WO1996032010A2 - Fungicidal compositions for the enhancement of turf quality - Google Patents

Fungicidal compositions for the enhancement of turf quality Download PDF

Info

Publication number
WO1996032010A2
WO1996032010A2 PCT/US1996/004487 US9604487W WO9632010A2 WO 1996032010 A2 WO1996032010 A2 WO 1996032010A2 US 9604487 W US9604487 W US 9604487W WO 9632010 A2 WO9632010 A2 WO 9632010A2
Authority
WO
WIPO (PCT)
Prior art keywords
compound
composition according
benzopoφhyrin
phosphite
active agent
Prior art date
Application number
PCT/US1996/004487
Other languages
French (fr)
Other versions
WO1996032010A3 (en
Inventor
Laurence C. Mudge
Original Assignee
Rhone-Poulenc, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=23647831&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1996032010(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Rhone-Poulenc, Inc. filed Critical Rhone-Poulenc, Inc.
Priority to NZ306688A priority Critical patent/NZ306688A/en
Priority to AU55314/96A priority patent/AU716396B2/en
Priority to EP96912527A priority patent/EP0820229A2/en
Priority to JP53104396A priority patent/JP3923521B2/en
Priority to BR9604942-1A priority patent/BR9604942A/en
Publication of WO1996032010A2 publication Critical patent/WO1996032010A2/en
Publication of WO1996032010A3 publication Critical patent/WO1996032010A3/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/26—Phosphorus; Compounds thereof

