Herbicidal compositions comprising, and metiiods of use of, iierbicidally active
pyrandiones
Tile present invention relates to new metiiods of use of a specific iierbicidally active pyrandione, specifically metiiods of controlling weeds (e.g. Eciiinociiloa and/or Leptocliloa) in crops of useful plants sucii as crops of rice comprising applying thiis specific pyrandione. whiicii is a specific substituted 4-(bipiienyl-3-yl)-pyran-3,5-dione compound. Tiie present invention also relates to a new iierbicidal composition comprising this specific pyrandione iierbicide.
Tlie present invention also relates to new herbicidal compositions, for example for controlling grasses and weeds in crops of useful plants, especially in crops of rice; which compositions comprise a herbicidally active cyclic dione (specifically a herbicidally active pyrandione, more specifically a substituted 4-(biphenyl-3-yl)-pyran-3,5-dione compound), a enol ketone tautomer thereof, or an enol group derivative of the enol ketone tautomer thereof; and a co-herbicide.
WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited) discloses pyrandione, thiopyrandione and cyclohexanedione compounds, and enol ketone tautomer derivatives thereof, suitable for use as herbicides. The pyrandione and derivative compounds of formula (I), as defined hereinbelow, are generically disclosed in WO 2008/071405 A1. WO 2008/071405 A1 also discloses mixtures of these pyrandione compounds and derivatives with various mixture partners such as imazosulfuron or pyroxasulfone (KIH-485).
WO 2008/071405 A1 discloses inter alia the following two specific compounds A-66 and A-167 on pages 95 and 109 respectively:
°^o "^c. °>^o ^^c.
WO 2008/071405 compound A-66 WO 2008/071405 compound A-167
Compounds A-66 and A-167, as disclosed in WO 2008/071405 A1, are referred to in the present specification as "reference compound A-4" and "compound A-16" respectively.
2

Pyroxasulfone and other isoxazoline herbicides were disclosed originally in EP 1 364 946 A1 (Kumiai Chemical Industry Co., Ltd and Ihara Chemical Industry Co., Ltd), derived from WO 02/062770. Pyroxasulfone an inhibitor of very long chain fatty acids (VLCFAs) and/or inhibits cell division, in plants. Pyroxasulfone (CAS Registry no. 447399-55-5) is an isoxazoline herbicide having the following structure:
Me—N '•/>N
Fenoxasulfone, vi^ose CAS registry number is 639826-16-7, has the following structure:
CI N-Ov .
CHjCHjO y^ CI
I
and is covered by the scope of the isoxazoline herbicides disclosed in EP 1 203 768 A1 and CA 2 380 499 A1, both derived from WO 01/012613 A1 (Kumiai Chemical Industry Co., Ltd and Ihara Chemical Industry Co., Ltd). Mixtures of isoxazoline herbicides, e.g. specifically fenoxasulfone, with various other herbicides are disclosed in JP 2004/002324 A and JP 2005/145958 A (both publications Kumiai Chemical Industry Co., Ltd and Ihara Chemical Industry Co.. Ltd). EP 2 135 508 A1 (Kumiai Chemical Industry Co., Ltd), derived from WO 2008/114493, discloses a herbicidal composition containing: (A) an isoxazoline derivative, for example fenoxasulfone (which is compound no. 54 on Table 2 on page 12), and (B) a cyclohexanedione type compound, a phenylpyrazotine type compound, a sulfonyl-aminocarbonyltriazolinone type compound, or a compound selected from a list of other co-herbicides such as pinoxaden.
Imazosulfuron (CAS Registry no. 122548-33-8) is a herbicide having the following structure:
CI o O-CH3
^^ 0-CH3
The Pesticide Manual, 15* edition. 2009, British Crop Production Council, entry 482 (imazosulfuron), discloses that imazosulfuron is used to control most annual (excluding Echinochloa oryzicola) and perennial broad-leaf weeds and sedges in paddy rice (at 75-95 g/ha) and turf (at 500-1000 g/ha).
3

Copending PCT application no. PCT/EP2010/057121, filed on 25 May 2010 in tiie name of Syngenta Limited, and published on 2 December 2010 as WO 2010/136431 A1, discloses a new process for making some of the compounds disclosed in WO 2008/071405 A1 and a new final-stage intermediate, which for the purposes of the present specification we will name a compound of formula (laa), which can be used in this process. Specifically, WO 2010/136431 A1 discloses a compound of the following formula (laa) as this final-stage intermediate:
R' (laa).
Page 5 of WO 2010/136431 A1 discloses that, in a preferred group of compounds of the above formula (laa), Ri is ethyl, trifluoromethyl, cyclopropyl, difiuoromethoxy, trifluoromethoxy.fluoro, bromine or iodine; R4, R5, Re and R7, independently of each other, are hydrogen or methyl; Rais bromine, 4-chlorophenyl, 2-fluoro-4-chlorophenyl, or 2,4-di-chlorophenyl; R3 is hydrogen; and Y is O;
or, more preferably, R, is ethyl or cyclopropyl; R^, Rs, Re and R? are methyl; R2 is bromine, 4-chlorophenyl, 2-fluoro-4-chlorophenyl or 2,4-di-chlorophenyl; Rsis H; and Y is O.
Page 6 of WO 2010/136431 A1 also discloses that, in a further aspect of that invention, it was found that the compounds of formula (laa) could easily be converted into {inter alia) 4-phenyl-3,5-pyrandiones of formula (A), according to Reaction Scheme 1 below, in the presence of an acid.
Reaction Scheme 1 from page 6 of WO 2010/136431 A1 discloses the following:
T| ^ \=/ protic acid or R1 J ]1 Hr(R),
R\^ Jl PN/ Lewis add p5_Y..'--^5^.^^V>i;;=^^p2
Y—K.p6 ^X^^°
R' R' R' (A)
(laa)
I
wherein Y, R\ R^ R', r, R^ R*. R« and R^ are as defined in WO 2010/136431 A1.
4

This copending PCT application publislied as WO 2010/136431 A1 discloses the above-shown Reaction Scheme 1 method for making the above compounds of fonnuia (A) and the fact that these compounds are herbicides. There is no disclosure in WO 2010/136431 A1 of any specific types of weeds to be killed by these herbicides, or specific crops on which these herbicides are to be used, or any mixtures of these herbicides with any other active ingredient, or any formulations of these herbicides.
It is desirable to discover new compounds within, new uses of, and co-herbicide mixture partners for, the pyrandione compounds or enol-ketone-tautomer-derivative compounds disclosed in WO 2008/071405 A1, especially uses in (or mixtures suitable for use in) crops of rice, and/or uses for (or mixtures suitable for) controlling grasses and/or weeds such as Echinochloa and/or Leptochloa which can be found in rice crops.
A first aspect of the invention provides a method of controlling weeds (e.g. comprising Echinochloa and/or Leptochloa; and/or flooded weeds) in crops of rice (e.g. flooded rice; and/or transplanted or wet-sown (wet seeded) or dry-sown (dry seeded) rice; preferably transplanted flooded rice), which comprises applying compound A-13, whose structure is
' ^ (and which can alternatively or additionally be present
'V'^o ^^'^'^ci
as ^ ^ ), to the plants (e.g. flooded plants) or to the locus (e.g. flooded
locus) thereof. This method can use an application rate of 30-250 g/ha or 60-250 g/ha or
80-250 g/ha, preferably 80-200 g/ha, e.g. 90-150 g/ha, e.g. 120-125 g/ha, of the compound
A-13.
More preferably, the weeds to be controlled comprise Echinochloa (e.g. Echinochloa crus-galli (ECHCG), Echinochloa oryzoides, Echinochloa colona or colonum (ECHCO), Echinochloa crus-pavonis, or Echinochloa oryzicola; or Echinochloa muricata or Echinochloa stagnina) and/or Leptochloa (e.g. Leptochloa chinensis (LEFCH) or Leptochloa panicoides); most preferably Echinochloa crus-galli (ECHCG) and/or Leptochloa chinensis (LEFCH).
5

A second aspect of the invention provides a method of controlling Echinochloa weeds (e.g. flooded Echinochloa vtreeds) and/or Leptochloa weeds (e.g. flooded Leptochloa weeds) in crops of useful plants (e.g. rice; e.g. flooded rice; and/or transplanted or wet-sown (wet seeded) or dry-sown (dry seeded) rice), vt^ich comprises applying compound A-13, whose
O II I I
structure is ^ ^ (and which can alternatively or additionally be present
as ^ ^ ), to the plants (e.g. flooded plants) or to the locus (e.g. flooded
locus) thereof. This method can use an application rate of 30-250 g/ha or 60-250 g/ha or 80-250 g/ha, preferably 80-200 g/ha, e.g. 90-150 g/ha, e.g. 120-125 g/ha. of the compound A-13.
More preferably, the weeds to be controlled comprise Echinochloa (e.g. Echinochloa crus-ga///(ECHCG), Echinochloa oryzoides, Echinochloa colona orcolonum (ECHCO), Echinochloa crus-pavonis, or Echinochloa oryzicola; or Echinochloa muricata or Echinochloa stagnina) and/or Leptochloa (e.g. Leptochloa chinen&s (LEFCH) or Leptochloa panicoides); most preferably Echinochloa crus-galli (ECHCG) and/or Leptochloa chinensis (LEFCH).
A third aspect of the present invention provides a herbicidal composition that comprises as active ingredient a mixture of:
a) a herbicidally effective amount of a compound of formula (I)
R R (I).
6

wherein
R^ is cyclopropyl,
R^ is phenyl or phenyl substituted by C1-C4 alkyl, C1-C4 haloalkyi, C1-C4 alkoxy, C1-C4
haloalkoxy or halogen,
R", R*. R* and R^, independently of each other, are hydrogen or C1-C4 alkyl,
Y is O, and
G is hydrogen, an alkali metal, alkaline earth metal, sulfonium, or ammonium, or G is a
latentiating group which is C(0)-R^ or C(0)-0-R'';
wherein R' is H, CrCiealkyI, Ca-dsalkenyl, CrCiealkynyl, Ci-Ciohaloalkyl, CrCiocyanoalkyI, Ci-CionitroalkyI, C,-Cioamlnoalkyl, Ci-CsaikylaminoCi-CealkyI, C2-C8dialkylamtnoCi-Csalkyl, Ca-CycycloalkylCi-CsalkyI, Ci-CsalkoxyCi-CsalkyI, Cj-CsalkenyloxyCi-CsalkyI, C3-CsaikynyloxyCi-Csalkyl, d-CsalkylthioCi-Csalkyl, Ci-CsalkylsulfinylCi-Csalkyi, d-CsalkylsulfonylCi-Csalkyl, C2-CealkylKleneaminoxyCi-C5alkyl, Ci-CsalkylcarbonylCi-Csalkyl, Ci-CsalkoxycarbonylCrCsalkyi, aminocarbonylCi-CsalkyI, Ci-CsalkylaminocarbonylCr Csalkyl, Cz-CsdialkyiaminocarbonylCi-Csalkyl, Ci-CsalkylcarbonylaminoCi-CsalkyI, A/-C1-Csalkyicarbonyl-ZV-Ci-CsalkyiaminoCrCsalkyl, Ca-CetrialkylsilylCi-Csalkyl, phenyld-Csalkyl (wherein the phenyl is optionally substituted by d-CaalkyI, Ci-CshaioalkyI, Ci-dalkoxy, Ci-Cshaloalkoxy, d-Csalkylthio, CrCsalkylsulfinyi, Ci-dalkylsulfonyl, halogen, cyano, or by nitro), heteroaryld-Csaiky! (wherein the heteroaryl is optionally substituted by Ci-CsalkyI, C,-dhaloalkyl. d-Caalkoxy, Ci-Cahaloalkoxy, Ci-Caalkylthio, d-Csalkylsulfinyl, C,-Caalkylsulfonyl, halogen, cyano, or by nitro), Ca-Cshaloaikenyl, Ca-Cacycloalkyl, phenyl or phenyl substituted by Ci-CsaikyI, Ci-CahaloalkyI, Ci-Caalkoxy, CrCahaloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by Ci-CaalkyI, d-CahaloalkyI, Ci-Caalkoxy, Ci-Cshaloalkoxy, halogen, cyano or nitro; and
R" is Ci-CiealkyI, Ca-Ciaalkenyl, Ca-Ciaalkynyl, Cz-CiohaloalkyI, CrCiocyanoalkyl, Ci-Cionitroalkyl, d-Cioaminoalkyl, d-CsalkylaminoCi-CsalkyI, C2-ddialkyiaminod-C5alkyl, C3-Cycycloalkyld-Csalkyl, d-CsalkoxyCi-Csaikyl, Ca-CgalkenyloxyCrCsalkyI, C3-CsalkynyloxyCi-Csalkyl, Ci-Csalkylthiod-CsalkyI, Ci-CsalkylsulfinylCi-Csalkyi. Ci-CgalkylsulfonylCi-Csalkyl, C2-C8alkylideneaminoxyCi-C5alkyl, Ci-CsalkylcarbonylCi-Csalkyl, Ci-CsalkoxycarbonylCi-CsalkyI, aminocarbonylCi-CsalkyI, Ci-CsalkylaminocarbonylCi-Csalkyl, Cz-CedialkylaminocarbonylCrCsalkyI, Ci-CsalkylcarbonylaminoCi-CsalkyI, A/-C1-Csalkylcarbonyl-ZV-Ci-CsalkylaminoCi-Csalkyl, Cs-CetrialkylsilyiCi-Csalkyl, phenyld-CsalkyI
7

