The present invention relates to novel herbicidal pyridazinone derivatives, to
processes for their preparation, to compositions which comprise the herbicidal
compounds, and to their use for controlling weeds, in particular in crops of useful
plants, or for inhibiting plant growth. Herbicidal pyridine derivatives are known, for
example, from EP1982978 and pyrimidone derivatives from WO201 1/03 1658. It has
now been discovered that pyridazinone derivatives exhibit advantageous herbicidal
properties.
Thus, according to the present invention there is provided a herbicidal
compound of Formula (I):
or an agronomically acceptable salt of said compound, wherein:-
R1 is selected from the group consisting of hydrogen, Ci-C 6alkyl, Ci-C 6haloalkyl, Ci-
C3alkoxy-Ci-C3 alkyl, C1-C3 alkoxy-Ci-C 3alkoxy-Ci-C3-alkyl, Ci-C 3alkoxy-Ci-C3-
haloalkyl, Ci-C3-alkoxy-Ci-C3-alkoxy-Ci-C3-haloalkyl, C4-C6 -oxasubstituted
cycloalkoxy-Ci-C3 -alkyl, C4-C6 -oxasubstituted cycloalkyl-Ci-C3-alkoxy-Ci-C3-alkyl,
C4-C6 -oxasubstituted cycloalkoxy-Ci-C3 -haloalkyl, C4-C6 -oxasubstituted cycloalkyl-
Ci-C3-alkoxy-Ci-C3-haloalkyl, (C1-C3 alkanesulfonyl-Ci-C3 alkylamino)-Ci-C3 alkyl,
(C1-C3 alkanesulfonyl-C3-C4 cycloalkylamino)-Ci-C 3alkyl, Ci-Cealkylcarbonyl-CiCsalkyl,
C3-C6Cycloalkyl-C2-Cealkenyl, C2-C6alkynyl, C2-C6-alkenyl, C2-C6-
haloalkenyl, cyano-Ci-C 6-alkyl, arylcarbonyl-Ci-C 3-alkyl (wherein the aryl may be
optionally substituted with one or more substituents from the group consisting of halo,
Ci-C3-alkoxy, Ci-C3-alkyl, Ci-C3 haloalkyl), aryl-Ci-C 6alkyl, aryloxy-Ci-Cealkyl
(wherein both cases the aryl may be optionally substituted with one or more
substituents from the group consisting of halo, Ci-C3-alkoxy, Ci-C3-alkyl, Ci-C3
haloalkyl), and a three- to ten-membered mono- or bicyclic ring system, which may
be aromatic, saturated or partially saturated and can contain from 1 to 4 heteroatoms
each independently selected from the group consisting of nitrogen, oxygen and
sulphur the ring system being optionally substituted by one or more substituents
selected from the group consisting of Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3alkenyl, Ci-
C3alkynyl, Ci-C3 alkoxy, Ci-C3 haloalkoxy, Ci-C6alkyl-S(0)p-, Ci-C6haloalkyl-
S(0)p-, aryl, aryl-S(0)p, heteroaryl-S(0)p, aryloxy, heteroaryloxy, Ci-C3
alkoxycarbonyl, Ci-C3 alkylamino-S(0)p-, Ci-C3 alkylamino-S(0)p-Ci-C 3 alkyl, Ci-
C3 dialkylamino-S(0)p-, Ci-C3 dialkylamino-S(0)p-Ci-C 3 alkyl, Ci-C3
alkylaminocarbonyl-, Ci-C3 alkylaminocarbonyl-Ci-C 3 alkyl, Ci-C3
dialkylaminocarbonyl, Ci-C3 dialkylaminocarbonyl-Ci-C 3 alkyl, Ci-C3
alkylcarbonylamino, Ci-C3 alkyl-S(0)p-amino, cyano and nitro; the heteroaryl
substituents containing one to three heteroatoms each independently selected from the
group consisting of oxygen, nitrogen and sulphur, and wherein the aryl or heteroaryl
component may be optionally substituted by one or more substituents selected from
the group consisting of halo, Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3 alkoxy, Ci-C3
haloalkoxy, phenyl, cyano and nitro;
R2 is selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-
C6alkyl, C3-Cecycloalkyl, C2-C6-alkenyl, C2-C6alkynyl, Ci-C6haloalkyl, Ci-C6alkoxy,
Ci-C3haloalkoxy, Ci-C6alkoxy-Ci-C 3 alkyl, Ci-C6alkyl-S(0)p- and Ci-C6haloalkyl-
S(0)p-;
p = 0, 1 or 2;
A1 is selected from the group consisting of O, C(O) and (CReRf) ; and
Ra, Rb, R , Rd, Re and Rf are each independently selected from the group consisting of
hydrogen and Ci-C4alkyl wherein Ra and R may together form a Ci-C3alkylene
chain.
Halogen encompasses fluorine, chlorine, bromine or iodine. The same
correspondingly applies to halogen in the context of other definitions, such as
haloalkyl or halophenyl.
Haloalkyl groups having a chain length of from 1 to 6 carbon atoms are, for
example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,
dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl,
pentafluoroethyl, l,l-difluoro-2,2,2-trichloroethyl, 2,2,3, 3-tetrafluoroethyl and 2,2,2-
trichloroethyl, heptafluoro-n-propyl and perfluoro-n-hexyl.
Suitable alkylenyl radicals include, for example CH2, CHCH3, C(CH3)2,
CH2CHCH3, CH2CH(C2H ) .
Suitable haloalkenyl radicals include alkenyl groups substituted one or more
times by halogen, halogen being fluorine, chlorine, bromine or iodine and especially
fluorine or chlorine, for example 2,2-difluoro-l-methylvinyl, 3-fluoropropenyl, 3-
chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl
and 4,4,4-trifluorobut-2-en-l-yl. Preferred C2-C6alkenyl radicals substituted once,
twice or three times by halogen are those having a chain length of from 2 to 5 carbon
atoms. Suitable haloalkylalkynyl radicals include, for example, alkylalkynyl groups
substituted one or more times by halogen, halogen being bromine or iodine and,
especially, fluorine or chlorine, for example 3-fluoropropynyl, 5-chloropent-2-yn-l-yl,
5-bromopent-2-yn-l-yl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-l-yl.
Preferred alkylalkynyl groups substituted one or more times by halogen are those
having a chain length of from 3 to 5 carbon atoms.
Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms.
Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy,
sec-butoxy or tert-butoxy or a pentyloxy or hexyloxy isomer, preferably methoxy and
ethoxy. Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for
example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl,
n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl,
preferably methoxycarbonyl, ethoxycarbonyl or tert-butoxycarbonyl.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy,
trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-
chloroethoxy, 2,2-difluoroethoxy or 2,2,2-trichloroethoxy, preferably
difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.
Alkylthio groups preferably have a chain length of from 1 to 6 carbon atoms.
Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio,
isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.
Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl,
isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tertbutylsulfinyl,
preferably methylsulfinyl or ethylsulfinyl.
Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl,
isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tertbutylsulfonyl,
preferably methylsulfonyl or ethylsulfonyl.
Alkylamino is, for example, methylamino, ethylamino, n-propylamino,
isopropylamino or a butylamino isomer. Dialkylamino is, for example, dimethylamino,
methylethylamino, diethylamino, n-propylmethylamino, dibutylamino or
diisopropylamino. Preference is given to alkylamino groups having a chain length of
from 1 to 4 carbon atoms.
Cycloalkylamino or dicycloalkylamino is for example cyclohexylamino or
dicyclopropylamino.
Alkoxyalkyl groups preferably have from 1 to 6 carbon atoms. Alkoxyalkyl is,
for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, npropoxymethyl,
n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
Alkylthioalkyl groups preferably have from 1 to 6 carbon atoms.
Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl,
ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl,
isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.
Three- to ten-membered mono- or bicyclic ring system may be aromatic,
saturated or partially saturated and can contain from 1 to 4 heteroatoms each
independently selected from the group consisting of nitrogen, oxygen and sulphur the
ring system being optionally substituted by one or more substituents independently
selected from the group consisting of Ci-C 3alkyl, Ci-C 3haloalkyl, Ci-C 3alkenyl, Ci-
C3alkynyl, C1-C3 alkoxy, Ci-C 3 haloalkoxy, Ci-C 6alkyl-S(0)p-, Ci-C 6haloalkyl-
S(0)p-, aryl, aryl-S(0)p, heteroaryl-S(0)p, aryloxy, heteroaryloxy, Ci-C 3
alkoxycarbonyl, Ci-C 3 alkylamino-S(0)p-, Ci-C 3 alkylamino-S(0)p-Ci-C 3 alkyl, Ci-
C3 dialkylamino-S(0)p-, Ci-C 3 dialkylamino-S(0)p-Ci-C 3 alkyl, Ci-C 3
alkylaminocarbonyl-, Ci-C 3 alkylaminocarbonyl-Ci-C 3 alkyl, Ci-C 3
dialkylaminocarbonyl, Ci-C 3 dialkylaminocarbonyl-Ci-C 3 alkyl, Ci-C 3
alkylcarbonylamino, Ci-C 3 alkyl-S(0)p-amino, cyano and nitro. Such ring systems
thus include, for example, cycloalkyl, phenyl, heterocyclyl and heteroaryl. Examples
of "partially saturated" rings include, for example, 1,4 benzodioxin and 1,3
benzodioxole.
Cycloalkyl groups preferably have from 3 to 6 ring carbon atoms and may be
substituted by one or more methyl groups; they are preferably unsubstituted, for
example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Aryl includes benzyl, phenyl, including phenyl as part of a substituent such as
phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl or tosyl,
may be in mono- or poly-substituted form, in which case the substituents may, as
desired, be in the ortho-, meta- and/or para-position(s).
Heterocyclyl, for example, includes morpholinyl, tetrahydrofuryl.
Heteroaryl, including heteroaryl as part of a substituent such as heteroaryloxy,
means, for example, a five or six member heteroaryl containing one to three
heteroatoms, each independently selected from the group consisting of oxygen,
nitrogen and sulphur. It should be understood that the heteroaryl component may be
optionally mono or poly substituted. The term heteroaryl thus includes, for example,
furanyl, thiophenyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyrazolyl, isothiazolyl,
pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl and triazolyl.
Compounds of Formula I may contain asymmetric centres and may be present
as a single enantiomer, pairs of enantiomers in any proportion or, where more than
one asymmetric centre are present, contain diastereoisomers in all possible ratios.
Typically one of the enantiomers has enhanced biological activity compared to the
other possibilities.
Similarly, where there are disubstituted alkenes, these may be present in E or
Z form or as mixtures of both in any proportion.
Furthermore, compounds of Formula I may be in equilibrium with alternative
hydroxyl tautomeric forms. It should be appreciated that all tautomeric forms (single
tautomer or mixtures thereof), racemic mixtures and single isomers are included
within the scope of the present invention.
In one embodiment R1 is selected from the group consisting of hydrogen, Ci-
C6alkyl, Ci-C6haloalkyl, Ci-C3alkoxyCi.C3alkyl, Ci-C3alkoxy C2-C3alkoxyCi.C3alkyl,
Ci-C6haloalkyl, C2-C6haloalkenyl and Ci-C3alkoxy-Ci.C3haloalkyl.
In another preferred embodiment R1 is aryl, preferably phenyl, or a 5 or 6-
membered heteroaryl containing one to three heteroatoms each independently selected
from the group consisting of oxygen, nitrogen and sulphur, and wherein the aryl or
heteroaryl may be optionally substituted by one or more substituents selected from the
group consisting of halo, Ci-C3alkyl, Ci-Cshaloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy,
Ci-C6alkyl-S(0)p-, Ci-C6haloalkyl-S(0)p-, cyano and nitro. Especially preferred is
wherein R1 is an optionally substituted aryl selected from the group consisting of
phenyl, phenoxy, phenoxy-Ci-Cealkyl, benzyl, thiophenyl, 1,4 benzodioxinyl, 1,3
benzodioxoleyl and pyridyl, most preferably an optionally substituted phenyl or
pyridyl.
In another preferred embodiment R2 is selected from the group consisting of
hydrogen, CVG, alkyl (preferably methyl), halogen (preferably chlorine), C2-C
alkoxy (preferably methoxy), Ci-Ce haloalkyl (preferably CF3) and CN. In a more
preferred embodiment R2 is hydrogen of methyl.
In another embodiment A1 is CReRf and wherein Ra, Rb, R , Rd, Re and Rf are
hydrogen. In another embodiment of the present invention A1 is CReRf, wherein Rb,
Rd, Re and Rf are hydrogen, Ra and R together form an ethylene chain.
