Field of the Invention

[0001] The present invention relates to compounds and compositions comprising said compounds, which may have agrichemical activity such as herbicides, insecticides, fungicides and plant growth regulators; and to methods for the use of said compounds. The agrichemical compounds of the present invention may have beneficial volatility properties that reduce the extent of drift of the compounds from target areas to non-target areas.

[0002] In one form, the present invention relates to compounds having herbicidal activity, and methods for the use of said compounds for controlling the growth of auxin-susceptible plants.

Background Art

[0003] An extensive range of chemicals are used in agriculture. For example, the protection of crops from pests that impact crop yields is a recurring problem in agriculture. Researchers have produced an extensive variety of pesticides and pesticidal formulations effective in the control of such pests. As a further example, plant growth regulators such as daminozide are used to modify growth and ripening behaviours to optimise harvests.

[0004] However, many such agrichemicals are volatile and suffer from drift. Localised application of agrichemical compounds is highly desirable. For example, unintentional application of herbicides to a sensitive plant generally causes severe injury, loss of yield, and even death of the non-target plants, and unintentional application of insecticides and fungicides are associated with undesirable environmental impact.

[0005] For example, the protection of crops from weeds that inhibit crop growth is a recurring problem in agriculture. Researchers have produced an extensive variety of herbicides and herbicidal formulations effective in the control of such unwanted weeds.

[0006] Synthetic auxin herbicides are one such class of herbicides. Auxin herbicides kill auxin-susceptible plants by inducing hormonal effects that promote unsustainable growth. Dicamba (3,6-dichloro-2-methoxybenzoic acid) is an auxin herbicide. Dicamba has been in use since the 1960s. However, it was traditionally used sparingly, and not on some growing crops as they were susceptible to damage and additionally the free-acid form of dicamba is volatile and suffers from drift.

[0007] The term drift can be used to describe two distinct phenomena. Spray drift is the movement of pesticide dust or droplets through the air at the time of application or soon thereafter, to any site other than the area intended. The term drift is also used to describe post-application movement arising from volatilisation of the active agent in a herbicidal composition. Volatilization occurs when pesticide surface residues change from a solid or liquid to a vapor after application. Once airborne, volatile pesticides can move long distances off site (longer distances compared to spray drift).

[0008] Non-target plant damage associated with auxin herbicide volatilization is a major concern for crop growers. Unintentional application of auxin herbicides to a sensitive plant generally causes severe injury, loss of yield, and even death of the non-target plants.

[0009] An object of the present invention is to provide compounds with agrichemical activity and reduced volatility relative to at least some currently available agrichemical compounds, or to at least provide a useful alternative thereto.

[0010] An object of certain embodiments of the present invention is to provide compounds that are known saccharide conjugated metabolites of currently available agrichemical compounds, or saccharide conjugates of currently available agrichemical compounds, having reduced volatility or tendency to drift, relative to the agrichemical compound from which they are derived, but that have not hitherto been utilised as agrichemical compounds themselves.

[0011] An object of certain embodiments of the of the present invention is to provide novel compounds with herbicidal activity and reduced volatility or tendency to drift, relative to at least some currently available auxin herbicides, or to at least provide a useful alternative thereto.

[0012] The discussion of the background art is included exclusively for the purpose of providing a context for the present invention. It is not an acknowledgement or admission that any of the material referred to was common general knowledge in the field relevant to the present invention in Australia or elsewhere before the priority date.

Disclosure of the Invention

[0013] In a first aspect, the invention comprises a compound of Formula (A), as defined in the following detailed description of the invention.

[0014] In a preferred form of the first aspect of the invention, the invention comprises a compound of Formula (A1) or Formula (A2) as defined in the following detailed description of the invention.

[0015] In a second aspect, the invention comprises a compound when used in agriculture, or the use of a compound in agriculture, wherein the compound is a known metabolite or saccharide conjugate of a currently available agrichemical compound, that has not hitherto (ie; before the earliest priority date of the present application) been utilised as an agrichemical compound.

[0016] In a third aspect, the invention comprises compositions comprising an agriculturally effective amount of a compound of the first or second aspects of the invention, a salt or solvate thereof, and an agriculturally acceptable adjuvant or carrier. Examples of the third aspect of the invention are herbicidal compositions comprising a herbicidally effective amount of a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite of a currently available agrichemical compound, or a known saccharide conjugate of a currently available agrichemical compound, that has not hitherto been utilised as an agrichemical compound, and an agriculturally acceptable adjuvant or carrier.

[0017] In a preferred form of the third aspect of the invention, the invention comprises a herbicidal composition comprising a herbicidally-effective amount of a compound of Formula (A1) or Formula (A2) as defined in the following detailed description of the invention, or salts and solvates thereof, and an agriculturally acceptable adjuvant or carrier:

[0018] In fourth aspect, the invention comprises a method for supressing the growth of an auxin-susceptible plant, the method comprising applying to the plant a herbicidally effective amount of a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite of a currently available agrichemical compound, or a known saccharide conjugate of a currently available agrichemical compound, or salts or solvates thereof.

[0019] In fifth aspect, the invention comprises a method for supressing the growth of an auxin-susceptible plant, the method comprising applying to the plant a herbicidal composition comprising a herbicidally-effective amount of a compound of Formula (A), or a compound of Formula (A1 ) or Formula (A2), or a known saccharide conjugated metabolite of a currently available agrichemical compound, or a known saccharide conjugate of a currently available agrichemical compound, or salts and solvates thereof, and an agriculturally acceptable adjuvant or carrier.

Detailed Description of the Invention

[0020] Compounds

[0021] The inventors have identified a means for modifying known volatile agrichemical compounds to form new compounds of reduced volatility, and that are thus less prone to drift issues, while retaining activity, in some cases, possessing activity comparable to the original agrichemical compound. [0022] The invention is readily applicable to known agrichemical compounds having at least one carboxylic acid group, thiocarboxylic acid group (both thione and thiol), or dithiocarboxylic acid group, and derivatives, analogues or esters thereof.

[0023] Examples of known agrichemical compounds that are structurally related to example compounds of the invention are discussed below.

[0024] Daminozide (4-(2,2-Dimethylhydrazinyl)-4-oxobutanoic acid; also known as Alar, Kylar, B-NINE, DMASA, SADH, or B 995) is a plant growth regulator sprayed on fruit to regulate growth, make harvest easier, and keep apples from falling off the trees before they ripen so they are red and firm for storage.

[0025] Daminozide has regulatory approval for use in the EU and is also used in Australia and USA. It is highly soluble in water and volatile. Based on its chemical properties it is not expected to leach to groundwater. Data suggests it is not persistent in soil systems but can be persistent in some water systems. It is relatively non-toxic to mammals but has a high potential for bioaccumulation. Daminozide is a recognised irritant. It has a moderate toxicity to aquatic invertebrates and earthworms but is less harmful to birds, fish and honeybees.

Daminozide

[0026] Endothall (7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid; as the dipotassium salt or the mono-/V,/V-dimethylalkylamine salt) is used as a herbicide for both terrestrial and aquatic plants. It is used as an aquatic herbicide for submerged aquatic plants and algae in lakes, ponds and irrigation canals, as a desiccant on potatoes, hops, cotton, clover and alfalfa, and a biocide to control molluscs and algae in cooling towers.

[0027] Endothall does not have regulatory approval for use in the EU. It is highly soluble in water and semi-volatile. Based on its chemical properties it is not expected to leach to groundwater. It is generally non-persistent in soils. Endothall is highly toxic to mammals but is not expected to bioaccumulate. It is a recognised irritant. It is moderately toxic to fish and aquatic organisms but is less toxic to birds.

Endothall

[0028] Metalaxyl (methyl 2-[(2,6-dimethylphenyl)(methoxyacetyl)amino]propanoate) is an acylalanine fungicide with systemic function. It can be used to control diseases caused by air- and soil-borne Peronosporales in many different crops, including Pythium in vegetable crops, and Phytophthora in peas. Metalaxyl-M or Ridomil Gold are trade names for the optically pure (-) / D / R active stereoisomer, which is also known as Mefenoxam. It is the active ingredient in the seed treatment agent Apron XL LS.

[0029] Metsulfuron

(2-{[[(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)amino]-oxomethyl]sulfamoyl}benzoic acid methyl ester) is a sulfonylurea herbicide, which kills broadleaf weeds and some annual grasses, mainly in cereals and land temporarily removed from production. It is also be a pesticide transformation product. It has residual activity in soils, allowing it to be used infrequently but requiring up to 22 months before planting certain crops (sunflowers, flax, corn, or safflower).

Metsulfuron

[0030] Mesosulfuron methyl (methyl-2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl] amino]sulfonyl]-4-[[(methylsulfonyl)amino]methyl] benzoate) is a systemic herbicide used for post-emergence control of grasses and other weeds in cereals.

Mesosulfuron methyl

[0031] Dicamba (3,6-dichloro-2-methoxybenzoic acid) is a broad-spectrum herbicide first registered in 1967, and sold under names including Dianat, Banvel, Diablo, Oracle and Vanquish. Dicamba is a chlorinated derivative of o-anisic acid. Dicamba's use has come under significant scrutiny due to its tendency to spread from treated fields into neighboring fields, causing damage.

Dicamba

[0032] Aminopyralid (4-amino-3,6-dichloropyridine-2-carboxylic acid) is a pyridine carboxylic acid herbicide that is currently under approval consideration for use in the EU. It is highly soluble in water and, based on its chemical properties, is mobile and has a high potential for leaching to groundwater. It may be moderately persistent in soil systems but would not be expected to persistent in surface water under normal conditions. It has a low mammalian toxicity and there is some concern regarding its potential for bioaccumulation. Aminopyralid has a low to moderate toxicity to most terrestrial and aquatic species. Aminopyralid

[0033] Clopyralid (3,6-dichloropyridine-2-carboxylic acid) is a herbicide approved for use in the EU. It has a high aqueous solubility, is volatile and, based on its chemical properties, there is a high risk of it leaching to groundwater. It can be persistent in both soil and water systems depending upon conditions. It has a low mammalian toxicity and is not expected to bioaccumulate. It is an irritant. It is moderately toxic to birds, fish, aquatic invertebrates, honeybees and earthworms. It has a low toxicity to aquatic plants and algae.

Clopyralid

[0034] Fluroxypyr ([(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]acetic acid) is a post- emergence herbicide used to control economically important broad-leaved weeds.

Fluroxypyr

[0035] Chloramben (3-amino-2,5-dichlorobenzoic acid) is an obsolete pre-emergence herbicide that is no longer approved in the EU. It is highly soluble in water, volatile, mobile and has a tendency to leach to groundwater. It is not normally persistent in soil or water systems. It has a low mammalian toxicity but a high potential for bioaccumulation. It is a recognised irritant and there are concerns that it may be a developmental / reproduction toxicant. Chloramben has a low toxicity to birds and aquatic invertebrates but is moderately toxic to fish and honeybees. Chloramben

[0036] 2,3,6-TBA (2,3,6-trichlorobenzoic acid) is a post-emergence herbicide that does not have EU approval for use. It is highly soluble in water and most organic solvents. It is considered volatile. Little has been reported on its environmental persistence or mobility. It is moderately toxic to mammals and a recognised irritant. There are gaps in knowledge regarding its toxicity to biodiversity however data has shown that it is moderately toxic to bids, fish and honeybees.

[0037] Quinclorac (3,7-dichloro-8-quinolinecarboxylic acid) is a herbicide used for post- emergence weed control on grass and turf.

Quinclorac

[0038] Quinmerac (7-Chloro-3-methyl-8-quinolinecarboxylic acid) is a residual herbicide used to control broad-leaved weeds on a range of crops including cereals.

[0039] Imazamox (2-[4,5-Dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H-imidazol-2-yl]-5- (methoxymethyl)-3-pyridinecarboxylic acid) is a post-emergence herbicide used to control weeds including those in aquatic situations.

[0040] 2,4-D (2,4-Dichlorophenoxyacetic acid) is a systemic herbicide which kills most broadleaf weeds by causing uncontrolled growth in them but most grasses such as cereals, lawn turf, and grassland are relatively unaffected. It can be found in numerous commercial lawn herbicide mixtures, and is widely used as a weedkiller on cereal crops, pastures, and orchards. It is absorbed through the leaves and is translocated to the meristems of the plant. Uncontrolled, unsustainable growth ensues, causing stem curl-over, leaf withering, and eventual plant death. Drift is problematic with 2,4-D due to its volatility, and attempts to address this have included choline salt formation, and co-administration with glyphosate.

[0041] 2,4-DB (4-(2,4-dichlorophenoxy)butanoic acid) is a post-emergence herbicide that has approval for use in the EU. It is highly soluble in water and most organic solvents. It is relatively volatile but it may leach to groundwater under certain conditions. It is not persistent in soil systems but may tend to be persistent in aquatic systems. It is moderately toxic to mammals and there is some concern regarding its potential for bioaccumulation. It is moderately toxic to birds, earthworms, honeybees and most aquatic organisms.

[0042] MCPB (4-(4-chloro-2-methylphenoxy)butanoic acid) is a herbicide for post- emergence control of annual and perennial broad-leaved weeds

[0043] Imazapic (5-methyl-2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1 H-imidazol-2- yl]pyndme-3-carboxyhc acid) is a selective pre- and post-emergent herbicide without EU regulatory approval for use. It has a high aqueous solubility, is volatile and, based on its chemical properties, is moderately mobile and may leach to groundwater. It is may be persistent in soil systems but usually degrades quickly in aquatic systems via photolysis. It has a low mammalian toxicity and has a high potential for bioaccumulation. It has a low level of toxicity to birds but is more toxic to aquatic life and honeybees.

Imazapic

[0044] Imazethapyr (2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H-imidazol-2-yl]-5- ethyl-3-pyridinecarboxylic acid) is a herbicide used to control a variety of broad-leaved weeds and grasses in numerous crops.

Imazethapyr

[0045] Imazaquin (2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H-imidazol-2-yl]-3- quinolinecarboxylic acid) is used as a pre- and post-emergence herbicide particularly for the control of grasses and broad-leaved weeds.

Imazaquin

[0046] Imazapyr (2-(4-Methyl-5-oxo-4-propan-2-yl-1 H-imidazol-2-yl)pyridine-3-carboxylic acid) is a herbicide for non-crop land applications which is particularly effective on hard-to- control perennial grasses.

Imazapyr [0047] Benazolin ethyl (ethyl 2-(4-chloro-2-oxo-2,3-dihydro-1 ,3-benzothiazol-3-yl)acetate) is a post emergence herbicide that does not have EU approval for use. It has a low aqueous solubility, is volatile with a low tendency to leach to groundwater. It is not persistent in soil systems but may be persistent in water. Benazolin ethyl has a low mammalian toxicity and is not expected to bioaccumulation. It has a low toxicity to birds and is moderately toxicity to most aquatic organisms and earthworms.

Benazolin ethyl

[0048] Diflufenzopyr (2-[1 -[2-[[(3,5-difluorophenyl)amino]carbonyl]hydrazinylidene]eth yl]-3- pyridinecarboxylic acid) is used as a herbicide, post-emergence, to control annual broad- leaved and perennial weeds in a variety of crops.

Diflufenzopyr

[0049] Naptalam (2-[(1-naphthalenylamino)carbonyl]benzoic acid) is a herbicide without EU approval for use. It is usually used as the sodium salt as this is more soluble. Whilst naptalam is not particularly toxic to humans its major metabolite 1 -naphthylamine is a carcinogen. Its environmental fate is pH sensitive. It may pose a threat to groundwaters. Virtually non toxic to mammals, birds, honeybees and most aquatic species. No data for earthworms has been identified.

Naptalam

[0050] Acibenzolar-S-Methyl (S-Methyl 1 ,2,3-benzothiadiazole-7-carbothioate) is a fungicide.

Acibenzolar-S-Methyl [0051] Bifenox (2,4-dichlorophenyl 3'-carbomethoxy-4'-nitrophenyl ether) is a herbicide approved for use in the EU. It has a low aqueous solubility, is volatile and would not be expected to leach to groundwater. It would also not be expected to persistent in soil or water systems. It has a low mammalian toxicity and no serious health concerns have been identified. Bifenox is moderately toxic to fish, aquatic invertebrates and earthworms but is highly toxic to algae.

Bifenox

[0052] Cinidon-ethyl (ethyl (2Z)-2-chloro-3-[2-chloro-5-(1 ,3,4,5,6,7-hexahydro-1 ,3-dioxo-2H- isoindol-2-yl)phenyl]prop-2-enoate) is a post-emergence herbicide that has EU approval for use. It has a low aqueous solubility, is relatively volatile with a low tendency to leach to groundwater. It is slightly mobile. It is not persistent in soil or water systems. Cinidon-ethyl has a low mammalian toxicity and is not expected to bioaccumulate. It is moderately toxic to earthworms but more toxic to aquatic organisms. It is relatively non- toxic to honeybees.

[0053] MCPA (2-(4-chloro-2-methylphenoxy)acetic acid) is extensively used in agriculture to control broad-leaf weeds as a growth regulator primarily in pasture and cereal crops. The mode of action of MCPA is as an auxin. MCPA can be moderately toxic to mammal and aquatic organisms, and relatively less toxic to birds. Ester forms of MCPA are known to be quite volatile and therefore prone to drift.

[0054] MCPP (Mecoprop), (methylchlorophenoxypropionic acid), (2-(4-chloro-2- methylphenoxy)propanoic acid) is a common general use herbicide found in many household weed killers and "weed-and-feed" type lawn fertilizers. It is primarily used to control broadleaf weeds. It is often used in combination with other chemically related herbicides such as 2,4-D, dicamba, and MCPA. Ester forms of MCPA are known to be quite volatile and therefore prone to drift.

[0055] Picloram (4-amino-3,5,6-trichloropicolinic acid) is a systemic herbicide used for general woody plant control. It also controls a wide range of broad-leaved weeds, but most grasses are resistant. Ester derivatives are volatile and subject to drift issues.

Picloram

[0056] Triclopyr (2-((3,5,6-trichloropyridin-2-yl)oxy)acetic acid) is used to control broadleaf weeds while leaving grasses and conifers unaffected or to control rust diseases on crops. The compound is slightly toxic to ducks and quail. It has been found nontoxic to bees and very slightly toxic to fish. Ester derivatives are volatile and subject to drift issues.

[0057] Dichlorprop (2-(2,4-dichlorophenoxy)propanoic acid) is used to kill annual and perennial broadleaf weeds. It is a component of many common weedkillers. Dichlorprop is thought to increase cell wall plasticity, biosynthesis of proteins, and the production of ethylene. The abnormal increase in these processes result in abnormal and excessive cell division and growth, damaging vascular tissue. Ester derivatives are volatile and subject to drift issues.

Dichlorprop

[0058] pCPC (p-Chlorophenoxyacetic acid), also known as 4-CPA is a plant growth regulator with auxin activity used to regulate root and fruit development. It can be used as a herbicide as well. It is taken up by the root, stem, leaf, bloom, and fruit of the plant. It is used to reduce bloom and fruit abscission, restrict bean roots, increase fruit set, and induce formation of seedless fruit. Also used for fruit thinning and ripening. When used with 0.1 percent monopotassium phosphate, it works better. At larger doses, it has a herbicidal effect and under higher temperatures encountered in agricultural environments, can exhibit drift due to volatility.

[0059] In a first aspect, the invention comprises a compound of Formula (A); accharide

Formula (A) wherein;

P is independently selected in each instance from the group consisting of; and

A is independently selected in each instance from the group consisting of O, S and NR ³ ;

B is independently selected in each instance from the group consisting of O, S, Se and NR ³ ;

R ³ is independently selected in each instance from the group consisting of H, -C ₁ -C ₆ alkyl, -C ₁ -C ₆ haloalkyl, -C ₃ -C ₆ cycloalkyl, -C ₃ -C ₆ cyclohaloalkyl, -C ₂ -C ₆ alkenyl, -C ₃ -C ₆ haloalkenyl, -C ₃ -C ₆ cycloalkenyl, -C ₃ -C ₆ cyclohaloalkenyl, -aryl, -heteroaryl, -C ₁ -C ₆ alkyl-R ^a , -C ₁ -C ₆ haloalkyl-R ^a , -C ₃ -C ₆ cycloalkyl-R ^a , -C ₃ -C ₆ cyclohaloalkyl-R ^a , -C ₂ -C ₆ alkenyl-R ^a , -C ₂ -C ₆ haloalkenyl-R ^a , -C ₃ -C ₆ cycloalkenyl-R ^a , -C ₃ -C ₆ cyclohaloalkenyl-R ^a , -aryl-R ^a , -heteroaryl-R ^a , -(C=O)R ^b , -(C=O)OR ^b , -(C=O)SR ^b , -(C=O)N(R ^b ) ₂ , -(C=S)R ^b , -(C=S)OR ^b , -(C=S)SR ^b , -(C=S)N(R ^b ) ₂ , and -Si(R ^b ) ₃ ;

R ^a is independently selected in each instance from the group consisting of halogen, -C ₁ -C ₆ alkyl, -C ₁ -C ₆ haloalkyl, -C ₃ -C ₆ cycloalkyl, -C ₃ -C ₆ cyclohaloalkyl, -C ₂ -C ₆ alkenyl, -C ₂ -C ₆ haloalkenyl, -C ₃ -C ₆ cycloalkenyl, -C ₃ -C ₆ cyclohaloalkenyl, -aryl, -heteroaryl, -(C=O)R ^b , -(C=O)OR ^b , -(C=O)SR ^b , -(C=O)N(R ^b ) ₂ , -(C=S)R ^b , -(C=S)OR ^b , -(C=S)SR ^b , -(C=S)N(R ^b ) ₂ , and -Si(R ^b ) ₃ ;

R ^b is independently selected in each instance from the group consisting of H, -C ₁ -C ₆ alkyl, -C ₁ -C ₆ haloalkyl, -C ₃ -C ₆ cycloalkyl, -C ₃ -C ₆ cyclohaloalkyl, -C ₂ -C ₆ alkenyl, -C ₂ -C ₆ haloalkenyl, -C ₃ -C ₆ cycloalkenyl, -C ₃ -C ₆ cyclohaloalkenyl, -aryl, -heteroaryl, -C ₁ -C ₆ alkyl-aryl, and -C ₁ -C ₆ alkyl-heteroaryl ; wherein the saccharide moiety is bonded to each B, via condensation with a hydroxyl group on the saccharide moiety; wherein the saccharide moiety is selected from the group consisting of; a monosaccharide, a disaccharide, a trisaccharide, a tetrasaccharide, a pentasaccharide, a hexasaccharide, a heptasaccharide, an octasaccharide, and an oligosaccharide, including oxidised derivatives, reduced derivatives, deoxy-derivatives, ester derivatives, amide derivatives, glycosides, alditols, carboxylic acid containing derivatives, amino group containing derivatives thio group containing derivatives, anhydro derivatives, and sulphated derivatives thereof; and n is an integer of between, 1 and the number of hydroxyl groups on the saccharide moiety; and salts, stereoisomers, isotopologues, solid forms, polymorphs, clathrates, or solvates thereof; wherein, when P is selected from and A is O, and B is O, and n is 1 , then the saccharide moiety is not an ester derivative of a monosaccharide or an ester derivative of a disaccharide; and wherein, when then the saccharide moiety is not 3-O-sucrose; and wherein, when then the saccharide moiety is not an ester derivative of a monosaccharide; and with the proviso that the compound is not a compound published prior to the earliest priority date of the present application or a compound made publicly available prior to the earliest priority date of the present application.

[0060] In a preferred aspect, the compound of Formula A is not a compound selected from the group consisting of;

X4 (CAS RN: 68162-99-2);

X43; (4aR,6R,7R,8S,8aR)-6-hydroxy-2- X44; (4aR,6R,7R,8S,8aR)-6-hydroxy- methylhexahydropyrano[3,2- 2-methylhexahydropyrano[3,2- d][1 ,3]dioxine-7,8-diyl bis(2-(2,4- d][1 ,3]dioxine-7,8-diyl bis(2-(4- dichlorophenoxy)acetate); chlorophenoxy)acetate):

X45; sodium (2R,3R,4S,5R,6R)-2-(2- X46; sodium ((2R,3S,4S,5R,6R)-6-(2- (2,4-dichlorophenoxy)acetamido)-6- (2,4-dichlorophenoxy)acetamido)- ((sulfonatooxy)methyl)tetrahydro-2H- 3,4,5-trihydroxytetrahydro-2H-pyran- pyran-3,4,5-triyl tris(sulfate); 2-yl)methyl sulfate;

XX6 (CAS RN: 79432-95-4);

XX15 (CAS RN: 40245-91 -8); XX16 (CAS RN: 40245-92-9); and

XX17 (CAS RN: 40245-96-3).

