WO2010116264A2 - Safening agent - Google Patents

Safening agent Download PDF

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Publication number
WO2010116264A2
WO2010116264A2 PCT/IB2010/001034 IB2010001034W WO2010116264A2 WO 2010116264 A2 WO2010116264 A2 WO 2010116264A2 IB 2010001034 W IB2010001034 W IB 2010001034W WO 2010116264 A2 WO2010116264 A2 WO 2010116264A2
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WO
WIPO (PCT)
Prior art keywords
acid
auxin
indole
iaa
composition
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Application number
PCT/IB2010/001034
Other languages
French (fr)
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WO2010116264A3 (en
Inventor
Richard Williams
Peter Roose
Johan Josef De Saegher
Original Assignee
Taminco, Naamloze Vennootschap
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.)
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Application filed by Taminco, Naamloze Vennootschap filed Critical Taminco, Naamloze Vennootschap
Priority to BRPI1013985-0A priority Critical patent/BRPI1013985A2/en
Priority to EP10719076A priority patent/EP2416647A2/en
Priority to AU2010233406A priority patent/AU2010233406A1/en
Priority to MX2011010542A priority patent/MX2011010542A/en
Priority to GB1118911.5A priority patent/GB2481951A/en
Priority to CN2010800224619A priority patent/CN102438447A/en
Priority to US13/263,674 priority patent/US20120088667A1/en
Publication of WO2010116264A2 publication Critical patent/WO2010116264A2/en
Publication of WO2010116264A3 publication Critical patent/WO2010116264A3/en

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    • 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
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions

Definitions

  • This invention relates to a method and composition for improving crop safety by treating plants with, particularly but not exclusively, a composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof.
  • Chemical fertilisers, fungicides, insecticides and herbicides are applied to plants in order to promote growth and reduce or destroy unwanted fungi, pests, weeds and other unwanted species. This is of particular importance in the field of commercial farming, where obtaining the maximum yield is of the utmost importance.
  • Chemical fertilisers, fungicides, pesticides, insecticides and herbicides available to- date often have negative effects on crops, as well as the positive effect of reducing unwanted species and promoting growth. For example, such chemicals may damage the crops to which they are applied, as well as the species to which they are targeted. This is a particular problem in the field of non-selective fertilisers. These fertilisers, fungicides, pesticides, insecticides and herbicides may also be hazardous. Other compositions applied to plants such as plant growth regulators, chemical thinners and abscission delay agents also often have negative effects on crops and may also be hazardous.
  • the present invention relates to the novel use of compositions comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof for use as a plant safener.
  • the present invention also relates to the novel use of compounds selected from a) glucose, hydrolysed starch, sucrose, fructose, glycerol, glyceraldehydes, erythrose, ribulose, xylulose or arabinose, monosaccharides including aldoses such as D-Ribose, D-Xylose, L-Arabinose, D-Glucose, D-Mannose and D-Galactose; ketoses such as D- Ribulose and D-Fructose; deoxyaidoses such as 2-Deoxy-D-ribose, L-Fuccose; acetylated amino sugars such as N-Acteyl-D-glucosamine and N-Acetyl-D- galactosamine; acidic monosaccharides such as D-Glucuronic acid, L-Iduronic acid and N-Acetylneuraminic acid, Sugar alcohols such as D-Sorbit
  • Anthranilic acid is used as an intermediate for production of dyes, pigments and saccharin. It and its esters are also used in preparing perfumes to imitate jasmine and orange, pharmaceuticals (loop diuretics such as furosemide) and UV -absorbers, as well as corrosion inhibitors for metals and mold inhibitors in soya sauce. Its usefulness as part of a safening package is surprising.
  • Acetaminophen is widely used as an over-the-counter analgesic and antipyretic. It will be appreciated that its efficacy as part of a safening package is surprising.
  • the present invention is directed to the treatment of a plant with an effective amount of a composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof to improve safety.
  • composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof for use as a plant safener.
  • the combination envisaged Ln the present invention may give rise to a synergistic effect.
  • auxin-related compound For ease of reference we will refer to an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite or a mixture thereof as an "auxin-related compound".
  • the auxin-related compound is based on an indolic ring. In another embodiment the auxin-related compound is based on a phenolic ring.
  • the derivative is an acid, a conjugate, a salt, an ester, or an amide of the auxin, auxin precursor, or auxin metabolite.
  • the derivative is in the form of a conjugate, e.g. conjugated to a sugar, an alcohol, an amino acid, a peptide or a protein.
  • the auxin precursor is chorismate, anthranilic acid, phosphoribosyl anthraniliate, l-(O-carboxyphenulamino)-l-deoxyribulose-5- phosphate, indole-3-glycerol-phosphate, indole, indole-3-acetic acid, tryptophan, tryptamine, N-hydroxy tryptamine, indole-3-acetaldoxime, l-aci-nitro-2- indolylethane, indolic glucosinate, indole-3-acetonitrile (IAN), indole-3-acetaIdehyde, indole-3-lactic acid, indole-3-pyruvic acid, or indole-3-ethanol.
  • the auxin precursor is anthranilic acid or a derivative thereof.
  • the derivative of anthranilic acid is one of the compounds set out in Fig. 1.
  • the auxin-related compound may be a natural, such as is obtainable from seaweed or algae, or synthetic auxin.
  • the natural auxin is indole-3-acetic acid (IAA), 4-chloro-indole-3- acetic acid (4-Cl-IAA), phenylacetic acid (PAA), indole-3-butyric acid (CBA), indole- 3-acetyl-l-O- ⁇ -D-glucose (IAAgIc).
  • the conjugate of the natural auxin is IAA-Inositol, IAA-Inositol- arabinose, IAPl, an IAA-peptide, an IAA glycoprotein, an IAA-glucan, IAA- aspartate, IAA-glucose, LAA-1-O-gIucose, IAA-myo-Inositol, IAA-4-O-glucose, LAA-6-O-glucose, IAA-Inositol-galactose, an IAA amide conjugate, or an IAA-amino acid conjugate.
  • the synthetic auxin is 1-naphthaleneacetic acid (NAA), 2,4- dichlorophenoxyacetic acid (2,4-D), 2-methoxy-3,6-dichlorobenzoic acid (dicamba), 4-amino-3,5,6-trichloropicolinic acid (tordon), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 2,3,6-trichlorobenzoic acid, 4-chloro-2 methylphenoxyacetic acid (MCPA) or N,N-dimethylethylthiocarbarnate.
  • NAA 1-naphthaleneacetic acid
  • dicamba 2-methoxy-3,6-dichlorobenzoic acid
  • tordon 4-amino-3,5,6-trichloropicolinic acid
  • 2,4,5-trichlorophenoxyacetic acid 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)
  • 2,3,6-trichlorobenzoic acid 4-chloro-2 methylphenoxyace
  • the auxin metabolite is indole-3-lactic acid or indole-3-ethanol.
  • composition of the present invention employs the use of acetaminophen or an analog or derivative thereof.
  • use is made of acetaminophen.
  • the acetaminophen derivative is a compound as set out in Fig. 3.
  • composition further comprises cobalt.
  • the present invention includes a method of protecting desired plants from the effect of an agrochemical comprising applying an effective amount of a composition of the present invention to the desired plant such that a protective effective against the agrochemical occurs.
  • composition of the present invention seeks to protect plants from damage that may occur through the application of an agrochemical, preferably wihtout interfering or reducing the intended effect of the agrochemical.
  • a safener in the context of the application of a herbicide protects crop plants from herbicide damage without reducing activity in target weed species.
  • composition of the present invention can be applied as a mixture with the agrochemical or before or after it.
  • the agrochemical may be, for example, at least one of a fungicide, an insecticide, a herbicide, a fertiliser, a plant growth regulator, a chemical thinning agent and an abscission delay agent.
  • the composition further comprises at least one of a fungicide, an insecticide, a herbicide, a fertiliser, a plant growth regulator, a chemical thinning agent and an abscission delay agent.
  • a safenening composition according to the present invention further comprising at least one of compunds (a) to (f), as described above.
  • the combination may give rise to a synergistic effect.
  • safener may comprises, e.g., at least one compound selected from c) a vitamin or coenzyme, or a precursor thereof; d) a purine or pyrimidine nucleoside, nucleotide or metabolic precursor thereof; or f) an amino acid.
  • composition comprising an effective amount of an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite for use as a safener.
  • anthranilic acid also referred to as "AN”
  • an effective salt, ester, or amide thereof including analogs of the AN and effective salts, ester and amides thereof is further described.
  • composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof is (amongst other benefits in plants) an effective safening agent, wherever this is deemed useful.
  • composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite or a mixture thereof is (amongst other benefits in plants) an effective safening agent, wherever this is deemed useful.
  • the present invention can provide a reduction in phytotoxicity in crops treated with fungicides, fertilizers, herbicides and pesticides, as well as plant growth regulators, chemical thinning agents and abscission delay agents.
  • the safening systems of the present invention can be used alone (without e.g. fungicides, fertilizers, herbicides, pesticides) to provide a boost in growth and/or vigour, especially when applied under conditions of potential or actual plant stress, such as high/low pH, high/low temperatures, high/low salinity, drought or other unfavourable plant conditions.
  • the composition of the present invention may include trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the composition of the present invention includes cobalt. We have found that cobalt increases nodulation in nitrogen fixing crops.
  • compositions of the present invention may give rise to a synergistic effect.
  • Fig. 1 shows structures of examples of analogs of anthranilic acid.
  • Fig. 2 shows structures of examples of naturally occurring auxins and conjugates.
  • Fig. 3 shows structures of examples of derivatives of acetaminophen.
  • Fig. 4 shows an overview of the reactions leading from chorismate to IAA and tryptophan.
  • Fig. 5 shows the structure of some synthetic auxins.
  • the present invention relates to the use of anthranilic acid (AN):
  • AN also known as anthraniliate, has the CAS number 1 18-92-3.
  • useful derivatives of AN Preferably such derivatives are water soluble.
  • Representative salts include inorganic salts such as ammonium, ⁇ thium, sodium, potassium, magnesium and calcium salts and organic amine salts such as the triethanolamine, dimethylethanolamine and ethanolamine salts.
  • the present invention involves the use of auxins.
  • auxins are a class of plant growth hormones.
  • An auxin is an organic substance that promotes cell elongation growth when applied in low concentrations to plant tissue segments in a bioassay.
  • the most studied member of the auxin family is indole-3- acetic acid (IAA).
  • IAA indole-3- acetic acid
  • IAA indole-3- acetic acid
  • EBA EBA
  • PAA 4-Cl-IAA.
  • Naturally occurring auxins are found Ln plants as the free acid and in conjugated forms.
  • auxin has been defined as a compound that gives rise to curvature in the grass coleoptile curvature (or growth) test.
  • Such an assay is described by Fritz Went Ln 1926 and 1928.
  • coleoptile tips of grass seedlings are placed on an agar plate containing the substance to be assayed. If an auxin response is present then the coleoptile bends in darkness and the angle of curvature can be measured. Went's results indicated that the curvatures of stems were proportional to the amount of growth substance in the agar.
  • This test is also called the avena curvature test.
  • Other functional tests which can be employed to determine auxin activity include the ability to cause rooting in stem cuttings and the ability to promote cell division in tissue or cell culture.
  • auxins their synthesis and metabolism can be found in e.g. Normanly, Slovin and Cohen in "Plant Hormones, Biosynthesis, Signal Transduction and Action!, Ed Peter J. Davies, [2004] Chapter “Bl. Auxin Biosynthesis and Metabolism” pages 36-62.
  • auxin activity In addition to indolic auxins, various phenolic auxins have auxin activity. Some examples of naturally occurring auxins and some examples of the lower molecular weight conjugates which may be used in the present invention are shown in Fig. 2.
  • the present invention may also make use of conjugates. It is believed that plants use conjugates for storage purposes and/or to regulate the amount of free auxin available in the plant. IAA is primarily conjugated to the amino acid aspartate.
  • IAA-Inos Related low molecular weight conjugates, such as IAA-Inos, LAA-Inos-arabinose and conjugates with other amino acids, and higher molecular weight conjugates, such as the IAA protein IAPl, IAA-peptides, IAA glycoprotein and IAA-glucans, have also been isolated from plants.
  • EBA has been found to occur naturally in plants; although some references refer to it as a synthetic auxin. Some commentators refer to it as an auxin per se and other as a precursor to LAA.
  • ester-linked One general class of conjugated forms consists of those linked through carbon- oxygen-carbon bridges. These compounds have been referred to generically as "ester- linked", although some 1-0 sugar conjugates such as 1-O-IAA-Gluc are actually linked by acyl alkyl acetal bonds. Typical ester-linked moieties include 6-0-IAGluc, IAA-Inos, IAA-glycoproteins, IAA-glucans and simple methyl and ethyl esters.
  • the other type of conjugates present in plants are linked through carbon-nitrogen-carbon amide bonds (referred to as "amide-linked"), as in the IAA-amino acid and protein and peptide conjugates (see Fig. 2).
  • Biochemical pathways that result in IAA production within a plant tissue include: (A) de novo synthesis, whether from tryptophan [referred to as Trp-dependent (Trp-D) LAA synthesis], or from indolic precursors of Trp [referred to as Trp-independent (Trp-I) IAA synthesis, since these pathways bypass Trp]; (B) hydrolysis of both amide- and ester-linked LAA conjugates; (C) transport from one site in the plant to another site; and (D) conversion of IBA to LAA.
  • IAA turnover mechanisms include: (E) oxidative catabolism; (F) conjugate synthesis; (G) transport away from a given site; and (H) conversion of IAA to IBA.
  • the present invention makes use of such precursors and metabolites along this pathway.
  • the present invention does not make use of inactive metabolites, such as arise from catabolism of the auxin.
  • the present invention also encompasses the use of synthetic auxins. Some examples of synthetic auxins are shown in Fig. 5.
  • a comparison of the compounds that possess auxin activity reveals that at neutral pH they all have a strong negative charge on the carboxyl group of the side chain that is separated from a weaker positive charge on the ring structure by a distance of about 0.5 nm. It has been proposed that an indole is not essential for activity, but that it can be an aromatic or fused aromatic ring of a similar size.
  • a model has been proposed as being a planar aromatic ring-binding platform, a carboxylic acid-binding site and a hydrophobic transition region that separates the two binding sites.
  • the present invention involves the use of acetaminophen.
  • Acetaminophen has the IUPAC name, N-(4-hydroxypheyl)acetamide and is commonly referred to as paracetamol. It has the CAS number 103-90-2.
  • derivatives of acetaminophen are also useful in the present invention.
  • the compounds or compositions of the present invention can be used in combination with other components, as appropriate.