The present invention also includes agronomically acceptable salts that the
compounds of Formula I may form with amines (for example ammonia,
dimethylamine and triethylamine), alkali metal and alkaline earth metal bases or
quaternary ammonium bases. Among the alkali metal and alkaline earth metal
hydroxides, oxides, alkoxides and hydrogen carbonates and carbonates used as salt
formers, emphasis is to be given to the hydroxides, alkoxides, oxides and carbonates
of lithium, sodium, potassium, magnesium and calcium, but especially those of
sodium, magnesium and calcium. The corresponding trimethylsulfonium salt may also
be used.
The compounds of Formula (I) according to the invention can be used as
herbicides by themselves, but they are generally formulated into herbicidal
compositions using formulation adjuvants, such as carriers, solvents and surfaceactive
agents (SFAs). Thus, the present invention further provides a herbicidal
composition comprising a herbicidal compound according to any one of the previous
claims and an agriculturally acceptable formulation adjuvant. The composition can be
in the form of concentrates which are diluted prior to use, although ready-to-use
compositions can also be made. The final dilution is usually made with water, but can
be made instead of, or in addition to, water, with, for example, liquid fertilisers,
micronutrients, biological organisms, oil or solvents.
The herbicidal compositions generally comprise from 0.1 to 99 % by weight,
especially from 0.1 to 95 % by weight, compounds of Formula I and from 1 to 99.9 %
by weight of a formulation adjuvant which preferably includes from 0 to 25 % by
weight of a surface-active substance.
The compositions can be chosen from a number of formulation types, many of
which are known from the Manual on Development and Use of FAO Specifications
for Plant Protection Products, 5th Edition, 1999. These include dustable powders
(DP), soluble powders (SP), water soluble granules (SG), water dispersible granules
(WG), wettable powders (WP), granules (GR) (slow or fast release), soluble
concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL),
emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in
water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates
(SC), aerosols, capsule suspensions (CS) and seed treatment formulations. The
formulation type chosen in any instance will depend upon the particular purpose
envisaged and the physical, chemical and biological properties of the compound of
Formula (I).
Dustable powders (DP) may be prepared by mixing a compound of Formula (I)
with one or more solid diluents (for example natural clays, kaolin, pyrophyllite,
bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium
phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other
organic and inorganic solid carriers) and mechanically grinding the mixture to a fine
powder.
Soluble powders (SP) may be prepared by mixing a compound of Formula (I)
with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium
carbonate or magnesium sulphate) or one or more water-soluble organic solids (such
a s a polysaccharide) and, optionally, one or more wetting agents, one or more
dispersing agents or a mixture of said agents to improve water dispersibility/solubi1ity.
The mixture is then ground to a fine powder. Similar compositions may also be
granulated to form water soluble granules (SG).
Wettable powders (WP) may be prepared by mixing a compound of Formula
(I) with one or more solid diluents or carriers, one or more wetting agents and,
preferably, one or more dispersing agents and, optionally, one or more suspending
agents to facilitate the dispersion in liquids. The mixture is then ground to a fine
powder. Similar compositions may also be granulated to form water dispersible
granules (WG).
Granules (GR) may be formed either by granulating a mixture of a compound
of Formula (I) and one or more powdered solid diluents or carriers, or from pr e
formed blank granules by absorbing a compound of Formula (I) (or a solution thereof,
in a suitable agent) in a porous granular material (such as pumice, attapulgite clays,
fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a
compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core
material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and
drying if necessary. Agents which are commonly used to aid absorption or adsorption
include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers,
ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols,
dextrins, sugars and vegetable oils). One or more other additives may also be
included in granules (for example an emulsifying agent, wetting agent or dispersing
agent).
Dispersible Concentrates (DC) may be prepared by dissolving a compound of
Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether.
These solutions may contain a surface active agent (for example to improve water
dilution or prevent crystallisation in a spray tank).
Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be
prepared by dissolving a compound of Formula (I) in an organic solvent (optionally
containing one or more wetting agents, one or more emulsifying agents or a mixture
of said agents). Suitable organic solvents for use in ECs include aromatic
hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by
SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered
Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols
(such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as Nmethylpyrrolidone
or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C -
Cio fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may
spontaneously emulsify on addition to water, to produce an emulsion with sufficient
stability to allow spray application through appropriate equipment.
Preparation of an EW involves obtaining a compound of Formula (I) either as
a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable
temperature, typically below 70°C) or in solution (by dissolving it in an appropriate
solvent) and then emulsifying the resultant liquid or solution into water containing
one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for
use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes),
aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate
organic solvents which have a low solubility in water.
Microemulsions (ME) may be prepared by mixing water with a blend of one
or more solvents with one or more SFAs, t o produce spontaneously a
thermodynamically stable isotropic liquid formulation. A compound of Formula (I) is
present initially in either the water or the solvent/SFA blend. Suitable solvents for use
in MEs include those hereinbefore described for use in in ECs or in EWs. An ME
may be either an oil-in-water or a water-in-oil system (which system is present may
be determined by conductivity measurements) and may be suitable for mixing watersoluble
and oil-soluble pesticides in the same formulation. An ME is suitable for
dilution into water, either remaining as a microemulsion or forming a conventional
oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous
suspensions of finely divided insoluble solid particles of a compound of Formula (I).
SCs may be prepared by ball or bead milling the solid compound of Formula (I) in a
suitable medium, optionally with one or more dispersing agents, to produce a fine
particle suspension of the compound. One or more wetting agents may be included in
the composition and a suspending agent may be included to reduce the rate at which
the particles settle. Alternatively, a compound of Formula (I) may be dry milled and
added to water, containing agents hereinbefore described, to produce the desired end
product.
Aerosol formulations comprise a compound of Formula (I) and a suitable
propellant (for example w-butane). A compound of Formula (I) may also be dissolved
or dispersed in a suitable medium (for example water or a water miscible liquid, such
as «-propanol) to provide compositions for use in non-pressurised, hand-actuated
spray pumps.
Capsule suspensions (CS) may be prepared in a manner similar to the
preparation of EW formulations but with an additional polymerisation stage such that
an aqueous dispersion of oil droplets is obtained, in which each oil droplet is
encapsulated by a polymeric shell and contains a compound of Formula (I) and,
optionally, a carrier or diluent therefor. The polymeric shell may be produced by
either an interfacial polycondensation reaction or by a coacervation procedure. The
compositions may provide for controlled release of the compound of Formula (I) and
they may be used for seed treatment. A compound of Formula (I) may also be
formulated in a biodegradable polymeric matrix to provide a slow, controlled release
of the compound.