[0061] In some forms of the invention, the compound of Formula A is a compound wherein P is independently selected in each instance from the group consisting of; [0062] In a preferred form, the compound of Formula (A) is a compound wherein P is independently selected in each instance from;

[0063] In a particularly preferred form, the invention comprises a compound of Formula (A) as defined above, which is a compound of Formula (A1) or Formula (A2): wherein;

A is independently selected in each instance from the group consisting of O, S and NR ³ ;

B is independently selected in each instance from the group consisting of O, S, Se and NR ³ ;

R ³ is independently selected in each instance from the group consisting of H, -C ₁ -C ₆ alkyl, -C ₁ -C ₆ haloalkyl, -C ₃ -C ₆ cycloalkyl, -C ₃ -C ₆ cyclohaloalkyl, -C ₂ -C ₆ alkenyl, -C ₃ -C ₆ haloalkenyl, -C ₃ -C ₆ cycloalkenyl, -C ₃ -C ₆ cyclohaloalkenyl, -aryl, -heteroaryl, -C ₁ -C ₆ alkyl-R ^a , -C ₁ -C ₆ haloalkyl-R ^a , -C ₃ -C ₆ cycloalkyl-R ^a , -C ₃ -C ₆ cyclohaloalkyl-R ^a , -C ₂ -C ₆ alkenyl-R ^a , -C ₂ -C ₆ haloalkenyl-R ^a , -C ₃ -C ₆ cycloalkenyl-R ^a , -C ₃ -C ₆ cyclohaloalkenyl-R ^a , -aryl-R ^a , -heteroaryl-R ^a , -(C=O)R ^b , -(C=O)OR ^b , -(C=O)SR ^b , -(C=O)N(R ^b ) ₂ , -(C=S)R ^b , -(C=S)OR ^b , -(C=S)SR ^b , -(C=S)N(R ^b ) ₂ , and -Si(R ^b ) ₃ ;

R ^a is independently selected in each instance from the group consisting of halogen, -C ₁ -C ₆ alkyl, -C ₁ -C ₆ haloalkyl, -C ₃ -C ₆ cycloalkyl, -C ₃ -C ₆ cyclohaloalkyl, -C ₂ -C ₆ alkenyl, -C ₂ -C ₆ haloalkenyl, -C ₃ -C ₆ cycloalkenyl, -C ₃ -C ₆ cyclohaloalkenyl, -aryl, -heteroaryl, -(C=O)R ^b , -(C=O)OR ^b , -(C=O)SR ^b , -(C=O)N(R ^b ) ₂ , -(C=S)R ^b , -(C=S)OR ^b , -(C=S)SR ^b , -(C=S)N(R ^b ) ₂ , and -Si(R ^b ) ₃ ;

R ^b is independently selected in each instance from the group consisting of H, -C ₁ -C ₆ alkyl, -C ₁ -C ₆ haloalkyl, -C ₃ -C ₆ cycloalkyl, -C ₃ -C ₆ cyclohaloalkyl, -C ₂ -C ₆ alkenyl, -C ₂ -C ₆ haloalkenyl, -C ₃ -C ₆ cycloalkenyl, -C ₃ -C ₆ cyclohaloalkenyl, -aryl, -heteroaryl, -C ₁ -C ₆ alkyl-aryl, and -C ₁ -C ₆ alkyl-heteroaryl ; wherein the saccharide moiety is bonded to each B, via condensation with a hydroxyl group on the saccharide moiety; wherein the saccharide moiety is selected from the group consisting of; a monosaccharide, a disaccharide, a trisaccharide, a tetrasaccharide, a pentasaccharide, a hexasaccharide, a heptasaccharide, an octasaccharide, and an oligosaccharide, including oxidised derivatives, reduced derivatives, deoxy-derivatives, ester derivatives, amide derivatives, glycosides, alditols, carboxylic acid containing derivatives, amino group containing derivatives thio group containing derivatives, anhydro derivatives, and sulphated derivatives thereof; and n is an integer of between, 1 and the number of hydroxyl groups on the saccharide moiety; and salts, stereoisomers, isotopologues, solid forms, polymorphs, clathrates, or solvates thereof.

[0064] As used herein, the term “stereoisomer”, and grammatical variations thereof such as “stereoisomers”, “stereoisomerism”, “stereoisomeric”, et cetera, refers to spatial isomerism in the molecular entity to which it is contextually applied. More specifically, the term is to be understood to include molecules having the same molecular formula and sequence of bonded atoms (constitution) but differing in the three-dimensional orientations of their atoms in space. Thus stereoisomers are to be understood as including optical isomers or enantiomers, diastereoisomers, cis-trans or E-Z isomers, conformers, anomers, atropisomers, configurational stereoisomers and epimers of the molecular entity to which the term is applied. By definition, molecules that are stereoisomers of each other represent the same structural isomer, and the same constitutional isomer.

[0065] All chiral, diastereomeric, racemic mixtures, non-racemic mixtures and geometric isomeric forms of a structure are intended, unless specific stereochemistry or isomeric form is specifically indicated. All processes used to prepare compounds of the present invention and intermediates made therein are considered to be part of the present invention. All tautomers of shown or described compounds are also considered to be part of the present invention.

[0066] As used herein, the term “isotopologue”, and grammatical variations thereof such as “isotopologues”, et cetera, is to be understood to mean molecules that differ only in their isotopic composition. That is to say, the term refers to molecules having the same chemical formula and bonding arrangement of atoms, but at least one atom has a different number of neutrons than the parent.

[0067] As used herein, the term “conjugate”, and grammatical variations thereof such as “conjugated”, et cetera, is to be understood to mean a compound formed by the joining of two or more chemical compounds to form a covalent bond therebetween. Such covalent bonds are typically formed via notional condensation of a carboxylic acid group (or an analogue thereof, such as a thiocarboxylic acid, imidic acid, thioic acid or amide group) on one chemical compound (such as an agrichemical compound bearing a carboxylic acid group or an analogue thereof), with a hydroxyl group (or an analogue thereof, such as a thiol or amine group) on another chemical compound (such as a saccharide compound), to form a conjugate compound wherein the two chemical compounds are covalently bonded via an ester linkage (or an analogue thereof). Other conjugation processes are also possible and are intended to be included within the meaning of the term, such as notional condensation between a carboxylic acid group (or an analogue thereof, such as a thiocarboxylic acid, imidic acid, thioic acid or amide group) on one chemical compound (such as an agrichemical compound bearing a carboxylic acid group or an analogue thereof), with a carboxylic acid group (or an analogue thereof, such as a thiocarboxylic acid, imidic acid, thioic acid or amide group) on another chemical compound (such as a saccharide compound), to form a conjugate compound wherein the two chemical compounds are covalently bonded via an acid anhydride linkage (or an analogue thereof). Alternatively a hydroxyl group (or an analogue thereof, such as a thiol or amine group) on one chemical compound (such as an agrichemical compound bearing a hydroxyl group or an analogue thereof), with a hydroxyl group (or an analogue thereof, such as a thiol or amine group) on another chemical compound (such as a saccharide compound), may notionally condense to form a conjugate compound wherein the two chemical compounds are covalently bonded via an ether linkage (or an analogue thereof, such as a thioether or -NH- linkage). The notional condensation process may occur enzymatically or otherwise. For example, when used in the context of a “saccharide conjugated metabolite of a currently available agrichemical compound”, the term “conjugated” refers to a metabolite of a currently available agrichemical compound, wherein the currently available agrichemical compound is covalently bonded to a saccharide moiety as a result of condensation of a functional group on the currently available agrichemical compound, with a functional group on the saccharide compound from which the a saccharide moiety is derived, via a metabolic process in a plant or animal, which metabolic process may be optionally be facilitated by an enzyme. When used in the context of a “known saccharide conjugate of a currently available agrichemical compound”, the term “conjugate” refers to a compound comprising a currently available agrichemical compound, covalently bonded to a saccharide moiety as a result of condensation of a functional group on the currently available agrichemical compound, with a functional group on the saccharide compound from which the a saccharide moiety is derived, wherein the condensation may occur as a result of any process, including a synthetic process, or a naturally occurring process.

[0068] As used herein, the term “metabolite”, and grammatical variations thereof such as “metabolites”, et cetera, is to be understood to mean any intermediate or end product of metabolism by a living organism, wherein “metabolism” refers to the sum of all chemical reactions that occur in living organisms, including digestion and the transportation of substances into and between different cells.

[0069] Compounds of the Invention may exist in free or salt form, e.g., as acid addition salts. In this specification unless otherwise indicated language such as “Compounds of the Invention” is to be understood as embracing the compounds in any form, for example free or acid addition salt form, or where the compounds contain acidic substituents, in base addition salt form. The Compounds of the Invention are intended for use as agrichemicals, therefore agriculturally acceptable salts are preferred. Salts which are unsuitable for agricultural uses may be useful, for example, for the isolation or purification of free Compounds of the Invention or their salts or agriculturally acceptable salts, are therefore also included, “agriculturally acceptable salts” include, without limitation, sodium, magnesium, calcium, lithium, potassium, chloride, bromide, iodide, hydrochloride, hydrobromide, sulfate, acetate, tartrate, malate and tosylate salts, for example.

[0070] Compounds of the invention may exist in one or more different solid forms. The term “solid forms” is intended to embrace any crystalline forms, amorphous forms, and polymorphic forms, as well as co-crystallised forms including clathrates or solvates, for example.

[0071] As used herein, the term “alkyl”, by itself or as part of another substituent, will be understood to mean unless otherwise stated, a straight or branched chain hydrocarbon, and where designated, having the number of carbon atoms designated (i.e. , “-C ₁ -C ₆ alkyl” means an alkyl having between one to six carbon atoms). By way of illustration, but without limitation, the term "-C ₁ -C ₈ alkyl" refers to a straight chain or branched hydrocarbon moiety having from 1 , 2, 3, 4, 5, 6, 7, or 8 carbon atoms. "-C ₁ -C ₆ alkyl" refers to a straight chain or branched hydrocarbon moiety having from 1 , 2, 3, 4, 5, or 6 carbon atoms. "-C ₁ -C4alkyl" refers to a straight chain or branched hydrocarbon moiety having from 1 , 2, 3, or 4 carbon atoms, including methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and tert- butyl. The term “-C ₁ -C ₆ haloalkyl” refers to a straight chain or branched hydrocarbon moiety having from 1 , 2, 3, 4, 5, or 6 carbon atoms, wherein one or more of said carbon atoms are substituted with one or more halogen atoms selected from F, Cl, Br or I.

[0072] As used herein, the term “parent molecular structure”, “parent molecule”, and grammatical variations thereof, when used in the context of defining variable substituents of Markush Formulae, will be understood to refer to the core structure or non-variable portion of the Markush Formula to which it is being applied. For example, Formula (A1) as defined herein has the variables A and B-Saccharide, attached to the parent molecular structure: Saccharide

Formula (A1 )

[0073] As used herein, the term "alkenyl" employed alone or in combination with other terms means, unless otherwise stated, a straight chain or branched hydrocarbon group containing at least one double bond, and where designated, having the number of carbon atoms designated. For example, from two to six carbon atoms (i.e., -C ₂ -C ₆ alkenyl). Whenever it appears herein, a numerical range such as "2 to 6" or “2-6”, refers to each integer in the given range; e.g., "2 to 6 carbon atoms" means that the -C ₂ -C ₆ alkenyl group can consist of 2, 3, 4, 5, or 6 carbon atoms. The alkenyl group is attached to the parent molecular structure by a single bond, for example, ethenyl (i.e., vinyl), propen-1 -yl (i.e., allyl), buten-1 -yl, penten-1 - yl, penta-1 , 4-dienyl, and the like. The one or more carbon-carbon double bonds can be internal (such as in 2-butenyl) or terminal (such as in 1 -butenyl). Examples of -C ₂ -C ₄ alkenyl groups include ethenyl (C ₂ ), 1 -propenyl (C ₃ ), 2-propenyl (C ₃ ), 1 -butenyl (C ₄ ), 2-butenyl (C ₄ ), 2-methylprop-2-enyl (C ₄ ), butadienyl (C ₄ ) and the like. Examples of -C ₂ -C ₆ alkenyl groups include the aforementioned -C _2-4 alkenyl groups as well as pentenyl (C ₅ ), pentadienyl (C ₅ ), hexenyl (C ₆ ), 2,3-dimethyl-2-butenyl (C ₆ ) and the like. Additional examples of alkenyl include heptenyl (C ₇ ), octenyl (C ₈ ), octatrienyl (C ₈ ) and the like. Further examples include vinyl, propenyl (or allyl), crotyl, isopentenyl, butadienyl, 1 ,3-pentadienyl, 1 ,4-pentadienyl, and the higher homologs and isomers. An example of a functional group representing an alkene is - CH ₂ -CH=CH ₂ . The term “-C ₂ -C ₆ haloalkenyl” refers to a straight chain or branched hydrocarbon moiety containing at least one double bond, having 2, 3, 4, 5, or 6 carbon atoms, wherein one or more of said carbon atoms are substituted with one or more halogen atoms selected from F, Cl, Br or I.

[0074] As used herein, the term "halo", employed alone or in combination with other terms will be understood to mean, unless otherwise stated, one or more halogen atom substituents independently selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). The term “halo” is understood to be used interchangeably with the term “halogen”.

[0075] As used herein, the term "cyclo" employed in combination with other terms will be understood to mean, unless otherwise stated, a cyclic moiety. [0076] As used herein, the term "aromatic" refers to a carbocycle or heterocycle with one or more polyunsaturated rings and having aromatic character, i.e. having (4n+2) delocalized TT (pi) electrons, where n is an integer.

[0077] As used herein, the term "aryl" employed alone or in combination with other terms means, unless otherwise stated, a carbocyclic aromatic system containing one or more rings (typically one, two or three rings) wherein such rings may be fused, such as naphthalene. In a multi-ring group, only one ring is required to be aromatic, so groups such as indanyl are encompassed by the aryl definition, provided the aromatic ring of such groups is attached directly to the parent molecule. The ring or ring system can have 6 to 14 ring atoms (e.g., C ₆ -C ₁₄ aromatic or C ₆ -C ₁₄ aryl). Whenever it appears herein, a numerical range such as "6 to 14 aryl" refers to each integer in the given range; e.g., " C ₆ -C ₁₄ aryl" means that the aryl group can consist of 6, 7, 8, 9, 10, 11 , 12, 13, or 14 ring atoms. Non-limiting examples of aryl groups include phenyl, phenalenyl, naphthalenyl, tetrahydronaphthyl, phenanthrenyl, anthracenyl, fluorenyl, indolyl, indanyl, and the like.

[0078] As used herein, the term “hetero” employed in combination with other terms will be understood to mean, unless otherwise stated, replacement of one or more carbon atoms in the other term to which it is applied, with a heteroatom independently selected in each instance from the group consisting of oxygen (O), nitrogen (N), sulfur (S), selenium (Se) or phosphorus (P).

[0079] The term "heteroaryl" as used herein includes 5-, 6- and 7-membered monocyclic or poly cyclic (e.g., bicyclic or tricyclic) aromatic ring systems having ring carbon atoms and 1 , 2, 3, or 4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, selenium and sulfur. For example, a heteroaryl can have one or two 5-, 6- or 7-membered rings and 1 to 4 heteroatoms selected from N, O, and S. Heteroaryl bicyclic ring systems can include 1 , 2, 3, or 4 heteroatoms in one or both rings. Exemplary heteroaryls include, but are not limited to, pyrrole, furan, thiophene, imidazole, oxazole, oxadiazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine, azepine, oxepine, oxazine, triazine, pyrimidine, indole, and benzoimidazole, and the like. Those aryl groups having heteroatoms in the ring structure may also be referred to as "aryl heterocycles" or "heteroaromatics."

[0080] The term “-C ₁ -C ₆ alkyl-aryl” will be understood to mean a substituent comprising an aryl (aromatic) group connected to the parent molecule via a branched chain or straight chain fully saturated linker wherein said linker comprises 1 , 2, 3, 4, 5, or 6 carbon atoms. [0081] The term “-C ₁ -C ₆ alkyl-heteroaryl” will be understood to mean a substituent comprising an heteroaryl (heteroaromatic) group connected to the parent molecule via a branched chain or straight chain fully saturated linker wherein said linker comprises 1 , 2, 3, 4, 5, or 6 carbon atoms.

[0082] As used herein, the term "cycloalkyl" employed alone or in combination with other terms will be understood to mean, unless otherwise stated, a cycloalkyl moiety. Where a number of carbon atoms is specified, the cycloalkyl moiety will contain the specified number of carbon atoms. Where a range in the number of carbon atoms is specified, the cycloalkyl moiety will contain a number of carbon atoms selected from an integer within the specified range. For example, “-C ₃ -C ₆ cycloalkyl” will be understood to mean a saturated carbocyclic ring moiety comprising 3, 4, 5, or 6 carbon atoms, and will therefore be understood to include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl moieties. “-C ₃ -C ₆ cyclohaloalkyl” will be understood to mean a saturated carbocyclic ring moiety comprising 3, 4, 5, or 6 carbon atoms wherein one or more of the carbon atoms is substituted with one or more halo groups independently selected in each instance from F, Cl, Br and I.

[0083] As used herein, the term "cycloalkenyl" employed alone or in combination with other terms will be understood to mean, unless otherwise stated, a cycloalkyl moiety containing one or more double bonds. Where a number of carbon atoms is specified, the cycloalkenyl moiety will contain the specified number of carbon atoms. Where a range in the number of carbon atoms is specified, the cycloalkenyl moiety will contain a number of carbon atoms selected from an integer within the specified range. For example, “-C ₃ -C ₆ cycloalkenyl” will be understood to mean a carbocyclic ring moiety having at least one double bond, and comprising 3, 4, 5, or 6, carbon atoms, and will therefore be understood to include cyclopropenyl, cyclobutenyl, cyclobutadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, and cyclohexadienyl moieties. “-C ₃ -C ₆ cyclohaloalkenyl” will be understood to mean a carbocyclic ring moiety having at least one double bond, comprising 3, 4, 5, or 6, carbon atoms wherein one or more of the carbon atoms is substituted with one or more halo groups independently selected in each instance from F, Cl, Br and I.

[0084] As used herein, the term “saccharide” may refer to a monosaccharide, a disaccharide, a trisaccharide, a tetrasaccharide, a pentasaccharide, a hexasaccharide, a heptasaccharide, an octasaccharide, and an oligosaccharide, including oxidised derivatives, reduced derivatives, deoxy-derivatives, ester derivatives, amide derivatives, glycosides, alditols, carboxylic acid containing derivatives, amino group containing derivatives thio group containing derivatives, anhydro derivatives, and sulphated derivatives thereof. [0085] As used herein, the term “monosaccharide” and grammatical variations thereof such as “monosaccharides”, will be understood to mean; a triose (three-carbon sugar), selected from the group consisting of; D- glyceraldehyde, L-Glyceraldehyde and Dihydroxyacetone. a tetrose (four-carbon sugar), selected from the group consisting of; tetrose, D- Erythrose (D-Erythrofuranose), L-Erythrose (L-Erythrofuranose), D-Threose (D- Threofuranose) and L-Threose (L-Threofuranose); or a pentose (five-carbon sugar), selected from the group consisting of; pentose, D- Ribose (D-Ribofuranose), D-Ribose (D-Ribopyranose), D-Arabinose (D-Arabinofuranose), D- Arabinose (D-Arabinopyranose), L-Arabinose (L-Arabinofuranose), L-Arabinose (L- Arabinopyranose), D-Xylose (D-Xylopyranose), and D-Lyxose (D-Lyxopyranose); or a hexose (six-carbon sugar), selected from the group consisting of; Hexose, D- Glucose (D-Glucopyranose), D-Galactofuranose, D-Galactose (D-Galactopyranose), L- Galactose (L-Galactopyranose), D-Mannose (D-Mannopyranose), D-Allose (D- Allopyranose), L-Altrose (L-Altropyranose), D-Gulose (D-Gulopyranose), L-ldose (L- Idopyranose), D-Talose (D-Talopyranose), A Heptose (seven-carbon sugar), Heptose, L- glycero-D-manno-Heptose, (L-glycero-D-manno-Heptopyranose), and D-glycero-D-manno- Heptose (D-glycero-D-manno-Heptopyranose); or a Deoxysugar (hexose or pentose without a hydroxyl group at the 6-position or the 2- position), selected from the group consisting of; 6-Deoxy-L-altrose (6-Deoxy-L- altropyranose), 6-Deoxy-D-gulose (6-Deoxy-D-gulopyranose), 6-Deoxy-D-talose (6-Deoxy- D-talopyranose), D-Fucose (6-Deoxy-D-galactopyranose), L-Fucose 6-Deoxy-L- galactopyranose), D-Rhamnose (6-Deoxy-D-mannopyranose), L-Rhamnose (6-Deoxy-L- mannopyranose), D-Quinovose (6-Deoxy-D-glucopyranose), 2-Deoxyglucose (2-Deoxy-D- arabino-hexose), and 2-Deoxyribose (2-Deoxy-D-erythro-pentose); or a Di-deoxysugar (hexose without hydroxyl groups at the 6-position and another position), selected from the group consisting of; Olivose (2,6-Dideoxy-D-arabino- hexopyranose), Tyvelose (3,6-Dideoxy-D-arabino-hexopyranose), Ascarylose (3,6-Dideoxy- L-arabino-hexopyranose), Abequose (3,6-Dideoxy-D-xylo-hexopyranose), Paratose (3,6- Dideoxy-D-ribo-hexopyranose), Digitoxose (2,6-Dideoxy-D-ribo-hexopyranose), and Colitose (3,6-Dideoxy-L-xylo-hexopyranose); or an Amino sugar (hexose with an amino group at the 2-position), selected from the group consisting of; D-Glucosamine (2-Amino-2-deoxy-D-glucopyranose), D-Galactosamine (2-Amino-2-deoxy-D-galactopyranose), D-Mannosamine (2-Amino-2-deoxy-D- mannopyranose), D-Allosamine (2-Amino-2-deoxy-D-allopyranose), L-Altrosamine (2-Amino- 2-deoxy-L-altropyranose), D-Gulosamine (2-Amino-2-deoxy-D-gulopyranose), L-ldosamine (2-Amino-2-deoxy-L-idopyranose), and D-Talosamine (2-Amino-2-deoxy-D-talopyranose); or an Amino sugar (hexose with an N-acetylated amino group at the 2-position), selected from the group consisting of; N-Acetyl-D-glucosamine (2-Acetamido-2-deoxy-D- glucopyranose), N-Acetyl-D-galactosamine (2-Acetamido-2-deoxy-D-galactopyranose), N- Acetyl-D-mannosamine (2-Acetamido-2-deoxy-D-mannopyranose), N-Acetyl-D-allosamine (2-Acetamido-2-deoxy-D-allopyranose), N-Acetyl-L-altrosamine (2-Acetamido-2-deoxy-L- altropyranose), N-Acetyl-D-gulosamine (2-Acetamido-2-deoxy-D-gulopyranose), N-Acetyl-L- idosamine (2-Acetamido-2-deoxy-L-idopyranose), N-Acetyl-D-talosamine (2-Acetamido-2- deoxy-D-talopyranose), N-Acetyl-D-fucosamine (2-Acetamido-2,6-dideoxy-D- galactopyranose), N-Acetyl-L-fucosamine (2-Acetamido-2,6-dideoxy-L-galactopyranose), N- Acetyl-L-rhamnosamine (2-Acetamido-2,6-dideoxy-L-mannopyranose), N-Acetyl-D- quinovosamine (2-Acetamido-2,6-dideoxy-D-glucopyranose), N-Acetyl-6-deoxy-L- altrosamine (2-Acetamido-2,6-dideoxy-L-altropyranose), and N-Acetyl-6-deoxy-D-talosamine (2-Acetamido-2,6-dideoxy-D-talopyranose); or a Uronic acid (hexose with a negatively charged carboxylate at the 6-position), selected from the group consisting of; D-Glucuronic acid (D-Glucopyranuronic acid), D- Galacturonic acid (D-Galactopyranuronic acid), D-Mannuronic acid, (D-Mannopyranuronic acid), D-Alluronic acid (D-Allopyranuronic acid), L-Altruronic acid (L-Altropyranuronic acid), D-Guluronic acid (D-Gulopyranuronic acid), L-Guluronic acid (L-Gulopyranuronic acid), L- Iduronic acid (L-ldopyranuronic acid), and D-Taluronic acid (D-Talopyranuronic acid); or a Sialic acid (nine-carbon acidic sugar), selected from the group consisting of; Sialic acid, Neuraminic acid (5-Amino-3,5-dideoxy-D-glycero-D-galacto-non-2-ulosonic acid), N- Acetylneuraminic acid (5-Acetamido-3,5-dideoxy-D-glycero-D-galacto-non-2-ulosonic acid, and N-Glycolylneuraminic acid (5-Glycolylamido-3,5-dideoxy-D-glycero-D-galacto-non-2- ulosonic acid); or a Sugar alcohol, selected from the group consisting of; Erythritol, Arabinitol, Xylitol, Ribitol, Glucitol, Galactitol, and Mannitol; or a Ketose, selected from the group consisting of; D-Psicose (D-ribo-Hex-2- ulopyranose), D-Fructose (D-arabino-Hex-2-ulofuranose), (D-fructofuranose), D-Fructose (D- arabino-Hex-2-ulopyranose), L-Sorbose (L-xylo-Hex-2-ulopyranose), D-Tagatose (D-lyxo- Hex-2-ulopyranose), D-Xylulose (D-threo-Pent-2-ulopyranose), and D-Sedoheptulose (D- altro-Hept-2-ulopyranose); or another monosaccharide, selected from the group consisting of; Apiose (3-C- (Hydroxymethyl)-D-erythofuranose), Bacillosamine (2,4,6-Trideoxy-2,4-diamino-D- glucopyranose), Thevetose (6-Deoxy-3-O-methyl-D-glucose), Acofriose (3-O-Methyl-D- rhamnose), L-Acofriose (3-O-Methyl-L-rhamnose), Cymarose (2,6-Dideoxy-3-methyl-D-ribo- hexose), Muramic acid (2-Amino-3-O-[(R)-1-carboxyethyl]-2-deoxy-D-glucopyranose), N- Acetylmuramic acid (2-Acetamido-3-O-[(R)-carboxyethyl]-2-deoxy-D-glucopyranose) , N- Glycolylmuramic acid (2-Glycolylamido-3-O-[(R)-1 -carboxyethyl]-2-deoxy-D-glucopyranose), 3-Deoxy-lyxo-heptulosaric acid 3-Deoxy-D-lyxo-hept-2-ulopyranosaric acid, Ketodeoxyoctonic acid (3-Deoxy-D-manno-oct-2-ulopyranosonic acid), Ketodeoxynononic acid (3-Deoxy-D-glycero-D-galacto-non-2-ulopyranosonic acid), Pseudaminic acid (5,7- Diamino-3,5,7,9-tetradeoxy-L-glycero-L-manno-non-2-ulopyrano sonic acid), Acinetaminic acid (5,7-Diamino-3,5,7,9-tetradeoxy-L-glycero-L-altro-non-2-ulop yranosonic acid), Legionaminic acid (5,7-Diamino-3,5,7,9-tetradeoxy-D-glycero-D-galacto-non-2- ulopyranosonic acid), and 4-Epilegionaminic acid (5,7-Diamino-3,5,7,9-tetradeoxy-D-glycero- D-talo-non-2-ulopyranosonic acid).