  • the present invention provides the use in a safening composition of a compound selected from a) glucose, hydrolysed starch, sucrose, fructose, glycerol, glyceraldehydes, erythrose, ribulose, xylulose or arabinose, monosaccharides including aldoses such as D-Ribose, D-Xylose, L- Arabinose, D-Glucose, D-Mannose and D-Galactose; ketoses such as D-Ribulose and D-Fructose; deoxyaldoses such as 2-Deoxy-D-ribose, L-Fuccose; acetylated amino sugars such as N-Acteyl-D- glucosamine and N-Acetyl-D-galactosamine; acidic monosaccharides such as D- Glucuronic acid, L-Iduronic acid and N-Acetylneuraminic acid, Sugar alcohols such
  • the compound may be defined as belonging to one or more of the following classes (a) to (f); although two or more such additives in the same or different classes may be used:
  • NADH reduced nicotinamide adenine dinucleotide
  • NADPH reduced nicotamide adenine dinucleotide phosphate
  • an organic acid of the Krebs Tricarboxylic Acid Cycle or a metabolic precursor thereof, including citric, succinic, malic, pyruvic, acetic and fumaric acids, which will normally be applied at similar rates to and used for similar functions as the carbohydrate source;
  • a vitamin or coenzyme e.g. thiamine, riboflavin, pyridozine, pyridoxamine, pyridoxal, nicotinamide, folic acid, or a precursor thereof including nicotinic acid, which will normally be applied at 0.01 to 500 g/ha to stimulate metabolic processes dependent on enzymatic action;
  • a purine or pyrimidine nucleoside, nucleotide or a metabolic precursor thereof e.g. adenine, adenosine, thymine, thymidine, cytosine, guanine, guanosine, hypoxanthine, uracil, uridine or inosine, which will normally be applied at 1 to 500 g/ha to act as structural precursors for nucleic acid synthesis;
  • a naturally occurring fat or oil including olive, soya, coconut and corn oils, which can be degraded by living organisms to fatty acids and which will normally be applied at 10 to 10,000 g/ha;
  • an amino acid of a type that occurs naturally in plant proteins e.g. glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, aspartic acid, glutamic, acid, glutamine, asparagine, lysine, hyroxylysine, arginine, histidine, phenylalanine, tyrosine, tryptophan, proline or hydroxyproline, which will normally be applied at 1 to 500 g/ha to act as structural units for newly formed proteins or by their degradation to function in a similar manner to fatty acids and carbohydrates.
  • the adjuvants can facilitate spreading and efficacy, and improve the adhesion properties of the composition, and generally include oils, antifoaming agents and surfactants.
  • Such components which are useful in the present invention include, but are not limited to: terpene, Brij family (polyoxyethylene fatty alcohol ether) from Uniqema (Castle, DE); surfactant in Tween family (Polyoxyethylene sorbitan esters) from Uniqema (Castle, DE); Silwet family (Organosilicone) from Union Carbide (Lisle, DL); Triton family (Octylphenol ethoxylate) from The Dow Chemical Company (Midland, MI); Tomadol family (ethoxylated linear alcohol) from Tomah3 Products, Inc.
  • wetting agents include silicone surfactants, nonionic surfactants such as alkyl ethoxylates, anionic surfactants such as phosphate ester salts and amphoteric or cationic surfactants such as fatty acid amido alkyl betaines).
  • the compounds of the invention may be the sole active ingredient of the composition or they may be admixed with further active ingredients such as nematicides, insecticides, synergists, herbicides, fungicides, fertilisers, chemically thinning agents, abscission delay agents or plant growth regulators where appropriate.
  • the one or more compounds of the invention are administered in combination optionally with one or more active agents.
  • the compounds of the invention may be administered consecutively, simultaneously or sequentially with each other or the one or more active agents.
  • the major advantages of combining the compounds are that it may promote additive or possible synergistic effects through e.g. biochemical interactions. Beneficial combinations may be suggested by studying the activity of the test compounds. This procedure can also be used to determine the order of administration of the agents, i.e. before, simultaneously or after delivery.
  • the composition may be used as a concentrate or more usually is formulated into a composition which includes an effective amount of the composition of the present invention together with a suitable inert diluent, carrier material and/or surface active agent.
  • a suitable inert diluent, carrier material and/or surface active agent Preferably the composition is in the form of an aqueous solution which may be prepared from the concentrate.
  • effective amount we mean that the composition (and/or its individual components) provides an improved effect effect.
  • the applied concentration of chemical can vary widely depending on the water volume applied to plants as well as other factors such as plant age and size, and plant sensitivity to the product.
  • Typical rates of AN-related compounds would be 1-10 g/ha (preferably and as used in these trials, Ig per hectare was applied), typical rates of acetaminophen or its derivatives would be 1-10 g/ha (preferably and as used in these trials, 3g per hectare was applied).
  • Typical rates of the agrochemically acceptable additive of the present invention would be 1-lOg/ha (preferably and as used in these trials, less than 3g per hectare was applied).
  • the rate of other components such as spreaders and stickers can be 50-200 ml per ha.
  • Non-limiting examples of insecticides in relation to which the composition of the present invention may be useful include chlorinated hydrocarbons such as Aldrin, Chlordane, Chlordecone, DDT, Dieldrin, Endosulfan, Endrin, Heptachlor, Hexachlorobenzene, Lindane (gamma-Hexachlorocyclohexane), Methoxychlor, Mirex, Pentachlorophenol, TDE; organophosphates such as Acephate, Azinphos- methyl, Bensulide, Chlorethoxyfos, Chlo ⁇ yrifos, Chlo ⁇ yriphos-methyl, Diazinon, Dichlorvos (DDVP), Dicrotophos, Dimethoate, Disulfoton, Ethoprop, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Malathion, Methamidophos, Methidathion, Mevinphos, Naled, Omethoate,
  • Non-limiting examples of fungicides in relation to which the composition of the present invention may be useful include (3-ethoxypropyl)mercury bromide, 2- methoxyethylmercury chloride, 2-phenylphenol, 8-hydroxyquinoline sulfate,8- phenylmercurioxyquinoline, acibenzolar, acylamino acid fungicides, acypetacs, aldimo ⁇ h, aliphatic nitrogen fungicides, ally] alcohol, amide fungicides, ampropylfos, anilazine, anilide fungicides, antibiotic fungicides, aromatic fungicides, aureofungin, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benzalkonium chloride
  • Mefenoxam metam, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl isothiocyanate, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, metiram, metominostrobin, metrafenone, metsulfovax, milneb, mo ⁇ holine fungicides, myclobutanil, myclozolin, N-(ethylmercury)-p-toIuenesulfonanilide, nabam, natamycin, nystatin, nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace, oprodione, organomercury fungicides, organophosphorus fungicides, organotin fungicides, orysastro
  • Non-limiting examples of fertilizers in relation to which the composition of the present invention may be useful include nitrogen fertilizers such as ammonium, ammonium sulphate, ammonium chloride, ammonium sulphate nitrate, ammonium nitrate, calcium ammonium nitrate, sodium nitrate, calcium nitrate, potassium nitrate, urea; phosphate fertilizers such as single superphosphate, triple superphosphate, diammonium phosphate, monoammonium phosphate, ground phosphate rock, rock phosphate, rock phosphate; potash fertilizers such as muriate of potash (potassium chloride), sulphate of potash, sulphate of potash magnesia; magnesium fertilizers such as kieserite, epsom salts, magnesium sulfate (Epsom salts); complex fertilizers such as urea-ammonium nitrate NPK fertilizers, NP fertilizers, NK fertilizers and PK fertilizers; aluminium s
  • Non-limiting examples of plant growth regulators in relation to which the composition of the present invention may be useful include abscisic acid or a derivative thereof, a cytokinin, ethylene or a gibberlin.
  • Non-limiting examples of the plant growth regulator in relation to which the composition of the present invention may be useful include p-Chlorophenoxyacetic acid (4-CPA), 2-CPA, 2,4-Dichlorophenoxyacetic acid, 2,4-Dichlorophenoxyacetic acid Sodium salt, Indole-3 -acetic acid Free acid (LAA), Indole-3-acetic acid Sodium salt, Indole-3-acetic acid methyl ester, Indole-3-acery-L-aspartic acid, IndoIe-3- butyric acid (IBA), Indole-3-butyric acid Potassium salt (K-IBA), alpha- Naphthaleneacetic acid Free acid (NAA), beta-Naphthoxy acetic acid Free acid (NOA), Phenylacetic acid (PAA), Picloram, 2,4,5-Trichlorophenoxyacetic acid (2,4,5- T), 2,3,5-Triiodobenzoic acid Free acid (TIBA), Adenine Free base, Adenine hemisulf
  • the plant growth regulator may be other than a naturally occurring plant hormone.
  • the plant growth regulator include antiauxins, such as: clofibric acid and 2,3,5-tri-iodobenzoic acid; auxins such as 4-CPA, 2,4-D, 2,4- DB, 2,4-DEP, dichlorprop, fenoprop, IAA, EBA, naphthaleneacetamide, ⁇ - naphthaleneacetic acid, 1-naphthol, naphthoxyacetic acid, potassium naphthenate, sodium naphthenate, 2,4,5-T; cytokinins such as 2iP, benzyladenine, kinetin, zeatin; defoliants such as calcium cyanamide, dimethipin, endothal, ethephon, merphos, metoxuron, pentachlorophenol, thidiazuron, tribufos; ethylene inhibitors such as aviglycine, 1-methylcyclopropene; ethylene releasers such as ACC,
  • Non-limiting examples of herbicides in relation to which the composition of the present invention may be useful include aminopyralid, glufosinate ammonium, fluroxypyr, imazapic, pendimethlin, sodium chlorate, chloroacetamindes such as metalchlor, acetochlor, butachlor, propachlor, thenylchlor; amides such as dimethenamid, propanil, naptalam, pronamide, bensulide, pethoxamid; organoarsenicals such as cacodylic acid and its sodium salt, disodium methanearsonate, monosodium methanearsonate; benzoic acids and derivatives thereof such as dicamba, chlorfenac, chloramben; nitriles such as dichlobenil and bromoxynil, 2,6-dichlorobenzonitrile, Ioxynil; benzothiadiazoles such as bentazone; bipyridyliums such as diquat, paraquat
  • abscission delay agents in relation to which the composition of the present invention may be useful include 1-naphthaleneacetic acid (NAA), NAAm, 2,4-D, 2,4,5-T, 2,4,5-TP, amino-oxyacetic acid, aminoethoxyvinylglycine (AVG) and daminozide.
  • NAA 1-naphthaleneacetic acid
  • NAAm NAAm
  • 2,4-D 2,4,5-T
  • 2,4,5-TP amino-oxyacetic acid
  • AVG aminoethoxyvinylglycine
  • daminozide daminozide
  • composition of the present invention may also include trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the trace element is cobalt.
  • cobalt is in the form of cobalt sulphate.
  • the one or more compounds of the invention are administered in combination optionally with one or more active agents.
  • the compounds of the invention may be administered consecutively, simultaneously or sequentially with each other or the one or more active agents.
  • the major advantages of combining the compounds are that it may promote additive or possible synergistic effects through e.g. biochemical interactions. Beneficial combinations may be suggested by studying the activity of the test compounds. This procedure can also be used to determine the order of administration of the agents, i.e. before, simultaneously or after delivery.
  • the rate and timing of application will depend on a number of factors known to those skilled in the art, such as the type of species etc.
  • a second or further application(s) can be made as appropriate.
  • the timings between each application may be in the region of 5 days or more.
  • the present invention relates to a method of safening plants which comprises applying to the plants or to the locus thereof an effective controlling amount of the compounds/compositions of the present invention.
  • compositions of the present invention can be applied to the soil, plant, seed, or other area to be protected.
  • the present invention is applied to the foliage of plants.
  • the composition may be applied in the form of dusting powders, wettable powders, granules (slow or fast release), water dispersible granules, emulsion or suspension concentrates, liquid solutions, emulsions, seed dressings, or controlled release formulations such as microencapsulated granules or suspensions, soil drench, irrigation component, or preferably a foliar spray.
  • Dusting powders are formulated by mixing the active ingredient with one or more finely divided solid carriers and/or diluents, for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers.
  • solid carriers and/or diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers.
  • Granules are formed either by absorbing the active ingredient in a porous granular material for example pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths, ground corn cobs, and the like, or on to hard core materials such as sands, silicates, mineral carbonates, sulfates, phosphates, or the like.
  • Agents which are commonly used to aid in impregnation, binding or coating the solid carriers include aliphatic and aromatic petroleum solvents, alcohols, polyvinyl acetates, polyvinyl alcohols, ethers, ketones, esters, dextrins, sugars and vegetable oils, with the active ingredient.
  • Other additives may also be included, such as emulsifying agents, wetting agents or dispersing agents.
  • Microencapsulated formulations may also be used, particularly for slow release over a period of time, and for seed treatment.
  • the compositions may be in the form of liquid preparations to be used as dips, irrigation additives or sprays, which are generally aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents (surface active agents).
  • the compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of an emulsifiable concentrate (EC) or a suspension concentrate (SC) containing a high proportion of the active ingredient or ingredients.
  • EC emulsifiable concentrate
  • SC suspension concentrate
  • An EC is an homogeneous liquid composition, usually containing the active ingredient dissolved in a substantially non-volatile organic solvent.
  • An SC is a fine particle size dispersion of solid active ingredient in water. To apply the concentrates they are diluted in water and are usually applied by means of a spray to the area to be treated.
  • Suitable liquid solvents for ECs include methyl ketone, methyl isobutyl ketone, cyclohexanone, xylenes, toluene, chlorobenzene, paraffins, kerosene, white oil, alcohols (for example, butanol), methylnaphthalene, trimethylbenzene, trichloroethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THFA).
  • concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • the concentrates may contain 1-85% by weight of the active ingredient or ingredients.
  • When diluted to form aqueous preparations such preparations may contain varying amounts of the active ingredient depending upon the purpose for which they are to be used.
  • the composition may also be formulated as powders (dry seed treatment DS or water dispersible powder WS) or liquids (flowable concentrate FS, liquid seed treatment LS), or microcapsule suspensions CS for use in seed treatments.
  • the formulations can be applied to the seed by standard techniques and through conventional seed treaters.
  • the compositions are applied to the plants, to the locus of the plants, by any of the known means of applying fertiliser compositions, for example, by dusting, spraying, or incorporation of granules.
  • the composition of the present invention can be applied at the same time as or at an appropriate interval to the agrochemical. This can be readily determined by a skilled worker, e.g. it may be in the range of 1-3 days prior to application of the agrochemical.
  • compositions according to this present invention may be applied to the foliage of plants but may also be applied to the soil or added to the irrigation water.
  • the present invention is useful in relation to crops. It will be appreciated that the present invention may be applicable to all horticultural and agricultural species.
  • the present invention is useful in relation to fruit crops.
  • the crops can include trees, bushes, shrubs and vines.
  • the present invention is useful in relation to vegetable crops.
  • the present invention is useful in relation to agricultural and horticultural crops including ornamentals.
  • the present invention is useful in relation to cereals and grasses and to pod-bearing, bean and oilseed crops.
