HERBICIDAL COMPOSITONS COMPRISING TRIFLUOROME
THANESULFONANILIDES AND SAFENERS
The present invention relates to compositions comprising certain herbicidal
sulphonanilide derivatives and a safener and methods for protecting cultivated plants from
the damaging effects of the herbicidal sulphonanilide derivatives.
5 It is known that when herbicides are used to control the growth of undesired plants,
there may be some damage to the cultivated plants. The amount of damage will depend on a
number of factors but, in some cases, the cultivated plants can be protected from the effect of
the herbicide by using a compound termed a safener.
Accordingly, the present invention provides a composition for protecting crop plants
10 from the harmful effects of a sulphonanilide derivative herbicide of formula (I)
or a salt or N-oxide thereof wherein
R1 is H, C1.4alky1, C3-salkeny1, propargyl, C1. 4alkoxyC1-2 alky1, C1. 4alkoxyC1.
2alkoxyC1.2alky1, C1.4alkylthioC1.2alky1, arylCl -2alkyl optionally substituted by 1-3 groups
15 R20, heteroarylCl.2alkyl optionally substituted by 1-3 groups R20, phenylthioClaalkyl arylC1.
2alkoxyC1.2alkyl optionally substituted by 1-3 groups R20, Cl.5alkylcarbonyl, C2.
~alkenylcarbonylC, 1.4haloalkylcarbony1, C3.6cycloalkylcarbonyl, arylcarbonyl optionally
substituted by 1-3 groups R20, Cl-loalkoxycarbonyl; C1.4haloalkoxycarbonyl, C3.
~alkenyloxycarbonyl,p ropargyloxycarbonyl, C1. 4alkoxyC1.2 alkoxycarbonyl, C1.
20 4alkylthiocarbony1, aryloxycarbonyl optionally substituted by 1-3 groups R20, arylCl.
2alkoxycarbonyl optionally substituted by 1-3 groups R20, aminocarbonyl, C1.
4alkylaminocarbony1, di(C1.4alkyl)aminocarbonyl, C1.4alkylsulphonyl or C1.
4haloalkylsulphonyl and each R20 is, independently, halogen, C1.4alkyl, C1.4haloalkyl, C1
4alkoxy, C1-4haloalkoxy, C1.2alkoxyC1.2alkoxy, hydroxy, phenyl or phenoxy;
R2 is halogen or methyl;
X is oxygen or cR3R4;
R3 and R4 are independently H or C1.4alkyl;
Y is oxygen or cR5R6;
R5 and R6 are independently H, Cl-~alkylC, 1. 4haloalkyl, C3.6cycloalkyl, C1. 4alkoxyC1.
10 4alkyl or aryl optionally substituted by 1-3 groups R21 or R5 and R6 together form a C2.
~alkylenec hain or an 0x0 group and each R21 is, independently, halogen, C1.4alkyl,C 1.
4haloalky1, C1-4alkoxy, C1_4haloalkoxy,C 1.2alko~yC~.~alkoxhyy,d roxy, phenyl or phenoxy;
Z is oxygen, cR8R9 or NR";
R8 and R9 are independently H, halogen, C1.4alkyl, C1.4alkoxy, C1.4alkylthio or C1.
15 4alkoxycarbonyl;
R1° is H, C1.4alky1, aryl optionally substituted by 1-3 groups R ~C1~.4a,lk ylcarbonylo r
C1.4alkoxycarbonyl and each R~~ is, independently, halogen, C1.4alkyl, C1 .4haloalkyl, C1.
4alkoxy, C1.4haloalkoxy, C1.2alkoxyCl .2alkoxy, hydroxy, phenyl or phenoxy;
provided that only one of X, Y and Z is oxygen;
and wherein said composition comprises, in addition to the sulphonanilide derivative
herbicide of formula (I), at least one safener selected from the group consisting of benoxacor,
cloquintocet-mexyl, cyometrinil, the (Z) isomer of cyometrinil, cyprosulfamide (CAS RN
22 1667-3 1 -8), dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, isoxadifen-
25 ethyl, mefenpyr-diethyl, naphthalic anhydride (CAS RN 8 1-84-5), oxabetrinil, N-(2-
methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R-
29148 (CAS RN 52836-3 1-4) or a 2,2,4,5-tetrasubstituted 3-dichloroacetyl-l,3-oxazolidine.
Except where more narrow ranges are stated, in general, "alkyl" means a linear
saturated monovalent hydrocarbon radical of one to ten carbon atoms or a branched saturated
5 monovalent hydrocarbon radical of three to ten carbon atoms, e.g. methyl, ethyl, n-propyl,
iso-propyl, n-butyl, see-butyl, iso-butyl, tert-butyl, neopentyl, and the like. Suitably, linear
alkyl groups contain one to five, one to four or one to three carbon atoms, more suitably are
selected from methyl, ethyl or n-propyl and, most suitably, are methyl or ethyl. Suitably,
branched alkyl groups contain three to five or three to four carbon atoms and more suitably
10 are selected from iso-propyl, see-butyl, iso-butyl or tert-butyl. It is noted that this definition
applies both when the term is used alone and when it is used as part of a compound term,
such as "haloalkyl" and similar terms.
Except where more narrow ranges are stated, in general, "cycloalkyl" means a
monovalent cyclic hydrocarbon radical of three to six ring carbons e.g. cyclopropyl,
15 cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkyl groups are fully saturated. Suitably,
cycloalkyl groups are cyclopropyl or cyclobutyl.
Except where more narrow ranges are stated, in general, "alkenyl" means a linear
monovalent unsaturated hydrocarbon radical of two to five carbon atoms, or a branched
monovalent hydrocarbon radical of three to five carbon atoms containing at least one double
20 bond, e.g. ethenyl, propenyl and the like. Where appropriate, an alkenyl group can be of
either the (Q- or (z)-configuration. Suitably, linear alkenyl groups contain two to five
carbon atoms, more suitably two to four carbon atoms and, most suitably are ethenyl (vinyl),
prop- 1 -enyl (1 -propenyl) or prop-2-enyl (allyl). Suitably, branched alkenyl groups contain
three to five carbon atoms, more suitably from three to four and, most suitably, are 1-
25 methylethenyl(2-propenyl), 1 -methylprop- 1 -enyl, 1 -methylprop-2-enyl, 2-methylprop- 1 -
enyl and 2-methylprop-2-enyl(2-methylallyl).
Except where more narrow ranges are stated, in general, "alkylene" means a linear
saturated divalent hydrocarbon radical of one to six carbon atoms or a branched saturated
divalent hydrocarbon radical of three to six carbon atoms, e.g. methylene, ethylene,
30 propylene, 2-methylpropylene and the like.
"Alkoxy" means a radical -OR, wherein R is alkyl as defined above. Alkoxy groups
include, but are not limited to, methoxy, ethoxy, 1 -methylethoxy, propoxy, butoxy, 1 -
methylpropoxy and 2-methylpropoxy. Preferably alkoxy means methoxy or ethoxy.
"Alkoxyalkyl" means a radical -ROR, wherein each R is, independently, alkyl as
5 defined above.
"Alkoxyalkoxy" means a radical -OROR, wherein each R is, independently, alkyl as
defined above.
"Alkoxyalkoxyalkyl" means a radical -ROROR, wherein each R is, independently,
alkyl as defined above.
10 "Aryl" or "aromatic ring" refers to an aromatic substituent which may be a single
ring or multiple rings which are hsed together, linked covalently or linked to a common
group such as an ethylene (-CH2-CH2-) or methylene (-CH2-) moiety. Representative
examples of aryl include, for example, phenyl, naphthyl, azulenyl, indanyl, indenyl,
anthracenyl, phenanthrenyl, tetrahydronaphthyl, biphenyl, diphenylmethyl and 2,2-diphenyl-
15 1-ethyl. Preferred aryl groups are phenyl and naphthyl groups.
"Arylalkyl" means a radical -RAryl, wherein R is alkyl as defined above.
"Arylalkoxyalkyl" means a radical -RORAryl, wherein each R is, independently,
alkyl as defined above.
"Heteroaryl" means a ring system consisting either of a single aromatic ring or of
20 two or more hsed rings, at least one of which is aromatic, the other or others independently
being saturated, unsaturated or aromatic, containing one, two, three or four ring heteroatoms
selected, independently, from N, 0 or S, the remaining ring atoms being carbon. Examples
of heteroaryl groups include, but are not limited to pyridyl, pyridazinyl, pyrimidinyl,
pyrazinyl, triazinyl, hranyl, thiophenyl, oxazo lyl, isoxazo lyl, oxadiazo lyl, thiazo lyl,
25 isothiazolyl, thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl. Examples
of bicyclic groups are benzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl,
cinnolinyl, quinoxalinyl and pyrazolo[l,5-alpyrimidinyl. Preferred heteroaryl groups
include pyridyl, pyrimidinyl, hranyl, thiophenyl, thiazolyl, pyrrolyl, pyrazolyl, imidazolyl,
triazolyl, benzothiophenyl, benzimidazolyl and quinolinyl.
