1,2,4 -TRIAZOLE DERIVATIVES AS HERB I IDAL
The present invention relates to novel herbicidal compounds, to processes for
their preparation, to herbicidal compositions which comprise the novel compounds,
and to their use for controlling weeds, in particular in crops of useful plants, or for
inhibiting plant growth.
Herbicidal N-(Tetrazol-5-yl) and N-(Triazol-5-yl) arylcarboxamides are
known from WO2012/028579. The present invention relates to the provision of
further herbicidal triazolyl compounds.
Thus, according to the present invention there is provided a compound of Formula (I):
(I)
or an agronomically acceptable salt thereof,
wherein: -
R1 and R7 are independently selected from the group consisting of hydi
Ci-Ce alkyl, Ci-Cehaloalkyl and Ci-Cealkoxy-Ci-Csalkyl;
or together R1 and R7 form a C -C alkylene chain, a C -C haloalkylene chain
or a Ci-Csalkyleneoxy-Ci-Csalkylene chain;
R is selected from the group consisting of C -C alkyl-, C -C haloalkyl-, Ci-
C alkoxy-Ci-Cealkyl-, C1-C3alkoxy-C2-C3alkoxy-C1-C3alkyl-, halogen, cyano,
nitro, Ci-C6alkyl-S(0)p- and Ci-C6haloalkyl-S(0) p-;
X is CR orN;
R is selected from the group consisting of hydrogen, halo, Ci-Cealkyl, Ci-
C6haloalkyl, Ci-Cealkoxy-Ci-Cealkyl, Ci-Cehaloalkoxy-Ci-Cealkyl, Ci-
Cealkoxy-Ci-Cealkoxy-Ci-Cealkyl, Ci-Cealkoxy, Ci-Cehaloalkoxy, C -
Cealkoxy-Ci-Cealkoxy, Ci-Cealkylamino, Ci-Cedialkylamino-, piperidino,
morpholino, cyano, Ci-C6alkyl-S(0)p- and Ci-C6haloalkyl-S(0) p-;
R4 is selected from the group consisting of hydrogen, Ci-Cealkyl, C -
C6haloalkyl, Ci-Cealkoxy-Ci-Cealkyl, halo, cyano, nitro, Ci-C6alkyl-S(0)pand
Ci-C6haloalkyl-S(0) p-;
or R and R4 together form a saturated 5- or 6-membered ring, optionally
containing an oxygen or a S(0) p heteroatom, the 5- or 6-membered ring being
optionally substituted by one or more R6,
R5 is selected from the group consisting of, hydrogen, halogen, C -Ce alkyl
and Ci-Cehaloalkyl;
or R4 and R5 together form a 5- or 6-membered aromatic ring, optionally
containing a nitrogen heteroatom, the 5- or 6-membered aromatic ring being
optionally substituted by one or more R6;
R6 is selected from the group consisting of halo, Ci-Cealkyl, Ci-Cehaloalkyl,
Ci-Cealkoxy-Ci-Cea lky 1, Ci-Cehaloalkoxy-Ci-Cealkyl, Ci-Cealkoxy-Ci-
Cealkoxy-Ci-Cealkyl-, Ci-Cealkoxy and Ci-Cehaloalkoxy; and
p = 0, 1 or 2.
Halogen (or halo) 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.
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. It should also be appreciated that two alkoxy substituents present on the same
carbon atom may may be joined to form a spiro group. Thus, the methyl groups
present in two methoxy substituents may be joined to form a spiro 1,3 dioxolane
substituent, for example. Such a possibility is within the scope of the present
invention.
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.
Ci-C6alkyl-S- (alkylthio) is, for example, methylthio, ethylthio, propylthio,
isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably
methylthio or ethylthio.
Ci-C6alkyl-S(0)- (alkylsulfinyl) is, for example, methylsulfmyl, ethylsulfmyl,
propylsulfmyl, isopropylsulfmyl, n-butylsulfmyl, isobutylsulfmyl, sec-butylsulfinyl or
tert-butylsulfmyl, preferably methylsulfmyl or ethylsulfmyl.
Ci-C6alkyl-S(0)2- (alkylsulfonyl) is, for example, methylsulfonyl,
ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl,
sec-butylsulfonyl or tert-butylsulfonyl, 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 1to 4 carbon atoms.
Alkoxyalkyl groups preferably have from 1to 6 carbon atoms. Alkoxyalkyl is,
for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, npropoxymethyl,
n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
In a preferred embodiment of the invention R1 is methyl or ethyl.
