US00945.1773B2
(12) United States Patent (10) Patent No.: US 9.451,773 B2 Fefer et al. (45) Date of Patent: *Sep. 27, 2016
(54) PARAFFINIC OIL-IN-WATER EMULSIONS 359: A 3. 12: R et al. FOR CONTROLLING INFECTION OF CROP 4,002,628- - A 1/1977 Benefieltledge et al. PLANTS BY FUNGAL PATHOGENS 4,015,970 A 4, 1977 Hennart 4,041,164 A 8, 1977 Albrecht et al. (75) Inventors: Michael Fefer, Whitby (CA); Jun Liu, 4,094,845. A 6/1978 De Long 4,124,720 A 11/1978 Wenmaekers Oakville (CA) 4.243,405 A 1/1981 Balasubramanyan et al. (73) Assignee: Suncor Energy Inc., Calgary, Alberta 4,584,0134,431,554 A 4,2, 19841986 BryhnerB (CA) 4,618,360 A 10, 1986 Brunner 4,693,745 A 9, 1987 Brunner (*) Notice: Subject to any disclaimer, the term of this is: A 13. Es al. patent is extended or adjusted under 35 4,737,515- I A 4, 1988 HallenbachZego et al. et al. U.S.C. 154(b) by 0 days. 4,761,423. A 8/1988 Szego et al. 4,826,863. A 5, 1989 S tal. This patent is Subject to a terminal dis- 4,834,908 A 5, 1989 E. claimer. 4,853,026 A 8, 1989 Frisch et al. 4.902.333 A 2/1990 Quimby, Jr. (21) Appl. No.: 14/123,716 4,971,840 A 11/1990 Boho et al. 5,084,087 A 1/1992 HaZen et al. 5,102.442 A 4, 1992 HaZen et al. (22) PCT Filed: Jun. 4, 2012 5,137,726 A 8/1992 Ogawa 5,178,795 A 1/1993 Roberts (86). PCT No.: PCT/CA2O12/OSO376 5,229,356 A 7, 1993 Tocker 5,238,604 A 8, 1993 HaZen et al. S 371 (c)(1), 5,308,827. A 5/1994 Sakamoto et al. (2), (4) Date: Dec. 3, 2013 5.330,995 A 7/1994 Eicken et al. (87) PCT Pub. No.: WO2012/162846 (Continued) PCT Pub. Date: Dec. 6, 2012 FOREIGN PATENT DOCUMENTS
(65) Prior PublicationO O Data CA 2069311964482 4f19913, 1975 US 2014/O107070 A1 Apr. 17, 2014 (Continued) OTHER PUBLICATIONS Related U.S. Application Data Iowa State University. "Fungicides: Triazoles.” (c) 2006. Available (60) Provisional application No. 61/493,118, filed on Jun. from: < http://www.ipm.iastate.edu/ipm/icm/2006/5-30/fungicides. 3, 2011, provisional application No. 61/496,500, filed htm> * On Jun. 13, 2011 The Seed Site. "Monocots and Dicots.” (c) Feb. 24, 2010. Available • - s from: < Available from: < http://web.archive.org/web/ 20100224074428/http://theseedsite.co.uk/monocothtml >.* (51) Int. Cl. Iowa State University. "Fungicides: Qol Fungicides.” (c) 2006. AOIN 55/00 (2006.01) Available from: < http://www.ipm.iastate.edu/ipm.icm/2006/5-22/ AOIN 43/56 (2006.01) fungicides.html D.* AOIN 25/04 (2006.01) t enomyl-ResistantWE. R Guignardiaal E. citricarpa YSE on Valencia for 6AOranges ofin 39ty 2%, R South Africa.” Plant Disease. (2003), vol. 87, No. 7, pp. 784-788.* ( .01) Material Data Safety Sheet. “Sunspray 6E.” (c) Jun. 1, 2009.* (52) U.S. Cl. ( ) The National Turfgrass Research Initiative. (c) Apr. 2003.* CPC ...... AOIN 43/56 (2013.O1): 40 IN 25/04 (2013.01); A0IN 27/00 (2013.01);s A0IN (Continued)Cont d 43/653 (2013.01); A0IN 55/00 (2013.01) b1 11 (58) Field of Classification Search Primary Examiner - Noble Jarre CPC ...... AoN 5500 Assistant Examiner John S Kenyon See application file for complete search history. (74) Attorney, Agent, or Firm — Fish & Richardson P.C. (56) References Cited (57) ABSTRACT This disclosure features fungicidal combinations that U.S. PATENT DOCUMENTS include a paraflinic oil and an emulsifier. The combinations 2,714,062 A 7/1955 Lockrey et al. can further include one or more of the following: pigments, 2,786,821 A 3, 1957 Gardner et al. silicone Surfactants, anti-settling agents, conventional fun 2,870,037 A 1/1959 Converse et al. gicides Such as demethylation inhibitors (DMI) and quinone 3,131,119 A 4/1964 Fordyce et al. 3,426,126 A 2f1969 Thorne et al. outside inhibitors (Qol) and water. The fungicidal combina 3,615,799 A 10, 1971 Gannon et al. tions are used for controlling infection of a crop plant by a 3,689,574 A 9/1972 Engelhart fungal pathogen. 3,799,758 A 3, 1974 Franz 3,948,635 A 4, 1976 Vachette et al. 35 Claims, 6 Drawing Sheets US 9.451,773 B2 Page 2
(56) References Cited 2006/02931.88 A1 12/2006 Norton et al. 2007. O184005 A1 8, 2007 Policello et al. U.S. PATENT DOCUMENTS 2007/0197387 A1 8/2007 Polge 2007/0287720 A1 12/2007 Royalty et al. 5,336,661 A 8, 1994 Lucas 2008, OO646O1 A1 3/2008 Casanello et al. 5,352,729 A 10, 1994 Birkhofer et al. 2008/0085832 A1 4/2008 Fefer et al. 5,362,167 A 11/1994 Loftin 2008/O112909 A1 5.2008 Faler et al. 5,393,770 A 2/1995 Grayson 2008. O153702 A1 6/2008 Voeste et al. 5,393,791 A 2, 1995 Roberts 2008. O161367 A1 7/2008 Voeste et al. 5,409,885. A 4, 1995 Derian et al. 2008/0280763 Al 11/2008 Hodge et al. 5,504,054 A 4/1996 Murphy 2008/0293567 A1 11/2008 Birner et al. 5,547,918 A 8, 1996 Newton et al. 2009/0325922 A1 12/2009 Fefer et al. 5,558,806 A 9/1996 Policello et al. 2010, OO16447 A1 1/2010 Fefer 5,580,567 A 12/1996 Roberts 2010/0317527 A1 12/2010 Takeuchi et al. 5,599,768 A 2/1997 Hermansky 2011/0306495 Al 12/2011 Samarajeewa et al. 5,599,804 A 2/1997 Mudge 2012fO245232 A1 9/2012 Bousque et al. 5,643,852 A 7/1997 Lucas et al. 2013,025301.6 A1 9, 2013 Fefer et al. 5,658,851 A 8/1997 Murphy et al. 2013/0303374. A1 11, 2013 Fefer et al. 5,665,672 A 9, 1997 Lucas 2013,0324620 A1 12/2013 Fefer 5,668,086 A 9/1997 Tadayuki et al. 2014/0228218 A1 8, 2014 Fefer et al. 5,703,016 A 12/1997 Magin et al. 2014/0256556 A1 9/2014 Fefer et al. 5,739,371 A 4, 1998 O'Lenick, Jr. 2015,0065475 A1 3/2015 Fefer et al. 5,741,502 A 4, 1998 Roberts 2015/0237869 A1 8, 2015 Fefer 5,919,858 A 7, 1999 Loftin 5,958, 104 A 9, 1999 Nonomura et al. FOREIGN PATENT DOCUMENTS 6,033,647 A 3, 2000 Touzan et al. 6,117,820 A 9, 2000 Cutler et al. 6,146,652. A 1 1/2000 Gore et al. A 3. 29: 6,159,900 A 12/2000 Bieringer et al. CA 2472806 11/2005 6,162,763 A 12/2000 Tateno CA 25O7482 * 11/2005 6,221,811 B1 4/2001 Policello et al. CA 256.2718 4/2008
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FIGURE U.S. Patent Sep. 27, 2016 Sheet 2 of 6 US 9,451,773 B2
FIGURE 2 U.S. Patent Sep. 27, 2016 Sheet 3 of 6 US 9,451,773 B2
FIGURE 3 U.S. Patent Sep. 27, 2016 Sheet 4 of 6 US 9,451,773 B2
FIGURE 4 U.S. Patent Sep. 27, 2016 Sheet S of 6 US 9,451,773 B2
FIGURE 5 U.S. Patent Sep. 27, 2016 Sheet 6 of 6 US 9,451,773 B2
FIGURE 6 US 9,451,773 B2 1. 2 PARAFFINIC OIL-IN-WATEREMULSIONS nance. The rust fungus attacks the parts of the plant which FOR CONTROLLING INFECTION OF CROP are above ground. Spores that land on green wheat plants PLANTS BY FUNGAL PATHOGENS form a pustule that invades the outer layers of the stalk. Where infection has occurred on the stem or leaf, elliptical CROSS REFERENCE TO RELATED blisters or pustules called uredia develop. Infected plants APPLICATIONS produce fewer tillers and set fewer seed. Soybean rust is a disease that primarily affects soybeans This application claims the benefit of U.S. Provisional and other legumes. It is caused by two species of fungi, Application No. 61/493,118, filed Jun. 3, 2011, and U.S. Phakopsora pachyrhizi and Phakopsora meibomiae. Soy Provisional Application No. 61/496,500, filed Jun. 13, 2011, 10 bean rust has been reported in Asia, Australia, Africa, South each of which is incorporated by reference in its entirety. America and North America. Soybean rust is spread by wind-borne spores, which are released in cycles of seven TECHNICAL FIELD days to two weeks. Yield losses can be severe with this disease and losses of 10-80% have been reported. This disclosure features combinations that include a par 15 Multi-pronged approaches are desirable to address the aflinic oil. The combinations can further include (but are not spread of fungal infection. A variety of preventative methods limited to) one or more of the following: one or more may be employed. For example, rust diseases are correlated emulsifiers, one or more pigments, one or more silicone to relatively high moisture. Accordingly, avoidance of over Surfactants, one or more anti-settling agents, one or more head watering at night, using drip irrigation, reducing crop conventional chemical fungicides (e.g., a DMI or a QoI), density, and the use of fans to circulate air flow may serve and water. In some implementations, the combinations can to lower the relative moisture and decrease the severity of be in the form of a single composition (e.g., which is rust infection. contained within a storage pack or a vessel (e.g., a tank) Other strategies may include reducing the area of the plant Suitable for applying the composition to a plant, e.g., crop that the pathogen destroys, or slowing down the spread of plant). Typically, the composition is applied to a plant after 25 the fungus. Fungus-resistant plants may be used to interrupt dilution with water. In other implementations, the combina the disease cycle because many rusts are host-specific. This tions can include two or more separately contained (e.g., approach has proven very Successful in the past for control packaged) compositions, each containing one or more of the of wheat stem rust; however, Ug.99 is currently virulent above-mentioned components. Said compositions can be against most wheat varieties. Currently, there are no com combined and applied to a plant typically after dilution with 30 mercial Soybean varieties with resistance to Soybean rust. water, or each composition can be applied separately to the Accordingly, soybean rust is managed with fungicides. same plant either simultaneously or sequentially, and typi In large agricultural operations, conventional synthetic cally after dilution with water. This disclosure also features fungicides can be used to control fungal pathogens. De methods of using the combinations for controlling infection methylation inhibitors (DMI) such tebuconazole (FolicurTM. of a crop plant by a fungal pathogen as well as methods of 35 Bayer) and propioconazole (TiltTM) may be effective for the formulating combinations that include both oil and water as control of wheat stem rust, while tetraconazole (DomarkTM, oil-in-water (O/W) emulsions. Valent) be effective for the control of soybean rust. Quinone Outside Inhibitors (QoI), such as pyraclostrobin (Head BACKGROUND lineTM, BASF), may be effective for the control of soybean 40 rust, while azoxystrobin (QuadrisTM) may be effective for Rusts are plant diseases caused by fungal pathogens of the the control of wheat stem rust. order Pucciniales. Rusts can affect a variety of plants, Conventional fungicides are generally applied by air to including monocotyledons and dicotyledons, as well as the foliage as contact between the pathogen with the fungi various plant organs, including leaves, stems, fruits and cide is required for efficacy. This process can expensive and seeds. Rust is typically observed as colored powdery pus 45 fungicide application is often reserved for seasons when tules composed off tiny spores that form on the lower plant foliar diseases are severe. Second, conventional fungicides organ Surfaces. Common rust-causing fungal species include typically target specific sites of important pathogen proteins. Gymnosporangium juniperi-virginianae (Cedar-apple rust) Accordingly, strains may develop resistance to the fungicide which attacks apple and pear and hawthorn; Cronartium after repeat applications. Third, the efficacy of conventional ribicola (White pine blister rust); which attacks white pines 50 chemical fungicides is not always satisfactory for some of and currants; Hemileia vastatrix (Coffee rust) which attacks the diseases, such as Fusarium Head Blight (Scab). Finally, coffee plant; Puccinia graminis (wheat stem rust) which conventional fungicides are generally not acceptable for use attacks Kentucky bluegrass, barley, and wheat; Puccinia in organic farming. coronata (Crown Rust of Oats and Ryegrass) which attacks As an alternative approach to conventional chemical oats; Phakopsora meibomiae and P. pachyrhizi (soybean 55 fungicides, oil-in-water emulsions comprising paraffinic oils rust) which attacks Soybean and various legumes; Uromyces (paraflinic oil-in-water emulsions) and paraflinic spray oils phaseoli (Bean rust) which attacks bean; Puccinia hemero have been used in turfgrass management practices for con callidis (Daylily rust) which attacks Daylily; Puccinia per trolling turfgrass pests (see, for example, Canadian Patent sistens subsp. triticina causes (wheat rust in grains, also Application 2.472,806 and Canadian Patent Application known as brown or red rust); P Sriiformis (yellow or stripe 60 2,507,482). In addition, oil-in-water formulations compris rust); Uromyces appendeculatus which attacks bean. ing paraflinic oils and a pigment for controlling turfgrass Wheat stem rust is caused by the fungus Puccinia pests have been reported (see, for example, WO 2009/ graminis and is a significant disease affecting cereal crops, 155693). For example, Petro-Canada produces CIVITASTM, particularly wheat (Triticum spp.) An epidemic of stem rust is a paraflinic oil-in-water emulsion that functions as a broad on wheat caused by race Ug.99 is currently spreading across 65 spectrum fungicide and insecticide for use on golf course Africa, the Middle East, and Asia, and threatening large turf and landscape ornamentals, used for example to control numbers of people who are dependent on wheat for suste powdery mildew, adelgids and webworms on landscape US 9,451,773 B2 3 4 ornamentals (US EPA REG. NO. 69526-13). Product label for controlling infection of a crop plant (e.g., vascular crop) ing indicates that CIVITASTM may be applied as part of an plant by a fungal pathogen. In some implementations, two alternating spray program or in tank mixes with other turf (or more) components of the combination (e.g., the paraf and ornamental protection products; and that CIVITASTM finic oil and one or more conventional chemical fungicides, may be used as a preventative treatment with curative 5 such as a DeMethylation Inhibitor (DMI) or a Quinone properties for the control of many important diseases on turf, outside Inhibitor (QoI) fungicide and/or the pigment) are including fairways and roughs. present in amounts in which the combined effect of two (or more) components is greater than the expected Sum of each SUMMARY components individual effect on controlling a fungal dis 10 ease (e.g., wheat stem rust, soybean rust, leaf rust, stripe This disclosure features combinations that include a par rust, fitsarium head blight, spot blotch, and Septoria com aflinic oil. The combinations can further include (but are not plex in vascular crop plants). In certain implementations, the limited to) one or more of the following: one or more paraflinic oil and conventional chemical fungicide are pres emulsifiers, one or more pigments, one or more silicone ent in amounts that are synergistically effective when Surfactants, one or more anti-settling agents, one or more 15 applied to a plant for controlling a fungal pathogen of the conventional chemical fungicides (e.g., a DMI or a QoI), plant. and water. In some implementations, the combinations can In another aspect, uses are provided for combinations be in the form of a single composition (e.g., which is (e.g., fungicidal compositions) that include a paraflinic oil contained within a storage pack or a vessel (e.g., a tank) in-water emulsion in controlling infection of a vascular plant Suitable for applying the composition to a plant, e.g., crop by a fungal pathogen. The paraflinic oil-in-water emulsion plant). Typically, the composition is applied to a plant after includes paraflinic oil and an emulsifier and can further dilution with water. In other implementations, the combina include any one or more of the components listed above. tions can include two or more separately contained (e.g., The plant can be a crop plant. packaged) compositions, each containing one or more of the The plant may be monocotyledonous. The monocotyle above-mentioned components. Said compositions can be 25 donous plant may be of the order Poaceae. The plant may be combined and applied to a plant typically after dilution with of the genus Triticum, Secale, Hordeum, Oryza, Zea, or water, or each composition can be applied separately to the Elymus. The fungal pathogen may be of the order Puccini same plant either simultaneously or sequentially, and typi ales. The fungal pathogen may be of the genus Puccinia. The cally after dilution with water. This disclosure also features fungal pathogen may be of the species Puccinia graminis, methods of using the combinations for controlling infection 30 Puccinia triticina, or Puccinia Sriiformis. The fungal patho of a crop plant by a fungal pathogen as well as methods of gen can also be Bipolaris Sorokiniana or Fusarium formulating combinations that include both oil and water as graminearum. oil-in-water (O/W) emulsions. The plant can be dicotyledonous. The plant can be of the It has been found that the combinations described herein order Fabaceae. The plant can be of the species Glycine max. (e.g., combinations that include one or more conventional 35 The fungal pathogen can be of the genus Phakopsora. The chemical fungicides, such as a DeMethylation Inhibitor fungal pathogen can be Phakopsora