Note: Descriptions are shown in the official language in which they were submitted.
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1
Description
Formulation of herbicides and plant growth regulators
The invention relates to the technical field of
the formulation of herbicides and plant growth regulators,
in particular of herbicides for controlling undesirable
vegetation, for example of broad-leaved weeds and weed
grasses in crops of useful plants.
It is known that sulfonylureas have herbicidal and
plant-growth-regulating properties. For use in
agrochemistry, it is customary to formulate the
sulfonylureas. Here, the chemical stability and the
concentration of the active compound in the formulation are
important for their activity.
Surprisingly, it has now been found that
formulations based on certain sulfonylurea salts have
excellent properties.
Summary of Invention
The present invention provides a herbicide
formulation, comprising a) at least one phosphonium or
sulfonium salt of a sulfonylurea, where the phosphonium or
sulfonium cation of the salt has at least one substituent
which is different from hydrogen, and b) at least one of an
auxiliary or an additive.
The present invention further provides use of the
formulation as described herein as a herbicidal or plant-
growth-regulating composition.
The present invention further provides a compound
of the formula (Ia) as described herein.
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la
The present invention further provides use of one
or more compounds of the formula (Ia) as described herein as
a herbicidal or plant-growth-regulating agent.
The present invention further provides a process
for preparing the compound of the formula (Ia) as described
herein, comprising deprotonating a neutral sulfonylurea
using a base of formula M+B- wherein B- is a hydroxyl or
alkoxy anion or an anion of a herbicide formulation
auxiliary which has at least one OH group, and M+ is a
phosphonium or sulfonium ion.
The present invention further provides a process
for preparing the compound of the formula (Ia) as described
herein, comprising exchanging a cation of a metal salt of a
sulfonylurea with a reagent of formula M+X_ wherein M+ is a
phosphonium or sulfonium ion, and X- is a halide ion or an
organic or inorganic phosphate, sulphate or carboxylate
anion.
The present invention further provides a process
for preparing the compound of the formula (Ia) as described
herein comprising deprotonating and exchanging a cation of a
neutral sulfonylurea with the reagent of formula M+X- as
described herein, and a base of the formula MetB wherein Met
is an alkali metal cation and B is a hydroxy or alkoxy
anion.
The present invention further provides a process
for preparing the compound of the formula (Ia) as described
herein comprising reacting a sulphonamide salt with an
isocyanate, wherein the sulphonamide salt is prepared by
reacting a sulphonamide with the base M+B- as described
herein.
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lb
The present invention further provides a process
for preparing the compound of the formula (Ia) as described
herein comprising reacting a sulphonamide salt with a
carbamate wherein the sulphonamide salt is prepared by
reacting a sulphonamide with the base M+B- as described
herein.
The present invention further provides use of a
compound of the formula (XVIII)
R-0(EO)u,(PO)x(EO)y(PO) M6 (XVIII)
in which
w, x, y and z independently of one another are
integers from 0 to 50,
R is a C8-C40-hydrocarbon,
EO is an ethoxy unit,
PO is a propoxy unit and
M is a phosphonium or sulfonium ion,
for preparing the herbicide formulation as described herein.
Accordingly, the present invention provides
formulations, in particular agrochemical, for example
herbicidal, formulations, comprising a) at least one
phosphonium or sulfonium salt of a sulfonylurea, where the
phosphonium and sulfonium cation of the salt has at least
one substituent which is different from hydrogen, and b)
customary auxiliaries and additives.
In a preferred embodiment, the present invention
relates to formulations, in particular emulsifiable
concentrates (EC), comprising at least one primary,
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is
secondary, tertiary or quaternary, preferably a quaternary,
phosphonium salt or at least one primary, secondary or
tertiary, preferably a tertiary, sulfonium salt of a
sulfonylurea.
Preference is given to formulations comprising a
sulfonylurea salt of the formula (Ia),
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WO 00/44227 2 PCT/EPOO/00469
MO
0
Ra-SO2-N-CONRI -R b
(Ia)
in which Ra is a substituted aliphatic, aromatic or heterocyclic radical or an
electron-withdrawing group, such as a substituted sulfonamide radical;
preferably
Ra is a radical of the formula ll-lVc,
O
R3
3 R" 3 2 C NRsRs'
4 2 4
RZ-SOZ N- R5 R7
5 1 O 5 1
6 6
(11) (III) (IVa)
0
II OR6õ 4 R6"
R 2 5 3
R7õ
~' 45 6 N 2
6 1
(IVb) (IVc)
Rb is a heterocyclyl radical, preferably a nitrogen-containing
heterocyclyl radical, particularly preferably a heterocyclyl radical having 2
or 3 nitrogen atoms in the ring, very particularly preferably a radical
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Y
N--~
~ Z
N=4
X
in which
R~ is H or a Ci-C10-hydrocarbon radical, such as (C1-C6)-alkyl,
R2 is a substituted or unsubstituted C1-C20-hydrocarbon radical, such
as substituted or unsubstituted (Ci-C6)-alkyl, substituted or unsubstituted
(C2-C6)-alkenyl, substituted or unsubstituted (C2-C6)-alkynyl, substituted or
unsubstituted (C3-C7)-cycloalkyl,
R3 is a substituted or unsubstituted C1-C20-hydrocarbon radical, such
as substituted or unsubstituted (C1-C6)-alkyl, substituted or unsubstituted
(C2-C6)-alkenyl, substituted or unsubstituted (C2-C6)-alkynyl, substituted or
unsubstituted (C3-C7)-cycloalkyl,
R4 is halogen, such as F, Cl, Br, I, or a substituted or unsubstituted
C1-C20-hydrocarbon radical or C1-C20-hydrocarbonoxy radical, such as
(C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C1-C6)-alkoxy, (C3-C6)-
alkenyloxy, (C3-C6)-alkynyloxy, where the 6 last-mentioned radicals may
be substituted by one or more radicals, preferably from the group
consisting of halogen, such as F, Cl, Br or I, and (C1-C3)-alkoxy,
R5 is H, halogen, such as F, Cl, Br, I, or a substituted or unsubstituted
C1-C20-hydrocarbon radical or C1-C20-hydrocarbonoxy radical, such as
(Ci-C6)-alkyl, which may be substituted by one or more radicals from the
group consisting of halogen, such as F, Cl, Br or I, and (C1-C3)-alkoxy, or
(C1-C5)-alkoxy which may be substituted by one or more radicals from the
group consisting of halogen (F, Cl, Br, I) and (Cj-C3)-alkoxy,
R 6 and R are identical or different and are H or a substituted or
unsubstituted C1-C20-hydrocarbon radical, such as Cl-C6-alkyl (for
example Me, Et, nPr, i Pr, cPr), where R6 and R6 may form an
unsubstituted or substituted ring,
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R7 is H, halogen, such as F, Cl, Br or I, OH, NR" Ry, in which Rx and Ry
are H or (C1-C3)-alkyl, or R7 is N-(C1-C3)-alkyl-N-acylamino, N-acylamino
or a substituted or unsubstituted C1-C20-hydrocarbon radical or
hydrocarbonoxy radical, such as (C1-C3)-alkyl, (C1-C3)-haloalkyl, halogen,
(C1-C3)-alkyl-(N-(C1-C3)-alkyl-N-acylamino), (C1-C3)-alkyl-(N-acylamino)
or (C1-C3)-alkoxy,
6"
R is a substituted or unsubstituted C1-C20-hydrocarbon radical, such
as substituted or unsubstituted (C1-C6)-alkyl, substituted or unsubstituted
(C3-C6)-alkenyl, substituted or unsubstituted (C3-C6)-cycloalkyl, substituted
or unsubstituted (C3-C7)-alkynyl, substituted or unsubstituted (C4-C8)-
cycloalkylalkyl,
71
R
is halogen, such as F, Cl, Br or I, OH, NRxRy, in which Rx and Ry
are H or (C1-C3)-alkyl, or R71 is N-(C1-C3)-alkyl-N-acylamino, N-acylamino
or a substituted or unsubstituted C1-C20-hydrocarbon radical or C1-C20-
hydrocarbonoxy radical, such as (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)-
alkyl-(N-(C1-C3)-alkyl-N-acylamino), (C1-C3)-alkyl-(N-acylamino) or (C1-
C3)-alkoxy,
6"'
R is halogen, such as F, Cl, Br or I, or a substituted or unsubstituted
C1-C20-hydrocarbon-containing radical, such as (C1-C6)-alkyl, which may
be substituted by one or more radicals from the group consisting of halogen
(F, Cl, Br, I) and (C1-C3)-alkoxy, (C1-C6)-alkoxy which may be substituted
by one or more radicals from the group consisting of halogen (F, Cl, Br, I)
or (C1-C3)-alkoxy, substituted or unsubstituted alkoxycarbonyl, substituted
or unsubstituted dialkylamino carbonyl, substituted or unsubstituted (C1-
C6)-alkylsulfonyl (C1-C6)-mono- or -dialkylamino, N-(C1-C6)-alkyl-N-
acylamino or N-acylamino,
R is halogen, such as F, Cl, Br or I, OH, NRxRy, in which Rx and Ry
õ
are H or (C1-C3)-alkyl, or R T t
a substituted or unsubstituted C1-C20-
hydrocarbon radical or hydrocarbonoxy radical, such as (C1-C6)-alkyl, (C1-
C6)-haloalkyl, (C1-C6)-alkoxy or (C1-C6)-haloalkoxy,
M is a quaternary phosphonium ion or a tertiary sulfonium ion,
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28976-184
X is substituted or unsubstituted (C1-C6)-alkyl, substituted or
unsubstituted (C1-Ce)-alkoxy, halogen, such as F, Cl, Br or I, substituted or
unsubstituted (C1-C6)-mercaptoalkyl or (C1-C3)-mono- or (C1-C3)-
dialkylamino,
5
Y is substituted or unsubstituted (C1-C6)-alkyl, substituted or
unsubstituted (C1-C6)-alkoxy, halogen, such as F, Cl, Br or I, substituted or
unsubstituted (C1-C6)-mercaptoalkyl or (C1-C3)-mono- or (C1-C3)-
dialkylamino, and
Z is C-halogen, such as CF, CCI, CBr or Cl, CH or N.