The composition may include one or more additives to improve the biological
performance of the composition, for example by improving wetting, retention or
distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of
a compound of Formula (I). Such additives include surface active agents (SFAs),
spray additives based on oils, for example certain mineral oils or natural plant oils
(such as soy bean and rape seed oil), and blends of these with other bio-enhancing
adjuvants (ingredients which may aid or modify the action of a compound of Formula
(I))-
Wetting agents, dispersing agents and emulsifying agents may be SFAs of the
cationic, anionic, amphoteric or non-ionic type.
Suitable SFAs of the cationic type include quaternary ammonium compounds
(for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
Suitable anionic SFAs include alkali metals salts of fatty acids, salts of
aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of
sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate,
calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of
sodium di- propyl- and tri-zsopropyl-naphthalene sulphonates), ether sulphates,
alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates
(for example sodium laureth-3-carboxylate), phosphate esters (products from the
reaction between one or more fatty alcohols and phosphoric acid (predominately
mono-esters) or phosphorus pentoxide (predominately di-esters), for example the
reaction between lauryl alcohol and tetraphosphoric acid; additionally these products
may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates
and lignosulphonates.
Suitable SFAs of the amphoteric type include betaines, propionates and
glycinates.
Suitable SFAs of the non-ionic type include condensation products of alkylene
oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof,
with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such
as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain
fatty acids or hexitol anhydrides; condensation products of said partial esters with
ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide);
alkanolamides; simple esters (for example fatty acid polyethylene glycol esters);
amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
Suitable suspending agents include hydrophilic colloids (such a s
polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and
swelling clays (such as bentonite or attapulgite).
The composition of the present may further comprise at least one additional
pesticide. For example, the compounds according to the invention can also be used in
combination with other herbicides or plant growth regulators. In a preferred
embodiment the additional pesticide is a herbicide and/or herbicide safener. Examples
of such mixtures are (in which T represents a compound of Formula I). I + acetochlor,
I + acifluorfen, I + acifluorfen-sodium, I + aclonifen, I + acrolein, I + alachlor, I +
alloxydim, I + ametryn, I + amicarbazone, I + amidosulfuron, I + aminopyralid, I +
amitrole, I + anilofos, I + asulam, I + atrazine, I + azafenidin, I + azimsulfuron, I +
BCPC, I + beflubutamid, I + benazolin, I + bencarbazone, I + benfluralin, I +
benfuresate, I + bensulfuron, I + bensulfuron-methyl, I + bensulide, I + bentazone, I +
benzfendizone, I + benzobicyclon, I + benzofenap, I + bicyclopyrone, I + bifenox, I +
bilanafos, I + bispyribac, I + bispyribac-sodium, I + borax, I + bromacil, I +
bromobutide, I + bromoxynil, I + butachlor, I + butamifos, I + butralin, I +
butroxydim, I + butylate, I + cacodylic acid, I + calcium chlorate, I + cafenstrole, I +
carbetamide, I + carfentrazone, I + carfentrazone-ethyl, I + chlorflurenol, I +
chlorflurenol-methyl, I + chloridazon, I + chlorimuron, I + chlorimuron-ethyl, I +
chloroacetic acid, I + chlorotoluron, I + chlorpropham, I + chlorsulfuron, I + chlorthal,
I + chlorthal-dimethyl, I + cinidon-ethyl, I + cinmethylin, I + cinosulfuron, I +
cisanilide, I + clethodim, I + clodinafop, I + clodinafop-propargyl, I + clomazone, I +
clomeprop, I + clopyralid, I + cloransulam, I + cloransulam-methyl, I + cyanazine, I +
cycloate, I + cyclosulfamuron, I + cycloxydim, I + cyhalofop, I + cyhalofop-butyl,, I
+ 2,4-D, I + daimuron, I + dalapon, I + dazomet, I + 2,4-DB, I + I + desmedipham, I +
dicamba, I + dichlobenil, I + dichlorprop, I + dichlorprop-P, I + diclofop, I + diclofopmethyl,
I + diclosulam, I + difenzoquat, I + difenzoquat metilsulfate, I + diflufenican,
I + diflufenzopyr, I + dimefuron, I + dimepiperate, I + dimethachlor, I +
dimethametryn, I + dimethenamid, I + dimethenamid-P, I + dimethipin, I +
dimethylarsinic acid, I + dinitramine, I + dinoterb, I + diphenamid, I + dipropetryn, I
+ diquat, I + diquat dibromide, I + dithiopyr, I + diuron, I + endothal, I + EPTC, I +
esprocarb, I + ethalfluralin, I + ethametsulfuron, I + ethametsulfuron- methyl, I +
ethephon, I + ethofumesate, I + ethoxyfen, I + ethoxysulfuron, I + etobenzanid, I +
fenoxaprop-P, I + fenoxaprop-P-ethyl, I + fentrazamide, I + ferrous sulfate, I +
flamprop-M, I + flazasulfuron, I + florasulam, I + fluazifop, I + fluazifop-butyl, I +
fluazifop-P, I + fluazifop-P -butyl, I + fluazolate, I + flucarbazone, I + flucarbazonesodium,
I + flucetosulfuron, I + fluchloralin, I + flufenacet, I + flufenpyr, I +
flufenpyr-ethyl, I + flumetralin, I + flumetsulam, I + flumiclorac, I + flumicloracpentyl,
I + flumioxazin, I + flumipropin, I + fluometuron, I + fluoroglycofen, I +
fluoroglycofen-ethyl, I + fluoxaprop, I + flupoxam, I + flupropacil, I + flupropanate, I
+ flupyrsulfuron, I + flupyrsulfuron-methyl-sodium, I + flurenol, I + fluridone, I +
flurochloridone, I + fluroxypyr, I + flurtamone, I + fluthiacet, I + fluthiacet-methyl, I
+ fomesafen, I + foramsulfuron, I + fosamine, I + glufosinate, I + glufosinateammonium,
I + glyphosate, I + halosulfuron, I + halosulfuron-methyl, I + haloxyfop, I
+ haloxyfop-P, I + hexazinone, I + imazamethabenz, I + imazamethabenz-methyl, I +
imazamox, I + imazapic, I + imazapyr, I + imazaquin, I + imazethapyr, I +
imazosulfuron, I + indanofan, I + indaziflam, I + iodomethane, I + iodosulfuron, I +
iodosulfuron-methyl-sodium, I + ioxynil, I + isoproturon, I + isouron, I + isoxaben, I
+ isoxachlortole, I + isoxaflutole, I + isoxapyrifop, I + karbutilate, I + lactofen, I +
lenacil, I + linuron, I + mecoprop, I + mecoprop-P, I + mefenacet, I + mefluidide, I +