pachyrhizi and Phako (DMI) or a Quinone outside Inhibitor (QoI) fungicide, and psora meibomiae. The plant can be of the genus Gossypium. the components present in CIVITASTM/CIVITAS HARMO The fungal pathogen can be Phakopsora gossypii. NIZERTM) are surprisingly effective in controlling fungal The paraflinic oil can include a paraffin having a number diseases, including, e.g., wheat stem rust, soybean rust, leaf 40 of carbon atoms of from 12 to 50. The paraffin can have a rust, Stripe rust, fitsarium head blight, spot blotch, and number of carbon atoms of from about 16 to 35. The paraffin Septoria complex in vascular crop plants. In some imple can have an average number of carbon atoms of 23. mentations, the combined effect of two (or more) compo The paraffinic oil may have a paraffin content of at least nents of the combination (e.g., the paraffinic oil and one or 80%. The paraffinic oil may have a paraffin content of at more conventional chemical fungicides, such as a DeMeth 45 least 90%. The paraffinic oil may have a paraffin content of ylation Inhibitor (DMI) or a Quinone outside Inhibitor (QoI) at least 99%. fungicide and/or the pigment) on controlling fungal disease The paraffinic oil can be used in a range from 13 to 3200 is greater than the expected Sum of each components oz/acre (i.e. 0.3 to 75 oz/1000 square feet). The paraffinic oil individual effect on controlling a fungal disease (e.g., wheat can be used in a range from 40 to about 640 oz/acre. The stem rust, soybean rust, leaf rust, stripe rust, fusarium head 50 oil-in-water emulsion can be used in a range from 2 to 50 blight, spot blotch, and Septoria complex in vascular crop gallons per acre for foliar application. The oil-in-water plants). In certain implementations, the combined effect of emulsion can be used in a range from 200 to 400 gallons per the two (or more) components present in the combinations acre for soil drench application or water-in application with described herein is a synergistic effect. The Examples illus irrigation. trate that combined use of paraflinic oil with a pigment, a 55 The combinations (e.g., fungicidal compositions) can DMI fungicide, and or a QoI fungicide provides an unex further include a demethylation inhibitor (DMI). The DMI pected synergistic response in the control of wheat stem rust, may be tetraconazole, tebuconazole, propioconazole, aza Soybean rust, leafrust, fitsarium head blight, and spot blotch, conazole, bitertanol, bromuconazole, cyproconazole, in crop plants. In certain implementations, the dosage of difenoconazole, diniconazole, epoxiconazole, etaconazole, Such conventional chemical fungicides can be reduced sig 60 fenbuconazole, fluquinconazole, flusilaZole, flutriafol, hexa nificantly, such as to 50% the recommended label rates, as conazole, imibenconazole, ipconazole, metconazole, well provide significant reduction in the dosage of the myclobutanil, penconazole, prothioconazole, Simeconazole, combinations described herein. triadimefon, triadimenol, triticonazole, imazalil, Oxpocon In one aspect, combinations (e.g., fungicidal composi azole, pefurazoate, prochloraz, triflumizole, fenarimol, nua tions) are featured that include various combinations of a 65 rimol, triforine, or pyrifenox. The DMI can be tebuconazole, paraffinic oil-in-water emulsion with a pigment and/or a and may be used in a range from about 0.02 to about 0.5 lb. conventional chemical fungicide. Such as a DMI or a QoI. ai/acre. The DMI may be propioconazole, and can be used US 9,451,773 B2 5 6 in a range from about 0.01 to about 0.6 lb. ai./acre. The DMI The fungicidal composition can be applied to the root can be tetraconazole, and may be used in a range from 0.015 tissue of the plant. The application to the root tissue can be to 0.15 lb. ai./acre. The DMI can be prothioconazole, and by soil drench. may be used in a range from 0.02 to 0.4 lb. ai./acre. The compositions further include one or more anti-set The combinations (e.g., fungicidal compositions) can tling agents. further include a Quinone outside Inhibitor (QoI). The QoI This disclosure also features combinations that include a may be azoxystrobin, enestrobin, picoxystrobin, pyra paraflinic oil and a QoI fungicide. The combinations can clostrobin, trifloxystrobin, dimoxystrobin, metominostrobin, further include (but are not limited to) one or more of the orysastrobin, famoxadonem, fluoxastrobin, fenamidone, or following: one or more emulsifiers, one or more pigments, pyribencarb. The QoI can be azoxystrobin, and may be used 10 one or more silicone surfactants, one or more anti-settling in a range from 0.01 to 0.50 lb. ai./acre. The QoI can be agents, and water. pyraclostrobin, and may be used in a range from 0.02 to 0.40 Definitions lb. ai./acre. As used herein, the term “oil-in-water emulsion” refers to The combinations (e.g., fungicidal compositions) can a mixture in which one of the paraffinic oil and water (e.g., further include an emulsifier (e.g., a natural or synthetic 15 the paraffinic oil) is dispersed as droplets in the other (e.g., alcohol ethoxylate, an alcohol alkoxylate, an alkyl polysac the water). In some implementations, an oil-in-water emul charide, a glycerol oleate, a polyoxyethylene-polyoxypro sion is prepared by a process that includes combining the pylene block copolymer, an alkyl phenol ethoxylate, a paraflinic oil, water, and any other components and the polymeric Surfactant, a polyethylene glycol, a Sorbitan fatty paraflinic oil and applying shear until the emulsion is acid ester ethoxylate, or a combination thereof). obtained (typically a white milky color is indicative of the The combinations (e.g., fungicidal compositions) can formation of an emulsion in the absence of any pigment; a further include a pigment (e.g., a polychlorinated (Cu II) green color is observed in the presence of a pigment). In phthalocyanine). other implementations, an oil-in-water emulsion is prepared The combinations (e.g., fungicidal compositions) can by a process that includes combining the paraffinic oil, further include a silicone surfactant. 25 water, and any other components in the mixing tank and The combinations (e.g., fungicidal compositions) can sprayed through the nozzle of a spray gun. further include a pigment and a silicone Surfactant. As used herein, the term “control a fungal pathogen of a The combinations (e.g., fungicidal compositions) can plant’ or “control a disease caused by a fungal pathogen further include a pigment, a silicone surfactant, and an (and the like) means to diminish, ameliorate, or stabilize the emulsifier. 30 disease and/or any other existing unwanted condition or side In certain implementations, the combinations (e.g., fun effect that is caused by the association of a fungal pathogen gicidal compositions) can further include an emulsifier and with the plant. a combination of a pigment and a silicone Surfactant, and the As used herein, the term “crop plant” refers to a non combined effect of the emulsifier, the paraffinic oil, the woody plant, which is grown, tended to, and harvested in a pigment and the silicone surfactant is greater than the 35 cycle of one year or less as source of foodstuffs and/or expected Sum of each components individual effect on energy. Examples of crop plants include, without limitation, controlling infection by the fungal pathogen (e.g., the afore Sugar cane, wheat, rice, corn (maize), potatoes, Sugar beets, mentioned components can be present in amounts that, when barley, Sweet potatoes, cassava, Soybeans, tomatoes, applied to the plant, are synergistically effective at control legumes (beans and peas). ling infection by the fungal pathogen). The pigment can be 40 In certain implementations, the combinations, e.g., fun a polychlorinated (CuII) phthalocyanine. The pigment can gicidal compositions, exhibit a synergistic response, for be dispersed in water. The emulsifier can include a natural or example in controlling a fungal pathogen in a crop plant. In synthetic alcohol ethoxylate, an alcohol alkoxylate, an alkyl certain implementations, the combinations, e.g., fungicidal polysaccharide, a glycerol oleate, a polyoxyethylene-poly compositions may be synergistic fungicidal compositions oxypropylene block copolymer, an alkyl phenol ethoxylate, 45 for treating a fungal pathogen in crop plants. In selected a polymeric Surfactant, a polyethylene glycol, a Sorbitan implementations, the fungicidal compositions may exhibit a fatty acid ester ethoxylate, or a combination thereof. The synergistic response, for example in controlling stem rusts in pigment can be be dispersed in oil, and the emulsifier may crop plants. As for example is Suggested by Burpee and include a natural or synthetic alcohol ethoxylate, a poly Latin (Plant Disease Vol.92 No. 4, April 2008, 601-606), the meric Surfactant, a Sorbitan fatty acid ester, or a combination 50 term “synergy”, “synergistic’, or the like, may refer to the thereof, and the combination may further comprises a poly interaction of two or more agents so that their combined ethylene glycol according to formula IV: effect is greater than the sum of their individual effects, this may include, in the context of the invention, the action of two or more fungicidal agents in which the total response of wherein R1 =H or CH2=CH-CH2 or COCH3; R2=H or 55 a fungus to the fungicidal agent combination is greater than CH2=CH-CH2 or COCH3; and f1. the Sum of the individual components. Applying the The ratio of the paraffinic oil-in-water emulsion to the approach to identifying synergy a set out in S. R. Colby, combination of the pigment and the silicone Surfactant can “Calculating synergistic and antagonistic responses of her be from 32:1 to 4:1. bicide combinations'. Weeds 15, 20-22 (1967), expected The ratio of the paraffinic oil to the pigment can be from 60 efficacy, E, may be expressed as: E=X+Y(100-X)/100, about 5:1 to 100:1, such as 30:1). where X is the efficacy, expressed in % of the untreated The weight ratio of the paraffinic oil to the emulsifier can control, of a first composition, and Y is the efficacy, be from 10:1 to 100:1. expressed in % of the untreated control, of the second The weight ratio of the pigment to the silicone Surfactant composition. can be from 2:1 to 50:1. 65 The details of one or more implementations of the com The weight ratio of the paraffinic oil to the conventional binations and methods described herein are set forth in the chemical fungicide can be from 2:1 to 10,000:1 accompanying description below. Other features and advan US 9,451,773 B2 7 8 tages of the combinations and methods described herein will 1. be apparent from the description and drawings, and from the In some implementations, the conventional fungicide is a claims. DMI fungicide. In certain implementations, the DMI fungicide is at least one fungicide selected from the group consisting of tetra DESCRIPTION OF DRAWINGS conazole, tebuconazole, propioconazole, azaconazole, biter tanol, bromuconazole, cyproconazole, difenoconazole, dini FIG. 1 is an image of a leaf blade of a wheat plant conazole, epoxiconazole, etaconazole, fenbuconazole, displaying splotch blot disease after inoculation with Bipo fluquinconazole, flusilaZole, flutriafol, hexaconazole, imi laris Sorokiniana without prior treatment with a fungicidal 10 benconazole, ipconazole, metconazole, myclobutanil, pen composition. conazole, prothioconazole, Simeconazole, triadimefon, tri adimenol, triticonazole, imazalil, Oxpoconazole, FIG. 2 is an image of a leaf blade of a wheat plant pefurazoate, prochloraZ, triflumizole, fenarimol, nuarimol, inoculated with Bipolaris Sorokiniana following foliar appli triforine, and pyrifenox. cation of a fungicidal composition comprising CivitasTM. In certain implementations, the DMI fungicide is at least HarmonizerTM. and FolicurTM seven days before inoculation. 15 one fungicide selected from the group consisting of tetra FIG. 3 is an image of a leaf blade of a wheat plant conazole, tebuconazole, and propioconazole. Tetraconazole inoculated with Bipolaris Sorokiniana following soil drench can be obtained commercially, for example, as a product application of a fungicidal composition comprising Civi identified as DomarkTM (available from Valent). Tebucon azole can be obtained commercially, for example, as a tasTM and HarmonizerTM seven days before inoculation. product identified as FolicurTM (available from Bayer Crop FIG. 4 is an image of a leaf blade of a wheat plant Science). Propioconazole can be obtained commercially, for displaying splotch blot disease after inoculation with Puc example, in the product identified as QuiltTM (available from cinia triticina without prior treatment with a fungicidal Syngenta). composition. In other implementations, the DMI fungicides described FIG. 5 is an image of a leaf blade of a wheat plant 25 herein can be synthesized using conventional techniques inoculated with Puccinia triticina following foliar applica known in the art of synthetic organic chemistry. tion of a fungicidal composition comprising CivitasTM. Har 2 In some implementations, the conventional fungicide is a monizerTM. and FolicurTM seven days before inoculation. QoI fungicide. FIG. 6 is an image of a leaf blade of a wheat plant In certain implementations, the QoI fungicide is at least inoculated with Puccinia triticina following soil drench 30 one fungicide selected from the group consisting of pyra application of a fungicidal composition comprising Civi clostrobin, azoxystrobin, fluoxastrobin, trifloxystrobin, cou tasTM and HarmonizerTM seven days before inoculation. moxystrobin, dimoxystrobin, enoxastrobin, famoxadone, fenamidone, fenaminostrobin, flufenoxystrobin, kresoxim methyl, metominostrobin, orysastrobin, pyraoxystrobin DETAILED DESCRIPTION 35 picoxystrobin, pyrametastrobin, pyribencarb, and triclopy ricarb. This disclosure features combinations that include a par In certain implementations, the QoI fungicide is at least aflinic oil. The combinations can further include (but are not one fungicide selected from the group consisting of pyra limited to) one or more of the following: one or more clostrobin, azoxystrobin, fluoxastrobin, and trifloxystrobin. emulsifiers, one or more pigments, one or more silicone 40 In certain implementations, the QoI fungicide is at least Surfactants, one or more anti-settling agents, one or more one fungicide selected from the group consisting of pyra conventional chemical fungicides (e.g., a DMI or a QoI), clostrobin and azoxystrobin. and water. In some implementations, the combinations can In certain implementations, the QoI fungicide is methyl be in the form of a single composition (e.g., which is (2E)-2-2-(3-butyl-4-methyl-2-oxo-2H-chromen-7-yl) contained within a storage pack or a vessel (e.g., a tank) 45 oxymethylphenyl-3-methoxyacrylate (coumoxystrobin): Suitable for applying the composition to a plant, e.g., crop CAS No. 850881-70-8. plant). Typically, the composition is applied to a plant after In certain implementations, the QoI fungicide is (E)-2- dilution with water. In other implementations, the combina (methoxyimino)-N-methyl-2-O-(2,5-xylyloxy)-o-tolylac tions can include two or more separately contained (e.g., etamide (dimoxystrobin): CAS No. 149961-52-4. packaged) compositions, each containing one or more of the 50 In certain implementations, the QoI fungicide is enoxas above-mentioned components. Said compositions can be trobin. In alternative implementations, the QoI fungicide combined and applied to a plant typically after dilution with may be, for example, (RS)-3-anilino-5-methyl-5-(4-phe water, or each composition can be applied separately to the noxyphenyl)-1,3-oxazolidine-2,4-dione (famoxadone): same plant either simultaneously or sequentially, and typi CAS No. 131807-57-3. cally after dilution with water. This disclosure also features 55 In certain implementations, the QoI fungicide is (S)-1- methods of using the combinations for controlling infection anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one of a vascular crop plant by a fungal pathogen as well as (fenamidone): CAS No. 161326-34-7. methods of formulating combinations that include both oil In certain implementations, the QoI fungicide is fenamin and water as oil-in-water (O/W) emulsions. ostrobin. 