- -
haloalkoxy, Ci-C alkoxy Ci-C alkoxy, C2-C8 alkenyl, C2-C8 alkynyl, C2-C cyanoalkenyl, C2-C
cyanoalkynyl, C2-C alkenyloxy, C2-C alkynyloxy, C2-C haloalkenyl, C2-C haloalkynyl, C2-C
haloalkenyloxy, C2-C haloalkynyloxy, Ci-C alkoxy C2-C alkenyl, Ci-C alkoxy C2-C alkynyl, -
C alkylsulfinyl, Ci-C alkylsulfonyl, Ci-C haloalkylthio, Ci-C haloalkylsulfinyl, Ci-C
haloalkylsulfonyl, Ci-C alkylsulfonyloxy, Ci-C alkylcarbonyl, Ci-C haloalkylcarbonyl, C2-C
alkenylcarbonyl, C2-C alkynylcarbonyl, C2-C haloalkenylcarbonyl, C2-C haloalkynylcarbonyl, tri
-C alkylsilyl C2-C alkynyl, a group R R N-, a group R C(0)N(R 6)-, a group R S(0 2)N(R6)-, a
group R R NS0 2- , a group R R NC(0) Ci-C alkyl, a C -Ci 0 aryloxy group optionally substituted
by from 1 to 3 groups independently selected from halogen, nitro, cyano, C -C3 alkyl, C -C3
alkoxy, C -C3 haloalkyl and C -C3 haloalkoxy, a C -Ci 0 aryl Ci-C3 alkyl group optionally
substituted by from 1 to 3 groups independently selected from halogen, nitro, cyano, Ci-C3 alkyl,
Ci-C3 alkoxy, Ci-C3 haloalkyl and Ci-C3 haloalkoxy, a C -Ci 0 benzyloxy group optionally
substituted by from 1 to 3 groups independently selected from halogen, nitro, cyano, Ci-C3 alkyl,
Ci-C3 alkoxy, Ci-C3 haloalkyl and Ci-C3 haloalkoxy, a C3-C heterocyclyl group optionally
substituted by from 1 to 3 groups independently selected from C -C4 alkyl, a C3-C cycloalkyl
group optionally substituted with from 1 to 3 groups independently selected from halogen, cyano,
Ci-C alkoxy and Ci-C alkyl and a C3-C cycloalkenyl group optionally substituted with from 1 to
3 groups independently selected from halogen, cyano, Ci-C alkoxy and Ci-C alkyl;
Rd is selected from hydrogen, halogen, cyano, Ci-C alkyl and Ci-C haloalkyl;
or R and Rd together with the carbon atoms to which they are attached form a 3-7 membered
saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms
independently selected from S, O and N and optionally substituted with from 1 to 3 groups
independently selected from halogen, Ci-C alkyl and Ci-C haloalkyl;
R is selected from hydrogen, Ci-C alkyl optionally substituted with NR 0R1 1 , Ci-C3 haloalkyl and
Ci-C alkoxy; wherein R 0 and R are independently selected from hydrogen, Ci-C alkyl and d -
C haloalkyl.
R2 is selected from hydrogen, hydroxyl, halogen, -C alkyl, C2-C alkenyl, C2-C alkynyl, Ci-C
alkoxy, Ci-C haloalkyl, Ci-C haloalkoxy, Ci-C alkoxy Ci-C alkyl, Ci-C cyanoalkyl and the
group -NR 2R13 , wherein R 2 and R 3 are independently selected from hydrogen and Ci-C alkyl.
or R and R2 together with the nitrogen and carbon atoms to which they are attached form a 3-7
membered saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms
independently selected from S, O and N and optionally substituted with from 1 to 3 groups
independently selected from hydroxyl, =0, Ci-C alkyl or Ci-C haloalkyl.
R3 is selected from halogen, hydroxyl, -NR 4R15 , Ci-C alkoxy or any one of the following groups
- -
R5 and R6 are independently selected from hydrogen, Ci-C alkyl, Ci-C haloalkyl, C 2-C alkenyl,
C2-C alkynyl, or R5 and R6 together with the carbon atoms to which they are attached form a 3-6
membered saturated or partially unsaturated ring optionally comprising from 1 to 3 heteroatoms
independently selected from S, O and N and optionally substituted with from 1 to 3 groups
independently selected from halogen and Ci-C alkyl;
R7 and R8 are independently selected from hydrogen, Ci-C alkyl, Ci-C haloalkyl, C 2-C alkenyl,
C 2-C alkynyl, a C 5-Ci 0 heteroaryl group which can be mono- or bicyclic comprising from 1 to 4
heteroatoms independently selected from N, O and S and optionally substituted with 1 to 3
groups independently selected from halogen, C - 3 alkyl, C - 3 haloalkyl and C - 3 alkoxy, a C -
C o aryl group optionally substituted with 1 to 3 groups independently selected from halogen,
nitro, cyano, C - 3 alkyl, Ci-C3 alkoxy, Ci-C3 haloalkyl and Ci-C3 haloalkoxy, or R7 and R8
together with the atoms to which they are attached form a 3-6 membered saturated or partially
unsaturated ring optionally comprising from 1 to 3 heteroatoms independently selected from S, O
and N and optionally substituted with from 1 to 3 groups independently selected from halogen or
-C alkyl;
R9 is selected from Ci-C alkyl or benzyl optionally substituted with 1 to 3 groups independently
selected from halogen, nitro, cyano, Ci-C3 alkyl, Ci-C3 alkoxy, Ci-C3 haloalkyl and Ci-C3
haloalkoxy;
R 4 and R 5 are, independently, selected from hydrogen, Ci-C20 alkyl, Ci-C20 haloalkyl, C 2-C 20
alkenyl, C2-C20 alkynyl, or R 4 and R 5 together with the carbon atoms to which they are attached
form a 3-6 membered saturated or partially unsaturated ring optionally comprising from 1 to 3
heteroatoms independently selected from S, O and N and optionally substituted with from 1 to 3
groups independently selected from halogen and Ci-C alkyl;
or an N-oxide or salt form thereof.
In a second aspect, the invention provides herbicidal compositions comprising a
compound of the invention together with at least one agriculturally acceptable adjuvant or diluent.
- -
In a third aspect, the invention provides the use of a compound or a composition of the
invention for use as a herbicide.
In a fourth aspect, the invention provides a method of controlling weeds in crops of useful
plants, comprising applying to said weeds or to the locus of said weeds, or to said useful crop
plants, a compound or a composition of the invention.
In a fifth aspect, the invention relates to processes useful in the preparation of
compounds of the invention.
In a sixth aspect, the invention relates to intermediates useful in the preparation of
compounds of the invention.
Detailed Description
In particularly preferred embodiments of the invention, the preferred groups for X, Ra, R ,
Rd, R , R2 and R3, in any combination thereof, are as set out below.
Preferably, X is O.
Preferably Ra is hydrogen.
Preferably, R is selected from Ci-C 8 alkyl, Ci-C haloalkyl, C2-C8 alkenyl, Ci-C
cyanoalkyi, Ci-C alkoxy, Ci-C hydroxyalkyi, Ci-C alkoxy Ci-C alkyl, C2-C alkenyloxy Ci-C
alkyl, C3-C cycloalkyi optionally substituted by from 1 to 3 groups independently selected from
cyano, C - 3 alkyl and C - 3 alkoxy and a group R R NC(0) Ci-C alkyl.
More preferably, R is selected from Ci-C 8 alkyl, Ci-C haloalkyl, C2-C8 alkenyl, Ci-C
cyanoalkyi, Ci-C alkoxy Ci-C alkyl and C3-C cycloalkyi optionally substituted by from 1 to 3
groups independently selected from cyano and Ci-C 3 alkyl.
More preferably, R is selected from Ci-C 8 alkyl, Ci-C haloalkyl, C2-C8 alkenyl, Ci-C
cyanoalkyi and C3-C cycloalkyi optionally substituted by from 1 to 3 groups independently
selected from cyano and Ci-C 3 alkyl.
Even more preferably, R is selected from Ci-C alkyl, Ci-C 3 haloalkyl, Ci-C cyanoalkyi
and C3-C cycloalkyi optionally substituted by from 1 to 3 groups independently selected from
cyano and Ci-C 3 alkyl.
- -
Even more preferably R is selected from methyl, ethyl, /so-propyl, (2-methyl)-prop-1 -yl,
( 1-methyl)-prop-1 -yl, ieri-butyl, ( 1,1-dimethyl)-prop-1 -yl, ( 1,1-dimethyl)-but-1 -yl, ( 1-methyl-1 -
ethyl)-prop-1 -yl, cyclobutyl, cyclopropyl, ( 1-methyl)cycloprop-1 -yl, ( 1-methyl-1 -cyano)-eth-1 -yl, ( 1-
methyl-1 -ethyl-2-cyano)-prop-1 -yl, ( 1,1-dimethyl-2-cyano)-prop-1 -yl, 1-fluoroethyl, 1,1-
difluoroethyl, difluorom ethyl, 1-fluoro-1 -methylethyl and trifluoromethyl.
Even more preferably R is selected from methyl, ethyl, /so-propyl, (2-methyl)-prop-1 -yl,
( 1-methyl)-prop-1 -yl, ieri-butyl, ( 1,1-dimethyl)-prop-1 -yl, ( 1,1-dimethyl)-but-1 -yl, ( 1-methyl-1 -
ethyl)-prop-1 -yl, cyclobutyl, cyclopropyl, ( 1-methyl)cycloprop-1 -yl, ( 1-methyl-1 -cyano)-eth-1 -yl, ( 1-
methyl-1 -ethyl-2-cyano)-prop-1 -yl, ( 1,1-dimethyl-2-cyano)-prop-1 -yl, 1-fluoroethyl, 1,1-
difluoroethyl, difluorom ethyl, 1-fluoro-1 -methylethyl, trifluoromethyl and 1-chloro-1 -methylethyl.
Most preferably, R is selected from ieri-butyl, ( 1-methyl-1-cyano)-eth-1 -yl, 1,1-
difluoroethyl, 1-fluoro-1 -methylethyl and trifluoromethyl.
Preferably, Rd is hydrogen.
In particular, the substituted pyrimidine may be 6-ierf-butylpyrimidin-4-yl, 6-(1 -fluoro-1 -
methyl-ethyl)pyrimidin-4-yl, 6-((1 -methyl-1 -cyano)-eth-1 yl)pyrimidin-4-yl or 6-(1 ,1-
difluoroethyl)pyrimidin-4-yl.
Preferably R is C1-C3 alkyl, C1-C3 alkoxy or C1-C3 haloalkyl. More preferably R is methyl
or methoxy.
Preferably R2 is hydrogen, hydroxyl, C1-C3 alkyl, Ci-C 3 alkoxy, Ci-C 3 haloalkyl, Ci-C 3
haloalkoxy allyl. More preferably R2 is hydrogen, methyl or ethoxy.
In one embodiment, preferably, R3 is selected from halogen, hydroxyl, or any one of the
following groups
In this embodiment, preferably, R3 is selected from halogen, hydroxyl, or any of the
following groups
- -
R 7 may be as defined above but preferably, R 7 is selected from Ci-C alkyl, Ci-C
haloalkyi, C 2-C alkenyl, C 2-C alkynyl, a C 5-Ci 0 monocyclic heteroaryl group comprising from 1
to 4 heteroatoms independently selected from N, O and S and optionally substituted with 1 to 3
groups independently selected from halogen, C - 3 alkyl, C - 3 haloalkyi and C - 3 alkoxy, a C -
C o aryl group optionally substituted with 1 to 3 groups independently selected from halogen,
nitro, cyano, C - 3 alkyl, Ci-C3 alkoxy, Ci-C3 haloalkyi and Ci-C3 haloalkoxy.
More preferably, R 3 is selected from hydroxyl, halogen, Ci-C alkylcarbonyloxy, Ci-C
alkoxycarbonyloxy or aryloxycarbonyloxy wherein the aryl group may be substituted with 1 to 3
groups independently selected from halogen, nitro, cyano, Ci-C3 alkyl, Ci-C3 alkoxy, Ci-C3
haloalkyi and Ci-C3 haloalkoxy.
Even more preferably, R 3 is selected from hydroxyl or halogen.
Most preferably, R 3 is hydroxyl.
In another embodiment, preferably, R 3 is selected from halogen, hydroxyl, -NR 4R 15, -
C alkoxy or any of the following groups
R 7 may be as defined above but preferably, R 7 is selected from Ci-C alkyl, Ci-C
haloalkyi, C 2-C alkenyl, C 2-C alkynyl, a C 5-Ci 0 monocyclic heteroaryl group comprising from 1
to 4 heteroatoms independently selected from N, O and S and optionally substituted with 1 to 3
groups independently selected from halogen, Ci-C3 alkyl, Ci-C3 haloalkyi and Ci-C3 alkoxy, a C -
C o aryl group optionally substituted with 1 to 3 groups independently selected from halogen,
nitro, cyano, Ci-C3 alkyl, Ci-C3 alkoxy, Ci-C3 haloalkyi and Ci-C3 haloalkoxy.
More preferably, R 3 is selected from hydroxyl, halogen, -NR 4R 15,Ci-C
alkylcarbonyloxy, Ci-C alkoxycarbonyloxy or aryloxycarbonyloxy wherein the aryl group may be
substituted with 1 to 3 groups independently selected from halogen, nitro, cyano, Ci-C3 alkyl, -
C 3 alkoxy, Ci-C3 haloalkyi and Ci-C3 haloalkoxy.
- -
Even more preferably, R3 is selected from hydroxyl or halogen. Most preferably, R3 is
hydroxy I.
The compounds of formula (I) may exist as different geometric isomers, or in different
tautomeric forms. This invention covers all such isomers and tautomers, and mixtures thereof in
all proportions, as well as isotopic forms such as deuterated compounds.
The compounds of this invention may contain one or more asymmetric centers and may
thus give rise to optical isomers and diastereomers. While shown without respect to
stereochemistry, the present invention includes all such optical isomers and diastereomers as
well as the racemic and resolved, enantiomerically pure R and S stereoisomers and other
mixtures of the R and S stereoisomers and agrochemically acceptable salts thereof. It is
recognized certain optical isomers or diastereomers may have favorable properties over the
other. Thus when disclosing and claiming the invention, when a racemic mixture is disclosed , it is
clearly contemplated that both optical isomers, including diastereomers, substantially free of the
other, are disclosed and claimed as well.
Alkyl, as used herein refers to an aliphatic hydrocarbon chain and includes straight and
branched chains e. g . of 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, and isohexyl.
Alkenyl, as used herein, refers to an aliphatic hydrocarbon chain having at least one
double bond , and preferably one double bond, and includes straight and branched chains e. g . of
2 to 8 carbon atoms such as ethenyl (vinyl), prop-1 -enyl, prop-2-enyl (allyl), isopropenyl, but-1 -
enyl, but-2-enyl, but-3-enyl, 2-methypropenyl.
