OA20326A

OA20326A - Herbicidal compositions.

Info

Publication number: OA20326A
Application number: OA1202100363
Authority: OA
Inventors: James Nicholas Scutt; Nigel James Willetts; Ravindra SONAWANE; Mangala Phadte; Sandeep Reddy KANDUKURI; Sarah Armstrong; Andrea MCGRANAGHAN; Sean NG; Gavin John Hall; Julia FELLMANN; Raymond Joseph WUERFFEL; Sian MOORHOUSE; Niall Rae THOMSON
Original assignee: Syngenta Crop Protection Ag
Priority date: 2019-02-15
Filing date: 2020-01-30
Publication date: 2022-05-10

Abstract

The present invention relates to novel herbicidal combinations and their use in controlling plants or inhibiting plant growth. In particular, herbicidal combinations of the invention comprise at least one pyridazine derivative of Formula (I), in combination with at least one futher herbicide that is a non-selective herbicide, a herbicide that acts through the inhibition of protoporphoryinogen oxidase, or a herbicide that inhibits photosystem II in photosynthesis.

Description

HERBICIDAL COMPOSITIONS

The présent invention relates to novel herbicidal combinations and their use in controlling plants or inhibiting plant growth. In particular, herbicidal combinations ofthe invention comprise at least one pyridazine dérivative as defined herein, in combination with at least one further herbicide that is a non5 sélective herbicide, a herbicide that acts through the inhibition of protoporphoryinogen oxidase, or a herbicide that inhibits photosystem II in photosynthesis.

Herbicidal pyridazine dérivatives are described in co-pending PCT application PCT/EP2018/072280.

The object of the présent invention is to provide herbicidal mixtures which are highly effective 10 against various weed species (particularly at low dose), and is based on the finding that pyridazine compounds of Formula (I) as defined herein, in combination with the partner herbicides described herein, are particularly efficacious at mediating such weed control.

Thus in a first aspect ofthe invention, there is provided a composition comprising as component (A) a compound of Formula (I), or an agrochemically acceptable sait or a zwitterionic species thereof,

wherein:

A is 6-membered heteroaryl selected from the group consisting of:

A-V A-VI A-VII wherein the jagged line defines the point of attachment to the remaining part of a compound of Formula 20 (I), p is 0, 1 or 2 and each R⁸ is independently selected from the group consisting of NH₂, methyl and methoxy;

R¹ and R² are each independently hydrogen or methyl; Q is (CR^1aR^2b)m; m is 0, 1, or 2; each R^1a and R^2b are independently selected from the group consisting of hydrogen, hydroxy, methyl, and NH2; Z is S(O)₂OR¹⁰, -C(O)OR¹⁰, -C(O)NHS(O)2R¹² and -C(O)NHCN; R¹⁰ is hydrogen, methyl, benzyl or phenyl; 25 and R¹² is methyl, -NH2, -N(CH3)₂, or -NHCH3;

and as component (B), at least one herbicide, or sait thereof, selected from the group consisting of:

B1 a non-selective herbicide selected from the group consisting of glyphosate, glufosinate, hydantocidin, pelargonic acid, paraquatand diquat;

B2 a herbicide that acts through the inhibition of protoporphoryinogen oxidase; and

B3 a herbicide that inhibits photosystem II in photosynthesis.

In a second aspect, the invention provides the use of a composition of the invention as a herbicide.

In a third aspect, the invention provides methods of (i) inhibiting plant growth, and (il) controlling plants, said methods comprising applying to the plants orto the locus thereof, a herbicidally effective amount of a composition ofthe invention.

In a fourth aspect, the invention provides methods of (i) inhibiting plant growth, and (ii) controlling plants, said methods comprising applying to the plants orto the locus thereof: (A): a compound of Formula (I) as defined herein, and (B) a herbicide as defined in B1, B2 or B3 as defined herein.

In a fifth aspect, the invention provides a method of selectively controlling grasses and/or weeds 15 in crops of useful plants which comprises applying to the useful plants or locus thereof or to the area of cultivation a herbicidally effective amount of a composition ofthe invention.

When active ingrédients are combined, the activity to be expected (E) for any given active ingrédient combination obeys the so-called Colby Formula and can be calculated as follows (Colby, S.R., Calculating synergistic and antagonistic responses of herbicide combination, Weeds, Vol. 15, 20 pages 20-22; 1967):

ppm = milligrams of active ingrédient (a.i.) per liter

X = % action by first active ingrédient using p ppm ofthe active ingrédient

Y = % action by second active ingrédient sing q ppm ofthe active ingrédient.

According to Colby, the expected action of active ingrédients A +B using p + q ppm of active 25 ingrédient is represented by the following formula:

E=X+YX Y

100

If the action actually observed (O) is greaterthan the expected action E then the action ofthe combination is super-additive, i.e. there is a synergistic effect. In mathematical terms, synergism corresponds to a positive value for the différence of (O-E). In the case of purely complementary addition of activities (expected activity), said différence (O-E) is zéro. A négative value of said différence (O-E) signais a loss of activity compared to the expected activity.

Compounds of Formula (I) and compounds within groups B1, B2 and B3 are ail effective herbicidal compounds, as shown herein with respect to compounds of Formula (I) and as well known in the art for the compounds glyphosate, glufosinate, hydantocidin, pelargonic acid, paraquat and diquat 35 as well as herbicides that act through the inhibition of protoporphoryinogen oxidase; and herbicides that inhibit photosystem II in photosynthesis.

Accordingly, the combination of the présent invention takes advantage of any additive herbicidal activity, and certain embodiments may even exhibit a synergistic effect. This occurs wheneverthe action of an active ingrédient combination is greaterthan the sum ofthe actions ofthe individual components.

Combinations ofthe invention may also provide for an extended spectrum of activity in comparison to that obtained by each individual component, and/or permit the use of lower rates of the individual components when used in combination to that when used alone, in order to médiate effective herbicidal activity.

In addition, it is also possible that the composition ofthe invention may show increased crop tolérance, when compared with the effect ofthe compound A alone. This occurs when the action of an active ingrédient combination is less damaging to a useful crop than the action of one ofthe active ingrédients alone.

As stated above, compositions ofthe invention comprise as component (A) a compound of Formula (I) as defined herein. More details with respect to compounds of Formula (I) are provided below.

The presence of one or more possible asymmetric carbon atoms in a compound of Formula (I) means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also atropisomers may occur as a resuit of restricted rotation about a single bond. Formula (I) is intended to include ail those possible isomeric forms and mixtures thereof. The présent invention includes ail those possible isomeric forms and mixtures thereof for a compound of Formula (I). Likewise, Formula (I) is intended to include ail possible tautomers (including lactam-lactim tautomerism and ketoenol tautomerism) where présent. The présent invention includes ail possible tautomeric forms for a compound of Formula (I). Similarly, where there are di-substituted alkenes, these may be présent in E or Z form or as mixtures of both in any proportion. The présent invention includes ail these possible isomeric forms and mixtures thereof for a compound of Formula (I).

The compounds of Formula (I) will typically be provided in the form of an agronomically acceptable sait, a zwitterion or an agronomically acceptable sait of a zwitterion. This invention covers ail such agronomically acceptable salts, zwitterions and mixtures thereof in ail proportions.

For example a compound of Formula (I) wherein Z comprises an acidic proton, may exist as a zwitterion, a compound of Formula (l-l), or as an agronomically acceptable sait, a compound of Formula (l-ll) as shown below:

(l-D

wherein, Y represents an agronomically acceptable anion and j and k represent integers that may be selected from 1,2 or 3, dépendent upon the charge ofthe respective amon Y.

A compound of Formula (I) may also exist as an agronomically acceptable sait of a zwitterion, a compound of Formula (l-lll) as shown below:

wherein, Y represents an agronomically acceptable anion, M represents an agronomically acceptable cation (in addition to the pyridazinium cation) and the integers j, k and q may be selected from 1,2 or 3, dépendent upon the charge ofthe respective anion Y and respective cation M.

Thus where a compound of Formula (I) is drawn in protonated form herein, the skilled person would appreciate that it could equally be represented in unprotonated or sait form with one or more relevant counter ions.

In one embodiment ofthe invention there is provided a compound of Formula (l-ll) wherein k is 1 or 2, j is 1 and Y is selected from the group consisting of halogen, trifluoroacetate and pentafluoropropionate. In this embodiment a nitrogen atom in ring A may be protonated or a nitrogen atom comprised in Q may be protonated (for example see compound 1.030 or 1.035 in table A). Preferably, in a compound of Formula (l-ll), k is 1 or 2, j is 1 and Y is chloride, wherein a nitrogen atom in ring A is protonated.

Suitable agronomically acceptable salts for component (A), i.e. a compound of Formula (l-ll) or (l-lll), as employed in the présent invention, and represented by an anion Y, include but are not limited chloride, bromide, iodide, fluoride, 2-naphthalenesulfonate, acetate, adipate, methoxide, ethoxide, propoxide, butoxide, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, butylsulfate, butylsulfonate, butyrate, camphorate, camsylate, caprate, caproate, caprylate, carbonate, citrate, diphosphate, edetate, edisylate, enanthate, ethanedisulfonate, ethanesulfonate, ethylsulfate, formate, fumarate, gluceptate, gluconate, glucoronate, glutamate, glycérophosphate, heptadecanoate, hexadecanoate, hydrogen sulfate, hydroxide, hydroxynaphthoate, isethionate, lactate, lactobionate, laurate, malate, maleate, mandelate, mesylate, methanedisulfonate, methylsulfate, mucate, myristate, napsylate, nitrate, nonadecanoate, octadecanoate, oxalate, pelargonate, pentadecanoate, pentafluoropropionate, perchlorate, phosphate, propionate, propylsulfate, propylsulfonate, succinate, sulfate, tartrate, tosylate, tridecylate, triflate, trifluoroacetate, undecylinate and valerate.

Suitable cations represented by M in a compound of Formula (l-lll), include, but are not limited to, metals, conjugate acids of amines and organic cations. Examples of suitable metals include aluminium, calcium, césium, copper, lithium, magnésium, manganèse, potassium, sodium, iron and zinc. Examples of suitable amines include allylamine, ammonia, amylamine, arginine, benethamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecylamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine, 5 lysine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, methylpentadecylamine, morpholine, Ν,Ν-diethylethanolamine, N-methylpiperazine, nonylamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, picoline, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, 10 sec-butylamine, stearylamine, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane, and undecylamine. Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, 15 tetraethylammonium, tetraethylphosphonium, tétraméthylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxonium, triethylsulfonium, triethylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium and tripropylsulfoxonium.

Preferred compounds of Formula (I), wherein Z comprises an acidic proton, can be represented 20 as either Formual (l-l) or (l-ll). For compounds of Formula (l-ll) emphasis is given to salts when Y is chloride, bromide, iodide, hydroxide, bicarbonate, acetate, pentafluoropropionate, triflate, trifluoroacetate, methylsulfate, tosylate and nitrate, wherein j and k are 1. Preferably, Y is chloride, bromide, iodide, hydroxide, bicarbonate, acetate, trifluoroacetate, methylsulfate, tosylate and nitrate, wherein j and k are 1. For compounds of Formula (l-ll) emphasis is also given to salts when Y is 25 carbonate and sulfate, wherein j is 2 and k is 1, and when Y is phosphate, wherein j is 3 and k is 1.

Where appropriate compounds of Formula (I) may also be in the form of (and/or be used as) an N-oxide.

Compounds of Formula (I) wherein m is 0 may be represented by a compound of Formula (l-la) as shown below:

wherein R¹, R², A and Z are as defined for compounds of Formula (I).

Compounds of Formula (I) wherein m is 1 may be represented by a compound of Formula (l-lb) as shown below:

Z

R^2b (Mb) wherein R¹, R², R^1a, R^2b, A and Z are as defined for compounds of Formula (I).

Compounds of Formula (I) wherein m is 2 may be represented by a compound of Formula (l-lc) as shown below:

(l-lc) wherein R¹, R², R^1a, R^2b, A and Z are as defined for compounds of Formula (I).

Compounds of Formula (I) wherein m is 3 may be represented by a compound of Formula (l-ld) as shown below:

(Md) wherein R¹, R², R^1a, R^2b, A and Z are as defined for compounds of Formula (I).

Preferred values of A, R¹, R², R^1a, R^2b, R⁸, R¹⁰, R¹², Q, Z, m and p are as set out below, and a compound of Formula (I) according for use in the invention may comprise any combination of said values, unless explictly stated otherwise. The skilled man will appreciate that values for any specified set of embodiments may be combined with values for any other set of embodiments where such combinations are not mutually exclusive, and where not explicitly stated to the contrary.

With respect to substituents R¹ and R², the following combinations may ail be found in compounds of Formula (I): R¹ is hydrogen and R² is hydrogen, R¹ is methyl and R² is hydrogen (or R¹ is hydrogen and R² is methyl), R¹ is methyl and R² is methyl. However, most commonly, R¹ is hydrogen and R² is hydrogen.

As stated herein, m is an integer of 0, 1 or 2. Preferably m is 1 or 2, and most preferably m is 1. Where m is 1, it is preferred that R^1a and R^2b are each independently selected from the group consisting of hydrogen, hydroxy and methyl. In such cases where m is 1, it is particularly preferred that at least one of R^1a and R^2b is hydrogen.

Where m is 2 or more, it is preferred that the R^1a and R^2b borne by the carbon atom adjoining the CR¹CR² moiety, are each independently selected from the group consisting of hydrogen, hydroxy and methyl, and more preferably that at least one of said R^1a and R^2b is hydrogen.

As stated herein A is 6-membered heteroaryl selected from the group consisting of:

A-V A-VI A-VII wherein the jagged line defines the point of attachment to the remaining part of a compound of Formula (l), p is 0, 1 or 2 and each R⁸ is independently selected from the group consisting of NH2, methyl and methoxy.

Where p is an integer of 2, it is preferred that each R⁸ is methyl. However, preferably p is 0 or 1.

In certain embodiments A is preferably A-l, A-ll or A-lll, and p is preferably 0 or 1. In such embodiments, where p is 0, the skilled man will appreciate that any nitrogen atom in A may be protonated.

Preferably Z is selected from the group consisting of: -C(O)OH, -C(O)OCH3, -S(O)2OH, C(O)OCH₂C₆H5, -C(O)OC_bH5, -C(O)NHS(O)₂N(CH₃)2. More preferably Z is -C(O)OH or -S(O)₂OH.

Spécifie compounds of Formula (I) for use in the invention as component (A), are described below in the Examples. These include compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021,1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 2.001,2.002, 2.003, 2.004, 2.005, 2.006, 2.007, 2.008, 2.009, 2.010, and 2.011. Particularly preferred compounds of Formula (I) for use as component (A) in the invention are selected from 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011,1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034 and 1.035. More preferred still are compounds 1.001, 1.002, 1.003, 1.010, 1.011, 1.021, 1.022, 1.023, 1.027, 1.030, 1.031,1.032, 1.034 and 1.035.

The compounds of Formula (I) may be prepared according to the following schemes, in which the substituents A, R¹, R², R^1a, R^2b, R⁸, R¹⁰, R¹², Q, Z, m and p hâve (unless otherwise stated explicitly) the définitions described hereinbefore.

The compounds of Formula (I) may be prepared by the alkylation of compounds of formula (X), wherein A is as defined for compounds of Formula (I), with a suitable alkylating agent of formula (W), wherein R¹, R², Q,and Z are as defined for compounds of Formula (I) and LG is a suitable leaving group, for example, halide or pseudohalide such as triflate, mesylate or tosylate, in a suitable solvent at a suitable température, as described in reaction scheme 1. Example conditions include stirring a compound of formula (X) with an alkylating agent of formula (W) in a solvent, or mixture of solvents, such as acetone, dichloromethane, dichloroethane, Λ/,/V-dimethylformamide, acetonitrile, 1,4-dioxane, water, acetic acid ortrifluroacetic acid at a température between -78°C and 150°C. An alkylating agent of formula (W) may include, but is not limited to, bromoacetic acid, methyl bromoacetate, 3bromopropionoic acid, methyl 3-bromopropionate, 2-bromo-N-methoxyacetamide, sodium 2bromoethanesulphonate, 2,2-dimethylpropyl 2-(trifluoromethylsulfonyloxy)ethanesulfonate, 2-bromo-N5 methanesulfonylacetamide, 3-bromo-N-methanesulfonylpropanamide, and dimethoxyphosphorylmethyl trifluoromethanesulfonate. -Such alkylating agents and related compounds are either known in the literature or may be prepared by known literature methods. Compounds of Formula (I) which may be described as esters of N-alkyl acids, which include, but are not limited to, esters of carboxylic acids, phosphonic acids, phosphinic acids, sulfonic acids and sulfinic acids, may be 10 subsequently partially or fully hydrolysed by treament with a suitable reagent, for example, aqueous hydrochloric acid or trimethylsilyl bromide, in a suitable solvent at a suitable température between 0°C and 100°C.

Reaction scheme 1

LG Q /F ^Z

R^l/ R² formula (W)

L II .N/

R² ₁₅ ^formula <^X> formula (I)

Additonally, compounds of Formula (I) may be prepared by reacting compounds of formula (X), wherein A is as defined for compounds of Formula (I), with a suitably activated electrophilic alkene of formula (B), wherein Z is -S(O)₂OR¹⁰, or -C(O)OR¹⁰ and R¹, R², R^1a, and R¹⁰ are as defined for compounds of Formula (I), in a suitable solvent at a suitable température. Compounds of formula (B) 20 are known in the literature, or may be prepared by known methods. Example reagents include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, 3,3-dimethylacrylic acid, methyl acrylate, ethene sulfonic acid, isopropyl ethylenesulfonate, and 2,2-dimethylpropyl ethenesulfonate. The direct products of these reactions, which may be described as esters of N-alkyl acids, which include, but are not limited to, esters of carboxylic acids and sulfonic acids, may be subsequently partially or fully 25 hydrolysed by treament with a suitable reagent in a suitable solvent at a suitable température, as described in réaction scheme 2.

Reaction scheme 2

formula (I), wherein m=1, and Z=S(O)₂OR¹⁰, C(O)OR¹⁰ formula (I), wherein m=1, and Z=SO₃H, C(O)OH

In a related reaction compounds of Formula (I), wherein Q is C(R^1aR^2b), m is 1,2 or 3 and Z is 5 S(O)2OH, may be prepared by the reaction of compounds of formula (X), wherein A is as defined for compounds of Formula (I), with a cyclic alkylating agent of formula (E), (F) or (AF), wherein Y^a is C(R^1aR^2b), and R¹, R², R^1a and R^2b are as defined for compounds of Formula (I), in a suitable solvent at a suitable température, as described in reaction scheme 3.

Reaction scheme 3

formula (E), wherein m=1

formula (F), where m=2

formula (X) o—s=o

R^2b

R

formula (I), wherein m is 1, 2 or 3, and Z=SO₃H formula (AF) where m=1

Suitable solvents and suitable températures are as previously described. An alkylating agent of formula (E) or (F) may include, but is not limited to, 1,3-propanesultone, 1,4-butanesultone, ethylenesulfate, 1,3-propylene sulfate and 1,2,3-oxathiazolidine 2,2-dioxide. Such alkylating agents and related compounds are either known in the literature or may be prepared by known literature methods.

A compound of Formula (I), wherein m is 0, and Z is -S(O)2OH, may be prepared from a compound of Formula (I), wherein m is 0, and Z is C(O)OR¹⁰, by treatment with trimethylsilylchloro sulfonate in a suitable solvent at a suitable température, as described in reaction scheme 4. Preferred

conditions include heating the carboxylate precursor in neat trimethylsilylchlorosulfonate at a température between 25°C and 150°C.

Réaction scheme 4

formula (I) wherein m=0, and Z=C(O)OR¹⁰ formula (I), wherein m=0, and Z=SO₃H

Furthermore, compounds of Formula (I) may be prepared by reacting compounds of formula (X), wherein A is as defined for compounds of Formula (I), with a suitable alcohol of formula (WJ\f), wherein R¹, R², Q, and Z are as defined for compounds of Formula (I), under Mitsunobu-type conditions such as those reported by Petit et al, Tet. Lett. 2008, 49 (22), 3663. Suitable phosphines include triphenylphosphine, suitable azodicarboxylates include diisopropylazodicarboxylate and suitable acids include fluoroboric acid, triflic acid and bis(trifluoromethylsulfonyl)amine, as described in reaction scheme 5. Such alcohols are either known in the literature or may be prepared by known literature methods.