The sulfonylurea salts of the formula (la) are novel and likewise form part of
the subject matter of this invention.
In the formula (la) and in the other formulae used in this application, the
radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and
the corresponding unsaturated and/or substituted radicals can in each case
be straight-chain or branched in the carbon skeleton. Alkyl radicals,
are, for example, methyl, ethyl, n- or isopropyl, n-, iso-, t- or 2-butyl,
pentyls,
hexyls, such as n-hexyl, isohexyl and 1,3-dimethylbutyl, heptyls, such as
n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals
have the meaning of the possible unsaturated radicals which correspond to
the alkyl radicals, alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl,
2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yi, 1-methylbut-3-en-1-yl
and 1-methylbut-2-en-1-yl; alkynyl is, for example, propargyl, but-2-yn-1-yl,
but-3-yn-1-yl, 1-methylbut-3-yn-1-yl.
The abbreviations used in this application have the following meanings:
Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, nPr = n-propyl,
Pr = isopropyl, CPr = cyclopropyl, nBu = n-butyl, iBu = isobutyl,
S t C
Bu = secondary butyl, Bu = tertiary butyl, Bu = cyclobutyl, Ph = phenyl.
Halogen is, for example, fluorine, chlorine, bromine or iodine. Haloalkyl,
-alkenyl and -alkynyl are alkyl, alkenyl and alkynyl, respectively, which are
partially or fully substituted by halogen, preferably by fluorine, chlorine
and/or bromine, in particular by fluorine or chlorine, for example CF3,
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CHF2, CH2F, CF3CF2, CH2FCHCI, CC13, CHC12, CH2CH2CI; haloalkoxy is,
for example, OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 and
OCH2CH2CI; this applies correspondingly to haloalkenyl and other
halogen-substituted radicals.
Aryl is a mono-, bi- or polycyclic aromatic system, for example phenyl,
naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the
like, preferably phenyl.
A heterocyclic radical or ring (heterocyclyl) can be saturated, unsaturated
or heteroaromatic and unsubstituted or substituted; it preferably contains
one or more heteroatoms in the ring, preferably selected from the group
consisting of N, 0 and S; it is preferably an aliphatic heterocyclyl radical
having 3 to 7 ring atoms or a heteroaromatic radical having 5 to 6 ring
atoms and contains 1, 2 or 3 heteroatoms. The heterocyclic radical can, for
example, be a heteroaromatic radical or ring (heteroaryl), such as, for
example, a mono-, bi- or polycyclic aromatic ring system in which at least
one ring contains one or more heteroatoms, for example pyridyl,
pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, oxazolyl,
furyl,
pyrrolyl, pyrazolyl and imidazolyl, or it is a partially or fully hydrogenated
radical, such has oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl,
dioxolanyl, morpholinyl, tetrahydrofuryl. Suitable substituents for a
substituted heterocyclic radical are the substituents mentioned further
below, and additionally also oxo. The oxo group can also be present at the
heteroring atoms which can exist in different oxidation states, for example
in the case of nitrogen and sulfur.
Substituted radicals, such as substituted hydrocarbon radicals, for example
substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted
heteroaryl, a substituted bicyclic radical or ring or a substituted bicyclic
radical, if appropriate with aromatic moieties, are, for example, substituted
radicals which are derived from the unsubstituted parent compounds,
where the substituents are, for example, one or more, preferably 1, 2 or 3,
radicals selected from the group consisting of halogen, alkoxy, haloalkoxy,
alkylthio, hydroxyl, amino, nitro, cyano, azido, alkoxycarbonyl,
alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl,
substituted amino, such as acylamino, mono- and dialkylamino, and
alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the
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case of cyclic radicals, also alkyl and haloalkyl, and also unsaturated
aliphatic radicals which correspond to the saturated hydrocarbon-
containing radicals mentioned, such as alkenyl, alkynyl, alkenyloxy,
alkynyloxy, etc. In the case of radicals having carbon atoms, preference is
given to those having 1 to 4 carbon atoms, in particular 1 or 2 carbon
atoms.
Mono- and disubstituted amino is, for example, alkylamino, dialkylamino,
acylamino, arylamino, N-aryl-N-alkylamino.
An acyl radical is the radical of an organic acid, for example the radical of
a
carboxylic acid and radicals of acids derived therefrom, such as
thiocarboxylic acid, optionally N-substituted iminocarboxylic acids, or the
radical of carbonic monoesters, optionally N-substituted carbamic acid,
sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids. Acyl is,
for example, formyl, alkylcarbonyl, such as (C1-C4-alkyl)carbonyl,
phenylcarbonyl, where the phenyl ring may be substituted, for example as
indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl,
benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and
other radicals of organic acids.
The formula (la) also embraces all stereoisomers of the formula (la), and
mixtures thereof. Such compounds of formula (Ia) contain one or more
asymmetric carbon atoms or else double bonds, which are not indicated
separately in the general formula (la). The possible stereoisomers defined
by their specific spatial form, such as enantiomers, diastereomers and Z
and E isomers, are all embraced by the formulae (la) and can be obtained
by conventional methods from mixtures of these stereoisomers or else can
be prepared by stereoselective reactions in combination with the use of
stereochemically pure starting materials.