Alkynyl, as used herein, refers to an aliphatic hydrocarbon chain having at least one triple
bond, and preferably one triple bond, and includes straight and branched chains e. g . of 2 to 8
carbon atoms such as ethynyl, prop-1 -ynyl, prop-2-ynyl (propargyl) but-1 -ynyl, but-2-ynyl and but-
3-ynyl.
Cycloalkyl, as used herein, refers to a cyclic, saturated hydrocarbon group having from 3
to 6 ring carbon atoms. Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl
and cyclohexyl.
Cycloalkenyl, as used herein, refers to a cyclic, partially unsaturated hydrocarbon group
having from 3 to 6 ring carbon atoms.
Alkoxy as used herein refers to the group -OR, wherein R is alkyl as defined above.
Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy,
sec-butoxy, t-butoxy, n-pentoxy, isopentoxy, neo-pentoxy, n-hexyloxy, and isohexyloxy.
- -
Alkenyloxy refers to the group -OR, wherein R is alkenyl as defined above. Examples of
alkenyloxy groups are ethenyloxy, propenyloxy, isopropenyloxy, but-1 -enyloxy, but-2-enyloxy,
but-3-enyloxy, 2-methypropenyloxy etc.
Alkynyloxy refers to the group -OR, wherein R is alkynyl is as defined above. Examples
of alkynyloxy groups are ethynyloxy, propynyloxy, but-1-ynyloxy, but-2-ynyloxy and but-3-
ynyloxy.
Alkoxyalkyl as used herein refers to the group -ROR, wherein each R is, independently,
an alkyl group as defined above.
Alkoxyalkenyl as used herein refers to the group -ROR', wherein R is an alkyl group as
defined above and R' is an alkenyl group as defined above.
Alkoxyalkynyl as used herein refers to the group -ROR', wherein R is an alkyl group as
defined above and R' is an alkynyl group as defined above.
Alkoxyalkoxy, as ued herein, refers to the group -OROR, wherein each R is,
independently, an alkyl group as defined above.
Cyanoalkyl as used herein refers to an alkyl group substituted with one or more cyano
groups.
Cyanoalkenyl as used herein refers to an alkenyl group substituted with one or more
cyano groups.
Cyanoalkynyl as used herein refers to an alkynyl group substituted with one or more
cyano groups.
Cyanocycloalkyl as used herein refers to an cycloalkyl group substituted with one or
more cyano groups.
Cyanoalkoxy as used herein refers to the group -OR, wherein R is cyanoalkyl as defined
above.
Halogen, halide and halo refer to iodine, bromine, chlorine and fluorine.
Haloalkyi as used herein refers to an alkyl group as defined above wherein at least one
hydrogen atom has been replaced with a halogen atom as defined above. Examples of haloalkyi
groups include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl and
- -
trifluoromethyl. Preferred haloalkyi groups are fluoroalkyi groups {i.e. haloalkyi groups, containing
fluorine as the only halogen). More highly preferred haloalkyi groups are perfluoroalkyi groups,
i.e. alkyl groups wherein all the hydrogen atoms are replaced with fluorine atoms.
Haloalkenyl as used herein refers to an alkenyl group as defined above wherein at least
one hydrogen atom has been replaced with a halogen atom as defined above.
Haloalkynyl as used herein refers to an alkynyl group as defined above wherein at least
one hydrogen atom has been replaced with a halogen atom as defined above.
Haloalkoxy as used herein refers to the group -OR, wherein R is haloalkyi as defined
above.
Haloalkenyloxy as used herein refers to the group -OR, wherein R is haloalkenyl as
defined above.
Haloalkynyloxy as used herein refers to the group -OR, wherein R is haloalkynyl as
defined above.
Alkylthio as used herein refers to the group -SR, wherein R is an alkyl group as defined
above. Alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, tertbutylthio,
and the like.
Alkylthioalkyl as used herein refers to the group -RSR, wherein each R is,
independently, an alkyl group as defined above.
Haloalkylthio as used herein refers to the group -SR, wherein R is a haloalkyi group as
defined above.
Alkylsulfinyl as used herein refers to the group -S(0)R, wherein R is an alkyl group as
defined above.
Alkylsulfonyl as used herein refers to the group -S(0) 2R, wherein R is an alkyl group as
defined above.
Haloalkylsulfinyl as used herein refers to the group -S(0)R, wherein R is a haloalkyi
group as defined above.
Haloalkylsulfonyl as used herein refers to the group -S(0) 2R, wherein R is a haloalkyi
group as defined above.
- -
Alkylsulfonyloxy, as used herein refers to the group -OS0 2R, wherein R is an alkyl group
as defined above.
Alkylcarbonyl, as used herein refers to the group -COR, wherein R is an alkyl group as
defined above. Examples of alkylcarbonyl groups include ethanoyi, propanoyi, n-butanoyl, etc.
Alkenylcarbonyl, as used herein refers to the group -COR, wherein R is an alkenyl group
as defined above.
Alkynylcarbonyl, as used herein refers to the group -COR, wherein R is an alkynyl group
as defined above.
Haloalkylcarbonyl, as used herein refers to the group -COR, wherein R is a haloalkyl
group as defined above.
Haloalkenylcarbonyl, as used herein refers to the group -COR, wherein R is a
haloalkenyl group as defined above.
Haloalkynylcarbonyl, as used herein refers to the group -COR, wherein R is a
haloalkynyl group as defined above.
Alkoxycarbonyloxy as used herein, refers to the group -OC(0)OR, wherein R is an alkyl
group as defined above. Examples of alkoxycarbonyloxy groups are methoxycarbonyloxy,
ethoxycarbonyloxy, propoxycarbonyloxy, but-1-oxycarbonyloxy, but-2-oxycarbonyloxy and but-3-
oxycarbonyloxy.
Trialkylsilylalkynyl, as used herein, refers to the group -RSi(R') 3, wherein R is an alkynyl
group as defined above and each R' is, independently, selected from an alkyl group as defined
above.
Formyl, as used herein, refers to the group -C(0)H.
Hydroxy or hydroxyl, as used herein, refers to the group -OH.
Nitro, as used herein, refers to the group -N0 2.
Cyano as used herein, refers to the group -CN.
Aryl, as used herein, refers to an unsaturated aromatic carbocyclic group of from 6 to 10
carbon atoms having a single ring (e. g., phenyl) or multiple condensed (fused) rings, at least one
- -
of which is aromatic (e.g., indanyl, naphthyl). Preferred aryl groups include phenyl, naphthyl and
the like. Most preferably, an aryl group is a phenyl group.
Aryloxy, as used herein, refers to the group -O-aryl, wherein aryl is as defined above.
Preferred aryloxy groups include phenoxy, naphthyloxy and the like.
Aryloxycarbonyloxy as used herein, refers to the group -OC(0)0-aryl wherein aryl is a
as defined above.
Benzyl, as used herein, refers to the group -CH 2C H5.
Benzyloxy, as used herein, refers to the group -OCH 2C H5.
Heterocyclyl, as used herein, refers to a non-aromatic ring system containing 3 to 10 ring
atoms, at least one ring heteroatom and consisting either of a single ring or of two or more fused
rings. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms
which will preferably be chosen from nitrogen, oxygen and sulfur. Examples of such groups
include pyrrolidinyl, imidazolinyl, pyrazolidinyl, piperidyl, piperazinyl, quinuclidinyl, morpholinyl,
together with unsaturated or partially unsaturated analogues such as 4,5,6,7-tetrahydrobenzothiophenyl,
chromen-4-onyl, 9H-fluorenyl, 3,4-dihydro-2H-benzo-l,4-dioxepinyl, 2,3-dihydrobenzofuranyl,
piperidinyl, 1,3-dioxolanyl, 1,3-dioxanyl, 4,5-dihydro-isoxazolyl, tetrahydrofuranyl
and morpholinyl.
Heteroaryl, as used herein, refers to a ring system containing 5 to 10 ring atoms, 1 to 4
ring heteroatoms and consisting either of a single aromatic ring or of two or more fused rings, at
least one of which is aromatic. Preferably, single rings will contain up to three and bicyclic
systems up to four heteroatoms which will preferably be independently chosen from nitrogen,
oxygen and sulfur. Examples of such groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl,
triazinyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl,
pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl. Examples of bicyclic groups are
benzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl, cinnolinyl, quinoxalinyl and
pyrazolo[1 ,5-a]pyrimidinyl.
'Saturated ring', as used herein, refers to a ring system in which the atoms in the ring are
linked by single bonds.
'Partially unsaturated ring', as used herein, refers to a ring system in which at least two
atoms in the ring are linked by a double bond. Partially unsaturated ring systems do not include
aromatic rings.
- -
"Optionally substituted" as used herein means the group referred to can be substituted at
one or more positions by any one or any combination of the radicals listed thereafter. For most
groups, one or more hydrogen atoms are replaced by the radicals listed thereafter. For
halogenated groups, for example, haloalkyi groups, one or more halogen atoms are replaced by
the radicals listed thereafter.
Suitable salts include those derived from alkali or alkaline earth metals and those derived
from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and
ammonium cations of the formula N+(R R20R2 R22) wherein R 9 , R20, R2 and R22 are
independently selected from hydrogen, Ci-C alkyl and Ci-C hydroxyalkyl. Salts of the
compounds of Formula I can be prepared by treatment of compounds of Formula I with a metal
hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine,
diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine,
cyclododecylamine, or benzylamine. Amine salts are often preferred forms of the compounds of
Formula I because they are water-soluble and lend themselves to the preparation of desirable
aqueous based herbicidal compositions.
Acceptable salts can be formed from organic and inorganic acids, for example, acetic,
propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic,
hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic,
benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids when a
compound of this invention contains a basic moiety.
In another aspect the present invention provides intermediates useful in the preparation
of compounds of the invention.
In one embodiment, there are provided intermediates of the formula (II I), wherein R , R2,
Ra, R and Rd are as defined above. These intermediates can also display herbicidal activity.
- -
Compounds of the invention may be prepared by techniques known to the person skilled
in the art of organic chemistry. General methods for the production of compounds of formula (I)
are described below. Unless otherwise stated in the text, the substituents X, R , R2, R3, Ra, R
and Rd are as defined hereinbefore. The starting materials used for the preparation of the
compounds of the invention may be purchased from usual commercial suppliers or may be
prepared by known methods. The starting materials as well as the intermediates may be purified
before use in the next step by state of the art methodologies such as chromatography,
crystallization, distillation and filtration.
For example, compounds of formula (IX) wherein R is an alkyl or alkoxy group and R2 is
a hydrogen or alkyl group may be prepared by reaction of amino-pyrimidine (IV) with
phenylchloroformate to give carbamate product (V). The subsequent reaction with an
appropriately substutited amino-ester (VI) gives compounds of type (VI I) and subsequent
cyclisation gives compounds of type (VI II) and reduction with e.g . with sodium borohydride gives
compounds of type (IX). The methyl amino-ester (VI) may also be replaced by other amino esters
or amino-acids. Phenyl chloroformate may be replaced by other activating groups such as
phosgene or para-nitrophenyl chlorofomate. The cyclisation to (VII I) may occur in situ or require
heating for carboxylic acids or esters or treatment with a reagent such as thionyl chloride for
carboxylic acids. Compounds of type (VII) can be converted to compounds of type (IX) directly by
treatment with a reducing reagent such as DIBAL-H or NaBH4.
Alternatively, compounds of formula (IX) wherein R is an alkyl group or alkoxy group
and R2 is a hydrogen or alkyl group may be prepared by Palladium catalysed reaction of chloropyrimidine
(X) with urea (XI) to give (XI I) (for a reference to a related reaction see
WO2006048249, example 3 .1) and then subsequent cyclisation gives compounds of type (IX).
- -
Urea (XI) may be formed by reaction of ester (XI II) with Grignard reagents, reductive
amination of the product ketone (XIV) with amines and finally reaction of the subsequent product
amine (XV) with TMS-isocyanate to give compounds of type (XI). Alternatively (XV) can be
formed by a Grignard addition of type R2MgCI to appropriate imines. Alternatively, a nitrile can
replace the ester group of (XII I) in the reaction with Grignard reagents.
(XIII) (XV) (XI)
Alternatively, reaction of compounds of type (XIV) with methoxylamine following by
reduction of the oxime ether formed gives compounds of type (XV) which can form compounds of
type (XI) where R 1 is alkoxy. Alternatively, reaction of compounds of type (XIV) where R2 is
hydrogen with methoxylamine followe by addition of Grignard reagents to the formed oxime also
can give compounds of type (XV).
(XIV) (XV) (XI)
R = alkoxy R = a\ o
Compounds of formula (XVII I) wherein R3 is an hydroxy group may be prepared by the
Palladium catalysed reaction of chloro-pyrimidine (X) with urea (XVI) to give urea (XVI I) (for a
reference to a related reaction see WO2006048249, example 3 .1) , which can react with aqueous
glyoxal solution to give product (XVII I). Compounds of formula (IX) where R2 is an alkoxy group
may be prepared by reacting compounds of formula (XVI II) with alcohols of type R4-OH under
acidic conditions.
- -
Alternatively, compounds of formula (V) may be reacted with compounds of formula (XIX)
wherein R2 is a hydrogen or alkyl group to give products of type (XX). Cyclisation with a suitable
reagent such as thionyl chloride gives compounds of formula (XXI), which can be alkylated with a
suitable base such as LiHMDS and a suitable alkylating agent such as methyl iodide (for R-i =
Me) to give compound (VII I). Reduction as before gives compounds of type (IX).
LiHMDS
Ri-X
Alternatively oxidative cleavage (using ozonolysis or Os0 4/Nal0 4 or similar conditions) of
an appropriate vinyl compound such as (XXII) or derivatives thereof and cyclisation could give
the desired product.
Alternatively, compounds of type (XXII I) may be coupled with compounds of type (X)
under transition metal catalysis such as Palladium catalysed conditions to give compounds of
type (VI II) and then standard reduction with NaBH4 for example gives products of type (IX).
- -
m no an c oro-pyr m nes may e ma e y s an ar proce ures suc as ose
outlined below.
Suitable conditions for effecting these transformations are set out in texts such as J.
March, Advanced Organic Chemistry, 4th ed. Wiley, New York, 1992.
The compounds of formula (I) according to the invention can be used as herbicides in
unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal
compositions in various ways using formulation adjuvants, such as carriers, solvents and surfaceactive
substances. Therefore, the invention also relates to a herbicidal composition which
comprises a herbicidally effective amount of a compound of formula (I) in addition to formulation
adjuvants. The formulations can be in various physical forms, e.g. in the form of dusting powders,
gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent
pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oilflowables,
aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions,
emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible
organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the
Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th
Edition, 1999. Such formulations can either be used directly or they are diluted prior to use. The
dilutions can be made, for example, with water, liquid fertilizers, micronutrients, biological
organisms, oil or solvents.