(wherein the phenyl is optionally substituted by CrCsalkyI, Ci-CahaloalkyI, Ci-Caalkoxy, Ci-Cshaloalkoxy, Ci-Csalkylthio, d-Caaikylsulfinyl, Ci-Caalkylsulfonyl, halogen, cyano, or by nitro), heteroarylCi-CsalkyI (wherein the heteroaryl is optionally substituted by Ci-CaaikyI, Ci-Cahaloalkyl, Ci-Csalkoxy, Ci-Cahaloalkoxy, Ci-Cgalkylthio, d-Csalkylsulfinyl, Ci-Caalkylsulfonyl, halogen, cyano, or by nitro), Cs-Cshaloalkenyl, Ca-Cscycloalkyl, phenyl or phenyl substituted by Ci-CaalkyI, Ci-CshaloalkyI, Ci-Caalkoxy, Ci-Cshaloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by Ci-CaalkyI, Ci-CahaloalkyI, Ci-Caaikoxy, Ci-Cahaloalkoxy, halogen, cyano or nitro;
and
b) a co-herbicide selected from the group consisting of fenoxasulfone, ipfencarbazone, propyrisulfuron, and W-[2-l(4,6-dimethoxy-1.3,5-tria2in-2-yl)carbonyl]-6-fluorophenyl]-1,1 -difluoro-A/-methylmethanesulfonamide.
A fourth aspect of the present invention provides a herbiddal composition comprising
(a) a compound A-13, whose structure is '^ and which can
"V^o ^^^'''^ci
alternatively or additionally be present as ^ ^ . and
(b) a carrier, a solvent and/or a surface-active substance.
Preferably, e.g. in the fourth aspect of the invention, the herbicidal composition is a formulation in the form of a wettable powder, a water-dispersibte granule, an emulsifiabte concentrate, a microemulslfiable concentrate, an oil-in-water emulsion, an oil flowable, an aqueous dispersion, an oily dispersion, a soluble liquid, or a water-soluble concentrate wherein the water-soluble concentrate is vMth water or a water-miscible organic solvent as carrier. More preferably, the herbicidal composition is a formulation is in the form of an emulsifiable concentrate.
8

In the substituent definitions of the compounds of the formula (I), each alkyl moiety either alone or as part of a larger group such as haloaikyi or alkoxy, is a straight or branched chain having 1 to 4 carbon atoms and is, preferably, methyl, ethyl, propyl or butyl.
Preferred halogens are fluorine, chlorine and bromine.
Haloaikyi groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF3, CF2CI, CF2H. CCI2H, FCH2, CICH2, BrCHz, CH3CHF. (CH3)2CF, CF3CH2 or CHF2CH2.
The group G denotes hydrogen, an alkali metal cation, alkaline earth metal cation, sulfonium cation (preferably -SCCi.CealkyU) *) or ammonium cation (preferably -NH4 * or -N(Ci. Cealkyl)4*), or a latentiating group. These latentiating groups G are selected to allow its removal by one or a combination of biochemical, chemical or physical processes to afford compounds of formula (i) where G is H before, during or following (preferably during or following, more preferably following) application to the treated area or plants. Examples of these processes include enzymatic cleavage, chemical hydrolysis and photoloysis. Compounds bearing such groups G may in some cases offer certain advantages, such as improved penetration of the cuticula of the plants treated, increased tolerance of crops, improved compatibility or stability in formulated mixtures containing other herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides, or reduced leaching in soils.
The latentiating group G is C(0)-R'' or C(0).0-R''; wherein R' is H, Ci-Ci8alkyl. C2-Cijalkenyl, C2-Ci8alkynyl, Ci-Ciohaloalkyl, Ci-CiocyanoalkyI, Ci-CionitroalkyI, Ct-Cioaminoalkyl, Ci-CsalkylaminoCi-CsalkyI, Cj-CsdialkylaminoCi-CsalkyI, Cs-CycycloalkylCi-Cgalkyl, Ci-CgalkoxyCi-Cgalkyl, Cs-CsalkenyloxyCi-CsalkyI, Ca-CsalkynyloxyCi-Cgalkyl, Ci-CgalkylthioCi-Csalkyl, Ci-CsalkylsulfinylCi-CsalkyI, Ci-CsalkylsulfonylCi-Csalkyl. C2-Cealkylideneaminoxyd-Csalkyl, Ci-CsalkylcarbonylCi-CsalkyI, Ci-CsalkoxycarbonylCr Cgalkyl, aminocarbonylCi-Cgalkyl, Ci-CsalkylaminocarbonylCi-CsalkyI, C2-CadialkylaminocarbonylCi-Csalkyl, d-CsalkylcarbonylaminoCi-Csalkyl, W-Ci-Csalkylcarbonyl-/V-CrCsalkylaminoCi-Csalkyl, Cg-CetrialkylsilylCi-Csalkyl, phenylCi-Cgalkyl (wherein the phenyl is optionally substituted by Ci-CsalkyI, Ci-Cshaloalkyl. Ci-Csalkoxy, Ci-Cshaloalkoxy, Ci-Csalkylthio, Ci-Caalkylsulfinyl, d-Csalkylsulfonyl, halogen, cyano, or by nitro),
9

heteroarylCi-Csalkyl (wherein the heteroaryl is optionally substituted by Ci-Csalkyl, Ci-Cshaloalkyl, Ci-Cjalkoxy, d-Cahaloalkoxy, Ci-Csalkylthio, Ci-Csalkylsulfinyl, Ci-Csalkylsulfonyl, halogen, cyano, or by nitro), Ca-Cshaloalkenyl, Cs-Cscycloalkyl, phenyl or phenyl substituted by Ci-Csalkyi, Ci-CshaloalkyI, Ci-Csaikoxy, Ci-Cshaloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by d-Csaikyl, Ci-CshaloalkyI, Cr Csalkoxy, Ci-Cshaloalkoxy, halogen, cyano or nitro; and
R** is Ci-Cisaikyl, Ca-Cwalkenyl, Cs-Ciealkynyl, C2-C,ohaloalkyl, Ci-Ciocyanoalkyl, Ci-Cionitroalkyl, CrCioaminoalkyI, Ci-CsalkylaminoCi-Csalkyl, Ca-OsdialkylaminoCt-CsalkyI, C3-CrcycloalkylCi-Cgalkyl, C-CsalkoxyCi-Csalkyi, Ca-CsalkenyloxyC-Csalkyl, C3-CsalkynyloxyCi-Csalkyl, Ci-CsalkylthioCi-CsalkyI, Ci-CsalkylsulfinylCi-CsalkyI, C,-CsalkylsulfonylCi-Csalkyl, Cz-CeaikylideneaminoxyCi-Csalkyl, Ci-CsalkylcarbonylCi-Csalkyl, Ci-CsalkoxycarbonylCi-Csalkyl, aminocarbonylCi-Csalkyl, Ci-CsalkylaminocarbonylCi-Csaikyl, Cz-CsdialkylaminocarbonylCi-CsalkyI, Ci-CsalkylcarbonylantinoCi-Csalkyl, A/-C1-Csalkylcarbonyl-ZV-Ci-CsalkylaminoCrCsalkyl, Cs-CetrialkylsilylCi-Csalkyi, phenylCi-Csalkyl (wherein the phenyl Is optionally substituted by Ci-Caalkyl, Ci-CshaloalkyI, Ci-Csalkoxy, Ci-Cshaloalkoxy, Ci-Csalkylthio, Ci-Csalkylsulfinyl, Ci-Csaikylsulfonyl, halogen, cyano, or by nitro), heteroarylCrCsalkyI (wherein the heteroaryl is optionally substituted by Ci-Cjalkyl, d-Cahaloalkyl, Ci-Caalkoxy. Ci-Cshaloalkoxy, Ci-Caalkylthio, Ci-Csalkylsulfinyl, Ci-Caalkylsulfonyl, halogen, cyano, or by nitro), Ca-Cshaloalkenyl, Cs-Cscydoalkyl, phenyl or phenyl substituted by Ci-CaalkyI, CrCahaloalkyI, Ci-Caalkoxy, Ci-Cshaloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by Ci-CsalkyI, Ci-CshaloalkyI, Ci-Csalkoxy, Ci-Cshaloalkoxy, halogen, cyano or nitro.
In the compound of formula (I), preferably R^ is phenyl substituted by methyl, methoxy, or halogen, more preferably fluorine or chlorine, such as chlorine.
Still more preferably, R^ is 4-chlorophenyl, 4-chloro-2-fluorophenyl, 2.4-dichlorophenyl, 4-chloro-2-methylphenyl, or 4-chloro-2-methoxyphenyl. Most preferably, R* is 4-chloro-2-fluorophenyl or 2,4-dichlorophenyl.
Preferred are those compounds of formula (I), wherein R*, R*. R® and R', independently of each other, are hydrogen or C1-C2 alkyl, more preferably methyl.
Preferably, R' and R" are Ci-CealkyI; more preferably methyl, ethyl, n-propyl, isopropyl or f-butyl; still more preferably methyl.
10

Preferably, G is hydrogen, C(0)-R' or C(0)-0-R''; wherein R^ and R" are Ct-Cealkyl. more preferably methyl, ethyl, n-propyl, isopropyl or f-butyl, still more preferably methyl.
In a particular embodiment, G is hydrogen.
When G is hydrogen, then the compound of formula (I) can be present as the first or the second of the two equilibrating tautomeric forms shown below or as a mixture of both tautomeric forms. The compound of formula (I), as used in the present invention, encompasses the first tautomeric form, the second tautomeric form, and a mixture of the first and second tautomeric forms:
R' R' R' R'
compound of formula (I) wherein G is hydrogen
Preferably, the compound of formula (I) is:
"V^o ^■^^'^^ci
' ^ (compound A-12, which can alternatively or additionally be present as
"V^o ^"^^^^ci
11

' ^ (compound A-13, which can alternatively or additionally be present
as ' ^ ).
'^ (compound A-14), '^ (compound A-15), or
' ^ (compound A-16, which can alternatively or additionally be present as
More preferably, the compound of formula (I) is compound A-12, A-13, A-14 or A-15.
Still more preferably, the compound of formula (I) is compound A-12 or A-13.
Most preferably, the compound of formula (I) is compound A-13.
Compound A-16, within the present invention, was previously disclosed as compound A-167 in WO 2008/071405 A1, and can be synthesized using the methods of preparation disclosed therein.
Preferred or particular or optional embodiments for the co-herbicide are as follows.
12

In one particular embodiment, the co-herbicide is ipfencarbazone. Ipfencarbazone, whose CAS (Chemical Abstracts Service) registry number is 212201-70-2, is a herbicide of the triazolone (or "tetrazolinone") class, and is believed to be an inhibitor of very long chain fatty acids, which usually inhibit cell division, in plants. Ipfencarbazone has the following structure:
Ipfencarbazone may also be in the form of a salt (e.g. agriculturally acceptable salt) thereof, and salts are encompassed within the meaning of ipfencarbazone. Ipfencarbazone is disclosed as Compound no. 231 in Table la on page 32 of EP 0 974 587 A1 (Hokko Chemical Industry Co. Ltd.) derived from WO 98/38176.
In the particular embodiment wherein the co-herbicide is ipfencarbazone, preferably, the compound of formula (I) is compound A-12, A-13, A-14 or A-15, more preferably compound A-12 or A-13, most preferably compound A-13.
In one particular embodiment, the co-herbicide is propyrisulfuron. Propyrisulfuron (TH-547), whose CAS registry number is 570415-88-2, has the following stmcture:
CI o O-CH3
\^N 0-CH,
Propyrisulfuron may also be in the form of a salt (e.g. agriculturally acceptable salt) thereof, and salts are encompassed within the meaning of propyrisulfuron. Propyrisulfuron and its synthesis is disclosed as Compound no. 38 in Synthesis Example 4 on pages 44-45 of EP 1 466 527 A1 (Sumitomo Chemical Takeda Agro Company, Ltd) derived from WO 03/061388.
In the particular embodiment wherein the co-herbicide is propyrisulfuron, preferably, the compound of formula (I) Is compound A-12, A-13, A-14 or A-15, more preferably compound A-12 or A-13, most preferably compound A-13. The embodiment with compound A-13, e.g. when applied as an emulsifiable concentrate (EC) formulation and/or in flooded conditions, appears to have certain advantages, as disclosed in Biological Example 1 and the comments thereon hereinafter.
13

In one particular embodiment, the co-herbicide is A/-[2-[(4,6-dimethoxy-1,3,5-trtazin-2-yl)carbonyl]-6-fluorophenylJ-1,1-difluoro-W-methylmethanesulfonamide. This compound, whose CAS registry number is 874195-61-6, has the following structure:
o' 'J' 9
°-CH, .
f
and is a herbicide of the keto sulfonanilide class, currently underdevelopment by Bayer CropScience AG. It is disclosed inter alia in WO 2006/008159 A1 (for fungiddal use; Bayer CropScience AG). Its proposed ISO common name is triafamone (SN 1211). It may also be in the form of a salt (e.g. agriculturally acceptable salt) thereof. Therefore, all references herein to /V-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-/y/-methylmethanesulfonamide are intended to encompass the compound or a salt (e.g. an agriculturally acceptable salt) thereof.
However, preferably, the co-herbicide is fenoxasulfone. Fenoxasulfone, whose CAS registry number is 639826-16-7, is a herbicide of the 4,5-dihydro-1,2-oxazole (4,5-dihydro-isoxazole) class. Fenoxasulfone is likely to be an inhibitor of very long chain fatty acids, and/or is likely to inhibit cell division, in plants. Fenoxasulfone has the following structure:
I ''^
JL^ o 0
CI
Fenoxasulfone may also be in the form of a salt (e.g. agriculturally acceptable salt) thereof, and salts are encompassed within the meaning of fenoxasulfone. Fenoxasulfone is covered by the scope of the isoxazoline herbicides disclosed in EP 1 203 768 A1 and CA 2 380 499 A1, both derived from WO 01/012613 A1 (Kumiai Chemical Industry Co., Ltd and Ihara Chemical Industry Co., Ltd). Mixtures of isoxazoline herbicides, e.g. specifically fenoxasulfone, with various other herbicides are disclosed in JP 2004/002324 A and JP 2005/145958 A (both publications Kumiai Chemical Industry Co., Ltd and Ihara Chemical Industry Co., Ltd). EP 2135 508 A1 (Kumiai Chemical Industry Co.. Ltd), derived from WO 2008/114493, discloses a herbicidal composition containing: (A) an isoxazoline derivative, for example specifically fenoxasulfone (which is compound no. 54 on Table 2 on page 12), and (B) a cyclohexanedione type compound, a phenylpyrazoline type compound, a sulfonyl-
14

