The present invention relates to 5/-/-quinoxaline-6-one derivatives, to processes
and intermediates for making these compounds, to herbicidal compositions comprising
these compounds, and to methods of using these compounds to control plant growth.
WO 2008/009908, WO 2008/071918 A 1 and WO 2009/090402 (all Syngenta
Limited) disclose herbicidal pyrido[2,3-b]pyrazine derivatives.
WO 2009/063180 (Syngenta Limited) discloses certain 1/-/-2-th ia-1,5, 8-triazanaphthalene-
2,2-dioxides derivatives with herbicidal and plant-growth-inhibiting
properties.
WO201 0/1 30970 (Syngenta Limited), filed on 6 May 2010 with a priority date of
14 May 2009, discloses certain 6,6-dioxo-6-thia-1 ,4-diaza-naphthalene derivatives
having herbicidal properties.
US201 1/105329 (BASF SE), discloses substituted quinolinones and their use as
herbicides.
It has now surprisingly been found that certain 5/-/-quinoxaline-6-one derivatives
have herbicidal and/or plant-growth-inhibiting properties.
The present inven formula (I):
wherein: R and R2 are independently hydrogen, halogen, CrC 4alkyl, CrC 2fluoroalkyl,
Ci-C 2alkoxy-Ci-C 2alkyl-, hydroxy, C C alkoxy, CrC 2fluoroalkoxy, or C C2alkoxy-
CH2CH20-; R a and R are independently halogen (e.g. fluorine or chlorine), C C alkyl,
Ci-C fluoroalkyl, CrC chloroalkyl, Ci-C 2alkoxy-Ci-C 2alkyl-, C2-C alkenyl, C2-
C fluoroalkenyl, C2-C chloroalkenyl, C2-C alkynyl, C2-C fluoroalkynyl, C2-
C chloroalkynyl, C3-C6cycloalkyl-(CH 2)m- or C3-C6cycloalkyl-(CH 2)m-substituted on the
cycloalkyl ring by 1 or 2 methyl groups and wherein m is 0 or 1, CrC 3alkyl-carbonyl-, C
C3alkoxy-carbonyl-, CrC 2chloroalkyl-carbonyl-, or CrC 2fluoroalkyl-carbonyl-; phenyl or
phenyl substituted by one or two of independently fluorine and/or methyl; or
heterocyclyl-methyl- in which the heterocyclyl is a 4-, 5-, or 6- membered saturated
monocyclic heterocyclic ring in which there are 1 or 2 ring heteroatoms independently
selected from O, N and S and wherein the heterocyclyl is optionally substituted on a ring
carbon and/or (if present) on a ring nitrogen by 1 or 2 methyl groups; or heteroarylmethyl-
in which the heteroaryl is a 5-membered monocyclic heteroaromatic ring in
which there are 1, 2 or 3 ring heteroatoms independently selected from O, N and S and
wherein the heteroaryl is optionally substituted on the ring by 1 or 2 methyl groups; or
R a and R , together with the carbon atom to which they are attached, form a 3-, 4-, 5-
or 6- membered carbocyclic ring optionally substituted by 1 or 2 methyl groups; or R a
and R taken together are -(CH2)n-X -(CH 2)P- , wherein X3 is O, S, NH or NMe, and
wherein n is 1, 2 , 3 or 4 and p is 0 , 1 or 2 provided that n + p is 2 , 3 or 4 ; R4 is of subformula
(a) or (b):
(a) (b)
wherein, in sub-formula (a): R and R are independently hydrogen, halogen, d -
C2alkyl, Cifluoroalkyl, hydroxy, Ci-C 2alkoxy, Cifluoroalkoxy, methyl-S(0) 2- , H2N-S(0) 2- ,
MeNH-S(0) 2- , or Me2N-S(0) 2- ; and R4 , R4c and R4d are independently hydrogen,
halogen, cyano, CrC 4alkyl, C C2fluoroalkyl, Ci-C 3alkoxy-CrC 2alkyl-, dfluoroalkoxy-Cr
C2alkyl-, MeOCH2CH2OCH2- , C3-C6cycloalkyl, hydroxy, C C4alkoxy, C C2fluoroalkoxy,
thiol (HS-), C C3alkylthio-, dfluoroalkylthio-, C C3alkyl-S(0)-, dfluoroalkyl-S(O)-, C
C3alkyl-S(0) 2- , dfluoroalkyl-S(0) 2- , H2N-S(0) 2- , d-C 4alkyl-NH-S(0) 2- , (C C3alkyl)2NS(
0) 2- , d-C 4alkyl-C(0)-, H-C(O)-, d-C 3alkoxy-C(0)-, HO-C(O)-, H2N-C(0)-, C C4alkyl-
NH-C(O)-, (C C3alkyl)2N-C(0)-, ( 1-pyrrolidinyl)-C(O)-, (l-piperidinyl)-C(O)-, amino, C
C4alkyl-NH-, (C C3alkyl)2N-, 1-pyrrolidinyl, 1-piperidinyl, C C4alkyl-C(0)-NH-, HC(
0)-NH-, d-C 3alkyl-C(0)-N(d-C 3alkyl)-, 2-oxo-1-pyrrolidinyl, 2-oxo-1-piperidinyl, C
C3alkyl-S(0) 2-NH-, C C3alkyl-S(0) 2-N(CrC 3alkyl)-, phenyl or phenyl substituted by one,
two or three of R7, or phenoxy or phenoxy substituted by one, two or three of R7;
provided that none of, or only one of, R4 , R4c and R4d is C3-C6cycloalkyl, (1-pyrrolidinyl)-
C(O)-, (l-piperidinyl)-C(O)-, 1-pyrrolidinyl, 1-piperidinyl, 2-oxo-1-pyrrolidinyl, 2-oxo-1-
piperidinyl, phenyl, substituted phenyl, phenoxy or substituted phenoxy; wherein each
R7, independently of any other R7, is fluorine, chlorine, d-C 2alkyl, Cifluoroalkyl, d -
C2alkoxy or Cifluoroalkoxy; and wherein, in sub-formula (b):A1 is N or C-R4f, A2 is N or
C-R49 , A3 is N or C-R4h, A2 is N or C-R4i, and A5 is N or C-R4 , provided that one or two of
A1, A2, A3, A4 and A5 are nitrogen and the remaining ones of A1, A2, A3, A4 and A5 are not
nitrogen; wherein R4f and R4 are independently hydrogen, halogen, Ci-C 2alkyl,
Cifluoroalkyl, hydroxy (inclusive of any tautomer thereof), Ci-C 2alkoxy, or
Cifluoroalkoxy; and R49 , R4h and R4' are independently hydrogen, halogen, Ci-C alkyl,
C C2fluoroalkyl, C C3alkoxy-methyl-, dfluoroalkoxy-methyl-, MeOCH2CH2OCH2- , C3-
C6cycloalkyl, hydroxy (inclusive of any tautomer thereof), d-C alkoxy, d -
C2fluoroalkoxy, C C4alkyl-C(0)-, H-C(O)-, C C3alkoxy-C(0)-, HO-C(O)-, H2N-C(0)-, d -
C4alkyl-NH-C(0)-, (CrC 3alkyl)2N-C(0)-, (l-pyrrolidinyl)-C(O)-, (l-piperidinyl)-C(O)-,
amino, C C4alkyl-NH-, (C C3alkyl)2N-, 1-pyrrolidinyl, 1-piperidinyl, C C4alkyl-C(0)-NH-,
H-C(0)-NH-, C C3alkyl-C(0)-N(C C3alkyl)-, 2-oxo-1-pyrrolidinyl, 2-oxo-1-piperidinyl,
phenyl or phenyl substituted by one, two or three of R7, or phenoxy or phenoxy
substituted by one, two or three of R7; wherein R7 is as defined hereinabove; provided
that none of, or only one of, R49 , R4h and R4i is C3-C6cycloalkyl, ( 1-pyrrolidinyl)-C(O)-, (1-
piperidinyl)-C(O)-, 1-pyrrolidinyl, 1-piperidinyl, 2-oxo-1-pyrrolidinyl, 2-oxo-1-piperidinyl,
phenyl, substituted phenyl, phenoxy or substituted phenoxy; and R5 is hydroxy, R6-oxy-,
R8-C(0)-0-, C C10alkyl-S(O)2O-, dfluoroalky-S(0) 20-, dchloroalkyl-S(0) 20-, phenyl-
S(0) 20 - or (4-methyl-phenyl)-S(0) 20-; wherein R6 is C C10alkyl, C C4fluoroalkyl, C2-
C 0alkenyl, C2-C 0alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-CrC alkyl-, d-C alkoxy-
CH2CH2- , CrC 4alkoxy-CH2CH2CH2- , phenyl-C C4alkyl-, or phenyl-C C4alkyl- wherein
the phenyl moiety is substituted by one, two or three R9; R8 is Cr C 0alkyl, d -
C fluoroalkyl, C2-C 0alkenyl, C2-C 0alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-CrC alkyl-,
Ci-C alkoxy-CrC alkyl-, phenyl, phenyl substituted by one, two or three R9, phenyl-d-
C alkyl-, or phenyl-d-C alkyl- wherein the phenyl moiety is substituted by one, two or
three R9; or R8 is Cr C 0alkoxy, d-C fluoroalkoxy, Cr C 0alkenyloxy, Cr C 0alkynyloxy,
C3-C8cycloalkoxy, C3-C8cycloalkyl-CrC alkoxy-, CrC alkoxy-CH2CH20-, d-C alkoxy-
CH2CH2CH20-, phenoxy, phenoxy substituted by one, two or three R9, phenyl-d-
C alkoxy-, or phenyl-d-C alkoxy- wherein the phenyl moiety is substituted by one, two
or three R9; or R8 is C C 0alkylthio-, Ci-Cioalkyl-NH-, or (C C6alkyl)2N-; and wherein
each R9, independently of any other R9, is fluorine, chlorine, d-C alkyl, Cifluoroalkyl,
Ci-C 3alkoxy or Cifluoroalkoxy; or a salt (e.g. agriculturally acceptable salt) thereof.
In the description and claims of this specification, when references are made to a
compound of formula (I), or to a compound of the invention, or to a compound (which is
implicitly a compound of formula (I) or a compound of the invention), these references
are intended to encompass the compound or a salt (e.g. agriculturally acceptable salt)
thereof.
The compounds of formula (I) may exist in different geometric or optical isomers
or tautomeric forms. The present invention covers all such isomers and tautomers and
mixtures thereof in all proportions. Furthermore, it is possible that atropisomers are
obtained in those cases where the rotation of the R4 group is restricted, for example in
those cases where the R4 group (e.g. of sub-formula (a)) has at least one orthosubstituent,
and all such atropisomers are included in the invention.
As an example of tautomerism, a compound of formula (la), i.e. a compound of
formula (I) where R5 is hydroxy, can be drawn in two tautomeric forms illustrated below,
and the present invention covers each of these tautomeric forms as well as a mixture of
these two tautomeric forms.
(la)
The compounds of formula (I) may contain one or more asymmetric carbon
atoms, for example, at the -CR aR - group, and may exist as enantiomers (or as pairs of
diastereoisomers) or as mixtures of such, and all such isomers and mixtures of isomers
are covered by the present invention.
Alkyl groups (either alone or as part of a larger group, such as alkoxy, alkoxycarbonyl-,
alkylcarbonyl-, et al.) can be in the form of a straight or branched chain.
Typical examples are methyl, ethyl, propan-1-yl (n-propyl or propyl), propan-2-yl
(isopropyl or 1-methylethyl), butan-1-yl (n-butyl or butyl), butan-2-yl (sec-butyl or 1-
methylpropyl), 2-methylpropan-1-yl (isobutyl or 2-methylpropyl), or 2-methylpropan-2-yl
( -butyl or 1,1-dimethylethyl). Except where more narrow ranges are stated, in
general, alkyl groups are preferably C C6 alkyl, more preferably C C alkyl, most
preferably C 3 alkyl groups.
Alkenyl groups (either alone or as part of a larger group, such as alkenyloxy) can
be in the form of a straight or branched chain, and can be, where appropriate, of either
the (E)- or ©-configuration. Typical examples are vinyl, allyl (prop-2-enyl) or 3-methylbut-
2-enyl. Except where more narrow ranges are stated, in general, alkenyl groups are
preferably C2-C6, more preferably C2-C , most preferably C2-C3 alkenyl groups.
Alkynyl groups (either alone or as part of a larger group, such as alkynyloxy) can
be in the form of a straight or branched chain. Typical examples are ethynyl, propargyl
(prop-2-ynyl) or but-2-ynyl. Except where more narrow ranges are stated, in general,
alkynyl groups are preferably C2-C6, more preferably C2-C , most preferably C2-C3
alkynyl groups.
Halogen is fluorine, chlorine, bromine or iodine. Preferably, e.g. in the
compound of formula (I), halogen is fluorine, chlorine or bromine; such as fluorine or
chlorine.
Fluoroalkyl groups (either alone or as part of a larger group, such as fluoroalkoxy
or fluoroalkylthio-) are alkyl groups (straight-chain or branched) which are substituted by
one or more (e.g. 1, 2 or 3) fluorine atoms. Typical examples are trifluoromethyl (CF3) ,
difluoromethyl, monofluoromethyl, 2,2,2-trifluoro-ethyl, 2,2-difluoro-ethyl (CHF2CH2-),
2-fluoro-ethyl or perfluorobutan-1-yl; in particular trifluoromethyl or 2,2,2-trifluoro-ethyl.
Typical examples of fluoroalkoxy groups are difluoromethoxy, trifluoromethoxy,
monofluoromethoxy, 2,2,2-trifluoro-ethoxy, 2,2-difluoro-ethoxy or 2-fluoro-ethoxy; in
particular difluoromethoxy (CHF20).
Chloroalkyl groups (either alone or as part of a larger group, such as
chloroalkoxy or chloroalkylthio-) are alkyl groups (straight-chain or branched) which are
substituted by one or more (e.g. 1, 2 or 3) chlorine atoms. Typical examples are
dichloromethyl, trichloromethyl or monochloromethyl, 2,2,2-trichloro-ethyl, 2,2-dichloroethyl,
or 2-chloroethyl.
Fluoroalkenyl and chloroalkenyl groups are alkenyl groups which are substituted
by one or more (e.g. 1, 2 or 3) fluorine or chlorine atoms respectively. Typical examples
of fluoroalkenyl are 1-fluorovinyl, 2,2-difluoro-vinyl or 1,2,2-trifluoro-vinyl. Typical
examples of chloroalkenyl are 1-chlorovinyl, 1,2-dichloro-vinyl, 2,2-dichloro-vinyl or
1,2,2-trichloro-vinyl.
Fluoroalkynyl and chloroalkynyl groups are alkynyl groups which are substituted
by one or more (e.g. 1, 2 or 3) fluorine or chlorine atoms respectively. Typical examples
of fluoroalkenyl are 1-fluoro-prop-2-ynyl, 1,1-difluoro-prop-2-ynyl or 3-fluoro-prop-2-ynyl.
Typical examples of chloroalkynyl are 1-chloro-prop-2-ynyl or 3-chloro-prop-2-ynyl.