The formulations can be prepared e.g. by mixing the active ingredient with the
formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules,
solutions, dispersions or emulsions. The active ingredients can also be formulated with other
adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified
oils of vegetable or animal origin, organic solvents, water, surface-active substances or
combinations thereof. The active ingredients can also be contained in very fine microcapsules
consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This
enables the active ingredients to be released into the environment in controlled amounts (e.g .
slow-release). Microcapsules usually have a diameter of from 0 .1 to 500 microns. They contain
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active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The
active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or
liquid dispersion or in the form of a suitable solution. The encapsulating membranes comprise, for
example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile,
polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers
and starch xanthates or other polymers that are known to the person skilled in the art in this
connection. Alternatively, very fine microcapsules can be formed in which the active ingredient is
contained in the form of finely divided particles in a solid matrix of base substance, but the
microcapsules are not themselves encapsulated.
The formulation adjuvants that are suitable for the preparation of the compositions
according to the invention are known per se. As liquid carriers there may be used: water, toluene,
xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid
anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate,
chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-
dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate,
diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,Ndimethylformamide,
dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl
ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol,
ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate,
ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone,
glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol,
isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate,
lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl
ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane,
n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol,
polyethylene glycol (PEG400), propionic acid , propyl lactate, propylene carbonate, propylene
glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol,
xylenesulfonic acid , paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl
acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol,
ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl
alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-
pyrrolidone and the like. Water is generally the carrier of choice for diluting the concentrates.
Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite
clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed
husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar
substances, as described , for example, in CFR 180. 1001 . (c) & (d).
A large number of surface-active substances can advantageously be used in both solid
and liquid formulations, especially in those formulations which can be diluted with a carrier prior
to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can
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be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical
surface-active substances include, for example, salts of alkyl sulfates, such as
diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate;
alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate;
alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as
sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium
dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-
ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as
lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene
glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and
di-alkylphosphate esters; and also further substances described e.g . in "McCutcheon's
Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 .
Further adjuvants that can usually be used in pesticidal formulations include
crystallization inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming
agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralizing or pHmodifying
substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up
enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes,
microbicides, and also liquid and solid fertilizers.
The compositions according to the invention can additionally include an additive
comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures
of such oils and oil derivatives. The amount of oil additive in the composition according to the
invention is generally from 0.01 to 10 %, based on the spray mixture. For example, the oil
additive can be added to the spray tank in the desired concentration after the spray mixture has
been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for
example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO®
(Rhone-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl
derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains,
for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 %
by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH
modifiers. Especially preferred oil additives comprise alkyl esters of C8-C2 2 fatty acids, especially
the methyl derivatives of C 2-C 8 fatty acids, for example the methyl esters of lauric acid, palmitic
acid and oleic acid, being of importance. Those esters are known as methyl laurate (CAS-1 11-
82-0), methyl palmitate (CAS-1 12-39-0) and methyl oleate (CAS-1 12-62-9). A preferred fatty acid
methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those and other oil
derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern
Illinois University, 2000.
The application and action of the oil additives can be further improved by combination
with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of
suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485.
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Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type,
especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate
type. Special preference is given to ethoxylated C12-C22 fatty alcohols having a degree of
ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol
types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified
heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also
perfluorinated surfactants. The concentration of the surface-active substances in relation to the
total additive is generally from 1 to 30 % by weight. Examples of oil additives consisting of
mixtures of oil or mineral oils or derivatives thereof with surfactants are Edenor ME SU®,
Turbocharge® (Syngenta AG, CH) or ActipronC (BP Oil UK Limited, GB).
If desired , it is also possible for the mentioned surface-active substances to be used in
the formulations on their own, that is to say, without oil additives.
Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture may
contribute to an additional enhancement of action. Suitable solvents are, for example, Solvesso®
(ESSO) or Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be
from 10 to 80 % by weight of the total weight. Oil additives that are present in admixture with
solvents are described, for example, in US-A-4,834,908. A commercially available oil additive
disclosed therein is known by the name MERGE® (BASF Corporation). A further oil additive that
is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada).
In addition to the oil additives listed above, for the purpose of enhancing the action of the
compositions according to the invention it is also possible for formulations of alkylpyrrolidones
(e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic lattices, e.g.
polyacrylamide, polyvinyl compounds or poly-1 -p-menthene (e.g. Bond®, Courier® or Emerald®)
may also be used . It is also possible for solutions that contain propionic acid, for example
Eurogkem Pen-e-trate®, to be added to the spray mixture as action-enhancing agent.
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. Whereas commercial products will preferably be formulated as concentrates, the end
user will normally employ dilute formulations.
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 post-emergence; seed
dressing ; application to the seed furrow; no tillage application etc.), the crop plant, the grass or
weed 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.
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Preferred formulations have especially the following compositions (% = percent by
weight):
Emulsifiable concentrates:
active ingredient: 1 to 95 %, preferably 60 to 90 %
surface-active agent: 1 to 30 %, preferably 5 to 20 %
liquid carrier: 1 to 80 %, preferably 1 to 35 %
Dusts:
active ingredient: 0 .1 to 10 %, preferably 0 .1 to 5 %
solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates :
active ingredient: 5 to 75 %, preferably 10 to 50 %
water: 94 to 24 %, preferably 88 to 30 %
surface-active agent: 1 to 40 %, preferably 2 to 30 %
Wettable powders:
active ingredient: 0.5 to 90 %, preferably 1 to 80 %
surface-active agent: 0.5 to 20 %, preferably 1 to 15 %
solid carrier: 5 to 95 %, preferably 15 to 90 %
Granules :
active ingredient: 0 .1 to 30 %, preferably 0 .1 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The following Examples further illustrate, but do not limit, the invention.
Formulation Examples for herbicides of formula (I) (% = % by weight)
F 1. Emulsifiable concentrates a) b) c) d)
active ingredient 5 % 10 % 25 % 50 %
calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 %
castor oil polyglycol ether 4 % 4 % 4 %
(36 mol of ethylene oxide)
octylphenol polyglycol ether 4 % 2 %
(7-8 mol of ethylene oxide)
Emulsions of any desired concentration can be obtained from such concentrates by dilution with
water.
F2. Solutions a) b) c) d)
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active ingredient 5 % 10 % 50 % 90 %
1-methoxy-3-(3-methoxypropoxy)-
propane 20 % 20 %
polyethylene glycol MW 400 20 % 10 %
NMP 30 % 10 %
arom. hydrocarbon mixture 75 % 60 %
The solutions are suitable for use in the form of microdrops.
F3. Wettable powders a) b) c) d)
active ingredient 5 % 25 % 50 % 80 %
sodium lignosulfonate 4 % 3 %
sodium lauryl sulfate 2 % 3 % 4 %
sodium diisobutylnaphthalenesulfonate
6 % 5 % 6 %
octylphenol polyglycol ether 1 % 2 %
(7-8 mol of ethylene oxide)
highly dispersed silicic acid 3 % 5 % 10 %
kaolin 62 % 35 %
The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground
in a suitable mill, affording wettable powders which can be diluted with water to give suspensions
of any desired concentration.
F4. Coated granules a) b) c)
active ingredient 0 .1 % 5 % 15 %
highly dispersed silicic acid 0.9 % 2 % 2 %
inorganic carrier 99.0 % 93 % 83 %
(diameter 0 .1 - 1 mm)
e.g. CaC0 3 or Si0 2
The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying,
and the solvent is then evaporated off in vacuo.
F5. Coated granules a) b) c)
active ingredient 0 .1 % 5 % 15 %
polyethylene glycol MW 200 1.0 % 2 % 3 %
highly dispersed silicic acid 0.9 % 1 % 2 %
inorganic carrier 98.0 % 92 % 80 %
(diameter 0 .1 - 1 mm)
e.g. CaC0 3 or Si0 2
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The finely ground active ingredient is uniformly applied , in a mixer, to the carrier moistened with
polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruder granules a) b) c) d)
active ingredient 0 .1 % 3 % 5 % 15 %
sodium lignosulfonate 1.5 % 2 % 3 % 4 %
carboxymethylcellulose 1.4 % 2 % 2 % 2 %
kaolin 97.0 % 93 % 90 % 79 %
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with
water. The mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c)
active ingredient 0 .1 % 1 % 5 %
talcum 39.9 % 49 % 35 %
kaolin 60.0 % 50 % 60 %
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the
mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d)
active ingredient 3 % 10 % 25 % 50 %
ethylene glycol 5 % 5 % 5 % 5 %
nonylphenol polyglycol ether 1 % 2 %
( 15 mol of ethylene oxide)
sodium lignosulfonate 3 % 3 % 4 % 5 %
carboxymethylcellulose 1 % 1 % 1 % 1 %
37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 %
solution
silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 %
water 87 % 79 % 62 % 38 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension
concentrate from which suspensions of any desired concentration can be obtained by dilution
with water.
The invention also provides a method of controlling plants which comprises applying to
the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I).
The invention also provides a method of inhibiting plant growth which comprises applying
to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I).
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The invention also provides a method of controlling weeds in crops of useful plants,
comprising applying to said weeds or to the locus of said weeds, or to said useful plants or to the
locus of said useful plants, a compound or a composition of the invention.
The invention also provides a method of selectively controlling grasses and/or weeds in
crops of useful plants which comprises applying to the useful plants or locus thereof or to the
area of cultivation a herbicidally effective amount of a compound of formula (I).
The term "herbicide" as used herein means a compound that controls or modifies the
growth of plants. The term "herbicidally effective amount" means the quantity of such a
compound or combination of such compounds that is capable of producing a controlling or
modifying effect on the growth of plants. Controlling or modifying effects include all deviation from
natural development, for example: killing, retardation, leaf burn, albinism, dwarfing and the like.
The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings,
roots, tubers, stems, stalks, foliage, and fruits. The term "locus" is intended to include soil, seeds,
and seedlings, as well as established vegetation and includes not only areas where weeds may
already be growing, but also areas where weeds have yet to emerge, and also to areas under
cultivation with respect to crops of useful plants. "Areas under cultivation" include land on which
the crop plants are already growing and land intended for cultivation with such crop plants. The
term "weeds" as used herein means any undesired plant, and thus includes not only
agronomically important weeds as described below, but also volunteer crop plants.
The compounds of the invention can be applied before or after planting of the crops,
before weeds emerge (pre-emergence application) or after weeds emerge (post-emergence
application), and are particularly effective when applied post-emergence to the weeds.
Crops of useful plants in which the composition according to the invention can be used
include, but are not limited to, perennial crops, such as citrus fruit, grapevines, nuts, oil palms,
olives, pome fruit, stone fruit and rubber, and annual arable crops, such as cereals, for example
barley and wheat, cotton, oilseed rape, maize, rice, soy beans, sugar beet, sugar cane,
sunflowers, ornamentals, switchgrass, turf and vegetables, especially cereals, maize and soy
beans.
The grasses and weeds to be controlled may be both monocotyledonous species, for
example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria,
Echinochloa, Eriochloa, Lolium, Monochoria, Panicum, Poa, Rottboellia, Sagittaria, Scirpus,
Setaria, Sida and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus,
Chenopodium, Chrysanthemum, Euphorbia, Galium, Ipomoea, Kochia, Nasturtium, Polygonum,
Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.
In all aspects of the invention, in a particular embodiment, the weeds, e.g. to be
controlled and/or growth-inhibited may be monocotyledonous or dicotyledonous weeds, which
are tolerant or resistant to one or more other herbicides for example, HPPD inhibitor herbicides
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such as mesotrione, PSI I inhibitor herbicides such as atrazine or EPSPS inhibitors such as
glyphosate. Such weeds include, but are not limited to resistant Amaranthus biotypes.
Crops are to be understood as also including those crops which have been rendered
tolerant to herbicides or classes of herbicides (e.g. auxins or ALS-, EPSPS-, PPO- and HPPDinhibitors)
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®, respectively.
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 synthesize 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 as being 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 flavor).
Any method of application to weeds/crop of useful plant, or locus thereof, which is
routinely used in agriculture may be used , for example application by spray or broadcast method
typically after suitable dilution of a compound of formula (I) (whether said compound is formulated
and/or in combination with one or more further active ingredients and/or safeners, as described
herein).
The compounds of formula (I) according to the invention can also be used in combination
with other active ingredients, e.g. other herbicides, and/or insecticides, and/or acaricides, and/or
nematocides, and/or molluscicides, and/or fungicides, and/or plant growth regulators. Such
mixtures, and the use of such mixtures to control weeds and/or undesired plant growth, form yet
further aspects of the invention. For the avoidance of doubt, mixtures of invention also include
mixtures of two or more different compounds of formula (I). In particular, the present invention
- -
also relates to a composition of the invention which comprises at least one further herbicide in
addition to the compound of formula (I).
