US00945.1776B2 (12) United States Patent (10) Patent No.: US 9.451,776 B2 Mann et al. (45) Date of Patent: *Sep. 27, 2016 (54) HERBICIDAL COMPOSITIONS (58) Field of Classification Search COMPRISING FLUROXYPYR AND None FLUMETSULAM See application file for complete search history. (71) Applicant: Dow AgroSciences LLC, Indianapolis, (56) References Cited IN (US) U.S. PATENT DOCUMENTS (72) Inventors: Richard K. Mann, Franklin, IN (US); 6.294,503 B1* 9/2001 Gupta .................... AON 43.84 Andrea C. McVeigh-Nelson, 504,225 Indianapolis, IN (US); Amy Gwinn, 2009/0215797 A1 8/2009 Hopkins Indianapolis, IN (US) 2011/0203017 A1 8/2011 Wright (73) Assignee: Dow AgroSciences LLC, Indianapolis, FOREIGN PATENT DOCUMENTS IN (US) CN 102283220 * 12/2011 (*) Notice: Subject to any disclaimer, the term of this EP O512737 A1 11, 1992 patent is extended or adjusted under 35 OTHER PUBLICATIONS U.S.C. 154(b) by 0 days. Extended European Search Report under PCT/US2013076494, EP This patent is Subject to a terminal dis Application No. 13864104.8, Mail date Apr. 19, 2016. claimer. * cited by examiner (21) Appl. No.: 14/853,678 Primary Examiner — Alton Pryor (22) Filed: Sep. 14, 2015 (74) Attorney, Agent, or Firm — Michael J. Terapane: Meunier Carlin & Curfman, LLC (65) Prior Publication Data (57) ABSTRACT US 2016/OOOOO82 A1 Jan. 7, 2016 Herbicidal compositions containing (a) fluroxypyr or an Related U.S. Application Data agriculturally acceptable salt or ester thereof and (b) flu metSulam or an agriculturally acceptable salt thereof provide (63) Continuation of application No. 14/135,048, filed on synergistic herbicidal control of undesirable vegetation, e.g., Dec. 19, 2013, now Pat. No. 9,131,696. in wheat, barley, oats, rye, Sugarcane, rice, sorghum, corn/ (60) Provisional application No. 61/740.248, filed on Dec. maize, soybean, rice, Sunflower, canolafoilseed rape, Sugar 20, 2012. cane, Sorghum, cotton, pastures, grasslands, rangelands, fallowland, turf, tree and vine orchards, industrial vegetation (51) Int. C. management and rights-of-way; or crops comprising an AOIN 43/60 (2006.01) aad-12 gene. Also provided herein are methods of using AOIN 43/90 (2006.01) herbicidal compositions containing (a) fluroxypyr or an AOIN 43/40 (2006.01) agriculturally acceptable salt or ester thereof and (b) flu (52) U.S. C. metSulam or an agriculturally acceptable salt thereof. CPC ............... A0IN 43/90 (2013.01); A0IN 43/40 (2013.01) 12 Claims, No Drawings US 9,451,776 B2 1. 2 HERBICIDAL COMPOSITIONS described herein (e.g., soybean or cotton crops comprising COMPRISING FLUROXYPYR AND anaad-12 gene, or crops comprising an aad-12 gene that are FLUMETSULAM tolerant to ALS herbicides). In some embodiments, the compositions or methods described herein are useful for CROSS REFERENCE TO RELATED weed control in crops that are tolerant to ALS mode-of APPLICATIONS action herbicides (e.g., flumetSulam), including but not limited to, crops comprising an aad-12 gene. In some This application is a continuation of U.S. application Ser. embodiments, the compositions or methods described herein No. 14/135,048, filed on Dec. 19, 2013, and claims the are useful for weed control in crops that are normally benefit of U.S. Provisional Patent Application Ser. No. 10 tolerant to fluroxypyr and flumetSulam. In some embodi 61/740,248, filed Dec. 20, 2012, the disclosure of which are ments, the compositions or methods described herein are expressly incorporated herein by reference. useful for weed control in non-crop situations. In one embodiment, auxinic herbicide-resistance genes FIELD may be employed with the plants or crops being treated by 15 a composition or in a method described herein. The plants or Provided herein are synergistic herbicidal compositions crops may be transformed to contain one or more of a family comprising (a) fluroxypyr or a salt or ester thereof and (b) of resistance genes (designated aad) that code for an flumetsulam or a salt thereof. Also provided herein are enzyme, aryloxyalkanoate dioxygenase (AAD), which then methods of controlling undesirable vegetation comprising inactivates an auxin herbicide in planta. Such herbicide applying (a) fluroxypyr or a salt or ester thereof and (b) resistance may be conferred by aad-1 (originally from flumetsulam or a salt thereof. Sphingobium herbicidovorans), aad-12 (originally from Delfia acidovorans), and aad-13 genes as disclosed in U.S. BACKGROUND Pat. No. 7,838,733, U.S. Pat. No. 8,283,522, and U.S. Pat. No. 8,278.505, respectively; these publications are incorpo The protection of crops from weeds and other vegetation 25 rated herein by reference. The aad-12 gene (originally from which inhibit crop growth is a constantly recurring problem Delfia acidovorans) encodes the aryloxyalkanoate dioxy in agriculture. To help combat this problem, researchers in genase (AAD-12) protein. The trait confers tolerance to the field of synthetic chemistry have produced an extensive 2,4-dichlorophenoxyacetic acid (2,4-D), for example, and to variety of chemicals and chemical formulations effective in pyridyloxyacetate herbicides. The aad-12 gene, itself, for the control of such unwanted growth. Chemical herbicides 30 herbicide tolerance in plants is disclosed in, e.g., U.S. Pat. of many types have been disclosed in the literature and a No. 8,283,522. large number are in commercial use. However, there remains a need for additional compositions and methods that are DETAILED DESCRIPTION effective in controlling undesirable vegetation. 