[0086] As used herein, the term “disaccharide” will be understood to mean, a dimer formed between any two monosaccharides.

[0087] As used herein, the term “trisaccharide” will be understood to mean, a trimer formed between any three monosaccharides.

[0088] As used herein, the term “tetrasaccharide” will be understood to mean, a tetramer formed between any four monosaccharides.

[0089] As used herein, the term “pentasaccharide” will be understood to mean, a pentamer formed between any five monosaccharides.

[0090] As used herein, the term “hexasaccharide” will be understood to mean, a hexamer formed between any six monosaccharides.

[0091] As used herein, the term “heptasaccharide” will be understood to mean, a heptamer formed between any seven monosaccharides.

[0092] As used herein, the term “octasaccharide” will be understood to mean, an octamer formed between any eight monosaccharides.

[0093] As used herein, the term “oligosaccharide” will be understood to mean, an oligomer (or short chain polymer of monosaccharides) formed between any three to twelve monosaccharides.

[0094] In a preferred embodiment, the saccharide group of Formula (A) or Formula (A1 ) or Formula (A2) is a monosaccharide selected from the group consisting of M1 to M33;

wherein; ’represents, independently in each instance, a single bond or a double bond; when is a single bond, or when R ₄ is attached via a single bond, R ₄ is independently selected in each instance from the group consisting of H, -C ₁ -C ₆ alkyl, -OR ³ , -N(R ³ ) ₂ , -SR ³ , and the variable B in accordance with Formula (A) or Formula (A1 ) or Formula (A2), provided at least one R ₄ is not H or -C ₁ -C ₆ alkyl; and/or any two substituents R ₄ may together form an anhydro linkage selected from the group consisting of -O-, -S-, or -NR ³ -; and/or any pair of R ₄ substituents (R ₄ , R ₄ ) situated proximally to each other in a 1 ,2- or 1 ,3- relationship, may together form an acetal ring, a ketal ring, an X,Y-acetal ring or an X,Y-ketal ring selected from the group consisting of; wherein “ - ” represents the points of attachment to the saccharide backbone, each -R ₄ - is independently selected in each instance from the group consisting of -O-, -S-, or -NR ³ -, and each R ^c is independently selected in each instance from the group consisting of H, -C ₁ -C ₆ alkyl, -C ₁ -C ₆ haloalkyl, -C ₃ -C ₆ cycloalkyl, -C ₃ -C ₆ cyclohaloalkyl, -C ₂ -C ₆ alkenyl, -C ₂ -C ₆ haloalkenyl, -C ₃ -C ₆ cycloalkenyl, -C ₃ -C ₆ cyclohaloalkenyl, -aryl, -heteroaryl, -C ₁ -C ₆ alkyl-aryl, and -C ₁ -C ₆ alkyl-heteroaryl; when is a double bond, R ₄ is independently selected in each instance from the group consisting of O, NR ³ , Se, and S; with the proviso that at least one is a single bond, wherein R ₄ is the variable B in accordance with Formula (A) or Formula (A1 ) or Formula (A2);

R ₅ is independently selected in each instance from the group consisting of H, -OR ³ , -N(R ³ ) ₂ , and -SR ³ ; and/or any pair of R ₄ and R ₅ substituents (R ₄ , R ₅ ) situated proximally to each other in a 1 ,2- or 1 ,3- relationship, wherein the R ₄ substituent of said pair of R ₄ and R ₅ substituents (R ₄ , R ₅ ) is attached to the saccharide via a single bond, may together form an acetal ring, a ketal ring, an X,Y-acetal ring or an X,Y-ketal ring selected from the group consisting of; wherein “ - ” represents the points of attachment to the saccharide backbone, each -R ₄ - and -R ₅ - is independently selected in each instance from the group consisting of -O-, -S-, or -NR ³ -, and each R ^c is independently selected in each instance from the group consisting of H, -C ₁ -C ₆ alkyl, -C ₁ -C ₆ haloalkyl, -C ₃ -C ₆ cycloalkyl, -C ₃ -C ₆ cyclohaloalkyl, -C ₂ -C ₆ alkenyl, -C ₂ -C ₆ haloalkenyl, -C ₃ -C ₆ cycloalkenyl, -C ₃ -C ₆ cyclohaloalkenyl, -aryl, -heteroaryl, -C ₁ -C ₆ alkyl-aryl, and -C ₁ -C ₆ alkyl-heteroaryl;

Re is independently selected in each instance from the group consisting of H, -C ₁ -C ₆ alkyl, -C ₁ -C ₆ haloalkyl, -C ₃ -C ₆ cycloalkyl, -C ₃ -C ₆ cyclohaloalkyl, -C ₂ -C ₆ alkenyl, -C ₂ -C ₆ haloalkenyl, -C ₃ -C ₆ cycloalkenyl, -C ₃ -C ₆ cyclohaloalkenyl, -aryl, -heteroaryl, -C ₁ -C ₆ alkyl-aryl, and -C ₁ -C ₆ alkyl-heteroaryl; m is an integer selected from the group consisting of 1 , 2, 3, 4, 5 and 6; and p is an integer selected from the group consisting of 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10 and 1 1 ; or wherein the saccharide moiety is a disaccharide comprising a first monosaccharide independently selected from the group consisting of M1 to M33, linked to a second monosaccharide independently selected from the group consisting of M1 to M33, via a glycosidic bond -O-, -NR ³ - or -S-, formed via condensation of a first substituent R ₄ of the first monosaccharide, with a second substituent R ₄ of the second monosaccharide, wherein said first substituent R ₄ and said second substituent R ₄ , are independently selected from the group consisting of -OH, -NR ³ H and -SH; or wherein the saccharide moiety is a trisaccharide comprising a first monosaccharide independently selected from the group consisting of M1 to M33, linked to a second monosaccharide independently selected from the group consisting of M1 to M33, via a glycosidic bond -O-, -NR ³ - or -S-, formed via condensation of a first substituent R ₄ of the first monosaccharide, with a second substituent R ₄ of the second monosaccharide, and a third monosaccharide independently selected from the group consisting of M1 to M33, linked to the second monosaccharide, via a glycosidic bond -O-, -NR ³ - or -S-, formed via condensation of a third substituent R ₄ of the second monosaccharide, and a fourth substituent R ₄ of the third monosaccharide wherein said first, second, third and fourth substituents R ₄ , are independently selected from the group consisting of -OH, -NR ³ H and -SH.

[0095] Saccharide moieties of compounds of the invention may form “anhydro” linkages selected from the group consisting of -O-, -S-, or -NR ³ - via condensation of any two substituents R ₄ . For example, without limitation and by way of illustration, where the monosaccharide moiety is derived from alpha glucose, or stereoisomers thereof;

Alpha glucose Stereoisomers Saccharide moiety the saccharide moiety will be attached to the parent molecule of Formula (A) or Formula (A1) or Formula (A2) via at least one substituent R ₄ , wherein at least one substituent R ₄ is the variable linking moiety B in accordance with Formula (A) or Formula (A1) or Formula (A2).

Meanwhile, any two of the remaining substituents R ₄ , may optionally form, via condensation, an “anhydro” linkage selected from the group consisting of -O-, -S-, or -NR ³ -. Such anhydro linkages may be formed between two substituents R ₄ , that are situated proximally to each other in, for example and without limitation, a 1 ,2-, 1 ,3-, 1 ,4-, or 1 ,5- relationship;

1 ,4- anhydro linkages

1 ,5- anhydro linkages. [0096] As used herein, the terms “X,Y-acetal ring” and “X,Y-ketal ring” refer to heteroacetal rings and heteroketal rings respectively, wherein one or more of the oxygen atoms of the acetal or ketal rings, respectively, is replaced with nitrogen, or sulfur atom(s).

[0097] In a particularly preferred embodiment, the saccharide group of Formula (A) or Formula (A1 ) or Formula (A2) is a monosaccharide selected from the group consisting of M34 to M50;

and wherein; R ₄ is independently selected in each instance from the group consisting of H, -C ₁ -C ₆ alkyl, -OR ³ , -N(R ³ ) ₂ , -SR ³ , and the variable B in accordance with Formula (A) or Formula (A1 ) or Formula (A2), provided at least one R ₄ is not H or -C ₁ -C ₆ alkyl; and/or any pair of R ₄ substituents (R ₄ , R ₄ ) situated proximally to each other in a 1 ,2- or 1 ,3- relationship, may together form an acetal ring, a ketal ring, an X,Y-acetal ring or an X,Y-ketal ring selected from the group consisting of; wherein “ - ” represents the points of attachment to the saccharide backbone; each -R ₄ - is independently selected in each instance from the group consisting of

-O-, -S-, or -NR ³ -, and each R ^c is independently selected in each instance from the group consisting of H, -C ₁ -C ₆ alkyl, -C ₁ -C ₆ haloalkyl, -C ₃ -C ₆ cycloalkyl, -C ₃ -C ₆ cyclohaloalkyl, -C ₂ -C ₆ alkenyl, -C ₂ -C ₆ haloalkenyl, -C ₃ -C ₆ cycloalkenyl, -C ₃ -C ₆ cyclohaloalkenyl, -aryl, -heteroaryl, -C ₁ -C ₆ alkyl-aryl, and -C ₁ -C ₆ alkyl-heteroaryl; with the proviso that at least one R ₄ is the variable B in accordance with Formula (A) or Formula (A1 ) or Formula (A2); m is an integer selected from the group consisting of 1 , 2, 3, 4, 5 and 6; and p is an integer selected from the group consisting of 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11 ; or wherein the saccharide moiety is a disaccharide comprising a first monosaccharide independently selected from the group consisting of M34 to M50, linked to a second monosaccharide independently selected from the group consisting of M34 to M50, via a glycosidic bond -O-, -NR ³ - or -S-, formed via condensation of a first substituent R ₄ of the first monosaccharide, with a second substituent R ₄ of the second monosaccharide, wherein said first substituent R ₄ and said second substituent R ₄ , are independently selected from the group consisting of -OH, -NR ³ H and -SH; or wherein the saccharide moiety is a trisaccharide comprising a first monosaccharide independently selected from the group consisting of M34 to M50, linked to a second monosaccharide independently selected from the group consisting of M34 to M50, via a glycosidic bond -O-, -NR ³ - or -S-, formed via condensation of a first substituent R ₄ of the first monosaccharide, with a second substituent R ₄ of the second monosaccharide, and a third monosaccharide independently selected from the group consisting of M34 to M50, linked to the second monosaccharide, via a glycosidic bond -O-, -NR ³ - or -S-, formed via condensation of a third substituent R ₄ of the second monosaccharide, and a fourth substituent R ₄ of the third monosaccharide wherein said first, second, third and fourth substituents R ₄ , are independently selected from the group consisting of -OH, -NR ³ H and -SH.

[0098] In some embodiments, the variable B in the compound of Formula (A) or the compound of Formula (A1 ) or Formula (A2) is independently selected in each instance from O or S.

[0099] It will be understood that the description of compounds herein is limited by principles of chemical bonding and valency known to those skilled in the art. Accordingly, where a group may be substituted by one or more of a number of substituents, such substitutions are selected so as to comply with principles of chemical bonding with regard to valencies, and to give compounds which are not inherently unstable. [00100] In some embodiments, the saccharide moiety of the compound of Formula (A) or Formula (A1 ) or Formula (A2) has a molecular weight of ≤ 900 g/mol, or ≤ 850 g/mol, or ≤ 800 g/mol, or ≤ 750 g/mol, or ≤ 700 g/mol, or ≤ 650 g/mol, or ≤ 600 g/mol, or ≤ 550 g/mol, or ≤ 500 g/mol, or ≤ 450 g/mol, or ≤ 400 g/mol or ≤ 350 g/mol, or ≤ 300 g/mol, or ≤ 250 g/mol, or ≤ 200 g/mol, or ≤ 150 g/mol, or ≤ 100 g/mol.

[00101] In some embodiments, the saccharide moiety of the compound of Formula (A) or Formula (A1 ) or Formula (A2) is derived from a saccharide that is soluble in aqueous solution.

[00102] In some embodiments, the saccharide moiety of the compound of Formula (A) or Formula (A1 ) or Formula (A2) is derived from a saccharide that is soluble in aqueous solution, as determined by formation of a transparent and homogeneous aqueous solution at a pH in the range of 5.5 to 10.0, and at a concentration in the range of 0.5 mM to 5.0 M, and at a temperature in the range of 15°C to 30°C.

[00103] In a preferred embodiment, the compound of Formula (A) or Formula (A1) or Formula (A2) is selected from the group consisting of; and salts, stereoisomers, isotopologues, solid forms, polymorphs, clathrates, or solvates thereof.

[00104] In a particularly preferred embodiment, the compound of Formula (A) or Formula (A1) or Formula (A2) is selected from the group consisting of;

D1 ; D2;

2,4-D2; and salts, stereoisomers, isotopologues, solid forms, polymorphs, clathrates, or solvates thereof.

[00105] In a highly preferred embodiment, the compound of Formula (A) or Formula

(A1 ) or Formula (A2) is compound D1 ;

D1 (((2R,3S,4S,5R)-3,4,5,6-tetrahydroxytetrahydro-2H-pyran-2-yl )methyl 3,6-dichloro-2- methoxybenzoate); or compound 2,4-D2;

2,4-D2

(R)-2-hydroxy-2-((2R,3R,4R,5S)-3,4,5-trihydroxytetrahydro furan-2-yl)ethyl 2-(2,4- dichlorophenoxy)acetate or a salt, stereoisomer, isotopologue, solid form, polymorph, clathrate, or solvate thereof.

[00106] In a second aspect, the present invention provides a known saccharide conjugated metabolite of a currently available agrichemical compound, or a known saccharide conjugate of a currently available agrichemical compound, when used in agriculture; or the use of a known saccharide conjugated metabolite of a currently available agrichemical compound, or a known saccharide conjugate of a currently available agrichemical compound in agriculture; provided the known saccharide conjugated metabolite of a currently available agrichemical compound, or the known saccharide conjugate of a currently available agrichemical compound has not been used in agriculture, before the earliest priority date of the present application.

[00107] In a preferred form, the present invention provides a known saccharide conjugated metabolite of a currently available agrichemical compound, or a known saccharide conjugate of a currently available agrichemical compound, when used in agriculture; or the use of a known saccharide conjugated metabolite of a currently available agrichemical compound, or a known saccharide conjugate of a currently available agrichemical compound in agriculture; wherein the known saccharide conjugated metabolite of a currently available agrichemical compound, or the known saccharide conjugate of a currently available agrichemical compound is selected from the group consisting of compounds X1 to X46;

X26;

X38;

or salts or solvates thereof.

[00108] In a preferred form, the invention comprises a salt of the compound of Formula (A), or Formula (A1 ) or Formula (A2), or a salt of any one of the compounds X1 to X46. Preferably still, the salt is an agriculturally acceptable salt. [00109] The person skilled in the art will be aware that saccharide units containing at least four carbons can exist in two forms, open-chain or cyclic, that interconvert in aqueous solutions. Furthermore, the person skilled in the art will be aware that saccharide units containing at least five carbons and a free 4-hydroxyl group and 5-hydroxyl group will generally exist in three forms, pyranose (six-membered ring), open-chain, or furanose (five- membered ring) forms, that interconvert in aqueous solutions, as depicted in the equilibrium reaction scheme below for a six-carbon saccharide:

It is to be understood that throughout this specification, where one of these multiple forms (pyranose, open chain or furanose) is depicted or claimed, all other possible forms are also depicted or claimed.

[00110] In one form of the invention, the salt is selected from the group consisting of: chloride, bromide, iodide, bromide, acetate, dihydrogen phosphate, hydrogen sulphate, mesylate, tosylate, citrate, salicylate, fatty acid anions.

[00111] In a preferred form of the invention, the salt is selected from the group consisting of: chloride, acetate, dihydrogen phosphate, hydrogen sulphate, citrate.

[00112] Further and still preferably, the salt is a hydrochloride salt.

[00113] In a preferred form of the invention, the compound is a salt of an aminosugar derived compound in accordance with the invention.

[00114] Without wishing to be bound by theory, the inventors understand that the compounds of the invention are absorbed by the target plant intact, which would explain the improved volatility properties (in terms of reduced volatility compared to the currently available agrichemical compounds from which they are derived), of certain compounds of the invention.

[00115] Agricultural compositions

[00116] In a third aspect, the invention comprises an agricultural composition comprising an effective amount of a compound of Formula (A), or a compound of Formula (A1 ) or Formula (A2), or any one of compounds X1 to X46, including salts and solvates thereof, and an agriculturally acceptable adjuvant or carrier;

[00117] In a preferred form of the third aspect, the invention comprises a herbicidal composition comprising a herbicidally-effective amount of a compound [00118] In a preferred form of the invention, the herbicidal composition comprises a salt of a compound of Formula (A), or Formula (A1) or Formula (A2), or a salt of any one of the compounds X1 to X46. Preferably still, the salt is an agriculturally acceptable salt.

[00119] In one form of the invention, the salt is selected from the group consisting of: chloride, bromide, iodide, bromide, acetate, dihydrogen phosphate, hydrogen sulphate, mesylate, tosylate, citrate, salicylate, fatty acid anions.

[00120] In a preferred form of the invention, the salt is selected from the group consisting of: chloride, acetate, dihydrogen phosphate, hydrogen sulphate, citrate.

[00121 ] Further and still preferably, the salt is a hydrochloride salt.

[00122] In a preferred form of the invention, the herbicidal composition comprises an effective amount of a compound of Formula (A1) or Formula (A2), or a salt thereof.

[00123] In a highly preferred form of the invention, the herbicidal composition comprises an effective amount of the compound D1 ; ((2R, 3S,4S,5R)-3, 4,5,6- tetrahydroxytetrahydro-2H-pyran-2-yl)methyl 3,6-dichloro-2-methoxybenzoate, or of the compound 2,4-D2; (R)-2-hydroxy-2-((2R,3R,4R,5S)-3,4,5-trihydroxytetrahydrofur an-2- yljethyl 2-(2,4-dichlorophenoxy)acetate, or a salt or solvate thereof.

[00124] The compounds of the invention may be combined with a selection of adjuvants to enhance one or more of the compounds’ properties.

[00125] Broadly defined, “an adjuvant is an ingredient that aids or modifies the action of the principal active ingredient.” The use of adjuvants with herbicides generally falls into two categories: (1) formulation adjuvants are present in the container when purchased by the dealer or grower; and (2) spray adjuvants are added along with the formulated product to a carrier such as water. The liquid that is sprayed over the top of a crop, weeds, or insect pest often will contain both formulation and spray adjuvants.

[00126] Formulation adjuvants may be added to the active ingredient for several reasons, including better mixing and handling, increased effectiveness and safety, better distribution, and drift reduction. These traits are accomplished by altering the solubility, volatility, specific gravity, corrosiveness, shelf-life, compatibility, or spreading and penetration characteristics. With the large number of formulation options available (solutions, emulsions, wettable powders, flowables, granules, and encapsulated materials), adjuvants can be advantageous in assuring consistent performance.

[00127] Spray adjuvants may be added to the tank to improve herbicide performance. Literally hundreds of chemical additives are now available that fall into this category. Spray adjuvants can be grouped into two broad categories: (1) activator adjuvants, including surfactants, wetting agents, stickers-spreaders, and penetrants; and (2) special purpose or utility modifiers, such as emulsifiers, dispersants, stabilizing agents, coupling agents, co- solvents, compatibility agents, buffering agents, antifoam agents, drift control agents, and nutritionals.

[00128] Thus, agricultural compositions, and in specific embodiments the herbicidal compositions, may further comprise conventional additives such as drift reduction agents, safeners, thickening agents, flow enhancers, foam-moderating agents, UV protectants, preservatives, antimicrobials solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and inorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, colorants and tackifiers or binders (e.g. for seed treatment formulations) that are necessary or desirable to improve the performance, crop safety, or handling of the composition.

[00129] Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols (such as ethylene glycol or 1 ,2-propylene glycol), ketones such as cyclohexanone and gamma-butyrolactone, fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, e.g. amines such as N-methylpyrrolidone.

[00130] The preferred solvent is water.

[00131] Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, iron sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

[00132] Suitable surfactants (adjuvants, wetters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene-sulfonic acid (Nekal® types, BASF, Germany), and fatty acids, alkylsulfonates, alkylarylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and proteins, denatured proteins, polysaccharides (e. g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols (Mowiol® types, Clariant, Switzerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvinylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers thereof. Further suitable surfactants (especially for agrochemical compositions comprising glyphosate) are alkoxylated C ₄ -22-alkylamines, such as ethoxylated tallow amine (POEA) and the surfactants disclosed in EP1389040 (e.g., those in Examples 1 to 14 of EP1389040).

[00133] Surfactants may be selected from the group consisting of alkoxylated tertiary etheramines, alkoxylated quaternary etheramines, alkoxylated etheramine oxides, alkoxylated tertiary amines, alkoxylated quaternary amines, alkoxylated polyamines, sulfates, sulfonates, phosphate esters, alkyl polysaccharides, alkoxylated alcohols, and combinations thereof.

[00134] The weight ratio of the compound equivalent to surfactant can be readily determined by those skilled in the art (e.g., from 1 :1 to 20:1 , from 2:1 to 10:1 or from 3:1 to 8:1 ).

[00135] Examples for thickeners (/.e., compounds that impart a modified flowability to compositions, i.e., high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA).

[00136] Bactericides may be added for preservation and stabilization of the composition. Examples for suitable bactericides are those based on dichlorophene and benzylalcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie).

[00137] Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

[00138] Examples for anti-foaming agents are silicone emulsions (such as Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof. [00139] Examples for tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).

[00140] Examples of colorants are both sparingly water-soluble pigments and water- soluble dyes. Examples which may be mentioned are the dyes known under the names Rhodamin B, C.L Pigment Red 112 and C.L Solvent Red 1 , and also pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

[00141] The compounds of the invention may be used in the preparation of concentrates, tank-mixes, or ready-to-use (RTU) formulations. Tank-mix and RTU formulations comprising one or more of the compounds of the invention typically comprise from 0.1 g a.s./L to 50 g a.s./L total herbicide loading, while concentrate formulations typically comprise from 50 to 1000 g a.s./L, from 300 to 1000 g a.s./L, from 350 to 1000 g a.s./L, from 400 to 1000 g a.s./L, from 450 to 1000 g a.s./L, or even from 500 to 1000 g a.s./L total herbicide loading.

[00142] In one form of the invention, the herbicidal composition comprises a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite of a currently available agrichemical compound, or a known saccharide conjugate of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof, and a polysaccharide.

[00143] In one form of the invention, the polysaccharide is selected from the group: galactomannans, chitosan, pectin, alginate, hyaluronic acid, agar, xanthan, dextrin, starch, cellulose, amylose, amylopectin, alteman, gellan, levan, mutan, dextran, pullulan, fructan, gum arabic, carrageenan, glycogen, glycosaminoglycans, murein, xyloglucans, bacterial capsular polysaccharides and combinations thereof.

[00144] In one form of the invention, the polysaccharide is selected from the group: galactomannans such as guars, including guar derivatives, xanthans, polyfructoses such as levan, starches, including starch derivatives, such as amylopectin, xyloglucans such as tamarind gum and tamarind gum derivatives such as hydroxypropyl tamarind gum, and cellulose, including cellulose derivatives, such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate.

[00145] In one form of the invention, the herbicidal composition comprises a compound of the invention and a nitrogen-containing polybasic polymer.

[00146] In one form of the invention, the nitrogen-containing polybasic polymer preferably has from 4 to about 100,000 nitrogen atoms per molecule, from about 15 to about 100,000 nitrogen atoms per molecule, from about 25 to about 100,000 nitrogen atoms per molecule, from about 50 to about 100,000 nitrogen atoms per molecule, or even from about 100 to about 100,000 nitrogen atoms per molecule, or mixtures of polybasic polymers having an average number of nitrogen atoms within the above ranges.

[00147] For nitrogen containing polybasic polymers or a combination of polymers, an average nitrogen content of from 10% to about 50% by weight, from 13% to about 50%, from 15% to about 50%, from about 20% to about 50%, from about 30% to about 45% by weight, or even about 30% to about 40% by weight is preferred.

[00148] In one form of the invention, the herbicidal composition comprises a compound of the invention, a polysaccharide derivative and a nitrogen containing polybasic polymer, as described in International Patent Application WO 2019/158601 , the contents of which are incorporated herein by reference, in their entirety.

[00149] The herbicidal compositions of the present invention optionally may further comprise at least one further herbicide.

[00150] In one form, the herbicide is a non-auxin herbicide.