"Heteroarylalkyl" means a radical -RHeteroaryl, wherein R is alkyl as defined above.
"Alkylthio" means a radical -SR, wherein R is alkyl as defined above. Alkylthio
5 groups include, but are not limited to, methylthio, ethylthio, propylthio, tert-butylthio, and
the like.
"Alkylthioalkyl" means a radical -RSR, wherein each R is, independently, alkyl as
defined above.
"Phenylthioalkyl" means a radical -RSPhenyl, wherein R is alkyl as defined above.
10 "Alkylcarbonyl" means a radical -C(O)R, wherein R is alkyl as defined above.
"Alkylthiocarbonyl" means a radical -C(O)SR, wherein R is alkyl as defined above.
"Alkenylcarbonyl" means a radical -C(O)R, wherein R is alkenyl as defined above.
"Cycloalkylcarbonyl" means a radical -C(O)R, wherein R is cycloalkyl as defined
above.
15 "Alkoxycarbonyl" means a radical -C(O)OR, wherein R is alkyl as defined above.
"Alkenyloxycarbonyl" means a radical -C(O)OR, wherein R is alkenyl as defined
above.
"Propargyloxycarbonyl" means a radical -C(O)OR, wherein R is propargyl.
"Alkoxyalkoxycarbonyl" means a radical -C(O)OROR, wherein each R is,
20 independently, alkyl as defined above.
"Arylcarbonyl" means a radical -C(O)Aryl.
"Aryloxycarbonyl" means a radical -C(O)OAryl.
"Arylalkoxycarbonyl" means a radical -C(O)ORAryl, wherein R is alkyl as defined
above.
"Aminocarbonyl" means a radical -C(0)NH2.
"Alkylaminocarbonyl" means a radical -C(O)NRH, wherein R is alkyl as defined
above.
"Dialkylaminocarbonyl" means a radiacal -C(O)NRR, wherein each R is,
5 independently, alkyl as defined above.
"Alkylsulphonyl" means a radical -S(0)2R, wherein R is alkyl as defined above.
"Halo" or "halogen" means fluoro, chloro, bromo or iodo, preferably chloro or
fluoro .
"Haloalkyl" means alkyl as defined above substituted with one or more of the same
10 or different halo atoms. Examples of haloalkyl groups include, but are not limited to
chloromethyl, fluoromethyl, dichloromethyl, difluoromethyl, trichloromethyl,
trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 1,l -difluoroethyl, 1,2-difluoroethyl, 2,2-
difluoroethyl, pentafluoroethyl, 2-chloroethyl, 3-fluoropropyl, 3-chloropropyl, 2,2,2-
trifluoro- 1 -chloroethyl and heptafluoropropyl.
15 "Haloalkoxy" means a radical -OR, wherein R is haloalkyl as defined above.
"Haloalkylcarbonyl" means -C(O)R, wherein R is haloalkyl as defined above.
"Haloalkoxycarbonyl" means -C(O)OR, wherein R is haloalkyl as defined above.
"Haloalkylsulphonyl" means -S(0)2R, wherein R is haloalkyl as defined above.
"Hydroxy" or "hydroxyl" means an -OH group.
"0x0" means the group =O.
The compounds of formula I may exist in different geometric or optical isomeric
forms or in different tautomeric forms. One or more centres of chirality may be present, in
which case compounds of the formula I may be present as pure enantiomers, mixtures of
enantiomers, pure diastereomers or mixtures of diastereomers. There may be double bonds
25 present in the molecule, such as C=C bonds, in which case compounds of formula I may
exist as single isomers or mixtures of isomers. Centres of tautomerisation may be present.
This invention covers all such isomers and tautomers and mixtures thereof in all proportions
as well as isotopic forms such as deuterated compounds.
Suitable salts include those formed by contact with bases. Suitable salts of the
compounds of formula I thus include those derived from alkali or alkaline earth metals and
5 those derived from ammonia and amines. Preferred cations include sodium, potassium,
magnesium, and ammonium cations of the formula N'(R'RJR~R') wherein Ri, RJ, Rk and R'
are independently selected from hydrogen, C1.6 alkyl and C1.6 hydroxyalkyl. Salts of the
compounds of formula I can be prepared by treatment of compounds of formula I with a
metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine,
10 diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine,
cyclododecylamine, or benzylamine. Amine salts are often preferred forms of the
compounds of Formula I because they are water-soluble and lend themselves to the
preparation of desirable aqueous based herbicidal compositions.
N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen
15 containing heteroaromatic compounds. They are described in many books for example in
"Heterocyclic N-oxides" by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton,
Florida, 199 1.
In a preferred embodiment, the preferred groups for R1, R2, R3, R4, R5, R6, R8, R9,
RlO, R20, R21, R ~X~, Y,, Z and A as well as the preferred values for m and n, in any
20 combination thereof, are as set out below.
In a preferred embodiment, R1 is as described above and R20 is halogen, C1.2alkyl or
C .2haloalkyl.
In a further preferred embodiment, R1 is H, Cl.5alkoxycarbonyl, C1.
4haloalkoxycarbonyl or trifluoromethylsulphonyl.
25 In a preferred embodiment, m is 0.
In a preferred embodiment, X is oxygen or CH2.
In a preferred embodiment, R5 is H, C1.4alky1, Cl.2haloalkyl or cyclopropyl.
In a preferred embodiment, R6 is H, C1.4alkyl or aryl optionally substituted by 1-3
groups R21, wherein R21 is as described above or, preferably, R21 is halogen, C1.2alkyl or C1
2haloalkyl
In a preferred embodiment, R5 and R6 together form a C2.5alkylene chain.
In a preferred embodiment, R8 is H, halogen or C1.2alkyl.
In a preferred embodiment, R9 is H, halogen, C1.2alkyl or Claalkylthio.
In a preferred embodiment, R1° is H, C1.2alkyl or C1.4alkoxycarbonyl.
The compounds described below are illustrative of compounds for use in the novel
safened compositions of the invention. Table 1 below provides 152 compounds designated
10 compounds 1 to 152 respectively, of formula (I).
TABLE 1
C P ~
N 0
1
2
3
4
5
6
7
8
9
10
11
12
R1
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
"rCO
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
A n
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
0
0
0
0
1
1
1
1
1
1
1
1
X
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
Y
cR5R6
cR5R6
cR5R6
cR5R6
cR5R6
cR5R6
cR5R6
cR5R6
cR5R6
cR5R6
cR5R6
cR5R6
R5
H
H
H
H
H
H
H
H
H
Me
Me
Me
R6
H
H
H
H
H
H
H
H
H
Me
Me
Me
Z
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
13
14
15
16
17
18
19
20
21
2 2
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
t ~ u ~ ~ 2 0 ~ ~
F3CS02
H
EtCO
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
CICH20C0
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
1
1
1
1
1
1
1
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
CH2
CH2
CH2
CH2
CH2
CH2
CH2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
Me
Me
H
H
H
H
H
Me
Me
Me
Me
Me
H
H
H
H
Me
Me
Me
Me
c F3
c F3
c F3
c F3
Me
Me
H
H
H
H
H
Me
Me
Me
Me
Me
H
H
H
H
Me
Me
Me
Me
Me
Me
Me
Me
(CHZ)~
CH2
CH2
CHSMe
CHSMe
CHSMe
CHSMe
CHSMe
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
38
39
40
4 1
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
1
1
1
1
1
1
1
1
0
0
0
CH2
CH2
CH2
CH2
CMe2
CMe2
CMe2
CMe2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CR5R6
CR5R6
CR5R6
0
0
0
0
0
0
0
0
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
N(2,6-
dichlorophenyl)
N(2,6-
dichlorophenyl)
N(2,6-
dichlorophenyl)
N(2,6-
dichlorophenyl)
NH
NH
NH
NH
NMe
NMe
NMe
NMe
(CHZ)~
(CHZ)~
H
H
H
H
H
H
H
H
H
H
H
H
(CHZ)~
H
H
H
H
H
H
H
H
H
H
H
H
6 1
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
8 2
83
84
85
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
0
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
0
0
0
0
CH2
CH2
CH2
CH2
CH2
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
H
H
H
H
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
H
H
H
H
H
H
H
H
Me
H
H
H
H
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
H
H
H
H
H
H
H
H
Me
NC02Et
NC02Et
NC02Et
NC02Et
NH
NH
NH
NH
NMe
NMe
NMe
NMe
NC02Et
NC02Et
NC02Et
NC02Et
NMe
NMe
NMe
NMe
0
0
0
0
0
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
CICH20C0
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
Me
Me
Me
'P r
'P r
'P r
'P r
Me
Me
Me
Me
Me
Me
Me
Me
c F3
c F3
c F3
c F3
c F3
c F3
c F3
c F3
c F3
Et
Me
Me
Me
Me
Me
Me
Me
2-fluorophenyl
2-fluorophenyl
2-fluorophenyl
2-fluorophenyl
Me
Me
Me
Me
Me
Me
Me
Me
Me
Et
Et
Et
Et
Et
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
MeOCO
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
nPrOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
SO2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CMe2
CMe2
CMe2
CMe2
CMe2
CH2
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
Et
Et
Et
'P r
'P r
'P r
'P r
Et
Et
Et
Me
Me
Me
Me
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
CH2
(CHZ)~
(CHZ)~
(CHZ)~
(CHZ)~
H
H
H
H
H
H
H
H
H
H
H
2,6-
difluorophenyl
2,6-
difluorophenyl
2,6-
difluorophenyl
2,6-
difluorophenyl
2,6-
difluorophenyl
H
H
H
H
H
H
In a preferred embodiment, the safener is selected from benoxacor, cloquintocetmexyl,
isoxadifen-ethyl, cyprosulfamide, fenchlorazole-ethyl, fluxofenim, mefenpyr-diethyl,
dichlormid, naphthalic anhydride and N-(2-methoxybenzoy1)-4-
5 [(methylaminocarbonyl)amino]benzenesulfonamide.