Reaction scheme 5

HO Q

Acid, Ph₃P

Compounds of Formula (I) may also be prepared by reacting compounds of formula (C), wherein Q, Z, R¹, R², and A are as defined for compounds of Formula (I), with a hydrazine of formula (D) in a 20 suitable solvent or mixture of solvents, in the presence of a suitable acid at a suitable température, between -78°C and 150°C, as described in reaction scheme 6. Suitable solvents, or mixtures thereof, include, but are not limited to, alcohols, such as methanol, éthanol and isopropanol, water, aqueous hydrochloric acid, aqueous sulfuric acid, acetic acid and trifluoroacetic acid. Hydrazine compounds of formula (D), for example 2,2-dimethylpropyl 2-hydrazinoethanesulfonate, are either known in the 25 literature or may be prepared by known literature procedures.

Reaction scheme 6

formula (C) formula (I)

R' = H, C₁-C₄alkyl,

C₁-C₄alkylcarbonyl

Compounds of formula (C) may be prepared by reacting compounds of formula (G), wherein A is as defined for compounds of Formula (I), with an oxidising agent in a suitable solvent at a suitable température, between -78°C and 150°C, optionally in the presence of a suitable base, as described in reaction scheme 7.

Reaction scheme 7

A

Base formula (G) _{formu|a (c)}

R' = H, C₁-C₄alkyl, C₁-C₄alkyl carbonyl

Suitable oxidising agents include, but are not limited to, bromine and suitable solvents include, but are not limited to alcohols such as méthanol, éthanol and isopropanol. Suitable bases include, but are not limited to, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate and potassium acetate. Similar reactions are known in the literature (for example Hufford, D. L.; Tarbell, D. S.; Koszalka, T. R. J. Amer. Chem. Soc., 1952, 3014). Furans of formula (G) are known in the literature or may be prepared using literature methods. Example methods include, but are not limited to, transition métal cross-couplings such as Stille (for example Farina, V.; Krishnamurthy, V.; Scott, W. J. Organic Reactions, Vol. 50. 1997, and Gazzard, L. et al. J. Med. Chem., 2015, 5053), Suzuki-Miyaura (for example Ando, S.; Matsunaga, H.; Ishizuka, T. J. Org. Chem. 2017, 1266-1272, and Ernst, J. B.; Rakers, L.; Glorius, F. Synthesis, 2017,260), Negishi (for example Yang, Y.; Oldenhius, N. J.; Buchwald, S. L. Angew. Chem. Int. Ed. 2013, 615, and Braendvang, M.; Gundersen, L. Bioorg. Med. Chem. 2005, 6360), and Kumada (for example Heravi, Μ. M.; Hajiabbasi, P. Monatsh. Chem., 2012, 1575). The coupling partners may be selected with reference to the spécifie cross-coupling reaction and target product. Transition métal catalysts, ligands, bases, solvents and températures may be selected with reference to the desired cross-coupling and are known in the literature. Cross-coupling reactions using pseudo halogens, including but not limited to, triflates, mesylates, tosylates and anisoles, may also be achieved under related conditions.

In another approach a compound of Formula (I), wherein Q, Z, R¹, R², and A are as defined for compounds of Formula (I), may be prepared from a compound of formula (R) and an oxidant, in a suitable solvent at a suitable température, as outlined in reaction scheme 8. Example oxidants include, but are not limited to, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro-p-benzoqumone, potassium permanganate, manganèse dioxide, 2,2,6,6-tetramethyl-1-piperidinyloxy and bromine. Related reactions are known in the literature.

Reaction scheme 8

formula (R) formula (I)

A compound of formula (R), wherein Q, Z, R¹, R², and A are as defined for compounds of Formula (I), may be prepared from a compound of formula (S), wherein Q, Z, X, n, R¹, and R² are as defined for compounds of Formula (I), and an organometallic of formula (T), wherein A is as defined for compounds of Formula (I) and M” includes, but is not limited to, organomagnesium, organolithium, organocopper and organozinc reagents, in a suitable solvent at a suitable température, optionally in the presence of an additonal transition métal additive, as outlined in reaction scheme 9. Example conditions include treating a compound of formula (S) with a Grignard of formula (T), in the presence of 0.05-100 mol% copper iodide, in a solvent such as tetrahydrofuran at a température between -78°C and 100°C. Organometallics of formula (T) are known in the literature, or may be prepared by known literature methods. Compounds of formula (S) may be prepared by analogous reactions to those for the préparation of compounds of Formula (I) from a compound of formula (XX).

Reaction scheme 9

formula (S) formula (R)

Biaryl pyridazines of formula (X) are known in the literature or may be prepared using literature methods. Example methods include, but are not limited to, the transition métal cross-coupling of compounds of formula (H) and formula (J), or alternatively compounds of formula (K) and formula (L), in which compounds of formula (J) and formula (L), wherein M’ is either an organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organocopper or organozinc, as outlined in reaction scheme 10. Hal is defined as a halogen or pseudo halogen, for example triflate, mesylate and tosylate. Such cross-couplings include Stille (for example Sauer, J.; Heldmann, D. K. Tetrahedron, 1998, 4297), Suzuki-Miyaura (for example Luebbers, T.; Flohr, A.; Jolidon, S.; DavidPierson, P.; Jacobsen, H.; Ozmen, L.; Baumann, K. Bioorg. Med. Chem. Lett., 2011,6554), Negishi (for example Imahori, T.; Suzawa, K.; Kondo, Y. Heterocycles, 2008, 1057), and Kumada (for example Heravi, Μ. M.; Hajiabbasi, P. Monatsh. Chem., 2012,1575). The coupling partners may be selected with reference to the spécifie cross-coupling reaction and target product. Transition métal catalysts, ligands, bases, solvents and températures may be selected with reference to the desired cross-coupling and are known in the literature. Compounds of formula (H), formula (K) and formula (L) are known in the literature, or may be prepared by known literature methods.

Reaction scheme 10

A —Hal +

formula (J)

Transition métal catalyst Ligand

formula (H) formula (X)

Transition métal catalyst Ligand

formula (L) formula (K) formula (X)

A compound of formula (J), wherein M’ is either an organostannane, organoboronic acid or ester, organotrifluoroborate, organomagnesium, organocopper or organozinc, may be prepared from a 10 compound of formula (XX), by metallation, as outlined in reaction scheme 11. Similar reactions are known in the literature (for example Ramphal et al, WO2015/153683, Unsinn et al., Organic Letters, 15(5), 1128-1131; 2013, Sadler et al., Organic & Biomolecular Chemistry, 12(37), 7318-7327; 2014. Alternatively, an organometallic of formula (J) may be prepared from compounds of formula (K), wherein Hal is defined as a halogen or pseudo halogen, for example triflate, mesylate and tosylate, as described 15 in scheme 11. Example conditions to préparé an compound of formula (J) wherein M’ is an organostannane, include treatment of a compound of formula (K) with lithium tributyl tin in an appropriate solvent at an appropriate température (for example see WO 2010/038465). Example conditions to préparé compound of formula (J) wherein M’ is an organoboronic acid or ester, include treatment of a compound of formula (K) with bis(pinacolato)diboron, in the presence of an appropriate transition métal 20 catalyst, appropriate ligand, appropriate base, in an appropriate solvent at an appropriate température (for example KR 2015135626). Compounds of formula (K) and formula (XX) are either known in the literature or can be prepared by known methods.

Reaction scheme 11

formula (K)

formula (J)

formula (XX)

Compositions ofthe invention also comprise, as component (B), at least one herbicide, or sait thereof, selected from the group consisting of:

B1 a non-selective herbicide selected from the group consisting of glyphosate, glufosinate, 5 hydantocidin, pelargonic acid, paraquat and diquat;

B3 a herbicide that inhibits photosystem II in photosynthesis.

Some ofthe herbicides of component B are commonly used in the form of agronomically acceptable salts. Where a spécifie herbicide is described as being suitable for use as component B, 10 the skilled man will appreciate that this includes any suitable agronomically aceptable sait of that herbicide, for example any sait which may form with amines (for example ammonia, dimethylamine and triethylamine), alkali métal and alkaline earth métal bases orquatemary ammonium bases. Among the alkali métal and alkaline earth métal hydroxides, oxides, alkoxides and hydrogen carbonates and carbonates used as sait formers, emphasis is to be given to the hydroxides, alkoxides, 15 oxides and carbonates of lithium, sodium, potassium, magnésium and calcium, but especially those of sodium, magnésium and calcium. The corresponding trimethylsulfonium sait may also be used. The présent invention also include the use of hydrates which may be formed during the sait formation for any herbicide of component B.

Herbicides that act through the inhibition of protoporphoryinogen oxidase, and are thus included 20 in group B2, include the diphenyl ethers (bifenox, ethoxyfen-ethyl, halosafen, lactofen, acifluorfensodium, chlomethoxyfen, fluoroglycofen-ethyl, oxyfluorfen, fomesafen), the thiadiazoles (fluthiacetmethyl, thidazimin), the phenylpyrazoles (fluazolate, pyraflufen-ethyl), the oxadiazoles (oxadiargyl, oxadiazon), the N-phenylphthalimides (cinidon-ethyl, flumiclorac-pentyl, flumioxazin), the pyrmidinediones (benzfendizone, butafenacil, saflufenacil), the triazolinones (azafenidin, 25 bencarbazone, carfentrazone-ethyl, sulfentrazone), the oxazolidinedione pentoxazone, as well as flufenpyr ethyl, pyraclonil, profluazol, the compound of formula B2.9

B2.9, and the compound of B2.10

Preferred herbicides from B2 for use in the invention are selected from the group consisting of:

B2(i) saflufenacil, B2(ii) fomesafen, B2(iii) oxyfluorfen, B2(iv) butafenacil, B2(v) carfentrazoneethyl, B2(vi) pyraflufen-ethyl, B2(vii) sulfentrazone, B2(vni) flumioxazm, B2(ix) compound B2.9,

More preferred herbicides from B2 for use in the invention are selected from the group consisting of: B2(i) saflufenacil, B2(ii) fomesafen, B2(iii) oxyfluorfen, B2(iv) butafenacil, B2(v) carfentrazone-ethyl, B2(vi) pyraflufen-ethyl, B2(vii) sulfentrazone, B2(viii) flumioxazin, and B2(ix) compound B2.9,

Herbicides that inhibit photosystem II in photosynthesis, and are thus included in group B3, include the pyridazinone chloridazon/pyrazon, the phenyl carbamates (desmedipham, desmedipham), the uracils (bromacil, lenacil, terbacil, tiafenacil), the triazinones (hexazinone, metamitron, metribuzin), the ureas (fenuron, metobromuron, neburon, chlorobromuron, fluometuron, methabenzthiazuron, siduron, chlorotoluron, isoproturon, metoxuron, tebuthiuron, chloroxuron, isouron, monlinuron, dimefuron, linuron, diuron, ethidimuron), the triazolinone amicarbozone, the triazines (atrazine, desmetryne, propazine, terbuthylazine, dimethametryn, simetryne, terbutryne, ametryne, prometon, simazine, trietazine, prometryne, terbumeton), the amides (pentanochlor, propanil), the nitriles (bromofenoxim, bromoxynil, ioxynil), the phenyl-pyridazines (pyridate, pyridafol), and the benzothiadiazinone bentazone.

Preferred herbicides from B3 for use in the invention are selected from the group consisting of: B3(i) atrazine, B3(ii) ametryn, B3(iii) metribuzin, B3(iv) hexazinone, B3(v) diuron, B3(vi) propanil, B3(vii) prometryn, B3(viii) tiafenacil, and B3(ix) trifludimoxazin.

Herbicides of groups B1, B2 and B3 as described above, are well known in the art, and can either be obtained commercially, or manufactured using methods available in the art.

In Tables 1 to 3 below, 840 spécifie combinations of components A and B, are described according to the invention.

Table 1 Compositions of the invention comprising as component (A), a compound of Formula (I) and as 5 component (B), a herbicide from group B1. This table explicitly recites 210 spécifie compositions of the invention (M1 to M204, and M817 to M822 respectively), wherein the compound of Formula (I) is specified in column 1, and the herbicide of component (B) is specified in columns 2 to 7 respectively.
	1.001	COMPONENT (B)
Glyphosate	Glufosinate	Hydantocidin	Pelargonic Acid	Paraquat	Diquat
M1	M35	M69	M103	M137	M171
1.002	M2	M36	M70	M104	M138	M172
1.003	M3	M37	M71	M105	M139	M173
1.004	M4	M38	M72	M106	M140	M174
1.005	M5	M39	M73	M107	M141	M175
1.006	M6	M40	M74	M108	M142	M176
1.007	M7	M41	M75	M109	M143	M177
1.008	M8	M42	M76	M110	M144	M178
1.009	M9	M43	M77	M111	M145	M179
1.010	M10	M44	M78	M112	M146	M180
1.011	M11	M45	M79	M113	M147	M181
1.012	M12	M46	M80	M114	M148	M182
„ 1.013	M13	M47	M81	M115	M149	M183
T 1.014	M14	M48	M82	M116	M150	M184
<= 1.015	M15	M49	M83	M117	M151	M185
A E 1.016	M16	M50	M84	M118	M152	M186
s ü 1.017	M17	M51	M85	M119	M153	M187
O £ 1.018	M18	M52	M86	M120	M154	M188
Ξ = 1.019	M19	M53	M87	M121	M155	M189
8 g- 1.020	M20	M54	M88	M122	M156	M190
o 1.021	M21	M55	M89	M123	M157	M191
“ 1.022	M22	M56	M90	M124	M158	M192
1.023	M23	M57	M91	M125	M159	M193
1.024	M24	M58	M92	M126	M160	M194
1.025	M25	M59	M93	M127	M161	M195
1.026	M26	M60	M94	M128	M162	M196
1.027	M27	M61	M95	M129	M163	M197
1.028	M28	M62	M96	M130	M164	M198
1.029	M29	M63	M97	M131	M165	M199
1.030	M30	M64	M98	M132	M166	M200
1.031	M31	M65	M99	M133	M167	M201
1.032	M32	M66	M100	M134	M168	M202
1.033	M33	M67	M101	M135	M169	M203
1.034	M34	M68	M102	M136	M170	M204
1.035	M817	M818	M819	M820	M821	M822

Table 2 Compositions of the invention comprising as component (A), a compound of Formula (I) and as component (B), a herbicide from group B2. This table explicitly recites 350 spécifie compositions of the invention (M205 to M510, M823 to M831, and M841 to M875) wherein the compound of Formula (I) is specified in column 1, and the herbicide of component (B) is specified in columns 2 to 11 respectively.

„ 1001	COMPONENT (B)
Saflufen -acil	Fomesafen	Oxyfluorfen	Butafenacil	Carfentrazone-ethyl	Pyrafluf en-ethyl	Sufentrazone	Flumioxazin	B2.9	B2.10
M205	M239	M273	M307	M341	M375	M409	M443	M477	M841
— 2 1002	M206	M240	M274	M308	M342	M376	M410	M444	M478	M842
S 1.003	M207	M241	M275	M309	M343	M377	M411	M445	M479	M843
z i 1.004	M208	M242	M276	M310	M344	M378	M412	M446	M480	M844
z -o = 1.005	M209	M243	M277	M311	M345	M379	M413	M447	M481	M845
& g 1006	M210	M244	M278	M312	M346	M380	M414	M448	M482	M846
O g· 1.007	M211	M245	M279	M313	M347	M381	M415	M449	M483	M847
° S 1.008	M212	M246	M280	M314	M348	M382	M416	M450	M484	M848
“ 1.009	M213	M247	M281	M315	M349	M383	M417	M451	M485	M849

	COMPONENT (B)
Saflufen -acil	Fomesafen	Oxyfluorfen	Butafenacil	Carfentrazone-ethyl	Pyraflufen-ethyl	Sufentrazone	Flumioxazin	B2.9	B2.10
1.010	M214	M248	M282	M316	M350	M384	M418	M452	M486	M850
1.011	M215	M249	M283	M317	M351	M385	M419	M453	M487	M851
1.012	M216	M250	M284	M318	M352	M386	M420	M454	M488	M852
1.013	M217	M251	M285	M319	M353	M387	M421	M455	M489	M853
1.014	M218	M252	M286	M320	M354	M388	M422	M456	M490	M854
1.015	M219	M253	M287	M321	M355	M389	M423	M457	M491	M855
1.016	M220	M254	M288	M322	M356	M390	M424	M458	M492	M856
1.017	M221	M255	M289	M323	M357	M391	M425	M459	M493	M857
1.018	M222	M256	M290	M324	M358	M392	M426	M460	M494	M858
1.019	M223	M257	M291	M325	M359	IVI393	M427	M461	M495	M859
1.020	M224	M258	M292	M326	M360	M394	M428	M462	M496	M860
1.021	M225	M259	M293	M327	M361	M395	M429	M463	M497	M861
1.022	M226	M260	M294	M328	M362	M396	M430	M464	M498	M862
1.023	M227	M261	M295	M329	M363	M397	M431	M465	M499	M863
1.024	M228	M262	M296	M330	M364	M398	M432	M466	M500	M864
1.025	M229	M263	M297	M331	M365	M399	M433	M467	M501	M865
1.026	M230	M264	M298	M332	M366	M400	M434	M468	M502	M866
1.027	M231	M265	M299	M333	M367	M401	M435	M469	M503	M867
1.028	M232	M266	M300	M334	M368	M402	M436	M470	M504	M868
1.029	M233	M267	M301	M335	M369	M403	M437	M471	M505	M869
1.030	M234	M268	M302	M336	M370	M404	M438	M472	M506	M870
1.031	M235	M269	M303	M337	M371	M405	M439	M473	M507	M871
1.032	M236	M270	M304	M338	M372	M406	M440	M474	M508	M872
1.033	M237	M271	M305	M339	M373	M407	M441	M475	M509	M873
1.034	M238	M272	M306	M340	M374	M408	M442	M476	M510	M874
1.035	M823	M824	M825	M826	M827	M828	M829	M830	M831	M875

Table 3 Compositions of the invention comprising as component (A), a compound of Formula (I) and as component (B), a herbicide from group B3. This table explicitly recites 315 spécifie compositions of the invention (M511 to M816, and M832 to M840) wherein the compound of Formula (I) is specified in column 1, and the herbicide of component (B) is specified in columns 2 to 10 respectively.

1.001	COMPONENT (B)
Atrazine	Ametryn	Metribuzin	Hexazinone	Diuron	Propanil	Prometryn	Tiafenacil	Trifludimoxazin
M511	M545	M579	M613	M647	M681	M715	M749	M783
1.002	M512	M546	M580	M614	M648	M682	M716	M750	M784
1.003	M513	M547	M581	M615	M649	M683	M717	M751	M785
1.004	M514	M548	M582	M616	M650	M684	M718	M752	M786
1.005	M515	M549	M583	M617	M651	M685	M719	M753	M787
1.006	M516	M550	M584	M618	M652	M686	M720	M754	M788
1.007	M517	M551	M585	M619	M653	M687	M721	M755	M789
1.008	M518	M552	M586	M620	M654	M688	M722	M756	M790
1.009	M519	M553	M587	M621	M655	M689	M723	M757	M791
1.010	M520	M554	M588	M622	M656	M690	M724	M758	M792
= 1.011	M521	M555	M589	M623	M657	M691	M725	M759	M793
rç 1.012	M522	M556	M590	M624	M658	M692	M726	M760	M794
É 1.013	M523	M557	M591	M625	M659	M693	M727	M761	M795
£ 1.014	M524	M558	M592	M626	M660	M694	M728	M762	M796
o 1.015	M525	M559	M593	M627	M661	M695	M729	M763	M797
T 1.016	M526	M560	M594	M628	M662	M696	M730	M764	M798
S 1.017	M527	M561	M595	M629	M663	M697	M731	M765	M799
E 1.018	M528	M562	M596	M630	M664	M698	M732	M766	M800
Si 1.019	M529	M563	M597	M631	M665	M699	M733	M767	M801
< 1.020	M530	M564	M598	M632	M666	M700	M734	M768	M802
t= 1.021	M531	M565	M599	M633	M667	M701	M735	M769	M803
s 1.022	M532	M566	M600	M634	M668	M702	M736	M770	M804
o 1.023	M533	M567	M601	M635	M669	M703	M737	M771	M805
Ξ 1.024	M534	M568	M602	M636	M670	M704	M738	M772	M806
8 1.025	M535	M569	M603	M637	M671	M705	M739	M773	M807
1.026	M536	M570	M604	M638	M672	M706	M740	M774	M808
1.027	M537	M571	M605	M639	M673	M707	M741	M775	M809
1.028	M538	M572	M606	M640	M674	M708	M742	M776	M810
1.029	M539	M573	M607	M641	M675	M709	M743	M777	M811
1.030	M540	M574	M608	M642	M676	M710	M744	M778	M812
1.031	M541	M575	M609	M643	M677	M711	M745	M779	M813
1.032	M542	M576	M610	M644	M678	M712	M746	M780	M814
1.033	M543	M577	M611	M645	M679	M713	M747	M781	M815
1.034	M544	M578	M612	M646	M680	M714	M748	M782	M816
1.035	M832	M833	M834	M835	M836	M837	M838	M839	M840

In one set of embodiments, it is preferred that component B is selected from the group consisting 10 of glyphosate, glufosinate, hydantocidin, diquat; B2(i) saflufenacil, B2(ii) fomesafen, B2(iii) oxyfluorfen, B3(i) atrazine, and B3(iii) metribuzin.