When a compound of formula (I) is combined with at least one additional herbicide, the
following mixtures of the compound of formula (I) are preferred. Compound of formula (I) +
acetochlor, compound of formula (I) + acifluorfen, compound of formula (I) + acifluorfen-sodium,
compound of formula (I) + aclonifen, compound of formula (I) + acrolein, compound of formula (I)
+ alachlor, compound of formula (I) + alloxydim, compound of formula (I) + allyl alcohol,
compound of formula (I) + ametryn, compound of formula (I) + amicarbazone, compound of
formula (I) + amidosulfuron, compound of formula (I) + aminocyclopyrachlor, compound of
formula (I) + aminopyralid, compound of formula (I) + amitrole, compound of formula (I) +
ammonium sulfamate, compound of formula (I) + anilofos, compound of formula (I) + asulam,
compound of formula (I) + atrazine, formula (I) + aviglycine, formula (I) + azafenidin, compound
of formula (I) + azimsulfuron, compound of formula (I) + BCPC, compound of formula (I) +
beflubutamid, compound of formula (I) + benazolin, formula (I) + bencarbazone, compound of
formula (I) + benfluralin, compound of formula (I) + benfuresate, compound of formula (I) +
bensulfuron, compound of formula (I) + bensulfuron-methyl, compound of formula (I) + bensulide,
compound of formula (I) + bentazone, compound of formula (I) + benzfendizone, compound of
formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) +
bicyclopyrone, compound of formula (I) + bifenox, compound of formula (I) + bilanafos,
compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of
formula (I) + borax, compound of formula (I) + bromacil, compound of formula (I) + bromobutide,
formula (I) + bromophenoxim, compound of formula (I) + bromoxynil, compound of formula (I) +
butachlor, compound of formula (I) + butafenacil, compound of formula (I) + butamifos,
compound of formula (I) + butralin, compound of formula (I) + butroxydim, compound of formula
(I) + butylate, compound of formula (I) + cacodylic acid, compound of formula (I) + calcium
chlorate, compound of formula (I) + cafenstrole, compound of formula (I) + carbetamide,
compound of formula (I) + carfentrazone, compound of formula (I) + carfentrazone-ethyl,
compound of formula (I) + CDEA, compound of formula (I) + CEPC, compound of formula (I) +
chlorflurenol, compound of formula (I) + chlorflurenol-methyl, compound of formula (I) +
chloridazon, compound of formula (I) + chlorimuron, compound of formula (I) + chlorimuron-ethyl,
compound of formula (I) + chloroacetic acid, compound of formula (I) + chlorotoluron, compound
of formula (I) + chlorpropham, compound of formula (I) + chlorsulfuron, compound of formula (I) +
chlorthal, compound of formula (I) + chlorthal-dimethyl, compound of formula (I) + cinidon-ethyl,
compound of formula (I) + cinmethylin, compound of formula (I) + cinosulfuron, compound of
formula (I) + cisanilide, compound of formula (I) + clethodim, compound of formula (I) +
clodinafop, compound of formula (I) + clodinafop-propargyl, compound of formula (I) +
clomazone, compound of formula (I) + clomeprop, compound of formula (I) + clopyralid,
compound of formula (I) + cloransulam, compound of formula (I) + cloransulam-methyl,
compound of formula (I) + CMA, compound of formula (I) + 4-CPB, compound of formula (I) +
CPMF, compound of formula (I) + 4-CPP, compound of formula (I) + CPPC, compound of
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formula (I) + cresol, compound of formula (I) + cumyluron, compound of formula (I) + cyanamide,
compound of formula (I) + cyanazine, compound of formula (I) + cycloate, compound of formula
(I) + cyclosulfamuron, compound of formula (I) + cycloxydim, compound of formula (I) +
cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-D,
compound of formula (I) + 3,4-DA, compound of formula (I) + daimuron, compound of formula (I)
+ dalapon, compound of formula (I) + dazomet, compound of formula (I) + 2,4-DB, compound of
formula (I) + 3,4-DB, compound of formula (I) + 2,4-DEB, compound of formula (I) +
desmedipham, formula (I) + desmetryn, compound of formula (I) + dicamba, compound of
formula (I) + dichlobenil, compound of formula (I) + ortho-dichlorobenzene, compound of formula
(I) + para-dichlorobenzene, compound of formula (I) + dichlorprop, compound of formula (I) +
dichlorprop-P, compound of formula (I) + diclofop, compound of formula (I) + diclofop-methyl,
compound of formula (I) + diclosulam, compound of formula (I) + difenzoquat, compound of
formula (I) + difenzoquat metilsulfate, compound of formula (I) + diflufenican, compound of
formula (I) + diflufenzopyr, compound of formula (I) + dimefuron, compound of formula (I) +
dimepiperate, compound of formula (I) + dimethachlor, compound of formula (I) + dimethametryn,
compound of formula (I) + dimethenamid , compound of formula (I) + dimethenamid-P, compound
of formula (I) + dimethipin, compound of formula (I) + dimethylarsinic acid, compound of formula
(I) + dinitramine, compound of formula (I) + dinoterb, compound of formula (I) + diphenamid,
formula (I) + dipropetryn, compound of formula (I) + diquat, compound of formula (I) + diquat
dibromide, compound of formula (I) + dithiopyr, compound of formula (I) + diuron, compound of
formula (I) + DNOC, compound of formula (I) + 3,4-DP, compound of formula (I) + DSMA,
compound of formula (I) + EBEP, compound of formula (I) + endothal, compound of formula (I) +
EPTC, compound of formula (I) + esprocarb, compound of formula (I) + ethalfluralin, compound
of formula (I) + ethametsulfuron, compound of formula (I) + ethametsulfuron-methyl, formula (I) +
ethephon, compound of formula (I) + ethofumesate, compound of formula (I) + ethoxyfen,
compound of formula (I) + ethoxysulfuron, compound of formula (I) + etobenzanid, compound of
formual (I) + fenoxaprop, compound of formula (I) + fenoxaprop-P, compound of formula (I) +
fenoxaprop-ethyl, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) +
fentrazamide, compound of formula (I) + ferrous sulfate, compound of formula (I) + flamprop-M,
compound of formula (I) + flazasulfuron, compound of formula (I) + florasulam, compound of
formula (I) + fluazifop, compound of formula (I) + fluazifop-butyl, compound of formula (I) +
fluazifop-P, compound of formula (I) + fluazifop-P-butyl, formula (I) + fluazolate, compound of
formula (I) + flucarbazone, compound of formula (I) + flucarbazone-sodium, compound of formula
(I) + flucetosulfuron, compound of formula (I) + fluchloralin, compound of formula (I) + flufenacet,
compound of formula (I) + flufenpyr, compound of formula (I) + flufenpyr-ethyl, formula (I) +
flumetralin, compound of formula (I) + flumetsulam, compound of formula (I) + flumiclorac,
compound of formula (I) + flumiclorac-pentyl, compound of formula (I) + flumioxazin, formula (I) +
flumipropin, compound of formula (I) + fluometuron, compound of formula (I) + fluoroglycofen,
compound of formula (I) + fluoroglycofen-ethyl, formula (I) + fluoxaprop, formula (I) + flupoxam,
formula (I) + flupropacil, compound of formula (I) + flupropanate, compound of formula (I) +
flupyrsulfuron, compound of formula (I) + flupyrsulfuron-methyl-sodium, compound of formula (I)
- -
+ flurenol, compound of formula (I) + fluridone, compound of formula (I) + flurochloridone,
compound of formula (I) + fluroxypyr, compound of formula (I) + flurtamone, compound of formula
(I) + fluthiacet, compound of formula (I) + fluthiacet-m ethyl, compound of formula (I) + fomesafen,
compound of formula (I) + foramsulfuron, compound of formula (I) + fosamine, compound of
formula (I) + glufosinate, compound of formula (I) + glufosinate-ammonium, compound of formula
(I) + glyphosate, compound of formula (I) + halauxifen, compound of formula (I) + halauxifenmethyl,
compound of formula (I) + halosulfuron, compound of formula (I) + halosulfuron-methyl,
compound of formula (I) + haloxyfop, compound of formula (I) + haloxyfop-P, compound of
formula (I) + HC-252, compound of formula (I) + hexazinone, compound of formula (I) +
imazamethabenz, compound of formula (I) + imazamethabenz-methyl, compound of formula (I) +
imazamox, compound of formula (I) + imazapic, compound of formula (I) + imazapyr, compound
of formula (I) + imazaquin, compound of formula (I) + imazethapyr, compound of formula (I) +
imazosulfuron, compound of formula (I) + indanofan, compound of formula (I) and indaziflam,
compound of formula (I) + iodomethane, compound of formula (I) + iodosulfuron, compound of
formula (I) + iodosulfuron-methyl-sodium, compound of formula (I) + ioxynil, compound of formula
(I) and ipfencarbazone, compound of formula (I) + isoproturon, compound of formula (I) +
isouron, compound of formula (I) + isoxaben, compound of formula (I) + isoxachlortole,
compound of formula (I) + isoxaflutole, formula (I) + isoxapyrifop, compound of formula (I) +
karbutilate, compound of formula (I) + lactofen, compound of formula (I) + lenacil, compound of
formula (I) + linuron, compound of formula (I) + MAA, compound of formula (I) + MAMA,
compound of formula (I) + MCPA, compound of formula (I) + MCPA-thioethyl, compound of
formula (I) + MCPB, compound of formula (I) + mecoprop, compound of formula (I) + mecoprop-
P, compound of formula (I) + mefenacet, compound of formula (I) + mefluidide, compound of
formula (I) + mesosulfuron, compound of formula (I) + mesosulfuron-methyl, compound of
formula (I) + mesotrione, compound of formula (I) + metam, compound of formula (I) +
metamifop, compound of formula (I) + metamitron, compound of formula (I) + metazachlor,
compound of formula (I) and metazosulfuron, compound of formula (I) + methabenzthiazuron,
formula (I) + methazole, a compound of formula (I) and methiozolin, compound of formula (I) +
methylarsonic acid, compound of formula (I) + methyldymron, compound of formula (I) + methyl
isothiocyanate, compound of formula (I) + metobenzuron, formula (I) + metobromuron, compound
of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound of formula (I) +
metosulam, compound of formula (I) + metoxuron, compound of formula (I) + metribuzin,
compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound
of formula (I) + MK-61 6 , compound of formula (I) + molinate, compound of formula (I) +
monolinuron, a compound of formula (I) and monosulfuron, a compound of formula (I) and
monosulfuron-ester compound of formula (I) + MSMA, compound of formula (I) + naproanilide,
compound of formula (I) + napropamide, compound of formula (I) + naptalam, formula (I) + NDA-
402989, compound of formula (I) + neburon, compound of formula (I) + nicosulfuron, formula (I) +
nipyraclofen, formula (I) + n-methyl glyphosate, compound of formula (I) + nonanoic acid,
compound of formula (I) + norflurazon, compound of formula (I) + oleic acid (fatty acids),
compound of formula (I) + orbencarb, compound of formula (I) + orthosulfamuron, compound of
- -
formula (I) + oryzalin, compound of formula (I) + oxadiargyl, compound of formula (I) +
oxadiazon, compound of formula (I) + oxasulfuron, compound of formula (I) + oxaziclomefone,
compound of formula (I) + oxyfluorfen, compound of formula (I) + paraquat, compound of formula
(I) + paraquat dichloride, compound of formula (I) + pebulate, compound of formula (I) +
pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) +
pentachlorophenol, compound of formula (I) + pentanochlor, compound of formula (I) +
pentoxazone, compound of formula (I) + pethoxamid, compound of formula (I) + petrolium oils,
compound of formula (I) + phenmedipham, compound of formula (I) + phenmedipham-ethyl,
compound of formula (I) + picloram, compound of formula (I) + picolinafen, compound of formula
(I) + pinoxaden, compound of formula (I) + piperophos, compound of formula (I) + potassium
arsenite, compound of formula (I) + potassium azide, compound of formula (I) + pretilachlor,
compound of formula (I) + primisulfuron, compound of formula (I) + primisulfuron-methyl,
compound of formula (I) + prodiamine, compound of formula (I) + profluazol, compound of
formula (I) + profoxydim, formula (I) + prohexadione-calcium, compound of formula (I) +
prometon, compound of formula (I) + prometryn, compound of formula (I) + propachlor,
compound of formula (I) + propanil, compound of formula (I) + propaquizafop, compound of
formula (I) + propazine, compound of formula (I) + propham, compound of formula (I) +
propisochlor, compound of formula (I) + propoxycarbazone, compound of formula (I) +
propoxycarbazone-sodium, compound of formula (I) + propyzamide, compound of formula (I) +
prosulfocarb, compound of formula (I) + prosulfuron, compound of formula (I) + pyraclonil,
compound of formula (I) + pyraflufen, compound of formula (I) + pyraflufen-ethyl, formula (I) +
pyrasulfotole, compound of formula (I) + pyrazolynate, compound of formula (I) + pyrazosulfuron,
compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen,
compound of formula (I) + pyribenzoxim, compound of formula (I) + pyributicarb, compound of
formula (I) + pyridafol, compound of formula (I) + pyridate, compound of formula (I) + pyriftalid ,
compound of formula (I) + pyriminobac, compound of formula (I) + pyriminobac-methyl,
compound of formula (I) + pyrimisulfan, compound of formula (I) + pyrithiobac, compound of
formula (I) + pyrithiobac-sodium, formula (I) + pyroxasulfone, formula (I) + pyroxulam, compound
of formula (I) + quinclorac, compound of formula (I) + quinmerac, compound of formula (I) +
quinoclamine, compound of formula (I) + quizalofop, compound of formula (I) + quizalofop-P,
compound of formula (I) + quizalofop-ethyl, compound of formula (I) + quizalofop-P-ethyl,
compound of formula (I) + rimsulfuron, compound of formula (I) + saflufenacil, compound of
formula (I) + sethoxydim, compound of formula (I) + siduron, compound of formula (I) + simazine,
compound of formula (I) + simetryn, compound of formula (I) + SMA, compound of formula (I) +
sodium arsenite, compound of formula (I) + sodium azide, compound of formula (I) + sodium
chlorate, compound of formula (I) + sulcotrione, compound of formula (I) + sulfentrazone,
compound of formula (I) + sulfometuron, compound of formula (I) + sulfometuron-methyl,
compound of formula (I) + sulfosate, compound of formula (I) + sulfosulfuron, compound of
formula (I) + sulfuric acid, compound of formula (I) + tar oils, compound of formula (I) + 2,3,6-
TBA, compound of formula (I) + TCA, compound of formula (I) + TCA-sodium, formula (I) +
tebutam, compound of formula (I) + tebuthiuron, formula (I) + tefuryltrione, compound of formula
- -
1 + tembotrione, compound of formula (I) + tepraloxydim, compound of formula (I) + terbacil,
compound of formula (I) + terbumeton, compound of formula (I) + terbuthylazine, compound of
formula (I) + terbutryn, compound of formula (I) + thenylchlor, compound of formula (I) +
thiazafluron, compound of formula (I) + thiazopyr, compound of formula (I) + thifensulfuron,
compound of formula (I) + thiencarbazone, compound of formula (I) + thifensulfuron-methyl,
compound of formula (I) + thiobencarb, compound of formula (I) + tiocarbazil, compound of
formula (I) + topramezone, compound of formula (I) + tralkoxydim, a compound of formula (I) and
triafamone compound of formula (I) + tri-allate, compound of formula (I) + triasulfuron, compound
of formula (I) + triaziflam, compound of formula (I) + tribenuron, compound of formula (I) +
tribenuron-methyl, compound of formula (I) + tricamba, compound of formula (I) + triclopyr,
compound of formula (I) + trietazine, compound of formula (I) + trifloxysulfuron, compound of
formula (I) + trifloxysulfuron-sodium, compound of formula (I) + trifluralin, compound of formula (I)
+ triflusulfuron, compound of formula (I) + triflusulfuron-methyl, compound of formula (I) + trifop,
compound of formula (I) + trifop-methyl, compound of formula (I) + trihydroxytriazine, compound
of formula (I) + trinexapac-ethyl, compound of formula (I) + tritosulfuron, compound of formula (I)
+ [3-[2-chloro-4-fluoro-5-(1 -methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-
yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS RN 353292-31 -6), compound of formula (I)
+ 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl-1 ,3-
cyclohexanedione and the compound of formula (I) + VX-573.
In particular, the following mixtures are important:
mixtures of a compound of formula (I) with an acetanilide (e.g. compound of formula (I) +
acetochlor, compound of formula (I) + dimethenamid, compound of formula (I) + metolachlor,
compound of formula (I) + S-metolachlor, or compound of formula (I) + pretilachlor) or with other
inhibitors of very long chain fatty acid esterases (VLCFAE) (e.g. compound of formula (I) +
pyroxasulfone).
mixtures of a compound of formula (I) with an HPPD inhibitor (e.g . compound of formula (I)
+ isoxaflutole, compound of formula (I) + mesotrione, compound of formula (I) + pyrasulfotole,
compound of formula (I) + sulcotrione, compound of formula (I) + tembotrione, compound of
formula (I) + topramezone, compound of formula (I) + bicyclopyrone;
mixtures of a compound of formula (I) with a triazine (e.g . compound of formula (I) +
atrazine, or compound of formula (I) + terbuthylazine);
mixtures of a compound of formula (I) with glyphosate;
mixtures of a compound of formula (I) with glufosinate-ammonium;
- -
mixtures of a compound of formula (I) with a PPO inhibitor (e.g. compound of formula (I) +
acifluorfen-sodium, compound of formula (I) + butafenacil, compound of formula (I) +
carfentrazone-ethyl, compound of formula (I) + cinidon-ethyl, compound of formula (I) +
flumioxazin, compound of formula (I) + fomesafen, compound of formula (I) + lactofen, or
compound of formula (I) + SYN 523 ([3-[2-chloro-4-fluoro-5-(1 -methyl-6-trifluoromethyl-2,4-dioxo-
1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester) (CAS RN 353292-
3 1-6)).