  • the present invention when used in combination with a chemical thinner the present invention is useful in relation to fruit crops.
  • the crops can include trees, bushes, and vines.
  • the present invention is useful in relation to nitrogen-fixing crops.
  • the nitrogen-fixing crops can include soybean, navy bean and pea.
  • the present invention can be used on the following plants as non-limiting examples: Almond ⁇ Prunus dulcis), Apple (Malus domestica), Apricot ⁇ Prunus armeniaca), Avocado ⁇ Persea americana), Banana, Plantain ⁇ Musa spp.), Blackberries ⁇ Rubus spp), Blueberries ⁇ Vaccinium spp), Cacao or cocoa ⁇ Theobroma cacao), Cashew ⁇ Anacardium occidentale), Cherries ⁇ Prunus cerasus, P. avium), Chestnuts ⁇ Castanea spp.), Coconut (Cocos nucifera), Coffee (Cqffea arabica, C.
  • Azaleastrum Kalanchoe, Bulb crops, Crocus, Tulip, Narcissus, Hyacinth, Poinsettia and Roses, tomatoes, squash, pumpkin, beans, broccoli, green beans, asparagus, peas, corn, carrots, spinach, cauliflower, lima beans, broad beans, firench beans, runner beans, navy beans, kidney beans, lentils, cabbage, onions, courgettes, aubergines, sweet basil, leeks, artichokes, lettuce, cassava leaves, tomatoes, cucumbers and gherkins, marrows, gourds, squashes, chillies and peppers, green onions, dry onions, red onions, shallots, garlic, chives, other alliaceous vegetables, okra, mushrooms, watermelons, cantaloupe melons, other melons, bamboo shoots, beets, chards, capers, cardoons, celery, chervil, cress, fennel, horseradish, marjoram, oyster plant, parsley, parsnips
  • compositions according to the invention include cereals, for example barley and wheat, cotton, oilseed rape, maize, rice, soy beans, sugar beet and sugar cane, especially cereals and maize.
  • Crops can also include trees, such as palm trees, coconut trees or other nuts, and vines such as grapes.
  • the grasses and weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Bromus, Cyperus, Digitaria, Echinochloa, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, Sida and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Chenopodium, Chrysanthemum, Galium, Ipomoea, Nasturtium, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.
  • monocotyledonous species for example Agrostis, Alopecurus, Avena, Bromus, Cyperus, Digitaria, Echinochloa, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, Sida and Sorghum
  • dicotyledonous species for example Abutilon,
  • Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola).
  • crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.
  • Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).
  • Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds).
  • the Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria.
  • Examples of toxins, or transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529.
  • transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
  • Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events).
  • seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
  • NAA/other auxins or auxin mixes (eg NAA/BA).
  • the safener (SAF) may be one set out as in classes (a) to (f) above. Two or more such additives in the same or different classes may be used.
  • the additive is selected from class (a) it is preferably one or more of glucose, sucrose, fructose or glycerol.
  • the additive is selected from class (b) it is preferably one or more of citric or succinic acid.
  • the additive is selected from class (c) it is preferably one or more of thiamine, riboflavin, pyridoxine, nicotinamide, folic acid, ascorbic acid, biotin or vitamin B 12.
  • the additive is selected from class (d) it is preferably adenine, thymidine, cytosine or uracil.
  • the additive is selected from class (e) it is preferably a corn oil.
  • an amino acid (f) is it preferably one of more of glycine, alanine, valine, leucine, threonine, cysteine, methionine, glutamine, asparagine or lysine.
  • Safening systems were applied to crops of winter barley, winter wheat and lettuce treated with various fertilizers (Potassium Phosphite, potassium phosphite + ammonium thiosulphate, general NPK fertiliser). The safening system and the fertilizer were applied either simultaneously or sequentially.
  • SAF at least one from class (f) each at ⁇ 3 g/I, plus at least one from class (c).
  • Tables 1.1 to 1.9 The results are shown in Tables 1.1 to 1.9 below.
  • each of the safening formulations showed a significant reduction in phytotoxicity when applied to a range of species in combination with a fertilizer, when compared to the application of fertilizers alone.
  • the safening systems improve crop safening in a range of species. Vigour was also boosted.
  • Safening systems were applied to crops of winter barley, winter wheat and maize treated with various fungicides (Prochloraz, Flutriafol, Fenpropidin).
  • the safening system and the fungicide were applied to the crops either simultaneously or sequentially, either as foliar applications or as a seed treatment.
  • SAF at least one from class (f) each at ⁇ 3 g/1, plus at least one from class (c).
  • each of the safening formulations showed a significant reduction in phytotoxicity when applied to a range of species in combination with fungicides, when compared to the application of fungicides alone.
  • the safening systems improve crop safening in a range of species. This applies to either the safening formulations applied in foliar applications (Tables 2.1 to 2.6) or as seed treatments (Table 2.7). Increases in vigour and early shoot weight are also noted.
  • Safening systems were applied to crops of oilseed rape and winter treated with various herbicides (Bifenox (with insecticide), Carbetamide, Propaquizafop, Chlorotoluron, Isoproturon, Flumioxazin).
  • Bifenox with insecticide
  • Carbetamide Propaquizafop
  • Chlorotoluron Chlorotoluron
  • Isoproturon Flumioxazin
  • Oilseed rape cv Excalibur, sown 26 April 2008, at two seeds per 9 cm pot, sown in normal pH multi-purpose compost. Date of spraying: 6 June; Dates of measurement/scoring: 13 June, 20 June, 5 July. Winter wheat: cv Alchemy, sown 23 April 2008, at seven seeds per 9 cm pot, sown in normal pH multi-purpose compost. Date of spraying: 24 May; Dates of measurement/scoring: 31 May, 7 June, 21 June.
  • SAF at least one from class (f) each at ⁇ 3 g/1, plus at least one from class (c).
  • each of the safening formulations showed a significant reduction in phytotoxicity when applied to a range of species in combination with an herbicide, when compared to the addition of herbicides alone.
  • the safening systems improve crop safening in a range of species.
  • An increase in vigour and greenness is also noted.
  • Maize cv Sundance i.e. not Roundup ® Ready
  • sown 27 April 2008 to obtain 1 even plant per 1 litre pot, grown in John Innes No 3 compost of pH 6.5.
  • Treated with glyphospate date of first spraying 15 June. Dates of measurement/scoring: 29 June, 13 JuIy, 26 JuIy.
  • SAF at least one from class (f) each at ⁇ 3 g/1, plus at least one from class (c).
  • EXAMPLE 5 SAFENING OF GL YPHOSATE HERBICIDE (GM maize, University of Illinois)
  • SAF at least one from class (f) each at ⁇ 3 g/1, plus at least one from class (c).
  • Safening systems were applied to crops of oilseed rape and winter wheat treated with various herbicides (Bifenox (with insecticide), Carbetamide, Propaquizafop), either without or without AN and/or AC.
  • Bifenox with insecticide
  • Carbetamide Carbetamide
  • Propaquizafop Propaquizafop
  • Safening compounds were selected from the list of compounds below. The compounds used are highlighted in bold.
  • Glucose GL
  • hydrolysed starch sucrose (S), fructose (FR), glycerol (G), glyceraldehydes, erythrose, ribulose, xylulose or arabinose or an ester or glycoside or metabolic equivalent of such a carbohydrate;
  • an organic acid of the Krebs Tricarboxylic Acid Cycle or a metabolic precursor thereof including citric (C), succinic (SU), malic, pyruvic, acetic and fumaric acids);
  • a vitamin or coenzyme eg thiamine (T), riboflavin (R), pyridoxine (P), pyridoxamine, pyridoxal, nicotinamide (N), folic acid (F), ascorbic acid (AA), Biotin (B) and vitamin B12 (B12) or a precursor thereof including nicotinic acid
  • a purine or pyrimidine nucleoside, nucleotide or a metabolic precursor thereof eg adenine, adenosine, thymine, thymidine, cytosine, guanine, guanosine, hypoxanthine, uracil, uridine or inosine, to act as structural precursors for nucleic acid synthesis.
  • a naturally occurring fat or oil including olive, soya, coconut and corn (Oil) oils;
  • GLY glycine
  • AL alanine
  • LE valine
  • L leucine
  • L leucine
  • CY cysteine
  • ME methionine
  • AS asparagine
  • LY hydroxylysine
  • arginine histidine
  • phenylalanine tyrosine
  • tryptophan proline
  • proline or hydroxyproline.
  • a reduction in phytotoxicity, along with increases in vigour and rooting, are shown from the use of the safening systems above (either combinations of compounds from classes (a) to (f) alone or in combination AN and/or AC) in combination with a herbicide, in contrast to application of a herbicide alone.
  • EXAMPLE 7 ROOT NODULATION AND SAFENING IN A RANGE OF NITROGEN-FIXING CROPS
  • Safening systems were applied to crops of soybean, navy bean and pea either alone or in combination with cobalt and/or a general foliar fertilizer, either without or without AN and/or AC.
  • the safener/safening system and the fertiliser were applied to the crops either simultaneously or sequentially.
  • Co 100% Cobalt Sulphate (2Og per litre and per hectare).
  • FFl 2Og per litre Cobalt Sulphate (as per Co above) plus "Miracle-Gro" at xl recommended rate (applied at 15g per 2.5 sq metres).
  • Miracle-Gro contains: 24% N, 4% P, 13% K, plus 0.02% B, 0.03% Cu, 0.19% Fe, 0.05% Mn, 0.001% Mo and 0.03% Zn.
  • SAF at least one from class (f) each at ⁇ 3 g/1, plus at least one from class (c).
  • NAVY BEAN cv Mogex Scored/Counted +28 Days after Spraying. Dates as per Example 7.3 Above, but sown in compost of normal pH (6.5). Each treatment represents the mean value from 12 plants, within four replicates. No inoculum applied. 27 FF2 + AN + 37.9 5.8 38.3 5.8 7.2 7.5
  • PEA - TRIAL 5 - cv Ragtime Scored/Counted +28 Days after Spraying. Sown in Compost of Low pH (5.0-5.5) on 28 April 2008.
  • PEA - TRIAL 7.6 - cv Ragtime Dates as per Example 7.5 above, but sown in compost of normal pH (6.5). Each treatment represents the results from 12 plants, within four replicates. No inoculum was applied.
  • EXAMPLE 8 SAFENING OF HERBICIDES FROM ADDITION OF AUXIN/AUXIN PRECURSOR AND ACETAMINOPHEN

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Abstract

A composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof for use as a plant safener.

Description

SAFENING AGENT
FIELD OF THE INVENTION
This invention relates to a method and composition for improving crop safety by treating plants with, particularly but not exclusively, a composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof.
BACKGROUND OF THE INVENTION
Chemical fertilisers, fungicides, insecticides and herbicides are applied to plants in order to promote growth and reduce or destroy unwanted fungi, pests, weeds and other unwanted species. This is of particular importance in the field of commercial farming, where obtaining the maximum yield is of the utmost importance.
Chemical fertilisers, fungicides, pesticides, insecticides and herbicides available to- date often have negative effects on crops, as well as the positive effect of reducing unwanted species and promoting growth. For example, such chemicals may damage the crops to which they are applied, as well as the species to which they are targeted. This is a particular problem in the field of non-selective fertilisers. These fertilisers, fungicides, pesticides, insecticides and herbicides may also be hazardous. Other compositions applied to plants such as plant growth regulators, chemical thinners and abscission delay agents also often have negative effects on crops and may also be hazardous.
Thus, there is a continuing need for safeners and which may provide improved properties.
SUMMARY OF THE INVENTION
The present invention relates to the novel use of compositions comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof for use as a plant safener.
The present invention also relates to the novel use of compounds selected from a) glucose, hydrolysed starch, sucrose, fructose, glycerol, glyceraldehydes, erythrose, ribulose, xylulose or arabinose, monosaccharides including aldoses such as D-Ribose, D-Xylose, L-Arabinose, D-Glucose, D-Mannose and D-Galactose; ketoses such as D- Ribulose and D-Fructose; deoxyaidoses such as 2-Deoxy-D-ribose, L-Fuccose; acetylated amino sugars such as N-Acteyl-D-glucosamine and N-Acetyl-D- galactosamine; acidic monosaccharides such as D-Glucuronic acid, L-Iduronic acid and N-Acetylneuraminic acid, Sugar alcohols such as D-Sorbitol and D-Mannitol, disaccharides including maltose, lactose and sucrose, or an ester or glycoside or metabolic equivalent of such a carbohydrate; b) an organic acid of the Krebs tricarboxylic acid cycle or a metabolic precursor thereof; c) a vitamin or coenzyme, or a precursor thereof; d) a purine or pyrimidine nucleoside, nucleotide or metabolic precursor thereof; e) a naturally occurring fat or oil; or f) an amino acid in combination with the afore-mentioned compositions. Such compounds have previously been associated with providing useful additive effects, but their use as part of a safening package is surprising.
Anthranilic acid is used as an intermediate for production of dyes, pigments and saccharin. It and its esters are also used in preparing perfumes to imitate jasmine and orange, pharmaceuticals (loop diuretics such as furosemide) and UV -absorbers, as well as corrosion inhibitors for metals and mold inhibitors in soya sauce. Its usefulness as part of a safening package is surprising.
Acetaminophen is widely used as an over-the-counter analgesic and antipyretic. It will be appreciated that its efficacy as part of a safening package is surprising.
STATEMENTS OF THE INVENTION
The present invention is directed to the treatment of a plant with an effective amount of a composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof to improve safety.
According to one aspect of the present invention there is provided a composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof for use as a plant safener.
The combination envisaged Ln the present invention may give rise to a synergistic effect.
For ease of reference we will refer to an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite or a mixture thereof as an "auxin-related compound".
In one embodiment the auxin-related compound is based on an indolic ring. In another embodiment the auxin-related compound is based on a phenolic ring.
In one embodiment the derivative is an acid, a conjugate, a salt, an ester, or an amide of the auxin, auxin precursor, or auxin metabolite.
In one embodiment the derivative is in the form of a conjugate, e.g. conjugated to a sugar, an alcohol, an amino acid, a peptide or a protein.
In one embodiment the auxin precursor is chorismate, anthranilic acid, phosphoribosyl anthraniliate, l-(O-carboxyphenulamino)-l-deoxyribulose-5- phosphate, indole-3-glycerol-phosphate, indole, indole-3-acetic acid, tryptophan, tryptamine, N-hydroxy tryptamine, indole-3-acetaldoxime, l-aci-nitro-2- indolylethane, indolic glucosinate, indole-3-acetonitrile (IAN), indole-3-acetaIdehyde, indole-3-lactic acid, indole-3-pyruvic acid, or indole-3-ethanol.
In a particularly preferred embodiment the auxin precursor is anthranilic acid or a derivative thereof. In one embodiment the derivative of anthranilic acid is one of the compounds set out in Fig. 1.
The auxin-related compound may be a natural, such as is obtainable from seaweed or algae, or synthetic auxin.