35 Definitions SUMMARY As used herein, unless otherwise specified, fluroxypyr has Provided herein are synergistic herbicidal compositions the following structure: which unexpectedly provide increased control of undesir able vegetation comprising an herbicidally effective amount 40 of (a) fluroxypyr or an agriculturally acceptable salt or ester NH2 thereof and (b) flumetSulam or an agriculturally acceptable salt thereof. The compositions may also contain an agricul C N C turally acceptable adjuvant or carrier. Provided herein are also methods of controlling undesir 45 2 OH. able vegetation comprising applying (a) fluroxypyr or an F N r agriculturally acceptable salt or ester thereof and (b) flu O metSulam or an agriculturally acceptable salt thereof. In some embodiments, the compositions or methods described herein provide synergistic weed control. In some 50 In some embodiments, as used herein, unless otherwise embodiments, the compositions or methods described herein specified, a fluroxypyr derivative such as fluroxypyr or a salt provide Safening from crop injury. In some embodiments, or ester thereof has the following structure: the compositions or methods described herein are for foliar applications to a crop, including but not limited to, corn/ (I) maize, wheat, barley, Soybean, rice, Sunflower, canolafoil 55 NH2 Seed rape, Sugarcane, Sorghum, oats, rye, and cotton crops. In some embodiments, the compositions or methods C C described herein are for use in crops comprising an aad-12 gene (e.g., aad-12 soybean or cotton crops, or other aceto r 2 OR, lactate synthase (ALS) resistant crops comprising an aad-12 60 gene, e.g., ALS broadleaf or grass resistant crops comprising F N r anaad-12 gene). See, e.g., U.S. Pat. No. 8,283,522; U.S. Pat. O No. 8,460,891; US 2012/0110688; US 2012/0277104; all of which are incorporated herein by reference in their entire wherein R is hydrogen, a counterion of carboxylic acid, or ties. In some embodiments, the compositions or methods 65 an optionally Substituted alkyl, heteroalkyl, cycloalkyl, het described herein are useful for control of a broad spectrum erocyclyl, aryl, or heteroaryl; or a salt thereof. In some of broadleaf and ALS resistant broadleaf weeds in crops embodiments, R is H. In some embodiments, R is a coun US 9,451,776 B2 3 4 terion of the carboxylic acid (e.g., a positively charged limited to applications to the vegetation or locus thereof, moiety to form an agriculturally acceptable salt of the e.g., application to the area adjacent to the vegetation, as carboxylic acid). In some embodiments, R is 1-methylheptyl well as pre-emergence, post-emergence, foliar, and in-water or meptyl (i.e., —CH(CH)—(CH2)5 CH), and the cor applications. responding fluroxypyr derivative may be referred to as 5 As used herein, plants and vegetation include, but are not fluroxypyr-meptyl. In some embodiments, R is 2-butoxy-1- limited to, germinant seeds, emerging seedlings, plants methylethyl or butometyl (i.e., —CH(CH)—CH2—O— emerging from vegetative propagules, immature vegetation, (CH) CH), and the corresponding fluroxypyr derivative and established vegetation. may be referred to as fluroxypyr-butometyl. Fluroxypyr can As used herein, agriculturally acceptable salts and esters be identified by a chemical name: 4-amino-3,5-dichloro-6- 10 refer to salts and esters that exhibit herbicidal activity or that fluoro-2-pyridyloxyacetic acid, or a salt or ester thereof. For are or can be converted in plants, water, or soil to the example, fluroxypyr-meptyl can be identified as: (RS)-1- referenced herbicide. Exemplary agriculturally acceptable methylheptyl 4-amino-3,5-dichloro-6-fluoro-2-pyridyloxy esters are those that are or can by hydrolyzed, oxidized, acetate; and fluroxypyr-butometyl can be identified as: (RS)- metabolized, or otherwise converted, e.g., in plants, water, 15 or soil, to the corresponding carboxylic acid which, depend 2-butoxy-1-methylethyl 4-amino-3,5-dichloro-6-fluoro-2- ing upon the pH, may be in the dissociated or undissociated pyridyloxyacetate. form. As used herein, unless otherwise specified, flumetSulam Exemplary salts include those derived from alkali or has the following structure: alkaline earth metals and those derived from ammonia and 2O amines. Exemplary cations include Sodium, potassium, mag (II) nesium, and aminium cations of the formula: wherein R', R, R and R each independently represents 21 25 hydrogen or C-C alkyl, C-C alkenyl, or C-C alky nyl, each of which is optionally substituted by one or more hydroxy, C-C alkoxy, C-C alkylthio or phenyl groups, CI)--(Y provided that R.