60 In certain implementations, the QoI fungicide is flufenox I. Components ystrobin. A Conventional Chemical Fungicides In certain implementations, the QoI fungicide is methyl The combinations include isomers such as geometrical (E)-methoxyiminoC-(o-tolyloxy)-o-tolyl)acetate (kre isomers, optical isomers based on asymmetric carbon, Ste soxim-methyl): CAS No. 143390-89-0. reoisomers and tautomers of the compounds described 65 In certain implementations, the QoI fungicide is (E)-2- herein and are not limited by the description of the com (methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide pounds for the sake of convenience. (metominostrobin): CAS No. 133408-50-1. US 9,451,773 B2 10 In certain implementations, the QoI fungicide may be, for to 35 carbon atoms, 12 carbon atoms to 21 carbon atoms; example, (2E)-2-(methoxyimino)-2-2-I (3E.5E,6E)-5- e.g., 16 carbon atoms to 35 carbon atoms). (methoxyimino)-4,6-dimethyl-2,8-dioxa-3,7-diazanona-3,6- In certain implementations, the paraflinic oil includes a dien-1-yl)phenyl-N-methylacetamide (orysastrobin): CAS paraffin having an average number of carbon atoms that is No. 248593-16-0. less than or equal to about 20 (e.g., 16). In certain implementations, the QoI fungicide is methyl In certain implementations, the paraflinic oil includes a (2E)-2-(2-3-(4-chlorophenyl)-1-methylpyrazol-5-yl) paraffin having an average number of carbon atoms of from oxymethylphenyl)-3-methoxyacrylate (pyraoxystrobin): 16 to 30 e.g., 23 or 27). CAS No. 862.588-11-2. In certain implementations, the paraflinic oil includes a In certain implementations, the QoI fungicide is methyl 10 paraffin having from 16 carbon atoms to 35 carbon atoms and an average number of carbon atoms of 23. (2E)-3-methoxy-2-(2-6-(trifluoromethyl)-2-pyridyloxym In certain implementations, the paraffin is an isoparaffin ethylphenylacrylate (picoxystrobin): CAS No. 117428-22 (e.g., a synthetic isoparaffin manufactured from two-stage 5. Severe Hydrocracking/Hydroisomerization process). In certain implementations, the QoI fungicide is pyram 15 In some implementations, a paraffin is present in the etastrobin. paraflinic oil in an amount, that is at least 80% (e.g., at least In certain implementations, the QoI fungicide is methyl 90%, at least 99%). {2-chloro-5-(1E)-1-(6-methyl-2-pyridylmethoxyimino) 2 ethylbenzylcarbamate (pyribencarb): CAS No. 799247 In some implementations, the paraflinic oil has been 52-2. refined to remove compounds that are associated with plant In certain implementations, the QoI fungicide is triclopy injury, for example, aromatic compounds or compounds ricarb. containing Sulfur, nitrogen, or oxygen. In certain implemen In certain implementations, the QoI fungicide is carbamic tations, the paraffinic oil includes relatively low levels of acid, 2-1-(4-chlorophenyl)-1H-pyrazol-3-yl)oxy aromatic compounds and/or compounds containing Sulfur, methyl-phenylmethoxy-, methyl ester (pyraclostrobin). 25 nitrogen, or oxygen, e.g., less than 10 weight percent (less Pyraclostrobin may be commercially available, for example, than 5 weight percent, less than 2 weight percent, less than as a product identified as InsigniaTM (available from BASF 0.5 weight percent) of aromatic compounds and/or com Corporation, 26 Davis Drive, Research Triangle Park, N.C. pounds containing Sulfur, nitrogen, or oxygen. 27709). 3) In certain implementations, the QoI fungicide is methyl 30 Non-limiting examples of Suitable paraflinic oils include, (E)-2-(2-6-(2-cyano-phenoxy)pyrimidin-4-yloxyphenyl HT60, HT100, High Flash Jet, LSRD, and N65DW (avail 3-methoxy-acrylate (azoxystrobin). Azoxystrobin may be able from Petro-Canada, Calgary, AB, Canada). commercially available, for example, as a product identified C Emulsifier as HeritageTM (available from Syngenta Crop Protection, In some implementations, the combinations include both Inc., Greensboro, N.C. 27.409). 35 paraflinic oil, emulsifier, and water. It can be advantageous In certain implementations, the QoI fungicide is (1E)- to store and/or apply such combinations as oil-in-water 2-6-(2-chlorophenoxy)-5-fluoro-4-pyrimidinyloxyphe (O/W) emulsions. nyl5,6-dihydro-1,4,2-dioxazin-3-yl)methanone-O-methyl Emulsions tend to be thermodynamically unstable due to oxime (fluoxastrobin). Fluoxastrobin may be commercially excess free energy associated with the Surface of the dis available, for example, as a product identified as DisarmTM 40 persed droplets such that the particles tend to flocculate (available from Arysta LifeScience North America, LLC, (clumping together of dispersed droplets or particles) and 15401 Weston Parkway, Suite 150, Cary, N.C. 27513). Subsequently coalesce (fusing together of agglomerates into In certain implementations, the QoI fungicide is benze a larger drop or droplets) to decrease the Surface energy. If neacetic acid, (E.E)-alpha-(methoxyimino)-2((((1-(3-trif. these droplets fuse, the emulsion will “break” (i.e., the luoromethyl)phenyl)ethylidene)-amino)oxy)methyl)-. 45 phases will separate) destroying the emulsion, which in methyl ester (trifloxystrobin). Trifloxystrobin may be com some cases can be detrimental to the storage shelf-life of the mercially available, for example, as a product identified as combinations. While not wishing to be bound by theory, it CompassTM (available from Bayer Environmental Science, is believed that the addition of one (or more) emulsifying 2T. W. Alexander Drive, Research Triangle Park, N.C. agents or emulsifiers can prevent or slow the “breaking of 27709). 50 an emulsion. As the skilled artisan will appreciate, the type In other implementations, the QoI fungicides described and concentration of a particular emulsifying agent will herein can be synthesized using conventional techniques depend, inter alfa, on the emulsion phase components and known in the art of synthetic organic chemistry. the desired result. B. Paraffinic Oil 1. The paraflinic oil confers properties (e.g., fungicidal prop 55 In some implementations, the emulsifier is a “fast break” erties) that are useful for promoting the health of a plant or "quick break' emulsifier. While not wishing to be bound (e.g., crop plant). While not wishing to be bound by theory, by theory, it is believed that a “fast break” or “quick break” it is believed that the paraffinic oil is able to provoke an emulsifier allows the paraffinic oil to be quickly released induced systemic resistance (ISR) response, a systemic from the O/W emulsion upon application to the turfgrass for acquired resistance (SAR), or other defense response in a 60 contact, e.g., with a fungal pathogen. When a “fast break' or plant. “quick break' emulsifier is present in a suitable amount (for 1. example a selected proportion or ratio with respect to the In some implementations, the paraflinic oil includes an oil paraffinic oil), the resulting “fast break” or “quick break” enriched in paraffin. O/W emulsion quickly releases the oil phase upon applica In certain implementations, the paraflinic oil includes a 65 tion to the turfgrass. As such, there is less runoff of the O/W paraffin having from 12 carbon atoms to 50 carbon atoms emulsion from the grass blades (as compared to more stable (e.g., 12 carbon atoms to 40 carbon atoms, 16 carbon atoms O/W emulsions) resulting in more oil adhering to the turf US 9,451,773 B2 11 12 grass for a longer period of time to more effectively contact In certain implementations, the emulsifier is (or includes) and control, e.g., associated fungal pathogen. In certain a polymeric Surfactant, e.g., a graft copolymer, a random implementations, the oil phase resides on the turfgrass for a copolymer, or any combination thereof. For example, the period of not less than one hour. In certain implementations, graft copolymer can be a polymethacrylic acid and acrylate the oil phase resides on the turfgrass for a period of from not 5 with polyoxyethylene chains. For example, the random less than 1 hour but not more than 30 days. In certain copolymer can be a random copolymer having ester and implementations, the “fast break” or "quick break' emulsion ether groups. may be, for example, an emulsion having an oil phase that, In certain implementations, the emulsifier is (or includes) after mixing with water, is reconstituted in 0.5 to 15 minutes a polyethylene glycol, e.g., a polyethylene glycol having a according to the following test: 10 molecular weight (“MW) (or relative molar mass) of from 1. Fill 100 mL graduated cylinder with tap water. 200 to 8000, e.g., MW 400 PEG dioleate; or MW600 PEG 2. Add 1 mL of emulsified oil. dioleate. 3. Invert graduated cylinder 5 times. In certain implementations, the emulsifier is (or includes) 4. Using a stop watch and human observation, measure a sorbitan fatty acid ester ethoxylate, e.g., polyoxyethylene how long it takes for the oil phase to reconstitute after 15 (20) sorbitan tristearate, polyoxyethylene (20) sorbitan inversion (step 3). monooleate, polyoxyethylene (5) Sorbitan monooleate, poly In some implementations, the oil phase is reconstituted in oxyethylene (20) sorbitan trioleate, or any combination from 2 minutes to 5 minutes according to the test described thereof. For example, the sorbitan fatty acid ester can be a above. In some instances, the “fast break” or “quick break” Sorbitan tristearate, a Sorbitan triolate, or any combination property of the O/W emulsion is balanced with the need to thereof. provide an O/W emulsion with a suitable shelf life under In certain implementations, the emulsifier is (or includes) Suitable storing conditions, and for a Suitable timeframe. an alkyl phenol ethoxylate, a mixture of an ethoxylated 2 alcohol and a glycerol oleate, or any combination thereof. In some implementations, the emulsifier is (or includes) In certain implementations, the emulsifier is (or includes) one (or more of the following) a natural or synthetic alcohol 25 a mixture of an ethoxylated alcohol and a glycerol oleate, ethoxylate, an alcohol alkoxylate, an alkyl polysaccharide, a e.g.: a C10 to C16 alcohol ethoxylate and a glycerol oleate glycerol oleate, a polyoxyethylene-polyoxypropylene block combination; or polyoxyethylene lauryl ether, C10 to C16 copolymer, an alkyl phenol ethoxylate, a polymeric Surfac alcohol ethoxylates, and glycerol oleate; or ethoxylated tant, a polyethylene glycol, a Sorbitan fatty acid ester alcohols having primary C5-C20 carbon chains with an ethoxylate, or any combination thereof. 30 average of about 2 to about 7 ethoxylation groups, and a In certain implementations, the emulsifier is (or includes) glycerol oleate; or a polyoxyethylene (11) C16-18 alcohol. a natural or synthetic alcohol ethoxylate, a polymeric Sur In certain implementations, the emulsifier is (or includes) factant, a Sorbitan fatty acid ester, or any combination a sorbitan tristearate. thereof. Non-limiting examples of suitable emulsifiers include In certain implementations, the natural or synthetic alco 35 AL3149 (available from Uniqema), AL3313 (available from hol ethoxylate is a polyoxyethylene (4 to 12) lauryl ether Uniqema), PC Emuls Green (available from Petro-Canada, (C12), polyoxyethylene (10) cetyl ether (C16), polyoxyeth Calgary, AB, Canada), LutensolTM AT11 (available from ylene (10) stearyl ether (C18), polyoxyethylene (10) oleyl BASF), SPAN65 (available from Uniqema), and ether (C18 mono-unsaturated), a polyoxyethylene (2 to 11) S-MAZTM65 K (available from BASF). C12-C15 alcohol, a polyoxyethylene (3 to 9). C11-C14 40 3) alcohol, a polyoxyethylene (9) C12-C14 alcohol, a polyoxy In some implementations, the weight ratio of the paraf ethylene (11) C16-C18 alcohol, a polyoxyethylene (20) finic oil to the emulsifier is from 10:1 to 500:1 (e.g., from C12-C15 alcohol, or any combination thereof. For example, 98:2 to 99.9:0.1, from 98:2 to 99.5:0.5). By way of example, the natural or synthetic alcohol ethoxylate can be a poly the weight ratio of the paraffinic oil to the emulsifier can be oxyethylene (4 to 7) lauryl ether (C12), polyoxyethylene 45 95:5, 98:2, 98.5:1.5, 99:1, 99.5:0.5. (10) cetyl ether (C16), a polyoxyethylene (2 to 11) C12-C15 D Pigment alcohol, a polyoxyethylene (3 to 9). C11-C14 alcohol, a In some implementations, the combinations can include polyoxyethylene (9) C12-C14 alcohol, or any combination one (or more) pigments. The pigments can provide color to thereof. As another example, the alcohol alkoxylate can be the plant being treated (e.g., turf grass) and/or in some a butyl ether polyoxyethylene/polyoxypropylene block 50 implementations, the pigment(s) and the paraflinic oil can copolymer. exhibit a greater than additive effect in promoting the health In certain implementations, the emulsifier is (or includes) of a plant (e.g., controlling a fungal pathogen of a plant; see, an alkyl polysaccharide, e.g., a C8-C11 alkylpolysaccharide for example, WO 2009/155693). or any combination thereof. In some implementations, the pigment is a water-based In certain implementations, the emulsifier is (or includes) 55 pigment dispersion. a glycerol oleate, e.g., a glycerol mono-, di-, tri-oleate, or In Some implementations, the pigment is an oil-based any combination thereof. pigment dispersion. In certain implementations, the emulsifier is (or includes) In some implementations, the pigment is a phthalocyanine a polyoxyethylene-polyoxypropylene block copolymer, e.g., compound. a polyoxyethylene-polyoxypropylene block copolymer hav 60 In certain implementations, the pigment is a metal-free ing a molecular weight (or relative molar mass) of from phthalocyanine compound. In certain implementations, the 1100 to about 11400 and 10 to 80% (ethylene oxide) EO. pigment is a halogenated, metal-free phthalocyanine, e.g., a In certain implementations, the emulsifier is (or includes) polychlorinated metal-free phthalocyanine. an alkyl phenol ethoxylate, e.g., a nonyl phenol ethoxylate, In certain implementations, the pigment is a metal phtha a dodecyl phenol ethoxylate, or any combination thereof. 65 locyanine compound. For example, the nonyl phenol ethoxylate can be a poly In certain implementations, the pigment is a copper phtha oxyethylene (2 to 8) nonylphenol. locyanine. US 9,451,773 B2 13 14 In certain implementations, the copper phthalocyanine is In certain implementations, the silicone surfactant is (or a non-halogenated copper phthalocyanine, e.g., a nonchlo includes) a silicone polyether of the formula I wherein rinated copper phthalocyanine. As an example, the pigment R—COCH; X=1 to 24; and na1. can be Phthalocyanine Blue BN (CAS 147-14-8). In certain implementations, the silicone surfactant is (or In certain implementations, the copper phthalocyanine is includes) an H-capped dimethyl methyl (polyethylene a halogenated copper phthalocyanine. As an example, the oxide) silicone polymer; e.g., having a molecular weight (or pigment can be Phthalocyanine Green 6G (CAS 14302-13 relative molar mass) from 200 to 6000. 7). As another example, the pigment can be polychlorinated In certain implementations, the silicone surfactant is (or (Cu II) phthalocyanine, such as Phthalocyanine Green G includes) a silicone polyether of the formula II: (CAS 1328–45-6 and 1328-53-6). 10 Non-limiting examples of Suitable pigments include Sun sperseTM Green 7 (Pigment Green 7 dispersed in water, available from Sun Chemical Corp. Performance Pigments Cincinnati, Ohio, USA), SunsperseTM EXP 006-102 and 15 006-95B (Pigment Green 7 dispersed in oil, available from Sun Chemical Corp. Performance Pigments, Cincinnati, CH, CH Ohio, USA), and Pigment Green 7 powder (available from Hercules Exports, Mumbai, India). wherein c=2-16; and b=2-70. In certain implementations, El Silicone Surfactant the average b–44. In certain implementations, the average In some implementations, it can be advantageous to c=10. In certain implementations, the average b=44, and the further include one (or more) silicone Surfactants in combi average c=10. nations that further include one or more pigments. In certain implementations, the silicone surfactant is (or 1. includes) an H-capped trisiloxane. Such as a silicone In some implementations, the silicone Surfactant is (or 25 polyether of the formula III: includes) a silicone polyether. In certain implementations, the silicone surfactant is (or includes) a silicone polyether having a suitable alkoxy group (III) with hydrogen end groups (H-capped), methyl end groups CH2CH2CH2O(CH2CH2O).H (CH-capped), or acetyl end groups (COCH-capped). In 30 (CH)Si-O-Si-O-Si(CH) certain implementations, the silicone surfactant is (or includes) a trisiloxane having a suitable alkoxy group with CH hydrogen end groups (H-capped), methyl end groups (CH capped), or acetyl end groups (COCH-capped). wherein d=1-24. In certain implementations, d=1-20. In In certain implementations, the silicone surfactant is (or 35 certain implementations, the average d=8-10 (e.g., 8). includes) a silicone polyether of the formula I: In certain implementations, the silicone surfactant is (or includes) a silicone copolyol, containing a hydrogen end group and one pendant polyethylene oxide group and has an average molecular weight between about 600 to about 1000 40 Daltons. In certain implementations, the silicone Surfactant is (or includes) a trisiloxane with an ethoxylated alkyl group th t having a hydrogen end group (H-End); e.g., having a num cit-i-o--o —o Si(CH3)3 ber of ethoxylation groups in the range of 1-20. In certain CH CH CH implementations, the silicone Surfactant the silicone surfac 45 tant is (or includes) a methyl (propylhydroxide, ethoxylated) in which R is H, CH or COCH; x is 1 to 24; and n is 0 or bis(trimethylsiloxy) silane; e.g., a dimethyl, methyl (poly 21. ethylene oxide) silicone polymer. In certain implementations, the silicone surfactant is (or 2 includes) a silicone polyether of the formula I wherein 50 In some implementations, commercial preparations of the R—H; X=1 to 24; and n=0; e.g., a silicone polyether of the silicone surfactants may or may not contain Small amounts formula I wherein n=0; x=1-24; the average x=8-10; and of polyethylene glycols (PEG) or other low molecular R. H. weight polydimethyl siloxanes (PDMS). In some implementations, the silicone surfactant further In certain implementations, the silicone surfactant is (or includes a polyethylene glycol. includes) a silicone polyether of the formula I wherein 55 R—H; X=1 to 24; and ne1. In certain implementations, the polyethylene glycol is (or In certain implementations, the silicone surfactant is (or includes) a polyethylene glycol of the formula IV: includes) a silicone polyether of the formula I wherein R—CH: X=1 to 24; and n=0. In certain implementations, the silicone surfactant is (or 60 wherein R'—H or CH=CH-CH or COCH: R–H includes) a silicone polyether of the formula I wherein or CH=CH-CH or COCH; and f1. R—CH: X=1 to 24; and na1. In certain implementations, the polyethylene glycol has a In certain implementations, the silicone surfactant is (or relatively low molecular weight, e.g. from 300 Daltons to includes) a silicone polyether of the formula I wherein 1500 Daltons. In certain implementations, the polyethylene R—COCH; X=1 to 24; and n=0; e.g., a silicone polyether 65 glycol is a low molecular weight polyethylene glycol allyl of the formula I wherein n=0; x=1-24, the average X-8-10; ether, Such as a low molecular weight polyethylene glycol and R—COCH. mono-allyl ether having an average molecular of from about US 9,451,773 B2 15 16 300 to about 600 Daltons and having from 1 to 20 moles of In certain implementations, the organically modified clay ethylene glycol with an average ethylene oxide unit (EO) of is activated by a chemical activator. 