mesosulfuron, I + mesosulfuron-methyl, I + mesotrione, I + metam, I + metamifop, I
+ metamitron, I + metazachlor, I + methabenzthiazuron, I + methazole, I +
methylarsonic acid, I + methyldymron, I + methyl isothiocyanate, I + metolachlor, I +
S-metolachlor, I + metosulam, I + metoxuron, I + metribuzin, I + metsulfuron, I +
metsulfuron-methyl, I + molinate, I + monolinuron, I + naproanilide, I + napropamide,
I + naptalam, I + neburon, I + nicosulfuron, I + n-methyl glyphosate, I + nonanoic
acid, I + norflurazon, I + oleic acid (fatty acids), I + orbencarb, I + orthosulfamuron, I
+ oryzalin, I + oxadiargyl, I + oxadiazon, I + oxasulfuron, I + oxaziclomefone, I +
oxyfluorfen, I + paraquat, I + paraquat dichloride, I + pebulate, I + pendimethalin, I +
penoxsulam, I + pentachlorophenol, I + pentanochlor, I + pentoxazone, I +
pethoxamid, I + phenmedipham, I + picloram, I + picolinafen, I + pinoxaden, I +
piperophos, I + pretilachlor, I + primisulfuron, I + primisulfuron-methyl, I +
prodiamine, I + profoxydim, I + prohexadione-calcium, I + prometon, I + prometryn,
I + propachlor, I + propanil, I + propaquizafop, I + propazine, I + propham, I +
propisochlor, I + propoxycarbazone, I + propoxycarbazone-sodium, I + propyzamide,
I + prosulfocarb, I + prosulfuron, I + pyraclonil, I + pyraflufen, I + pyraflufen-ethyl, I
+ pyrasulfotole, I + pyrazolynate, I + pyrazosulfuron, I + pyrazosulfuron-ethyl, I +
pyrazoxyfen, I + pyribenzoxim, I + pyributicarb, I + pyridafol, I + pyridate, I +
pyriftalid, I + pyriminobac, I + pyriminobac-methyl, I + pyrimisulfan, I + pyrithiobac,
I + pyrithiobac-sodium, I + pyroxasulfone, I + pyroxsulam, I + quinclorac, I +
quinmerac, I + quinoclamine, I + quizalofop, I + quizalofop-P, I + rimsulfuron, I +
saflufenacil, I + sethoxydim, I + siduron, I + simazine, I + simetryn, I + sodium
chlorate, I + sulcotrione, I + sulfentrazone, I + sulfometuron, I + sulfometuron-methyl,
I + sulfosate, I + sulfosulfuron, I + sulfuric acid, I + tebuthiuron, I + tefuryltrione, I +
tembotrione, I + tepraloxydim, I + terbacil, I + terbumeton, I + terbuthylazine, I +
terbutryn, I + thenylchlor, I + thiazopyr, I + thifensulfuron, I + thiencarbazone, I +
thifensulfuron-methyl, I + thiobencarb, I + topramezone, I + tralkoxydim, I + tri-allate,
I + triasulfuron, I + triaziflam, I + tribenuron, I + tribenuron-methyl, I + triclopyr, I +
trietazine, I + trifloxysulfuron, I + trifloxysulfuron-sodium, I + trifluralin, I +
triflusulfuron, I + triflusulfuron-methyl, I + trihydroxytriazine, I + trinexapac-ethyl, I
+ tritosulfuron, I + [3-[2-chloro-4-fluoro-5-(l-methyl-6-trifluoromethyl-2,4-dioxol,
2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS
RN 353292-31-6). The compounds of the present invention may also be combined
with herbicidal compounds disclosed in WO06/024820 and/or WO07/096576.
The mixing partners of the compound of Formula I may also be in the form of
esters or salts, as mentioned e.g. in The Pesticide Manual, Fourteenth Edition, British
Crop Protection Council, 2006.
The compound of Formula I can also b e used in mixtures with other
agrochemicals such as fungicides, nematicides or insecticides, examples of which are
given in The Pesticide Manual.
The mixing ratio of the compound of Formula I to the mixing partner is
preferably from 1 : 100 to 1000:1.
The mixtures can advantageously be used in the above-mentioned
formulations (in which case "active ingredient" relates to the respective mixture of
compound of Formula I with the mixing partner).
The compounds of Formula I according to the invention can also be used in
combination with one or more safeners. Likewise, mixtures of a compound of
Formula I according to the invention with one or more further herbicides can also be
used in combination with one or more safeners. The safeners can be AD 67 (MON
4660), benoxacor, cloquintocet-mexyl, cyprosulfamide (CAS RN 2 1667-31-8),
dichlormid, fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole and the
corresponding R isomer, isoxadifen-ethyl, mefenpyr-diethyl, oxabetrinil, N-isopropyl-
4-(2-methoxy-benzoylsulfamoyl)-benzamide ( C A S R N 2 2 16 6 8-34-4). Other
possibilities include safener compounds disclosed in, for example, EP0365484 e.g N-
(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Particularly preferred are mixtures of a compound of Formula I with cyprosulfamide,
isoxadifen-ethyl, cloquintocet-mexyl and/or N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)
amino]benzenesulfonamide. These safeners have shown particularly
good results in maize and/or cereals such as wheat and barley when higher rates
(e.g >50g/ha) of compounds of Formula (I) are used.
The safeners of the compound of Formula I may also be in the form of esters
or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006. The
reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium,
magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium
salt thereof a s disclosed in WO 02/34048, and the reference to
fenchlorazole-ethyl also applies to fenchlorazole, etc.
Preferably the mixing ratio of compound of Formula I to safener is from 100: 1
to 1:10, especially from 20:1 to 1:1.
The mixtures can advantageously b e used in the above-mentioned
formulations (in which case "active ingredient" relates to the respective mixture of
compound of Formula I with the safener).
The present invention still further provides a method of selectively controlling
weeds at a locus comprising crop plants and weeds, wherein the method comprises
application to the locus of a weed controlling amount of a composition according to
the present invention. 'Controlling' means killing, reducing or retarding growth or
preventing or reducing germination. Generally the plants to be controlled are
unwanted plants (weeds). 'Locus' means the area in which the plants are growing or
will grow.
The rates of application of compounds of Formula I may vary within wide
limits and depend on the nature of the soil, the method of application (pre- or postemergence;
seed dressing; application to the seed furrow; no tillage application etc.),
the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and
other factors governed by the method of application, the time of application and the
target crop. The compounds of Formula I according to the invention are generally
applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha.
