Ascaloside salt

Abstract

This application relates to salts of ascaryosides that can provide various benefits over the corresponding ascaryosides. For example, certain ascaryoside salts can provide beneficial nutrients to plants to which, or near which, the salt is applied. Compositions and methods containing such ascaryoside salts are also provided herein. In certain embodiments, such compositions and methods are useful in the context of pesticides. Such compositions and methods generally relate, in some embodiments, to salts of ascaryosides that can provide various benefits to organisms (such as plants, animals, or microorganisms) to which such salts are applied or administered.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the benefit of priority of U.S. Provisional Patent Application No. 63 / 341,332, entitled "Ascaroside Salts," filed on May 12, 2022, which is hereby incorporated by reference herein in its entirety.

[0002] This application generally relates to pesticidal compounds, compositions, and methods of treating plants to promote resistance to pathogens.

Background Art

[0003] Ascaroside natural products are secondary metabolites produced by nematodes. A number of structurally diverse ascarosides have been identified in nature, and the molecules are thought to function as an evolutionarily conserved chemical language that nematodes use to control many aspects of their development. Ascarosides are also perceived by other organisms and have been shown to have various effects on a number of organisms, including bacteria, fungi, plants, and mammals, including humans. Ascarosides have potential as products for human pharmaceuticals, pesticides, and other diverse and valuable applications.

[0004] Ascaroside treatment has been shown to be effective in increasing plant resistance to specific pathogens and / or inducing and priming the plant's defense response (which can inhibit pathogen growth and / or parasitism) when applied to plants. Ascarosides can prevent pathogen proliferation and / or protect crops from the harmful effects caused by various pathogens by activating and / or priming the plant's innate defenses.

[0005] It would be useful to provide other forms of ascarosides to modify the physical properties of the compounds and further provide additional benefits to the plants or other organisms to which the ascarosides are applied or administered.

Summary of the Invention

[0006] The present disclosure provides compositions and methods for ascaloside delivery. In certain embodiments, such compositions and methods are useful in the context of pesticides. Such compositions and methods generally relate, in some embodiments, to salts of ascalosides that can provide various benefits to an organism (e.g., a plant, animal, or microorganism) to which such salts are applied or administered.

[0007] The present disclosure includes, without limitation, the following embodiments.

[0008] Embodiment 1: A salt of the formula [A-(C(O)O) - p M p+ wherein A is an ascaloside moiety, M is a metal or ammonium cation, p is an integer from 1 to 3, and when p is 2 or 3, each A may be the same or different.

[0009] Embodiment 2: The salt of Embodiment 1, wherein p is 1.

[0010] Embodiment 3: The salt of Embodiment 1, wherein p is 2.

[0011] Embodiment 4: The salt of Embodiment 1, wherein p is 3.

[0012] Embodiment 5: The salt of any one of Embodiments 1 - 4, wherein M is a metal.

[0013] Embodiment 6: The salt of Embodiment 5, wherein the metal is selected from the group consisting of potassium (K), calcium (Ca), magnesium (Mg), zinc (Zn), manganese (Mn), iron (Fe), copper (Cu), molybdenum (Mo), and nickel (Ni).

[0014] Embodiment 7: The salt of Embodiment 6, wherein the metal is selected from the group consisting of copper (Cu), zinc (Zn), manganese (Mn), and iron (Fe). ​

[0015] Embodiment 8: A salt according to any one of Embodiments 1 to 4, wherein M is an ammonium cation or an analog thereof.

[0016] Embodiment 9: A salt comprising at least one boron atom coordinated to ascarylose (A).

[0017] Embodiment 10: A is of structure (I) [Chemical formula] having, wherein Z is an optionally substituted C 2-40 aliphatic group, and each of R a and R b is independently -H, or an optionally substituted C 1-20 aliphatic, C 1-20 acyl, C 1-20 heteroaliphatic, aryl, heteroaryl, hydroxyl protecting group, phosphorus-bonding functional group, sulfur-bonding functional group, silicon-bonding functional group, C 2-20 carbonate (e.g., - moiety -C(O)OR c ), C 2-20 carbamate (e.g., - moiety -C(O)N(R c )) 2 ), C 2-20 thioester (e.g., moiety -C(S)R c ), C 2-20 thiocarbonate (e.g., moiety -C(S)OR c ), C 2-20 dithiocarbonate (e.g., moiety -C(S)SR c ), C 1-20 thiocarbamate (e.g., moiety -C(S)N(R c )) 2 ), a sugar moiety, a peptide, a polymer chain, or a moiety selected from the group consisting of a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety, and R c is independently at each occurrence -H, an optionally substituted C 1-12 aliphatic, an optionally substituted C 1-12Selected from a bond to a heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, polymer chain, or another ascarylose molecule or a linkage via a carbon-containing linker moiety, R a and R b together may form an optionally substituted ring containing optionally one or more heteroatoms and optionally one or more unsaturated sites, a salt of any of Embodiments 1-9.

[0018] Embodiment 11: Z is i. -CH(CH 3 )-R 1 (R 1 is an optionally substituted C 1-40 aliphatic group), ii. -CH(CH 3 )-(CH 2 ) n -CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), iii. -CH(CH 3 )-(CH 2 ) n -CH=CH-CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), iv. -CH(CH 3 )-(CH 2 ) n -CH(OH)-CH-CO 2 R2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a linkage to another ascarylose molecule or a linkage via a carbon-containing linker moiety), v. -CH(CH 3 )-(CH 2 ) n -C(O)-CH-CO 2 R 2 (wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a linkage via a carbon-containing linking moiety to another ascarylose molecule), vi. -(CH 2 ) n -CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a linkage to another ascarylose molecule or a linkage via a carbon-containing linker moiety), vii. -(CH 2 ) n -CH=CH-CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20a bond to a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or another ascarylose molecule or a linkage via a carbon-containing linker moiety), viii. -(CH 2 ) n -CH(OH)-CH-CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), and ix. -(CH 2 ) n -C(O)-CH-CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), selected from the group consisting of, the salt of Embodiment 10.

[0019] Embodiment 12: R a and R b are each -H, the salt of Embodiment 10 or 11.

[0020] Embodiment 13: Z is -CH(CH 3 )-(CH 2 ) n -CO 2 R 2 where n is an integer from 1 to 40 and R 2 is -H, a metal cation, an optionally substituted C 1-20A salt according to any one of Embodiments 10 to 12, which is an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide, or a nucleotide.

[0021] Embodiment 14: A salt according to any one of Embodiments 1 to 13, wherein A is ascr#18.

[0022] Embodiment 15: A salt of the following formula:

Chemical formula

[0023] Embodiment 16: A composition comprising a salt according to any one of Embodiments 1 to 14.

[0024] Embodiment 17: The composition of Embodiment 16 in solid form.

[0025] Embodiment 18: The composition of Embodiment 17, wherein the solid form comprises powder or granules.

[0026] Embodiment 19: The composition of Embodiment 16 in liquid form.

[0027] Embodiment 20: The composition of Embodiment 19, wherein the liquid form is a sprayable formulation.

[0028] Embodiment 21: One or more additional components selected from the group consisting of surfactants including emulsifiers, dispersants, foaming agents, colorants, processing aids, lubricants, fillers, reinforcing agents, flame retardants, light stabilizers, ultraviolet absorbers, weather stabilizers, plasticizers, release agents, fragrances, heat preservation additives (e.g., silica), crosslinking agents, antioxidants, defoaming agents, buffers, pH adjusters, compatibilizers, drift control additives, bulking agents / tackifiers, tackifiers, plant penetration agents, toxicity moderators, spreading agents, and wetting agents, further comprised in a composition according to any one of Embodiments 16 to 20.

[0029] Embodiment 22: A method for enhancing the physical properties of ascaloside and providing one or more nutrients to a plant, the method comprising contacting the plant or a part thereof, or the soil surrounding the plant or a part thereof, with a salt according to any one of Embodiments 1 to 15, or a composition according to any one of Embodiments 16 to 21.

[0030] Embodiment 23: The method of Embodiment 22, wherein the part thereof is selected from the group consisting of roots, stems, leaves, seeds, and flowers.

[0031] Embodiment 24: The method of Embodiment 22 or 23, wherein the plant is a vegetable or fruit plant.

[0032] These and other features, aspects, and advantages of the present disclosure will become apparent from the following detailed description read in conjunction with the accompanying drawings, which are briefly described below. The present invention, like any combination of two, three, four or more of the above embodiments, includes any combination of two, three, four or more features or elements described in the present disclosure, whether or not such features or elements are explicitly combined in a particular embodiment herein. The present disclosure is intended to be read as a whole such that any separable feature or element of the disclosed invention can be combined in any of its various aspects and embodiments, unless the context clearly indicates otherwise. Other aspects and advantages of the present disclosure will become apparent from the following.

[0033] Definitions For a better understanding of the present disclosure, certain terms are first defined below. Further definitions of the following terms and other terms are set forth throughout this specification.

[0034] Unless otherwise clearly defined from the context, the term "a" can be understood to mean "at least one" in this application. When used in this application, the term "or" can be understood to mean "and / or". In this application, the terms "comprising" and "including" can be understood to encompass the separately listed components or steps, whether shown by themselves only or together with one or more additional components or steps. When used in this application, the term "comprise", as well as variations of this term such as "comprising" and "comprises", are not intended to exclude other additives, components, integers or steps.