8 to 10. In certain implementations, the chemical activator In certain implementations, the polyethylene glycol is (or includes a low-molecular-weight polar organic compound, includes) a polyethylene glycol of the formula IV wherein 5 e.g., a least one compound selected from the group consist R"—CH=CH-CH, R—H, and f-1-20 with an average ing of a low-molecular weight ketone, a low-molecular f=8, a polyethylene glycol of the formula IV wherein weight alcohol and propylene carbonate. R=CH=CH-CH or COCH, and R—COCH, a poly In certain implementations, the chemical activator ethylene glycol of the formula IV wherein R'=CH=CH includes water and at least one compound selected from the 10 group consisting of a low-molecular weight ketone, a low CH, and R=H, or any combination thereof. molecular weight alcohol and propylene carbonate. In certain implementations, the polyethylene glycol is (or In certain implementations, the chemical activator includes) a polyethylene glycol of the formula IV wherein includes a low-molecular weight ketone; or a low-molecular R"—CH=CH-CH or COCH, and R—COCH, a poly weight ketone and water (Such as a low molecular weight ethylene glycol of the formula IV wherein R'=CH=CH 15 ketone and water in a weight ratio of 95/5). An example of CH, and R=H, or any combination thereof. a low-molecular weight ketone is acetone. In certain implementations, the polyethylene glycol is (or In certain implementations, the chemical activator includes) a polyethylene glycol of the formula IV wherein includes a low-molecular weight alcohol; or a low-molecu R"—CH=CH-CH, R—H, and f-1-20 with an average lar weight alcohol and water (Such as a low-molecular f=8. weight alcohol and water in a weight ratio of 95/5). In certain implementations, the polyethylene glycol is (or Examples of low-molecular weight alcohols include metha includes) a polyethylene glycol of the formula IV wherein nol or ethanol. R=CH=CH-CH, or COCH, and R—COCH, In certain implementations, the chemical activator In certain implementations, the polyethylene glycol is (or includes propylene carbonate; or propylene carbonate and includes) a polyethylene glycol of the formula IV wherein 25 water (such as, propylene carbonate and water in a weight R=CH=CH-CH, and R—H. ratio of 95/5). Non-limiting examples of Suitable polyethylene glycols G Water may include Polyglykol A500 (available from Clariant). In some implementations, the combinations can further In certain implementations, the silicone Surfactant include water. includes from 10 to 30 weight percent of a polyethylene 30 In Some implementations, the pigment is dispersed in glycol as described anywhere herein. water before it is added to the remaining components of the 3 combination (typically water is 1:1 weight percent with with Non-limiting examples of Suitable silicone surfactants pigment), resulting in, e.g., the presence of 3 parts per may include SylgardTM 309 (available from Dow Corning, weight of water in the combination. Midland, Mich., USA), SilfsurftMA008-UP (available from 35 In some implementations, the combinations can further Siltech Corp. Toronto, ON, Canada), Lambent MFF 199 SW include water, e.g., as a diluent, e.g., as a diluent added prior (available from Lambent Technologies Corp., Gurnee, Ill., to application of the combinations to a plant (e.g., a turf USA), and Lambent MFF 159-100 (available from Lambent grass). Technologies Corp., Gurnee, Ill., USA). In some implementations, the combinations can further FAnti-Settling Agent 40 include both sources of water described above. In some implementations, the combination can include In some implementations the water is distilled water one (or more) “anti-settling agents, which reduce the like and/or other waters having a low mineral electrolyte content. lihood of having Solids Suspended in a dispersion from H. Other Components settling out under the influence of gravity. In some implementations, the combinations further In some implementations, the anti-setting agent is (or 45 include one or more other components that are customary includes) a metal oxide and/or an organically modified clay. additives or adjuvants for the preparation of compositions in In some implementations, the anti-setting agent is (or the field of crop protection and/or components that are inert includes) a metal oxide. (e.g., may not materially affect the activity and/or overall In certain implementations, the anti-setting agent is (or performance of the combinations) and/or one or more other includes) a fumed metal oxide and/or a precipitated metal 50 active components. As an example, the combinations can oxide. further include customary additives or adjuvants that may be In certain implementations, the anti-setting agent is (or present in a commercially available conventional chemical includes) one or more of the following forms of silica: fungicide. precipitated silica (e.g., an untreated, precipitated silica) or In some implementations, the combinations include only fumed silica (e.g., an untreated, fumed silica). As used 55 combinations of the components set forth is sections A herein, the term “untreated fumed silica', or the like, is used through G above. to refer to a hydrophilic fumed silica. As used herein, the In certain implementations, the combinations do not term “treated fumed silica', or the like, is used to refer to a include one or more other components that are customary hydrophobic fumed silica. additives or adjuvants for the preparation of compositions in In some implementations, the anti-settling agent is (or 60 the field of crop protection and/or components that are inert includes) an organically modified clay. In certain implemen (e.g., may not materially affect the activity and/or overall tations, the anti-setting agent is (or includes) one or more of performance of the combinations) and/or one or more other the following organically modified clays: an organically active components that are other than conventional chemical modified Smectite clay, an organically modified hectorite fungicides. clay, an organically modified bentonite clay, an organically 65 In certain implementations, the combinations are free of modified montmorillonite clay and an organically modified one or more other components that are customary additives attapulgite clay. or adjuvants for the preparation of compositions in the field US 9,451,773 B2 17 18 of crop protection and/or components that are inert (e.g., In some implementations, the composition includes (i), may not materially affect the activity and/or overall perfor (iii), and (vi). mance of the combinations) and/or one or more other active In some implementations, the composition includes (i), components that are other than conventional chemical fun (iii), (iv), and (V). gicides; (e.g., the combinations contain less than 5%, less In some implementations, the composition includes (i), than 4%, less than 3%, less than 2%, less than 1% (w/w or (iii), (iv), (v), and (vi). w/v) of one or more other components that are customary In some implementations, the composition includes (i), additives or adjuvants for the preparation of compositions in (ii), and (iii). the field of turf or field crop protection and/or components In some implementations, the composition includes (i), 10 (ii), (iii), and (vi). that are inert (e.g., may not materially affect the activity In some implementations, the composition includes (i), and/or overall performance of the combinations) and/or one (ii), (iii), (iv), and (V). or more other active components that are other than con In some implementations, the composition includes (i), ventional chemical fungicides. (ii), (iii), (iv), (v), and (vi). In some implementations, the combinations are Substan 15 2 Concentrates tially free of one or more other components that are cus In some of the implementations described in section tomary additives or adjuvants for the preparation of com IIIA1), one or more of the following applies: positions in the field of crop protection and/or components (2-a) the weight ratio of paraffinic oil to the emulsifier is that are inert (e.g., may not materially affect the activity from 10:1 to 500:1 (e.g., from 45:1 to 55:1, e.g., 49:1, 50:1): and/or overall performance of the combinations) and/or one (2-b) the weight ratio of paraffinic oil to the pigment is or more other active components that are other than con from 5:1 to 100:1 (e.g., from 25:1 to 35:1, e.g., 28:1, 30:1): ventional chemical fungicides (e.g., the combinations con (2-c) the weight ratio of pigment to the silicone Surfactant tain less than 0.5%, less than 0.2, less than 0.1, less than is from 2:1 to 50:1 (e.g., from 3:1 to 6:1, e.g., 4.5:1); 0.05% (w/w or w/v), do not include a detectable amount of (2-d) the weight ratio of paraffinic oil to the conventional one or more other components that are customary additives 25 chemical fungicide (e.g., one or more DMI fungicides or adjuvants for the preparation of compositions in the field and/or one or more QoI fungicides) is from 2:1 to 10000:1 of turf or field crop protection and/or components that are (e.g., from 100:1 to 160:1; from 90:1 to 120:1, e.g., 111:1, inert (e.g., may not materially affect the activity and/or 110:1; from 130:1 to 150:1, e.g., 139:1, 140:1). overall performance of the combinations) and/or one or In certain implementations, (2-a) applies; or (2-a), (2-b) more other that are other than conventional chemical fun 30 and (2-c) apply; or (2-b), and (2-c) apply. In certain imple gicides. mentations, (2-d) further applies to any one of the above II. Non-Limiting Combinations of Components listed combinations of (2-a), (2-b) and (2-c). A Combinations that Include a Single Composition In some of the implementations described in section 1. IIIA1), one or more of the following applies: In some implementations, the combinations can be in the 35 (2-aa) the concentrate includes from 50 to 300 parts per form of a single composition (e.g., contained within a weight (e.g., 200-300, e.g., 260; e.g., 50-150, e.g., 100) parts storage pack or a vessel Suitable for applying the composi per weight of the paraffinic oil; tion to a plant, e.g., turf grass). These compositions are (2-bb) the concentrate includes from 1 to 10 parts per Sometimes referred to herein (without limitation, e.g., as to Weight (e.g., 3-7, e.g. 5; e.g., 1-5, e.g., 1.9, e.g. 2) parts per quantity or application mode) as a 1-pack formulations or 40 weight of the emulsifier; concentrates in the absence of water for dilution. (2-cc) the concentrate includes from 1 to 15 parts per In some implementations, the composition includes one weight (e.g., 7-11, e.g., 9; e.g., 2-5, e.g., 3.5) parts per weight (or more) paraflinic oils, which can include any one or more of the pigment; of the features described in any one or more of sections (2-dd) the concentrate includes from 0.1 to 10 parts per IB1, IB2, and IB3 above. 45 Weight (e.g., 0.5-1, e.g., 0.8, e.g., e.g., 2-5, e.g., 3.1) parts per In some implementations, the combination further weight of the silicone Surfactant; includes (but is not limited to) one or more of the following: (2-ee) the concentrate includes from 0.5 to 20 parts per (ii) one (or more) conventional chemical fungicides, weight (e.g., 6-10, e.g., 8: e.g., 2-5, e.g., 3.1) parts per weight which can include any one or more of the features described of the anti-settling agent; or in any one or more of sections IIA 1 and/or ILA2 50 (2-ff) the concentrate includes from 0.01 to 10 parts per (e.g., one or more DMI fungicides and/or one or more QoI Weight (e.g., 0.5-1, e.g., 0.8, e.g., e.g., 1-3, e.g., 2) parts per fungicides); weight of the conventional chemical fungicide. (iii) one (or more) emulsifiers, which can include any one In certain implementations, (2-aa) and (2-bb) apply; or or more of the features described in any one or more of (2-cc) and (2-dd) apply; or (2-aa), (2-bb), and (2-ff) apply: sections IC1, ICI2, and IC3 above: 55 or (2-cc), (2-dd), and (2-ff) apply; or (2-aa), (2-bb), (2-cc), (iv) one (or more) pigments which can include any one or and (2-dd) apply, or (2-aa), (2-bb), (2-cc), (2-dd), and (2-ff) more of the features described in section ID above: apply. In certain implementations, (2-ee) further applies to (v) one (or more) silicone surfactants, which can include each of the above-listed implementations. any one or more of the features described in any one or more In some implementations, any one or more of the features of sections II E1. IE2, and IE3 above; 60 described in one or more of (2-a) and (2-d) can be combined (vi) one (or more) anti-settling agents, which can include with any one or more of the features described in one or any one or more of the features described in section ID more of (2-aa) and (2-ff). above; and In Some implementations, the pigment is dispersed in (vii) one (or more) components described in section compatible oil, e.g., a paraflinic oil, e.g., the same paraflinic IIH. 65 oil as is used to provide the fungicidal properties as In some implementations, the composition includes (i) described herein, for addition to the other components of the and (iii). combinations described herein. In certain implementations, US 9,451,773 B2 19 20 a silicone Surfactant and/or emulsifier and/or anti-settling (1) the first and separately contained composition agent can be included, e.g., to stabilize the pigment in the includes: oil-based combination. one (or more) paraflinic oils, which can include any one For example, polychlorinated Cu (II) phthalocyanine can or more of the features described in any one or more of be dispersed in a paraffinic oil, such as N65DW (available sections 1B1, 1B2, and IB3 above: from Petro-Canada) to provide about 18% polychlorinated one (or more) conventional chemical fungicides, which CU (II) phthalocyanine (SUNSPERSE(R) EXP 006-102, can include any one or more of the features described available from Sun Chemical Corp. Performance Pigments, in any one or more of sections (IA1 and/or ILA Cincinnati, Ohio USA) prior to mixing with the remaining 2 (e.g., one or more DMI fungicides and/or one or components. In certain implementations, a silicone surfac 10 more QoI fungicides); and one (or more) emulsifiers, which can include any one or tant and/or emulsifier and/or anti-settling agent can be more of the features described in any one or more of included. While not wishing to be bound by theory, it is sections IC1, ICI2, and IC3 above; and believed that the addition of these components can provide (2) the second and separately contained composition an intermolecular hydrophilic and lipophilic balance within 15 includes: the fungicidal formulation so as to Substantially prevent the one (or more) pigments, which can include any one or polychlorinated Cu (II) phthalocyanine from separating out more of the features described in section ID above of Suspension during application, e.g., to a turfgrass. and In Some of the implementations described in section one (or more) silicone Surfactants, which can include any IIA1, the composition includes the components present one or more of the features described in any one or in CivitasTM 1-pack and those present in commercially more of sections IE1, IE2, and IE3 available conventional chemical fungicides described any above. where herein. In some implementations, the combinations include a first 3 and separately contained composition and a second and In some of the implementations described in sections 25 separately contained composition, in which: IIA1 and IIIA2, the composition further includes (1) the first and separately contained composition water. In certain implementations, weight percent ratio of includes: the undiluted composition to water is from 1:1 to 1:100 (e.g., one (or more) paraflinic oils, which can include any one from 1-50, 1-30, 1-20, 1-15). In certain implementations, the or more of the features described in any one or more of weight percent of the paraffinic oil in the diluted composi 30 sections IB1, IB2, and IB3 above: tions is from 2-50 weight percent (e.g., 15%). In certain one (or more) emulsifiers, which can include any one or implementations, the composition is in the form of an oil in more of the features described in any one or more of water emulsion as described anywhere herein. sections IC1, ICI2, and IC3 above: In some implementations, the pigment is dispersed in one (or more) pigments, which can include any one or 35 more of the features described in section ID above: water for addition to the other components of the combina one (or more) silicone Surfactants, which can include any tions described herein. In certain implementations, a silicone one or more of the features described in any one or Surfactant and/or emulsifier and/or anti-settling agent can be more of sections IE1, IE2, and IE3 included, e.g., to stabilize the pigment in the oil/water-based above; and combination. 