In another embodiment R is selected from the group consisting hydrogen,
methyl and ethyl.
In another embodiment of the present invention R is selected from the group
consisting of methyl, fluoro, chloro, nitro, methoxyethoxymethyl-, trifluoromethyl
and methyl-S(0) 2- .
In another embodiment of the present invention R is selected from the group
consisting of methyl, fluoro, chloro, trifluoromethyl and methyl-S(0) 2- .
In another preferred embodiment of the present invention, X is CR .
In another preferred embodiment of the present invention, X is CR3 and R3 is
hydrogen or CF3CH2OCH2- .
In another embodiment, R4 is selected from the group consisting of hydrogen,
trifluoromethyl, fluorine, chlorine and methyl-S(0) 2- .
In another embodiment, R4 is selected from the group consisting of hydrogen,
trifluoromethyl and methyl-S(0) 2- .
In another embodiment, R5 is selected from the group consisting of hydrogen,
fluorine, chlorine, bromine and methyl.
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
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.
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
as a polysaccharide) and, optionally, one or more wetting agents, one or more
dispersing agents or a mixture of said agents to improve water dispersibility/solubility.
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 n-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 n-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-z 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 olefme 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 as
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 + halauxifen, 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 + norfiurazon, 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 + primisulfuronmethyl,
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-dioxo-l,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 be 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 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 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 22 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 (CAS RN 221668-34-4). 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.
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 as 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 be 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.
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 HPPD-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 HPPDinhibitors
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-45 1 878, 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 according to Schemes 1to 2.
Scheme 1:- Reaction of an activated carboxylic acid:
DMAP = 4-dimethylaminopyridine, PPAA = 1-propanephosphonic acid cyclic
anhydride, and the solvent is a non-protic organic solvent such as ethyl acetate.
Scheme 2:- Reaction of an acid chloride with a 3-amino-l,2,4-triazole:
The carboxylic acids are known, or can be prepared by known methods or methods
analogous to known methods. N-4-alkylated 3-amino-l,2,4-triazoles can be prepared
by the method shown in Scheme 3.
Scheme 3:- N-4-alkylation of 3-amino-l,2,4-triazoles:
5-Substituted 3-amino-l,2,4-triazoles can be prepared by the method shown in
Scheme 4.
Scheme 4:- Preparation of 5-substituted 3-amino-l,2,4-triazoles:
Example PI: Experimental procedure for the preparation of Compound 1.008.
STEP 1: Oxalyl chloride (0.386 ml, 4.47 mmol) was added dropwise to a solution of
the benzoic acid El (400 mg, 1.49 mmol) in HPLC grade dichloromethane (15 ml),
containing a catalytic amount of DMAP. The reaction mixture was allowed to stir at
room temperature for 2 hours. The solvent was then removed under reduced pressure
to leave the crude benzoyl chloride, which was used without further purification.
STEP 2 : The crude benzoyl chloride from step 1 was dissolved in 10 ml HPLC grade
dichloromethane, and the solution was cooled to 0C and the aminotriazole E2 (150
mg, 1.49 mmol) was added. The reaction mixture was then allowed to warm to room
temperature, and triethylamine (0.3 15 ml, 2.23 mmol) was added. Stirring was
continued for another 3 hours, then the reaction mixture was diluted with
dichloromethane (50 ml) and washed with water (2x20 ml) and brine (1x10 ml). The
dichloromethane layer was then dried over sodium sulfate, and evaporated under
reduced pressure to afford the crude product. This was purified on a Combiflash,
eluting with ethyl acetate-hexane, to afford the pure product as a white solid (90 mg).
Yield: 17%
Example P2: Experimental procedure for the preparation of Compound 1.013
STEP 1: Oxalyl chloride (0.224 ml, 2.60 mmol) was added dropwise to a solution of
the benzoic acid E3 (300 mg, 0.867 mmol) in HPLC grade dichloromethane (15 ml),
containing a catalytic amount of DMAP. The reaction mixture was allowed to stir at
room temperature for 2 hours, and the solvent was then removed under reduced
pressure to afford the crude benzoyl chloride, which was used without further
purification.
STEP 2 : The crude acid chloride from step 1 mass was dissolved in HPLC grade
dichloromethane (10 ml) and the solution was cooled to 0C. The aminotriazole E4
( 110 mg, 0.867mmol) was added. The reaction mixture was then allowed to warm to
room temperature, and triethylamine (0.1 10 ml,0.867 mmol) was added. Stirring was
continued for another 3 hours, then the reaction mixture was diluted with
dichloromethane (50 ml) and washed with water (2x20 ml) and brine (1x10 ml). The
dichloromethane layer was then dried over sodium sulfate, and evaporated under
reduced pressure to afford the crude product. This was purified on a Combiflash,
eluting with ethyl acetate-hexane, to afford the pure product as a white solid ( 110 mg).