In one embodiment the natural auxin is indole-3-acetic acid (IAA), 4-chloro-indole-3- acetic acid (4-Cl-IAA), phenylacetic acid (PAA), indole-3-butyric acid (CBA), indole- 3-acetyl-l-O-β-D-glucose (IAAgIc).
In one embodiment the conjugate of the natural auxin is IAA-Inositol, IAA-Inositol- arabinose, IAPl, an IAA-peptide, an IAA glycoprotein, an IAA-glucan, IAA- aspartate, IAA-glucose, LAA-1-O-gIucose, IAA-myo-Inositol, IAA-4-O-glucose, LAA-6-O-glucose, IAA-Inositol-galactose, an IAA amide conjugate, or an IAA-amino acid conjugate.
In one embodiment the synthetic auxin is 1-naphthaleneacetic acid (NAA), 2,4- dichlorophenoxyacetic acid (2,4-D), 2-methoxy-3,6-dichlorobenzoic acid (dicamba), 4-amino-3,5,6-trichloropicolinic acid (tordon), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 2,3,6-trichlorobenzoic acid, 4-chloro-2 methylphenoxyacetic acid (MCPA) or N,N-dimethylethylthiocarbarnate.
In one embodiment the auxin metabolite is indole-3-lactic acid or indole-3-ethanol.
The composition of the present invention employs the use of acetaminophen or an analog or derivative thereof. In a preferred embodiment use is made of acetaminophen. In another embodiment the acetaminophen derivative is a compound as set out in Fig. 3.
In one embodiment the composition further comprises cobalt.
In another aspect of the present invention there is provided a method for improving plant safety comprising the application of a composition of the invention as described above to a plant or its environs or plant propagation material. Thus, the present invention includes a method of protecting desired plants from the effect of an agrochemical comprising applying an effective amount of a composition of the present invention to the desired plant such that a protective effective against the agrochemical occurs.
The composition of the present invention seeks to protect plants from damage that may occur through the application of an agrochemical, preferably wihtout interfering or reducing the intended effect of the agrochemical. For example, a safener in the context of the application of a herbicide protects crop plants from herbicide damage without reducing activity in target weed species.
The composition of the present invention can be applied as a mixture with the agrochemical or before or after it.
Thus, we provide a kit for use in crops compirising the agrochemical, and the components of the present invention, preferably in separate containers.
The agrochemical may be, for example, at least one of a fungicide, an insecticide, a herbicide, a fertiliser, a plant growth regulator, a chemical thinning agent and an abscission delay agent.
Thus, in one embodiment the composition further comprises at least one of a fungicide, an insecticide, a herbicide, a fertiliser, a plant growth regulator, a chemical thinning agent and an abscission delay agent.
It will be appreciated that the components of the safening composition and the compound it is safening against should be different.
There is also described a compound selected from a) glucose, hydrolysed starch, sucrose, fructose, glycerol, glyceraldehydes, erythrose, ribulose, xylulose or arabinose, monosaccharides including aldoses such as D-Ribose, D-Xylose, L- Arabinose, D-Glucose, D-Mannose and D-Galactose; ketoses such as D-Ribulose and D-Fructose; deoxyaldoses such as 2-Deoxy-D-ribose, L-Fuccose; acetylated amino sugars such as N-Acteyl-D-glucosamine and N-Acetyl-D-galactosamine; acidic monosaccharides such as D-Glucuronic acid, L-Iduronic acid and N- Acetylneuraminic acid, Sugar alcohols such as D-Sorbitol and D-Mannitol, disaccharides including maltose, lactose and sucrose, or an ester or glycoside or metabolic equivalent of such a carbohydrate; b) an organic acid of the Krebs tricarboxylic acid cycle or a metabolic precursor thereof; c) a vitamin or coenzyme, or a precursor thereof; d) a purine or pyrimidine nucleoside, nucleotide or metabolic precursor thereof; e) a naturally occurring fat or oil; or f) an amino acid for use as a safener.
Moreover, according to the present invention, according to another aspect there is provided a safenening composition according to the present invention further comprising at least one of compunds (a) to (f), as described above.
The combination may give rise to a synergistic effect.
In one embodiment therefore safener may comprises, e.g., at least one compound selected from c) a vitamin or coenzyme, or a precursor thereof; d) a purine or pyrimidine nucleoside, nucleotide or metabolic precursor thereof; or f) an amino acid.
There is further described a composition comprising an effective amount of an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite for use as a safener.
The treatment of a plant with an effective amount of the compound anthranilic acid (also referred to as "AN") or an effective salt, ester, or amide thereof including analogs of the AN and effective salts, ester and amides thereof is further described.
ADVANTAGES
We have found that a composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof is (amongst other benefits in plants) an effective safening agent, wherever this is deemed useful.
We have found that a compound selected from a) glucose, hydrolysed starch, sucrose, fructose, glycerol, glyceraldehydes, erythrose, ribulose, xylulose or arabinose or an ester or glycoside, monosaccharides including aldoses such as D-Ribose, D-Xylose, L-Arabinose, D-Glucose, D-Mannose and D-Galactose; ketoses such as D-Ribulose and D-Fructose; deoxyaldoses such as 2-Deoxy-D-ribose, L-Fuccose; acetylated amino sugars such as N-Acteyl-D-glucosamine and N-Acetyl-D-galactosamine; acidic monosaccharides such as D-Glucuronic acid, L-Iduronic acid and N- Acetylneuraminic acid, Sugar alcohols such as D-Sorbitol and D-Mannitol, disaccharides including maltose, lactose and sucrose, or metabolic equivalent of such a carbohydrate; b) an organic acid of the Krebs tricarboxylic acid cycle or a metabolic precursor thereof; c) a vitamin or coenzyme, or a precursor thereof; d) a purine or pyrimidine nucleoside, nucleotide or metabolic precursor thereof; e) a naturally occurring fat or oil; or f) an amino acid is (amongst other benefits in plants) an effective safening agent, wherever this is deemed useful.
We have also found that a composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite or a mixture thereof is (amongst other benefits in plants) an effective safening agent, wherever this is deemed useful.
We have found that the present invention can provide a reduction in phytotoxicity in crops treated with fungicides, fertilizers, herbicides and pesticides, as well as plant growth regulators, chemical thinning agents and abscission delay agents.
We have also found that the safening systems of the present invention can be used alone (without e.g. fungicides, fertilizers, herbicides, pesticides) to provide a boost in growth and/or vigour, especially when applied under conditions of potential or actual plant stress, such as high/low pH, high/low temperatures, high/low salinity, drought or other unfavourable plant conditions. The composition of the present invention may include trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc. In a particularly preferred embodiment, the composition of the present invention includes cobalt. We have found that cobalt increases nodulation in nitrogen fixing crops.
The combinations envisaged in the compositions of the present invention may give rise to a synergistic effect.
BRJEF DESCRIPTION OF THE FIGURES
Fig. 1 shows structures of examples of analogs of anthranilic acid.
Fig. 2 shows structures of examples of naturally occurring auxins and conjugates.
Fig. 3 shows structures of examples of derivatives of acetaminophen.
Fig. 4 shows an overview of the reactions leading from chorismate to IAA and tryptophan.
Fig. 5 shows the structure of some synthetic auxins.
DETAILED DESCRIPTION OF THE INVENTION
Various preferred features and embodiments of the present invention will now be described by way of non-limiting example.
The present invention relates to the use of anthranilic acid (AN):
Figure imgf000009_0001
AN, also known as anthraniliate, has the CAS number 1 18-92-3. We have described useful derivatives of AN above. Preferably such derivatives are water soluble. Representative salts Include inorganic salts such as ammonium, ϋthium, sodium, potassium, magnesium and calcium salts and organic amine salts such as the triethanolamine, dimethylethanolamine and ethanolamine salts.
The present invention involves the use of auxins.
Auxins are a class of plant growth hormones. An auxin is an organic substance that promotes cell elongation growth when applied in low concentrations to plant tissue segments in a bioassay. The most studied member of the auxin family is indole-3- acetic acid (IAA). In addition to IAA, there are several other naturally occurring auxins that have been described to date: IAA, EBA, PAA and 4-Cl-IAA. Naturally occurring auxins are found Ln plants as the free acid and in conjugated forms.
An auxin has been defined as a compound that gives rise to curvature in the grass coleoptile curvature (or growth) test. Such an assay is described by Fritz Went Ln 1926 and 1928. In this bioassay coleoptile tips of grass seedlings are placed on an agar plate containing the substance to be assayed. If an auxin response is present then the coleoptile bends in darkness and the angle of curvature can be measured. Went's results indicated that the curvatures of stems were proportional to the amount of growth substance in the agar. This test is also called the avena curvature test. Other functional tests which can be employed to determine auxin activity include the ability to cause rooting in stem cuttings and the ability to promote cell division in tissue or cell culture.
A review of auxins, their synthesis and metabolism can be found in e.g. Normanly, Slovin and Cohen in "Plant Hormones, Biosynthesis, Signal Transduction and Action!", Ed Peter J. Davies, [2004] Chapter "Bl. Auxin Biosynthesis and Metabolism" pages 36-62.
In addition to indolic auxins, various phenolic auxins have auxin activity. Some examples of naturally occurring auxins and some examples of the lower molecular weight conjugates which may be used in the present invention are shown in Fig. 2.
The present invention may also make use of conjugates. It is believed that plants use conjugates for storage purposes and/or to regulate the amount of free auxin available in the plant. IAA is primarily conjugated to the amino acid aspartate.
Related low molecular weight conjugates, such as IAA-Inos, LAA-Inos-arabinose and conjugates with other amino acids, and higher molecular weight conjugates, such as the IAA protein IAPl, IAA-peptides, IAA glycoprotein and IAA-glucans, have also been isolated from plants.
IAA and its precursors undergo metabolic conversions to indole-3-lactic acid, indole- 3-ethanol and EBA. EBA has been found to occur naturally in plants; although some references refer to it as a synthetic auxin. Some commentators refer to it as an auxin per se and other as a precursor to LAA.
One general class of conjugated forms consists of those linked through carbon- oxygen-carbon bridges. These compounds have been referred to generically as "ester- linked", although some 1-0 sugar conjugates such as 1-O-IAA-Gluc are actually linked by acyl alkyl acetal bonds. Typical ester-linked moieties include 6-0-IAGluc, IAA-Inos, IAA-glycoproteins, IAA-glucans and simple methyl and ethyl esters. The other type of conjugates present in plants are linked through carbon-nitrogen-carbon amide bonds (referred to as "amide-linked"), as in the IAA-amino acid and protein and peptide conjugates (see Fig. 2).
Biochemical pathways that result in IAA production within a plant tissue include: (A) de novo synthesis, whether from tryptophan [referred to as Trp-dependent (Trp-D) LAA synthesis], or from indolic precursors of Trp [referred to as Trp-independent (Trp-I) IAA synthesis, since these pathways bypass Trp]; (B) hydrolysis of both amide- and ester-linked LAA conjugates; (C) transport from one site in the plant to another site; and (D) conversion of IBA to LAA. IAA turnover mechanisms include: (E) oxidative catabolism; (F) conjugate synthesis; (G) transport away from a given site; and (H) conversion of IAA to IBA. The present invention makes use of such precursors and metabolites along this pathway. The present invention does not make use of inactive metabolites, such as arise from catabolism of the auxin.
Normally the present invention makes use of the tryptophan-dependent pathway. A summary of the reactions leading from chorismate - the first committed step of indolic metabolism - to LAA and tryptophan is shown in Fig 4.
The present invention also encompasses the use of synthetic auxins. Some examples of synthetic auxins are shown in Fig. 5.
A comparison of the compounds that possess auxin activity reveals that at neutral pH they all have a strong negative charge on the carboxyl group of the side chain that is separated from a weaker positive charge on the ring structure by a distance of about 0.5 nm. It has been proposed that an indole is not essential for activity, but that it can be an aromatic or fused aromatic ring of a similar size. A model has been proposed as being a planar aromatic ring-binding platform, a carboxylic acid-binding site and a hydrophobic transition region that separates the two binding sites.
The present invention involves the use of acetaminophen.
Acetaminophen has the IUPAC name, N-(4-hydroxypheyl)acetamide and is commonly referred to as paracetamol. It has the CAS number 103-90-2.
Its formula is:
Figure imgf000012_0001
As described above, derivatives of acetaminophen are also useful in the present invention. The compounds or compositions of the present invention can be used in combination with other components, as appropriate.
The present invention provides the use in a safening composition of a compound selected from a) glucose, hydrolysed starch, sucrose, fructose, glycerol, glyceraldehydes, erythrose, ribulose, xylulose or arabinose, monosaccharides including aldoses such as D-Ribose, D-Xylose, L- Arabinose, D-Glucose, D-Mannose and D-Galactose; ketoses such as D-Ribulose and D-Fructose; deoxyaldoses such as 2-Deoxy-D-ribose, L-Fuccose; acetylated amino sugars such as N-Acteyl-D- glucosamine and N-Acetyl-D-galactosamine; acidic monosaccharides such as D- Glucuronic acid, L-Iduronic acid and N-Acetylneuraminic acid, Sugar alcohols such as D-Sorbitol and D-Mannitol, disaccharides including maltose, lactose and sucrose, or an ester or glycoside or metabolic equivalent of such a carbohydrate; b) an organic acid of the Krebs tricarboxylic acid cycle or a metabolic precursor thereof; c) a vitamin or coenzyme, or a precursor thereof; d) a purine or pyrimidine nucleoside, nucleotide or metabolic precursor thereof; e) a naturally occurring fat or oil; or f) an amino acid in some embodiments.
By "effective amount" we include an amount of the compound or composition of the present invention which is sufficient to achieve the desired "safening response". In general by "safening response" we mean protecting the crop plants whilst not reducing the activity of the active ingredient being applied to the crop.