40 one (or more) anti-settling agents, which can include any For example, polychlorinated Cu (II) phthalocyanine can one or more of the features described in section ID be dispersed in a water to provide about 40% polychlori above; and nated CU (II) phthalocyanine (SUNSPERSER GREEN 7, (2) the second and separately contained composition available from Sun Chemical Corp. Performance Pigments, includes: Cincinnati, Ohio USA) prior to mixing with the remaining 45 one (or more) conventional chemical fungicides, which components. In certain implementations, a silicone surfac can include any one or more of the features described tant and/or emulsifier and/or anti-settling agent can be in any one or more of sections (IA1 and/or ILA included. While not wishing to be bound by theory, it is 2 (e.g., one or more DMI fungicides and/or one or believed that the addition of these components can provide more QoI fungicides). an intermolecular network So as to Substantially prevent the 50 In some implementations, the combinations include a first polychlorinated Cu (II) phthalocyanine from separating out and separately contained composition and a second and of Suspension during application, e.g., to a turfgrass. separately contained composition, in which: (1) the first and separately contained composition B Combinations that Include Two or More Composi includes: tions 55 one (or more) paraflinic oils, which can include any one 1. or more of the features described in any one or more of In some implementations, the combinations include two sections IB1, IB2, and IB3 above; and or more separately contained (e.g., packaged) compositions, one (or more) emulsifiers, which can include any one or each containing one or more of the components described in more of the features described in any one or more of sections IA-IIF and IIIH). These implementations are 60 sections IC1, ICI2, and IC3 above: Sometimes referred to (as appropriate and without limitation, (2) the second and separately contained composition e.g., as to quantity or application mode) as 2-pack and includes: 3-pack formulations, compositions, or concentrates in the one (or more) conventional chemical fungicides, which absence of water for dilution. can include any one or more of the features described In some implementations, the combinations include a first 65 in any one or more of sections (IA1 and/or ILA and separately contained composition and a second and 2 (e.g., one or more DMI fungicides and/or one or separately contained composition, in which: more QoI fungicides); US 9,451,773 B2 21 22 one (or more) pigments, which can include any one or (2-ddd) the weight ratio of paraflinic oil in a composition more of the features described in section ID above: to the weight ratio of paraffinic oil to the conventional and chemical fungicide (e.g., one or more DMI fungicides one (or more) silicone surfactants, which can include any and/or one or more QoI fungicides) in the same or a different one or more of the features described in any one or 5 composition is from 2:1 to 10,000:1 (e.g., from 100:1 to more of sections IE1, IE2, and IE3 160:1; from 90:1 to 120:1, e.g., 111:1, 110:1; from 130:1 to above. 150:1, e.g., 139:1, 140:1). In some implementations, the combinations include a first In certain implementations, (2-aaa) applies; or (2-aaa), and separately contained composition and a second and (2-bbb) and (2-ccc) apply; or (2-bbb), and (2-ccc) apply. In separately contained composition, in which: 10 certain implementations, (2-ddd) further applies to any one (1) the first and separately contained composition of the above-listed combinations of (2-aaa), (2-bbb) and includes: (2-ccc). one (or more) paraflinic oils, which can include any one In some of the implementations described in section or more of the features described in any one or more of IIIB1), one or more of the following applies: sections IB1, IB2, and IB3 above; and 15 (2-aaaa) the composition (concentrate) includes from 50 one (or more) emulsifiers, which can include any one or to 300 parts per weight (e.g., 100) parts per weight of the more of the features described in any one or more of paraffinic oil; sections IC1, ICI2, and IC3 above: (2-bbbb) the composition (concentrate) includes from 1 to (2) the second and separately contained composition 10 parts per weight (e.g., 1.9, e.g. 2) parts per weight of the includes: emulsifier; one (or more) pigments, which can include any one or (2-cccc) the composition (concentrate) includes from 1 to more of the features described in section ID above: 10 parts per weight (e.g., 3.5) parts per weight of the and pigment; one (or more) silicone surfactants, which can include any (2-dddd) the composition (concentrate) includes from 0.1 one or more of the features described in any one or 25 to 10 parts per weight (e.g., 0.8) parts per weight of the more of sections IE1, IE2, and IE3 silicone Surfactant; above. (2-eeee) the composition (concentrate) includes from 0.5 In some implementations, the combinations include a first to 20 parts per weight (e.g., 3.1) parts per weight of the and separately contained composition, a second and sepa anti-settling agent; or rately contained composition, and a third and separately 30 (2-ffff) the composition (concentrate) includes from 0.01 contained composition, wherein: to 10 parts per weight (e.g., 0.8) parts per weight of the (1) the first and separately contained composition conventional chemical fungicide (e.g., one or more DMI includes: fungicides and/or one or more QoI fungicides). one (or more) paraflinic oils, which can include any one In certain implementations, (2-aaaa) and (2-bbbb) apply: or more of the features described in any one or more of 35 or (2-aaaa) through (2-eeee) apply; or (2-ffff) applies; or sections IB1, IB2, and IB3 above; and (2-cccc), (2-dddd), and (2-ffff) apply; or (2-cccc) and one (or more) emulsifiers, which can include any one or (2-dddd) apply. more of the features described in any one or more of In certain implementations, (2-aaaa) through (2-eeee) sections IC1, ICI2, and IC3 above; and apply in a composition (concentrate), and (2-ffff) applies in (2) the second and separately contained composition 40 another composition (concentrate). includes: In certain implementations, (2-aaaa) and (2-bbbb) apply one (or more) pigments, which can include any one or in a composition (concentrate), and (2-cccc), (2-dddd), and more of the features described in section ID above (2-ffff) apply in another composition (concentrate). and In certain implementations, (2-aaaa) and (2-bbbb) apply one (or more) silicone surfactants, which can include any 45 in a composition (concentrate), and (2-cccc) and (2-dddd) one or more of the features described in any one or apply in another composition (concentrate). more of sections IE1, IE2, and IE3 In certain implementations, (2-aaaa) through (2-eeee) above; and apply in a composition (concentrate), (2-cccc) and (2-dddd) (3) the third and separately contained composition apply in a second composition (concentrate), and (2-ffff) includes: 50 applies in a third composition (concentrate). one (or more) conventional chemical fungicides, which In some implementations, any one or more of the features can include any one or more of the features described described in one or more of (2-aaa) and (2-ddd) can be in any one or more of sections (IA1 and/or ILA combined with any one or more of the features described in 2 (e.g., one or more DMI fungicides and/or one or one or more of (2-aaaa) and (2-ffff). more QoI fungicides). 55 In some of the implementations described in section 2 Component Amounts in Combinations Having Two or IIIB1), the second composition can further include water More Composition (Concentrates) (e.g., resulting in a dispersion of the pigment in the water). In Some of the implementations described in section In some of the implementations described in section IIIB1), one or more of the following applies: IIIB1), the first and second composition include the (2-aaa) the weight ratio of paraffinic oil to the emulsifier 60 components present in CivitasTM 2-pack (CivitasTM/Harmo is from 10:1 to 500:1 (e.g., from 45:1 to 55:1, e.g., 49:1, nizerTM 16:1) and those present in commercially available 50:1); conventional chemical fungicides described anywhere (2-bbb) the weight ratio of paraffinic oil in a composition herein. to the pigment (in the same or a different composition) is In some of the implementations described in section from 5:1 to 100:1 (e.g., from 25:1 to 35:1, e.g., 28:1, 30:1); 65 IIIB1), the first and second composition include the (2-ccc) the weight ratio of pigment to the silicone surfac components present in CivitasTM 2-pack (CivitasTM/Harmo tant is from 2:1 to 50:1 (e.g., from 3:1 to 6:1, e.g., 4.5:1); nizerTM 16:1), and the third composition includes the com US 9,451,773 B2 23 24 ponents present in commercially available conventional lbs/acre (e.g., from 0.060 lbs/acre to 0.25 lbs/acre); or chemical fungicides described anywhere herein. a rate from (e.g., tebuconazole, prothioconazole) 0.02 3 to about 0.45 lbs./acre; or at a rate from (e.g., tetacon In some of the implementations described in sections azole) 0.015 to about 0.15 lbs./acre: IIIB1 and IIIB2, each of the compositions, indepen QoI fungicide is applied to a plant (e.g., crop plant) at a dently, further includes water. In certain implementations, rate from 0.01 lbs/acre to 0.50 lbs/acre (e.g., azox the combination of compositions (concentrates) described ystrobin); or a rate from 0.02 lbs/acre to 0.40 lbs/acre above are combined and diluted with water (e.g., spray (e.g., pyraclostrobin); or a rate from and volume of the diluted end product is 5 to 50 gal/acre, e.g., conventional chemical fungicide (e.g., one or more DMI 10 to 20 gal/acre). In certain implementations, oil in the end 10 fungicides and/or one or more QoI fungicides) is used product is from 80 to 640 oz/acre (other components can be or applied to the plant 1 to 5 times during growing calculated based on ratio with oil). season until harvest, with intervals greater or equal to C 14 days. As the skilled artisan will appreciate, the weight percent In certain implementations, the interval rates for the of a given component(s) can vary, e.g., due to dilution with 15 paraflinic oil and the conventional chemical fungicide (e.g., water or whether the combination is in the form of a single one or more DMI fungicides and/or one or more QoI composition or two or more separately contained composi fungicides) overlap (e.g., when tank-mixed and applied at tions. In some implementations, the weight ratio of any two the same time). In other implementations, the interval rates or more components is essentially the same regardless of for the paraflinic oil and the conventional chemical fungi whether the combination is in the form of a single compo cide (e.g., one or more DMI fungicides and/or one or more sition (diluted with water or undiluted) or in the form two or QoI fungicides) do not overlap (e.g., when applied sepa more separately contained compositions (diluted with water rately and/or sequentially). or undiluted). In the latter case, this can be achieved by In Some implementations, the combinations described adjusting the component amounts in each of the separately herein can be prepared using the methods described in, for contained compositions to match, for example, a weight 25 example, WO 2009/155693. percent ratio employed in single composition combination. The features described in section III above can be com III. Application of Combinations bined with any one or more of the features described in In general, the combinations can be applied to the plant by sections I and II above. conventional methods known in the art, e.g., spraying, In some implementations, the fungal pathogen may be, for misting, sprinkling, pouring, or any other Suitable method. 30 example, Gymnosporangium juniperi-virginianae, Cronar The compositions may be reapplied as required. tium ribicola, Hemileia vastatrix Puccinia graminis, Puc In some implementations, the combinations include both cinia coronata, Puccinia hemerocallidis, Puccinia persis paraffinic oil and water. It is advantageous to apply Such tens subsp. Triticina, Puccinia sriiformis, Puccinia triticina, combinations as oil-in-water (O/W) emulsions. In some Phakopsora meibomiae, Phakopsora pachyrhizi, Uromyces implementations, an oil-in-water emulsion is prepared by a 35 phaseoli, Uromyces appendeculatus, Fusarium process that includes combining the paraflinic oil, water, and graminearum, Bipolaris Sorokiniana, or a combination any other components and the paraflinic oil and applying thereof. In alternative implementations, the fungal disease shear until the emulsion is obtained. In other implementa may be, for example: cedar-apple rust, which attacks, for tions, an oil-in-water emulsion is prepared by a process that example, apple and pear and hawthorn); white pine blister includes combining the paraflinic oil, water, and any other 40 rust, which attacks, for example, white pines and currants; components at the nozzle of a spray gun. coffee rust, which attacks, for example, the coffee plant; In other implementations, the combinations can include wheat stem rust, which attacks, for example, Kentucky two or more separately contained (e.g., packaged) compo bluegrass, barley, and wheat; crown rust, which attacks, for sitions, each containing one or more of the above-mentioned example, oats and ryegrass; soybean rust, which attacks, for components. Said compositions can be combined and 45 example, soybean and various legumes; leaf rust, which applied to a plant (e.g., crop plant) with or without prior attacks, for example, wheat; bean rust which attacks, for dilution with water, or each composition can be applied example, bean: Daylily rust, which attacks, for example, separately to the same plant (e.g., crop plant) either simul Daylily; wheat rust in grains, also known as “brown' or “red taneously or sequentially, and each independently applied rust'): 'yellow' or “stripe rust', which attacks, for example, with or without prior dilution with water. 