Definitions

  • the present invention relates to methods and compositions for the enhancement of turf quality and the control of crown and root rot in turfgrass, and more particularly to synergistic combinations of fungicides useful therefore.
  • Crown and root rot is a serious disease of turf grasses, especially highly maintained turf grasses as found in lawns, golf courses, nursery crops, and other landscape architecture applications. Current techniques for controlling this disease are not entirely satisfactory, and there is a continuing need for new treatments thereof.
  • U.S. Patent No. 4,698,334 to Horriere et al. and U.S. Patent No. 4,806,445 to Horriere et al. propose fungicidal compositions based on alkyl phosphites in combination with various contact fungicides such as Mancozeb. These compositions are useful for treating mildew in vines.
  • U.S. Patent No. 4, 139,616 to Ducret et al. describes fungicidal compositions based on alkyl phosphites. None of these references relate to the treatment of turf grasses.
  • U.S. Patent No. 5,336,661 to Lucas discloses methods of enhancing turf quality of bentgrass using compositions comprising a mixture of a monoester salt of a phosphorous acid, and an ethylenebisdithiocarbamate contact fungicide. High quality, healthy turfgrass is essential to the golfing industry.
  • the present invention provides a fungicidal composition for enhancing the quality of turfgrass and protecting against crown and root rot.
  • the compositions comprise a synergistic combination of: (a) a first active agent selected from the group consisting of
  • R is an alkyl radical having 2 to 4 carbon atoms
  • Me is an alkali metal, alkaline earth metal, or aluminum atom
  • n is a whole number from 1 to 3 equal to the valence of Me
  • phosphorous acid or an alkali or alkali earth metal salt thereof
  • the present invention provides a method of enhancing turf quality and protecting against crown and root rot. The method comprises applying
  • the compounds are applied in an amount effective to enhance turf quality and/or protect against crown and root rot.
  • the active agents applied consist essentially of the monoester salt and the benzoporphyrin compound.
  • benzoporphyrin compounds useful in the method of the present invention include substituted and unsubstituted benzoporphyrins and derivatives thereof.
  • Suitable benzoporphyrins include tetrabenzopo ⁇ hyrine, alkyl-substituted benzopo ⁇ hyrins, halo-substituted benzopo ⁇ hyrins, and the like.
  • the benzopo ⁇ hyrin is a coordination complex of the Formula L,L 2 -X,X 2 -L 3 L 4 , wherein X t and X 2 are each H or X, and X 2 together are a transition metal, and L,, I__, L,, and L 4 are each substituted or unsubstituted isoindole groups, and wherein L,, !__, L,, and L 4 are covalently joined to one another.
  • L,, I.-., L,, and L 4 together form a ligand of Formula (II)
  • a, b, c, and d are each independently selected from positive integers 0-4, and R,, R 2 , R 3 , and « are each independently selected from the group consisting of H, halogen, C ⁇ o substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic alkyl, alkoxy, alkylamino, alkylthio, onium, sulphonium, sulphate, and carboxylate.
  • the methods and compositions described herein are useful for improving turf quality and color in turfgrasses.
  • the methods and compositions described herein are useful for treating crown and root rot in turfgrass.
  • Crown and root rot which causes a decline in turfgrass quality during hot, wet weather, is a disease complex apparently caused by Pythium species and Rhizoctonia species in combination with environmental and management stresses.
  • the first active agent is selected from the group consisting of monoester salts of phosphorous acid and phosphorous acid or alkali or alkali earth metal salts thereof.
  • Monoester salts of phosphorus acids useful for carrying out the present invention, as given in Formula (I) above, are known. See, e.g. , U.S. Patent No.
  • Examples include calcium ethyl phosphite, sodium ethyl phosphite, aluminum ethyl phosphite, magnesium isopropyl phosphite, calcium isopropyl phosphite, aluminum isopropyl phosphite, magnesium ethyl phosphite, magnesium isobutyl phosphite, magnesium sec-butyl phosphite, calcium isobutyl phosphite, aluminum N-butyl phosphite, aluminum .sec-butyl phosphite, and aluminum isobutyl phosphite. Most preferred is aluminum ethyl phosphite (also called aluminum tris (O-ethyl phosphonate)).
  • the first active agent may be phosphorous acid or an alkali or alkali earth metal salt thereof.
  • Suitable alkali or alkali earth metal salts include, for example, lithium, sodium, potassiu, rubidium, cesium, beryllium, magnesium, calciu, strontium, and barium salts of phosphorous acid.
  • the sodium, potassium and calcium salts or phosphorous acid are currently preferred.
  • Benzopo ⁇ hyrin compounds are the preferred class of po ⁇ hine compounds and derivatives thereof, which are useful in the methods of the present invention.
  • useful po ⁇ hine compounds include substituted and unsubstituted po ⁇ hines and derivatives thereof.
  • Suitable derivatives of po ⁇ hines include substituted and unsubstituted po ⁇ hyrins.
  • the po ⁇ hyrins may be benzopo ⁇ hyrins such as tetrabenzopo ⁇ hyrins, alkyl-substituted benzopo ⁇ hyrins, halo-substituted benzopoiphyrins, and the like.
  • the benzopo ⁇ hyrin is a coordination complex of the Formula L,L 2 -X 1 X 2 -L 3 L 4 , wherein X, and X 2 are each H or Xj and X together are a metal selected from the group consisting of alkali metals, alkali earth metals and transition metals, and I.-, 1 ⁇ , L 3 , and L 4 are each substituted or unsubstituted isoindole groups, and wherein L,, L j , L j , and L 4 are covalently joined to one another (e.g. , through a nitrogen or carbon atom, preferably a nitrogen atom).
  • L, L j , L, and L 4 are covalently joined as a cyclic structure, i.e. , -L 1 -L--L r L 4 -cy, where cy means L 4 is covalently joined to L,.
  • X, and X 2 together are a transition metal from Groups IB and VIIIB.
  • the isoindole groups represented by L,, L j , L,, and L 4 may be unsubstituted, or alternatively, they may be each independently substituted from 1 to 4 times with a substituent selected from the group consisting of halogen, C,.
  • a, b, c, and d are each independently selected from positive integers 0-4, and Rj, R 2 , R 3 , and R, are each independently selected from the group consisting of H, halogen, C,. 20 substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic alkyl, alkoxy, alkylamino, alkylthio, onium, sulphonium, sulphate, and carboxylate.
  • Suitable benzopo ⁇ hyrins of the coordination complex L,L 2 -X,X 2 -L 3 L 4 include phthalocyanine dyes.
  • Suitable phthalocyanine dyes may be metal-free phthalocyanines, or metal phthalocyanines.
  • the metal of metal phthalocyanines may be selected from alkali metals, alkali earth metals and transition metals, with transition metals being preferred.
  • suitable metals include but are not limited to, lithium, sodium, potassium, rubidium and cesium from the alkali metal family; berillium, magnesium, calcium, strontium, barium, and radium from the alkali earth metal family; and copper, silver, gold, zinc, cadmium, mercury, scandium, yittrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nichel, palladium, and platinum from the transition metal family. Copper, nickel, cobalt, iron and zinc phthalocyanine dyes are particularly preferred in the methods of the present invention.
  • Phthalocyanine dyes which are useful in the methods of the present invention include subsituted and unsubstituted dyes.
  • Suitable substituted phthalocyanine dyes may be metal-free phthalocyanines, or metal phthalocyanines, and may be substituted from 1 to 4 times on each isoindole group independently.
  • suitable substituents for the isoindole groups of phthalocyanine dyes include but are not limited to, halogens, substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic alkyl, alkoxy, alkylamino, alkylthio, onium, sulphonium, sulphate, and carboxylate.
  • Suitable phthalocyanine dyes are commercially available and include but are not limited to Pigment Blue 16, Vat Blue 29, Pigment Blue 15, Heliogen Green GG, Ingrain Blue 14, Ingrain Blue 5, Ingrain Blue 1, Pigment Green 37, and Pigment Green 7.
  • the phthalocyanine dye is Pigment Blue 15.
  • the phthalocyanine dye is any phthalocyanine dye other than Pigment Blue 15.
  • the active material includes 1 part by weight of the compound of Formula (I) above in combination with from 0.01 to 0.1 parts by weight of the benzopo ⁇ hyrin compound.
  • a particularly preferred combination is 1 part by weight of the compound of Formula (I) above in combination with from 0.04 to 0.05 parts by weight of Pigment Blue 15.
  • synergistic combinations according to the invention may be used with advantage in admixture with one another or with other known fungicides, such as basic salts or hydroxides of copper (oxychloride. oxysulphate), (tetrahydro)phthalimides (Captan.
  • synergistic combinations according to the invention may also be mixed with other fungicidal, anti-mildew phosphorus derivatives, especially 2- hydroxy-l,3,2-dioxaphospholanes, (3-hydroxy ethyl phosphites and phosphorous acid and its salts.
  • the active ingredients in the synergistic combinations are used as part of a formulated product which, as a rule, contains a support and/or a surfactant in addition to the active material according to the invention.
  • a support is an organic or mineral, natural or synthetic material with which the active material is associated to facilitate its application to plants, seeds or soil, or its transportation and/or handling.
  • the support can be solid (clays, natural or synthetic silicates, resins, waxes, solid fertilizers) or fluid (water, alcohols, ketones, petroleum fractions, chlorinated hydrocarbons, liquefied gases).
  • the surfactant can be an ionic or non-ionic emulsifier, dispersant or wetting agent such as, for example, salts of polyacrylic acids and lignin- sulphonic acids, condensates of ethylene oxide with fatty alcohols, fatty acids or fatty amines.
  • compositions according to the invention can be prepared in the form of wettable powders, soluble powders, dusting powders, granulates, solutions, emulsifiable concentrates, emulsions, suspended concentrates and aerosols.
  • the wettable powders according to the invention can be prepared in such a way that they contain from 20 to 95 % by weight of the active material, and they normally contain, in addition to a solid support, from 0 to 5% by weight of a wetting agent, from 3 to 10% by weight of a dispersant and, when necessary, from 0 to 10% by weight of one or more stabilizers and/or other additives, such as penetration agents, adhesives or anti-lumping agents, colorants, etc.
  • compositions of a wettable powder is given in Table 1 below:
  • active material 80 sodium lignosulphonate (deflocculant) 5 anionic wetting agent 1 antilumping silica 5 kaolin (filler) 9
  • Powders soluble in water are obtained by mixing from 20 to 95% by weight of the active material, from 0 to 10% of an antilumping agent, the remainder being a hydrosoluble filler mainly a salt.
  • composition of the present invention as a soluble powder is given in Table 2 below:
  • Aqueous dispersions and emulsions for example compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included within the general scope of the invention.
  • These emulsions can be of the water-in-oil type or of the oil-in-water type, and can have a thick consistency resembling that of a "mayonnaise" .
  • compositions according to the invention can contain other ingredients, for example protective colloids, adhesives or thickeners, thixotropic agents, stabilizers or sequestrants, as well as other active materials known to have pesticidal properties, especially acaricides or insecticides.
  • protective colloids for example protective colloids, adhesives or thickeners, thixotropic agents, stabilizers or sequestrants, as well as other active materials known to have pesticidal properties, especially acaricides or insecticides.
  • the present invention can be practiced with all turfgrasses, including cool season turfgrasses and warm season turfgrasses.
  • cool season turfgrasses are Bluegrasses (Poa L.), such as Kentucky Bluegrass (Poa pratensis L.), Rough Bluegrass (Poa trivialis L.), Canada Bluegrass (Poa compressa L.), Annual Bluegrass (Poa annua L.), Upland Bluegrass (Poa glaucantha Gaudin), Wood Bluegrass (Poa nemoralis L.), and Bulbous Bluegrass (Poa bulbosa L.); the Bentgrasses and Redtop (Agrostis L.), such as Creeping Bentgrass (Agrostis palustris Huds.), Colonial Bentgrass (Agrostis tenius Sibth.), Velvet Bentgrass (Agrostis canina L.), South German Mixed Bentgrass (Agrostis L.), and Redtop (Agrostis alba
  • the active materials are, in general, applied to turfgrass either together or separately by spraying a liquid formulation (e.g., an aqueous formulation, including emulsions, or an oil-based formulation) thereof on the turfgrass.
  • a liquid formulation e.g., an aqueous formulation, including emulsions, or an oil-based formulation
  • the ethylenebisdithiocarbamate contact fungicide is typically applied in an amount of from 10 to 25 pounds per acre (about 10 to 25 Kilograms per Hectare), more preferably in an amount of from 15 to 20 pounds per acre (about 15 to 20 Kg per hectare), and still more preferably in an amount of from 17 to 18 pounds per acre (about 17 to 18 Kg per Hectare).
  • the compound of Formula (I) is, in general, applied in an amount of from about 5 to 17 pounds per acre.
  • Fungicides were evaluated on a one- year-old stand of the bentgrass cultivar "Penncross" planted in Raleigh, North Carolina, USA. The bentgrass was planted in native soil and maintained under conditions similar to a golf green with a mowing height of 0.635 cm (.25 inches).
  • the fungicides which have activity against Pythium species include KOBANTM (active ingredient: etridiazole) obtained from Grace-Sierra, ALIETTETM (active ingredient: fosetyl-Al) obtained from Rhone-Poulenc, and SUBDUETM (active ingredient: metalaxyl) obtained from Ceba-Giegy.
  • the fungicides which have activity against Pythium and Rhizoctonia species is FORETM (active ingredient: mancozeb also including Pigment Blue 15) obtained from Rhom and Haas, MANZATETM (active ingredient: mancozeb) obtained from DuPont, LESCO MN80TM (active ingredient: mancozeb) obtained from Lesco, PENCOZEB DF 75TM (active ingredient: mancozeb) obtained from Elf Atochem.
  • PROTECT DG 80TM active ingredient: mancozeb obtained from W.A. Cleary
  • DITHANETM active ingredient: mancozeb obtained from Rhom and Haas.
  • the fungicides were applied separately and in combination at labelled rates to 1.5 m x 1.5 m (5 ft x 5 ft) plots of bentgrass prior to evidence of any decline in turf quality due to crown and root rot.
  • a CO 2 backpack sprayer was used to apply the fungicide treatments at (30 lbs psi) using TEEJETTM 8004 nozzles to apply 9.5 liters (2.5 gallons) of fungicide dilutions per 93 square meters (1000 sq ft).
  • the fungicides were initially applied and subsequently reapplied according to a 14 day schedule.
  • an electrical pump sprayer was used to apply the treatments at 30 psi using a Teejet 8004 nozzle.
  • Turf quality, color and percent disease ratings were recorded weekly, based on a scale from 1-9, with 9 being ideal turf quality and color and 1 being all turf dead. The percent disease ratings were calculated based on the percent of area in each plot showing symptoms of brown patch. Turf quality and color ratings were used as an indicator of the health of the bentgrass and the amount of decline associated with crown and root rot. Pythium and Rhizoctonia species of fungi were isolated from the bentgrass in the experiment during the test period.
  • Table 1 below indicates that an improvement in turf quality and color was observed from application of ALIETTETM + FORETM (treatment #4), with a turf quality of 7.5 and a turf color of 7.8 with 9 being ideal.
  • the combination of ALIETTETM + MANZATETM had a lower turf quality rating of 6.8 and a turf color of 7.0.
  • Table 3 is a comparative study of the effects of different formulations of mancozeb.