The compound may be defined as belonging to one or more of the following classes (a) to (f); although two or more such additives in the same or different classes may be used:
(a) glucose, hydrolysed starch, sucrose, fructose, glycerol, glyceraldehyde, erythrose, xylulose or arabinose, monosaccharides including aldoses such as D- Ribose, D-Xylose, L-Arabinose, D-Glucose, D-Mannose and D-Galactose; ketoses such as D-Ribulose and D-Fructose; deoxyaldoses such as 2-Deoxy-D-ribose, L- Fuccose; acetylated amino sugars such as N-Acteyl-D-glucosamine and N-Acetyl-D- galactosamine; acidic monosaccharides such as D-Glucuronic acid, L-Iduronic acid and N-Acetylneuraminic acid, Sugar alcohols such as D-Sorbitol and D-Mannitol, disaccharides including maltose, lactose and sucrose, or an ester or glycoside or metabolic equivalent of such a carbohydrate, which will normally be applied at 10 to 10,000 g/ha (grams per hectare). Without wishing to be bound by any theory the component may function as
(I ) A source for the production of high energy bonds as in adenosine trisephosphate (ATP) production,
(2) For the formation of reduced nicotinamide adenine dinucleotide (NADH) and reduced nicotamide adenine dinucleotide phosphate (NADPH) and
(3) As precursors of amino acids and nucleotides;
(b) an organic acid of the Krebs Tricarboxylic Acid Cycle or a metabolic precursor thereof, (including citric, succinic, malic, pyruvic, acetic and fumaric acids), which will normally be applied at similar rates to and used for similar functions as the carbohydrate source;
(c) a vitamin or coenzyme, e.g. thiamine, riboflavin, pyridozine, pyridoxamine, pyridoxal, nicotinamide, folic acid, or a precursor thereof including nicotinic acid, which will normally be applied at 0.01 to 500 g/ha to stimulate metabolic processes dependent on enzymatic action;
(d) a purine or pyrimidine nucleoside, nucleotide or a metabolic precursor thereof, e.g. adenine, adenosine, thymine, thymidine, cytosine, guanine, guanosine, hypoxanthine, uracil, uridine or inosine, which will normally be applied at 1 to 500 g/ha to act as structural precursors for nucleic acid synthesis;
(e) a naturally occurring fat or oil including olive, soya, coconut and corn oils, which can be degraded by living organisms to fatty acids and which will normally be applied at 10 to 10,000 g/ha;
(f) an amino acid of a type that occurs naturally in plant proteins, e.g. glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, aspartic acid, glutamic, acid, glutamine, asparagine, lysine, hyroxylysine, arginine, histidine, phenylalanine, tyrosine, tryptophan, proline or hydroxyproline, which will normally be applied at 1 to 500 g/ha to act as structural units for newly formed proteins or by their degradation to function in a similar manner to fatty acids and carbohydrates.
Other ingredients such as adjuvants may be added to the safening solution. The adjuvants can facilitate spreading and efficacy, and improve the adhesion properties of the composition, and generally include oils, antifoaming agents and surfactants. Such components which are useful in the present invention include, but are not limited to: terpene, Brij family (polyoxyethylene fatty alcohol ether) from Uniqema (Castle, DE); surfactant in Tween family (Polyoxyethylene sorbitan esters) from Uniqema (Castle, DE); Silwet family (Organosilicone) from Union Carbide (Lisle, DL); Triton family (Octylphenol ethoxylate) from The Dow Chemical Company (Midland, MI); Tomadol family (ethoxylated linear alcohol) from Tomah3 Products, Inc. (Milton, WI); Myrj family (Polyoxyethylene (POE) fatty acid esters) from Uniqema (Castle, DE); Span family (Sorbitan ester) from Uniqema (Castle, DE); and Trylox family (Ethoxylated Sorbitol and Ethoxylated Sorbitol Esters) from Cognis Corporation (Cincinnati, OH) as well as commercial surfactant Latron B- 1956 (77.0% modified phthalic/glycerol alkyl resin and 23.0% Butyl alcohol) from Rohm & Haas (Philadelphia, PA); Caspil (Blend of Polyether-polymethylsiloxanecopolymer and nonionic surfactant) from Aquatrols (Paulsboro, NJ); Agral 90 (Nonyl phenol ethoxylate) from Norac Concept, Inc. (Orleans, Ontario, Canada); Kinetic (99.00% Proprietary blend of polyalkyleneoxide modified polydimethylsiloxane and nonionic surfactants) from Setre Chemical Company (Memphis, TN); and Regulaid (90.6% 2- butoxyethanol, poloxalene, monopropylene glycol) from KALO, Inc. (Overland Park, KS).
When the final solution is to be applied to plants which, because of their hairy or waxy surface, may be difficult to wet, it may be particularly advantageous to include such other additives, commonly known in the agrochemical industry, such as surfactants, wetting agents, spreaders and stickers. (Examples of wetting agents include silicone surfactants, nonionic surfactants such as alkyl ethoxylates, anionic surfactants such as phosphate ester salts and amphoteric or cationic surfactants such as fatty acid amido alkyl betaines). The compounds of the invention may be the sole active ingredient of the composition or they may be admixed with further active ingredients such as nematicides, insecticides, synergists, herbicides, fungicides, fertilisers, chemically thinning agents, abscission delay agents or plant growth regulators where appropriate.
In a particularly preferred embodiment, the one or more compounds of the invention are administered in combination optionally with one or more active agents. In such cases, the compounds of the invention may be administered consecutively, simultaneously or sequentially with each other or the one or more active agents. The major advantages of combining the compounds are that it may promote additive or possible synergistic effects through e.g. biochemical interactions. Beneficial combinations may be suggested by studying the activity of the test compounds. This procedure can also be used to determine the order of administration of the agents, i.e. before, simultaneously or after delivery.
In order to apply the composition to the plant or environs of the plant, the composition may be used as a concentrate or more usually is formulated into a composition which includes an effective amount of the composition of the present invention together with a suitable inert diluent, carrier material and/or surface active agent. Preferably the composition is in the form of an aqueous solution which may be prepared from the concentrate. By effective amount we mean that the composition (and/or its individual components) provides an improved effect effect.
The applied concentration of chemical can vary widely depending on the water volume applied to plants as well as other factors such as plant age and size, and plant sensitivity to the product. Typical rates of AN-related compounds would be 1-10 g/ha (preferably and as used in these trials, Ig per hectare was applied), typical rates of acetaminophen or its derivatives would be 1-10 g/ha (preferably and as used in these trials, 3g per hectare was applied). Typical rates of the agrochemically acceptable additive of the present invention would be 1-lOg/ha (preferably and as used in these trials, less than 3g per hectare was applied). The rate of other components such as spreaders and stickers can be 50-200 ml per ha. Non-limiting examples of insecticides in relation to which the composition of the present invention may be useful include chlorinated hydrocarbons such as Aldrin, Chlordane, Chlordecone, DDT, Dieldrin, Endosulfan, Endrin, Heptachlor, Hexachlorobenzene, Lindane (gamma-Hexachlorocyclohexane), Methoxychlor, Mirex, Pentachlorophenol, TDE; organophosphates such as Acephate, Azinphos- methyl, Bensulide, Chlorethoxyfos, Chloφyrifos, Chloφyriphos-methyl, Diazinon, Dichlorvos (DDVP), Dicrotophos, Dimethoate, Disulfoton, Ethoprop, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Malathion, Methamidophos, Methidathion, Mevinphos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phorate, Phosalone, Phosmet, Phostebupirim, Phoxim, Pirimiphos-methyl, Profenofos, Terbufos, Tetrachlorvinphos, Tribufos, Trichlorfon; carbamates such as Aldicarb, Carbofuran, Carbaryl, Fenoxycarb, Methomyl, 2-(l-Methylpropyl)phenyl methylcarbamate; Phenothiazine; pyrethroids such as Allethrin, Bifenthrin, Cypermethrin, Deltamethrin, Lambda-cyhalothrin, Permethrin, Resmethrin, Tetramethrin, Tralomethrin, Transfluthrin; neonicotinoids such as Acetamiprid, Clothianidin, Imidacloprid, Nitenpyram, Nithiazine, Thiacloprid, Thiamethoxam; plant derived such as Caffeine, Derris (rotenone), Anabasine, Anethole, Annonin, Asimina, Azadirachtin, Carapa, Cinnamon leaf oil, Cinnamaldehyde, Cinnamyl acetate, Deguelin, Derris, Desmodium caudatum, Eugenol, Linalool, Myristicin, Neem (Azadirachtin), Nicotiana rustica (Nicotine), Peganum harmala, Oregano oil, Polyketide, Pyrethrum, j2«α.ss/α,Tetranortriterpenoid, Thymol.
Non-limiting examples of fungicides in relation to which the composition of the present invention may be useful include (3-ethoxypropyl)mercury bromide, 2- methoxyethylmercury chloride, 2-phenylphenol, 8-hydroxyquinoline sulfate,8- phenylmercurioxyquinoline, acibenzolar, acylamino acid fungicides, acypetacs, aldimoφh, aliphatic nitrogen fungicides, ally] alcohol, amide fungicides, ampropylfos, anilazine, anilide fungicides, antibiotic fungicides, aromatic fungicides, aureofungin, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benzalkonium chloride, benzamacril, benzamide fungicides, benzamorf, benzanilide fungicides, benzimidazole fungicides, benzimidazole precursor fungicides, benzimidazolylcarbamate fungicides, benzohydroxamic acid, benzothiazole fungicides, bethoxazin, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S, Bordeaux mixture, boscalid, bridged diphenyl fungicides, bromuconazole, bupirimate, Burgundy mixture, buthiobate, butylamine, calcium polysulfide, captafol, captan, carbamate fungicides, carbamoφh, carbanilate fungicides, carbendazim, carboxin, caφropamid, carvone, Cheshunt mixture, chinomethionat, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chlorodinitronaphthalene, chloroneb, chloropicrin, chlorothalonil, chlorquinox, chlozolinate, ciclopirox, climbazole, clotrimazole, conazole fungicides, conazole fungicides (imidazoles), conazole fungicides (triazoles), copper(II) acetate, copper(II) carbonate, basic, copper fungicides, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper(II) sulfate, copper sulfate, basic, copper zinc chromate, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cyclic dithiocarbamate fungicides, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomeζ DBCP, debacarb, decafentin, dehydroacetic acid, dicarboximide fungicides dichlofluanid, dichlone, dichlorophen, dichlorophenyl, dicarboximide fungicides, dichlozoline, diclobutrazol, diclocymet, diclomezine, dicloran, diethofencarb, diethyl pyrocarbonate, difenoconazole, diflumetorim, dimethirimol, dimethomoφh, dimoxystrobin, diniconazole, diniconazole-M, dinitrophenol fungicides, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon, dithiocarbamate fungicides, DNOC, dodemoφh, dodicin, dodine, DONATODINE, drazoxolon, edifenphos, epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethylmercury 2,3- dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpropimoφh, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumoφh, fluopicolide, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, formaldehyde, foseryl, fuberidazole, furalaxyl, furametpyr, furamide fungicides, furanilide fungicides, furcarbanil, furconazole, furconazole-cis, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos, hydrargaphen, hymexazol, imazalil, imibenconazole, imidazole fungicides, iminoctadine, inorganic fungicides, inorganic mercury fungicides, iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isovaledione, kasugamycin, kresoxim-methyl, Lime sulfur (lime sulphur), mancopper, mancozeb, maneb, mebenil, mecarbinzid, mepanipyrim, mepronil, mercuric chloride, mercuric oxide, mercurous chloride, mercury fungicides, metalaxyl, metalaxyl-M (a.k.a. Mefenoxam), metam, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl isothiocyanate, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, metiram, metominostrobin, metrafenone, metsulfovax, milneb, moφholine fungicides, myclobutanil, myclozolin, N-(ethylmercury)-p-toIuenesulfonanilide, nabam, natamycin, nystatin, nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace, oprodione, organomercury fungicides, organophosphorus fungicides, organotin fungicides, orysastrobin, oxadixyl, oxathiin fungicides, oxazole fungicides, oxine copper, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivative of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, phenylsulfamide fungicides, phosdiphen, phthalide, phthalimide fungicides, picoxystrobin, piperalin, polycarbamate, polymeric dithiocarbamate fungicides, polyoxins, polyoxorim, polysulfide fungicides, potassium azide, potassium polysulfide, potassium thiocyanate, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrazole fungicides, pyrazophos, pyridine fungicides, pyridinitril, pyrifenox, pyrimethaniJ, pyrimidine fungicides, pyroquilon, pyroxychlor, pyroxyfur, pyrrole fungicides, quinacetol, quinazamid, quinconazole, quinoline fungicides, quinomethionate, quinone fungicides, quinoxaline fungicides, quinoxyfen, quintozene, rabenzazole, salicylanilide, silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, spiroxamine, streptomycin, strobilurin fungicides, sulfonanilide fungicides, sulfur, sultropen, TCMTB, tebuconazole, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thiazole fungicides, thicyofen, thifluzamide, triforine, thiocarbamate fungicides, thiochlorfenphim, thiomersal,thiophanate, thiophanate-methyl, thiophene fungicides, thioquinox, thiram, tiadinil, tioxymid, tivedo, tolclofos-methyl, tolnaftate, tolylfluanid, tolylmercury acetate, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazine fungicides, triazole fungicides, triazoxide, tributyltin oxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, unclassified fungicides, Undecylenic acid, uniconazole, uniconazole-P, urea fungicides, validamycin, valinamide fungicides, vinclozolin, zarilamid, zinc naphthenate, zineb, ziram, zoxamide.
Non-limiting examples of fertilizers in relation to which the composition of the present invention may be useful include nitrogen fertilizers such as ammonium, ammonium sulphate, ammonium chloride, ammonium sulphate nitrate, ammonium nitrate, calcium ammonium nitrate, sodium nitrate, calcium nitrate, potassium nitrate, urea; phosphate fertilizers such as single superphosphate, triple superphosphate, diammonium phosphate, monoammonium phosphate, ground phosphate rock, rock phosphate, rock phosphate; potash fertilizers such as muriate of potash (potassium chloride), sulphate of potash, sulphate of potash magnesia; magnesium fertilizers such as kieserite, epsom salts, magnesium sulfate (Epsom salts); complex fertilizers such as urea-ammonium nitrate NPK fertilizers, NP fertilizers, NK fertilizers and PK fertilizers; aluminium sulfate, Ferrous sulfate, phosphite fertilizers; thiosulphate fertilizers.
Non-limiting examples of plant growth regulators in relation to which the composition of the present invention may be useful include abscisic acid or a derivative thereof, a cytokinin, ethylene or a gibberlin.
Non-limiting examples of the plant growth regulator in relation to which the composition of the present invention may be useful include p-Chlorophenoxyacetic acid (4-CPA), 2-CPA, 2,4-Dichlorophenoxyacetic acid, 2,4-Dichlorophenoxyacetic acid Sodium salt, Indole-3 -acetic acid Free acid (LAA), Indole-3-acetic acid Sodium salt, Indole-3-acetic acid methyl ester, Indole-3-acery-L-aspartic acid, IndoIe-3- butyric acid (IBA), Indole-3-butyric acid Potassium salt (K-IBA), alpha- Naphthaleneacetic acid Free acid (NAA), beta-Naphthoxy acetic acid Free acid (NOA), Phenylacetic acid (PAA), Picloram, 2,4,5-Trichlorophenoxyacetic acid (2,4,5- T), 2,3,5-Triiodobenzoic acid Free acid (TIBA), Adenine Free base, Adenine hemisulfate salt, 6-Benzylaminopurine (BA), 6-Benzylaminopurine Hydrochloride, N-Benzyl-9-(2-tetrahydropyranyl) adenine (BPA), N-(2-Chloro -4-pyridyl)N'- phenylurea (4-CPPU), 6-(gamma, gamma-Dimethylallylamino)purine (2iP), 1,3- Diphenylurea (DPU), Kinetin, Kinetin Hydrochloride, l-Phenyl-3-(l,2,3-thiadiazol-5- yl) urea, trans-Zeatin Free base, Zeatin, trans-Zeatin Hydrochloride, trans-Zeatin riboside, (±)-cis,trans-Abscisic acid (ABA), Ancymidol, Chlorocholine chloride (CCC), chlormequat chloride + choline chloride (5C chlormequat), 3,6-Dichloro-o- anisic acid (Dicamba), Gibberellic acid (GA3), Gibberellic acid Potassium salt (K- GA3), Gibberellin A4 Free acid (GA4), (±)-jasmonic acid, Phloroglucinol, N- (Phosphonomethyl)glycine (Glyphosate), Succinic acid 2,2-dimethylhydrazide, trinexapacethyl or metconazole.