50 wheat; spot blotch, which attacks, for example, wheat; and In the above-described implementations, application of Fusarium head blight, which attacks, for example, wheat. any one (or more) compositions can be repeated one or more In alternative implementations, the fungal pathogen may times. be, for example, a fungus that blights leaf tissue in a crop In some implementations, any one or more of the follow plant. In selected implementations, the crop plant pathogen ing can apply: 55 is the fungal pathogen Gymnosporangium juniperi-virgini the paraflinic oil is applied to a plant (e.g., crop plant) at anae, and the disease may be, for example, cedar-apple rust. a rate from 80 to 640 oz/acre (e.g., from 100 oz/acre to In alternative implementations, the crop plant pathogen is 400 oz/acre); the fungal pathogen Cronartium ribicola, and the disease the paraflinic oil is used or applied to the plant (e.g., crop may be, for example, white pine blister rust. In selected plant) 1 to 10 times during growing season until 60 implementations, the crop plant pathogen is the fungal harvest, with intervals greater or equal to 7 days; pathogen, and the disease may be, for example, coffee rust. conventional chemical fungicide (e.g., one or more DMI In alternative implementations, the crop plant pathogen is fungicides and/or one or more QoI fungicides) is the fungal pathogen Pucciniagraminis, and the disease may applied to a plant (e.g., crop plant) at a rate from 0.01 be, for example, wheat stem rust. In selected implementa lbs/acre to 1.50 lbs/acre; 65 tions, the crop plant pathogen is the fungal pathogen Puc DMI fungicide (e.g., propioconazole) is applied to a plant cinia coronata, and the disease may be, for example, crown (e.g., crop plant) at a rate from 0.015 lbs/acre to 0.6 rust. In alternative implementations, the crop plant pathogen US 9,451,773 B2 25 26 is the fungal pathogen Phakopsora meibomiae or Phako TABLE 1-continued spora pachyrhizi, and the disease may be, for example, Soybean rust. In alternative implementations, the crop plant Fungal diseases of Wheat. pathogen is the fungal pathogen Uromyces phaseoli, and the Disease Causative fungal pathogen(s) disease may be, for example, bean rust. In selected imple Eyespot = foot rot, Tapesia valiundae mentations, the crop plant pathogen is the fungal pathogen strawbreaker Rantispora herpoirichoides anamorph = Puccinia hemerocallidis, and the disease may be, for Pseudocercosporella herpotrichoides example, Daylily rust. In alternative implementations, the W-pathotype crop plant pathogen is the fungal pathogen Puccinia persis Tapesia actifornis 10 Rantispora actformis anamorph = tens Subsp. triticina, and the disease may be, for example, Pseudocercosporella herpotrichoides brown rust or red rust. In selected implementations, the crop var. actifornis R-pathoytpe False eyespot Gibeina cereais plant pathogen is the fungal pathogen Puccinia Sriiformis, Flag Smut Urocystis agropyri and the disease may be, for example, yellow rust or strip Foot rot = dryland Fusarium spp. rust. In alternative implementations, the crop plant pathogen foot rot is the fungal pathogen Uromyces appendeculatus, and the 15 Halo spot Pseudoseptoria donacis = Selenophoma donacis disease may be, for example, bean rust. In selected imple Karnal bunt = Tilletia indica = mentations, the crop plant pathogen is the fungal pathogen partial bunt Neovossia indica Puccinia triticina, and the disease may be, for example, leaf Leaf rust = Puccinia triticina = brown rust Puccinia recondita f.sp. tritici rust. In alternative implementations, the crop plant fungal Puccinia tritici-diuri pathogen is Fusarium graminearum and the disease may be, Leptosphaeria Phaeosphaeria herpotrichoides = for example, Fusarium head blight. In selected implemen leaf spot Leptosphaeria herpoirichoides Stagonospora sp. anamorph tations, the crop plant pathogen is the fungal pathogen Loose Smut Ustilago tritici = Bipolaris Sorokiniana, and the disease may be, for example, Ustilago Segettin var. tritici spot blotch. 25 Ustilago Segettin var. nuda Ustilago Segettin var. avenae In various additional implementations wherein the crop Microscopica Phaeosphaeria microscopica = plant is wheat, the fungal pathogen may be any one of the leaf spot Leptosphaeria microscopica Phoma spot Phoma spp. fungal pathogens listed in the right hand column of Table 1, Phoma glomerata and the disease may be the corresponding disease of wheat 30 Phoma sorghina = listed in the left column of Table 1. Phoma insidiosa Pink Snow Microdochium nivale = mold = Fusarium Fusarium nivale TABLE 1. patch Monographeila nivais teleomorph Platyspora Clathrospora pentamera = Fungal diseases of wheat. leaf spot Platyspora pentamera 35 Powdery Erysiphe graminis f.sp. tritici Disease Causative fungal pathogen(s) mildew Blumeria graminis = Erysiphe graminis Alternaria leaf blight Alternaria triticina Anthracnose Colletotrichum graminicola Oidium monioides anamorph Glomerella graminicola teleomorph Pythium root Pythium aphanidermatum Ascochyta leaf spot Ascochyta tritici 40 rot Pythium arrhenomanes Aureobasidium Microdochium boileyi = Pythium graminicola decay Aureobasidium boileyi Pythium myriotylum Black head molds = Alternaria spp. Pythium volutum Sooty molds Cladosporium spp. Rhizoctonia Rhizoctonia Soiani Epicoccim spp. root rot Thanatephorus cucumenis teleomorph Sporobotomyces spp. 45 Ring spot = Pyrenophora seminiperda = Siemphylium spp. and other genera Wirrega blotch Drechslera Campanulata Cephalosporium Hymenula cerealis = Drechslera wirreganensis stripe Cephalosporium graninet in Scab = head Fusarium spp. Common bunt = Tilletia tritici = blight Gibbereia zeae Stinking Smut Tilletia caries Fusarium graminear in Group II anamorph Tilletia iaevis = 50 Gibbereia avenacea Tilletia foetida Fusarium avenacetin anamorph Common root rot Cochliobolus sativus teleomorph Fusarium cuinorum Bipolaris Sorokiniana anamorph = Microdochium nivale = Helminthosporium sativum Fusarium nivale Cottony Snow mold Coprinus psychromorbidus Monographeila nivais teleomorph Crown rot = foot rot, Fusarium spp. 55 Scierotinia Myriosclerotinia borealis = Seedling blight, Fusarium pseudograminearlin Snow mold = Snow Scierotinia boreais dryland root rot Gibbereia zeae Scald Fusarium graminearlin Group II anamorph Scierotium Sclerotium rolfsii Gibberelia avenacea wilt (see Southern Athelia rolfsii teleomorph Fusarium avenacetin anamorph blight) Fusarium cuinorum 60 Septoria Septoria tritici Dilophospora leaf Dilophospora alopectiri blotch Mycosphaerella graminicola teleomorph spot = twist Sharp Rhizoctonia cereais Downy mildew = Sclerophthora macrospora eyespot Ceratobasidium cereale teleomorph crazy top Snow rot Pythium spp. Dwarf bunt Tilletia controversa Pythium aristosporum Ergot Claviceps purpurea 65 Pythium iwayamae Sphacelia Segettin anamorph Pythiin Okanoganense US 9,451,773 B2 27 28 TABLE 1-continued TABLE 1-continued Fungal diseases of Wheat. Fungal diseases of Wheat. Disease Causative fungal pathogen(s) 5 Disease Causative fungal pathogen(s) Southern Sclerotium rolfsii Stripe rust = Puccinia Striiformis blight = Sclerotium Athelia rolfsii teleomorph yellow rust Uredo glunarum anamorph base rot Take-all Gaeli mannomyces graminis var. tritici Speckled Typhula idahoensis Gaeli mannomyces graminis var. avenae Snow mold = gray Tiphatia incarnata Tan spot = Pyrenophora tritici-repentis Snow mold or Typhula ishikariensis 10 yellow leaf spot, red Drechslera tritici-repentis anamorph Typhula blight Tiphatia ishikariensis var. Canadensis Smudge Spot blotch Cochliobolus sativus teleomorph Tar spot Phyllachora graminis Bipolaris Sorokiniana anamorph = Linochora graminis anamorph Helminthosporium sativum Wheat Blast Magnaporthe grisea Stagonospora Phaeosphaeria avenaria f. sp. triticae Zoosporic Lagena radicicola blotch Stagonospora avenae f.sp. triticae anamorph = is root rot Ligniera pilorum Septoria avenae f.sp. triticea Olipidium brassicae Phaeosphaeria nodorum Rhizophydium graminis Stagonospora nodorum anamorph = Septoria nodorum Stem rust = Puccinia graminis = In various additional embodiments wherein the crop plant blackStorage rust AspergiliusPuccinia graminis spp. f.sp. tritici (Ug99) 20 is of the genus Zea, the fungal pathogen may be any one of molds Penicilium spp. the fungal pathogens listed in the right hand column of Table and others 2, and the disease may be the corresponding disease of wheat listed in the left column of Table 2. TABLE 2 Fungal diseases of maize. Disease Causative fungal pathogen Anthracnose leaf blight Colleiotrichum graminicola Anthracnose stalk rot Glomerella graminicola teleomorph Giomerelia iucumanensis Glomerelia falcatum anamorph Aspergilius ear and Aspergiiitisfia vils kernel rot Banded leaf and Rhizoctonia Soiani = Rhizoctonia microsclerotia sheath spot Thanatephorus cucumenis teleomorph Black bundle disease Acremonium strictum = Cephalosporium acremonium Black kernel rot Lasiodiplodia theobromae = Botryodiplodia theobromae Borde blanco Marasnielius sp. Brown spot Physoderma maydis Black spot Stalk rot Cephalosporium kernel Acremonium strictum = Cephalosporium acremonium rot Charcoal rot Macrophomina phaseolina Coricitin ear rot Thanatephorus cucumenis = Corticium Sasaki Curvularia leaf spot Curvularia clavata Curvularia eragrostidis = Curvularia maculans Cochliobolus eragrostidis teleomorph Curvularia inaequalis Curvularia intermedia Cochliobolus intermedius teleomorph Curvularia iunata Cochliobolus lunatus teleomorph Curvularia pallescens Cochliobolus pallescens teleomorph Curvularia Senegaliensis Curvularia tuberculata Cochliobolus tuberculatus teleomorph Didymella leaf spot Didymella exitalis Diplodia ear rot and Diplodia frumenti stalk rot Botryosphaeria festicae teleomorph Diplodia ear rot Diplodia maydis Stalk rot Seed rot Seedling blight Diplodia leaf spot or Stenocarpella macrospora = Diplodia macrospora leaf streak Brown stripe downy Sclerophthora rayssiae mildew US 9,451,773 B2 29 30 TABLE 2-continued Fungal diseases of maize. Disease Causative fungal pathogen Crazy top downy Sclerophthora macrospora = Sclerospora macrospora mildew Green ear downy Sclerospora graminicola mildew Graminicola downy mildew Java downy mildew Peronosclerospora maydis = Sclerospora maydis Philippine downy Peronosclerospora philippinensis = mildew Sclerospora philippinensis Sorghum downy Peronosclerospora sorghi = Scierospora sorghi mildew Spontaneim downy Peronosclerospora spontanea = Sclerospora spontanea mildew Sugarcane downy Peronosclerospora sacchari = Scierospora sacchari mildew Dry ear rot Nigrospora oryzae Cob, kernel and stalk rot Khuskia oryzae teleomorph Ear rots, minor Alternaria alternata = Alternaria tentiis Aspergilius glaucus Aspergilius niger Aspergilius spp. Botrytis cinerea Botryotinia fuckeiana teleomorph Cunninghamelia sp. Curvilaria pallescens Doratomyces stemonitis = Cephalotrichum stemonitis Fusarium cuinorum Gonatobotry's simplex Pithomyces maydicus Rhizopus microsports Rhizopus Stoionifer = Rhizopus nigricans Scopulariopsis brainpiii Ergot Claviceps gigantea Horse's tooth Sphacelia sp. anamorph Eyespot Aureobasidium zeae = Kabaiella zeae Fusarium ear and stalk Fusarium subglutinans = Fusarium moniiforme rot Fusarium kernel, root Fusarium moniiforme and stalk rot, seed rot and Gibberella filiikuroi teleomorph Seedling blight Fusarium stalk rot Fusaritin avenacetim Seedling root rot Gibberella avenacea teleomorph Gibbereia ear and Gibbereia zeae stalk rot Fusarium graminearlin anamorph Gray ear rot Botryosphaeria zeae = Physalospora zeae Macrophoma zeae anamorph Gray leaf spot Cercospora Sorghi = Cercospora Sorghi Cercospora leaf spot Cercospora zeae-maydis Helminthosporium root Exserohilum pedicellatum = rot Helminthosporium pedicellatum Setosphaeria pedicellata teleomorph Hormodendrum ear rot Cladosporium cladosporioides = Cladosporium rot Hormodendrum cladosporioides Cladosporium herbarium Mycosphaerelia tassiana teleomorph Hyalothyridium leaf Hyalothyridium maydis spot Late wilt Cephalosporium maydis Leaf spots, minor Alternaria alternata Ascochyta maydis Ascochyta tritici Ascochyta zeicola Bipolaris victoriae = Heiminthosporium victoriae Cochliobolus victoriae teleomorph Cochioboius Saiivus Bipolaris Sorokiniana anamorph = Helminthosporium sorokinianum = H. sativum Epicocci in nigrin Exserohilum prolatum = Drechslera prolata Setosphaeria prolata teleomorph Graphium penicillioides Leptosphaeria maydis Leptothyrium zeae Ophiosphaerella herpotricha Scolecosporiella sp. anamorph Paraphaeosphaeria michotii Phoma sp. US 9,451,773 B2 31 32 TABLE 2-continued Fungal diseases of maize. Disease Causative fungal pathogen Septoria zeae Septoria zeicola Septoria zeina Northern corn leaf Setosphaeria turcica blight Exserohium turcictim anamorph = White blast Helminthosporium turcicum Crown stalk rot Stripe Northern corn leaf spot Cochiobolus carbonium Helminthosporium ear rot Bipolaris zeicola anamorph = (race 1) Helminthosporium carbonium Penicilium ear rot Penicillium spp. Blue eye Penicillium chrysogenium Blue mold Penicillium expansum Penicium oxalicum Phaeocytostroma stalk Phaeocytostrona ambiguum = Phaeocytosporelia zeae rot and root rot Phaeosphaeria leaf Phaeosphaeria maydis = Sphaerulina maydis spot Physalospora ear rot Botryosphaeria festicae = Physalospora zeicola Botryosphaeria ear rot Diplodiafitinenii anamorph Purple leaf sheath Hemiparasitic bacteria and fungi Pyrenochaeta stalk rot Phoma terrestris = Pyrenochaeta terrestris and root rot Pythium root rot Pythium spp. Pythium arrhenomanes Pythium graminicola Pythium stalk rot Pythium aphanidermatum = Pythium butleri Red kernel disease Epicocci in nigrin Ear mold, leaf and seed rot Rhizoctonia ear rot Rhizoctonia zeae Sclerotial rot Waitea circinata teleomorph Rhizoctonia root rot Rhizoctonia Soiani and stalk rot Rhizoctonia zeae Root rots, minor Alternaria alternata Cercospora Sorghi Dictochaeta fertilis Fusarium acuminatum Gibberella acuminata teleomorph Fusarium equiseti Gibberella intricans teleomorph Fusarium oxysportin Fusarium pallidoroseum Fusarium poae Fusaritin roseum Gibberella cyanogena Fusarium sulphureum anamorph Microdochium boileyi Mucor sp. Periconia circinata Phytophthora cactorum Phytophthora drechsleri Phytophthora nicotianae Rhizopus arrhizus Rostratum leaf spot Setosphaeria rostrata = Heiminthosporium rostratum Helminthosporium leaf disease, ear and stalk rot Rust, common corn Puccinia sorghi Rust, southern corn Puccinia polysora Rust, tropical corn Physopeia pallescens Physopeia zeae = Angiopsora zeae Scierotium ear rot Sclerotium rolfsii Southern blight Athelia rolfsii teleomorph Seed rot-seedling blight Bipolaris Sorokiniana Bipolaris zeicola = Heiminthosporium carbonium Diplodia maydis Exserohilum pediciliatum Exserohilum turcicum = Heiminthosporium turcicum Fusaritin avenacetim Fusarium cuinorum Fusarium moniiforme Gibbereia zeae Fusarium graminearlin anamorph Macrophomina phaseolina Penicillium spp. Phomopsis spp. Pythium spp. US 9,451,773 B2 33 34 TABLE 2-continued Fungal diseases of maize. Disease Causative fungal pathogen Rhizoctonia Soiani Rhizoctonia zeae Sclerotium rolfsii Spicaria spp. Selenophoma leaf spot Selenophoma sp. Sheath rot Gaeli mannomyces graminis Shuck rot Myrothecium gramineum Silage mold Monascus purpureus Monascus ruber Smut, common Ustilago zeae = Ustilago maydis Smut, false Ustilaginoidea virens Smut, head Sphacelotheca reiliana = Sporisorium holici-sorghi Southern corn leaf Cochliobolus heterostrophus blight and stalk rot Bipolaris maydis anamorph = Heiminihosporium maydis Southern leaf spot Stenocarpella macrospora = Diplodia macrospora Stalk rots, minor Cercospora Sorghi Fusarium episphaeria Fusarium merismoides Fusarium oxysportin Fusarium poae Fusaritin roseum Fusarium Soiani Nectria haematococca teleomorph Fusarium tricincitin Mariannaea elegans Mucor spp. Rhopographits zeae Spicaria spp. Storage rots Aspergilius spp. Penicillium spp. and other fungi Tar spot Phyllachora maydis Trichoderma ear rot Trichoderma viride = Trichoderma ignorum and root rot Hypocreasp. teleomorph White ear rot, root and Stenocarpella maydis = Diplodia zeae stalk rot Yellow leaf blight Ascochyta ischaemi Phyllosticta maydis Mycosphaerella zeae-maydis teleomorph Zonate leaf spot Gloeocercospora Sorghi