[0035] As used herein, the terms "about" and "approximately" are used as equivalents. Unless otherwise specified, the terms "about" and "approximately" can be understood to allow for a standard deviation, as understood by one of ordinary skill in the art. When ranges are provided herein, the endpoints are included. Any numbers used in this application, whether or not preceded by "about" or "approximately", are meant to cover any normal variations understood by one of ordinary skill in the relevant technical field. In some embodiments, the term "approximately" or "about", unless otherwise specified or clear from the context, refers to a range of values that fall within 25%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or less in either direction (greater or less) from the stated standard reference value (except where such a number exceeds 100% of the possible values).

[0036] The definitions of specific functional groups and chemical terms are described in more detail below. For the purposes of the present invention, chemical elements are defined in The Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75 thEd., identified according to the inside cover, and specific functional groups are generally defined as described therein. In addition, general principles of organic chemistry, as well as specific functional moieties and reactivities, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999, Smith and March March’s Advanced Organic Chemistry, 5 th Edition, John Wiley & Sons, Inc., New York, 2001, Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989, Carruthers, Some Modern Methods of Organic Synthesis, 3 rd Edition, Cambridge University Press, Cambridge, 1987, and the entire contents of each are hereby incorporated by reference into this specification.

[0037] The specific salts provided herein can contain one or more asymmetric centers and can thus exist in various stereoisomeric forms, such as enantiomers and / or diastereomers. Accordingly, the salts of the invention and their compositions can be in the form of the individual enantiomers, diastereomers or geometric isomers, or alternatively in the form of mixtures of stereoisomers. In certain embodiments, the salts and compositions of the invention described herein can include enantiopure salts. In certain other embodiments, mixtures of enantiomers or diastereomers are provided.

[0038] Furthermore, the specific salts described herein may have one or more double bonds that can exist as either the Z or E isomer, unless otherwise indicated. The salts can be provided as individual isomers substantially free of other isomers and, alternatively, as mixtures of various isomers, such as racemic mixtures of enantiomers.

[0039] As used herein, the term "isomer" includes any and all geometric and stereoisomers. For example, "isomer" includes cis and trans isomers, E and Z isomers, R and S isomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof, as are within the scope of the present disclosure. For example, in some embodiments, a salt may be provided substantially free of one or more corresponding stereoisomers and may be referred to as "stereochemically enriched."

[0040] When a particular enantiomer is preferred, in some embodiments, it may be provided substantially free of the opposite enantiomer and may be referred to as "optically enriched." As used herein, "optically enriched" means that the salts of the invention are composed of a significantly higher proportion of one enantiomer. In certain embodiments, the salt is composed of at least about 90% by weight of one enantiomer. In some embodiments, the salt is composed of at least about 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8% or 99.9% by weight of one enantiomer. In some embodiments, the enantiomeric excess of the salt provided is at least about 90%, 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8% or 99.9%. In some embodiments, the enantiomers may be separated from the racemic mixture by any well-known method such as chiral high performance liquid chromatography (HPLC) as well as the formation and crystallization of chiral salts, or may be prepared by asymmetric synthesis. See, for example, Jacques, et al., Enantiomers, Racemates and Resolutions (Wiley Interscience, New York, 1981), Wilen, S.H., et al., Tetrahedron 33:2725 (1977), Eliel, E.L. Stereochemistry of Carbon Compounds (McGraw-Hill, NY, 1962), and Wilen, S.H. Tables of Resolving Agents and Optical Resolutions p.268 (E.L. Eliel, Ed., Univ. of Notre Dame Press, Notre Dame, IN 1972), which are hereby incorporated by reference.

[0041] As used herein, the terms "halo" and "halogen" refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (iodo, -I).

[0042] As used herein, the term "aliphatic" or "aliphatic group" refers to a hydrocarbon moiety that can be linear (i.e., unbranched), branched, or cyclic (including fused, bridged, and spiro-fused polycyclic), can be completely saturated, or can contain one or more units of unsaturation, but is not aromatic. Unless otherwise specified, aliphatic groups contain from 1 to 30 carbon atoms. In certain embodiments, aliphatic groups contain from 1 to 12 carbon atoms. In certain embodiments, aliphatic groups contain from 1 to 8 carbon atoms. In certain embodiments, aliphatic groups contain from 1 to 6 carbon atoms. In some embodiments, aliphatic groups contain 1 to 5 carbon atoms, in some embodiments, aliphatic groups contain 1 to 4 carbon atoms, in still other embodiments, aliphatic groups contain 1 to 3 carbon atoms, and in still other embodiments, aliphatic groups contain 1 to 2 carbon atoms. Suitable aliphatic groups include, but are not limited to, linear or branched alkyl, alkenyl, and alkynyl, and their hybrids such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl.

[0043] As used herein, the term "heteroaliphatic" or "heteroaliphatic group" refers to an aliphatic group in which one or more carbon atoms or hydrogen atoms are replaced by heteroatoms (e.g., oxygen, nitrogen, sulfur, phosphorus, boron, etc.).

[0044] As used herein, the term "unsaturated" means that the moiety has one or more double bonds or triple bonds.

[0045] As used herein, the term "alkyl" refers to a saturated, straight-chain or branched-chain hydrocarbon radical derived from an aliphatic moiety containing 1 to 6 carbon atoms by removal of one hydrogen atom. Unless otherwise specified, an alkyl group contains 1 to 12 carbon atoms. In certain embodiments, an alkyl group contains 1 to 8 carbon atoms. In certain embodiments, an alkyl group contains 1 to 6 carbon atoms. In some embodiments, an alkyl group contains 1 to 5 carbon atoms, in some embodiments, an alkyl group contains 1 to 4 carbon atoms, in yet other embodiments, an alkyl group contains 1 to 3 carbon atoms, and in yet other embodiments, an alkyl group contains 1 to 2 carbon atoms. Examples of alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, etc.

[0046] As used herein, the term "alkenyl" refers to a monovalent group derived from a straight-chain or branched-chain aliphatic moiety having at least one carbon-carbon double bond by removal of one hydrogen atom. Unless otherwise specified, an alkenyl group contains 2 to 12 carbon atoms. In certain embodiments, an alkenyl group contains 2 to 8 carbon atoms. In certain embodiments, an alkenyl group contains 2 to 6 carbon atoms. In some embodiments, an alkenyl group contains 2 to 5 carbon atoms, in some embodiments, an alkenyl group contains 2 to 4 carbon atoms, in yet other embodiments, an alkenyl group contains 2 to 3 carbon atoms, and in yet other embodiments, an alkenyl group contains 2 carbon atoms. Examples of alkenyl groups include, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, etc.

[0047] The term "aryl", when used alone or as part of a larger moiety, such as "aralkyl", "aralkoxy", or "aryloxyalkyl", refers to monocyclic and polycyclic ring systems having a total of 5 to 20 ring members, at least one ring in the system being aromatic, and each ring in the system containing 3 to 12 ring members. The term "aryl" may be used interchangeably with the term "aryl ring". In certain embodiments, "aryl" refers to aromatic ring systems including, but not limited to, phenyl, biphenyl, naphthyl, anthracyl, etc., which may have one or more substituents. Also, as used herein 「 the scope of the term "aryl" also includes groups in which the aromatic ring is fused to one or more additional rings such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenanthridinyl, or tetrahydronaphthyl.

[0048] As described herein, the salts provided herein may contain a "optionally substituted" moiety. In general, the term "substituted", whether or not preceded by the term "optionally", means that one or more hydrogens of the specified moiety are replaced by a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have suitable substituents at each substitutable position of the group, and when two or more positions in any given structure may be substituted with two or more substituents selected from the recited group, the substituents may be the same or different at each position. Combinations of substituents that are contemplated are preferably those that result in the formation of stable or chemically possible compounds / salts. As used herein, the term "stable" refers to compounds or salts that do not substantially change when subjected to conditions that allow for their manufacture, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.

