CHEMICAL COMPOUNDS
The present invention relates to certain substituted picolinic acid derivatives, to
processes for their preparation, herbicidal compositions comprising them and their use in
controlling plants or inhibiting plant growth.
Herbicidal 4-aminopicolinates are disclosed in WO 01/51468, WO 03/01 1853, WO
2004/089906, WO 2005/016887 and WO 2006/062979.
In part, due to the evolution of herbicide-resistant weed populations, and herbicideresistant
crops becoming volunteer weeds, there is a continuing need to control such
undesired plant growth in particular in crops of useful plants. Other factors, for example, the
demand for cheaper, more effective herbicides, and for herbicides with an improved
environmental profile (e.g. safer, less toxic etc.) also drive the need to identify novel
herbicidal compounds.
It has now been found that certain picolinic acid derivatives display pre- and postemergence
herbicidal activity.
Accordingly, the present invention provides a compound of formula (I)
or salt or N-oxide thereof, wherein:
A is halogen, cyano, optionally substituted alkoxy, optionally substituted aryloxy,
optionally substituted heteroaryloxy, optionally substituted alkylthio, optionally substituted
arylthio, or optionally substituted heteroarylthio;
W is hydrogen, halogen, cyano, nitro, hydroxyl, amino, optionally substituted alkyl,
optionally substituted haloalkyl, optionally substituted cycloalkyl, optionally substituted
alkoxy, optionally substituted alkylamino, optionally substituted dialkylamino, optionally
substituted alkylthio, optionally substituted alkylsulphinyl, optionally substituted
alkylsulphonyl or optionally substituted aryl;
X is azido, nitro, optionally substituted alkoxy, optionally substituted alkylthio or -N
R5R6 and
(i) R5 is hydrogen, optionally substituted C alkyl provided said substitution
does not comprise a ring system, optionally substituted C haloalkyl
provided said substitution does not comprise a ring system, optionally
substituted C3-6 cycloalkyl, C2-4 alkenyl, C2-4 alkynyl, -S0 2R2, or - C(0)R 3
and R6 is hydrogen, optionally substituted C alkyl provided said substitution
does not comprise a ring system, optionally substituted C haloalkyl
provided said substitution does not comprises a ring system, optionally
substituted C3. cycloalkyl, C2 - alkenyl, or C2-4 alkynyl, or
(ii) R5 and R6 together form a group =C(R8)OR9, =C(R1 )SR9, =C(R ')NR 7
2, or
(iii) R5 and R6 together with the N atom to which they are attached form a 3 to 8
membered optionally substituted heterocyclyl or heteroaryl ring system, said
ring system optionally containing 1to 2 further heteroatoms independently
selected from O, S and N,
and R2 is optionally substituted C alkyl or phenyl optionally substituted by 1 to 3 groups
R4, R3 is optionally substituted C alkyl, phenyl optionally substituted by 1 to 3 groups R4,
C alkoxy, or -NR 7
2, each R4 is independently halogen, CM alkyl, CM alkoxy, or CM
alkylsulphonyl, R8 is hydrogen, CM alkyl, C3-6 cycloalkyl, phenyl, CM alkoxy, CM alkylthio,
or - NR 2, R9 is CM alkyl, R10 is hydrogen, CM alkyl, C3- cycloalkyl, phenyl, C alkylthio,
or -NR 2, R1 1 is hydrogen, CM alkyl, C3-6 cycloalkyl, phenyl, or-NR 7
2, and each R7 is
independently hydrogen or C alkyl;
Y is optionally substituted alkyl, optionally substituted haloalkyl, optionally
substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl or
optionally substituted aryl;
Z is -C(0)R 12 , -C(S)R 13 , or-C(=NR 14)R15 and R12 is hydrogen, hydroxyl, optionally
substituted alkoxy, optionally substituted alkenyloxy, optionally substituted cycloalkoxy,
optionally substituted alkylthio, amino, optionally substituted alkylamino or optionally
substituted dialkylamino, R1 is optionally substituted alkoxy, optionally substituted
cycloalkoxy, optionally substituted alkylthio, amino, optionally substituted alkylamino or
optionally substituted dialkylamino, R14 is hydrogen, optionally substituted alkyl, optionally
substituted alkoxy, optionally substituted cycloalkoxy, amino, optionally substituted
alkylamino or optionally substituted dialkylamino and R15 is hydrogen, optionally substituted
alkoxy, optionally substituted cycloalkoxy, optionally substituted alkylthio, amino,
optionally substituted alkylamino or optionally substituted dialkyamino.
"Alkyl" means a linear saturated monovalent hydrocarbon radical of one to twenty
carbon atoms or a branched saturated monovalent hydrocarbon radical of three to twenty
carbon atoms, e.g. methyl, ethyl, n-propyl, wo-propyl, w-butyl, sec-butyl, wo-butyl, tertbutyl,
and the like. Suitably, linear alkyl groups contain one to ten, one to six, one to five or
one to four carbon atoms, more suitably are selected from methyl, ethyl or -propyl and,
most suitably, are methyl or ethyl. Suitably, branched alkyl groups contain three to ten, three
to six or three to five carbon atoms and more suitably are selected from wo-propyl, sec-butyl,
wo-butyl or tert-butyl. It is noted that this definition applies both when the term is used
alone and when it is used as part of a compound term, such as "haloalkyl" and similar terms.
"Cycloalkyl" means a monovalent cyclic hydrocarbon radical of three to ten ring
carbons e.g. cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkyl groups are
fully saturated. Suitably, cycloalkyl groups contain three to six carbon atoms and, more
suitably, are cyclopropyl or cyclobutyl.
"Alkenyl" means a linear monovalent unsaturated hydrocarbon radical of two to ten
carbon atoms, or a branched monovalent hydrocarbon radical of three to ten carbon atoms
containing at least one double bond, e.g. ethenyl, propenyl and the like. Where appropriate,
an alkenyl group can be of either the (E)- or (Z)-configuration. Suitably, linear alkenyl
groups contain two to six carbon atoms, more suitably two to four carbon atoms and, most
suitably are ethenyl (vinyl), prop-l-enyl ( 1-propenyl) or prop-2-enyl (allyl). Suitably,
branched alkenyl groups contain three to six carbon atoms, more suitably from three to four
and, most suitably, are 1-methylethenyl (2-propenyl), 1-methylprop-l-enyl, 1-methylprop-2-
enyl, 2-methylprop-l-enyl and 2-methylprop-2-enyl (2-methylallyl).
"Alkynyl" means a linear monovalent unsaturated hydrocarbon radical of two to ten
carbon atoms, e.g. ethynyl, propynyl and the like. Suitably, alkynyl groups contain two to
six carbon atoms and more suitably two to four carbon atoms e.g. ethynyl, prop-l-ynyl, prop-
2-ynyl, but-l-ynyl, but-2-ynyl and but-3-ynyl.
"Alkoxy" means a radical -OR, where R is alkyl as defined above. Alkoxy groups
include, but are not limited to, methoxy, ethoxy, 1-methylethoxy, propoxy, butoxy, 1-
methylpropoxy and 2-methylpropoxy. Preferably alkoxy means methoxy or ethoxy.
"Cycloalkoxy" means a radical -OR, where R is cycloalkyl as defined above.
"Alkoxyalkyl" means a radical -ROR, where each R is, independently, alkyl as
defined above.
"Alkoxyalkoxy" means a radical -OROR, wherein each R is, independently, alkyl as
defined above.
"Aryl" or "aromatic ring" refers to an aromatic substituent which may be a single
ring or multiple rings which are fused together, linked covalently or linked to a common
group such as an ethylene (-CH2-CH2-) or methylene (-CH2-) moiety. Representative
examples of aryl include, for example, phenyl, naphthyl, azulenyl, indanyl, indenyl,
anthracenyl, phenanthrenyl, tetrahydronaphthyl, biphenyl, diphenylmethyl and 2,2-diphenyl-
1-ethyl. Preferred aryl groups are phenyl and naphthyl groups.
"Heteroaryl" means a ring system consisting either of a single aromatic ring or of two
or more fused rings, at least one of which is aromatic, the other or others independently
being saturated, unsaturated or aromatic, containing one, two, three or four ring heteroatoms
selected, independently, from N, O or S, the remaining ring atoms being carbon. Examples
of heteroaryl groups include, but are not limited to 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[l,5-a]pyrimidinyl. Preferred heteroaryl groups
include pyridyl, pyrimidinyl, furanyl, thiophenyl, thiazolyl, pyrrolyl, pyrazolyl, imidazolyl,
triazolyl, benzothiophenyl, benzimidazolyl and quinolinyl.
"Heterocyclyl" means a ring system consisting either of a single ring or of two or
more fused rings, which may be saturated or unsaturated, containing one, two, three or four
ring heteroatoms selected, independently, from N, O or S, the remaining atoms being carbon.
Examples of heterocyclyl groups include, but are not limited to pyrrolidinyl, imidazolinyl,
pyrazolidinyl, piperidyl, piperazinyl, quinuclidinyl, morpholinyl, together with unsaturated
or partially unsaturated analogues such as 4,5,6,7-tetrahydro-benzothiophenyl, chromen-4-
onyl, 9H-fluorenyl, 3,4-dihydro-2H-benzo-l,4-dioxepinyl, 2,3-dihydro-benzofuranyl,
piperidinyl, 1,3-dioxolanyl, 1,3-dioxanyl, 4,5-dihydro-isoxazolyl, tetrahydrofuranyl and
morpholinyl. Preferred heterocyclyl groups include aziridinyl, azetidinyl, pyrrolidinyl,
piperidinyl, piperazinyl and morpholinyl.
"Halo" or "halogen" means fluoro, chloro, bromo or iodo, preferably chloro or
fluoro.
"Haloalkyl" means alkyl as defined above substituted with one or more of the same
or different halo atoms. Examples of haloalkyl groups include, but are not limited to
chloromethyl, fluoromethyl, dichloromethyl, difluoromethyl, trichloromethyl,
trifiuoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,2-difluoroethyl, 2,2-
difluoroethyl, pentafluoroethyl, 2-chloroethyl, 3-fluoropropyl, 3-chloropropyl, 2,2,2-
trifluoro-l-chloroethyl and heptafluoropropyl.
"Haloalkenyl" means alkenyl as defined above substituted with one or more of the
same or different halo atoms. Examples of haloalkenyl groups include, but are not limited to
2,2-dibromoethenyl, 2-fluoro-2-bromoethenyl, and 3,3-dichloroprop-2-enyl.
"Haloalkoxy" means a radical -OR, wherein R is haloalkyl as defined above.
"Aryloxy" means a radical -OR, wherein R is an aryl group as defined above.
"Heteroaryloxy" means a radical -OR, wherein R is a heteroaryl group as defined
above.
"Alkylthio" means a radical -SR, where R is an alkyl group as defined above.
Alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, tertbutylthio,
and the like.
"Haloalkylthio" means a radical -SR, where R is a haloalkyl group as defined above.
"Arylthio" means a radical -SR, wherein R is an aryl group as defined above.
"Heteroarylthio" means a radical -SR, wherein R is a heteroaryl group as defined
above.
"Alkylsulphinyl" means -S(0)R, wherein R is an alkyl group as defined above.
"Alkylsulphonyl" means -S(0) 2R, wherein R is an alkyl group as defined above.
"Alkylsulphonylamino" means a radical -NHS(0) 2R, wherein R is an alkyl group as
defined above.
"Alkylcarbonyl" means a radical -C(0)R, wherein R is alkyl as defined above.
"Aminocarbonyl" means a radical -C(0)NH .
"Alkylcarbonylamino" means a radical -NHC(0)R, wherein R is alkyl as defined
above
"Cyano" means a -CN group.
"Hydroxy" or "hydroxyl" means an -OH group.
"Nitro" means an -NO 2 group.
"Amino" means an -NH 2 group.
"Carboxy" or "carboxyl" means a -C(0)OH group.
"Azido" means the group -N=N=N.
"Oxo" means the group =0.
"Alkylamino" means a radical -NRH, where R is alkyl as defined above. Examples
of alkylamino groups are methylamino, ethylamino, n-propylamino, i-propylamino etc
"Dialkylamino" means a radical -NRR, where each R is, independently, alkyl as
defined above. Examples of dialkylamino groups are dimethylamino, diethylamino, di-npropylamino,
methylethylamino, methyisopropylamino, etc.
"Alkoxycarbonyl" means -C(0)OR, wherein R is an alkyl group as defined above.
Examples of alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, ipropoxycarbonyl,
n-propoxycarbonyl, n-butoxycarbonyl and s-butoxycarbonyl etc.
"Alkylcarbonyloxy" means -OC(0)R, wherein R is an alkyl group as defined above.
"Arylalkoxy" means -OR-aryl, wherein R is an alkyl group as defined above.
"Trialkylsilyl" means the group -Si(R)3, wherein each R is, independently, an alkyl
group as defined above.
The groups defined above when used alone or as part of a compound term (e.g. alkyl
when used alone or as part of, for example, haloalkyl) may be optionally substituted where
possible by one or more substituents, preferably by one, two, three or four substituents. In
particular, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, cycloalkoxy, haloalkoxy,
alkylamino, dialkylamino, alkylthio, haloalkylthio, alkylsulphinyl, alkylsulphonyl, aryl,
heteroaryl, aryloxy, arylthio, heteroaryloxy and heteroarylthio groups may be optionally
substituted.
Suitably, for alkyl, haloalkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, alkylamino,
dialkylamino, alkylthio, haloalkylthio, alkylsulphinyl, alkylsulphonyl, cycloalkyl or
cycloalkoxy groups, these optional substituents are independently selected from hydroxyl,
halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkoxyalkoxy,
alkylcarbonyloxy, carboxyl, trialkylsilyl, aryl (in particular, phenyl), heteroaryl, amino,
alkylamino, dialkylamino, -SRa, -S(0)R a, S(0) 2Ra (wherein Ra is alkyl, haloalkyl, alkenyl,
alkynyl, cycloalkyl or alkylcarbonylamino), C(0)R b (wherein Rb is hydrogen, hydroxyl,
alkyl, haloalkyl, cycloalkyl, alkoxy, arylalkoxy (in particular phenylalkoxy), cycloalkoxy,
amino, alkylamino, dialkylamino or alkylsulphonylamino) or any two geminal optional
substituents may form an oxo group. Aryl and heteroaryl optional substituents on these
groups may be further substituted by one or more substituents independently selected from
halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, alkylsulphonyl or
alkoxycarbonyl.