The application is generally made by spraying the composition, typically by
tractor mounted sprayer for large areas, but other methods such as dusting (for
powders), drip or drench can also be used.
Useful plants in which the composition according to the invention can be used
include crops such as cereals, for example barley and wheat, cotton, oilseed rape,
sunflower, maize, rice, soybeans, sugar beet, sugar cane and turf. Maize is particularly
preferred.
Crop plants can also include trees, such as fruit trees, palm trees, coconut trees
or other nuts. Also included are vines such as grapes, fruit bushes, fruit plants and
vegetables.
Crops are to be understood as also including those crops which have been
rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-,
PPO-, ACCase- and FIPPD-inhibitors) by conventional methods of breeding or by
genetic engineering. An example of a crop that has been rendered tolerant to
imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield®
summer rape (canola). Examples of crops that have been rendered tolerant to
herbicides by genetic engineering methods include e.g. glyphosate- and glufosinateresistant
maize varieties commercially available under the trade names
RoundupReady® and LibertyLink®.
In a preferred embodiment the crop plant is rendered tolerant to HPPDinhibitors
via genetic engineering. Methods of rending crop plants tolerant to FIPPDinhibitors
are known, for example from WO0246387. Thus in an even more preferred
embodiment the crop plant is transgenic in respect of a polynucleotide comprising a
DNA sequence which encodes an HPPD-inhibitor resistant HPPD enzyme derived
from a bacterium, more particularly from Pseudomonas fluorescens or Shewanella
colwelliana, or from a plant, more particularly, derived from a monocot plant or, yet
more particularly, from a barley, maize, wheat, rice, Brachiaria, Chenchrus, Lolium,
Festuca, Setaria, Eleusine, Sorghum or Avena species.
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® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally
by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to
synthesise such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278,
WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants
comprising one or more genes that code for an insecticidal resistance and express one
or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B®
(cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
Plant crops or seed material thereof can be both resistant to herbicides and, at the
same time, resistant to insect feeding ("stacked" transgenic events). For example, seed
can have the ability to express an insecticidal Cry3 protein while at the same time
being tolerant to glyphosate.
Crops are also to be understood to include those which are obtained by
conventional methods of breeding or genetic engineering and contain so-called output
traits (e.g. improved storage stability, higher nutritional value and improved flavour).
Other useful plants include turf grass for example in golf-courses, lawns, parks
and roadsides, or grown commercially for sod, and ornamental plants such as flowers
or bushes.
The compositions can be used to control unwanted plants (collectively,
'weeds'). The weeds to be controlled may be both monocotyledonous species, for
example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus,
Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus,
Setaria and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus,
Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium,
Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium. Weeds can also
include plants which may be considered crop plants but which are growing outside a
crop area ('escapes'), or which grow from seed left over from a previous planting of a
different crop ('volunteers'). Such volunteers or escapes may be tolerant to certain
other herbicides.
The compounds of the present invention can be prepared using the following methods.
Preparation of compounds of the present invention is outlined in the following
schemes.
Preparation of compounds Formula (I) is carried out analogously to known processes
(for example those described in WO97/46530, EP0353187 and US 6,498,125) and
comprises reacting a compound of the following formula:
where the definitions of R1 and R2 are as for Formula (I) and LG is a suitable leaving
group, for example a halogen atom, such as chlorine, or an alkoxy or aryloxy group,
such as 4-nitrophenoxy, in an inert organic solvent, such as dichloromethane or
acetonitrile, in the presence of a base, such as triethylamine, with compounds
wherein
A1 and Ra, Rb, R , Rd are as defined previously;
to give the following esters (3a)
which may be rearranged using catalysts, such as 4-dimethylaminopyridine, or
acetone cyanohydrin, or a metal cyanide salt, such as sodium cyanide, in the presence
of a suitable base, such as triethylamine, to give compounds of Formula (I), as shown
in Scheme 1. It is advantageous to have a dehydrating agent, such as molecular
sieves, present in the reaction medium to ensure any water initially present in the
solvent or associated with the other components of the reaction mixture is prevented
from causing any unwanted hydrolysis of intermediates.
Examples
The following non-limiting preparation examples are provided. Abbreviations as used
in the following Examples are as follows: s= singlet, d=doublet, t= triplet, m=
multiplet, bs = broad signal, bm = broad multiplet, dd = double doublet, dt = double
triplet, td = triple doublet and dq = double quartet.
Example 1. Preparation of 2-(3-Oxo-2-phenyl-2,3-dihydropyridazine-4-carbonyl)-
cyclohexane-l,3-dione (Compound 1.1)
3-Oxo-2-phenyl-2,3-dihydropyridazine-4-carboxylic acid (0.52 g, 2.42 mmol) was
stirred in anhydrous dicloromethane (13 ml) and 1 drop of anhydrous
dimethylformamide was added. Oxalyl chloride (0.25 mL, 2.90 mmol) was added
dropwise to the suspension resulting in a brown solution. After 1.5 h the reaction was
concentrated in vacuo. The residue obtained was dissolved in dichloromethane (20
ml). To the brown solution anhydrous triethylamine ( 1 ml), then cyclohexanedione
(0.33g, 2.90 mmol) was added, producing a reddish coloured solution. A further 0.33
ml of anhydrous triethylamine was added. The reaction mixture was stirred at room
temperature for 2 h (reaction monitored by LCMS), then acetone cyanohydrin ( 1 drop)
and anhydrous triethylamine (0.67 ml) was added and the reaction mixture was stirred
overnight. LCMS indicated the desired product had been formed. The reaction
mixture was concentrated in vacuo. The residue obtained was purified using column
chromatography (Si0 2, Toluene/Triethylamine/Dioxane/EtOH/Water 100:40:20:20:5
by volume), and then further purified by column chromatography (Si02, hexane/ethyl
acetate/acetic acid 2:1:0.02 to 0:100:2) to afford the title compound as an orange oil
(25 mg, 3% yield). 1H MR (CDC13) 2.04 (m, 2H), 2.61 (br s, 4H), 7.18 (d, 1H) 7.46
(m, 2 H), 7.59 (m, 3 H) 7.96 (d, 1H) ppm.
Example 2. Preparation of 2-(6-Methyl-3-oxo-2-phenyl-2,3-dihydropyridazine-4-
carbonyl)-cyclohexane- 1,3-dione (Compound 1.2).