Whilst two-way mixtures of a compound of formula (I) and another herbicide are explicitly
disclosed above, the skilled man will appreciate that the invention extends to three-way, and
further multiple combinations comprising the above two-way mixtures. In particular, the invention
extends to:
mixtures of a compound of formula (I) with a triazine and an HPPD inhibitor (e.g .
compound of formula (I) + triazine + isoxaflutole, compound of formula (I) + triazine + mesotrione,
compound of formula (I) + triazine + pyrasulfotole, compound of formula (I) + triazine +
sulcotrione, compound of formula (I) + triazine + tembotrione, compound of formula (I) + triazine
+ topramezone, compound of formula (I) + triazine + bicyclopyrone;
mixtures of a compound of formula (I) with glyphosate and an HPPD inhibitor (e.g .
compound of formula (I) + glyphosate + isoxaflutole, compound of formula (I) + glyphosate +
mesotrione, compound of formula (I) + glyphosate + pyrasulfotole, compound of formula (I) +
glyphosate + sulcotrione, compound of formula (I) + glyphosate + tembotrione, compound of
formula (I) + glyphosate + topramezone, compound of formula (I) + glyphosate + bicyclopyrone;
mixtures of a compound of formula (I) with glufosinate-ammonium and an HPPD inhibitor
(e.g. compound of formula (I) + glufosinate-ammonium + isoxaflutole, compound of formula (I) +
glufosinate-ammonium + mesotrione, compound of formula (I) + glufosinate-ammonium +
pyrasulfotole, compound of formula (I) + glufosinate-ammonium + sulcotrione, compound of
formula (I) + glufosinate-ammonium + tembotrione, compound of formula (I) + glufosinateammonium
+ topramezone, compound of formula (I) + glufosinate-ammonium + bicyclopyrone;
mixtures of a compound of formula (I) with a VLCFAE inhibitor and an HPPD inhibitor (e.g.
compound of formula (I) + S-metolachlor + isoxaflutole, compound of formula (I) + S-metolachlor
+ mesotrione, compound of formula (I) + S-metolachlor + pyrasulfotole, compound of formula (I)
+ S-metolachlor + sulcotrione, compound of formula (I) + S-metolachlor + tembotrione,
compound of formula (I) + S-metolachlor + topramezone, compound of formula (I) + Smetolachlor
+ bicyclopyrone, compound of formula (I) + acetochlor + isoxaflutole, compound of
formula (I) + acetochlor + mesotrione, compound of formula (I) + acetochlor + pyrasulfotole,
compound of formula (I) + acetochlor + sulcotrione, compound of formula (I) + acetochlor +
tembotrione, compound of formula (I) + acetochlor + topramezone, compound of formula (I) +
- -
acetochlor + bicyclopyrone, compound of formula (I) + pyroxasulfone + isoxaflutole, compound of
formula (I) + pyroxasulfone + mesotrione, compound of formula (I) + pyroxasulfone +
pyrasulfotole, compound of formula (I) + pyroxasulfone + sulcotrione, compound of formula (I) +
pyroxasulfone + tembotrione, compound of formula (I) + pyroxasulfone + topramezone,
compound of formula (I) + pyroxasulfone + bicyclopyrone.
Particularly preferred are mixtures of the compound of formula (I) with mesotrione,
bicyclopyrone, isoxaflutole, tembotrione, topramezone, sulcotrione, pyrasulfotole, metolachlor, Smetolachlor,
acetochlor, pyroxasulfone, P-dimethenamid, dimethenamid , flufenacet, pethoxamid ,
atrazine, terbuthylazine, bromoxynil, metribuzin, amicarbazone, bentazone, ametryn, hexazinone,
diuron, tebuthiuron, glyphosate, paraquat, diquat, glufosinate, acifluorfen-sodium, butafenacil,
carfentrazone-ethyl, cinidon-ethyl, flumioxazin, fomesafen, lactofen, [3-[2-chloro-4-fluoro-5-(1 -
methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic
acid ethyl ester.
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, 14th Edition (BCPC), 2006. The reference to
acifluorfen-sodium also applies to acifluorfen, the reference to dimethenamid also applies to
dimethenamid-P, the reference to glufosinate-ammonium also applies to glufosinate, the
reference to bensulfuron-methyl also applies to bensulfuron, the reference to cloransulam-methyl
also applies to cloransulam, the reference to flamprop-M also applies to flamprop, and the
reference to pyrithiobac-sodium also applies to pyrithiobac, etc.
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 active ingredients, in particular with one or more further
herbicides, can also be used in combination with one or more safeners. The term "safener" as
used herein means a chemical that when used in combination with a herbicide reduces the
undesirable effects of the herbicide on non-target organisms, for example, a safener protects
crops from injury by herbicides but does not prevent the herbicide from killing the weeds. Where
a compound of formula (I) is combined with a safener, the following combinations of the
compound of formula (I) and the safener are particularly preferred. Compound of formula (I) + AD
67 (MON 4660), compound of formula (I) + benoxacor, compound of formula (I) + cloquintocet-
-
mexyl, compound of formula (I) + cyometrinil and a compound of formula (I) + the corresponding
(Z) isomer of cyometrinil, compound of formula (I) + cyprosulfamide (CAS RN 22 1667-31 -8),
compound of formula (I) + dichlormid, compound of formula (I) and dicyclonon, compound of
formula (I) and dietholate, compound of formula (I) + fenchlorazole-ethyl, compound of formula (I)
+ fenclorim, compound of formula (I) + flurazole, compound of formula (I) + fluxofenim,
compound of formula (I) + furilazole and a compound of formula (I) + the corresponding R isomer
or furilazome, compound of formula (I) + isoxadifen-ethyl, compound of formula (I) + mefenpyrdiethyl,
compound of formula (I) and mephenate, compound of formula (I) + oxabetrinil,
compound of formula (I) + naphthalic anhydride (CAS RN 8 1-84-5), compound of formula (I) and
TI-35, compound of formula (I) + N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS
RN 221 668-34-4) and a compound of formula (I) + N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide. Particularly preferred are mixtures of a
compound of formula (I) with benoxacor, a compound of formula (I) with cloquintocet-mexyl, a
compound of formula (I) + cyprosulfamide and a compound of formula (I) with 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 cloquintocet and to a lithium, sodium, potassium, calcium,
magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt
thereof as disclosed in WO02/34048 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) and any
further active ingredient, in particular a further herbicide, with the safener).
It is possible that the safener and a compound of formula (I) and one or more additional
herbicide(s), if any, are applied simultaneously. For example, the safener, a compound of formula
(I) and one or more additional herbicide(s), if any, might be applied to the locus pre-emergence or
might be applied to the crop post-emergence. It is also possible that the safener and a compound
of formula (I) and one or more additional herbicide(s), if any, are applied sequentially. For
example, the safener might be applied before sowing the seeds as a seed treatment and a
compound of formula (I) and one or more additional herbicides, if any, might be applied to the
locus pre-emergence or might be applied to the crop post-emergence.
Preferred mixtures of a compound of formula (I) with further herbicides and safeners
include:
Mixtures of a compound of formula with S-metolachlor and a safener, particularly
benoxacor.
Mixtures of a compound of formula with isoxaflutole and a safener.
Mixtures of a compound of formula with mesotrione and a safener.
Mixtures of a compound of formula with sulcotrione and a safener.
Mixtures of a compound of formula with tembotrione and a safener.
Mixtures of a compound of formula with topramezone and a safener.
Mixtures of a compound of formula with bicyclopyrone and a safener.
Mixtures of a compound of formula with a triazine and a safener.
Mixtures of a compound of formula with a triazine and isoxaflutole and a safener.
Mixtures of a compound of formula with a triazine and mesotrione and a safener.
Mixtures of a compound of formula with a triazine and sulcotrione and a safener.
Mixtures of a compound of formula with a triazine and tembotrione and a safener.
Mixtures of a compound of formula with a triazine and topramezone and a safener.
Mixtures of a compound of formula with a triazine and bicyclopyrone and a safener.
Mixtures of a compound of formula with glyphosate and a safener.
Mixtures of a compound of formula with glyphosate and isoxaflutole and a safener.
Mixtures of a compound of formula with glyphosate and mesotrione and a safener.
Mixtures of a compound of formula with glyphosate and sulcotrione and a safener.
Mixtures of a compound of formula with glyphosate and tembotrione and a safener.
Mixtures of a compound of formula with glyphosate and topramezone and a safener.
- -
Mixtures of a compound of formula (I) with glyphosate and bicyclopyrone and a safener.
Mixtures of a compound of formula (I) with glufosinate-ammonium and a safener.
Mixtures of a compound of formula (I) with glufosinate-ammonium and isoxaflutole and a
safener.
Mixtures of a compound of formula (I) with glufosinate-ammonium and mesotrione and a
safener.
Mixtures of a compound of formula (I) with glufosinate-ammonium and sulcotrione and a
safener.
Mixtures of a compound of formula (I) with glufosinate-ammonium and tembotrione and a
safener.
Mixtures of a compound of formula (I) with glufosinate-ammonium and topramezone and a
safener.
Mixtures of a compound of formula (I) with glufosinate-ammonium and bicyclopyrone and a
safener.
Mixtures of a compound of formula (I) with S-metolachlor and a safener.
Mixtures of a compound of formula (I) with S-metolachlor and isoxaflutole and a safener.
Mixtures of a compound of formula (I) with S-metolachlor and mesotrione and a safener.
Mixtures of a compound of formula (I) with S-metolachlor and sulcotrione and a safener.
Mixtures of a compound of formula (I) with S-metolachlor and tembotrione and a safener.
Mixtures of a compound of formula (I) with S-metolachlor and topramezone and a safener.
Mixtures of a compound of formula (I) with S-metolachlor and bicyclopyrone and a safener
Mixtures of a compound of formula (I) with pyroxasulfone and a safener.
Mixtures of a compound of formula (I) with pyroxasulfone and isoxaflutole and a safener.
- -
Mixtures of a compound of formula with pyroxasulfone and mesotrione and a safener.
Mixtures of a compound of formula with pyroxasulfone and sulcotrione and a safener.
Mixtures of a compound of formula with pyroxasulfone and tembotrione and a safener.
Mixtures of a compound of formula with pyroxasulfone and topramezone and a safener.
Mixtures of a compound of formula with pyroxasulfone and bicyclopyrone and a safener
Mixtures of a compound of formula with acetochlor and a safener.
Mixtures of a compound of formula with acetochlor and isoxaflutole and a safener.
Mixtures of a compound of formula with acetochlor and mesotrione and a safener.
Mixtures of a compound of formula with acetochlor and sulcotrione and a safener.
Mixtures of a compound of formula with acetochlor and tembotrione and a safener.
Mixtures of a compound of formula with acetochlor and topramezone and a safener.
Mixtures of a compound of formula with acetochlor and bicyclopyrone and a safener
Various aspects and embodiments of the present invention will now be illustrated in more
detail by way of example. It will be appreciated that modification of detail may be made without
departing from the scope of the invention.
For the avoidance of doubt, where a literary reference, patent application, or patent, is
cited within the text of this application, the entire text of said citation is herein incorporated by
reference.
Examples
Preparation Examples
The following abbreviations were used in this section: s = singlet; bs = broad singlet; d
doublet; dd = double doublet; dt = double triplet; t = triplet, tt = triple triplet, q = quartet, sept
septet; m = multiplet; RT = retention time, MH+ = molecular mass of the molecular cation.
1H NMR spectra were recorded at 400MHz either on a Varian Unity Inova instrument or
Bruker AVANCE - II instrument.
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Where R2 is not H, the compounds may exist in a mixture of diastereoisomers, which
may be observed by LC-MS and NMR. The stereochemistry of the chiral centre at the carbon
containing the R3 group was generally found to interconvert at room temperature. Depending on
the nature of R2 substitution and the conditions for product synthesis, purification and analysis
the ratio of diastereromers may change.
Example 1 - Preparation of 3-(6-ferf-butylpyrimidin-4-yl)-4-hydroxy-1-methyl-imidazolidin-
2-one (A1)
Procedure for synthesis of 1-(2,2-dimethoxyethyl)-1 -methyl-urea (Step-1)
A solution of (methylamino)acetaldehyde dimethyl acetal ((commercially available) (20 g , 0 .167
mo ) in DCM (46 mL) was treated with trimethylsilyl isocyanate (commercially available) (46 mL,
335 mmol) over 15mins, keeping internal temperature below 25°C. The reaction was then left to
stir at room temperature for 8 days. Reaction was evaporated at reduced pressure ( 100 to 1
mBar with liquid N2 trap at 20 to 40°C) to give a white solid/gum mix, which was dissolved in
100ml water. After 22 h, was evaporated at reduced pressure ( 1mbar at 30-40°C) and left dry for
8h under these conditions to give product as a tacky white solid mass (26.0 g , 95% yield).
H NMR (CDCI3) : 4.80 (br s , 2H), 4.45 (t, 1H), 3.44 (s, 6H), 3.36 (d, 2H), 2.96 (s, 3H).
Procedure for synthesis of 3-(6-ferf-butylpyrimidin-4-yl)-1-(2,2-dimethoxyethyl)-1 -methylurea
(Step-2)
- -
A solution of 1-(2,2-dimethoxyethyl)-1 -methyl-urea ((243 mg, 1.50 mmol), 4-ieri-butyl-6-chloropyrimidine
(for a synthesis see WO 201 1045353) (256 mg, 1.50mmol),
tris(dibenzylideneacetone)dipalladium(0) (34.3 mg, 0.0375 mmol) and 4,5-
bis(diphenylphosphino)-9,9-dimethylxanthene (89.5 mg, 0.150mmol), in 1,4-dioxane (7.5 mL)
was added Cs2C0 3 (733mg, 2.25 mmol) under a Nitrogen atmosphere and the reaction was then
heated at 90°C for 65 minutes in a sealed vial. The mixture was allowed to cool to room
temperature, filtered then chromatographed on silica eluting with 10-85% EtOAc in isohexane.
Fractions containing product were evaporated to give desired product as an amber gum which
was without further purification in the next reaction.
HNMR (CDCI3) : 8.74 (s, 1H), 7.98 (s, 1H), 4.52 (t, 1H), 3.52 (s, 6H), 3.47 (d, 2H), 3.09 (s, 3H),
1.34 (s, 9H).