Throughout this document the expression “composition” should be interpreted as meaning the various mixtures or combinations of components (A) and (B), for example in a single “ready-mix” form, in a combined spray mixture composed from separate formulations ofthe single active ingrédient components, such as a “tank-mix”, and in a combined use ofthe single active ingrédients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the components (A) and (B) is not essential for working the présent invention.

The term “herbicide” as used herein means a compound that contrais or modifies the growth of plants. The term “herbicidally effective amount” means the quantity of such a compound or combination of such compounds that is capable of producing a controlling or modifying effect on the growth of plants. Controlling or modifying effects include ail déviation from natural development, for 5 example killing, retardation, leaf burn, albinism, dwarfing and the like.

The term “locus” as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established végétation.

The term “plants” refers to ail physical parts of a plant, including seeds, seedlings, saplings, 10 roots, tubers, stems, stalks, foliage, and fruits.

The term plant propagation material” dénotés ail generative parts of a plant, for example seeds or végétative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants.

The term “safener” as used herein means a Chemical that when used in combination with a 15 herbicide reduces the undesirabie effects ofthe herbicide on non-target organisms, for example, a safener protects crops from injury by herbicides but does not prevent the herbicide from killing the weeds.

Crops of useful plants in which the composition according to the invention can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, 20 raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed râpe (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, 25 fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, 30 aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.

Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved 35 flavour).

Crops are to be understood as also including those crops which hâve been rendered tolérant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolérant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® 40 summer râpe (canola). Examples of crops that hâve been rendered tolérant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available underthe trade names RoundupReady®and Liberty Lin k®.

Crops are also to be understood as being those which hâve been rendered résistant to harmful insects by genetic engineering methods, for example Bt maize (résistant to European corn borer), Bt cotton (résistant to cotton boll weevil) and also Bt potatoes (résistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal résistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seed material thereof can be both résistant to herbicides and, at the same time, résistant to insect feeding (stacked transgenic events). For example, seed can hâve the ability to express an insecticidal Cry3 protein while at the same time being tolérant to glyphosate.

Compositions ofthe invention can typically be used to control a wide variety of monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that can typically be controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi and Sorghum bicolor. Examples of dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica and Xanthium strumarium.

In ail aspects ofthe invention, in any particular embodiment, the weeds, e.g. to be controlled and/or growth-inhibited, may be monocotyledonous or dicotyledonous weeds, which are tolérant or résistant to one or more other herbicides for example, HPPD inhibitor herbicides such as mesotrione, PSII inhibitor herbicides such as atrazine or EPSPS inhibitors such as glyphosate. Such weeds include, but are not limited to résistant Amaranthus biotypes.

Compositions of this invention can also be mixed with one or more further pesticides including herbicides [typically different to the herbicides of Formula (I) and those of component (B)] fungicides, insecticides, nematocides, bactéricides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.

Similarly compositions ofthe invention (which includes those comprising one or more additional pesticide as described in the preceding paragraph) can further include one or more safeners. In particular, the following safeners are especially preferred: AD 67 (MON 4660), benoxacor, cloquintocet-mexyl, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazoleethyl, fenclorim, flurazole, fluxofenim, furilazole, furilazome, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, oxabetrinil, naphthalic anhydride (CAS RN 81-84-5), TI-35, N-isopropyl-4-(2-methoxybenzoylsulfamoyl)-benzamide (CAS RN 221668-34-4) and N-(2-methoxybenzoyl)-420326

[(methylaminocarbonyl)amino]benzenesulfonamide. Such safeners may also be used in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 15th Ed. (BCPC), 2009. Thus, the reference to cloquintocet-mexyl also applies to cloquintocet and to a lithium, sodium, potassium, calcium, magnésium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium sait thereof as disclosed in WO02/34048 and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.

The compositions ofthe invention can be applied before or after planting ofthe crops, before weeds emerge (pre-emergence application) or after weeds emerge (post-emergence application). Where a safener is combined with mixtures ofthe invention, it is preferred that the mixing ratio of compound of Formula (I) to safener is from 100:1 to 1:10, especially from 20:1 to 1:1.

It is possible that the safener and the compositions ofthe invention are applied simultaneously. For example, the safener and the composition of the invention might be applied to the locus preemergence or might be applied to the crop post-emergence. It is also possible that the safener and the composition ofthe invention are applied sequentially. For example, the safener might be applied before sowing the seeds as a seed treatment and the composition ofthe invention might be applied to the locus pre-emergence or might be applied to the crop post-emergence.

However, the skilled man will appreciate that compositions of the invention are particularly useful in non-selective burn-down applications, and as such may also be used to control volunteer or escape crop plants. In such situations, it is clearly not necessary to include a safener in a composition 20 ofthe invention.

In general, the mixing ratio (by weight) ofthe compound of Formula (I) to the compound of component B is from 0.01:1 to 100:1, more preferably from 0.025:1 to 20:1, even more preferably from 1:30 to 20:1. Thus, the preferred ratio ranges for preferred compositions ofthe invention are given in Table 4 below.

Table 4: Exemplar ratio ranges for spécifie compositions of the invention____________

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M1	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M2	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M3	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M4	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M5	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M6	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M7	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M8	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M9	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M10	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M11	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M12	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M13	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M14	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M15	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M16	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M17	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M18	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M19	0.01:1 to 100:1	0.025:1 to20:1	1:30 to 16:1
M20	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M21	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M22	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M23	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M24	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M25	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M26	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M27	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M28	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M29	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M30	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M31	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M32	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M33	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M34	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M35	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M36	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M37	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M38	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M39	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M40	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M41	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M42	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M43	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M44	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M45	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M46	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M47	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M48	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M49	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M50	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M51	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M52	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M53	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M54	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M55	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M56	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M57	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M58	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M59	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M60	0.01:1 to 100:1	0,025:1 to 20:1	1:30 to 16:1
M61	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M62	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M63	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M64	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M65	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M66	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M67	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M68	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M69	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M70	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M71	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M72	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M73	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M74	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M75	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M76	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M77	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M78	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M79	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M80	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M81	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M82	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M83	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M84	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M85	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M86	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M87	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M88	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M89	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M90	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M91	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M92	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M93	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M94	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M95	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M96	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M97	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M98	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M99	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M100	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M101	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M1C2	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M103	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M104	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M105	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M106	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M107	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M108	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M109	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M110	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M111	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M112	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M113	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M114	0.01:1 to 100:1	0.025:1 to20:1	1:30 to 16:1
M115	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M116	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M117	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M118	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M119	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M120	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M121	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M122	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M123	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M124	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M125	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M126	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M127	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M128	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M129	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M130	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M131	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M132	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M133	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M134	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M135	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M136	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M137	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M138	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M139	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M140	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M141	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M142	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M143	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M144	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M145	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M146	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M147	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M148	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M149	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M150	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M151	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M152	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M153	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M154	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M155	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M156	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M157	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M158	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M159	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M160	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M161	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M162	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M163	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M164	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M165	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M166	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M167	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M168	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M169	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M170	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M171	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M172	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M173	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M174	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M175	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M176	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M177	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M178	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M179	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M180	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M181	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M182	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M183	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M184	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M185	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M186	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M187	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M188	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M189	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M190	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M191	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M192	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M193	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M194	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M195	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M196	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M197	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M198	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M199	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M200	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M201	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M202	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M203	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M204	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M205	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M206	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M207	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M208	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M209	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M210	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M211	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M212	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M213	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M214	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M215	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M216	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M217	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M218	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M219	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M220	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M221	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M222	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M223	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M224	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M225	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M226	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M227	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M228	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M229	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M230	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M231	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M232	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M233	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M234	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M235	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M236	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M237	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M238	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M239	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M240	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M241	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M242	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M243	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M244	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M245	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M246	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M247	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M248	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M249	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M250	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M251	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M252	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M253	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M254	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M255	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M256	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M257	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M258	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M259	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M260	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M261	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M262	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M263	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M264	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M265	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M266	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M267	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M268	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M269	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M270	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M271	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M272	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M273	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M274	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M275	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M276	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M277	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M278	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M279	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M280	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M281	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M282	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M283	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M284	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M285	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M286	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M287	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M288	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M289	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M290	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M291	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M292	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M293	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M294	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M295	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M296	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M297	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M298	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M299	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M300	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M301	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M302	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M303	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M304	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M305	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M306	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M307	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M308	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M309	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M310	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M311	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M312	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M313	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M314	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M315	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M316	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M317	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M318	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M319	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M320	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M321	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M322	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M323	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M324	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M325	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M326	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M327	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M328	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M329	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M330	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M331	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M332	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M333	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M334	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M335	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M336	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M337	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M338	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M339	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M340	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M341	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M342	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M343	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M344	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M345	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M346	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M347	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M348	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M349	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M350	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M351	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M352	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M353	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M354	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M355	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M356	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M357	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M358	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M359	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M360	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M361	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M362	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M363	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M364	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M365	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M366	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M367	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M368	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M369	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M370	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M371	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M372	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M373	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M374	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M375	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M376	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M377	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M378	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M379	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M380	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M381	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M382	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M383	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M384	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M385	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M386	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M387	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M388	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M389	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M390	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M391	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M392	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M393	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M394	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M395	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M396	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M397	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M398	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M399	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M400	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M401	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M402	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M403	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M404	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M405	0.01:1 to 100:1	0.025:1 ta 20:1	1:30 to 16:1
M406	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M407	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M408	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M409	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M410	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M411	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M412	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M413	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M414	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M415	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M416	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M417	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M418	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M419	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M420	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M421	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M422	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M423	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M424	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M425	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M426	0.01:1 to 100:1	0.025:1 ta 20:1	1:30 to 16:1
M427	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M428	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M429	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M430	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M431	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M432	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M433	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M434	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M435	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M436	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M437	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M438	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M439	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M440	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M441	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M442	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M443	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M444	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M445	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M446	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M447	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M448	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M449	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M450	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M451	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M452	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M453	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M454	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M455	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M456	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M457	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M458	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M459	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M460	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M461	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M462	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M463	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M464	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M465	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M466	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M467	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M468	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M469	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M470	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M471	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M472	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M473	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M474	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M475	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M476	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M477	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M478	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M479	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M480	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M481	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M482	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M483	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M484	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M485	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M486	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M487	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M488	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M489	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M490	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M491	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M492	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M493	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M494	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M495	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M496	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M497	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M498	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M499	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M500	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M501	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M502	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M503	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M504	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M505	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M506	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M507	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M508	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M509	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M510	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M511	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M512	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M513	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M514	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M515	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M516	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M517	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M518	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M519	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M520	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M521	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M522	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M523	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M524	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M525	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M526	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M527	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M528	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M529	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M530	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M531	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M532	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M533	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M534	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M535	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M536	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M537	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M538	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M539	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M540	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M541	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M542	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M543	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M544	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M545	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M546	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M547	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M548	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M549	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M550	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M551	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M552	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M553	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M554	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M555	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M556	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M557	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M558	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M559	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M560	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M561	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M562	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M563	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M564	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M565	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M566	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M567	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M568	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M569	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M570	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M571	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M572	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M573	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M574	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M575	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M576	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M577	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M578	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M579	0.01:1 to 100:1	0.025:1 to20:1	1:30 to 16:1
M580	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M581	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M582	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M583	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M584	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M585	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M586	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M587	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M588	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M589	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M590	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M591	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M592	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M593	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M594	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M595	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M596	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M597	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M598	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M599	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M600	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M601	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M602	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M603	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M604	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M605	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M606	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M607	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M608	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M609	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M610	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M611	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M612	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M613	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M614	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M615	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M616	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M617	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M618	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M619	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M620	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M621	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M622	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M623	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M624	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M625	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M626	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M627	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M628	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M629	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M630	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M631	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M632	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M633	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M634	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M635	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M636	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M637	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M638	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M639	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M640	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M641	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M642	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M643	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M644	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M645	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M646	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M647	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M648	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M649	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M650	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M651	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M652	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M653	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M654	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M655	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M656	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M657	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M658	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M659	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M660	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M661	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M662	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M663	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M664	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M665	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M666	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M667	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M668	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M669	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M670	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M671	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M672	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M673	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M674	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M675	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M676	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M677	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M678	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M679	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M680	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M681	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M682	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M683	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M684	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M685	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M686	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M687	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M688	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M689	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M690	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M691	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M692	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M693	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M694	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M695	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M696	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M697	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M698	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M699	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M700	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M701	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M702	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M703	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M704	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M705	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M706	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M707	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M708	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M709	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M710	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M711	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M712	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M713	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M714	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M715	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M716	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M717	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M718	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M719	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M720	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M721	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M722	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M723	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M724	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M725	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M726	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M727	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M728	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M729	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M730	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M731	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M732	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M733	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M734	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M735	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M736	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M737	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M738	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M739	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M740	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M741	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M742	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M743	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M744	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M745	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M746	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M747	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M748	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M749	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M750	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M751	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M752	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M753	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M754	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M755	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M756	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M757	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M758	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M759	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M760	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M761	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M762	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M763	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M764	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M765	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M766	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M767	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M768	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M769	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M770	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M771	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M772	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M773	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M774	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M775	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M776	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M777	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M778	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

Composition Number	Typical Weight Ratio	Preferred Weight Ratio	More Preferred Weight Ratio
M779	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M780	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M781	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M782	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M783	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M784	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M785	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M786	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M787	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M788	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M789	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M790	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M791	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M792	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M793	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M794	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M795	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M796	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M797	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M798	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M799	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M800	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M801	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M802	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M803	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M804	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M805	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M806	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M807	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M808	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M809	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M810	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M811	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M812	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M813	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M814	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M815	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M816	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M817	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M818	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M819	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M820	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M821	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M822	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M823	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M824	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M825	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M826	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M827	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M828	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M829	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M830	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M831	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M832	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M833	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M834	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M835	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M836	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M837	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M838	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M839	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M840	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M841	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

35
Composition	Typical Weight	Preferred Weight	More Preferred
Number	Ratio	Ratio	Weight Ratio
M842	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M843	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M844	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M845	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M846	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M847	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M848	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M849	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M850	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M851	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M852	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M853	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M854	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M855	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M856	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M857	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M858	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M859	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M860	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M861	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M862	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M863	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M864	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M865	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M866	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M867	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M868	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M869	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M870	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M871	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M872	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M873	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M874	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1
M875	0.01:1 to 100:1	0.025:1 to 20:1	1:30 to 16:1

The skilled man will appreciate that the most preferred ratio range of A:B for any one of composition numbers M1 to M875 described in Table 4 above is from 1:30 to 20:1, and that each one of composition numbers M1 to M875 described in Table 4 may used at any one ofthe following individualised ratios: 1:30, 1:15, 2:15, 3:20, 1:6, 1:5, 1:4, 4:15, 3:10, 1:3, 5:14, 3:8, 2:5, 8:15, 3:5, 5:7, 3:4, 4:5, 1:2, 1:1, 16:15, 6:5, 4:3, 10:7, 3:2, 8:5, 5:3, 2:1, 12:5, 8:3, 20:7, 16:5, 10:3, 4:1,8:1, 12:1, and 16:1.

When applied in a composition ofthe invention component (A) is typically applied at a rate of 50 to 2000 g ha, more particularly 50, 75, 100, 125, 150, 200, 250, 300, 400, 500, 750, 800, 1000, 1250, 10 1500, 1800, or 2000 g/ha. Such rates of component (A) are applied typically in association with 5 to 2000g/ha of component B, and more specifically in association with 5, 10, 15, 20, 25, 50, 75, 100, 125, 140, 150, 200, 250, 300, 400, 500, 750, 1000, 1250, 1500, 1800, or2000g/ha of component (B). The Examples described herein illustrate but fo not limit the range of rates of components A and B that may be employed in the invention.

The amount of a composition according to the invention to be applied, will dépend on various factors, such as the compounds employed; the subject ofthe treatment, such as, for example plants, soil or seeds; the type of treatment, such as, for example spraying, dusting orseed dressing; orthe application time. In agricultural practice the application rates ofthe composition according to the invention dépend on the type of effect desired, and typically range from 55 to 4000 g of total composition per hectare, and more commonly between 55 and 2000g/ha. The application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip ordrench can also be used.

The compositions ofthe invention can advantageously be used in the below-mentioned formulations (in which case active ingrédient relates to the respective mixture of compound of Formula (I) with a compound of component B or, when a safener is also used, the respective mixture ofthe compound of Formula (I) with the compound of component B and the safener).

The individual components ofthe composition ofthe invention may be utilised as the technical active ingrédient as produced. More typically however, the compositions according to the invention may be formulated in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrâtes, microemulsifiable concentrâtes, oil-in-water émulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrâtes (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Spécifications for Pesticides, United Nations, First Edition, Second Révision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingrédient with the formulation adjuvants in orderto obtain compositions in the form of finely divided solids, granules, solutions, dispersions or émulsions. The active ingrédients can also be formulated with other adjuvants, such as finely divided solids, minerai oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.

The active ingrédients can also be contained in very fine microcapsules. Microcapsules contain the active ingrédients in a porous carrier. This enables the active ingrédients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually hâve a diameter of from 0.1 to 500 microns. They contain active ingrédients in an amount of about from 25 to 95 % by weight ofthe capsule weight. The active ingrédients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyuréthane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingrédient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

The formulation adjuvants that are suitable for the préparation ofthe compositions according to the invention are known perse. As liquid carriers there may be used: water, toluene, xylene, Petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylène carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, Λ/,/V-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobomyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, 10 methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phénol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, minerai oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, éthanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, /V-methyl-2-pyrrolidone and the like.

Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, 20 attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.

A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.

Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents orsuspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stéarate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stéarate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and di35 alkylphosphate esters; and also further substances described e.g. in McCutcheon's Détergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, 40 corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.

The formulations according to the invention can include an additive comprising an oil of vegetable or animal origin, a minerai oil, alkyl esters of such oils or mixtures of such oils and oil dérivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise minerai oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl dérivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8C22 fatty acids, especially the methyl dérivatives of C12-C18 fatty acids, for example 10 the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil dérivatives are known from the Compendium of Herbicide Adjuvants, 10^1h Edition, Southern Illinois University, 2010.

The formulations generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds (A) and (B) and from 1 to 99.9 % by weight of a formulation adjuvant which 15 preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrâtes, the end user will normally employ dilute formulations.

The rates of application vary within wide limits and dépend on the nature ofthe soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and 20 other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.

Preferred formulations can hâve the following compositions (weight %), wherein the term “active ingrédient” refers to the total weight % ofthe combination of ail active ingrédients in the 25 composition:

Emulsifiable concentrâtes:

active ingrédient: surface-active agent: liquid carrier: 30 Dusts: active ingrédient: solid carrier: Suspension concentrâtes: active ingrédient: 35 water: surface-active agent:

1 to 95 %, preferably 60 to 90 % 1 to 30 %, preferably 5 to 20 % 1 to 80 %, preferably 1 to 35 % 0.1 to 10 %, preferably 0.1 to 5 % 99.9 to 90 %, preferably 99.9 to 99 % 5 to 75 %, preferably 10 to 50 % 94 to 24 %, preferably 88 to 30 % 1 to 40 %, preferably 2 to 30 %

Wettable powders:

active ingrédient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %

Granules:

active ingrédient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %

Various aspects and embodiments ofthe présent invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from 10 the scope ofthe invention.

EXAMPLES

FORMULATION EXAMPLES

Wettable powders	a)	b)	c)
active ingrédients	25%	50%	75%
sodium lignosulfonate	5%	5%	-
sodium lauryl sulphate	3%	-	5%
sodium diisobutylnaphthalenesulfonate	-	6%	10%
phénol polyethylene glycol ether	-	2%	-
(7-8 mol of ethylene oxide)
highly dispersed silicic acid	5%	10%	10%
Kaolin	62%	27%	-

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground 15 in a suitable mill, affording wettable powders that can be diluted with waterto give suspensions ofthe desired concentration.