[00151] The term “non-auxin herbicide” refers to a herbicide having a primary mode of action other than as an auxin herbicide. Representative examples of non-auxin herbicides include acetyl CoA carboxylase (ACCase) inhibitors, acetolactate synthase (ALS) inhibitors, acetohydroxy acid synthase (AHAS) inhibitors, photosystem II inhibitors, photosystem I inhibitors, protoporphyrinogen oxidase (PPO or Protox) inhibitors, carotenoid biosynthesis inhibitors, enolpyruvyl shikimate-3-phosphate (EPSP) synthase inhibitors, glutamine synthetase inhibitors, dihydropteroate synthetase inhibitors, mitosis inhibitors, and nucleic acid inhibitors; salts and esters thereof; racemic mixtures and resolved isomers thereof; and combinations thereof.

[00152] In one form of the invention, the non-auxin herbicide is a protoporphyrinogen oxidase (PPO or Protox) inhibitor. For example, the protoporphyrinogen oxidase inhibitor may be the products Luximo™ and/or Tirexor ^TM by BASF. [00153] The agricultural, and in specific embodiments herbicidal, compositions of the invention may further comprise glyphosate or glufosinate, or an agriculturally acceptable salt thereof such as, for example, the ammonium, diammonium, dimethylammonium, monoethanolamine, isopropylamine, and/or potassium salt thereof.

[00154] The agricultural, and in specific embodiments herbicidal, compositions of the invention may be provided as any of the customary types of agrochemical compositions, e.g., solutions, emulsions, suspensions, dusts, powders, pastes and granules. The composition type depends on the intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.

[00155] Examples for composition types are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), which can be water-soluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF). Usually the composition types (e. g. SC, OD, FS, EC, WG, SG, WP, SP, SS, WS, GF) are employed diluted. Composition types such as DP, DS, GR, FG, GG and MG are usually used undiluted. The compositions are prepared in a known manner. When the agrochemical composition is an aqueous composition, the salt according to the invention may dissociate into anions and cations.

[00156] Among the various composition presentations of the invention are the following: a. a ready-to-use herbicidal composition that can be applied to unwanted plants without the need for further dilution with a solvent or other preparation; b. a herbicidal composition concentrate that is diluted with a solvent, e.g. water, and optionally combined with other herbicide and non-herbicide materials, prior to application (including, e.g., dry mixes and premixes); c. a herbicidal composition application mixture prepared by diluting a herbicidal composition concentrate with a solvent, e.g., water, to form the herbicidal composition application mixture which then can be applied to auxin susceptible plants; d. a herbicidal composition application mixture prepared by combining two or more separate components with a solvent, e.g., water, (e.g., a tank mix) to form the herbicidal composition application mixture which then can be applied to auxin-susceptible plants; and e. a herbicidal composition application mixture prepared by introducing separate feed streams to a spraying or application system so that the feed streams are co-mixed to form the herbicidal composition application mixture immediately prior to use.

[00157] Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the compounds of the invention and, if appropriate, further active substances, with at least one solid carrier. Granules, e.g., coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers.

[00158] Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

[00159] Methods for use of the agricultural compositions of the invention.

[00160] In a fourth aspect, the invention comprises a method for use of a compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof wherein the method comprises applying to a plant an effective amount of the compound.

[00161] In a preferred form, the invention comprises a method for use of a compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; wherein the method comprises applying to a plant an effective amount of the compound.

[00162] In a preferred form, the method comprises applying to the plant an effective amount of an agricultural composition containing a compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof. [00163] In a preferred form, the method comprises applying to the plant an effective amount of a herbicidal composition containing a compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof.

[00164] In a preferred form, the method comprises applying to the plant a herbicidally effective amount of a herbicidal composition containing a compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof.

[00165] Some herbicidal compositions of the invention are preferably diluted to form an application mixture before being applied to the plant. Application mixtures may be prepared by dissolving the herbicidal composition in water or other suitable solvent or by suitable dilution of a concentrate agricultural composition and applying to the foliage of plants by methods known in the art.

[00166] According to any one of the invention embodiments, the methods of controlling the growth of auxin-susceptible plants comprise the steps of: (a) preparing an aqueous herbicidal application mixture by diluting with water a herbicidal composition concentrate of any of the herbicidal composition concentrates disclosed in this application; and (b) applying a herbicidally effective amount of the application mixture to the auxin- susceptible plants.

[00167] The herbicidal compositions of the invention, or application mixtures thereof, can be applied before planting, at planting, pre-emergence, or post-emergence to crop plants, such as in a field of the crop plants to control weeds in a field of the crop plants, depending on the particular herbicide salt and crop plant.

[00168] In a further embodiment, the composition according to the invention can be applied by treating seed. The treatment of seed comprises essentially all procedures familiar to the person skilled in the art (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the compositions according to the invention. Here, the herbicidal compositions can be applied diluted or undiluted. [00169] The term seed comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings and similar forms. Here, preferably, the term seed describes corns and seeds.

[00170] The present invention further provides a method for treating an agricultural field comprising spraying the field with a herbicidal composition of the invention, or an application mixture thereof.

[00171] The present invention further provides, the invention comprises a method for controlling insect activity, the method comprising applying to the plant an insecticidally effective compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof.

[00172] The present invention further provides, the invention comprises a method for controlling fungal activity, the method comprising applying to the plant an insecticidally effective compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof.

[00173] The present invention further provides, the invention comprises a method for regulating the growth of a crop plant, the method comprising applying to the plant an effective compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof.

[00174] Methods for controlling the growth of an auxin-susceptible plant

[00175] In a fifth aspect, the invention comprises a method for supressing the growth of an auxin-susceptible plant, the method comprising applying to the plant a herbicidally effective amount of a compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1 ) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof. [00176] In a preferred form, the method comprises applying to the plant a herbicidally effective amount of a herbicidal composition containing a compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof.

[00177] In a preferred form, method comprises applying to the plant a herbicidally effective amount of a herbicidal composition of the invention, as described above.

[00178] In a specific form of the invention, the herbicidal composition further comprises a herbicidally effective amount of a protoporphyrinogen inhibitor.

[00179] Some herbicidal compositions of the invention are preferably diluted to form an application mixture before being applied to the plant. Application mixtures may be prepared by dissolving the herbicidal composition in water or other suitable solvent or by suitable dilution of a concentrate herbicidal composition and applying to the foliage of unwanted plants by methods known in the art.

[00180] According to any one of the invention embodiments, the methods of controlling the growth of auxin-susceptible plants comprise the steps of: (a) preparing an aqueous herbicidal application mixture by diluting with water a herbicidal composition concentrate of any of the herbicidal composition concentrates disclosed in this application; and (b) applying a herbicidally effective amount of the application mixture to the auxin- susceptible plants.

[00181] The herbicidal compositions of the invention, or application mixtures thereof, can be applied before planting, at planting, pre-emergence, or post-emergence to crop plants, such as in a field of the crop plants to control weeds in a field of the crop plants, depending on the particular herbicide salt and crop plant.

[00182] In a further embodiment, the composition according to the invention can be applied by treating seed. The treatment of seed comprises essentially all procedures familiar to the person skilled in the art (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the compositions according to the invention. Here, the herbicidal compositions can be applied diluted or undiluted. [00183] The term seed comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings and similar forms. Here, preferably, the term seed describes corns and seeds.

[00184] The present invention further provides a method for treating an agricultural field comprising spraying the field with a herbicidal composition of the invention, or an application mixture thereof.

[00185] The auxin-susceptible plant may be a weed or a crop plant.

[00186] Crop plants include, for example, vegetable crops, grain crops, flowers, orchard crops, trees, and root crops.

[00187] In a preferred form of the method of the invention, herbicidal compositions of the invention or application mixtures thereof are applied to the foliage of crop plants and/or weed plants in the proximity of crop plants.

[00188] In one form of the invention, the weed plant is resistant to non-selective herbicides. In one form of the invention, the weed plant is resistant to glyphosate.

[00189] Crop plants include hybrids, in-breeds, and transgenic or genetically modified plants having specific traits or combinations of traits including, without limitation, herbicide tolerance (e.g., tolerant to carboxylic acid herbicides, such as auxin herbicides, or other herbicides), Bacillus thuringiensis (Bt), high oil, high lysine, high starch, nutritional density, and drought resistance.

[00190] In one form of the invention, the crop plant is selected from the group consisting of: corn, peanuts, potatoes, soybeans, canola, alfalfa, sugarcane, sugar beets, peanuts, grain sorghum, field beans, rice, sunflowers, wheat and cotton.

[00191] Crop plants that have been modified by breeding, mutagenesis or genetic engineering, e.g., have been rendered tolerant to applications of specific classes of herbicides are particularly useful with the compositions according to the invention.

[00192] In particular, tolerance to classes of herbicides has been developed such as auxin herbicides such as dicamba and 2,4-D; bleacher herbicides such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvyl shikimate 3- phosphate synthase (EPSP) inhibitors such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase (PPO) inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (/.e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering. [00193] These herbicide resistance technologies are, for example, described in Pest Management Science 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Science 57, 2009, 108; Australian Journal of Agricultural Research 58, 2007, 708; Science 316, 2007, 1185; and references quoted therein, each herein incorporated by reference in their entirety.

[00194] Further examples of these herbicide resistance technologies are described in US 2008/0028482, US2009/0029891 , WO 2007/143690, WO 2010/080829, US 6307129, US 7022896, US 2008/0015110, US 7,632,985, US 7105724, and US 7381861 , each herein incorporated by reference in their entirety. [00195] In one form of the invention, the crop plant is a glyphosate resistant sugar beet.

[00196] In a preferred form of the invention, the crop plant is auxin herbicide tolerant.

[00197] In a preferred form of the invention, the crop plant is resistant to herbicides having the formula , wherein: P ¹ is selected from the group consisting of;

A ⁴ is O;

B ⁴ is O or S;

R ⁷ is H, or C1-C ₂ alkyl.

[00198] The soil bacterium Pseudomonas maltophilia (strain DI-6) converts dicamba to 3,6-dichlorosalicylic acid (3,6-DCSA), which is adsorbed to soil much more strongly than is dicamba, but lacks herbicidal activity.

[00199] The enzymes responsible for this first breakdown step is a three-component system called dicamba O-demethylase. Monsanto recently incorporated one component of the three enzymes into the genome of soybean, cotton, and other broadleaf crop plants, making them resistant to dicamba.

[00200] In a preferred form of the invention, the crop plant is dicamba tolerant.

[00201 ] In one form, the crop plant is a dicamba resistant sugar beet.

[00202] In a specific form, the invention comprises a method for supressing the growth of an auxin-susceptible weed in the proximity of a dicamba resistant crop, the method comprising applying to the weed a herbicidally effective amount of a herbicidal composition comprising a compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1 ) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof. In one form of the invention, the weed is resistant to non-selective herbicides. In one form of the invention, the weed is resistant to glyphosate.

[00203] In a preferred form of the invention, the crop plant is modified by introduction of the dmo gene from Stenotrophomonas maltophilia strain DI-6.

[00204] In a preferred form of the invention, the crop plant is a cotton plant Gossypium hirsutum L. selected from the group consisting of: a. COT102 x MON15985 x MON88913 x MON88701 (code SYN-IR102-7 x MON-15985-7 x MON-88913-8 x MON 88701 -3); b. MON88701 (code MON 88701 -3); c. MON88701 x MON88913 (code MON 88701-3 x MON-88913-8); and d. MON88701 x MON88913 x MON15985 (code MON 88701-3 x MON-88913-8 x MON-15985-7).

[00205] In a preferred form of the invention, the crop plant is a maize plant Zea mays L. selected from the group consisting of: a. MON87419 (code MON87419-8); b. MON87427 x MON89034 x MIR162 x MON87419 x NK603 (code MON- 87427-7 x MON-89034-3 x SYN-IR162-4 x MON87419-8 x MON-00603-6); c. MON87427 x MON89034 x MON810 x MIR162 x MON87411 x MON87419 (code MON-87427-7 x MON-89034-3 x MON-00810-6 x SYN-IR162-4 x MON-87411 -9 x MON87419-8); d. MON87427 x MON87419 x NK603 (code MON-87427-7 x MON87419-8 x MON-00603-6); and e. MON87427 x MON89034 x TC1507 x MON87411 x 59122 x MON87419 (code MON-87427-7 x MON-89034-3 x DAS-01507-1 x MON-87411-9 x DAS-59122-7 x MON87419-8).

[00206] In a preferred form of the invention, the crop plant is a soybean plant Glycine max L. selected from the group consisting of: a. DP305423 x MON87708 (code DP-305423-1 x MON-87708-9); b. DP305423 x MON87708 x MON89788 (code DP-305423-1 x MON-87708-9 x MON-89788-1); c. MON87705 x MON87708 (code MON-87705-6 x MON-87708-9) d. MON87705 x MON87708 x MON89788 (code MON-87705-6 x MON-87708- 9 x MON-89788-1) e. MON87708 (code MON-87708-9); f. MON87708 x MON89788 (code MON-87708-9 x MON-89788-1 ); g. MON87708 x MON89788 x A5547-127 (code MON-87708-9 x MON-89788-1 x ACS-GM006-4); and h. MON87751 x MON87701 x MON87708 x MON89788 (code MON-87751-7 x MON-87701-2 x MON87708 x MON89788).

[00207] The codes referenced in the preceding paragraphs are those utilised by the International Service for the Acquisition of Agri-Biotech Applications (ISAAA).

[00208] In a specific form, the invention comprises a method for supressing the growth of an auxin-susceptible weed in the proximity of a dicamba and protoporphyrinogen oxidase inhibitor resistant crop, the method comprising applying to the weed a herbicidally effective amount of a herbicidal composition comprising compound, wherein the compound is a compound of Formula (A), or a compound of Formula (A1) or Formula (A2), or a known saccharide conjugated metabolite compound of a currently available agrichemical compound, or a known saccharide conjugate compound of a currently available agrichemical compound, or a compound selected from any one of compounds X1 to X46; or a salt or solvate thereof, and a protoporphyrinogen oxidase inhibitor. In one form of the invention, the weed is resistant to non-selective herbicides.

[00209] Methods for generating a protoporphyrinogen oxidase inhibitor resistant crop may be found in, inter alia, US patent application 2017/0058290 and US patents 10041087, 5939602 and 5767373, the contents of which are incorporated by reference.

[00210] The rates of application of the active compound are from 0.0001 to 3.0, preferably 0.01 to 1.0 kg/ha of active substance (a.s.), depending on the control target, the season, the target plants and the growth stage.

[00211] Where the compositions according to the invention are applied to the plants by spraying the leaves, the application can be carried out using, for example, water as carrier by customary spraying techniques using spray liquor amounts of from about 100 to 1000 l/ha (for example from 300 to 400 l/ha). The herbicidal compositions may also be applied by the low-volume or the ultra-low-volume method, or in the form of microgranules.

[00212] To treat the seed, the pesticides are generally employed in amounts of from 0.001 to 10 kg per 100 kg of seed.

[00213] The herbicidal composition can be applied to the foliage of a plant or plants at an application rate sufficient to give a commercially acceptable rate of weed control. This application rate is usually expressed as amount of herbicide per unit area treated, e.g., grams active substance per hectare (g a.s./ha).

[00214] Depending on plant species and growing conditions, the time required to achieve a commercially acceptable rate of weed control can be as short as a week or as long as three weeks, four weeks, or 30 days.

[00215] Moreover, it may be advantageous to apply the compositions of the present invention on their own or jointly in combination with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria or with groups of active compounds which regulate growth.

[00216] The herbicidal compositions of the present invention may be used in conjunction with agents that convert herbicide resistant weeds to herbicide susceptible weeds, such as RNAi. In a specific form of the invention, the herbicidal compositions of the present invention may be used in conjunction with agents that convert auxin-resistant weeds to auxin-susceptible weeds, such as RNAi. See, for example U.S. Patent 9,121 ,022 - Sammons, R.D., Ivashutu, S., Liu, H., Wang, D., Feng, P.C.C., Kouranov, A.Y., and Andersen, S.E. 2015. Method for controlling herbicide-resistant plants.

[00217] General

[00218] Throughout this specification, unless the context requires otherwise, the phrase “compounds of the invention” includes salts and solvates of the compounds of Formula (A), and/or compounds of Formula (A1) or Formula (A2), or known saccharide conjugated metabolite compounds of currently available agrichemical compounds that have not hitherto (ie; before the earliest priority date of the present application) been used as agrichemical compounds themselves, or known saccharide conjugate compounds of currently available agrichemical compounds that have not hitherto (ie; before the earliest priority date of the present application) been used as agrichemical compounds themselves, or compounds selected from compounds X1 to X46, as appropriate.

[00219] As used in this application and unless otherwise indicated, the terms “herbicide” and “herbicide composition” refers to a mixture that is produced, sold, or used in a field in order to kill or otherwise inhibit unwanted plants such as, but not limited to, deleterious or annoying weeds, broadleaf plants, grasses, and sedges; and can be used for crop protection, edifice protection or turf protection. The terms “herbicide” and “herbicide composition” includes the end-use herbicidal product. This composition can be a pure compound, a solution of chemical compounds, a mixture of chemical compounds, an emulsion, a suspension, a solid-liquid mixture, or a liquid-liquid mixture. The terms “herbicide” and “herbicide composition” also refer to the product that passes through the commercial channels from the manufacturer to the ultimate end user who can either apply the herbicide to the affected field as sold, as an application mixture and/or mix it with other excipients.

[00220] The term “weed” means and includes any plant which grows where it is not wanted, including volunteer crop plants or insecticide resistant plants.

[00221] The term “effective”, when used with respect to an herbicide, or the phrase “herbicidally effective amount” means an amount necessary to produce an observable herbicidal effect on unwanted plant growth, including one or more of the effects of necrosis, death, growth inhibition, reproduction inhibition, inhibition of proliferation, and removal, destruction, or otherwise diminishing the occurrence and activity of unwanted plants. [00222] The term “controlling”, as in “controlling plant growth”, means producing an observable herbicidal effect on the plant, including one or of the effects of necrosis, death, growth inhibition, reproduction inhibition, inhibition of proliferation, and removal, destruction, or otherwise diminishing the occurrence and activity of unwanted plants.

[00223] The phrase “agriculturally acceptable" as used herein refers to a component that is not unacceptably damaging to a plant or its environment, and/or not unsafe to the user or others that may be exposed to the material when used as described herein

[00224] The phrase “herbicidal activity” as used herein in respect to the properties of the compounds of the invention, means that the compound of the invention inhibits the normal growth of a plant. Activity such as inducing chlorosis is included within the definition of herbicidal activity, as it affects the normal growth of a plant. In some instances, the herbicidal activity of the compounds of the invention is such that it causes the death of the plant, but the term herbicidal activity as used in the specification is not intended to be limited to this outcome.

[00225] Throughout this specification, unless the context requires otherwise, the word “comprise”, or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.

[00226] The present invention includes and expressly contemplates any and all combinations of embodiments, features, characteristics, parameters, and/or ranges disclosed herein. That is, the invention may be defined by any combination of embodiments, features, characteristics, parameters, and/or ranges mentioned herein.

[00227] It is contemplated that any ingredient, component, or step that is not specifically named or identified as part of the invention may be explicitly excluded by at least some embodiments of the invention.

[00228] While attempts have been made to be precise, the numerical values and ranges described herein should be considered to be approximations (even when not qualified by the term “about”). These values and ranges may vary from their stated numbers depending upon the desired properties sought to be obtained by the present invention as well as the variations resulting from the standard deviation found in the measuring techniques. Moreover, the ranges described herein are intended and specifically contemplated to include all sub-ranges and values within the stated ranges. For example, a range of 50 to 100 is intended to describe and include all values within the range including sub-ranges such as 60 to 90 and 70 to 80. [00229] Any two numbers of the same property or parameter reported in the working examples may define a range. Those numbers may be rounded off to the nearest thousandth, hundredth, tenth, whole number, ten, hundred, or thousand to define the range.

[00230] The content of all documents cited herein, including patents as well as non- patent literature, is hereby incorporated by reference in their entirety. To the extent that any incorporated subject matter contradicts with any disclosure herein, the disclosure herein shall take precedence over the incorporated content. Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

Examples

[00231] The present invention will now be described with reference to a series of examples. The description of the examples should not be understood to be limiting the generality of the preceding description of the invention. The Figures referenced in the description of the Examples are as follows: a. Figure 1A is series of photographs of Arabidopsis thaliana (top view) illustrating the comparative efficacy of 6-OGIu Dicamba (compound D1), and 1-OGIu Dicamba (compound D2) as representative compounds of the invention compared to the known auxin herbicide Dicamba at a range of concentrations, in mg/L b. Figure 1 B is series of photographs of Arabidopsis thaliana (top view) illustrating the comparative efficacy of 2,4-D and 6-OGIu 2,4-D (Compound 2,4-D2) as a representative compound of the invention compared to the known auxin herbicide Dicamba at a range of concentrations, in pM c. Figure 2A is series of photographs of Arabidopsis thaliana (top view) illustrating the comparative efficacy of 6-OGIu Dicamba (compound D1), 6- OGal Dicamba (compound D3), 5-ORib Dicamba (compound D7), 5-OXyl Dicamba (compound D6), 1 -OSorb Dicamba (compound D5), and 1 -OFruc Dicamba (compound D4), as representative compounds of the invention compared to the known auxin herbicide Dicamba at a range of concentrations, in mol L ^-1 d. Figure 2B is series of photographs of Arabidopsis thaliana (top view) illustrating the comparative efficacy of 6-OGIu Dicamba (compound D1 ), Glycerone Dicamba (compound D34), Bis-glycerone Dicamba (compound D35), 2-OGIu Dicamba (compound D8), 3-OGIu Dicamba (compound D9), 4- OGIu Dicamba (compound D10), 2-O-L-Ara Dicamba (compound D20), 4-O- L-Ara Dicamba (compound D21 ), 5-O-D-Ara Dicamba (compound D23), 6- OMan Dicamba (compound D24), 1 -O-D-Mannoheptulose Dicamba (compound D26), 6-O-GlcNAc Dicamba (compound D28), 6-O-GlcN Dicamba (compound D29), 6-SGIu Dicamba (compound D31) and 6-NGIu Dicamba (compound D33) as representative compounds of the invention compared to the known auxin herbicide Dicamba at a range of concentrations, in pM-mM. e. Figure 3 represents a series of photographs of Arabidopsis thaliana illustrating the compatibility of both dicamba (at 0.5 mM) and 6-OGIu Dicamba (compound D1), 6-OGal Dicamba (compound D3), 5-ORib Dicamba (compound D7), 5-OXyl Dicamba (compound D6), 1 -OSorb Dicamba (compound D5), and 1 -OFruc Dicamba (compound D4) (all at 2 mM), with the commercial dicamba tolerance trait. The volume sprayed per pot was 500 pL. Plants are wild type (WT) or a transgenic line expressing a dicamba monooxygenase (DMOc) gene. Plants were imaged at Day 11 of growth f. Figure 4 is series of photographs of Arabidopsis thaliana illustrating the different volatility characteristics and resistance to drift of the compound D1 of the invention (at concentrations of 20 mM and 40 mM) and the known auxin herbicide dicamba (at 1.25, 2.5, 5 and 10 mM) g. Figure 5 is series of photographs of Arabidopsis thaliana illustrating the different volatility characteristics and resistance to drift of the compounds D1 and D3 to D7 of the invention and the known auxin herbicide dicamba at concentrations of 5 mM and 10 mM. h. Figure 6 is a plot of the degradation of the compounds D1 and D3 to D7 of the invention to dicamba at ~25°C in water over a 4-week period, as measured via HPLC with detection of dicamba by UV absorption at 220nm. i. Figure 7 is a plot of the degradation of the compounds D1 and D3 to D7 of the invention to dicamba at ~25°C in aqueous buffer at pH 5.0 over a 4 week period, as measured via HPLC with detection of dicamba by UV absorption at 220nm. j. Figure 8 is a plot of the degradation of the compounds D1 and D3 to D7 of the invention to dicamba at ~25°C in aqueous buffer at pH 7.0 over a 4-week period, as measured via HPLC with detection of dicamba by UV absorption at 220nm. k. Figure 9 is a plot of the degradation of the compounds D1 and D3 to D7 of the invention to dicamba at ~25°C in aqueous buffer at pH 8.0 over a 4-week period, as measured via HPLC with detection of dicamba by UV absorption at 220nm.