Procedure for synthesis of 3-(6-ferf-butylpyrimidin-4-yl)-4-hydroxy-1-methyl-imidazolidin-
2-one (Step-3)
A solution of 3-(6-ieri-butylpyrimidin-4-yl)-1-(2,2-dimethoxyethyl)-1-methyl-urea (213 mg, 0.719
mmol) in acetic acid (2 mL) was treated with water (2 mL) and then heated to 100°C. After 50
minutes, the reaction mixture was evaporated and azeotroped with 5 ml toluene. The amber gum
residue was chromatographed on silica (eluting with with 30-55% EtOAc in isohexane. Fractions
containing product were evaporated to give the desired product as an amber gum.
H NMR (CDCI 3) : 8.77 (s, 1H), 8.24 (s, 1H), 6.07 (m, 1H), 5.00 (br s , 1H), 3.71 (dd, 1H), 3.40 (dd,
1H), 2.95 (s, 3H), 1.36 (s, 9H).
LC-MS: (positive ES MH+ 251).
Example 2 and 3 - Preparation of 1-(6-ferf-butylpyrimidin-4-yl)-4,5-dihydroxy-3-methylimidazolidin-
2-one (A4) and 1-(6-ferf-butylpyrimidin-4-yl)-4-ethoxy-5-hydroxy-3-methylimidazolidin-
2-one (A5)
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Procedure for synthesis of 1-(6-tert-butylpyrimidin-4-yl)-3-methyl-urea (Step-1)
A mixture of tris(dibenzylideneacetone)dipalladium(0) (0.0859 g , 0.0938 mmol), 4,5-
bis(diphenylphosphino)-9,9-dimethylxanthene (0.21 0 g , 0.352 mmol), potassium carbonate
(0.822 g , 5.86 mmol) and methylurea (0. 174 g , 2.34 mmol) in 1,4-dioxane ( 15 mL) was treated
with 4-iert-butyl-6-chloro-pyrimidine (for a synthesis see WO 201 1045353)(0.400g, 2.34 mmol).
The mixture was warmed to 75-80°C with stirring under a N2 atmosphere for 3 h.
The reaction mixture was diluted with EtOAc (20ml) and water ( 10ml_) and filtered through a pad
of celite, rinsing through with further small portions of EtOAc and water. The organic phase was
separated and the aqueous further extracted with EtOAc (5ml_). The organic extracts were
combined, washed with brine ( 10ml_), dried over MgS0 4, filtered and the filtrate evaporated
giving an orange liquid. This was chromatographed (eluting with an EtOAc/iso-hexane gradient)
and fractions containing product were evaporated to give the desired product as a light yellow
powder (0. 178 g , 36%).
H NMR (CDCI3) : 9.08 (br.s, 1H), 8.92 (br.s, 1H), 8.71 (s, 1H), 6.79 (s, 1H), 2.97 (d, 3H), 1.33 (s,
9H).
Procedure for synthesis of 1-(6-ferf-butylpyrimidin-4-yl)-4,5-dihydroxy-3-methylimidazolidin-
2-one (A4) (Step-2)
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To 1-(6-ieri-butylpyrimidin-4-yl)-3-methyl-urea (0. 170 g , 0.81 6 mmol) in ethanol (5 mL) was
added glyoxal (40% aqueous solution) (0.71 1 g , 4.90 mmol, 0.562 mL). The mixture was then
heated at reflux for 2 h. The pale yellow reaction mixture was allowed to cool and stand at room
temperature overnight. The reaction mixture was concentrated in vacuo and the residue was
treated with DCM (20ml_) and washed with water (2 x 5ml_). The organic phase was dried over
MgS0 4, filtered and the filtrate concentrated giving the crude product as a yellow oil. This was
chromatographed (eluting with with an EtOAc/iso-hexane gradient) and fractions containing
product were evaporated and dried under high vacuum to give the desired product as a white
foam ( 140mg , 64%). H NMR indicated approximately a 3 :1 ratio of diastereoisomers.
Major diastereoisomer: H NMR (CDCI3) : 8.69 (d , 1H), 8 .14 (d, 1H), 5.71 (s, 1H), 4.98 (s, 1H),
2.99 (s, 3H), 1.34 (s, 9H).
Minor diastereoisomer: H NMR (CDCI3) : 8.75 (d , 1H), 8.21 (d, 1H), 5.92 (d , 1H), 5 .13 (d , 1H),
2.96 (s, 3H), 1.34 (s, 9H).
LC-MS: (positive ES MH+ 267).
Procedure for synthesis of 1-(6-ferf-butylpyrimidin-4-yl)-4-ethoxy-5-hydroxy-3-methylimidazolidin-
2-one (A5 (Step-3)
To a solution of 1-(6-ieri-butylpyrimidin-4-yl)-4,5-dihydroxy-3-methyl-imidazolidin-2-one (0. 120 g,
0.451 mmol) in ethanol (2 mL) was added cone sulfuric acid (0.05 mL) and the mixture was
heated at reflux for 1 h. The reaction mixture was allowed to cool, and was evaporated in vacuo
to give a pale yellow oil. The oil was treated with DCM ( 15 mL) and washed with water (2 x 3
mL), the organic phase dried over MgS0 4, filtered and the filtrate concentrated giving a cloudy,
colourless gum. This was chromatographed (eluting with with an EtOAc/iso-hexane gradient) and
fractions containing product were evaporated to give the desired product ( 17 mg, 13%), which
NMR nOe experiments indicated was the trans diastereoisomer.
- -
H NMR (CDCI3) : 8.76 (d, 1H), 8 .16 (d, 1H), 5.72 (d, 1H), 4.80 (d, 1H), 4.70 (s, 1H), 3.65 (ddq,
2H), 2.99 (s, 3H), 1.34 (s, 9H), 1.27 (t, 3H).
LC-MS: (positive ES MH+ 295).
Example 4 - 1-(6-ferf-butylpyrimidin-4-yl)-5-hydroxy-3-methoxy-4-methyl-imidazolidin-2-
one (A6)
Procedure for s nthesis of N,1 ,1-trimethoxypropan-2-imine (Step-1 )
Methoxylamine hydrochloride (2 1.2 g) was suspended in methanol (65 mL) then potassium
acetate (50.4g, quickly ground in pestle and mortar to break up lumps) was added all at once and
the thick white suspension resulting was stirred at room temp for 15mins then cooled to 15°C and
then 1,1-dimethoxypropan-2-one (30g) was addded slowly over 25mins. The reaction was stirred
at room temperature for 50 mins and then diluted with 200ml DCM, then 100ml sat. NaHC0 3(aq)
was added cautiously over 15mins. After effervescence subsided , the layers were separated,
extracted a further 2 x 80ml DCM, dried Na2S0 4, filtered and concentrated at 220 mbar and 35°C
(care as desired product is volatile) to give 37g amber liquid, which was used without further
purification.
H NMR (CDCI3) showed a 3 :1 ratio of E:Z isomers
Procedure for synthesis of N,1 ,1-trimethoxypropan-2 -amine (Step-2)
N,1,1-trimethoxypropan-2-imine (20g) was dissolved in acetic acid (80 mL) then was cooled to
13°C. NaBH3CN (9.82 g) was added portionwise over 10mins. After 18hrs at rt, reaction was
concentrated to remove bulk of HOAc then residue dissolved in DCM (300ml_) and satd.
NaHC0 3(aq) (300ml_) was added slowly with stirring. The mixture was stirred at rt for 90 mins,
and then 40% NaOH(aq) was added until the solution reached pH 12 . The layers were
separated, extracted with further DCM (3x1 00ml). The combined DCM layers were dried
(Na2S0 4) , filtered and evaporated to give 16.4g of crude product as a pale amber oil, which was
further purified by Kugelrohr distillation ( 120°C at 70mBar) to give product ( 12.0 g, 59% yield)
which was approximately 95% pure by NMR and used without further purification.
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Procedure for synthesis of 1-(2,2-dimethoxy-1-methyl-ethyl)-1-methoxy-urea (Step-3)
N,1,1-trimethoxypropan-2-amine (2.000 g, 13.4 1 mmol) was dissolved in IPA (5ml) and the
mixture was cooled to 0°C under N2, then trimethylsilyl isocyanate (commercially available) (4.83
mL 33.51 mmol) was added and the reaction was allowed to warm to rt and was stirred at room
temp for 24 h. The reaction mixture was worked up by adding DCM (30ml_) and water ( 15 mL),
extracting with further DCM (2x1 5mL), dried (Na2S0 4) , filtered and evaporated to give product as
a white solid ( 1g , 39% yield).
H NMR (CDCI3) : 5.36 (br s , 2H), 4.47 (d, 1H), 4.32 (pentet, 1H), 3.75 (s, 3H), 3.37 (d, 6H) , 1.24
(d, 3H).
Procedure for synthesis of 3-(6-ferf-butylpyrimidin-4-yl)-1-(2,2-dimethoxy-1-methyl-ethyl)-
1-methoxy-urea Step-4)
1-(2,2-dimethoxy-1 -methyl-ethyl)-1 -methoxy-urea ( 150mg, 0.780mmol), 4-ieri-butyl-6-chloropyrimidine
(for a synthesis see WO 201 1045353) ( 160mg), potassium carbonate ( 162 mg),
tris(dibenzylideneacetone)dipalladium(0) ( 15 mg), 4,5-bis(diphenylphosphino)-9,9-
dimethylxanthene (35 mg) were were suspended in 1-4-dioxane ( 1.5ml_) and the mixture was
then heated at 110°C in a sealed vial for 40mins. Further 1-(2,2-dimethoxy-1 -methyl-ethyl)-1 -
methoxy-urea (30 mg), tris(dibenzylideneacetone)dipalladium(0) ( 15 mg) and 4,5-
bis(diphenylphosphino)-9,9-dimethylxanthene (35 mg) was added and the the mixture was then
heated at 110°C in a sealed vial for a further 50mins. The mixture was allowed to cool to room
temperature, diluted with 6ml EtOAc, filtered then chromatographed on silica eluting with 0-1 00%
EtOAc in isohexane. Fractions containing product were evaporated to give the desired product
as a colourless gum (60mg).
H NMR (CDCI3) : 8.77 (s, 1H), 8.35 (br s , 1H), 8 .15 (s, 1H), 4.50 (d , 1H), 4.40 (pentet, 1H), 3.83
(s, 3H), 3.39 (d, 6H), 1.36 (s, 9H), 1.32 (d, 3H).
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Procedure for synthesis of 1-(6-ferf-butylpyrimidin-4-yl)-5-hydroxy-3-methoxy-4-methylimidazolidin-
2-one (Step-5
3-(6-ferf-butylpyrimidin-4-yl)-1 -(2,2-dimethoxy-1 -m (45 mg) was
dissolved in acetic acid ( 1 mL) and water (0.5 mL) and stirred at room temperature for 25 mins
and then at 60°C for 20 mins and at at 85°C for 20 mins. The reaction was left at room
temperature for 3 days before heating again at 80°C for 140 minutes. Reaction mixture was
evaporated and then chromatographed on silica eluting with 0-85% EtOAc in isohexane.
Fractions containing product were evaporated to give the desired product as a colourless gum
(24mg).
NMR indicated a ratio of diastereoisomers in approximately a 2 :1 ratio.
Major diastereoisomer: H NMR (CDCI3) 8.79 (d, 1H), 8.24 (s, 1H), 5.53 (d, 1H), 5 .10 (very br s ,
1H), 3.90 (s, 3H), 3.70 (m, 1H), 1.44 (d, 3H), 1.35 (s, 9H).
Minor diastereoisomer: H NMR (CDCI3) 8.82 (d, 1H), 8.24 (s, 1H), 5.87 (d, 1H), 4.60 (very br s ,
1H), 3.93 (s, 3H), 3.79 (m, 1H), 1.48 (d , 3H), 1.35 (s, 9H).
LC-MS: (positive ES MH+ 281 ) .
Example 5: (A12), (A13), (A14) and (A15):
A sample of compound A3 was separated into four isomers (isomers 1, 2 , 3 and 4) by preparative
chiral HPLC (CHIRALPAK IC column, eluting with isoHexane (containing 0 .1% TFA) and IPA.
The first eluting isomer (isomer 1) and the third eluting isomer (isomer 3) were each found to
equilibrate in solution to each give a mixture of isomers 1 and 3 overnight. The second eluting
isomer (isomer 2) and the fourth eluting isomer (isomer 4) were each found to equilibrate in
solution to each give a mixture of isomers 2 and 4 overnight.
A synthesis from ethyl (2S)-2-(methylamino)propanoate (see Example 6 below) showed that
isomers 2 and 4 were of (S)-configuration at the four position of the dihydro-hydantoin ring.
Similarly, it could be shown that isomers 1 and 3 were of (R)-configu ration at the four position of
the dihydro-hydantoin ring.
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The absolute configuration could also be proven by X-ray crystallography.
Example A12/13 is therefore a readily interconverting mixture of (4R,5S)-1-(6-ieri-butylpyrimidin-
4-yl)-5-hydroxy-3,4-dimethyl-imidazolidin-2-one and (4R,5R)-1-(6-ieri-butylpyrimidin-4-yl)-5-
hydroxy-3,4-dimethyl-imidazolidin-2-one.
Example A14/15 is therefore a readily interconverting mixture of (4S,5S)-1-(6-ieri-butylpyrimidin-
4-yl)-5-hydroxy-3,4-dimethyl-imidazolidin-2-one and (4S,5R)-1-(6-ieri-butylpyrimidin-4-yl)-5-
hydroxy-3,4-dimethyl-imidazolidin-2-one.
Example 6 - (4S,5S)-1-(6-ferf-butylpyrimidin-4-yl)-5-hydroxy-3,4-dimethyl-imidazolidin-2-
one and (4S,5/?)-1 -(6-ferf-butylpyrimidin-4-yl)-5-hydroxy-3,4-dimethyl-imidazolidin-2-one.
(A14 and A15, alternative synthesis)
Procedure for synthesis 6-tert-butylpyrimidin-4-amine (Step-1)
4-iert-butyl-6-chloro-pyrimidine (for a synthesis see WO 201 1045353) (20 g , 117.204 mmol) and
saturated aqueous ammonia (75 mL) were sealed in a pressure tube and heated at 100°C for
18h. The reaction was cooled and the solid filtered off. More solid was removed from tube by
washing with methanol and then evaporating to give further crude product. The combined crude
product was washed with water and dried to give the desired product as a white solid, (16. 1g
(77%).
LC-MS: (positive ES MH+ 152).