Cycloalkyl groups and carbocyclic rings (either alone or as part of a larger group,
such as cycloalkyl-alkyl-) are monocyclic carbocycles. Typical examples are
cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Except where more narrow ranges are
stated, in general, cycloalkyl groups are preferably C3-C6, more preferably C3-C5
cycloalkyl groups.
Heterocyclyl groups and heterocyclic rings (either alone or as part of a larger
group, such as heterocyclyl-alkyl-) are monocyclic saturated ring systems containing at
least one ring heteroatom. Preferably, heterocyclyl groups will have one or two ring
heteroatoms selected from nitrogen, oxygen and sulfur. Typical examples of
heterocyclic groups include oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, azetidinyl,
pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, or thietanyl. Heterocyclyl groups having
a single oxygen or nitrogen atom as the ring heteroatom are preferred. Except where
more narrow ranges are stated, in general, heterocyclyl groups are preferably 4-, 5- or
6-membered rings, more preferably 5- or 6-membered rings.
Aryl groups (either alone or as part of a larger group, such as aryloxy- or
arylthio-) are monocyclic or fused bicyclic aromatic ring systems. Examples of such rings
include phenyl, naphthyl, or indenyl. The preferred aryl group is phenyl.
Heteroaryl groups (either alone or as part of a larger group, such as
heteroaryloxy- or heteroarylthio-) are monocyclic or fused bicyclic aromatic ring systems
containing at least one ring heteroatom. Preferably, single rings will have one, two or
three heteroatoms selected from nitrogen, oxygen and sulfur. Typical examples of
monocyclic heteroaryl groups are pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl,
pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thiophenyl, oxazolyl,
isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl or thiadiazolyl. Preferably, bicyclic systems
will have one, two, three or four ring heteroatoms selected from nitrogen, oxygen and
sulfur. Typical examples of bicyclic heteroaryl groups are quinolinyl, cinnolinyl,
quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothiophenyl or benzothiadiazolyl.
Monocyclic heteroaryl groups are preferred, and pyridyl is generally most preferred.
Where R5 is other than hydroxy, the R5 group is in most cases intended to be
metabolised by a plant to a hydroxy group. In some cases, a R5 group, which is other
than hydroxy, might increase penetration of the compound of formula (I) into a plant, e.g.
might increase penetration across the cuticule of the leaf of a plant, before metabolism
by the plant of the R5 group to a hydroxy group. Plant metabolism means the
conversion or breakdown of a substance from one form to another by a plant (in planta).
Salts comprise a charged version of a compound of formula (I) and a counter ion
of the opposite charge. The salt is preferably agriculturally acceptable. The compounds
of formula (I) can have a negative charge, for example, on an oxygen atom of a hydroxy
group, if the hydroxy group is deprotonated with a base (e.g. ammonia or an alkali metal
hydroxide). Suitable cationic counter ions include, for example, alkali metals such as
sodium or potassium, or alkaline earth metals such as magnesium or calcium, or
quaternary ammonium such as ammonium or tetramethylammonium. Alternatively, the
compounds of formula (I) can have a positive charge, for example, on the nitrogen atom
in a nitrogen-containing heteroaryl group; for example: if the nitrogen atom is
quaternised by protonation with an organic or inorganic acid, or if the nitrogen atom is
quaternised by alkylation for example with a methyl group, or if the nitrogen atom is
quaternised by amination. Suitable anionic counter ions include, for example, an anion
of an organic acid, or an inorganic anion such as hydroxide, fluoride, chloride, bromide,
iodide, sulfate, phosphate or nitrate.
The compounds of formula (I) according to the invention (encompassing a
compound or a salt thereof) also include hydrates, which, for example, may be formed
during salt formation.
Preferred, particular, suitable, typical or optional values, e.g. preferred, particular,
suitable, typical or optional values of R , R2, R a , R , R4, R5, R6, R7, R8 and R9, et al.,
are as set out below, and these preferred features can be taken together in any
combination.
Preferably R is hydrogen, halogen, CrC 3alkyl (e.g. methyl or ethyl),
Cifluoroalkyl (e.g. CF3) , C C2alkoxy (e.g. methoxy) or Cifluoroalkoxy (e.g. CHF20 ,
CF30 or CH2FO, in particular CHF20); more preferably hydrogen, fluorine, chlorine,
methyl or ethyl; still more preferably hydrogen or methyl; most preferably hydrogen.
Preferably R2 is hydrogen, halogen, CrC 3alkyl (e.g. methyl or ethyl),
Cifluoroalkyl (e.g. CF3) , C C2alkoxy (e.g. methoxy) or Cifluoroalkoxy (e.g. CHF20 ,
CF3O or CH2FO, in particular CHF20); more preferably hydrogen, fluorine, chlorine,
methyl or ethyl; still more preferably hydrogen or methyl; most preferably hydrogen.
Preferably, m is 1.
Preferably, when R a and/or R are independently heterocyclyl-methyl-, then the
heterocyclyl is a 4- or 5- membered saturated monocyclic heterocyclic ring linked by a
ring carbon, in which there are 1 or 2 (in particular one) ring heteroatoms independently
selected from O, N and S (in particular O), and wherein the heterocyclyl is unsubstituted
or is substituted on a ring carbon and/or (if present) on a ring nitrogen by 1 or 2 methyl
groups. Typical examples of the heterocyclyl-methyl- are: oxetan-3-yl-methyl-, oxetan-
2-yl-methyl-, tetrahydrofuran-3-yl-methyl-, or tetrahydrofuran-2-yl-methyl-; or (when the
heterocyclyl is a 5- or 6-membered monocyclic heterocyclic ring linked by a ring
nitrogen) piperazin-1-yl-methyl-, 4-methyl-piperazin-1-yl-methyl-, pyrrolidin-1 -yl-methyl-,
or piperidin-1 -yl-methyl-.
Preferably, when R a and/or R are independently heteroaryl-methyl-, then the
heteroaryl is a 5-membered monocyclic heteroaromatic ring in which there are 1 or 2
(e.g. 1) ring heteroatoms independently selected from O, N and S (e.g. selected from O
and N) and wherein the heteroaryl is unsubstituted or is substituted on the ring by 1 or 2
(e.g. 1) methyl groups; in particular unsubstituted or substituted furanyl-methyl-. Typical
examples of the heteroaryl-methyl- are furan-3-yl-methyl- or furan-2-yl-methyl-.
Preferably, when R a and R , together with the carbon atom to which they are
attached, form a 3-, 4-, 5- or 6- membered carbocyclic ring optionally substituted by 1 or
2 methyl groups, then preferably they form a 3-, 4- or 5- (e.g. 3- or 4-) membered
optionally substituted carbocyclic ring; and more preferably they form an unsubstituted
cyclopropyl ring.
In a particular embodiment, X3 is O, NH or NMe; more particularly O.
In a particular embodiment, n is 1, 2 or 3 and p is 0 or 1 provided that n + p is 2
or 3 .
Preferably, neither R nor R is hydrogen. This avoids or minimizes possible
aromatization of the right-hand, carbocyclic, ring illustrated in formula (I).
Preferably R a is C C4alkyl, C C3fluoroalkyl (e.g. dfluoroalkyl-CHr), C2-
C3alkenyl, C2-C3fluoroalkenyl, C2chloroalkenyl (e.g. 1-chloro-vinyl), C2-C3alkynyl, C3-
C5cycloalkyl, C3-C cycloalkyl-CH 2- , or phenyl. More preferably, R a is methyl, ethyl, npropyl,
isopropyl, Cifluoroalkyl-CH 2- (e.g. 2-fluoro-ethyl, 2,2-difluoro-ethyl or 2,2,2-
trifluoro-ethyl), vinyl, allyl, C2fluoroalkenyl (e.g. 2,2-difluoro-vinyl or 1,2,2-trifluoro-vinyl),
propargyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopropyl-methyl-, or phenyl. Still more
preferably, R a is methyl, ethyl, Cifluoroalkyl-CH 2- (e.g. 2-fluoro-ethyl, 2,2-difluoro-ethyl
(CHF2CH2-), or 2,2,2-trifluoro-ethyl), vinyl, allyl, 2,2-difluoro-vinyl, 1,2,2-trifluoro-vinyl,
propargyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclopropyl-methyl-. Most preferably,
R a is methyl.
Preferably R is C C4alkyl, C C3fluoroalkyl (e.g. dfluoroalkyl-CH 2-), C2-
C3alkenyl, C2-C3fluoroalkenyl, C2chloroalkenyl (e.g. 1-chloro-vinyl), C2-C3alkynyl, C3-
C5cycloalkyl, C3-C cycloalkyl-CH 2- , or phenyl. More preferably, R is methyl, ethyl, npropyl,
isopropyl, Cifluoroalkyl-CH 2- (e.g. 2-fluoro-ethyl, 2,2-difluoro-ethyl or 2,2,2-
trifluoro-ethyl), vinyl, allyl, C2fluoroalkenyl (e.g. 2,2-difluoro-vinyl or 1,2,2-trifluoro-vinyl),
propargyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopropyl-methyl-, or phenyl. Still more
preferably, R is methyl, ethyl, Cifluoroalkyl-CH 2- (e.g. 2-fluoro-ethyl, 2,2-difluoro-ethyl
or 2,2,2-trifluoro-ethyl), vinyl, allyl, 2,2-difluoro-vinyl, 1,2,2-trifluoro-vinyl, propargyl,
cyclopropyl, cyclobutyl, cyclopentyl, or cyclopropyl-methyl-. Yet more preferably, R is
methyl, ethyl, dfluoroalkyl-CH 2- (e.g. 2-fluoro-ethyl, 2,2-difluoro-ethyl (CHF2CH2-), or
2,2,2-trifluoro-ethyl), vinyl, allyl or propargyl; in particular methyl.
Most preferably, R a is methyl and R is as defined in one of the abovementioned
preferable definitions of R .
In an alternative preferred embodiment, R a and R , together with the carbon
atom to which they are attached, form an unsubstituted cyclopropyl, cyclobutyl or
cyclopentyl (in particular cyclopropyl) ring.
In one preferred embodiment both R a and R are methyl.
In one preferred embodiment R a is methyl and R is ethyl.
In one preferred embodiment R a is methyl and R is 2,2-difluoro-ethyl
(CHF2CH2-).
In one preferred embodiment R a is methyl and R is 2,2,2-trifluoro-ethyl
(CF3CH2-).
In one preferred embodiment R a is methyl and R is vinyl.
In one preferred embodiment R a is methyl and R is allyl.
In one preferred embodiment R a is methyl and R is propargyl.
In one preferred embodiment R and R , together with the carbon atom to
which they are attached, form an unsubstituted cyclopropyl ring.
In one particular embodiment R a is methyl and R is cyclopentyl.
In one particular embodiment R a is methyl and R is phenyl.
In one particular embodiment both R a and R are allyl.
In one particular embodiment both R a and R are cyclopentyl.
In R4, sub-formula (a), preferable features are as follows.
Preferably, at least one of R4a and R4e is not hydrogen or fluorine.
Preferably, R4a and R4e are independently hydrogen, fluorine, chlorine, bromine,
iodine, methyl, ethyl, CifluoroalkyI (e.g. CF3) , methoxy, Cifluoroalkoxy (e.g. CHF20 ,
CF30 or CH2FO, in particular CHF20), methyl-S(0) 2- or H2N-S(0) 2- . More preferably,
R4a and R4e are independently hydrogen, fluorine, chlorine, bromine, methyl,
CifluoroalkyI (e.g. CF3) , methoxy, Cifluoroalkoxy (e.g. CHF20 , CF30 or CH2FO, in
particular CHF20), or methyl-S(0) 2- . Still more preferably, R4a and R4e are
independently hydrogen, fluorine, chlorine, bromine, methyl, CF3 or methoxy.
Preferably, in these cases, at least one of R4a and R4e is not hydrogen or fluorine.
Most preferably, R4a is chlorine; in which case preferably R4e is hydrogen,
fluorine, chlorine, bromine, methyl, CF3 or methoxy.
Preferably, R4 , R4c and R4d are independently hydrogen, halogen (fluorine,
chlorine, bromine or iodine), -C4alkyl (e.g. methyl or ethyl), CifluoroalkyI (e.g. CF3) ,
methoxymethyl-, MeOCH2CH2OCH2- , C3-C5cycloalkyl (e.g. cyclopropyl), C C3alkoxy
(e.g. methoxy or ethoxy), Cifluoroalkoxy (such as CHF20 , CF30 or CH2FO, in particular
CHF20), Ci-C 3alkyl-S(0) 2- (e.g. methyl-S(0) 2-), H2N-S(0) 2- , C C3alkyl-NH-S(0) 2- (e.g.
MeNH-S(0) 2-), or (C C3alkyl)2N-S(0) 2- (e.g. Me2N-S(0) 2-); or phenyl or phenyl
substituted by one or two of R7, wherein each R7, independently of any other R7, is
fluorine, chlorine, methyl, CifluoroalkyI (e.g. CF3) , methoxy or Cifluoroalkoxy (e.g.
CHF20 , CF30 or CH2FO, in particular CHF20); provided that none of, or only one of,
R4 , R4c and R4d is C3-C5cycloalkyl, phenyl or substituted phenyl.
More preferably, R4 , R4c and R4d are independently hydrogen, fluorine, chlorine,
bromine, methyl, ethyl, CifluoroalkyI (e.g. CF3) , cyclopropyl, methoxy, ethoxy,
Cifluoroalkoxy (such as CHF20 , CF30 or CH2FO, in particular CHF20), or methyl-S(0) 2-
; or phenyl or phenyl substituted by one or two (e.g. one) of R7, wherein each R7,
independently of any other R7, is fluorine, chlorine, methyl, CF3, methoxy, CHF20 or
CH2FO;
provided that none of, or only one of, R4 , R4c and R4d is cyclopropyl, phenyl or
substituted phenyl.
Still more preferably, R , R and R are independently hydrogen, fluorine,
chlorine, bromine, methyl, ethyl, CifluoroalkyI (e.g. CF3) , cyclopropyl, methoxy,
Cifluoroalkoxy (such as CHF20 , CF30 or CH2FO, in particular CHF20), or methyl-S(0) 2-
provided that none of, or only one of, R4 , R4c and R4d is cyclopropyl.
Preferably, one or two (e.g. two) of R4 , R4c and R4d are hydrogen.
Preferably, in R4 sub-formula (a) or (b), R7, independently of any other R7, is
fluorine, chlorine, methyl, CifluoroalkyI (e.g. CF3) , methoxy or Cifluoroalkoxy (e.g.
CHF20 , CF30 or CH2FO, in particular CHF20).
In one particular embodiment R4 is 2-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 2-chloro-phenyl-.
In one particular embodiment R4 is 2-bromo-phenyl-.
In one particular embodiment R4 is 2-methyl-phenyl-.
In one particular embodiment R4 is 2-methoxy-phenyl-.
In one particular embodiment R4 is 2,4-difluoro-phenyl-.
In one particular embodiment R4 is 2,6-dichloro-phenyl-.
In one particular embodiment R4 is 2,3-dichloro-6-fluoro-phenyl-.
In one particular embodiment R4 is 2-chloro-3,6-difluoro-phenyl-.