aminocarbonyltriazolinone type compound, or a compound selected from a list of other co-herblddes such as pinoxaden.
More preferably, the compound of formula (I) is compound A-12, A-13, A-14 or A-15 (still more preferably compound A-12 or A-13, most preferably compound A-13), and the co-herbicide is fenoxasulfone. The embodiment with compound A-13 appears to have certain advantages, as disclosed in Biological Example 1 and the comments thereon hereinafter, such as generally good herbicidal activity in flooded conditions against both Echinichloa crus-galli (ECHCG) and Leptochloa chinensis (LEFCH) weeds, when compound A-13 is applied as an emulsifiable concentrate (EC) formulation.
Preferably, the weight ratio of the compound of fomiula (I) (e.g. compound A-12, A-13, A-14 or A-15, more preferably compound A-12 or A-13, most preferably compound A-13) to the fenoxasulfone is from 1:6 to 3:2 (e.g. 60:200, 90:200,120:200, or 240:200); or more preferably is from 1:5 to 1:1 or is from 1:4 to 4:5 (e.g. 60:200, 90:200, or 120:200), or still more preferably is from 3:10 to 4:5 or is from 3:10 to 7:10 (e.g. 60:200,90:200, or 120:200). Yet more preferably, the weight ratio of the compound of formula (I) (e.g. compound A-12, A-13, A-14 or A-15, more preferably compound A-12 or A-13, most preferably compound A-13) to the fenoxasulfone Is from 2:5 to 4:5 or is from 2:5 to 7:10 or is from 9:20 to 7:10 (e.g. 90:200 or 120:200). Most preferably, the weight ratio of the compound of formula (I) (e.g. compound A-12, A-13, A-14 or A-15, more preferably compound A-12 or A-13, most preferably compound A-13) to the fenoxasulfone is from 1:2 to 7:10 (e.g. 120:200), preferably 3:5.
Preferably, the weight ratio of the compound of formula (I) (e.g. compound A-12, A-13, A-14 or A-15, more preferably compound A-12 or A-13, most preferably compound A-13) to the ipfencarbazone is from 1:7 to 1:1 (e.g. 60:250, 90:250,120:250, or 240:250), or more preferably is from 1:5 to 2:3 or is from 6:25 to 1:2 (e.g. 60:250, 90:250, or 120:250).
Preferably, the weight ratio of the compound of formula (I) (e.g. compound A-12, A-13, A-14 or A-15, more preferably compound A-12 or A-13, most preferably compound A-13) to the propyrisulfuron is from 1:2 to 3:1 (e.g. 60:80, 90:80,120:80, or 240:80), or more preferably is from 1:2 to 2:1 or is from 3:4 to 3:2 (e.g. 60:80,90:80, or 120:80).
In one particular embodiment, the weight ratio of the compound of formula (I) (e.g. compound A-12, A-13, A-14 or A-15, more preferably compound A-12 or A-13, most preferably
15

compound A-13) to the /y/-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-A/-methylmethanesulfonamide is from 1:20 to 20:1, e.g. from 1:10 to 10:1.
The herbicjdal compositions of the present invention can be prepared in a variety of ways using formulation adjuvants, such as carriers (e.g. liquid or solid carrier), solvents and/or surface-active substances. Therefore, preferably, the herbicidal composition of the present invention is a formulation comprising a carrier (e.g. liquid or solid carrier), a solvent and/or a surface-active substance.
The formulation can be in various physical forms, for example in the fomi of a dustable powder (DP), a gel, a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), a water-dispersible tablet (WT), an effervescent compressed tablet, an emulsifiable concentrate (EC), a micro-emulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO)), an aqueous dispersion (e.g. aqueous suspension concentrate (SC)), an oily dispersion (OD), a suspo-emulsion (SE), a capsule suspension (CS), a soluble liquid, a water-soluble concentrate (SL) (with water or a water-miscible organic solvent as carrier), an impregnated polymer film, or in another form such as a form known, for example, from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999.
Preferably, the formulation is in the form of a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), an emulsifiable concentrate (EC), a microemulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO)), an aqueous dispersion (e.g. aqueous suspension concentrate (SC)), an oily dispersion (OD), a soluble liquid, or a water-soluble concentrate (SL) (wherein the water-soluble concentrate is with water or a water-miscible organic solvent as carrier). More preferably, the formulation is in the fomn of an emulsifiable concentrate (EC).
Such formulations can either be used directly or can be diluted prior to use. Diluted formulations can be prepared, for example, by mixing with water, liquid fertiliser(s), micro-nutrient(s), biological organism(s), oil and/or solvent(s).
16

The formulations can be prepared, for example, by mixing the active ingredient with formula¬tion adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, for example finely divided solids, mineral oils, vegetable oils, modified vegetable oils, organic solvents, water, surface-active substances or combinations thereof. The active ingredients can also be contained in very fine microcapsules consisting of a polymer. Microcapsules contain the adive ingredients in a porous carrier. This enables the active ingredients to be released into their surroundings in controlled amounts (e.g. slow release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be present 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 comprise, for example, natural and synthetic gums, cellulose, styrene-butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art in this connection. Alternatively it is possible for very fine microcapsules to be formed wherein the active ingredient is present in the form of finely divided particles in a solid matrix of a base substance, but In that case the microcapsule is not encapsulated.
The formulation adjuvants suitable for the preparation of the compositions according to the invention can include those known per se.
As liquid carrier (and/or solvent) there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amy! acetate, 2-butanone, butylenes carbonate, chlorobenzene, cyclo-hexane, cyclohexanol, alkyl esters of acetic acid (e.g. ethyl acetate, butyl acetate, amyl acetate, or isoamyl acetate, et al.), 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, A/,/V-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethyl-hexanol, ethylene carbonate, 1,1,1-trichloroethane, 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, isobornyl acetate, isooctane. isophorone,
17

isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xyiene, n-hexane, n-octylamlne, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG 400), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichioroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, or higher molecular weight alcohols (i.e. an alcohol having a higher molecular weight than isopropanol, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, 2-ethyl-hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, hexylene glycol, or glycerol), or W-methyl-2-pyrrolidone, /V-octyl-2-pyrrolidone, a mixture of heavy aromatic hydrocarbons (e.g. containing a mixture of Ci-C4alkylnaphthalenes and optionally also naphthalene, e.g. Solvesso 200 ^) or a similar liquid earner (and/or a similar solvent).
Water is generally the carrier of choice for the dilution of a concentrate formulation.
Suitable solid earners are, for example, talc, titanium dioxide, pyrophyllite clay, silica (silicon dioxide), attapulgite clay, kieseiguhr, limestone, calcium carbonate, bentonite, calcium montomorillonite, cottonseed husks, wheatmeal, soybean flour, pumice, wood flour, ground walnut shells, lignin and/or similar materials, as described, for example, in CFR 180.1001. (c) &(d).
A large number of surface-active substances can advantageously be used both in solid and in 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 may be used as emulsifiying, wetting or suspending 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 dodecyl-benzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of aikylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyi esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)5ulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride, polyethylene glycol esters of fatty acids, such as
18

polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyi phosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., RIdgewood, New Jersey, 1981.
Further adjuvants which can usually be used in pesticidal formulations include crystallisation inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion-inhibitors, fragrances, wetting agents, absorption improvers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, anti-freezes, microbiocides, and also liquid and solid fertilisers.
The formulations may also comprise additional active substances, for example further herbicides, herbickle safeners, plant growth regulators, fungicides or insecticides.
The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive used in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil. emulsified vegetable oil, such as AMIGO® (Rhdne-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of CB-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being important. Those esters are known as methyl laurate (CAS-111-82-0). methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
The application and action of the oil additives can be further improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples
19

of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34465. Preferred surface-active substances are anionic surfactants of the dodecyl-benzyisulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C12-C22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants. The concentration of surface-active substances in relation to the total additive is generally from 1 to 30 % by weight. Examples of oil additives that comprise or consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®. Turbocharge® (a mixture of surfactant, 1-octanol and petroleum oil) (Syngenta AG, CH), and Actipron® (BP Oil UK Limited, GB).
The said surface-active substances may also be used in the formulations alone, that is to say without oil additives.
Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture can contribute to a further enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation).The concentration of such solvents can be from 10 to 80 % by weight of the total weight. Such oil additives, vy/hich may be in admixture with solvents, are described, for example, in US-A-4 834 908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation). A further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada.)
In addition to the oil additives listed above, in order to enhance the activity of the composi¬tions according to the invention it is also possible for formulations of alkylpyrrolidones, (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. Bond®, Courier® or Emerald®) can also be used. Solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, can also be mixed into the spray mixture as activity-enhancing agents.
The herbicidal formulations / herbicidal compositions of the invention generally contain: (a) from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, more especially from 0.5 to 60 % by weight or from 1 to 40 % by weight, of a compound of fomnula (I); and
20

(b) from 1 to 99.9 % by weight (such as from 5 to 99.9%, or from 40 to 99.5%, or from 60% to 99%, by weight) of a formulation adjuvant(s) (e.g. a total of from 1 to 99.9 %, e.g. from 5 to 99.9% or from 40 to 99.5%, by weight of the herbicidal composition /formulation, of: any carrier (e.g. liquid or solid earner) (if present), any solvent (if present), any surface-active substance (if present), and any other formulation adjuvant(s) present). The formulation adjuvant(s) preferably include(s) from 0 to 25 % (e.g. from 1 to 25 %) by weight of a surface-active substance.
Unless the context requires othenvise, in this specification, % by weight means % by weight of the herbicidal composition or formulation.
Whereas commercial products (e.g. liquid compositions / formulations) will preferably be formulated as concentrates, the end user will normally employ diluted formulations.
Pretended formulations have especially the following compositions: (% = percent by weight of the herbicidal composition or formulation):
Emulsifiable concentrates:
active ingredient: 1 to 95 %, in particular 1 to 60 % (e.g. 1 to 40 %) or 60 to
90%
surface-active agent: 1 to 30 %, preferably 5 to 30 % or 5 to 20 %
liquid carrier (and/or solvent): 1 to 90 % or 1 to 80 %, in particular 1 to 35 % or 35 to 90
% (such as 35 to 80 %)
Dusts:
active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %
solid earner: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates:
active ingredient: 2 to 75 % or 5 to 75 %, preferably 10 to 50 %
water: 94 to 24 %, preferably 88 to 30 %
surface-active agent: 1 to 40 %, preferably 2 to 30 %
Wettable powders:
active ingredient: 0.5 to 90 %, preferably 1 to 80 %
surface-active agent: 0.5 to 20 %, preferably 1 to 15 %
21

solid carrier: 6 to 95 %, preferably 15 to 90 %
Granules:
active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %,
where the term "active ingredient" refers to the mixture of compound of formula (I) with a co-herbicide.
The following Examples further illustrate, but do not limit, the invention.
F1 ■ Emulsifiable concentrates a) b) c) d)
active ingredient 5% 10% 25% 50%
calcium dodecylbenzene-
sulfonate 6% 8% 6% 8%
castor oil polyglycol ether 4 % - 4 % 4 %
(36 mol of ethylene oxide)
octylphenol polyglycol ether - 4 % - 2 %
(7-8 mol of ethylene oxide)
NMP (W-methylpyn^olidone) - - 10% 20%
aromatic hydrocarbon 85% 78% 55% 16%
mixture Cg-Ciz
Emulsions of any desired concentration can be prepared from such concentrates by dilution
with water.
F2. Solutions a) b) c) d)
active ingredient 5% 10% 50% 90%
1 -methoxy-3-(3-methoxy-
propoxy)-propane - 20% 20%
polyethylene glycol MW 400 20% 10%
NMP (/V-methylpyrrolidone) - - 30% 10%
aromatic hydrocarbon 75% 60%
mixture C9-C12
The solutions are suitable for application in the form of microdrops.
22

F3. Wettable powders a) b) c) d)
active ingredient 5% 25% 50% 80%
sodium lignosulfonate 4% ~ 3% -
sodium lauryl sulfate 2% 3% - 4%
sodium diisobutylnaplithalene-
sulfonate - 6% 5% 6%
octylphenoi poiyglycol ether - 1 % 2 %
(7-8 mo! of ethylene oxide)
highly dispersed silicic acid 1% 3% 5% 10%
kaolin 88% 62% 35%
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly
ground in a suitable mill, yielding wettable powders which can be diluted with water to give
suspensions of any desired concentration.
F4. Coated granules a) b) c)
active ingredient 0.1% 5% 15%
highly dispersed silicic acid 0.9 % 2 % 2 %
inorganic carrier 99.0 % 93 % 83 %
(diameter 0.1 -1 mm) e.g. CaCOa or SiOa
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is subsequently evaporated off in vacuo.
F5. Coated granules a) b) c)
active ingredient 0.1% 5% 15%
polyethylene glycol MW 200 1.0% 2% 3%
highly dispersed silicic acid 0.9 % 1 % 2 %
inorganic canrier 98.0 % 92 % 80 %
(diameter 0.1 -1 mm) e.g. CaCOa or SiOz
The finely ground active ingredient is applied uniformly, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruder granules a) b) c) d)
active Ingredient 0.1% 3% 5% 15%
sodium lignosulfonate 1.5% 2 % 3 % 4 %
23