[0049] Suitable monovalent substituents on a substitutable carbon atom of an "optionally substituted" group are, independently, halogen, -(CH 2 ) 0-4 R°, -(CH 2) 0-4 OR°, -O-(CH 2 ) 0-4 C(O)OR°, -(CH 2 ) 0-4 CH(OR°) 2 、-(CH 2 ) 0-4 SR°, -(CH which may be substituted with R° 2 ) 0-4 Ph, -(CH which may be substituted with R° 2 ) 0-4 O(CH 2 ) 0-1 Ph, -CH=CHPh which may be substituted with R°, -NO 2 、-CN、-N 3 、-(CH 2 ) 0-4 N(R°) 2 、-(CH 2 ) 0-4 N(R°)C(O)R°, -N(R°)C(S)R°, -(CH 2 ) 0-4 N(R°)C(O)NR° 2 、-N(R°)C(S)NR° 2 、-(CH 2 ) 0-4 N(R°)C(O)OR°, -N(R°)N(R°)C(O)R°, -N(R°)N(R°)C(O)NR° 2 、-N(R°)N(R°)C(O)OR°, -(CH 2 ) 0-4 C(O)R°, -C(S)R°, -(CH 2 ) 0-4 C(O)OR°, -(CH 2 ) 0-4 C(O)N(R°) 2 、-(CH 2 ) 0-4 C(O)SR°, -(CH 2 ) 0-4 C(O)OSiR° 3 、-(CH 2 ) 0-4 OC(O)R°, -OC(O)(CH 2 ) 0-4 SR-, SC(S)SR°, -(CH 2 ) 0-4 SC(O)R°, -(CH 2 )0-4 C(O)NR° 2 、 -C(S)NR° 2 、 -C(S)SR°、 -SC(S)SR°、 -(CH 2 ) 0-4 OC(O)NR° 2 、 -C(O)N(OR°)R°、 -C(O)C(O)R°、 -C(O)CH 2 C(O)R°、 -C(NOR°)R°、 -(CH 2 ) 0-4 SSR°、 -(CH 2 ) 0-4 S(O) 2 R°、 -(CH 2 ) 0-4 S(O) 2 OR°、 -(CH 2 ) 0-4 OS(O) 2 R°、 -S(O) 2 NR° 2 、 -(CH 2 ) 0-4 S(O)R°、 -N(R°)S(O) 2 NR° 2 、 -N(R°)S(O) 2 R°、 -N(OR°)R°、 -C(NH)NR° 2 、 -P(O) 2 R°、 -P(O)R° 2 、 -OP(O)R° 2 、 -OP(O)(OR°) 2 、 SiR° 3 、 -(C 1-4 linear or branched alkylene)O-N(R°) 2 、 or -(C 1-4 linear or branched alkylene)C(O)O-N(R°) 2 wherein each R° may be substituted as defined below and is independently hydrogen, C 1-8 aliphatic, -CH 2 Ph, -O(CH 2 ) 0-1A 5- to 6-membered saturated, partially unsaturated, or aryl ring having 0 to 4 heteroatoms independently selected from Ph, or nitrogen, oxygen, or sulfur, or, regardless of the above definition, two independent occurrences of R° together with the intervening atom(s) thereof form a 3- to 12-membered saturated, partially unsaturated, or aryl monocyclic or polycyclic ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

[0050] Suitable monovalent substituents on R° (or the ring formed by the two independent occurrences of R° together with the intervening atoms thereof) are independently halogen, -(CH 2 ) 0-2 R ● , -(haloR ● ), -(CH 2 ) 0-2 OH, -(CH 2 ) 0-2 OR ● , -(CH 2 ) 0-2 CH(OR ● ) 2 , -O(haloR ● ), -CN, -N 3 , -(CH 2 ) 0-2 C(O)R ● , -(CH 2 ) 0-2 C(O)OH, -(CH 2 ) 0-2 C(O)OR ● , -(CH 2 ) 0-4 C(O)N(R°) 2 , -(CH 2 ) 0-2 SR ● , -(CH 2 ) 0-2 SH, -(CH 2 ) 0-2 NH 2 , -(CH 2 ) 0-2 NHR ● , -(CH 2 ) 0-2 NR ● 2 , -NO2 、 -SiR ● 3 、 -OSiR ● 3 、 -C(O)SR ● 、 -(C 1-4 a linear or branched alkylene)C(O)OR ● 、 or -SSR ● and each R ● is unsubstituted or, when preceded by "halo", substituted only with one or more halogens and independently selected from C 1-4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0-1 Ph, or a 5- to 6-membered saturated, partially unsaturated, or aryl ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. Suitable divalent substituents on the saturated carbon atoms of R° include =O and =S.

[0051] Suitable divalent substituents on the saturated carbon atoms of a "optionally substituted" group include, hereinafter, =O, =S, =NNR * 2 、 =NNHC(O)R * 、 =NNHC(O)OR * 、 =NNHS(O) 2 R * 、 =NR * 、 =NOR * 、 -O(C(R * 2 )) 2-3 O-, or -S(C(R * 2 )) 2-3 S-, and each independent occurrence of R * is hydrogen, C 1-6 aliphatic which may be substituted as defined hereinafter, or an unsubstituted 5- to 6-membered saturated, partially unsaturated, or aryl ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. Suitable divalent substituents bonded to a substitutable carbon proximal to an "optionally substituted" group include -O(CR * 2 ) 2-3O- is exemplified, and R * each independent occurrence of which may be hydrogen, C 1-6 aliphatic, or an unsubstituted 5- to 6-membered saturated, partially unsaturated, or aryl ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

[0052] R * suitable substituents on the aliphatic group of which include halogen, -R ● , -(haloR ● ), -OH, -OR ● , -O(haloR ● ), -CN, -C(O)OH, -C(O)OR ● , -NH 2 , -NHR ● , -NR ● 2 , or -NO 2 is included, and each R ● is unsubstituted or, when "halo" precedes, is substituted only with one or more halogens and independently is C 1-4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0-1 Ph, or a 5- to 6-membered saturated, partially unsaturated, or aryl ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

[0053] Suitable substituents on the nitrogen of the "optionally substituted" group include -R † , -NR † 2 , -C(O)R † , -C(O)OR † , -C(O)C(O)R † , -C(O)CH 2 C(O)R † , -S(O) 2 R † , -S(O) 2 NR † 2 , -C(S)NR † 2 , -C(NH)NR † 2 , or -N(R† )S(O) 2 R † includes, each R † is independently hydrogen, C 1-6 aliphatic which may be substituted as defined below, unsubstituted -OPh, or an unsubstituted 5-6 membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or regardless of the above definition, two independent occurrences of R † together with the intervening atom(s) form an unsubstituted 3-12 membered saturated, partially unsaturated, or aryl monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

[0054] R † Suitable substituents on the aliphatic group of R ● are independently halogen, -R ● , -(haloR ● ), -OH, -OR ● ), -O(haloR ● ), -CN, -C(O)OH, -C(O)OR 2 ), -NH ● ), -NHR ● 2 ), or -NO 2 ), where R ● is unsubstituted or, when preceded by "halo", is substituted by only one or more halogens and is independently C 1-4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0-1 Ph, or a 5-6 membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

[0055] As used herein, the term "substantially" refers to a qualitative condition indicating the entire degree or almost the entire degree or extent of a characteristic or property of an object.

[0056] Ascalarosides are named with a few-letter prefix followed by the pound sign (#), and there is a convention of using numbers (e.g., ascr#18). This convention is used in the scientific literature, and those skilled in the art will understand that each such name is associated with the specific chemical structure of a known composition and will immediately understand the structure of the molecule denoted using this nomenclature. Unless otherwise indicated, all compound identifiers of this form used herein conform to the definitions described in the C. elegans Small Molecule Identifier Database (SMID-DB) maintained at http: / / www.smid-db.org.

[0057] The term "pathogen" refers to any bacterium, fungus, oomycete, virus, nematode (e.g., cyst or root-knot nematode), or insect that has a pathogenic effect on plants. The teachings described herein will be more fully understood from the following description of various exemplary embodiments when read in conjunction with the accompanying drawings. It should be understood that the drawings described below are for illustrative purposes only and are not intended to limit the scope of the teachings in any way. The foregoing and other objects, aspects, features, and advantages of the present disclosure will become more apparent and better understood by referring to the following description in conjunction with the accompanying drawings.

Brief Description of the Drawings

[0058]

Figure 1

Modes for Carrying Out the Invention

[0059] The present disclosure relates to salt forms of ascaryosides (also referred to herein as "ascaryoside salts"), as well as compositions and methods comprising such ascaryoside salts. In some embodiments, the use of ascaryosides in salt form can provide benefits in various formulations (e.g., improved handling properties and / or simplified or improved incorporation within pesticidal or pharmaceutical compositions) compared to the corresponding ascaryosides. In some embodiments, the use of ascaryosides in certain salt forms can also provide benefits to plants to which the ascaryoside salts are applied beyond those generally provided by the application of ascaryosides, such as providing micronutrients, macronutrients, and / or other beneficial molecules.

[0060] Ascaryosides are derivatives of the sugar ascarylose, which is a dideoxy sugar lacking hydroxyl groups at its 3- and 6-positions. Ascaryosides have the general structure shown in Formula I:

Chemical formula

[0061] In certain embodiments, Z is (i) -CH(CH 3 )-R 1 (where R 1 is an optionally substituted C 1-40 aliphatic group), (ii) -CH(CH 3 )-(CH 2 ) n -CO 2 R 2 (where n is an integer from 1 to 40 and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon - containing linker moiety), (iii) -CH(CH 3 )-(CH 2 ) n- -CH=CH-CO 2 R 2 (where n is an integer from 1 to 40 and R 2is a bond to -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), (iv) -CH(CH 3 )-(CH 2 ) n -CH(OH)-CH-CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), (v) -CH(CH 3 )-(CH 2 ) n -C(O)-CH-CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), (vi)-(CH 2 ) n -CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20a bond to a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or another ascarylose molecule, or a linkage via a carbon-containing linker moiety), (vii) -(CH 2 ) n -CH=CH-CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), (viii) -(CH 2 ) n -CH(OH)-CH-CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), or (ix) -(CH 2 ) n -C(O)-CH-CO 2 R 2 (n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety).