Suitably, for aromatic groups, these optional substituents are independently selected
from hydroxyl, halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy,
alkoxyalkoxy, alkylcarbonyloxy, amino, alkylamino, dialkylamino, -SRa, -S(0)R a, S(0) Ra
(wherein Ra is alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl or alkylcarbonylamino), C(0)R
(wherein R is hydrogen, hydroxyl, alkyl, haloalkyl, cycloalkyl, alkoxy, arylalkoxy (in
particular phenylalkoxy), cycloalkoxy, amino, alkylamino, dialkylamino or
alkylsulphonylamino) or any two geminal optional substituents may form, where possible, a
group selected from oxo, =CRd
2, =NORe or =NNReR (wherein each Rd is, independently,
hydrogen, halogen, cyano, nitro, alkyl, cycloalkyl, alkylcarbonyl, alkoxycarbonyl,
alkylsulphonyl or aminocarbonyl; each Re is, independently, hydrogen, alkyl or cycloalkyl;
each R is, independently, hydrogen or alkyl). Optional substituents on an aromatic ring may
be further substituted by one or more substituents independently selected from hydroxyl,
cyano, cycloalkyl, alkoxy, haloalkoxy, alkoxyalkoxy, alkylcarbonyloxy, amino, alkylamino,
dialkylamino, -SRa, -S(0)R a, S(0) 2Ra (wherein R is alkyl, haloalkyl, alkenyl, alkynyl,
cycloalkyl or alkylcarbonylamino), C(0)R b (wherein Rb is hydrogen, hydroxyl, alkyl,
haloalkyl, cycloalkyl, alkoxy, arylalkoxy (in particular phenylalkoxy), cycloalkoxy, amino,
alkylamino, dialkylamino or alkylsulphonylamino).
It is noted that, when X is -NR 5R6 and either or both of R5 and R6 are optionally
substituted alkyl or haloalkyl, said substitution does not comprise a ring system. In this
context, a 'ring system' encompasses cycloalkyl, aryl, heteroaryl and heterocyclyl ring
systems and substitutions wherein said ring systems form part of a compound substitution for
example, aryloxy and arylalkoxy.
The compounds of formula I may exist in different geometric or optical isomeric
forms or in different tautomeric forms. One or more centres of chirality may be present, in
which case compounds of the formula I may be present as pure enantiomers, mixtures of
enantiomers, pure diastereomers or mixtures of diastereomers. There may be double bonds
present in the molecule, such as C=C or C=N bonds, in which case compounds of formula I
may exist as single isomers or mixtures of isomers. Centres of tautomerisation may be
present. This invention covers all such isomers and tautomers and mixtures thereof in all
proportions as well as isotopic forms such as deuterated compounds.
Suitable salts include those formed by contact with acids or bases. Suitable salts of
the compounds of formula I thus 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 R R1) wherein R', R Rk and R
are independently selected from hydrogen, C ]- alkyl and 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.
Suitable salts of the compounds of formula I also include acid addition salts such as
those with an inorganic acid such as hydrochloric, hydrobromic, sulphuric, nitric or
phosphoric acid, an organic acid such as acetic, butyric, propionic or hexanoic, an organic
carboxylic acid such as citric, fumaric, lactic, maleic, malonic, mandelic, malic, oxalic,
succinic, tartaric, toluic or phthalic acid, or a sulphonic acid such as methane, benzene,
naphthalene, camphor or toluene sulphonic acid.
N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen
containing heteroaromatic compounds. They are described in many books for example in
"Heterocyclic N-oxides" by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton,
Florida, 1991.
In particularly preferred embodiments of the invention, the preferred groups for A,
W, X, Y and Z, in any combination thereof, are as set out below.
In a preferred embodiment, A is halogen, cyano, Ci- alkoxy optionally substituted by
1 to 3 groups R16 , Ci-6 haloalkoxy optionally substituted by 1 to 3 groups R16, Ci^ alkylthio
optionally substituted by 1 to 3 groups R16, C1-6 haloalkylthio optionally substituted by 1 to 3
groups R 6, aryloxy optionally substituted by 1 to 3 groups R1, heteroaryloxy optionally
substituted by 1 to 3 groups R1, arylthio optionally substituted by 1 to 3 groups R1 or
heteroarylthio optionally substituted by 1 to 3 groups R1, each R16 is independently cyano,
hydroxyl, C3- cycloalkyl, -OR 17 , -S(0) aR18 , -C(0)R 19 or-NR 2, each R1 is independently
halogen, cyano, nitro, hydroxyl, Ci- alkyl optionally substituted by 1 to 4 groups R16 , Ci-6
haloalkyl optionally substituted by 1 to 4 groups R16, -OR 17, -S(0) aR18 , -C(0)R 19 , or -
NR 2 or any two geminal groups R together form a group selected from oxo, =CR2
2,
=NOR22, or =N R R23 and
(i) each R 7 is independently Ci- alkyl, Ci- haloalkyl, C alkoxy(Ci.4)alkyl, or
Ci-6 alkylcarbonyl,
(ii) each R is independently C - alkyl, C1-6 haloalkyl, C2-6 alkenyl, C2 -6 alkynyl,
C3 - cycloalkyl, or C - alkylcarbonylamino and each a is, independently, 0, 1,
or 2,
(iii) each R 9 is independently hydrogen, hydroxyl, C1-6 alkyl, Ci haloalkyl, C3-6
cycloalkyl, Ci- alkoxy, phenyl(Ci - )alkoxy, C3- cycloalkoxy, amino, C].6
alkylamino, di(C ].4 )alkylamino, or C1-6 alkylsulphonylamino,
(iv) each R2 is independently hydrogen or Ci-4 alkyl,
(v) each R2 1 is independently hydrogen, halogen, cyano, nitro, Ci.6 alkyl, C3-6
cycloalkyl, Ci- alkylcarbonyl, Ci- alkoxycarbonyl, Ci_6 alkylsulphonyl, or
aminocarbonyl,
(vi) each R22 is independently hydrogen, Ci- alkyl, or C3-6 cycloalkyl and
(vii) each R23 is independently hydrogen or Ci- alkyl.
In a more preferred embodiment, A is halogen, Ci-4 alkylthio optionally substituted
by 1 to 3 groups R , C1-4 haloalkylthio optionally substituted by 1 to 3 groups R or aryloxy
optionally substituted by 1 to 3 groups R1 wherein each R and each R1 are, independently
as defined above. In a yet more preferred embodiment, A is halogen or aryloxy optionally
substituted by 1 to 3 groups R wherein each R is as defined above or, in a more preferred
embodiment, each Rl is independently halogen, cyano, C -2 alkyl, Ci-2 haloalkyl, Ci-2
alkoxy, Ci-2 haloalkoxy, or di(Ci. 2)alkylamino. In a yet more preferred embodiment, A is
halogen and, most preferably, A is chlorine.
In a preferred embodiment, W is hydrogen, halogen, cyano, nitro, hydroxyl, amino,
Ci-6 alkyl optionally substituted by 1 to 3 groups R 0, C1-6 haloalkyl optionally substituted by
1 to 3 groups R30, C3- cycloalkyl optionally substituted by 1 to 3 groups R30, Ci- alkoxy
optionally substituted by 1 to 3 groups R30, Ci-6 alkylamino optionally substituted by 1 to 3
groups R30, di(C 1-6)alkylamino optionally substituted by 1 to 3 groups R30, C1-6 alkylthio
optionally substituted by 1 to 3 groups R30, Ci-6 alkylsulphinyl optionally substituted by 1 to
3 groups R30, C1- alkylsulphonyl optionally substituted by 1 to 3 groups R30 or C5- io aryl
optionally substituted by 1 to 3 groups R and each R is independently selected from
halogen, hydroxyl, cyano, amino, nitro, C1-6 alkylamino, di( .^alkylamino, C1-6 alkyl, Ci-
haloalkyl, C3-6 cycloalkyl, Ci-6 alkoxy, Ci- haloalkoxy, C - alkylthio, alkylcarbonyl or
Ci-6 alkoxycarbonyl. In a yet more preferred embodiment, W is hydrogen, halogen, C).3
alkyl, Ci- haloalkyl, Ci-2 alkoxy(Ci - )alkyl or cyclopropyl optionally substituted by 1 or 2
groups independently selected from halogen or Ci- alkyl. In a yet more preferred
embodiment, W is hydrogen, halogen, -2 alkyl, C -2 haloalkyl, Ci-2 alkoxy(C]. 2)alkyl, or
cyclopropyl. In a yet more preferred embodiment, W is hydrogen or halogen and, most
preferably, W is hydrogen, fluorine or chlorine.
In a preferred embodiment, X is azido, nitro, alkoxy optionally substituted by 1 to 3
groups R , alkylthio optionally substituted by 1 to 3 groups R 1 or -NR 5R6, and
(i) R5 is hydrogen, C alkyl optionally substituted by 1 to 4 groups R24, C
haloalkyl optionally substituted by 1 to 4 groups R24, C3-6 cycloalkyl
optionally substituted by 1 to 4 groups R24, C2-4 alkenyl, C2-4 alkynyl, -S0 2R2,
or -C(0)R 3 and R6 is hydrogen, C alkyl optionally substituted by 1 to 4
groups R24, C haloalkyl optionally substituted by 1 to 4 groups R24, C3-
cycloalkyl optionally substituted by 1 to 4 groups R24 , C2-4 alkenyl, or C2-4
alkynyl, or
(ii) R5 and R6 together form a group =C(R )OR9, =C(R 10)SR9, =C(R 1)NR7
2 or
(iii) R5 and R together with the N atom to which they are attached form a 3 to 8
membered heterocyclyl or heteroaryl ring system, said ring system optionally
containing 1 to 2 further heteroatoms independently selected from O, S and N
and being optionally substituted by 1 to 3 groups R33
and R2, R3, R8, R9, R10 , R11 and R7 are as defined above, each R 1 is independently selected
from halogen, hydroxyl, cyano, amino, nitro, C1-6 alkylamino, di(Ci -6)alkylamino, C3-
cycloalkyl, aryl optionally substituted by 1 to 3 groups R , heteroaryl optionally substituted
by 1 to 3 groups R32,Ci - alkoxy, Ci- haloalkoxy, Ci-6 alkylthio, Ci- alkylcarbonyl or Ci-
alkoxycarbonyl, each R24 is independently halogen, hydroxyl, cyano, amino, nitro, Ci-6
alkylamino, di( ^alkylamino, C -6 alkyl, Ci- haloalkyl, Cj.6 alkoxy, Ci- haloalkoxy, Ci-
alkoxy(Ci-6)alkoxy, carboxy, C - alkylthio, Ci. 6 alkylcarbonyl Ci- alkoxycarbonyl or tri(Cl-
4)alkylsilyl, each R32 is independently selected from halogen, hydroxyl, cyano, amino, nitro,
Ci-6 alkylamino, di(Cj ^alkylamino, C1-6 alkyl, C1-6 haloalkyl, C3-6 cycloalkyl, Ci-6 alkoxy,
Ci-6 haloalkoxy, Ci-6 alkylthio, Ci- alkylcarbonyl or Ci- alkoxycarbonyl and each R is
independently halogen, hydroxyl, cyano, amino, nitro, Ci.6 alkylamino, di(Ci.6)alkylamino,
Ci- alkyl, C1-6 haloalkyl, Ci-6 alkoxy, C1-6 haloalkoxy, Ci-6 alkylthio, Ci-6 alkylcarbonyl or
Ci- alkoxycarbonyl or two geminal groups R33 form an oxo group. Preferably, R2 is C1-4
alkyl optionally substituted by 1 to 4 groups R25, C1-4 haloalkyl optionally substituted by 1 to
4 groups R25 or phenyl optionally substituted by 1 to 3 groups R4 wherein each R25 is
independently cyano, C alkoxy, C3-6 cycloalkyl, phenyl optionally substituted by 1-3
groups R4, heteroaryl optionally substituted by 1-3 groups R4, or Ci-4 alkoxycarbonyl and R4
is as defined above and, more preferably, R is C alkyl, C haloalkyl or phenyl optionally
substituted by 1 to 3 groups R4. Preferably, R3 is C l optionally substituted by 1 to 4
groups R25, haloalkyl optionally substituted by 1 to 4 groups R25, phenyl optionally
substituted by 1 to 3 groups R4, C alkoxy, or -NR 2, wherein each R25 is independently
cyano, C alkoxy, C3-6 cycloalkyl, phenyl optionally substituted by 1-3 groups R4,
heteroaryl optionally substituted by 1-3 groups R4, or C alkoxycarbonyl and R4 and R7 are
as defined above.
In a yet more preferred embodiment, X is -NR 5R6 wherein R5 is hydrogen, C alkyl
optionally substituted by 1 to 4 groups R24, C M haloalkyl optionally substituted by 1 to 4
groups R24, C3.6 cycloalkyl optionally substituted by 1 to 4 groups R24, C2-4 alkenyl, -S0 2R2
or -C(0)R 3 and R6 is hydrogen, C alkyl optionally substituted by 1 to 4 groups R24, C
haloalkyl optionally substituted by 1 to 4 groups R24 or C2-4 alkenyl or R5 and R6 together
form a group =C(R1')NR 2 and R2 is C - alkyl, C haloalkyl, or phenyl optionally
substituted by 1 to 3 groups R4, R3 is C alkyl optionally substituted by 1 to 4 groups
CM haloalkyl optionally substituted by 1 to 4 groups R25, phenyl optionally substituted by 1
to 3 groups R4, C alkoxy, or -NR 2, R11 is hydrogen or CM alkyl, each R24 is
independently hydroxyl, cyano, CM alkoxy, CM alkoxy(CM) alkoxy, carboxy, CM
alkoxycarbonyl, or tri(CM )alkylsilyl and R4, R and R25 are as defined above.
In a yet more preferred embodiment, X is -NR R6 wherein R3 is hydrogen, CM alkyl
optionally substituted with 1 or 2 hydroxy or CM alkoxy groups, CM haloalkyl optionally
substituted with 1 or 2 hydroxy or CM alkoxy groups, C3.6 cycloalkyl, C2-4 alkenyl, -S0 2R2,
or -C(0)R 3, wherein R2 and R3 are each independently Ci-3 alkyl or phenyl and R6 is
hydrogen, CM alkyl optionally substituted with 1 or 2 hydroxy or CM alkoxy groups, C
haloalkyl optionally substituted with 1 or 2 hydroxy or CM alkoxy groups, or C2-4 alkenyl.
In a yet more preferred embodiment, X is -NR R6 wherein R5 and R6 are, independently,
hydrogen or CM alkyl and, most preferably, X is -NH .