40 In various additional embodiments wherein the crop plant TABLE 3-continued is barley, the fungal pathogen may be any one of the fungal pathogens listed in the right hand column of Table 3, and the Fungal diseases of barley. disease may be the corresponding disease of wheat listed in Disease Causative fungal pathogen(s) the left column of Table 3. 45 Kernel blight = black point Alternaria spp. TABLE 3 Arthrinium arundinis’ Apiospora montagnei teleomorph Fungal diseases of barley. Cochioboitius Saiivus Fusarium spp. Disease Causative fungal pathogen(s) 50 Ascochyta leaf spot Ascochyta hordei Ascochyta graminea Anthracnose Coileiotrichum cerealie Manns Ascochyta Sorghi Barley stripe Pyrenophora graminea = Ascochyta tritici Drechslera graminea Net blotch Drechsiera teres Cephalosporium stripe Hymenula cerealis = Pyrenophora teres teleomorph Cephalosporium graninetim 55 Net blotch (spot form) Drechslera feres f. maculata Common root rot, crown rot and Cochioboius Saiivus = Powdery mildew Erysiphe graminis f.sp. hordei = Seedling blight Bipolaris Sorokiniana Blumeria graminis Fusarium cuinorum Oidium monilioides anamorph Fusarium graminearlin Pythium root rot Pythium spp. Gibberella zeae teleomorph Pythium arrhenomanes Downy mildew Sclerophthora rayssiae 60 Pythium graminicola Dwarf bunt Tieiia controversa Pythium tardicrescens Ergot Claviceps purpurea Rhizoctonia root rot Rhizoctonia Soiani Sphacelia Segettin anamorph Thanatephorus cucumenis teleomorph Eyespot Pseudocercosoporella herpotrichoides Crown rust Puccinia Coronata war. hordei Tapesia waitindae teleomorph Leaf rust Puccinia hordei Halo spot Pseudoseptoria donacis = 65 Stem rust Puccinia graminis f.sp. Secais Selenophoma donacis Puccinia graminis f.sp. tritici US 9,451,773 B2 35 36 TABLE 3-continued TABLE 4-continued Fungal diseases of barley. Fungal diseases of rice. Disease Causative fungal pathogen(s) 5 Disease Causative fungal pathogen(s) Stripe rust = yellow rust Puccinia Striiformis f.sp. hordei Narrow brown leaf spot Cercosporalianseana = Scab = head blight Fusarium spp. Cercospora oryzae Fusarium graminearlin Sphaerulina oryzina teleomorph Scald Rhynchosporium secalis Pecky rice (kernel spotting) Damage by many fungi including Septoria speckled leaf blotch Septoria passerinii Cochliobolus miyabeanus Stagonospora avenae f.sp. triticae 10 Curvilaria spp. Sharp eyespot Rhizoctonia cereais Fusarium spp. Ceratobasidium cereale teleomorph Microdochium oryzae Covered Smut Ustilago hordei Sarocladium oryzae False loose Smut Ustilago nigra = and other fungi. Ustilago a venae Root rots Fusarium spp. Loose Smut Ustilago nuda = 15 Pythium spp. Ustilago tritici Pythium dissotocum Gray Snow mold = Typhula Tiphatia incarnata Pythium spinosum blight Typhula ishikariensis Seedling blight Cochliobolus miyabeanus Pink Snow mold = Fusarium Microdochium nivale = Curvilaria spp. patch Fusarium nivale Fusarium spp. Monographeila nivais teleomorph Rhizoctonia Soiani Speckled Snow mold Typhula idahoensis 2O Sclerotium rolfsii Snow rot Pythium iwayamae Athelia rolfsii teleomorph Pythiin Okanoganense and other pathogenic fungi. Pythium paddicum Sheath blight Thanatephorus cucumenis Snow scald = Scierotinia Snow Myriosclerotinia borealis = Rhizoctonia Soiani anamorph mold Scierotinia borea is Sheath rot Sarocladium oryzae = Southern blight Sclerotium rolfsii 25 Acrocylindrium oryzae Athelia rolfsii teleomorph Sheath spot Rhizoctonia oryzae Spot blotch Cochioboius Saiivus Stackburn (Alternaria leaf spot) Alternaria padwickii Drechslera feres anamorph Stem rot Magnaporthe Salvini Stagonospora blotch Stagonospora avenae f.sp. triticae Sclerotium oryzae Synanamorph Phaeosphaeria avenaria f. sp. triticae Water-mold (seed-rot and seedling Achiya conspicua teleomorph 30 disease) Achlya kiebsiana Stagonospora nodorum = Fusarium spp. Septoria nodorum Pythium spp. Phaeosphaeria nodorum teleomorph Pythium dissotocum Take-all Gaeli mannomyces graminis war tritici Pythium spinosum Tan spot Pyrenophora tritici-repentis = Pyrenophora trichostoma 35 DrechsleraHelminthosporium tritici-repentis tritici-repentis (anamorph) = In various additional embodiments wherein the crop plant Verticillium wiltill Verticilium dahiae is soybean, the fungal pathogen may be any one of the fungal Wirrega blotch Drechslera wirreganensis pathogens listed in the right hand column of Table 5, and the disease may be the corresponding disease of wheat listed in 40 the left column of Table 5. In various additional embodiments wherein the crop plant is rice, the fungal pathogen may be any one of the fungal TABLE 5 pathogens listed in the right hand column of Table 4, and the disease may be the corresponding disease of wheat listed in Fungal diseases of soybean. the left column of Table 4. 45 a. Disease Causative fungal pathogen(s) TABLE 4 Alternaria leaf spot Alternaria spp. Anthracnose Colleiotrichum truncatum Fungal diseases of rice. Colleiotrichum dematium f. truncatum Glomerella glycines Disease Causative fungal pathogen(s) 50 Colleiotrichum destructivum anamorph Aggregate sheath spot Ceratobasidium oryzae-Saiivae Black leaf blight Arkoola nigra Rhizoctonia oryzae-Saiivae Black root rot Thiela viopsis basicola anamorph Chaiara elegans synanamorph Black kernel Curviliaria iunata Brown spot Septoria glycines Cochliobolus lunatus teleomorph) ss Mycosphaerella isoenskaiae Blast (leaf, neck rotten neck, Pyricularia grisea = teleomorph nodal and collar) Pyricularia oryzae Brown stem rot Phialophora gregata = Magnaporihe grisea teleomorph Cephalosporium gregatin Brown spot Cochliobolus miyabeanus Charcoal rot Macrophomina phaseolina Bipolaris Oryzae anamorph Choanephora leaf blight Choanephora infundibulifera Crown sheath rot Gaeli mannomyces graminis 60 Choanephora trispora Downy mildew Sclerophthora macrospora Damping-off Rhizoctonia Soiani Eyespot Drechslera gigantea Thanatephorus cucumenis False Smut Ustilaginoidea virens teleomorph Kernel Smut Tilletia barclayana = Pythium aphanidermatum Neovossia horrida Pythium debaryanum Leaf Smut Entwioma oryzae Pythium irregulare Leafscald Microdochium oryzae = 65 Pythium myriotylum Rhynchosporium oryzae Pythium ultimum US 9,451,773 B2 37 38 TABLE 5-continued TABLE 6-continued Fungal diseases of Soybean. Fungal diseases of potato. Disease Causative fungal pathogen(s) 5 Disease Causative fungal pathogen(s) Downy mildew Peronospora manshurica Choanephora blight Choanephora cucurbitarum Drechslera blight Drechslera glycines Common rust Puccinia pittieriana Frogeye leaf spot Cercospora Sojina Deforming rust Aecidium cantensis Fusarium root rot Fusarium spp. Early blight Alternaria Soiani Leptosphaerulina leaf spot Leptosphaerulina trifolii Fusarium dry rot Fusarium spp. Mycoleptodiscus root rot Mycoleptodiscus terrestris 10 Gibberella pulicaris = Neocosmospora stem rot Neocosmospora vasinfecta Fusarium Soiani Acremonium spp. anamorph Other Fusarium spp. include: Phomopsis seed decay Phomopsis spp. Fusaritin avenacetin Phytophthora root and stem rot Phytophthora soiae Fusarium oxysportin Phyllosticta leaf spot Phyllosticta soiaecola Fusarium cuinorum Phymatotrichum root rot = Phymatotrichopsis omnivora : 15 Less common Fusarium spp. include: cotton root rot Phymatotrichum omnivorum Fusaritin actiminatin Pod and stem blight Diaporihe phaseolorum Fusarium equiseti Phomopsis Soiae anamorph Fusarium crookweilense Powdery mildew Microsphaera diffusa Fusarium wilt Fusarium spp. Purple seed stain Cercospora kikuchii Fusaritin avenacetin Pyrenochaeta leaf spot Pyrenochaeta glycines Fusarium oxysportin Pythium rot Pythium aphanidermatum 2O Fusarium Solani f.sp. etinarii Pythium debaryanum Gangrene Phoma Solanicola f. foveata Pythium irregulare Phoma foveata = Pythium myriotylum Phoma exigua var. foveata = Pythium ultimum Phoma exigua f. sp. foveata Red crown rot Cylindrocladium crotaiariae Phoma exigua var. exigua Caionectria crotaiariae 25 Gray mold Botrytis cinerea teleomorph Botryotinia fuckeiana teleomorph Red leaf blotch = Dactitiochaeta glycines = Late blight Phytophthora infestans Dactuliophora leaf spot Pyrenochaeta glycines Leak Pythium spp. Dactitiophora glycines Pythium ultimum var. ultimum = synanamorph Pythium debaryanum Rhizoctonia aerial blight Rhizoctonia Soiani 30 Pythium aphanidermatum Thanatephorus cucumenis Pythium deliense teleomorph Phoma leaf spot Phoma andigena var. andina Rhizoctonia root and stem rot Rhizoctonia Soiani Pink rot Phytophthora spp. Rust Phakopsora pachyrhizi Phytophthora cryptogea Scab Spaceioma glycines Phytophthora drechsleri Scierotinia stem rot Scierotinia Scierotiorum 35 Phytophthora erythroseptica Southern blight (damping-off Sclerotium rolfsii Phytophthora megasperma and stem rot) = Sclerotium Athelia rolfsii teleomorph Phytophthora nicotianae var. parasitica blight Powdery mildew Erysiphe cichoracearum Stem canker Diaporihe phaseolorum Powdery scab Spongospora subterranea f.sp. subterranea Diaporihe phaseolorum Rhizoctonia canker and Rhizoctonia Soiani black scurf Thanatephorus cucumenis teleomorph var. cautivora * Rosellinia black rot Rosellinia sp. Phomopsis phaseoli anamorph Dematophora sp. anamorph Stemphylium leaf blight Siemphyllium botryosum Septoria leaf spot Septoria lycopersici var. malaguti Pleospora tarda teleomorph Silver scurf Helminthosporium solani Sudden death syndrome Fusarium Soiani f.sp. glycines Skin spot Polyscytalum pistians Target spot Corynespora cassicola Stem rot (southern blight) Sclerotium rolfsii Yeast spot Nematospora Coryli 45 Athelia rolfsii teleomorph Thecaphora Smut Angiosorus Soiani = Thecaphora Solani Ulocladium blight Uiociadium atrum In various additional embodiments wherein the crop plant Verticilium wilt Verticilium aibo-airtin is potato, the fungal pathogen may be any one of the fungal Verticilium dahiae pathogens listed in the right hand column of Table 6, and the 50 Wart Synchytrium endobioticum disease may be the corresponding disease of wheat listed in White mold Scierotinia Scierotiorum the left column of Table 6. Various alternative embodiments and examples of the TABLE 6 invention are described herein. These embodiments and 55 examples are illustrative, and not limiting. Fungal diseases of potato. Various implementations and examples of the combina tions are described herein. These implementations and Disease Causative fungal pathogen(s) examples are illustrative, and not limiting. Black dot Colleiotrichum coccodes = Colleiotrichum atramentarium EXAMPLES Brown spot and Black pit Alternaria alternata = 60 Alternaria tentiis Example 1 Cercospora leaf blotch Mycoveliosiella concors = Cercospora concors Cercospora Soiani Greenhouse Stem Rust Evaluation Study Cercospora Soiani-tuberosi Charcoal rot Macrophonina phaseolina = 65 The efficacy of CivitasTM alone or in combination with Scierotium bataiicola HarmonizerTM in controlling infection of wheat (Triticum aestivum Norin43) by Puccinia graminis f. sp. tritici US 9,451,773 B2 39 40 (“Pgt”) was tested under greenhouse conditions. Briefly, The experimental design was a randomized complete each treatment consisted of four pots containing four plants. block with five replicates. PumaTM (0.4 pt/A) and Bronate Plants were planted on March 2nd. CivitasTM, Harmo AdvancedTM (0.8 pt/A) were applied on June 10th to control nizerTM. and combinations thereof were applied to test weeds. On July 14th, urediniospores of Pgt were collected plants, by foliar application, on March 10th, seven days from nearby trap plots and applied to the spreader rows in a before inoculation (DBI) on March 17th as indicated in 0.1% water agar Suspension using a hand-powered backpack Table 7. The average severity of infection, in terms of% leaf sprayer. On July 20th, fungicide treatments were applied area infected, was evaluated 12 with a CO-powered backpack sprayer in a carrier Volume of TABLE 7 Results of greenhouse stem rust evaluation study. Greenhouse Stem Rust Evaluation Study Pathogen: Puccinia graminis f.sp. tritici % Leaf Area Treat Carrier Civitas Harmonizer severity Infection Type ID Method (gal/A) Timing (oz?acre) (oZacre) Treated Avg. Sev SD 9% Avg. IT SD 9.6 1. Foliar 2O 7DBI 160 O 3,10 2O.OO 7.07 2.25 O.SO 2 Foliar 2O 7DBI 32O O 3,10 1S.OO 4.08 2.25 O.SO 3 Foliar 2O 7DBI O 10 3,10 26.25 6.29 3.SO O.S8 4. Foliar 2O 7DBI O 2O 3,10 2S.OO 4.08 3.25 O.SO 5. Foliar 2O 7DBI 40 2.5 3,10 16.OO 2.71 2.50 O.S8 6 Foliar 2O 7DBI 160 10 3,10 11.25 4.79 1.75 O.SO 7 Foliar 2O 7DBI 32O 2O 3,10 8.75 4.79 1.25 O.SO 8 Drench 400 7DBI 160 O 3,10 17.50 6.45 2.25 O.SO 9 Drench 400 7DBI 32O O 3,10 16.25 2.50 2.25 O.SO 10 Drench 400 7DBI O 10 3,10 26.25 4.79 3.25 O.96 11 Drench 400 7DBI O 2O 3,10 2S.OO 7.07 3.25 O.SO 12 Drench 400 7DBI 40 2.5 3,10 17.50 2.89 2.00 O.82 13 Drench 400 7DBI 160 10 3,10 1O.OO 4.08 1...SO O.S8 14 Drench 400 7DBI 32O 2O 3,10 7.50 2.89 1.25 O.SO 15 Control 2O NA O O 3,10 27.50 6.45 3.75 O.SO days after inoculation on March 29th.
Example 2 20 gal/A using XR8002 flat fan nozzles and an application 35 pressure of 40 PSI. The plants in each plot were at Feekes Wheat Stem Rust Study 10.51 (early anthesis). At 48 hr after fungicide application, the experimental plots were inoculated as previously The efficacy of CivitasTM alone or in combination with described with Pgt and misted at night for 7 days (3 min on HarmonizerTM, FolicurTM, or QuiltTM in controlling infection per each 30 min) to facilitate infection and disease devel of wheat (Triticum aestivum Norin43) by Pgt was tested 40 opment. One treatment received a second application 7 days between May and July. A field was treated with RoundupTM later (Treatment 5, see Table 8 below). Plots were rated for on May 9th and cultivated twice before planting. Plots were stem rust severity at 14 d after inoculation by visually planted on May 28 using a seeding rate of 1.25 bu? A, and estimating the percentage of stem area covered with pustules were 15 ft long by 5 ft wide with 7 rows. Due to flooding in for 50 plants per plot (5 randomly chosen locations of 10 the field shortly after planting, plots lengths were reduced to 45 plants each). Plots were harvested with a small plot combine 7 ft long prior to cutting of the alleys. Plots consisting of a and yield was determined. Data were analyzed using an highly susceptible rust spreader mixture were alternated ANOVA and pair-wise comparisons were performed using with the experimental units. Tukey's HSD (P=0.05). TABLE 8 Results of Wheat Stern Rust Study Average Upper Stem Stem Severity (% Severity Yield Trt App Rate infected (% infected Yield (% of No. (oZ/acre) area) area) (g plot) Control) Non-inoculated 37.50 39.17 67.325 6 Control Inoculated 38.00 39.00 63.4 O Control Civitas (160) 27.25 29.33 80. OS 26 Civitas (320) 25.75 28.50 63.475 O Civitas + Harmonizer 26.25 29.50 71.65 13 (160 + 10) (1 app) Civitas + Harmonizer 27.00 29.75 96.225 52 (160 + 10) (2 apps) Civitas + Harmonizer 25.50 30.00 78.525 24 US 9,451,773 B2 41 42 TABLE 8-continued Results of Wheat Stern Rust Study Average Upper Stem Stem Severity (% Severity Yield Trt App Rate infected (% infected Yield (% of No. (oz?acre) area) area) (g plot) Control) (320 + 20) 8 Folicur (4) 2S.OO 29.08 142.175 124 9 Quilt (14) 14.50 19.17 161.75 155 10 Civitas + 1.2 Folicur 20.75 24.75 169.75 168 (160 + 2) 11 Civitas + Harmonizer + 19.25 24.25 176.2 178 1/2 Folicur (80 + 5 + 2) 12 Civitas + Harmonizer + 16.75 22.17 2O3S 221 1/2 Folicur (160 + 10 + 2) 13 Civitas + Harmonizer + 11.OO 16.92 185.175 192 1/2 Folicur (320 + 20 + 2) 14 Civitas + Harmonizer + 19.50 2S.OO 162.075 1/2 Quilt (80 + 5 + 7)
Example 3 that were treated with CivitasTM/HarmonizerTM (160+10 oz/acre) and Folicur (2 oz/acre) by foliar application 7 DBI. Greenhouse Spot Blotch Evaluation Study Note the near lack of symptoms, Small pustule size, and 25 chlorotic halos. FIG.3 shows leaves of inoculated plants that The efficacy of CivitasTM/HarmonizerTM, alone or in com were treated with CivitasTM/HarmonizerTM (320+20 oz/acre) bination with FolicurTM in controlling infection of wheat by soil drench application 7 DBI. Note the near lack of (Triticum aestivum Baart) by Bipolaris Sorokiniana was symptoms, chlorotic halos, and reduced pustule size. TABLE 9 Results of Greenhouse Spot Blotch Evaluation Study Greenhouse Spot Blotch Evaluation Study Pathogen: Bipolaris Sorokiniana O-4, R to % Leaf Area Susceptible Carrier severity Infection Type Treat ID Method (gal/A) Timing Civitas Harmonizer Folicur Treated Rep 1 Rep 2 Rep 3 Rep 1 Rep 2 Rep 3 Avg. Sev IT O1 Foliar O 7DBI 160 10 O 3,8 5 5 5 2 1 1 S.O 1.3 O2 Foliar O 7DBI 32O 2O O 3,8 O 10 3 O 2 1 4.3 1.O O3 Drench OO 7DBI 160 10 O 3,8 5 5 O 1 1 O 3.3 0.7 O4 Drench OO 7DBI 32O 2O O 3,8 O O O O O O O.O O.O 05 Foliar O 1DBI 160 10 O 3.14 10 10 10 3 3 1 1O.O 2.3 O6 Foliar O 1DBI O O 2 3.14 5 5 O 1 2 O 3.3 1.O O7 Foliar O 1DBI O O 4 3.14 5 O 2 1 O 1 2.3 0.7 O8 Foliar O 1DBI 160 10 2 3.14 5 O O 1 O O 1.7 O.3 Control NAA FA FA O O O NA 15 2O 15 4 4 4 16.7 4.0 tested undergreenhouse conditions. Briefly, each treatment Example 4 consisted of three pots (4" by 4") containing three plants 50 Greenhouse Leaf Rust Evaluation Study each. Plants were planted on March 1st. CivitasTM/Harmo nizerTM, FolicurTM, and combinations thereof were applied The efficacy of CivitasTM/HarmonizerTM, alone or in com bination with FolicurTM in controlling infection of wheat to test plants, by foliar application on March 8 (seven DBI), (Triticum aestivum Bawl) by Puccinia triticina was tested by soil drench on March 8th (7 DBI), or by foliar application under greenhouse conditions. Briefly, each treatment con on March 14th (1 DEBI), as indicated in Table 9 (rates of 55 sisted of three pots (4" by 4") containing three plants each. Civitas, Harmonizer, and Folicur are expressed in oZ/acre). Plants were planted on March 1st. CivitasTM/HarmonizerTM. For foliar application, the treatments were applied in 0.2 mL FolicurTM. and combinations thereof were applied to test per pot, which is the equivalent of 20 gal/A. For soil drench, plants, by foliar application on March 8 (seven DBI), by soil treatments were applied in 3.8 mL, which is the equivalent drench on March 8th (7 DBI), or by foliar application on March 14th (1 DBI), as indicated in Table 10 (rates of of 400 gal/A. Plants were innoculated on March 15th. The 60 Civitas, Harmonizer, and Folicur are expressed in oZ/acre). average severity of infection, in terms of % leaf area For foliar application, the treatments were applied in 0.2 mL infected, was evaluated 14 days after inoculation on March per pot, which is the equivalent of 20 gal/A. For soil drench, 29th. treatments were applied in 3.8 mL, which is the equivalent Images of the untreated, inoculated control are presented of 400 gal/A. Plants were innoculated on March 15th. The in FIG. 1. Note the number of pustules (dark spots), near 65 average severity of infection, in terms of % leaf area lack of chlorosis (light halos Surrounding dark spots), and infected, was evaluated 14 days after inoculation on March large pustule size. FIG. 2 shows leaves of inoculated plants 29th. US 9,451,773 B2 43 44 TABLE 10 Results of Greenhouse Leaf Rust Evaluation Study Greenhouse Leaf Rust Evaluation Study Pathogen: Pucciaia triticina O-4, R to % Leaf Area Susceptible Carrier severity Infection Type Avg. Treat ID Method (gal/A) Timing Civitas Harmonizer Folicur Treated Rep 1 Rep 2 Rep 3 Rep 1 Rep 2 Rep 3 Sev Avg. IT 1 Foliar 2O 7DBI 160 10 O 3.8 15 2O 15 2 1 1 16.7 1.3 2 Foliar 2O 7DBI 320 2O O 3.8 15 15 10 1 1 2 13.3 1.3 3 Drench 400 7DBI 160 10 O 3.8 2O 2O 25 2 2 2 21.7 2.0 4 Drench 400 7DBI 320 2O O 3.8 2O 15 2O 2 2 1 18.3 1.7 5 Foliar 2O 1DBI 160 10 O 3.14 15 15 15 1 1 2 1S.O 1.3 6 Foliar 2O 1DBI O O 2 3.14 5 5 5 1 1 1 S.O 1.O 7 Foliar 2O 1DBI O O 4 3.14 O O O O O O O.O O.O 8 Foliar 2O 1DBI 160 10 2 3.14 O 5 5 O 1 1 3.3 0.7 Control Control NA NA O O O NA 25 30 30 3 3 3 28.3 3.0