Powders for dry seed treatment	a)	b)	c)
active ingrédients	25%	50%	75%
light minerai oil	5%	5%	5%
highly dispersed silicic acid	5%	5%	-
Kaolin	65%	40%	-
Talcum	-		20

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

Emulsifiable concentrate
active ingrédients	10%
octylphenol polyethylene glycol ether	3%
(4-5 mol of ethylene oxide)
calcium dodecylbenzenesulfonate	3%
castor oil polyglycol ether (35 mol of ethylene oxide)	4%
Cyclohexanone	30%
xylene mixture	50%

Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

Dusts	a)	b)	C)
Active ingrédients	5%	6%	4%
Talcum	95%	-	-
Kaolin	-	94%	-
minerai filler	-	-	96%

Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

Extruded granules
Active ingrédients	15%
sodium lignosulfonate	2%
Carboxymethylcellulose	1 %
Kaolin	82%

The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Coated granules
Active ingrédients	8%
polyethylene glycol (mol. wt. 200)	3%
Kaolin	89%

The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Suspension concentrate
active ingrédients	40%
propylene glycol	10%
nonylphenol polyethylene glycol ether (15 mol of ethylene oxide)	6%
Sodium lignosulfonate	10%
Carboxymethylcellulose	1 %
silicone oil (in the form of a 75 % émulsion in water)	1 %
Water	32%

The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Flowable concentrate for seed treatment
active ingrédients	40%
propylene glycol	5%
copolymer butanol PO/EO	2%

Tristyrenephenole with 10-20 moles EO	2%
1,2-benzisothiazolin-3-one (in the form of a 20% solution in water)	0.5 %
monoazo-pigment calcium sait	5%
Silicone oil (in the form of a 75 % émulsion in water)	0.2 %
Water	45.3 %

The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected 5 against infestation by microorganisms, by spraying, pouring or immersion.

•	41
	Tristyrenephenole with 10-20 moles EO	2%
1,2-benzisothiazolin-3-one (in the form of a 20% solution in water)	0.5 %
monoazo-pigment calcium sait	5%
Silicone oil (in the form of a 75 % émulsion in water)	0.2 %
Water	45.3 %

Slow Release Capsule Suspension

Parts ofthe combination are mixed with 2 parts of an aromatic solvent and 7 parts oftoluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture 10 of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this émulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% ofthe active ingrédients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

List of Abbreviations:

Boc = fert-butyloxycarbonyl br = broad

CDCh = chloroform-d

CDsOD = methanol-d °C = degrees Celsius

D2O = water-d

DCM = dichloromethane d = doublet dd = double doublet dt = double triplet

DMSO = dimethylsulfoxide

EtOAc = ethyl acetate h = hour(s)

HCl = hydrochloric acid

HPLC = high-performance liquid chromatography (description of the apparatus and the methods used for HPLC are given below) m = multiplet

M = molar min = minutes

MHz = mega hertz mL = millilitre mp = melting point ppm = parts per million q = quartet quin = quintet rt = room température s = singlet t = triplet

THF = tetrahydrofuran

LC/MS = Liquid Chromatography Mass Spectrometry

Préparative Reverse Phase HPLC Method:

Compounds purified by mass directed préparative HPLC using ES+/ES- on a Waters FractionLynx Autopurification system comprising a 2767 injector/collector with a 2545 gradient pump, two 515 isocratic pumps, SFO, 2998 photodiode array (Wavelength range (nm): 210 to 400), 2424 ELSD and QDa mass spectrometer. A Waters Atlantis T3 5micron 19x1 Omm guard column was used with a Waters

Atlantis T3 OBD, 5micron 30x100mm prep column.

Ionisation method: Electrospray positive and négative: Cône (V) 20.00, Source Température (°C) 120,

Cône Gas Flow (L/Hr.) 50

Mass range (Da): positive 100 to 800, négative 115 to 800.

The préparative HPLC was conducted using an 11.4 minute run time (not using at column dilution, 5 bypassed with the column selector), according to the following gradient table:

Time (mins)	Solvent A (%)	Solvent B (%)	Flow (ml / min)
0.00	100	0	35
2.00	100	0	35
2.01	100	0	35
7.0	90	10	35
7.3	0	100	35
9.2	0	100	35
9.8	99	1	35
11.35	99	1	35
11.40	99	1	35

515 pump Oml/min Acetonitrile (ACD)

515 pump 1ml/min 90% Methanol/10% Water (make up pump)

Solvent A: Water with 0.05% Trifluoroacetic Acid

Solvent B: Acetonitrile with 0.05% Trifluoroacetic Acid

PREPARATION EXAMPLES FOR COMPOUNDS OF FORMULA (I)

EXAMPLE 1: Préparation of 2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)ethanesulfonate (compound 1.001)

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Step 1: Préparation of tributyl(pyridazin-4-yl)stannane

To a solution of lithium diisopropylamide (1M solution in tetrahydrofuran, 125 mL) at -78°C under nitrogen was added a solution of pyridazine (10g) and tri-n-butyltin chloride (44.6g) in THF (100 mL) drop wise. The reaction mixture was stirred at—78°C for 1 hour. The reaction mixture was warmed to room température and quenched with saturated aqueous ammonium chloride (100 mL) and extracted with ethyl acetate (3x150 mL). The organic layer was dried over sodium sulfate, concentrated and purified by chromatography on silica eluting with 30% ethyl acetate in hexanes to afford tributyl(pyridazin-4-yl)stannane as a pale brown liquid.

¹H NMR (400MHz, CDCI₃) 9.17 (t, 1H) 9.02 (dd, 1H) 7.54 (dd, 1H) 1.57-1.49 (m, 6H) 1.37-1.29 (m, 6H) 1.19-1.13 (m, 6H) 0.92-0.86 (m, 9H).

Step 2: Préparation of 2-pyridazin-4-ylpyrimidine

A solution of 2-bromopyrimidine (2.50g) and tributyl(pyridazin-4-yl)stannane (5.80g) in tetrahydrofuran (25 mL) was degassed with argon for 20 min. Tetrakis (triphenylphosphine) palladium 10 (0) (1,80g) was added to the reaction mixture at room température and then irradiated in a microwave at 120°C for 30 minutes. The reaction mixture was poured into water and extracted with ethyl acetate (100 mL). The organic layer was concentrated and purified by chromatography on silica eluting with 80% ethyl acetate in hexanes to give 2-pyridazin-4-ylpyrimidine as a beige solid.

¹H NMR (400MHz, CDCI3) 10.17 (dd, 1H) 9.39 (dd, 1H) 8.92 (d, 2H) 8.43 (dd, 1H) 7.39 (t, 1H).

Step 3: Préparation of 2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)ethanesulfonate (1.001)

A mixture of 2-pyridazin-4-ylpyrimidine (0.120g) and sodium 2-bromoethanesulfonate (0.196g) was stirred in water (2.3 mL) at 100°C for 42 hours. The reaction mixture was concentrated and purified by préparative reverse phase HPLC to give 2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)ethanesulfonate as 20 a beige solid.

¹HNMR (400MHz, D2O) 10.19 (d, 1H) 9.84 (d, 1H) 9.20 (dd, 1H) 8.99 (d, 2H) 7.64 (t, 1H) 5.27-5.18 (m, 2H) 3.71-3.63 (m, 2H).

EXAMPLE 2: Préparation of 4-pyridazin-4-ylpyrimidine

A microwave vial was charged with tributyl(pyridazin-4-yl)stannane (0.387g), 4-chloropyrimidine (0.100g), palladium (0) tetrakis(triphenylphosphine) (0.101g), césium fluoride (0.265g), cuprous iodide (0.00665g) and 1,4-dioxane (4.37 mL) and heated to 140°C under microwave conditions for 1 hour. The 30 reaction mixture was concentrated and purified by chromatography on silica eluting with a gradient from 0 to 70% acetonitrile in dichloromethane to give 4-pyridazin-4-ylpyrimidine as an orange solid.

¹H NMR (400MHz, CDCh) 9.90-9.83 (m, 1H) 9.41 (dd,2H) 8.97 (d, 1H) 8.21-8.13 (m, 1H) 7.89 (dd, 1H).

EXAMPLE 3: Préparation of methyl 2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)acetate bromide (compound 2.001)

Methyl bromoacetate (0.755g) was added drop wise to a solution of 2-pyridazin-4-ylpyrimidine (0.505g) in acetone (6.4mL) and heated at 60°C for 24 hours. The reaction mixture was concentrated and the residue triturated with dichloromethane. The resulting solid was filtered, washed with acetone and dried to give methyl 2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)acetate bromide as a brown solid. ¹HNMR (400MHz, D₂O) 10.22 (d, 1 H) 9.84 (d, 1H) 9.30 (dd, 1H) 9.01 (d, 2H) 7.66 (t, 1H) 5.84 (s, 2H) 3.79 (s, 3H).

EXAMPLE 4: Préparation of (4-pyrimidin-2-ylpyridazin-1-ium-1-yl)methanesulfonate (compound 2.002)

O

Methyl 2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)acetate bromide (0.420g) was stirred in trimethylsilyl chlorosulfonate (4.96g) at 80°C for 66 hours. The reaction mixture was carefully quenched with water, concentrated and purified by préparative reverse phase HPLC to give (4-pyrimidin-2ylpyridazin-1-ium-1-yl)methanesulfonate as a pale brown solid.

¹H NMR (400MHz, D₂O) 10.26 (brs, 1H) 9.94 (brd, 1H) 9.27-9.39 (m, 1H) 8.96-9.14 (m, 2H) 7.56-7.73 (m, 1H) 5.97 (s, 2H).

EXAMPLE 5: Préparation of 3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propane-1-sulfonate (compound 1.003)

To a solution of 2-pyridazin-4-ylpyrimidine (0.200g) in 1,4-dioxane (3.79mL) was added 1,3propanesultone (0.189g). The mixture was stirred at 90°C for 44 hours. The resulting solid was filtered off and washed with acetone. The solid was purified by préparative reverse phase HPLC to give 3-(420326 pyrimidin-2-ylpyridazin-1 -ium-1 -yl)propane-1 -sulfonate.

NMR (400MHz, D₂O) 10.18 (d, 1H) 9.80 (d, 1H) 9.19 (dd, 1H) 9.00 (d, 2H) 7.64 (t, 1H) 5.01 (t, 2H) 2.98 (t, 2H) 2.53 (quin, 2H).

EXAMPLE 6: Préparation of 3-(4-pyrazin-2-ylpyridazin-1-ium-1-yl)propanoic acid 2,2,2trifluoroacetate (compound 1.005)

Step 1: Préparation of 2-pyridazin-4-ylpyrazine

A mixture of tributyl(pyridazin-4-yl)stannane (3.87g), 2-chloropyrazine (1.00g), palladium (0) tetrakis(triphenylphosphine) (1.03g) and 1,4-dioxane (43.7 mL) was heated to 140°C under microwave conditions for 1 hour. The reaction mixture was concentrated and purified on silica using a gradient of 0% to 50% acetonitrile in dichloromethane to give 2-pyridazin-4-ylpyrazine as an off white solid.

¹H NMR (400MHz, CDCb) 9.87 (dd, 1H) 9.39 (dd, 1H) 9.19 (d, 1H) 8.81-8.75 (m, 1H) 8.72 (d, 1H) 8.11 (dd, 1H).

Step 2: Préparation of methyl 3-(4-pyrazin-2-ylpyridazin-1-ium-1-yl)propanoate bromide

Methyl 3-bromopropanoate (0.518 mL) was added to a solution of 2-pyridazin-4-ylpyrazine (0.250g) in acetonitrile (15.8 mL). The reaction mixture was heated to 80°C for 24 hours. The reaction mixture was concentrated and the residue taken up in water and washed with dichloromethane. The aqueous phase was concentrated to give crude methyl 3-(4-pyrazin-2-ylpyridazin-1-ium-1yl)propanoate bromide (as a 1:1 mixture with 3-(5-pyrazin-2-ylpyridazin-1-ium-1-yl)propanoic acid 25 bromide) as a brown gum, which was used crude in subséquent reactions.

Step 3: Préparation of 3-(4-pyrazin-2-ylpyridazin-1-ium-1-yl)propanoic acid 2,2,2-trifluoroacetate (1.005)

The crude mixture of methyl 3-(4-pyrazin-2-ylpyridazin-1-ium-1-yl)propanoate bromide (0.515g) 30 and conc. hydrochioric acid (11.1 mL) was heated to 80°C for 4 hours. The reaction mixture was cooled and allowed to stand overnight. The reaction mixture was concentrated and purified by préparative reverse phase HPLC to give 3-(4-pyrazin-2-ylpyridazin-1-ium-1-yl)propanoic acid 2,2,2-trifluoroacetate as a brown gum.

¹H NMR (400MHz, CD₃OD) 10.28 (d, 1H) 10.00 (d, 1H) 9.62 (d, 1H) 9.28 (dd, 1H) 8.96-8.93 (m, 1H)

8.90 (d, 1H) 5.19-5.12 (t, 2H) 3.28 (t, 2H).

EXAMPLE 7: Préparation of 2-(4-pyridazin-4-ylpyridazin-1-ium-1-yl)ethanesulfonate (compound 1.006)

O /

Step 1: Préparation of 2,2-dimethylpropyl 2-(2-tert-butoxycarbonyIhydrazino)ethanesulfonate

Boc-hydrazide (1.00g) was added to a solution of 2,2-dimethylpropyl ethenesulfonate (1.35g) in methanol (10.1 mL) and heated to 70°C for 24 hours. The reaction was concentrated to give 2,2dimethylpropyl 2-(2-tert-butoxycarbonylhydrazino)ethanesulfonate as a thick yellow liquid.

¹H NMR (400MHz, CDCI3) 3.90 (s, 2H) 3.38-3.30 (m, 4H) 1.50-1.43 (s, 9H) 1.00-0.97 (s, 9H).

Step 2: Préparation of [2-(2,2-dimethylpropoxysulfonyl)ethylamino]ammonium chloride

A mixture of 2,2-dimethylpropyl 2-(2-tert-butoxycarbonylhydrazino)ethanesulfonate (1.00g) and 20 3M methanolic hydrogen chloride (24.2 mL) was heated to 70°C for 7 hours. The reaction mixture was concentrated to give [2-(2,2-dimethylpropoxysulfonyl)ethylamino]ammonium chloride as a pink gum that solidified on standing.

¹H NMR (400MHz, CD3OD) 3.95 (s, 2H) 3.59-3.53 (m, 2H) 3.44-3.39 (m, 2H) 1.00 (s, 9H) sample contained ~20% methanol and was used as such.

Step 3: Préparation of 4-(3-furyl)pyridazine

To a mixture of 4-bromopyridazin-1-ium bromide (2.50g), sodium carbonate (2.2g), degassed toluene (17.3 mL) and 1,1'-bis(diphenylphosphino)ferrocenepalladium (II) dichloride (0.634g) was added a solution of 3-furylboronic acid (1.00g) in éthanol (17.3 mL). The mixture was heated to 80°C under nitrogen atmosphère for 24 hours. The reaction mixture was filtered through celite and concentrated. The residue was partitioned between water and dichloromethane then extracted with further dichloromethane. The combined organic layers were washed with brine and dried with magnésium sulfate. The concentrated filtrate was purified on silica eluting with a gradient of 0-100% ethyl acetate in iso-hexane to give 4-(3-furyl)pyridazine as a dark red semi-solid.

¹H NMR (400 MHz, CD3OD) 9.45 (s, 1H) 9.03-9.16 (m, 1H) 8.36 (s, 1H) 7.86 (dd, 1 H) 7.71 (t, 1H) 7.04 (d, 1H).

Step 4: Préparation of 4-(2,5-dimethoxy-2,5-dihydrofuran-3-yl)pyridazine

A mixture of 4-(3-furyl)pyridazine (0.025g) and sodium bicarbonate (0.14g) in methanol (0.5 mL) was cooled to -10°C and bromine (0.069g) was added drop wise. After 30 minutes the reaction was quenched with 1:1 sat. aqueous sodium bicarbonate and 1M aqueous sodium thiosulfate (3 mL). The 15 aqueous layer was extracted with ethyl acetate. The organic layer was concentrated to give crude 4(2,5-dimethoxy-2,5-dihydrofuran-3-yl)pyridazine.

¹H NMR (400 MHz, CD3OD) 9.42-9.41 (m, 1H) 9.20-9.19 (m, 1H) 7.85 (dt, 1H) 7.02-6.94 (m, 1H) 6.085.77 (m, 2H) 3.46 (d, 3H) 3.42 (d, 3H).

Step 5: Préparation of 2-(4-pyridazin-4-ylpyridazin-1-ium-1-yl)ethanesulfonate 1.006

A mixture of 4-(2,5-dimethoxy-2,5-dihydrofuran-3-yl)pyridazine (0.500g) and [2-(2,2dimethylpropoxysulfonyl)ethylamino]ammonium chloride (0.658g) was heated in aqueous 3M hydrochloric acid (12mL) at 60°C for 2 hours. The reaction mixture was concentrated and purified by préparative reverse phase HPLC to give 2-(4-pyridazin-4-ylpyridazin-1-ium-1-yl)ethanesulfonate as a 25 brown solid.

¹H NMR (400MHz, D₂O) 9.80-9.97 (m, 2H) 9.62-9.75 (m, 1H) 9.35-9.50 (m, 1H) 8.97 (dd, 1H) 8.19-8.42 (m, 1H) 5.20-5.29 (m, 2H) 3.59-3.73 (m, 2H).

EXAMPLE 8: Préparation of 3-(4-pyrazin-2-ylpyridazin-1-ium-1-yl)propanoic acid chloride (compound 1.012)

A column packed with ion exchange resin (5.84g, Discovery DSC-SCX) was washed with water (3 column volumes). The 3-(4-pyrazin-2-ylpyridazin-1-ium-1-yl)propanoic acid 2,2,2-trifluoroacetate (0.292g) dissolved in a minimum amount of water was loaded onto the column. The column was first eluted with water (3 column volumes) and then eluted with 2M hydrochloric acid (3 column volumes). The collected washings were concentrated to give 3-(4-pyrazin-2-ylpyridazin-1-ium-1-yl)propanoic acid chloride as a yellow solid.

¹H NMR (400MHz, D₂O) 10.03 (d, 1H) 9.80 (d, 1H) 9.35 (d, 1H) 9.05 (dd, 1H) 8.87-8.82 (m, 1H) 8.76 (d, 1H) 5.08 (t, 2H) 3.22 (t, 2H).

EXAMPLE 9: Préparation of methyl 3-(4-pyrazin-2-ylpyridazin-1-ium-1-yl)propanoate chloride (compound 1.013)

A column packed with ion exchange resin (1.6g, Discovery DSC-SCX) was washed with methanol (3 column volumes). The 3-(4-pyrazin-2-ylpyridazin-1-ium-1-yl)propanoic acid 2,2,2trifluoroacetate (0.081g) dissolved in a minimum amount of methanol was loaded onto the column. The column was first eluted with methanol (3 column volumes) and then eluted with 3M methanolic hydrochloric acid (3 column volumes). The collected washings were concentrated to give methyl 3-(4pyrazin-2-ylpyridazin-1-ium-1-yl)propanoate chloride as a blue gum.

¹H NMR (400MHz, CD3OD) 10.30-10.26 (m, 1H) 10.04-10.00 (m, 1H) 9.66-9.64 (m, 1H) 9.33-9.30 (m, 1H) 8.97-8.93 (m, 1H) 8.91-8.88 (m, 1H) 5.25-5.14 (m, 2H) 3.71-3.68 (m, 3H) 3.35-3.27 (m, 2H).

EXAMPLE 10: Préparation of 3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propanoic acid bromide (compound 1.021)

A mixture of methyl 3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propanoate 2,2,2-trifluoroacetate (0.2g), concentrated hydrogen bromide (1 mL, 48 mass%) and water (5 mL) was heated to 80°C for 4 hours and left to cool overnight. After a further 4 hours heating at 80°C the reaction mixture was concentrated and the resulting yellow gum was triturated with acetone to give 3-(4-pyrimidin-2ylpyridazin-1-ium-1-yl)propanoic acid bromide as a cream solid.

Ή NMR (400MHz, D₂O) 10.16 (d, 1H) 9.86 (d, 1H) 9.21-9.15 (m, 1H) 8.99 (d, 2H) 7.64 (t, 1H) 5.11 (t, 2H) 3.24 (t, 2H).

EXAMPLE 11: Préparation of 1-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propane-2-sulfonate (compound 1.026)

Step 1 : Préparation of methyl 2-(2,2-dimethylpropoxysulfonyl)acetate

Methyl 2-chlorosulfonylacetate (0.5g) was added drop wise to a cooled (ice bath) solution of 2,2-dimethylpropan-1-ol (0.306g) and pyridine (0.284 mL) in dichloromethane (14.5 mL). The reaction mixture was stirred cold for a further 2 hours then partitioned with aqueous sat. ammonium chloride.