In a preferred embodiment, Y is optionally substituted alkyl, optionally substituted
haloalkyl, optionally substituted cycloalkyl, optionally substituted alkenyl or optionally
substituted alkynyl. In a yet more preferred embodiment, Y is Ci- alkyl optionally
substituted by 1 to 3 groups R34, C i- haloalkyl optionally substituted by 1 to 3 groups R34,
C3-6 cycloalkyl optionally substituted by 1 to 3 groups R35, C2-6 alkenyl optionally substituted
by 1 to 3 groups R36 or C2-6 alkynyl optionally substituted by 1 to 3 groups R37 and each R34
is independently halogen, cyano, nitro, hydroxyl, C3-6 cycloalkyl, Ci-6 alkoxy, CM alkylthio,
CM alkylcarbonyl, CM alkoxycarbonyl or two geminal groups R34 form an oxo group, each
R35 is independently halogen, cyano, nitro, hydroxyl, Ci- alkyl, C3-6 cycloalkyl, C - alkoxy,
CM alkylthio, CM alkylcarbonyl or CM alkoxycarbonyl, each R36 is independently halogen,
cyano, nitro, C3-6 cycloalkyl, Ci- alkoxy, CM alkylcarbonyl, CM alkoxycarbonyl or .
3alkylsulphonyl and each R is independently halogen, cyano, C -6 cycloalkyl, C
alkylcarbonyl, CM alkoxycarbonyl or tri(Ci -3)alkylsilyl.
In a yet more preferred embodiment, Y is Ci-3 alkyl, Ci-3 haloalkyl, C1.2 alkoxy(C .
2)alkyl, cyclopropyl optionally substituted by 1 or 2 groups independently selected from
halogen or Ci- alkyl, C2-4 alkenyl, C2 -4 haloalkenyl or C2-4 alkynyl optionally substituted by
1 or 2 groups independently selected from halogen or tri(C 1-3)alkylsilyl. In a yet more
preferred embodiment, Y is Ci-2 alkyl, Ci-2 haloalkyl, Ci-2 alkoxy(Ci -2)alkyl, C2 - alkenyl or
C2 - alkynyl. In a yet more preferred embodiment, Y is C2.3 alkenyl and, most preferably, Y
is ethenyl.
In a preferred embodiment, Z is -C(0)R 12 , -C(S)R 13 , or -C(=NR 14)R1 and R 2 is
hydrogen, hydroxyl, optionally substituted alkoxy, optionally substituted cycloalkoxy,
optionally substituted alkylthio, amino, optionally substituted alkylamino or optionally
substituted dialkylamino, R is optionally substituted alkoxy, optionally substituted
cycloalkoxy, optionally substituted alkylthio, amino, optionally substituted alkylamino or
optionally substituted dialkylamino, R14 is hydrogen, optionally substituted alkyl, optionally
substituted alkoxy, optionally substituted cycloalkoxy, amino, optionally substituted
alkylamino or optionally substituted dialkylamino and R1 is hydrogen, optionally substituted
alkoxy, optionally substituted cycloalkoxy, optionally substituted alkylthio, amino,
optionally substituted alkylamino or optionally substituted dialkyamino.
In a more preferred embodiment, Z is -C(0)R 12, -C(S)R 13 , or-C(=NR 14)R15 and R12
is hydrogen, hydroxyl, C1-2o alkoxy optionally substituted by 1 to 3 groups R , C1-10
alkenyloxy optionally substituted by 1 to 3 groups , C3-6 cycloalkoxy optionally
substituted by 1 to 3 groups R38, .ioalkylthio optionally substituted by 1 to 3 groups R38,
amino, Ci- alkylamino optionally substituted by 1 to 3 groups R or di(Ci ^alkylamino
optionally substituted by 1 to 3 groups R38, R13 is Ci-20 alkoxy optionally substituted by 1 to
3 groups R38, C3- cycloalkoxy optionally substituted by 1 to 3 groups R38, Ci-io alkylthio
optionally substituted by 1 to 3 groups R , amino, Ci- alkylamino optionally substituted by
1 to 3 groups R38 or di(Ci - ) alkylamino optionally substituted by 1 to 3 groups R38, R 4 is
hydrogen, Ci- alkyl optionally substituted by 1 to 3 groups R38, Ci-2o alkoxy optionally
substituted by 1 to 3 groups R38, C3 -6 cycloalkoxy optionally substituted by 1 to 3 groups R38,
amino, Ci-6 alkylamino optionally substituted by 1 to 3 groups R38 or di(C . )alkylamino
optionally substituted by 1 to 3 groups R and R is hydrogen, C1-20 alkoxy optionally
substituted by 1 to 3 groups R38, C3-6 cycloalkoxy optionally substituted by 1 to 3 groups R38,
Ci.io alkylthio optionally substituted by 1 to 3 groups R , amino, Ci- alkylamino optionally
substituted by 1 to 3 groups R or di(Ci -6) alkyamino optionally substituted by 1 to 3 groups
R38 and each R38 is independently Ci- alkoxy, phenyl optionally substituted by 1 to 3 groups
R39 or heteroaryl optionally substituted by 1 to 3 groups R39, each R39 is independently
halogen, cyano, C alkyl, C haloalkyl, Ci-3 alkoxy(Ci -3)alkyl, C alkoxy, C haloalkoxy,
C alkylsulphonyl, or C alkoxycarbonyl and, preferably, each R is independently
halogen, C alkyl, C M haloalkyl, C M alkoxy or C M alkoxycarbonyl.
9 9
n a yet more preferred embodiment, Z is -C(0)R , wherein R is as defined in the
9 paragraph above. In a yet more preferred embodiment, Z is -C(0)R , wherein R is
hydroxyl, C alkylthio, Ci-2o alkoxy optionally substituted by 1 or 2 groups R38, -io
alkenyloxy optionally substituted by 1 or 2 groups R or C|.2o haloalkoxy optionally
substituted by 1 to 2 groups R and each R is independently as defined above. In a yet
1 more preferred embodiment, Z is -C(0)R wherein R is hydroxyl, Ci-10 alkoxy, Ci-5
alkenyloxy, Ci-5 alkoxy(C1-s)alkoxy, or phenyl(Ci -2)alkoxy and, most preferably, Z is -
C(0)R 2 wherein R 2 is hydroxyl or C Oalkoxy.
The compounds described below are illustrative of novel compounds of the
invention. Table 1 below provides 192 compounds designated compounds 1-1 to 1-192
respectively, of formula (I) wherein X is -NH 2 and Z is -C0 2H.
TABLE 1

192 compounds are described, designated compounds 2-1 to 2-192 respectively, of
formula (I) wherein X is NH2 and Z is C0 2Me, and the values of A, W and Y are as defined
in Table 1.
192 compounds are described, designated compounds 3-1 to 3-192 respectively, of
formula (I) wherein X is NH and Z is C0 2Et, and the values of A, W and Y are as defined in
Table 1.
192 compounds are described, designated compounds 4-1 to 4-192 respectively, of
formula (I) wherein X is NH2 and Z is C0 2CH2CH2OEt, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 5-1 to 5-192 respectively, of
formula (I) wherein X is NH2 and Z is C0 2CH2Ph, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 6-1 to 6-192 respectively, of
formula (I) wherein X is NHMe and Z is C0 2H, and the values of A, W and Y are as defined
in Table 1.
192 compounds are described, designated compounds 7-1 to 7-192 respectively, of
formula (I) wherein X is NHMe and Z is C0 2Me, and the values of A,W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 8-1 to 8-192 respectively, of
formula (I) wherein X is NMe2 and Z is C0 2H, and the values of A, W and Y are as defined
in Table 1.
192 compounds are described, designated compounds 9-1 to 9-192 respectively, of
formula (I) wherein X is NMe2 and Z is C0 2Me, and the values of A, Wand Y are as defined
in Table 1.
192 compounds are described, designated compounds 10-1 to 10-192 respectively, of
formula (I) wherein X is NH'Pr and Z is C0 2H, and the values of A, W and Y are as defined
in Table 1.
192 compounds are described, designated compounds 11-1 to 11- 2 respectively, of
formula (I) wherein X is NH'Pr and Z is C0 2Me, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 12-1 to 12-192 respectively, of
formula (I) wherein X is NHprop-2-enyl and Z is C0 2H, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 13-1 to 13-192 respectively, of
formula (I) wherein X is NHprop-2-enyl and Z is C0 2Me, and the values of A, W and Y are
as defined in Table 1.
192 compounds are described, designated compounds 14-1 to 14-192 respectively, of
formula (I) wherein X is NHCOMe and Z is C0 2H, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 15-1 to 15-192 respectively, of
formula (I) wherein X is NHCOMe and Z is C0 2Me, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 16-1 to 16-192 respectively, of
formula (I) wherein X is NHC0 2Me and Z is C0 2H, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 17-1 to 17-192 respectively, of
formula (I) wherein X is NHC0 2Me and Z is C0 2Me, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 18-1 to 18-192 respectively, of
formula (I) wherein X is NHS0 2Me and Z is C0 2H, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 19-1 to 19-192 respectively, of
formula (I) wherein X is NHS0 2Me and Z is C0 2Me, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 20-1 to 20-192 respectively, of
formula (I) wherein X is NHC¾CH(OH)Me and Z is C0 2H, and the values of A, W and Y
are as defined in Table 1.
192 compounds are described, designated compounds 21-1 to 21-192 respectively, of
formula (I) wherein X is NHCH 2CH(OH)Me and Z is C0 2Me, and the values of A, W and Y
are as defined in Table 1.
192 compounds are described, designated compounds 22-1 to 22-192 respectively, of
formula (I) wherein X is NHcyclopropyl and Z is C0 2H, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 23-1 to 23-192 respectively, of
formula (I) wherein X is NHcyclopropyl and Z is C0 2Me, and the values of A, W and Y are
as defined in Table 1.
192 compounds are described, designated compounds 24-1 to 24-192 respectively, of
formula (I) wherein X is NHcyclobutyl and Z is C0 2H, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 25-1 to 25-192 respectively, of
formula (I) wherein X is NHcyclobutyl and Z is C0 2Me, and the values of A, W and Y are
as defined in Table .
192 compounds are described, designated compounds 26-1 to 26-192 respectively, of
formula (I) wherein X is NHcyclopentyl and Z is C0 2H, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 27-1 to 27-192 respectively, of
formula (I) wherein X is NHcyclopentyl and Z is C0 Me, and the values of A, W and Y are
as defined in Table 1.
192 compounds are described, designated compounds 28-1 to 28-192 respectively, of
formula (I) wherein X is NHcyclohexyl and Z is C0 2H, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 29-1 to 29-192 respectively, of
formula (I) wherein X is NHcyclohexyl and Z is C0 2 e, and the values of A,W and Y are
as defined in Table 1.
192 compounds are described, designated compounds 30-1 to 30-192 respectively, of
formula (I) wherein X is 1-pyrrolidinyl and Z is C0 H, and the values of A,W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 31-1 to 31-192 respectively, of
formula (I) wherein X is 1-pyrrolidinyl and Z is C0 2Me, and the values of A, W and Y are as
defined in Table 1.
192 compounds are described, designated compounds 32-1 to 32-192 respectively, of
formula (I) wherein X is NH2 and Z is C0 2CH CH2O Bu, and the values of A, W and Y are
as defined in Table 1.
192 compounds are described, designated compounds 33-1 to 33-192 respectively, of
formula (I) wherein X is NH2 and Z is C0 2CH2CH=CH2, and the values of A, W and Y are
as defined in Table .
In a particular embodiment, there is provided a salt of the compound of formula (I) as
described or listed above. In particular, the salt of the compound of formula (I) may be
derived from an alkali metal, an alkaline earth metal, ammonia or an amine. Preferably, the
salt is a sodium salt, a potassium salt or a triethylammonium salt.
General methods for the production of compounds of formula (I) are described
below. Unless otherwise stated in the text, the substituents R5, R6, A, W, X, Y and Z are as
defined hereinbefore. The abbreviation LG as used herein refers to any suitable leaving
group, and includes halogen, sulphonate, and sulphone groups. 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.
Compounds of formula (I) may be prepared from compounds of formula (A) as
shown in reaction scheme 1.
Reaction Scheme 1
(A) (I)
For example (see reaction scheme 2) a compound of formula (I), in which A is a
group attached through a sulfur or oxygen atom, may be prepared by reacting an alcohol or
thiol (e.g. phenol or thiophenol) with a compound of formula (A) in the presence of a
suitable base (e.g. an inorganic base, such as sodium hydride or potassium carbonate) in a
suitable solvent (e.g. dimethylformamide). This transformation may also be performed in the
presence of a suitable metal (e.g. palladium) catalyst, optionally complexed by any suitable
ligands (e.g. phosphine ligands, such as tetrakis(triphenylphosphine)palladium).
Reaction scheme 2
(A) (I)
In a second example (see reaction scheme 3) a compound of formula (I), in which A
is a group attached through a sulfur or oxygen atom, may be prepared by reacting a metal salt
of an alcohol or thiol (e.g. sodium phenoxide or sodium thiophenolate) with a compound of
formula (A) in a suitable solvent (e.g. dimethylformamide). This transformation may also be
performed in the presence of a suitable metal (e.g. palladium) catalyst, optionally complexed
by any suitable ligands (e.g. phosphine ligands, such as
tetrakis(triphenylphosphine)palladium).
In a third example (see reaction scheme 3) a compound of formula (I), in which A is
a halogen, may be prepared by reacting a metal halide or metalloid derivative A-M (e.g.
potassium fluoride, sodium iodide or bromotrimethylsilane) with a compound of formula (A)
in a suitable solvent (e.g. acetonitrile or dimethyl sulfoxide).
in a fourth example (see reaction scheme 3) a compound of formula (I), in which A is
a cyano group, may be prepared by reacting a metal cyanide (e.g. copper(I) cyanide) with a
compound of formula (A) in a suitable solvent (e.g. dimethylformamide or Nmethylpyrrolidone).
This transformation may also be performed in the presence of a suitable
metal (e.g. palladium) catalyst, optionally complexed by any suitable ligands (e.g. phosphine
ligands, such as l,l'-bis(diphenylphosphino)ferrocene).
Reaction scheme 3
(A) (I)
Compounds of formula (I) may be prepared from compounds of formula (B) as
shown in reaction scheme 4.