Yield: 28%
Example P3: Experimental procedure for the preparation of aminotriazole E2
N-N DMF-DMA N _ N a N-N M e „ , N-N
DDiiooxxaannee,l1O0O0CC . N H HCI
H
8 hours
E 5 E 6 E 7
NaOMe
F
STEP 1: A solution of aminotriazole E5 (10.0 g, 119.05 mmol) in 1,4 dioxane (100
ml) was treated with DMF-DMA ( 3 1.62 ml, 238 mmol) at room temperature. The
reaction mixture was then heated under reflux for 3 hours, during which time a clear
solution inititially formed and then a solid began to form after around 30 min. The
reaction mixture was cooled to room temperature, and the solvent and excess DMFDMA
was evaporated under reduced pressure to afford the crude product. This was
triturated with diethyl ether-hexane to obtain the pure E6 as an off white solid (8.0 g).
Yield: 48%
STEP 2 : Sodium hydride (60 % > in mineral oil, 4.3 g, 107 mmol) was added
portionwise to a stirred solution of E6 ( 15 .0 g, 107 mmol) in anhydrous
dimethylformamide (150 ml) at 0°C. The reaction mixture was then allowed to stir at
room temerature for 1.5 hours, before being cooled to 0°C and treated dropwise with
methyl iodide (10 ml, 161 mmol). The reaction mixture was then stirred at room
temperature for 6 hours. The reaction mixture was then diluted with water (300 ml)
and extracted with ethyl acetate (3x150 ml). The combined ethyl acetate extracts were
dried over sodium sulfate, and the solvent was evaporated under reduced pressure to
afford the crude product. This was purified on a Combiflash, eluting with methanoldichloromethane,
to afford pure E7 (5.0 g). Yield: 30%
STEP 3 : A stirred solution of E7 (5.0 g, 32.68 mmol) in tetrahydrofuran (50 ml) was
treated with cone hydrochloric acid (5 ml) at room temperature, and was then heated
under reflux for 16 hours. The tetrahydrofuran was removed by evaporation under
reduced pressure, and the resultant wet solid was dried by azeotroping under reduced
pressued with toluene. The dry solid was triturated with diethyl ether-hexane to afford
the salt E8 as a white solid (4.0 g). Yield: 93%
STEP 4 : Sodium methoxide (1.8 gm, 33 mmol) was added portionwise to a stirred
suspension of E8 (4.9 g, 37 mmol) in anhydrous THF (50 ml) at 0°C. Immediately
after the addition, the reaction mixture formed a clear solution. This was stirred for a
further 2 hours, during which time a solid slowly precipitated out. This was filtered
off and dried, yielding the amine E2 as a white solid (0.7g). Yield: 20%>
Example P4: Experimental procedure for the preparation of aminotriazole E4
E9 E10
STEP 1: Cyanamide (20 g, 0.476 mmol) was added portionwise to a solution of 1,1,1
trimethoxy propane (84 g, 476 mmol) in acetic anhydride (90 ml) at room temperature.
The reaction mixture was then heated at 145C for 3 hrs. After cooling E9 (65 g) was
isolated by distillation. Yield: 63%>
STEP 2 : Hydrazine hydrate (32 ml, 657 mmol) was added dropwise to a solution of
E9 (69 g, 547 mmol) in methanol (300 ml) at room temperature. The reaction mixture
was stirred at room temperature for 4 hours, after which the solvent was removed by
concentrating under reduced pressure to afford crude E10, which was used in the next
step without further purification. Yield: 81%
E10 was then converted to E4 by the procedure described in preparative example P3.
TABLE 1 - Examples of herbicidal compounds of the present invention.

TABLE 2 - Examples of herbicidal compounds of the present invention.
Biological Examples
Seeds of a variety of test species are sown in standard soil in pots Alopecurus
myosuroides (ALOMY), Amaranthus retoflexus (AMARE), Setaria faberi (SETFA),
Echinochloa crus-galli (ECHCG), Lolium perenne (LOLPE), Solarium nigrum
(SOLNI), Stellaria media (STEME) and Digitaria sanguinalis (DIGSA). 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 24/16°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 damage caused to the plant. The
biological activities are shown in the following table on a five point scale (5 = 80-
100%; 4 = 60-79%; 5=40-59%; 2=20-39%; 7=0-19%).