carboxymethylcellulose 1.4% 2% 2% 2%
kaolin 97.0% 93% 90% 79%
The active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water. The resulting mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c)
active ingredient 0.1 % 1 % 5 %
talcum 39.9% 49% 35%
kaolin 60.0% 50% 60%
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d)
active ingredient 3% 10% 25% 50%
ethylene glycol 5% 5% 5% 5%
nonylphenol polyglycol ether - 1 % 2 %
(16 mol of ethylene oxide)
sodium lignosulfonate 3 % 3 % 4 % 5 %
carboxymethylcellulose 1 % 1 % 1 % 1 %
37 % aqueous fomialdehyde 0.2% 0.2% 0.2% 0.2%
solution
silicone oil emulsion 0.8% 0.8% 0.8% 0.8%
water 87% 79% 62% 38%
The finely ground active ingredient is intimately mixed with the adjuvants, yielding a suspen-sion concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
The term "active ingredient" in the examples mentioned above refers to the mixture of compound of formula (I) with a co-herbicide.
The invention relates also to a method for the control (e.g. selective control) of grasses and weeds in crops of useful plants, which comprises treating the useful plants (e.g. flooded plants), or the area under cultivation (e.g. flooded area), or the locus (e.g. flooded locus) thereof, with a herbicidal composition according to this invention.
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The invention also relates to a method of controlling grasses and weeds in crops of useful plants, which comprises applying a herbicidal composition of the invention as defined herein to the plants (e.g. flooded plants) or to the locus (e.g. flooded locus) thereof.
The invention also relates to a herbicidal composition as defined herein, for controlling grasses and weeds in crops of useful plants (e.g. flooded plants), especially in crops of rice (e.g. flooded rice). The grasses and weeds to be controlled can for example comprise Echinochloa and/or Leptochloa.
The crops of useful plants, e.g. in which the compositions according to the invention can be used, are in particular cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape (e.g. oilseed rape), maize or rice; or more particularly cotton, soybeans, sugar beet, rape (e.g. oilseed rape), or rice.
The crops of useful plants are preferably rice, in particular indica rice (such as IR-64, Ciherang, Pusa e.g. Pusa-1121, Jiayu 293, or NK-3326 hybrid); orjaponica rice (such as Koshihikari, Arborio, or Liangyou peiju e.g. Liangyou peiju PS3100).
The rice is preferably flooded rice.
The rice can for example be direct-seeded (e.g. dry sown or wet-sown) rice; which can optionally be flooded (e.g. before the herbicidal composition is applied). However, preferably the rice Is transplanted rice, which is typically flooded (e.g. before the herbicidal composition is applied).
Non-selective weed control might also be a possibility in some circumstances.
The grasses and/or weeds to be controlled may be monocotyledonous and/or dicotyledonous weeds, such as, for example, Setaria, Echinochloa (e.g. Echinochloa crus-galli), Leptochloa (e.g. Leptochloa chinensis), Scirpus, Monochoria, Brachiaria, Commelina, Cyperus, Sagittaria, Elatine, Lindernia, Ludwigia, Schoenoplectus, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Sinapis, Lolium, Solanum, Bromus, Alopecurus, Sorghum, Rottboellia, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and/or Veronica.
25

preferably, the grasses and/or weeds to be controlled comprise: monocotyledonous weeds, and/or grasses and/or weeds found in rice fields e.g. rice paddy fields; and/or preferably the grasses and/or weeds to be controlled comprise Echinochloa (e.g. Echinochloa crus-galli (ECHCG), Echinochloa oryzoides, Echinochloa cdona or colonum (ECHCO), Echinochloa crus-pavonis, or Echinochloa oryzicola; or Echinochloa muricata or Echinochloa stagnina), Leptochloa (e.g. Leptochloa chlnensis (LEFCH) or Leptochloa panicoides), Scirpus (e.g. Scirpus fluviatilis, Scirpus pendulus, Scirpus triangulatus, or one of many other Scirpus species), Monochoria (e.g. Monochoria vaginalis (MOOVA) or Monochotia /(orsakovii), Brachiaria, Commelina, Cyperus (e.g. Cyperus serotinus), Sagittaria, Elatine, Lindernia, Ludwjgia and/or Schoenoplectus (e.g. Schoenoplectus mucronatus or Schoenoplectus juncoides).
More preferably, the grasses and/or weeds to be controlled comprise Echinochloa (e.g. Echinochloa co/s-gfa///(ECHCG), Echinochloa oryzoides, Echinochloa colona or colonum (ECHCO), Echinochloa crus-pavonis, or Echinochloa oryzicola; or Echinochloa muricata or Echinochloa stagnina) and/or Leptochloa (e.g. Leptochloa chlnensis (LEFCH) or Leptochloa panicoides); most preferably Echinochloa crus-galli (ECHCG) and/or Leptochloa chlnensis (LEFCH).
Still more preferably, the grasses and/or weeds to be controlled (e.g. comprising Echinochloa and/or Leptochloa) are in crops of flooded rice, especially crops of flooded transplanted rice.
The term "crops" is to be understood as also including crops that have been rendered tolerant to herbicides or classes of herbicides (for example ALS, GS, EPSPS, PPO, ACCase or HPPD inhibitors) as a result of conventional methods of breeding or genetic engineering. Examples of crop that have been rendered tolerant e.g. to imidazolinones, such as imazamox, by conventional methods of breeding are Clearfield® summer rape (Canola) or Clearfield® rice. Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate-resistant or glufosinate-resistant maize or rice varieties, e.g. those commercially available under the trade names RoundupReady® (glyphosate-resistant maize or rice) or LibertyLink® (glufosinate-resistant maize or rice).
Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt-176 maize hybrids of NK®
26

(Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins and 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 that contain one or more genes which code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Card® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops and their seed material can be resistant to herbicides and at the same time also to insect feeding ("stacked" transgenic events). Seed can, for example, have the ability to express an insecticidally active CryS protein and at the same time be glyphosate-tolerant. The term "crops" is to be understood as also including crops obtained as a result of conventional methods of breeding or genetic engineering which contain so-called output traits (e.g. improved flavour, storage stability, nutritional content).
Areas under cultivation are to be understood as including land where the crop plants are already growing as well as land intended for the cultivation of those aop plants.
The rate of applicatk>n of the herbicides (compound of formula (I) in admixture with the co-herbicide) may vary within wide limits, and for example can depend upon the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed or grass to be controlled, the prevailing climatic conditions, and/or other factors governed by the method of application, the time of application and/or the target crop.
The mixture (herbicidal composition) according to the invention can for example be applied at an application rate of 1 to 4000 g of the mixture of herbicides (compound of formula (I) in admixture with the co-herbicide) per ha, especially from 5 to 1000 g/ha or 80 to 800 g/ha. "ha" means hectare.
In the method of controlling (or for the control of) grasses and weeds in crops of useful plants (e.g. rice) and/or in the herbicidal composition for controlling grasses and weeds in crops of useful plants (e.g. rice), according to the invention, preferably, the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 30 to 240 g of the compound of formula (I) (e.g. compound A-12, A-13, A-14 or A-15, more preferably compound A-12 or A-13, most preferably compound A-13) per hectare, calculated as the weight of the compound of formula (I) excluding the weight of any optional counterions thereof. More preferably, the herbicidal composition is applied to the plants or to the locus
27

thereof at an application rate of 50 to 150 g of the compound of formula (I) (e.g. compound A-12, A-13, A-14 or A-15, more preferably compound A-12 or A-13, most preferably compound A-13) per hectare, calculated as the weight of the compound of formula (I) excluding the weight of any optional counterions thereof. Still more preferably, the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 60 to 125 g (e.g. 60 g, 90 g, or 120 g) of the compound of formula (I) (e.g. compound A-12, A-13, A-14 or A-15, more preferably compound A-12 or A-13, most preferably compound A-13) per hectare, calculated as the weight of the compound of formula (i) excluding the weight of any optional counterions thereof. Most preferably, the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 90 to 125 g, or 90 to 120 g (e.g. 90 g or 120 g), of the compound of formula (I) (e.g. compound A-12, A-13. A-14 or A-15, more preferably compound A-12 or A-13, most preferably compound A-13) per hectare, calculated as the weight of the compound of formula (I) excluding the weight of any optional counterions thereof.
In the method of controlling (or for the control of) grasses and weeds in crops of useful plants (e.g. rice) and/or in the herbicidal composition for controlling grasses and weeds in crops of useful plants (e.g. rice), according to the invention, preferably, the co-herbicide is fenoxasulfone, ipfencarbazone, or propyrisulfuron; and
- when the co-herbicide is fenoxasulfone, then the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 100 to 400 g (more preferably 120 to 400 g, or 150 g to 300 g, still more preferably 175 g to 250 g, most preferably 200 g) of fenoxasulfone per hectare, calculated as the weight of fenoxasulfone excluding the weight of any optional counterions thereof; and
- when the co-herbicide is ipfencarbazone, then the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 120 to 500 g (more preferably 180 g to 320 g, most preferably 250 g) of ipfencarbazone per hedare, calculated as the weight of ipfencarbazone excluding the weight of any optional counterions thereof; and
- when the co-herbicide is propyrisulfuron, then the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 40 to 160 g (more preferably 60 g to 120 g, still more preferably 60 g to 100 g, most preferably 80 g) of propyrisulfuron per hectare, calculated as the weight of propyrisulfuron excluding the weight of any optional counterions thereof.
28

The compounds of formula (I) are genericaliy disclosed in WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited), and one specific compound of formula (I) (e.g. present compound A-16 herein, disclosed therein as compound A-167) Is specifically disclosed In WO 2008/071405 A1.
The syntheses of compounds A-13 and A-12, used in the present invention, are described in the Preparation Examples disclosed hereinafter, and illustrates one possible synthetic route for the compounds of formula (I) used in the present invention.
The mixing partners (co-herbicides, e.g. fenoxasulfone, ipfencarbazone, or propyrisulfuron) for the compound of formula (I), may also be in the form of salts (e.g. agriculturally acceptable salts).
Preferred herbicidal compositions comprise fenoxasulfone as co-herbicide. Another group of preferred compositions comprise ipfencarbazone as co-herbicide. A further group of preferred compositions comprise propyrisulfuron as co-herbicide.
The herbicidal compositions according to the invention can also be used in combination with safeners. The following mixtures with safeners, especially, come into consideration:
compound of formula (I) + cloquintocet-mexyl, compound of formula (I) + cloquintocet acid and salts thereof, compound of fomnula (I) + fenchlorazole-ethyl, compound of formula (I) + fenchlorazole acid and salts thereof, compound of formula (I) + mefenpyr-diethyl, compound of formula (I) + mefenpyr diacid, compound of fonnula (I) + isoxadifen-ethyl, compound of formula (I) + isoxadifen acid, compound of formula (I) + furilazole, compound of formula (I) + furilazole R isomer, compound of formula (I) + benoxacor, compound of formula (I) + dichlormid, compound of formula (I) + AD-67, compound of formula (I) + oxabetrinil, compound of formula (I) + cyometrinil, compound of formula (I) + cyometrinil Z-isomer, compound of formula (I) + fenclorim, compound of formula (I) + cyprosulfamide, compound of formula (I) + naphthalic anhydride, compound of formula (I) + flurazole, compound of formula (I) + CL 304,415, compound of formula (1) + dicyclonon, compound of formula (I) + fluxofenim, compound of formula (I) + DKA-24, compound of formula (I) + R-29148 and compound of formula (I) + PPG-1292. A safening effect can also be observed for the mixtures compound of the formula (I) + dymron, compound of the formula (I) + MCPA, compound of the formula (I) + mecoprop and compound of the formula (I) + mecoprop-P.
29

The above-mentioned safeners and herbicides are described, for example, in the Pesticide Manual, Twelfth Edition, British Crop Protection Council, 2000. R-29148 is described, for example by P.B. Goldsbrough et al.. Plant Physiology, (2002), Vol. 130 pp. 1497-1505 and references therein and PPG-1292 is known from WO09211761.
The rates of application of the herbicide mixture are generally from 0.001 to 2 kg/ha, but preferably from 0.005 to 1 kg/ha.
The ratio by weight of the compound of formula (i) to the co-herbicide in the composition according to the invention is in particular from 1:20 to 20:1, more particulariy from 1:10 to 10:1. See elsewhere herein for more specific weight ratios for specific co-herbicides (e.g. fenoxasulfone, ipfencarbazone or propyrisulfuron).
The rate of application of safener in relation to herbicide depends largely on the method of application. In the case of field treatment, which is effected either using a tank mixture comprising a combination of safener and herbicide mixture or by separate application of safener and herbicide mixture, the ratio of herbicides to safener is generally from 100:1 to 1:10, preferably from 20:1 to 1:1. In the case offiekl treatment, from 0.001 to 1.0 kg of safener/ha, preferably from 0.001 to 0.25 kg of safener/ha, is generally applied.
In the composition according to the invention, the amounts of oil additive employed are generally from 0.01 to 2 %, based on the spray mixture. The oil additive can, for example, be added to the spray tank in the desired concentration after the spray mixture has been prepared.
Some non-limiting examples of the present invention are disclosed in the following Formulation Examples and/or Biological Examples. The following Preparation Examples show possible synthetic preparations of compounds A-13 and A-12.
30