Reaction scheme 4
(B) (I)
For example (see reaction scheme 5) a compound of formula (I), may be prepared by
reacting a suitable metal or metalloid derivative Y-M (e.g. a boronic acid or ester, a
trialkyltin derivative, a zinc derivative, a copper derivative or a Grignard reagent) with a
compound of formula (B) in the presence of a suitable base (e.g. an inorganic base, such as
potassium phosphate or caesium fluoride), a metal source (e.g. a palladium source, such as
Pd(OAc)2) and, optionally, a ligand for the metal (e.g. a phosphine ligand, such as
triphenylphosphine) in a suitable solvent (e.g. a single solvent, such as dimethylformamide,
or a mixed solvent system, such as a mixture of dimethoxyethane and water or toluene and
water). The metal catalyst and ligands may also be added as a single, pre-formed, complex
(e.g. a palladium/phosphine complex, such as bis(triphenylphosphine)palladium dichloride
or [l , -bis(diphenylphosphino)ferrocene] palladium dichloride dichloromethane adduct).
Reaction scheme 5
(B) (I)
Alternatively a compound of formula (I) in which Y is an alkene or alkyne may be
prepared by reacting a compound of formula (B) with an alkene or alkyne in the presence of
a suitable base (e.g. an inorganic base, such as potassium phosphate or caesium fluoride or
an organic base, such as triethylamine or diisopropylamine), a metal source (e.g. a palladium
source, such as Pd(OAc)2), optionally a second metal source (for example a copper salt, such
as copper(I) iodide and, optionally, a ligand for the metal (e.g. a phosphine ligand, such as
triphenylphosphine or tris(2-methylphenyl)phosphine) in a suitable solvent (e.g. a single
solvent, such as dimethylformamide or acetonitrile, or a mixed solvent system, such as a
mixture of dimethoxyethane and water or toluene and water). The metal catalyst and ligands
may also be added as a single, pre-formed, complex (e.g. a palladium/phosphine complex,
such as tetrakis(triphenylphosphine)palladium or bis(triphenylphosphine)palladium
dichloride).
Compounds of formula (I) may be prepared from compounds of formula (C) as
shown in reaction scheme 6.
Reaction scheme 6
(C) (I)
For example (see reaction scheme 7) a compound of formula (I) in which X is
NR R6, may be prepared from a compound of formula (C) by a reaction with a reagent
R5R N-H or its salt (e.g. a hydrogen halide salt, such as R R NH2C1) in the presence of a
suitable base (e.g. an organic base, such as N,N -diisopropylethylamine or an inorganic base,
such as potassium carbonate), in a suitable solvent (e.g. an organic solvent, such as
dimethylformamide or N-methylpyrrolidone). This transformation may also be performed in
the presence of a suitable metal catalyst (e.g. a metal catalyst, such as a palladium source),
optionally complexed by any suitable ligands (e.g. phosphine ligand).
Reaction scheme 7
(C) (I)
In a second example (see reaction scheme 8) a compound of formula (I) in which X
azide, may be prepared by reacting a metal azide (e.g. sodium azide) with a compound of
formula (C) in a suitable solvent (e.g. dimethylformamide).
Reaction scheme 8
(C) (I)
In a third example (see reaction scheme 9) a compound of formula (I), in which X is
a group attached through a sulfur or oxygen atom, may be prepared by reacting an alcohol or
thiol (e.g. methanol or methanethiol) with a compound of formula (C) in the presence of a
suitable base (e.g. an organic base, such as N,N -diisopropylethylamine or an inorganic base,
such as potassium carbonate or sodium hydride) in a suitable solvent (e.g.
dimethylformamide).
Reaction scheme 9
(C) (I)
In a fourth example (see reaction scheme 0) a compound of formula (I), in which X
is a group attached through a sulfur or oxygen atom, may be prepared by reacting a metal salt
of an alcohol or thiol (e.g. sodium methoxide or sodium methanethiolate) with a compound
of formula (C) in a suitable solvent (e.g. dimethylformamide).
Reaction scheme 10
(C) (I)
A compound of formula (I) in which X is an amino group, may be prepared from a
compound of formula (I) in which X is an azido group, by a reaction with a suitable reducing
agent (e.g. sodium borohydride) in a suitable solvent (e.g. methanol) as shown in reaction
scheme 1.
Reaction scheme 11
(I) (I)
Compounds of formula (I) may be prepared from compounds of formula (D) as
shown in reaction scheme 12.
Reaction scheme 12
(D) (I)
For example (see reaction scheme 13) a compound of formula (I), in which W is a
group attached through a carbon atom, may be prepared by reacting a suitable metal or
metalloid derivative W-M (e.g. a boronic acid or ester, a trialkyltin derivative, a zinc
derivative, a copper derivative or a Grignard reagent) with a compound of formula (D) in the
presence of a suitable base (e.g. an inorganic base, such as potassium phosphate or caesium
fluoride), a metal source (e.g. a palladium source, such as Pd(OAc)2) and, optionally, a
ligand for the metal (e.g. a phosphine ligand, such as triphenylphosphine) in a suitable
solvent (e.g. a single solvent, such as dimethylformamide, or a mixed solvent system, such as
a mixture of dimethoxyethane and water or toluene and water). The metal catalyst and
ligands may also be added as a single, pre-formed, complex (e.g. a palladium/phosphine
complex, such as bis(triphenylphosphine)palladium dichloride or [1,1 ' -
bis(diphenylphosphino)ferrocene] palladium dichloride dichloromethane adduct).
In a second example (see reaction scheme 13) a compound of formula (I), in which
W is a cyano group, may be prepared by reacting a metal cyanide (e.g. copper(I) cyanide)
with a compound of formula (D) in a suitable solvent (e.g. dimethylformamide or Nmethylpyrrolidone).
This transformation may also be performed in the presence of a suitable
metal (e.g. palladium) catalyst, optionally complexed by any suitable ligands (e.g. phosphine
ligands. such as l,l'-bis(diphenylphosphino)ferrocene).
Reaction scheme 13
(D) (I)
Compounds of formula (D) may be prepared from compounds of formula (E) as
shown in reaction scheme 14.
For example (see reaction scheme 14) a compound of formula (D) in which LG is a
halogen may be prepared from a compound of formula (E) by reaction with a halogenating
agent (e.g. Selectfluor®, an N-halosuccinimide such as N-chlorosuccinimide or Niodosuccinimide,
or an elemental halogen such as bromine) in a suitable solvent (e.g.
acetonitrile). This transformation may also be performed by first deprotonating the
compound of formula (E) with a suitable base, followed by a reaction with a halogenating
agent (e.g. Selectfluor®, an N-halosuccinimide such as N-chlorosuccinimide or Niodosuccinimide,
or an elemental halogen such as bromine).
Reaction scheme 14
Compounds of formulae (A), (B), (C) and (E) may be prepared from compounds of
formula (G) by suitable combinations of the methods described above. Compounds of
formula (D) may be prepared from compounds of formula (H) by suitable combinations of
the methods described above (see reaction scheme 15).
Reaction scheme I
(H) (D)
Compounds of formula (H) are known in the literature or can be made from
compounds know in the literature by standard methods.
Compounds of formula (G) may be prepared from compounds of formula (F) as
shown in reaction scheme 16. A compound of formula (G) in which LG is a halogen may be
prepared from a compound of formula (F) by treatment with a suitable reagent (e.g. a
phosphoryl halide such as phosphorous oxychloride).
Reaction scheme 16
(F) (G)
Compounds of formula (F) may be prepared from compounds of formula (J) as
shown in reaction scheme 17. A compound of formula (F) in which LG is a halogen may be
prepared from a compound of formula (J) by treatment with a suitable oxidizing agent (e.g.
urea hydrogen peroxide) and a suitable acid anhydride (e.g. trifluoroacetic anhydride) in a
suitable solvent (e.g. dichloromethane).
Reaction scheme 17
(J) (F)
Compounds of formula (J) may be prepared from compounds of formula ( ) as
shown in reaction scheme 18. A compound of formula (J) in which LG is a halogen may be
prepared from a compound of formula (K) by treatment with a suitable reagent (e.g. a
phosphoryl halide such as phosphorous oxychloride).
Reaction scheme 18
(K) (J)
Compounds of formula (K) may be prepared from compounds of formula (L) as
shown in reaction scheme 19. A compound of formula (K) in which LG is a halogen may be
prepared from a compound of formula (L) by treatment with a suitable oxidizing agent (e.g.
urea hydrogen peroxide) and a suitable acid anhydride (e.g. trifluoroacetic anhydride) in a
suitable solvent (e.g. dichloromethane).
Reaction scheme 19
Compounds of formula (L) may be prepared from compounds of formula (M) as
shown in reaction scheme 20. A compound of formula (L) in which Z is an ester may be
prepared from a compound of formula (M) by treatment with a catalytic amount of suitable
acid (e.g. concentrated sulphuric acid) in a suitable solvent (e.g. methanol).
Reaction scheme 20
( ) (L)
Compounds of formula (M) may be prepared from compounds of formula (N) as
shown in reaction scheme 1. A compound of formula (M) may be prepared from a
compound of formula (N) by treatment with a suitable base (e.g. lithium
tetramethylpiperidide) in a suitable solvent (e.g. tetrahydrofuran) followed by a treatment
with a halogenating agent (e.g. iodine or hexachloroethane).
Reaction scheme 2 1
(N) (M)
One skilled in the art will realise that it is often possible to alter the order in which
the transformations described above are conducted, or to combine them in alternative ways
to prepare a wide range of compounds of formula (I). All such variations are contemplated
within the scope of the invention.
The skilled man will also be aware that some reagents will be incompatible with
certain values or combinations of the substituents R5, R6, A, W, X, Y and Z as defined
herein, and any additional steps, such as protection and/or deprotection steps, which are
necessary to achieve the desired transformation will be clear to the skilled man.
Compounds of formula (I) may be used in unmodified form, i.e. as obtainable from
synthesis, but preferably are formulated in any suitable manner using formulation adjuvants,
such as carriers, solvents and surface-active substances, for example, as described
hereinafter. Accordingly, the present invention provides a herbicidal formulation comprising
a compound of formula (I) together with at least one agriculturally acceptable adjuvant or
diluent.
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, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule
suspensions, suspension concentrates, 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. The formulations can
be in the form of concentrates which are diluted prior to use, although ready-to-use
formulations can also be made. The dilutions can be made, for example, with water, liquid
fertilisers, micronutrients, biological organisms, oil or solvents.
The formulations can be prepared e.g. by mixing the active 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 usually have a diameter of from
0.1 to 500 microns. Typically, they will contain 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 known polymers. 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 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
(e.g. butyl acetate, ethyl acetate, isoamyl acetate, amyl acetate), 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,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol,
dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,
2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, dlimonene,
ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl
ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate,
hexadecane, hexylene glycol, , 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 (PEG), propionic acid,
propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, pxylene,
toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral
oil, trichloroethylene, perchloroethylene, methanol, ethanol, isopropanol, and alcohols of
higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol,
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 may advantageously be used in the
formulations, especially in those formulations designed to be diluted with a carrier prior to
use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can
be used as emulsifiers, wetting agents 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 alkylnaphthalenesulfonates, 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
crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants,
foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents,
neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances,
wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants,
dispersants, thickeners, antifreezes, microbicides, and also liquid and solid fertilisers.
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 AM1GO® (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 -22 fatty acids, especially the methyl derivatives of C -i 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- 112-39-0) 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.
Another preferred adjuvant is Adigor® (Syngenta AG) which is a methylated rapeseed oilbased
adjuvant.
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 W097/34485. 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
C12-22 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 0 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-l-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.
Herbicidal compositions of the invention 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.
Examples of preferred formulation types and their typical compositions are given
below (% is percent by weight). Wettable powders as described herein are one particularly
preferred type of formulation for use in the invention. In other preferred embodiments, in
particular where the compound/composition/formulation of the invention is intended for use
on turf, granular (inert or fertiliser) formulations as described herein are particularly suitable.
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) (% =% bv weight)
Fl. 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)
N-methyl pyrrolidone - - 10% 20%
arom. hydrocarbon mixture 85% 78% 55% 16%
Emulsions of any desired concentration can be obtained from such concentrates by
dilution with water.
F2. Solutions a) b) c) d)
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%
(C -C 2)
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 sulphate 2% 3% 4%
sodium diisobutylnaphthalenesulfonate
6% 5% 6%
octylphenol polyglycol ether - 1% 2%
(7-8 ol of ethylene oxide)
highly dispersed silicic acid 1% 3% 5% 10%
kaolin 88% 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 - 1mm)
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 - 1mm)
e.g. CaC0 3 or Si0 2
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) )
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 mol of ethylene oxide) - 1% 2% -
sodium lignosulfonate 3% 3% 4% 5%
carboxymethylcellulose 1% 1% 1% 1%
37% aqueous formaldehyde
solution 0.2 % 0.2% 0.2% 0.2%
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.
Compounds of the invention (as well as mixtures and/or formulations containing the
same) find utility as herbicides, and may thus be employed in methods of controlling plant
growth. Such methods involve applying to the plants or to the locus thereof a herbicidally
effective amount of said compound, or composition comprising the same (or mixture as
described hereinafter). The invention thus also relates to 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), composition, or mixture of the invention. In particular the
invention provides a method of controlling weeds in crops of useful plants, which comprises
applying to said weeds or the locus of said weeds, or to said crop of useful plants, a
compound of formula I or a composition or mixture containing the same.
The term "locus" as used herein 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.
A compound, composition, and/or mixture of the invention may be used in a preemergence
application and/or in a post-emergence application in order to mediate its effect.
Crops of useful plants in which compounds of formula (I), as well as formulations
and/or mixtures containing the same, may be used according to the invention include
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 and
vegetables, especially cereals and maize.
Compounds of formula (I), formulations and/or mixtures containing the same may
also be used on turf, pasture, rangeland, rights of way etc. In particular they may be used on
golf-courses, lawns, parks, sports-fields, race-courses and the like.
Crops are to be understood as also including those crops which have been rendered
tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPDinhibitors
and synthetic auxins) 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 glufosinate-resistant maize varieties commercially
available under the trade names RoundupReady® and LibertyLink®.
Crops are also to be understood as being those which have been rendered resistant to
harmful insects by genetic engineering methods, for example Bt maize (resistant to European
corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to
Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta
Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil
bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are
described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073
and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code
for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield
Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes),
NatureGard® and Protexcta®. Plant crops or seed material thereof can be both resistant to
herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events).
For example, seed can have the ability to express an insecticidal Cry3 protein while at the
same time being tolerant to glyphosate.
Crops are also to be understood 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 flavour).
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.