In one particular embodiment R4 is 3-bromo-2-chloro-6-fluoro-phenyl-.
In one particular embodiment R4 is 2,3,6-trichloro-phenyl-.
In one particular embodiment R4 is 2-chloro-5-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 2-chloro-6-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 2,5-bis-(trifluoromethyl)-phenyl-.
In one particular embodiment R4 is 2-bromo-5-chloro-phenyl-.
In one particular embodiment R4 is 4-bromo-2-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 4-chloro-2-methylsulfonyl-phenyl-.
In one particular embodiment R4 is 4-chloro-2-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 5-chloro-2-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 3,5-difluoro-2-trifluoromethyl-phenyl-
In one particular embodiment R4 is 2-ethyl-4-(4'-chloro-phenyl)-phenyl-.
In one particular embodiment R4 is 2,4,6-trimethyl-phenyl-.
In one embodiment R4 is 4-chloro-phenyl-.
In one embodiment R4 is 3-trifluoromethyl-phenyl-.
In R4, sub-formula (b), preferable features are as follows.
Preferably, one of A1, A2, A3, A4 and A5 is nitrogen and the remaining ones of A1,
A2, A3, A4 and A5 are not nitrogen. That is, in R4, sub-formula (b) is preferably pyridinyl
or substituted pyridinyl.
In one particular embodiment, A1 is nitrogen and A2, A3, A4 and A5 are not
nitrogen. That is, in R4, sub-formula (b) is particularly pyridin-2-yl or substituted pyridin-
2-yl.
In one particular embodiment, A2 is nitrogen and A1, A3, A4 and A5 are not
nitrogen. That is, in R4, sub-formula (b) is particularly pyridin-3-yl or substituted pyridin-
3-yl.
In one particular embodiment, A3 is nitrogen and A1, A2, A4 and A5 are not
nitrogen. That is, in R4, sub-formula (b) is particularly pyridin-4-yl or substituted pyridin-
4-yl.
Preferably, at least one of R4f and R4 is not hydrogen or fluorine.
Preferably, R4f and R4 are independently hydrogen, fluorine, chlorine, methyl,
Cifluoroalkyl (e.g. CF3) , or hydroxy (inclusive of any tautomer thereof). More preferably,
R4f and R4 are independently hydrogen, fluorine, chlorine, methyl or Cifluoroalkyl (e.g.
CF3) . Still more preferably, R4f and R4 are independently hydrogen, chlorine or CF3.
Preferably, in these cases, at least one of R4f and R4 is not hydrogen or fluorine.
More preferably, one of R4f and R4 is chlorine. In this case, preferably, the other
of R4f and R4 is hydrogen, fluorine, chlorine, methyl, Cifluoroalkyl (e.g. CF3) , or hydroxy
(inclusive of any tautomer thereof); or more preferably the other of R4f and R4 is
hydrogen, fluorine, chlorine, methyl or Cifluoroalkyl (e.g. CF3) ; or still more preferably
the other of R4f and R4 is hydrogen, chlorine or CF3.
Preferably, R49 , R4h and R4' are independently hydrogen, fluorine, chlorine,
Ci-C 4alkyl (e.g. methyl or ethyl), Cifluoroalkyl (e.g. CF3) , methoxymethyl-,
MeOCH2CH2OCI-l2- , C3-C5cycloalkyl (e.g. cyclopropyl), hydroxy (inclusive of any
tautomer thereof); Ci-C 3alkoxy (e.g. methoxy or ethoxy), or Cifluoroalkoxy (such as
CHF20 , CF30 or CH2FO, in particular CHF20); or phenyl or phenyl substituted by one,
two or three of R7, wherein R7, independently of any other R7, is fluorine, chlorine,
methyl, Cifluoroalkyl (e.g. CF3) , methoxy or Cifluoroalkoxy (e.g. CHF20 , CF30 or
CH2FO, in particular CHF2O);
provided that none of, or only one of, R49 , R4h and R4' is C3-C5cycloalkyl, phenyl or
substituted phenyl.
More preferably, R49 , R4h and R4' are independently hydrogen, fluorine, chlorine,
methyl, or Cifluoroalkyl (e.g. CF3) .
Preferably, one or two (e.g. two) of R49 , R4h and R4' are hydrogen.
Preferable examples of groups for R4, sub-formula (b), are 3,5-dichloro-pyridin-2-
yl, 3,6-dichloro-pyridin-2-yl, 3-chloro-5-fluoro-pyridin-2-yl, 3-chloro-5-trifluoromethylpyridin-
2-yl, 3,5,6-trichloro-pyridin-2-yl, 2,4-dichloro-pyridin-3-yl, 2,5-dichloro-pyridin-3-yl,
2,6-dichloro-pyridin-3-yl, 4,6-dichloro-pyridin-3-yl, 2-chloro-4-trifluoromethyl-pyridin-3-yl,
2-chloro-6-trifluoromethyl-pyridin-3-yl, 2-hydroxy-pyridin-3-yl (inclusive of its pyridone
tautomer), 2,3-dichloro-pyridin-4-yl, 2,5-dichloro-pyridin-4-yl, 3,5-dichloro-pyridin-4-yl, 3-
chloro-5-trifluoromethyl-pyridin-4-yl, 2,3,5-trichloro-pyridin-4-yl, or 5-chloro-pyrimidin-4-
yi-
Alternative particular examples of groups for R4, sub-formula (b), are 6-hydroxypyridin-
2-yl 6-hydroxy-pyridin-3-yl, or 2-hydroxy-pyridin-4-yl (all inclusive of their
pyridone tautomers).
When R5 is CrC 10alkyl-S(O) 2O-, Cifluoroalkyl-S(0) 20-, CiChloroalkyl-S(0) 20-,
phenyl-S(0) 20 - or (4-methyl-phenyl)-S(0) 20-, then it can for example be
methanesulfonyloxy-, ethanesulfonyloxy-, trifluoromethanesulfonyloxy-,
trichloromethanesulfonyloxy-, benzenesulfonyloxy- or para-toluenesulfonyloxy-.
Preferably, R5 is hydroxy, R6-oxy- or R8-C(0)-0-.
More preferably, R5 is hydroxy or R8-C(0)-0-.
Preferably, R6 is C C8alkyl (e.g. C C6alkyl, such as C C4alkyl),
CrC 2fluoroalkyl, C2-C5alkenyl-CH 2- (e.g. allyl), C2-C5alkynyl-CH 2- (e.g. propargyl),
C3-C6cycloalkyl, C3-C6cycloalkyl-CrC 2alkyl-, C C2alkoxy-CH 2CH2- ,
CrC 2alkoxy-CH 2CH2CH2- , phenyl-C C2alkyl-, or phenyl-C C2alkyl- wherein the phenyl
moiety is substituted by one or two R9; and wherein each R9, independently of any other
R9, is fluorine, chlorine, C C2alkyl, CifluoroalkyI, C C2alkoxy or Cifluoroalkoxy.
In one particular embodiment, R5 is R6-oxy- and is: methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, te/f-butoxy, allyloxy, propargyloxy, or benzyloxy.
Preferably, R8 is Ci-C8alkyl (e.g. CrC 6alkyl, such as C2-C alkyl, e.g. isopropyl or
te/f-butyl), Ci-C2fluoroalkyl (e.g. CifluoroalkyI), C2-C6alkenyl, C2-C6alkynyl,
C3-C6cycloalkyl, C3-C6cycloalkyl-Ci-C 2alkyl-, C C2alkoxy-CH 2- , CrC 2alkoxy-CH 2CH2- ,
Ci-C2alkoxy-CH 2CH2CH2- , phenyl-Ci-C 2alkyl-, or phenyl-Ci-C 2alkyl- wherein the phenyl
moiety is substituted by one or two R9; or R8 is Ci-C8alkoxy (e.g. CrC 6alkoxy, such as
Ci-C alkoxy, e.g. methoxy or ethoxy), Ci-C2fluoroalkoxy (e.g. Cifluoroalkoxy),
C2-C5alkenyl-CH 2-oxy (e.g. allyloxy), C2-C5alkynyl-CH 2-oxy (e.g. propargyloxy),
C3-C6cycloalkoxy, C3-C6cycloalkyl-Ci-C 2alkoxy-, CrC 2alkoxy-CH 2CH20-,
Ci-C2alkoxy-CH 2CH2CH20-, phenoxy, phenoxy substituted by one, two or three R9,
phenyl-Ci-C 2alkoxy-, or phenyl-Ci-C 2alkoxy- wherein the phenyl moiety is substituted by
one or two R9; or R8 is C C6alkylthio-, CrC 6alkyl-NH-, or (C C4alkyl)2N-;
and wherein each R9, independently of any other R9, is fluorine, chlorine, methyl, ethyl,
CifluoroalkyI (e.g. trifluoromethyl), methoxy or Cifluoroalkoxy (e.g. difluoromethoxy or
trifluoromethoxy).
More preferably, R8 is Ci-C8alkyl (in particular CrC 6alkyl, such as C2-C alkyl,
e.g. isopropyl or te/f-butyl) or Ci-C8alkoxy (e.g. CrC 6alkoxy, such as C C alkoxy, e.g.
methoxy or ethoxy).
Most preferably, R8 is -C8alkyl (in particular CrC 6alkyl, such as C2-C4alkyl, e.g.
isopropyl or te/f-butyl).
In one particularly preferred embodiment, R5 is R8-C(0)-0- and is: propan-2-
ylcarbonyloxy- (isopropylcarbonyloxy-), 2-methyl-propan-2-ylcarbonyloxy- (tertbutylcarbonyloxy-),
methoxycarbonyloxy-, ethoxycarbonyloxy-, or ethylthiocarbonyloxy-.
In one even more particularly preferred embodiment, R5 is R8-C(0)-0- and is:
propan-2-ylcarbonyloxy- (isopropylcarbonyloxy-) or 2-methyl-propan-2-ylcarbonyloxy-
(te/f-butylcarbonyloxy-).
In an alternative particularly preferred embodiment, R5 is hydroxy.
Preferably, the compound of formula (I) is one of compounds E 1, E2, E3, E4, E5,
E6, E7, F1, F2, F3, F4, F5, or F6, which have the structures shown in Example 2.4
Table E and/or Example 2.5 Table F hereinafter, or an agriculturally acceptable salt
thereof.
More preferably, the compound of formula (I) is one of compounds E 1, E2, E3,
E4, E5, F1, F2, F3 or F4, which have the structures shown in Example 2.4 Table E
and/or Example 2.5 Table F hereinafter, or an agriculturally acceptable salt thereof.
Certain intermediates, useable in a process for preparing a compound of formula
(I), are thought to be novel, and thus form other aspects of the present invention.
Thus, a further aspect of the present invention provides a compound of formula
(8):
wherein R , R2, R a , R and R4 are as defined for the compound of formula (I) and R6a is
Ci-C alkyl. Preferably, R and R2 are both hydrogen. Suitably, R6a is methyl, ethyl, npropyl,
isopropyl or n-butyl, or more preferably methyl or ethyl.
A yet further aspect of the present invention provides a compound of formula
(10):
wherein R , R2, R a , R and R4 are as defined for the compound of formula (I).
Preferably, R and R2 are both hydrogen.
Processes for preparing the compound of formula (I)
A first part of a process for preparing a compound of formula (I), namely
preparing an intermediate compound of formula (6), is shown in Scheme 1 below.
The steps of Scheme 1 are as follows:
1. A malonate compound of formula (3) wherein R and R2 are as defined
for a compound of formula (I) and R6a is C C alkyl can be prepared by reacting a 2,3-
dichloropyrazine of formula (2) wherein R and R2 are as defined for a compound of
formula (I). The reaction can be carried out using a malonate ester of formula (7) with a
base, such as sodium or potassium carbonate, in a non-aqueous (e.g. anhydrous)
organic solvent, such as A/,A/-dimethylformamide (DMF) or /V-methyl-pyrrolidinone
(NMP). Suitably, R6a is methyl, ethyl, n-propyl, isopropyl or n-butyl, or more preferably
methyl or ethyl. Suitably, the reaction to prepare the malonate compound of formula (3)
is heated at 50 to 170 °C, e.g. 80 to 140 °C, such as about 100-120 °C. Malonates of
formula (7) are commercially available and/or can be prepared by methods known to the
person skilled in the art.
2 . A carboxylic acid of formula (4) wherein R and R2 are as defined for a
compound of formula (I) can be prepared by reacting an aqueous solution of a hydroxide
salt (such as an alkali metal hydroxide, e.g. NaOH or KOH, or an alkaline earth metal
hydroxide) with a malonate compound of formula (3) where R and R2 are as defined for
a compound of formula (1), in a solvent, such as ethanol and/or methanol. Suitably, the
reaction temperature for preparing the carboxylic acid of formula (4) is 40 to 100 °C, e.g.
50 to 90 °C, such as about 60-80 °C.
Schem
3 . An ester of formula (5), wherein R and R2 are as defined for a compound
of formula (I), and wherein R6a is C C alkyl such as methyl, ethyl, n-propyl, isopropyl or
n-butyl, or more preferably methyl or ethyl, can be prepared by reacting an acid of
formula (4) where R and R2 are as defined for a compound of formula (1) with an
activating agent, such as 1,1'-carbonyldiimidazole, in the presence of an alcohol
R6a-OH, preferably methanol or ethanol, in a solvent such as A/,A/-dimethylformamide.
4 . An ester of formula (6), wherein R and R2 are as defined for a compound
of formula (I), and wherein R6a is C C alkyl such as methyl, ethyl, n-propyl, isopropyl or
n-butyl, or more preferably methyl or ethyl, can be prepared by reacting an ester of
formula (5), wherein R and R2 are as defined for a compound of formula (I) and R6a is
CrC 4alkyl, with alkylating agents R a-X a and R -X , wherein X a and X are
independently a leaving group, in the presence of a base, preferably a lithium amide
base, in a non-aqueous (e.g. anhydrous) organic solvent, such as N,Ndimethylformamide
(DMF) and/or tetrahydrofuran. Preferably, X a and X are
independently iodine, bromine, chlorine, p-toluenesulfonate, benzenesulfonate,
methanesulfonate or trifluoromethanesulfonate. It is noted that R a-X a and R -X can
be the same single alkylating agent when R a = R ; for example, when R a = R =
methyl then preferably R a-X a and R -X are both methyl iodide. Preferably, the
lithium amide base is lithium hexamethyldisilazide (LHMDS), lithium diisopropylamide
(LDA) or lithium dimethylamide. The reaction temperature can for example be -20 to 30
°C such as 0 to 25 °C.
1A. In an alternative shorter route, an ester of formula (6) where R and R2
are as defined for a compound of formula (I) can be prepared by reacting an ester of
formula (14) with a 2,3-dichloropyrazine of formula (2) (wherein R and R2 are as defined
for a compound of formula (I)), in the presence of a base, preferably a lithium amide
base such as lithium hexamethyldisilazide (LHMDS) or lithium diisopropylamide (LDA)
or lithium dimethylamide, in a non-aqueous (e.g. anhydrous) organic solvent, such as
tetrahydrofuran and/or A/,A/-dimethylformamide (DMF). The reaction temperature can
for example be -20 to 30 °C such as 0 to 25 °C. The ester of formula (14) can for
example be: 2-methyl butyric acid methyl ester (CH3CH2-CH(Me)-C(0)OMe), for when
R a = methyl and R = ethyl; or the methyl or ethyl ester of isobutyric acid
(Me2CH-C(0)OMe or Me2CH-C(0)OEt), for when R a and R are both methyl.
