to 1 7 19 96 98 Benzyl - 140 280 1 to 2 20 16 97 98

(16) TABLE-US-00005 TABLE 5 Safening Activity in Rice (Furilazole) Visual Injury (%) - 20 DAA Compound Herbicide ORYSA- A Furilazole to safener Clearfield 171 ECHCG g ae/ha g ai/ha ratio Obs Exp Obs Exp Acid - 140 0 38 96 Methyl - 140 0 12 98 Benzyl - 140 0 15 99 0 140 0 0 0 280 0 0 Acid - 140 140 1 to 1 30 38 99 96 Acid - 140 280 1 to 2 20 38 99 96 Methyl - 140 140 1 to 1 0 12 93 98 Methyl - 140 280 1 to 2 0 12 95 98 Benzyl - 140 140 1 to 1 17 15 99 99 Benzyl - 140 280 1 to 2 20 15 100 99

(17) TABLE-US-00006 TABLE 6 Safening Activity in Rice (Furilazole) Visual Injury (%) - 20 DAA Compound Herbicide ORYSA- A Furilazole to safener Clearfield 171 ECHCG g ae/ha g ai/ha ratio Obs Exp Obs Exp Acid - 140 0 43 98 Benzyl - 140 0 13 98 0 140 7 0 0 280 18 0 Acid - 140 140 1 to 1 57 47 96 98 Acid - 140 280 1 to 2 55 54 95 98 Benzyl - 140 140 1 to 1 12 19 96 98 Benzyl - 140 280 1 to 2 8 29 95 98

(18) TABLE-US-00007 TABLE 7 Safening Activity in Rice (Isoxadifen-ethyl) Visual Injury (%) - 21 DAA Isoxadifen- ORYSA- ORYSA- ORYSA- Compound A ethyl Herbicide to Neptune Wells Clearfield 171 g ae/ha g ai/ha safener ratio Obs Exp Obs Exp Obs Exp Acid - 70 0 40 12 22 Benzyl - 70 0 5 0 0 0 70 0 0 0 0 140 0 0 0 0 280 0 0 Acid - 70 70 1 to 1 0 40 0 12 0 22 Acid - 70 140 1 to 2 0 40 0 12 0 22 Acid - 70 280 1 to 4 0 40 3 12 0 22 Benzyl - 70 70 1 to 1 0 5 0 0 0 0 Benzyl - 70 140 1 to 2 0 5 0 0 0 0 Benzyl - 70 280 1 to 4 0 5 0 0 0 0

(19) TABLE-US-00008 TABLE 8 Safening Activity in Rice (Mefenpyr-diethyl) Visual Injury (%) - 21 DAA Mefenpyr- ORYSA- ORYSA- ORYSA- Compound A diethyl Herbicide to Neptune Wells Clearfied 171 g ae/ha g ai/ha safener ratio Obs Exp Obs Exp Obs Exp Acid - 70 0 40 12 22 Benzyl - 70 0 5 0 0 0 70 0 0 3 0 140 0 0 0 0 280 3 0 Acid - 70 70 1 to 1 37 40 7 12 22 24 Acid - 70 140 1 to 2 33 40 12 12 15 22 Acid - 70 280 1 to 4 25 42 10 12 18 22 Benzyl - 70 70 1 to 1 23 5 12 0 12 3 Benzyl - 70 140 1 to 2 25 5 10 0 7 0 Benzyl - 70 280 1 to 4 18 8 3 0 7 0

(20) TABLE-US-00009 TABLE 9 Safening Activity in Rice (Naphthalic anhydride) Visual Injury (%) - 20 DAA Compound Naphthalic Herbicide ORYSA- A anhydride to safener Clearfield 171 ECHCG g ae/ha g ai/ha ratio Obs Exp Obs Exp Acid - 140 0 38 96 Methyl - 140 0 12 98 Benzyl - 140 0 15 99 0 140 0 0 0 280 3 0 Acid - 140 140 1 to 1 38 38 98 96 Acid - 140 280 1 to 2 20 40 99 96 Methyl - 140 140 1 to 1 8 12 98 98 Methyl - 140 280 1 to 2 8 15 99 98 Benzyl - 140 140 1 to 1 10 15 99 99 Benzyl - 140 280 1 to 2 12 18 98 99

(21) TABLE-US-00010 TABLE 10 Safening Activity in Rice (Naphthalic anhydride) Visual Injury (%) - 20 DAA Compound Naphthalic Herbicide ORYSA- A anhydride to safener Clearfield 171 ECHCG g ae/ha g ai/ha ratio Obs Exp Obs Exp Acid - 140 0 43 98 Benzyl - 140 0 13 98 0 140 0 0 0 280 0 0 Acid - 140 140 1 to 1 48 43 96 98 Acid - 140 280 1 to 2 58 43 95 98 Benzyl - 140 140 1 to 1 13 13 95 98 Benzyl - 140 280 1 to 2 3 13 98 98