The aqueous phase was extracted with further dichloromethane (x2). The combined organic extracts were concentrated and passed through a plug of silica eluting with diethyl ether. The filtrate was concentrated to give methyl 2-(2,2-dimethylpropoxysulfonyl)acetate as a yellow liquid.

¹H NMR (400MHz, CDCh) 4.11 (s, 2H) 4.00 (s, 2H) 3.84 (s, 3H) 1.01 (s, 9H).

Step 2: Préparation of methyl 2-(2,2-dimethylpropoxysulfonyl)propanoate

A mixture of sodium hydride (60% in minerai oil, 0.039g) in tetrahydrofuran (4.46 mL) was cooled (ice bath) to 0°C under nitrogen atmosphère. To this was added a solution of methyl 2-(2,220 dimethylpropoxysulfonyl)acetate (0.2g) in tetrahydrofuran (1.78 mL) and stirred at this température for 5 minutes, lodomethane (0.067 mL) was added and the reaction was allowed to warm to room température and stirred for 1 hour. The reaction mixture was partitioned between 2M hydrochloric acid and ethyl acetate. The aqueous layer was extracted with further ethyl acetate (x2). The combined organic extracts were dried with magnésium sulfate and concentrated to give methyl 2-(2,225 dimethylpropoxysulfonyl)propanoate as a yellow liquid.

¹H NMR (400MHz, CDCh) 4.12-4.09 (m, 1H) 3.97 (d, 2H) 3.83 (s, 3H) 1.69 (d, 3H) 0.99 (s, 9H).

Step 3: Préparation of 2,2-dimethylpropyl 1-hydroxypropane-2-sulfonate

To a cooled (ice bath) solution of methyl 2-(2,2-dimethylpropoxysulfonyl)propanoate (1g) in dichloromethane (126 mL) was added dropwise, under nitrogen atmosphère, diisobutylaluminum hydride (1M in dichloromethane, 10.5 mL) maintaining the température below 5°C during the addition. The reaction mixture was stirred at 0°C for 1 hour. Propan-2-ol (12.6 mL) was added and the reaction mixture was stirred at 0°C for 1 hour and then allowed to warm to room température. The reaction mixture was partitioned between 2M aqueous hydrochloric acid and dichloromethane. The organic phase was dried with magnésium sulfate, concentrated and chromatographed on silica using a gradient from 0 to 100% EtOAc in isohexane to give 2,2-dimethylpropyl 1-hydroxypropane-2-sulfonate as a colourless liquid.

¹H NMR (400MHz, CDCh) 4.03-3.84 (m, 4H) 3.43-3.33 (m, 1 H) 2.60-2.52 (m, 1 H) 1.45 (d, 3H) 1.00 (s, 9H).

Step 4: Préparation of 1-hydroxypropane-2-sulfonic acid

A mixture of 2,2-dimethylpropyl 1-hydroxypropane-2-sulfonate (0.25g) and 6M aqueous hydrochloric acid (9.51 mL) was heated to 95°C for 4 hours. The reaction mixture was cooled and concentrated by freeze drying.

¹H NMR (400MHz, D₂O) 3.88-3.78 (m, 1H) 3.56-3.47 (m, 1H) 2.98-2.89 (m, 1 H) 1.18 (d, 3H).

Step 5: Préparation of 1-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propane-2-sulfonate 1.026

To a cooled (ice bath) solution of 2-pyridazin-4-ylpyrimidine (0.1g) in dry acetonitrile (6.32 mL) was added 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (0.131 mL) and the reaction mixture was stirred at room température for 15 minutes. To this mixture was added triphenylphosphine (0.332g) and a solution of 1-hydroxypropane-2-sulfonic acid (0.133g) in acetonitrile (0.5mL), followed by drop wise addition of diisopropyl azodicarboxylate (0.25 mL). The reaction mixture was heated at 80°C for 170 hours. The reaction mixture was concentrated and partitioned between water and diethyl ether. The aqueous layer was concentrated and purified by préparative reverse phase HPLC to givel(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propane-2-sulfonate as a white solid.

¹H NMR (400MHz, D2O) 10.20-10.18 (m, 1H) 9.81 (dd, 1H) 9.19 (dd, 1H) 9.00 (d, 2H) 7.65 (t, 1H) 5.105.07 (m, 2H) 3.84-3.74 (m, 1H) 1.39 (d, 3H).

EXAMPLE 12: Préparation of 3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)butanoic acid 2,2,2trifluoroacetate (compound 2.003)

To a mixture of 2-pyridazin-4-ylpyrimidine (0.5g) in water (10 mL) was added but-2-enoic acid (0.816g). The mixture was heated at reflux for 40 hours. The reaction mixture was concentrated and the resulting solid was triturated with tert-butylmethylether and acetone. The solid was purified by préparative reverse phase HPLC to give 3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)butanoic acid 2,2,2trifluoroacetate.

i 'H NMR (400MHz, D₂O) 10.22 (d, 1H) 9.92 (d, 1H) 9.18-9.26 (m, 1H) 8.99-9.05 (m, 2H) 7.68 (t, 1H) 5.49-5.60 (m, 1 H) 3.39 (dd, 1 H) 3.10-3.21 (m, 1 H) 1.71 (d, 3H).

EXAMPLE 13: Préparation of 3-bromo-N-methylsulfonyl-propanamide

To a solution of methanesulfonamide (0.5g) in toluene (25.8 mL) was added 3-bromopropionyl chloride (1,77g) drop wise at room température. The reaction mixture was heated at 110°C for 4 hours. The reaction was cooled in ice and the resulting solid was filtered and washed with cold toluene to give 3-bromo-/V-methylsulfonyl-propanamide as a colourless solid.

¹H NMR (400MHz, CDCh) 8.28 (brs, 1H) 3.62 (t, 2H) 3.34 (s, 3H) 2.94 (t, 2H).

EXAMPLE 14: Préparation of 2-hydroxy-3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propane-1sulfonate (compound 2.004)

O

A mixture of 2-pyridazin-4-ylpyrimidine (0.3g), water (6 mL) and sodium 3-chloro-2-hydroxypropane-1-sulfonate (0.45g) was heated at reflux for 3 days. The reaction mixture was concentrated and the resulting solid was washed with Abutylmethyl ether and acetone. The solid was purified by préparative reverse phase HPLC to give 2-hydroxy-3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propane-1sulfonate, 2.004.

¹H NMR (400MHz, D₂O) 10.24 (d, 1H) 9.80 (d, 1H) 9.25 (dd, 1H) 9.04 (d, 2H) 7.68 (t, 1H) 5.21 (dd, 1H)

4.93 (dd, 1H) 4.64-4.71 (m, 1H) 3.19-3.36 (m, 2H).

EXAMPLE 15: Préparation of 3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propanoic acid 2,2,25 trifluoroacetate (compound 1.023) A125

3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propanoic acid chloride (0.119g) was stirred in 2,2,2trifluoroacetic acid (4 mL) at room température for two hours. The reaction mixture was concentrated and freeze dried to give 3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propanoic acid 2,2,2-trifluoroacetate, 10 A125, as a pale yellow gum, which solidified on standing.

¹H NMR (400MHz, D₂O) 10.18-10.13 (m, 1H) 9.87-9.82 (m, 1H) 9.20-9.14 (m, 1H) 8.98 (d, 2H) 7.63 (s, 1H) 5.10 (s, 2H) 3.24 (t, 2H).

EXAMPLE 16: Préparation of 3-methyl-3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)butanoic acid

2,2,2-trifluoroacetate (compound 1.025)

OH F

A mixture of 2-pyridazin-4-ylpyrimidine (1g), 3,3-dimethylacrylic acid (1.96g), 2,2,2trifluoroacetic acid (5 mL) and water (5 mL) was heated at 100°C under microwave conditions for 18 20 hours. The reaction mixture was concentrated and the resulting solid was washed with diethyl ether (5x10 mL). The solid was purified by preparative reverse phase HPLC to give 3-methyl-3-(4-pyrimidin2-ylpyridazin-1 -ium-1 -yl)butanoic acid 2,2,2-trifluoroacetate, 1.025.

¹H NMR (400MHz, D2O) 10.18 (m, 1H) 9.97 (m, 1H) 9.21 (m, 1H) 8.98 (m, 2H) 7.61 (m, 1H) 3.36 (s, 2H) 1.94 (S, 6H).

EXAMPLE 17: Préparation of 3-(4-pyridazin-3-ylpyridazin-1-ium-1-yl)propanoic acid chloride (compound 1.027)

O

Step 1 : Préparation of 3-pyridazin-4-ylpyridazine

A microwave vial, under nitrogen atmosphère, was charged with tributyl(pyridazin-4-yl)stannane (0.697g), 3-bromopyridazine (0.25g), palladium (0) tetrakis(triphenylphosphine) (0.185g) and 1,4dioxane (7.86 mL) and heated at 140°C in the microwave for 1 hour. The reaction mixture was concentrated and purified on silica using a gradient of 0% to 50% acetonitrile in dichloromethane to give 3-pyridazin-4-ylpyridazine as an orange solid.

1H NMR (400MHz, CDCh) 9.94-9.89 (m, 1H) 9.42 (dd, 1H) 9.35 (dd, 1H) 8.24 (dd, 1H) 8.09 (dd, 1H) 7.79-7.72 (m, 1H).

Step 2: Préparation of 3-(4-pyridazin-3-ylpyridazin-1-ium-1-yl)propanoic acid 2,2,2trifluoroacetate (compound 2.005)

A mixture of 3-pyridazin-4-ylpyridazine (0.25g), water (15 mL) and 3-bromopropanoic acid (0.363g) was heated at 100°C for 25 hours. The mixture was concentrated and purified by préparative reverse phase HPLC (trifluoroacetic acid is présent in the eluent) to give 3-(4-pyridazin-3-ylpyridazin-1ium-1-yl)propanoic acid 2,2,2-trifluoroacetate, 2.005.

1H NMR (400MHz, D₂O) 10.11 (d, 1H) 9.88 (d, 1H) 9.32 (dd, 1H) 9.10 (dd, 1H) 8.50 (dd, 1H) 7.99 (dd, 1H) 5.13 (t, 2H) 3.26 (t, 2H) (one CO2H proton missing).

Step 3: Préparation of 3-(4-pyridazin-1-ium-3-ylpyridazin-1-ium-1-yl)propanoic acid dichloride (compound 1.034)

A mixture of 3-(4-pyridazin-3-ylpyridazin-1-ium-1-yl)propanoic acid 2,2,2-trifluoroacetate (6.56g) and 2M aqueous hydrochloric acid (114 mL) was stirred at room température for 3 hours. The mixture was concentrated and the residue was taken up in a small amount of water and freeze dried. The resulting glassy yellow solid was stirred in acetone (105 mL) ovemight. The solid material was collected by filtration, washed with further acetone and dried under vacuum to give 3-(4-pyridazin-1-ium-320326 ylpyridazin-1-ium-1-yl)propanoic acid dichloride, 1.034, as a beige solid.

1H NMR (400MHz, D₂O) 10.11 (d, 1H) 9.88 (d, 1H) 9.36 (brd, 1H) 9.10 (dd, 1 H) 8.48-8.56 (m, 1H) 7.928.07 (m, 1H) 4.98-5.20 (m, 2H) 3.18-3.32 (m, 2H) (one CO₂H proton missing)

Step 4: Préparation of 3-(4-pyridazin-3-ylpyridazin-1-ium-1-yl)propanoic acid chloride (compound 1.027)

A mixture of 3-(4-pyridazin-1-ium-3-ylpyridazin-1-ium-1-yl)propanoic acid dichloride (0.541g) and 2-propanol (10 mL) was heated at 90°C. Water was added drop wise until a clear solution was obtained, this took ~0.8 mL. To this was added further hot 2-propanol (10 mL) and the solution left to cool. Filtered off the precipitate and washed with cold 2-propanol and acetone and dried under vacuum to give 3-(4-pyridazin-3-ylpyridazin-1-ium-1-yl)propanoic acid chloride, 1.027, as a beige solid.

1H NMR (400 MHz, D₂O) 10.11 (d, 1H) 9.87 (d, 1H) 9.32 (dd, 1H) 9.12-9.08 (m, 1H) 8.50 (dd, 1H) 7.99 (dd, 1 H) 5.12 (t, 2H) 3.24 (t, 2H) (one CO2H proton missing)

EXAMPLE 18: Préparation of 2-(4-pyridazin-1-ium-3-ylpyridazin-1-ium-1-yl)ethanesulfonate chloride (compound 1.031)

Step 1: Préparation of 2-(4-pyridazin-3-ylpyridazin-1-ium-1-yl)ethanesulfonate (compound 1.002)

A mixture of 3-pyridazin-4-ylpyridazine (0.41g), sodium 2-bromoethanesulfonic acid (0.656g) and water (7.78 mL) was heated at 100°C for 17 hours. The reaction mixture was cooled, filtered through a syringe filter and purified by préparative reverse phase HPLC (trifluoroacetic acid is présent in the 25 eluent) to give 2-(4-pyridazin-3-ylpyridazin-1-ium-1-yl)ethanesulfonate as a yellow solid.

1H NMR (400MHz, D₂O) 10.15 (d, 1H) 9.87 (d, 1 H) 9.33 (dd, 1H) 9.12 (dd, 1H) 8.52 (dd, 1H) 7.99 (dd, 1H) 5.32-5.19 (m, 2H) 3.73-3.65 (m, 2H)

Step 2: Préparation of 2-(4-pyridazin-1-ium-3-ylpyridazin-1-ium-1-yl)ethanesulfonate chloride 5 (compound 1.031)

A solution of 2-(4-pyridazin-3-ylpyridazin-1-ium-1-yl)ethanesulfonate (0.2g) and 2M aqueous hydrochloric acid (5 mL) was stirred at room température for 2 hours. The mixture was concentrated and the residue was taken up in a small amount of water and freeze dried to give 2-(4-pyridazin-1-ium3-ylpyridazin-1-ium-1-yl)ethanesulfonate chloride as a cream glass like solid.

1H NMR (400MHz, D₂O) 10.13 (d, 1H) 9.86 (d, 1H) 9.35 (dd, 1H) 9.11 (dd, 1H) 8.57 (dd, 1H) 8.05 (dd, 1H) 5.27-5.21 (m, 2H) 3.71-3.64 (m, 2H) (one NH proton missing)

EXAMPLE 19: Préparation of 4-pyridazin-4-ylpyrimidin-2-amine

A microwave vial, under nitrogen atmosphère, was charged with tributyl(pyridazin-4-yl)stannane (3.42g), 4-pyridazin-4-ylpyrimidin-2-amine (0.727g), palladium (0) tetrakis(triphenylphosphine) (0.892g), Λ/,/V-diisopropylethylamine (1.35 mL) and 1,4-dioxane (38.6 mL) and heated to 140°C in the microwave for 1 hour. The reaction mixture was concentrated and purified on silica using a gradient of 0% to 70% 20 acetonitrile in dichloromethane to give 4-pyridazin-4-ylpyrimidin-2-amine as a beige solid.

1H NMR (400MHz, de-DMSO) 9.82 (dd, 1H) 9.41 (dd, 1H) 8.47 (d, 1H) 8.22 (dd, 1H) 7.38 (d, 1H) 6.98 (br s, 2H)

EXAMPLE 20: Préparation of 2-methyl-2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propane-1sulfonate (compound 2.006)

Step 1: Préparation of 2,2-dimethylpropyl methanesulfonate

A solution of triethylamine (8.1 mL) and 2,2-dimethylpropan-1-ol (2.3g) in dichloromethane (40 mL) was cooled to 0°C in an ice/acetone bath. To this was added methanesulfonyl chloride (2.2 mL) drop wise. The reaction mixture was stirred cold for 2 hours and washed with aqueous ammonium chloride. The organic layer was concentrated and the residue dissolved in ether. The ether solution was passed through a plug of silica eluting with further ether. Concentration ofthe ether filtrate gave 2,2dimethylpropyl methanesulfonate as a light yellow liquid.

1H NMR (400MHz, CDCb) 3.90-3.85 (m, 2H) 3.01 (s, 3H) 1.00 (s, 9H)

Step 2: Préparation of 2,2-dimethylpropyl 2-hydroxy-2-methyl-propane-1-sulfonate

A solution of 2,2-dimethylpropyl methanesulfonate (1.75g) in tetrahydrofuran (22.1 mL) was cooled to -78°C under nitrogen atmosphère. Tothis was added drop wise n-butyllithium (2.5 mol/L in hexane, 5.1 mL). The reaction mixture was gradually warmed to -30°C over 2 hours and acetone (7.73 mL) was added. The reaction mixture was warmed to room température and stirred for a further 1.5 hours. The reaction was quenched with 2M aqueous hydrochloric acid and extracted with ethyl acetate (x3). The combined organic extracts were dried with magnésium sulfate, concentrated and purified on silica using a gradient from 0 to 100% ethyl acetate in iso-hexane to give 2,2-dimethylpropyl 2-hydroxy2-methyl-propane-1-sulfonate as a colourless liquid.

1H NMR (400MHz, CDCb) 3.90 (s, 2H) 3.32 (s, 2H) 2.79 (brs, 1H) 1.44 (s, 6H) 0.99 (s, 9H)

Step 3: Préparation of 2-hydroxy-2-methyl-propane-1-sulfonic acid

I o \\ OH —Y X

HO O

A mixture of 2,2-dimethylpropyl 2-hydroxy-2-methyl-propane-1-sulfonate (1.84g) and 6M aqueous hydrochloric acid (32.8 mL) was heated at 95°C for 4 hours. The reaction mixture was cooled to room température and freeze dried overnightto give 2-hydroxy-2-methyl-propane-1-sulfonic acid as an off white solid.

1H NMR (400 MHz, D2O) 2.99 (s, 2H) 1.24 (s, 6H) (one OH proton and one SO3H proton missing)

Step 4: Préparation of 2-methyl-2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propane-1-sulfonate (2.006)

A mixture of 2-pyridazin-4-ylpyrimidine (0.507g) in dry acetonitrile (32.1 mL) was cooled in an ice bath. To this was added 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (0.663 mL) 5 and the reaction mixture stirred at room température for 15 minutes. To this was added triphenylphosphine (1.68g) and a solution of2-hydroxy-2-methyl-propane-1-sulfonic acid (0.741g) in dry acetonitrile (0.5 mL) followed by drop wise addition of diisopropyl azodicarboxylate (1.26 mL, 1.30 g). The reaction mixture was then heated at 80°C for 144 hours. The reaction mixture was partitioned between water and dichloromethane and the aqueous layer purified by préparative reverse phase HPLC 10 (trifluoroacetic acid is présent in the eluent) to give 2-methyl-2-(4-pyrimidin-2-ylpyridazin-1-ium-1yl)propane-1-sulfonate as a yellow solid.

1H NMR (400MHz, CD3OD) 10.41-10.35 (m, 1H) 10.05-9.99 (m, 1H) 9.31 (dd, 1H) 9.12 (d, 2H) 7.67 (t,

H) 3.67 (s, 2H)2.10(s, 6H)

EXAMPLE 21: Préparation of 2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propane-1-sulfonate (compound 2.007)

Step 1: Préparation of 2,2-dimethylpropyl 2-hydroxypropane-1-sulfonate

A solution of 2,2-dimethylpropyl methanesulfonate (2g) in tetrahydrofuran (25 mL) was cooled to -78°C under nitrogen atmosphère and n-butyllithium (2.5 mol/L in hexane, 5.8 mL) was added drop wise. The reaction mixture was gradually warmed to -30°C over 1 hour and acetaldehyde (6.8 mL) was 25 added.

The reaction mixture was warmed to room température and stirred for a further 2.5 hours. The reaction was quenched with 2M aqueous hydrochloric acid and extracted with ethyl acetate (x3). The combined organic extracts were dried with magnésium sulfate, concentrated and purified on silica using a gradient from 0 to 100% ethyl acetate in iso-hexane to give 2,2-dimethylpropyl 2-hydroxypropane-130 sulfonate as a yellow liquid.

1H NMR (400MHz, CDCh) 4.47-4.34 (m, 1H) 3.96-3.87 (m, 2H) 3.25-3.17 (m, 2H) 3.01 (brs, 1H) 1.34 (d, 3H) 1.00 (s, 9H)

Step 2: Préparation of 2-hydroxypropane-1-sulfonic acid

A mixture of 2,2-dimethylpropyl 2-hydroxypropane-1-sulfonate (1.35g) and 6M aqueous hydrochloric acid (32.8 mL) was heated at 95°C for 4 hours. The reaction mixture was cooled to room température and freeze dried overnight to give 2-hydroxypropane-1-sulfonic acid as a brown solid.