A second part of a process for preparing a compound of formula (I), namely
converting an intermediate compound of formula (6) into a compound of formula (I), is
shown in Scheme 2 below.
The subsequent steps, in Scheme 2 are as follows:
5 . An alkyne ester of formula (8), wherein R , R2, R a , R and R4 are as
defined for a compound of formula (I), and wherein R6a is C C alkyl such as methyl,
ethyl, n-propyl, isopropyl or n-butyl, or more preferably methyl or ethyl, can be prepared
by reacting an ester of formula (6) wherein R , R2, R a and R are as defined for a
compound of formula (I) and having the same R6a group, with an alkyne of formula (13)
in the presence of a base, such as an alkali metal carbonate such as caesium
carbonate (e.g. in solid form), a palladium catalyst, such as ( 1 ,1'-
bis(diphenylphosphino)-ferrocene)dichloro palladium(2), a phosphine, such as 4,5-
(bisdiphenylphosphino)-9,9-dimethylxanthene ("Xantphos") or triphenylphosphine, in a
non-aqueous (e.g. anhydrous) organic solvent, such as acetonitrile, for example under
an inert (e.g. nitrogen) atmosphere. Suitably, the reaction temperature is 60 to 100 °C
(e.g. 70 to 80 °C) and/or the reflux temperature of the organic solvent used.
6 . A carboxylic acid of formula (9) where R , R2, R a , R and R4 are as
defined for a compound of formula (I) can be prepared by reacting an alkyne ester of
formula (8), wherein R , R2, R a , R and R4 are as defined for a compound of formula (I)
and R6a is C C alkyl e.g. Me or Et, with an aqueous solution of a hydroxide salt (such as
an alkali metal hydroxide, e.g. NaOH or KOH, or an alkaline earth metal hydroxide), in a
solvent, such as ethanol and/or methanol. Suitably, the reaction temperature is 40 to
100 °C, e.g. 50 to 90 °C, such as about 60-80 °C.
Scheme 2
(10) (9)
( 1 1) (12)
7 . A pyranopyrazinone of formula (10) where R , R2, R a , R and R4 are as
defined for a compound of formula (I) can be prepared by reacting an acid of formula
(9), wherein R , R2, R a , R and R4 are as defined for a compound of formula (I), with a
gold-based catalyst, preferably a gold(l) salt such as gold(l) chloride triphenylphosphine
[AuCI(PPh3)], preferably also in the presence of a silver-based catalyst (preferably a
silver(l) salt such as silver(l) tetrafluoroborate or silver(l) trifluoromethanesulfonate), in
an organic solvent, such as carbon tetrachloride, chloroform or dichloromethane.
Suitably, the reaction temperature is 15 to 90 °C (e.g. 40 to 70 °C, such as about 50-60
°C) and/or the reflux temperature of the organic solvent used.
8 . A quinoxaline dione of formula ( 1 1) where R , R2, R a , R and R4 are as
defined for a compound of formula (I) can be prepared by reacting a pyranopyrazinone
of formula (10) where R , R2, R a , R and R4 are as defined for a compound of formula
(I) in the presence of a base, preferably a tertiary amine base such as triethylamine or
A/,A/-diisopropylethylamine, and a cyanide (CN ) source, such as acetone cyanohydrin
(Me2C(OH)-CN), in a non-aqueous (e.g. anhydrous) organic solvent, such as
acetonitrile. Molecular sieves can optionally be used in the reaction to remove water.
Suitably, the reaction temperature is 0 to 30 °C, such as room temperature which is
usually ca. 18-25 °C.
9 . A quinoxalinyl ester of formula (12) where R , R2, R a , R and R4 are as
defined for a compound of formula (I) can be prepared by reacting a quinoxaline dione
of formula ( 1 1) where R , R2, R a , R and R4 are as defined for a compound of formula
(I), optionally in unpurified form, with a suitable acid chloride, such as isobutryl chloride
(isopropyl-C(O)-CI, for when R8 is isopropyl), in the presence of a base, such as pyridine
or a tertiary amine base such as triethylamine or A/,A/-diisopropylethylamine, in a non
aqueous (e.g. anhydrous) organic solvent, such as dichloromethane. Suitably, the
reaction temperature is 0 to 30 °C, such as room temperature which is usually ca. 18-25
°C. The prepared quinoxalinyl ester of formula (12) can then preferably be purified.
10. A quinoxaline dione of formula ( 1 1) where R , R2, R a , R and R4 are as
defined for a compound of formula (I) can be prepared by reacting a quinoxalinyl ester of
formula (12) where R , R2, R a , R and R4 are as defined for a compound of formula (I)
with an aqueous solution of a hydroxide salt, such as aqueous lithium hydroxide, in a
solvent such as ethanol and/or methanol. Suitably, the reaction temperature is 0 to 30
°C, such as room temperature which is usually ca. 18-25 °C. Step 10 can optionally be
used, after purification of a quinoxalinyl ester of formula (12), to prepare purified
quinoxaline dione of formula ( 1 1).
Herbicidal compositions, methods of use, and mixtures
The compounds of formula (I) according to the invention can be used as
herbicides in unmodified form, as obtained in the synthesis, but they are generally
formulated into herbicidal compositions in various ways my mixing with various
substances (e.g. inert (i.e. substantially non-herbicidal) substances), such as carriers,
solvents, adjuvants and/or surface-active substances.
The present invention therefore also provides a herbicidal composition (e.g.
liquid herbicidal composition) which comprises a compound of formula (I) (e.g. a
herbicidally effective amount thereof), and preferably also a carrier (e.g. liquid or solid
carrier) and/or one or more solvents; and optionally also an adjuvant and/or a surfaceactive
substance.
The herbicidal compositions (e.g. formulations) of the invention disclosed can be
in various physical forms, for example in the form of dusting powders, gels, wettable
powders, water-dispersible granules, water-dispersible tablets, effervescent pellets,
emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oilflowables,
aqueous dispersions, oily dispersions, suspo-emulsions, capsule
suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with
water or a water-miscible organic solvent as carrier), impregnated polymer films or in
other forms known e.g. from the Manual on Development and Use of FAO Specifications
for Plant Protection Products, 5th Edition, 1999. The herbicidal compositions (e.g.
formulations) can either be used directly or they are diluted prior to use. The dilutions
can be made, for example, with water, liquid fertilisers, micronutrients, biological
organisms, oil or solvents.
The herbicidal compositions (e.g. formulations) can be prepared for example, 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 micro
capsules consisting of a polymer. Microcapsules contain the active ingredients in a
porous carrier. This enables the active ingredients to be released into the environment in
controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from
0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to
95% by weight of the capsule weight. The active ingredients can be in the form of a
monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of
a suitable solution. The encapsulating membranes comprise, for example, natural or
synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile,
polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified
polymers and starch xanthates or other polymers that are known to the person skilled in
the art in this connection.
Alternatively, very fine microcapsules can be formed in which the active
ingredient is contained in the form of finely divided particles in a solid matrix of base
substance, but the microcapsules are not themselves encapsulated.
The inert substances that are suitable for the preparation of the compositions
according to the invention are known perse.
As liquid carriers there may be used: water, toluene, xylene, petroleum ether,
vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides,
acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate,
chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone
alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol,
diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether,
diethylene glycol methyl ether, A/,A/-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane,
dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate,
diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate,
1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene
glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone,
glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene
glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene,
isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl
isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate,
methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine
acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400),
propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol
methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic
acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl
acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether,
methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl
alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol,
glycerol, A/-methyl-2-pyrrolidone and the like. Water is generally the liquid carrier of
choice for diluting the concentrates.
Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay,
silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium
montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour,
ground walnut shells, lignin and similar substances, as described, for example, in CFR
180.1001 . (c) & (d).
A large number of surface-active substances can advantageously be used in
both solid and liquid formulations, especially in those formulations which can be diluted
with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic
or polymeric and they can 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 dialkylphosphate
esters; and also further substances described e.g. in "McCutcheon's
Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey,
1981 .
Further inert substances that can typically be used in herbicidal compositions
(e.g. formulations) include crystallisation inhibitors, viscosity modifiers, suspending
agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries,
antifoams, complexing agents, neutralizing 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 fertilizers.
The compositions according to the invention can additionally include an additive
comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or
mixtures of such oils and oil derivatives. The amount of oil additive in the composition
according to the invention is generally from 0.01 to 10%, based on the spray mixture.
For example, the oil additive can be added to the spray tank in the desired concentration
after the spray mixture has been prepared. Preferred oil additives comprise mineral oils
or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil,
emulsified vegetable oil, such as AMIGO® (Rhone-Poulenc Canada Inc.), alkyl esters of
oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin,
such as fish oil or beef tallow. A preferred additive contains, for example, as active
components essentially 80% by weight alkyl esters of fish oils and 15% by weight
methylated rapeseed oil, and also 5% by weight of customary emulsifiers and pH
modifiers. Especially preferred oil additives comprise alkyl esters of C8-C22 fatty acids,
especially the methyl derivatives of C 2-C 8 fatty acids, for example the methyl esters of
lauric acid, palmitic acid and oleic acid, being of importance. Those esters are known as
methyl laurate (CAS-1 11-82-0), methyl palmitate (CAS- 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.
The application and action of the oil additives can be further improved by
combination with surface-active substances, such as non-ionic, anionic or cationic
surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed
on pages 7 and 8 of WO 97/34485. Preferred surface-active substances are anionic
surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and
also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is
given to ethoxylated C12-C22 fatty alcohols having a degree of ethoxylation of from 5 to
40. Examples of commercially available surfactants are the Genapol types (Clariant
AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified
heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also
perfluorinated surfactants. The concentration of the surface-active substances in relation
to the total additive is generally from 1 to 30% by weight. Examples of oil additives
consisting of mixtures of oil or mineral oils or derivatives thereof with surfactants are
Edenor ME SU®, Turbocharge® (Syngenta AG, CH) or ActipronC (BP Oil UK Limited,
GB).
If desired, it is also possible for the mentioned surface-active substances to be
used in the formulations on their own, that is to say without oil additives.
Furthermore, the addition of an organic solvent to the oil additive/surfactant
mixture may contribute to an additional enhancement of action. Suitable solvents are, for
example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation). The
concentration of such solvents can be from 10 to 80% by weight of the total weight. Oil
additives that are present in admixture with solvents are described, for example, in USA-
4,834,908. A commercially available oil additive disclosed therein is known by the
name MERGE® (BASF Corporation). A further oil additive that is preferred according to
the invention is SCORE® (Syngenta Crop Protection Canada).
In addition to the oil additives listed above, for the purpose of enhancing the
action of the compositions according to the invention it is also possible for formulations
of alkylpyrrolidones (e.g. Agrimax®) to be added to the spray mixture. Formulations of
synthetic lattices, e.g. polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g.
Bond®, Courier® or Emerald®) may also be used. It is also possible for solutions that
contain propionic acid, for example Eurogkem Pen-e-trate®, to be added to the spray
mixture as action-enhancing agent.
The herbicidal compositions generally comprise from 0.1 to 99% by weight,
especially from 0.1 to 95% by weight, compounds of formula (I) and from 1 to 99.9% by
weight of a formulation adjuvant which preferably includes from 0 to 25% by weight of a
surface-active substance. Whereas commercial products will preferably be formulated
as concentrates, the end user will normally employ dilute formulations.
Preferred formulations have especially the following compositions (% = percent
by weight):
Emulsifiable concentrates:
active ingredient: 1 to 95%, preferably 60 to 90%
surface-active agent: 1 to 30%, preferably 5 to 20%
liquid carrier: 1 to 80%, preferably 1 to 35%
Dusts:
active ingredient: 0.1 to 10%, preferably 0.1 to 5%
solid carrier: 99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates:
active ingredient: 5 to 75%, preferably 10 to 50%
water: 94 to 24%, preferably 88 to 30%
surface-active agent: 1 to 40%, preferably 2 to 30%
Wettable powders:
active ingredient: 0.5 to 90%, preferably 1 to 80%
surface-active agent: 0.5 to 20%, preferably 1 to 15%
solid carrier: 5 to 95%, preferably 15 to 90%
Granules:
active ingredient: 0.1 to 30%, preferably 0.1 to 15%
solid carrier: 99.5 to 70%, preferably 97 to 85%
The following formulation examples further illustrate, but do not limit, the inventior
Formulation examples for herbicides of formula (1) (% = percent by weight)
F 1. Emulsifiable concentrates a) b) c) )
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)
NMP - - 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%
The solutions are suitable for use in the form of microdrops.
F3. Wettable powders a) b) c) d)
active ingredient 5% 25% 50% 80%
sodium lignosulfonate 4% - 3%
sodium lauryl sulfate 2% 3% - 4%
sodium diisobutylnaphthalenesulfonate
- 6% 5% 6%
octylphenol polyglycol ether - 1% 2%
(7-8 mol of ethylene oxide)
highly dispersed silicic acid 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 - 1 mm)
for example CaC0 3 or
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)
for example 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) )
active ingredient 0.1% 3% 5% 15%
sodium lignosulfonate 1.5% 2% 3% 4%
carboxymethylcellulose 1.4% 2% 2% 2%
kaolin 97.0% 93% 90% 79%
The active ingredient is mixed and ground with the adjuvants, and the mixture is
moistened with water. The mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c)
active ingredient 0.1% 1% 5%
talcum 39.9% 49% 35%
kaolin 60.0% 50% 60%
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and
grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b)
active ingredient 3% 10% 25%
ethylene glycol 5% 5% 5%
nonylphenol polyglycol ether 1% 2%
(15 mol of ethylene oxide)
sodium lignosulfonate 3% 3% 4%
carboxymethylcellulose 1% 1% 1%
37% aqueous formaldehyde 0.2% 0.2% 0.2% 0.2%
solution
silicone oil emulsion 0.8% 0.8% 0.8% 0.8%
water 87% 79% 62% 38%
The finely ground active ingredient is intimately mixed with the adjuvants, giving a
suspension concentrate from which suspensions of any desired concentration can be
obtained by dilution with water.
Methods of use
The present invention further relates to a method of controlling a plant (e.g. a
grass and/or a weed) which comprises applying to the plant (e.g. to a crop of useful
plants) or to the locus thereof a herbicidally effective amount of a compound of formula
(I).
The invention also relates to a method of inhibiting plant growth (e.g. in a grass
and/or a weed) which comprises applying to the plant (e.g. to a crop of useful plants) or
to the locus thereof a herbicidally effective amount of a compound of formula (I).
The invention also relates to a method of selectively controlling a grass and/or a
weed in a crop of a useful plants which comprises applying to the useful plants or locus
thereof or to the area of cultivation a herbicidally effective amount of a compound of
formula (I).