(22) TABLE-US-00011 TABLE 11 Safening Activity in Rice (Dicyclonon) Visual Injury (%) - 20 DAA Compound Herbicide ORYSA- A Dicyclonon to safener Clearfield 171 ECHCG g ae/ha g ai/ha ratio Obs Exp Obs Exp Acid - 140 0 38 96 Methyl - 140 0 12 98 Benzyl - 140 0 15 99 0 140 0 NT 0 280 0 3 Acid - 140 140 1 to 1 57 38 99 NT Acid - 140 280 1 to 2 38 38 99 96 Methyl - 140 140 1 to 1 3 12 98 NT Methyl - 140 280 1 to 2 5 12 98 98 Benzyl - 140 140 1 to 1 18 15 98 NT Benzyl - 140 280 1 to 2 17 15 98 99

(23) TABLE-US-00012 TABLE 12 Safening Activity in Rice (Dicyclonon) Visual Injury (%) - 20 DAA Compound Herbicide ORYSA- A Dicyclonon to safener Clearfield 171 ECHCG g ae/ha g ai/ha ratio Obs Exp Obs Exp Acid - 140 0 43 98 Benzyl - 140 0 13 98 0 140 0 NT 0 280 3 0 Acid - 140 140 1 to 1 45 43 98 NT Acid - 140 280 1 to 2 57 45 99 98 Benzyl - 140 140 1 to 1 5 13 98 NT Benzyl - 140 280 1 to 2 8 16 95 98

(24) TABLE-US-00013 TABLE 13 Safening Activity in Rice (Fenclorim) Visual Injury (%) - 20 DAA Compound Herbicide ORYSA- A Fenclorim to safener Clearfield 171 ECHCG g ae/ha g ai/ha ratio Obs Exp Obs Exp Acid - 140 0 38 96 Methyl - 140 0 12 98 Benzyl - 140 0 15 99 0 140 0 0 0 280 0 0 Acid - 140 140 1 to 1 22 38 98 96 Acid - 140 280 1 to 2 20 38 99 96 Methyl - 140 140 1 to 1 7 12 98 98 Methyl - 140 280 1 to 2 0 12 95 98 Benzyl - 140 140 1 to 1 10 15 99 99 Benzyl - 140 280 1 to 2 5 15 99 99

(25) TABLE-US-00014 TABLE 14 Safening Activity in Rice (Fenclorim) Visual Injury (%) - 20 DAA Compound Herbicide ORYSA- A Fenclorim to safener Clearfield 171 ECHCG g ae/ha g ai/ha ratio Obs Exp Obs Exp Acid - 140 0 43 98 Benzyl - 140 0 13 98 0 140 0 0 0 280 0 0 Acid - 140 140 1 to 1 58 43 98 98 Acid - 140 280 1 to 2 32 43 98 98 Benzyl - 140 140 1 to 1 3 13 95 98 Benzyl - 140 280 1 to 2 0 13 98 98

(26) TABLE-US-00015 TABLE 15 Post-emergence Foliar Activity of Compound A Mean Visual Injury (%) - 20-22 DAA Compound A ORYSA ORYSA g ae/ha Clearfield 171 Wells ECHCG Acid - 32 24 12 96 Acid - 16 11 7 95 Acid - 8 2 0 91 Acid - 4 0 0 81 Acid - 2 0 0 57 Benzyl - 32 3 3 96 Benzyl - 16 8 3 95 Benzyl - 8 0 0 94 Benzyl - 4 0 0 91 Benzyl - 2 0 0 63 0 0 0 0

Example II: Evaluation of In-Water Applied Herbicides and Safeners in Transplanted Paddy Rice

(27) Weed seeds or nutlets of the desired test plant species were planted in puddled soil (mud) prepared by mixing a shredded, non-sterilized mineral soil (50.5 percent silt, 25.5 percent clay, and 24 percent sand, with a pH of about 7.6 and an organic matter content of about 2.9 percent) and water at a 1:1 volumetric ratio. The prepared mud was dispensed in 365 mL aliquots into 16-ounce (oz.) non-perforated plastic pots with a surface area of 86.59 square centimeters (cm.sup.2) leaving a headspace of 3 centimeters (cm) in each pot. Rice seeds were planted in Sun Gro MetroMix 306 planting mixture, which typically has a pH of 6.0 to 6.8 and an organic matter content of about 30 percent, in plastic plug trays. Seedlings at the second or third leaf stage of growth were transplanted into 860 mL of mud contained in 32-oz. non-perforated plastic pots with a surface area of 86.59 cm.sup.2 4 days prior to herbicide application. The paddy was created by filling the headspace of the pots with 2.5 to 3 cm of water. When required to ensure good germination and healthy plants, a fungicide treatment and/or other chemical or physical treatment was applied. The plants were grown for 4-22 days in a greenhouse with an approximate 14 h photoperiod which was maintained at about 29C during the day and about 26 C. during the night. Nutrients were added as Osmocote (17:6:10, N:P:K+minor nutrients) at 2 g per 16-oz. pot and 4 g per 32-oz. pot. Water was added on a regular basis to maintain the paddy flood, and supplemental lighting was provided with overhead metal halide 1000-Watt lamps as necessary. The plants were employed for testing when they reached the second or third true leaf stage.