Compound POST Application PRE Application
SOLNI AMARE SETFA ALOMY ECHCG IPOHE SOLNI AMARE SETFA ALOMY ECHCG IPOHE
1.008 5 5 3 3 4 5 5 5 3 2 5 4
1.009 4 2 1 2 1 3 2 4 1 1 1 1
1.010 2 1 2 2 2 2 1 1 1 1 1 1
1.01 1 5 5 2 2 4 5 5 5 2 1 4 4
1.013 2 1 1 2 1 1 1 1 1 1 1 1
1.014 5 5 5 5 5 5 5 5 5 5 5
1.015 4 4 1 2 2 4 4 4 1 1 1 2
2.003 1 1 1 1 1 1 1 1 1 1 1 1
2.005 4 4 1 1 1 4 2 2 1 1 1 3
2.006 4 2 1 1 1 2 3 2 1 1 1 3
Claims
1. A compound of Formula (I) :
or an agronomically acceptable salt thereof,
wherein:-
R1 and R7' are independently selected from the group consisting of hydrogen,
Ci-Ce alkyl, Ci-Cehaloalkyl and Ci-Cealkoxy-Ci-Csalkyl;
or together R1 and R7 form a C -C alkylene chain, a C -C haloalkylene chain
or a Ci-Csalkyleneoxy-Ci-Csalkylene chain;
R is selected from the group consisting of Ci-Ce alkyl-, Ci-Ce haloalkyl-, Ci-
C alkoxy-Ci-Cealkyl-, C1-C3alkoxy-C2-C3alkoxy-C1-C3alkyl-, halogen, cyano,
nitro, Ci-C6alkyl-S(0)p- and Ci-C6haloalkyl-S(0) p-;
X is CR orN;
R is selected from the group consisting of hydrogen, halo, Ci-Cealkyl, Ci-
Cehaloalkyl, Ci-Cealkoxy-Ci-Cealkyl, Ci-Cehaloalkoxy-Ci-Cealkyl, Ci-
C6alkoxy-Ci-C6alkoxy-Ci-C 6alkyl, Ci-Cealkoxy, Ci-Cehaloalkoxy, C -
Cealkoxy-Ci-Cealkoxy, Ci-Cealkylamino, Ci-Cedialkylamino-, piperidino,
morpholino, cyano, Ci-C6alkyl-S(0)p- and Ci-C6haloalkyl-S(0) p-;
R4 is selected from the group consisting of hydrogen, Ci-C6alkyl, Ci-
C6haloalkyl, Ci-Cealkoxy-CrCealkyl, halo, cyano, nitro, C1-C6alkyl-S(0)pand
C1-C6haloalkyl-S(0) p-;
or R and R4 together form a saturated 5- or 6-membered ring, optionally
containing an oxygen or a S(0) p heteroatom, the 5- or 6-membered ring being
optionally substituted by one or more R6,
R5 is selected from the group consisting of, hydrogen, halogen, Ci-C6 alkyl
and Ci-Cehaloalkyl;
or R4 and R5 together form a 5- or 6-membered aromatic ring, optionally
containing a nitrogen heteroatom, the 5- or 6-membered aromatic ring being
optionally substituted by one or more R6;
R6 is selected from the group consisting of halo, Ci-Cealkyl, Ci-Cehaloalkyl,
Ci-Cealkoxy-Ci-Cea lky 1, Ci-Cehaloalkoxy-Ci-Cealkyl, Ci-Cealkoxy-Ci-
Cealkoxy-Ci-Cealkyl-, Ci-Cealkoxy and Ci-Cehaloalkoxy; and
p = 0, 1 or 2.
2. A compound according to claim 1, wherein R1 is methyl or ethyl.
3. A compound according to any one of the previous claims, wherein R is
selected from the group consisting of methyl, fluoro, chloro, trifluoromethyl
and methyl-S(0) 2- .
4. A compound according to any one of the previous claims, wherein X is CR .
5. A compound according to any one of the previous claims, wherein R4 is
selected from the group consisting of hydrogen, trifluoromethyl and methyl-
S(0) 2- .
6. A herbicidal composition comprising a herbicidal compound according to any
one of the previous claims and an agriculturally acceptable formulation
adjuvant.
7. A herbicidal composition according to claim 6, further comprising at least one
additional pesticide.
8. A herbicidal composition according to claim 7, wherein the additional
pesticide is a herbicide or herbicide safener.
9. 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
6 to 8.
10. Use of a compound of Formula (I) as defined in claim 1 as a herbicide.