A compound of formula (I), and/or a herbicidal composition and/or mixture
containing the same, may also be applied to turf, pasture, rangeland, a right of way etc.
In particular they may be used on a golf-course, a lawn, a park, a sports-field, a race
course or similar.
The term "herbicide" as used herein means a compound that controls or modifies
the growth of plants. The term "herbicidally effective amount" means the quantity of such
a compound or combination of such compounds that is capable of producing a
controlling or modifying effect on the growth of plants. Controlling or modifying effects
include all deviation from natural development, for example: killing, retardation, leaf
burn, albinism, dwarfing or similar. The term "plant" or "plants" refers to all physical
parts of a plant, such as seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage,
or fruits. The term "locus" is intended to include soil, seeds, or seedlings, as well as
established vegetation.
The crop of useful plants, e.g. in or to which a compound, composition, mixture
or method according to the invention can be used or applied, can for example be a
perennial crop, such as citrus fruit, grapevines, nuts, oil palms, olives, pome fruit, stone
fruit or rubber; or an annual arable crop, such as a cereal (e.g. wheat, barley, rye, or
triticale, etc.), cotton, oilseed rape, maize (corn), rice, soybean, sugarbeet, sugarcane,
sunflowers, an ornamental or a vegetable; especially a cereal, maize or soybean.
The grass and/or weed to be controlled can be monocotyledonous and/or
dicotyledonous species. The grass and/or weed to be controlled can be a
monocotyledonous species, for example Agrostis, Alopecurus (e.g. Alopecurus
myosuroides), Avena (e.g. Avena fatua), Bromus, Cyperus, Digitaria (e.g. Digitaria
sanguinalis), Echinochloa (e.g. Echinochloa crus-galli), Lolium (e.g. Lolium perenne),
Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria (e.g. Setaria faberi), or Sorghum; or
more preferably is a dicotyledonous species, for example Abutilon (e.g. Abutilon
theophrasti), Amaranthus (e.g. Amaranthus retroflexus), Bidens (e.g. Bidens pilosa),
Chenopodium (e.g. Chenopodium album), Chrysanthemum, Euphorbia (e.g. Euphorbia
hetrophylla), Galium (e.g. Galium aparine), Ipomoea (e.g. Ipomea hederaceae),
Nasturtium, Sida (e.g. Sida spinosa), Sinapis (e.g. Sinapis arvensis), Solanum (e.g.
Solanum nigrum), Stellaria (e.g. Stellaria media), Veronica (e.g. Veronica persica or
Veronica hederifolia), Viola (e.g. Viola arvensis) orXanthium.
Crops are to be understood as also including those crops which have been
rendered tolerant to herbicides or classes of herbicides (e.g. auxins or ALS-, GS-,
EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic
engineering. An example of a crop that has been rendered tolerant to imidazolinones,
e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape
(canola). Examples of crops that have been rendered tolerant to herbicides by genetic
engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties
commercially available under the trade names RoundupReady® and LibertyLink®.
Crops are also to be understood as including those which have been rendered
resistant to harmful insects by genetic engineering methods, for example Bt maize
(resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt
potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize
hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by
Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to
synthesize such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278,
WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants
comprising one or more genes that code for an insecticidal resistance and express one
or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton),
Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or
seed material thereof can be both resistant to herbicides and, at the same time, resistant
to insect feeding ("stacked" transgenic events). For example, seed can have the ability
to express an insecticidal Cry3 protein while at the same time being tolerant to
glyphosate.
Crops are also to be understood as including those which are obtained by
conventional methods of breeding or genetic engineering and contain so-called output
traits (e.g. improved storage stability, improved stress (e.g. drought) resistance, higher
nutritional value and/or improved flavor).
Areas under cultivation include land on which the crop plants are already
growing and land intended for cultivation with those crop plants. The compounds of the
invention can be applied before weeds emerge (pre-emergence application) or after
weeds emerge (post-emergence application), and are particularly effective when applied
post-emergence.
The rates of application of compounds of formula (I) (e.g. rate of application to a
crop of useful plants, or to a grass and/or a weed, or to the locus thereof, or to the area
of cultivation) may vary within wide limits and may 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., whether the compound of formula (I) is applied as a
mixture with a further herbicide), the crop plant, the grass and/or weed to be controlled,
the prevailing climatic conditions, and/or 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 (e.g. to a crop of useful plants, or to a
grass and/or a weed, or to the locus thereof, or to the area of cultivation) at a rate of
from 10 to 2000 g/ha, in particular from 50 to 1000 g/ha, e.g. whether applied as a sole
herbicide or as a mixture containing a further herbicide.
Mixtures / combinations
The compounds of formula (I) according to the invention can also be used in
combination with one or more further herbicides. Some of the combinations / mixtures
may lead to synergistic effects and/or may confer one or more technical effects and/or
advantages.
The invention therefore provides a mixture (e.g. herbicidal composition, e.g.
liquid or solid), which comprises a herbicidally effective amount of a compound of
formula (I), and a further herbicide as a mixture partner for the compound of formula (I).
In particular, the following mixtures of the compound of formula (I) are important,
where numbers given in brackets after compound names are often the corresponding
reference numbers given in The Pesticide Manual, 13th Edition (BCPC), 2003:
Mixtures of a compound of formula (I) with a synthetic auxin (e.g. a compound of
formula (I) with clopyralid (162); a compound of formula (I) with 2,4-D (21 1); a
compound of formula (I) with dicamba (228); a compound of formula (I) with diphenamid
(274); a compound of formula (I) with MCPA (499); a compound of formula (I) with
quinclorac (712); a compound of formula (I) with aminopyralid (CAS RN 1501 14-71-9); a
compound of formula (I) with 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-
pyridinecarboxylic acid (CAS RN 943832-60-8); or a compound of formula (I) with
4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid,
methyl ester (CAS RN 943831-98-9)).
Mixtures of a compound of formula (I) with diflufenzopyr (252).
Mixtures of a compound of formula (I) with an acetanilide (e.g. a compound of
formula (I) with acetochlor (5), a compound of formula (I) with dimethenamid (260), a
compound of formula (I) with metolachlor (548), a compound of formula (I) with Smetolachlor
(549), or a compound of formula (I) with pretilachlor (656)).
Mixtures of a compound of formula (I) with flamprop-M (355).
Mixtures of a compound of formula (I) with flufenacet (BAY FOE 5043) (369).
Mixtures of a compound of formula (I) with pyroxasulfone (CAS RN 447399-55-
5).
Mixtures of a compound of formula (I) with an HPPD inhibitor (e.g. a compound
of formula (I) with isoxaflutole (479), a compound of formula (I) with mesotrione (515), a
compound of formula (I) with pyrasulfotole (CAS RN 365400-1 1-9), a compound of
formula (I) with sulcotrione (747), a compound of formula (I) with tembotrione (CAS RN
335104-84-2), compound of formula (I) with topramezone (CAS RN 210631-68-8), a
compound of formula (I) with 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-
a 5), or compound of formula (I) with 4-hydroxy-3-[[2-(3-methoxypropyl)-6-
(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one (CAS RN 894355-80-
7)).
Mixtures of a compound of formula (I) with a triazine (e.g. a compound of formula
(I) with atrazine (37); or a compound of formula (I) with terbuthylazine (775)).
Mixtures of a compound of formula (I) with a triazine and an HPPD inhibitor (e.g.
a compound of formula (I) with triazine with isoxaflutole, a compound of formula (I) with
triazine with mesotrione, a compound of formula (I) with triazine with pyrasulfotole, a
compound of formula (I) with triazine with sulcotrione, a compound of formula (I) with
triazine with tembotrione, a compound of formula (I) with triazine with topramezone,
compound of formula (I) with triazine with 4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-
(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one, or a compound of
formula (I) with triazine with 4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-
pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one).
Mixtures of a compound of formula (I) with glyphosate (419).
Mixtures of a compound of formula (I) with glyphosate and an HPPD inhibitor
(e.g. a compound of formula (I) with glyphosate with isoxaflutole, a compound of formula
(I) with glyphosate with mesotrione, a compound of formula (I) with glyphosate with
pyrasulfotole, a compound of formula (I) with glyphosate with sulcotrione, a compound
of formula (I) with glyphosate with tembotrione, a compound of formula (I) with
glyphosate with topramezone, a compound of formula (I) with glyphosate with 4-
hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-
bicyclo[3.2.1]oct-3-en-2-one, or a compound of formula (I) with glyphosate with 4-
hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-
bicyclo[3.2.1]oct-3-en-2-one).
Mixtures of a compound of formula (I) with glufosinate-ammonium (418).
Mixtures of a compound of formula (I) with glufosinate-ammonium and an HPPD
inhibitor (e.g. a compound of formula (I) with glufosinate-ammonium with isoxaflutole, a
compound of formula (I) with glufosinate-ammonium with mesotrione, a compound of
formula (I) with glufosinate-ammonium with pyrasulfotole, a compound of formula (I) with
glufosinate-ammonium with sulcotrione, a compound of formula (I) with glufosinateammonium
with tembotrione, a compound of formula (I) with glufosinate-ammonium with
topramezone, a compound of formula (I) with glufosinate-ammonium with 4-hydroxy-3-
[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-
3-en-2-one, or a compound of formula (I) with glufosinate-ammonium with 4-hydroxy-3-
[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-
one).
Mixtures of a compound of formula (I) with an ALS or an AHAS inhibitor (e.g. a
compound of formula (I) with bensulfuron-methyl (64), a compound of formula (I) with
chlorimuron-ethyl (135), compound of formula (I) with cloransulam-methyl (164), a
compound of formula (I) with florasulam (359), a compound of formula (I) with
flucarbazone-sodium (364), a compound of formula (I) with imazamox (451), a
compound of formula (I) with imazapyr (453), a compound of formula (I) with
imazethapyr (455), a compound of formula (I) with iodosulfuron-methyl-sodium (466), a
compound of formula (I) with mesosulfuron-methyl (514), a compound of formula (I) with
nicosulfuron (577), a compound of formula (I) with penoxsulam (622), a compound of
formula (I) with pyroxsulam (triflosulam) (CAS RN 422556-08-9), a compound of formula
(I) with thifensulfuron-methyl (thiameturon-methyl) (795), a compound of formula (I) with
triasulfuron (817), a compound of formula (I) with tribenuron-methyl (822), a compound
of formula (I) with trifloxysulfuron-sodium (833), a compound of formula (I) with
thiencarbazone (4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo-1/-/-1 ,2,4-triazol-1-
yl)carbonylsulfamoyl]-5-methylthiophene-3-carboxylic acid, BAY636)), or a compound of
formula (I) with thiencarbazone-methyl (methyl 4-[(4,5-dihydro-3-methoxy-4-methyl-5-
OXO -1 - - 1,2,4-triazol-1-yl)carbonylsulfamoyl]-5-methylthiophene-3-carboxylate, CAS RN
317815-83-1 , BAY636-methyl)).
Mixtures of a compound of formula (I) with a PPO inhibitor (e.g. compound of
formula (I) with acifluorfen-sodium (7), a compound of formula (I) with butafenacil (101),
a compound of formula (I) with carfentrazone-ethyl (121), a compound of formula (I) with
cinidon-ethyl (152), a compound of formula (I) with flumioxazin (376), a compound of
formula (I) with fomesafen (401), a compound of formula (I) with lactofen (486), or a
compound of formula (I) with [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-
dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester)
(CAS RN 353292-31-6)).
Mixtures of a compound of formula (I) with an acetyl-CoA carboxylase inhibitor
(ACCase inhibitor) (e.g. a compound of formula (I) with butroxydim (106), a compound
of formula (I) with clethodim (155), a compound of formula (I) with clodinafop-propargyl
(156), a compound of formula (I) with cycloxydim (190), a compound of formula (I) with
cyhalofop-butyl (195), a compound of formula (I) with diclofop-methyl (238), a compound
of formula (I) with fenoxaprop-P-ethyl (339), a compound of formula (I) with fluazifopbutyl
(361), a compound of formula (I) with fluazifop-P-butyl (362), a compound of
formula (I) with haloxyfop (427), a compound of formula (I) with haloxyfop-P (428), a
compound of formula (I) with propaquizafop (670), a compound of formula (I) with
quizalofop (717), a compound of formula (I) with quizalofop-P (718), compound of
formula (I) with sethoxydim (726), a compound of formula (I) with tepraloxydim (771), a
compound of formula (I) with tralkoxydim (81 1)), or a compound of formula (I) with
pinoxaden (CAS RN 243973-20-8).
Mixtures of a compound of formula (I) with prosulfocarb (683), or a compound of
formula (I) with tri-allate (816).
Mixtures of a compound of formula (I) with bromoxynil (95), a compound of
formula (I) with chloridazon (134), a compound of formula (I) with chlorotoluron (143), a
compound of formula (I) with diuron (281), or a compound of formula (I) with metribuzin
(554).
Mixtures of a compound of formula (I) with clomazone (159), a compound of
formula (I) with diflufenican (251), a compound of formula (I) with flurochloridone (389),
or a compound of formula (I) with flurtamone (392).
Mixtures of a compound of formula (I) with pendimethalin (621) or a compound of
formula (I) with trifluralin (836).
Mixtures of a compound of formula (I) with difenzoquat metilsulfate (248).
Mixtures of a compound of formula (I) with diquat dibromide (276).
Mixtures of a compound of formula (I) with paraquat dichloride (614).
The mixing partners of the compound of formula (I) may also be in the form of
esters or salts, as mentioned for example in The Pesticide Manual, 13th Edition (BCPC),
2003. The reference to glufosinate-ammonium also applies to glufosinate, the reference
to cloransulam-methyl also applies to cloransulam, the reference to dimethenamid also
applies to dimethenamid-P, the reference to flamprop-M also applies to flamprop, and
the reference to pyrithiobac-sodium also applies to pyrithiobac, etc.
The mixing ratio of the compound of formula (I) to the mixing partner (e.g. further
herbicide) is typically from 1: 300 to 300:1 by weight or from 1: 100 to 100:1 by weight;
or preferably from 1: 30 to 30:1 by weight.
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).