(28) Treatments consisted of the acid or esters of 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)pyridine-2-carboxylic acid (compound A) and various safeners alone and in combination. Forms of compound A were applied on an acid equivalent basis. Safener components were applied on an active ingredient or acid equivalent basis depending on the compound.

(29) Forms of compound A (compound of formula I) tested include:

(30) ##STR00029##

(31) Treatment requirements for each compound or herbicidal component were calculated based upon the rates being tested, the concentration of active ingredient or acid equivalent in the formulation, an application volume of 2 mL per component per pot, and an application area of 86.59 cm.sup.2 per pot.

(32) For formulated compounds, a measured amount was placed in an individual 100 or 200 mL glass vial and was dissolved in a volume of 1.25% (v/v) Agri-Dex crop oil concentrate to obtain application solutions. If the test compound did not dissolve readily, the mixture was warmed and/or sonicated.

(33) For technical grade compounds, a weighed amount can be placed in an individual 100 to 200 mL glass vial and dissolved in a volume of acetone to obtain concentrated stock solutions. If the test compound does not dissolve readily, the mixture can be warmed and/or sonicated. The concentrated stock solutions obtained can be diluted with an equivalent volume of an aqueous mixture containing 2.5% (v/v) crop oil concentrate so that the final application solutions contain 1.25% (v/v) crop oil concentrate.

(34) Applications were made by injecting with a pipetter appropriate amounts of the application solutions, individually and sequentially, into the aqueous layer of the paddy. Control plants were treated in the same manner with the solvent blank. Applications were made so that all treated plant material received the same concentrations of acetone and crop oil concentrate.

(35) The treated plants and control plants were placed in a greenhouse as described above and water was added as needed to maintain a paddy flood. After approximately 3 weeks the condition of the test plants as compared with that of the untreated plants was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury or growth inhibition and 100 corresponds to complete kill.

(36) Colby's equation was used to determine the herbicidal effects expected from the mixtures (Colby, S. R. 1967. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 15:20-22.).

(37) The following equation was used to calculate the expected activity of mixtures containing two active ingredients, A and B:
Expected=A+B(AB/100)

(38) A=observed efficacy of active ingredient A at the same concentration as used in the mixture.

(39) B=observed efficacy of active ingredient B at the same concentration as used in the mixture.

(40) Some of the safener-herbicide combinations tested, application rates and ratios employed, plant species tested, and results are given in Tables 16-17. The results demonstrate the utility of Compound A acid and benzyl ester as in-water treatments in water-seeded rice and flooded transplanted rice, with significant ECHCG weed control activity at rates safe to rice. Based on the relative rice and barnyardgrass responses to Compound A acid and Compound Abenzyl ester, Compound A benzyl ester showed an improved selectivity margin over that of the acid. In the Tables, DAA=Days After Application; ECHCG=Echinochloa crus-galli; NT=not tested; and ORYSA=Orysa sativa, Rice.

(41) TABLE-US-00016 TABLE 16 Safening Activity in Rice (Fenclorim) Isoxadifen- Herbicide Visual Injury (%) - 21 DAA Compound A ethyl to safener ORYSA - M202 g ae/ha g ai/ha ratio Obs Exp Methyl - 140 0 17.5 0 140 0 0 280 0 0 560 0 Methyl - 140 140 1 to 1 0 17.5 Methyl - 140 280 1 to 2 0 17.5 Methyl - 140 560 1 to 4 0 17.5

(42) TABLE-US-00017 TABLE 17 In-Water Applied Activity of Compound A Mean Visual Injury (%) - 21 DAA Compound A* ORYSA - ORYSA - g ae/ha M202 Wells ECHCG Acid - 140 25 8 95 Acid - 70 3 0 63 Acid - 35 0 0 10 Acid - 17.5 0 0 0 Acid - 8.75 0 0 0 Benzyl - 140 22 15 100 Benzyl - 70 0 0 100 Benzyl - 35 0 3 81 Benzyl - 17.5 0 0 43 Benzyl - 8.75 0 0 23 0 0 0 0

(43) The present invention is not limited in scope by the embodiments disclosed herein which are intended as illustrations of a few aspects of the invention and any embodiments which are functionally equivalent are within the scope of this invention. Various modifications of the compositions and methods in addition to those shown and described herein will become apparent to those skilled in the art and are intended to fall within the scope of the appended claims. Further, while only certain representative combinations of the composition components and method steps disclosed herein are specifically discussed in the embodiments above, other combinations of the composition components and method steps will become apparent to those skilled in the art and also are intended to fall within the scope of the appended claims. Thus a combination of components or method steps may be explicitly mentioned herein; however, other combinations of components and method steps are included, even though not explicitly stated. The term comprising and variations thereof as used herein is used synonymously with the term including and variations thereof and are open, non-limiting terms.