Compounds of formula (I) may be used against a large number of agronomically
important weeds. The weeds that may be controlled include both monocotyledonous and
dicotyledonous weeds, such as, for example, Alisma spp, Leptochloa chinensis, Stellaria,
Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa,
Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus and
especially Cyperus iria, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea,
Chrysanthemum, Galium, Viola, Veronica, Bidens, Euphorbia, Ischaemum, Polygonum,
Helianthus, Panicum, Eriochloa, Brachiaria, Cenchrus, Commelina, Spermacoce, Senna,
Tridax, Richardia, Chamaesyce, and Conyza spp.
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, 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 0 to 2000 g/ha, especially
from 25 to 1000 g/ha.
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).
Where a compound of formula (I) is combined with at least one additional herbicide,
the following mixtures of the compound of formula (I) are particularly 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 (1) + 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 (1) + 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) + 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) + chlorfiurenol-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 formula (I) + cresol, compound of formula (T) + 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) + diclofopmethyl,
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) +
fiumioxazin, 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-methyl, 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) + 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) + imazamethabenzmethyl,
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) + 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) + Smetolachlor,
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-616, 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) +
pyrazosulfiiron, 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) + triallate,
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-(l-methyl-6-
trifluoromethyl-2,4-dioxo-l,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic
acid ethyl ester (CAS RN 353292-31-6), compound of formula (I) + 4-hydroxy-3-[[2-[(2-
methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-
one (CAS RN 352010-68-5), compound of formula (I) + 4-amino-3-chloro-6-(4-chloro-2-
fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid (CAS RN 943832-60-8), and compound
of formula (I) + 4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-
pyridinyl]carbonyl]-bicyclo[3.2 .1]oct-3-en-2-one .
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 threeway,
and further multiple combinations comprising the above two-way mixtures.
In preferred embodiments a compound of formula (I) is combined with an
acetolactate synthase inhibitor, (e.g. one or more of florasulam, flumetsulam, metsulfuron,
nicosulfuron, prosulfuron, thifensulfuron, tribenuron, triasulfuron, flucarbazone,
flupyrsulfuron, iodosulfuron, mesosulfuron, primisulfuron, primisulfuron-methyl,
propoxicarbazone, rimsulfuron, sulfosulfuron, pyroxsulam and tritosulfuron, as well as salts
or esters thereof), a synthetic auxin herbicide (e.g. one or more of aminocyclopyrachlor,
aminopyralid, clopyralid, 2,4-D, 2,4-DB, dicamba, dichlorprop, fluroxypyr, MCPA, MCPB,
mecoprop, mecoprop-P and 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methox) ,phenyl)-2-
pyridinecarboxylic acid (CAS RN 943832-60-8)), an ACCase-inhibiting herbicide (e.g. one
or more of phenylpyrazolin; pinoxaden; an aryloxyphenoxypropionic herbicide such as
clodinafop, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, quizalofop, trifop and
mixtures thereof, as well as the isomers thereof, for example, fenoxaprop-P, fluazifop-P,
haloxyfop-P, quizalofop-P; and a cyclohexanedione herbicide such as alloxydim;
butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim and
tralkoxydim, as well as salts or esters thereof), an auxin transport inhibitor such as
semicarbazone (e.g. diflufenzopyr, in particular the sodium salt), or phthalamate compound
(e.g. naptalam), an HPPD inhibiting herbicide (e.g. mesotrione, topramezone, tembotrione), a
glutamine synthetase inhibitor such as glufosinate or glufosinate-ammonium and/or an
EPSPS inhibitor such as glyphosate.
Particularly preferred mixture partners for compounds of formula (I) are: florasulam,
flumetsulam, iodosulfuron-methyl-sodium, mesosulfuron-methyl, metsulfuron-methyl,
nicosulfuron, primisulfuron-methyl, prosulfuron, rimsulfuron, thifensulfuron, triasulfuron,
tribenuron-methyl or pyroxsulam; dicamba, fluroxypyr, MCPA, mecoprop or mecoprop-P;
clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-Pethyl,
fluazifop-butyl, fluazifop-P-butyl, haloxyfop-methyl, haloxyfop-P-methyl, pinoxaden,
propaquizafop, quizalofop-ethyl, quizalofop-P-ethyl, tralkoxydim, trifop-methyl,
diflufenzopyr-Na, mesotrione, tembotrione, topramezone, naptalam, glufosinate and
glyphosate.
For the avoidance of doubt, even if not explicitly stated above, the mixing partners of
the compound of formula (I) may also be in the form of any suitable agrochemically
acceptable ester or salt, as mentioned e.g. in The Pesticide Manual, Thirteenth Edition,
British Crop Protection Council, 2003.
The mixing ratio of the compound of formula (I) to the mixing partner is preferably
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.
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 221667-31-8), compound of formula (I) + dichlormid, 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) + mefenpyr-diethyl,
compound of formula (I) + oxabetrinil, compound of formula (I) + naphthalic anhydride
(CAS RN 81-84-5), compound of formula (I) + N-isopropyl-4-(2-methoxybenzoylsulfamoyl)-
benzamide (CAS RN 221668-34-4) and a compound of formula (I) + N-
(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.
Particularly preferred safeners for use in the invention are cloquintocet-mexyl,
cyprosulfamide, fenchlorazole-ethyl, mefenpyr-diethyl and N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide.In particular, the present invention
provides a composition comprising any one of compounds 1-1 to 1-192, 2-2 to 2-192, 3-2 to
3-192, 4-2 to 4-192, 5-2 to 5-192, 6-2 to 6-192, 7-2 to 7-192, 8-2 to 8-192, 9-2 to 9-192, 10-2
to 10-192, 11-2 to 11-192, 12-2 to 12-192, 13-2 to 13-192, 14-2 to 14-192, 15-2 to 15-192,
16-2 to 16-192, 17-2 to 17-192, 18-2 to 18-192, 19-2 to 19-192, 20-2 to 20-192, 21-2 to 21-
192, 22-2 to 22-192, 23-2 to 23-192, 24-2 to 24-192, 25-2 to 25-192, 26-2 to 26-192, 27-2 to
27-192, 28-2 to 28-192, 29-2 to 29-192, 30-2 to 30-192, 31-2 to 31-1 92, 32-2 to 32-192 and
33-2 to 33-1 92 with cloquintocet-mexyl .
In particular, the present invention provides a composition comprising any one of
compounds 1-1 to 1-192, 2-2 to 2-192, 3-2 to 3-192, 4-2 to 4-192, 5-2 to 5-192, 6-2 to 6-192,
7-2 to 7-192, 8-2 to 8-192, 9-2 to 9-192, 10-2 to 10-192, 11-2 to 11-192, 12-2 to 12-192, 13-
2 to 13-192, 14-2 to 14-192, 15-2 to 15-192, 16-2 to 16-192, 17-2 to 17-192, 18-2 to 18-192,
19-2 to 19-192, 20-2 to 20-192, 21-2 to 21-192, 22-2 to 22-192, 23-2 to 23-192, 24-2 to 24-
192, 25-2 to 25-192, 26-2 to 26-192, 27-2 to 27-192, 28-2 to 28-192, 29-2 to 29-192, 30-2 to
30-192, 31-2 to 31-192, 32-2 to 32-192 and 33-2 to 33-192 with cyprosulfamide.
In particular, the present invention provides a composition comprising any one of
compounds 1-1 to 1-192, 2-2 to 2-192, 3-2 to 3-192, 4-2 to 4-192, 5-2 to 5-192, 6-2 to 6-192,
7-2 to 7-192, 8-2 to 8-192, 9-2 to 9-192, 10-2 to 10-192, 11-2 to 11-192, 12-2 to 12-192, 13-
2 to 13-192, 14-2 to 14-192, 15-2 to 15-192, 16-2 to 16-192, 17-2 to 17-192, 18-2 to 18-192,
19-2 to 19-192, 20-2 to 20-192, 21-2 to 21-192, 22-2 to 22-192, 23-2 to 23-192, 24-2 to 24-
192, 25-2 to 25-192, 26-2 to 26-192, 27-2 to 27-192, 28-2 to 28-192, 29-2 to 29-192, 30-2 to
30-192, 31-2 to 31-192, 32-2 to 32-192 and 33-2 to 33-192 with fenchlorazole-ethyl.
In particular, the present invention provides a composition comprising any one of
compounds 1-1 to 1-192, 2-2 to 2-192, 3-2 to 3-192, 4-2 to 4-192, 5-2 to 5-192, 6-2 to 6-192,
7-2 to 7-192, 8-2 to 8-192, 9-2 to 9-192, 10-2 to 10-192, 1-2 to 11-192, 12-2 to 12-192, 13-
2 to 13-192, 14-2 to 14-192, 15-2 to 15-192, 16-2 to 16-192, 17-2 to 17-192, 18-2 to 18-192,
19-2 to 19-192, 20-2 to 20-192, 21-2 to 21-192, 22-2 to 22-192, 23-2 to 23-192, 24-2 to 24-
192, 25-2 to 25-192, 26-2 to 26-192, 27-2 to 27-192, 28-2 to 28-192, 29-2 to 29-192, 30-2 to
30-192, 31-2 to 31-192, 32-2 to 32-192 and 33-2 to 33-192 with mefenpyr-diethyl.
In particular, the present invention provides a composition comprising any one of
compounds 1-1 to 1-192, 2-2 to 2-192, 3-2 to 3-192, -2 to 4-192, 5-2 to 5-192, 6-2 to 6-192,
7-2 to 7-192, 8-2 to 8-192, 9-2 to 9-192, 10-2 to 10-192, 11-2 to 11-192, 12-2 to 12-192, 13-
2 to 13-192, 14-2 to 14-192, 15-2 to 15-192, 16-2 to 16-192, 17-2 to 17-192, 18-2 to 18-192,
19-2 to 19-192, 20-2 to 20-192, 21-2 to 21-192, 22-2 to 22-192, 23-2 to 23-192, 24-2 to 24-
192, 25-2 to 25-192, 26-2 to 26-192, 27-2 to 27-192, 28-2 to 28-192, 29-2 to 29-192, 30-2 to
30-192, 31-2 to 31-192, 32-2 to 32-192 and 33-2 to 33-192 with N-(2-methoxybenzoyl)-4-
[(methylaminocarbony l)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, 13th Edition supra. The reference to
cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium,
aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof
as disclosed in 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)
with the safener).
Preferred mixtures of a compound of formula (I) with further herbicides and safeners
include: a compound of formula (I) + pinoxaden + cloquintocet-mexyl, a compound of
formula (1) + clodinafop + cloquintocet-mexyl, and a compound of formula (I) + clodinafoppropargyl
+ cloquintocet-mexyl, a compound of formula (I) + glyphosate + cyprosulfamide
(CAS RN 221667-31-8), a compound of formula (I) + glyphosate + N-(2-methoxybenzoyl)-
4-[(methylaminocarbonyl)amino]benzenesulfonamide.
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
EXAMPLE 1 Synthesis of 3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester.
3-Bromo-6-chloro-pyridine-2-carboxylic acid (50.00 g, 2 11.5 mmol) was dissolved
in methanol (235 mL), and concentrated sulphuric acid (5.6 mL) was added. The resulting
reaction mixture was heated to reflux for 28 h. The reaction mixture was cooled to room
temperature, and the resulting precipitate was recrystallized from methanol to give 3-bromo-
6-chloro-pyridine-2-carboxylic acid methyl ester (54.38 g, quantitative) as a solid.
Characterising data for the compound are as follows: 1H NMR (400 MHz, CDC13) d ppm
7.94 (d, 1H), 7.34 (d, 1H) and 4.01 (s, 3H).
EXAMPLE 2 Synthesis of 3-bromo-4,6-dichloro-pyridine-2-carboxylic acid methyl
ester.
2.1 Preparation of 3-bromo-6-chloro-pyridine-2-carboxylic acid N-oxide
Urea hydrogen peroxide (65.32 g, 347.2 mmol) was added portionwise to a solution
of trifluoroacetic anhydride (145.8 g, 694.4 mmol, 96.5 mL) in dichloromethane (577 mL) at
0 °C. 3-Bromo-6-chloro-pyridine-2-carboxylic acid methyl ester (27.18 g, 108.5 mmol) was
added to the mixture portionwise and the reaction was stirred at room temperature for 19 h.
The reaction was quenched by the addition of water, and the organic layer was washed with
water and saturated aqueous K2C0 3. The organic layer was dried (MgS0 4) and concentrated
in vacuo to give 3-bromo-6-chloro-pyridine-2-carboxylic acid N-oxide as a yellow oil.
Characterising data for the compound are as follows: NMR (400 MHz, CD OD) d ppm
7.77-7.75 (m, 2H) and 4.01 (s, 3H).
2,2 Preparation of 3-bromo-4,6-dichloro-pyridine-2-carboxylic acid methyl ester
3-Bromo-6-chloro-pyridine-2-carboxylic acid N-oxide was dissolved in POCl (166
g, 1.085 mol, 101 mL) and stirred at room temperature for 2 h, then at reflux for 3 h. The
reaction mixture was concentrated in vacuo, and purified by silica gel chromatography
(gradient elution: 0-100% EtOAc in s -hexane) followed by reverse phased silica gel
chromatography (gradient elution: 0-100% MeOH in water) to give 3-bromo-4,6-dichloropyridine-
2-carboxylic acid methyl ester (9.45 g, 31%) as a solid. Characterising data for the
compound are as follows: NMR (400 MHz, CDC13) d ppm 7.57 (s, 1H) and 4.01 (s, 3H).
EXAMPLE 3 Synthesis of 4-amino-3-bromo-6-chloro-pyridine-2-carboxylic acid
methyl ester.
3_T Preparation of 4-azido-3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester
3-Bromo-4,6-dichloro-pyridine-2-carboxylic acid methyl ester (4.036 g, 14.16 mmol)
and sodium azide (1.105 g, 17.00 mmol) was dissolved in DMF (7.1 mL) and heated to 60
°C. After 2 h, the reaction mixture was cooled to room temperature and poured on to water.
The aqueous layer was extracted with dichloromethane, the combined organic extracts were
dried (MgS0 ), and concentrated in vacuo. The resulting residue was purified by silica gel
chromatography (gradient elution: 0-100% EtOAc in wo-hexane) to give 4-azido-3-bromo-6-
chloro-pyridine-2-carboxylic acid methyl ester (3.999 g, 97%) as a yellow solid.
Characterising data for the compound are as follows: 1H NMR (400 MHz, CDC1 ) ppm
7.19 (s, 1H) and 4.00 (s, 3H).