Additionally, one or more of the following further herbicides or plant growth
regulators (typically plant growth inhibitors) can be used in combination with a
compound of formula (I) according to the invention or in combination with a mixture as
described above: aclonifen (8), acrolein (10), alachlor (14), alloxydim (18), ametryn (20),
amicarbazone (21), amidosulfuron (22), aminocyclopyrachlor (CAS RN 858956-08-8),
amitrole (aminotriazole) (25), ammonium sulfamate (26), anilofos (31), asulam (36),
aviglycine (39), azafenidin (CAS RN 68049-83-2), azimsulfuron (43), BAS 800H (CAS
RN 372137-35-4), beflubutamid (55), benazolin (57), bencarbazone (CAS RN 173980-
17-1), benfluralin (59), benfuresate (61), bensulide (65), bentazone (67), benzfendizone
(CAS RN 158755-95-4), benzobicyclon (69), benzofenap (70), bilanafos (bialaphos)
(77), bispyribac-sodium (82), borax (86), bromacil (90), bromobutide (93), bromofenoxim
(CAS RN 13181-17-4), butachlor (100), butamifos (102), butralin (105), butylate (108),
cafenstrole ( 1 10), carbetamide ( 1 17), chlorbromuron (CAS RN 13360-45-7),
chlorflurenol-methyl (133), chloroacetic acid (138), chlorpropham (144), chlorsulfuron
(147), chlorthal-dimethyl (148), cinmethylin (153), cinosulfuron (154), clomeprop (160),
cumyluron (180), cyanamide (182), cyanazine (183), cyclanilide (186), cycloate (187),
cyclosulfamuron (189), daimuron (213), dalapon (214), dazomet (216), desmedipham
(225), desmetryn (CAS RN 1014-69-3), dichlobenil (229), dichlorprop (234), dichlorprop-
P (235), diclosulam (241), dimefuron (256), dimepiperate (257), dimethachlor (258),
dimethametryn (259), dimethipin (261), dimethylarsinic acid (264), dinitramine (268),
dinoterb (272), dipropetryn (CAS RN 4147-51-7), dithiopyr (280), DNOC (282), DSMA
(CAS RN 144-21-8), endothal (295), EPTC (299), esprocarb (303), ethalfluralin (305),
ethametsulfuron-methyl (306), ethephon (307), ethofumesate (31 1), ethoxyfen (CAS RN
188634-90-4), ethoxyfen-ethyl (CAS RN 131086-42-5), ethoxysulfuron (314),
etobenzanid (318), fentrazamide (348), ferrous sulfate (353), flazasulfuron (356),
fluazolate (isopropazol) (CAS RN 174514-07-9), flucetosulfuron (CAS RN 412928-75-7),
fluchloralin (365), flufenpyr-ethyl (371), flumetralin (373), flumetsulam (374), flumicloracpentyl
(375), flumipropyn (flumipropin) (CAS RN 84478-52-4), fluometuron (378),
fluoroglycofen-ethyl (380), flupoxam (CAS RN 119126-15-7), flupropacil (CAS RN
120890-70-2), flupropanate (383), flupyrsulfuron-methyl-sodium (384), flurenol (387),
fluridone (388), fluroxypyr (390), fluthiacet-methyl (395), foramsulfuron (402), fosamine
(406), halosulfuron-methyl (426), HC-252 (429), hexazinone (440), imazamethabenzmethyl
(450), imazapic (452), imazaquin (454), imazosulfuron (456), indanofan (462),
ioxynil (467), isoproturon (475), isouron (476), isoxaben (477), isoxachlortole (CAS RN
141 112-06-3), isoxapyrifop (CAS RN 87757-18-4), karbutilate (482), lenacil (487),
linuron (489), MCPA-thioethyl (500), MCPB (501), mecoprop (503), mecoprop-P (504),
mefenacet (505), mefluidide (507), metam (519), metamifop (mefluoxafop) (520),
metamitron (521), metazachlor (524), methabenzthiazuron (526), methazole (CAS RN
20354-26-1), methylarsonic acid (536), 1-methylcyclopropene (538), methyldymron
(539), methyl isothiocyanate (543), metobenzuron (547), metobromuron (CAS RN 3060-
89-7), metosulam (552), metoxuron (553), metsulfuron-methyl (555), MK-616 (559),
molinate (560), monolinuron (562), MSMA (CAS RN 2163-80-6), naproanilide (571),
napropamide (572), naptalam (573), neburon (574), nipyraclofen (CAS RN 99662-1 1-0),
n-methyl-glyphosate, nonanoic acid (583), norflurazon (584), oleic acid (fatty acids)
(593), orbencarb (595), orthosulfamuron (CAS RN 213464-77-8), oryzalin (597),
oxadiargyl (599), oxadiazon (600), oxasulfuron (603), oxaziclomefone (604), oxyfluorfen
(610), pebulate (617), pentachlorophenol (623), pentanochlor (624), pentoxazone (625),
pethoxamid (627), petrolium oils (628), phenmedipham (629), picloram (645),
picolinafen (646), piperophos (650), primisulfuron-methyl (657), prodiamine (661),
profluazol (CAS RN 190314-43-3), profoxydim (663), prohexadione calcium (664),
prometon (665), prometryn (666), propachlor (667), propanil (669), propazine (672),
propham (674), propisochlor (667), propoxycarbazone-sodium (procarbazone-sodium)
(679), propyzamide (681), prosulfuron (684), pyraclonil (pyrazogyl) (CAS RN 158353-
15-2), pyraflufen-ethyl (691), pyrazolynate (692), pyrazosulfuron-ethyl (694),
pyrazoxyfen (695), pyribenzoxim (697), pyributicarb (698), pyridafol (CAS RN 40020-01-
7), pyridate (702), pyriftalid (704), pyriminobac-methyl (707), pyrimisulfan (CAS RN
221205-90-9), pyrithiobac-sodium (709), quinmerac (713), quinoclamine (714),
rimsulfuron (721), sequestrene, siduron (727), simazine (730), simetryn (732), sodium
chlorate (734), sulfentrazone (749), sulfometuron-methyl (751), sulfosate (CAS RN
81591-81-3), sulfosulfuron (752), sulfuric acid (755), tar oils (758), TCA-sodium (760),
tebutam (CAS RN 35256-85-0), tebuthiuron (765), tefuryltrione (CAS RN 473278-76-1),
terbacil (772), terbumeton (774), terbutryn (776), thenylchlor (789), thidiazimin (CAS RN
123249-43-4), thiazafluron (CAS RN 25366-23-8), thiazopyr (793), thiobencarb (797),
tiocarbazil (807), triaziflam (819), triclopyr (827), trietazine (831), triflusulfuron-methyl
(837), trihydroxytriazine (CAS RN 108-80-5), trinexapac-ethyl (CAS RN 95266-40-3),
tritosulfuron (843), N-[(1 R,2S)-2,6-dimethyl-2,3-dihydro-1H-inden-1-yl]-6-(1-fluoroethyl)-
1,3,5-triazine-2,4-diamine (CAS RN 950782-86-2), 1-(2-chloro-6-propylimidazo[1 ,2-
b]pyridazin-3-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea (CAS RN 570415-88-2), or
5-(2,6-difluoro-benzyloxymethyl)-5-methyl-3-(3-methyl-thiophen-2-yl)-4,5-dihydroisoxazole
(CAS RN 403640-27-7).
The mixing partners of the compound of formula (I) may also be in the form of
esters or salts, as mentioned e.g. in The Pesticide Manual, 13th Edition (BCPC), 2003.
The reference to acifluorfen-sodium also applies to acifluorfen, and the reference to
bensulfuron-methyl also applies to bensulfuron, etc.
The mixing ratio of the compound of formula (I) to the mixing partner (e.g. further
herbicide) is typically from 1: 300 to 300:1 by weight or from 1: 100 to 100:1 by weight;
or preferably from 1: 30 to 30:1 by weight.
The mixtures can advantageously be used in the above-mentioned formulations
(in which case "active ingredient" relates to the respective mixture of compound of
formula (I) with the mixing partner).
The compounds of formula (I) according to the invention can also be used in
combination with one or more safeners. Likewise, mixtures of a compound of formula (I)
according to the invention with one or more further herbicides can also be used in
combination with one or more safeners. The term "safener" as used herein means a
chemical that when used in combination with a herbicide reduces the undesirable effects
of the herbicide on non-target plants, for example, typically a safener protects crop
plants from injury by herbicides, or minimizes such injury, but does not prevent the
herbicide from killing or inhibiting the growth of weeds.
The invention therefore provides a mixture (e.g. herbicidal composition, e.g.
liquid or solid), which comprises a herbicidally effective amount of a compound of
formula (I) and a safener.
The invention also provides a mixture (e.g. herbicidal composition, e.g. liquid or
solid), which comprises a herbicidally effective amount of a compound of formula (I), a
further herbicide as a mixture partner for the compound of formula (I), and a safener.
The safener can be AD-67 ( 1 1), benoxacor (63), cloquintocet-mexyl (163),
cyometrinil (CAS RN 78370-21-5), cyprosulfamide (CAS RN 221667-31-8), dichlormid
(231), dicyclonon (CAS RN 79260-71-2), fenchlorazole-ethyl (331), fenclorim (332),
flurazole (386), fluxofenim (399), furilazole (413) or the corresponding R isomer thereof,
isoxadifen-ethyl (478), mefenpyr-diethyl (506), 2-methoxy-N-[[4-
[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide (CAS RN 129531-12-0),
naphthalic anhydride (CAS RN 81-84-5), N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide, or oxabetrinil (598).
In one particular embodiment, the safener is benoxacor, cloquintocet-mexyl,
mefenpyr-diethyl, cyprosulfamide or N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide.
The mixture with the safener can be applied to a crop of useful plants, for
example a perennial crop, such as citrus fruit, grapevines, nuts, oil palms, olives, pome
fruit, stone fruit or rubber; or an annual arable crop, such as a cereal (e.g. wheat, barley,
rye, or triticale, etc.), cotton, oilseed rape, maize (corn), rice, soybean, sugarbeet,
sugarcane, sunflowers, an ornamental or a vegetable.
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 (BCPC), 2003. The
reference to cloquintocet-mexyl also applies to cloquintocet, the reference to mefenpyrdiethyl
also applies to mefenpyr, and the reference to fenchlorazole-ethyl also applies to
fenchlorazole, etc.
Preferably, in the mixture, the ratio of the compound of formula (I) to the safener
is from 100:1 to 1:10 by weight, especially from 20:1 to 1:1 by weight.
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). It is possible that the safener and a compound of formula
(I) and one or more additional herbicide(s), if any, are applied simultaneously. For
example, the safener, a compound of formula (I) and one or more additional
herbicide(s), if any, might be applied to the locus pre-emergence or might be applied to
the crop post-emergence. It is also possible that the safener and a compound of formula
(I) and one or more additional herbicide(s), if any, are applied sequentially. For example,
the safener might be applied before sowing the seeds as a seed treatment and a
compound of formula (I) and one or more additional herbicides, if any, might be applied
to the locus pre-emergence or might be applied to the crop post-emergence.
Preferred mixtures of a compound of formula (I) with further herbicides and
safeners include:
Mixtures of a compound of formula (I) with S-metolachlor and a safener,
particularly benoxacor.
Mixtures of a compound of formula (I) with S-metolachlor and mesotrione and a
safener, particularly benoxacor.
Mixtures of a compound of formula i I) with isoxaflutole and a safener.
Mixtures of a compound of formula i I) with mesotrione and a safener, particularly
benoxacor.
Mixtures of a compound of formula i I) with sulcotrione and a safener.
Mixtures of a compound of formula i I) with a triazine and a safener.
Mixtures of a compound of formula i I) with a triazine and isoxaflutole and a
safener.
Mixtures of a compound of formula i I) with a triazine and mesotrione and a
safener.
Mixtures of a compound of formula i I) with a triazine and sulcotrione and a
safener.
Mixtures of a compound of formula i I) with glyphosate and a safener.
Mixtures of a compound of formula i I) with glyphosate and isoxaflutole and a
safener.
Mixtures of a compound of formula i I) with glyphosate and mesotrione and a
safener.
Mixtures of a compound of formula i I) with glyphosate and sulcotrione and a
safener.
Mixtures of a compound of formula i I) with glufosinate-ammonium and a safener.
Mixtures of a compound of formula i I) with glufosinate-ammonium and
isoxaflutole and asafener.
Mixtures of a compound of formula i I) with glufosinate-ammonium and
mesotrione and a safener.
Mixtures of a compound of formula i I) with glufosinate-ammonium and
sulcotrione and a safener.
Mixtures of a compound of formula i I) with florasulam and a safener, particularly
cloquintocet-mexyl.
Mixtures of a compound of formula i I) with clodinafop-propargyl and a safener,
particularly cloquintocet-mexyl.
Mixtures of a compound of formula i I) with pinoxaden and a safener, particularly
cloquintocet-mexyl.
Mixtures of a compound of formula i I) with bromoxynil and a safener, particularly
cloquintocet-mexyl.
The following Examples further illus rate, but do not limit, the invention.
EXAMPLES
Abbreviations:
DMF dimethylformamide
LHMDS lithium hexamethyldisilazide
NMR nuclear magnetic resonance
LCMS liquid chromatography - mass spectrometry
GCMS gas chromatography - mass spectrometry
RT (in the context of LCMS or GCMS) retention time
RT (in the context of temperature) room temperature (ambient temperature),
which is usually about 18-25 °C.
EXAMPLE1 . REACTIONS COVERED BY REACATION SCHEME 1
Example 1.1 Preparation of 2-(3-Chloro-pyrazin-2-yl)-malonic acid diethyl ester
To a solution of 2,3-dichloro-pyrazine (10 g) (commercially available) and N,Ndimethylformamide
("DMF") (80 ml) was added diethylmalonate (26.87 g) and potassium
carbonate (23.19 g). The reaction mixture was heated to 110°C for 8 hours. The reaction
mixture was cooled to ambient temperature, filtered and the filtrate concentrated. The
residue was purified by chromatography on silica gel (eluent 5-95% ethyl acetate in
isohexane) to give 2-(3-Chloro-pyrazin-2-yl)-malonic acid diethyl ester (12.93 g). HNMR
(400MHz, CDCI3) : 8.50 (s, 1H), 8.40 (s, 1H), 5.20 (s, 1H), 4.30 (q, 4H), 1.30 (t, 6H)
ppm.
Example 1.2 Preparation of (3-Chloro-pyrazin-2-yl)-acetic acid
To a solution of 2-(3-chloro-pyrazin-2-yl)-malonic acid diethyl ester (10.0 g) in
ethanol (100 ml) was added 2M sodium hydroxide (100 ml) and the reaction mixture
heated to 60°C for 4 hours. The reaction mixture was cooled to ambient temperature
then poured onto water and 1M hydrochloric acid followed by extraction with ethyl
acetate (3x). The combined organic layers were dried (magnesium sulfate), filtered and
the filtrate concentrated to give the crude title compound as a yellow solid. The solid was
slurried with diethylether to give (3-chloro-pyrazin-2-yl)-acetic acid (4.35 g). MH+ = 173,
RT = 0.72 min (Method A).
Example 1.3 Preparation of (3-Chloro-pyrazin-2-yl)-acetic acid ethyl ester
Ethanol, DMF
To a solution of (3-chloro-pyrazin-2-yl)-acetic acid (2.00 g) in N,Ndimethylformamide
("DMF") (20 ml) was added 1,1'-carbonyldiimidazole ( 1 .88 g) and the
mixture stirred for 1 hour. To the reaction mixture was added ethanol (20 ml) and the
mixture stirred for 1 hour at ambient temperature. The reaction mixture was
concentrated and then purified by chromatography on silica gel (eluent 5-95% ethyl
acetate in isohexane) to give (3-chloro-pyrazin-2-yl)-acetic acid ethyl ester ( 1 .93 g). 1HNMR
(400MHz, CDCI3) : 8.50 (s, 1H), 8.30 (s, 1H), 4.20 (q, 2H), 4.00 (s, 2H), 1.30 (t, 3H)
ppm.