1H NMR (400 MHz, D₂O) 4.17-4.06 (m, 1H) 2.99-2.85 (m, 2H) 1.16 (d, 3H) (one OH proton and one SO3H proton missing)

Step 3: Préparation of 2-(trifluoromethylsulfonyloxy)propane-1 -sulfonic acid

To a mixture of 2-hydroxypropane-1-sulfonic acid (0.2g) in dichloromethane (2.57 mL) was added 2,6-dimethylpyridine (0.33 mL) and the resulting mixture was cooled to 0°C. To this was added drop wise trifluoromethylsulfonyl trifluoromethanesulfonate (0.264 mL) and stirring continued at this température for 15 minutes. Cooling was removed and the reaction mixture was stirred at room température for a further hour. The reaction mixture was quenched with water and extracted with dichloromethane (x3). The combined organic extracts were dried with magnésium sulfate and concentrated to give 2-(trifluoromethylsulfonyloxy)propane-1-sulfonic acid as a brown gum, ~50% purity. The product was used immediately in subséquent reactions without further purification.

1H NMR (400MHz, CDCI3) product peaks only 5.57-5.41 (m, 1H) 4.18-3.98 (m, 1H) 3.58-3.35 (m, 1H) 1.76-1.65 (m, 3H) (one SO3H proton missing)

Step 4: Préparation of 2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propane-1-sulfonate 2.007

A mixture of 2-pyridazin-4-ylpyrimidine (0.15g), 2-(trifluoromethylsulfonyloxy)propane-1sulfonate (0.55g) and 1,4-dioxane (7.8 mL) was heated at 90°C for 24 hours. The reaction mixture was partitioned between water and dichloromethane and the aqueous layer purified by préparative reverse phase HPLC (trifluoroacetic acid is présent in the eluent) to give 2-(4-pyrimidin-2-ylpyridazin-1-ium-1yl)propane-1-sulfonate as a yellow solid.

1H NMR (400MHz, CD3OD) 10.43-10.37 (m, 1H) 9.93 (dd, 1H) 9.34 (dd, 1H) 9.11 (d, 2H) 7.68 (t, 1H) 5.66-5.53 (m, 1H) 3.66 (dd, 1H) 3.43 (dd, 1H) 1.83 (d, 3H)

EXAMPLE 22: Préparation of [(1S)-1-carboxy-3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propyl]ammonium 2,2,2-trifluoroacetate (compound 1.035)

Step 1: Préparation of [(1S)-3-bromo-1-methoxycarbonyl-propyl]ammonium chloride

O

To a mixture of (2S)-2-amino-4-bromo-butanoicacid (0.2g) in dry methanol (4 mL) at 0°C, under nitrogen atmosphère, was added thionyl chloride (0.392g) drop wise. The reaction mixture was stirred overnight at room température and concentrated to give crude [(1S)-3-bromo-1-methoxycarbonylpropyl]ammonium chloride as an orange gum, which was used without further purification.

Step 2: Préparation of methyl (2S)-2-(benzyIoxycarbonylamino)-4-bromo-butanoate

Crude [(1S)-3-bromo-1-methoxycarbonyl-propyl]ammonium chloride was stirred in dichloromethane (4 mL) and a solution of sodium hydrogen carbonate (0.28g) in water (4 mL) was added. The mixture was cooled to 0°C and benzyl carbonochloridate (0.225g) was added. The reaction mass was warmed to room température and stirred for 15 hours. The reaction mixture was diluted with water (10 mL) and extracted with dichloromethane (3x20 mL). The combined organic layers were dried over sodium sulfate, concentrated and purified on silica using a gradient from 0 to 100% ethyl acetate in cyclohexane to give methyl (2S)-2-(benzyloxycarbonylamino)-4-bromo-butanoate.

1H NMR (400MHz, CDCh) 7.30-7.40 (m, 5H) 5.37-5.43 (m, 1 H) 5.13 (s, 2H) 3.78 (s, 3H) 3.42-3.46 (m, 2H) 2.25-2.49 (m, 2H)

Step 3: Préparation of methyl (2S)-2-(benzyloxycarbonylamino)-4-(4-pyrimidin-2-ylpyridazin-1ium-1 -yl)butanoate iodide

To a solution of methyl (2S)-2-(benzyloxycarbonylamino)-4-bromo-butanoate (0.1g) in dry acetone (2 mL), under nitrogen atmosphère, was added sodium iodide (0.054g). The reaction mixture was stirred at room température overnight. To this was added 2-pyridazin-4-ylpyrimidine (0.048g) and the mixture heated at reflux for 16 hours. The reaction mixture was concentrated and the crude methyl (2S)-2-(benzyloxycarbonylamino)-4-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)butanoate iodide was used in the next step without further purification.

Step 4: Préparation of [(1S)-1-carboxy-3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propyl]ammonium 2,2,2-trifluoroacetate 1.035

A mixture of methyl (2S)-2-(benzyloxycarbonylamino)-4-(4-pyrimidin-2-ylpyridazin-1-ium-1yl)butanoate iodide (0.5g) and concentrated hydrochloric acid (4.9 mL) was heated at 80°C for 30 minutes. The reaction mixture was concentrated, dissolved in water and extracted with ethyl acetate (3x20 mL). The aqueous layer was purified by preparative reverse phase HPLC (trifluoroacetic acid is présent in the eluent) to give [(1S)-1-carboxy-3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propyl]ammonium 2,2,2-trifluoroacetate.

1H NMR (400 MHz, D₂O) 10.26 (d, 1H) 9.90 (d, 1H) 9.27 (dd, 1H) 9.06 (d, 2H) 7.72 (t, 1H) 5.17 (t, 2H) 4.09 (dd, 1H) 2.76-2.79 (m, 2H) (Three NH protons and one CO2H proton missing)

EXAMPLE 23: Préparation of [(1R)-1-carboxy-3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propyl]ammonium 2,2,2-trifluoroacetate (compound 1.029)

Step 1: Préparation of [(1R)-3-bromo-1-methoxycarbonyl-propyl]ammonium chloride

To a mixture of [(1 R)-3-bromo-1-carboxy-propyl]ammonium bromide (0.1g) in dry methanol (2 mL) at 0°C, under nitrogen atmosphère, was added thionyl chloride (0.083 mL) drop wise. The reaction mixture was stirred ovemight at room température and concentrated to give crude [(1S)-3-bromo-110 methoxycarbonyl-propyl]ammonium chloride as a yellow solid, which was used without further purification.

Step 2: Préparation of [(1R)-1-methoxycarbonyl-3-(4-pyrimidin-2-ylpyridazin-1-ium-1yl)propyl]ammonium bromide chloride

To a mixture of 2-pyridazin-4-ylpyrimidine (0.1g) in acetonitrile (3.16 mL) was added [(1R)-3bromo-1-methoxycarbonyl-propyl]ammonium chloride (0.16g) The mixture was heated at reflux for 12 hours. The reaction mixture was concentrated to give crude [(1R)-1-methoxycarbonyl-3-(4-pyrimidin-2ylpyridazin-1-ium-1-yl)propyl]ammonium bromide as a dark brown gum, which was used without further 20 purification.

Step 3: Préparation of [(1R)-1-carboxy-3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propyl]ammonium 2,2,2-trifluoroacetate, 1.029

A mixture of [(1 R)-1-methoxycarbonyl-3-(4-pyrimidin-2-ylpyridazin-1-ium-1yl)propyl]ammonium bromide (0.5g) and 2M aqueous hydrochloric acid (7.29 mL) was heated at 80°C for 2 hours. The reaction mixture was concentrated and purified by préparative reverse phase HPLC (trifluoroacetic acid is présent in the eluent) to give [(1R)-1-carboxy-3-(4-pyrimidin-2-ylpyridazin-1-ium1-yl)propyl]ammonium 2,2,2-trifluoroacetate.

1H NMR (400 MHz, D₂O) 10.22 (s, 1H) 9.87 (d, 1H) 9.24 (d, 1H) 8.99-9.04 (m, 2H) 7.66 (t, 1H) 5.16 (t, 2H) 4.17 (dd, 1H) 2.69-2.85 (m, 2H) (Three NH protons and one CO2H proton missing)

EXAMPLE 24: Préparation of [(1S)-1-carboxy-2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)ethyl]ammonium 2,2,2-trifluoroacetate (compound 2.009)

Step 1: Préparation of (2S)-2-(tert-butoxycarbonylamino)-3-(4-pyrimidin-2-ylpyridazin-1-ium-1yl)propanoate

To a mixture of 2-pyridazin-4-ylpyrimidine (0.05g) in dry acetonitrile (1 mL) was added tert-butyl N-[(3S)-2-oxooxetan-3-yl]carbamate (0.071g) and the reaction mixture was stirred at room température 20 for 48 hours. Concentration ofthe reaction mixture gave crude (2S)-2-(tert-butoxycarbonylamino)-3-(4pyrimidin-2-ylpyridazin-1-ium-1-yl)propanoate, which was used without further purification.

Step 2: Préparation of [(1S)-1-carboxy-2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)ethyl]ammonium 2,2,2-trifluoroacetate, 2.009 ^{25 A} mixture of (2S)-2-(tert-butoxycarbonylamino)-3-(4-pyrimidin-2-ylpyridazin-1-ium-1yl)propanoate (0.4g) and 2M aqueous hydrochloric acid (10 mL) was stirred at room température for 18 hours. The reaction mixture was concentrated and purified by préparative reverse phase HPLC (trifluoroacetic acid is présent in the eluent) to give [(1S)-1-carboxy-2-(4-pyrimidin-2-ylpyridazin-1-ium1 -yl)ethyl]ammonium 2,2,2-trifluoroacetate.

1H NMR (400 MHz, D₂O) 10.26 (s, 1H) 9.94 (d, 1H) 9.31-9.34 (m, 1H) 9.04 (dd, 2H) 7.69 (t, 1H) 5.48 5 (d, 2H) 4.75 (t, 1 H) (Three NH protons and one CO2H proton missing)

EXAMPLE 25: Préparation of dimethylsulfamoyl-[2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)acetyl]azanide (compound 1.032)

Step 1 : Préparation of 2-bromo-A/-(dimethylsulfamoyl)acetamide

H

To a solution of dimethylsulfamide (0.5g) and 4-(dimethylamino)pyridine (0.541g) in dichloromethane (19.9 mL) at 0°C was added bromoacetyl bromide (0.903g) drop wise. The reaction 15 was slowly warmed to room température and stirred for 24 hours. The reaction was partitioned with 0.5M aqueous hydrochioric acid. The organic layer was dried over magnésium sulfate and concentrated to give crude 2-bromo-N-(dimethylsulfamoyl)acetamide as a pale yellow oil. The product was used without further purification.

Step 2: Préparation of dimethylsulfamoyl-[2-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)acetyl]azanide 1.032

To a solution of 2-pyridazin-4-ylpyrimidine (0.15g) in acetonitrile (10 mL) was added 2-bromo/V-(dimethylsulfamoyl)acetamide (0.21g) and the mixture heated at 80°C for 16 hours. The resulting precipitate was filtered, washed with acetonitrile (2x20 mL) to give dimethylsulfamoyl-[2-(4-pyrimidin-225 ylpyridazin-1-ium-1-yl)acetyl]azanide as a light green solid.

1H NMR (400 MHz, ds-DMSO) 10.36 (s, 1H) 10.06-10.10 (m, 1H) 9.56-9.62 (m, 1H) 9.18-9.22 (m, 2H)

7.82-7.86 (m, 1H) 5.88-5.94 (m, 2H) 2.80-2.86 (m, 6H)

EXAMPLE 26: Préparation of 3-bromo-N-cyano-propanamide

To a stirred solution of cyanamide (0.5g) in water (10 mL) and tetrahydrofuran (10 mL) at 0°C was added sodium hydroxide (1.427g). After 10 minutes at 0°C a solution of 3-bromopropanoyl chloride (1.27 mL) in tetrahydrofuran (5 mL) was added drop wise. The resulting reaction mixture was stirred at room température for 3 hours. Water was added and the mixture was extracted with dichloromethane (2x75 mL). The combined organic layers were dried over sodium sulfate and concentrated to give 3bromo-/V-cyano-propanamide as a light yellow liquid.

1H NMR (400 MHz, de-DMSO) 12.40 (brs, 1H) 3.54-3.70 (m, 2H) 2.80-2.94 (m, 2H)

EXAMPLE 27: Préparation of [(1S)-1-carboxy-4-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)butyl]ammonium dichloride (compound 1.030)

Step 1: Préparation of dimethyl (2S)-2-[bis(tert-butoxycarbonyl)amino]pentanedioate

To a solution of dimethyl (2S)-2-(tert-butoxycarbonylamino)pentanedioate (0.3g) in acetonitrile (6 mL), under nitrogen atmosphère, was added 4-dimethylaminopyridine (0.028g). The mixture was cooled to 0°C and di-terf-butyl dicarbonate (0.264g) was added. The reaction was allowed to warm to room température and stirred for 18 hours. The reaction mixture was partitioned between water and ethyl acetate (80 mL) and extracted with further ethyl acetate (80 mL). The combined organic layers were washed with 10% aqueous citric acid, followed by saturated sodium bicarbonate solution and brine.

The combined organic layers were dried over sodium sulfate, concentrated and purified on silica using ethyl acetate in cyclohexane to give dimethyl (2S)-2-[bis(tert-butoxycarbonyl)amino]pentanedioate as a colourless gum.

1H NMR (400MHz, CDCb) 4.95 (dd, 1H) 3.73 (s, 3H) 3.68 (s, 3H) 2.36-2.54 (m, 3H) 2.15-2.23 (m, 1H)

1.50 (s, 18H)

Step 2: Préparation of methyl (2S)-2-[bis(tert-butoxycarbonyl)amino]-5-oxo-pentanoate

Cooled a solution of dimethyl (2S)-2-[bis(tert-butoxycarbonyl)amino]pentanedioate (0.28g) in diethyl ether (5.6 mL), under nitrogen atmosphère, to -78°C and added slowly diisobutylaluminum hydride (1M in Toluene, 0.82 mL). The reaction was stirred at-78°C for 10 minutes, then quenched with water (0.094 mL) and stirred for a further 30 minutes. After warming to room température solid sodium sulfate was added. The mixture was filtered through Celite, washed with fert-butylmethylether and the filtrate concentrated to give methyl (2S)-2-[bis(tert-butoxycarbonyl)amino]-5-oxo-pentanoate.

1H NMR (400MHz, CDCb) 9.78 (s, 1H)4.90 (dd, 1H) 3.73 (m, 3H) 2.45-2.66 (m, 3H) 2.11-2.28 (m, 1H) 1.42-1.63 (m, 18H)

Step 3: Préparation of methyl (2S)-2-[bis(tert-butoxycarbonyl)amino]-5-hydroxy-pentanoate

Cooled a solution of methyl (2S)-2-[bis(tert-butoxycarbonyl)amino]-5-oxo-pentanoate (0.2g) in dry methanol (4 mL), under nitrogen atmosphère, to 0°C and added sodium borohydride (0.025g) portion wise and stirred for 2 hours. The reaction mixture was concentrated and purified on silica using ethyl acetate in cyclohexane to give methyl (2S)-2-[bis(tert-butoxycarbonyl)amino]-5-hydroxy-pentanoate as a colourless gum.

1H NMR (400MHz, CDCb) 4.90 (dd, 1 H) 3.74-3.67 (m, 5H) 2.30-2.20 (m, 1 H) 1.99-1.89 (m, 1 H) 1.681.41 (s, 20H) (one OH proton missing)

Step 4: Préparation of methyl (2S)-2-[bis(tert-butoxycarbonyl)amino]-5-bromo-pentanoate

Cooled a solution of methyl (2S)-2-[bis(tert-butoxycarbonyl)amino]-5-hydroxy-pentanoate (4g) in dry tetrahydrofuran (40 mL) to 0°C and added carbon tetrabromide (5.728g). To this was added drop wise a solution of triphenylphosphine (4.576g) in tetrahydrofuran (40 mL). The reaction was allowed to warm to room température and stirred for 24 hours. The reaction mixture was concentrated and purified on silica using ethyl acetate in cyclohexane to give methyl (2S)-2-[bis(tert-butoxycarbonyl)amino]-5bromo-pentanoate.

1H NMR (400MHz, CDCb) 4.88 (dd, 1H) 3.73 (s, 3H) 3.38-3.50 (m, 2H) 2.24-2.27 (m, 1H) 1.85-2.12 (m, 3H) 1.51 (s, 18H)

Step 5: Préparation of [(1S)-1-methoxycarbonyl-4-(4-pyrimidin-2-ylpyridazin-1-ium-1yl)butyl]ammonium 2,2,2-trifluoroacetate

To a mixture of 2-pyridazin-4-ylpyrimidine (0.4g) in acetonitrile (12.6 mL) was added methyl (2S)-2-[bis(tert-butoxycarbonyl)amino]-5-bromo-pentanoate (1.141g) and the reaction mixture was heated at reflux for 12 hours. The reaction mixture was concentrated and purified by préparative reverse phase HPLC (trifluoroacetic acid is présent in the eluent which led to the loss ofthe BOC-protecting groups) to give [(1S)-1-methoxycarbonyl-4-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)butyl]ammonium 2,2,2trifluoroacetate.

1H NMR (400 MHz, D2O) 10.22 (d, 1H) 9.80-9.86 (m, 1H) 9.20-9.27 (m, 1H) 8.99-9.06 (m, 2H) 7.667.73 (m, 1H) 4.90-5.01 (m, 2H) 4.20 (t, 1H) 3.76-3.84 (m, 3H) 2.20-2.40 (m, 2H) 1.97-2.18 (m, 2H) (NH protons are missing)

Step 6: Préparation of [(1S)-1-carboxy-4-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)butyl]ammonium dichlonde, 1.030

A mixture of [(1S)-1-methoxycarbonyl-4-(4-pyrimidin-2-ylpyridazin-1-ium-1yl)butyl]ammonium;2,2,2-trifluoroacetate (0.1g) and 4M aqueous hydrochloric acid (0.78 mL) was heated at 60°C for 14 hours. The reaction mixture was concentrated to give [(1S)-1-carboxy-4-(4pyrimidin-2-ylpyridazin-1-ium-1-yl)butyl]ammonium dichloride.

1H NMR (400 MHz, D₂O) 10.24 (dd, 1H) 9.87 (dd, 1H) 9.27 (dd, 1H) 9.06 (d, 2H) 7.72 (t, 1H) 4.99 (t, 2H) 4.08 (t, 1 H) 2.23-2.44 (m, 2H) 2.00-2.16 (m, 2H) (three NH protons and one CO2H proton missing)

EXAMPLE 28: Préparation of 3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propanoic acid chloride (compound 1.010)

Step 1: Préparation of methyl 3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propanoate 2,2,2trifluoroacetate (compound 2.011)

A mixture of methyl 3-bromopropanoate (1.58g), 2-pyridazin-4-ylpyrimidine (0.5g) in acetonitrile (31.6 mL) was heated at 80°C for 24 hours. The reaction mixture was cooled, concentrated and partitioned between water (10 mL) and dichloromethane (20 mL). The aqueous layer was purified by préparative reverse phase HPLC (trifluoroacetic acid is présent in the eluent) to give methyl 3-(4pyrimidin-2-ylpyridazin-1-ium-1-yl)propanoate 2,2,2-trifluoroacetate as an orange gum.

¹H NMR (400MHz, D₂O) 10.15 (d, 1H) 9.85 (d, 1H) 9.18 (dd, 1H) 8.98 (d, 2H) 7.63 (t, 1H) 5.12 (t, 2H) 3.59 (s, 3H) 3.25 (t, 2H) ⁴ H NMR (400MHz, CD₃OD) 10.43-10.32 (m, 1H) 10.04 (d, 1H) 9.43 (dd, 1H) 9.12 (d, 2H) 7.65 (t, 1H) 5.18 (t, 2H) 3.70 (s, 3H) 3.36-3.27 (m, 2H)

Step 2: 3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propanoic acid chloride, 1.010

A mixture of methyl 3-(4-pyrimidin-2-ylpyridazin-1-ium-1-yl)propanoate;2,2,2-trifluoroacetate (0.392g) and conc. hydrochloric acid (7.66 mL) was heated at 80°C for 3 hours. The reaction mixture was cooled, concentrated and triturated with acetone to give 3-(4-pyrimidin-2-ylpyridazin-1-ium-1yl)propanoic acid çhloride as a beige solid.

¹H NMR (400MHz, D₂O) 10.16 (d, 1H) 9.85 (d, 1H) 9.18 (dd, 1H) 8.99 (d, 2H) 7.64 (t, 1H) 5.11 (t, 2H) 3.24 (t, 2H) (one CO₂H proton missing)

Additional compounds in Table A (below) were prepared by analogues procedures, from appropriate starting materials. The skilled person would understand that the compounds of Formula (I) may exist as an agronomically acceptable sait, a zwitterion or an agronomically acceptable sait of a zwitterion as described hereinbefore. Where mentioned the spécifie counterion is not considered to be 10 limiting, and the compound of Formula (I) may be formed with any suitable counter ion.