32 Preparation of 4-amino-3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester
Sodium borohydride (0.588 g, 15.55 mmol) was added protionwise to a solution of 4-
azido-3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester (2.266 g, 7.78 mmol) in
methanol (16 mL) at 0 °C. After 30 min, the reaction mixture was poured on to water, and
the aqueous layer was extracted successively with dichloromethane and EtOAc. The
combined organic layers were dried (MgS0 ), concentrated in vacuo and purified by silica
gel chromatography (gradient elution: 0-100% EtOAc in dichloromethane) to give 4-amino-
3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester (1.463 g, 71%) as a solid.
Characterising data for the compound are as follows: 1H NMR (400 MHz, CDCI3) d ppm
6.72 (s, 1H), 5.00 (br s, 2H) and 3.98 (s, 3H).
EXAMPLE 4 Alternative synthesis of 4-amino-3-bromo-6-chloro-pyridine-2-
carboxylic acid methyl ester.
A solution of 3-bromo-6-chloro-4-[(2,4-dimethoxyphenyl)methylamino]-pyridine-2-
carboxylic acid methyl ester (18.0 g, 43.4 mmol; prepared as described in example 5) in
methanolic hydrogen chloride (1.25 M; 250 ml) was stirred at 48 °C for 3 hours then cooled
and filtered. The filtrate was concentrated in vacuo and the residue partitioned between ethyl
aceate and saturated aqueous sodium bicarbonate. The aqueous phase was extracted with
ethyl acetate and the combined organic phases washed with saturated aqueous sodium
bicarbonate, water and brine, dried (MgS0 ) and concentrated in vacuo to provide 4-amino-
3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester (9.3 g, 80%) as a beige solid.
Characterising data for the compound are as follows: NMR (400 MHz, CDC13) d ppm
6.71 (s, 1H), 5.00 (br s, 2H) and 3.98 (s, 3H).
EXAMPLE 5 Synthesis of 3-bromo-6-chloro-4-cyclopropylamino-pyridine-2-
carboxylic acid methyl ester.
A solution of 3-bromo-4,6-dichloro-pyridine-2-carboxylic acid methyl ester (0.545 g, 1.91
mmol) in N-methylpyrrolidone (2 mL) was added to a mixture of cyclopropylamine (109 mg,
1.91 mmol) and diisopropyethylamine (0.66 ml, 3.82 mmol) and the resulting mixture heated
at 80 °C for 20 h. The reaction mixture was cooled to room temperature, water (2 ml) and
dichloromethane (2 ml) added and the mixture stirred for 5 min. The phases were separated
and the organic phase concentrated in vacuo. The residue was purified by reverse phase
preparative HPLC, using FractionLynx (X Bridge column, ammonium acetate buffer) to give
3-bromo-6-chloro-4-cyclopropylamino-pyridine-2-carboxylic acid methyl ester, which was
used directly in the next reaction.
Other compounds made using this general method are listed in Table 2 below.
TABLE 2 Compounds made according to the general method described in Example
5. Characteristic data is melting point (°C) or nmr data (400 MHz,
CDCb) dH ppm.
Name Structure Characteristic Data
EXAMPLE 6 Synthesis of 4-amino-6-chloro-3-ethenyl-pyridine-2-carboxylic acid
methyl ester (compound 2-4).
A mixture of 4-amino-3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester
(186 mg, 0.70 mmol), tributyl(vinyl)tin (222 mg, 0.70 mmol, 0.205 mL) and
bis(triphenylphosphine)palladium(II) dichloride (39 mg, 0.06 mmol) in DMF (3.5 mL) was
heated to 150 °C under microwave irradiation for 30 min. More tributyl(vinyl)tin (33 mg,
0.10 mmol, 0.03 mL) and bis(triphenylphosphine)palladium(II) dichloride (5 mg, 0.007
mmol) were added to the mixture, and the reaction mixture was heated again to 150 °C under
microwave irradiation for 30 min. The reaction mixture was filtered through Celite® and the
resulting solution was purified by reverse phase preparative HPLC, using FractionLynx (X
Bridge column, ammonium acetate buffer) to give 4-amino-6-chloro-3-ethenyl-pyridine-2-
carboxylic acid methyl ester (71 mg, 48%) as a gum. Characterising data for the compound
are as follows: NMR (400 MHz, CD3OD) ppm 6.70 (s, 1H), 6.64 (dd, 1H), 5.53 (dd,
1H), 5.42 (dd, 1H), 4.59 (br s, 2H) and 3.83 (s, 3H).
Other compounds made using this general method are listed in Table 3 below.
TABLE 3 Compounds made according to the general method described in Example
6. Characteristic data is melting point (°C) or lH nmr data (400 MHz,
CDC13) dH ppm.
Compound No. Name Structure Characteristic
data
2-5 (Z isomer) (Z)-4-Amino-6- NH 94-97
chloro-3-(prop-
1-enyl)-
pyridine-2-
carboxylic acid
methyl ester

EXAMPLE 7 Synthesis of 4-amino-6-chloro-3-methyl-pyridine-2-carboxylic acid
methyl ester (compound 2-1).
A mixture of 4-amino-3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester
( 186 mg, 0.70 mmol), tetramethyltin (125 mg, 0.70 mmol, 0.097 mL) and
bis(triphenylphosphine)palladium(II) dichloride (39 mg, 0.06 mmol) in DMF (3.5 mL) was
heated to 150 °C under microwave irradiation for 30 min. The reaction mixture was filtered
through Celite®and the resulting solution was purified by reverse phase preparative HPLC,
using FractionLynx (X Bridge column, ammonium acetate buffer) to give 4-amino-6-chloro-
3-methyl-pyridine-2-carboxylic acid methyl ester (74 mg, 53%) as a solid. Characterising
data for the compound are as follows: NMR (400 MHz, CD OD) d ppm 6.67 (s, 1H), 4.59
(br s, 2H), 3.89 (s, 3H) and 2.13 (s, 3H).
EXAMPLE 8 Synthesis of 4-amino-6-chloro-3-(2-methyl-prop-2-enyl)-pyridine-2-
carboxylic acid methyl ester (compound 2-8).
A mixture of 4-amino-3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester
(186 mg, 0.70 mmol), methallyltri-n-butylstannane (242 mg, 0.70 mmol, 0.162 mL) and
bis(triphenylphosphine)palladium(II) dichloride (39 mg, 0.06 mmol) in DMF (3.5 mL) was
heated to 150 °C under microwave irradiation for 30 min. More methallyltri-n-butylstannane
(45 g, 0.13 mmol, 0.03 mL) and bis(triphenylphosphine)palladium(II) dichloride (5 mg,
0.007 mmol) were added to the mixture, and the reaction mixture was heated again to 150 °C
under microwave irradiation for 30 min. The reaction mixture was filtered through
Celite®and the resulting solution was purified by reverse phase preparative HPLC, using
FractionLynx (X Bridge column, ammonium acetate buffer) to give 4-amino-6-chloro-3-(2-
methyl-prop-2-enyl)-pyridine-2-carboxylic acid methyl ester (71 mg, 42%) as a gum.
Characterising data for the compound are as follows: 1H NMR (400 MHz, CD3OD) d ppm
6.70 (s, IH), 4.79-4.77 ( , IH), 4.59 (br s, 2H), 4.52-4.50 (m, IH), 3.85 (s, 3H), 3.39-3.37
(m, 2H) and 1.74 (s, 3H).
EXAMPLE 9 Synthesis of 4-amino-6-chloro-3-(prop-2-enyI)-pyridine-2-carboxylic acid
methyl ester (compound 2-7).
A mixture of 4-amino-3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester (159 mg,
0.60 mmol), allyltri-n-butylstannane (2 1 mg, 0.66 mmol, 0.203 mL) and
bis(triphenylphosphine)palladium(II) dichloride (42 mg, 0.06 mmol) in DMF (3.0 mL) was
heated to 150 °C under microwave irradiation for 60 min. The reaction mixture was filtered
through Celite®and the resulting solution was purified by reverse phase preparative HPLC,
using FractionLynx (X Bridge column, ammonium acetate buffer) to give 4-amino-6-chloro-
3-(prop-2-enyl)-pyridine-2-carboxylic acid methyl ester (53 mg, 39%) as a solid.
Characterising data for the compound are as follows: NMR (400 MHz, d -DMSO) d ppm
6.65 (s, IH), 6.50 (br s, 2H), 5.83-5.72 ( , IH), 5.04-4.95 ( , 2H), 3.79 (s, 3H) and 3.29 (d,
2H).
EXAMPLE 10 Synthesis of 4-amino-6-chloro-3-trifluoromethyl-pyridine-2
carboxylic acid methyl ester (compound 2-2).
A mixture of 4-amino-3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester (199 mg,
0.75 mmol), methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (158 mg, 0.83 mmol, 0.105 mL)
and copper (I) iodide (43 mg, 0.23 mmol) in DMF (3.0 L) was heated to 150 °C under
microwave irradiation for 30 min. The reaction mixture was filtered through Celite®and the
resulting solution was purified by reverse phase preparative HPLC, using FractionLynx (X
Bridge column, ammonium acetate buffer) to give 4-amino-6-chloro-3-trifluoromethylpyridine-
2-carboxylic acid methyl ester (10.6 mg, 6%) as a gum. Characterising data for the
compound are as follows: NMR (400 MHz, CD3OD) d pp 6.83 (s, 1H), 4.59 (br s, 2H)
and 3.89 (s, 3H).
EXAMPLE 11 Synthesis of 4-amino-6-chloro-3-ethenyl-5-fluoro-pyridine-2-
carboxylic acid methyl ester (compound 2-12).
1.1 Preparation of 4-amino-3-bromo-6-chloro-5-fluoro-pyridine-2-carboxylic acid methyl
ester
A mixture of 4-amino-3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester
(864 mg, 3.25 mmol) and Selectfluor® (1.268 g, 3.58 mmol) in acetonitrile (20 mL) was
heated to reflux for 1 0 min. More Selectfluor® (1.15 g, 3.25 mmol) was added, and the
reaction mixture was further refluxed for 100 min. The reaction mixture was poured on to
water and the aqueous layer was extracted with dichloromethane. The combined organic
layers were dried (MgS0 ), concentrated in vacuo and purified by silica gel chromatography
(gradient elution: 0-40% EtOAc in wo-hexane) to give impure 4-amino-3-bromo-6-chloro-5-
fluoro-pyridine-2-carboxylic acid methyl ester (559 mg).
1.2 Preparation of 4-amino-6-chloro-3-ethenyl-5-fluoro-pyridine-2-carboxylic acid
methyl ester
A mixture of crude 4-amino-3-bromo-6-chloro-5-fluoro-pyridine-2-carboxylic acid
methyl ester (559 mg), tributyl(vinyl)tin (360 mg, 1.13 mmol, 0.331 mL) and
bis(triphenylphosphine)palladium(II) dichloride (125 mg, 0.18 mmol) in DMF (10 mL) was
heated to 150 °C under microwave irradiation for 60 min. The reaction mixture was
concentrated in vacuo and purified by silica gel chromatography (gradient elution: 0-40%
EtOAc in wo-hexane) followed by reverse phase preparative HPLC, using FractionLynx (X
Bridge column, ammonium acetate buffer) to give 4-amino-6-chloro-3-ethenyl-5-fluoropyridine-
2-carboxylic acid methyl ester (38 mg, 5% over two steps) as a solid.
Characterising data for the compound are as follows: NMR (400 MHz, CDC13) d ppm
6.88 (dd, 1H), 5.73 (dd, 1H), 5.53 (dd, 1H), 4.80 (br s, 2H) and 3.92 (s, 3H).
EXAMPLE 12 Alternative synthesis of 4-amino-6-chloro-3-ethenyl-5-fluoropyridine-
2-carboxylic acid methyl ester (compound 2-12)
A solution of Selectfluor® (2.92 g, 8.25 mmol) in water (10 ml) was added to a
solution of 4-amino-6-chloro-3-ethenyl-pyridine-2-carboxylic acid methyl ester (877 mg,
4.12 mmol) in acetonitrile (10 mL) and the resulting mixture was heated at 70 °C for 4 hours.
The reaction mixture was allowed to cool, poured on to water and extracted with
dichloromethane. The combined organic layers were dried (MgS0 ), concentrated in vacuo
and purified by reverse phase preparative HPLC, using a FractionLynx (X Bridge column,
ammonium acetate buffer) followed by silica gel chromatography (gradient elution: 0-80%
EtOAc in wo-hexane) to give 4-amino-6-chloro-3-ethenyl-5-fluoro-pyridine-2-carboxylic
acid methyl ester (41 mg, 4%).
EXAMPLE 13 Synthesis of 4-amino-5,6-dichloro-3-ethenyl- -pyridine-2-
carboxylic acid methyl ester (compound 2-20)
13.1 Preparation of 4-amino-3-bromo-5,6-dichloro-pyridine-2-carboxylic acid methyl
ester
JV-Chlorosuccinimide (12.6 g, 95 mmol) was added portionwise to a stirred solution of 4-
amino-3-bromo-6-chloro-pyridine-2-carboxylic acid methyl ester (23.0 g, 86 mmol) in DMF
(150 ml) and the resulting solution stirred at ambient temperature for 20 hours, then poured
into cold water. The resulting mixture was filtered and the solid dissolved in ethyl acetate.
The resulting solution was washed with water and brine, dried (MgS0 4) and concentrated in
vacuo to provide 4-amino-3-bromo-5,6-dichloro-pyridine-2-carboxylic acid methyl ester
(21 .0 g, 81%) as a white solid. Characterising data for the compound are as follows: 1H
NMR (400 MHz, CDC13) d ppm 5.50 (br s, 2H) and 3.98 (s, 3H).
13.2 Preparation of 4-amino-5,6-dichloro-3-ethenyl- -pyridine-2-carboxylic acid methyl
ester
A mixture of 4-amino-3-bromo-5,6-dichloro-pyridine-2-carboxylic acid methyl ester
(1.00 g, 3.33 mmol), tributyl(vinyl)tin (1.16 g, 3.67 mmol) and
bis(triphenylphosphine)palladium(II) dichloride ( 117 mg, 0.17 mmol) in DMF (10 mL) was
heated to 160 °C under microwave irradiation for 15 min. The reaction mixture was cooled,
brine added and extracted with dichloromethane. The combined organic extracts were
concentrated in vacuo and purified by reverse phase preparative HPLC, using a
FractionLynx (X Bridge column, ammonium acetate buffer) followed by silica gel
chromatography (gradient elution: 10-60% EtOAc in wo-hexane) to give 4-amino-5,6-
dichloro-3-ethenyl- -pyridine-2-carboxylic acid methyl ester (422 mg, 51%) as a white solid.