Abstract

Fungicidal compositions for the protection of turfgrass against crown and root rot are disclosed. The compositions comprise, as the active material, (a) a first active agent selected from the group consisting of (i) a monoester salt of a phosphorous acid (preferably aluminum ethyl phosphite), and (ii) phosphorous acid or an alkali or alkali earth metal salt thereof; and (b) a benzoporphyrin compound. Preferred compositions comprise 1 part by weight of the first active agent, and between about 0.01 and about 0.1 parts by weight of the benzoporphyrin compound.

Description

FUNGICroAL COMPOSITIONS FOR THE ENHANCEMENT OF TURF QUALITY
Field of the Invention
The present invention relates to methods and compositions for the enhancement of turf quality and the control of crown and root rot in turfgrass, and more particularly to synergistic combinations of fungicides useful therefore.
Background of the Invention
Crown and root rot is a serious disease of turf grasses, especially highly maintained turf grasses as found in lawns, golf courses, nursery crops, and other landscape architecture applications. Current techniques for controlling this disease are not entirely satisfactory, and there is a continuing need for new treatments thereof.
U.S. Patent No. 4,698,334 to Horriere et al. and U.S. Patent No. 4,806,445 to Horriere et al. propose fungicidal compositions based on alkyl phosphites in combination with various contact fungicides such as Mancozeb. These compositions are useful for treating mildew in vines. U.S. Patent No. 4, 139,616 to Ducret et al. describes fungicidal compositions based on alkyl phosphites. None of these references relate to the treatment of turf grasses.
U.S. Patent No. 5,336,661 to Lucas discloses methods of enhancing turf quality of bentgrass using compositions comprising a mixture of a monoester salt of a phosphorous acid, and an ethylenebisdithiocarbamate contact fungicide. High quality, healthy turfgrass is essential to the golfing industry.
Accordingly, there remains a need in the art for fungicidal compositions which enhance turf quality and protect against crown and root rot in turfgrass to provide high quality, healthy turfgrass. Summary of the Invention
As a first aspect, the present invention provides a fungicidal composition for enhancing the quality of turfgrass and protecting against crown and root rot. The compositions comprise a synergistic combination of: (a) a first active agent selected from the group consisting of
(i) a monoester salt of a phosphorous acid of Formula (I):
Figure imgf000004_0001
wherein:
R is an alkyl radical having 2 to 4 carbon atoms, Me is an alkali metal, alkaline earth metal, or aluminum atom, and n is a whole number from 1 to 3 equal to the valence of Me; and (ii) phosphorous acid or an alkali or alkali earth metal salt thereof; and
(b) a benzoporphyrin compound. As a second aspect, the present invention provides a method of enhancing turf quality and protecting against crown and root rot. The method comprises applying
(a) a first active agent selected from the group consisting of
(i) a monoester salt of a phosphorous acid of Formula (I) above, and
(ii) phosphorous acid or an alkali or alkali earth metal salt thereof, and
(b) a benzoporphyrin compound.
The compounds are applied in an amount effective to enhance turf quality and/or protect against crown and root rot. In one embodiment, the active agents applied consist essentially of the monoester salt and the benzoporphyrin compound.
The benzoporphyrin compounds useful in the method of the present invention include substituted and unsubstituted benzoporphyrins and derivatives thereof. Suitable benzoporphyrins include tetrabenzopoφhyrine, alkyl-substituted benzopoφhyrins, halo-substituted benzopoφhyrins, and the like. According to one embodiment, the benzopoφhyrin is a coordination complex of the Formula L,L2-X,X2-L3L4, wherein Xt and X2 are each H or X, and X2 together are a transition metal, and L,, I__, L,, and L4 are each substituted or unsubstituted isoindole groups, and wherein L,, !__, L,, and L4 are covalently joined to one another. In one preferred coordination complex, L,, I.-., L,, and L4 together form a ligand of Formula (II)
Figure imgf000005_0001
wherein a, b, c, and d are each independently selected from positive integers 0-4, and R,, R2, R3, and « are each independently selected from the group consisting of H, halogen, C^o substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic alkyl, alkoxy, alkylamino, alkylthio, onium, sulphonium, sulphate, and carboxylate.
The foregoing and other aspects of the present invention are explained in detail in the detailed description set forth below.
Detailed Description of the Invention
The methods and compositions described herein are useful for improving turf quality and color in turfgrasses. In addition, the methods and compositions described herein are useful for treating crown and root rot in turfgrass. Crown and root rot, which causes a decline in turfgrass quality during hot, wet weather, is a disease complex apparently caused by Pythium species and Rhizoctonia species in combination with environmental and management stresses. The first active agent is selected from the group consisting of monoester salts of phosphorous acid and phosphorous acid or alkali or alkali earth metal salts thereof. Monoester salts of phosphorus acids useful for carrying out the present invention, as given in Formula (I) above, are known. See, e.g. , U.S. Patent No. 4,139,616 to Ducret et al., U.S. Patent No. 4,698,334 to Horriere et al., and U.S. Patent No. 4,806,445 to Horriere et al. (the disclosures of all U.S. patents cited herein are to be incoφorated herein by reference). Examples include calcium ethyl phosphite, sodium ethyl phosphite, aluminum ethyl phosphite, magnesium isopropyl phosphite, calcium isopropyl phosphite, aluminum isopropyl phosphite, magnesium ethyl phosphite, magnesium isobutyl phosphite, magnesium sec-butyl phosphite, calcium isobutyl phosphite, aluminum N-butyl phosphite, aluminum .sec-butyl phosphite, and aluminum isobutyl phosphite. Most preferred is aluminum ethyl phosphite (also called aluminum tris (O-ethyl phosphonate)).
Alternativly, the first active agent may be phosphorous acid or an alkali or alkali earth metal salt thereof. Suitable alkali or alkali earth metal salts include, for example, lithium, sodium, potassiu, rubidium, cesium, beryllium, magnesium, calciu, strontium, and barium salts of phosphorous acid. The sodium, potassium and calcium salts or phosphorous acid are currently preferred.
Benzopoφhyrin compounds are the preferred class of poφhine compounds and derivatives thereof, which are useful in the methods of the present invention. Examples of useful poφhine compounds include substituted and unsubstituted poφhines and derivatives thereof. Suitable derivatives of poφhines include substituted and unsubstituted poφhyrins. The poφhyrins may be benzopoφhyrins such as tetrabenzopoφhyrins, alkyl-substituted benzopoφhyrins, halo-substituted benzopoiphyrins, and the like. According to one embodiment, the benzopoφhyrin is a coordination complex of the Formula L,L2-X1X2-L3L4, wherein X, and X2 are each H or Xj and X together are a metal selected from the group consisting of alkali metals, alkali earth metals and transition metals, and I.-, 1^, L3, and L4 are each substituted or unsubstituted isoindole groups, and wherein L,, Lj, Lj, and L4 are covalently joined to one another (e.g. , through a nitrogen or carbon atom, preferably a nitrogen atom). As will be apparent, they are covalently joined as a cyclic structure, i.e. , -L1-L--LrL4-cy, where cy means L4 is covalently joined to L,. Preferably, X, and X2 together are a transition metal from Groups IB and VIIIB. The isoindole groups represented by L,, Lj, L,, and L4 may be unsubstituted, or alternatively, they may be each independently substituted from 1 to 4 times with a substituent selected from the group consisting of halogen, C,.20 substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic alkyl, alkoxy, alkylamino, alkylthio, onium, sulphonium, sulphate, and carboxylate.
In one preferred embodiment of the coordination complex of L,L2-X1X2-L3L4, L,, __-,, L,, and L4 together form a ligand of Formula (II)
Figure imgf000007_0001