Of particular interest are formulations comprising sulfonylurea salts of the
formula (Ia) in which
R1 is H or Me,
R2 is (C1-C3)-alkyl or (C1-C3)-haloalkyl, in particular Me and Et,
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R3 is (C1-C3)-alkyl or (C1-C3)-haloalkyl, in particular Me and Et,
R4 is (C1-C6)-alkyl or (C1-C6)-haloalkyl or (Cl-C6)-alkoxy, in particular
Me, Et, OMe, OEt or CF3,
R5 is H, halogen, such as F, Cl, Br or I, OMe, OEt, Me, CF3, where the
radicals R5 in the formula (III) which are different from hydrogen are
preferably located in the 5-position on the phenyl ring,
R6 and R 61 are identical or different C1-C6-alkyl radicals, preferably R6 =
Me, R6 = Me; R6 = Me, R = Et and R6 = Et, R6 = Et,
R7 is H, Me, Et, CF3, F, Cl, Br, I, N[(C1-C3)-alkyl]-R8, NH-R9,
CH2N[(C1-C3)-alkyl]-R10, CH2NH-R11, CH2CH2N[(Cl-C3)-alkyl]-R12,
CH2CH2NH-R13, where the radicals R7 in the formula (lVa) which are
different from hydrogen are preferably located in the 5-position on the
phenyl ring and the radicals R8 to R13 are H, (C1-C6)-alkyl, (C1-C6)-
haloalkyl, CHO, COO(C1-C6)-alkyl, COO(C1-C6)-haloalkyl, S02-(C1-C6)-
alkyl or S02-(C1-C6)-haloalkyl, CO-(C1-C6)-alkyl or CO-(C1-C6)-haloalkyl,
R is Me, Et, nPr, iPr, cPr, nBu, iBu, SBu, tBu, cBu, in particular Me or
Et,
R7 is H, Me, Et, CF3, F, Cl, Br, I, N[1C1-C3)-alkyl]-R8, NH-(C1-C3)-alkyl,
CH2N[(C1-C3)-alkyl]-R 0, CH2NH-R , CH2CH2N[(C1-C3)-alkyl]-R ,
CH2CH2NH-R1 , where the radicals R7 in the formula (lVb) which are
different from hydrogen are preferably located in the 5-position on the
phenyl ring and the radicals R8 and R10 to R13 are H, (C1-C6)-alkyl,
(C1-C6)-haloalkyl, CHO, COO(C1-C6)-alkyl, COO(C1-C6)-haloalkyl,
SO2-(C1-C6)-alkyl, SO2-(C1-C6)-haloalkyl, CO-(C1-C6)-alkyl or
CO-(C1-C6)-haloalkyl,
R is Me, Et, Pr, CH2CH2CF3, OMe, OEt, O Pr, OCH2CH2CI, F, CI,
COOMe, COOEt, COOnPr, COO'Pr, CONMe2, CONEt2, SO2Me, SO2Et,
SO2iPr, unsubstituted or substituted NH-(C1-C6)-alkyl-acyl, unsubstituted
or substituted NH-(C3-C7)-cycloalkyl, unsubstituted or substituted (C4-C8)-
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cycloalkylalkyl, unsubstituted or substituted N-(C3-C7)-cycloalkyl-aryl,
unsubstituted or substituted N-(C4-C8)-cycloalkylalkyl-acyl, preferably
N-(C1-C6)-alkyl-CHO, N-(C1-C6)-alkyl-CO-R, N-(C1-C6)-alkyl-SO2R,
NH-CHO, NH-CO-R, NHSO2R, where the radicals R are (C1-C6)-
(halo)alkyl, (C1-C6)-(halo)alkoxy, (C1-C3)-alkoxy-(C1-C6)-alkyl, (C1-C3)-
alkoxy-(C 1-C6)-alkoxy or mono- and di-(C1-C6)-alkylamino,
7"
R is H, F, Cl, Me, Et, CF3, OCH3, OEt, OCH2CF3, preferably H,
M+ is [SR18R19R20]+ or [PR21 R22R23R24 ]+, where
R18 to R25 are identical or different from one another and are substituted or
unsubstituted (C1-C30)-alkyl, substituted or unsubstituted (C1-C1o)-alkyl-
(hetero)aryl, substituted or unsubstituted (C3-C30)-(oligo)alkenyl,
substituted or unsubstituted (C3-C10)-(oligo)alkenyl-(hetero)aryl,
substituted or unsubstituted (C3-C30)-(oligo)alkynyl, substituted or
unsubstituted (C3-C10)-(oligo)alkynyl-(hetero)aryl, substituted or
unsubstituted (hetero)aryl and where two radicals R18/R19, R21/R22 and
R23/R24 together may form an unsubstituted or substituted ring,
X is Me, Et, Pr, 'Pr, CF3, CC13, OMe, OEt, O'Pr, OCHCI2, OCH2CC13,
OCH2CF3, F, Cl, Br, SMe, SEt, NHMe, NMe2, NHEt, preferably OMe, OEt,
Me, Cl
Y is Me, Et, Pr, 'Pr, CF3, CCI3, OMe, OEt, O'Pr, OCHCI2, OCH2CCI3,
OCH2CF3, F, Cl, Br, SMe, SEt, NHMe, NMe2, NHEt, preferably OMe, OEt,
Me, Cl
and
Z is CH or N.
Suitable cations M include cyclic cations of the formula
[SR18R19R20]+ or [PR21 R22R23R24]+
in which two radicals R18/R19, R21/R22 or R23/R24 together form an
unsubstituted or substituted ring.
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WO 00/44227 10 PCT/EPOO/00469
R18/R19 together with the charge-bearing sulfur atom can, for example,
form a heterocyclic ring, such as, for example, shown in formulae X-XII
0
O(~+
Q
S s
R20 I I -
R20 R20
(X) (XI) (XII)
or
R21/R22 together with the charge-bearing phosphorus atom form a
heterocyclic ring, such as, for example, shown in formulae Xa-Xlla
0
G
P P P
R23 R24 R23 R24 R23 R24
(Xa) (XIa) (XIIa)
Particular preference is given to cations M+ in which
R18 to R24 are identical or different from one another and are (C1-C22)-
alkyl, unsubstituted or substituted by one or more radicals selected from
the group consisting of (C1-C5)-alkyl, (C1-C5)-alkoxy, (C1-C5)-haloalkoxy,
halogen, such as fluorine, chlorine, bromine and iodine, O-(CH2-CH2-O)XH,
O-(CH2-CH2-0)x-(C1-C3)-alkyl, O-(CH2-CH2-0)x-(CO)-(C1-C3)-alkyl or
0-(CH2-CH2-O)x-(CO)-(C1-C3)-alkoxy,
phenyl, unsubstituted or substituted by one or more radicals selected from
the group consisting of (C1-C5)-alkyl, (C1-C5)-alkoxy, (C1-C5)-haloalkoxy,
halogen, such as fluorine, chlorine, bromine and iodine, O-(CH2-CH2-O)XH,
O-(CH2-CH2-0)x-(C1-C3)-alkyl, O-(CH2-CH2-0)x-(CO)-(C1-C3)-alkyl,
O-(CH2-CH2-O)X(CO)-(C1-C3)-alkoxy, C1-C10-alkyl, which may likewise be
substituted by one of the radicals O-(CH2-CH2)X-OH, O-(CH2-CH2)X-
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WO 00/44227 11 PCT/EPOO/00469
O-(C1-C3)-alkyl, O-(CH2-CH2-0)x-(CO)-(CI-C3)-alkyl or O-(CH2-CH2-O)x-
(CO)-(C 1-C3)-alkoxy,
(C3-C22)-alkenyl, unsubstituted or substituted by one or more radicals
selected from the group consisting of (C1-C5)-alkyl, (C1-C5)-alkoxy, (Ct-
C5)-haloalkoxy, halogen, such as fluorine, chlorine, bromine and iodine, 0-
(CH2-CH2-O)xH, O-(CH2-CH2-O)x-(Cj-C3)-alkyl, O-(CH2-CH2-O)x-(CO)-
(C1-C3)-alkyl or O-(CH2-CH2-0)x-(CO)-(Cl-C3)-alkoxy, where the alkenyl
radical is mono- or polyunsaturated and preferably carries from one to
three double bonds,
(C3-C22)-alkynyl, unsubstituted or substituted by one or more radicals
selected from the group consisting of (Ci-C5)-alkyl, (C1-C5)-alkoxy,
(C1-C5)-haloalkoxy, halogen, such as fluorine, chlorine, bromine and
iodine, O-(CH2-CH2-O)XH, O-(CH2-CH2-0)x-(CI-C3)-alkyl, 0-(CH2-CH2)x-
(CO)-(C1-C3)-alkyl or O-(CH2-CH2-0)x-(CO)-(Cl-C3)-alkoxy, where the
alkynyl radical is mono- or polyunsaturated, and preferably carries from one
to three triple bonds,
where x is an integer of from 1 to 40.
The abovementioned sulfonylurea salts, preferably those of the
formula (la), in combination with auxiliaries and additives, are suitable for
preparing formulations, in particular for preparing EC formulations.
The following are examples of possible formulations: wettable powders
(WP), water-soluble powders (SP), water-soluble concentrates,
emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and
water-in-oil emulsions, sprayable solutions, suspension concentrates (SC),
oil- or water-based dispersions, solutions which are miscible with oils,
capsule suspensions (CS), dusts (DP), seed-dressing products, granules
for broadcasting and soil application, granules (GR) in the form of
microgranules, spray granules, coated granules and adsorption granules,
water-dispersible granules (WG), water-soluble granules (SG), ULV
formulations, microcapsules and waxes.
These individual types of formulation are known in principle and are
described, for example, in: Winnacker-Kuchler, "Chemische Technologic"
[Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986,
Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y.,
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WO 00/44227 12 PCT/EP00/00469
1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin
Ltd. London.
Formulation auxiliaries such as inert materials, surfactants, solvents and
other additives are also known and are described, for example, in: Watkins,
"Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland
Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry";
2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide"; 2nd Ed.,
Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers
Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia
of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt,
"Grenzflachenaktive Athylenoxidaddukte" [Surface-active ethylene oxide
adducts], Wiss. Verlagsgesell., Stuttgart 1976;
Winnacker-Kuchler, "Chemische Technologie" [Chemical Technology],
Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986.