Characterising data for the compound are as follows: H NMR (400 MHz, CDC13) d ppm
6.86 (m, 1H), 5.72 (dd, 1H), 5.53 (dd, 1H), 5.19 (br s, 2H) and 3.92 (s, 3H).
Other compounds made using this general method are listed in Table 4 below.
TABLE 4 Compounds made according to the general method described in Example
13.
4 Synthesis of 4-amino-5,6-dichloro-3-(l-methylethenyl)-pyridine-2-
A mixture of 4-amino-3-bromo-5,6-dichloro-pyridine-2-carboxylic acid methyl ester
(200 mg, 0.67 mmol), isopropenylboronic acid pinacol ester (134 mg, 0.80 mmol), caesium
fluoride (203 mg, 1.33 mmol) and tetrakis(triphenylphosphine)palladium (39 mg, 0.033
mmol) in dioxane (3 mL) and water ( 1 ml) was heated to 150 °C under microwave
irradiation for 20 min. The reaction mixture was cooled, added to water and extracted with
dichloromethane. The combined organic extracts were concentrated in vacuo and purified
by silica gel chromatography (gradient elution: 0-80% EtOAc in wo-hexane) and then by
reverse phase preparative HPLC, using a FractionLynx (X Bridge column, ammonium
acetate buffer) followed by to give 4-amino-5 ,6-dichloro-3 -(1-methylethenyl)-pyridine-2-
carboxylic acid methyl ester as a white solid. Characterising data for the compound are as
follows: 1H NMR (400 MHz, CDC13) d ppm 5.42 (m, 1H), 5.03 (br s, 2H), 4.99 (m, 1H),
3.90 (s, 3H) and 2.09 (m, 3H).
Other compounds made using this general method are listed in Table 5 below.
TABLE 5 Compounds made according to the general method described in Example
14. Characteristic data is melting point (°C) or nmr data (400 MHz,
CDC dH ppm.
2-165 4-Amino-6- 6.68 (s, 1H), 6.03
chloro-3-(2- ( , 1H), 4.52 (br s,
methylprop-1- 2H), 3.87 (s, 3H),
enyl)-pyridine- N C0 Me 1.93 (d, 3H), 1.51
2-carboxylic (s, 3H)
acid methyl
ester
EXAMPLE 15 Synthesis of 4-amino-6-chloro-3-formyl-pyridine-2-carboxylic acid
(compound 2-162).
Ozone was bubbled through a stirred solution of 4-amino-6-chloro-3-ethenylpyridine-
2-carboxylic acid methyl ester (150 mg, 1.66 mmol) in DCM (50 ml) at -78 °C for
40 mins, then dimethyl sulphide (2 ml) was added and the resulting mixture allowed to warm
to ambient temperature and evaporated under reduced pressure. The residue was purified by
silica gel chromatography (gradient elution: 33-50% EtOAc in wo-hexane) to provide 4-
amino-6-chloro-3-formyl-pyridine-2-carboxylic acid (78 mg, 22%) as a cream solid.
Characterising data for the compound are as follows: M.p. 146-148 °C; 1H NMR (400 MHz,
CDC13) ppm 10.25 (s, 1H), 6.70 (s, 1H), 4.00 (s, 3H) (amine protons not observed).
EXAMPLE 16 Synthesis of 4-amino-6-chloro-3-difluoromethyl-pyridine-2-
carboxylic acid (compound 2-161).
Diethylaminosulphur trifiuoride (328 mg, 2.0 mmol) was added to a solution of 4-
amino-6-chloro-3-formyl-pyridine-2-carboxylic acid (50 mg, 0.23 mmol) in DCM (3.5 ml)
and diethyl ether (2 ml). After stirring for 40 hours further diethylaminosulphur trifiuoride
(160 mg, 1.0 mmol) was added and stirring continued for a further 3 days. Methanol was
added and the resulting mixture concentrated in vacuo and purified by silica gel
chromatography (1:2 EtOAc -hexane) to provide 4-amino-6-chloro-3-difluoromethylpyridine-
2-carboxylic acid (27 mg, 49%) as a cream solid. Characterising data for the
compound are as follows: M.p. 149-151 °C; 1H NMR (400 MHz, CDC13) d ppm 7.43 (t, IH),
6.73 (s, IH), 5.10 (br s, 2H), 3.99 (s, 3H).
EXAMPLE 17 Synthesis of 4-amino-6-chloro-3-ethenyl-pyridine-2-carboxylic
acid (compound 1-4).
Sodium hydroxide (64 mg, 1.6 mmol) was added to a stirred solution of 4-amino-6-
chloro-3-ethenyl-pyridine-2-carboxylic acid methyl ester (150 mg, 0.71 mmol) in THF (20
mL) and water (9 ml). The reaction mixture was stirred overnight at ambient temperature,
then washed with ether, neutralised by the addition of 2N hydrochloric acid and extracted
with ethyl acetate (3 x 50 ml). The combined ethyl acetate extracts were dried over
magnesium sulphate, filtered and evaporated under reduced pressure to provide 4-amino-6-
chloro-3-ethenyl-pyridine-2-carboxylic acid (34 mg, 24%) as a pale yellow solid.
Characterising data for the compound are as follows: M.p. 141-146 °C (dec); NMR (400
MHz, d6-DMSO) d ppm 6.64 (s, IH), 6.60 (dd, IH), 6.50 (br s, 2H), 5.49 (d, IH), 5.44 (dd,
IH) (acid proton not observed).
Other compounds made using this general method are listed in Table 6 below.
TABLE 6 Compounds made according to the general method described in Example
17. Characteristic data is melting point (°C) or nmr data (400 MHz,
CD OD) dH ppm.
EXAMPLE 18 Pre-emergence biological efficacy
Seeds of Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa
crus-galli (ECHCG), Solarium nigrum (SOLNI), Amaranthus retroflexus (AMARE) and
Ipomoea hederaceae (IPOHE) were sown in standard soil in pots. After cultivation for one
day 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 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) to give a final
dose of 1000 g ha of test compound.
The test plants were then grown under controlled conditions in the glasshouse (at
24/1 6°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days
the test was evaluated (100 = total damage to plant; 0 = no damage to plant). Results are
shown below in Table 7.
TABLE 7 Percentage damage caused to weed species by compounds of the
invention when applied pre-emergence.
Compound Rate Species
Number (g/ha) SOLNI AMARE SETFA ALOMY ECHCG IPOHE
1-4 1,000 100 100 100 90 90 100
1-12 1,000 100 100 100 90 90 100
1-20 1,000 100 100 90 90 90 100
2-1 1,000 100 100 80 90 70 80
2-2 1,000 80 80 0 20 10 90
2-4 1,000 100 100 90 90 90 100
2-5
(E isomer) 1,000 100 90 100 90 70 100
2-5
(Z isomer) 1,000 100 100 100 90 70 90
2-7 1,000 90 90 40 30 40 70
2-8 1,000 80 40 10 10 0 80
2-12 1,000 100 100 90 100 100 100
2-20 1,000 100 100 90 90 90 100
2-161 1,000 90 90 60 40 10 80
2-162 1,000 80 80 20 20 20 70
2-165 1,000 100 100 90 80 70 90
2-168 1,000 80 90 0 30 20 80
21-4 1,000 100 100 90 90 90 80
23-4 1,000 100 100 80 70 70 80
27-4 1,000 100 100 70 50 10 50
31-4 1,000 90 100 50 60 10 80
EXAMPLE 19 Post-emergence biological efficacy
Seeds of Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa
crus-galli (ECHCG), Solarium nigrum (SOLNI), Amaranthus retroflexus (AMARE) and
5 Ipomoea hederaceae (IPOHE) were sown in standard soil in pots. After cultivation for 8
days 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 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) to give a final
lo dose of 1000 g ha of test compound.
The test plants were then grown on under controlled conditions in a glasshouse (at
24/1 6°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days
the test was evaluated (100 = total damage to plant; 0 = no damage to plant). Results are
shown below in Table 8.
1 TABLE 8 Percentage damage caused to weed species by compounds of the
invention when applied post-emergence
Compound Rate Species
Number (g ha) SOLNI AMARE SETFA ALOMY ECHCG IPOHE
1-4 1,000 100 100 100 80 80 70
1-12 1,000 90 100 90 90 90 100
1-20 1,000 90 100 90 90 90 100
2-1 1,000 90 100 100 90 60 50
2-2 1,000 80 80 10 10 10 70
2-4 1,000 100 100 100 90 80 80
2-5 1,000 90 100 70 50 60 70
(E isomer)
2-5
(Z isomer) 1,000 100 100 80 50 60 50
2-7 1,000 90 90 30 20 10 50
2-8 1,000 80 70 10 10 0 50
2-12 1,000 100 100 90 80 80 80
2-20 1,000 100 100 90 90 90 100
2-161 1,000 90 80 20 30 10 30
2-162 1,000 90 80 10 10 10 70
2-165 1,000 90 100 90 70 70 70
2-168 1,000 80 100 20 20 10 70
21-4 1,000 100 100 80 70 80 50
23-4 1,000 100 100 80 60 30 70
27-4 1,000 80 100 70 10 10 60
31-4 1,000 90 90 50 20 20 70
1-4 1,000 100 100 100 80 80 70
EXAMPLE 20 Safening on Corn
Maize seeds were sown into standard soil in pots and cultivated under controlled
conditions in a glasshouse (at 24/18 °C day/night; 16 hours light; 65% humidity).
When the plants were at the vegetative stage of 3 leaves they were sprayed with an
aqueous spray solution containing the components of the invention alone and where
appropriate the herbicide safener (N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide). All the compounds used for the spray
solution were present as an EC or SC formulation respectively. In addition a non-ionic
surfactant (X-77 Spreader) was added to form a 0.2% v/v solution.
The spray solution was applied with a cabinet tracksprayer with a flat fan nozzle
(Teejet 11002VS) and an application volume of 200L/ha (at 2 bar).
The test plants were then grown on in a glasshouse under controlled conditions (at
24/18 °C day/night; 16 hours light; 65% humidity) and watered twice a day. After 7 and 7
days the test was evaluated for general crop injury (100% equals total damage to plant; 0%
equals no damage to plant).
Results are shown below in Table 9.
TABLE 9 Percentage damage caused to corn by the compositions of the invention
alone and in the presence of a safener (N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide).
Although the invention has been described with reference to preferred embodiments
and examples thereof, the scope of the present invention is not limited only to those
described embodiments. As will be apparent to persons skilled in the art, modifications and
adaptations to the above-described invention can be made without departing from the spirit
and scope of the invention, which is defined and circumscribed by the appended claims. All
publications cited herein are hereby incorporated by reference in their entirety for all
purposes to the same extent as if each individual publication were specifically and
individually indicated to be so incorporated by reference.
CLAIMS
1. A compound of formula (I)
or salt or N-oxide thereof, wherein:
A is halogen, cyano, optionally substituted alkoxy, optionally substituted aryloxy,
optionally substituted heteroaryloxy, optionally substituted alkylthio, optionally
substituted arylthio, or optionally substituted heteroarylthio;
W is hydrogen, halogen, cyano, nitro, hydroxyl, amino, optionally substituted alkyl,
optionally substituted haloalkyl, optionally substituted cycloalkyl, optionally
substituted alkoxy, optionally substituted alkylamino, optionally substituted
dialkylamino, optionally substituted alkylthio, optionally substituted alkylsulphinyl,
optionally substituted alkylsulphonyl or optionally substituted aryl;
X is azido, nitro, optionally substituted alkoxy, optionally substituted alkylthio or -N
R5R6 and
(i) R5 is hydrogen, optionally substituted Ci. alkyl provided said substitution does
not comprise a ring system, optionally substituted C haloalkyl provided said
substitution does not comprise a ring system, optionally substituted C3-
cycloalkyl, C2-4 alkenyl, C2- alkynyl, -S0 2R2, or - C(0)R 3 and R6 is hydrogen,
optionally substituted C 1- alkyl provided said substitution does not comprise a
ring system, optionally substituted C haloalkyl provided said substitution does
not comprises a ring system, optionally substituted C3- cycloalkyl, C2-4 alkenyl,
or C2-4 alkynyl, or
(ii) R5 and R6 together form a group =C(R )OR9, =C(R, )SR9, =C(R ')NR7 , or
(iii) R5 and R6 together with the N atom to which they are attached form a 3 to 8
membered optionally substituted heterocyclyl or heteroaryl ring system, said ring
system optionally containing 1 to 2 further heteroatoms independently selected
from O, S and N,
and R2 is optionally substituted C alkyl or phenyl optionally substituted by 1 to 3
groups R4, R3 is optionally substituted C alkyl, phenyl optionally substituted by 1 to
3 groups R4, C alkoxy, or -NR 2, each R4 is independently halogen, C alkyl, CM
alkoxy, or CM alkylsulphonyl, R is hydrogen, C alkyl, C3-6 cycloalkyl, phenyl, C1-4
alkoxy, CM l hio or -NR' 2, R9 is CM alkyl, R10 is hydrogen, C alkyl, C3-6
cycloalkyl, phenyl, CM alkylthio, or-NR 7
2, R1 1 is hydrogen, CM alkyl, C3-6
cycloalkyl, phenyl, or -NR 2, and each R7 is independently hydrogen or CM alkyl;
Y is optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted
cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally
substituted aryl;
Z is -C(0)R 2, -C(S)R 13 , or -C(=NR 1 )R15 and R12 is hydrogen, hydroxyl, optionally
substituted alkoxy, optionally substituted alkenyloxy, optionally substituted
cycloalkoxy, optionally substituted alkylthio, amino, optionally substituted alkylamino
or optionally substituted dialkylamino, R is optionally substituted alkoxy, optionally
substituted cycloalkoxy, optionally substituted alkylthio, amino, optionally substituted
alkylamino or optionally substituted dialkylamino, R14 is hydrogen, optionally
substituted alkyl, optionally substituted alkoxy, optionally substituted cycloalkoxy,
amino, optionally substituted alkylamino or optionally substituted dialkylamino and
R15 is hydrogen, optionally substituted alkoxy, optionally substituted cycloalkoxy,
optionally substituted alkylthio, amino, optionally substituted alkylamino or optionally
substituted dialkyamino.