PREPARATION EXAMPLES
The following preparation examples show possible synthetic preparations of compounds A-13andA-12.
Example P8: Preparation of 4-(4'-Chloro-4«cyclopropyi>2'>fluoroblphenyl-3^l)-2,2,6,6-tetramethylpyran-3,5-dione (compound A-13)
OHlV^ F
yr o ^^ CI
step 1: Preparation of4'-cf}loro-2'-fluoro-4-tiydroxybiptienyl-3-carbaldehyde
H ^<^
^^^ CI
To a mixture of 5-bromosalicyaldehyde (30.Og, O.ISmol), 2-fluoro-4-chtorophenyiboronic acid (SO.Og, 0.17mol) and sodium carbonate (24.0g, 0.23mol) is added 1,2-dimethoxyethane (225ml) and distilled water (75ml), and the suspension is stirred under a nitrogen atmosphere. To this mixture is then added [1,1'-bis(diphenylphosphino)fen'ocene]-palladium(li)chloride (4.5g, 7.5mmol), followed by heating at reflux overnight. After cooling to room temperature and dilution with distilled water (500ml) and dichloromethane (500ml), the two phases are separated, and the aqueous phase extracted again with dichloromethane (2 X 500ml). Organic fractions are combined, washed vwth brine (800ml) tfien dried over magnesium sulphate. The suspension is filtered and the filtrate is concentrated in vacuo. Then crude material is purified by flash column purification (5-10% ethyl acetate in isohexane eluant) to afford 4'-chloro-2'-fluoro-4-hydroxybiphenyl-3-carbaldehyde (33.61g, 89%) as a pale yellow solid.
31

step 2: Preparation of Trifluoromethanesulfonic acid 4'-cf)loro-2'-fluoro-3-fofmylbiphenyl-4-y/ ester
To an ice-cold mixture of 4'-chloro-2'-fluoro-4-hydroxybiphenyi-3-carbaldeiiyde (33.60g, 0.13mol) and pyridine (31.0mi, 0.36mol) In anhydrous dichloromethane (700ml) is added triflic anhydride (27.0ml, 0.16mmol) dropwise over 30 minutes, maintaining temperature below 10'C. The reaction mixture is then allowed to warm to room temperature, followed by stin-ing overnight. After dilution with distilled water (500ml) and dichloromethane (500ml), the two layers are separated and the aqueous phase is extracted again with dichloromethane (2 X 500ml). Organic fractions are combined, washed with brine (800ml), then dried over magnesium sulfate and concentrated in vacuo. The crude product is purified by flash column chromatography (10% ethyl acetate in hexane eluant) to afford trifluoromethanesulfonic acid 4'-chloro-2'-fluoro-3-formylbiphenyl-4-yl ester as a yellow oil.
Step 3: Preparation of4'-Chlorx)-4-cyclopropyl-2'-fluorobipttenyl-3-cai1)aldettyd6
^^ CI
To a mixture of trifluoromethanesulfonic acid 4'-chloro-2'-fluoro-3-formylbiphenyl-4-yl ester (30.0g, 0.078mol), cyclopropyl boronic acid (8.80g, O.lOmol), potassium phosphate (58.40g, 0.28mol) and sodium bromide (8.0g, 0.078mol) is added toluene (300ml) then distilled water (30ml) under a nitrogen atmosphere. To this mixture is then added tetrakis(triphenylphosphine) palladium (9.60g, 8.40mmol) in one portion, and the mixture is then heated at 100'C overnight. After cooling to room temperature the mixture is diluted with
32

distilled water (SOOml) and ethyl acetate {500ml), and the two layers are separated and the aqueous phase extracted again with ethyl acetate (2 x SOOml). Organic fractions are combined, washed with distilled water (1L) then brine (1L), and then dried over magnesium sulphate. The suspension is filtered and the filtrate concentrated in vacuo. The crude product is purified by flash column chromatography on silica gel, then additionally by flash column chromatography on basic alumina (10% ethyl acetate in hexane as eluant) to afford 4*>chloro-4-cyclopropyl-2'-fluoro-biphenyl-3-carbaldehyde (7.6g, 36%).
Step4:4-[1~(4'-Chloro-4-cyclopropyl-2'-nuorobiphenyl-3-yl)methyliclene]-2,2.5.5-tetramethylclihydrvfuran-3-one
—4—0
To an ice-cold solution of dlhydro-2,2,5,5-tetramethylfuran-3-one (8.40g, 0.059mol) in anhydrous 1,2-dimethoxyethane (75ml) is added sodium methoxide (3.60g, 0.066mol) in one portion, and the mixture Is stirred at this temperature for 30 minutes. A solution of 4'-chloro-4-cyclopropyl-2'-fluorobiphenyl-3-carbaldehyde (14.80g, 0.054mmol) is then added dropwise over 20 minutes, maintaining temperature below lO'C. The reaction mixture is stirred at this temperature for 1 hour, then allowed to warm to room temperature before diluting with diethyl ether and distilled water. The two phases are separated, and the aqueous phase is extracted again with diethyl ether (x 2). Organic fractions are combined, washed with brine, then dried over magnesium sulfate. The suspension is filtered and the filtrate concentrated in vacuo to afford 4-[1-(4'-chIoro-4-cyclopropyl-2'-fluorobiphenyl-3-yl)methylidene]-2,2,5,5-tetramethyldihydrofuran-3-one (19.80g) which is of sufficient purity to use directly in the next step.
Sfep 5. 2-(4 '-Chloro-4-cyclopropyl-2'-fluorobiphenyl-3-yl)-4,4,6. S-tetramethyl-l. 5-dioxa-spiro[2.4]heptan-7-one
33

To a solution of 4-(1-(4'-chloro-4-cyclopropyl-2'-fluorobiphenyl-3-yl)methj^idene]-2,2,5,5-tetramethylclihydrofuran-3-one (19.80g, O.OSOmol) in methanol (830ml) at 35*C is added 50% aqueous hydrogen peroxide (5.00ml, 0.075mmol), followed immediately by 2M lithium hydroxide (5.00ml, 0.01 mo!) solution. The mixture is stirred at this temperature for a further 2 hours, then allowed to cool to room temperature. Then reaction mixture is quenched with 10% sodium metabisulfite (negative Kl-starch indicator test) then diluted with diethyl ether. Most of the methanol is removed under vacuum, and the crude mixture is partitioned between distilled water and diethyl ether. The aqueous phase is further extracted with diethyl ether (x 2), then all organics are combined and washed with saturated sodium bicarbonate (x 2) then brine. After anhydrousing over magnesium sulfate the suspension is filtered and the filtrate concentrated in vacuo to afford 2-(4'-chloro-4-cyclopropyl-2'-fluorobiphenyl-3-yl)-4,4,6,6-tetramethyl-1,5-dioxa-spiro[2.4Jheptan-7-one (18.2g) as an orange foam. This material is of sufficient purity to use directly in the next step without further purification.
1H NMR (CDCI3): 5 7.48 (s. 1H), 7.39 (d, 1H), 7.32 (t, 1H), 7.24-7.12 (m, 2H), 7.00 (d, 1H). 4.76 (s. 1H). 1.84-1.76 (m, 1H). 1.42-1.26 (m. 9H). 1.11-0.96 (m, 2H). 0.88-0.79 (m. 4H). 0.78-0.71 (m. 1H).
Step 6: Preparation of4-(4'-Chloro-4'Cyclopropyl-2'-fluorobiplienyl-3-yl)'2,2.6.6-tetramethylpyran-3.5-clione (compound A-13)
34

V^o ^^ CI
To a mixture of 2-(4'-chloro-4-cyclopropyl-2'-fluorobiphenyl-3-yl)-4,4,6,6-tetramethyl-1,5-clioxaspiro[2.4]heptan-7-one (18.20g, 0.044mol) and ytterbium trifiate (2.40g, 4.40mmol] is added a solution of 5M lithium perchlorate (prepared from 46ml diethyl ether and 24.40g lithium perchlorate). The resulting suspension is stirred at room temperature for 3 days, ttien is diluted with diethyl ether {85ml) and additional ytterbium trifiate (7.80g. 0.014mol) is added. After stimng at room temperature for a further 3 days additional ytterbium trifiate (13.63g, 0.025mol) is added, and the reaction mixture is stirred for 11 days. Finally, extra lithium perchlorate (24.40g, 0.23mol) is added in one portion, and the mixture is heated at 270C (internal temperature) for 1 day. The reaction mixture is partitioned between diethyl ether and distilled water, the two phases separated, and the aqueous phase is extracted with diethyl ether (x 2). The organic fractions are combined, washed with brine then dried over magnesium sulphate. The suspension is filtered and the filtrate concentrated in vacuo. The crude material purified by flash column chromatography (10% ethyl acetate in hexanes as eluant) to afford an oil which is triturated with hexanes to afford 4-(4'-chloro-4-cyclopropyl-2'-fluorobiphenyl-3-yl)-2,2,6,6-tetramethylpyran-3,5-dione (4.78g) as a white solid.
1H NMR (CDCI3): 6 7.47 (d. 1H), 7.38 (t, 1H). 7.23 (s, 1H), 7.21-7.12 (m. 3H). 5.68 (s. 1H), 1.75 (m, 1H), 1.62 (s, 6H), 1.49 (s, 6H). 0.92-0.82 (m. 2H), 0.81-0.75 (m. 1H). 0.61-0.53 (m, 1H)
Example P9: Preparation of 4-(2*,4'-Dichloro-4-cyclopropylbiphenyl-3-yl)-2,2,6,6-tetramethylpyran-3,S-dlone (compound A-12)
35

OHV^^ CI
V^^o ^^ CI
step 1: Preparation of2',4'-Dich!oro-4~hydroxybipfienyl-3-carbaldehyde
^c.
To a mixture of 5-bromosalicyaldehyde (30.0g, 0.15mol), 2,4-clichlorophenylboronic acid (32.0g, 0.17mol) and sodium carbonate (24.0g, 0.23mol) is added 1,2-dimethoxyethane (225ml) and distilled water (75ml), and the suspension is stirred under a nitrogen atmosphere. To this mixture is then added [1,1'-
bis(dtphenylphosphino)ferrocene]palladium(ll)chloride (4.5g, 7.5mmol), followed by heating at reflux overnight. After cooling to room temperature and dilution with distilled water (500ml) and dichloromethane (500ml), the two phases are separated, and the aqueous phase extracted again with dichloromethane (2 x 500ml). Organic fractions are combined, washed with brine (800ml) then dried over magnesium sulphate. The suspension is filtered and the filtrate concentrated in vacuo. Then crude material is finally purified by flash column purification (10% ethyl acetate in Isohexane eluant) to afford 2',4'-dichloro-4-hydroxybiphenyl-3-carbaldehyde (32.73g, 82%) as a pale yellow solid.
Step 2: Preparation of Trifluorometlianesuifonic acid 2'i4'-dichloro-3-fomiylbiptienyl-4-yl ester
36

To an ice-cold mixture of 2',4'-dJchloro-4-hydroxybiphenyl-3-carbalclehyde (31.70g, 0.12mol) and pyridine (25.0ml, 0.29mol) in anhydrous dichloromethane (650ml) is added triflic anhydride (22.0ml, 0.13mmol) dropwise over 30 minutes, maintaining temperature between 0-1CC. The reaction mixture is then allowed to warm to room temperature, followed by stirring overnight. After dilution with distilled water (500ml) and dichloromethane (300ml), the two layers are separated and the organic phase is further washed with saturated aqueous copper sulfate solution (3 x 500ml), water (500mi), then brine (500ml). After anhydrousing over magnesium sulfate the solvent is removed under vacuum and the crude product is purified by flash column chromatography (10% ethyl acetate in hexane eluant) to afford trifluoromethanesulfonic acid 2',4'-dichloro-3-formylbiphenyl-4-yl ester as an orange oil.
Step 3: Preparation of2'.4'-Dichloro-4'Cydopropylbiphenyl-3-carbaldehyde
^Sj^ CI
H K^
^^ CI
To a mixture of trifluoromethanesulfonic acid 2',4'-dichloro-3-formylbiphenyl-4-yl ester (30.0g, 0.075mol), cyclopropyl boronic acid (8.50g, 0.097mol), potassium phosphate (56.30g, 0.27mol) and sodium bromide (7.7g, 0.075mol) is added toluene (300ml) then distilled water (30ml) under a nitrogen atmosphere. To this mixture is then added tetrakis(triphenylphosphine) palladium (9.30g, 0.0081 mol) in one portion, and the mixture is then heated at 100'C overnight. After cooling to room temperature the mixture is diluted with distilled water (500ml) and ethyl acetate (500ml), and the two layers are separated. The aqueous phase is extracted again with ethyl acetate (2 x 500ml), then alt organic fractions are combined, then washed with distilled water (1L) then brine (1L). After drying over
37

magnesium sulfate the suspension is filtered and the filtrate is concentrated in vacuo. Ttie crude product Is purified by flasli column chromatography on silica gel (2-10% ethyl acetate in hexanes as eluant), then additionally by flash column chromatography on basic alumina (10% ethyl acetate in hexane as eluant) to afford 2',4'-dichloro-4-cyclopropyibiphenyl-3-carbaldehyde (11.7g, 54%).
Step 4:4-[1-(2', 4 '-DichlofX)-4-cyclopropylbiphenyl-3-yl)-methylidene]-2,2,5,5-tetramethyldihydmfuran-3-one
^^Nj^ CI
—V-O
To an ice-cold solution of dihydro-2,2,5,5-tetramethylfuran-3-one (15.70g, 0.1 Imol) in anhydrous 1,2'dimethoxyethane (285ml) is added sodium methoxide (6.50g, 0.12mol) in one portion, and the mixture is stirred at this temperature for 30 minutes. A solution of 2',4'-dichloro-4-cyclopropylbiphenyl-3-carbaldehyde (13.70g, 0.047mmol) is then added dropwise over 20 minutes, maintaining temperature below 10°C. The reaction mixture is stirred at this temperature for 2 hours, then allowed to warm to room temperature before diluting with diethyl ether and distilled water. The two phases are separated, and the aqueous phase is extracted again with diethyl ether (x 2). Organic fractions are combined, washed with brine, then dried over magnesium sulphate. The suspension is filtered and filtrate concentrated in vacuo. The aqueous phase is further acidified with 2M hydrochloric acid then extracted again with diethyl ether (x 2), dried over magnesium sulfate and concentrated in vacuo. All organics are combined, then diluted with toluene and azeotroped (x 4) to afford 4-[1-(2',4'-dichlQro-4-cyclopropylbiphenyl-3-yl)-methylidene]-2,2,5,5-tetramethyldihydrofuran-3-one(20.0g) which is of sufficient purity to use directly in the next step.
Step5:2-(2',4'-Dichloro-4-cyclopropylbiplienyl'3-yl)-4,4,6,6-tetramettiyl-1,5-dioxa-spiro[2.4]heptan-7-one
38

To a solution of 4-(1-(2',4'-dichloro-4-cycloprDpylbiphenyl-3-yl)-methy}iclene|-2,2,5,6-tetramethyldihydrofuran-3-one (20.0g, 0.048mol) in methanol (800ml) at 35'C is added 50% aqueous hydrogen peroxide (4.80ml, 0.072mmol}, followed immediately by 2M lithium hydroxide (4.80ml, 9.60mmol) solution. The mixture is stirred at this temperature for a further 2 hours, then allowed to cool to room temperature. Then reaction mixture is quenched with 10% sodium metabisulTite (negative Kl-starch indicator test) then diluted with diethyl ether. Most of the methanol is removed under vacuum, and the crude mixture is partitioned between distilled water and diethyl ether. The aqueous phase is further extracted with diethyl ether (x 2), then all organics are combined and washed with saturated sodium bicarbonate (x 2) then brine. After drying over magnesium sulfate the suspension is filtered and the filtrate concentrated in vacuo to afford 2-(2',4'-dichloro-4-cyclopropylbiphenyl-3-yl)-4,4,6,6-tetramethyl-1,5-dioxa-spiroI2.4Jheptan-7-one (17.80g) as an orange foam. This material is of sufTicient purity to use directly in the next step without further purification.
1H NMR (CDCI3): 6 7.49 (s, 1H), 7.37 (s, 1H), 7.37-7.25 (m, 2H), 7.20 (d, 1H). 6.99 (d, 1H). 4.75 (s, 1H), 1.80 (m, 1H), 1.40-1.28 (m. 9H), 1.10-0.98 (m, 2H), 0.90-0.80 (m, 4H). 0.75-0.80 (m.lH).
Step 6: Preparation of4~(2',4'-Dichloro-4-cyclopropylbipt)enyl-3-yl)-2.2,6,6-tetramett)ylpyran-3,5-dione (compound A-12)
39