Based on these formulations, it is also possible to prepare combinations
with other pesticidally active substances, such as, for example,
insecticides, acaricides, herbicides, fungicides, and also with safeners,
such as ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-
2-pyrazoline-3-carboxylate (Mefenpyr) or ethyl 5,5-diphenyl-2-isoxazoline-
carboxylate, fertilizers and/or growth regulators, for example in the form of
a ready mix or a tank mix.
Wettable powders are preparations which are. uniformly dispersible in water
and which, besides the active substance, also comprise ionic and/or
nonionic surfactants (wetting agents, dispersants), for example poly-
ethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated
fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates,
alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthyl-
methane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or else
sodium oleoylmethyltaurinate, in addition to a diluent or inert substance. To
prepare the wettable powders, the herbicidally active substances are
ground finely, for example in customary equipment such as hammer mills,
blower mills and air-jet mills, and simultaneously or subsequently mixed
with the formulation auxiliaries.
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WO 00/44227 13 PCT/EPOO/00469
Emulsifiable concentrates are prepared, for example, by dissolving the
active substance in an organic solvent, for example butanol, cyclo-
hexanone, dimethylformamide, xylene, or else higher-boiling aromatics or
hydrocarbons or mixtures of the organic solvents with the addition of one or
more ionic and/or nonionic surfactants (emulsifiers). Examples of
emulsifiers which can be used are: calcium salts of alkylarylsulfonic acids
such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as
alkylaryl polyglycol ethers which are different than para-alkyl phenol
ethoxylates, fatty acid polyglycol esters, fatty alcohol polyglycol ethers,
propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan
esters, for example sorbitan fatty acid esters or polyoxyethylene sorbitan
esters, for example polyoxyethylene sorbitan fatty acid esters.
Dusts are obtained by grinding the active substance with finely divided solid
substances, for example talc, natural clays such as kaolin, bentonite and
pyrophyllite, or diatomaceous earth.
Suspension concentrates can be water- or oil-based. They can be
prepared, for example, by wet grinding using commercially available bead
mills with an optional addition of surfactants such as have already been
mentioned above for example in the case of the other types of formulation.
Emulsions, for example oil-in-water emulsions (EW), can be prepared for
example by means of stirrers, colloid mills and/or static mixers using
aqueous organic solvents and, if appropriate, surfactants such as have
already been mentioned above for example in the case of the other types
of formulation.
Granules can be prepared either by spraying the active substance onto
adsorptive granulated inert material or by applying active substance
concentrates to the surface of carriers such as sand, kaolinites or of
granulated inert material by means of binders, for example sugar and
pentoses and hexoses or else mineral oils. Suitable active substances can
also be granulated in the manner which is conventional for the production
of fertilizer granules, if desired as a mixture with fertilizers.
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WO 00/44227 14 PCT/EPOO/00469
Water-dispersible granules are generally prepared by the customary
processes such as spray drying, fluidized-bed granulation, disk granulation,
mixing with high-speed mixers and extrusion without solid inert material.
For the preparation of disk, fluidized-bed, extruder and spray granules, see,
for example, the processes in "Spray-Drying Handbook" 3rd ed. 1979, G.
Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and
Engineering 1967, pages 147 et seq.; "Perry's Chemical Engineer's
Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
For further details on the formulation of crop protection products see, for
example, G.C. Klingman, "Weed Control as a Science", John Wiley and
Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans,
"Weed Control Handbook", 5th Ed., Blackwell Scientific Publications,
Oxford, 1968, pages 101-103.
In addition, the abovementioned formulations of active substances
comprise, if appropriate, the adhesives, wetting agents, dispersants,
emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers,
carriers, colorants, antifoams, evaporation inhibitors and pH and viscosity
regulators which are customary in each case.
Novel and also part of the subject matter of this invention is the use of the
auxiliaries of the formula (XVIII) as formulation auxiliaries for agrochemical
formulations and their use in the synthesis of salts of agrochemically active
compounds having acidic proton(s).
R-O(EO)w(PO)X(EO)y(PO)ze M
(XVIII)
The auxiliaries of the formula (XVIII) can be used as a pure substance or in
the form of a solid or liquid mixture. In the formula (XVIII), the indices w,
x,
y and z can, independently of one another, be an integer of from 0 to 50,
preferably from 0 to 20, particularly preferably from 1 to 20. The radical R
is
an unsubstituted or substituted C8-C40-hydrocarbon radical, for example a
C8-C40-alkyl radical. This can be saturated or unsaturated, linear or
branched. Suitable substituents are, for example, F, Cl, Br or I or a hydroxyl
CA 02360624 2001-07-26
WO 00/44227 15 PCT/EP00/00469
or amino group. This definition also includes substitution of a carbon atom
of the alkyl chain by one or more oxygen or nitrogen atoms. M is a
phosphonium or sulfonium ion or a metal cation, such as, for example, an
alkali metal ion, such as a sodium or potassium ion. EO is an ethoxy unit
and PO is a propoxy unit.
Components which can be used in combination with the sulfonylurea salts
in the formulations according to the invention are, for example, known
active substances as they are described, for example, in Weed
Research 26, 441-445 (1986), or "The Pesticide Manual", 11th edition, The
British Crop Protection Council and the Royal Soc. of Chemistry, 1997, and
the literature cited therein. Examples of active substances which may be
mentioned as herbicides which are known and which can be combined with
the sulfonylurea salts are the following (note: either the common names in
accordance with the International Organization for Standardization (ISO) or
the chemical names, if appropriate together with a customary code number,
of the compounds are given):
acetochlor; acifluorfen; aclonifen; AKH 7088, i.e. [[[1-[5-[2-chloro-4-(tri-
fluoromethyl)phenoxy]-2-n itrophenyl]-2-methoxyethylidene]amino]oxy]-
acetic acid and its methyl ester; alachlor; alloxydim; ametryn;
amidosulfuron; amitrol; AMS, i.e. ammonium sulfamate; anilofos; asulam;
atrazine; azafenidin; azimsulfurone (DPX-A8947); aziprotryn; barban;
BAS 516 H, i.e. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; BAS 620 H;
BAS 65400H; BAY FOE 5043; benazolin; benfluralin; benfuresate;
bensulfuron-methyl; bensulide; bentazone; benzofenap; benzofluor;
benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bispyribac-Na;
bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos;
busoxinone; butachior; butamifos; butenachior; buthidazole; butralin;
butroxydim; butylate; cafenstrole (CH-900); caloxydim; carbetamide;
carfentrazone-ethyl; CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamide;
CDEC, i.e. 2-chloroallyl diethyldithiocarbamate; chlomethoxyfen;
chloramben; chlorazifop-butyl; chlorbromuron; chlorbufam; chlorfenac;
chlorflurecol-methyl; chloridazon; chlorimuron-ethyl; chlornitrofen;
chlorotoluron; chlorouron; chiorpropham; chlorsulfuron; chlorthal-dimethyl;
chlorthiamid; cinmethylin; cinosulfuron; clethodim; clodinafop and its ester
derivatives (for example clodinafop-propargyl); clomazone; clomeprop;
cloproxydim; clopyralid; cloransulam-methyl; cumyluron (JC 940);
cyanazine; cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron;
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WO 00/44227 16 PCT/EPOO/00469
cyhalofop and its ester derivatives (for example butyl ester, DEH-112);
cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB; dalapon;
desmedipham; desmetryn; di-allate; dicamba; dichlobenil; dichlorprop;
diclofop and its esters, such as diclofop-methyl; diclosulam, i.e.