NMR spectra contained herein were recorded on either a 400MHz Bruker AVANCE III HD equipped with a Bruker SMART probe unless otherwise stated. Chemical shifts are expressed as ppm downfield from TMS, with an internai reference of either TMS or the residual solvent signais. The following multiplicities are used to describe the peaks: s = singlet, d = doublet, t = triplet, dd = double 15 doublet, dt = double triplet, q = quartet, quin = quintet, m = multiplet. Additionally br. is used to describe a broad signal and app. is used to describe and apparent multiplicity.

Compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 20 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034 and 1.035 were prepared using the general methods as described above, or in an analagous manner. Table A below shows the structure of these compounds and NMR characterising data.

Table A Préparation Examples of compounds of Formula (I)

Compound No.	Structure	¹H NMR
1.001	Οχ /° / ⁰ô 0	(400MHz, D2O) 10.19 (d, 1H) 9.84 (d, 1H) 9.20 (dd, 1H) 8.99 (d, 2H) 7.64 (t, 1H) 5.27-5.18 (m, 2H) 3.71-3.63 (m, 2H)
1.002	z--> / \ Z A // z. A w / z--' # o 0 I	(400MHz, D2O) 10.15 (d, 1H) 9.87 (d, 1H) 9.33 (dd, 1H) 9.12 (dd, 1H) 8.52 (dd, 1H) 7.99 (dd,1H) 5.32-5.19 (m, 2H) 3.73-3.65 (m, 2H)
1.003	p z X \ / z=/ ζθ o I 0	(400MHz, D2O) 10.18 (d, 1H) 9.80 (d, 1H) 9.19 (dd, 1H) 9.00 (d, 2H) 7.64 (t, 1H) 5.01 (t, 2H) 2.98 (t, 2H) 2.53 (quin, 2H)

Compound No.	Structure	¹H NMR
1.004	Y l₁₊ ^OH o / Il G ^X _S. \A - A⁰ >r o ⁰ F I F	(400MHz, D₂O) 10.08 (d, 1H) 9.79 (d, 1H) 9.39 (d, 1H) 9.08 (dd, 1H) 8.89-8.83 (m, 1 H) 8.78 (d, 1H) 5.24-5.16 (t, 2H) 3.65 (t, 2H)
1.005	X o Γ ô / ° z^z	(400MHz, CD3OD) 10.28 (d, 1H) 10.00 (d, 1H) 9.62 (d, 1 H) 9.28 (dd, 1 H) 8.96-8.93 (m, 1 H) 8.90 (d, 1H) 5.19-5.12 (t, 2H) 3.28 (t, 2H) (one CO2H proton missing)
1.006	O o< // / o y-------- I r=z / \ 4 ^z	(400MHz, D2O) 9.80-9.97 (m, 2H) 9.62-9.75 (m, 1H) 9.35-9.50 (m, 1H) 8.97 (dd, 1H) 8.19-8.42 (m, 1H) 5.20-5.29 (m, 2H) 3.59-3.73 (m, 2H)
1.007	z / y--Z V 'ύ z ') t \ / O z=^/ \ / + \=o Ο_χ / Tl T\| f/ O '	(400MHz, D₂O) 9.86-9.95 (m, 2H) 8.90-9.00 (m, 3H) 8.35 (brd, 2H) 5.27 (t, 2H) 3.69 (t, 2H) (one N H proton missing)
1.008	nh₂ îS O ll₊ o Y A g // F JL ^G \G 'c TA O ❖ ^XOH F^X\| O F	(400 MHz, D2O) 10.11 (d, 1H) 9.96 (d, 1H) 9.13 (dd, 1H) 8.29 (d, 1H) 6.83 (d, 1H) 5.31 (m, 2H) 3.73(m, 2H) (Two NH2 protons and one SO3H proton missing)
1.009	I O A / ^ωχ __/ ^SO z=z r	(400 MHz, D2O) 10.22 (d, 1H) 9.86 (d, 1H) 9.21 (dd, 1H) 8.90 (s, 2H) 5.25-5.31 (m, 2H) 3.69-3.77 (m, 2H) 2.44 (s, 3H)

Compound No.	Structure	Ή NMR
1.010	O ^cl L N/ j OH	(400 MHz, D₂0) 10.16 (d, 1H) 9.85 (d, 1H) 9.18 (dd, 1H) 8.99 (d, 2H) 7.64 (t, 1 H) 5.11 (t, 2H) 3.24 (t, 2H) (one CO2H proton missing)
1.011	I ^! ô o x V—o /=2 / \ G Z y /“€ \ ^z _z=/	(400MHz, CD3OD) 10.32 (d, 1H) 10.13 (d, 1H) 9.56 (s, 1H) 9.42-9.35 (m, 1H) 9.23 (d, 1H) 8.61 (d, 1H) 5.21 (t, 2H) 3.32-3.27 (m, 2H) (one CO₂H proton missing)
1.012	Op IL .n) oh JJ O or	(400MHz, D2O) 10.03 (d, 1H) 9.80 (d, 1H) 9.35 (d, 1H) 9.05 (dd, 1H) 8.87-8.82 (m, 1H) 8.76 (d, 1H) 5.08 (t, 2H) 3.22 (t, 2H) (one CO2H proton missing)
1.013	A IL A/ .o JJ O	(400MHz, CD3OD) 10.30-10.26 (m, 1H) 10.0410.00 (m, 1H) 9.66-9.64 (m, 1H) 9.33-9.30 (m, 1H) 8.97-8.93 (m, 1H) 8.91-8.88 (m, 1H) 5.255.14 (m, 2H) 3.71-3.68 (m, 3H) 3.35-3.27 (m, 2H)
1.014	1 O °x // ω_χz—z c=/ y=z	(400MHz, D₂O) 10.12 (d, 1H) 9.83 (d, 1H) 9.08 (dd, 1H) 8.42 (d, 1H) 7.89 (d, 1H) 5.28-5.19 (m, 2H) 3.71-3.64 (m, 2H) 2.74 (s, 3H)
1.015	(S IL Wy o	(400MHz, D2O) 10.20 (d, 1H) 9.91 (d, 1H) 9.22 (dd, 1H) 8.86 (d, 1H) 7.58 (d, 1 H) 5.18 (t, 2H) 3.31 (t, 2H) 2.66 (s, 3H)

Compound No.	Structure	Ή NMR
1.016	nh₂ (S L oh o [f Il o f. JL F I F	(400 MHz, D₂0) 10.06 (s, 1H) 10.00 (d, 1 H) 9.13 (dd, 1H) 8.28 (d, 1H) 6.85 (d, 1H) 5.20 (t, 2H) 3.31 (t, 2H) (Two NH2 protons and one CO₂H proton missing)
1.017	ll₊ X/^N\/N^⁰O	(400 MHz, D2O) 10.09 (d, 1H) 9.81 (d, 1H) 9.10 (m, 1H) 7.37 (s, 1H) 5.08 (t, 2H) 3.21 (t, 2H) 2.51 (s, 6H)
1.018	ΓΧ n ^N O Il r I o fI F	(400MHz, CD3OD) 10.21-10.34 (m, 1H) 9.97 (d, 1H) 9.25-9.35 (m, 1H) 9.10-9.15 (m, 2H) 7.607.76 (m, 1 H) 7.16-7.34 (m, 5H) 5.16-5.24 (m, 2H) 5.05-5.15 (m, 2H) 3.31-3.39 (m, 2H)
1.019	O O W/ θ=ω r—H C / _z=/	(400MHz, CD3OD) 10.24-10.20 (m, 1H) 9.93 (d, 1H) 9.24 (dd, 1H) 9.02 (d, 1H) 7.89 (d, 1H) 5.11 (t, 2H) 4.11 (s, 3H) 2.93 (t, 2H) 2.61 (quin, 2H)
1.020	q o y A ^Nf>t ° ° F	(400MHz, CD3OD) 10.35-10.47 (m, 1H) 10.05 (d, 1H) 9.37-9.44 (m, 1H) 9.08-9.15 (m, 2H) 7.657.78 (m, 1H) 7.32-7.43 (m, 2H) 7.18-7.27 (m, 1H) 7.03-7.15 (m, 2H) 5.30 (t, 2H) 3.58 (t, 2H)
1.021	^N (T\ L Y OH Y Br- ⁰	(400MHz, D2O) 10.16 (d, 1H) 9.86 (d, 1H) 9.219.15 (m, 1H) 8.99 (d, 2H) 7.64 (t, 1H) 5.11 (t, 2H) 3.24 (t, 2H) (one CO2H proton missing)

Compound No.	Structure	Ή NMR
1.022	Aï ^N V o L /N* JL foH Il fr Xx y A ^F II o A< 0 I F F	(400MHz, D₂O) 10.16 (d, 1H) 9.79 (d, 1H) 9.20 (dd, 1 H) 9.00 (d, 2H) 7.64 (t, 1 H) 5.04 (s, 2H) 1.25 (s, 6H) (one CO2H proton missing)
1.023	Cu 0 U N* .OH Yx F. JL >r ° o F I F	(400MHz, D2O) 10.18-10.13 (m, 1H) 9.87-9.82 (m, 1H) 9.20-9.14 (m, 1H) 8.98 (d, 2H) 7.63 (s, 1H) 5.10 (s, 2H) 3.24 (t, 2H) (one CO₂H proton missing)
1.024	_F j U^OH fY ° ⁰ F	(400MHz, D2O) 10.16-10.25 (m, 1H) 9.81-9.89 (m, 1H) 9.19-9.27 (m, 1H) 8.97-9.09 (m, 2H) 7.63-7.74 (m, 1H) 5.08-5.20 (m, 1H) 4.92-5.01 (m, 1H) 3.35-3.47 (m, 1H) 1.31 (d, 3H) (one CO2H proton missing)
1.025	^''hr'Y^Y 0 ll₊ Il Ux^NLxYx^OH R JL if 4 °~ ^A S F	(400 MHz, D2O) 10.18 (m, 1H) 9.97 (m, 1H) 9.21 (m, 1H) 8.98 (m, 2H) 7.61 (m, 1H) 3.36 (s, 2H) 1.94 (s, 6H) (one CO2H proton missing)
1.026	Ou ^N 11 i I l ₊ o IL /N7 JL / Yx ₀«-°	(400MHz, D2O) 10.20-10.18 (m, 1H) 9.81 (dd, 1 H) 9.19 (dd, 1H) 9.00 (d, 2H), 7.65 (t, 1H) 5.105.07 (m, 2H) 3.84-3.74 (m, 1H) 1.39 (d, 3H)
1.027	4 2 y—z f o	(400 MHz, D₂O) 10.11 (d, 1H) 9.87 (d, 1H) 9.32 (dd, 1H) 9.12-9.08 (m, 1H) 8.50 (dd, 1H) 7.99 (dd, 1H) 5.12 (t, 2H) 3.24 (t, 2H) (one CO2H proton missing)
1.028	'o \ ..o : z=z Q	(400 MHz, D2O) 10.24 (d, 1H) 9.80 (d, 1H) 9.25 (dd, 1H) 9.04 (d, 2H) 7.68 (t, 1H) 5.21 (dd, 1H) 4.93 (dd, 1H) 4.64-4.71 (m, 1H) 3.19-3.36 (m, 2H) (one OH proton missing)

Compound No.	Structure	¹H NMR
1.029	o n \|\| 1 F oh ll₊ 1 o M M Il F JL = o“ nhÎ fY F	(400 MHz, D₂O) 10.22 (s, 1H) 9.87 (d, 1H) 9.24 (d, 1H) 8.99-9.04 (m, 2H) 7.66 (t, 1H) 5.16 (t, 2H) 4.17 (dd, 1H) 2.69-2.85 (m, 2H) (Three NH protons and one CO2H proton missing)
1.030	L AL _ ^Hc> .O τγ ci n₊ Γ ^cr L. AK	(400MHz, D2O) 10.24 (dd, 1H) 9.87 (dd, 1H) 9.27 (dd, 1H) 9.06 (d, 2H) 7.72 (t, 1H) 4.99 (t, 2H) 4.08 (t, 1H) 2.23-2.44 (m, 2H) 2.00-2.16 (m, 2H) (three NH protons and one CO2H proton missing)
1.031	cr \|i j jL AL z\ rr 7^ η II ₊ o A A< ❖ o °	(400 MHz, D2O) 10.13 (d, 1H) 9.86 (d, 1H) 9.35 (dd, 1 H) 9.11 (dd, 1H) 8.57 (dd, 1H) 8.05 (dd, 1 H) 5.27-5.21 (m, 2H) 3.71-3.64 (m, 2H) (one NH proton missing)
1.032	o 1 W _χω O'' * i r=z / \ G z y /	(400 MHz, ds-DMSO) 10.36 (s, 1H) 10.06-10.10 (m, 1H) 9.56-9.62 (m, 1H) 9.18-9.22 (m, 2H) 7.82-7.86 (m, 1 H) 5.88-5.94 (m, 2H) 2.80-2.86 (m, 6H)
1.033	A^n Il ^N n Y >X a^- O	(400 MHz, D2O) 10.16 (s, 1H) 9.86 (d, 1H) 9.169.20 (m, 1H) 8.96-9.02 (m, 2H) 7.60-7.66 (m, 1H) 5.08-5.14 (m, 2H) 3.20-3.28 (m, 2H)
1.034	H 1 ₊ N Cl S ^N ( A ΜΑΆα^ν ll ₊ ^N /° ^Cl’ 0	(400MHz, D2O) 10.11 (d, 1H) 9.88 (d, 1H) 9.36 (brd, 1H) 9.10 (dd, 1H)8.48-8.56 (m, 1H) 7.928.07 (m, 1 H) 4.98-5.20 (m, 2H) 3.18-3.32 (m, 2H) (one CO2H proton missing)
1.035	Tl “Π /=° 9 \ ° C) z=z Z—< \ i \ >=o “⁺ Λ—° / V i q o ¹	(400 MHz, D2O) 10.26 (d, 1H) 9.90 (d, 1H) 9.27 (dd, 1H) 9.06 (d, 2H) 7.72 (t, 1H) 5.17 (t, 2H) 4.09 (dd, 1H) 2.76-2.79 (m, 2H) (Three NH protons and one CO2H proton missing)

BIOLOGICAL EFFICACY FOR COMPOUNDS OF FORMULA (I)

B1 Post-emergence efficacy

Seeds of a variety of test species were sown in standard laom-based soil in pots:- Ipomoea hederacea (IPOHE), Euphorbia heterophylla (EPHHL), Chenopodium album (CHEAL), Amaranthus 5 palmeri (ΑΜΑΡΑ), Lolium perenne (LOLPE), Digitaria sanguinalis (DIGSA), Eleusine indice (ELEIN), Echinochloa crus-galli (ECHCG), Setaria faberi (SETFA), . After cultivation for 14 days (postemergence) under controlled conditions in a glasshouse (at 24/16 °C, day/night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the dissolution ofthe technical active ingrédient Formula (I) in a small amount of acetone and a spécial solvent and emulsifier 10 mixture referred to as IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether), to create a 50g/l solution which was then diluted to required concentration using 0.25% or 1% Empicol ESC70 (Sodium lauryl ether sulphate) + 1% ammonium sulphate as diluent. The delivery of the aqueous spray solution was via a laboratory track sprayer which delivered the aqueous spray composition at a rate of 200 litres per hectare, using a fiat fan nozzle (Teejet 11002VS) 15 and an application volume of 200litre/ha (at2 bar).

The test plants were then grown in a glasshouse under controlled conditions (at 24/16 °C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant).

The results are shown in Table B (below). A value of n/a indicates that this combination of weed 20 and test compound was not tested/assessed.

Table B Control of weed species by compounds of Formula (I) after post-emergence application

Compound Number	Application Rate g/Ha	ΑΜΑΡΑ	CHEAL	EPHHL	IPOHE	SETFA	ECHCG	ELEIN	DIGSA	LU Q. _J O _l
1.001	500	100	100	100	100	100	70	100	100	70
1.002	500	100	100	100	40	90	100	100	100	100
1.003	500	100	100	100	60	100	80	100	100	60
1.004	500	100	100	100	60	90	80	100	100	60
1.005	500	100	100	70	30	60	100	100	100	80
1.006	500	100	100	100	100	30	60	100	80	80
1.007	500	100	100	40	30	70	80	100	100	90
1.008	500	n/a	100	80	40	100	100	100	100	60
1.009	500	n/a	100	70	30	100	100	100	100	80
1.010	500	n/a	100	100	40	100	100	100	100	90
1.011	500	100	100	100	100	100	90	100	90	70
1.012	500	100	100	100	20	90	90	90	100	50
1.013	500	100	90	100	80	100	80	100	100	70
1.014	500	100	100	100	n/a	100	80	90	100	90
1.015	500	n/a	100	80	30	100	100	100	100	80
1.016	500	n/a	90	90	30	100	100	100	100	70
1.017	500	n/a	100	80	50	100	70	100	100	60
1.018	500	90	90	100	30	100	80	100	100	40
1.019	500	n/a	100	100	60	100	70	90	100	30
1.020	500	100	80	80	30	100	90	100	100	80
1.021	500	100	100	100	100	100	100	100	100	70
1.022	500	100	80	100	100	100	90	100	100	60

Compound Number	Application Rate g/Ha	ΑΜΑΡΑ	CHEAL	EPHHL	IPOHE	SETFA	ECHCG	ELEIN	DIGSA	LOLPE
1.023	500	100	80	100	30	100	100	100	100	90
1.024	500	100	90	100	40	100	100	100	90	80
1.025	500	100	70	40	50	100	100	100	90	30
1.026	500	100	80	90	70	100	80	100	100	80
1.027	500	100	100	100	30	100	100	80	100	100
1.028	500	100	90	80	30	100	100	100	90	70
1.029	500	100	100	90	90	100	60	100	90	20
1.030	500	100	100	100	60	100	100	90	100	60
1.031	500	100	90	100	70	100	100	100	100	90
1.032	500	100	100	100	40	90	100	100	100	80
1.033	500	100	100	100	50	90	90	100	100	90
1.034	500	100	100	100	60	100	100	100	100	90
1.035	500	100	100	90	90	100	60	100	90	20

BIOLOGICAL EFFICACY FOR COMBINATIONS OF THE INVENTION

Using the methodology described above under B1, the efficacy of various combinations ofthe 5 invention were tested against plants selected from the following species: Ipomoea hederacea (IPOHE), Euphorbia heterophylla (EPHHL), Chenopodium album (CHEAL), Amaranthus palmeri (ΑΜΑΡΑ), Lolium perenne (LOLPE), Digitaria sanguinalis (DIGSA), Eleusine indica (ELEIN), Echinochloa crusgalli (ECHCG), Setaria faberi (SETFA), Triticum aestivum (TRZAW), Portulaca oleracea (POROL), Digitaria horizontalis (DIGHO), Lolium multiflorum (LOLMU), Conyza canadensis (ERICA), Conyza 10 bonariensis (ERIBO), Alopecurus myosuroides (ALOMY). After 21 days the tests were evaluated (100 = total damage to plant; 0 = no damage to plant), and the results are shown below in tables B2.1 to B2.21.