The plant growth regulator may be other than a naturally occurring plant hormone.
Further non-limiting examples of the plant growth regulator include antiauxins, such as: clofibric acid and 2,3,5-tri-iodobenzoic acid; auxins such as 4-CPA, 2,4-D, 2,4- DB, 2,4-DEP, dichlorprop, fenoprop, IAA, EBA, naphthaleneacetamide, α- naphthaleneacetic acid, 1-naphthol, naphthoxyacetic acid, potassium naphthenate, sodium naphthenate, 2,4,5-T; cytokinins such as 2iP, benzyladenine, kinetin, zeatin; defoliants such as calcium cyanamide, dimethipin, endothal, ethephon, merphos, metoxuron, pentachlorophenol, thidiazuron, tribufos; ethylene inhibitors such as aviglycine, 1-methylcyclopropene; ethylene releasers such as ACC, etacelasil, ethephon, glyoxime; gibberellins such as gibberellins, gibberellic acid; growth inhibitors such as abscisic acid, ancymidol, butralin, carbaryl, chlorphonium, chloφropham, dikegulac, flumetralin, fluoridamid, fosamine, glyphosine, isopyrimol, jasmonic acid, maleic hydrazide, mepiquat, mepiquat chloride, piproctanyl, prohydrojasmon, propham, 2,3,5-tri-iodobenzoic acid; morphactins such as chlorfluren, chlorflurenol, dichlorflurenol, flurenol; growth retardants such as chlormequaζ daminozide, fluφrimidol, mefluidide, paclobutrazol tetcyclacis, uniconazole; growth stimulators such as brassinolide, forchlorfenuron, hymexazol; and unclassified plant growth regulators such as benzofluor, buminafos, carvone, ciobutide, clofencet, cloxyfonac, cyanamide, cyclanilide, cycloheximide, cyprosulfamide, epocholeone, ethychlozate, ethylene, fenridazon, heptopargil, holosulf, inabenfide, karetazan, lead arsenate, methasulfocarb, prohexadione, pydanon, sintofen, triapenthenol, trinexapac. Non-limiting examples of herbicides in relation to which the composition of the present invention may be useful include aminopyralid, glufosinate ammonium, fluroxypyr, imazapic, pendimethlin, sodium chlorate, chloroacetamindes such as metalchlor, acetochlor, butachlor, propachlor, thenylchlor; amides such as dimethenamid, propanil, naptalam, pronamide, bensulide, pethoxamid; organoarsenicals such as cacodylic acid and its sodium salt, disodium methanearsonate, monosodium methanearsonate; benzoic acids and derivatives thereof such as dicamba, chlorfenac, chloramben; nitriles such as dichlobenil and bromoxynil, 2,6-dichlorobenzonitrile, Ioxynil; benzothiadiazoles such as bentazone; bipyridyliums such as diquat, paraquat, difenzoquat; carbamates such as propham, chloropropham, asulam; phenyl-carbamates such as phenmedipham, desmedipham; chlorinated aliphatic acids such as TCA, dalapon; cyclohexanediones such as sethoxydim, clethodim, cycloxydim, tralkoxydim, tepraloxydim; dinitroanilines such as benefin, oryzalin, pendimethalin, isopropalin; dinitrophenols such as DNOC, DINOSEB; diphenyl ethers such as nitrophen, bifenox, fomesafen, acifluorfen, lactofen, oxyfluorfen; imidazolinones such as imazamox, imazapyr, imazaquin, imazamethabenz-methyl, imazethapyr; triazolopyrimidines such as fiumetsulam, metosulam, chloransulam, disclosulam; aryloxphenoxy propionates such as fluazifop- butyl, propaquizafop, quizalofop-P, metamifop, pyriftalid; phenoxys such as 2,4-D, 2,4,5-T, 2,4-DB, MCPA, silvex, 2,4-DP, MCPB, MCPP; ureas such as fluometuron, linuron, diuron and monuron, fenuron-TCA, siduron, tebuthiuron, isoproturon, cumyluron; phosphono amino acids such as glyphosate, glufosinate, fosamine and glyphosate trimesium; phthalic acid such as chlorthal, endothall; pyridazinones such as pyrazon, norflurazon, fluridone, fluorochloridone, clomazone, oxadiazon, beflubutamid, picolinafen, oxadiargyl; carboxylic acids such as picloram, triclopyr, fluoroxypyr, clopyralid, quinclorac; pyridines such as dithiopyr, thiazopyr; sulfonylureas such as chlorsulfuron, chlorimuron-ethyl, metsulfuron-methyl, sulfometuron-methyl, halosulfuron-methyl, sulfometuron-methyl, bensulfuron, nicosulfuron, triasulfuron, primisulfuron-methyl, amidosulfuron, azimsulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flupyrsulfuron-methyl, foramsulfuron, iodosulfuron-methyl, mesosulfuron-methyl, oxasulfuron, prosulfuron, rimsulfuron, sulfosulfuron, tribenuron-methyl, trifloxysufuron, triflusulfuron-methyl, tritosulfuron, foramsulfuron, iodosulfuron-methyl, thiocarbamates such as EPTC, pebulate, thiobencarb, butylate, cycloate, molinate, vernolate, diallate, triallate; triazines such as atrazine, prometryn, ametryn, and terbutryne; triazinones such as metribuzin and hexazinone; triazoles such as amitrol; uracils such as bromacil, terbacil, Ienacil; benzoylcyclohexanediones such as mesotrione, sulcotrione, benzofenap; N-phenyl-phthalimides-cinidon-ethyl; oxazolidinediones such as pentoxazone; phenyl-pyrazoles such as pyraflufen-ethyl; pyrimidindiones such as butafenacil; sulfonyamino-carbonyl-triazolinones such as flucarbazone, propoxycarbazone; tetrazolinones such as fentrazamide; triazolinones such as amicarbazone; flufenpyr-ethyl; oxoziclomefone; benzobicyclon; soaps; petroleum oils.
Non-limiting examples of abscission delay agents in relation to which the composition of the present invention may be useful include 1-naphthaleneacetic acid (NAA), NAAm, 2,4-D, 2,4,5-T, 2,4,5-TP, amino-oxyacetic acid, aminoethoxyvinylglycine (AVG) and daminozide.
It will be appreciated that the active ingredient and safener should be different to each other.
The composition of the present invention may also include trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc. Preferably, the trace element is cobalt. In one embodiment cobalt is in the form of cobalt sulphate.
In a particularly preferred embodiment, the one or more compounds of the invention are administered in combination optionally with one or more active agents. In such cases, the compounds of the invention may be administered consecutively, simultaneously or sequentially with each other or the one or more active agents. The major advantages of combining the compounds are that it may promote additive or possible synergistic effects through e.g. biochemical interactions. Beneficial combinations may be suggested by studying the activity of the test compounds. This procedure can also be used to determine the order of administration of the agents, i.e. before, simultaneously or after delivery.
The rate and timing of application will depend on a number of factors known to those skilled in the art, such as the type of species etc. A second or further application(s) can be made as appropriate. The timings between each application may be in the region of 5 days or more.
The present invention relates to a method of safening plants which comprises applying to the plants or to the locus thereof an effective controlling amount of the compounds/compositions of the present invention.
The compositions of the present invention can be applied to the soil, plant, seed, or other area to be protected. Preferably the present invention is applied to the foliage of plants. The composition may be applied in the form of dusting powders, wettable powders, granules (slow or fast release), water dispersible granules, emulsion or suspension concentrates, liquid solutions, emulsions, seed dressings, or controlled release formulations such as microencapsulated granules or suspensions, soil drench, irrigation component, or preferably a foliar spray.
Dusting powders are formulated by mixing the active ingredient with one or more finely divided solid carriers and/or diluents, for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers.
Granules are formed either by absorbing the active ingredient in a porous granular material for example pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths, ground corn cobs, and the like, or on to hard core materials such as sands, silicates, mineral carbonates, sulfates, phosphates, or the like. Agents which are commonly used to aid in impregnation, binding or coating the solid carriers include aliphatic and aromatic petroleum solvents, alcohols, polyvinyl acetates, polyvinyl alcohols, ethers, ketones, esters, dextrins, sugars and vegetable oils, with the active ingredient. Other additives may also be included, such as emulsifying agents, wetting agents or dispersing agents.
Microencapsulated formulations (microcapsule suspensions CS) or other controlled release formulations may also be used, particularly for slow release over a period of time, and for seed treatment. Alternatively and preferred the compositions may be in the form of liquid preparations to be used as dips, irrigation additives or sprays, which are generally aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents (surface active agents). The compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of an emulsifiable concentrate (EC) or a suspension concentrate (SC) containing a high proportion of the active ingredient or ingredients. An EC is an homogeneous liquid composition, usually containing the active ingredient dissolved in a substantially non-volatile organic solvent. An SC is a fine particle size dispersion of solid active ingredient in water. To apply the concentrates they are diluted in water and are usually applied by means of a spray to the area to be treated.
Suitable liquid solvents for ECs include methyl ketone, methyl isobutyl ketone, cyclohexanone, xylenes, toluene, chlorobenzene, paraffins, kerosene, white oil, alcohols (for example, butanol), methylnaphthalene, trimethylbenzene, trichloroethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THFA).
These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may contain 1-85% by weight of the active ingredient or ingredients. When diluted to form aqueous preparations such preparations may contain varying amounts of the active ingredient depending upon the purpose for which they are to be used.
The composition may also be formulated as powders (dry seed treatment DS or water dispersible powder WS) or liquids (flowable concentrate FS, liquid seed treatment LS), or microcapsule suspensions CS for use in seed treatments. The formulations can be applied to the seed by standard techniques and through conventional seed treaters. In use the compositions are applied to the plants, to the locus of the plants, by any of the known means of applying fertiliser compositions, for example, by dusting, spraying, or incorporation of granules. As indicated above, the composition of the present invention can be applied at the same time as or at an appropriate interval to the agrochemical. This can be readily determined by a skilled worker, e.g. it may be in the range of 1-3 days prior to application of the agrochemical.
As indicated above, the compositions according to this present invention may be applied to the foliage of plants but may also be applied to the soil or added to the irrigation water.
The present invention is useful in relation to crops. It will be appreciated that the present invention may be applicable to all horticultural and agricultural species.
The present invention is useful in relation to fruit crops. The crops can include trees, bushes, shrubs and vines.
The present invention is useful in relation to vegetable crops.
The present invention is useful in relation to agricultural and horticultural crops including ornamentals.
The present invention is useful in relation to cereals and grasses and to pod-bearing, bean and oilseed crops.
Particularly, but not exclusively, when the present invention is used in combination with a chemical thinner the present invention is useful in relation to fruit crops. The crops can include trees, bushes, and vines.
Particularly, but not exclusively, when the present invention is used in combination with cobalt the present invention is useful in relation to nitrogen-fixing crops. The nitrogen-fixing crops can include soybean, navy bean and pea.
The present invention can be used on the following plants as non-limiting examples: Almond {Prunus dulcis), Apple (Malus domestica), Apricot {Prunus armeniaca), Avocado {Persea americana), Banana, Plantain {Musa spp.), Blackberries {Rubus spp), Blueberries {Vaccinium spp), Cacao or cocoa {Theobroma cacao), Cashew {Anacardium occidentale), Cherries {Prunus cerasus, P. avium), Chestnuts {Castanea spp.), Coconut (Cocos nucifera), Coffee (Cqffea arabica, C. canephora), Cranberry {Vaccinium macrocarpon), Currants {Ribes spp), Date {Phoenix dactylifera), Fig {Ficus carica), Gooseberry {Ribes grossularia; R. hirtellum), Grapefruit {Citrus paradisi), Grapes {Vitis vinifera, other Vitis spp), Guava {Psidium guajava & related spp), Hazelnut or filbert {Corylus avellana), Juneberry {Amelanchier alnifolia), Kiwifruit {Actinidia deliciosa), Kumquat {Fortunella spp), Lemon {Citrus limoή), Lime {Citrus aurantifolia), Loquat {Eriobotrya japonica), Macadamia {Macadamia integrifolia), Mango {Mangifera indica), Mayhaw {Crataegus spp.), Oil Palm {Elaeis guineensis), Olive {Olea europaea), Orange {Citrus sinensis), Papaya {Carica papaya), Peach {Prunus persica), Pears {Pyrus communis, P. pyrifolia), Pecan {Carya illinoensis), Pineapple {Ananas comosus), Pistachio {Pistacia vera), Plums {Prunus domestica, P. salicina), Pomegranate {Punica granatum), Quince {Cydonia oblonga), Raspberries {Rubus idaeus, R occidentalis), Strawberry {Fragaria X ananassά), Tangerine {Citrus reticulata), Walnut {Juglans regia Chrysanthemum, and Rhododendron including Azalea species (e.g. Azaleastrum), Kalanchoe, Bulb crops, Crocus, Tulip, Narcissus, Hyacinth, Poinsettia and Roses, tomatoes, squash, pumpkin, beans, broccoli, green beans, asparagus, peas, corn, carrots, spinach, cauliflower, lima beans, broad beans, firench beans, runner beans, navy beans, kidney beans, lentils, cabbage, onions, courgettes, aubergines, sweet basil, leeks, artichokes, lettuce, cassava leaves, tomatoes, cucumbers and gherkins, marrows, gourds, squashes, chillies and peppers, green onions, dry onions, red onions, shallots, garlic, chives, other alliaceous vegetables, okra, mushrooms, watermelons, cantaloupe melons, other melons, bamboo shoots, beets, chards, capers, cardoons, celery, chervil, cress, fennel, horseradish, marjoram, oyster plant, parsley, parsnips, potato, radish, rhubarb, rutabaga, savory, scorzonera, sorrel, sprouts, swede, turnip, watercress and other vegetables, Maize, wheat, rye, oat, triticale, rice, barley, sorghum, millet, buckwheat, fonio, quinoa, spelt, other cereal crops, soybean, peanut, cotton, oilseed rape, sugar cane, bamboo, sesame, jute, canola, coconut, manihot, sunflower, tobacco, ground nuts, peanuts, oil palm, hemp, flax, lucerne, alfalfa tea, perennial grass. Particularly, but not exclusively, when the present invention is used in combination with a herbicide crops of useful plants in which the composition according to the invention can be used include cereals, for example barley and wheat, cotton, oilseed rape, maize, rice, soy beans, sugar beet and sugar cane, especially cereals and maize. Crops can also include trees, such as palm trees, coconut trees or other nuts, and vines such as grapes.