Example 1.4 Preparation of 2-(3-Chloro-pyrazin-2-yl)-2-methyl-propionic acid
To a solution of (3-chloro-pyrazin-2-yl)-acetic acid ethyl ester ( 1 .00 g) in N,Ndimethylformamide
("DMF") (10 ml) at 5-10°C was added lithiumhexamethyldisilazide
("LHMDS", 1M in tetrahydrofuran) (7.47 ml) dropwise followed by methyl iodide (0.84 g)
and the mixture stirred for 30 min at ambient temperature. The solution was cooled to 5-
10°C and a second portion of lithium hexamethyldisilazide ("LHMDS", 1M in
tetrahydrofuran) (7.47ml) added dropwise followed by a second portion of methyl iodide
(0.84g) and the mixture stirred for 120 min. The reaction was neutralised by the addition
of 1M hydrochloric acid, diluted with water and extracted with dichloromethane (3x). The
combined organic layers were dried (magnesium sulfate), filtered and the filtrate
concentrated. The residue was purified by chromatography on silica gel (eluent 5-95%
ethyl acetate in isohexane) to give 2-(3-Chloro-pyrazin-2-yl)-2-methyl-propionic acid
ethyl ester (0.70 g). MH+ = 229, RT = 1.51 min (Method A).
Example 1.5 Preparation of 2-(3-Chloro-pyrazin-2-yl)-2-methyl-butyric acid methyl
ester
To a solution of 2,3-dichloro-pyrazine (0.50g) (commercially available) and anhydrous
tetrahydrofuran ("THF") (5 ml) was added a solution of lithium hexamethyldisilazide
("LHMDS", 1M in tetrahydrofuran) (5 ml). The reaction mixture was stirred for 16 hours.
The reaction mixture was poured onto M hydrochloric acid and extracted with ethyl
acetate (3x). The combined organic layers were dried (magnesium sulfate), filtered and
the filtrate concentrated. The residue was purified by chromatography on silica gel
(eluent 5-95% ethyl acetate in isohexane) to give 2-(3-Chloro-pyrazin-2-yl)-2-methylbutyric
acid methyl ester (compound A 1 of Table A) (0.55g). MH+ = 229, RT = 1.55 min
(Method A).
Table (A) below shows characterising physical data for esters of formula (6)
en, R6 is methyl and R a and R have the values indicated.
(6)
Table A
Compound. R3a R3b MH+ RT LCMS
(min) Method
A 1 methyl ethyl 229 1.55 A
A2 methyl allyl 255 1.70 A
A3 methyl phenyl 277 1.65 A
A4 cyclopentyl cyclopentyl 241 1.60 A
EXAMPLE 2 REACTIONS COVERED BY REACTION SCHEME 2
Example 2.1 Preparation of 2-Methyl-2-(3-phenylethynyl-pyrazin-2-yl)-propionic
To a solution of 2-(3-Chloro-pyrazin-2-yl)-2-methyl-propionic acid ethyl ester
(0.70 g) in acetonitrile (7.0 ml) was added 1-ethynyl-2-trifluoromethylbenzene (0.781 g)
and caesium carbonate ("Cs2C0 3") (2.99 g) and nitrogen bubbled through the solution
for 20 min. To this solution was added as 4,5-(bisdiphenylphosphino)-9,9-
dimethylxanthene ("Xantphos") (0.133 g) and ( 1 ,1'-bis(diphenylphosphino)-
ferrocene)dichloro palladium(2) (0.125 g) and the reaction mixture heated to reflux for 30
min. The reaction mixture was cooled to ambient temperature then filtered and
concentrated. The residue was purified by chromatography on silica gel (eluent 5-95%
ethyl acetate in isohexane) to give 2-methyl-2-(3-phenylethynyl-pyrazin-2-yl)-propionic
acid ethyl ester (compound B 1 of Table B) (0.52 g).
Table (B) below shows characterising physical data for esters of formula (8)
where R and R2 are hydrogen, R a and R are methyl, R6 are ethyl and R4 have the
values indicated.
(8)
Table B
Compound MH+ RT (min) LCMS Method
B 1 2-Trifluoromethyl-phenyl 363 1.85 A
B2 2-Methoxy-phenyl- 325 1.68 A
B3 2,4-Difluoro-phenyl- 331 1.78 A
B4 2-Chloro-phenyl- 329 1.80 A
B5 2-Methyl-phenyl- 309 1.82 A
B6 4-Chloro-phenyl- 329 1.88 A
B7 3-Trifluoromethyl-phenyl 363 1.92 A
Example 2.2 Preparation of 2-Methyl -2-[3-(2-trifluoromethyl-phenylethynyl)-
pyrazin -2-yl]-propionic acid
To a solution of 2-methyl-2-(3-phenylethynyl-pyrazin-2-yl)-propionic acid ethyl
ester (0.52 g) in ethanol (5 ml) was added 4M sodium hydroxide (2.5 ml) and the
reaction mixture heated to 80°C for 8 hours. The reaction mixture was cooled to ambient
temperature then poured onto water and 2M hydrochloric acid followed by extraction
with ethyl acetate (3x). The combined organic layers were dried (magnesium sulfate),
filtered and the filtrate concentrated to give 2-methyl-2-[3-(2-trifluoromethylphenylethynyl)-
pyrazin-2-yl]-propionic acid (compound C 1 of Table C) (0.48 g).
Table (C) below shows characterising physical data for esters of formula (9)
gen, R a and R are methyl and R4 have the values indicated.
(9)
Compound. MH+ RT (min) LCMS Method
C 1 2-Trifluoromethyl-phenyl 335 1.50 A
C2 2-Methoxy-phenyl- 297 1.47 A
C3 2,4-Difluoro-phenyl- 303 1.48 A
C4 2-Chloro-phenyl- 301 1.50 A
C5 2-Methyl-phenyl- 281 1.48 A
C6 4-Chloro-phenyl- 301 1.55 A
C7 3-Trifluoromethyl-phenyl 335 1.62 A
Example 2.3 Preparation of 8,8-Dimethyl-5-[1-(2-trifluoromethyl-phenyl)-meth-(Z)-
-5,8-dihydro-pyrano[3,4-b]pyrazin-7-one
A solution of gold chloride triphenylphosphine (0.444 g) and silver
tetrafluoroborate (0.174 g) in carbon tetrachloride was stirred for 30 min. To this solution
was added a solution of 2-methyl-2-[3-(2-trifluoromethyl-phenylethynyl)-pyrazin-2-yl]-
propionic acid (0.50 g). The reaction mixture was flushed out with argon then heated to
55°C for 48 hours. The reaction mixture was cooled to ambient temperature, filtered,
concentrated and the residue purified by chromatography on silica gel (eluent 5-95%
ethyl acetate in isohexane) to give 8,8-dimethyl-5-[1-(2-trifluoromethyl-phenyl)-meth-(Z)-
ylidene]-5,8-dihydro-pyrano[3,4-b]pyrazin-7-one (compound D1 of Table D) (0.170 g)..
Table (D) below shows physical characterising data for esters of formula (10), in
which R and R2 are both hydrogen, R a and R are both methyl, and R4 has the value
indicated.
( 10)
Compound R4 MH+ RT (min) LCMS 1H-NMR (400 MHz, chemical
Method shifts in ppm)
D 1 2-Trifluoromethyl-phenyl- 8.60 (s, 2H), 8.20 (d, 1H), 7.70
(d, 1H), 7.60 (t, 1H), 7.50 (s, 1H),
7.40 (t, 1H), 1.70 (s, 6H) CDCI3
D2 2-Methoxy-phenyl- 297 17 7 A
D3 2,4-Difluoro-phenyl- 303 1.82 A
D4 2-Chloro-phenyl- 301 1.85 A
D5 2-Methyl-phenyl- 281 1.78 A
D6 4-Chloro-phenyl- 301 1.87 A
D7 3-Trifluoromethyl-phenyl- 335 1.90 A
Example 2.4 Preparation of 8,8-Dimethyl-6-(2-trifluoromethyl-ph
-5,7-dione
To a stirred solution of 8,8-dimethyl-5-[1-(2-trifluoromethyl-phenyl)-meth-(Z)-
ylidene]-5,8-dihydro-pyrano[3,4-b]pyrazin-7-one (0.170 g) in acetonitrile ( 1 .7 ml) at
ambient temperature was added triethylamine (0.154 g) and 4 molecular sieves. After
10 min acetone cyanohydrin (0.013 g) was added and the reaction mixture stirred for 16
hours. The reaction mixture was concentrated and the residue purified by
chromatography on silica gel (eluent 5-95% ethyl acetate in isohexane) to give the crude
8,8-dimethyl-6-(2-trifluoromethyl-phenyl)-8H-quinoxaline-5,7-dione (compound E 1 of
Table E) (0.190 g) which was carried over to the next step.
Table (E) shows characterising physical data for compounds of formula ( 1 1a)
wherein R4 has the value indicated, and which can be prepared in a similar manner to
Example 2.4 described immediately above.
Compound R4 MH+ RT (min) LCMS
Method
E 1 2-trifluoromethyl-phenyl- 335 1.47 A
E2 2-methoxy-phenyl- 297 1.47 A
E3 2,4-difluoro-phenyl- 303 1.47 A
E4 2-chloro-phenyl- 301 1.47 A
E5 2-methyl-phenyl- 281 1.45 A
E6 4-chloro-phenyl- 301 1.58 A
E7 3-trifluoromethyl-phenyl- 335 1.64 A
Example 2.5 Preparation of Isobutyric acid 8,8-dimethyl-7-oxo-6-(2-
trifluoromethyl-phenyl)-7,8-dihydro-quinoxalin-5-yl ester
To a stirred solution of crude 8,8-dimethyl-6-(2-trifluoromethyl-phenyl)-8Hquinoxaline-
5,7-dione (0.190 g) in dichloromethane (2.0 ml) at ambient temperature was
added pyridine (0.054 g) followed by isobutryl chloride (isopropyl-C(O)-CI, 0.064 g) and
the reaction mixture stirred for 1 hour. The reaction mixture was concentrated and the
residue purified by chromatography on silica gel (eluent 5-95% ethyl acetate in
isohexane) to give isobutyric acid 8,8-dimethyl-7-oxo-6-(2-trifluoromethyl-phenyl)-7,8-
dihydro-quinoxalin-5-yl ester (compound F 1 of Table F) (0.162 g).
Table (F) shows characterising physical data for ester compounds of formula
(12a) wherein R4 has the value indicated, and which can be prepared in a similar
manner to Example 2.5 immediately above.
Compound MH+ RT LCMS H-NMR (400 MHz, chemical
(min) Method shifts in ppm)
2-trifluoromethyl-phenyl- 8.60 (s, 1H), 8.50 (s, 1H), 7.75
(d, 1H), 7.60 (t, 1H), 7.50 (t,
1H), 7.20 (d, 1H), 2.70 (m, 1H),
1.70 (s, 3H), 1.60 (s, 3H), 1.05
(d, 3H), 0.95 (d, 3H) CDCI3
2,4-difluoro-phenyl- 373 1.87 A 8.60 (s, 1H), 8.50 (s, 1H), 7.25
(d, 1H), 6.90 (m, 2H), 2.80 (m,
1H), 1.65 (s, 6H), 1.20 (d, 6H)
CDC
2-chloro-phenyl- 371 1.87 A 8.60 (s, 1H), 8.50 (s, 1H), 7.50
(d, 1H), 7.20-7.40 (m, 3H), 2.75
(m, 1H), 1.70 (s, 3H), 1.65 (s,
3H), 1.15 (d, 3H), 1.10 (d, 3H)
CDCb
2-methyl-phenyl- 351 1.6 8.60 (s, 1H), 8.50 (s, 1H), 7.20-
7.30 (m, 3H), 7 .10 (d, 1H), 2.70
(m, 1H), 2 .15 (s, 3H), 1.70 (s,
3H), 1.65 (s, 3H), 1.00 (d, 6H)
CDC
4-chloro-phenyl- 371 1.95 A
3-trifluoromethyl-phenyl- 405 1.98 A
Example 2.6 Preparation of 8,8-Dimethyl-6-(2-trifluoromethyl-ph
-5,7-dione
To a solution of 8,8-dimethyl-6-(2-trifluoromethyl-phenyl)-8H-quinoxaline-5,7-
dione (0.121 g) in ethanol (0.60 ml) was added water (0.60ml) and lithium hydroxide
monohydrate (0.025g), and the reaction mixture stirred for 2 hours at ambient
temperature. The reaction mixture was reduced then quenched withIM hydrochloric acid
followed by extraction with chloroform (3x). The combined organic layers were dried
(magnesium sulfate), filtered and the filtrate concentrated. The residue was slurried in
diethyl ether to give 8,8-dimethyl-6-(2-trifluoromethyl-phenyl)-8H-quinoxaline-5,7-dione
(compound E 1 of Table E) (0.030 g). 1H-NMR (400MHz, CDCI3) : 8.75 (s, 1H), 8.50 (s,
1H), 7.80 (d, 1H), 7.60 (t, 1H), 7.50 (t, 1H), 7.30 (d, 1H), 1.65 (s, 3H), 1.60 (s, 3H) ppm.
LCMS analysis: Method A
Note: Compounds characterised by HPLC-MS were analysed using an Agilent 1100
Series HPLC equipped with a Waters Atlantis dC18 column (column length 20 mm,
internal diameter of column 3 mm, particle size 3 micron, temperature 40 °C), Waters
photodiode array and Micromass ZQ2000. The analysis was conducted using a three
minute run time, according to the gradient table shown below.
Gradient Table
Time (mins) Solvent A Solvent B Flow (ml /
( ) ( ) mn)
0.00 90.0 10.0 2.00
0.25 90.0 10.0 2.00
2.00 10.0 90.0 2.00
2.50 10.0 90.0 2.00
2.6 90.0 10.0 2.00
3.0 90.0 10.0 2.00
Solvent A: H20 with 0.1% HCOOH
Solvent B: 0.1% HCOOH in CH3CN
BIOLOGICAL EXAMPLES
Example B1 Herbicidal action post-emergence
Seeds of a variety of test species were sown in standard soil in pots. After 8 days
cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°C,
day/night; 14 hours light; 65% humidity), the plants were sprayed with an aqueous spray
solution derived from the formulation of the technical active ingredient in acetone / water
(50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate,
CAS RN 9005-64-5). The test plants were then grown under controlled conditions in a
glasshouse (at 24/16°C, day/night; 14 hours light; 65% humidity) and watered twice
daily. After 13 days, the test was evaluated (10 = total damage to plant; 0 = no damage
to plant).
Table B 1: Application post-emergence
Compound Rate SOLNI AMARE SETFA ECHCG IPOHE
(g/ha)
E 1 1000 10 10 9 9 9
SOLNI = Solanum nigrum; AMARE = Amaranthus retroflexus; SETFA = Setaria faberi;
ECHCG = Echinochloa crus-galli; IPOHE = Ipomea hederaceae.