[0062] In certain embodiments, Z is (x) -CH(CH 3 )-(CH 2 ) n -CON(R 3 ) 2 (where n is an integer from 1 to 40, and each R 3 is independently -H, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), (xi) -CH(CH 3 )-(CH 2 ) n -CH=CH-CON(R 3 ) 2 (where n is an integer from 1 to 40, and each R 3 is independently -H, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), (xii) -CH(CH 3 )-(CH 2 ) n -CH(OH)-CH-CON(R 3 ) 2 (wherein n is an integer from 1 to 40, and each R 3 is independently -H, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), (xiii) -CH(CH 3)-(CH 2 ) n -C(O)-CH-CON(R 3 ) 2 (n is an integer from 1 to 40, and each R 3 is independently -H, a C 1-20 aliphatic group optionally substituted, a C 1-20 heteroaliphatic group optionally substituted, an aromatic group optionally substituted, a heteroaryl group optionally substituted, a polymer chain, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), (xiv) -(CH 2 ) n -CON(R 3 ) 2 (n is an integer from 1 to 40, and each 3 is independently -H, a C 1-20 aliphatic group optionally substituted, a C 1-20 heteroaliphatic group optionally substituted, an aromatic group optionally substituted, a heteroaryl group optionally substituted, a polymer chain, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), (xv)-(CH 2 ) n -CH=CH-CON(R 3 ) 2 (n is an integer from 1 to 40, and each R 3 is independently -H, a C 1-20 aliphatic group optionally substituted, a C 1-20 heteroaliphatic group optionally substituted, an aromatic group optionally substituted, a heteroaryl group optionally substituted, a polymer chain, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), (xvi)-(CH 2 ) n -CH(OH)-CH-CON(R 3 ) 2 (n is an integer from 1 to 40, and each R 3 is independently -H, a C 1-20an aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or a bond to or linkage via a carbon-containing linker moiety to another ascarylose molecule), or (x)-(CH 2 ) n -C(O)-CH-CON(R 3 ) 2 (n is an integer from 1 to 40, and each R 3 is independently -H, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or a bond to or linkage via a carbon-containing linker moiety to another ascarylose molecule).

[0063] In certain embodiments, R a is -H.

[0064] In certain embodiments, R b is -H.

[0065] In certain embodiments, a and R b are the same. In certain embodiments, R a and R b are both -H.

[0066] In certain embodiments, R a and R b are different. In certain embodiments, R a is -H and R b is other than -H. In certain embodiments, R a is other than -H and R b is -H. In certain embodiments, R a is -H and R b is p-hydroxybenzoate. In certain embodiments, R ais -H, and R b is indole-3-carboxylate. In certain embodiments, R a is -H, and R b is (E)-2-methyl-2-butenoate. In certain embodiments, R a is -H, and R b is picolinate. In certain embodiments, R a is -H, and R b is nicotinate. In certain embodiments, R a is -H, and R b is (R)-2-hydroxy-2-((4-hydroxyphenyl)ethyl)amino)-4-oxobutanoate. In certain embodiments, R a is -H, and R b is 4-((4-hydroxyphenylethyl)amino)-4-oxobutanoate.

[0067] In certain embodiments, R a and R b are both -H, and Z is selected from the formulas defined in (i)-(ix) above. In certain embodiments, R a and b are both -H, and Z conforms to formula (i) above. In certain embodiments, R a and R b are both -H, and Z conforms to formula (ii) above. In certain embodiments, R a and R b are both -H, and Z complies with formula (iii) above. In certain embodiments, R a and R b are both -H, and Z complies with formula (iv) above. In certain embodiments, R a and R b are both -H, and Z complies with formula (v) above. In certain embodiments, R a and R b are both -H, and Z complies with formula (vi) above. In certain embodiments, R a and R bBoth are -H, and Z conforms to the above formula (vii). In certain embodiments, R a and R b Both are -H, and Z conforms to the above formula (viii). In certain embodiments, R a and R b Both are -H, and Z conforms to the above formula (ix). In certain embodiments, R a and R b Both are -H, and Z conforms to the above formula (x). In certain embodiments, R a and R b Both are -H, and Z conforms to the above formula (xi). In certain embodiments, R a and R b Both are -H, and Z conforms to the above formula (xii). In certain embodiments, R a and R b Both are -H, and Z conforms to the above formula (xiii). In certain embodiments, R a and R b Both are -H, and Z conforms to the above formula (xiv). In certain embodiments, R a and R b Both are -H, and Z conforms to the above formula (xv). In certain embodiments, R a and R b Both are -H, and Z conforms to the above formula (xvi). In certain embodiments, R a and R b Both are -H, and Z conforms to the above formula (xvii).

[0068] In certain embodiments, R 2 is -H. In certain embodiments, R 2 is a metal cation. In certain embodiments, R 2 is an organic cation (e.g., a nitrogen- or phosphorus-centered cationic group). In certain embodiments, R 2 is an optionally substituted C 1-20 aliphatic group. In certain embodiments, R 2 is an optionally substituted C 1-12It is an aliphatic group. In certain embodiments, R 2 is an optionally substituted C 1-8 aliphatic group. In certain embodiments, R 2 is an optionally substituted C 1-6 aliphatic group. In certain embodiments, R 2 is selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, and t-butyl. In certain embodiments, R 2 is an optionally substituted aromatic group. In certain embodiments, R 2 is a glycoside. In certain embodiments, R 2 contains an amino acid. In certain embodiments, R 2 contains a peptide. In certain embodiments, R 2 contains a nucleotide.

[0069] In certain embodiments, at least one R 3 is -H. In certain embodiments, both R 3 groups are -H. In certain embodiments, at least one R 3 is an optionally substituted C 1-20 aliphatic group. In certain embodiments, both R 3 groups may be the same or different, and are optionally substituted C 1-20 aliphatic groups. In certain embodiments, at least one R 3 is an optionally substituted C 1-12 aliphatic group. In certain embodiments, at least one R 3 is an optionally substituted C 1-8 aliphatic group. In certain embodiments, at least one R 3 is an optionally substituted C 1-6 aliphatic group. In certain embodiments, at least one R 3 is selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, and t-butyl. In certain embodiments, at least one R 3 is -CH 2 CH 2is OH. In certain embodiments, at least one R 3 is -CH 2 CH 2 OR 2 . R 2 is as defined in the genera and subgenera herein. In certain embodiments, at least one R 3 is an optionally substituted aromatic group. In certain embodiments, at least one R 3 contains a glycoside. In certain embodiments, at least one R 3 contains an amino acid. In certain embodiments, at least one R 3 contains a peptide. In certain embodiments, at least one R 3 contains a nucleotide.

[0070] In certain embodiments, the ascarioside is

Chemical Structure

[0071] , selected from the group consisting of, wherein x is an integer from 1 to 22, and each of R a , R b , and R 2 is as defined above and as defined in the genera and subgenera herein.

[0072] In certain embodiments, the ascarioside is

Chemical Structure

[0073] In certain embodiments, the ascarioside is

Chemical Structure

[0074] In certain embodiments, the ascaloside is [Chemical formula] selected from the group consisting of, wherein y, R a , and R b each is as defined in the genus and subgenus described above and in this specification.

[0075] In certain embodiments, the ascaloside is

[0076] [Chemical formula] selected from the group consisting of, wherein x is an integer from 1 to 22, and R 2 is as defined in the genus and subgenus described above and in this specification.

[0077] In certain embodiments, the ascaloside is [Chemical formula] selected from the group consisting of, wherein x is as defined in the genus and subgenus described above and in this specification.

[0078] In certain embodiments, the ascaloside is [Chemical formula] selected from the group consisting of, wherein y is an integer from 1 to 20, and R 2 is as defined in the genus and subgenus described above and in this specification.

[0079] In certain embodiments, the ascaloside is [Chemical formula] selected from the group consisting of, wherein y is as defined in the genera and subgenera described above and herein.

[0080] In certain embodiments, the ascaloside is

Chemical formula

[0081] In certain embodiments, the ascaloside is

Chemical formula

[0082] In certain embodiments, the ascaloside is

Chemical formula

[0083] In certain embodiments, the ascaloside is

Chemical formula

[0084] In one embodiment, the ascaloside useful in the context of the present disclosure has the general structure (I), wherein Z is -CH(CH3 )-(CH 2 ) n -CO 2 R 2 wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide, or a nucleotide, and can be used to inhibit the growth of human pathogenic bacteria in or on plants.

[0085] In one embodiment, the ascaryloside useful in the context of the present disclosure has the general structure (I), wherein Z is -CH(CH 3 )-(CH 2 ) n -CH=CH-CO 2 R 2 wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide, or a nucleotide.

[0086] In one embodiment, the ascaryloside useful in the context of the present invention has the general structure (I), wherein Z is -CH(CH 3 )-(CH 2 ) n- CO 2 R 2 wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide, or a nucleotide, and can be used to inhibit the growth of pathogenic bacteria in or on plants.

[0087] In one embodiment, the ascaryloside useful in the context of the present invention has the general structure (I), wherein Z is -CH(CH 3 )-(CH 2 ) n -CH=CH-CO 2 R 2where n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide, or a nucleotide.

[0088] Specific ascaryosides useful in the present invention include, but are not limited to, ascr#7 and ascr#18.

Chemical formula

[0089] In certain embodiments, the ascaryoside used in the provided salts, compositions, and / or methods is selected from the group consisting of ascr#9, ascr#12, ascr#14, ascr#1, ascr#10, ascr#16, ascr#18, ascr#20, ascr#22, ascr#24, ascr#26, ascr#28, ascr#30, ascr#32, ascr#34, and ascr#36. In certain embodiments, the ascaryoside used in the provided salts, compositions, and / or methods is selected from the group consisting of ascr#10, ascr#16, ascr#18, ascr#20, ascr#22, and ascr#24. In certain embodiments, the ascaryoside used in the provided method is selected from the group consisting of ascr#9, ascr#14, ascr#10, and ascr#18.