OHV^ CI
To a mixture of 2-(2',4'-dichloro-4-cyclopropylbiphenyl-3-yl)-4,4,6,6-tetramethyl-1,5-dioxa-spiro[2.4]heptan-7-one (17.80g, 0.041 mol) and ytterbium triflate (2.20g, 4.41 mmol) is added a solution of 5M lithium perchlorate (prepared from 42ml diethyl ether and 22.30g lithium perchlorate). The resulting suspension is stirred at room temperature for 17 days, at which stage further diethyl ether (42ml), lithium perchlorate (22.3g, 0.21 mol) and ytterbium triflate (19.8g, 0.035mol) is added. The reaction mixture is then heated at 27'*C (internal temperature) for 1 day, followed by partitioning between diethyl ether and distilled water. The two phases are separated, the aqueous phase is extracted with diethyl ether (x 2), and then all organic fractions are combined, washed with brine then dried over magnesium sulphate. The suspension is filtered and the filtrate is concentrated in vacuo. The crude material is purified by flash column chromatography (ethyl acetate/hexane eluant) to give an oil which is triturated with hexanes to afford 4-(2',4'-dichloro-4-cyclopropylbiphenyl-3-yl)-2,2,6,6-tetramethylpyran-3,5-dione (2.80g) as a white solid.
1H NMR (CDCI3): 6 7.48 (s. 1H). 7.38 (dd, 1H). 7.29 (s, 2H). 7.16-7.11 (m. 2H). 5.69 (s. 1H), 1.76 (m. 1H), 1.61 (d, 6H), 1.49 (d, 6H), 0.92-0.86 (m. 2H), 0.82-0.76 (m, 1H). 0.62-0.54 (m, 1H).
40

FORMULATION PCAMPLES
Formulation Example 1 - Emulslfiable concentrate (EC) fonnulation of compound A-13 (EC050 formulation)
Ingredient (chemical Role Chemical name Grade Concen-
structure / name or trade tration (g. 1"^)
name)
A Active gQ
rNy^^ P ingredient
"^^^o ^^*^ci
(compound A-13)
Emulsogen EL 360 ™ Emulsifier castor oil 36 moles of 044
ethoxylate ethylene oxide '
Nansa E\/M63/B ™ Emulsifier calcium salt of 63% in 422
dodecyl-benzene isobutanol
sulfonic acid
Acetophenone Solvent ^gj^y,. ^02.9
phenylketone
Solvesso 200 ™ Solvent mixture of heavy ultra low 4^ -, M^^
.. ' . .1. . to 1 tre
aromatic naphthalene
j I hydrocarbons | content |
Reference Fonnulation Example 2 - Emulslfiable concentrate (EC) formulation of reference compound A-4 (EC050 formulation)
Ingredient (chemical Role I Chemical name I Grade I Concen-
structure / name or trade tration (g.l'^)
name)
I Active
o ^-"^ F ingredient
°"^^^0 ^"^**^CI
(reference compound A-4) 50
Emulsifier castor oil 36 moles of
Emulsogen EL 360 ™ ethoxylate ethylene oxide 95
Emulsifier calcium salt of 63 % in
dodecyl-benzene isobutanol
Nansa EVM 63/B ^ | 1 sulfonic acid | | 63.3
41

EmulsifJer tristyrylphenol 16 moles of
Soprophor BSD '"* ethoxylate ethylene oxide 31.7
Solvent /\/-octyl-2-
A/-octyl-2-pyrrolidone pyrrolldone 211.1
2-ethyl-hexanol | Solvent ] 2-ethyl hexanol | | to 1 litre
Emulsifiable concentrate (EC) procedure (used for Formuiation Example 1 and for Reference Formulation Example 2)
The solvent(s) are added to the vessel, followed by the emulsifiers. The mixture is rolled until a clear solution is obtained. The active ingredient is then added, and rolled till a clear solution is obtained.
Formulation Example 3 - Emulsifiable concentrate (EC) formulation containing one of: [compound A-12, A-14, A-15 or A-16]
Formulation Example 3 is a variation of Formulation Example 1 in which, in the emulsifiable concentrate (EC), compound A-13 is replaced with an identical amount of one of: [compound A-12, A-14. A-15 or A-16).
Formulation Example 4 - Emulsifiable concentrate (EC) formulation containing a compound A-13 and a co-herbicide
Formulation Example 4 is a variation of Formulation Example 1 in which, in the emulsifiable concentrate (EC), in addition to compound A-13, there is present oQe co-herbicide selected from the group consisting of fenoxasulfone, ipfencarbazone, and propyrisulfuron, and wherein compound A-13 and the one co-herbicide are present in the following weight ratios:
Formulation Example 4A: weight ratio of compound A-13 to fenoxasulfone is: 60:200, or
90:200, or 120:200, or 240:200.
Formulation Example 4B: weight ratio of compound A-13 to ipfencarbazone is: 60:250, or
90:250, or 120:250; or 240:250.
Formulation Example 4C: weight ratio of compound A-13 to propyrisulfuron is: 60:80, or
90:80, or 120:80. or 240:80.
42

Formulation Example 5 - Emulslfiable concentrate (EC) formulation containing one of: [compound A-12, A-14, A-15 or A-16]; plus a co-herbicide
Formulation Example 5 is a variation of Formulation Example 3 in which, in the emulslfiable concentrate (EC), in addition to one of: [compound A-12, A-14, A-15 or A-16], there is present one co-herbicide selected from the group consisting of fenoxasulfone, ipfencarbazone, and propyrisulfuron, and wherein the one of: [compound A-12, A-14. A-16 or A-16) and the one co-herbicide are present in the following weight ratios:
Formulation Example 5A: weight ratio of [compound A-12, A-14, A-15 or A-161 to
fenoxasulfone is: 60:200, or 90:200, or 120:200, or 240:200.
Formulation Example 5B: weight ratio of compound [compound A-12. A-14, A-15 or A-163 to
ipfencarbazone is: 60:250, or 90:250, or 120:250. or 240:250.
Formulation Example 5C: weight ratio of compound [compound A-12. A-14. A-15 or A-16] to
propyrisulfuron is: 60:80. or 90:80. or 120:80. or 240:80.
Reference Formulation Example 6 - Suspension concentrate (SC) formulation of pyroxasuifone - SCOSO formulation
Ingredient (chemical Role Chemical name Grade Concen-
structure/name or tration (g.r^)
trade name)
Active pyroxasuifone
ingredient
pyroxasuifone (Al) 50
BORRESPERSE NA
™ Dispersant sodium ligninsuifonate 35
RHODOPOL 23 ^ Thickener xanthan gum 3.9
1,2-propylene glycol Antifreeze 1,2-propylene glycol 21
1,2-benzisothiazol-3-
PROXEL GXL ™ Preservative one solution 2.3
tristyrylphenol
ethoxylate, with 16
SOPROPHOR BSU moles of ethylene
^ Dispersant oxide (EO) 3.5
RHODORSIL AF-454
™ Antifoam polydimethylsiloxane 2
Water | carrier | | | Remainder
43

Suspension concentrate (SC) formulation procedure
All the Inert (i.e. non-herbicidal) substances are added to water, and are mixed until homogeneous. Then the active ingredient (here, pyroxasulfone) is added. The mixture is then subjected to high shear mixing to breai^ up very large particles to a size that is suitable for milling. This pre-mix is milled in a bead mill (shaker mill), until the median particle size (O50) reaches less than 5 microns.
44

BIOLOGICAL EXAMPLES
The test plants are grown in a greenhouse, simulating two main groups of rice cropping systems: direct seeded rice and transplanted rice (refer to S. K. De Datta (1981), Principle and Practices of Rice Production, John Wiley, New York for definitions of rice cropping systems). Plant preparation and chemical application are different in the two systems and examples of these are described in more detail in the Biological Examples below.
Biological Example 1 - Method for testing, and results for, mixtures of compounds of formula (I) and co-herbicides in flooded transplanted rice and In flooded Leptochloa chlnensis and Echinochloa crus-galli (test 125)
Rice seeds, variety IR-64 (an indica type of rice), were sown in seed trays. After 7 days the resulting plants were transplanted as 3 groups of 2 plants. Into pots containing a standard sandy loam soil saturated with water replicating swampy conditions. These were grown on for a further 9 days in a glasshouse bay (30/20°C day/night; 18/6 hours light/dark; 75% humidity). Leptochloa chinensis (LEFCH) and Echinochloa crus-galli (ECHCG) were sown as 2 separate groups of approx 10 -- 20 seeds into pots 13 days prior to application of the test substances, in the same glasshouse conditions as the rice. Therefore, each pot of weeds contained a group of LEFCH and a separate group of ECHCG. All pots of rice and all pots of weeds were flooded to 2-3 cm water depth the day prior to application of the test substances. Growth stages at time of application were as follows: Rice: from 2 leaves on the main stem up to tillering; ECHCG: from 2 leaves on the main stem up to tillering; LEFCH: 2-3 leaves.
Test solutions were prepared by mixing the appropriate aliquots of the test substances in deionised water to give the desired treatment concentration. Most of the test substances were used as formulated products. Specifically, compound A-13 was applied as the EC050 formulation disclosed in Formulation Example 1 herein (EC == emulsifiable concentrate). Reference compound A-4 was applied as the EC050 formulation disclosed in Reference Formulation Example 2 herein. Pyroxasulfone (a comparator co-herbicide) was applied as the SC050 formulation disclosed in Reference Formulation Example 6 herein (SC = Suspension concentrate). Imazosulfuron (a comparator co-herbicide) was applied as a GR0.25 formulation (GR = granule).
45

The test substances which were pure active ingredient (e.g. propyrisulfuron & fenoxasulfone & compound A-16) (labelled as Technical' In the following results table), were prepared by dissolving in 10.56% Emulsogen EL ™ (castor oil ethoxylate, CAS Registry number 61791-12-6), 42.22% W-methylpyrrolidone and 42.22% dipropylene glycol mono-ethyl ether to give a stocic solution containing 5% of the test substance and 95% of (Emulsogen EL ™, N-methylpyrrolidone and dipropylene glycol mono-ethyl ether).
Application of the test substances was made by pipetting the required amount of the test solution or the test formulation gently into the flood water of the appropriate pot.
The test plants were then grown on in the same glasshouse conditions, and watered twice daily keeping the flood water at a depth of 2 - 3 cm.
A visual assessment of the % herbicidal damage was made 7 & 14 days after application (DAA), and the results are presented herein as % visual herbicidal damage where 0 = no damage to plants and 100 = total kill.
Biological Example 1 • Results summary table for flooded transplanted rice and flooded ECHCG and LEFCH at 14 days after application (14 DAA) of mixtures of compounds of formula (I) with co-herbicides
compound
Compound of of formula Co- % %
formula (I) Co-herbiclde (I) herbicide damage damage %dam-
(and / mixture partner application application to Rice to age to
formulation) (and formulation) rate(fl/ha) rate(fl/ha) IR-64 ECHCG LEFCH
COMPOUND
A-13
compound
A-13
(EC050
Fomnulation
Example 1) none 60 • ^ 0
compound
A-13 (EC050) none 90 : 6 55 0
compound
A-13 (EC050) none 120 : 5 55 0
compound
A-13 (EC050) I none | 240 1 - | 10 I j
46

compound
A-13
(EC050 imazosulfuron
Formulation (GR0.25
Example 1) fom^ulation) 60 80 60 0
compound imazosulfuron
A-13(EC050) (GR0.25) 90 80 0 50 0
compound imazosulfuron
A-13 (EC050) (GR0.25) 120 80 0 45 0
compound imazosulfuron
A-13(EC050) (GR0.25) 240 80 0
compound
A-13
(EC050 propyrisulfuron
Formulation (TH-547)
Example 1) (Technicail) 60 80 85 0
compound propyrisulfuron
A-13(EC050) (Technical) 90 80 0 85 0
compound propyrisulfuron
A-13 (EC050) (Technical) 120 80 0 W 0
compound propyrisulfuron
A-13(EC050) (Technical) 240 80 5
compound
A-13
(EC050
Fomnulation fenoxasulfone
Example 1) (Technical) 60 200 80 90
compound fenoxasulfone
A-13(EC05O) (Technical) 90 200 5 85 90
compound fenoxasulfone
A-13(EC050) (Technical) 120 200 5 80 95
compound fenoxasulfone
A-13(EC050) (Technical) 240 200 5
COMPOUND
A-16
compound A-16
(Technical) none 60 ;; 40 0
compound A-16
(Technical) none 90 : M ^ 0
compound A-16
(Technical) none 120 - 0 55 0
compound A-16
(Technical) none 240 - 5
REFERENCE
COMPOUND
A-4 1 I I 1 I I
47