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
CICH20C0
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
H
EtOCO
'BUOCO
t ~ u ~ ~ 2 0 ~ ~
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
SO2
1
1
1
1
1
1
1
0
0
0
0
1
1
1
1
1
1
1
1
1
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CR5R6
CR5R6
CR5R6
0
0
0
0
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
CR5R6
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
CH2
CH2
CH2
CH2
CH2
CH2
CH2
NMe
NMe
NMe
NMe
NMe
NMe
NMe
NMe
NMe
0
0
0
0
In a more preferred embodiment, the saferner is selected from benoxacor,
cloquintocet-mexyl, isoxadifen-ethyl, cyprosulfamide, fluxofenim, mefenpyr-diethyl,
dichlormid, naphthalic anhydride and N-(2-methoxybenzoy1)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide.
5 In a more preferred embodiment, the safener is N-(2-methoxybenzoy1)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide.
In a further more preferred embodiment, the safener is cloquintocet-mexyl.
These sulphonanilide compounds used in the safened compositions of the present
invention may be made as the skilled man will appreciate by applying andlor adapting as
10 appropriate, the methods described in the prior art (see for example EP2085392, EP1852425,
W02008/102908, EP2336104 and W02010/119906).
The safeners of the invention are described in The Pesticide Manual, Edition,
2006. It is noted that the safeners for use in the compositions of the invention may also be in
the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14"' Edition supra.
15 Thus, the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium,
calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or
phosphonium salt thereof as disclosed in W002134048, etc. N-(2-methoxybenzoy1)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide is disclosed in EP 0 365 484 A and may
be made using the methods described therein. Oxylipins A and methods for their preparation
20 are disclosed in WO 201 11134539 and include oxophytodienoic acids, phytoprostane type I
and type I1 series, cyclopentanones, fatty acid hydroperoxides, mono-, di- and tri-hydroxy
fatty acids, keto- or o-0x0 fatty acids, epoxy alcohols of unsaturated fatty acids, fatty acids
containing ketodiene and ketotriene groups, alkenals and hydroxyalkenals, fatty acids
containing a- and y-ketol groups and fatty acids containing divinyl ether groups, including
25 salts thereof. 2,2,4,5-tetrasubstituted 3-dichloroacetyl-1,3-oxazolidines and methods for
making them are disclosed in Fu et al., Heterocycles, Vol83(1 I), 201 1, pp. 2607 to 2613.
Preferably the mixing ratio of compound of formula (I) to safener is from 100: 1 to
1 : 100, especially from 20: 1 to 1 :20.
In a further aspect, the present invention provides a method for protecting crops of
useful plants from the harmful effects of a herbicide of formula (I) as defined herein, which
comprises applying to the locus of the useful plants at least one safener selected from the
group consisting of benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of
5 cyometrinil, cyprosulfamide (CAS RN 22 1667-3 1 -8), dichlormid, fenchlorazole-ethyl,
fenclorim, flurazole, fluxofenim, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride
(CAS RN 8 1 -84-5), oxabetrinil, N-(2-methoxybenzoy1)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R-29148 (CAS RN
52836-3 1-4) or a 2,2,4,5-tetrasubstituted3 -dichloroacetyl- 1,3-oxazolidine.
10 In a still further aspect, the present invention provides a method for combating weeds
in crops of usehl plants, which comprises treating the usehl plants, seeds or cuttings thereof
or the locus of the usehl plants simultaneously or at separate times with a herbicidally active
amount of a compound of formula (I) and at least one safener selected from the group
consisting of benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of cyometrinil,
15 cyprosulfamide (CAS RN 22 1667-3 1 -8), dichlormid, fenchlorazole-ethyl, fenclorim,
flurazole, fluxofenim, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (CAS RN
8 1 -84-5), oxabetrinil, N-(2-methoxybenzoy1)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R-29148 (CAS RN
52836-3 1-4) or a 2,2,4,5-tetrasubstituted3 -dichloroacetyl- 1,3-oxazolidine.
20 Any method of application to weedslcrop of usehl plant, or locus thereof, which is
routinely used in agriculture may be used, for example application by spray or broadcast
method typically after suitable dilution of the composition of the invention.
The term "locus" as used herein includes not only areas where weeds may already be
growing, but also areas where weeds have yet to emerge, and also to areas under cultivation
25 with respect to crops of useful plants. Areas under cultivation include land on which the
crop plants are already growing and land intended for cultivation with such crop plants.
Crops of usehl plants in which compositions of the invention may be used or the
methods of the invention applied include perennial crops, such as citrus h i t , grapevines,
nuts, oil palms, olives, pome h i t , stone h i t and rubber, and annual arable crops, such as
30 cereals, for example barley and wheat, cotton, oilseed rape, maize (including sweet corn),
rice, sorghum, soy beans, sugar beet, sugar cane, sunflowers, ornamentals and vegetables,
especially cereals and maize. Preferred crops are cereals, maize, soy bean and rice. More
preferred are barley, wheat, maize, sweet corn and soy bean. Most preferred are wheat,
maize and soy bean.
5 Preferred safeners for use in maize are benoxacor, cloquintocet-mexyl, isoxadifenethyl,
cyprosulfamide, fluxofenim, mefenpyr-diethyl, dichlormid, naphthalic anhydride and
N-(2-methoxybenzoy1)-4-[ (methylaminocarbonyl)amino]b enzenesulfonamide. A
particularly suitable safener for use in maize is N-(2-methoxybenzoy1)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide.
10 Preferred safeners for use in wheat are cloquintocet-mexyl, fenchlorazole-ethyl,
isoxadifen-ethyl and mefenpyr-diethyl. A particularly suitable safener for use in wheat is
cloquintocet-mexyl.
Preferred safeners for use in soy bean are benoxacor, cloquintocet-mexyl, isoxadifenethyl,
cyprosulfamide, fluxofenim, mefenpyr-diethyl, dichlormid, naphthalic anhydride and
15 N-(2-methoxybenzoy1)-4-[ (methylaminocarbonyl)amino]b enzenesulfonamide. Particularly
suitable safeners for use in maize are benoxacor, fluxofenim, mefenpyr-diethyl, dichlormid,
naphthalic anhydride and N-(2-methoxybenzoy1)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide. Most preferred are benoxacor or N-(2-
methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.Compositions and
20 methods of the invention may also be used on turf, pasture, rangeland, rights of way etc. In
particular they may be used on golf-courses, lawns, parks, sports-fields, race-courses and the
like.
Crops are to be understood as also including those crops which have been rendered
tolerant to herbicides or classes of herbicides (e.g. ALS-, ACCase-, GS-, EPSPS-, PPO- and
25 HPPD-inhibitors and synthetic auxins) by conventional methods of breeding or by genetic
engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g.
imazamox, by conventional methods of breeding is clearfielda 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
30 available under the trade names RoundupReadya and LibertyLinka.