wherein a, b, c, and d are each independently selected from positive integers 0-4, and Rj, R2, R3, and R, are each independently selected from the group consisting of H, halogen, C,.20 substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic alkyl, alkoxy, alkylamino, alkylthio, onium, sulphonium, sulphate, and carboxylate.
Examples of suitable benzopoφhyrins of the coordination complex L,L2-X,X2-L3L4 include phthalocyanine dyes. Suitable phthalocyanine dyes may be metal-free phthalocyanines, or metal phthalocyanines. The metal of metal phthalocyanines may be selected from alkali metals, alkali earth metals and transition metals, with transition metals being preferred. Examples of suitable metals include but are not limited to, lithium, sodium, potassium, rubidium and cesium from the alkali metal family; berillium, magnesium, calcium, strontium, barium, and radium from the alkali earth metal family; and copper, silver, gold, zinc, cadmium, mercury, scandium, yittrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nichel, palladium, and platinum from the transition metal family. Copper, nickel, cobalt, iron and zinc phthalocyanine dyes are particularly preferred in the methods of the present invention.
Phthalocyanine dyes which are useful in the methods of the present invention include subsituted and unsubstituted dyes. Suitable substituted phthalocyanine dyes may be metal-free phthalocyanines, or metal phthalocyanines, and may be substituted from 1 to 4 times on each isoindole group independently. Examples of suitable substituents for the isoindole groups of phthalocyanine dyes include but are not limited to, halogens, substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic alkyl, alkoxy, alkylamino, alkylthio, onium, sulphonium, sulphate, and carboxylate. Suitable phthalocyanine dyes are commercially available and include but are not limited to Pigment Blue 16, Vat Blue 29, Pigment Blue 15, Heliogen Green GG, Ingrain Blue 14, Ingrain Blue 5, Ingrain Blue 1, Pigment Green 37, and Pigment Green 7. In one preferred embodiment, the phthalocyanine dye is Pigment Blue 15. In another preferred embodiment, the phthalocyanine dye is any phthalocyanine dye other than Pigment Blue 15. Synergistic combinations of the foregoirg two active ingredients (the two together being referred to herein as the "active material") are, in general, 1 part by weight of the compound of Formula (I) above in combination with from 0.01 to 0.1, preferably 0.04 to 0.05, parts by weight of the benzopoφhyrin compound. More preferably, the active material includes 1 part by weight of the compound of Formula (I) above in combination with from 0.01 to 0.1 parts by weight of the benzopoφhyrin compound. A particularly preferred combination is 1 part by weight of the compound of Formula (I) above in combination with from 0.04 to 0.05 parts by weight of Pigment Blue 15.
The synergistic combinations according to the invention may be used with advantage in admixture with one another or with other known fungicides, such as basic salts or hydroxides of copper (oxychloride. oxysulphate), (tetrahydro)phthalimides (Captan. Captafol, Folpel), methyl l-(butylcarbamoyl)-2- benzimidazolecarbamate (Benomyl), thiophanates such as dimethyl (1,2- phenylene)bis(imino-carbonothioyl)bis(carbamate) (Thiophanate-methyl), tetrachloroisophthalonitrile (Chlorothalonil) , 3-(3 , 5-dichlorophenyl)-N-( 1 - methylethyl)-2,4-dioxo-l-imidazolidine carboxamide (Iprodione), l-[2-(2,4- dichlorophenyl)-4-propyl- l ,3-dioxolan-2-yl methyl]- lH- l ,2,4-triazole (Propiconazole) 1 -(4-chlorophenoxy)-3 , 3-dimethy 1- 1 ( 1 H- 1 , 2 ,4-triazol- 1 -yl)-2- butanone (Triadimafon) or other fungicides, either to complete the range of activity of the compounds according to the invention or to increase their persistence.
The synergistic combinations according to the invention may also be mixed with other fungicidal, anti-mildew phosphorus derivatives, especially 2- hydroxy-l,3,2-dioxaphospholanes, (3-hydroxy ethyl phosphites and phosphorous acid and its salts.
For their practical application, the active ingredients in the synergistic combinations are used as part of a formulated product which, as a rule, contains a support and/or a surfactant in addition to the active material according to the invention.
In the context of the invention, a support is an organic or mineral, natural or synthetic material with which the active material is associated to facilitate its application to plants, seeds or soil, or its transportation and/or handling. The support can be solid (clays, natural or synthetic silicates, resins, waxes, solid fertilizers) or fluid (water, alcohols, ketones, petroleum fractions, chlorinated hydrocarbons, liquefied gases).
The surfactant can be an ionic or non-ionic emulsifier, dispersant or wetting agent such as, for example, salts of polyacrylic acids and lignin- sulphonic acids, condensates of ethylene oxide with fatty alcohols, fatty acids or fatty amines.
The compositions according to the invention can be prepared in the form of wettable powders, soluble powders, dusting powders, granulates, solutions, emulsifiable concentrates, emulsions, suspended concentrates and aerosols.
The wettable powders according to the invention can be prepared in such a way that they contain from 20 to 95 % by weight of the active material, and they normally contain, in addition to a solid support, from 0 to 5% by weight of a wetting agent, from 3 to 10% by weight of a dispersant and, when necessary, from 0 to 10% by weight of one or more stabilizers and/or other additives, such as penetration agents, adhesives or anti-lumping agents, colorants, etc.
One example of the compositions of a wettable powder is given in Table 1 below:
Table 1
Compound % by wt. active material 80 sodium lignosulphonate (deflocculant) 5 anionic wetting agent 1 antilumping silica 5 kaolin (filler) 9
Powders soluble in water are obtained by mixing from 20 to 95% by weight of the active material, from 0 to 10% of an antilumping agent, the remainder being a hydrosoluble filler mainly a salt.
An example of a composition of the present invention as a soluble powder is given in Table 2 below:
Table 2
Compound % by wt. active material 70 anionic wetting agent 0.5 antilumping silica 5 sodium sulfate (soluble filler) 24.5
Aqueous dispersions and emulsions, for example compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included within the general scope of the invention. These emulsions can be of the water-in-oil type or of the oil-in-water type, and can have a thick consistency resembling that of a "mayonnaise" .
The compositions according to the invention can contain other ingredients, for example protective colloids, adhesives or thickeners, thixotropic agents, stabilizers or sequestrants, as well as other active materials known to have pesticidal properties, especially acaricides or insecticides.
The present invention can be practiced with all turfgrasses, including cool season turfgrasses and warm season turfgrasses. Examples of cool season turfgrasses are Bluegrasses (Poa L.), such as Kentucky Bluegrass (Poa pratensis L.), Rough Bluegrass (Poa trivialis L.), Canada Bluegrass (Poa compressa L.), Annual Bluegrass (Poa annua L.), Upland Bluegrass (Poa glaucantha Gaudin), Wood Bluegrass (Poa nemoralis L.), and Bulbous Bluegrass (Poa bulbosa L.); the Bentgrasses and Redtop (Agrostis L.), such as Creeping Bentgrass (Agrostis palustris Huds.), Colonial Bentgrass (Agrostis tenius Sibth.), Velvet Bentgrass (Agrostis canina L.), South German Mixed Bentgrass (Agrostis L.), and Redtop (Agrostis alba L.); the Fescues (Festuca L.), such as Red Fescue (Festuca rubra L.), Chewings Fescue (Festuca rubra var. cornmutata Gaud.), Sheep Fescue (Festuca ovina L.), Hard Fescue (Festuca ovina var. duήuscula L. Koch), Hair Fescue (Festuca capillata Lam.), Tall Fescue (Festuca arundinacea Schreb.), Meadow Fescue (Festuca elatior L.); the Ryegrasses (Lolium L.), such as Perennial Ryegrass (Lolium perenne L.), Italian Ryegrass (Lolium multiflorum Lam.); the Wheatgrasses (Agropyron Gaertn.), such as Fairway Wheatgrass (Agropyron cήstatum (L.) Gaertn.), Western Wheatgrass (Agropyron smithii Rydb.). Other cool season turfgrasses include Beachgrass (Ammophila Host.), Smooth Brome (Bromus inermis Leyss.), Timothy (Phleum L.), Orchardgrass (Dactylis glomerata L.), Crested Dog's-Tail (Cynosurus cristatus L.). Examples of warm season turfgrasses are the Bermudagrasses (Cynodon L. C. Rich), Zoysiagrasses (Zoysia Willd.), St. Augustinegrass (Stenotaphrum secundatum (Walt.) Kuntze), Centipedegrass (Eremochioa ophiuroides (Munro.) Hack.), Caφetgrass (Axonopus Beauv.), Bahiagrass (Paspalum notatum Flugge.), Kikuyugrass (Pennisetum clandestinum Hochst. ex Chiov.), Buffalograss (Buchloe dactyloides (Nutt.) Engelm.), Blue Grama (Bouteloua gracilis (H.B.K.) Lag. ex Steud.), and Sideoats Grama (Bouteloua curtipendula (Michx. Torr.). Cool season turfgrasses are preferred. More preferred is Bluegrass, Bentgrass and Redtop, Fescue, and Ryegrass. Bentgrass is most preferred.