[0090] In certain embodiments, the ascaryosides used in the provided salts, compositions, and / or methods are selected from the group consisting of ascr#5, oscr#9, oscr#12, oscr#1, oscr#14, oscr#10, oscr#16, oscr#18, oscr#20, oscr#22, oscr#24, oscr#26, oscr#28, oscr#30, oscr#32, oscr#34, and oscr#36. In certain embodiments, the ascaryosides used in the provided salts, compositions, and / or methods are selected from the group consisting of oscr#10, oscr#16, oscr#18, oscr#20, and oscr#22. In certain embodiments, the ascaryosides used in the provided salts, compositions, and / or methods are selected from the group consisting of bhas#5, oscr#9, oscr#12, oscr#1, oscr#14, oscr#10, oscr#16, oscr#18, oscr#20, oscr#22, oscr#24, oscr#26, oscr#28, oscr#30, oscr#32, oscr#34, and oscr#36. In certain embodiments, the ascaryosides used in the provided salts, compositions, and / or methods are selected from the group consisting of oscr#10, oscr#16, oscr#18, oscr#20, and oscr#22.

[0091] In certain embodiments, the ascaryosides used in the provided salts, compositions, and / or methods are selected from the group consisting of bhas#9, bhas#10, bhas#16, bhas#18, bhas#22, bhas#24, bhas#26, bhas#28, bhas#30, bhas#32, bhas#34, bhas#36, bhas#38, bhas#40, and bhas#42.

[0092] In certain embodiments, the ascarylosides used in the provided salts, compositions, and / or methods are selected from the group consisting of bhos#10, bhos#16, bhos#18, bhos#22, bhos#24, bhos#26, bhos#28, bhos#30, bhos#32, bhos#34, bhos#36, bhos#38, bhos#40, and bhos#42.

[0093] In certain embodiments, the ascarylosides used in the provided salts, compositions, and / or methods are selected from the group consisting of ascr#18, oscr#16, oscr#17, oscr#15, bhas#18, bhos#16, glas#18, dhas#18, ibha#18, ibho#16, icas#18, icos#15, icos#16, and any combination of two or more thereof.

[0094] Ascarylosides can be obtained from natural sources (e.g., nematodes) or can be prepared synthetically. Ascarylosides can be prepared synthetically, for example, by converting 1-O-substituted rhamnose to 1-O-substituted ascarylose. Exemplary methods of preparing ascarylosides include providing 1-O-substituted rhamnose as a starting material, forming a monosulfonate ester at the 3-OH group of the starting material, and treating the monosulfonate ester with a hydride source to form 1-O-substituted ascarylose. In certain embodiments, the formation of the monosulfonate ester is performed on a substrate that does not contain a hydroxyl protecting group at the 2- or 4-position of the rhamnose starting material. In certain embodiments, such methods include contacting the starting material with a sulfonating agent (i.e., a sulfonyl halide, sulfonic anhydride, or similar reagent) in the presence of a Lewis acid. Specific details regarding the synthesis of 1-O-substituted ascarylose can be found in PCT Application No. PCT / IB2021 / 056981, which is incorporated herein by reference.

[0095] As described above, the present disclosure provides ascaryosides in salt form. Ascaryoside salts can be formed with suitable reagents, e.g., any suitable acidic or basic functional groups on the ascaryoside molecule.

[0096] For example, in some embodiments, carboxylic acid salts (also referred to as carboxylate salts) are provided. Such salts can be described according to Formula II below, where "M" is a metal (or other cation), and "A" is the remainder of the ascaryoside molecule to which the carboxylic acid moiety is attached (e.g., the structure according to Formula I provided above herein). [A-(C(O)O) - p M p+ (Formula II), p represents an integer from 1 to 4. In some embodiments, p is 1, and the salt contains one ascaryoside anion and one "M" cation (having a +1 charge). In some embodiments, p is 2, and the salt contains two ascaryoside anions and one "M" cation (having a +2 charge). In some embodiments, p is 3, and the salt contains three ascaryoside anions and one "M" cation (having a +3 charge). In some embodiments, p is 4, and the salt contains four ascaryoside anions and one "M" cation (having a +4 charge). In embodiments where p is greater than 1, the ascaryoside anions present in the salt may be the same or different.

[0097] Referring to the structure of the ascaryoside of Formula I above, it should be noted that the carboxylic acid salt can be formed, for example, with the "OR a " and / or "OR b " substituents of the tetrahydropyranyl ring. In some embodiments, the carboxylic acid can be formed with the OR a and / or OR b substituents, where R a and / or R b is -L-C(O)OR c ​and L is a divalent linker containing one or more carbon atoms and optionally containing one or more heteroatoms and optionally substituted, R c is H. In some embodiments, the carboxylic acid is OR a and / or OR b substituents, and R a and / or R b is a sugar moiety containing a carboxylic acid group (e.g., a sugar acid). In some embodiments, the carboxylic acid is OR a and / or OR b substituents, and R a and / or R b is a peptide containing a carboxylic acid group. In some embodiments, the carboxylic acid is OR a and / or OR b substituents, and R a and / or R b is a polymer containing a carboxylic acid group. In some embodiments, the carboxylic acid is OR a and / or OR b substituents, and R c is a polymer chain containing a carboxylic acid group. In some embodiments, the carboxylic acid is OR a and / or OR b substituents, and R a and / or R b is a monoester of a dibasic acid. In certain embodiments, such compounds are derived from the reaction of a compound in which R a and / or R b is -H with a cyclic acid anhydride such as phthalic anhydride, succinic anhydride, maleic anhydride, or glutaric anhydride, or a substituted analog thereof. Representative examples of such ascarylose anions are shown below.

Chemical formula

[0098] Referring again to the structure of the ascaryloside of formula I above, it should be noted that the carboxylic acid can be formed, for example, by the OZ substituent of the tetrahydropyranyl ring. In some embodiments, the carboxylic acid is, for example, where Z is -CH(CH 3 )-(CH 2 ) n- CO 2 R 2 ,-CH(CH 3 )-(CH 2 ) n- CH=CH-CO 2 R 2 ,-CH(CH 3 )-(CH 2 ) n- CH(OH)-CH-CO 2 R 2 ,-CH(CH 3 )-(CH 2 ) n- C(O)-CH-CO 2 R 2 ,-(CH 2 ) n- CO 2 R 2 ,-(CH 2 ) n- CH=CH-CO 2 R 2 , and -(CH 2 ) n- CH(OH)-CH-CO 2 R 2 selected from, n is an integer from 1 to 40, and R 2 is -H or a C 1-20 aliphatic group optionally substituted, an aromatic group optionally substituted, a glycoside, an amino acid, a peptide, or a nucleotide containing a carboxylic acid group, and can be formed by the OZ substituent.

[0099] In certain embodiments, the linker group -L- comprises a C 1-20 aliphatic, C 1-20 heteroaliphatic, aryl, or heteroaryl optionally substituted. Such linkers include ether bonds, ester bonds, carbonate bonds, carbamate bonds (e.g., A-OC(O)NR 3-), a thioester bond (e.g., A-OC(S)-), a thiocarbamate bond (e.g., A-OC(S)NR 3 -), a thiocarbonate bond (e.g., A-OC(S)O-), a dithiocarbonate bond (thiocarbonate bond (e.g., A-OC(S)S-), a sulfonate ester bond (e.g., A-OSO 2 -), or through a bond via a phosphorus atom, can be bonded to an oxygen atom on the ascarylose molecule.

[0100] In one embodiment, the salt of ascr#18 is provided, for example, according to the following formula.

Chemical formula

[0101] The present disclosure is not limited to the carboxylate salts of ascarylosides. Salts that can be formed together with other functional groups on the ascarylose molecule are also included in the present disclosure. For example, when the ascaryloside contains an amine group (e.g., R a 、R b 、or within the Z substituent), the ammonium salt can be formed with a suitable anionic group. Further, in some embodiments where the ascaryloside contains a hydroxyl (-OH) group, a specific M group can coordinate with it to form a salt, such as a borate or silicate derivative of the ascaryloside.

[0102] Non-limiting representative metal salts of ascarylosides formed through the carboxylic acid group of the side chain are shown below.

Chemical formula

[0103] Representative "ate" salts of ascarylosides formed through the hydroxy group of ascarylose sugar are shown below. [Chemical] In the formula, x is as defined in the genera and subgenera described above and in this specification.

[0104] The composition of "M" (e.g., as shown in Formulas II and IIb above) can vary widely. In some embodiments, M is a metal. Suitable metals are not particularly limited and, in various embodiments, are selected from alkali / group 1 metals, alkaline earth / group 2 metals, and transition metals. In some embodiments, M is a metalloid or nonmetal selected from main group elements. In some embodiments, M is an organic cation such as ammonium, guanidinium, amidinium, pyridinium, phosphonium, sulfonium, or any similar nitrogen, phosphorus, or sulfur-centered cation or analog thereof.

[0105] In some embodiments, M comprises a plant micronutrient or macronutrient. Plant micronutrients and macronutrients include, but are not limited to, nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), boron (B), silicon (Si), zinc (Zn), manganese (Mn), iron (Fe), copper (Cu), molybdenum (Mo), and nickel (Ni). Those skilled in the art will understand that not all such micronutrients and macronutrients can form salts with ascarioside in the same way.