[00232] Synthesis

[00233] The following scheme depicts the synthesis of Compounds D1 and D1 1 of the invention;

[00234] 6-O-2, 5-dichloro-6-methoxybenzoyl-1,2-O-isopropylidene-a-D-glucofu ranose;

(R)-2-hydroxy-2-((3aR,5R,6S,6aR)-6-hydroxy-2,2-dimethylte trahydrofuro[2,3-d][1,3]dioxol-5- yl)ethyl 3,6-dichloro-2-methoxybenzoate; (Compound D11 )

[00235] Dicamba (100 mg, 0.454 mmol) was dissolved in CH ₂ CI ₂ (2 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.051 mL, 0.59 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (1 mL) and added to a solution of 1 ,2-O-isopropylidene-a-D- glucofuranose (100 mg, 0.454 mmol) in 1 :1 pyridine/CH ₂ CI ₂ (1 mL) and stirred at r.t. for 2.5 h. The mixture was concentrated in vacuo and the residue diluted with EtOAc (10 mL), washed with water (10 mL), saturated NaHCO ₃ solution (10 mL), water (10 mL), and brine (10 mL), dried over MgSCO ₄ , filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (10-50% EtOAc/hexanes) to obtain 6-O-2, 5- dichloro-6-methoxybenzoyl-1 ,2-O-isopropylidene-a-D-glucofuranose (Compound D1 1 ) as a pale yellow resin (176 mg, 92%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.66 (d, J = 8.7 Hz, 1 H), 7.39 (d, J = 8.7 Hz, 1 H), 5.82 (d, J = 3.7 Hz, 1 H), 5.28 (d, J = 4.9 Hz, 1 H), 5.16 (d, J = 6.2 Hz, 1 H), 4.48 (dd, J = 11 .3, 2.3 Hz, 1 H), 4.41 (d, J = 3.7 Hz, 1 H), 4.25 (dd, J = 1 1 .3, 6.0 Hz, 1 H), 4.05 (dd, J = 4.9, 2.6 Hz, 1 H), 4.04-3.99 (m, 1 H), 3.93 (dd, J = 8.9, 2.6 Hz, 1 H), 3.85 (s, 3H), 1.36 (s, 3H), 1.23 (s, 3H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 163.9, 153.1 , 132.4, 129.9, 128.7, 126.2, 126.0, 110.6, 104.5, 84.7, 80.0, 72.8, 68.7, 65.1 , 62.2, 26.5, 26.1. [00236] 6-O-2, 5-dichloro-6-methoxybenzoyl-D-glucose (6-OGIu Dicamba);

((2R, 3S, 4S,5R)-3, 4, 5, 6-tetrahydroxytetrahydro-2H-pyran -2-yl) methyl 3,6-dichloro -2- methoxybenzoate (Compound D1)

[00237] 6-O-2, 5-dichloro-6-methoxybenzoyl-1 ,2-O-isopropylidene-a-D-glucofuranose

(compound D11 , 168 mg, 0.397 mmol) was dissolved in 4:1 TFA/H ₂ O (2 mL) and stirred at r.t. for 1 h, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The resultant residue was then purified by flash column chromatography (0-15% MeOH/CH ₂ CI ₂ ) to obtain 6-O-2, 5-dichloro-6-methoxybenzoyl-D-glucose (Compound D1) as a white resin (128 mg, 84%). ¹ H NMR (400 MHz, D ₂ O): δ 7.50 (d, J = 8.8 Hz, 0.6H), 7.49 (d, J = 8.8 Hz, 0.4H), 7.25 (d, J = 8.8 Hz, 0.6H), 7.25 (d, J = 8.8 Hz, 0.4H), 5.23 (d, J = 3.8 Hz, 0.4 H), 4.79- 4.76 (m, 0.6H), 4.73 (dd, J = 12.2, 2.3 Hz, 0.4 H), 4.68-4.64 (m, 1 H), 4.61 (dd, J = 12.1 , 5.9 Hz, 0.6H), 4.14 (ddd, J = 10.1 , 4.8, 2.2 Hz, 0.4H), 3.91 (s, 1.8H), 3.90 (s, 1.2H), 3.80-3.73 (m, 1 H), 3.55-3.48 (m, 2H), 3.28-3.24 (m, 0.6H); ¹³ C NMR (101 MHz, D ₂ O): δ 166.2, 166.1 , 152.7, 152.7, 132.8, 132.8, 129.1 , 129.0, 128.6, 128.5, 126.5, 126.5, 96.0, 92.1 , 75.6, 74.0, 73.5, 72.7, 71.4, 69.7, 69.7, 69.3, 65.3, 65.2, 62.6, 62.6.

[00238] The following scheme depicts the synthesis of Compound D2 of the invention;

[00239] 1-O-2,5-dichloro-6-methoxybenzoyl-D-glucopyranose (1-OGIu Dicamba); (3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2 H-pyran-2-yl 3,6-dichloro-2- methoxybenzoate (Compound D2)

[00240] D-glucose (200 mg, 1.1 mmol) was added to DMF (10 mL) and to this mixture was added dicamba (245 mg, 1.1 mmol) and PPh ₃ (582 mg, 2.2 mmol). DIAD (0.44 mL, 2.2 mmol) was then added dropwise and after addition the resulting mixture was allowed to stir vigorously for 30 minutes. The reaction was then quenched with MeOH (1 mL) and then concentrated. Flash column chromatography (5-8% MeOH/CHCI ₃ ) of the residue gave 1 -O- 2,5-dichloro-6-methoxybenzoyl-D-glucopyranose (Compound D2) as a white foam (350 mg, 82%). ¹ H NMR (500 MHz, CD ₃ OD): δ 7.51-7.49 (m, 1 H), 7.25-7.23 (m, 1 H), 6.35 (d, J = 3.0 Hz, 0.53H), 5.71 (d, J = 8.2 Hz, 0.47H), 3.93-3.86 (m, 3.53H). 3.82-3.71 (m, 2H), 3.67-3.62 (m, 1 H), 3.49-3.35 (m, 2.47H); ¹³ C NMR (125 MHz, CD3OD): δ 164.9, 164.6, 155.4, 155.2, 133.5, 133.4, 131.4, 131.0, 130.9, 130.7, 127.9, 127.2, 97.2, 95.7, 79.1 , 78.1 , 76.5, 74.6, 73.9, 72.1 , 70.9, 70.8, 63.2, 63.1 , 62.3, 62.2.

[00241 ] The following scheme depicts the synthesis of Compounds D12 and D3 of the invention;

[00242] 6-O-(2,5-dichloro-6-methoxybenzoyl)-1,2:3,4-di-O-isopropylid ene-a-D- galactopyranose (Compound D12); ((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro- 5H-bis([1,3]dioxolo)[4,5-b:4',5'-d]pyran-5-yl)methyl 3, 6-dichloro-2-methoxybenzoate

[00243] Dicamba (250 mg, 1.13 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (2 drops) was added, followed by oxalyl chloride (0.12 mL, 1.4 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (2 mL) and added to a 0 °C solution of 1 ,2:3,4-di-O- isopropylidene-a-D-galactopyranose (294 mg, 1.13 mmol) in 1 :1 pyridine/CH ₂ CI ₂ (4 mL) and stirred at r.t. for 1.5 h. The mixture was quenched with saturated NaHCO ₃ solution (2 mL), transferred to a separatory funnel, and the organic layer was separated. The aqueous layer was extracted with CH ₂ CI ₂ (10 mL) and the combined organic layers were washed with brine (10 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (8% EtOAc/hexanes) to obtain 6-O-(2,5- dichloro-6-methoxybenzoyl)-1 ,2:3,4-di-O-isopropylidene-a-D-galactopyranose (Compound D12), as a colourless oil (430 mg, 82%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.34 (d, J = 8.7 Hz, 1 H), 7.10 (d, J = 8.7 Hz, 1 H), 5.55 (d, J = 5.0 Hz, 1 H), 4.67-4.63 (m, 2H), 4.43 (dd, J = 11.5, 7.6 Hz, 1 H), 4.35-4.31 (m, 2H), 4.19-4.17 (m, 1 H), 3.92 (s, 3H), 1.51 (s, 3H), 1.47 (s, 3H), 1.34 (s, 3H), 1.32 (s, 3H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 164.6, 154.2, 132.0, 130.3, 130.0, 126.8, 125.9, 109.8, 108.9, 96.5, 71.1 , 70.8, 70.5, 66.0, 65.0, 62.5, 26.1 , 26.1 , 25.1 , 24.6.

[00244] 6-O-(2,5-dichloro-6-methoxybenzoyl)-D-galactose (6-OGal Dicamba); ((2R, 3R,4S, 5R)-3, 4, 5, 6-tetrahydroxytetrahydro-2H-pyran-2-yl)methyl 3, 6-dichloro-2- methoxybenzoate (Compound D3)

[00245] 6-O-(2,5-dichloro-6-methoxybenzoyl)-1 ,2:3,4-di-O-isopropylidene-a-D- galactopyranose (Compound D12) (417 mg, 0.900 mmol) was dissolved in 4:1 TFA/H ₂ O (4 mL) and stirred at r.t. for 0.5 h, then concentrated in vacuo, and co-evaporated with toluene (3 x 5 mL). The resultant residue was then purified by flash column chromatography (0-10% MeOH/CH ₂ CI ₂ ) to obtain 6-O-(2,5-dichloro-6-methoxybenzoyl)-D-galactose (Compound D3) as a white resin (330 mg, 96%). ¹ H NMR (500 MHz, D ₂ O): δ 7.46-7.43 (m, 1 H), 7.21 -7.19 (m, 1 H), 5.27 (d, J = 3.5 Hz, 0.4H), 4.68-4.63 (m, 1 H), 4.59-4.50 (m, 1.6 H), 4.38 (dd, J = 8.2, 3.9 Hz, 0.4H), 4.08-4.07 (m, 0.4 Hz), 4.01 -3.98 (m, 1.2H), 3.89-3.83 (m, 3.8H), 3.66 (dd, J = 9.9, 3.4 Hz, 0.6H), 3.53 (dd, J = 9.9, 7.9 Hz, 0.6H); ¹³ C NMR (126 MHz, D ₂ O): δ 166.6, 166.5, 153.5, 133.4, 129.8, 129.3, 129.2, 127.1 , 127.1 , 97.1 , 93.0, 93.3, 93.1 , 72.4, 70.0, 69.6, 69.4, 68.8, 68.8, 66.7, 66.4, 63.2, 63.2.

[00246] The following scheme depicts the synthesis of Compounds D13 and D4 of the invention;

[00247] 1-O-(2,5-dichloro-6-methoxybenzoyl)-2,3:4,5-di-O-isopropylid ene-β-D- fructopyranose (Compound D13); ((3aS,5aR,8aR,8bS)-2,2,7,7-tetramethyltetrahydro-3aH- bis([1,3]dioxolo)[4,5-b:4',5'-d]pyran-3a-yl)methyl 3, 6-dichloro-2-methoxybenzoate

[00248] Dicamba (250 mg, 1.13 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (2 drops) was added, followed by oxalyl chloride (0.12 mL, 1.4 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (2 mL) and added to a 0 °C solution of 1 ,2;4,5-di-O- isopropylidene-β-D-fructopyranose (294 mg, 1.13 mmol) in 1 :1 pyridine/CH ₂ CI ₂ (4 mL) and stirred at r.t. for 2 h. The mixture was quenched with saturated NaHCO ₃ solution (2 mL), transferred to a separatory funnel, and the organic layer was separated. The aqueous layer was extracted with CH ₂ CI ₂ (10 mL) and the combined organic layers were washed with brine (10 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (8% EtOAc/hexanes) to obtain 1 -O-(2,5- dichloro-6-methoxybenzoyl)-2,3:4,5-di-O-isopropylidene-β-D- fructopyranose (Compound D13), as a colourless oil (456 mg, 87%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.35 (d, J = 8.7 Hz, 1 H), 7.1 1 (d, J = 8.7 Hz, 1 H), 4.61 (dd, J = 7.9, 2.6 Hz, 1 H), (d, J = 11 .6 Hz, 1 H), 4.41 (d, J = 1 1 .6 Hz, 1 H), 4.35 (d, J = 2.6 Hz, 1 H), 4.24 (ddd, J = 7.9, 1 .9, 0.5 Hz, 1 H), 3.92 (dd, J = 13.0, 1.9 Hz, 1 H), 3.92 (s, 3H), 3.78 (dd, J = 13.0, 0.5 Hz, 1 H), 1.52 (s, 3H), 1.46 (s, 3H), 1.34 (s, 3H), 1.28 (s, 3H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 164.1 , 154.1 , 132.1 , 130.2, 129.9, 126.8, 125.9, 109.3, 109.1 , 101.4, 70.9, 70.7, 70.2, 67.0, 62.4, 61.4, 26.7, 26.0, 25.2, 24.3.

[00249] 1-O-(2,5-dichloro-6-methoxybenzoyl)-D-fructose (1-OFruc Dicamba); ( ( 3S, 4R,5R) -2, 3, 4, 5-tetrahydroxytetrahydro -2 H -pyran -2-yl) methyl 3, 6-dichloro-2- methoxybenzoate (Compound D4)

[00250] 1 -O-(2,5-dichloro-6-methoxybenzoyl)-2,3:4,5-di-O-isopropylide ne-β-D- fructopyranose (Compound D13) (440 mg, 0.950 mmol) was dissolved in 4:1 TFA/H ₂ O (4 mL) and stirred at r.t. for 0.75 h, then concentrated in vacuo, and co-evaporated with toluene (3 x 5 mL). The resultant residue was then purified by flash column chromatography (50- 100% EtOAc/hex) to obtain 1 -O-(2,5-dichloro-6-methoxybenzoyl)-D-fructose (Compound D4) as a white resin (242 mg, 66%). ¹ H NMR (500 MHz, D ₂ O): δ 7.56-7.54 (m, 1 H), 7.31 -7.29 (m, 1 H), 4.66 (d, J = 1 1.5 Hz, 0.7H), 4.52-4.50 (m, 0.6H), 4.40 (d, J = 11.5 Hz, 0.7H), 4.17- 4.15 (m, 0.6H), 4.06 (dd, J = 12.9, 1.3 Hz, 0.7H), 4.01 -4.00 (m, 0.7H), 3.96-3.93 (m, 3.7H), 3.89 (d, J = 9.9 Hz, 0.7H), 3.87-3.83 (m, 0.3H), 3.81 -3.78 (m, 0.3H), 3.72 (dd, J = 12.9, 1.9 Hz, 0.7H), 3.70-3.66 (m, 0.3H). ¹³ C NMR (126 MHz, CDCI ₃ ): δ 166.6, 166.5, 153.4, 133.6, 129.8, 129.6, 129.0, 127.2, 127.2, 127.2, 127.1 , 100.5, 97.5, 81.6, 77.0, 74.7, 70.1 , 69.6, 68.5, 67.5, 66.1 , 64.3, 63.3, 63.3, 62.7.

[00251 ] The following scheme depicts the synthesis of Compounds D14 and D5 of the invention;

[00252] 1-O-(2,5-dichloro-6-methoxybenzoyl)-2,3:4,6-di-O-isopropylid ene-a-L- sorbofuranose (Compound D14); ((3aS,3bR,7aS,8aS)-2,2,5,5-tetramethyltetrahydro-8aH- [ 1 , 3]dioxolo[4 5 ':4, 5]furo[3,2-d][ 1 , 3]dioxin -8a-y I) methyl 3, 6-dichloro -2-methoxybenzoate

[00253] Dicamba (250 mg, 1.13 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (2 drops) was added, followed by oxalyl chloride (0.12 mL, 1.4 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (2 mL) and added to a 0 °C solution of 2,3:4,6-di-O- isopropylidene-a-L-sorbofuranose (294 mg, 1.13 mmol) in 1 :1 pyridine/CH ₂ CI ₂ (4 mL) and stirred at r.t. for 2 h. The mixture was quenched with saturated NaHCO ₃ solution (2 mL), transferred to a separatory funnel, and the organic layer was separated. The aqueous layer was extracted with CH ₂ CI ₂ (10 mL) and the combined organic layers were washed with brine (10 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (16% EtOAc/hexanes) to obtain 1-O-(2,5- dichloro-6-methoxybenzoyl)-2,3:4,6-di-O-isopropylidene-a-L-s orbofuranose (Compound D14), as a colourless oil (440 mg, 84%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.35 (d, J = 8.7Hz, 1 H), 7.11 (d, J = 8.7Hz, 1 H), 4.66 (d, J = 11.7 Hz, 1 H), 4.57 (d, J = 11.7 Hz, 1 H), 4.48 (s, 1 H), 4.34-4.33 (m, 1 H), 4.15-4.14 (m, 1 H), 4.06 (dd, J = 13.5, 2.2 Hz, 1 H), 4.03-4.00 (m, 1 H), 3.92 (s, 3H), 1.49 (s, 3H), 1.42 (s, 3H), 1.33 (s, 3H), 1.29 (s, 3H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 164.0, 154.2, 132.0, 130.2, 129.8, 126.8, 125.9, 112.9, 112.6, 97.5, 84.8, 73.2, 72.9, 65.3, 62.4, 60.4, 28.9, 27.7, 26.5, 18.8.

[00254] 1-O-(2,5-dichloro-6-methoxybenzoyl)-L-sorbose (1-OSorb Dicamba); ((3S, 4R, 5S)-2, 3, 4, 5-tetrahydroxytetrahydro-2H-pyran-2-yl)methyl 3, 6-dichloro-2- methoxybenzoate (Compound D5)

[00255] 1-O-(2,5-dichloro-6-methoxy)benzoyl-2,3:4,6-di-O-isopropylid ene-a-L- sorbofuranose (Compound D14) (396 mg, 0.855 mmol) was dissolved in 4:1 TFA/H ₂ O (4 mL) and stirred at r.t. for 5 h, then concentrated in vacuo, and co-evaporated with toluene (3 x 5 mL). The resultant residue was then purified by flash column chromatography (50-100% EtOAc/hex) to obtain 1 -O-(2,5-dichloro-6-methoxybenzoyl)-L-sorbose (Compound D5) as a white resin (207 mg, 63%). ¹ H NMR (500 MHz, D ₂ O): δ 7.51-7.49 (m, 1 H), 7.26-7.24 (m, 1 H), 4.63 (d, J = 11.5 Hz, 1 H), 4.39 (d, J = 11.5 Hz, 1 H), 3.90 (s, 3H), 3.76-3.67 (m, 3H), 3.61-3.56 (m, 2H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 166.3, 153.4, 133.5, 129.7, 129.1, 127.2, 127.1 , 97.2, 74.3, 71.4, 69.9, 66.8, 63.2, 62.6.

[00256] The following scheme depicts the synthesis of Compounds D15 and D6 of the invention;

[00257] 5-O-(2,5-dichloro-6-methoxybenzoyl)-1,2-O-isopropylidene-a-D -xylofuranose

( Compound D15); ((3aR, 5R, 6S, 6aR)-6-hydroxy-2,2-dimethyltetrahydrofuro[2, 3-d][ 1,3]dioxol- 5-yl)methyl 3, 6-dichloro-2-methoxybenzoate

[00258] Dicamba (250 mg, 1.13 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (2 drops) was added, followed by oxalyl chloride (0.12 mL, 1.4 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (2 mL) and added to a 0 °C solution of 1 ,2-O- isopropylidene-a-D-xylofuranose (Compound D15) (215 mg, 1.13 mmol) in 1 :1 pyridine/CH ₂ CI ₂ (4 mL) and stirred at r.t. for 1.5 h. The mixture was quenched with saturated NaHCO ₃ solution (2 mL), transferred to a separatory funnel, and the organic layer was separated. The aqueous layer was extracted with CH ₂ CI ₂ (10 mL) and the combined organic layers were washed with brine (10 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (30% EtOAc/hexanes) to obtain 5-O-(2,5-dichloro-6-methoxybenzoyl)-1 ,2-O-isopropylidene-a-D- xylofuranose (Compound D15), as a pale yellow oil (330 mg, 75%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.38 (d, J = 8.7 Hz, 1 H), 7.13 (d, J = 8.7 Hz, 1 H), 5.96 (d, J = 3.6 Hz, 1 H), 4.82 (dd, J = 11 .1 , 7.5 Hz, 1 H), 4.58 (d, J = 3.6 Hz, 1 H), 4.47-4.40 (m, 2H), 4.28 (dd, J = 4.6, 2.5 Hz, 1 H), 3.92 (s, 3H), 2.77 (d, J = 4.6 Hz, 1 H), 1.50 (s, 3H), 1.32 (s, 3H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 165.3, 154.0, 132.4, 129.9, 129.7, 126.9, 126.1 , 112.1 , 105.0, 85.2, 78.1 ,

74.7, 62.5, 62.5, 27.0, 26.4.

[00259] 5-O-(2,5-dichloro-6-methoxybenzoyl)-D-xylose (5-OXyl Dicamba); ((2R, 3R,4R)-3, 4, 5-trihydroxytetrahydrofuran-2-yl)methyl 3, 6-dichloro-2-methoxybenzoate (Compound D6)

[00260] 5-O-(2,5-dichloro-6-methoxybenzoyl)-1 ,2-O-isopropylidene-a-D-xylofuranose (Compound D15) (318 mg, 0.809 mmol) was dissolved in 4:1 TFA/H ₂ O (4 mL) and stirred at r.t. for 1.5 h, then concentrated in vacuo, and co-evaporated with toluene (3 x 5 mL). The resultant residue was then purified by flash column chromatography (50-100% EtOAc/hex) to obtain 5-O-(2,5-dichloro-6-methoxybenzoyl)-D-xylose (Compound D6) as a colourless oil (150 mg, 52%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.35-7.33 (m, 1 H), 7.12-7.09 (m, 1 H), 4.50- 4.48 (m, 0.55H), 5.24 (s, 0.45H), 4.78 (dd, J = 11.3, 5.6 Hz, 0.45H), 4.66 (dd, J = 1 1.4, 5.0 Hz, 0.55H), 4.54 (dd, J = 1 1 .3, 6.6 Hz, 0.45H), 4.50-4.47 (m, 1 H), 1 .39 (dd, J = 1 1 .4, 6.0 Hz, 0.55H), 4.34-4.32 (m, 0.55H), 4.23 (s, 0.45H), 4.20-4.19 (m, 0.45H), 4.14-4.12 (m, 0.55H), 3.89 (s, 1.35H), 3.88 (s, 1.65H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 165.2, 164.9, 153.8, 132.3, 132.3, 130.0, 129.9, 129.7, 129.7, 126.9, 126.9, 126.1 , 103.1 , 96.3, 80.3, 79.9, 76.4, 76.2,

75.8, 65.0, 64.4, 62.6.

[00261 ] The following scheme depicts the synthesis of Compounds D16 and D7 of the invention;

[00262] Methyl 5-O-(2,5-dichloro-6-methoxybenzoyl)-2,3-O-isopropylidene-β- D- hbofuranoside (Compound D16); ((3aR,4R,6R,6aR)-6-methoxy-2,2- dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-yl)methyl 3, 6-dichloro-2-methoxybenzoate

[00263] Dicamba (250 mg, 1.13 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (2 drops) was added, followed by oxalyl chloride (0.12 mL, 1.4 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (2 mL) and added to a 0 °C solution of methyl 2,3-O- isopropylidene-β-D-ribofuranoside (230 mg, 1.13 mmol) in 1 :1 pyridine/CH ₂ CI ₂ (4 mL) and stirred at r.t. for 2 h. The mixture was quenched with saturated NaHCO ₃ solution (2 mL), transferred to a separatory funnel, and the organic layer was separated. The aqueous layer was extracted with CH ₂ CI ₂ (10 mL) and the combined organic layers were washed with brine (10 mL), dried over MgSO4, filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (8% EtOAc/hexanes) to obtain methyl 5-O- (2,5-dichloro-6-methoxybenzoyl)-2,3-O-isopropylidene-β-D-ri bofuranoside (Compound D16), as a colourless oil (306 mg, 66%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.36 (d, J = 8.7 Hz, 1 H), 7.12 (d, J = 8.7 Hz, 1 H), 5.01 (s, 1 H), 4.73 (d, J = 6.0 Hz, 1 H), 4.64 (d, J = 6.0 Hz, 1 H), 4.49- 4.46 (m, 1 H), 4.43-4.35 (m, 2H), 3.92 (s, 3H), 3.36 (s, 3H), 1.48 (s, 3H), 1.32 (s, 3H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 164.3, 154.1, 132.1 , 130.2, 129.8, 126.9, 126.0, 112.8, 109.5, 85.2, 84.0, 82.0, 66.2, 62.5, 55.1 , 26.5, 25.1.

[00264] 5-O-(2,5-dichloro-6-methoxybenzoyl)-D-ribose (5-ORib Dicamba); ((2R, 3S, 4R)-3, 4,5-trihydroxytetrahydrofuran-2-yl)methyl 3, 6-dichloro-2-methoxybenzoate (Compound D7)

[00265] 5-O-(2,5-dichloro-6-methoxybenzoyl)-2,3-O-isopropylidene-β- D- ribofuranoside (Compound D16) (290 mg, 0.712 mmol) was dissolved in 4:1 TFA/H ₂ O (4 mL) and stirred at r.t. for 2 h, then concentrated in vacuo, and co-evaporated with toluene (3 x 5 mL). The resultant residue was then purified by flash column chromatography (50-100% EtOAc/hex) to obtain 5-O-(2,5-dichloro-6-methoxybenzoyl)-D-ribose (Compound D7) as a colourless oil (179 mg, 71%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.36 (d, J = 8.7 Hz, 1 H), 7.14- 7.11 (m, 1 H), 5.35 (s, 0.7H), 5.30 (s, 0.3H), 4.70 (dd, J = 11.6, 3.8 Hz, 0.3H), 4.56 (dd, J = 1 1 .9, 3.6 Hz, 0.7H), 4.48-4.43 (m, 1 H), 4.38-4.33 (m, 1 H), 4.23-4.20 (m, 0.3H), 4.11 -4.09 (m, 1.4H), 4.06-4.03 (m, 0.3H), 3.91 (s, 0.9H), 3.90 (s, 2.1 H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 164.6, 164.5, 153.9, 153.7, 132.3, 130.1 , 130.0, 129.8, 129.7, 127.0, 126.3, 126.1 , 102.1 , 97.8, 80.9, 80.8, 75.7, 72.0, 71.5, 71.3, 66.5, 65.4, 62.8, 62.6.