Crops are also to be understood as being those which have been rendered resistant to
harmful insects by genetic engineering methods, for example Bt maize (resistant to European
corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to
Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK@ (Syngenta
5 Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil
bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are
described in EP-A-45 1 878, EP-A-374 753, WO 93107278, WO 95134656, WO 031052073
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 ~ n o c k ~ u(tm@aiz e), Yield
10 Gardm( maize), NUCOTIN~~B(c@ott on), ~ o l l ~ a r d(c@ott on), New~ea?( potatoes),
NatureGardm and ~rotexcta~Pl.a nt 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.
15 Crops are also to be understood as being those which are obtained by conventional
methods of breeding or genetic engineering and contain so-called output traits (e.g. improved
storage stability, higher nutritional value and improved flavour).
The term "weeds" as used herein means any undesired plant, and thus includes not
only agronomically important weeds as described below, but also volunteer crop plants.
20 Compounds of formula (I) may be used against a large number of agronomically
important weeds. The weeds that may be controlled include both monocotyledonous and
dicotyledonous weeds, such as, for example, Alisma spp, Leptochloa chinensis, Stellaria,
Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa,
Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus and
25 especially Cyperus iria, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea,
Chrysanthemum, Galium, Viola, Veronica, Bidens, Euphorbia, Ischaemum, Polygonum,
Helianthus, Panicum, Eriochloa, Brachiaria, Cenchrus, Commelina, Spermacoce, Senna,
Tridax, Richardia, Chamaesyce, and Conyza spp.
The compositions according to the invention are suitable for all the conventional
3 0 methods of application in agriculture, such as, e. g., pre-emergent application, post-emergent
application and seed dressing. Depending on the intended use, the safener can be employed
for pre-treatment of the seed of the crop plant (dressing of the seed or cuttings) or can be
introduced into the soil before or after sowing. However, it can also be applied by itself or
together with the herbicide before or after emergence of the plants. The treatment of the
5 plants or seed with the safener can therefore in principle be carried out independently of the
time of application of the herbicide. Treatment of the plants by simultaneous application of
the herbicide and safener (e.g, as a tank mix) is as a rule preferred. The application rate of
safener to herbicide to be applied largely depends of the method of use. For field treatment,
as a rule 0.00 1 to 5.0 kg of safenerlha, preferably 0.0 1 to 0.5 kg safenerlha and as a rule
10 between 0.005 to 2 kg of herbicidelha, but preferably between 0.01 to 1 kglha are applied.
For seed dressing, in general 0.00 1 to 10 g of safenerlkg seed, preferably 0.05 to 2g
safenerlkg seed are applied. If the safener is applied in liquid form, with soaking of the seed,
shortly before sowing, safener solutions which contain the safener in a concentration of 1 to
10,000, preferably 100 to 1000 ppm are expediently used.
15 The safened compositions of the present invention can be employed in unchanged
form as a herbicidal composition. However, as a rule the compositions of the invention are
preferably formulated in various ways using formulation adjuvants, such as carriers, solvents
and surface-active substances, for example, as described hereinafter. Accordingly, the
present invention provides a composition of the invention which further comprises at least
20 one agriculturally acceptable adjuvant or diluent.
The formulated compositions can be in various physical forms, e.g. in the form of
dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible
tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oilin-
water emulsions, oil- flowables, aqueous dispersions, oily dispersions, suspo-emulsions,
25 capsule suspensions, suspension concentrates, emulsifiable granules, soluble liquids, watersoluble
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
FA0 Specifications for Plant Protection Products, 5th Edition, 1999. The formulated
compositions can be in the form of concentrates which are diluted prior to use, although
30 ready-to-use formulations can also be made. The dilutions can be made, for example, with
water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
The formulated compositions can be prepared e.g. by mixing the active ingredient
and safener combination 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,
5 mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin,
organic solvents, water, surface-active substances or combinations thereof. The active
ingredients can also be contained in very fine microcapsules consisting of a polymer.
Microcapsules usually have a diameter of from 0.1 to 500 microns. Typically, they will
contain active ingredients in an amount of about from 25 to 95% by weight of the capsule
10 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, styrenelbutadiene
copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane
or chemically modified polymers and starch xanthates or other known polymers.
15 Alternatively, very fine microcapsules can be formed in which the active ingredient is
contained in the form of finely divided particles in a solid matrix of base substance, but the
microcapsules are not themselves encapsulated.
The formulation adjuvants that are suitable for the preparation of compositions
according to the invention are knownper se. As liquid carriers there may be used: water,
20 toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone,
cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone,
butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid
(e.g. butyl acetate, ethyl acetate, isoamyl acetate, amyl acetate), diacetone alcohol, 1,2-
dichloropropane, diethano lamine, p-diethylbenzene, diethylene g lyco 1, diethylene g lyco 1
25 abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol
methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glyco 1,
dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,
2-ethylhexano 1, ethylene carbonate, 1,1,1 -trichloro ethane, 2-heptanone, alp ha-pinene, dlimonene,
ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl
30 ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate,
hexadecane, hexylene glycol, isobornyl acetate, isooctane, isophorone, isopropylbenzene,
isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl
isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate,
methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine
acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG), propionic acid,
5 propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, pxylene,
toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral
oil, trichloroethylene, perchloroethylene, methanol, ethanol, isopropanol, and alcohols of
higher molecular weight, such as amyl alcohol, tetrahydrohrhryl alcohol, hexanol, octanol,
N-methyl-2-pyrrolidone and the like. Water is generally the carrier of choice for diluting the
10 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 180.100 1. (c)
& ( 4 .
15 A large number of surface-active substances may advantageously be used in the
formulations, especially in those formulations designed to be diluted with a carrier prior to
use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can
be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical
surface-active substances include, for example, salts of alkyl sulfates, such as
20 diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium
dodecylbenzenesulfonate; alkylphenoValkylene oxide addition products, such as nonylphenol
ethoxylate; alcohoValkylene 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-
25 ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as
lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as
polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and
salts of mono- and di-alkylphosphate esters; and also fbrther substances described e.g. in
"McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New
30 Jersey, 198 1.
Further adjuvants that can usually be used in such formulations include crystallisation
inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light
absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying
substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers,
5 micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes,
microbicides, and also liquid and solid fertilisers. An example of such an adjuvant is
ammonium sulp hate.
The formulated 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
10 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 lo%, 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,
15 emulsified vegetable oil, such as AMIGO~(R h6ne-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
20 oil additives comprise alkyl esters of C8.22 fatty acids, especially the methyl derivatives of
C12.18f atty 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-111-82-O), methyl
palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl
ester derivative is ~me$2230 and 223 1 (Cognis GmbH). Those and other oil derivatives
25 are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois
University, 2000. Another preferred adjuvant is ~ d i ~(Soynrge~nt a AG) which is a
methylated rapeseed oil-based adjuvant.
The application and action of the oil additives can be fbrther improved by
combination with surface-active substances, such as non-ionic, anionic or cationic
30 surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on
pages 7 and 8 of W097134485. 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
CI2.22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of
commercially available surfactants are the Genapol types (Clariant AG). Also preferred are
5 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@,~ urbochar~e(S@yn genta
10 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 additivelsurfactant mixture
may contribute to an additional enhancement of action. Suitable solvents are, for example,
15 ~olvesso@(E SSO) or Aromatic solvent@( Exxon Corporation). The concentration of such
solvents can be from 10 to 80% by weight of the total weight. Oil additives that are present
in admixture with solvents are described, for example, in US-A-4,834,908. A commercially
available oil additive disclosed therein is known by the name MERGE@ (BASF
Corporation). A fbrther oil additive that is preferred according to the invention is SCORE@
20 (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. rimax ax@) to be added to the spray mixture. Formulations of
synthetic lattices, e.g. polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g.
25 ~ond@C,o urier@ or ~merald@m)a y 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.
Formulated compositions of the invention generally comprise from 0.1 to 99% by
weight, especially from 0.1 to 95% by weight, of active compound mixture of the compound
30 of formula (I) with a safener 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.
Various methods and techniques are suitable for using safeners or compositions
5 containing them for protecting crop plants from the harmful actions of herbicides of formula
I, such as, for example, the following:
i) Seed dressing
a) Dressing of the seed with the safener formulated as a wettable powder by
shaking in a vessel until uniform distribution over the seed surface is
achieved (dry dressing). About 1 to 500g of safener (4g to 2kg of
wettable powder) per 100 kg of seed are used here.
b) Dressing of the seed with an emulsion concentrate of the safener by
method a) (wet dressing).
c) Dressing by immersing the seed in a liquor with 100-1000 ppm of safener
for 1 to 72 hours and optionally subsequent drying of the seed (immersion
dressing).