6-Methyl-3-oxo-2-phenyl-2,3-dihydropyridazine-4-carboxylic acid (0.56 g, 2.42
mmol) was stirred in anhydrous dicloromethane (13 ml) and 1 drop of anhydrous
dimethylformamide was added. Oxalyl chloride (0.25 mL, 2.90 mmol) was added
dropwise to the yellow solution. After 1.5 h the reaction was concentrated in vacuo.
The residue obtained was dissolved in dichloromethane (20 ml). To the brown
solution anhydrous triethylamine ( 1 ml), then cyclohexanedione (0.33g, 2.90 mmol)
was added, producing a reddish solution. A further 0.33 ml of anhydrous
triethylamine was added. The reaction mixture was stirred at room temperature for 2 h
(reaction monitored by LCMS), then acetone cyanohydrin ( 1 drop) and anhydrous
triethylamine (0.67 ml) was added and the reaction was stirred overnight. LCMS
indicated the desired product had been formed. The reaction mixture was concentrated
in vacuo. The residue obtained was purified using column chromatography (Si0 2,
Toluene/Triethylamine/Dioxane/EtOH/Water 100:40:20:20:5 by volume) to afford the
title compound as an orange oil (382 mg, 49%). 1H MR (CDC13) 2.05 (quin, 2H),
2.41 (m, 3H), 2.47 (br s, 2H), 2.73 (br s, 2H), 7.10 (s, 1H), 7.36 (m, 1H), 7.46 (m,
2H), 7.57 (m, 2H), 16.15 (br s, 1H) ppm.
Table 1 - Examples of herbicidal compounds of the present invention.
Cmp A Ra R R Rd R R MR 1H MR (CDC13)
1.10 CH -CH -CH - H H CH3 7.88 (IH, t), 7.61 (IH, d), 7.32 (IH, d),
7.13 (IH, s), 3.04 (2H, brs), 2.69 (3H, s),
2.42 (3H, s), 2.23 (IH, d), 2.16 (2H, brs),
1.90 (2H, brs), 1.73 (IH, dt).
1.1 1 CH H H H H CH3 7.95 (IH, t), 7.70 (IH, d), 7.37 (IH, d),
7.14 (IH, s), 2.73 (3H, s), 2.68 - 2.57
(4H, m), 2.43 (3H, s), 2.06 (2H, quintet).
1.12 C=0 CH3 CH3 CH3 CH3 CH3 16.47 (IH, s), 7.20-7.35 (5H, m), 2.43
(3H, s), 2.21 (3H, s), 1.52 (3H, s), 1.37
(3H, s),
1.13 CH -CH -CH - H H CH3 7.54 (2H,s), 7.38 (lH,s), 7.25 (lH,s),
3.06-3.14 (2H br,m) 2.23 (3H,s), 2.1 1-
2.24 (4H,m), 1.98 (lH,m),1.85 (lH,m)
1.14 CH -CH -CH - H H CH3 16.02 (lH,s), 7.25-7.32 (4H,m),
7.13(lH,s), 3.08 (IH br,t), 2.82(1H br ,t),
2.4(3H,s), 2.21(3H,s), 1.97-2.18 (6H,m)
1.15 CH H H H H CH3 7.7(lH,s), 7.67(2H,s), 7.38(lH,s), 2.87
(lH,m), 2.58 (4H,m), 2.21(3H,s), 2.09-
2.18 (2H,m)
1.16 CH H H H H CH3 16.02 (lH,s), 7.25-7.32
(4H,m),7.17(lH,s), 2.71(2H,m), 2.45
(2H,m), 2.41 (3H,s), 2.21 (3H,s), 1.98-
2.06 (2H,m)
1.17 CHCH 3 H H H H CH3 16.0 (s, IH), 7.6 (m, 2H), 7.3 (m, IH),
7.0 (s, IH), 2.8 (m, IH), 2.6 (m, 2H), 2.1
(m, IH), 1.1 (d, 3H)
1.18 CHCH 3 H H H H CH3 7.3 (2H, m) 7.0 (3H, m), 3.8 (3H, s), 2.5
(2H, m), 2.4 (IH, m), 2.3 (3H, s), 2.1
(2H, m), 1.2 (3H, d)
1.19 CH H H H H CH3 7.4 (IH, s), 7.1 (2H, s), 7.38 (2H, s), 3.8
(3H, s), 3.0 (2H, m), 2.4 (3H, s),
2.21(2H, s), 2.07-2.15 (2H, m)
1.20 CH -CH -CH - H H CH3 7.4 (IH, s), 7.1 (2H, s), 7.38 (2H, s), 5.5
(IH, s) 3.8 (3H s), 3.0 (2H, m), 2.0 (3H,
m), 2.21 (6H, s), 2.07-2.15 (3H, m)
Biological Examples
Seeds of a variety of test species are sown in standard soil in pots {Alopecurus
myosuroides (ALOMY), Setariafaberi (SETFA), Echinochloa crus-galli (ECHCG),
Abuthilon theophrasti (ABUTH) and Amaranthus retoflexus (AMARE)). After
cultivation for one day (pre-emergence) or after 8 days cultivation (post-emergence)
under controlled conditions in a glasshouse (at 24/1 6°C, day/night; 14 hours light;
65 % humidity), the plants are sprayed with an aqueous spray solution derived from
the formulation of the technical active ingredient in acetone / water (50:50) solution
containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-
64-5). Compounds ae applied at 1000 g/h.The test plants are then grown in a
glasshouse under controlled conditions in a glasshouse (at 24/1 6°C, day/night; 14
hours light; 65 % humidity) and watered twice daily. After 13 days for pre and postemergence,
the test is evaluated for the percentage herbicidal damage caused to the
plant. The biological activities are shown in the following table on a five point scale
(5 = 80-100% damage; 4 = 60-79% damage; 3 = 40-59% damage; 2 = 20-39%
damage; 1 = 0-19% damage).