N-(2,6-dichlorophenyl)-5-ethoxy-7-fluoro-[1,2,4]triazolo[1,5-c]pyrimidine-2-
sulfonamide; diethatyl; difenoxuron; difenzoquat; diflufenican; diflufenzopyr
(BAS 654 00H), dimefuron; dimethachlor; dimethametryn; dimethenamid
(SAN-582H); dimethazone, clomazon; dimethipin; dimetrasulfuron,
dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr;
diuron; DNOC; eglinazine-ethyl; EL 77, i.e. 5-cyano-1-(1,1-dimethylethyl)-
N-methyl-1 H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb;
ethalfluralin; ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate;
F5231, i.e. N-[2-ch loro-4-fl u oro-5-[4-(3-fl u oro pro pyl)-4,5-d i hyd ro-5-
oxo-
1H-tetrazol-1-yl]phenyl]ethanesulfonamide; ethoxyfen and its esters (for
example ethyl ester, HN-252); etobenzanid (HW 52); fenoprop; fenoxan,
fenoxaprop and fenoxaprop-P and their esters, for example fenoxaprop-P-
ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl;
flazasulfuron; fluazifop and fluazifop-P and their esters, for example
fluazifop-butyl and fluazifop-P-butyl; fluchloralin; flumetsulam; flumeturon;
flumiclorac and its esters (for example pentyl ester, S-23031); flumioxazin
(S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-
ethyl; flupropacil (UBIC-4243); flupyrsulfuron-methyl-sodium; fluridone;
flurochloridone; fluroxypyr; flurtamone; fluthiacet-methyl; fomesafen;
fosamine; furyloxyfen; glufosinate; glyphosate; halosafen; halosulfuron and
its esters (for example methyl ester, NC-319); haloxyfop and its esters;
haloxyfop-P (= R-haloxyfop) and its esters; hexazinone;
imazamethabenz-methyl; imazamox; imazapyr; imazaquin and salts, such
as the ammonium salt; imazethamethapyr; imazethapyr; imazosulfuron;
indanofan (MK-243), ioxynil; isocarbamid; isopropalin; isoproturon; isouron;
isoxaben; iodosulfuron, isoxaflutole; isoxapyrifop; karbutilate; lactofen;
lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidid;
metamitron; metazachlor; methabenzthiazuron; metham; methazole;
methoxyphenone; methyldymron; metobenzuron; metobromuron;
metolachlor; metosulam (XRD 511); metoxuron; metribuzin;
metsulfuron-methyl; MH; molinate; monalide; monocarbamide
dihydrogensulfate; monolinuron; monuron; MT 128, i.e. 6-chloro-
N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e.
N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide; naproanilide;
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WO 00/44227 17 PCT/EPOO/00469
napropamide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-
5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin;
nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl
(RP-020630); oxadiazon; oxasulfuron; oxazidomefone (MY-100);
oxyfluorfen; paraquat; pebulate; pendimethalin; pentoxazone (KPP-314);
perfluidone; phenisopham; phenmedipham; picloram; piperophos;
piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine;
prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn;
propachlor; propanil; propaquizafop and its esters; propazine; propham;
propisochlor; propyzamide; prosulfalin; prosulfocarb; prosuifuron
(CGA-1 52005); prynachlor; pyroflufen-ethyl; pyrazolinate; pyrazon;
pyrazosulfuron-ethyl; pyrazoxyfen; pyribenzoxim (LGC-40836);
pyributicarb; pyridate; pyriminobac-methyl; pyrithiobac (KIH-2031);
pyroxofop and its esters (for example propargyl ester); quinclorac;
quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P
and their ester derivates, for example quizalofop-ethyl; quizalofop-P-tefuryl
and -ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, i.e. 2-[4-chloro-
2-fluoro-5-(2-propynyloxy)phenyl]-4,5,6,7-tetrahydro-2H-indazole; sec-
bumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, i.e.
2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]propanoic
acid and its methyl ester; sulcotrione; sulfentrazone (FMC-97285, F-6285);
sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224); sulfosulfuron; TCA;
tebutam (GCP-5544); tebuthiuron; terbacil; terbucarb; terbuchlor;
terbumeton; terbuthylazine; terbutryn; TFH 450, i.e. N,N-diethyl-3-[(2-ethyl-
6-m ethyl phenyl)sulfonyl]-1 H-1,2,4-triazole-1-carboxamide; thenylchlor
(NSK-850); thiazafluron; thiazopyr (Mon-13200); thidiazimine (SN-24085);
thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate;
trisulfuron; triaziflam; triazofenamide; tribenuron-methyl; triclopyr;
tridiphane; trietazine; trifluralin; triflusulfuron and esters (for example
methyl
ester, DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, i.e.
5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1 H-tetrazole; JTC-101; UBH-509;
D-489; LS 82-556; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-
0774; DOWCO-535; DK-8910; V-53482; PP-600; MBH-001; KIH-9201; ET-
751; KIH-6127 and KIH-2023.
For use, the formulations, which are in commercially available form, are, if
appropriate, diluted in the customary manner, for example using water in
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WO 00/44227 18 PCT/EPOO/00469
the case of wettable powders, emulsifiable concentrates, dispersions and
water-dispersible granules.
In general, the formulations according to the invention comprise 0.1 to 99%
by weight, in particular 0.1 to 95% by weight, of active substance,
preferably a sulfonylurea salt of the formula (la). The active substance
concentration in wettable powders is, for example, approximately 10 to
90% by weight, the remainder to 100% by weight being composed of
customary formulation components. In the case of emulsifiable
concentrates, the active substance concentration may amount to
approximately 1 to 90, preferably 5 to 80, % by weight. Formulations in the
form of dusts comprise 1 to 30% by weight of active substance, in most
cases preferably 5 to 20% by weight of active substance, and sprayable
solutions comprise approximately 0.05 to 80, preferably 2 to 50, % by
weight of active substance. The active substance content of water-
dispersible granules depends partly on whether the active compound is in
liquid or solid form and on which granulation auxiliariesõ fillers and the
like
are being used. The active substance content of the water-dispersible
granules amounts to, for example, between 1 and 95% by weight,
preferably between 10 and 80% by weight.
Formulations in the form of dusts, granules for soil application or for
broadcasting and sprayable solutions are conventionally not diluted any
more with inert substances prior to use.
The proportion of sulfonylurea salts in the EC formulations according to the
invention is generally 0.01-70% by weight, preferably 0.1-70% by weight,
particularly preferably 0.1-50% by weight. In addition, the formulations can
comprise further agrochemicals from the field of crop protection - for
example herbicides, fungicides, insecticides, growth regulators, safeners or
fertilizers - in an amount of from 0 to 70% by weight. They can also
comprise from 1 to 40% by weight, preferably 2-40% by weight, of a
surfactant system. The surfactant system can be composed, for example,
of
a) one or more nonionic surfactants,
b) one or more betainic surfactants,
c) one or more anionic surfactants,
d) one or more cationic surfactants,
CA 02360624 2009-02-18
28976-184
19
or
e) a mixture of the surfactants mentioned under a)-d).
The EC formulations can comprise from 0 to 95% by weight, preferably
from 5 to 95% by weight, of a solvent system. Suitable solvent systems are,
for example,
a) a nonpolar solvent, for example aromatic hydrocarbons such as
Solvesso , esters of long-chain saturated or unsaturated (fatty)
acids and/or alcohols, such as, for example, rapeseed oil methyl
ester, or a mixture of nonpolar solvents
b) a polar protic or aprotic solvent, for example gamma-butyrolactone,
propylene carbonate, propionitrile or methanol, ethanol, or else
mixtures thereof
or
c) mixtures of the solvent systems mentioned above under a) and b).
In addition, the EC formulations according to the invention may optionally
comprise 3-90% by weight of a wetting agent, which may have
bioactivating properties, or else a mixture of different wetting agents, which
may have bioactivating properties.
The formulations may optionally comprise further stabilizing compounds,
for example pH-stabilizing reagents (for example pH 5-9), substances
having antifoam properties, acid scavengers, water scavengers or
crystallization inhibitors.
A further embodiment of the formulations according to the invention is
characterized by the fact that it . is a dispersion, where the liquid
homogeneous phase is composed as described above and in which one or
more insoluble compounds are dispersed. The insoluble compounds can
be agrochemicals, such as, for example, herbicides, insecticides,
fungicides, safeners or fertilizers, or else formulation auxiliaries, such as,
for example, surfactants which are insoluble in the organic phase, such as,
for example, Netzer IS (from Clariant).
The EC formulations according to the invention are preferably
characterized by the fact that the proportion of sulfonfylurea salt, in
particular of the formula (la), or of the mixture of sulfonylurea salts is
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WO 00/44227 20 PCT/EPOO/00469
generally 0.1-70.0% by weight, preferably 0.1-50.0% by weight. Suitable
solvents are polar solvents, such as, for example, gamma-butyrolactone,
acetonitrile, propionitrile; their proportion is 5.0-95.0% by weight. To
obtain
a stable emulsion after addition to water, the finished EC product should
comprise a proportion by weight of 2.0-40.0% by weight of a mixture of one
anionic and one nonionic surfactant or a mixture of cationic and nonionic
surfactants. In addition, it is possible to add, if appropriate, other
components to the EC formulations: by adding 1.0-90.0% by weight of a
hydrophobic solvent, it is possible to modify the emulsion formation in
aqueous spray mixtures advantageously. Suitable solvent components are,
for example, rapeseed oil methyl ester, aromatic solvents such as, for
example, Solvesso, esters of long-chain acids and alcohols, or else
mixtures of hydrophobic solvents.