Example B2 Herbicidal action post-emergence
Seeds of crop and representative weed species were sown in standard soil in
pots. After cultivation for 14 days under controlled conditions in a glasshouse (at
22/1 6°C, day/night; 16 hours light; 65 % humidity), the plants were sprayed. The spray
solution was prepared by dissolving the technical active ingredient in acetone containing
10.56 wt% Emulsogen EL, 42.22 wt% /V-methylpyrrolidone and 2.22 wt% DPGmonoethyl
ether to give a 5% stock solution. This was then diluted with water containing
0.2% (v/v) of the adjuvant X-77 to give the desired treatment concentration.
The test plants were then grown on under controlled conditions in a glasshouse (at
22/1 6°C, day/night; 16 hours light; 65 % humidity) and watered twice daily. After 15
days the test was evaluated (10 = total damage to plant; 0 = no damage to plant).
Results are shown below in Table B2.
Table B2: Application post-emergence
Compound Rate (g/ha) AMARE SETFA ECHCG IPOHE
E 1 500 10 7 3 8
F 1 500 10 8 8 8
AMARE = Amaranthus retroflexus; SETFA = Setaria faberi; ECHCG = Echinochloa
crus-galli; IPOHE = Ipomea hederaceae.
CLAIMS
1. A compound of for
wherein:
R and R2 are independently hydrogen, halogen, C C alkyl, CrC 2fluoroalkyl,
Ci-C 2alkoxy-Ci-C 2alkyl-, hydroxy, C C alkoxy, CrC 2fluoroalkoxy, or
Ci-C 2alkoxy-CH 2CH20-;
R a and R are independently halogen, C C alkyl, C C fluoroalkyl,
Ci-C chloroalkyl, Ci-C 2alkoxy-CrC 2alkyl-, C2-C alkenyl, C2-C fluoroalkenyl,
C2-C chloroalkenyl, C2-C alkynyl, C2-C fluoroalkynyl, C2-C chloroalkynyl,
C3-C6cycloalkyl-(CH 2)m- or C3-C6cycloalkyl-(CH 2)m- substituted on the cycloalkyl
ring by 1 or 2 methyl groups and wherein m is 0 or 1, CrC 3alkyl-carbonyl-,
CrC 3alkoxy-carbonyl-, CrC 2chloroalkyl-carbonyl-, or CrC 2fluoroalkyl-carbonyl-;
phenyl or phenyl substituted by one or two of independently fluorine and/or
methyl; or heterocyclyl-methyl- in which the heterocyclyl is a 4-, 5-, or 6-
membered saturated monocyclic heterocyclic ring in which there are 1 or 2 ring
heteroatoms independently selected from O, N and S and wherein the
heterocyclyl is optionally substituted on a ring carbon and/or (if present) on a ring
nitrogen by 1 or 2 methyl groups; or heteroaryl-methyl- in which the heteroaryl is
a 5-membered monocyclic heteroaromatic ring in which there are 1, 2 or 3 ring
heteroatoms independently selected from O, N and S and wherein the heteroaryl
is optionally substituted on the ring by 1 or 2 methyl groups;
or R a and R , together with the carbon atom to which they are attached, form a
3-, 4-, 5- or 6- membered carbocyclic ring optionally substituted by 1 or 2 methyl
groups;
or R a and R taken together are -(CH 2)n-X -(CH 2)p- , wherein X3 is O, S, NH or
NMe, and wherein n is 1, 2 , 3 or 4 and p is 0 , 1 or 2 provided that n + p is 2 , 3 or
4 ;
R4 is of sub-formula (a) or (b):
(a) (b)
wherein, in sub-formula (a):
R4a and R4e are independently hydrogen, halogen, CrC 2alkyl, CifluoroalkyI,
hydroxy, C C2alkoxy, dfluoroalkoxy, methyl-S(0) 2- , H2N-S(0) 2- , MeNH-S(0) 2- ,
or Me2N-S(0) 2- ; and
R4 , R4c and R4d are independently hydrogen, halogen, cyano, CrC 4alkyl,
Ci-C 2fluoroalkyl, Ci-C 3alkoxy-CrC 2alkyl-, Cifluoroalkoxy-CrC 2alkyl-,
MeOCH2CH2OCH2- , C3-C6cycloalkyl, hydroxy, C C alkoxy, C C2fluoroalkoxy,
thiol (HS-), C C3alkylthio-, dfluoroalkylthio-, C C3alkyl-S(0)-, dfluoroalkyl-
S(O)-, d-C 3alkyl-S(0) 2- , dfluoroalkyl-S(0) 2- , H2N-S(0) 2- ,
d-C 4alkyl-NH-S(0) 2- , (d-C 3alkyl)2N-S(0) 2- , d-C 4alkyl-C(0)-, H-C(O)-,
d-C 3alkoxy-C(0)-, HO-C(O)-, H2N-C(0)-, d-C 4alkyl-NH-C(0)-,
(d-C 3alkyl)2N-C(0)-, ( 1-pyrrolidinyl)-C(O)-, (l-piperidinyl)-C(O)-, amino,
d-C 4alkyl-NH-, (C C3alkyl)2N-, 1-pyrrolidinyl, 1-piperidinyl, C C4alkyl-C(0)-NH-,
H-C(0)-NH-, CrC 3alkyl-C(0)-N(d-C 3alkyl)-, 2-oxo-1 -pyrrolidinyl, 2-oxo-1-
piperidinyl, C C3alkyl-S(0) 2-NH-, C C3alkyl-S(0) 2-N(CrC 3alkyl)-, phenyl or
phenyl substituted by one, two or three of R7, or phenoxy or phenoxy substituted
by one, two or three of R7;
provided that none of, or only one of, R4 , R4c and R4d is C3-C6cycloalkyl,
( 1-pyrrolidinyl)-C(O)-, (l-piperidinyl)-C(O)-, 1-pyrrolidinyl, 1-piperidinyl,
2-OXO-1-pyrrolidinyl, 2-oxo-1-piperidinyl, phenyl, substituted phenyl, phenoxy or
substituted phenoxy;
wherein each R7, independently of any other R7, is fluorine, chlorine, d-C 2alkyl,
CifluoroalkyI, Ci-C 2alkoxy or Cifluoroalkoxy;
and wherein, in sub-formula (b):
A1 is N or C-R4f, A2 is N or C-R49 , A3 is N or C-R4h, A2 is N or C-R4i, and A5 is N or
C-R4 , provided that one or two of A1, A2, A3, A4 and A5 are nitrogen and the
remaining ones of A1, A2, A3, A4 and A5 are not nitrogen;
wherein R4f and R4 are independently hydrogen, halogen, -C2alkyl,
Cifluoroalkyl, hydroxy (inclusive of any tautomer thereof), CrC 2alkoxy, or
Cifluoroalkoxy; and
R49 , R4h and R4' are independently hydrogen, halogen, CrC 4alkyl,
CrC 2fluoroalkyl, CrC 3alkoxy-methyl-, Cifluoroalkoxy-methyl-,
MeOCH 2CH2OCI-l2- , C3-C6cycloalkyl, hydroxy (inclusive of any tautomer thereof),
C C4alkoxy, C C2fluoroalkoxy, C C4alkyl-C(0)-, H-C(O)-, C C3alkoxy-C(0)-,
HO-C(O)-, H2N-C(0)-, C C4alkyl-NH-C(0)-, (C C3alkyl)2N-C(0)-,
( 1-pyrrolidinyl)-C(O)-, (l-piperidinyl)-C(O)-, amino, C C4alkyl-NH-,
(CrC 3alkyl)2N-, 1-pyrrolidinyl, 1-piperidinyl, C C4alkyl-C(0)-NH-, H-C(0)-NH-,
CrC 3alkyl-C(0)-N(Ci-C 3alkyl)-, 2-oxo-1 -pyrrolidinyl, 2-oxo-1-piperidinyl, phenyl
or phenyl substituted by one, two or three of R7, or phenoxy or phenoxy
substituted by one, two or three of R7; wherein R7 is as defined hereinabove;
provided that none of, or only one of, R49 , R4h and R4' is C3-C6cycloalkyl,
( 1-pyrrolidinyl)-C(O)-, (l-piperidinyl)-C(O)-, 1-pyrrolidinyl, 1-piperidinyl,
2-OXO-1-pyrrolidinyl, 2-oxo-1-piperidinyl, phenyl, substituted phenyl, phenoxy or
substituted phenoxy; and
R5 is hydroxy, R6-oxy-, R8-C(0)-0-, C C10alkyl-S(O) 2O-, dfluoroalkyl-S(0) 20-,
dchloroalkyl-S(0) 20-, phenyl-S(0) 20 - or (4-methyl-phenyl)-S(0) 20-;
wherein
R6 is CrCioalkyI, Ci-C fluoroalkyl, C2-Ci 0alkenyl, C2-Ci 0alkynyl, C3-C8cycloalkyl,
C3-C8cycloalkyl-CrC 4alkyl-, CrC 4alkoxy-CH 2CH2- , CrC 4alkoxy-CH 2CH2CH2- ,
phenyl-CrC alkyl-, or phenyl-Ci-C alkyl- wherein the phenyl moiety is
substituted by one, two or three R9;
R8 is CrCioalkyI, Ci-C fluoroalkyl, C2-Ci 0alkenyl, C2-Ci 0alkynyl, C3-C8cycloalkyl,
C3-C8cycloalkyl-CrC alkyl-, Ci-C alkoxy-CrC alkyl-, phenyl, phenyl substituted
by one, two or three R9, phenyl-Ci-C alkyl-, or phenyl-Ci-C alkyl- wherein the
phenyl moiety is substituted by one, two or three R9;
or R8 is CrCi 0alkoxy, CrC fluoroalkoxy, CrCi 0alkenyloxy, CrCi 0alkynyloxy,
C3-C8cycloalkoxy, C3-C8cycloalkyl-CrC alkoxy-, CrC alkoxy-CH 2CH20-,
CrC alkoxy-CH 2CH2CH20-, phenoxy, phenoxy substituted by one, two or three
R9, phenyl-CrC alkoxy-, or phenyl-Ci-C alkoxy- wherein the phenyl moiety is
substituted by one, two or three R ;
or R8 is C C10alkylthio-, CrC 10alkyl-NH-, or (CrC6alkyl)2N-;
and wherein each R9, independently of any other R9, is fluorine, chlorine,
CrC 4alkyl, CifluoroalkyI, CrC 3alkoxy or Cifluoroalkoxy;
or a salt thereof.
2 . The compound of formula (I) according to claim 1, wherein R and R2 are each
independently hydrogen, halogen, -C3alkyl, Cifluoroalky, CrC 2alkoxy, or
Cifluoroalkoxy.
3 . The compound of formula (I) according to claim 1 or claim 2 , wherein R and R2
are each independently hydrogen, fluorine, chlorine, methyl or ethyl
4 . The compound of formula (I) according to any one of claims 1-3, wherein R a and
R are each independently C -C alkyl, CrC 3fluoroalkyl, C2-C3alkenyl, C2-
C3fluoroalkenyl, C2chloroalkenyl, C2-C3alkynyl, C3-C5cycloalkyl, C3-C cycloalkyl-
CH2- , or phenyl.
5 . The compound of formula (I) according to any one of the preceding claims,
wherein R a and R are each independently methyl, ethyl, n-propyl, isopropyl,
Cifluoroalkyl-CH 2- , vinyl, allyl, C2fluoroalkenyl, propargyl, cyclopropyl, cyclobutyl,
cyclopentyl, cyclopropyl-methyl-, or phenyl.
6 . The compound of formula (I) according to any one of the preceding claims,
whererin R4 is of sub-formula (a) and,
R4a and R4e are independently hydrogen, fluorine, chlorine, bromine, methyl,
CifluoroalkyI (e.g. CF3) , methoxy, Cifluoroalkoxy (e.g. CHF20 , CF30 or CH2FO,
in particular CHF20), or methyl-S(0) 2- ;
R4 , R4c and R4d are independently hydrogen, halogen, C -C alkyl, CifluoroalkyI,
methoxymethyl-, MeOCH2CH2OCH2- , C3-C5cycloalkyl, C C3alkoxy,
Cifluoroalkoxy, C C3alkyl-S(0) 2- , H2N-S(0) 2- , C C3alkyl-NH-S(0) 2- , or (C
C3alkyl)2N-S(0) 2- ; phenyl or phenyl substituted by one or two of R7;
and wherein each R7, independently of any other R7, is fluorine, chlorine, methyl,
Cifluoroalkyl, methoxy or Cifluoroalkoxy; provided that none of, or only one of,
R4 , R4c and R4d is C3-C5cycloalkyl, phenyl or substituted phenyl.
7 . The compound of formula (I) according to any one of the preceding claims,
wherein R4 is of sub-formula (a), and,
R4a and R4e are independently hydrogen, fluorine, chlorine, bromine, methyl, CF3
or methoxy;
R4 , R4c and R4d are independently hydrogen, fluorine, chlorine, bromine, methyl,
ethyl, Cifluoroalkyl (e.g. CF3) , cyclopropyl, methoxy, ethoxy, Cifluoroalkoxy,
methyl-S(0) 2- , phenyl, or phenyl substituted by one or two of R7;
and wherein each R7, independently of any other R7, is fluorine, chlorine, methyl,
CF3, methoxy, CHF20 or CH2FO;
provided that none of, or only one of, R4 , R4c and R4d is cyclopropyl, phenyl or
substituted phenyl
8 . The compound of formula (I) according to any one claims 1-5, wherein R4 is of
sub-formula (b), and is an optionally substituted pyridinyl moiety.
9 . The compound of formula (I) according to claim 8 , wherein R4f and R4 are
independently hydrogen, fluorine, chlorine, methyl, Cifluoroalkyl, or hydroxy;
R49 , R4h and R4' are independently hydrogen, fluorine, chlorine, Ci-C 4alkyl,
Cifluoroalkyl, methoxymethyl-, MeOCH2CH2OCH2- , C3-C5cycloalkyl, hydroxy,
Ci-C 3alkoxy, Cifluoroalkoxy, phenyl or phenyl substituted by one, two or three of
R7;
and wherein each R7, independently of any other R7, is fluorine, chlorine, methyl,
Cifluoroalkyl, methoxy or Cifluoroalkoxy,
provided that none of, or only one of, R49 , R4h and R4' is C3-C5cycloalkyl, phenyl
or substituted phenyl.
10 . The compound of formula (I) according to any one of the preceding claims,
wherein R5 is hydroxy, R6-oxy- or R8-C(0)-0-.
11. The compound of formula (I) according to any one of the preceding claims,
wherein R5 is hydroxy or R8-C(0)-0-.
A method of controlling unwanted plants which comprises applying to the plants
or to the locus thereof a herbicidally effective amount of a compound of formula
(I) as defined in any one of claims 1-1 1.
A compound of formula (8)
wherein R , R2, R a , R , R4, are as defined for a compound of formula (I) in any
one of claims 1-1 1, and wherein R6a is C C alkyl.
A compound of formula (10)
wherein R , R2, R a , R , R4, are as defined for a compound of formula (I) in any
one of claims 1-1 1.
A herbicidal composition which comprises a herbicidally effective amount of a
compound of formula (I) as defined in any one of claims 1-13 in addition to at
least one formulation carrier, and/or solvent.
A herbicidal composition which comprises a herbicidally effective amount of a
compound of formula (I) as defined in any one of claims 1-13, in combination
with at least one further herbicide, and optionally at least one safener.