The dressing of the seed or the treatment of the sprouted seed are of
course the preferred methods of application, because the treatment with
the safener is directed entirely at the target crop. As a rule, 1 to lOOOg of
safener, preferably 5 to 250g of safener are used per 100 kg of seed, it
being possible to deviate upwards or downwards from the limit
concentrations stated (repeat dressing), depending on the methods, which
also allows the addition of other active compounds or micronutrients.
ii) Application as a tank mix
A liquid processed mixture of safener and herbicide of formula I (reciprocal
ratio of amounts between 10: 1 and 1 : 100) is used, the application rate of
herbicide being 0.005 to 5.0 kg per hectare. Such tank mixes are applied
before or after sowing.
iii) Application into the seed furrow
The safener is introduced into the open sown seed furrow as an emulsion
concentrate, wettable powder or as granules. After the seed h o w has been
covered, the herbicide is applied by the pre-emergent method in a
conventional method.
iv) Controlled release of the safener
The safener is absorbed in solution on to mineral carrier granules
orpolymerised granules (urealformaldehyde) and dried. A coating which
allows the safener to be released over a certain period of time can optionally
be applied (coated granules).
In particular, preferred formulations have the following composition (% = per cent by
weight; active mixture of active compounds means the mixture of a compound of formula I
with a safener):
Emulsifiable concentrates
15 Active mixture of active compounds: 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 mixture of active compounds: 0.1 to lo%, preferably 0.1 to 5%
20 Solid carrier: 99.9% to 90%, preferably 99.9 to 99%
Suspension concentrates
Active mixture of active compounds: 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%
25 Wettable powders
Active mixture of active compounds: 0.5 to 90%, preferably 1 to 80%
Surface-active agent: 0.5 to 20%, preferably 10 to 15%
Solid carrier: 5 to 95%, preferably 15 to 90%
Granules
Active mixture of active compounds: 0.1 to 30%, preferably 0.1 to 15%
5 Solid carrier: 99.5 to 70%, preferably 97 to 85%
Formulation examples for mixtures of herbicides of formula (I) with safeners (% =% bv
weig- ht; EO = ethvlene oxide)
F 1. Emulsifiable concentrates a> b> c) d)
10 active compound mixture 5% 10% 25% 50%
calcium dodecylbenzenesulfonate 6% 8% 6% 8%
castor oil polyglycol ether (36 mol of EO) 4% - 4% 4%
octylphenol polyglycol ether (7-8 mol of EO) - 4% - 2%
N-methyl pyrrolidone - - 10% 20%
15 arom. hydrocarbon mixture (C9-Cl2) 85% 78% 55% 16%
Emulsions of any desired concentration can be obtained from such concentrates by dilution
with water.
F2. Solutions
20 active compound mixture 5% 10% 50% 90%
1 -methoxy-3 -(3 -methoxy-propoxy)-propane - 20% 20% -
polyethylene glycol MW 400 20% 10% - -
NMP - - 30% 10%
arom. hydrocarbon mixture (C9-Cl2) 75% 60% - -
25 The solutions are suitable for use in the form of microdrops.
F3. Wettable powders
active compound mixture 5% 25% 50% 80%
sodium lignosulfonate 4% - 3% -
sodium lauryl sulp hate 2% 3% - 4%
5 sodium diisobutylnaphthalene-sulfonate - 6% 5% 6%
octylphenol polyglycol ether (7-8 mol EO) - 1% 2% -
highly dispersed silicic acid 1% 3% 5% 10%
kaolin 88% 62% 35% -
The active compound mixture is mixed thoroughly with the adjuvants and the resulting
10 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 compound mixture 0.1% 5% 15%
15 highly dispersed silicic acid 0.9% 2% 2%
inorganic carrier (diameter 0.1-1 mm) e.g. CaC03 or Si02 99.0% 93% 83%
The active compound mixture is dissolved in methylene chloride and applied to the carrier
by spraying, and the solvent is then evaporated off in vacuo.
20 F5. Coated granules a> b> c)
active compound mixture 0.1% 5% 15%
polyethylene glycol MW 200 1.0% 2% 3%
highly dispersed silicic acid 0.9% 1% 2%
inorganic carrier (diameter 0.1-1 mm) e.g. CaC03 or Si02 98.0% 92% 80%
25 The finely ground active compound mixture is uniformly applied, in a mixer, to the carrier
moistened with polyethylene glyco 1. Non-dusty coated granules are obtained in this manner.
F6. Extruded granules a> b> c) d)
active compound mixture
sodium lignosulfonate
carboxymethylcellulose
5 kaolin
The active compound mixture 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)
10 active compound mixture
talcum
kaolin
Ready-to-use dusts are obtained by mixing the active compound mixture with the carriers
and grinding the mixture in a suitable mill.
F8. Suspension concentrates a> b> c) d)
active compound mixture
ethylene glyco 1
nonylphenol polyglycol ether (1 5 mol EO)
20 sodium lignosulfonate
carboxymethylcellulose
37% aqueous formaldehyde solution
silicone oil emulsion
water
25 The finely ground active compound mixture is intimately mixed with the adjuvants, giving a
suspension concentrate from which suspensions of any desired concentration can be obtained
by dilution with water.
It is often more practical to formulate the active compound of formula I and the
safener individually and then to bring them together as a 'tank mix' in water in the
application equipment in the desired mixing ratio shortly before application.
The compositions of the present invention can also be used in combination with other
5 active ingredients, e.g. other herbicides, andlor insecticides, andlor acaricides, andlor
nematocides, andlor molluscicides, andlor fungicides, andlor plant growth regulators. Such
mixtures, and the use of such mixtures to control weeds andlor undesired plant growth form
yet fbrther aspects of the invention. For the avoidance of doubt, mixtures of invention also
include mixtures of two or more different compounds of formula (I). In particular, the
10 present invention also relates to a composition of the invention which comprises at least one
further herbicide in addition to the compound of formula (I) and the safener.
Where a composition of the invention is combined with at least one additional
herbicide, the following mixtures of the composition of the invention are particularly
preferred: composition of the invention + acetochlor, composition of the invention +
15 acifluorfen, composition of the invention + acifluorfen-sodium, composition of the invention
+ aclonifen, composition of the invention + acrolein, composition of the invention +
alachlor, composition of the invention + alloxydim, composition of the invention + ally1
alcohol, composition of the invention + ametryn, composition of the invention +
amicarbazone, composition of the invention + amidosulfuron, composition of the invention +
20 aminocyclopyrachlor, composition of the invention + aminopyralid, composition of the
invention + amitrole, composition of the invention + ammonium sulfamate, composition of
the invention + anilofos, composition of the invention + asulam, composition of the
invention + atrazine, composition of the invention + aviglycine, composition of the invention
+ azafenidin, composition of the invention + azimsulfuron, composition of the invention +
25 BCPC, composition of the invention + beflubutamid, composition of the invention +
benazolin, composition of the invention + bencarbazone, composition of the invention +
benfluralin, composition of the invention + benfuresate, composition of the invention +
bensulfuron, composition of the invention + bensulfuron-methyl, composition of the
invention + bensulide, composition of the invention + bentazone, composition of the
30 invention + benzfendizone, composition of the invention + benzobicyclon, composition of
the invention + benzofenap, composition of the invention and bicyclopyrone, composition of
the invention + bifenox, composition of the invention + bilanafos, composition of the
invention + bispyribac, composition of the invention + bispyribac-sodium, composition of
the invention + borax, composition of the invention + bromacil, composition of the invention
+ bromobutide, composition of the invention + bromophenoxim, composition of the
5 invention + bromoxynil, composition of the invention + butachlor, composition of the
invention + butafenacil, composition of the invention + butamifos, composition of the
invention + butralin, composition of the invention + butroxydim, composition of the
invention + butylate, composition of the invention + cacodylic acid, composition of the
invention + calcium chlorate, composition of the invention + cafenstrole, composition of the
10 invention + carbetamide, composition of the invention + carfentrazone, composition of the
invention + carfentrazone-ethyl, composition of the invention + CDEA, composition of the
invention + CEPC, composition of the invention + chlorflurenol, composition of the
invention + chlorflurenol-methyl, composition of the invention + chloridazon, composition
of the invention + chlorimuron, composition of the invention + chlorimuron-ethyl,
15 composition of the invention + chloroacetic acid, composition of the invention +
chlorotoluron, composition of the invention + chlorpropham, composition of the invention +
chlorsulfuron, composition of the invention + chlorthal, composition of the invention +
chlorthal-dimethyl, composition of the invention + cinidon-ethyl, composition of the
invention + cinmethylin, composition of the invention + cinosulfuron, composition of the
20 invention + cisanilide, composition of the invention + clethodim, composition of the
invention + clodinafop, composition of the invention + clodinafop-propargyl, composition of
the invention + clomazone, composition of the invention + clomeprop, composition of the
invention + clopyralid, composition of the invention + cloransulam, composition of the
invention + cloransulam-methyl, composition of the invention + CMA, composition of the