The EC formulations thus described may optionally comprise 3.0 - 90.0%
by weight of a wetting agent, which may have bioactivating properties, or of
a mixture of wetting agents.
Agrochemical combination preparations can be obtained by adding 20.0 -
50.0% by weight of agrochemically active compounds which are chemically
inert to sulfonylurea salts and readily soluble in the solvent systems which
are typical for the formulation type according to the invention. This is the
case for a large number of commercial agrochemicals. The formulations
according to the invention may optionally also comprise stabilizers which,
for example, stabilize the pH of the tank mix at between 6 and 8.
EC formulations according to the invention preferably have the following
composition:
1) the sulfonylurea salt content is generally 0.1 - 70.0% by weight,
preferably 0.1 - 50.0% by weight; the formulation may comprise one or
more active compounds
2) the formulation may optionally comprise between 0 and 50.0% by
weight of other agrochemicals (herbicides, insecticides, fungicides,
growth regulators, safeners, fertilizers),
3) 5.0 - 95.0% by weight of a polar solvent, such as, for example, gamma-
butyrolactone, acetonitrile, propionitrile, propylene carbonate, or else
mixtures thereof
4) optionally 1.0 - 90.0% by weight of a hydrophobic solvent, for example
rapeseed oil methyl ester, aromatic solvents, esters of long-chain acids
and alcohols
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WO 00/44227 21 PCT/EPOO/00469
5) 2.0 - 40.0% by weight of a mixture of anionic and nonionic compounds
or
6) 2.0 - 40.0% by weight of a mixture of cationic and nonionic compounds
7) optionally 3.0 - 90.0% by weight of a wetting agent, which may have
bioactivating properties, or of a mixture of different wetting agents,
which may have bioactivating properties,
8) optionally other stabilizing agents - for example pH-stabilizing reagents
(pH between 6 and 8), substances having antifoam properties,
substances which can serve as acid scavengers, water scavengers or
crystallization inhibitors.
To prepare an EC formulation, it is possible to dissolve, for example, from
0.1 to 15.0% by weight of a sulfonylurea salt in from 15.0 to 25.0% by
weight of propylene carbonate and from 30.0 to 50.0% by weight of an
aromatic compound or a mixture of aromatic compounds (boiling range
219-282 C) with stirring at 20 C - 30 C.
After the sulfonylurea salt has been completely dissolved, from 5.0 to
15.0% by weight of the calcium or sodium salt of dodecylbenzenesulfonic
acid or of a salt mixture, from 5.0 to 15.0% by weight of a (C12-C18)-fatty
acid polyglycol ester 40 EO and from 15.0 to 20.0% by weight of a fatty
alcohol polyglycol ether are added with stirring to the solution.
If appropriate, a water scavenger, an acid scavenger, and antifoam or a
crystallization inhibitor may also be added.
The sulfonylurea salts comprised in the formulations according to the
invention, for example those of the formula (Ia) can be prepared from
known sulfonylureas or sulfonylurea metal salts, in particular alkali metal
salts (see, for example, EP-A-30138, EP-A-7687), or else from sulfonamide
salts, for example by the following routes:
1) Deprotonation of neutral sulfonylureas, for example of the
formula (XIII), with a suitable base of the formula M+B- (Eq. 1), where
B is, for example, hydroxyl or alkoxy anions, such as methoxy, ethoxy,
npropoxy, 'propoxy, nbutoxy or tbutoxy, or anions of formulation
auxiliaries which carry at least one OH group, for example alkoxides,
which can be alkoxylated, for example ethoxylated or propoxylated,
such as CBH17(OCH2CH2)Oe, and where M+ is a phosphonium or
sulfonium ion.
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WO 00/44227 22 PCT/EPOO/00469
Y M (D
Y
N + M
R~-S02-NH-CO-NRI~ Z HB Ra SOZ N-CONR1 OZ (1)
HB
N
N
x (Ia) X
(XIII)
To this end, the sulfonylurea, for example of the formula (XIII), is
dissolved or suspended in an inert solvent or solvent mixture and
reacted with one equivalent of M+B at temperatures between -20 C
and 100 C, preferably between -10 C and 50 C.
2) Cation exchange of metal salts of sulfonylureas, for example of the
formula (XIV), in which Met is a metal cation, preferably an alkali
metal ion, such as Na+ or K+, with suitable reagents of the formula
M+X' (Eq. 2), where M+' is a phosphonium or sulfonium ion and X'- is
an anion, for example a halide anion, such as F , Cl or Br, or a
phosphate, sulfate or carboxylate anion, where this definition includes
inorganic and organic salts, as are customarily used, for example, in
surfactant chemistry (for example organic phosphate anions,
phosphonate anions, sulfate anions, sulfonate anions, carboxylates).
Metes MQ
Y Y
O N N ~~(
Ra-SO2N-CO-NR1 --<O Z MeMX~' R-SO2OCONR' O Z (2)
(XIV) ~X N~X
(la)
To this end, the metal salts, for example alkali metal salts (for example
Mete = Na, K+), which are known from the literature or prepared in a
manner known from the literature, of the corresponding sulfonylureas
are dissolved in an inert solvent or solvent mixture and reacted with
one equivalent of the reagent M+X'-. After the reaction has ended, the
salt, for example the alkali metal salt (such as NaCl), which is obtained
as a by-product, can be removed by filtration.
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WO 00/44227 23 PCT/EPOO/00469
3) In situ deprotonation and cation exchange (Eq. 3), starting from neutral
sulfonylureas, for example of the formula (XIII), with suitable reagents
a) of the formula M+X' , where M+ is a phosphonium or sulfonium ion
and X is an anion, for example a halide anion, such as F , Cl or Br,
or a phosphate, sulfate or carboxylate anion, where this definition
includes inorganic and organic salts, as are customarily used, for
example, in surfactant chemistry (for example organic phosphate
anions, phosphonate anions, sulfate anions, sulfonate anions,
carboxylates) and b) of the formula MetB, where Met is a metal cation,
in particular an alkali metal cation, such as Na+ or K+, and B is a
suitable base, for example a hydroxy or alkoxy anion, such as
methoxy, ethoxy, npropoxy, 'propoxy or nbutoxy.
MO
Y + Y
+MX O N-~
R1SOZ-NH-CO-NR' O Z R-SOZ-N-CONR1 O Z (3)
- McUC
(X111) X -HB N ~ X
(la)
To this end, the sulfonylurea is dissolved in an inert solvent or solvent
mixture and reacted with one equivalent each of the reagents M+X'
and MetB. After the reaction has ended, the metal salt, in particular
alkali metal salt (for example NaCI) which is obtained as a by-product,
can be removed by filtration.
4) Reaction of a sulfonamide salt, for example of the formula XV, with
an isocyanate, for example of the formula XVI (Eq. 4).
Y
Y M N' (30
N a Z
---- R S02-N-CONH N"j~ x (4)
R SO2-NHM + O_C =N O Z i
(XV) (XVI) N (Ia)
X
The reaction is carried out in an inert solvent or solvent mixture -
such as, for example, tetrahydrofuran (THF) - at temperatures
between -20 C and 100 C, preferably between -10 C and 70 C, by
CA 02360624 2001-07-26
WO 00/44227 24 PCT/EPOO/00469
reacting equimolar amounts of the isocyanate, for example of the
formula XVI, with the sulfonamide salt, for example of the
formula XV. The sulfonamide salt, for example of the formula XV,
can be employed directly or formed in situ - for example by reacting
the corresponding sulfonamide with a suitable base M+X , where M+
is a phosphonium or sulfonium ion and X is, for example, a hydroxy
or alkoxy anion. Isocyanates, for example of the formula XVI, are
well known from the literature. These reactions always lead to
compounds in which R1 is hydrogen.
5) Reaction of a sulfonamide salt, for example of the formula XV, with a
carbamate, for example of the formula XVII (Eq. 5).
MO
Y Y
OO+ /N 0 N ~:~
Ra_SO2NHM +ArO-CO-NR' -{ O Z A., Ra-SO2-N-CONR1 O z (5) --~ N~ ArOH N
()(V) (XVII) X
X
(la)
The reaction is carried out in an inert solvent (or solvent mixture) - such as
tetrahydrofuran - at temperatures between -20 C and 100 C, preferably
between -10 C and 70 C, by reacting equimolar amounts of the
carbamate, for example of the formula XVII, with the sulfonamide salt, for
example of the formula XV. The sulfonamide salt, for example of the
formula XV, can be employed directly or formed in situ - for example by
reacting the corresponding sulfonamide with a suitable base MX , where
M is a phosphonium or sulfonium ion and X is, for example, a hydroxy or
alkoxy anion. Carbamates, for example of the formula XVII, are well known
from the literature. In the formula XVII, Ar is a substituted or unsubstituted
aromatic radical, such as phenyl or 2,4-dichlorophenyl.