r
reference
compound A-4 I I
{EC050 Reference Formulation
Example 2) none 60 : 55 0
reference compound A-4
(EC050) none 90 : 0 85 0
reference compound A-4
(EC050) none 120 : 0 90 20
reference compound A-4
(EC050) none 240 : 10
reference
compound A-4
(EC050
Reference imazosulfuron
Fonnulatton {GR0.25
Example 2) fonnulation) 60 80 65 0
reference
compound A-4 imazosulfuron
(ECOSO) (GR0.2S) 90 80 10 70 0
reference
compound A-4 imazosulfuron
(ECOSO) (GR0.25) 120 80 10 75 0
reference
compound A-4 imazosulfuron
(ECOSO) (GR0.25) 240 80 15
reference
compound A-4
(ECOSO
Reference propyrisulfuron
Fomiulation (TH-547)
Example 2) (Technical) 60 80 85 0
reference
compound A-4 propyrisulfuron
(ECOSO) (Technical) 90 80 5 86 0
reference
compound A-4 propyrisulfuron
(ECOSO) (Technical) 120 80 M 86 0
reference
compound A-4 propyrisulfuron
(ECOSO) (Technical) 240 80 10
reference
compound A-4
(ECOSO
Reference
Fonnulatlon fenoxasulfone
Example 2) (Technical) 60 200 95 95
reference
compound A-4 fenoxasulfone
(ECOSO) I (Technical) I 90 I 200 I 10 I 90 I 95
48

reference
compound A-4 fenoxasulfone
(EC050) (Technical) 120 200 25 99 95
reference
compound A-4 fenoxasulfone
(EC050) (Technical) 240 200 35
CO-
HERBICIDES
ALONE
imazosulfUron
(GR0.25
None fomiulation) ;^ 80 0 50 0
propyrisulfuron
(TH-547)
None (Technical) : 80 0 80 0
pyroxasulfone
(SC050 Reference
Formulation
None Example 6) - 10 45 60 70
fenoxasulfone
None I (Technical) I - I 200 I 10 I 65 I 70
Notes to above results table:
Assessed on a scale of 0 -100% visual herbicidal damage, where 0 = no damage and 100 = total kill.
M = data point missing.
An empty box for % damage to Rice. ECHCG or LEFCH means that that particular mixture was not tested at the specified amounts either against rice or against the weeds. % damage to ECHCG and LEFCH was tested at 60 + 90 + 120 g/ha of compound A-13, A-16 and reference compound A-4. % damage to IR-64 rice was tested at 90 + 120 + 240 g/ha of compound A-13, A-16 and reference compound A-4.
Comments on the results from Biological Example 1
1. Addition of fenoxasulfone to compound A-13 and reference compound A-4 increased the low (0 to 5%) herbicidal activity achieved by compound A-13 (60, 90 or 120 g/ha) or reference compound A-4 (60 or 90 g/ha) alone against LEFCH.
2. Full control of LEFCH was achieved with 200g/ha fenoxasulfone combined with any of: 60, 90 or 120 g/ha of compound A-13 (90, 90 and 95% LEFCH control respectively), or 60, 90 or 120 g/ha of reference compound A-4 (95% LEFCH control at ail three doses). This
49

was a greater level of control of LEFCH than that achieved (70%) with 200g/ha fenoxasulfone applied alone.
3. Good control of ECHCG was achieved with 200g/ha fenoxasulfone combined with any of: 60,90 or 120 g/ha of compound A-13 (80, 85 and 80% ECHCG control respectively), or 60, 90 or 120 g/ha of reference compound A-4 (95, 90 and 99% ECHCG control respectively). This was a greater level of control of ECHCH than that achieved (65%) with 200g/ha fenoxasulfone applied alone. For compound A-13 and fenoxasulfone mixtures, this was also a greater level of control of ECHCH than that achieved (35%, 55% and 55%) with 60,90 or 120 g/ha of compound A-13 applied alone.
4. In some cases. Inclusion of a mixture partner (fenoxasulfone or propyrisuifuron) with compound A-13 or reference compound A-4 improved herbicidal activity against ECHCG without a substantial increase in IR-64 rice damage (phytotoxicity), thus apparently improving the selectivity margin. These cases, with apparently improved IR-64 rice vs. ECHCG selectivity, were: 80g/ha propyrisuifuron with compound A-13 (60, 90 or 120 g/ha) or reference compound A-4 (60g/ha); and also 200g/ha fenoxasulfone with compound A-13 (60, 90 or 120 g/ha) or reference compound A-4 (60g/ha).
5. Mixtures of 200g/ha fenoxasulfone with 60,90 or 120 g/ha of compound A-13 all show good control of ECHCG and LEFCH together with low (5%) phytotoxicity (damage) to IR-64 rice. In comparison, mixtures of 200g/ha fenoxasulfone with 60, 90 or 120 g/ha of reference compound A-4 give higher (10%, 25%, 35% respectively) phytotoxicity (damage) to IR-64 rice. Therefore, mixtures of 200g/ha fenoxasulfone with compound A-13 appear to be more selective herbicides when used on IR-64 transplanted flooded rice than mixtures of 200g/ha fenoxasulfone with reference compound A-4.
6. Mixtures of BOg/ha propyrisuifuron with compound A-13 or reference compound A-4 in general tended to be more efficacious against ECHCG than mixtures of 80g/ha of the comparator co-herbicide imazosulfuron with compound A-13 or reference compound A-4.
7. Compound A-13 generally showed very low phytotoxicity (damage) to IR-64 transplanted flooded rice, either when used alone or with the tested mixtures with imazosulfuron, propyrisuifuron or fenoxasulfone. In comparison, mixtures of reference compound A-4 with imazosulfuron or fenoxasulfone tend to show higher phytotoxicity to rice especially at higher application rates of compound A-4.
Biological Example 2 - Evaluation of the selectivity margin of compound A-13 alone in transplanted rice (test 109)
50

Rice seeds, variety iR-64, were sown in seed trays, after 7 days they were transplanted as 3
groups of 2 plants, into pots containing a standard sandy loam soil saturated with water
replicating swampy conditions. Ttiese were grown on for 9 days in a glasshouse bay (
30/20"*C day/night; 18^ hours light/dark; 75% humidity). Approx 10-20 seeds of
Echinochloa crus-galliwere sown into pots 13 days prior to application, in the same
conditions as the rice. All pots were flooded to 2-3 cm water depth the day prior to
application. Growth stages at time of application were: Rice: 2-3 leaves, ECHCG: 2-3
leaves.
The test solutions were prepared by mixing the appropriate aliquots of the test substance
(here, compound A-13 as the EC050 Formulation Example 1 disclosed herein) in de-ionised
water to give the desired treatment concentration.
Application was made by pipetting the required amount of the test solution gently into the
flood water of the appropriate pot.
The test plants were grown on in the same glasshouse conditions, and watered twice daily
keeping the flood water at a depth of 2 -■ 3cm.
A visual assessment of the % herbicidal damage was made 14 days after application (0 = no
damage to plants, 100 = total kill).
Biological Example 2 - Results - compound A-13 at 14 days after application
Application
Treatment Rate (gorio rice: from 3 leaves on
the main stem to tillering; ECHCG: at two different leaf stages: 0 ~ 0.5 leaf and 2-3 leaf;
LEFCH: 3 leaf. Glasshouse bay conditions were 30/20°C day/night; 18/6 hours light/dark;
75% humidity.
The test solutions were prepared by mixing the appropriate aliquots of the test substance
(here, compound A-13 as EC050 Formulation Example 1) and adjuvant (0.2% Adsee as
adjuvant) in de-ionised water to give the desired treatment concentration.
Application was as a foliar spray, made using a tracksprayer. 3 days after application the
trays were flooded to 2-3cm water depth, and maintained at this level for the duration of the
test.
No. of repetitons: 1 test only.
A visual assessment of the % herbicidal damage was made 14 days after application (0 = no
damage to plants, 100 = total kill).
Dry seeded rice (DSR) growing method
Echinochloa colona (ECHCO) seeds were sown in seed trays containing a standard sandy
loam soil. They were sown at intervals to achieve plants at 0 - 0.5 leaf and 2-3 leaves at the
time of application. Irrigation occurred to maintain the soil at moist but not saturated
conditions. Glasshouse bay conditions were 30/20°C day/night; 18/6 hours light/dark; 75%
humidity.
The test solutions were prepared by mixing the appropriate aliquots of the test substance
(here, compound A-13 as EC050 Formulation Example 1) and adjuvant (0.2% Adsee as
adjuvant) in de-ionised water to give the desired treatment concentration.
Application was as a foliar spray, made using a tracksprayer.
The test plants were grown on in the same glasshouse conditions, and watered to maintain
moist conditions.
No. of repetitons: 1 test only.
A visual assessment of the % herbicidal damage was made 14 days after application (0 = no
damage to plants, 100 = total kill).
54

Biological Example 4 - Results
I Trans- I I I WSR I I j I i j I
planted / DSR
Appli- appli-
cation Trans- Trans- cation
rates planted planted rates WSR WSR WSR WSR WSR DSR DSR
Com-pound
(and Appl. Rice Appl. Rice ECH- ECH- ECH-
formu- Rate Koshi- ECH- Rate Rice Arb- ECH- CG LEF- CO CO
latlon) (q/ha) hikari CG (g/ha) IR-64 orio CG 3lf 0.5lf CH 3lf D.SIf
Com¬
pound
A-13
(EC050
Fomu-
lation
Ex¬
ample
1) 30 M 0 B 0 0 65 45 10 85 0
60 IS 20 60 0 0 100 90 10 100 90
125 20 75 125 5 0 100 100 65 100 90
I 500 I 60 I 99 I 500 I 35 I 60 I 100 | 100 j 75 | 100 | 90
M = missed data point
Comments on Biological Example 4
Transplanted rice: There was a certain selectivity margin between rice and ECIHCG at 125g/ha of coinpounci A-13.
Wet seeded rice: ECHCG at 2 different growth stages, 0.5 leaf and 3 leaf, was controlled (90-100%) with 60 and 125 g/ha of compound A-13 with little or no (0 to 5%) damage to the 2 varieties of rice tested (IR-64 and Arborio). Thus, there appeared to be a good selectivity margin between rice and ECHCG. There was good activity (65%) but not complete control of LEFCH at 125g/ha of compound A-13, again with minimal rice damage.
Dry seeded rice: ECHCG at 2 different growth stages, 0.5 leaf and 3 leaf, was controlled with 60 and 125 g/ha of compound A-13. Rice data was not obtained due to poor growth of untreated units, thus the extent of any selectivity margin could not be determined.
55

Biological Example 5 -> Generalised methods for testing mixtures of compounds of formula (I) and co-herbicides in or direct seeded rice systems or transplanted rice systems
For the direct seeded system, monocotyledonous and/or dicotyledonous test weeds and/or rice plants (indica and/or japonica varieties) are sown in troughs aA different intervals before the chemical application depending on the species and the desired growth stages required for the test (typically around 2 weeks). The plants so prepared are used to simulate a post-emergence application. Moreover, in order to simulate also a pre-emergence application, the same species plants are sown 1 or 2 days before the chemical applications. After application, the troughs are flooded at different intervals to simulate wet and dry seeded flooded rice systems.
The chemical application for direct seeded rice systems consists of spraying the plants with an aqueous spray solution derived from the formulation of the technical active ingredient in 0.6 ml acetone and 45 ml formulation solution containing 10.6% Emulsogen EL ™ (castor oil ethoxylate, Registry number 61791-12-6), 42.2% W-methyl pyrrolidone, 42.2% dipropylene glycol monomethyi ether (Registry number 34590-94-8) and 0.2 % X-77 (Registry number 11097-66-8).
The plants included in the tests in direct seeded are Echinochloa crus-galli (ECHCG) at two growth stages(GS), 0 and 12-13 using 6BCH scale, Leptochloa chinensis (LEFCiH) at GS 12-13. Brachiaria spp at GS 12-13; Commelina spp at GS 12-13, Cyperus spp at GS 12-13 and Monochoria vaginalis (IWOOVA) at GS 12-13 and other grasses; varieties of japonica and indica rice (for example, rice variety IR-64 (an indica rice) or Arborio) are included as well.
To simulate transplanted rice systems, monocotyledonous and dicotyledonous test weeds are sown following the same procedures as for the direct seeded rice system. The rice plants are initially grown in nursery trays until they reach the growth stage (GS) of 12-13 (using the BBCH scale), then they are transplanted in the same troughs alongside the previously sown weeds. After transplanting, the troughs are flooded. The chemical treatment is performed between 4 to 9 days after the transplantation (DAT) of rice. The chemical Is applied as a 10 ml aliquot of chemical solution formulated as for the direct seeded system in each trough.
56

The plants included in the tests in transplanted system are Echincxhioa spp at two growth stages (0 and 12-13 BBCH scale); Cyperus spp at GS 12-13 and Monochoria vaginalis (MOOVA).
The test plants are grown in a greenhouse under optimum conditions for 21 days after application (DM) of chemical. The test is evaluated at 14 and 21 DM. The assessment consists of evaluating the visual damage of treated plants compared to an untreated control. The severity of damage is expressed using a 0-100 scale (0 = no damage to plant; 100 = plants were killed).
57

CLAIMS:
1. A method of controlling weeds in crops of rice, which comprises applying compound
A-13, whose structure is ' ^ and which can alternatively or
additionally be present as ' ^ , to the plants or to the locus thereof.
2. A method as claimed in claim 1, wherein the weeds comprise Echinochloa and^or Leptochloa.
3. A method as claimed in claim 1 or 2, wherein the rice is flooded rice.
4. A method as claimed in claim 3, wherein the rice is transplanted flooded rice.
5. A method as claimed in claim 1, 2, 3 or 4, wherein an application rate of 80 to 200 g/ha of the compound A-13 is used.
6. A method of controlling Echinochloa weeds and/or Leptochloa weeds in ca-ops of useful plants, which comprises applying compound A-13, whose structure is
"^o^Sr^ F
^ ^ and which can alternatively or additionally be present
as ' ^ , to the plants or to the locus thereof.
58