Table B2.1 Herbicidal activity of a compound of Formula (I) (compound 1.001) as component (A) and ________________glufosinate as component (B)_______________________________________________________________

Composition ID no.	Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A: B	ZEAMX	TRZAW	POROL	SETFA	LOLMU
C1	125	250	1:2	37	40	97	72	67
C2	250	250	1:1	33	53	93	73	72
C3	500	250	2:1	50	78	100	90	75

Table B2.2	Herbicidal activity of a compound glufosinate as component (B)	I of Formul;	3 (I) (compound 1.002) as component (A) and
Composition	Component	Component	Ratio	DIGSA	CHEAL	ΑΜΑΡΑ	IPOHE
ID no.	(A) (g/Ha)	(B) (g/Ha)	A: B
C4	50	200	1:4	95	92	98	77
C5	100	200	1:2	88	93	93	69
C6	200	200	1:1	95	97	100	83
C7	400	200	2:1	87	98	100	91

	Table B2.3	Herbicidal activity of a compound of Formula (I) (compound 1.001) glyphosate as component (B)	as component (A) and
	Composition ID no.	Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A: B	ZEAMX	TRZAW	POROL	SETFA LOLMU
	C8 C9 C10	125 250 500	500 500 500	1:4 1:2 1:1	52 70 80	83 92 80	92 99 100	93 72 91 75 93 78
5	Table B2.4	Herbicidal activity of a compound of Formula (I) (compound 1.002) glyphosate as component (B)	as component (A) and
	Composition ID no.	Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A: B	DIGSA	CHEAL	ΑΜΑΡΑ	IPOHE
	C11 C12 C13 C14	50 100 200 400	200 200 200 200	1:4 1:2 1:1 2:1	93 90 96 96	77 80 88 91	96 98 98 98	53 57 58 60
10	Table B2.5	Herbicidal activity of a compound of Formula (1) (compound 1.001) hydantocidin as component (B)	as component (A) and
	Composition ID no.	Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A: B	ZEAMX	TRZAW	POROL	SETFA LOLMU
	C15 C16 C17	125 250 500	250 250 250	1:2 1:1 2:1	38 40 40	52 68 70	100 100 100	70 82 75 77 83 80

Table B2.6 15 ___________ Composition ID no.	Herbicidal activity of a compound of Formula (I) (compound 1.001) <	is component (A) and diquat as
component (B)	LOLPE	ECHCG
Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A:B	IPOHE	ERICA	ΑΜΑΡΑ
C18	50	100	1:2	80	83	25	100	83
C19	100	100	1:1	100	75	25	100	92
C20	200	100	2:1	100	97	25	100	77
C21	400	100	4:1	100	97	88	100	90

Table B2.7 Herbicidal activity of a compound of Formula (I) (compound 1.001) as component (A) and diquat as _______________component (B)_______________________________________________________________________

Composition Component Component Ratio ZEAMX TRZAW POROL SETFA LOLMU ID no.(A) (g/Ha) (B) (g/Ha) A: B

C22	125	150	1:2	38	81	100	47	95
C23	250	150	1:1	38	86	100	58	95
C24	500	150	2:1	53	90	100	57	94

Table B2.8 Herbicidal activity of a compound of Formula (I) (compound 1.002) as component (A) and diquat as

component (B)
Composition ID no.	Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A:B	IPOHE	LOLPE	ECHCG	ERICA	ΑΜΑΡΑ
C25	50	100	1:2	95	85	35	100	78
C26	100	100	1:1	100	95	40	100	90
C27	200	100	2:1	100	91	40	100	87
C28	400	100	4:1	100	99	69	100	92

Table B2.9 Herbicidal activity of a compound of Formula (I) (compound 1.010) as component (A) and diquat as _______________component (B)________________________________________________________________________

Composition ID no.	Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A:B	IPOHE	ELEIN	LOLPE	ECHCG	ERICA	ΑΜΑΡΑ
C29	50	100	1:2	100	93	88	96	100	100
C30	100	100	1:1	100	83	97	94	100	100
C31	200	100	2:1	100	40	78	98	100	100
C32	400	100	4:1	100	50	85	94	100	100

5 Table B2.10	Herbicidal activity of a compound of Formula (I) (compound 1.027) as component (A) and diquat as component (B)
Composition ID no.	Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A: B	IPOHE	ELEIN	LOLPE	ECHCG	ERICA	ΑΜΑΡΑ
C33	50	100	1:2	100	83	96	95	100	100
C34	100	100	1:1	100	75	97	100	100	100
C35	200	100	2:1	100	70	97	95	100	100
C36	400	100	4:1	100	60	97	98	100	100

Table B2.11

Herbicidal activity of a compound of Formula (I) (compound 1.001) as component (A) and saflufenacil as component (B)

Composition ID no.	Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A: B	ERICA	ERIBO
C37	50	25	2:1	100	98
C38	100	25	4:1	100	100
C39	200	25	8:1	100	100
C40	400	25	16:1	100	100
Table B2.12	Herbicidal activity of a compound of Formula (I) (compound 1.001) as component (A) and fomesafen
	as component (B)
Composition	Component	Component	Ratio	IPOHE	ELEIN LOLPE ECHCG ERICA ΑΜΑΡΑ
ID no.	(A) (g/Ha)	(B) (g/Ha)	A: B
C41	50	200	1:4	100	88 78 83 100 100
C42	100	200	1:2	100	88 73 90 100 100
C43	200	200	1:1	100	90 80 83 100 100
C44	400	200	2:1	99	83 80 78 100 100

Table B2.13 Herbicidal activity of a compound of Formula (I) (compound 1.001) as component (A) and fomesafen

as component (B)
Composition ID no.	Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A:B	ZEAMX	TRZAW	POROL	DIGHO	SETFA	LOLMU	ERIBO
C45	75	200	3:8	17	40	99	75	48	25	40
C46	150	200	3:4	17	57	99	83	62	33	68
C47	300	200	3:2	18	70	98	97	84	53	89

Table B2.14 20	Herbicidal activity of a compound of Formula (I) (compound 1.002) as component (A) and fomesafen as component (B)
Composition ID no.	Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A:B	ZEAMX	TRZAW	POROL	DIGHO	SETFA	LOLMU	ERIBO
C48	75	200	3:8	22	33	98	55	97	53	50
C49	150	200	3:4	22	58	98	75	87	77	67
C50_______	300	200	3:2	25	75	98	66	88	88	75

•	79
Table B2.15	Herbicidal activity of a compound of Formula (1) (compound 1.001) as component (A) and oxyfluorfen as component (B)
	Composition	Component Component Ratio ZEAMX TRZAW DIGHO SETFA LOLMU ERICA ERIBO
	ID no.	(A) (g/Ha) (B) (g/Ha) A:B
	C51	100 100 1:1 62 87 97 99 87 100 77
	C52	400 100 4:1 58 95 97 99 96 100 90
	C53	800 100 8:1 68 98 99 99 96 100 94
	Table B2.16	Herbicidal activity of a compound of Formula (I) (compound 1.002) as component (A) and
5		oxyfluorfen as component (B)
	Composition	Component Component Ratio ZEAMX TRZAW DIGHO SETFA LOLMU ERICA ERIBO
	ID no.	(A) (g/Ha) (B) (g/Ha) A:B
	C54	100 100 1:1 48 92 97 98 97 100 80
	C55	400 100 4:1 43 95 95 97 98 100 91
	C56	800 100 8:1 72 97 98 99 99 100 100
	Table B2.17	Herbicidal activity of a compound of Formula (I) (compound 1.001) as component (A) and atrazine
		as component (B)
	Composition	Component Component Ratio IPOHE ELEIN LOLPE ECHCG ERICA ΑΜΑΡΑ
	ID no.	(A) (g/Ha) (B) (g/Ha) A:B
	C57	50 150 1:3 25 95 88 100 100 93
	C58	100 150 2:3 50 96 88 100 100 100
	C59	200 150 4:3 70 98 95 100 100 98
	C60	400 150 8:3 73 96 96 100 100 100
	C61	50 300 1:6 73 95 98 100 100 100
	C62	100 300 1:3 78 95 98 100 100 100
	C63	200 300 2:3 83 98 98 100 100 100
	C64	400 300 4:3 85 97 98 100 100 100
10	Table B2.18	Herbicidal activity of a compound of Formula (I) (compound 1.001) as component (A) and atrazine
		as component (B)
	Composition	Component Component Ratio ZEAMX TRZAW POROL DIGHO SETFA LOLMU ERIBO
	ID no.	(A) (g/Ha) (B) (g/Ha) A:B
	C65	75 250 3:10 17 20 99 63 86 88 62
	C66	150 250 3:5 17 22 99 65 77 98 72
	C67	300 250 6:5 28 50 100 73 85 98 88
	Table B2.19	Herbicidal activity of a compound of Formula (1) (compound 1.002) as component (A) and atrazine
		as component (B)
	Composition	Component Component Ratio ZEAMX TRZAW POROL DIGHO SETFA LOLMU ERIBO
	ID no.	(A) (g/Ha) (B) (g/Ha) A:B
	C68	75 250 3:10 20 67 100 88 98 98 82
	C69	150 250 3:5 22 81 100 95 98 98 86
	C70	300 250 6:5 27 94 100 100 98 98 93
15
	Table B2.20	Herbicidal activity of a compound of Formula (I) (compound 1.002) as component (A) and atrazine
		as component (B)
	Composition	Component Component Ratio DIGSA CHEAL ΑΜΑΡΑ IPOHE
	ID no.	(A) (g/Ha) (B) (g/Ha) A: B
	C71	50 250 1:5 96 98 100 27
	C72	100 250 2:5 96 98 100 30
	C73	200 250 4:5 98 98 100 40
	C74	400__________250__________8:5 96_________99_________100 38

Table B2.21	Herbicidal activity of a compound of Formula (I) (compound 1.001) as component (A) and metribuzin as component (B)
	Composition	Component	Component	Ratio	IPOHE	ELEIN LOLPE ECHCG ERICA ΑΜΑΡΑ
	ID no.	(A) (g/Ha)	(B) (g/Ha)	A: B
	C75	50	140	5:14	96	98 100 100 100 15
	C76	100	140	5:7	96	96 100 100 100 15
	C77	200	140	10:7	96	98 100 100 100 18
	C78	400	140	20:7	94	97 100 100 100 20
5
	Table B2.22a	Herbicidal activity against IPOHE of a compound of Formula (1) (compound 1.010) as component
		__(A) and compuond B2.9 as component (B) (*Expected activity as caclulated by the Colby Formula)
	Composition	Component	Component	Ratio	IPOHE
	ID no.	(A) (g/Ha)	(B) (g/Ha)	A: B	Observed	(*Expected)
	C79	50	12.5	4:1	100	100
	C80	100	12.5	8:1	100	100
	C81	200	12.5	16:1	100	100
	C82	400	12.5	32:1	100	100
	C83	-	12.5	-	100	-
	C84	50	-	-	23	-
	C85	100	-	-	23	-
	C86	200	-	-	28	-
	C87	400	-	-	28	-
	Table B2.22b	Herbicidal activity against ELEIN of a compound of Formula (I) (compound 1.010) as component (A)
10		_ and compuond B2.9 as component (B) (*Expected activity as caclulated by the Colby Formula)
	Composition	Component	Component	Ratio	ELEIN
	ID no.	(A) (g/Ha)	(B) (g/Ha)	A: B	Observed	(*Expected)
	C88	50	12.5	4:1	98	98
	C89	100	12.5	8:1	96	98
	C90	200	12.5	16:1	96	98
	C91	400	12.5	32:1	93	98
	C92	-	12.5	-	90	-
	C93	50	-	-	80	-
	C94	100	-	-	83	-
	C95	200	-	-	78	-
	C96	400	-	-	75	-
	Table B2.22c	Herbicidal activity against LOLPE of a compound of Formula (I) (compound 1.010) as component
		(A) and compuond B2.9 as component (B) (*Expected activity as caclulated by the Colby Formula)
	Composition	Component	Component	Ratio	LOLPE
	ID no.	(A) (g/Ha)	(B) (g/Ha)	A: B	Observed	(*Expected)
	C97	50	12.5	4:1	43	18
	C98	100	12.5	8:1	63	45
	C99	200	12.5	16:1	63	54
	C100	400	12.5	32:1	75	50
	C101	-	12.5	-	3	-
	C102	50	-	-	15	-
	C103	100	-	-	40	-
	C104	200	-	-	53	-
	C105	400	-	-	48	-

Table B2.22d	Herbicidal activity against	ECHCG of a compound of Formula (I) (compound 1.010) as component
Composition ID no.	(A) and corr Component (A) (g/Ha)	ipuond B2.9 as component (B) (Expected activity as caclulated by the Colby Formula) Component Ratio ECHCG (B) (g/Ha) A: B Observed (Expected)
C106	50	12.5	4:1	93	98
C107	100	12.5	8:1	93	99
C108	200	12.5	16:1	97	99
C109	400	12.5	32:1	93	99
C110	-	12.5	-	73
cm	50	-	-	94
C112	100	-	-	98	-
0113	200	-	-	98
0114	400	-	-	98	-
5 Table B2.22e	Herbicidal activity against ΑΜΑΡΑ of a compound of Formula (I) (compound 1.010) as component
Composition ID no.	(A) and compuond B2.9 as component (B) (Expected activity as caclulated by the Colby Formula) Component Component Ratio ΑΜΑΡΑ (A) (g/Ha) (B) (g/Ha) A: B Observed (Expected)
0115	50	12.5	4:1	92	100
0116	100	12.5	8:1	80	100
0117	200	12.5	16:1	100	100
0118	400	12.5	32:1	100	100
0119	-	12.5	-	100	-
C120	50	-	-	60	-
0121	100	-	-	88	-
0122	200	-	-	100
C123	400	-	-	100	-

Table B2.23a	Herbicidal activity against IPOHE of a compound of Formula (I) (compound 1.027) as component
10 ___________ Composition ID no.	(A) and comopund B2.9 as Component Component (A) (g/Ha) (B) (g/Ha)	component (B) Ratio ΑΜΑΡΑ A: B Observed	(*Expected)
C124	50	10.0	5:1	100	100
C125	100	10.0	10:1	100	100
C126	200	10.0	20:1	100	100
C127	400	10.0	40:1	100	100
C128	-	10.0	-	100	-
C129	50	-	-	15	-
C130	100	-	-	15	-
C131	200	-	-	15
C132	400	-	-	15	-
Table B2.23b	Herbicidal activity against ECHCG of a compound of Formula (I) (compound 1.027) as component
Composition ID no.	(A) and compuond B2.9 as Component Component (A) (g/Ha) (B) (g/Ha)	component (B) (Expected activity as caclulated by the Colby Formula) Ratio ECHCG A:B Observed (Expected)
C133	50	10.0	5:1	100	100
C134	100	10.0	10:1	100	100
C135	200	10.0	20:1	100	100
C136	400	10.0	40:1	100	100
C137	-	10.0	-	80	-
C138	50	-	-	100	-
C139	100	-	-	100	-
C140	200	-	-	100	-
C141	400	-	-	100	-

Table B2.23c Herbicidal activity against ΑΜΑΡΑ of a compound of Formula (I) (compound 1.027) as component (A) and compuond B2.9 as component (B) (*Expected activity as caclulated by the Colby Formula)

Composition ID no.	Component (A) (g/Ha)	Component (B) (g/Ha)	Ratio A: B	ΑΜΑΡΑ Observed	(*Expected)
C142	50	10.0	5:1	100	100
C143	100	10.0	10:1	93	100
C144	200	10.0	20:1	100	100
C145	-	10.0	-	100	-
C146	50	-	-	83
C147	100	-	-	100	-
C148	200	-	-	100	-

Claims

1. A composition comprising as component (A) a compound of Formula (I), or an agrochemically acceptable sait or a zwitterionic species thereof,

A

(I), wherein:

heteroaryl selected from the group consisting of:

(R⁸)p

A-l

(R⁸)p \ N

N

A-IV

A-VII wherein the jagged line defines the point of attachaient to the remaining part of a compound of Formula (I), p is 0, 1 or 2, and each R⁸ is independently selected from the group consisting of NH₂, methyl, and methoxy;

R¹ and R² are each independently hydrogen or methyl;

Q is (CR^1aR^2b)_m;

m is 0, 1, or 2;

each R^1a and R^2b are independently selected from the group consisting of hydrogen, hydroxy, methyl, and NH2;

Z is -S(O)₂OR¹⁰, -C(O)OR¹⁰, -C(O)NHS(O)₂R¹² and -C(O)NHCN;

R¹⁰ is hydrogen, methyl, benzyl or phenyl;

and R¹² is methyl, -NH₂, -N(CH₃)₂, or-NHCH₃;

and, as component (B), at least one herbicide or sait thereof selected from the group consisting of:

B1 a non-selective herbicide selected from the group consisting of glyphosate, glufosinate, hydantocidin, pelargonic acid, paraquat and diquat;

B3 a herbicide that inhibits photosystem II in photosynthesis.

2. The composition of claim 1, wherein Z is selected from the group consisting of:

-C(O)OH, -C(O)OCH₃, -S(O)2OH, -C(O)OCH₂C₆H₅, -C(O)OCeHs, and -C(O)NHS(O)2N(CH₃)2.

5 3. The composition of claim 1 or claim 2, wherein A is selected from A-l, A-ll, and A-lll as defined in claim 1.

4.

The composition of claim 1, wherein component (A) is selected from the group of 35 compounds shown in the table below:

Compound No. Structure

1.011 O o 'X x V— O r=z Çj \ ²

1.012 Qp IL .Ni _yOH GG YY O CF

1.013 Cip c- ! y O

1.014 1 O // ^wx Z—Z FA V Z \ / )=2

1.015 X f O 1

1.016 nh₂ OL ^νΥΥ<Ύν L ⁰ Π Il o ^Fx Yx L>r ^û F 1 F

5. The composition of any one of claims 1 to 4, wherein component (B) is selected from the group of herbicides consisting of:

5 B1 glyphosate, glufosinate, hydantocidin, pelargonic acid, paraquat and diquat;

B2 a herbicide that acts through the inhibition of protoporphoryinogen oxidase, wherein said herbicide is a diphenyl ether, a thiadiazole, a phenypyrazole, an oxadiazole, an Nphenylphthalimides, a pyrimidinedione, a triazolinone, an oxazolidinedione, flufenpyr ethyl, pyraclonil, profluazol, the compound of formula B2.9

10 B2.9, or the compound of formula B2.10

B2.10; and

B3 a herbicide that inhibits photosystem II in photosynthesis, wherein said herbicide is a pyridazinone, a phenyl carbamate, a uracil, a triazinone, an urea, a triazolinone, a 15 triazine, an amide, a nitrile, a phenyl-pyridazine, or a benzothiadiazinone.

6. The composition of claim 5, wherein component B is selected from the group of herbicides consisting of:

B1 glyphosate, glufosinate, hydantocidin, pelargonic acid, paraquat, diquat;

B2 bifenox, ethoxyfen-ethyl, halosafen, lactofen, acifluorfen-sodium, chlomethoxyfen, fluoroglycofen-ethyl, oxyfluorfen, fomesafen, fluthiacet-methyl, thidazimin, fluazolate, pyraflufen-ethyl, oxadiargyl, oxadiazon, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, benzfendizone, butafenacil, saflufenacil, azafenidin, bencarbazone, carfentrazoneethyl, sulfentrazone, pentoxazone, flufenpyr ethyl, pyraclonil, profluazol, the compound of formula B2.9

B3 chloridazon/pyrazon, desmedipham, desmedipham, bromacil, lenacil, terbacil, tiafenacil, hexazinone, metamitron, metribuzin, fenuron, metobromuron, neburon, chlorobromuron, fluometuron, methabenzthiazuron, siduron, chlorotoluron, isoproturon, metoxuron, tebuthiuron, chloroxuron, isouron, monlinuron, dimefuron, linuron, diuron, ethidimuron, amicarbozone, atrazine, desmetryne, propazine, terbuthylazine, dimethametryn, simetryne, terbutryne, ametryne, prometon, simazine, trietazine, prometryne, terbumeton, pentanochlor, propanil, bromofenoxim, bromoxynil, ioxynil, pyridate, pyridafol, and bentazone.

7. The composition of claim 5, or claim 6, wherein component B is selected from the group of herbicides consisting of:

B1 : glyphosate, glufosinate, hydantocidin, pelargonic acid, paraquat, diquat;

B2: B2(i) saflufenacil, B2(ii) fomesafen, B2(iii) oxyfluorfen, B2(iv) butafenacil, B2(v) carfentrazone-ethyl, B2(vi) pyraflufen-ethyl, B2(vii) sulfentrazone, B2(viii) flumioxazin,

B2(ix) the compound of formula

B2.9

B2(x) the compound of formula B2.10

B2.10;

B3: B3(i) atrazine, B3(ii) ametryn, B3(iii) metribuzin, B3(iv) hexazinone, B3(v) diuron, B3(vi) propanil, B3(vii) prometryn, B3(viii) tiafenacil, and B3(ix) trifludimoxazin.

10

8. The composition of any one ofthe preceding claims, wherein the weight ratio of component (A) to component (B) is from 0.01:1 to 100:1.

9. The composition of any one of the preceding claims wherein the weight ratio of component (A) to component (B) is from 0.025:1 to 20:1.

10. The composition of any one ofthe preceding claims, wherein the weight ratio of component (A) to component (B) is from 1:30 to 16:1.

11. The herbicidal composition of any one ofthe preceding claims additionally comprising an 20 agriculturally acceptable formulation adjuvant.

12. The herbicidal composition of claim 11, further comprising at least one additional pesticide.

13. The herbicidal composition according to claim 12, wherein the additional pesticide is a herbicide

25 or herbicide safener.

14. A method of controlling unwanted plant growth, comprising applying a compound of Formula (I) as defined in any one of claims 1 to 5, and a herbicide selected from groups B1, B2 or B3 as defined in any one of claims 1,5, 6, or 7, to the unwanted plants or to the locus thereof.

15. The method of claim 14, wherein the compounds of Formula (I) and the herbicide selected from groups B1, B2,or B3, are applied in the form of a composition as defined in any one of claims 1 to 12.