This reaction is carried out at temperatures of from -20 C to +100 C,
preferably between -10 C and 50 C, in inert solvents, such as, for example,
THF, CH2CI2 or MeOH or solvent mixtures.
The definitions used in the Preparation Processes 1) to 5) have - unless
indicated otherwise - the same meaning as given above for the formulae la
and lb.
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WO 00/44227 25 PCT/EPOO/00469
Inert solvents means that the solvents or solvent mixtures used are
chemically inert under the reaction conditions mentioned.
Using the Preparation Processes 1) to 5), it is possible to prepare and
isolate the sulfonylurea salts in a simple manner. Alternatively, the
sulfonylurea salts can also be prepared by Processes 1), 2) and 3) even
during the formulation process.
The preparation processes of the compounds of the formula (Ia) according
to the invention are likewise novel and also form part of the subject matter
of this invention.
The preparation processes mentioned above can be used to prepare, for
example, the compounds listed in the tables below.
Compounds of the formula (A) below are listed in Table 1:
R3 MO Y
C) N
R2-SO2-N-SO2-N-CO-NR' --~ 0 Z
N
X
(A)
Table 1
Ex. R1 R2 R3 M X Y Z
1 H Me Me S6Me3 OMe OMe CH
2 H Me Me SePh3 OMe OMe CH
3 H Me Me P'Ph4 OMe OMe CH
4 H Me Me PPh3CH2Ph OMe OMe CH
5 H Me Me PPh3Me OMe OMe CH
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WO 00/44227 26 PCT/EPOO/00469
Compounds of the formula (B) below are listed in Table 2:
R4
0 M+(D Y
o N-{\
R5 OSOZ~ICONR: O Z
N -^/
(8) X
Table 2
Ex. R1 R4 R5 M X Y Z
1 H OEt H SMe3 OMe OMe CH
2 H OEt H SPh3 OMe OMe CH
3 H OEt H PPh4 OMe OMe CH
4 H OEt H PPh3Me(' OMe OMe CH
Compounds of the formula (C) below are listed in Table 3:
CONR6R6' +(D Y
O M N--{
O
R7 SOZNCONR' O Z
(C) Nc
X
Table 3
Ex. R1 NR6R6 R7 M X Y Z
1 H NMe2 NHCOOMe SMe3 OMe OMe CH
2 H NMe2 NHCOOMe SPh3 OMe OMe CH
3 H NMe2 NHCOOMe PPh4(D OMe OMe CH
4 H NMe2 NHCOOMe PPh3Me OMe OMe CH
5 H NMe2 NHCHO SMe3 OMe OMe CH
6 H NMe2 NHCHO SPh3 OMe OMe CH
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WO 00/44227 27 PCT/EPOO/00469
Ex. R1 NR6R6 R7 M(D X Y Z
7 H NMe2 NHCHO PPh4 OMe OMe CH
8 H NMe2 NHCHO PPh3Me OMe OMe CH
9 H NMe2 NHCOCH3 SMe3 OMe OMe CH
H NMe2 NHCOCH3 SPh3(D OMe OMe CH
11 H NMe2 NHCOCH3 PPh4 OMe OMe CH
12 H NMe2 NHCOCH3 PPh3Me OMe OMe CH
Compounds of the formula (D) below are listed in Table 4:
Y
COOR6"
O MO N Z
R7' S02NCONR' N
X
5 (D)
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WO 00/44227 28 PCT/EPOO/00469
Table 4
Ex. R1 R6 R7 M X Y Z
1 H Me I SMe3 Me OMe N
2 H Me I SPh3(D Me OMe N
3 H Me I PPh4 Me OMe N
4 H Me I PPh3Me(D Me OMe N
H Me CH2NH SMe3 OMe OMe CH
CHO
6 H Me CH2NH SPh3 OMe OMe CH
CHO
7 H Me CH2NH PPh4 OMe OMe CH
CHO
8 H Me CH2NH PPh3Me OMe OMe CH
CHO
9 H Me CH2NH- SMe3 OMe OMe CH
COOMe
H Me CH2NH- SPh3 OMe OMe CH
COOMe
11 H Me CH2NH- PPh4 OMe OMe CH
COOMe
12 H Me CH2NH- PPh3Me OMe OMe CH
COOMe
13 H Me CH2NH- SMe3 OMe OMe CH
S02Me
14 H Me CH2NH- SPh3 OMe OMe CH
S02Me
H Me CH2NH- PPh4 OMe OMe CH
S02Me
16 H Me CH2NH- PPh3Me OMe OMe CH
S02Me
17 H Me CH2N SMe3 OMe OMe CH
McS02Me
18 H Me CH2N SPh3 OMe OMe CH
McS02Me
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WO 00/44227 29 PCT/EPOO/00469
Ex. R1 R6 R7- M X Y Z
19 H Me CH2N PPh4 OMe OMe CH
McS02Me
20 H Me CH2N PPh3Me OMe OMe CH
McS02Me
21 H Me I SMe3 OMe OMe N
22 H Me I SPh3(D OMe OMe N
23 H Me I PPh4 OMe OMe N
24 H Me I PPh3Me OMe OMe N
25 Me Me H SMe3 OMe Me N
26 Me Me H SPh3 OMe Me N
27 Me Me H PPh4 OMe Me N
28 Me Me H PPh3Me OMe Me N
29 H Me H SMe3 OMe Me N
30 H Me H SPh3 OMe Me N
31 H Me H PPh4 OMe Me N
32 H Me H PPh3Me OMe Me N
33 H Me F SMe3 OMe Me N
34 H Me F SPh3 OMe Me N
35 H Me F PPh4 OMe Me N
36 H Me F PPh3Me OMe Me N
37 H Me CI SMe3 OMe Me N
38 H Me CI SPh3 OMe Me N
39 H Me CI PPh4 OMe Me N
40 H Me CI Ph3Me Ome Me N
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WO 00/44227 30 PCT/EPOO/00469
Compounds of the formula (E) below are listed in Table 5:
R61" +
MO Y
0 N
R" N S02NCONR1 Z
N
X
(E)
Table 5
Ex. R1 R6 R7 M X Y Z
1 H Me Cf PPh3Me OMe Me N
2 H NMeS02Me H SMe3 OMe OMe CH
3 H NMeS02Me H SPh3 OMe OMe CH
4 H NMeS02Me H PPh4 OMe OMe CH
5 H NMeS02Me H PPh3Me OMe OMe CH
6 H NHSO2Me H SMe3 OMe OMe CH
7 H NHS02Me H SPh3 OMe OMe CH
8 H NHS02Me H PPh4 OMe OMe CH
9 H NHS02Me H PPh3Me OMe OMe CH
H NEtCOCH3 H SMe3 OMe OMe CH
11 H NEtCOCH3 H SPh3 OMe OMe CH
12 H NEtCOCH3 H PPh4 OMe OMe CH
13 H NEtCOCH3 H PPh3Me OMe OMe CH
14 H NEtCHO H SMe3 OMe OMe CH
H NEtCHO H SPh3 OMe OMe CH
16 H NEtCHO H PPh4 OMe OMe CH
17 H NEtCHO H PPh3Me OMe OMe CH
18 H NnPrCHO H SMe3 OMe OMe CH
19 H NnPrCHO H SPh3 OMe OMe CH
H NnPrCHO H PPh4 OMe OMe CH
21 H NnPrCHO H PPh3Me We OMe CH
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WO 00/44227 31 PCT/EPOO/00469
The compounds of the formula (la) according to the invention and the
formulations according to the invention can be employed as herbicides
against a broad spectrum of economically important monocotyledonous
and dicotyledonous harmful plants. The active compounds also act
efficiently on perennial weeds which produce shoots from rhizomes, root
stocks or other perennial organs and which are difficult to control. In this
context, it is immaterial whether the substances are applied pre-sowing,
pre-emergence or post-emergence. Specifically, examples may be
mentioned of some representatives of the monocotyledonous and
dicotyledonous weed flora which can be controlled by the compounds
according to the invention, without these being restricted to certain species.
Examples of weed species on which the active compounds and
formulations act efficiently are, from amongst the monocotyledons, Avena,
Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and also
Cyperus species from the annual sector and from amongst the perennial
species Agropyron, Cynodon, Imperata and Sorghum, and also perennial
Cyperus species.