25 invention + 4-CPB, composition of the invention + CPMF, composition of the invention + 4-
CPP, composition of the invention + CPPC, composition of the invention + cresol,
composition of the invention + cumyluron, composition of the invention + cyanamide,
composition of the invention + cyanazine, composition of the invention + cycloate,
composition of the invention + cyclosulfamuron, composition of the invention + cycloxydim,
30 composition of the invention + cyhalofop, composition of the invention + cyhalofop-butyl,
composition of the invention + 2,4-D, composition of the invention + 3,4-DA, composition
of the invention + daimuron, composition of the invention + dalapon, composition of the
invention + dazomet, composition of the invention + 2,4-DB, composition of the invention +
3,4-DB, composition of the invention + 2,4-DEB, composition of the invention +
desmedipham, composition of the invention + desmetryn, composition of the invention +
dicamba, composition of the invention + dichlobenil, composition of the invention + ortho-
5 dichlorobenzene, composition of the invention + para-dichlorobenzene, composition of the
invention + dichlorprop, composition of the invention + dichlorprop-P, composition of the
invention + diclofop, composition of the invention + diclofop-methyl, composition of the
invention + diclosulam, composition of the invention + difenzoquat, composition of the
invention + difenzoquat metilsulfate, composition of the invention + diflufenican,
10 composition of the invention + diflufenzopyr, composition of the invention + dimefuron,
composition of the invention + dimepiperate, composition of the invention + dimethachlor,
composition of the invention + dimethametryn, composition of the invention +
dimethenamid, composition of the invention + dimethenamid-P, composition of the
invention + dimethipin, composition of the invention + dimethylarsinic acid, composition of
15 the invention + dinitramine, composition of the invention + dinoterb, composition of the
invention + diphenamid, composition of the invention + dipropetryn, composition of the
invention + diquat, composition of the invention + diquat dibromide, composition of the
invention + dithiopyr, composition of the invention + diuron, composition of the invention +
DNOC, composition of the invention + 3,4-DP, composition of the invention + DSMA,
20 composition of the invention + EBEP, composition of the invention + endothal, composition
of the invention + EPTC, composition of the invention + esprocarb, composition of the
invention + ethalfluralin, composition of the invention + ethametsulfuron, composition of the
invention + ethametsulfuron-methyl, composition of the invention + ethephon, composition
of the invention + ethofumesate, composition of the invention + ethoxyfen, composition of
25 the invention + ethoxysulfuron, composition of the invention + etobenzanid, composition of
the invention + fenoxaprop, composition of the invention + fenoxaprop-P, composition of the
invention + fenoxaprop-ethyl, composition of the invention + fenoxaprop-P-ethyl,
composition of the invention + fenoxasulfone, composition of the invention + fentrazamide,
composition of the invention + ferrous sulfate, composition of the invention + flamprop-M,
30 composition of the invention + flazasulfuron, composition of the invention + florasulam,
composition of the invention + fluazifop, composition of the invention + fluazifop-butyl,
composition of the invention + fluazifop-P, composition of the invention + fluazifop-P-butyl,
composition of the invention + fluazolate, composition of the invention + flucarbazone,
composition of the invention + flucarbazone-sodium, composition of the invention +
flucetosulfuron, composition of the invention + fluchloralin, composition of the invention +
flufenacet, composition of the invention + flufenpyr, composition of the invention +
5 flufenpyr-ethyl, composition of the invention + flumetralin, composition of the invention +
flumetsulam, composition of the invention + flumiclorac, composition of the invention +
flumiclorac-pentyl, composition of the invention + flumioxazin, composition of the invention
+ flumipropin, composition of the invention + fluometuron, composition of the invention +
fluoroglyco fen, composition of the invention + fluoroglyco fen-ethyl, composition of the
10 invention + fluoxaprop, composition of the invention + flupoxam, composition of the
invention + flupropacil, composition of the invention + flupropanate, composition of the
invention + flupyrsulfuron, composition of the invention + flupyrsulfuron-methyl-sodium,
composition of the invention + flurenol, composition of the invention + fluridone,
composition of the invention + flurochloridone, composition of the invention + fluroxypyr,
15 composition of the invention + flurtamone, composition of the invention + fluthiacet,
composition of the invention + fluthiacet-methyl, composition of the invention + fomesafen,
composition of the invention + foramsulfuron, composition of the invention + fosamine,
composition of the invention + glufosinate, composition of the invention + glufosinateammonium,
composition of the invention + glyphosate, composition of the invention +
20 halosulfuron, composition of the invention + halosulfuron-methyl, composition of the
invention + haloxyfop, composition of the invention + haloxyfop-P, composition of the
invention + HC-252, composition of the invention + hexazinone, composition of the
invention + imazamethabenz, composition of the invention + imazamethabenz-methyl,
composition of the invention + imazamox, composition of the invention + imazapic,
25 composition of the invention + imazapyr, composition of the invention + imazaquin,
composition of the invention + imazethapyr, composition of the invention + imazosulfuron,
composition of the invention + indano fan, composition of the invention + indaziflam,
composition of the invention + iodomethane, composition of the invention + iodosulfuron,
composition of the invention + iodosulfuron-methyl-sodium, composition of the invention +
30 ioxynil, composition of the invention + ipfencarbazone, composition of the invention +
isoproturon, composition of the invention + isouron, composition of the invention +
isoxaben, composition of the invention + isoxachlortole, composition of the invention +
isoxaflutole, composition of the invention + isoxapyrifop, composition of the invention +
karbutilate, composition of the invention + lactofen, composition of the invention + lenacil,
composition of the invention + linuron, composition of the invention + MAA, composition
of the invention + MAMA, composition of the invention + MCPA, composition of the
5 invention + MCPA-thioethyl, composition of the invention + MCPB, composition of the
invention + mecoprop, composition of the invention + mecoprop-P, composition of the
invention + mefenacet, composition of the invention + mefluidide, composition of the
invention + mesosulfuron, composition of the invention + mesosulfuron-methyl, composition
of the invention + mesotrione, composition of the invention + metam, composition of the
10 invention + metamifop, composition of the invention + metamitron, composition of the
invention + metazachlor, composition of the invention + metazosulfuron, composition of the
invention + methabenzthiazuron, composition of the invention + methazo le, composition of
the invention + methylarsonic acid, composition of the invention + methyldymron,
composition of the invention + methyl isothiocyanate, composition of the invention +
15 metobenzuron, composition of the invention + metobromuron, composition of the invention
+ metolachlor, composition of the invention + S-metolachlor, composition of the invention +
metosulam, composition of the invention + metoxuron, composition of the invention +
metribuzin, composition of the invention + metsulfuron, composition of the invention +
metsulfuron-methyl, composition of the invention + MK-6 16, composition of the invention +
20 molinate, composition of the invention + monolinuron, composition of the invention +
monosulfuron, composition of the invention + monosulfuron-ester, composition of the
invention + MSMA, composition of the invention + naproanilide, composition of the
invention + napropamide, composition of the invention + naptalam, composition of the
invention + NDA-402989, composition of the invention + neburon, composition of the
25 invention + nicosulfuron, composition of the invention + nipyraclofen, composition of the
invention + n-methyl glyphosate, composition of the invention + nonanoic acid, composition
of the invention + norflurazon, composition of the invention + oleic acid (fatty acids),
composition of the invention + orbencarb, composition of the invention + orthosulfamuron,
composition of the invention + oryzalin, composition of the invention + oxadiargyl,
30 composition of the invention + oxadiazon, composition of the invention + oxasulfuron,
composition of the invention + oxaziclomefone, composition of the invention + oxyfluorfen,
composition of the invention + paraquat, composition of the invention + paraquat dichloride,
composition of the invention + pebulate, composition of the invention + pendimethalin,
composition of the invention + penoxsulam, composition of the invention +
pentachlorophenol, composition of the invention + pentanochlor, composition of the
invention + pentoxazone, composition of the invention + pethoxamid, composition of the
5 invention + petrolium oils, composition of the invention + phenmedipham, composition of
the invention + phenmedipham-ethyl, composition of the invention + picloram, composition
of the invention + picolinafen, composition of the invention + pinoxaden, composition of the