[00266] The following scheme depicts the synthesis of Compounds D17, D18 and D8 of the invention;

[00267] Benzyl 4,6-O-benzylidene-2-O-(2,5-dichloro-6-methoxybenzoyl)-a-D- glucopyranoside (Compound D17); (4aR,6S,7R,8S,8aS)-6-(benzyloxy)-8-hydroxy-2- phenylhexahydropyrano[3,2-d][1,3]dioxin-7-yl 3, 6-dichloro-2-methoxybenzoate

[00268] Dicamba (339 mg, 1.53 mmol) was dissolved in CH ₂ CI ₂ (10 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.17 mL, 2.0 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (1 mL) and added dropwise to a -30 °C solution of benzyl 4,6-O-benzylidene-a-D-glucopyranoside (500 mg, 1.40 mmol, prepared in accordance with the previously reported method of J. Am. Chem. Soc. 2002, 124 (50), 15001 -15005) in 4:1 pyridine/CH ₂ CI ₂ (2.5 mL). The solution was gradually warmed to 0 °C over 2.5h, then kept at r.t. for 18 h. The mixture was concentrated in vacuo and the residue diluted with EtOAc (10 mL), washed with saturated NaHCO ₃ solution (10 mL), water (3 x 5 mL), and brine (5 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (0-30% EtOAc/hexanes) to obtain benzyl 4,6-O- benzylidene-2-O-(2,5-dichloro-6-methoxybenzoyl)-a-D-glucopyr anoside (Compound D17) as a white solid (347 mg, 44%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.52-7.50 (m, 2H), 7.39-7.29 (m, 9H), 7.13 (d, J = 8.7 Hz, 1 H), 5.58 (s, 1 H), 5.33 (d, J = 3.8 Hz, 1 H), 5.14 (dd, J = 9.6, 3.8 Hz, 1 H), 4.75 (d, J = 1 1 .8 Hz, 1 H), 4.60 (d, J = 11 .8 Hz, 1 H), 4.36 (ddd, J = 9.6, 9.5, 2.7 Hz, 1 H), 4.25 (dd, J = 10.3, 4.9 Hz, 1 H), 3.96 (ddd, J = 10.2, 9.6, 4.8 Hz, 1 H), 3.87 (s, 3H), 3.79 (dd, J = 10.3, 10.2 Hz, 1 H), 3.68 (dd, J = 9.5, 9.5 Hz, 1 H), 2.70 (d, J = 2.7 Hz, 1 H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 164.2, 154.1 , 137.0, 136.7, 132.3, 129.8, 129.7, 129.4, 128.6, 128.5, 128.3, 128.2, 126.9, 126.4, 126.0, 102.1 , 96.1 , 81 .3, 75.4, 70.4, 69.0, 68.8, 62.7, 62.5. [00269] 2-O-(2,5-dichloro-6-methoxybenzoyl)-D-glucose (2-OGIu Dicamba); (3R,4S,5S,6R)-2,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2 H-pyran-3-yl 3,6-dichloro-2- methoxybenzoate (Compound D8)

Benzyl 4,6-O-benzylidene-2-O-(2,5-dichloro-6-methoxybenzoyl)-a-D-gl ucopyranoside (Compound D17) (320 mg, 0.570 mmol) was dissolved in 2:1 MeOH/CHCI ₃ (5 mL) and p- toluenesulfonic acid monohydrate (40 mg) was added. The solution was stirred at r.t. for 1.5h, then concentrated in vacuo and the residue diluted with EtOAc (10 mL), washed with saturated NaHCO ₃ solution (2 x 10 mL), and brine (5 mL), dried over MgSO ₄ , filtered and concentrated in vacuo, then adsorbed onto a plug of silica, washed with 40% EtOAc/hex, and eluted with EtOAc to yield benzyl 2-O-(2,5-dichloro-6-methoxybenzoyl)-a-D- glucopyranoside (Compound D18) as a white foam (204 mg, 75%). ¹ H NMR (400 MHz, CDCI ₃ ): δ 7.36 (d, J = 8.7 Hz, 1 H), 7.33-7.27 (m, 5H), 7.12 (d, J = 8.7 Hz, 1 H), 5.28 (d, J = 3.7 Hz, 1 H), 5.04 (dd, J = 10.0, 3.7 Hz, 1 H), 4.72 (d, J = 11 .9 Hz, 1 H), 4.56 (d, J = 11 .9 Hz, 1 H), 4.13 (dd, J = 10.0, 8.6 Hz, 1 H), 3.88-3.84 (m, 1 H), 3.85 (s, 3H), 3.83-3.71 (m, 3H); ¹³ C NMR (101 MHz, CDCI ₃ ): δ 164.4, 154.0, 136.9, 132.3, 129.9, 129.7, 128.6, 128.2, 128.1 , 126.9, 126.1 , 95.6, 75.2, 71.7, 71.4, 70.5, 70.2, 92.6, 61.9.

[00270] Benzyl 2-O-(2,5-dichloro-6-methoxybenzoyl)-a-D-glucopyranoside

(Compound D18) (188 mg, 0.397 mmol) was dissolved in MeOH (2 mL) and placed under N ₂ . 10% Pd/C (25 mg) was added, and the flask was evacuated and filled with H ₂ (x3), then stirred under H ₂ for 18h, then filtered through celite and purified by flash column chromatography (0-20% MeOH/CH ₂ CI ₂ , followed by 50-100% EtOAc/hexanes) to obtain 2- 0-(2,5-dichloro-6-methoxybenzoyl)-D-glucose (Compound D8) as a white resin (60 mg, 39%). ¹ H NMR (400 MHz, D ₂ O): δ 7.60-7.57 (m, 1 H), 7.35-7.32 (m, 1 H), 5.58 (d, J = 3.7 Hz, 0.5H), 5.05 (dd, J = 10.1 , 3.7 Hz, 0.5H), 5.02-4.98 (m, 0.5H), 4.94 (d, J = 8.0 Hz, 0.5H), 4.00-3.88 (m, 5H), 3.84-3.75 (m, 1.5H), 3.61-3.54 (m, 1.5 H); ¹³ C NMR (126 MHz, D ₂ O): δ 166.4, 166.2, 153.3, 153.2, 133.5, 133.5, 129.7, 129.6, 129.3, 129.2, 127.3, 127.3, 127.2, 127.1 , 94.6, 89.9, 77.1 , 76.6, 75.7, 74.2, 71 .9, 70.9, 70.6, 63.2, 61 .3, 61 .1 .

[00271] The following scheme depicts the synthesis of Compounds D19 and D9 of the invention [00272] 3-O-(2,5-dichloro-6-methoxybenzoyl)-1,2:4,6-di-O-isopropylid ene-a-D- glucofuranose; (3aR,5R,6S,6aR)-5-((R) -2, 2-di methyl- 1 , 3-dioxolan-4-yl) -2, 2- dimethyltetrahydrofuro[2, 3-d][ 1 ,3]dioxol-6-yl 3, 6-dichloro-2-methoxybenzoate ( Compound D19)

[00273] Dicamba (467 mg, 2.1 1 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.24 mL, 2.8 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in pyridine (3 mL) and 1 ,2;5,6-di-O-isopropylidene-a-D-glucofuranose (500 mg, 1 .92 mmol) was added and stirred at r.t. for 5.5 h. The mixture was concentrated in vacuo and the residue diluted with EtOAc (20 mL), washed with water (20 mL), saturated NaHCO ₃ solution (20 mL), water (10 mL), and brine (10 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (0-30% EtOAc/hexanes) to obtain 3-O-(2,5-dichloro-6-methoxybenzoyl)- 1 ,2:5,6-di-O-isopropylidene-a-D-glucofuranose (Compound D19) as a colourless resin (334 mg, 38%). ¹ H NMR (600 MHz, CDCI ₃ ): δ 7.37 (d, J = 8.7 Hz, 1 H), 7.12 (d, J = 8.7 Hz, 1 H), 5.89 (d, J = 3.7 Hz, 1 H), 5.55 (d, J = 2.5 Hz, 1 H), 4.68 (d, J = 3.7 Hz, 1 H), 4.30-4.25 (m, 2H), 4.07 (dd, J = 8.8, 5.6 Hz, 1 H), 3.99 (dd, J = 8.8, 4.7 Hz, 1 H), 3.91 (s, 3H), 1.55 (s, 3H), 1.43 (s, 3H), 1.34 (s, 3H), 1.31 (s, 3H); ¹³ C NMR (151 MHz, CDCI ₃ ): δ 163.3, 154.1 , 132.3, 129.8, 129.7, 126.9, 126.0, 1 12.7, 109.6, 105.3, 83.2, 80.0, 77.7, 72.1 , 67.5, 62.6, 27.0, 26.9, 26.4, 25.4.

[00274] 3-O-(2,5-dichloro-6-methoxybenzoyl)-D-glucose (3-OGIu Dicamba); (3R,4S,5R,6R)-2,3,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2 H-pyran-4-yl 3,6- dichloro-2-methoxybenzoate (Compound D9)

[00275] 3-O-(2,5-Dichloro-6-methoxybenzoyl)-1 ,2:5,6-di-O-isopropylidene-a-D- glucofuranose (Compound D19) (307 mg, 0.663 mmol) was dissolved in 4:1 TFA/H ₂ O (5 mL) and stirred at r.t. for 1 h, then concentrated in vacuo, and co-evaporated with toluene (2 x 10 mL). The resultant residue was then purified by flash column chromatography (0-10% MeOH/CH ₂ CI ₂ ) to obtain 3-O-(2,5-dichloro-6-methoxybenzoyl)-D-glucose (Compound D9) as a white resin (191 mg, 75%). ¹ H NMR (600 MHz, D ₂ O): δ 7.51 (d, J = 8.8 Hz, 1 H), 7.27 (d, J = 8.8 Hz, 1 H), 5.48 (dd, J = 9.8 Hz, 0.5H), 5.31 -5.28 (m, 1 H), 4.80-4.79 (m, 0.5H), 3.99 (ddd, J = 10.1 , 5.2, 2.2 Hz, 0.5H), 3.95 (dd, J = 12.3, 2.2 Hz, 0.5H), 3.91 (s, 1.5 H). 3.90 (s, 1.5H), 3.90-3.88 (m, 0.5H), 3.81 -3.79 (m, 1 H), 3.76 (dd, J = 12.3, 5.8 Hz, 0.5H), 3.72-3.67 (m, 1 H), 3.62 (ddd, J = 9.9, 5.8, 2.2 Hz, 1 H), 3.51 (dd, J = 9.7, 7.9 Hz, 0.5H); ¹³ C NMR (151 MHz, D ₂ O): δ 166.8, 166.6, 153.3, 133.4, 133.3, 129.7, 129.6, 129.5, 127.3, 127.2, 96.8, 92.9, 79.4, 77.7, 76.7, 72.9, 72.2, 70.3, 68.4, 68.3, 63.2, 61.2, 61.0. [00276] The following scheme depicts the synthesis of Compound D10 of the invention

[00277] Benzyl 2,3,6-tri-O-benzyl-4-O-(2,5-dichloro-6-methoxybenzoyl)-a-D- glucopyranoside

Dicamba (412 mg, 1.86 mmol) was dissolved in CH ₂ CI ₂ (10 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.21 mL, 2.4 mmol). The mixture was stirred at r.t. for 1.5 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL), then dissolved in anhydrous DMF (2 mL). Benzyl 2,3,6-tri-O-benzyl-a-D-glucopyranoside {662 mg, 1.22 mmol - prepared from benzyl 2,3-bis-O-(benzyl)-4,6-O-benzylidene-a-D-glucopyranoside (Org. Lett. 2020, 22 (2), 523-527) with NaCNBH ₃ /HCI (Carb. Res. 2001 , 335 (3), 159-165)} was dissolved in anhydrous DMF (5 mL) and cooled to 0 °C. NaH (60% in mineral oil, 72 mg, 1.8 mmol) was added, and the mixture was stirred at 0 °C for 45 min, then at r.t. for 30 min, then cooled to 0 °C. The acid chloride/DMF solution was added dropwise, then stirred at r.t. for 2h. The mixture was quenched with MeOH (0.5 mL), diluted with water (20 mL) and extracted with EtOAc (4 x 20 mL). The organic phases were combined, washed with water (2 x 20 mL) and saturated NaHCO ₃ solution (20 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (5-30% EtOAc/hexanes) to obtain benzyl 2,3,6-tri-O-benzyl-4-O-(2,5- dichloro-6-methoxybenzoyl)-a-D-glucopyranoside as a colourless oil (269 mg, 30%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.42-7.21 (m, 21 H), 7.08 (d, J = 8.7 Hz, 1 H), 5.41 (dd, J = 10.1 , 9.3 Hz, 1 H), 4.96 (d, J = 11 .1 Hz, 1 H), 4.89 (d, J = 3.6 Hz, 1 H), 4.83 (d, J = 1 1 .1 Hz, 1 H), 4.74 (d, J = 12.2 Hz, 1 H), 4.67-4.61 (m, 2H), 4.59-4.50 (m, 3H), 4.13 (dd, J = 9.4, 9.2 Hz, 1 H), 4.01 (ddd, J = 10.1 , 5.2, 2.1 Hz, 1 H), 3.76 (dd, J = 10.9, 2.1 Hz, 1 H), 3.71 -3.67 (m, 5H); ¹³ C NMR (101 MHz, CDCI ₃ ): δ 163.6, 154.2, 139.0, 138.3, 138.0, 137.1 , 132.1 , 130.4, 129.7, 128.6, 128.6, 128.5, 128.5, 128.2, 128.2, 128.1 , 128.0, 127.8, 127.7, 127.5, 127.3, 126.9, 126.1 , 95.3, 79.9, 78.7, 74.9, 73.8, 73.2, 72.3, 69.4, 69.3, 68.8, 62.4.

[00278] 4-O-(2,5-dichloro-6-methoxybenzoyl)-D-glucose (4-OGIu Dicamba); (2R,3S,4R,5R, 6S)-4,5, 6-trihydroxy-2-(hydroxymethyl)tetrahydro-2H-pyran-3-yl 3, 6- dichloro-2-methoxybenzoate (Compound D10) [00279] Benzyl 4-O-(2,5-dichloro-6-methoxybenzoyl)-2,3,6-tri-O-benzyl-a-D- glucopyranoside (249 mg, 0.335 mmol) was dissolved in MeOH (5 mL) and EtOAc (1 mL) and placed under N ₂ . 20% Pd(OH) ₂ /C (27 mg) was added, and the flask was evacuated and filled with H ₂ (x3), then stirred under H ₂ for 2h, then filtered and purified by flash column chromatography (EtOAc) to obtain 4-O-(2,5-dichloro-6-methoxybenzoyl)-D-glucose (Compound D10) as a white resin (68 mg, 53%). ¹ H NMR (500 MHz, D ₂ O): δ 7.43 (d, J = 8.7 Hz, 0.5H), 7.43 (d, J = 8.7 Hz, 0.5H), 7.19 (d, J = 8.7 Hz, 0.5H), 7.18 (d, J = 8.7 Hz, 0.5H), 5.31 (d, J = 3.6 Hz, 0.5H), 5.18-5.13 (m, 1 H), 4.71 (d, J = 8.0 Hz, 0.5H), 4.11 -4.08 (m, 0.5H), 3.99 (dd, J = 9.6, 9.6 Hz, 0.5H), 3.89-3.82 (m, 4H), 3.79-3.67 (m, 2.5H), 3.40 (dd, J = 9.2, 8.0 Hz, 0.5H); ¹³ C NMR (126 MHz, D ₂ O): δ 166.0, 165.9, 153.3, 153.3, 133.4, 133.4, 129.5, 129.4, 129.3, 127.2, 127.1 , 127.1 , 96.5, 92.7, 75.1 , 74.3, 74.2, 73.1 , 72.8, 72.4, 71.2, 69.8, 63.1 , 60.8, 60.7.

[00280] The following scheme depicts the synthesis of Compound D20 of the invention

[00281] Benzyl 2-O-(2, 5-dichloro-6-methoxybenzoyl) -3,4-O-isopropylidene-a-L- arabinopyranoside

[00282] Dicamba (250 mg, 1.13 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.13 mL, 1.5 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (1 mL) and added dropwise to a solution of benzyl 3,4-O- isopropylidene-a-L-arabinopyranoside (215 mg, 0.767 mmol) in pyridine (1 mL). The solution was stirred at r.t. for 1.5 h. The mixture was washed with water (5 mL), dried over MgSC>4, filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (0-20% EtOAc/hexanes) to obtain benzyl 2-O-(2,5-dichloro-6- methoxybenzoyl)-3,4-O-isopropylidene-a-L-arabinopyranoside as a white solid (172 mg, 46%). ¹ H NMR (400 MHz, CDCI ₃ ): δ 7.36-7.28 (m, 6H), 7.10 (d, J = 8.6 Hz, 1 H), 5.24-5.22 (m, 2H), 4.74 (d, J = 11.8 Hz, 1 H), 4.55 (d, J = 11.8 Hz, 1 H), 4.46-4.43 (m, 1 H), 4.30-4.28 (m, 1 H), 4.08 (d, J = 13.4 Hz, 1 H), 4.02 (dd, J = 13.4, 2.7 Hz, 1 H), 3.86 (s, 3H), 1.60 (s, 3H), 1.37 (s, 3H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 164.3, 154.1 , 136.9, 132.0, 130.1 , 129.8, 128.6, 128.1 , 128.1 , 126.8, 125.8, 109.6, 95.6, 74.1 , 73.9, 72.8, 70.1 , 62.3, 59.2, 28.2, 26.6.

[00283] 2-O-(2,5-Dichloro-6-methoxybenzoyl)-a-L-arabinose (2-O-L-Ara Dicamba); (2R,3R,4S,5S)-2,4-dihydroxy-5-(hydroxymethyl)tetrahydrofuran -3-yl 3,6-dichloro-2- methoxybenzoate (Compound D20)

[00284] Benzyl 2-O-(2,5-dichloro-6-methoxybenzoyl)-3,4-O-isopropylidene-a-L - arabinopyranoside (150 mg, 0.310 mmol) was dissolved in CH ₂ CH ₂ (1 mL) and 9:1 TFA/H ₂ O (0.05 mL) was added. The solution was stirred at r.t. for 18 h, then quenched with saturated NaHCO ₃ solution (5 mL), the organic phase was separated, and the aqueous phase was extracted with CH ₂ CH ₂ (5 mL). The organic phases were combined, dried over MgSO ₄ , filtered and concentrated in vacuo, then dissolved in MeOH (1 mL). 10% Pd/C (14 mg) was added, and the flask was evacuated and filled with H ₂ (x3), then stirred under H ₂ for 48 h, then filtered through celite and purified by flash column chromatography (50-100% EtOAc/hex then 0-5% MeOH/CH ₂ CI ₂ ) to obtain 2-O-(2,5-dichloro-6-methoxybenzoyl)-a-L- arabinose (Compound D20) as a white foam (45 mg, 41%). ¹ H NMR (400 MHz, D ₂ O): δ 7.58-7.55 (m, 1 H), 7.32-7.30 (m, 1 H), 5.59 (d, J = 3.6 Hz, 0.4H), 5.32 (dd, J = 10.2, 3.6 Hz, 0.4H), 5.22 (dd, J = 9.9, 8.0 Hz, 0.6H), 4.8 (m, 0.6H), 4.17-4.11 (m, 1.4H), 4.0-3.92 (m, 4.6H), 3.75-3.72 (m, 1 H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 166.7, 166.4, 153.3, 153.3, 133.5, 133.5, 129.7, 129.6, 129.4, 129.2, 127.3, 127.3, 127.2, 127.1 , 95.3, 90.5, 76.1 , 74.0, 71.1 , 69.8, 69.4, 67.0, 66.8, 63.2, 63.2, 63.0.

[00285] The following scheme depicts the synthesis of Compound D21 of the invention

[00286] Benzyl 4-O-(2,5-dichloro-6-methoxybenzoyl)-a-L-arabinopyranoside

[00287] Dicamba (438 mg, 1.98 mmol) was dissolved in CH ₂ CI ₂ (10 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.23 mL, 2.7 mmol). The mixture was stirred at r.t. for 4 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (0.5 mL) and added dropwise to a solution of benzyl 2,3-O- isopropylidene-a-L-arabinopyranoside (370 mg, 1.32 mmol, prepared in accordance with Aust. J. Chem. 2007, 60, 211-213) in 1 :1 pyridine/CH ₂ CI ₂ (4 mL). The solution was stirred at r.t. for 18 h, then quenched with saturated NaHCO ₃ solution (5 mL), the organic phase was separated and washed with 1 M HCI (2 x 10 mL), dried over MgSO ₄ , filtered and concentrated in vacuo, then dissolved in MeOH (2 mL). 32% HCI (0.02 mL) was added and the solution allowed to stand for 10 min, then purified by flash column chromatography (20- 100% EtOAc/hexanes) to obtain benzyl 4-O-(2,5-dichloro-6-methoxybenzoyl)-a-L- arabinopyranoside as a cream resin (451 mg, 77%). ¹ H NMR (400 MHz, CDCI ₃ ): δ 7.40-7.30 (m, 6H), 7.13 (d, J = 8.7 Hz, 1 H), 5.49-5.48 (m, 1 H), 5.02 (d, J = 3.7 Hz, 1 H), 4.77 (d, J = 11.7 Hz, 1 H), 4.55 (d, J = 11.7 Hz, 1 H), 4.06 (dd, J = 9.8, 3.6 Hz, 1 H), 3.99 (dd, J = 13.2, 1.3 Hz, 1 H), 3.93 (s, 3H), 3.92 (dd, J = 13.2, 2.1 Hz, 1 H), 3.81 (dd, J = 9.8, 3.7 Hz, 1 H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 164.3, 154.0, 136.9, 132.3, 130.0, 129.8, 128.8, 128.3, 128.2, 126.9, 126.1 , 98.1 , 73.5, 70.3, 70.2, 69.3, 62.6, 61.0.

[00288] 4-O-(2,5-Dichloro-6-methoxybenzoyl)-a-L-arabinose (4-O-L-Ara Dicamba); (3S,4R,5R)-4,5,6-trihydroxytetrahydro-2H-pyran-3-yl 3,6-dichloro-2-methoxybenzoate (Compound D21)

[00289] Benzyl 4-O-(2,5-dichloro-6-methoxybenzoyl)-a-L-arabinopyranoside (431 mg, 0.972 mmol) was dissolved in MeOH (5 mL) and placed under N ₂ . 10% Pd/C (43 mg) was added and the flask was evacuated and filled with H ₂ (x3), then stirred under H ₂ for 1.5 h, then filtered through celite and purified by flash column chromatography (0-10% MeOH/CH ₂ CI ₂ ) to obtain 4-O-(2,5-dichloro-6-methoxybenzoyl)-a-L-arabinose (Compound D21) as a white foam (177 mg, 52%). ¹ H NMR (500 MHz, CD ₃ CN): δ 7.51-7.49 (m, 1 H), 7.26-7.24 (m, 2H), 5.35-5.34 (m, 0.5H), 5.31-5.30 (m, 0.5H), 5.09-5.08 (m, 0.5H), 4.72-4.72 (m, 0.5H), 4.42-4.39 (m, 1 H), 4.08 (dd, J = 13.0, 1.5 Hz, 0.5H), 4.01 (dd, J = 13.3, 2.9 Hz, 0.5H), 3.98-3.95 (m, 0.5H), 3.92 (s, 1.5H), 3.91 (s, 1.5H), 3.77-3.73 (m, 1 H), 3.69 (dd, J = 13.3, 1.5 Hz, 0.5H), 3.61-3.57 (m, 0.5H), 3.43 (bd, J = 5.2 Hz, 0.5H), 3.41 (bs, 0.5H), 3.37- 3.38 (m, 0.5H), 3.26 (bd, J = 5.3 Hz, 0.5H), 2.99-2.97 (m, 0.5H); ¹³ C NMR (126 MHz, CD ₃ CN): δ 165.0, 164.9, 154.6, 154.6, 133.2, 133.2, 131.3, 131.2, 130.1 , 130.1, 127.7, 127.7, 127.1 , 127.1 , 98.1 , 93.7, 74.9, 74.0, 73.5, 72.0, 70.7, 68.6, 63.9, 63.3, 63.3, 60.9.

[00290] The following scheme depicts the synthesis of Compounds D22 and D23 of the invention [00291 ] 5-O-(2,5-Dichloro-6-methoxybenzoyl)-1,2-O-( 1 -isopropylidene)-/3-D- arabinofuranose; ((3aS,5R,6R,6aS)-6-hydroxy-2,2-dimethyltetrahydrofuro[2,3-d] [1,3]dioxol- 5-yl)methyl 3,6-dichloro-2-methoxybenzoate (Compound D22)

[00292] Dicamba (209 mg, 0.946 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.1 1 mL, 1 .2 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (2 mL) and added dropwise to a 0 °C solution of 1 ,2-O-(1 - isopropylidene)-β-D-arabinofuranose (prepared in accordance with J. Org. Chem. 2015, 80 (20), 10060-10075, 150 mg, 0.789 mmol) in 1 :1 pyridine/CFhCh (2 mL). The solution was stirred at r.t. for 3 h, then concentrated in vacuo and purified by flash column chromatography (10-40% EtOAc/hexanes) to obtain 5-O-(2,5-dichloro-6-methoxybenzoyl)- 1 ,2-O-(1 -isopropylidene)-β-D-arabinofuranose (Compound D22) as a white resin (167 mg, 54%). ¹ H NMR (400 MHz, CDCI ₃ ): δ 7.36 (d, J = 8.7 Hz, 1 H), 7.12 (d, J = 8.7 Hz, 1 H), 5.96 (d, J = 3.8 Hz, 1 H), 4.58-4.56 (m, 3H), 4.38-4.37 (m, 1 H), 4.30 (ddd, J = 6.8, 6.8, 1.7 Hz, 1 H), 3.92 (s, 3H), 1.55 (s, 3H), 1.33 (s, 3H); ¹³ C NMR (101 MHz, CDCI ₃ ): δ 164.3, 154.0, 132.2, 130.2, 129.8, 126.9, 126.0, 1 13.0, 106.1 , 86.8, 85.0, 76.5, 65.5, 62.6, 27.0, 26.2.