[0106] For example, salts of plant nutrients such as potassium, calcium, magnesium, zinc, manganese, iron, copper, molybdenum, and nickel can, in some embodiments, be formed with the carboxylic acid on ascarioside (e.g., according to Formula II or IIb above). Nitrogen is the ammonium or guanidinium salt of ascarioside (e.g., M is NH 4 + or H 2 N + =C(NH 2 ) 2 or the ammonium or guanidinium analog salt of ascarioside (e.g., NH 4+ or H 2 N + =C(NH 2 ) 2 One or more of the H atoms of can be provided in the form of being replaced by an alkyl group). Although plant nutrients such as boron, silicon, and molybdenum may not easily form salts with carboxylic acids, for example, in the form of borate, silicate, or molybdate, they can coordinate with the free OH present on the ascarylose molecule to form suitable salts. Thus, in some embodiments, salts containing at least one boron atom coordinated to ascarylose, salts containing at least one silicon atom coordinated to ascarylose, or salts containing at least one molybdenum atom coordinated to ascarylose are provided.

[0107] The salts provided herein can be prepared by adapting conventional methods known in the art. For example, salts are often the result of the reaction of an acid and a base. Thus, the ascarylose salts provided above in Formula II or IIb can be, for example, one or more ascarylose molecules (the number of molecules corresponding to the number "p", i.e., equivalent to the charge of "M" (e.g., a metal or ammonium cation)) in solution with M at a pH sufficient to obtain the desired salt. p+ It can be prepared by combining with. In other embodiments, the salt can be produced by metathesis, and the cation and / or anion in the first salt is replaced with a different cation or anion in the second salt.

[0108] The ascarylose salts disclosed herein can, in some embodiments, exhibit enhanced physical properties compared to the corresponding ascarylose molecules. For example, in some embodiments, the ascarylose salt can exhibit higher solubility in a particular solvent (e.g., water) than the corresponding ascarylose, thus simplifying the preparation of a particular formulation. In some embodiments, providing ascarylose in the form of a salt (rather than in its neutral / free acid or base form) makes it more compatible with a particular component of the desired composition, and thus stabilizes the resulting ascarylose-containing composition.

[0109] In some embodiments, for example, when M is a plant micronutrient or macronutrient, the ascarioside salts provided herein provide advantages beyond those of the formulation, such as providing nutrients to the plant to which it is applied (or in the vicinity thereof). Thus, in some embodiments, the salts provided herein may be referred to as ascarioside-based micronutrients or ascarioside-based macronutrients. In some embodiments, the salts described herein have improved application properties (e.g., enhanced ability to wet or adhere to surfaces such as leaves or skin), enhanced bioavailability, and / or enhanced uptake (e.g., by animals such as plants, microorganisms, or mammals).

[0110] In certain embodiments, the ascarioside salts and ascarioside salt-containing compositions provided herein include "multifunctional" products. In addition to the provision of the nutrients described above, in certain embodiments, such multifunctional products combine ascariosides with molecules having other different or complementary biological activities. In certain embodiments, such multifunctional products include salts formed from cations of molecules having biological activity as pesticides (e.g., insecticides, fungicides, herbicides, acaricides, nematicides), as antibacterial agents (e.g., antibiotics, antifungal agents, etc.), as antiviral agents, as signaling molecules (e.g., pheromones, hormones, etc.), or as vitamins or nutrients, and anions of ascariosides. Such multifunctional products can avoid the need for multiple applications (e.g., drug or agricultural treatments), thereby saving costs and / or simplifying treatment methods.

[0111] In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic pesticide molecules. In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic insecticide molecules. In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic herbicide molecules. In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic fungicide molecules. In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic antibacterial molecules. The identification (and provision or synthesis) of suitable bioactive cationic molecules is within the purview of those skilled in the art, such that the formation of such salts using simple acid-base chemistry or ion metathesis techniques.

[0112] In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic signaling molecules. In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic plant hormones. In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic pheromones.

[0113] In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic therapeutic molecules. In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic vitamins. In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic pharmaceuticals. In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic hormones. In certain embodiments, the salts or compositions provided herein comprise salts of ascarylose anions and cationic vitamins.

[0114] In certain embodiments, the ascaloside salts described herein can be used for the treatment of living plants, the soil surrounding the plants, or the soil in which seeds / seedlings are planted. In some embodiments, the ascaloside salt (or a composition containing such ascaloside salt) is applied to one or more of a part of the plant, such as roots, stems, leaves, seeds, and / or flowers. Such methods can be carried out at any one or more stages of the plant life cycle, for example, from seeds, seedlings, to immediately before harvesting of the growing plants.

[0115] In certain embodiments where the provided ascaloside salt incorporates a second bioactive molecule, the second bioactive molecule may be an anion, and the composition may comprise a mixed salt in which the ascaloside and the second bioactive anion molecule share a common cation. In certain embodiments, such a mixed salt may comprise a polycation capable of forming a salt simultaneously with the ascaloside and the second bioactive anion molecule. In certain embodiments, such a mixed salt may comprise a common monocationic species or a mixture of monocations that balances the anionic charges of both the ascaloside and the second bioactive anion molecule.

[0116] The disclosed treatment methods can, in some embodiments, protect growing plants by the method described in U.S. Patent No. 10,136,595, which is hereby incorporated by reference in its entirety. For example, such methods can enhance pathogen resistance and / or induce one or more plant defense responses (thereby inhibiting pathogen growth and / or parasitism) in plants to which an ascaloside salt (or a composition containing such an ascaloside) is applied (or near which it is applied). Pathogens against which the methods of the present disclosure can promote resistance include, but are not limited to, oomycetes, bacteria, nematodes, viruses, and insects, such as, for example, Pseudomonas syringae, Phytophthora infestans, Blumeria graminis, Heterodera schachtii, Meloidogyne incognita, Meloidogyne hapla, and turnip crinkle virus.

[0117] The disclosed treatment methods can, in some embodiments, protect plants or plant-based products from contamination by pathogens, or prevent or delay the onset of plant spoilage, or be manufactured by the methods described in Patent Applications PCT / US22 / 81895 and PCT / US23 / 17947, each of which is hereby incorporated by reference in its entirety.

[0118] The exact method by which the plant or soil is treated with the ascaloside salt or ascaloside salt-containing composition is not particularly limited. Treatment of plants and / or soil according to the present disclosure can be carried out, for example, by dipping, spraying, evaporation, atomization, spreading, coating, side application, or in-furrow application. For example, in certain embodiments, a suitable liquid composition can be sprayed onto the plant or soil, a solid plastic multi-composition can be applied to the soil around the plant, and / or a granular composition can be provided for in-furrow application or side application.

[0119] The types of plants that can be treated according to the method of the present disclosure are not particularly limited and can be, for example, fruit and vegetable plants, trees, and shrubs. Non-limiting examples of plants that can be treated according to the disclosed method include tobacco, Arabidopsis thaliana, tomato, barley, potato, sweet potato, yam, cotton, soybean, strawberry, sugarcane, sugar beet, corn, rice, wheat, rye, oats, sorghum, millet, legume, pea, apple, banana, European pear, cherry, peach, plum, apricot, almond, grape, kiwi, mango, melon, papaya, walnut, hazelnut, pistachio, raspberry, blackberry, loganberry, blueberry, cranberry, orange, lemon, grapefruit, tangerine, lettuce, carrot, onion, broccoli, cabbage, avocado, cocoa, cassava, cotton, and hemp, but are not limited thereto.

[0120] In the method provided herein, the ascaloside salt can be applied directly to the plant and / or soil or formulated into a composition that can be applied to the plant and / or soil. Accordingly, the present disclosure generally provides a composition comprising at least one ascaloside salt and one or more inert ingredients, such as one or more agriculturally acceptable carriers. In the method of the present disclosure, it is preferred that a non-toxic carrier be used.

[0121] The term "agronomically acceptable carrier" includes any carrier suitable for administration to plants or soil, such as solutions (e.g., directly sprayable or dilutable solutions), emulsions (e.g., emulsion concentrates and diluted emulsions), wettable powders, suspensions, soluble powders, powders, dusts, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, encapsulation in polymeric materials, coatable pastes, natural and synthetic materials impregnated with the active compound / salt, and those used to form microencapsulation in polymeric substances, etc., including conventional excipients in formulation technology. These compositions can be prepared in known ways, for example, by mixing an ascaroside salt(s) with one or more agronomically acceptable carriers such as a liquid solvent or a solid carrier, and optionally using additional components including surfactants (including emulsifiers), dispersants, foam formers, colorants, processing aids, lubricants, fillers, strengthening agents, flame retardants, light stabilizers, UV absorbers, weathering stabilizers, plasticizers, release agents, fragrances, heat retention additives (e.g., silica), crosslinking agents, antioxidants, defoamers, buffers, pH adjusters, compatibilizers, drift control additives, bulking agents / stickers, tackifiers, plant penetrants, toxicity moderators, spreading agents, wetting agents, etc., but not limited to these.

[0122] In some embodiments, the ascaroside salt is the only active agent in the composition. In some embodiments, the composition includes one or more additional ascarosides (e.g., another salt form or non-salt form). In some embodiments, one or more other active agents are included in the composition (e.g., one or more pesticides (e.g., insecticides, fungicides, herbicides, acaricides, nematicides), antibacterial agents (e.g., antibiotics, antifungal agents, etc.), antiviral agents, signaling molecules (e.g., pheromones, hormones, etc.), vitamins, nutrients, or fertilizers, etc.). The ascaroside salt-containing compositions provided herein can be in various forms including solid and liquid forms.