The grasses and weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Bromus, Cyperus, Digitaria, Echinochloa, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, Sida and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Chenopodium, Chrysanthemum, Galium, Ipomoea, Nasturtium, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.
Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.
Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
The addition of the following mixtures of the compounds of the present invention are particularly mentioned:
1. The addition of Anthranilic acid (AN).
2. The addition of NAA/other auxins, or auxin mixes (eg NAA/BA).
3. The addition of a safener (SAF).
4. The addition of Anthranilic acid (AN) to a safener (SAF).
5. The addition of SAF to NAA/other auxins, or auxin mixes (eg NAA/BA).
6. The addition of SAF to AN + AC.
7. The addition of SAF to AC + NAA/other auxins, or auxin mixes (eg NAA/BA).
8. The addition to AN to AC.
9. The addition of AC to NAA/other auxins, or auxin mixes (eg NAA/BA).
These combinations and others in accordance with the present invention may give rise to an additive or synergistic effect
The safener (SAF) may be one set out as in classes (a) to (f) above. Two or more such additives in the same or different classes may be used.
When the additive is selected from class (a) it is preferably one or more of glucose, sucrose, fructose or glycerol.
When the additive is selected from class (b) it is preferably one or more of citric or succinic acid.
When the additive is selected from class (c) it is preferably one or more of thiamine, riboflavin, pyridoxine, nicotinamide, folic acid, ascorbic acid, biotin or vitamin B 12. When the additive is selected from class (d) it is preferably adenine, thymidine, cytosine or uracil.
When the additive is selected from class (e) it is preferably a corn oil.
When the additive is selected from an amino acid (f) is it preferably one of more of glycine, alanine, valine, leucine, threonine, cysteine, methionine, glutamine, asparagine or lysine.
The following Examples further illustrate, but do not limit, the invention.
EXPERIMENTAL RESULTS
EXAMPLE 1 : SAFENING OF FERTILISERS
Safening systems were applied to crops of winter barley, winter wheat and lettuce treated with various fertilizers (Potassium Phosphite, potassium phosphite + ammonium thiosulphate, general NPK fertiliser). The safening system and the fertilizer were applied either simultaneously or sequentially.
Winter Barley: cv Saffron, sown 27 May 2008, at four/five seeds per 9 cm pot, sown in standard multi-purpose compost of pH 6.5. Date of spraying: 23 July; Dates of measurement/scoring: 30 July, 14 August, 22 August. Sprayed: mid-tillering phase (GS23).
Winter Wheat: cv Limerick, sown 4 June 2008, at four/five seeds per 9 cm pot, sown in standard multi-purpose compost of pH 6.5. Date of spraying: 23 July; Dates of measurement/scoring: 30 July, 14 August, 23 August. Sprayed: mid-tillering phase (GS23).
Lettuce: cv Set, sown 10 July 2008, at one seed per pot, in John Innes No 1 compost. Date of spraying: 30 July; Dates of measurement: 7 August, 14 August, 28 August. Sprayed: 2 true leaf stage.
SAF: at least one from class (f) each at < 3 g/I, plus at least one from class (c). The results are shown in Tables 1.1 to 1.9 below.
Tables 1.1, 1.2 and 1.3 (Winter Barley):
Figure imgf000031_0001
TABLE 1.1 WINTER BARLEY - CROP SAFENING BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANTLIC ACDD AND/OR ACETAMINOPHEN TO A PHOSPHITE FERTILISER
Figure imgf000031_0002
Figure imgf000032_0001
Figure imgf000033_0001
TABLE 1.2 - WINTER BARLEY - CROP SAFENING BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO A PHOSPHITE FERTILISER
Figure imgf000034_0001
TABLE 1.3 - WINTER BARLEY - CROP SAFENING BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO GENERAL FERTILISERS.
Figure imgf000035_0001
Figure imgf000036_0001
TABLE 1.4 - WTNTER WHEAT - CROP SAFENING BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACDD AND/OR ACETAMINOPHEN TO PHOSPHITE FERTILISER
Figure imgf000036_0002
Figure imgf000037_0001
Figure imgf000038_0001
TABLE 1.5 - WINTER WHEAT - CROP SAFENTNG BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THIOSULPHATE AND PHOSPHITE FERTILISERS
Figure imgf000038_0002
Figure imgf000039_0001
TABLE 1.6 - WINTER WHEAT - CROP SAFENING BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO GENERAL FERTILISERS.
Figure imgf000039_0002
Figure imgf000040_0001
Figure imgf000041_0001
TABLE 1.7 - LETTUCE - CROP SAFENING BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO PHOSPHITE FERTILISER
Figure imgf000041_0002
Figure imgf000042_0001
Figure imgf000043_0001
TABLE 1.8 - LETTUCE - CROP SAFENTNG BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANTLIC ACID AND/OR ACETAMINOPHEN TO PHOSPHITE FERTILISER.
Figure imgf000043_0002
Figure imgf000044_0001
TABLE 1.9 - LETTUCE - CROP SAFENTNG BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO GENERAL FERTILISERS.
Figure imgf000045_0001
As shown in Tables 1.1 to 1.9, each of the safening formulations showed a significant reduction in phytotoxicity when applied to a range of species in combination with a fertilizer, when compared to the application of fertilizers alone. Thus the safening systems improve crop safening in a range of species. Vigour was also boosted.
EXAMPLE 2: SAFENING OF FUNGICIDES
Safening systems were applied to crops of winter barley, winter wheat and maize treated with various fungicides (Prochloraz, Flutriafol, Fenpropidin). The safening system and the fungicide were applied to the crops either simultaneously or sequentially, either as foliar applications or as a seed treatment.
Winter Barley: cv Saffron, sown 27 May 2008, at four/five seeds per 9 cm pot, sown in standard multi-purpose compost of pH 6.5. Date of spraying: 23 July; Dates of measurement/scoring: 30 July, 14 August, 22 August. Sprayed: mid-tillering phase (GS23).
Winter Wheat: cv Limerick, sown 4 June 2008, at four/five seeds per 9 cm pot, sown in standard multi-purpose compost of pH 6.5. Date of spraying: 23 July; Dates of measurement/scoring: 30 July, 14 August, 23 August. Sprayed: mid-tillering phase (GS23).
Maize: cv Sundance, sown 25 May 2008, at 10 seeds per 25 cm pot, in John Innes No 1 compost. Date of measurement/assessment: 15 June. Seed treatment trial. Randomised block, mean of five replicates.
Safening systems:
1. Anthranilic Acid + Acetaminophen (AN + AC).
2. AN + AC + Safener (SAF).
3. Safener (SAF).
SAF: at least one from class (f) each at < 3 g/1, plus at least one from class (c).
Statistical Analyses (Least Significant Difference, 5% Level) for Tables 2.1 to 2.7: Tables 2.1, 2.2 and 2.3 (Winter Barley):
Figure imgf000047_0001
Tables 2.4, 2.5 and 2.6 (Winter Wheat):
Figure imgf000047_0002
Table 2.7 (Maize):
LSD (5%) Shoot Fresh % Vigour Treatment Means Weight (g) (0-9)
2.30 9.6 1.51
The results are shown in Tables 2.1 to 2.7 below.
TABLE 2.1 - WINTER BARLEY - CROP SAFENING BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THE FUNGICIDE PROCHLORAZ.
Figure imgf000047_0003
Figure imgf000048_0001
Figure imgf000049_0001
TABLE 2.2 - WTNTER BARLEY - CROP SAFENTNG BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THE FUNGICIDE FLUTRIAFOL.
Figure imgf000049_0002
Figure imgf000050_0001
Figure imgf000051_0001
TABLE 2.3 - WINTER BARLEY - CROP SAFENTNG BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THE FUNGICIDES FENPROPIDIN AND FLUTRIAFOL.
Figure imgf000051_0002
Figure imgf000052_0001
Figure imgf000053_0001
TABLE 2.4 - WINTER WHEAT - CROP SAFENING BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THE FUNGICIDE PROCHLORAZ.
Figure imgf000053_0002
Figure imgf000054_0001
Figure imgf000055_0001
TABLE 2.5 - WINTER WHEAT - CROP SAFENTNG BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRAMLIC ACID AND/OR ACETAMINOPHEN TO THE FUNGICIDE FLUTRIAFOL.
Figure imgf000055_0002
Figure imgf000056_0001
Figure imgf000057_0001
TABLE 2.6 - WINTER WHEAT - CROP SAFENING BENEFITS FROM ADDITION OF SAPENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THE FUNGICIDES FENPROPDDIN AND FLUTRIAFOL
Figure imgf000057_0002
Figure imgf000058_0001
TABLE 2.7 - MAIZE - BENEFITS TO CROP SAPENING/VIGOUR AND EARLY SHOOT FRESH WEIGHT 21 DAYS APTER SOWING FROM ADDITION OF SAPENER PLUS ANTHRANILIC ACDD PLUS ACETAMINOPHEN TO THE FUNGICIDE PROCHLORAZ WHEN APPLIED AS A SEED TREATMENT.
Figure imgf000058_0002
Figure imgf000059_0001
As shown in Tables 2.1 to 2.7, each of the safening formulations showed a significant reduction in phytotoxicity when applied to a range of species in combination with fungicides, when compared to the application of fungicides alone. Thus the safening systems improve crop safening in a range of species. This applies to either the safening formulations applied in foliar applications (Tables 2.1 to 2.6) or as seed treatments (Table 2.7). Increases in vigour and early shoot weight are also noted.
EXAMPLE 3: SAFENING OF HERBICIDES
Safening systems were applied to crops of oilseed rape and winter treated with various herbicides (Bifenox (with insecticide), Carbetamide, Propaquizafop, Chlorotoluron, Isoproturon, Flumioxazin). The safening system and the herbicide were applied to the crops either simultaneously or sequentially.
Oilseed rape: cv Excalibur, sown 26 April 2008, at two seeds per 9 cm pot, sown in normal pH multi-purpose compost. Date of spraying: 6 June; Dates of measurement/scoring: 13 June, 20 June, 5 July. Winter wheat: cv Alchemy, sown 23 April 2008, at seven seeds per 9 cm pot, sown in normal pH multi-purpose compost. Date of spraying: 24 May; Dates of measurement/scoring: 31 May, 7 June, 21 June.
SAF: at least one from class (f) each at < 3 g/1, plus at least one from class (c).
The results are shown in Tables 3.1 to 3.5 below.
Statistical Layout: Randomised Complete Block trials, under glasshouse conditions, United Kingdom.
Statistical Analyses (Least Significant Difference, 5% Level) for Tables 3.1 to 3.5: Tables 3.1 and 3.2:
Figure imgf000060_0001
Tables 3.3, 3.4 and 3.5:
Figure imgf000060_0002
TABLE 3.1 - OILSEED RAPE - CROP SAFENING BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THE HERBICIDE BIFENOX (with insecticide).
O
Figure imgf000061_0001
Figure imgf000062_0001
κ>
Figure imgf000063_0001
Figure imgf000064_0001
TABLE 3.2 - OILSEED RAPE - CROP SAFENING BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THE HERBICIDES CARBETAMIDE AND PROPAQUIZAFOP
Figure imgf000064_0002
4-
Figure imgf000065_0001
Ul
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
TABLE 3.3 - WINTER WHEAT - CROP SAFENING BENEFITS FROM ADDITION OF SAFENING SYSTEM AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THE HERBICIDE CHLOROTOLURON
Figure imgf000068_0002
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
TABLE 3.4 - WINTER WHEAT - CROP SAFENING BENEFITS FROM ADDITION OF SAFENING SYSTEM AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THE HERBICIDE ISOPROTURON
O
Figure imgf000071_0002
Figure imgf000072_0001
κ>
Figure imgf000073_0001
Figure imgf000074_0001
TABLE 3.5 - WINTER WHEAT - CROP SAFENING BENEFITS FROM ADDITION OF SAFENING SYSTEM AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THE HERBICIDE FLUMIOXAZIN
Figure imgf000074_0002
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
As shown in Tables 3.1 to 3.5, each of the safening formulations showed a significant reduction in phytotoxicity when applied to a range of species in combination with an herbicide, when compared to the addition of herbicides alone. Thus the safening systems improve crop safening in a range of species. An increase in vigour and greenness is also noted.
EXAMPLE 4: SAFENING OF GL YPHOSATE HERBICIDE (non-GM maize, UK)
Maize cv Sundance (i.e. not Roundup® Ready) sown 27 April 2008, to obtain 1 even plant per 1 litre pot, grown in John Innes No 3 compost of pH 6.5. Treated with glyphospate, date of first spraying 15 June. Dates of measurement/scoring: 29 June, 13 JuIy, 26 JuIy.
Statistical Layout: Randomised Complete Block trial, under glasshouse conditions, United Kingdom.
SAF: at least one from class (f) each at < 3 g/1, plus at least one from class (c).
Results are shown in Table 4.
Statistical Analyses (Least Significant Difference, 5% Level) for Table 4:
Figure imgf000079_0001
TABLE 4 - MAIZE - CROP SAFENING BENEFITS FROM ADDITION OF SAFENER AND/OR ANTHRANILIC ACID AND/OR ACETAMINOPHEN TO THE HERBICIDE GLYPHOSATE (360 g/1 formulation).
Figure imgf000079_0002
Figure imgf000080_0001
06 O
Figure imgf000081_0001
OO
Figure imgf000082_0001
Each of the safening systems used to safen glyphosate showed a reduction in phytotoxicity (measured on a scale of 0-9, where 0 = dead and 9 least phytotoxicity). Vigour was also boosted (measured on a scale of 0-9, where 0 = least vigour and 9 = most vigour).
EXAMPLE 5: SAFENING OF GL YPHOSATE HERBICIDE (GM maize, University of Illinois)
Trial Details: Randomised complete block, with four replicates per treatment. Plot size = 10 ft x 30 ft = 300 ft area.
Two varieties Roundup® ready soybean (glycine max) - Asgrow 3302 RR/STS and Pioneer 93M42 treated with glyphosate at crop growth stage V4-V5. Glyphosate was applied in the form of Roundup PowerMax, at a rate of 3.0 1/ha. This is a high rate of glyphospate, which was used in order to induce a phytotoxic response.
SAF: at least one from class (f) each at < 3 g/1, plus at least one from class (c).
TABLE 5.1
Phytotoxicity and Yield Results Variety A - Asgrow 3302 RJR/STS; Application timing: V4-V5 trifoliate leaf stage.
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
TABLE 3.2
Phytotoxicity and Yield Results Variety B - Pioneer 93M42. Application timing: V4- V5 trifoliate leaf stage.