[00293] 5-O-(2,5-Dichloro-6-methoxybenzoyl)-D-arabinofuranose (5-O-D-Ara Dicamba); ((2R, 3S, 4S)-3, 4,5-trihydroxytetrahydrofuran-2-yl)methyl 3, 6-dichloro-2- methoxybenzoate (Compound D23)

[00294] 5-O-(2,5-Dichloro-6-methoxybenzoyl)-1 ,2-O-(1 -isopropylidene)-β-D- arabinofuranose (Compound D22) (158 mg, 0.402 mmol) was dissolved in 4:1 TFA/H ₂ O (1 mL) and allowed to stand at r.t. for 20 min, then concentrated in vacuo and purified by flash column chromatography (50-100% EtOAc/hexanes) to obtain 5-O-(2, 5-dichloro-6- methoxybenzoyl)-D-arabinofuranose (Compound D23, 107 mg, 75%). ¹ H NMR (400 MHz, CDCI ₃ ): δ 7.33-7.30 (m, 1 H), 7.10-7.07 (m, 1 H), 5.30 (s, 1 H), 4.60-4.56 (m, 1 H), 4.47-4.43 (m, 1 H), 4.40-4.37 (m, 0.5H), 4.16-4.12 (m, 1 H), 4.09-4.01 (m, 1.5H), 3.88 (s, 1.5H), 3.87 (s, 1.5H); ¹³ C NMR (101 MHz, CDCI ₃ ): δ 164.8, 164.7, 153.8, 153.8, 132.3, 132.3, 129.9, 129.9, 129.8, 129.8, 126.9, 126.9, 126.2, 126.2, 102.4, 96.0, 82.0, 81.5, 79.3, 76.3, 67.4, 65.7, 62.7, 62.7.

[00295] The following scheme depicts the synthesis of Compound D24 of the invention

[00296] Benzyl 6-O-(2,5-dichloro-6-methoxybenzoyl)-a-D-mannopyranoside

[00297] Dicamba (265 mg, 1.20 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.14 mL, 1.6 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (1 mL) and added dropwise to a 0 °C solution of benzyl a- D-mannopyranoside (270 mg, 0.999 mmol) in pyridine (1 mL). The solution was stirred at r.t. for 18 h, then concentrated in vacuo and purified by flash column chromatography (50-100% EtOAc/hexanes) to obtain benzyl 6-O-(2,5-dichloro-6-methoxybenzoyl)-a-D- mannopyranoside as a white resin (337 mg, 71%). ¹ H NMR (600 MHz, CDCI ₃ ): δ 7.35-7.27 (m, 6H), 7.10 (d, J = 8.6 Hz, 1 H), 4.91 (d, J = 1.4 Hz, 1 H), 4.76 (dd, J = 11.9, 4.9 Hz, 1 H), 4.70 (d, J = 11 .9 Hz, 1 H), 4.55 (dd, J = 11 .9, 2.0 Hz, 1 H), 4.50 (d, J = 11 .9 Hz, 1 H), 3.97 (dd, J = 3.2, 1 .4 Hz, 1 H), 3.90 (s, 3H), 3.90-3.86 (m, 2H), 3.80 (dd, J = 9.6, 9.6 Hz, 1 H); ¹³ C NMR (151 MHz, CDCI ₃ ): δ 165.4, 154.0, 137.1 , 132.2, 130.1 , 129.8, 128.6, 128.1 , 128.1 , 126.9, 126.1 , 99.2, 71.7, 70.8, 70.7, 69.5, 67.8, 65.2, 62.6.

[00298] 6-O-(2,5-Dichloro-6-methoxybenzoyl)-a-D-mannopyranoside (6-OMan Dicam ba); ((2R, 3S, 4S, 5S, 6S)-3, 4, 5, 6-tetrahydroxytetrahydro-2H-pyran-2-yl)methyl 3, 6- dichloro-2-methoxybenzoate (Compound D24)

[00299] Benzyl 6-O-(2,5-dichloro-6-methoxybenzoyl)-a-D-mannopyranoside (322 mg, 0.680 mmol) was dissolved in MeOH (5 mL) and placed under N ₂ . 20% Pd(OH) ₂ /C (34 mg) was added and the flask was evacuated and filled with H ₂ (x3), then stirred under H ₂ for 1 .5 h, then filtered and purified by flash column chromatography (50-100% EtOAc/hexanes) to obtain 6-O-(2,5-dichloro-6-methoxybenzoyl)-a-D-mannose (Compound D24) as a white foam (99 mg, 38%). ¹ H NMR (500 MHz, D ₂ O): δ 7.57-7.54 (m, 1 H), 7.31 -7.29 (m, 1 H), 5.17 (d, J = 1.6 Hz, 0.8H), 4.92 (d, J = 0.9 Hz, 0.2H), 4.83-4.77 (m, 1 H), 4.64 (dd, J = 12.1 , 6.0 Hz, 0.8H), 4.58 (dd, J = 12.0, 6.1 Hz, 0.2H), 4.12 (ddd, J = 9.9, 6.0, 2.0 Hz, 0.8H), 3.96-3.94 (m, 4H), 3.88 (dd, J = 9.6, 3.3 Hz, 0.8H), 3.77 (dd, J = 9.9, 9.6 Hz, 0.8H), 3.73-3.65 (m, 0.6H); ¹³ C NMR (126 MHz, D ₂ O): δ 167.0, 167.0, 153.4, 133.6, 133.5, 129.7, 129.7, 129.2, 129.1, 127.2, 127.2, 127.1 , 127.1 , 94.7, 94.4, 74.3, 73.6, 71.8, 71.3, 70.9, 70.8, 67.5, 67.3, 66.4, 66.4, 63.3. [00300] The following scheme depicts the synthesis of Compounds D25 and D26 of the invention

[00301 ] 1-O-(2,5-Dichloro-6-methoxybenzoyl)-3,4:6,7-di-O-isopropylid ene-a-D- glycero-D-lyxo-hept-2-ulofuranose; ((3aS,4S,6R,6aS)-6-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)- 4-hydroxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-yl) methyl 3,6-dichloro-2- methoxybenzoate (Compound D25)

[00302] Dicamba (167 mg, 0.758 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.09 mL, 1 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 2 mL). The residue was dissolved in CH ₂ CI ₂ (0.5 mL) and added dropwise to a 0 °C solution of 3, 4:6,7- di-O-isopropylidene-a-D-glycero-D-lyxo-hept-2-ulofuranose (prepared in accordance with Org. Lett. 2011 , 13 (14), 3628-3631 ; 200 mg, 0.689 mmol) in pyridine (2 mL). The solution was stirred at 0 °C for 0.5 h, then at r.t. for 1 .5 h. Quenched with saturated NaHCO ₃ solution (5 mL), extracted with CH ₂ CI ₂ (2 x 5 mL), and the organic phases were washed with brine (5 mL), dried over MgSO4, filtered and concentrated in vacuo, then purified by flash column chromatography (10-20% EtOAc/hexanes) to obtain 1 -O-(2,5-dichloro-6-methoxybenzoyl)- 3,4:6,7-di-O-isopropylidene-a-D-glycero-D-lyxo-hept-2-ulofur anose (Compound D25) as a cream resin (255 mg, 75%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.38 (d, J = 8.7 Hz, 1 H), 7.13 (d, J = 8.7 Hz, 1 H), 4.88 (dd, J = 5.9, 3.7 Hz, 1 H), 4.65-4.62 (m, 2H), 4.55 (d, J = 1 1.7 Hz, 1 H), 4.41 -4.37 (m, 1 H), 4.14 (dd, J = 7.7, 3.7 Hz, 1 H), 4.06 (dd, J = 8.7, 6.2 Hz, 1 H), 3.99 (dd, J = 8.7, 4.6 Hz, 1 H), 3.91 (s, 3H), 3.24 (s, 1 H), 1 .49 (s, 3H), 1 .43 (s, 3H), 1 .37 (s, 3H), 1 .33 (s, 3H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 164.3, 154.1 , 132.3, 129.9, 126.9, 126.2, 1 13.3, 109.3, 103.9, 85.3, 80.3, 80.1 , 73.2, 66.9, 66.6, 62.6, 27.1 , 26.0, 25.4, 24.5.

[00303] 1-O-(2,5-Dichloro-6-methoxybenzoyl)-a-D-glycero-D-lyxo-hept- 2-ulopyranose ( 1 -O-mannoheptulose Dicamba); ((2S,3S,4S,5S,6R)-2,3,4,5-tetrahydroxy-6-

(hydroxymethyl)tetrahydro-2H-pyran-2-yl)methyl 3,6-dichloro-2-methoxybenzoate

(Compound D26) [00304] 1-O-(2,5-dichloro-6-methoxybenzoyl)-3,4:6,7-di-O-isopropylid ene-a-D- glycero-D-lyxo-hept-2-ulofuranose (Compound D25) (239 mg, 0.484 mmol) was suspended in 1 :5 THF/H ₂ O (6 mL) Amberlite IR-120 H ⁺ resin was added to pH 1. After 18h, the resin was filtered then concentrated in vacuo and purified by flash column chromatography (EtOAc) to obtain 1 -O-(2,5-dichloro-6-methoxybenzoyl)-a-D-glycero-D-lyxo-hept-2 - ulopyranose (Compound D26) as a white resin (136 mg, 68%). ¹ H NMR (600 MHz, D ₂ O): δ 7.54 (d, J = 8.8 Hz, 1 H), 7.29 (d, J = 8.8 Hz, 1 H), 4.60 (d, J = 11 .4 Hz, 1 H), 4.47 (d, J = 11 .4 Hz, 1 H), 3.96 (d, J = 3.4 Hz, 1 H), 3.95-3.92 (m, 1 H), 3.93 (s, 3H), 3.88 (dd, J = 11 .9, 2.1 Hz, 1 H), 3.86-3.83 (m, 1 H), 3.79 (dd, J = 11.9, 5.6 Hz, 1 H), 3.69 (dd, J = 9.7, 9.7 Hz, 1 H); ¹³ C NMR (151 MHz, D ₂ O): δ 166.6, 153.4, 133.5, 129.7, 129.1, 127.2, 127.1, 97.4, 73.9, 71.4, 70.4, 67.8, 67.2, 63.2, 61.5.

[00305] The following scheme depicts the synthesis of Compounds D27 and D28 of the invention

[00306] Benzyl 2-(acetamido)-2-deoxy-6-O-(2,5-dichloro-6-methoxybenzoyl)-β -D- glucopyranoside; ( (2R, 3S,4R, 5R, 6R) -5-acetamido-6-(benzyloxy) -3,4-dihydroxytetrahydro- 2H-pyran-2-yl)methyl 3,6-dichloro-2-methoxybenzoate (Compound D27)

[00307] Dicamba (250 mg, 1.86 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.13 mL, 1.5 mmol). The mixture was stirred at r.t. for 1.5 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (1 mL) and added dropwise to a 0 °C solution of benzyl 2- acetamido-2-deoxy-[3-D-glucopyranoside (271 mg, 0.870 mmol) in 5:1 pyridine/CH ₂ CI ₂ (9 mL). The mixture was stirred at r.t. for 18 h, then quenched with saturated NaHCO ₃ solution (5 mL), and diluted with water (10 mL) and CH ₂ CI ₂ (10 mL). The organic phase was separated and washed with 1 M HCI (2 x 20 mL) and saturated NaHCO ₃ solution (10 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The residue was recrystallised from MeOH (15 mL) to obtain benzyl 2-(acetamido)-6-O-(2,5-dichloro-6-methoxybenzoyl)-2- deoxy-β-D-glucopyranoside as white solid (251 mg, 56%). The filtrate was purified by flash column chromatography (0-20% MeOH/CH ₂ CI ₂ ) to obtain further benzyl 2-(acetamido) -2- deoxy-6-O-(2,5-dichloro-6-methoxybenzoyl)-β-D-glucopyranosi de (Compound D27) as a white solid (107 mg, 24%). ¹ H NMR (500 MHz, d ₆ -DMSO): δ 7.75 (d, J = 9.0 Hz, 1 H), 7.68 (d, J = 8.7 Hz, 1 H), 7.41 (d, J = 8.7 Hz, 1 H), 7.31 -7.23 (m, 5H), 5.36 (d, J = 5.6 Hz, 1 H), 5.06 (d, J = 5.6 Hz, 1 H), 4.72-4.69 (m, 2H), 4.49-4.39 (m, 3H), 3.85 (s, 3H), 3.55-3.48 (m, 2H), 3.39-3.34 (m, 1 H), 3.22-3.17 (m, 1 H), 1.18 (s, 3H); ¹³ C NMR (101 MHz, d ₆ -DMSO): δ 169.1 ,

163.7, 153.1 , 137.9, 132.6, 129.8, 128.6, 128.1 , 127.4, 127.2, 126.3, 126.2, 100.6, 73.8,

73.7, 70.5, 69.5, 65.6, 62.2, 55.3, 23.1 .

[00308] 2-(Acetamido)-2-deoxy-6-O-(2,5-dichloro-6-methoxybenzoyl)-/3 -D-glucose (6- OGIcNAc Dicam ba); ((2R, 3S, 4R, 5R)-5-acetamido-3, 4, 6-trihydroxytetrahydro-2H-pyran-2- yl)methyl 3,6-dichloro-2-methoxybenzoate (Compound D28)

[00309] Benzyl 2-(acetamido)-2-deoxy-6-O-(2,5-dichloro-6-methoxybenzoyl)-β -D- glucopyranoside (Compound D27) (300 mg, 0.583 mmol) in MeOH (15 mL) was placed under N ₂ . 10% Pd/C (25 mg) was added, and the flask was evacuated and filled with H ₂ (x3), then stirred under H ₂ for 18h, then filtered through celite and purified by flash column chromatography (0-20% MeOH/CH ₂ CI ₂ ) to obtain 2-(acetamido)-2-deoxy-6-O-(2,5-dichloro- 6-methoxybenzoyl)-β-D-glucose (Compound D28) as a white solid (223 mg, 90%). ¹ H NMR (400 MHz, d ₆ -DMSO): δ 7.74-7.65 (m, 2H), 7.40-7.38 (m, 1 H), 6.60 (d, J = 6.4 Hz, 0.4H), 6.60 (dd, J = 4.8, 1.0 Hz, 0.6H), 5.29-5.27 (m, 1 H), 4.97-4.96 (m, 0.4H), 4.92-4.90 (m, 0.6H), 4.76 (d, J = 5.7 Hz, 0.6H), 4.70-4.63 (m, 1 H), 4.50-4.47 (m, 0.4H), 4.33-4.26 (m, 1 H), 3.93- 3.89 (m, 0.8H), 3.85 (s, 1.2H), 3.84 (s, 1.8H), 3.63-3.58 (m, 0.6H), 3.54-3.48 (m, 0.6H), 3.45- 3.40 (m, 0.4H), 3.63-3.58 (m, 0.6H), 3.54-3.48 (m, 0.6H), 3.45-3.40 (m, 0.4H), 3.34-3.31 (m, 0.4H), 3.20-3.1 1 (m, 1 H), 1.82 (s, 1.8H), 1.81 (s, 1.2H); ¹³ C NMR (101 MHz, d ₆ -DMSO): δ 169.5, 169.4, 163.8, 163.7, 153.1 , 153.0, 132.6, 132.5, 129.9, 129.8, 128.6, 126.3, 126.1 , 126.1 , 95.4, 90.7, 74.1 , 73.4, 71.1 , 70.6, 70.3, 69.2, 65.9, 65.8, 62.3, 62.2, 57.1 , 54.9, 54.1 ,

23.1. 22.7,

[00310] The following scheme depicts the synthesis of the hydrochloride salt of Compound D29 of the invention

[00311 ] tert-Butyldimethylsilyl 2-azido-2-deoxy-6-O-(2,5-dichloro-6-methoxybenzoyl)-

(3-D-glucopyranoside [00312] Dicamba (145 mg, 0.656 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.072 mL, 0.85 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (1 mL) and added dropwise to a solution of tert- butyldimethylsilyl 2-azido-2-deoxy-β-D-glucopyranoside (174 mg, 0.545 mmol, prepared in accordance with ChemBioChem, 2009, 10 (15), 2522-2529) in 1 :5 pyridine/CH ₂ CI ₂ (1.2 mL). The solution was stirred at r.t. for 3 h, then concentrated in vacuo and the residue diluted with EtOAc (10 mL), washed with water (2 x 20 mL), and saturated NaHCO ₃ (10 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (20-60% EtOAc/hexanes) to obtain tert-butyldimethylsilyl 2- azido-2-deoxy-6-O-(2,5-dichloro-6-methoxybenzoyl)-β-D-gluco pyranoside as a colourless resin (178 mg, 62%). ¹ H NMR (400 MHz, CDCI ₃ ): δ 7.38 (d, J = 8.7 Hz, 1 H), 7.13 (d, J = 8.7 Hz, 1 H), 4.69 (dd, J = 12.0, 4.2 Hz, 1 H), 4.60-4.57 (m, 2H), 3.92 (s, 3H), 3.60 (dd, J = 9.7, 8.8 Hz, 1 H), 3.52 (ddd, J = 9.7, 4.1 , 2.3 Hz, 1 H), 3.38 (dd, J = 10.0, 8.8 Hz, 1 H), 3.23 (dd, J = 10.0, 7.6 Hz, 1 H), 3.03 (bs, 1 H), 2.74 (bs, 1 H), 0.90 (s, 9H), 0.13 (s, 3H), 0.12 (s, 3H); ¹³ C NMR (101 MHz, CDCI ₃ ): δ 165.3, 154.1, 132.3, 130.0, 129.8, 126.9, 126.0, 97.4, 74.5, 73.9, 70.0, 68.3, 64.8, 62.5, 25.7, 18.0, -4.2, -5.2.

[00313] 2-Amino-2-deoxy-6-O-(2,5-dichloro-6-methoxybenzoyl)-D-glucos e hydrochloride (6-OGIcN Dicamba); ((2R,3S,4R,5R,6R)-5-amino-3,4,6-trihydroxytetrahydro- 2H-pyran-2-yl)methyl 3,6-dichloro-2-methoxybenzoate hydrochloride (Compound D29 hydrochloride)

[00314] To a solution of tert-butyldimethylsilyl 2-azido-2-deoxy-6-O-(2,5-dichloro-6- methoxybenzoyl)-β-D-glucopyranoside (168 mg, 0.321 mmol) in anhydrous THE (2 mL) under N ₂ was added acetic acid (37 pL, 0.64 mmol). The solution was cooled to 0 °C, and TBAF (1 .0 M in THE, 0.64 mL, 0.64 mmol) was added. The solution was stirred at r.t. for 2.5 h, then concentrated in vacuo, adsorbed onto silica and purified by flash column chromatography (0-10% MeOH/CH ₂ CI ₂ ) to obtain 2-azido-6-O-(2,5-dichloro-6- methoxybenzoyl)-2-deoxy-D-glucose as a white foam (115 mg, 88%). ¹ H NMR (400 MHz, CDCI ₃ ): δ 7.38 (d, J = 8.7 Hz, 0.5H), 7.37 (d, J = 8.7 Hz, 0.5H), 7.13 (d, J = 8.7 Hz, 0.5H), 7.13 (d, J = 8.7 Hz, 0.5H), 5.32 (d, J = 3.5 Hz, 0.5H), 4.79 (dd, J = 12.2, 4.1 Hz, 0.5H), 4.75- 4.71 (m, 0.5H), 4.68 (d, J = 7.9 Hz, 0.5H), 4.61 (dd, J = 12.2, 1.4 Hz, 0.5H), 4.53 (dd, J =

12.2, 2.2 Hz, 0.5H), 4.15-4.11 (m, 0.5H), 4.06 (dd, J = 10.2, 8.9 Hz, 0.5H), 3.92 (s, 1.5H), 3.92 (s, 1.5H), 3.61-3.56 (m, 1.5H), 3.50-3.42 (m, 0.5H), 3.31-3.26 (m, 1 H); ¹³ C NMR (101 MHz, CDCI ₃ ): δ 165.5, 165.3, 154.0, 153.9, 132.4, 132.3, 130.0, 129.9, 129.8, 129.7, 127.0,

126.2, 96.5, 92.3, 74.7, 74.1 , 71.6, 70.8, 70.0, 69.9, 67.0, 64.8, 64.6, 63.5, 62.7, 62.6. [00315] 2-Azido-2-deoxy-6-O-(2,5-dichloro-6-methoxybenzoyl)-D-glucos e (69 mg, 0.17 mmol) was dissolved in MeOH (2 mL) and 32% HCI (2 drops) and placed under N2. 10% Pd/C (6 mg) was added, and the flask was evacuated and filled with H ₂ (x3), then stirred under H ₂ for 15 min, then filtered through celite and concentrated in vacuo to obtain 2-amino-2-deoxy-6-O-(2,5-dichloro-6-methoxybenzoyl)-D-glucos e hydrochloride (Compound D29 hydrochloride) as a peach powder (68 mg, 96%). ¹ H NMR (500 MHz, CD ₃ OD): δ 7.52- 7.50 (m, 1 H), 7.26-7.24 (m, 1 H), 5.31 (d, J = 3.4 Hz, 0.7H), 4.80-4.76 (m, 0.6H), 4.71 (dd, J = 1 1.8, 2.0 Hz, 0.7H), 4.47 (dd, J = 11.8, 5.7 Hz, 0.7H), 4.46-4.42 (m, 0.3H), 4.12-4.08 (m, 0.7H), 3.91 (s, 0.9H), 3.90 (s, 2.1 H), 3.83 (dd, J = 10.4, 8.9 Hz, 0.7H), 3.67-3.64 (m, 0.3H), 3.57-3.52 (m, 0.3H), 3.42-3.38 (m, 1 H), 3.07 (dd, J = 10.4, 3.4 Hz, 0.7H), 2.79 (dd, J = 10.5, 8.4 Hz, 0.3H); ¹³ C NMR (126 MHz, CD3OD): δ 165.7, 165.6, 155.2, 155.1 , 133.4, 133.4, 131.6, 131.5, 130.7, 130.7, 127.9, 127.2, 94.7, 90.8, 75.6, 74.0, 72.0, 72.0, 71.4, 71.0, 66.2, 66.1 , 63.1 , 63.0, 58.6, 56.1.

[00316] The following scheme depicts the synthesis of Compounds D30 and D31 of the invention

[00317] 6-Deoxy- 1,2:3,5-di-O-isopropylidene-6-thioacetyl-a-D-glucofuranose

[00318] To a solution of 1 ,2:3,5-di-O-isopropylidene-6-O-tosyl-a-D-glucofuranose (700 mg, 1.69 mmol, prepared in accordance with US 4996195) in anhydrous DMF (5 mL) was added potassium thioacetate (586 mg, 5.13 mmol) and the mixture was stirred at r.t. for 48 h, then diluted with water (50 mL), and extracted with EtOAc (3 x 20 mL). The combined organic layers were washed with brine (20 mL), dried over MgSO ₄ , filtered and concentrated. The residue was filtered through a silica plug with 20% EtOAc/hex, then purified by flash column chromatography (10% EtOAc/hexanes) to obtain 6-deoxy-1 ,2:3,5-di-O- isopropylidene-6-thioacetyl-a-D-glucofuranose as a yellow oil (456 mg, 88%). ¹ H NMR (400 MHz, CDCI ₃ ): δ 5.99 (d, J = 3.7 Hz, 1 H), 4.55 (d, J = 3.7 Hz, 1 H), 4.25 (dd, J = 6.9, 3.8 Hz, 1 H), 4.20 (d, J = 3.8 Hz, 1 H), 3.62 (ddd, J = 8.3, 6.9, 4.3 Hz, 1 H), 3.37 (dd, J = 13.7, 4.3 Hz, 1 H), 3.01 (dd, J = 13.7, 8.3 Hz, 1 H), 2.34 (s, 3H), 1.48 (s, 3H), 1.34 (s, 3H), 1.32 (s, 3H), 1.32 (s, 3H); ¹³ C NMR (101 MHz, CDCI ₃ ): δ 195.0, 112.4, 106.6, 101.2, 84.0, 82.6, 75.1 , 71.3, 32.3, 30.6, 27.3, 26.7, 24.1 , 24.0.

[00319] 6-Deoxy- 1 ,2:3,5-di-O-isopropylidene-6-thio-a-D-glucofuranose

[00320] To a solution of 6-deoxy-1 ,2:3,5-di-O-isopropylidene-6-thioacetyl-a-D- glucofuranose (445 mg, 1.45 mmol) in MeOH (5 mL) was added NaOMe (1 M in MeOH, 0.1 mL), and the solution was stirred at r.t. for 18 h. The reaction mixture was quenched with Amberlite IR-120 (H ⁺ ) resin until neutral, filtered and concentrated, then purified by flash column chromatography (10-20% EtOAc/hexanes) to obtain 6-deoxy-1 ,2:3,5-di-O- isopropylidene-6-thio-a-D-glucofuranose as a colourless oil (282 mg, 70%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 5.99 (d, J = 3.8 Hz, 1 H), 4.57 (d, J = 3.8 Hz, 1 H), 4.33 (dd, J = 7.1 , 3.9 Hz, 1 H), 4.20 (d, J = 3.9 Hz, 1 H), 3.61 (ddd, J = 7.4, 7.4, 3.6 Hz, 1 H), 2.82 (ddd, J = 13.7, 8.9, 3.6, 1 H), 2.68 (ddd, J = 13.7, 7.4, 7.1 , 1 H), 1 .66 (dd, J = 8.9, 7.4 Hz, 1 H), 1 .49 (s, 3H), 1 .36 (s, 6H), 1.32 (s, 3H); ¹³ C NMR (126 MHz, CDCI ₃ ): δ 112.4, 106.5, 101.3, 84.1 , 82.1 , 75.2, 73.2, 27.9, 27.3, 26.7, 24.2, 24.1.