Procedure for synthesis of phen l N-(6-tert-butylpyrimidin-4-yl)carbamate (Step 2)
6-ieri-butylpyrimidin-4-amine (900 mg, 5.952 mmol) in DCM was treated with N-ethyl-N-isopropylpropan-
2-amine ( 1 .14 mL, 16.547 mmol). The reaction was cooled with an ice bath to 0°C and
phenyl carbonochloridate (0.747 mL, 5.952 mmol) was added in portions over 30 min. keeping
reaction temperature <5°C. Cooling was removed and reaction was stirred at room temperature
- -
overnight. The reaction was cooled to 0°C again and further N-ethyl-N-isopropyl-propan-2-amine
(300 [it) and phenyl carbonochloridate (200 m I_) were added and reaction was stirred at room
temperature for a further 30 mins. The reaction cooled to 0°C again and further N-ethyl-Nisopropyl-
propan-2-amine ( 150 m I_) and phenyl carbonochloridate ( 100 m I_) were added and
reaction was stirred at room temperature for a further 30 mins. The reaction solution was then
washed twice with aq citric acid, twice with sodium hydrogen carbonate soln, dried (MgS0 4) and
evaporated. The residue was chromatographed (eluting with with an EtOAc/iso-hexane gradient)
and fractions containing product were evaporated to give desired product (580 mg).
LC-MS: (positive ES MH+ 272).
Procedure for synthesis of (5S)-3-(6-ferf-butylpyrimidin-4-yl)-1 ,5-dimethyl-imidazolidine-
2,4-dione (Step 3)
Phenyl N-(6-iert-butylpyrimidin-4-yl)carbamate (207 mg , 0.7623 mmol) and ethyl (2S)-2-
(methylamino)propanoate (for a similar preparation see Tetrahedron Letters 1997, pages 5085-
5086), ( 100 mg, 0.762 mmol ) were stirred at room temperature in DMSO ( 1 mL) for 2h. The
reaction mixture was poured into water and was extracted with DCM. Extracts were washed with
water, dried (MgS0 4) and evaporated to give residue which was then chromatographed on silica
eluting with EtOAc in isohexane. Fractions containing product were evaporated to give the
desired product as a colourless gum (96mg, 48%).
LC-MS: (positive ES MH+ 263).
Uncyclised intermediate ethyl (2S)-2-[(6-ieri-butylpyrimidin-4-yl)carbamoyl-methylamino]
propanoate was also observed. LC-MS: (positive ES MH+ 309). The reaction may be
heated to 80°C for 8h to convert ethyl (2S)-2-[(6-ieri-butylpyrimidin-4-yl)carbamoyl-methylamino]
propanoate to the desired product.
Procedure for synthesis of (4S,5S)-1 -(6-ferf-butylpyrimidin-4-yl)-5-hydroxy-3,4-dimethylimidazolidin-
2-one and (4S,5/?)-1 -(6-ferf-butylpyrimidin-4-yl)-5-hydroxy-3,4-dimethylimidazolidin-
2-one. (Step 4)
- -
(5S)-3-(6-iert-butylpyrimidin-4-yl)-1,5-dimethyl-imidazolidine (85 mg, 0.324 mmol) was
stirred in methanol (5 mL) and was cooled on an ice bath. Sodium borohydride (12.5 mg, 0.324
mmol, 1 equiv.) was added in a single portion and the reaction was stirred for 2h. Further sodium
borohydride (12.5 mg, 0.324 mmol, 1 equiv.) was added and the reaction was stirred for 45 mins
and then the reaction was treated with aq. citric acid solution and extracted with DCM. The
combined organics were washed with water, dried (MgS0 4) and evaporated to give residue
which was then chromatographed on silica eluting with EtOAc in isohexane. Fractions containing
product were evaporated to give the desired product (36 mg, 0.136 mmol, 42%) in an
approximate 2:1 trans:cis ratio by H NMR.
Approximately 10% of the minor enantiomers ((4R,5S)-1-(6-ieri-butylpyrimidin-4-yl)-5-hydroxy-
3,4-dimethyl-imidazolidin-2-one and (4R,5R)-1-(6-ieri-butylpyrimidin-4-yl)-5-hydroxy-3,4-dimethylimidazolidin-
2-one) was detected by chiral HPLC analysis. Levels of these enantiomeric products
could be reduced by keeping the reaction temperature below -10°C in similar reactions.
LC-MS: (positive ES MH+ 265).
Major diastereoisomer: 8.75 (s, 1H), 8.23 (s, 1H), 5.60 (d, 1H), 5.00 (very br s , 1H), 3.53 (m, 1H),
2.93 (s, 3H), 1.32-1.35 (m, 12H).
Minor diastereoisomer: 8.76 (s, 1H), 8.24 (s, 1H), 5.96 (d, 1H), 3.76 (m, 1H), 2.88 (s, 3H), 1.38
(d, 3H), 1.34 (s, 9H).
Table 1 lists examples of compounds of the general formula (I)
(I)
wherein Ra, R , Rd, R , R2, R3 and X are as defined above.
These compounds were made by the general methods described.
Table 1
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Example 7: Preparation of 2-(6-chloropyrimidin-4-yl )-2-methyl-propanenitrile
as used for synthesis of examples of the type A2, A24 and A25
Procedure for synthesis of 2-(6-chloropyrimidin -4-yl)-2-methyl-propanenitrile (Step-1):
Synthesis of fe/t-buty! 2-(6-chioropyrimidin-4-y!)-2-cyano-acetate
- -
4,6-dichloropyrimidine (commercially available) ( 150 g , 1006.847 mmol) and iert-butyl-2-
cyanoacetate (2.5 equiv., 251 7 .116 mmol) were dissolved in THF ( 10 mL/g). This was then
cooled to 0°C and sodium hydride (2.5 equiv, 251 7 .1 mmol) was added portion wise over 30 min.
Then reaction mixture was stirred at rt for 2h. then quenched with sat NH4CI and extracted with
ethyl acetate. Combined organic layers were dried over sodium sulphate, filtered and
concentrated under reduced pressure. Crude product was purified by column chromatography to
give desired ferf-butyl 2-(6-chloropyrimidin-4-yl)-2-cyano-acetate.
Procedure for synthesis of 2-(6-chloropyrimidin-4-yl)-2-methyl-propanenitrile (Steps 2 and
3): Synthesis of ferf-butyl 2-(6-chioropyrimidin-4-y!)-2-cyano-acetate
Step 2 :
Teri-butyl-2-(6-chloropyrimidin-4-yl)-2-cyano-acetate ( 150 g, 591 .3 mmol) was suspended in
dichloromethane ( 10 mL/g) and trifluoroacetic acid ( 15 equiv., 11232.5 mmol) was added at room
temp.The reaction mixture was stirred at rt for 2h. then water was added and DCM layer was
separated . The water layer was again extracted with DCM (500ml x 3). Combined organic layers
were dried over sodium sulphate, filtered and concentrated under reduced pressure. This crude
2-(6-chloropyrimidin-4-yl)acetonitrile material was used for the next step with out further
purification.
Step 3 :
2-(6-chloropyrimidin-4-yl)acetonitrile ( 150 g, 976.7406 mmol) was dissolved in DMF ( 10 mL/g,
19400 mmol) and treated with methyl iodide (5 equiv., 4883.7 mmol) and K2C0 3 (5 equiv. , 4883.7
mmol) at room temperature then the reaction mixture was stirred at rt overnight. Water was then
added and the reaction was extracted with ethyl acetate. The combined organic layers were dried
over sodium sulphate, filtered and concentrated under reduced pressure. The crude product was
purified by column chromatography to give 2-(6-chloropyrimidin-4-yl)-2-methyl-propanenitrile.
LC-MS: positive ES MH+ 182
Example 8: Preparation of 4-chloro-6-(1 -fluoro-1 -methyl-ethyl)pyrimidine as used for
synthesis of examples of the type A20, A21 and A22
- -
Procedure for synthesis of 4-chloro-6- 1-fluoro-1 -methyl-ethyl)pyrimidine (Step-1 ) :
4-(1 -fluoro-1 -methyl-ethyl)-1 H-pyrimidin-6-one (synthesis as described in W09944997) (5.573 g ,
35.69 mmol, 5.573 g) was suspended in POCI3 (55.27 g , 356.9 mmol, 10 equiv. , 33.60 ml.) and
the reaction mixture was heated to 80°C for 2 hours. The reaction mixture was allowed to cool to
ambient temperature, where left to stand overnight without stirring . The reaction mixture was
concentrated in vacuo to remove the excess POCI3. The resulting residue was quenched
carefully with water to destroy any remaining POCI3. The aqueous was extracted with DCM (x2).
The organics were combined and concentrated in vacuo to yield crude product as an orange oil,
which was purified by silica chromatography to give desired product as as a colourless oil (4.269
9)·
LC-MS: positive ES MH+ 175
Example 9 : Preparation of 1,1,3-trimethoxy-N-methyl-propan-2-amine as used for
synthesis of examples of the type A30 and A35
Procedure for synthesis of 1,1,3-trimethoxy-N-methyl-propan-2-amine (Step 1)
A solution of 2-bromo-1 ,1,3-trimethoxy-propane (commercially available) (7 g , 32.85 mmol) in
methylamine (40 % aqueous solution) ( 105 mL, 2 10 mmol) was divided into seven equal portions
and these were heated at 130°C for 1 h in a microwave. The combined reaction mixtures were
then concentrated and the residue obtained was treated with toluene and evaporated again. The
- -
residue was then stirred with DCM, filtered and evaporated to give the crude product that was
taken to next step without further purification.
Example 10: Preparation of 1,1,1 -trifluoro-3,3-dimethoxy-N-methyl-propan-2 -amine as used
for synthesis of examples of the type A31
Procedure for synthesis of 2,2-dimethoxy-N-methyl-ethanimine (Step 1)
Methylamine hydrochloride (4.05 g , 1.05 equiv.) in DCM (60 mL) was cooled to 0°C, then K2C0 3
(5.53 g , 1 equiv.) was added over 5 minutes. Reaction was stirred at 0°C for a further 10 minutes
then 2,2-dimethoxyacetaldehyde (6.04 mL, 40 mmol) was added and the reaction was stirred
vigorously at 0°C. After 5 minutes at 0°C, the reaction was allowed to warm to room temperature.
After 15 minutes at room temperature, DCM was decanted off, solid was extracted with DCM (2 x
15 mL). Combined DCM fractions were dried (Na2S0 4) , filtered, and evaporated to give product
which was used without further purification (4. 10 g, 87%).
Procedure for s nthesis of 1,1,1-trifluoro-3,3-dimethoxy-N-methyl-propan-2 -amine (Step 2)
KHF2 (2.01 g , 0.75 equiv.) was suspended in MeCN (69 mL) and DMF (8.0 mL) under Nitrogen,
and cooled to 0°C then 2,2-dimethoxy-N-methyl-ethanimine (4.02g, 1 equiv.) was added followed
by dropwise addition of TFA (3.28 mL, 1.25 equiv.) over 2 minutes. Reaction was stirred at 0°C
for 5 minutes, then trimethyl(trifluoromethyl)silane (7.6 mL, 1.5 equiv.) was added over 5 mintues
and the reaction was stirred at 0°C for 3h. Reaction was then treated with sat. aqueous NaHC03
(50 mL) over 3 minutes The reaction mixture was then extracted with diethyl ether (3 x 200 mL),
dried (Na2S0 4) , filtered and evaporated (care as product is volatile) to give product ( 14 .1 g , 44%),
which was used without further purification.
Example 11: Preparation of 4-chloro-6-(1 -chloro-1 -methyl-ethyl)pyrimidine as used for
synthesis of examples of the type A37
- -
Procedure for synthesis of 1,1,1-trifluoro-3,3-dimethoxy-N-methyl-propan-2-amine (Step 1)
4-chloro-6-isopropyl-pyrimidine (commercially available, 0.2 g , 1.277 mmol) was dissolved in
carbon tetrachloride (0.2 mL) and then N-chlorosuccinimide (0. 197 g , 1.40 mmol) and benzoyl
benzenecarboperoxoate (0.0639 mmol, 0.01 5 g) were added. The reaction mixture was heated in
a microwave at 150°C for 60 mins. The reaction mixture was then was purified directly by silica
chromatography to give desired product (40 mg, 16%), which was used in the next reaction
without further purification.
Example 12: Preparation of 4-chloro-6-[chloro(difluoro)methyl]pyrimidine as used for
synthesis of examples of the type A39
Procedure for synthesis of 4-chloro-6-[chloro(difluoro)methyl]pyrimidine (Step 1)
4-chloro-6-(difluoromethyl)pyrimidine (commercially available) (820 mg , 4.98 mmol) was
dissolved in CCI4 (5ml). Nitrogen gas was bubbled through for 5mins, then reaction mixture was
cooled to 5°C then tBuOCI ( 1.3eq, 0.74ml, freshly made) was added and stirred at 5°C and
reaction irradiated with 254nm UV probe for 7.25 h. Reaction mixture was evaporated, diluted
with isohexane (2 mL), then chromatographed on silica (eluting with 0-5% EtOAc in isohexane) to
give desired product as a colourless oil ( 160 mg), which was used without further purification.
H NMR (CDCI3) : 9 .15 (s, 1H), 7.68 (d, 1H).
- -
Example 13: Preparation of 4-chloro-6-(2-chloro-1 ,1-dimethyl-ethyl)pyrimidine as used for
synthesis of examples of the type A40
Procedure for synthesis of 4-chloro-6-(2-chloro-1 ,1 -dimethyl-ethyl)pyrimidine (Step 1)
4-tert-butyl-6-chloro-pyrimidine ( 1 g , 5.86 mmol) was dissolved in carbon tetrachloride 29.30 mL)
and N-chlorosuccinimide (0.90 g , 6.44 mmol) and benzoyl benzenecarboperoxoate (0.293 mmol,
0.071 g , 0.05) was added and the reaction mixture was heated in the microwave at 150°C for 30
mins. The solvent was reduced in vacuo and purified by column chromatography (eluting with
Hexane and Ethyl acetate) on a 15 m silica column (for best separation of product). Fractions
containing product were evaporated and giving 4-chloro-6-(2-chloro-1 ,1-dimethyl-ethyl)pyrimidine
(655 mg, 54%).
H NMR (CDCI3) : 8.82-9.07 (m, 1H), 7.29-7.47 (m, 1H), 3.70-3.91 (m, 2H), 1.34-1 .51 (m, 6H)
Example 14: Preparation of 4-chloro-6-(1 -methoxy-1 -methyl-ethyl)pyrimidine as used for
synthesis of examples of the type A41
Procedure for synthesis of 4-chloro-6-(1 -methoxy-1 -methyl-ethyl)pyrimidine (Step 1)
- -
2-(6-chloropyrimidin-4-yl)propan-2-ol (for a synthesis see Dinnell, Kevin et al, WO201 1045353)
( 130 mg , 0.75 mmol) dissolved in THF (2.6 mL) and then methyl iodide ( 1.51 mmol, 0.22g). NaH
( 1.5 equiv., 60 mass%) was then added and the reaction was stirred at rt for 16h.
The reaction mixture was then poured into water (500 mL), and then extracted with ethyl acetate
(3 x 400ml_). The combined organic layers were dried over sodium sulfate and purified by silica
column chromatography to give product as a colourless liquid (2.31 g , 15%), which was used
without further purification.
