US 20120088667A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2012/0088667 A1 Williams et al. (43) Pub. Date: Apr. 12, 2012 (54) SAFENINGAGENT (30) Foreign Application Priority Data (75) Inventors: Richard Williams, Colchester Apr. 7, 2009 (EP) .................................. O9447OO9.3 (GB); Peter Roose, Ghent (BE): Publication Classification Johan Josef De Saegher, Ghent (51) Int. Cl. (BE) AOIN 25/32 (2006.01) AOIP 2L/00 (2006.01) (73) Assignee: TAMINCO, NAAMLOZE AOIPI3/02 (2006.01) VENNOOTSCHAP, Ghent (BE) AOIP3/00 (2006.01) AOIP 7/04 (2006.01) (21) Appl. No.: 13/263,674 (52) U.S. Cl. ......... 504/105:504/112:504/104:504/108; 504/110 (22) PCT Fled: Apr. 7, 2010 (57) ABSTRACT A compound selected from a composition comprising an (86) PCT NO.: PCT/B10/O1034 auxin, an auxin precursor, an auxin metabolite or a derivative of said auxin, auxin precursor or auxin metabolite and S371 (c)(1), acetaminophen or a derivative thereof for use as a plant (2), (4) Date: Dec. 27, 2011 safener. NH, NH NH Br O- O OH NH H N boc Br c. CF OMe S. OMe Patent Application Publication Apr. 12, 2012 Sheet 1 of 16 US 2012/0088667 A1 FIG. 1(a) ON OH On-NHH O OH Nul OH ". Br O OH O NH H N boc CF OMe OMe Patent Application Publication Apr. 12, 2012 Sheet 2 of 16 US 2012/0088667 A1 O OH O OH H 1c. N CN C O r O OH O OH H S1 N DO Nin 1S ON O OH O OH Patent Application Publication Apr. 12, 2012 Sheet 3 of 16 US 2012/0088667 A1 O. NH O OH NH, H NH C O O N-N- O H \- NH O O HN-N- ( ) OM C N-N NH, NH NO, Patent Application Publication Apr. 12, 2012 Sheet 4 of 16 US 2012/0088667 A1 FIG. 1 (d) C C C C C C Patent Application Publication Apr. 12, 2012 Sheet 5 of 16 US 2012/0088667 A1 FIG. 1 (e) OH O Os-OS-1 O. OH ON OH HC ". ". o O. OH O. OH ON OH NH, ON OH NH, C NH CH t 2 3 OS, OH NH, O OH O OH O NH, NH, NH OH C F Br O OH NH, os-NH2 O OH H NH Ns H.N NH HN Patent Application Publication Apr. 12, 2012 Sheet 6 of 16 US 2012/0088667 A1 O. OH f ON O H N r HO MeO OMe O wo-)------oMeO OMe Patent Application Publication Apr. 12, 2012 Sheet 7 of 16 US 2012/0088667 A1 FG. 2 CHCOOH CHCH2CH2COOH Os ".. Os CH.br (OSN H e.g. for IAA-aspartate R: -NHCHCOOH CHCOOH w O Ho CHCOOH O HSYNohCH2OH N H Patent Application Publication Apr. 12, 2012 Sheet 8 of 16 US 2012/0088667 A1 FIG. 3(a) ACETAMINOPHENDERIVATIVES HC O C Patent Application Publication Apr. 12, 2012 Sheet 9 of 16 US 2012/0088667 A1 FIG. 3(b) HN CH, CH Patent Application Publication Apr. 12, 2012 Sheet 10 of 16 US 2012/0088667 A1 FIG. 3(c) O O cif als.CH SH N-1- -- - - O s CH Patent Application Publication Apr. 12, 2012 Sheet 11 of 16 US 2012/0088667 A1 FIG. 3(d) O OH l HC NH N* O Patent Application Publication Apr. 12, 2012 Sheet 12 of 16 US 2012/0088667 A1 FIG. 3(e) Hics CH s rolOH Patent Application Publication Apr. 12, 2012 Sheet 13 of 16 US 2012/0088667 A1 FIG. 3(f) OH H N H,C o HC CH CH, e H,C N Patent Application Publication Apr. 12, 2012 Sheet 14 of 16 US 2012/0088667 A1 FIG. 3(g) H He Sir C H O - "" O O Patent Application Publication Apr. 12, 2012 Sheet 15 of 16 US 2012/0088667 A1 FIG. 4 d s sC frch. - O N -- (OC--Oit- -sh-H-CH-O-Po, coo cH-0-Pd - - e-or Hot-choi-chro-Po, Glyceraldehyde-3-phosphate. Oy Serine m N. r coo N d N. -- -swamp N N H n es co Indole glucosinolates \ co ors. CS N". OS OS co N -- r OSh - OS Patent Application Publication Apr. 12, 2012 Sheet 16 of 16 US 2012/0088667 A1 F.G. 5 O-CH2-COOH o-CH2 -COOH o-CH-COOH C C CH3 f C C C C CH2 -COOH COOH COOH C C C OCH3 US 2012/0088.667 A1 Apr. 12, 2012 SAFENINGAGENT orange, pharmaceuticals (loop diuretics such as furosemide) and UV-absorbers, as well as corrosion inhibitors for metals FIELD OF THE INVENTION and mold inhibitors in Soya sauce. Its usefulness as part of a Safening package is Surprising. 0001. This invention relates to a method and composition for improving crop safety by treating plants with, particularly 0008 Acetaminophen is widely used as an over-the but not exclusively, a composition comprising an auxin, an counter analgesic and antipyretic. It will be appreciated that auxin precursor, an auxin metabolite or a derivative of said its efficacy as part of a safening package is Surprising. auxin, auxin precursor or auxin metabolite and acetami nophen or a derivative thereof. STATEMENTS OF THE INVENTION 0009. The present invention is directed to the treatment of BACKGROUND OF THE INVENTION a plant with an effective amount of a composition comprising 0002 Chemical