[00321 ] 6-Deoxy-6-S-(2,5-dichloro-6-methoxybenzoyl)-6-thio-D-glucose (6-SGIu Dicamba); S-(((2S,3S,4S,5R)-3,4,5,6-tetrahydroxytetrahydro-2H-pyran-2- yl)methyl) 3,6- dichloro-2-methoxybenzothioate (Compound D31)

[00322] Dicamba (70 mg, 0.32 mmol) was dissolved in CH ₂ CI ₂ (5 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.029 mL, 0.35 mmol). The mixture was stirred at r.t. for 1.5 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (1 mL) and added dropwise to a 0 °C solution of 6- deoxy-1 ,2:3,5-di-O-isopropylidene-6-thio-a-D-glucofuranose (80 mg, 0.29 mmol) in triethylamine (0.040 mL, 0.29 mmol) and CH ₂ CI ₂ (5 mL). The solution was stirred at 0 °C for 45 min, then at r.t. for 3.5 h, then concentrated in vacuo and the residue purified by flash column chromatography (0-20% EtOAc/hexanes) to obtain 6-deoxy-6-S-(2,5-dichloro-6- methoxybenzoyl)-1 ,2:3,5-di-O-isopropylidene-6-thio-a-D-glucofuranose (Compound D30) as a colourless oil (71 mg), which was taken up in 4:1 TFA/H ₂ O (1 mL) and allowed to stand for 45 min, then concentrated in vacuo, and co-evaporated with toluene (10 mL). The resultant residue was then purified by flash column chromatography (50-100% EtOAc/hexanes) to obtain 6-deoxy-6-S-(2,5-dichloro-6-methoxybenzoyl)-6-thio-D-glucose (Compound D31 ) as a white resin (25 mg, 12%). ¹ H NMR (400 MHz, CD ₃ OD): δ 7.51 (d, 8.7 Hz, 0.4H), 7.51 (d, 8.7 Hz, 0.6H), 7.25 (d, 8.7 Hz, 0.4H), 7.24 (d, 8.7 Hz, 0.6H), 5.06 (d, J = 3.7 Hz, 0.6H), 4.48 (d, J = 7.8 Hz, 0.4H), 4.01 (ddd, J = 9.6, 7.6, 2.9 Hz, 0.6H), 3.90 (s, 1.2H), 3.90 (s, 1.8H), 3.82 (dd, J = 13.7, 2.8 Hz, 0.4H), 3.74 (dd, J = 13.7, 2.9 Hz, 0.4H), 3.67 (dd, J = 9.6, 9.3 Hz, 0.4H), 3.50-3.45 (m, 0.4H), 3.38-3.33 (m, 1 H), 3.27-3.12 (m, 2.4H); ¹³ C NMR (101 MHz, CD ₃ OD): δ 191.9, 191.8, 154.8, 154.7, 136.4, 136.3, 133.6, 133.5, 130.2, 130.2, 128.0, 128.0, 127.4, 98.3, 94.0, 77.7, 76.3, 76.1 , 74.9, 74.7, 74.5, 73.8, 71 .2, 63.3, 63.3, 32.9, 32.8.

[00323] The following scheme depicts the synthesis of Compounds D32 and D33 of the invention

[00324] 6-(2,5-Dichloro-6-methoxybenzamido)-6-deoxy-1,2:3,5-di-O-iso propylidene-a- D-glucofuranose; 6-(2,5-Dichloro-6-methoxybenzamido)-6-deoxy-1,2:3,5-di-O- isopropylidene-a-D-glucofuranose (Compound D32)

[00325] Dicamba (500 mg, 2.26 mmol) was dissolved in CH ₂ CI ₂ (20 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.25 mL, 2.9 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (1 mL) and added dropwise to a solution of 6-amino-6- deoxy-1 ,2:3,5-di-O-isopropylidene-a-D-glucofuranose (587 mg, 2.26 mmol, prepared in accordance with Can. J. Chem. 1977, 55 (21), 3717-3720) in pyridine (5 mL). The solution was stirred at r.t. for 2 h then concentrated in vacuo. The residue was dissolved in CH ₂ CI ₂ (10 mL), washed with saturated NaHCO ₃ solution (20 mL), dried over MgSO ₄ , filtered and concentrated in vacuo, then purified by flash column chromatography (10-40% EtOAc/hexanes) to obtain 6-(2,5-dichloro-6-methoxybenzamido)-6-deoxy-1 ,2:3,5-di-O- isopropylidene-a-D-glucofuranose (Compound D32) as a tan resin (627 mg, 60%). ¹ H NMR (400 MHz, CDCI ₃ ): δ 7.33 (d, J = 8.7 Hz, 1 H), 7.11 (d, J = 8.7 Hz, 1 H), 6.03-6.00 (m, 2H), 4.57 (d, J = 3.7 Hz, 1 H), 4.57 (d, J = 3.8 Hz, 1 H), 4.37 (dd, J = 6.9, 3.8 Hz, 1 H), 4.19 (d, J = 3.8 Hz, 1 H), 3.90 (s, 3H), 3.86 (ddd, J = 13.6, 5.8, 3.8 Hz, 1 H), 3.75 (ddd, J = 6.9, 6.6, 3.8 Hz, 1 H), 3.64 (ddd, J = 13.6, 6.6, 6.0 Hz, 1 H), 1.49 (s, 3H), 1.34 (s, 3H), 1.33 (s, 3H), 1.32 (s, 3H); ¹³ C NMR (101 MHz, CDCI ₃ ): δ 164.1, 154.0, 133.2, 131.5, 130.1 , 127.1 , 126.1 , 112.4, 106.6, 101.2, 84.0, 80.5, 75.1 , 70.9, 62.8, 42.1 , 27.3, 26.7, 24.2, 24.2. [00326] 6-(2,5-Dichloro-6-methoxybenzamido)-6-deoxy-D-glucose (6-N-Glu

Dicamba); 3, 6-dichloro-2-methoxy-N-(( (2R, 3S,4S, 5R)-3, 4, 5, 6-tetrahydroxytetrahydro-2H- pyran-2-yl)methyl)benzamide (Compound D33)

[00327] 6-(2,5-Dichloro-6-methoxybenzamido)-6-deoxy-1 ,2:3,5-di-O-isopropylidene-a- D-glucofuranose (Compound D32) (300 mg, 0.649 mmol) was dissolved in 1 :1 TFA/H ₂ O (5 mL) and allowed to stand at r.t. for 2 h, then concentrated in vacuo. The residue was dissolved in 7:3 EtOH/EtOAc, and concentrated to 2 mL, diluted with EtOAc (1 mL) and the solid filtered, washed with EtOH (0.5 mL) and EtOAc (1 mL), and dried to yield 6-(2,5- dichloro-6-methoxybenzamido)-6-deoxy-D-glucose (Compound D33) as an off-white powder (74 mg, 30%). The filtrate was evaporated to 1 mL and the resultant solid filtered, washed EtOAc (1 mL), and dried to yield further 6-(2,5-dichloro-6-methoxybenzamido)-6-deoxy-D- glucose as a white powder (78 mg, 31%). ¹ H NMR (400 MHz, D ₂ O): δ 7.57-7.54 (m, 1 H), 7.33-7.31 (m, 1 H), 5.22 (d, J = 3.8 Hz, 0.4H), 4.66 (d, J = 8.0 Hz, 0.6H), 4.00-3.96 (ddd, J =

9.9, 6.2, 2.2 Hz, 0.4H), 3.93 (s, 1.8H), 3.92 (s, 1.2H), 3.89-3.84 (m, 0.6H), 3.80 (dd, J = 14.3, 2.7 Hz, 0.4H), 3.75-3.60 (m, 2H), 3.56-3.50 (m, 1 H), 3.45-3.40 (m, 1 H), 3.25 (dd, J = 9.3, 8.0 Hz, 0.6H); ¹³ C NMR (126 MHz, D ₂ O): δ 168.0, 153.1 , 132.9, 132.9, 132.1, 132.0, 129.9,

129.9, 127.2, 127.2, 127.1 , 96.6, 92.8, 76.2, 74.9, 74.8, 73.3, 72.2, 71.7, 71.6, 70.6, 63.2,

41.1. 40.9,

[00328] The following scheme depicts the synthesis of Compound D34 of the invention

[00329] Dicamba (500 mg, 2.26 mmol) was dissolved in CH ₂ CI ₂ (10 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.25 mL, 2.9 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in CH ₂ CI ₂ (1 mL) and added dropwise to a 0 °C solution of dihydroxyacetone (815 mg, 9.04 mmol) in pyridine (5 mL), then stirred at r.t. for 1.5 h. The mixture was diluted with with water (5 mL) and extracted with CH ₂ CI ₂ (3 x 2 mL), and the organic phases were combined, washed with water (5 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (10-50% EtOAc/hexanes) to obtain 3-hydroxy-2-oxopropyl 2,5-dichloro-6- methoxybenzoate (Compound D34) as a colourless oil (400 mg, 60%). ¹ H NMR (500 MHz, CDCI ₃ ): major form δ 7.41 (d, J = 8.7 Hz, 1 H), 7.16 (d, J = 8.7 Hz, 1 H), 5.03 (s, 2H), 4.49 (s, 2H), 3.95 (s, 3H); ¹³ C NMR (101 MHz, CDCI ₃ ): δ 203.9, 164.0, 154.3, 132.7, 129.8, 129.2, 127.1 , 126.1 , 67.5, 66.6, 62.6.

[00330] The following scheme depicts the synthesis of Compound D35 of the invention

[00331] 1, 1'-(2-Oxo-1,3-propanediyl) bis(2,5-dichloro-6-methoxybenzoate) (Bis- glycerone Dicamba); 2-oxopropane-1,3-diyl bis(3,6-dichloro-2-methoxybenzoate) (Compound D35)

[00332] Dicamba (500 mg, 2.26 mmol) was dissolved in CH ₂ CI ₂ (10 mL), and DMF (1 drop) was added, followed by oxalyl chloride (0.25 mL, 2.9 mmol). The mixture was stirred at r.t. for 2 hrs, then concentrated in vacuo, and co-evaporated with toluene (2 x 5 mL). The residue was dissolved in 1 :1 C^Ch/pyridine (5 mL) and dihydroxyacetone (92 mg, 1.0 mmol) was added and stirred at r.t. for 18h, then quenched with saturated NaHCO ₃ solution (10 mL). The aqueous phase was separated and extracted with CH ₂ CI ₂ (5 mL), the organic phases were combined, washed with 1 M HCI (2 x 10 mL) and water (10 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The resultant brown solid was taken up in hot 3:1 CH ₂ CI ₂ /EtOH (4 mL), concentrated to 2 mL, and allowed to cool to r.t. The resultant solid was filtered and washed with EtOH (3 x 1 mL) and CH ₂ CI ₂ (2 x 1mL) to obtain 1,1'-(2-oxo- 1 ,3-propanediyl) bis(2,5-dichloro-6-methoxybenzoate) (Compound D35), as a cream powder (234 mg, 46%). ¹ H NMR (500 MHz, CDCI ₃ ): δ 7.71 (d, J = 8.7 Hz, 2H), 7.43 (d, J = 8.7 Hz, 2H), 5.29 (s, 4H), 3.88 (s, 6H); ¹³ C NMR (101 MHz, CDCI ₃ ): δ 195.8, 163.1 , 153.4, 132.9, 128.9, 128.8, 126.5, 126.3, 67.3, 62.4.

[00333] The following scheme depicts the synthesis of Compounds 2,4-D1 and 2,4- D2 of the invention [00334] 6-O-((2,4-dichlorophenoxy)acetate)-1,2-O-isopropylidene-a-D- glucofuranose; (R)-2-hydroxy-2-((3aR,5R,6S,6aR)-6-hydroxy-2,2-dimethyltetra hydrofuro[2,3-d][1,3]dioxol-5- yl)ethyl 2-(2,4-dichlorophenoxy)acetate (Compound 2,4-D1)

[00335] 2,4-D (500 mg, 2.26 mmol) in thionyl chloride (2 mL) was heated to reflux for 4 h, then concentrated in vacuo. The residue was dissolved in CH ₂ CI ₂ (2 mL) and added to a 0°C solution of 1 ,2-O-isopropylidene-a-D-glucofuranose (415 mg, 1.89 mmol) in pyridine (2 mL) and stirred at r.t. for 18 h. The mixture was concentrated in vacuo and the residue diluted with EtOAc (20 mL), washed with water (2 x 20 mL), and brine (10 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. The resultant residue was then purified by flash column chromatography (20-60% EtOAc/hexanes) to obtain 6-O- ((2,4-dichlorophenoxy)acetate)-1 ,2-O-isopropylidene-a-D-glucofuranose (Compound 2,4- D1 ) as a white solid (371 mg, 81%). ¹ H NMR (400 MHz, CDCI ₃ ): δ 7.40 (d, J = 2.5 Hz, 1 H), 7.18 (dd, J = 8.8, 2.5 Hz, 1 H), 6.81 (dd, J = 8.8 Hz, 1 H), 5.96 (d, J = 3.6 Hz, 1 H), 4.75 (s, 2H), 4.57 (dd, J = 1 1 .8, 3.0 Hz, 1 H), 4.53 (d, J = 3.6 Hz, 1 H), 4.36 (d, J = 2.9 Hz, 1 H), 4.35 (dd, J = 1 1.8, 6.1 Hz, 1 H), 4.25 (ddd, J = 6.6, 6.1 , 3.0 Hz, 1 H), 4.08 (dd, J = 6.6, 2.9 Hz, 1 H), 2.78 (bs, 2H), 1.48 (s, 3H), 1.32 (s, 3H); ¹³ C NMR (101 MHz, CDCI ₃ ): δ 168.6, 152.4, 130.6, 127.9, 127.6, 124.5, 115.1 , 112.1 , 105.1 , 85.3, 79.3, 75.8, 69.1 , 67.0, 66.6, 27.0, 26.3.

[00336] 6-O-((2,4-dichlorophenoxy)acetate)-D-glucose (6-OGIu 2,4-D); (R)-2-hydroxy- 2-((2R, 3R,4R, 5S) -3, 4, 5-trihydroxytetrahydrofuran-2-yl)ethyl 2-(2,4-dichlorophenoxy)acetate (Compound 2,4-D2)

[00337] 6-O-((2,4-Dichlorophenoxy)acetate)-1 ,2-O-isopropylidene-a-D-glucofuranose (Compound 2,4-D1 ) (356 mg, 0.841 mmol) was dissolved in 4:1 TFA/H ₂ O (4 mL) and allowed to stand for 2 h, then concentrated in vacuo, and co-evaporated with toluene (3 x 5 mL). The resultant residue was then purified by flash column chromatography (50-100% EtOAc/hexanes) to obtain 6-O-((2,4-dichlorophenoxy)acetate)-D-glucose (Compound 2,4- D2) as a white powder (253 mg, 79%). ¹ H NMR (400 MHz, CD ₃ OD): δ 7.43-7.42 (m, 1 H), 7.27-7.22 (m, 1 H), 7.02-6.97 (m, 1 H), 5.07 (d, J = 3.7 Hz, 0.7H), 4.83 (s, 2H), 4.53 (dd, J =

1 1.8, 2.2 Hz, 0.3H), 4.50-4.45 (m, 1 H), 4.00-3.96 (m, 1 H), 3.98 (ddd, J = 10.0, 5.1 , 2.2 Hz, 0.7H), 3.67 (dd, J = 9.3, 9.3, 0.7H), 3.52-3.48 (m, 0.3H), 3.38-3.27 (m, 2H), 3.15-3.11 (m, 0.3H); ¹³ C NMR (101 MHz, CD3OD): δ 169.9, 169.9, 154.0, 130.9, 130.9, 128.9, 128.8, 127.6, 124.9, 116.2, 116.1 , 98.3, 94.0, 77.9, 76.2, 75.1 , 74.7, 73.7, 71.8, 71.6, 70.5, 66.9,

66.9, 65.5, 65.4.

[00338] Herbicidal activity assay

[00339] A. thaliana Col-0 seeds (~30) were sown in 63 x 63 x 59 mm pots consisting of Irish peat that was pre-wet prior to sowing. Seeds were cold-treated for 3 days in the dark at 4°C to synchronise germination and then grown in a chamber at 22°C, with 60% relative humidity and in a 16 h light/8 h dark photoperiod. Compounds were initially dissolved in dimethyl sulfoxide (DMSO) at 20 mg/mL or 200 mM and further diluted in water prior to treatments to a final concentration of DMSO of 2%. The surfactant Brushwet (SST Australia) was added to a final concentration of 0.02%. The carrier DMSO was used as a negative control. Seeds or seedlings were treated with solutions of compound that contained 2% of DMSO, using a pipette. Pre-emergence treatments were given at day zero as trays were moved into their first long day. Post-emergence treatments were done at three and six days after germination. Seedlings were grown for 16 days after germination before photos were taken (Figure 1A). The results show that on an equimolar basis, dicamba, 6-OGIu Dicamba (compound D1), and 1 -OGIu Dicamba (compound D2) have comparable activity against Arabidopsis thaliana. The experiment was repeated for comparison of 2,4-D with 6-OGIu 2,4-D (Compound 2,4-D2), under post-emergent conditions and with concentrations in the range of 31-500 pM, and demonstrates that on an equimolar basis, 2,4-D and 6-OGIu 2,4-D (Compound 2,4-D2) have comparable activity against Arabidopsis thaliana (Figure 1 B).

[00340] The experiment was repeated using 6-OGIu Dicamba (compound D1), 6- OGal Dicamba (compound D3), 5-ORib Dicamba (compound D7), 5-OXyl Dicamba (compound D6), 1-OSorb Dicamba (compound D5), and 1 -OFruc Dicamba (compound D4), as representative compounds of the invention compared to the known auxin herbicide Dicamba at concentrations ranging from 31 pM to 4 mM (Figure 2A).

[00341] The experiment was repeated again (post-emergence only) with 6-OGIu Dicamba (compound D1 ), Glycerone Dicamba (compound D34), Bis-glycerone Dicamba (compound D35), 2-OGIu Dicamba (compound D8), 3-OGIu Dicamba (compound D9), 4- OGIu Dicamba (compound D10), 2-O-L-Ara Dicamba (compound D20), 4-O-L-Ara Dicamba (compound D21), 5-O-D-Ara Dicamba (compound D23), 6-OMan Dicamba (compound D24), 1-O-D-Mannoheptulose Dicamba (compound D26), 6-O-GlcNAc Dicamba (compound D28), 6-O-GlcN Dicamba (compound D29), 6-SGIu Dicamba (compound D31 ) and 6-NGIu Dicamba (compound D33) as representative compounds of the invention compared to the known auxin herbicide Dicamba at a range of concentrations, from 31 pM to 2 mM or from 31 pM to 8 mM, as representative compounds of the invention compared to the known auxin herbicide Dicamba at concentrations ranging from (Figure 2B).

[00342] Creating a dicamba tolerant A. thaliana line

[00343] To recreate dicamba tolerance by dicamba monooxygenase in A. thaliana similarly to that made by Behrens et al. (2007, Science 316: 1185-1188) a synthetic gene encoding the oxygenaseDIC from Stenotrophomonas maltophilia strain DI-6 (GenBank accession AY786443) was made to include a 58-residue chloroplast targeting leader used by Anderson and Smith (1986, Biochem. J. 240: 709-715) and incorporated a Trp to Cys mutation said to provide useful changes in pH and temperature optima (See, for example, W112C in International Patent Application W02007146706A2). A BamHI site immediately preceding the sequence encoding the start Met and a Sacl site immediately after the stop codon were used to subclone this synthetic DMOc gene into pMDC ₄ 3 (Curtis and Grossniklaus 2003 Plant Physiol. 133: 462-469), from which the mGFP6 coding sequence and Gateway recombination cassette were removed by the same restriction enzymes, putting DMOc under control of a double CaMV35S promoter and providing it the nopaline synthase terminator. The plasmid pMDC ₄ 3-DMOc was transferred from E. coli containing the plasmid to Agrobacterium tumefaciens (strain LBA4404) using a helper strain (E. coli HB101 pRK2013). Wild type Col-0 Arabidopsis thaliana was transformed by in planta transformation. The first transgenic generation (Ti) was selected on MS-agar plates (1 % agar, 1X MS salts, pH 5.7, 1% glucose) containing 20 pg/mL hygromycin. Dicamba resistance of their progeny (T ₂ ) was used to identify lines segregating for resistance as a single T-DNA locus. Homozygous T3 seeds were identified by hygromycin resistance on plates and then confirmed by dicamba resistance on soil.

[00344] Demonstrating Compounds D1 and D3 to D7 are compatible with the DMOc trait

[00345] To test the conferral of dicamba tolerance by the DMOc transgene to some representative compounds of the invention, approximately 40 seeds of wild type Col-0 A. thaliana or T3 homozygous seeds for a single-locus DMOc line were sown on soil pots. After 4 days stratification, pots were moved to 23°C and 16 hour days. Seedlings were not sprayed (untreated), sprayed with dicamba (at 0.5 mM) or with 6-OGIu Dicamba (compound D1 ), 6-OGal Dicamba (compound D3), 5-ORib Dicamba (compound D7), 5-OXyl Dicamba (compound D6), 1-OSorb Dicamba (compound D5), or 1 -OFruc Dicamba (compound D4), (at 2 mM) with 2% DMSO and 0.02% Brushwet at 4 and 7 days after being moved to grow in the light. The volume sprayed per pot was 500 pL. Plants were imaged at Day 11 of growth and the results are shown in Figure 3.

[00346] Resistance to Drift

[00347] Compounds of the invention were tested for their resistance to volatility or drift under plant growth conditions. A small-scale drift assay was established. Pots (63 x 63 x 59 mm) were filled with Seedling Substrate Plus+ soil (Bord na Mona Horticulture Ltd, Newbridge, Ireland) consisting of Irish peat. Soil was pre-wet before sowing to saturation and a plastic lid from a 50 mL tube placed in the centre of each pot. Seeds of wild type Col-0 Arabidopsis thaliana were sown around each of the lids. Seeds were cold-treated for 3 days in the dark at 4 °C to synchronize germination and then grown in a chamber at 22 °C, with 60% relative humidity and in a 16 h light/8 h dark photoperiod.

[00348] In a first experiment, either dicamba or 6-OGIu Dicamba were dissolved in 0.85 mL of water with 0.02% surfactant Brushwet (SST Dandenong, Australia), to provide concentrations of dicamba at 1.25, 2.5, 5, or 10 mM and 6-OGIu Dicamba (compound D1), at 20 or 40 mM, and added to the lids. After growth for 2 weeks plants were imaged (Figure 4).

[00349] In a second experiment, either dicamba, 6-OGIu Dicamba (compound D1), 6- OGal Dicamba (compound D3), 5-ORib Dicamba (compound D7), 5-OXyl Dicamba (compound D6), 1 -OSorb Dicamba (compound D5), or 1-OFruc Dicamba (compound D4) were dissolved in 0.85 mL of water with 0.02% surfactant Brushwet (SST Dandenong, Australia), to provide concentrations of 5, or 10 mM and added to the lids. After growth for 2 weeks plants were imaged (Figure 5).

[00350] As can be seen in Figure 4, burn symptoms are apparent in dicamba (top row). By contrast no drift burn at all was visible for 6-OGIu Dicamba (compound D1 , bottom row). As can be seen in Figure 5, again, the compounds of the invention 6-O-glu-dicamba (compound D1 ), 6-OGal Dicamba (compound D3), 5-ORib Dicamba (compound D7), 5-OXyl Dicamba (compound D6), 1 -OSorb Dicamba (compound D5), or 1-OFruc Dicamba (compound D4), did not show any drift burn, where dicamba (bottom right) did.

[00351 ] Stability of compounds of the invention in solution

[00352] The degradation of 6-OGIu Dicamba (compound D1), 6-OGal Dicamba (compound D3), 5-ORib Dicamba (compound D7), 5-OXyl Dicamba (compound D6), 1 - OSorb Dicamba (compound D5), and 1 -OFruc Dicamba (compound D4) to dicamba at ~25°C was followed in a series of solutions (water; Figure 6, and aqueous buffer at pH 5.0; Figure 7, pH 7.0; Figure 8, and pH 8.0; Figure 9) over a 4 week period, as measured via HPLC with detection of dicamba by UV absorption at 220nm.

[00353] Separate solutions of each compound were prepared at concentrations of 1 .0 mg/mL in deionised water and in buffer (25mM sodium citrate/25mM sodium phosphate), at pH 5, 7, or 8. HPLC analysis was conducted on an Agilent Poroshell 120 EC-C18, 2.7 pm, 3.0 x 150 mm, with 1 pL sample injection, 1.0 mL/min flow rate, 5-100% B in 9 minutes (A: Water + 0.1% trifluoroacetic acid, B: Acetonitrile + 0.1% trifluoroacetic acid), at 25 °C, and UV absorbance measured at 220 nm;

[00354] The data for % Dicamba observed after 28 days at ~25°C (expressed as % of total integrated area at 220nm) are presented in the table below:

Buffers

Water pH 5.0 pH 7.0 pH 8.0

6-OGIu Dicamba 0.53 0.09 0.10 1.35

6-OGal Dicamba 1 .99 0.11 0.19 2.80

5-ORib Dicamba 14.17 1.17 29.22 63.90

5-OXyl Dicamba 2.84 1.21 7.38 26.71

1 -OSorb Dicamba 20.65 0.62 30.01 79.76 1 -OFruc Dicamba 20.06 0.83 39.36 88.64

[00355] [00356] The compounds all show excellent room temperature stability in solution at mildly acidic pH. Compounds 6-OGIu Dicamba (compound D1 ) and 6-OGal Dicamba (compound D3) even show excellent room temperature stability in solution at neutral pH.