Example 15 - Herbicidal action
Example 15a: Pre-emerqence herbicidal activity
Seeds of a variety of test species were sown in standard soil in pots. After cultivation for one day
(pre-emergence) under controlled conditions in a glasshouse (at 24/1 6°C, day/night; 14 hours
light; 65% humidity), the plants were 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). The test plants were
then grown in a glasshouse under controlled conditions (at 24/1 6°C, day/night; 14 hours light;
65% humidity) and watered twice daily. After 13 days, the test was evaluated (5= total damage to
plant; 0 = no damage to plant). Results are shown in Table 2 .
Table 2 : Application pre-emerqence
- -
A23 1000 5 5 2 4 1 1
A24 1000 5 5 5 5 4 2
A25 1000 5 5 5 5 4 4
A26 1000 2 1 0 0 0 1
A27 1000 1 1 0 0 0 0
A28 1000 0 0 0 0 0 0
A12 1000 5 5 5 5 3
A13 1000 5 5 5 5 3
A29 1000 5 5 4 4 4 1
A30 1000 5 5 4 4 4 1
A31 1000 2 2 4 3 3 0
A32 1000 3 2 1 1 1 0
A33 1000 5 5 4 5 4 3
A34 1000 4 5 2 1 1 0
A36 1000 5 5 4 4 4 3
A37 1000 5 5 5 5 3
A38 1000 5 5 5 5 2
A39 1000 5 5 5 5 2
A40 1000 5 5 5 5 2
Example 15b: Post-emergence herbicidal activity
Seeds of a variety of test species were sown in standard soil in pots. 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 were 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). The test plants were
then grown in a glasshouse under controlled conditions (at 24/1 6°C, day/night; 14 hours light;
65% humidity) and watered twice daily. After 13 days, the test was evaluated (5 = total damage
to plant; 0 = no damage to plant). Results are shown in Table 3 .
Table 3 : Application post-emergence
- -
A16 1000 5 5 5 3 5 4
A17 1000 5 5 5 3 5 4
A18 1000 5 5 5 4 5 5
A19 1000 2 5 5 3 3 5
A20 1000 5 5 5 4 5 4
A21 1000 5 5 5 5 5 4
A22 1000 5 5 5 5 5 5
A23 1000 5 5 4 1 4 4
A24 1000 5 5 5 4 5 5
A25 1000 5 5 5 5 5 5
A26 1000 2 1 0 1 0 1
A27 1000 3 4 0 1 0 2
A28 1000 0 0 0 0 0 0
A12 1000 5 5 5 5 4
A13 1000 5 5 5 5 4
A29 1000 5 5 5 4 4 1
A30 1000 4 5 5 4 3 1
A31 1000 5 5 1 4 3 1
A32 1000 2 5 2 3 2 1
A33 1000 5 5 5 5 5 3
A34 1000 3 5 2 3 0 2
A36 1000 5 5 5 5 5 5
A37 1000 5 5 5 5 4
A38 1000 5 5 5 5 5
A39 1000 5 5 5 5 5
A40 1000 5 5 5 5 5
ABUTH = Abutilon theophrasti; ; AMARE = Amaranthus retroflexus; SETFA = Setaria faberi;
ALOMY = Alopecurus myosuroides; ECHCG = Echinochloa crus-galli; ZEAMX = Zea mays.

CLAIMS
1. A herbicidal compound of formula (I)
(I)
wherein
X is selected from S and O;
Ra is selected from hydrogen and halogen;
R is selected from hydrogen, formyl, hydroxyl, halogen, nitro, cyano, Ci-C8 alkyl, Ci-C
cyanoalkyl, Ci-C haloalkyl, Ci-C hydroxyalkyl, C 2-C alkenyloxy Ci-C alkyl, Ci-C
alkylthio, C C alkoxy, -C alkoxy C C alkyl, -C alkthio -C alkyl, C C
cyanoalkoxy, Ci-C haloalkoxy, Ci-C alkoxy Ci-C alkoxy, C 2-C 8 alkenyl, C 2-C 8 alkynyl,
C 2-C cyanoalkenyl, C 2-C cyanoalkynyl, C 2-C alkenyloxy, C 2-C alkynyloxy, C 2-C
haloalkenyl, C 2-C haloalkynyl, C 2-C haloalkenyloxy, C 2-C haloalkynyloxy, Ci-C alkoxy
C 2-C alkenyl, Ci-C alkoxy C 2-C alkynyl, Ci-C alkylsulfinyl, Ci-C alkylsulfonyl, Ci-C
haloalkylthio, Ci-C haloalkylsulfinyl, Ci-C haloalkylsulfonyl, Ci-C alkylsulfonyloxy, Ci-C
alkylcarbonyl, Ci-C haloalkylcarbonyl, C 2-C alkenylcarbonyl, C 2-C alkynylcarbonyl, C 2-
C haloalkenylcarbonyl, C 2-C haloalkynylcarbonyl, tri Ci-C alkylsilyl C 2-C alkynyl, a
group R R N-, a group R C (0 )N (R6)-, a group R S(0 2)N(R6)-, a group R R NS0 2- , a group
R R N C (0) Ci-C alkyl, a C -Ci 0 aryloxy group optionally substituted by from 1 to 3 groups
independently selected from halogen, nitro, cyano, C - 3 alkyl, C - 3 alkoxy, C - 3
haloalkyl and C - 3 haloalkoxy, a C -Ci 0 aryl Ci-C3 alkyl group optionally substituted by
from 1 to 3 groups independently selected from halogen, nitro, cyano, Ci-C3 alkyl, Ci-C3
alkoxy, Ci-C3 haloalkyl and Ci-C3 haloalkoxy, a C -Ci 0 benzyloxy group optionally
substituted by from 1 to 3 groups independently selected from halogen, nitro, cyano, Ci-C3
alkyl, Ci-C3 alkoxy, Ci-C3 haloalkyl and Ci-C3 haloalkoxy, a C 3-C heterocyclyl group
optionally substituted by from 1 to 3 groups independently selected from C -C 4 alkyl, a C 3-
C cycloalkyl group optionally substituted with from 1 to 3 groups independently selected
from halogen, cyano, Ci-C alkoxy and Ci-C alkyl and a C 3-C cycloalkenyl group
optionally substituted with from 1to 3 groups independently selected from halogen, cyano,
Ci-C alkoxy and Ci-C alkyl;
Rd is selected from hydrogen, halogen, cyano, Ci-C alkyl and Ci-C haloalkyi;
or R and Rd together with the carbon atoms to which they are attached form a 3-7
membered saturated or partially unsaturated ring optionally comprising from 1to 3
heteroatoms independently selected from S, O and N and optionally substituted with from
1 to 3 groups independently selected from halogen, Ci-C alkyl and Ci-C haloalkyi;
R is selected from hydrogen, Ci-C alkyl optionally substituted with -NR 0R , C - 3
haloalkyi and Ci-C alkoxy; wherein R 0 and R are independently selected from
hydrogen, Ci-C alkyl and Ci-C haloalkyi;
R2 is selected from hydrogen, hydroxyl, halogen, -C alkyl, C2-C alkenyl, C2-C alkynyl,
Ci-C alkoxy, Ci-C haloalkyi, Ci-C haloalkoxy, Ci-C alkoxy Ci-C alkyl, Ci-C cyanoalkyi
and the group -NR 2R13 , wherein R 2 and R 3 are independently selected from hydrogen
and Ci-C alkyl.
or R and R2 together with the nitrogen and carbon atoms to which they are attached form
a 3-7 membered saturated or partially unsaturated ring optionally comprising from 1 to 3
heteroatoms independently selected from S, O and N and optionally substituted with from
1 to 3 groups independently selected from hydroxyl, =0, Ci-C alkyl or Ci-C haloalkyi.
R3 is selected from halogen, hydroxyl, -NR 4R15 , Ci-C alkoxy, or any one of the following
groups
R5 and R6 are independently selected from hydrogen, Ci-C alkyl, Ci-C haloalkyi, C2-C
alkenyl, C2-C alkynyl, or R5 and R6 together with the carbon atoms to which they are
attached form a 3-6 membered saturated or partially unsaturated ring optionally comprising
from 1 to 3 heteroatoms independently selected from S, O and N and optionally substituted
with from 1 to 3 groups independently selected from halogen and Ci-C alkyl;
R 7 and R 8 are independently selected from hydrogen, Ci-C alkyl, Ci-C haloalkyl, C2-C
alkenyl, C2-C alkynyl, a C5-C10 heteroaryl group which can be mono- or bicyclic
comprising from 1 to 4 heteroatoms independently selected from N, O and S and optionally
substituted with 1 to 3 groups independently selected from halogen, C1-C3 alkyl, C1-C3
haloalkyl and C1-C3 alkoxy, a C -Ci 0 aryl group optionally substituted with 1 to 3 groups
independently selected from halogen, nitro, cyano, C1-C3 alkyl, Ci-C 3 alkoxy, Ci-C 3
haloalkyl and Ci-C 3 haloalkoxy, or R 7 and R 8 together with the atoms to which they are
attached form a 3-6 membered saturated or partially unsaturated ring optionally comprising
from 1 to 3 heteroatoms independently selected from S, O and N and optionally substituted
with from 1 to 3 groups independently selected from halogen or Ci-C alkyl;
R 9 is selected from Ci-C alkyl or benzyl optionally substituted with 1 to 3 groups
independently selected from halogen, nitro, cyano, Ci-C 3 alkyl, Ci-C 3 alkoxy, Ci-C 3
haloalkyl and Ci-C 3 haloalkoxy;
R 4 and R 5 are independently selected from hydrogen, Ci-C 2 o alkyl, Ci-C 2 o haloalkyl, C 2 -
C 2 0 alkenyl, C 2 - C 2 0 alkynyl, or R 4 and R 5 together with the carbon atoms to which they
are attached form a 3-6 membered saturated or partially unsaturated ring optionally
comprising from 1 to 3 heteroatoms independently selected from S, O and N and optionally
substituted with from 1 to 3 groups independently selected from halogen and Ci-C alkyl;
or an N-oxide or salt form thereof.
The compound of claim 1, wherein X is O.
The compound of claim 1 or claim 2 , wherein Ra is hydrogen.
The compound of any one of claims 1 to 3 , wherein R is selected from Ci-C 8 alkyl, Ci-C
haloalkyl, C2-C8 alkenyl, Ci-C cyanoalkyl, Ci-C alkoxy, Ci-C hydroxyalkyl, Ci-C alkoxy
-C alkyl, C2-C alkenyloxy -C alkyl, a group R R NC(0) -C alkyl and C3-C
cycloalkyl optionally substituted by from 1 to 3 groups independently selected from cyano,
Ci-C 3 alkyl and Ci-C 3 alkoxy.
The compound of claim 4 , wherein R is selected from Ci-C 8 alkyl, Ci-C haloalkyl, C2-C8
alkenyl, Ci-C cyanoalkyl, Ci-C alkoxy Ci-C alkyl and C3-C cycloalkyl optionally
substituted by from 1 to 3 groups independently selected from cyano and Ci-C 3 alkyl.
6 . The compound of claim 5 , wherein R is selected from Ci-C alkyl, Ci-C 3 haloalkyl, Ci-C
cyanoalkyl and C3-C cycloalkyl optionally substituted by from 1 to 3 groups independently
selected from cyano and Ci-C 3 alkyl.
7 . The compound of claim 6 , wherein R is selected from methyl, ethyl, /'so-propyl, (2-methyl)-
prop-1 -yl, ( 1-methyl)-prop-1 -yl, ieri-butyl, ( 1,1-dimethyl)-prop-1 -yl, ( 1,1-dimethyl)-but-1 -yl,
( 1-methyl-1 -ethyl)-prop-1 -yl, cyclobutyl, cyclopropyl, ( 1-methyl)cycloprop-1 -yl, (1-methyl- 1-
cyano)-eth-1 -yl, ( 1-methyl-1-ethyl-2-cyano)-prop-1 -yl, ( 1,1-dimethyl-2-cyano)-prop-1 -yl, 1-
fluoroethyl, 1,1-difluoroethyl, difluoromethyl, 1-fluoro-1 -methylethyl, trifluoromethyl and 1-
chloro-1 -methylethyl.
8 . The compound of claim 7 , wherein R is selected from ieri-butyl, ( 1-methyl-1 -cyano)-eth-1 -
yl, 1,1-difluoroethyl, 1-fluoro-1 -methylethyl and trifluoromethyl.
9 . The compound of any one of claims 1 to 8 , wherein Rd is hydrogen.
10 . The compound of any one of claims 1 to 9 , wherein R3 is selected from halogen, hydroxyl,
-NR 4R15 Ci-C alkoxy, or any of the following groups
11. The compound of any one of claims 1 to 10 , wherein R7 is selected from Ci-C alkyl, Ci-C
haloalkyl, C 2-C alkenyl, C 2-C alkynyl, a C 5-Ci 0 monocyclic heteroaryl group comprising
from 1 to 4 heteroatoms independently selected from N, O and S and optionally substituted
with 1 to 3 groups independently selected from halogen, C - 3 alkyl, C - 3 haloalkyl and
C - 3 alkoxy, a C -Ci 0 aryl group optionally substituted with 1 to 3 groups independently
selected from halogen, nitro, cyano, C 1- C 3 alkyl, C 1- C 3 alkoxy, C 1- C 3 haloalkyl and C 1- C 3
haloalkoxy.
12 . The compound of claim 10 , wherein R3 is selected from hydroxyl, halogen, -NR 4R15 , -
C alkylcarbonyloxy, Ci-C alkoxycarbonyloxy or aryloxycarbonyloxy wherein the aryl
group may be substituted with 1 to 3 groups independently selected from halogen, nitro,
cyano, C 1- C 3 alkyl, C 1- C 3 alkoxy, C 1- C 3 haloalkyl and C 1- C 3 haloalkoxy.
13 . The compound of claim 12 , wherein R3 is selected from hydroxyl or halogen.
14 . The compound of claim 13 , wherein R3 is hydroxyl.
15 . The compound of any one of claims 1 to 14 , wherein R is C 1- C 3 alkyl, C 1- C 3 alkoxy or -
C 3 haloalkyl.
16 . The compound of claim 15 , wherein R is methyl or methoxy.
17 . The compound of any one of claims 1 to 16 , wherein R2 is hydrogen, hydroxyl, C 1- C 3 alkyl,
C 1- C 3 alkoxy, C 1- C 3 haloalkyl, C 1- C 3 haloalkoxy allyl.
The compound of claim 17 , wherein R2 is hydrogen, methyl or ethoxy.
19 . A herbicidal composition comprising a compound of formula I as defined in any one of
claims 1 to 18 together with at least one agriculturally acceptable adjuvant or diluent.
20. A composition according to claim 19 which comprises a further herbicide in addition to the
compound of formula I.
2 1. A composition according to claim 19 or 20 which comprises a safener.
22. Use of a compound of formula I as defined in any one of claims 1 to 18 or a composition as
defined in any one of claims 19 to 2 1 as a herbicide.
23. A method of controlling weeds in crops of useful plants, comprising applying to said weeds
or to the locus of said weeds, or to said useful plants or to the locus of said useful plants, a
compound of formula I as defined in any one of claims 1 to 18 or a composition as claimed
in any one of claims 19 to 2 1.