invention + piperophos, composition of the invention + potassium arsenite, composition of
the invention + potassium azide, composition of the invention + pretilachlor, composition of
10 the invention + primisulfuron, composition of the invention + primisulfuron-methyl,
composition of the invention + prodiamine, composition of the invention + pro fluazo 1,
composition of the invention + profoxydim, composition of the invention + prohexadionecalcium,
composition of the invention + prometon, composition of the invention +
prometryn, composition of the invention + propachlor, composition of the invention +
15 propanil, composition of the invention + propaquizafop, composition of the invention +
propazine, composition of the invention + propham, composition of the invention +
propisochlor, composition of the invention + propoxycarbazone, composition of the
invention + propoxycarbazone-sodium, composition of the invention + propyzamide,
composition of the invention + prosulfocarb, composition of the invention + prosulfuron,
20 composition of the invention + pyraclonil, composition of the invention + pyraflufen,
composition of the invention + pyraflufen-ethyl, composition of the invention +
pyrasulfotole, composition of the invention + pyrazolynate, composition of the invention +
pyrazosulfuron, composition of the invention + pyrazosulfuron-ethyl, composition of the
invention + pyrazoxyfen, composition of the invention + pyribenzoxim, composition of the
25 invention + pyributicarb, composition of the invention + pyridafol, composition of the
invention + pyridate, composition of the invention + pyrifialid, composition of the invention
+ pyriminobac, composition of the invention + pyriminobac-methyl, composition of the
invention + pyrimisulfan, composition of the invention + pyrithiobac, composition of the
invention + pyrithiobac-sodium, composition of the invention + pyroxasulfone, composition
30 of the invention + pyroxulam, composition of the invention + quinclorac, composition of the
invention + quinmerac, composition of the invention + quinoclamine, composition of the
invention + quizalofop, composition of the invention + quizalofop-P, composition of the
invention + quizalofop-ethyl, composition of the invention + quizalofop-P-ethyl,
composition of the invention + rimsulfuron, composition of the invention + saflufenacil,
composition of the invention + sethoxydim, composition of the invention + siduron,
composition of the invention + simazine, composition of the invention + simetryn,
5 composition of the invention + SMA, composition of the invention + sodium arsenite,
composition of the invention + sodium azide, composition of the invention + sodium
chlorate, composition of the invention + sulcotrione, composition of the invention +
sulfentrazone, composition of the invention + sulfometuron, composition of the invention +
sulfometuron-methyl, composition of the invention + sulfosate, composition of the invention
10 + sulfosulfuron, composition of the invention + sulfuric acid, composition of the invention +
tar oils, composition of the invention + 2,3,6-TBA, composition of the invention + TCA,
composition of the invention + TCA-sodium, composition of the invention + tebutam,
composition of the invention + tebuthiuron, composition of the invention + tefuryltrione,
composition of the invention + tembotrione, composition of the invention + tepraloxydim,
15 composition of the invention + terbacil, composition of the invention + terbumeton,
composition of the invention + terbuthylazine, composition of the invention + terbutryn,
composition of the invention + thenylchlor, composition of the invention + thiazafluron,
composition of the invention + thiazopyr, composition of the invention + thifensulfuron,
composition of the invention + thiencarbazone, composition of the invention +
20 thifensulfuron-methyl, composition of the invention + thiobencarb, composition of the
invention + tiocarbazil, composition of the invention + topramezone, composition of the
invention + tralkoxydim, composition of the invention + triafamone, composition of the
invention + tri-allate, composition of the invention + triasulfuron, composition of the
invention + triaziflam, composition of the invention + tribenuron, composition of the
25 invention + tribenuron-methyl, composition of the invention + tricamba, composition of the
invention + triclopyr, composition of the invention + trietazine, composition of the invention
+ trifloxysulfuron, composition of the invention + trifloxysulfuron-sodium, composition of
the invention + trifluralin, composition of the invention + triflusulfuron, composition of the
invention + triflusulfuron-methyl, composition of the invention + trifop, composition of the
30 invention + trifop-methyl, composition of the invention + trihydroxytriazine, composition of
the invention + trinexapac-ethyl, composition of the invention + tritosulfuron, composition
of the invention + [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-
tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetica cid ethyl ester (CAS RN 353292-
3 1-6), composition of the invention + 4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-
(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.l]oct-3-en-2-o(nCe AS RN 3520 10-68-
5), composition of the invention + 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-
5 methoxypheny1)-2-pyridinecarboxylic acid (CAS RN 943832-60-8), composition of the
invention + 4-amino-3 -chloro-6-(4-chloro-2-fluoro-3 -methoxyphenyl)-2-pyridinecarboxylic
acid methyl ester and the composition of the invention + 4-hydroxy-3-[[2-(3-
methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo 3.2.lloct-3-en-2-one.
Whilst compositions comprising a safener and a two-way mixture of a compound of
10 formula (I) and another herbicide are explicitly disclosed above, the skilled man will
appreciate that the invention extends to three-way, and fbrther multiple combinations
comprising the above two-way mixtures.
Particularly preferred mixture partners for use in the compositions of the invention
are: acetochlor, ametryn, amicarbazone, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-
15 methoxypheny1)-2-pyridinecarboxylic acid (CAS RN 943832-60-8), 4-amino-3-chloro-6-(4-
chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylica cid methyl ester, atrazine,
bicyclopyrone, clethodim, clodinafop, clodinafop-propargyl, clomazone, 2,4-D, dicamba,
diflufenican, dimethachlor, dimethenamid, dimethenamid-P, diuron, fenoxaprop,
fenoxaprop-P, fenoxaprop-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl,
20 flucarbazone, flucarbazone-sodium, flufenacet, flumetsulam, flumioxazin, fomesafen,
foramsulfuron, glufosinate, glufosinate-ammonium, glyphosate, haloxyfop, haloxyfop-P,
hexazinone, imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr,
imazaquin, imazethapyr, iodosulfuron, iodosulfuron-methyl-sodium, ip fencarbazone,
isoxaflutole, mesosulfuron, mesosulfuron-methyl, mesotrione, metazachlor, metolachlor, S-
25 metolachlor, metribuzin, metsulfuron, metsulfuron-methyl, nicosulfuron, oxyflurfen,
paraquat, paraquat dichloride, pinoxaden, prosulfocarb, pyroxasulfone, quizalofop,
quizalofop-P, quizalofop-ethyl, quizalofop-P-ethyl, rimsulfuron, saflufenacil, simazine,
sulfentrazone, tebuthiuron, tembotrione, terbuthylazine, thiencarbazone, and triasulfuron.
More particularly preferred mixture partners for use in the compositions of the
30 invention are: acetochlor, ametryn, atrazine, bicyclopyrone, glufosinate, glufosinateammonium,
glyphosate, isoxaflutole, mesotrione, metolachlor, S-metolachlor,
pyroxasulfone, tembotrione, terbuthylazine and topramezone.
For the avoidance of doubt, even if not explicitly stated above, the mixing partners
may also be in the form of any suitable agrochemically acceptable ester or salt, as mentioned
5 e.g. in The Pesticide Manual, Thirteenth Edition, British Crop Protection Council, 2003.
The mixing ratio of the compound of formula (I) to the mixing partner is preferably
from 1: 500 to 1000:l.
Various aspects and embodiments of the present invention will now be illustrated in
10 more detail by way of example. It will be appreciated that modification of detail may be
made without departing from the scope of the invention.
For the avoidance of doubt, where a literary reference, patent application, or patent, is
cited within the text of this application, the entire text of said citation is herein incorporated
by reference.
EXAMPLES
EXAMPLE 1 Safening on Corn and Wheat
Maize (variety Claxxon) and wheat (variety Hereward) seeds were treated with a
herbicide safener at a rate of 0.2 g safener per kg seed (maize) and 0.25 g safener per kg seed
20 (wheat) prior to sowing. Treated and untreated seeds were sown into standard soil in
troughs. The safeners used were N-(2-methoxybenzoy1)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide (safener A in Table 2) and cloquintocetmexyl.
The day after planting the troughs were sprayed with an aqueous spray solution
25 prepared by dissolving the technical active ingredient in an organic solvent and diluting with
deionised water to give a final dose of 250 glha of a compound of formula (I).
The spray solution was applied with a cabinet tracksprayer with a flat fan nozzle
(Teejet 11002VS) and an application volume of 200Llha (at 2 bar).
The test plants were then grown on in a glasshouse under controlled conditions (at
24/18 "C daylnight; 16 hours light; 65% humidity) and watered twice a day. After 21 days
5 the test was evaluated for general crop injury (100% equals total damage to plant; 0% equals
no damage to plant).
Results are shown below in Table 2 as the mean % visual phytotoxicity of two
replicates.