The active materials are, in general, applied to turfgrass either together or separately by spraying a liquid formulation (e.g., an aqueous formulation, including emulsions, or an oil-based formulation) thereof on the turfgrass. The ethylenebisdithiocarbamate contact fungicide is typically applied in an amount of from 10 to 25 pounds per acre (about 10 to 25 Kilograms per Hectare), more preferably in an amount of from 15 to 20 pounds per acre (about 15 to 20 Kg per hectare), and still more preferably in an amount of from 17 to 18 pounds per acre (about 17 to 18 Kg per Hectare). The compound of Formula (I) is, in general, applied in an amount of from about 5 to 17 pounds per acre.
The following examples are provided to illustrate the present invention, and should not be construed as limiting thereof.
EXAMPLES 1-3
These examples were carried out to identify fungicide and combinations thereof which will improve turf quality and color, and have activity against crown and root rot and brown patch. Fungicides were evaluated on a one- year-old stand of the bentgrass cultivar "Penncross" planted in Raleigh, North Carolina, USA. The bentgrass was planted in native soil and maintained under conditions similar to a golf green with a mowing height of 0.635 cm (.25 inches). The fungicides which have activity against Pythium species include KOBAN™ (active ingredient: etridiazole) obtained from Grace-Sierra, ALIETTE™ (active ingredient: fosetyl-Al) obtained from Rhone-Poulenc, and SUBDUE™ (active ingredient: metalaxyl) obtained from Ceba-Giegy. The fungicides which have activity against Pythium and Rhizoctonia species is FORE™ (active ingredient: mancozeb also including Pigment Blue 15) obtained from Rhom and Haas, MANZATE™ (active ingredient: mancozeb) obtained from DuPont, LESCO MN80™ (active ingredient: mancozeb) obtained from Lesco, PENCOZEB DF 75™ (active ingredient: mancozeb) obtained from Elf Atochem. PROTECT DG 80™ (active ingredient: mancozeb) obtained from W.A. Cleary, and DITHANE™ (active ingredient: mancozeb) obtained from Rhom and Haas.
The fungicides were applied separately and in combination at labelled rates to 1.5 m x 1.5 m (5 ft x 5 ft) plots of bentgrass prior to evidence of any decline in turf quality due to crown and root rot. A CO2 backpack sprayer was used to apply the fungicide treatments at (30 lbs psi) using TEEJET™ 8004 nozzles to apply 9.5 liters (2.5 gallons) of fungicide dilutions per 93 square meters (1000 sq ft). The fungicides were initially applied and subsequently reapplied according to a 14 day schedule. In some experiments, an electrical pump sprayer was used to apply the treatments at 30 psi using a Teejet 8004 nozzle.
Turf quality, color and percent disease ratings were recorded weekly, based on a scale from 1-9, with 9 being ideal turf quality and color and 1 being all turf dead. The percent disease ratings were calculated based on the percent of area in each plot showing symptoms of brown patch. Turf quality and color ratings were used as an indicator of the health of the bentgrass and the amount of decline associated with crown and root rot. Pythium and Rhizoctonia species of fungi were isolated from the bentgrass in the experiment during the test period.
Table 1 below indicates that an improvement in turf quality and color was observed from application of ALIETTE™ + FORE™ (treatment #4), with a turf quality of 7.5 and a turf color of 7.8 with 9 being ideal. The combination of ALIETTE™ + MANZATE™ had a lower turf quality rating of 6.8 and a turf color of 7.0.
TABLE 1
ALIETTE™/FORE™ Interaction
Pesticide %
Trt. Turf Turf Brown Disease No. Name Formu. LBai/A Quality Color Patch Control
01 CHECK — 4.5 5.3 50.0 0
02 ALIETTE™ WDG 80 8.712 6.5 6.8 0 100.0 CHP26019 WDG 50 2.72
03 ALIETTE'" WDG 80 8.712 6.8 7.0 0 100.0 MANZATE WP 70™ 16.34
04 ALIETTE™ WDG 80 8.712 7.5 7.8 0 100.0 FORE™ WP 80™ 17.42
05 FORE™ WDG 80 17.42 6.8 7.0 2.5 91.7
06 ALIETTE™ WDG 80 8.712 5.0 5.8 26.3 38.0
07 ALIETTE™ WDG 80 4.356 6.8 7.5 0 100.0 FORE™ WP 80™ 8.712
LSD (0.05) = 1.0 .8 9.1 23.5
STANDARD DEVIATION = .7 .5 6.2 16.1
COEFF. OF VARIABILITY = 10.8 8.2 71.2 19.9
Table 2 below indicates that similar results were observed in a second test. The data demonstrate that ALIETTE™ + FORE™ (treatment #8) gave better turf quality of 7.8 and 8.0 than ALIETTE™ + mancozeb + AURAGREEN™ (another type of green dye) (treatment #5) of 7.0 and 7.3. The combination of the experimental formulation of ALIETTE™ and the blue pigment (EXP 10622) + mancozeb (treatment #10) gave higher turf quality ratings of 7.5 and 8.0 than treatment #5, and ratings as high as the ratings for ALIETTE™ + FORE™. TABLE2
ALIETTE™/FORE™ Interaction
Pesticide Appli¬ % %
Tπ cation Phyto Turf Brown Turf Turf Brown
No Name Formu LBai/A Type rating Qua! Patch Qual Color Patch
01 CONTROL — 10 50 250 53 63 150
02 NCAD1 SG 100 0545 14 DAY 10 48 213 50 75 163
03 NCAD 1 SG 100 0545 14 DAY 18 58 150 63 75 50 AL-ETTE*" WDG80 8712 14 DAY
04 NCAD 1 SG 100 0545 14 DAY 13 63 75 68 78 0 MANCOZEB WDG80 1743 14 DAY
05 NCAD 1 SG100 0545 14 DAY 55 70 25 73 68 0
MANCOZEB WDG80 1743 14 DAY
ALIE'I E** WDG80 8712 14 DAY
06 ALIETTE*" WDG80 8712 14 DAY 25 53 163 60 63 25
07 MANCOZEB WDG80 1743 14 DAY 20 60 138 65 68 88
08 AL-ETTE™ WDG80 8712 14 DAY 10 78 0 80 80 0 FORE1" WP80*" 1743 14 DAY
09 EXP10622 WDG80 8712 14 DAY 15 58 100 65 68 6.3
10 EXP10622 WDG80 8712 14 DAY 33 75 0 80 75 0 MANCOZEB WP80™ 1743 14 DAY
LDS (005) = 8 10 94 6 10 68
STAND/ .RD DEVIATION = 6 7 65 4 7 47 COEFF C )F VARIABILITY = 272 110 584 59 94 873
Table 3 is a comparative study of the effects of different formulations of mancozeb. The formulations of FORE™ WP80™ and FL4.0™, which contain mancozeb + Pigment Blue 15, gave better turf quality and turf color than other formulations of mancozeb without the Pigment Blue 15. Treatment #7 of ALIETTE™ + FORE™ FIA0™+ BLENDEX™ (a blending agent) gave better results. Treatment #7 contains more Pigment Blue 25 than treatment #2. TABLE 3
ALIETTET"/MANCOZEB Intencuons
Pesticide Appli¬ % % %
Trt cation Turf Turf Brown Turf Turf Brown Turf Turf Brown Turf Turf No Name Formu LBaiA Type Qual Color Patch Qual Color Patch Qual Color Patch Qual Color
01 CONTROL ... — 38 45 600 33 40 675 28 38 750 48 63
02 ALIETTE" WDG80 8712 14 DAY 70 70 100 78 75 50 73 70 50 70 68 FORE™ WP80 1742 14 DAY
03 ALIETTE'" WDG80 8712 14 DAY 60 63 125 60 60 13 60 60 88 58 53 LESCO MN DG80 1742 14 DAY
04 ALIETTE*" WDG80 8712 14 DAY 63 65 138 60 60 25 60 63 125 60 55 PENCOZES DF75 1742 14 DAY
10 05 ALIETTE™ WDG80 8712 14 DAY 60 65 113 63 63 50 63 63 88 58 53 PROTECT DG80 1742 14 DAY
06 ALIETTE™ WDG80 8712 14 DAY 68 70 63 68 68 75 73 78 38 75 75 FORE™ FL40™ 1742 14 DAY
07 ALIETTE™ WDG80 8712 14 DAY 70 73 50 85 78 0 80 80 13 80 80
FORE™ FL40™ 1742 14 DAY
BLENDEX %C 14 DAY
08 ALIETTE™ WDG80 8712 14DAV 43 48 463 58 60 25 58 58 175 60 55 DITHANE WDG75 1742 14 DAY
09 | LESCOMN DG80 1742 14 DAY 48 55 213 50 53 88 48 48 225 58 60
15 LDS (005) = 10 7 213 5 7 103 7 6 91 7 STANDARD DEVIATION = 7 5 146 4 5 70 5 4 62 5 7
Figure imgf000016_0001
COEFF OF VARIABILITY = 117 83 706 74 633 85 66 361 76 116
Overall, the results indicate that the combination of ALIETTE™ + FORE™, containing the Pigment Blue 15, provides a better improvement in turf quality and color over other combinations of ALIETTE™ and mancozeb without the Pigment Blue 15. The results demonstrate that the presence of the Pigment Blue 15, enhances the activity of the ALIETTE™ and mancozeb in a synergistic interaction.
The foregoing is illustrative of the present invention and is not to be construed as limiting thereof. The invention is defined by the following claims, with equivalents of the claims to be included therein.