Compound POST Application PRE Application
ABUTH AMARE SETFA ALOMY ECHCG ABUTH AMARE SETFA ALOMY ECHCG
1.1 5 5 5 5 5 5 5 5 5 5
1.2 5 5 5 5 5 5 5 5 5 5
1.3 5 5 5 5 5 5 5 5 5 5
1.4 5 5 5 5 5 5 5 5 5 5
1.5 5 5 5 5 5 5 5 5 5 5
1.6 5 5 5 5 5 5 5 5 5 5
1.7 5 5 5 5 5 5 5 5 5 5
1.8 5 5 5 5 5 5 5 5 5 5
1.9 5 5 5 5 5 5 5 5 5 5

Claims
1 A herbicidal compound of Formula (I):
or an agronomically acceptable salt of said compound, wherein:-
R1is selected from the group consisting of hydrogen, Ci-Cealkyl, Ci-
Cehaloalkyl, Ci-C 3alkoxy-Ci-C3 alkyl, C1-C3 alkoxy-Ci-C3alkoxy-Ci-C3 -alkyl,
Ci-C 3alkoxy-Ci-C3-haloalkyl, Ci-C3-alkoxy-Ci-C3-alkoxy-Ci-C3-haloalkyl,
C4-C6 -oxasubstituted cycloalkoxy-Ci-C3 -alkyl, C4-C6 -oxasubstituted
cycloalkyl-Ci-C3-alkoxy-Ci-C3-alkyl, C4-C6 -oxasubstituted cycloalkoxy-Ci-
C 3 -haloalkyl, C4-C6 -oxasubstituted cycloalkyl-Ci-C3-alkoxy-Ci-C3-haloalkyl,
(C1-C3 alkanesulfonyl-Ci-C3 alkylamino)-Ci-C3 alkyl, (C1-C3 alkanesulfonyl-
C3-C4 cycloalkylamino)-Ci-C 3alkyl, Ci-C 6alkylcarbonyl-Ci-C 3alkyl, C3-
C6Cycloalkyl-C 2-C6alkenyl, C2-C6alkynyl, C2-C6-alkenyl, C2-C6-haloalkenyl,
cyano-Ci-C6-alkyl, arylcarbonyl-Ci-C3-alkyl (wherein the aryl may be
optionally substituted with one or more substituents from the group consisting
of halo, Ci-C3-alkoxy, Ci-C3-alkyl, C1-C3 haloalkyl), aryl-Ci-Cealkyl, aryloxy-
Ci-C 6alkyl (wherein both cases the aryl may be optionally substituted with one
or more substituents from the group consisting of halo, Ci-C3-alkoxy, C1-C3-
alkyl, C1-C3 haloalkyl), and a three- to ten-membered mono- or bicyclic ring
system, which may be aromatic, saturated or partially saturated and can
contain from 1 to 4 heteroatoms each independently selected from the group
consisting of nitrogen, oxygen and sulphur the ring system being optionally
substituted by one or more substituents selected from the group consisting of
Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3alkenyl, Ci-C3alkynyl, Ci-C3 alkoxy, Ci-C3
haloalkoxy, Ci-C6alkyl-S(0)p-, Ci-C6haloalkyl-S(0)p-, aryl, aryl-S(0)p,
heteroaryl-S(0)p, aryloxy, heteroaryloxy, Ci-C3 alkoxycarbonyl, Ci-C3
alkylamino-S(0)p-, Ci-C3 alkylamino-S(0)p-Ci-C 3 alkyl, Ci-C3 dialkylamino-
S(0)p-, Ci-C3 dialkylamino-S(0)p-Ci-C 3 alkyl, Ci-C3 alkylaminocarbonyl-,
Ci-C3 alkylaminocarbonyl-Ci-C 3 alkyl, Ci-C3 dialkylaminocarbonyl, Ci-C3
dialkylaminocarbonyl-Ci-C 3 alkyl, Ci-C3 alkylcarbonylamino, Ci-C3 alkyl-
S(0)p-amino, cyano and nitro; the heteroaryl substituents containing one to
three heteroatoms each independently selected from the group consisting of
oxygen, nitrogen and sulphur, and wherein the aryl or heteroaryl component
may be optionally substituted by one or more substituents selected from the
group consisting of halo, Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3 alkoxy, Ci-C3
haloalkoxy, phenyl, cyano and nitro;
R2 is selected from the group consisting of hydrogen, halogen, cyano, nitro,
Ci-C6alkyl, C3-Cecycloalkyl, C2-C6-alkenyl, C2-C6alkynyl, Ci-C6haloalkyl,
Ci-C6alkoxy, Ci-C3haloalkoxy, -C6alkoxy-Ci-C 3 alkyl, Ci-C6alkyl-S(0)pand
Ci-C6haloalkyl-S(0)p-;
p = 0, 1 or 2;
A1 is selected from the group consisting of O, C(O) and (CReRf) ; and
Ra, Rb, R , Rd, Re and Rf are each independently selected from the group
consisting of hydrogen and Ci-C4alkyl wherein Ra and R may together form a
Ci-C3alkylene chain.
A herbicidal compound according to claim 1, wherein R1 is selected from the
group consisting of hydrogen, Ci-Cealkyl, Ci-C6haloalkyl, Ci-C3alkoxyCi.
C3alkyl, Ci-C3alkoxy C2-C3alkoxyCi.C3alkyl, Ci-C6haloalkyl, C2-
Cehaloalkenyl Ci-C3alkoxy-Ci.C 3haloalkyl, aryl, a 5 or 6-membered
heteroaryl, a 5 or 6-membered heteroaryl-Ci-C 3alkyl and heterocyclyl-Ci-
C3alkyl, the heteroaryl or heterocyclyl containing one to three heteroatoms
each independently selected from the group consisting of oxygen, nitrogen
and sulphur, and wherein the aryl, heterocyclyl or heteroaryl component may
be optionally substituted by one or more substituents selected from the group
consisting of halo, Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3 alkoxy, cyano and nitro.
A herbicidal compound according to claim 3, wherein R1 is selected from the
group consisting of aryl, a 5 or 6-membered heteroaryl and a 5 or 6-membered
heteroaryl-Ci-C 3alkyl, the heteroaryl containing one to three heteroatoms each
independently selected from the group consisting of oxygen, nitrogen and
sulphur, and wherein the aryl or heteroaryl component may be optionally
substituted by one or more substituents selected from the group consisting of
halo, Ci-C3alkyl, Ci-C3haloalkyl, Ci-C3 alkoxy, cyano and nitro.
A herbicidal compound according to any one of the previous claims, wherein
R2 is hydrogen or methyl.
A herbicidal composition comprising a herbicidal compound according to any
one of the previous claims and an agriculturally acceptable formulation
adjuvant.
A herbicidal composition according to claim 5, further comprising at least one
additional pesticide.
A herbicidal composition according to claim 6, wherein the additional
pesticide is a herbicide or herbicide safener.
A method of controlling weeds at a locus comprising application to the locus
of a weed controlling amount of a composition according to any one of claims
5 to 7 .
9 . Use of a compound of Formula (I) as defined in claim 1 as a herbicide.