2 . A compound according to claim 1, wherein A is halogen, cyano, Ci- alkoxy optionally
substituted by 1 to 3 groups R 6, Ci- haloalkoxy optionally substituted by 1 to 3
groups R 6, Ci-6 alkylthio optionally substituted by 1 to 3 groups R16 , Ci_6 haloalkylthio
optionally substituted by 1 to 3 groups R1 , aryloxy optionally substituted by 1 to 3
groups R1, heteroaryloxy optionally substituted by 1 to 3 groups R , arylthio
optionally substituted by 1 to 3 groups R or heteroarylthio optionally substituted by 1
to 3 groups R , each R is independently halogen, cyano, nitro, hydroxyl, Ci- alkyl
optionally substituted by 1 to 4 groups R 6, Ci-6 haloalkyl optionally substituted by 1 to
4 groups R16, -OR 7, -S(0) aR18 , -C(0)R 19, or -NR 20
2 or any two geminal groups R1
together form a group selected from oxo, =CR2 1
2, =NOR22, or =NNR22R23, each R16 is
independently cyano, hydroxyl, C3. cycloalkyl, -OR 7, -S(0) R18 , -C(0)R 19 or -
NR 2, and
(i) each R17 is independently Ci-6 alkyl, Ci-6 haloalkyl, C alkoxy(C )alkyl, or .
6 alkylcarbonyl,
(ii) each R18 is independently Ci-6 alkyl, C - haloalkyl, C2.6 alkenyl, C2-6 alkynyl, C3-
cycloalkyl, or C1-6 alkylcarbonylamino and each a is, independently, 0, 1, or 2,
(iii) each R19 is independently hydrogen, hydroxyl, Ci- alkyl, Ci-6 haloalkyl, C3-6
cycloalkyl, Ci.6 alkoxy, phenyl(C . )alkoxy, C3-6 cycloalkoxy, amino, Ci-6
alkylamino, di(C )alkylamino, or Ci- alkylsulphonylamino,
(iv) each R is independently hydrogen or C alkyl,
(v) each R2 1 is independently hydrogen, halogen, cyano, nitro, alkyl, C3-6
cycloalkyl, C1-6 alkylcarbonyl, Ci-6 alkoxycarbonyl, Ci-6 alkylsulphonyl, or
aminocarbonyl,
(vi) each R22 is independently hydrogen, Ci- alkyl, or C3- cycloalkyl and
(vii) each R is independently hydrogen or Ci-6 alkyl.
A compound according to claim 2, wherein A is halogen, C alkylthio optionally
substituted by 1 to 3 groups R 6, C haloalkylthio optionally substituted by 1 to 3
groups R1 or aryloxy optionally substituted by 1 to 3 groups R1.
A compound according to claim 3 , wherein A is halogen or aryloxy optionally
substituted by 1 to 3 groups R .
A compound according to claim 4, wherein each R1 is independently halogen, cyano,
Cj 2 alkyl, Ci-2 haloalkyl, Ci-2 alkoxy, C -2 haloalkoxy, or di(Ci -2)alkylamino.
A compound according to any one of the previous claims, wherein W is hydrogen,
halogen, cyano, nitro, hydroxyl, amino, C i-6 alkyl optionally substituted by 1 to 3
groups R30, Ci-6 haloalkyl optionally substituted by 1 to 3 groups R30, C3-6 cycloalkyl
optionally substituted by 1 to 3 groups R30, Ci-6 alkoxy optionally substituted by 1 to 3
groups R30, Ci^ alkylamino optionally substituted by 1 to 3 groups R30, di(C).
)alkylamino optionally substituted by 1 to 3 groups R30, Ci-6 alkylthio optionally
substituted by 1 to 3 groups R , Cj. alkylsulphinyl optionally substituted by 1 to 3
groups R30, Ci-6 alkylsulphonyl optionally substituted by 1 to 3 groups R30 or Cs-io aryl
optionally substituted by 1 to 3 groups R30 and each R30 is independently selected from
halogen, hydroxyl, cyano, amino, nitro, Ci-6 alkylamino, di(Ci ^alkylamino, C i-6 alkyl,
Ci.6 haloalkyl, C - cycloalkyl, C 1-6 alkoxy, C i-6 haloalkoxy, Ci.6 alkylthio, Ci-6
alkylcarbonyl or C i- alkoxycarbonyl.
A compound according to claim 6, wherein W is hydrogen, halogen, C1.3 alkyl, Cihaloalkyl,
Cj. 2 alkoxy(Ci -2)alkyl or cyclopropyl optionally substituted by 1 or 2 groups
independently selected from halogen or Ci-6 alkyl.
A compound according to claim 7, wherein W is hydrogen, halogen, Ci. 2 alkyl, C i-2
haloalkyl, Ci-2 alkoxy(Ci -2)alkyl, or cyclopropyl.
A compound according to any one of the previous claims, wherein X is azido, nitro,
alkoxy optionally substituted by 1 to 3 groups R3 1, alkylthio optionally substituted by 1
to 3 groups R 1 or -NR R6, and
(i) R5 is hydrogen, .4 alkyl optionally substituted by 1 to 4 groups R24, C
haloalkyl optionally substituted by 1 to 4 groups R24, C -6 cycloalkyl optionally
substituted by 1 to 4 groups R24, C2-4 alkenyl, C2-4 alkynyl, -S0 2R2, or - C(0)R 3
and R6 is hydrogen, C alkyl optionally substituted by 1 to 4 groups R24, C
haloalkyl optionally substituted by 1 to 4 groups R24, C - cycloalkyl optionally
substituted by 1 to 4 groups R24, C -4 alkenyl, or C2-4 alkynyl, or
(ii) R5 and R6 together form a group =C(R )OR9, =C(R1 )SR9, =C(R ')NR 7
2 or
(iii) R5 and R6 together with the N atom to which they are attached form a 3 to 8
membered heterocyclyl or heteroaryl ring system, said ring system optionally
containing 1 to 2 further heteroatoms independently selected from O, S and N
and being optionally substituted by 1 to 3 groups R 3
and each R is independently selected from halogen, hydroxyl, cyano, amino, nitro,
Ci- alkylamino, di(C 1-6)alkylamino, C3-6 cycloalkyl, aryl optionally substituted by 1 to
3 groups R32, heteroaryl optionally substituted by 1 to 3 groups R32,Ci -6 alkoxy, Ci-
haloalkoxy, C - alkylthio, Ci- alkylcarbonyl or C1-6 alkoxycarbonyl, each R24 is
independently halogen, hydroxyl, cyano, amino, nitro, Ci-6 alkylamino, di(Ci.
6)alkylamino, C1-6 alkyl, Ci-6 haloalkyl, Ci- alkoxy, Ci-6 haloalkoxy, Ci- alkoxy(Ci-
6)alkoxy, carboxy, Ci-6 alkylthio, C -6 alkylcarbonyl Ci- alkoxycarbonyl or tri(Cl-
4)alkylsilyl, each R is independently selected from halogen, hydroxyl, cyano, amino,
nitro, Ci-6 alkylamino, di(C ^alkylamino, C \ .(, alkyl, Ci- haloalkyl, C3-6 cycloalkyl,
-6 alkoxy, C1-6 haloalkoxy, Ci-6 alkylthio, Ci- alkylcarbonyl or Ci- alkoxycarbonyl
and each R is independently halogen, hydroxyl, cyano, amino, nitro, Ci-6 alkylamino,
di(Ci -6)alkylamino, 6 alkyl, C1- haloalkyl, C - alkoxy, Ci- haloalkoxy, C
alkylthio, Ci-6 alkylcarbonyl or Ci- alkoxycarbonyl or two geminal groups R form an
oxo group.
10. A compound according to claim 9, wherein R2 is C alkyl optionally substituted by 1
to 4 groups R25, C haloalkyl optionally substituted by 1 to 4 groups R25 or phenyl
optionally substituted by 1 to 3 groups R4 and R3 is C M alkyl optionally substituted by
1to 4 groups R25, C haloalkyl optionally substituted by 1 to 4 groups R25, phenyl
optionally substituted by 1 to 3 groups R4, C M alkoxy, or-NR 2, wherein each R25 is
independently cyano, Ci- alkoxy, C3-6 cycloalkyl, phenyl optionally substituted by 1-3
groups R4, heteroaryl optionally substituted by 1-3 groups R4, or C1- alkoxycarbonyl.
11. A compound according to any one of claims 1to 10, wherein X is -NR 5R6, R5 is
hydrogen, C alkyl optionally substituted by 1 to 4 groups R24, C M haloalkyl
optionally substituted by 1 to 4 groups R24, C3. cycloalkyl optionally substituted by 1
to 4 groups R24, alkenyl, -S0 2R2 or -C(0)R 3 and R6 is hydrogen, CM alkyl
optionally substituted by 1 to 4 groups R24, C M haloalkyl optionally substituted by 1 to
4 groups R24 or C2-4 alkenyl or R5 and R6 together form a group =C(R )NR7
2 and R2 is
C M alkyl, C M haloalkyl, or phenyl optionally substituted by 1 to 3 groups R4, R3 is Cialkyl
optionally substituted by 1 to 4 groups R , C M haloalkyl optionally substituted
by 1 to 4 groups R , phenyl optionally substituted by 1to 3 groups R , C alkoxy, or
-NR 2 , R 11 is hydrogen or C alkyl and each R24 is independently hydroxyl, cyano,
C alkoxy, C1- alkoxy(CM ) alkoxy, carboxy, C alkoxycarbonyl, or tri(Ci.
4)alkylsilyl.
12. A compound according to claim 1 , wherein X is -NR 5R6 wherein R 5 is hydrogen, C
alkyl optionally substituted with 1 or 2 hydroxy or C M alkoxy groups, CM haloalkyl
optionally substituted with 1 or 2 hydroxy or C alkoxy groups, C3 -6 cycloalkyl, C2 -4
alkenyl, - S0 2R2 , or - C(0)R 3 , wherein R2 and R3 are each independently Ci-3 alkyl or
phenyl and R 6 is hydrogen, Ci-4 alkyl optionally substituted with 1 or 2 hydroxy or C
alkoxy groups, C M haloalkyl optionally substituted with 1 or 2 hydroxy or C M alkoxy
groups, or C2 -4 alkenyl.
13. A compound according to any one of the previous claims, wherein Y is alkyl
optionally substituted by 1 to 3 groups R 34 , Ci-6 haloalkyl optionally substituted by 1 to
3 groups R34 , C3-6 cycloalkyl optionally substituted by 1 to 3 groups R3 5, C2-6 alkenyl
optionally substituted by 1 to 3 groups R36 or C2-6 alkynyl optionally substituted by 1 to
3 groups R 37 and each R 4 is independently halogen, cyano, nitro, hydroxyl, C3-6
cycloalkyl, Ci- alkoxy, C M alkylthio, C M alkylcarbonyl, C M alkoxycarbonyl or two
geminal groups R3 4 form an oxo group, each R3 5 is independently halogen, cyano,
nitro, hydroxyl, Ci- alkyl, C3-6 cycloalkyl, Ci- alkoxy, C M alkylthio, C1-4
alkylcarbonyl or C M alkoxycarbonyl, each R3 6 is independently halogen, cyano, nitro,
C3-6 cycloalkyl, Ci-6 alkoxy, C M alkylcarbonyl, C M alkoxycarbonyl or Ci-
3alkylsulphonyl and each R 7 is independently halogen, cyano, C3.6 cycloalkyl, C M
alkylcarbonyl, C alkoxycarbonyl or tri(Ci -3)alkylsilyl.
14. A compound according to claim , wherein Y is C]-3 alkyl, C].3 haloalkyl, C -2
alkoxy(Ci-2)alkyl, cyclopropyl optionally substituted by 1 or 2 groups independently
selected from halogen or Ci- alkyl, C2-_ alkenyl, C2-4 haloalkenyl or C2-4 alkynyl
optionally substituted by 1 or 2 groups independently selected from halogen or tri(Ci.
3)alkylsilyl.
15. A compound according to claim 14, wherein Y is Ci-2 alkyl, C1-2 haloalkyl, Ci-2
alkoxy(Ci-2)alkyl, C2-4 alkenyl or C2-4 alkynyl.
16. A compound according to any one of the previous claims, wherein Z is -C(0)R 12 , -
C(S)R 3 , or-C(=NR 14)R15 and R 2 is hydrogen, hydroxyl, C,-20 alkoxy optionally
substituted by 1 to 3 groups R38, C Oalkenyloxy optionally substituted by 1 to 3
groups R , C3 - cycloalkoxy optionally substituted by 1 to 3 groups R , Ci-i 0 alkylthio
optionally substituted by 1 to 3 groups R , amino, Ci-6 alkylamino optionally
substituted by 1 to 3 groups R38 or di(Ci .^alkylamino optionally substituted by 1 to 3
groups R38, R 3 is C1-20 alkoxy optionally substituted by 1 to 3 groups R38, C3-6
cycloalkoxy optionally substituted by 1 to 3 groups R , C Oalkylthio optionally
substituted by 1 to 3 groups R38, amino, C -6 alkylamino optionally substituted by 1 to
3 groups R38 or i(C ) alkylamino optionally substituted by 1 to 3 groups R38, R14 is
hydrogen, C1-6 alkyl optionally substituted by 1 to 3 groups R , C -2o alkoxy optionally
substituted by 1 to 3 groups R , C 3.6 cycloalkoxy optionally substituted by 1 to 3
groups R , amino, Ci. 6 alkylamino optionally substituted by 1 to 3 groups R or
di(Ci - )alkylamino optionally substituted by 1 to 3 groups R38, R15 is hydrogen, Ci-20
alkoxy optionally substituted by 1 to 3 groups R , C3 -6 cycloalkoxy optionally
substituted by 1 to 3 groups R38, C Oalkylthio optionally substituted by 1 to 3 groups
R , amino, C - alkylamino optionally substituted by 1 to 3 groups R or di(C].6)
alkyamino optionally substituted by 1 to 3 groups R38 and each R38 is independently
C - alkoxy, phenyl optionally substituted by 1 to 3 groups R39 or heteroaryl optionally
substituted by 1 to 3 groups R39 and each R 9 is independently halogen, cyano, C
alkyl, C1 haloalkyl, Ci-3 alkoxy(C 1-3)alkyl, C alkoxy, C1-4 haloalkoxy, C
alkylsulphonyl, or C alkoxycarbonyl.
17. A compound according to claim 16, wherein Z is -C(0)R .
18. A compound according to any claim 15 or 16, wherein R12 is hydroxyl, CMO alkylthio,
Ci-20 alkoxy optionally substituted by 1 or 2 groups R38, CMO alkenyloxy optionally
substituted by 1 or 2 groups R or C1-2o haloalkoxy optionally substituted by 1 to 2
groups R38.
19. A herbicidal composition comprising a compound 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).
1. A composition according to claim 19 or 20, which comprises a safener.
22. Use of a compound 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 crop plants, a compound as
defined in any one of claims 1 to 18 or a composition as defined in any one of claims
19 to 21.