[0123] When the agriculturally acceptable carrier is water, in some embodiments, the organic solvent can optionally be incorporated as an auxiliary liquid solvent. Suitable liquid solvents include, for example, aromatic compounds (e.g., xylene, toluene, and alkylnaphthalene), chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons (e.g., chlorobenzene, chloroethylene, and methylene chloride), aliphatic hydrocarbons (e.g., cyclohexane), paraffins (e.g., petroleum fractions, mineral and vegetable oils), alcohols (e.g., ethanol, butanol, or glycols and their ethers and esters including propylene glycol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone), and strongly polar solvents (e.g., dimethylformamide and dimethyl sulfoxide).

[0124] Suitable solid agriculturally acceptable carriers include, for example, ammonium salts and ground natural minerals (e.g., kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, and diatomaceous earth), ground synthetic minerals (e.g., highly dispersed silica, alumina, and silicates), ground and fractionated natural rocks (e.g., calcite, marble, pumice, sepiolite, and dolomite), synthetic granules of inorganic and organic meals, and granules of organic materials (e.g., sawdust, coconut shells, corn cobs, and tobacco stalks).

[0125] Suitable emulsifiers and foam formers include, for example, nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g., alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, and aryl sulfonates) and protein hydrolysates.

[0126] Suitable dispersants include, for example, lignin-sulfite waste liquor and methyl cellulose. Adhesion promoters such as carboxymethyl cellulose in the form of powders, granules or grids and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids can be used in the disclosed compositions. Other additives can include, for example, mineral oils and vegetable oils.

[0127] Inorganic pigments such as coloring agents like iron oxide, titanium oxide, Prussian blue, organic dyes such as alizarin dyes, azo dyes, and metal phthalocyanine dyes, and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum, and zinc can also be included in the composition.

[0128] Methods for preparing solid and liquid compositions for pesticide use are generally known and can be used in accordance with the present disclosure (such methods include incorporating one or more ascaloside salts within such compositions). Compositions according to the present disclosure can, in some embodiments, be in the form of granular materials (including dusts, pellets, soluble powders, flowable powders, water-dispersible granules, etc.). In some embodiments, the compositions according to the present disclosure can be in liquid form (e.g., solutions, suspensions, concentrates, or emulsions). In some embodiments, the composition is in the form of a granular material treated with an ascaloside salt-containing liquid. In some embodiments, a composition containing an ascaloside salt can be formed into fibers or filaments, and in some such embodiments, a fabric or non-woven fabric (e.g., a film) can be manufactured therefrom. In some embodiments, the compositions provided herein are pelletized. In some embodiments, the compositions provided herein are in the form of a film, e.g., a plastic mulch. Any of the solid compositions provided herein can, if desired, be coated via methods generally known in the art to delay the release of the ascaloside salt. See, for example, the methods and compositions for modified release disclosed in PCT / US2023 / 20472, filed Apr. 28, 2023, which is incorporated herein by reference.

[0129] The compounds (including salts), compositions, and methods of the present application are intended to encompass variations and adaptations developed using information from the embodiments described in the present disclosure. Adaptations or modifications of the methods and processes described herein can be made by those skilled in the relevant art.

[0130] It will be understood that the use of headings in the present disclosure is provided for the convenience of the reader. The presence and / or placement of headings are not intended to limit the scope of the subject matter described herein. Unless otherwise specified, embodiments located in one section of the present application apply to other embodiments throughout the present application, both alone and in combination.

[0131] Throughout the description, when a composition, compound, or product is described as having, containing, or comprising a particular component, or when a process and method are described as having, containing, or comprising a particular step, it is further contemplated that there are articles, devices, and systems of the present application that consist essentially of or consist of the recited components, and that there are processes and methods according to the present application that consist essentially of or consist of the recited treatment steps.

Examples

[0132] To better understand the present application, the following examples are described. It should be understood that these examples are for illustrative purposes only and should not be construed as limiting in any way.

[0133] Various salts of ascaroside ascr#18 were prepared and tested for their ability to protect plants from pathogen damage.

[0134] Preparation of salts: To a solution of 1 mM ascr#18 in 2.5 mL of water, an equal volume of 0.5 mM aqueous zinc acetate solution was added. The mixture was stirred for 1 hour and then evaporated under vacuum to obtain (ascr#18) 2 Zn as a white solid.

[0135] To a solution of 1 mM ascr#18 in 2.5 mL of water, an equal volume of 1 mM aqueous potassium hydroxide solution was added. The mixture was stirred for 1 hour and then evaporated under vacuum to obtain (ascr#18)K as a white solid.

[0136] To a degassed solution of 1 mM ascr#18 in 2.5 mL, an equal volume of degassed 0.5 mM iron(II) acetate was added. The mixture was stirred under nitrogen for 1 hour and then evaporated under vacuum to obtain (ascr#18) 2 Fe as a yellow-orange solid, which was stored under nitrogen until use.

[0137] To a 2.5 mL solution of 1 mM ascr#18, an equal volume of 0.5 mM nickel(II) acetate trihydrate was added. The mixture was stirred for 1 hour and then evaporated under vacuum to obtain (ascr#18) 2 Ni as a greenish solid.

[0138] To a 2.5 mL solution of 1 mM ascr#18, an equal volume of 0.5 mM manganese(II) acetate tetrahydrate was added. The mixture was stirred for 1 hour and then evaporated under vacuum to obtain (ascr#18) 2 Mn as a brown solid.

[0139] Salt test The efficacy of the zinc salt of ascr#18 was compared with free ascr#18 in a greenhouse-based plant pathogen assay. Two-week-old wheat plants were sprayed with a solution containing 1 μM ascr#18 or 1 μM zinc salt (ascr#18) 2 containing Zn. Twenty-four hours after treatment, the plants were inoculated with spores of Bipolaris sorokiniana (root rot and brown spot disease). Disease symptoms were quantified 10 days after inoculation by measuring the symptomatic area on the leaves. As shown in Figure 1, the zinc salt provided better protection against pathogen damage than unmodified ascr#18 (data are mean ± SEM (n ≧ 13). *P ≦ 0.04, two-tailed t-test).

[0140] It should be understood that, as long as the described method is operable, the order of steps or the sequence of actions for performing a particular action is not important. Furthermore, two or more steps or actions may be performed simultaneously.

[0141] All publications and patent applications mentioned herein are indicative of the level of those skilled in the art to which the invention pertains. All publications and patent applications are incorporated herein by reference to the same extent as if each individual publication or patent application had been specifically and individually indicated to be incorporated by reference.

[0142] While the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims.

Claims

1. Formula [A - (C(O)O)] － ] ｐ M ｐ＋ It is a salt of, in the formula A is the ascaloside portion, M is a metal or an organic cation. p is an integer between 1 and 3, If p is 2 or 3, each A may be the same or different, the salt.

2. The salt according to claim 1, wherein p is 1.

3. The salt according to claim 1, wherein p is 2.

4. The salt according to claim 1, wherein p is 3.

5. The salt according to claim 1, wherein M is a metal.

6. The salt according to claim 5, wherein the metal is selected from the group consisting of potassium (K), calcium (Ca), magnesium (Mg), zinc (Zn), manganese (Mn), iron (Fe), copper (Cu), molybdenum (Mo), and nickel (Ni).

7. The salt according to claim 6, wherein the metal is selected from the group consisting of copper (Cu), zinc (Zn), manganese (Mn), and iron (Fe).

8. The salt according to claim 1, wherein M is an ammonium cation or an analogue thereof.

9. A salt containing at least one boron atom coordinated to ascaloside (A).

10. A has structure (I), 【Chemistry 21】 During the ceremony, Z is replaced by C as desired. ２－４０ It is an aliphatic group, R ａ and R ｂ each independently is -H, or C １－２０ aliphatic, C １－２０ acyl, C １－２０ heteroaliphatic, aryl, heteroaryl, hydroxyl protecting group, phosphorus bonding functional group, sulfur bonding functional group, silicon bonding functional group, C ２－２０ carbonate (e.g., moiety -C(O)OR ｃ ), C ２－２０ carbamate (e.g., moiety -C(O)N(R ｃ ) ２ ), C ２－２０ thioester (e.g., moiety -C(S)R ｃ ), C ２－２０ thiocarbonate (e.g., moiety -C(S)OR ｃ ), C ２－２０ dithiocarbonate (e.g., moiety -C(S)SR ｃ ), C １－２０ thiocarbamate (e.g., moiety -C(S)N(R ｃ ) ２ ), a sugar moiety, a peptide, a polymer chain, or a optionally substituted moiety selected from the group consisting of a bond to another ascarylose molecule or a linkage through a carbon-containing linker moiety, where R ｃ is independently at each occurrence -H, optionally substituted C １－１２ aliphatic, optionally substituted C １－１２ heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, a polymer chain, or a bond to another ascarylose molecule or a linkage through a carbon-containing linker moiety, and R ａ and R ｂ together may form an optionally substituted ring optionally containing one or more heteroatoms and optionally containing one or more unsaturated sites, the salt according to claim 1.