Claims

That Which Is Claimed Is:
1. A method of enhancing turf quality in turfgrass which comprises applying to said turfgrass in an amount effective to enhance turf quality: (a) a first active agent selected from the group consisting of (ii) 1 part by weight of a monoester salt of a phosphorous acid of Formula (I):
H I R-O-P-O- Me
II o (I)
wherein:
R is an alkyl radical having 2 to 4 carbon atoms, Me is an alkali metal, alkaline earth, or aluminum atom, and n is a whole number from 1 to 3 equal to the valence of Me; and (ii) phosphorous acid or an alkali or alkali earth metal salt thereof; and
(b) from 0.01 to 0.1 parts by weight of a benzopoφhyrin compound.
2. A method according to Claim 1 , wherein said benzopoφhyrin compound is a tetrabenzopoφhyrin compound.
3. The method according to Claim 1, wherein said benzopoφhyrin compound is a coordination complex of the Formula L1L2-X1X2-L3L4, wherein X, and X2 are each H or X, and X2 together are a transition metal, and L,, L>, L3, and L4 are each substituted or unsubstituted isoindole groups; and wherein L, , L-, L3, and L4 are covalently joined to one another. 6/32010 PC17US96/04487
-17-
4. The method according to Claim 1, wherein said benzopoφhyrin compound is a coordination complex of the Formula LIL2-X,X2-L3L4, wherein X, and X2 are each H or X, and X2 together are a transition metal; and L,, 1^, L,. and L4 together form a ligand of Formula (II)
Figure imgf000019_0001
wherein a, b, c, and d are each independently selected from positive integers 0-4, and R,, R2, R3, and R4 are each independently selected from the group consisting of H, halo, .20 substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic alkyl, alkoxy, alkylamino, alkylthio, onium, sulphonium, sulphate, and carboxylate.
5. A method according to Claim 1, wherein said benzopoφhyrin compound is a phthalocyanine compound.
6. The method according to Claim 1 , wherein said step of applying comprises applying 1 part by weight of said first active agent, and 0.05 parts by weight of said benzopoφhyrin compound.
7. The method according to Claim 5, wherein said phthalocyanine compound is Pigment Blue 15.
8. The method according to Claim 5, wherein said phthalocyanine compound is not Pigment Blue 15.
9. The method according to Claim 1 , wherein said step of applying is carried out by applying said first active agent and said benzopoφhyrin compound to said turfgrass together in a common carrier.
10. The method according to Claim 1 , wherein said turfgrass is bentgrass.
11. The method according to Claim 1 , wherein said turfgrass is bermudagrass.
12. The method according to Claim 1 , wherein said first active agent is applied to said turfgrass in an amount of from about 8 to about 16 pounds active ingredient per acre, and said benzopoφhyrin is applied to said turfgrass in an amount of from about 0.2 to about 0.8 pounds per acre.
13. The method according to Claim 1 consisting essentially of applying to said turfgrass, said first active agent in an amount of from about 8 to about 16 pounds active ingredient per acre, and said benzopoφhyrin in an amount of from about 0.2 to about 0.8 pounds per acre.
14. A fungicidal composition for enhancing turf quality which comprises an active material comprising:
(a) 1 part by weight of a first active agent selected from the group consisting of (i) a monoester salt of a phosphorous acid of Formula (I):
H
-O-P-O Me
(I)
wherein:
R is an alkyl radical having 2 to 4 carbon atoms,
Me is an alkali metal, alkaline earth, or aluminum atom, and n is a whole number from 1 to 3 equal to the valence of Me; and (ii) phosphorous acid or an alkali or alkali earth metal salt thereof; and
(b) from 0.01 to 0.1 parts by weight of a benzopoφhyrin compound.
15. A composition according to Claim 14, wherein said benzopoφhyrin compound is a tetrabenzopoφhyrin compound.
16. The composition according to Claim 14, wherein said benzopoφhyrin compound is a coordination complex of the Formula L1L2-XιX2-L3L4, wherein X, and X2 are each H or X, and X2 together are a transition metal, and L,, L2, L,, and L4 are each substituted or unsubstituted isoindole groups; and wherein L,, 1^, L,, and L4 are covalently joined to one another.
17. The composition according to Claim 14, wherein said benzopoφhyrin compound is a coordination complex of the Formula
L,L2-X,X2-L3L4, wherein X* and X2 are each H or X! and X2 together are a transition metal; and L,, __-,, L3. and L4 together form a ligand of Formula (II)
Figure imgf000021_0001
wherein a, b, c, and d are each independently selected from positive integers 0-4, and R,, R2, R3, and R4 are each independently selected from the group consisting of H, halo, Cι_20 substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic alkyl, alkoxy. alkylamino, alkylthio, onium, sulphonium, sulphate, and carboxylate.
18. A composition according to Claim 14, wherein said benzopoφhyrin compound is a phthalocyanine compound.
19. The composition according to Claim 14, wherein said first active agent is said monoester salt of phosphorous acid, and R is selected from the group consisting of ethyl, propyl, and butyl.
20. The composition according to Claim 14, wherein said first active agent is said monoester salt of phosphorous acid, and Me is selected from the group consisting of aluminum, calcium, magnesium, and sodium.
21. The composition according to Claim 17, wherein a, b, c, and d are each 0, and X, and X2 are H.
22. The composition according to Claim 17, wherein X, and X2 together represent a transition metal selected from the group consisting of Group IB and Group VIIIB transition metals.
23. The composition according to Claim 17, wherein X, and X2 together represent a transition metal selected from the group consisting of cobalt, copper, nickel, iron and zinc.
24. The composition according to Claim 17. wherein X, and X2 together are copper.
25. The composition according to Claim 17. wherein a, b, c, and d are each 2, and R,, R2, R3, and R4 are each halogen.
26. The composition according to Claim 17. wherein a, b, c, and d are each 4, and R,, R2, R3, and R4 are each halogen.
27. The composition according to Claim 17, wherein R,, R2, R3, and j are each onium.
28. The composition according to Claim 17, wherein R,, R2, R3, and R, are each sulphate.
29. The composition according to Claim 17, wherein a, b, c, and d are each 0, and X, and X2 together represent copper.
30. The composition according to Claim 14, wherein said first active agent is said monoester salt of phosphorous acid, and said compound of
Formula (I) is selected from the group consisting of calcium ethyl phosphite, sodium ethyl phosphite, aluminum ethyl phosphite, magnesium isopropyl phosphite, calcium isopropyl phosphite, aluminum isopropyl phosphite, magnesium ethyl phosphite, magnesium isobutyl phosphite, magnesium jec-butyl phosphite, calcium isobutyl phosphite, aluminum N-butyl phosphite, aluminum .sec-butyl phosphite, and aluminum isobutyl phosphite.
31. The composition according to Claim 14, wherein said first active agent is said monoester of phosphorous acid, and said compound of Formula (I) is aluminum ethyl phosphite.
32. The composition according to Claim 18, wherein said phthalocyanine compound is selected from the group consisting of Pigment Blue 16, Vat Blue 29, Pigment Blue 15. Heliogen Green GG. Ingrain Blue 14, Ingrain Blue 5, Ingrain Blue 1, Pigment Green 37, and Pigment Green 7.
33. The composition according to Claim 18, wherein said phthalocyanine compound is Pigment Blue 15.
34. The composition according to Claim 18, wherein said phthalocyanine compound is not Pigment Blue 15.
35. The composition according to Claim 14, comprising 1 part by weight of said first active agent and between about 0.01 and about 0.1 parts by weight of said benzopoφhyrin compound.
36. The composition according to Claim 14, consisting essentially of 1 part by weight of said first active agent and between about 0.01 and about 0.1 parts by weight of said benzopoφhyrin compound.
37. The composition according to Claim 14, wherein said composition is an aqueous suspension.
38. The composition according to Claim 14, wherein said composition is a wettable powder.
PCT/US1996/004487 1995-04-03 1996-04-01 Fungicidal compositions for the enhancement of turf quality WO1996032010A2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NZ306688A NZ306688A (en) 1995-04-03 1996-04-01 Fungicidal compositions for protecting turfgrass against crown and root rot
AU55314/96A AU716396B2 (en) 1995-04-03 1996-04-01 Fungicidal compositions for the enhancement of turf quality
EP96912527A EP0820229A2 (en) 1995-04-03 1996-04-01 Fungicidal compositions for the enhancement of turf quality
JP53104396A JP3923521B2 (en) 1995-04-03 1996-04-01 Disinfectant composition to improve lawn quality
BR9604942-1A BR9604942A (en) 1995-04-03 1996-04-01 Method and composition to improve the quality of the grass