In the case of the dicotyledonous weed species, the spectrum of action
extends to species such as, for example, Galium, Viola, Veronica, Lamium,
Stellaria, Amaranthus, Sinapis, lpomoea, Matricaria, Abutilon and Sida
from amongst the annuals, and Convolvulus, Cirsium, Rumex and
Artemisia in the case of the perennial weeds.
The active compounds according to the invention also effect outstanding
control of harmful plants which occur under the specific conditions of rice
growing such as, for example, Echinochloa, Sagittaria, Alisma, Eleocharis,
Scirpus and Cyperus.
If the compounds according to the invention are applied to the soil surface
prior to germination, then the weed seedlings are either prevented
completely from emerging, or the weeds grow until they have reached the
cotyledon stage but then their growth stops, and, eventually, after three to
four weeks have elapsed, they die completely.
If the active compounds are applied post-emergence to the green parts of
the plants, growth also stops drastically a very short time after the
treatment and the weed plants remain at the developmental stage of the
point in time of application, or they die completely after a certain time, so
that in this manner competition by the weeds, which is harmful to the crop
plants, is eliminated at a very early point in time and in a sustained manner.
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WO 00/44227 32 PCT/EP00/00469
Although the compounds and formulations according to the invention have
an excellent herbicidal activity against monocotyledonous and
dicotyledonous weeds, crop plants of economically important crops such
as, for example, wheat, barley, rye, rice, corn, sugarbeet, cotton and soya,
are not damaged at all, or only to a negligible extent. For these reasons,
the present compounds are highly suitable for selectively controlling
undesired plant growth in plantings for agricultural use or in plantings of
ornamentals.
The substances and formulations according to the invention furthermore
have outstanding growth-regulating properties on crop plants. They
intervene in a regulatory manner in the endogenous metabolism of the
plant and can thus be employed for influencing plant contents in a
controlled manner and for facilitating harvesting, such as, for example, by
triggering desiccation and stunting growth. They are furthermore also
suitable for general control and inhibition of undesirable vegetative growth
without killing the plants at the same time. Inhibition of vegetative growth
plays a major role in many mono- and dicotyledonous crops, since lodging
can be reduced or completely prevented by this means.
Owing to their herbicidal and plant growth-regulatory properties, the active
compounds and formulations can also be employed for controlling harmful
plants in crops of known or still to be developed genetically engineered
plants. The transgenic plants generally have particularly advantageous
properties, for example resistance to certain pesticides, in particular
certain
herbicides, resistance to plant diseases or causative organisms of plant
diseases, such as certain insects or microorganisms such as fungi, bacteria
or viruses. Other particular properties relate, for example, to the quantity,
quality, storability, composition and to specific ingredients of the harvested
product. Thus, transgenic plants having an increased starch content or a
modified quality of the starch or those having a different fatty acid
composition of the harvested product are known.
The use of the compounds and formulations according to the invention in
economically important transgenic crops of useful and ornamental plants,
for example of cereal, such as wheat, barley, rye, oats, millet, rice, maniok
and corn, or else in crops of sugarbeet, cotton, soya, rapeseed, potato,
tomato, pea and other vegetable species is preferred.
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WO 00/44227 33 PCT/EPOO/00469
The formulations and compounds according to the invention can preferably
be used as herbicides in crops of useful plants which are resistant or which
have been made resistant by genetic engineering toward the phytotoxic
effects of the herbicides.
Conventional ways of preparing novel plants which have modified
properties compared to known plants comprise, for example, traditional
breeding methods and the generation of mutants. Alternatively, novel
plants having modified properties can be generated with the aid of genetic
engineering methods (see, for example, EP-A 0 221 044, EP-A 0 131 624).
For example, there have been described several cases of
genetically engineered changes in crop plants in order to modify the
starch synthesized in the plants (for example WO 92/11376,
WO 92/14827, WO 91/19806),
- transgenic crop plants which are resistant to certain herbicides of the
glufosinate-type (cf., for example, EP-A 0 242 236, EP-A 0 242 246)
or glyphosate-type (WO 92/00377), or of the sulfonylurea-type
(EP-A 0 257 993, US-A 5013659),
- transgenic crop plants, for example cotton, having the ability to
produce Bacillus thuringiensis toxins (Bt toxins) which impart to the
plants resistance to certain pests (EP-A 0 142 924,
EP-A 0 193 259),
- transgenic crop plants having a modified fatty acid composition
(WO 91/13972).
Numerous molecular-biological techniques which allow the preparation of
novel transgenic plants having modified properties are known in principle;
see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory
Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring
Harbor, NY; or Winnacker "Gene and Klone" [Genes and Clones], VCH
Weinheim, 2nd edition 1996, or Christou, "Trends in Plant Science" 1
(1996) 423-431).
In order to carry out such genetic engineering manipulations, it is possible
to introduce nucleic acid molecules into plasmids which allow a
mutagenesis or a change in the sequence to occur by recombination of
DNA sequences. Using the abovementioned standard processes it is
possible, for example, to exchange bases, to remove partial sequences or
CA 02360624 2001-07-26
WO 00/44227 34 PCT/EPOO/00469
to add natural or synthetic sequences. To link the DNA fragments with each
other, it is possible to attach adaptors or linkers to the fragments.
Plant cells having a reduced activity of a gene product can be prepared, for
example, by expressing at least one appropriate antisense-RNA, a sense-
RNA to achieve a cosuppression effect, or by expressing at least one
appropriately constructed ribozyme which specifically cleaves transcripts of
the abovementioned gene product.
To this end, it is possible to employ both DNA molecules which comprise
the entire coding sequence of a gene product including any flanking
sequences that may be present, and DNA molecules which comprise only
parts of the coding sequence, it being necessary for these parts to be long
enough to cause an antisense effect in the cells. It is also possible to use
DNA sequences which have a high degree of homology to the coding
sequences of a gene product but which are not entirely identical.
When expressing nucleic acid molecules in plants, the synthesized protein
can be localized in any desired compartment of the plant cells. However, to
achieve localization in a certain compartment, it is, for example, possible to
link the coding region with DNA sequences which ensure localization in a
certain compartment. Such sequences are known to the person skilled in
the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227;
Wolter et al., Proc. NatI. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et
al., Plant J. 1 (1991), 95-106).
The transgenic plant cells can be regenerated to whole plants using known
techniques. The transgenic plants can in principle be plants of any desired
plant species, i.e. both monocotyledonous and dicotyledonous plants.
In this manner, it is possible to obtain transgenic plants which have
modified properties by overexpression, suppression or inhibition of
homologous (= natural) genes or gene sequences or by expression of
heterologous (= foreign) genes or gene sequences.
The compounds and formulations according to the invention can preferably
be used in transgenic crops which are resistant to herbicides from the
CA 02360624 2001-07-26
WO 00/44227 35 PCT/EPOO/00469
group consisting of the sulfonylureas, glufosinate-ammonium or
glyphosate-isopropylammonium and analogous active compounds.
When using the active compounds according to the invention in transgenic
crops, in addition to the effects against harmful plants which can be
observed in other crops, there are frequently effects which are specific for
the application in the respective transgenic crop, for example a modified or
specifically broadened spectrum of weeds which can be controlled,
modified application rates which can be used for the application, preferably
good combinability with the herbicides to which the transgenic crop is
resistant, and an effect on the growth and the yield of the transgenic crop
plants.
The invention therefore also provides for the use of the formulations
according to the invention and the compounds of the formula (la) according
to the invention as herbicides or plant growth regulators.
The EC formulations according to the invention have the advantage that
they are generally very user-friendly and can be prepared at low costs.
Moreover, this formulation type in principle offers the possibility to prepare
combination preparations in a simple and cost-effective manner, provided
that the combination partner is soluble in the desired concentration in the
chosen organic solvent system and is chemically inert.
The formulations according to the invention, in particular the EC
formulations, have high chemical stability. Moreover, the formulations
according to the invention, in particular the EC formulations, can, in
addition to the chemical stability, also have "higher loading" (a higher
concentration) of the formulation of active compound salts. The
formulations according to the invention can furthermore be prepared both
as a liquid formulation (for example EC formulation) or as a solid
formulation (for example WP or WG formulation).
CA 02360624 2009-02-18
28976-184
36
Examples
Formulation examples
The formulations mentioned in Table I are obtained by initially charging the
solvent Dowanot PM at room temperature and admixing successively with
mechanical stirring the sulfonylurea component and the auxiliaries
mentioned.
The examples of Table I show that, using specific sulfonylurea salts, it is
possible to prepare stable EC formulations having an economically
attractive loading of active compound(s), in contrast to the corresponding
neutral sulfonylureas or their metal salts.
CA 02360624 2009-02-18
28976-184
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