11. Z is i. -CH(CH ３ )-R １ (R １ C is replaced as desired. １－４０ (It is an aliphatic group.) ii. -CH(CH ３ )-(CH ２ ) ｎ -CO ２ R ２ (n is an integer from 1 to 40, R ２ C is -H, a metal cation, or optionally substituted C １－２０ Aliphatic group, optionally substituted C １－２０ (This may involve bonding to a heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, glycoside, amino acid, peptide, nucleotide, or another ascaloside molecule, or linkage via a carbon-containing linker moiety.) iii. -CH(CH ３ )-(CH ２ ) ｎ -CH=CH-CO ２ R ２ (n is an integer from 1 to 40, R ２ C is -H, a metal cation, or optionally substituted C １－２０ Aliphatic group, optionally substituted C １－２０ (This may involve bonding to a heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, glycoside, amino acid, peptide, nucleotide, or another ascaloside molecule, or linkage via a carbon-containing linker moiety.) iv. -CH(CH ３ )-(CH ２ ) ｎ -CH(OH)-CH-CO ２ R ２ (n is an integer from 1 to 40, R ２ C is -H, a metal cation, or optionally substituted C １－２０ Aliphatic group, optionally substituted C １－２０ (This may involve bonding to a heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, glycoside, amino acid, peptide, nucleotide, or another ascaloside molecule, or linkage via a carbon-containing linker moiety.) v. -CH(CH ３ )-(CH ２ ) ｎ -C(O)-CH-CO ２ R ２ (n is an integer from 1 to 40, R ２ C is -H, a metal cation, or optionally substituted C １－２０ Aliphatic group, optionally substituted C １－２０ (This may involve bonding to a heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, glycoside, amino acid, peptide, nucleotide, or another ascaloside molecule, or linkage via a carbon-containing linker moiety.) vi. - (CH ２ ) ｎ -CO ２ R ２ (n is an integer from 1 to 40, R ２ C is -H, a metal cation, or optionally substituted C １－２０ Aliphatic group, optionally substituted C １－２０ (This may involve bonding to a heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, glycoside, amino acid, peptide, nucleotide, or another ascaloside molecule, or linkage via a carbon-containing linker moiety.) vii. - (CH ２ ) ｎ -CH=CH-CO ２ R ２ (n is an integer from 1 to 40, R ２ C is -H, a metal cation, or optionally substituted C １－２０ Aliphatic group, optionally substituted C １－２０ (This may involve bonding to a heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, glycoside, amino acid, peptide, nucleotide, or another ascaloside molecule, or linkage via a carbon-containing linker moiety.) viiii. - (CH ２ ) ｎ -CH(OH)-CH-CO ２ R ２ (n is an integer from 1 to 40, R ２ C is -H, a metal cation, or optionally substituted C １－２０ Aliphatic group, optionally substituted C １－２０ (This includes heteroaliphatic groups, optionally substituted aromatic groups, optionally substituted heteroaryl groups, glycosides, amino acids, peptides, nucleotides, or linkage to other ascaloside molecules via carbon-containing linker moieties), and ix. -(CH ２ ) ｎ -C(O)-CH-CO ２ R ２ (n is an integer from 1 to 40, and R ２ is -H, a metal cation, an optionally substituted C １－２０ aliphatic group, an optionally substituted C １－２０ heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or a bond to another ascarylose molecule or a linkage via a carbon-containing linker moiety), the salt according to claim 10, selected from the group consisting of

12. Z is, x. -CH(CH3)-(CH2)n -CON(R3)2 (where n is an integer from 1 to 40, and each R3 is independently -H, optionally substituted C1-20 aliphatic group, optionally substituted C1-20 heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, polymer chain, amino acid, peptide, nucleotide, or linkage to another ascaloside molecule via a carbon-containing linker moiety). xi. -CH(CH3)-(CH2)n -CH=CH-CON(R3)2 (where n is an integer from 1 to 40, and each R3 is independently -H, optionally substituted C1-20 aliphatic group, optionally substituted C1-20 heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, polymer chain, amino acid, peptide, nucleotide, or linkage to another ascaloside molecule via a carbon-containing linker moiety). xi. -CH(CH3)-(CH2)n -CH(OH)-CH-CON(R3)2 (where n is an integer from 1 to 40, and each R3 is independently -H, optionally substituted C1-20 aliphatic group, optionally substituted C1-20 heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, polymer chain, amino acid, peptide, nucleotide, or linkage to another ascaloside molecule via a carbon-containing linker moiety). xiiii. -CH(CH3)-(CH2)n -C(O)-CH-CON(R3)2 (where n is an integer from 1 to 40, and each R3 is independently -H, optionally substituted C1-20 aliphatic group, optionally substituted C1-20 heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, polymer chain, amino acid, peptide, nucleotide, or linkage to another ascaloside molecule via a carbon-containing linker moiety). xiv. -(CH2)n-CON(R3)2 (where n is an integer from 1 to 40, and each R3 is independently -H, optionally substituted C1-20 aliphatic group, optionally substituted C1-20 heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, polymer chain, amino acid, peptide, nucleotide, or linkage to another ascaloside molecule via a carbon-containing linker moiety). xv. -(CH2)n -CH=CH-CON(R3)2 (where n is an integer from 1 to 40, and each R3 is independently -H, optionally substituted C1-20 aliphatic group, optionally substituted C1-20 heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, polymer chain, amino acid, peptide, nucleotide, or linkage to another ascaloside molecule via a carbon-containing linker moiety). xvi. -(CH2)n-CH(OH)-CH-CON(R3)2 (where n is an integer from 1 to 40, and each R3 is independently -H, optionally substituted C1-20 aliphatic group, optionally substituted C1-20 heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, polymer chain, amino acid, peptide, nucleotide, or linkage to another ascaloside molecule via a carbon-containing linker moiety), and xvii. The salt according to claim 10, wherein n is an integer from 1 to 40, and each R3 is independently selected from the group consisting of -H, optionally substituted C1-20 aliphatic group, optionally substituted C1-20 heteroaliphatic group, optionally substituted aromatic group, optionally substituted heteroaryl group, polymer chain, amino acid, peptide, nucleotide, or linkage to another ascaloside molecule via a carbon-containing linker moiety.

13. R ａ and R ｂ The salt according to claim 10, wherein each of them is -H.

14. A is, 【Chemistry 4】 Having a structure selected from the group consisting of, The salt according to claim 10, wherein x is an integer from 1 to 22.

15. Z is -CH(CH ３ )-(CH ２ ) ｎ -CO ２ R ２ where n is an integer from 1 to 40 and R ２ is -H, a metal cation, an optionally substituted C １－２０ aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide, or a nucleotide, the salt according to claim 10.

16. The salt according to claim 1, wherein A is ascr#18.

17. A is, 【Transformation 6】 Having a structure selected from the group consisting of, The salt according to claim 10, wherein y is an integer from 1 to 20.

18. The salt according to claim 10, wherein Z is -CH(CH3)-(CH2)n -CH=CH-CO2 R2, n is an integer from 1 to 40, and R2 is -H, a metal cation, optionally a substituted C1-20 aliphatic group, optionally a substituted aromatic group, a glycoside, an amino acid, a peptide, or a nucleotide.

19. The salt according to claim 1, wherein A is ascr#7.

20. The salt according to claim 10, wherein Z is -(CH₂)n-CO₂R₂, n is an integer from 1 to 40, and R₂ is -H, a metal cation, optionally a substituted C1-20 aliphatic group, optionally a substituted aromatic group, a glycoside, an amino acid, a peptide, or a nucleotide.

21. The salt according to claim 1, wherein A is selected from the group consisting of oscr#10, oscr#16, oscr#18, oscr#20, and oscr#22.

22. The salt of the following formula, 【Chemistry 22】 In the formula, M is a metal or an ammonium cation. The salt wherein p is an integer between 1 and 3.

23. The salt according to claim 22, wherein M is zinc (Zn).

24. A composition comprising the salt described in any one of claims 1 to 23.

25. The composition according to claim 24, in solid form.

26. The composition according to claim 25, wherein the solid form includes powder or granules.

27. The composition according to claim 24, in liquid form.

28. The composition according to claim 27, wherein the liquid form is a sprayable formulation.

29. The composition according to claim 24, further comprising one or more additional components selected from the group consisting of surfactants including emulsifiers, dispersants, foaming agents, colorants, processing aids, lubricants, fillers, reinforcing agents, flame retardants, light stabilizers, ultraviolet absorbers, weather stabilizers, plasticizers, release agents, fragrances, heat retention additives (e.g., silica), crosslinking agents, antioxidants, defoaming agents, buffers, pH adjusters, compatibility agents, drift control additives, bulking agents / tackeners, tackifiers, plant penetration agents, toxicity mitigators, spreading agents, and wetting agents.

30. A method for enhancing the physical properties of ascaloside and providing one or more nutrients to a plant, comprising contacting the plant or a part thereof, or the soil surrounding the plant or a part thereof, with the salt described in any one of claims 1 to 23.

31. The method according to claim 30, wherein the part is selected from the group consisting of roots, stems, leaves, seeds, and flowers.

32. The method according to claim 31, wherein the plant is a vegetable or fruit plant.

33. A method for enhancing the physical properties of ascaloside and providing one or more nutrients to a plant, comprising bringing a plant or a part thereof, or the soil surrounding the plant or a part thereof, into contact with the composition described in Claim 24.

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