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/415,934 1995-04-03
US08/415,934 US5599804A (en) 1995-04-03 1995-04-03 Fungicidal compositions for the enhancement of turf quality

Publications (2)

Publication Number Publication Date
WO1996032010A2 true WO1996032010A2 (en) 1996-10-17
WO1996032010A3 WO1996032010A3 (en) 1996-12-12

Family

ID=23647831

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/004487 WO1996032010A2 (en) 1995-04-03 1996-04-01 Fungicidal compositions for the enhancement of turf quality

Country Status (10)

Country Link
US (2) US5599804A (en)
EP (1) EP0820229A2 (en)
JP (2) JP3923521B2 (en)
KR (1) KR100433565B1 (en)
CN (1) CN1076952C (en)
AU (1) AU716396B2 (en)
BR (1) BR9604942A (en)
NZ (1) NZ306688A (en)
WO (1) WO1996032010A2 (en)
ZA (1) ZA962651B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1563734A1 (en) * 2004-02-13 2005-08-17 Bayer CropScience LP Method of improving turfgrass quality
WO2007017220A3 (en) * 2005-08-09 2008-06-12 Isagro Spa Synergistic mixtures and/or compositions with a high fungicidal activity
EP2273878A1 (en) * 2008-04-08 2011-01-19 Bayer Cropscience LP Composition and system for turf maintenance
US8153558B2 (en) 2004-02-13 2012-04-10 Bayer Cropscience Lp Method of improving grass quality
US8569210B2 (en) 2008-06-26 2013-10-29 Suncor Energy Inc. Turfgrass fungicide formulation with pigment
US9357768B2 (en) 2006-10-05 2016-06-07 Suncor Energy Inc. Herbicidal composition with increased herbicidal efficacy
US9750249B2 (en) 2010-09-09 2017-09-05 Suncor Energy Inc. Synergistic paraffinic oil and boscalid fungicides
US9999219B2 (en) 2004-05-18 2018-06-19 Suncor Energy Inc. Spray oil and method of use therof for controlling turfgrass pests
US10138171B2 (en) 2015-01-18 2018-11-27 Stacie Z. Berg Method for altering photosynthetic growth

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5599804A (en) * 1995-04-03 1997-02-04 Rhone-Poulenc, Inc. Fungicidal compositions for the enhancement of turf quality
US20070166340A1 (en) * 2003-06-23 2007-07-19 William Stringfellow Fungicidal composition for through periderm bark application to woody plants
DE602007009569D1 (en) * 2006-12-08 2010-11-11 Dsm Ip Assets Bv Postharvest treatment of fruits with antifungal composition
US8748345B2 (en) * 2007-05-10 2014-06-10 Tessenderlo Kerley Inc. Method and composition for improving turfgrass
US9717818B2 (en) * 2009-05-08 2017-08-01 Medline Industries, Inc. Absorbent articles having antimicrobial properties and methods of manufacturing the same
US20100291229A1 (en) * 2009-05-12 2010-11-18 Sipcam Argo Usa, Inc. Fungicidal compositions and methods of enhancing plants such as turfgrass
KR101696208B1 (en) * 2009-05-15 2017-01-13 바이엘 인텔렉쳐 프로퍼티 게엠베하 Fungicidal active compound compositions for turf treatment
US8377850B2 (en) 2009-05-15 2013-02-19 Bayer Cropscience Lp Fungicidal compositions for turf treatment and improvement
CA2836819C (en) 2011-06-03 2017-11-21 Suncor Energy Inc. Paraffinic oil-in-water emulsions for controlling infection of crop plants by fungal pathogens
US9820490B2 (en) 2011-11-03 2017-11-21 Bayer Cropscience Lp Compositions and methods for enhancing plant quality
ES2887953T3 (en) 2018-10-16 2021-12-29 Niacet Corp Procedure for the inhibition of fungi in living plants using carboxylic acids and their salts

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935242A (en) * 1973-07-13 1976-01-27 Procida Process for the preparation of colored maneb
DE2511077A1 (en) * 1975-03-13 1976-09-23 Nippon Chemical Works Co Turf grass coloration - using hexadentate cobalt phthalocyanine amine complex salts
US5336661A (en) * 1993-01-13 1994-08-09 North Carolina State University Method for enhancing turf quality of bent grass