Images of the untreated, inoculated control are presented 2 March 16th, as indicated in Table 11 (rates of Civitas, in FIG. 4. Note the large number of pustules (dark spots), Harmonizer, and Folicur are expressed in oz/acre). For foliar near lack of chlorosis, and large pustule size. FIG. 5 shows application, the treatments were applied in 0.2 mL per pot, leaves of inoculated plants that were treated with CivitasTM/ which is the equivalent of 20 gal/A. For soil drench, treat HarmonizerTM (160+10 oz/acre) and Folicur (2 oz/acre) by ments were applied in 3.8 mL, which is the equivalent of 400 foliar application 7 DBI. Note the near lack of pustules, 25 gal/A. Plants were innoculated on April 18th. The average Somewhat restricted size, and Small chlorotic halos indica severity of infection was evaluated 14 days after inoculation tive of a resistance response. FIG. 6 shows leaves of on May 2nd. TABLE 11 Results of Greenhouse Spot Blotch Evaluation Study Greenhouse Spot Blotch Evaluation Study Pathogen: Bipolaris Sorokiniana O-4, R to % Leaf Area Susceptible Carrier severity Infection Type Avg. Treat ID Method (gal/A) Timing Civitas Harmonizer Folicur Treated Rep 1 Rep 2 Rep 3 Rep 1 Rep 2 Rep 3 Sev Avg. IT 01. Foliar 2O 7DBI 160 10 O 3,8 5 5 5 2 1 1 S.O 1.3 02 Foliar 2O 7DBI 320 2O O 3,8 O 10 3 O 2 1 4.3 1.O O3 Drench 400 7DBI 160 10 O 3,8 5 5 O 1 1 O 3.3 0.7 04 Drench 400 7DBI 320 2O O 3,8 O O O O O O O.O O.O 05 Foliar 2O 1DBI 160 10 O 3.14 10 10 10 3 3 1 1O.O 2.3 06 Foliar 2O 1DBI O O 2 3.14 5 5 O 1 2 O 3.3 1.O 07 Foliar 2O 1DBI O O 4 3.14 5 O 2 1 O 1 2.3 0.7 08 Foliar 2O 1DBI 160 10 2 3.14 5 O O 1 O O 1.7 O.3 Control NAA NAA NAA O O O N.A. 15 2O 1S 4 4 4 16.7 4.0 inoculated plants that were treated with CivitasTM/Harmo- Example 6 nizerTM (320+20 gal/A) by soil drench application 7 DBI. So Note the lack of pustules, restricted size, and large chlorotic Soybean Rust Study in Georgia halos indicative of a resistance response. The efficacy of CivitasTM, HarmonizerTM, and HeadlineTM Example 5 (Pyraclostrobin, BASF), and Domark R230 ME (Tetracon 55 azole, Valent), alone or in combination, in controlling infec Greenhouse Fusarium Head Blight Evaluation tion of soybean (Glycine max) by Phakospora pachyrhizi Study was tested in the field in Georgia. Civitas was tested at 640 oz?a (5 gal/a) and 320 oz/a (2.5 gal/a), with and without The efficacy of CivitasTM, HarmonizerTM, and FolicurTM Harmonizer. Two conventional chemical fungicides that are alone or in combination, in controlling infection of wheat 60 labelled for soybean rust, Headline(R) and Domark R230 ME (Triticum aestivum Sonalika) by Fusarium graminearum were used alone, as well as tank mix partners with Civitas. was tested undergreenhouse conditions. Briefly, each treat- The total spray Volume is 15 gal/a, significantly lower than ment consisted of four pots (4" by 4") containing nine plants the spray volume for turf applications (50-100 gal/a). each. Plants were planted on March 2nd. CivitasTM, Harmo- Accordingly, the concentrations of the Civitas Solution were nizerTM. FolicurTM. and combinations thereof were applied 65 much higher than in turf application (16% to 33% in this to test plants, by foliar application or by Soil drench on study). The treatments are listed in Table 12. The results of March 10 (39 DBI), or 35 DBI by foliar application on this study are provided in Table 13. Civitas showed signifi US 9,451,773 B2 45 46 cant control of PhakOspora pachyrhizi on Soybean. The ventional fungicides with Civitas alone or Civitas/Har incidence and severity were equal to or exceeded control by monzier provided better efficacy than the conventional fun the conventional fungicides. The combination of the con gicides used alone. TABLE 12 List of treatments of soybean plants prior to innoculation
Form Rate Amoun Conc. Form (OZ Appl Application Production rt No. Treatment GAL (%) Type acre) Code Description to Measure 1 Headline 250 EC 6 AB R2-R3 9.375 ml/mix 2 Headline 250 EC 4 AB R2-R3 6.25 ml/mic 3 Headline 250 EC 4 AB R2-R3 6.25 ml/mix Civitas (1) L 640 AB R2-R3 1000.0 ml/mix 4 Headline 250 EC 4 AB R2-R3 6.25 ml/mix Civitas (1) L 320 AB R2-R3 500.0 ml/mix Harmonizer (1) L 2O AB R2-R3 31.25 ml/mix 5 Headline 250 EC 4 AB R2-R3 6.25 ml/mix Civitas (1) L 640 AB R2-R3 1000.0 ml/mix Harmonizer (1) L 40 AB R2-R3 62.25 ml/mix 6 Civitas (1) L 640 AB R2-R3 1000.0 ml/mix 7 Civitas (1) L 640 AB R2-R3 1000.0 ml/mix Harmonizer (1) L 40 AB R2-R3 62.25 ml/mix 8 Headline 250 EC 6 AB R2-R3 9.375 ml/mix Civitas (1) L 320 AB R2-R3 500. milmx Harmonizer (1) L 2O AB R2-R3 31.25 ml/mix 9 Domark 230 ME 23O ME 4 AB R2-R3 6.25 ml/mix 10 Domark 230 ME 23O ME 2 AB R2-R3 3.12 ml/mix 11 Domark 230 ME 23O ME 2 AB R2-R3 3.125 ml/mix Civitas (1) L 640 AB R2-R3 1000.0 ml/mix 12 Domark 230 ME 23O ME 2 AB R2-R3 3.125 ml/mix Civitas (1) L 320 AB R2-R3 500.0 ml/mix Harmonizer (1) L 2O AB R2-R3 31.25 ml/mix 13 Domark 230 ME 23O ME 2 AB R2-R3 3.125 ml/mix Civitas (1) L 640 AB R2-R3 1000.0 ml/mix Harmonizer (1) L 40 AB R2-R3 62.5 ml/mix 14 Civitas (1) L 640 AB R2-R3 1000.0 mmx 15 Civitas (1) L 640 AB R2-R3 1000.0 ml/mix Harmonizer (1) 40 AB R2-R3 62.5 ml/mix 16 Domark 230 ME 23O ME 4 AB R2-R3 6.25 ml/mix Civitas (1) L 320 AB R2-R3 500.0 ml/mix Harmonizer (1) L 2O AB R2-R3 31.25 ml/mix
TABLE 13 Results of Soybean Rust Study. Pest Type D Disease D Disease D Disease D Disease D Disease Pest Name SBR SBR SBR SBR SBR Crop Name Soy Bean Soy Bean Soy Bean Soy Bean Soy Bean Rating Date Oct. 21 Oct. 21 Oct. 21 Oct. 21 Nov. 17 Rating Date Type Defoliation Incidence Leaf Area Severity Yield Rating Unit % % Scale Lb. Sample Size Unit Plot Days After First Last Applic. 71.42 71.42 71.42 71.42 98.69
Trt Treatment No. Name 1 2 3 4 5
1 Headline 82.5 b-e 32.5 b-e 1.258 a O.58 a 23.7SS a 2 Headline 76.3 e 62.5 ab 3.423 a 1.45 ab 24.07O a 3 Headline 83.8 b-e 30.0 b-e 4.963 a 1.20 abc 19.660 cc Civitas 4 Headline 81.3 b-e 32.5 b-e 0.378 a 0.38 bcd 19.575 cc Civitas Harmonizer 5 Headline 83.8 b-e 20.0 code 0.213 a 0.30 cc 18.868 code Civitas Harmonizer 6 Civitas 83.8 b-e 27.5 b-e 0.218 a 0.30 cc 18.868 code 7 Civitas 88.8 ab 50.0 a-d 1.405 a. 0.85 bcd 18.325 def Harmonizer 8 Headline 80.8 cde 30.0 b-e 0.275 a. 0.33 cc 23.370 alb Civitas Harmonizer 9 Domark 230 ME 77.5 de 30.0 b-e 0.265 a. 0.30 cc 23.370 alb US 9,451,773 B2 47 48 TABLE 13-continued Results of Soybean Rust Study. O Domark 230 ME 87.5 abc. 20.0 code 0.158 a 0.20 cc 19.688 1 Domark 230 ME 87.5 abc 5.0 e OO15 a. O.OS 19.008 code Civitas 2 Domark 230 ME 85.0 a-d 17.5 de 0.105 a. 0.18 cc 21.030 bc. Civitas Harmonizer 3 Domark 230 ME 92.2 a. 12.5 de 0.073 a 0.13 cc 16.560 ef Civitas Harmonizer 4 Civitas 86.3 abc 57.5 abc 1.460 a 0.90 bcd 18.925 ccde 5 Civitas 87.2 abc. 37.5 b-e 1.880 a O.75 bcd 16.143 f Harmonizer 6 Domark 230 ME 88.8 ab 30.0 b-e 0.375 a. 0.35 cc 18.385 def Civitas Harmonizer 7 Untreated 82.5 b-e 82.5 a. 6.233 a 2.20 a 23.210 ab Control LSD (P = .05) 7.52 39.88 4.0345 1.082 2.4490 Standard Deviation S.26 27.91 2.8232 0.757 1.7137 CV 6.24 82.15 211.5 124.35 8.61 Bartletts x2 15.841 22.741 147.989 642O7 35.418 P(Bartlett's X2) O.393 O.121 0.001: 0.001: O.OO3: Replicate F 2.920 3.678 2.208 3.515 3.563 Replicate Prob(F) O.0439 O.O183 O.O992 O.O220 O.O2O8 Treatment F 2.545 1.946 1715 2.266 8.017 Treatment Prob(F) O.OO69 O.O387 O.O760 O.O149 O.OOO1
Example 7 TABLE 1.5 Mean Comparisons Between Treatments: Control of Leaf Rust on Wheat 30 Treatment Mean Group
Untreated 2.81 8. Leaf rust field trial was carried out on spring wheat Civitas, Harmonizer - 160:10 oz/acre O.88 b cultivars. Spores from the spreader plots were served as Prosaro - 6.5 oz?acre O.77 b innoculum Source for the natural infection of experimental 35 Civitas, Harmonizer - 320:20 oz/acre O.67 b plots. Treatments were applied at heading (Feekes 10.1/ 10.2) using a CO-powered backpack sprayer operating at *Treatment with same letters are not statistically different the pressure of ca. 276 kPa, fitted with flat-fan spray tip (TeeJet SS8003: Spraying Systems Co., Wheaton, Ill.), at the rate of 20 gal per acre. Prosaro (Bayer CropScience) was 40 Example 8 used as the standard chemical control. Disease rating was done 19 days after chemical spray. Control of Gray Leaf Spot on Corns Leaf rust severity was rated as percent leaf area infected on 12 randomly selected flag leaves per plot. Data were ana 45 Gray Leaf Spot (Cercospora zeae-maydis) field trial was lyzed using R statistical package. Data on leaf rust severity conducted on hybrid corns (NK 67 3000GT) with natural was transformed using square root and arcsin function for infection. Civitas treatments were applied at R1 and R3 analysis of variance. Means presented for rust severity in the growth stage with the spray rate of 20 gal per acre. Headline graph and tables are back transformed mean value. (BASF) and Stratego (Bayer CropScience) were applied at The treatments of Civitas/Harmonizer (160:10 oz/acre) 50 R1 as the standard chemical control. and Civitas/Harmonizer (320:20 oz/acre) resulted in signifi Disease rating was done about 16 days and 40 days after cantly low rust infection compared to control plots. The R1 application. Gray leaf spot severity was rated as percent efficacy of Civitas treatments are at par with the chemical leaf area infected in the plots. standard Prosaro (6.5 oz/acre). 55 All of the chemical treatments resulted in lower disease TABLE 1.4 severity than control plots. TABLE 1.5 ANOVA table 60 16DAA 4ODAA No of application % Leaf % Leaf Source DF MS F-value Prob > F treat- rate (fl.oz. Growth 808 88 ment Chemicals product A) Stage infected infected Treatment 12 6.199 2.617 O.O1157 untreated 2.5 A. 12.O Error 39 2.3686 1 Civitas + 640 R1 - R3 1.O C 7.8 65 Harmonizer 40 2 Headline 6 R1 1.O C O.8 US 9,451,773 B2 50 TABLE 15-continued 16. The method of claim 15, wherein the fungal pathogen is Phakopsora gossypii. 16DAA 4ODAA 17. The method of claim 10, wherein the fungal pathogen No of application % Leaf % Leaf treat- rate (fl.oz. Growth 808 88 is Phytophthora infestans. ment Chemicals product A) Stage infected infected 18. The method of claim 1, wherein the paraffinic oil comprises a paraffin having a number of carbon atoms 3 Stratego 10 R1 1.O C 1.0 P > F O.OO84 <.OOO1 ranging from about 12 to about 50. LSD 0.05 O.9 4.2 19. The method of claim 1, wherein the paraffinic oil has CV9% 46 73 a paraffin content of at least about 80%. 10 20. The method of claim 1, wherein the paraffinic oil is Although various embodiments of the invention are dis used in a range from about 1 to about 3,200 oz/acre. closed herein, many adaptations and modifications may be 21. The method of claim 1, wherein the ratio of the made within the scope of the invention in accordance with paraffinic oil to the emulsifier is from 10:1 to 500:1. the common general knowledge of those skilled in this art. 22. The method of claim 21, wherein the composition Such modifications include the substitution of known 15 comprises from 2 to 50 weight percent of the paraffinic oil. equivalents for any aspect of the invention in order to 23. The method of claim 1, wherein the fungicidal com achieve the same result in Substantially the same way. position further comprises a demethylation inhibitor (DMI). Citation of references herein is not an admission that Such 24. The method of claim 23, further including applying a references are prior art to the present invention. Any priority demethylation inhibitor (DMI) at a rate of 0.015 to 0.60 document(s) and all publications, including but not limited lbs/acre. to patents and patent applications, cited in this specification 25. The method of claim 23, wherein the DMI is tetra are incorporated herein by reference as if each individual conazole, tebuconazole, propioconazole, azaconazole, biter publication were specifically and individually indicated to tanol, bromuconazole, cyproconazole, difenoconazole, dini be incorporated by reference herein and as though fully set conazole, epoxiconazole, etaconazole, fenbuconazole, forth herein. 25 fluquinconazole, flusilaZole, flutriafol, hexaconazole, imi The invention includes all embodiments and variations benconazole, ipconazole, metconazole, myclobutanil, pen substantially as hereinbefore described and with reference to conazole, prothioconazole, Simeconazole, triadimefon, tri the examples. Other implementations are within the scope of adimenol, triticonazole, imazalil, Oxpoconazole, the following claims. pefurazoate, prochloraZ, triflumizole, fenarimol, nuarimol, 30 triforine, or pyrifenox. What is claimed is: 26. The method of claim 1, wherein the fungicidal com 1. A method of controlling infection of an annual crop position further comprises a Quinone outside Inhibitor plant by a fungal pathogen, the method comprising applying (QoI). a fungicidal composition to the plant, wherein the fungicidal 27. The method of claim 21, further including applying a composition comprises a pigment and a paraflinic oil-in 35 Quinone outside Inhibitor (QoI) to an aerial portion of the water emulsion, the paraflinic oil-in-water emulsion com plant. prising a paraflinic oil and an emulsifier. 28. The method of claim 26, wherein the QoI is azox 2. The method of claim 1, wherein the crop plant is wheat, yStrobin, enestrobin, picoxystrobin, pyraclostrobin, triflox barley, soybean, or corn. yStrobin, dimoxystrobin, metominostrobin, orysastrobin, 3. The method of claim 1, wherein the plant is mono 40 famoxadonem, fluoxastrobin, fenamidone, or pyribencarb. cotyledonous. 29. The method of claim 1, wherein the fungicidal com 4. The method of claim 3, wherein the plant is of the order position further comprises a silicone Surfactant, wherein the Poaceae. emulsifier, the paraflinic oil, the pigment and the silicone 5. The method of claim 4, wherein the plant is of the genus Surfactant are present in amounts that, when applied to the Triticum, Secale, Hordeum, Oryza, Zea, or Elymus. 45 plant, are synergistically effective at controlling infection by 6. The method of claim 1, wherein the fungal pathogen is the fungal pathogen. of the order Pucciniales. 30. The method of claim 1, wherein the pigment is a 7. The method of claim 6, wherein the fungal pathogen is polychlorinated (CuII) phthalocyanine. of the genus Puccinia. 31. The method of claim 1, wherein the pigment is 8. The method of claim 7, wherein the fungal pathogen is 50 dispersed in water and the emulsifier comprises a natural or of the species Puccinia graminis, Puccinia triticina, or synthetic alcohol ethoxylate, an alcohol alkoxylate, an alkyl Puccinia Sriiformis. polysaccharide, a glycerol oleate, a polyoxyethylene-poly 9. The method of claim 1, wherein the fungal pathogen is oxypropylene block copolymer, an alkyl phenol ethoxylate, selected from the group consisting of Bipolaris Sorokiniana, a polymeric Surfactant, a polyethylene glycol, a Sorbitan Fusarium graminearum, and Pyrenophora tritici-repentis. 55 fatty acid ester ethoxylate, or a combination thereof. 10. The method of claim 1, wherein the plant is dicoty 32. The method of claim 1, wherein the pigment is ledonous. dispersed in oil, the emulsifier comprises a natural or Syn 11. The method of claim 10, wherein the plant is of the thetic alcohol ethoxylate, a polymeric Surfactant, a Sorbitan order Fabaceae. fatty acid ester, or a combination thereof, and the compo 12. The method of claim 11, wherein the plant is of the 60 sition further comprises a polyethylene glycol according to species Glycine max. formula IV: 13. The method of claim 10, wherein the fungal pathogen is of the genus Phakopsora. 14. The method of claim 13, wherein the fungal pathogen wherein R1=H or CH2=CH-CH2 or COCH3; R2=H or is Phakopsora pachyrhizi or Phakopsora meibomiae. 65 CH2=CH-CH2 or COCH3; and f1. 15. The method of claim 10, wherein the plant is of the 33. The method of claim 1, wherein the ratio of the genus Gossypium. paraffinic oil to the pigment is from 5:1 to 100:1. US 9,451,773 B2 51 52 34. The method of claim 1, wherein the composition further comprises an anti-settling agent. 35. The method of claim 29, wherein the weight ratio of the pigment to the silicone surfactant is from 2:1 to 50:1. k k k k k