fertilisers, fungicides, insecticides and an auxin, an auxin precursor, an auxin metabolite or a deriva herbicides are applied to plants in order to promote growth tive of said auxin, auxin precursor or auxin metabolite and and reduce or destroy unwanted fungi, pests, weeds and other acetaminophen or a derivative thereof to improve safety. unwanted species. This is of particular importance in the field 0010. According to one aspect of the present invention of commercial farming, where obtaining the maximum yield there is provided a composition comprising an auxin, an is of the utmost importance. auxin precursor, an auxin metabolite or a derivative of said 0003 Chemical fertilisers, fungicides, pesticides, insecti auxin, auxin precursor or auxin metabolite and acetami cides and herbicides available to-date often have negative nophen or a derivative thereof for use as a plant safener. effects on crops, as well as the positive effect of reducing 0011. The combination envisaged in the present invention unwanted species and promoting growth. For example, Such may give rise to a synergistic effect. chemicals may damage the crops to which they are applied, as 0012 For ease of reference we will refer to an auxin, an well as the species to which they are targeted. This is a auxin precursor, an auxin metabolite or a derivative of said particular problem in the field of non-selective fertilisers. auxin, auxin precursor or auxin metabolite or a mixture These fertilisers, fungicides, pesticides, insecticides and her thereof as an “auxin-related compound'. bicides may also be hazardous. Other compositions applied to 0013. In one embodiment the auxin-related compound is plants such as plant growth regulators, chemical thinners and based on an indolic ring. In another embodiment the auxin abscission delay agents also often have negative effects on related compound is based on a phenolic ring. crops and may also be hazardous. 0014. In one embodiment the derivative is an acid, a con 0004 Thus, there is a continuing need for safeners and jugate, a salt, an ester, or an amide of the auxin, auxin pre which may provide improved properties. cursor, or auxin metabolite. 0015. In one embodiment the derivative is in the form of a SUMMARY OF THE INVENTION conjugate, e.g. conjugated to a Sugar, an alcohol, an amino 0005. The present invention relates to the novel use of acid, a peptide or a protein. compositions comprising an auxin, an auxin precursor, an 0016. In one embodiment the auxin precursor is choris auxin metabolite or a derivative of said auxin, auxin precursor mate, anthranilic acid, phosphoribosyl anthraniliate, 1-(O- or auxin metabolite and acetaminophenora derivative thereof carboxyphenulamino)-1-deoxyribulose-5-phosphate, for use as a plant safener. indole-3-glycerol-phosphate, indole, indole-3-acetic acid, 0006. The present invention also relates to the novel use of tryptophan, tryptamine, N-hydroxy tryptamine, indole-3-ac compounds selected from a) glucose, hydrolysed starch, etaldoxime, 1-aci-nitro-2-indolylethane, indolic glucosinate, Sucrose, fructose, glycerol, glyceraldehydes, erythrose, ribu indole-3-acetonitrile (IAN), indole-3-acetaldehyde, indole lose, Xylulose or arabinose, monosaccharides including 3-lactic acid, indole-3-pyruvic acid, or indole-3-ethanol. aldoses such as D-Ribose, D-Xylose, L-Arabinose, D-Glu 0017. In a particularly preferred embodiment the auxin cose, D-Mannose and D-Galactose; ketoses such as D-Ribu precursor is anthranilic acid or a derivative thereof. lose and D-Fructose; deoxyaldoses such as 2-Deoxy-D-ri 0018. In one embodiment the derivative of anthranilic acid bose, L-Fuccose:acetylated amino Sugars such as N-Acteyl is one of the compounds set out in FIG. 1. D-glucosamine and N-Acetyl-D-galactosamine; acidic 0019. The auxin-related compound may be a natural, such monosaccharides such as D-Glucuronic acid, L-Iduronic acid as is obtainable from seaweed or algae, or synthetic auxin. and N-Acetylneuraminic acid, Sugar alcohols such as D-Sor 0020. In one embodiment the natural auxin is indole-3- bitol and D-Mannitol, disaccharides including maltose, lac acetic acid (IAA), 4-chloro-indole-3-acetic acid (4-Cl-IAA), tose and Sucrose, or an ester or glycoside or metabolic equiva phenylacetic acid (PAA), indole-3-butyric acid (IBA), lent of such a carbohydrate; b) an organic acid of the Krebs indole-3-acetyl-1-O-B-D-glucose (IAAglc).