Family Cites Families (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2276860A (en) * 1935-12-19 1942-03-17 Gen Aniline & Film Corp Dyestuff of the phthalocyanine series
US2129013A (en) * 1936-05-14 1938-09-06 Ici Ltd Copper monochlorophthalocyanine and a process of making it
US2214454A (en) * 1936-12-11 1940-09-10 Ici Ltd Manufacture of finely divided phthalocyanine pigments
US2452606A (en) * 1945-11-20 1948-11-02 Du Pont Phthalocyanine pigments and process for producing same
US2460783A (en) * 1947-06-02 1949-02-01 American Cyanamid Co Preparation of phthalocyanine pigments from omega-chlorine or omaga-bromine substituted omicron-xylenes
US2460779A (en) * 1947-06-02 1949-02-01 American Cyanamid Co Synthesis of phthalocyanines from omega-chlorine or omega-bromine substituted omicron-tolunitriles
US2485167A (en) * 1948-04-01 1949-10-18 Du Pont Manufacture of metal-free phthalocyanine
US2485168A (en) * 1948-04-01 1949-10-18 Du Pont Manufacture of metal-free phthalocyanine
US2471794A (en) * 1948-07-15 1949-05-31 Roberts Chemical Company Manufacture of coloring matters of the phthalocyanine series from phthalyl halides
US2613128A (en) * 1948-10-29 1952-10-07 Bayer Ag Vat dyeing compositions, including a mixture of cobalt phthalocyanine dyes
US2556729A (en) * 1949-03-05 1951-06-12 Du Pont Metal-free phthalocyanine of novel color characteristics
NL277376A (en) * 1961-05-09
US3632328A (en) * 1967-08-31 1972-01-04 Scott & Sons Co O M Turf appearance improvement
FR1562940A (en) 1968-01-19 1969-04-11
DE2315641A1 (en) * 1973-03-29 1974-10-17 Hoechst Ag ACARICIDAL DISPERSIONS
FR2254276B1 (en) * 1973-12-14 1977-03-04 Philagro Sa
DE2412324C2 (en) * 1974-03-14 1985-01-24 Hoechst Ag, 6230 Frankfurt Stabilized dispersions of 2-alkyl-4,6-dinitro-phenol-esters
PL103345B1 (en) 1976-09-18 1979-05-31 Zjednoczone Zespoly Gospodarcz METHOD OF OBTAINING A COLORING FUNGALANT FOR WOOD IMPREGNATION
FR2377155A1 (en) 1977-01-14 1978-08-11 Philagro Sa FUNGICIDE COMPOSITIONS BASED ON ALCOYLPHOSPHITES
JPS5734781A (en) * 1980-08-04 1982-02-25 Toshiba Corp Operating device for single-phase induction motor
IN155696B (en) * 1980-09-09 1985-02-23 Ciba Geigy Ag
US4394316A (en) * 1980-09-11 1983-07-19 Rohm And Haas Company Copper modified mancozeb
IL82311A (en) * 1986-05-09 1992-06-21 Rhone Poulenc Agrochimie Bactericidal compositions based on phosphorous acid derivatives
JPS6341408A (en) * 1986-08-07 1988-02-22 Nippon Zeon Co Ltd Copper-containing composition
JPS63112701A (en) * 1986-10-29 1988-05-17 株式会社　ア−スクリ−ン Socks
JP2639409B2 (en) * 1987-12-15 1997-08-13 アグロカネショウ株式会社 How to control grass disease
JPH02138376A (en) * 1988-11-18 1990-05-28 Mitsubishi Yuka Badische Co Ltd Withered grass coloring composition
DE3932157A1 (en) 1989-09-27 1991-04-04 Desowag Materialschutz Gmbh WOOD PRESERVATIVES AND METHOD FOR THE PRODUCTION THEREOF
JP2799469B2 (en) * 1990-01-27 1998-09-17 三菱化学株式会社 Lawn colorants
US5350843A (en) * 1990-11-06 1994-09-27 Mitsui Toatsu Chemicals, Incorporated Halogenated phthalocyanine compound, method for preparing same
US5380842A (en) * 1991-06-20 1995-01-10 Mitsui Toatsu Chemicals, Incorporated Phthalocyanine compounds and usage thereof
US5171853A (en) * 1991-08-05 1992-12-15 North Carolina State University Process of cleaving nucleic acids with oxoruthenium(IV) complexes
US5206228A (en) * 1991-10-29 1993-04-27 Rhone-Poulenc Ag Company Control of arthropod pests with phosphorous acid and mono-esters and salts thereof
JPH0673397A (en) * 1992-08-27 1994-03-15 Nippon Shokubai Co Ltd New photoactivator, new bleaching agent, and new microbicide
US5665672A (en) * 1993-01-13 1997-09-09 North Carolina State University Fungicidal compositions for the treatment of crown and root rot in turfgrass
JPH06321711A (en) * 1993-05-07 1994-11-22 Nippon Oil & Fats Co Ltd Germicide and method for sterilization
US5599804A (en) * 1995-04-03 1997-02-04 Rhone-Poulenc, Inc. Fungicidal compositions for the enhancement of turf quality

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935242A (en) * 1973-07-13 1976-01-27 Procida Process for the preparation of colored maneb
DE2511077A1 (en) * 1975-03-13 1976-09-23 Nippon Chemical Works Co Turf grass coloration - using hexadentate cobalt phthalocyanine amine complex salts
US5336661A (en) * 1993-01-13 1994-08-09 North Carolina State University Method for enhancing turf quality of bent grass

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9259004B2 (en) 2004-02-13 2016-02-16 Bayer Intellectual Property Gmbh Method of improving grass quality
US8426343B2 (en) 2004-02-13 2013-04-23 Bayer Cropscience Lp Method of improving grass quality
EP1563734A1 (en) * 2004-02-13 2005-08-17 Bayer CropScience LP Method of improving turfgrass quality
US8153558B2 (en) 2004-02-13 2012-04-10 Bayer Cropscience Lp Method of improving grass quality
US20160073637A1 (en) * 2004-02-13 2016-03-17 Bayer Cropscience Lp Method of improving grass quality
US9999219B2 (en) 2004-05-18 2018-06-19 Suncor Energy Inc. Spray oil and method of use therof for controlling turfgrass pests
WO2007017220A3 (en) * 2005-08-09 2008-06-12 Isagro Spa Synergistic mixtures and/or compositions with a high fungicidal activity
US9357768B2 (en) 2006-10-05 2016-06-07 Suncor Energy Inc. Herbicidal composition with increased herbicidal efficacy
US9801369B2 (en) 2006-10-05 2017-10-31 Suncor Energy Inc. Herbicidal composition with increased herbicidal efficacy
EP2273878A4 (en) * 2008-04-08 2013-07-10 Bayer Cropscience Lp Composition and system for turf maintenance
AU2009234096B2 (en) * 2008-04-08 2015-06-18 Discovery Purchaser Corporation Composition and system for turf maintenance
EP2273878A1 (en) * 2008-04-08 2011-01-19 Bayer Cropscience LP Composition and system for turf maintenance
US9826738B2 (en) 2008-06-26 2017-11-28 Suncor Energy Inc. Turfgrass fungicide formulation with pigment
US8569210B2 (en) 2008-06-26 2013-10-29 Suncor Energy Inc. Turfgrass fungicide formulation with pigment
US9750249B2 (en) 2010-09-09 2017-09-05 Suncor Energy Inc. Synergistic paraffinic oil and boscalid fungicides
US10138171B2 (en) 2015-01-18 2018-11-27 Stacie Z. Berg Method for altering photosynthetic growth
US11306034B2 (en) 2015-01-18 2022-04-19 Stacie Z. Berg Method for altering photosynthetic growth

Also Published As

Publication number Publication date
ZA962651B (en) 1996-10-22
CN1179701A (en) 1998-04-22
EP0820229A2 (en) 1998-01-28
JP3923521B2 (en) 2007-06-06
US5599804A (en) 1997-02-04
AU716396B2 (en) 2000-02-24
BR9604942A (en) 1999-08-31
KR19980703565A (en) 1998-11-05
CN1076952C (en) 2002-01-02
KR100433565B1 (en) 2004-09-16
JPH11505209A (en) 1999-05-18
AU5531496A (en) 1996-10-30
JP2006213740A (en) 2006-08-17
NZ306688A (en) 1999-11-29
USRE42394E1 (en) 2011-05-24
WO1996032010A3 (en) 1996-12-12

Similar Documents

Publication Publication Date Title
US5599804A (en) Fungicidal compositions for the enhancement of turf quality
AU693349B2 (en) Fungicidal compositions for the enhancement of turf quality
AU2005200604B2 (en) Method of improving turfgrass quality
EP2273878B1 (en) Composition and system for turf maintenance
US20180303101A1 (en) Method of improving grass quality
US5336661A (en) Method for enhancing turf quality of bent grass
KR101696208B1 (en) Fungicidal active compound compositions for turf treatment
US5665672A (en) Fungicidal compositions for the treatment of crown and root rot in turfgrass
EP2807924A1 (en) A method for combating fungal turfgrass pathogens
US20240000080A1 (en) Stabilized compositions containing strobilurin fungicides and polyhydric alcohols

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 96192930.8

Country of ref document: CN

AK Designated states

Kind code of ref document: A2

Designated state(s): AL AM AT AT AU AZ BB BG BR BY CA CH CN CZ CZ DE DE DK DK EE EE ES FI FI GB GE HU IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SK TJ TM TR TT UA UG US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF

AK Designated states

Kind code of ref document: A3

Designated state(s): AL AM AT AT AU AZ BB BG BR BY CA CH CN CZ CZ DE DE DK DK EE EE ES FI FI GB GE HU IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SK TJ TM TR TT UA UG US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1996912527

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1019970706969

Country of ref document: KR

ENP Entry into the national phase

Ref document number: 1996 531043

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 306688

Country of ref document: NZ

WWP Wipo information: published in national office

Ref document number: 1996912527

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: CA

WWP Wipo information: published in national office

Ref document number: 1019970706969

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1996912527

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1019970706969

Country of ref document: KR