7. A method as claimed in claim 6, wherein the Echinochloa weeds and/or Leptochloa weeds are flooded.
8. A method as claimed in claim 6 or 7, wherein the weeds to be controlled comprise Echinochloa crus-galli, Echinochloa oryzoides, Echinochloa colona orcolonum, Echinochloa crus-pavonis, Echinochloa oryzicola, Echinochloa muricata, Echinochloa stagnina, Leptochloa chinensis and/or Leptochloa panicoides.
9. A herbicidal composition comprising as active ingredient a mixture of: a) a herbicidaiiy effective amount of a compound of formula (I)
^ ^ (I).
wherein:
R^ is cyclopropyl,
R^ is phenyl or phenyl substituted by C1-C4 alkyl, CrC4 haloalkyi, C1-C4 alkoxy, C1-C4
haloalkoxy or halogen,
R^, R*, R^ and R^, independently of each other, are hydrogen or C1-C4 alkyl,
Y is O, and
G is hydrogen, an alkali metal, alkaline earth metal, sulfonium, or ammonium, or G is a
latentiating group which is C(0)-R'' or CCO-O-R";
wherein R' is H, Ci-Cisalkyl. Ca-Ciealkenyl, Cz-Cisalkynyl, Ci-CiohaloalkyI, Ci-Ciocyanoalkyl, Ci-CionitroalkyI, CrCioaminoalkyI, Ci-CsalkylaminoCi-CsalkyI, C2-C8dialkylaminoCi-C5alkyl, Ca-CycycloalkylCi-CsalkyI, Ci-CsalkoxyCi-CsalkyI, Cs-CsalkenyloxyCrCsalkyl. C3-CjalkynyloxyCi-Csalkyl, Ci-CsalkylthioCi-Csalkyl. Ci-CsalkylsulfinylCi-CsalkyI, Ci-CsalkylsulfonylCi-Csalkyl, Cz-CsalkylideneaminoxyCrCsalkyl, CrCsalkylcarbonylCi-CsalkyI, Ci-CsalkoxycarbonylCi-CsalkyI, aminocarbonylCi-CsalkyI, Ci-CsalkylaminocarbonylCr Csalkyl, C2-C8dialkylaminocarbonylCi-C5alkyl, Ci-CsalkylcarbonylaminoCi-Cgalkyl, N-Cr
59

Csalkylcarbonyl-W-Ci-CsalkylaminoCi-Csalkyl, Ca-CetrialkylsilylCi-Csalkyl, phenylCi-Cjalkyl (wherein the phenyl is optionally substituted by d-Csalkyl, Ci-CahaloalkyI, Ci-Caalkoxy, Ci-Cshaloalkoxy, Ct-Csalkyithio, CrCsalkylsulfinyi, CrCsalkylsuifonyi, halogen, cyano, or by nitre), heteroaryiCi-CsalkyI (wherein the heteroaryl is optionally substituted by Ci-CsalkyI, Ci-Cahaioalkyl, Ci-Caalkoxy, Ci-Cahaloalkoxy, Ci-Csalkylthio, Ci-Csalkylsulfinyl, C,-Caalkylsulfonyl, halogen, cyano, or by nitro), C2-C6haloalkenyl, Cs-CscycloalkyI, phenyl or phenyl substituted by Ci-CaalkyI, Ci-CshaloalkyI, CrCjalkoxy, CrCshaloaikoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by Ci-CaalkyI, Ci-CahaloalkyI, d-Csalkoxy, Ci-Cshaloalkoxy, halogen, cyano or nitro; and
R"* is Ci-CfaalkyI, Ca-Cisalkenyl, Ca-Cisalkynyl, Cz-CiohaloalkyI, Ci-Cfocyanoalkyl, Ci-Cionitroalkyl, Ca-CioaminoalkyI, Ci-CsalkylaminoCi-CsalkyI, Cz-CsdialkylaminoCrCsalkyl, C3-CrcycloalkylCi-Csalkyl. Ci-CsalkoxyCi-CsalkyI, Ca-CgalkenyioxyCi-Csalkyl, Cj-CsalkynyloxyCi-Csalkyl, d-CsalkylthioCi-Csalkyl, Ci-CsalkylsulfinylCi-Csalkyl. Ci-CsalkylsulfonylCrCsalkyl, CrCBalkylideneaminoxyCi-CsalkyI, d-CsaikylcarbonylCi-Csaikyl, Ci-CsalkoxycarbonylCi-CsalkyI, aminocarbonylCi-Csalkyi, Ci-CsaikylaminocarbonylCi-Csalkyl, d-Cedialkylaminocarbonyld-Csalkyl, Ci-Csalkylcarbonylaminod-CsalkyI, A'-Ci-Csalkylcarbonyl-AZ-d-CsalkylaminoCi-dalkyl, Cs-dtrialkylsiiylCi-Csaikyl, phenylCi-Csalkyl (wherein the phenyl is optionally substituted by d-dalkyl, Ci-CahaioalkyI, d-Cjalkoxy, Ci-Cahaloalkoxy, Crdalkylthio, Ci-Caalkylsulfinyl, d-dalkylsulfonyl, halogen, cyano, or by nitro), heteroarylCi-Csalkyl (wherein the heteroaryl is optionally substituted by Crdalkyl, d-Cahaloalkyl, d-Caalkoxy, Ci-dhaloalkoxy. Ci-Caalkylthio, Ci-Caalkylsulfinyl, C,-Caalkylsulfonyl, halogen, cyano, or by nitro), Cs-Cshaloalkenyl, d-dcycloalkyi, phenyl or phenyl substituted by d-CsalkyI, Ci-CahaloalkyI, Ci-Caalkoxy, Ci-Cshaloalkoxy, halogen, cyano or nitro, heteroaryl or heteroaryl substituted by Ci-CjalkyI, CrCahaloalkyI, d-Caalkoxy, CrCshaloalkoxy, halogen, cyano or nitro;
and
b) a co-herbicide selected from the group consisting of fenoxasulfone, ipfencarbazone, propyrisulfuron, and /V-[2-I(4,6-dimethoxy-1,3,5-tr(a2in-2-yl)carbonyl]-6-fluorophenyl]-1.1 -difluoro-W-methylmethanesulfonamide.
60

10. A herbicJdal composition as claimed in claim 9, wherein R^ is phenyl substituted by fluorine or chlorine.
11. A herbicidal composition as claimed in claim 9 or 10, wherein R*. R*. R* and R' are methyl.
12. A herbicidal composition as claimed in claim 9,10 or 11, wherein G is hydrogen, C(0)-R'' or C(0)-0-R''; wherein R" and R" are C-Cealkyl.
13. A herbicidal composition as claimed in claim 12, wherein G is hydrogen.
14. A herbicidal composition as claimed in any one of claims 9 to 13, wherein the compound of formula (I) is:
' ^ (compound A-12, which can alternatively or additionally be present as
"V^o ^'■^'^^ci
"V^o ^■*^*^ci
' ^ {compound A-13, which can alternatively or additionally be present as
"V'^o ^^'^^^ci
61

V^o ^^^ CI A^° ^•^^ CI
'^ (compound A-14), '^ (compound A-15), or
^r^o ^^'^''^ci
' ^ (compound A-16, which can alternatively or additionally be present as
15. A herblcidal composition as claimed in claim 14, wherein the compound of formula (I) is compound A-12 or A-13.
16. A herbicidal composition as claimed in claim 14, wherein the compound of formula (I) is compound A-13.
17. A herbicidal composition as claimed in any one of claims 9 to 16, wherein the co-herbicide is fenoxasulfone or ipfencarbazone.
18. A herbicidal composition as claimed in any one of claims 9 to 16, wherein the co-herbicide is fenoxasulfone.
19. A herbicidal composHion as claimed in any one of claims 9 to 16, wherein the co-herbicide is ipfencarbazone.
20. A herbicidal composition as claimed in any one of claims 9 to 16, wherein the co-herbicide is propyrisulfuron.
21. A herbicidal composition as claimed in any one of claims 9 to 16, wherein the co-herbicide is A/-[2-[(4,6-dimethoxy-1,3,5-tria2in-2-yl)carbonyl]-6-fluorophenyl]-1 .l-difluoro-ZV-methylmethanesulfonamide.
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22. A herbicidal composition as claimed in claim 18, wherein the compound of formula (I) i$ compound A-13, and the co-herbicide is fenoxasulfone.
23. A herbicidal composition as claimed in any one of claims 9 to 18 or 22, wherein the weight ratio of the compound of formula (I) to the fenoxasulfone is from 1:6 to 3:2.
24. A herbicidal composition as claimed in any claim 23, wherein the weight ratio of the compound of formula (I) to the fenoxasulfone is from 3:10 to 7:10.
25. A herbicidal composition as claimed in any claim 24, wherein the weight ratio of the compound of formula (I) to the fenoxasulfone is from 2:5 to 7:10.
26. A herbicidal composition as claimed in any claim 25, wherein the weight ratio of the compound of formula (I) to the fenoxasulfone is from 1:2 to 7:10.
27. A herbicidal composition as claimed in any one of claims 9 to 17, or 19, wherein the co-herbicide is ipfencarbazone, and wherein the weight ratio of the compound of formula (1) to the ipfencarbazone Is from 1:7 to 1:1.
28. A herbicidal composition as claimed in any one of claims 9 to 16, or 20, wherein the co-herbidde is propyrisulfuron, and wherein the weight ratio of the compound of formula (I) to the propyrisulfuron is from 1:2 to 3:1.
29. A herbicidal composition as claimed in claim 28, wherein the weight ratio of the compound of formula (I) to the propyrisulfuron is from 3:4 to 3:2.
30. A herbicidal composition as claimed in any one of claims 9 to 29, which is a formulation comprising a earner, a solvent and/or a surface-active substance.
31. A herbicidal composition as claimed in claim 30, wherein the formulation is in the form of a wettable powder, a water-dispersible granule, an emulsifiable concentrate, a micro-emulsifiable concentrate, an oil-in-water emulsion, an oil flowable, an aqueous dispersion, an oily dispersion, a soluble liquid, or a water-soluble concentrate wherein the water-soluble concentrate is with water or a water-miscible organic solvent as carrier.
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32. A herbicida) composition as claimed in claim 31, wherein the formulation is in the form of an emulsifiable concentrate.
33. A herbicidal composition as claimed in any one of the preceding claims, comprising c) a safener and, optionally, d) an oil additive.
34. A herbicidal composition as claimed in any one of claims 9 to 33, which is for controlling grasses and weeds in crops of useful plants.
35. A herbicidal composition as claimed in claim 34, which is for controlling grasses and weeds in crops of rice.
36. A method of controlling grasses and weeds In crops of useful plants, which comprises applying a herbicidal composition as defined in any one of claims 9 to 35 to the plants or to the locus thereof.
37. A method as claimed in claim 36, wherein the crops of useful plants are crops of rice.
38. A method as claimed in claim 37, wherein the crops of useful plants are crops of flooded transplanted rice.
39. A method as claimed in claim 36, 37 or 38, wherein the grasses and weeds controlled comprise Echinochloa and/or Leptochloa.
40. A method as claimed in claim 36, 37, 38 or 39, wherein the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 30 to 240 g of the compound of formula (I) per hectare, calculated as the weight of the compound of formula (I) excluding the weight of any optional counterions thereof.
41. A method as claimed in claim 40, wherein the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 50 to 150 g of the compound of formula (I) per hectare, calculated as the weight of the compound of formula (I) excluding the weight of any optional counterions thereof.
42. A method as claimed in claim 36, 37,38. 39,40 or 41, wherein the co-herbicide is fenoxasulfone, ipfencarbazone, or propyrisulfuron; and
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- Vh4ien the co-herbicide is fenoxasulfone, then the herbicidal composition is applied to the
plants or to the locus thereof at an application rate of 100 to 400 g of fenoxasulfone per
hectare, calculated as the weight of fenoxasulfone excluding the weight of any optional
counterions thereof; and
• when the co-herbicide is ipfencarbazone, then the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 100 to 500 g of ipfencarbazone per hectare, calculated as the weight of ipfencarbazone excluding the weight of any optional counterions thereof; and
- when the co-herbicide is propyrisuifuron, then the herbicidal composition is applied to the
plants or to the locus thereof at an application rate of 40 to 160 g of propyrisuifuron per
hectare, calculated as the weight of propyrisuifuron excluding the weight of any optional
counterions thereof.
43. A method as claimed in claim 42, wherein the co-herbicide is fenoxasulfone,
ipfencarbazone, or propyrisuifuron; and
- when the co-herbicide is fenoxasulfone, then the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 200 g of fenoxasulfone per hectare, calculated as the weight of fenoxasulfone excluding the weight of any optional counterions thereof; and
- when the co-herbicide is ipfencarbazone, then the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 250 g of ipfencarbazone per hectare, calculated as the weight of ipfencarbazone excluding the weight of any optional counterions thereof; and
- when the co-herbicide is propyrisuifuron, then the herbicidal composition is applied to the plants or to the locus thereof at an application rate of 80 g of propyrisuifuron per hectare, calculated as the weight of propyrisuifuron excluding the weight of any optional counterions thereof.
44. A herbicidal composition comprising
(a) a compound A-13, whose structure is '^ and which can
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alternatively or additionally be present as ' ^ , and
(b) a carrier, a solvent and/or a surface-active substance.
45. A herbicidal composition as claimed in claim 44 containing:
(a) from 0.1 to 99 % by weight of a compound of formula (I); and
(b) from 1 to 99.9 % by weight of a formulation adjuvant or formulation adjuvants.
46. A herbicidal composition as claimed in claim 45 containing:
(a) from 0.5 to 60 % by weight of a compound of formula (I); and
(b) from 40 to 99.5% by weight of a formulation adjuvant or formulation adjuvants.
47. A herbicidal composition as claimed in claim 46 containing:
(a) from 0.5 to 60 % by weight of a compound of formula (I); and
(b) a total of from 40 to 99.5%, by weight of the herbicidal composition, of: any carrier (if present), any solvent (if present), any surface-active substance (if present), and any other formulation adjuvant(s) present.

48. A herbicidal composition as claimed in claim 45,46 or 47, wherein the formulation adjuvant or formulation adjuvants include from 1 to 25 % by weight of a surface-active substance.
49. A herbicidal composition as claimed in claim 44,45,46, 47 or 48, which is a formulation in the form of a wettable powder, a water-dispersible granule, an emutsifiable concentrate, a microemulsifiable concentrate, an oN-in-water emulsion, an oil flowable, an aqueous dispersion, an oily dispersion, a soluble liquid, or a water-soluble concentrate wherein the water-soluble concentrate is with water or a water-miscible organic solvent as carrier.
50. A herbicidal composition as claimed in claim 49, wherein the formulation is in the form of an emulsifiable concentrate.
Dated this 05* day of June 2012 U)V^
gg Of Anana and Anand Advocates
Agents for the Applicant