Figure imgf000086_0002
Figure imgf000087_0001
Figure imgf000088_0001
Each of the safening systems showed a statistically significant reduction in % phytotoxicity (Duncan's Multiple Range Test at 95% probability level: letters which are different between mean values are statistically different). This reduction in % phytotoxicity was seen for each of the two varieties of soybean. Yields were improved as a consequence. No notable difference between the effectiveness of any of the safening systems was evident. EXAMPLE 6: SAFENING OILSEED RAPE USING A VARIETY OF SAFENING SYSTEMS
Safening systems were applied to crops of oilseed rape and winter wheat treated with various herbicides (Bifenox (with insecticide), Carbetamide, Propaquizafop), either without or without AN and/or AC. The safener/safening system and the herbicide were applied to the crops either simultaneously or sequentially.
Safening compounds were selected from the list of compounds below. The compounds used are highlighted in bold.
(a) Glucose (GL), hydrolysed starch , sucrose (S), fructose (FR), glycerol (G), glyceraldehydes, erythrose, ribulose, xylulose or arabinose or an ester or glycoside or metabolic equivalent of such a carbohydrate;
(b) an organic acid of the Krebs Tricarboxylic Acid Cycle or a metabolic precursor thereof (including citric (C), succinic (SU), malic, pyruvic, acetic and fumaric acids);
(c) a vitamin or coenzyme, eg thiamine (T), riboflavin (R), pyridoxine (P), pyridoxamine, pyridoxal, nicotinamide (N), folic acid (F), ascorbic acid (AA), Biotin (B) and vitamin B12 (B12) or a precursor thereof including nicotinic acid
(d) a purine or pyrimidine nucleoside, nucleotide or a metabolic precursor thereof, eg adenine, adenosine, thymine, thymidine, cytosine, guanine, guanosine, hypoxanthine, uracil, uridine or inosine, to act as structural precursors for nucleic acid synthesis.
(e) a naturally occurring fat or oil including olive, soya, coconut and corn (Oil) oils;
(f) an amino acid of a type that occurs naturally in plant proteins, eg glycine (GLY), alanine (AL), valine, leucine (LE), isoleucLne, serine, threonine (THR), cysteine (CY), methionine (ME), aspartic acid, glutamic acid, glutamine (GLU), asparagine (AS), lysine (LY), hydroxylysine, arginine, histidine, phenylalanine, tyrosine, tryptophan, proline, or hydroxyproline.
Statistical Layout: Randomised Complete Block trial, under glasshouse conditions, United Kingdom.
Statistical Analyses (Least Significant Difference, 5% Level) for Table 6.1 : Table 6.1 :
Figure imgf000090_0001
TABLE 6.1 - OILSEED RAPE - CROP SAFENING BENEFITS FROM ADDITION OF VARIOUS SAFENING COMPOUNDS FROM CATEGORIES (a) to (f) ABOVE, TO THE HERBICIDE BIFENOX (with insecticide). EXAMPLES ARE SHOWN WITH AND WITHOUT ANTHRANILIC ACID/ANTHRANILIC ACID + ACETAMINOPHEN
Figure imgf000090_0002
O
Figure imgf000091_0001
VO
Figure imgf000092_0001
κ>
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Ul
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
00
Figure imgf000099_0001
Figure imgf000100_0001
O O
Figure imgf000101_0001
Figure imgf000102_0001
O κ>
Figure imgf000103_0001
o
Figure imgf000104_0001
Figure imgf000105_0001
O
Figure imgf000106_0001
O
Figure imgf000107_0001
TABLE 6.2 - OILSEED RAPE - CROP SAFENING BENEFITS FROM ADDITION OF VARIOUS SAFENING COMPOUNDS FROM CATEGORIES (a) to (f) ABOVE, TO THE HERBICIDE CARBETAMIDE (60% w/w) + PROPAQUIZAFOP (100 g/1) . EXAMPLES ARE SHOWN WITH AND WITHOUT ANTHRANILIC ACID/ANTHRANILIC ACID + ACETAMINOPHEN.
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Figure imgf000123_0001
Figure imgf000124_0001
A reduction in phytotoxicity, along with increases in vigour and rooting, are shown from the use of the safening systems above (either combinations of compounds from classes (a) to (f) alone or in combination AN and/or AC) in combination with a herbicide, in contrast to application of a herbicide alone.
EXAMPLE 7: ROOT NODULATION AND SAFENING IN A RANGE OF NITROGEN-FIXING CROPS
Safening systems were applied to crops of soybean, navy bean and pea either alone or in combination with cobalt and/or a general foliar fertilizer, either without or without AN and/or AC. The safener/safening system and the fertiliser were applied to the crops either simultaneously or sequentially.
Co = 100% Cobalt Sulphate (2Og per litre and per hectare).
FFl = 2Og per litre Cobalt Sulphate (as per Co above) plus "Miracle-Gro" at xl recommended rate (applied at 15g per 2.5 sq metres). Miracle-Gro contains: 24% N, 4% P, 13% K, plus 0.02% B, 0.03% Cu, 0.19% Fe, 0.05% Mn, 0.001% Mo and 0.03% Zn.
FF2 = 20 g per litre Cobalt Sulphate plus Miracle-Gro at x2 recommended rate.
SAF: at least one from class (f) each at < 3 g/1, plus at least one from class (c).
EXAMPLE 7.1 - SOYBEAN
Scored/Counted + 28 Days After Spraying. Sown in Compost of low pH (5.0-5.5) on 1 May 2008. Spray Date (VC) = 4 June, Vl Date = 20 June. Scored/Measured on 17 July. Each treatment is the mean result of 12 plants, within four replicates. Seed density approx 110 kg/ha. Soybean treated with standard inoculant at sowing.
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000126_0002
EXAMPLE 7.2 - Glycine max (SOYBEAN) Dates as per Example 7.1 above, but sown in compost of normal pH (6.5). Each treatment represents the mean values for 12 plants, within four replicates. Sowing density 1 10 kg/ha. Standard inoculant applied at sowing.
Figure imgf000127_0001
Figure imgf000128_0001
EXAMPLE 7.3 - Phaseolus vulgaris (Navy Bean)
NAVY BEAN cv Mogex. Scored/Counted + 28 Days after Spraying. Sown in Compost of low pH (5.0-5.5) on 29 April 2008. Spray Date (VC) = 27 May, Vl Date = 16 June. Scored/Measured on 1 1 July. Each treatment represents the mean value of 12 plants, within four replicates. No inoculum applied.
Figure imgf000128_0002
Figure imgf000129_0001
Figure imgf000129_0002
EXAMPLE 7.4 - Phaseolus vulgaris (Navy Bean)
NAVY BEAN cv Mogex. Scored/Counted +28 Days after Spraying. Dates as per Example 7.3 Above, but sown in compost of normal pH (6.5). Each treatment represents the mean value from 12 plants, within four replicates. No inoculum applied.
Figure imgf000130_0001
27 FF2 + AN + 37.9 5.8 38.3 5.8 7.2 7.5
AC + SAP
28 FF2 + AN + 38.1 5.8 37.7 5.7 7.5 7.8 AC + SAF + POL
Figure imgf000131_0001
EXAMPLE 7.5 - Pisum sativum (Pea)
PEA - TRIAL 5 - cv Ragtime. Scored/Counted +28 Days after Spraying. Sown in Compost of Low pH (5.0-5.5) on 28 April 2008. Spray Date (VC) = 26 May, Vl Date = 14 June. Scored/Measured on 9 July. Each treatment represents the results from 12 plants, within four replicates. No inoculum applied.
Figure imgf000131_0002
Figure imgf000132_0001
Figure imgf000132_0002
EXAMPLE 7. 6 - Pisum sativum (Pea)
PEA - TRIAL 7.6 - cv Ragtime. Dates as per Example 7.5 above, but sown in compost of normal pH (6.5). Each treatment represents the results from 12 plants, within four replicates. No inoculum was applied.
Figure imgf000132_0003
Figure imgf000133_0001
Figure imgf000133_0002
EXAMPLE 7.7 - Pisum sativum (Pea)
PEA - Comparison of Nodulation Results with Rooting Results: i.e. whereas under low pH conditions, nodulation was significantly improved by addition of various treatments, rooting was not improved under these conditions (data from Example 7.5). Sowing details etc as per Example 7.5.
Figure imgf000134_0001
Figure imgf000134_0002
The addition of safeners or a safening system greatly reduced any phytotoxicity.
The improvements in the degree of nodulation were obtained by applications at either VC (cotyledon stage) or at Vl (first true leaf stage). Such improvements would be highly advantageous from application as seed treatments, either applied alone or in combination with other seed treatments available e.g. fungicides, insecticides or those intended for any other purpose.
EXAMPLE 8: SAFENING OF HERBICIDES FROM ADDITION OF AUXIN/AUXIN PRECURSOR AND ACETAMINOPHEN
Cultural Details: winter wheat cv Alchemy, sown 15 April 2009, at seven seeds per 9cm pot, sown in normal pH multi-purpose compost. Date of spraying: 14 May. Dates of measurement/scoring: 28 May, 1 1 June.
The following auxins or precursors were compared, each at
Figure imgf000135_0001
Molar solutions. Addition of acetaminophen (AC) was at 3g per hectare equivalent in each case. Phytotoxicity reduction is on a 0-9 scale, where 0 = dead plant.
Figure imgf000135_0002
Figure imgf000136_0001
Addition of an auxin/auxin precursor plus acetaminophen provides a benefit to safening improvement (phytotoxicity reduction).
All publications mentioned in the above specification are herein incorporated by reference. Various modifications and variations of the described methods and systems of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes of carrying out the invention which are obvious to those skilled in the field are intended to be within the scope of the following claims.

Claims

1. A composition comprising an auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and acetaminophen or a derivative thereof for use as a plant safener.
2. The composition according to claim 1 wherein the auxin is an indolic auxin or a phenolic auxin.
3. The composition according to claim 1 or 2 wherein the auxin derivative is an acid, a conjugate, a salt, an ester, or an amide of the auxin, or an alkylated or halogenated auxin.
4. The composition according to claim 3 wherein the auxin is conjugated to a sugar, an alcohol, an amino acid or a protein.
5. The composition according to any one of claims 1 to 4 wherein the precursor is chorismate, anthranilic acid, phosphoribosyl anthraniliate, 1-(O- carboxyphenulamino)-l-deoxyribulose-5-phosphate, indole-3-glycerol-phosphate, indole, indole-3-acetic acid, trytophan, tryptamine, N-hydroxy tryptamine, indole-3- acetaldoxime, l-aci-nitro-2-indolylethane, indolic glucosinate, indole-3-acetonitrile (LAN), indole-3-acetaldehyde, indole-3-lactic acid, indole-3-pyruvic acid, or indole-3- ethanol.
6. The composition according to claim 5 wherein the precursor is anthranilic acid or a derivative thereof.
7. The composition according to claim 6 wherein the anthranilic acid derivative is a conjugate, a salt, an ester, or an amide of anthranilic acid, optionally substituted with an alkyl or halogen group.
8. The composition according to claim 7 wherein the anthranilic acid derivative is conjugated to a sugar, an alcohol, an amino acid, a peptide or a protein.
9. The composition according to any one of claims 6 to 8 wherein the derivative of anthranilic acid is one of the compounds set out in Fig 1.
10. The composition according to any one of claims 1 to 9 wherein the auxin is a natural or synthetic auxin.
11. The composition according to claim 10 wherein the natural auxin is indole-3- acetic acid (IAA), 4-chloro-indole-3-acetic acid (4-Cl-IAA), phenylacetic acid (PAA), indole-3-butyric acid (IBA), indole-3-acetyl-l-O-β-D-glucose (IAAgIc).
12. The composition according to claim 10 or 11 wherein the conjugate of the natural auxin is IAA-Inositol, IAA-Inositol-arabinose, IAPl, an IAA-peptide, an IAA glycoprotein, an IAA-glucan, IAA-aspartate, IAA-glucose, IAA-1-O-glucose, IAA- myo-Inositol, lAA-4-O-glucose, IAA-6-O-glucose, lAA-Inositol-galactose, an IAA amide conjugate, or an LAA-amino acid conjugate.
13. The composition according to claim 10 wherein the synthetic auxin is 1- naphthaleneacetic acid (NAA), 2,4-dichlorophenoxyacetic acid (2,4-D), 2-methoxy- 3,6-dichlorobenzoic acid (dicamba), 4-amino-3,5,6-trichloropicolinic acid (tordon), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 2,3,6-trichlorobenzoic acid or N5N- dimethylethylthiocarbamate.
14. The composition according to any one of claims 1 to 4 wherein the metabolite is indole-3-lactic acid or indole-3-ethanol.
15. The composition according to any one of the preceding claims wherein the composition further comprises cobalt.
16. The composition according to any one of the preceding claims wherein the composition further comprises a compound selected from a) glucose, hydrolysed starch, sucrose, fructose, glycerol, glyceraldehydes, erythrose, ribulose, xylulose or arabinose, monosaccharides including aldoses such as D-Ribose, D-Xylose, L- Arabinose, D-Glucose, D-Mannose and D-Galactose; ketoses such as D-Ribulose and D-Fructose; deoxyaldoses such as 2-Deoxy-D-ribose, L-Fuccose; acetylated amino sugars such as N-Acteyl-D-glucosamine and N-Acetyl-D-galactosamine; acidic monosaccharides such as D-Glucuronic acid, L-lduronic acid and N- Acerylneuraminic acid, Sugar alcohols such as D-Sorbitol and D-Mannitol, disaccharides including maltose, lactose and sucrose, or an ester or glycoside or metabolic equivalent of such a carbohydrate; b) an organic acid of the Krebs tricarboxylic acid cycle or a metabolic precursor thereof; c) a vitamin or coenzyme, or a precursor thereof; d) a purine or pyrimidine nucleoside, nucleotide or metabolic precursor thereof; e) a naturally occurring fat or oil; or f) an amino acid.
17. The composition of claim 16 wherein the compound is selected from c) a vitamin or coenzyme, or a precursor thereof; d) a purine or pyrimidine nucleoside, nucleotide or metabolic precursor thereof; or f) an amino acid.
18. The composition of any of the preceding claims wherein the acetaminophen derivative is one of the compounds set out in Fig. 3.
19. The composition of any of the preceding claims wherein the composition further comprises at least one of a fungicide, an insecticide, a herbicide, a chemical thinning agent, a fertiliser, a plant growth regulator and an abscission delay agent.
20. A method of protecting a desired plant from the effect of an agrochemical comprising applying an effective amount of the composition of any one of claims 1 to 19.
21. The method of claim 20 wherein the composition is applied by at least one of seed treatment, localised soil treatment, plant treatment, including seedling treatment.
22. The method of claim 20 or 21 wherein the application of the composition is in advance of the application of the agrochemical.
23. A method for improving plant safety comprising the application of the composition of any one of claims 1 to 19 to a plant or its environs.
24. The method of any one of claims 20 to 23 wherein application of the composition further provides a boost in plant vigour.
25. The method of any one of claims 20 to 24 wherein the composition is applied at conditions of at least one of low or high pH, temperature, salinity or drought.
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