10 TABLE 2 Percentage damage caused to corn and wheat, untreated and treated with
safeners, by compounds of formula (I)
EXAMPLE 2 Post-Emergence Crop Safening
Compound
1
5
6
7
16
20
2 1
4 1
53
8 5
102
103
133
145
146
147
15 Maize (variety Garland) and soya (variety Nikko) seeds were sown into standard soil
in pots and cultivated under controlled conditions in a glasshouse (at 24/18 "C daylnight; 16
hours light; 65% humidity).
Untreated
corn
30
55
8 0
9 8
8 6
40
30
8 0
40
65
5
10
20
20
22.5
15
Corn treated
with safener
A
5
25
5
10
2.5
0
20
5
5
15
0
0
10
0
0
2.5
Untreated
wheat
35
45
30
50
40
25
20
35
40
40
10
15
25
10
40
25
Wheat
treated with
cloquintocetmexyl
5
20
10
30
15
15
5
10
10
15
0
0
5
5
17.5
5
When the plants were at the vegetative stage of 2-3 leaves they were sprayed with an
aqueous spray solution containing a compound of formula (I) alone and in combination with
a number of different herbicide safeners. All the compounds used for the spray solution were
present as technical material and the safeners were either an EC, SC or WP formulation
5 respectively or technical material. In addition a non-ionic surfactant (Tween 20) was added
to form a 0.25% vlv solution.
The spray solution was applied with a cabinet tracksprayer with a flat fan nozzle
(Teejet 11002VS) and an application volume of 200Llha (at 2 bar).
The test plants were then grown on in a glasshouse under controlled conditions (at
10 24/18 "C daylnight; 16 hours light; 65% humidity) and watered twice a day. After 21 days
the test was evaluated for general crop injury (100% equals total damage to plant; 0% equals
no damage to plant).
Results are shown below in Table 3 as the mean % visual phytotoxicity of two
replicates and in Table 4 as the mean % visual phytotoxicity of a single replicate.
TABLE 3 Percentage damage caused to maize by compounds of formula (I) alone
and in the presence of a number of safeners
Com~osition Maize
500 glha Compound 4 1 Alone
500 glha 4 1 + 100 glha Benoxacor
500 glha 4 1 + 100gIha Cloquintocet-mexyl
500 glha 4 1 + 100gIha Isoxadifen-ethyl
500 glha 4 1 + 100gIha Cyprosulfamide
500 glha 41 + 100gIha Concep 111"
500 glha 4 1 + 100gIha Mefenpyr-diethyl
25
6
4
1
1
8
2
500 glha 4 1 + 100gIha Dichlormid
500 glha 4 1 + 100gIha Naphthalic anhydride
TABLE 4 Percentage damage caused to soya by compounds of formula (I) alone
and in the presence of a number of safeners
4
6
500 glha 4 1 + 100gIha + Safener A 0
"Concep I11 contains 74.3% fluxofenim.
Composition
200 rrlha Com~ound4 1 Alone
Soya
30
200 glha 41 + 100 glha Benoxacor
200 glha 4 1 + 100gIha Cloquintocet-mexyl
0
1
200 glha 4 1 + 100gIha Isoxadifen-ethyl
200 glha 41 + 100gIha Cyprosulfamide
200 glha 41 + 100gIha Concep 111"
200 glha 4 1 + 100gIha Mefenpyr-diethyl
200 glha 41 + 100gIha Dichlormid
0
2
0
2
0
200 glha 4 1 + 100gIha Naphthalic anhydride
200 rrlha 4 1 + 100rrIha + Safener A
2
2
200 glha Compound 106 Alone
200 rrlha 106 + 100 rrlha Benoxacor
15
2 u u
200 glha 106 + 100gIha Cloquintocet-mexyl
200 glha 106 + 100gIha Isoxadifen-ethyl
200 glha 106 + 100gIha Cyprosulfamide
200 glha 106 + 100gIha Concep 111"
200 glha 106 + 100gIha Mefenpyr-diethyl
40
10
10
5
5
200 glha 106 + 100gIha Dichlormid
200 glha 106 + 100gIha Naphthalic anhydride
Although the invention has been described with reference to preferred embodiments
5 and examples thereof, the scope of the present invention is not limited only to those
described embodiments. As will be apparent to persons skilled in the art, modifications and
adaptations to the above-described invention can be made without departing from the spirit
and scope of the invention, which is defined and circumscribed by the appended claims. All
publications cited herein are hereby incorporated by reference in their entirety for all
10 purposes to the same extent as if each individual publication were specifically and
individually indicated to be so incorporated by reference.
5
5
200 glha 106 + 100gIha + Safener A 10
"Concep I11 contains 74.3% fluxofenim.
CLAIMS
1. A composition for protecting crop plants from the harmful effects of a sulphonanilide
derivative herbicide of formula (I)
or a salt or N-oxide thereof wherein
R1 is H, C1.4alky1, C3-salkeny1, propargyl, C1.4alkoxyC1.2alky1, C1. 4alkoxyC1.2 alkoxyC1.
2alky1, C1.4alkylthi0C~.~alkyal,r ylC1.2alkyl optionally substituted by 1-3 groups R20,
heteroarylCl.2alkyl optionally substituted by 1-3 groups R20, phenylthioClaalkyl,
arylC1-2alkoxyC1.2alkyl optionally substituted by 1-3 groups R20, Cl.5alkylcarbonyl, C2.
~alkenylcarbonylC, 1.4haloalkylcarbony1, C3.6cycloalkylcarbonyl,a rylcarbonyl
optionally substituted by 1-3 groups R20, Cl.loalkoxycarbonyl, C1.4haloalkoxycarbonyl,
C3.~alkenyloxycarbonyl,p ropargyloxycarbonyl, C1.4alkoxyC1.2alkoxycarbonyl,C 1.
4alkylthiocarbony1, aryloxycarbonyl optionally substituted by 1-3 groups R20, arylCl.
2alkoxycarbonyl optionally substituted by 1-3 groups R20, aminocarbonyl, C1.
4alkylaminocarbony1, di(C1.4alkyl)aminocarbonyl, C1.4alkylsulphonyl or C1.
4haloalkylsulphonyl and each R20 is, independently, halogen, C1.4alkyl, C1.4haloalkyl,
C1.4alkoxy, C1.4haloalkoxy, C1 .2alkoxyC1 .2alkoxy, hydroxy, phenyl or phenoxy;
R2 is halogen or methyl;
X is oxygen or cR3R4;
R3 and R4 are independently H or C1.4alkyl;
Y is oxygen or cR5R6;
R5 and R6 are independently H, Cl-salkyl, C1-4haloalky1, C3.6~y~l~alkCy1. l4,a lkoxyC1.
4alkyl or aryl optionally substituted by 1-3 groups R21 or R5 and R6 together form a C2.
~alkylenec hain or an 0x0 group and each R2' is, independently, halogen, C1.4alkyl,C 1.
4haloalky1, C1.4alkoxy, C1_4haloalkoxy,C 1.2alko~yC~.~alkoxhyy,d roxy, phenyl or
phenoxy
Z is oxygen, cR8R9 or NR";
R8 and R9 are independently H, halogen, C1.4alkyl, C1.4alkoxy, C1.4alkylthio or C1.
4alkoxycarbonyl;
R1° is H, C1.4alky1, aryl optionally substituted by 1-3 groups R ~C1~.4a,lk ylcarbonylo r
C 1 -4alkoxycarbonyl and each R~~ is, independently, halogen, C -4alky1, C -4halo alkyl,
C1-4alkoxy, C1.4haloalkoxy, C1. 2alkoxyC1.2 alkoxy, hydroxy, phenyl or phenoxy;
provided that only one of X, Y and Z is oxygen;
and wherein said composition comprises, in addition to the sulphonanilide derivative
herbicide of formula (I), at least one safener selected from the group consisting of
benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of cyometrinil,
cyprosulfamide (CAS RN 22 1667-3 1 -8), dichlormid, fenchlorazole-ethyl, fenclorim,
flurazole, fluxofenim, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (CAS
RN 8 1 -84-5), oxabetrinil, N-(2-methoxybenzoy1)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R-29148 (CAS RN
52836-3 1-4) or a 2,2,4,5-tetrasubstituted3 -dichloroacetyl- 1,3-oxazolidine.
25 2. The composition according to claim 1, wherein R20 is halogen, C1.2alkyl or C1.
2haloalkyl.
3. The composition according to claim 1, wherein R1 is H, Cl.5alkoxycarbonyl, C1
4haloalkoxycarbonyl or trifluoromethylsulphonyl.
4. The composition according to any one of the previous claims, wherein m is 0.
5. The composition according to any one of the preceding claims, wherein X is oxygen or
5 CH2.
6. The composition according to any one of the preceding claims, wherein R5 is H, C1.
4alky1, C1.2haloalkyl or cyclopropyl.
7. The composition according to any one of the preceding claims, wherein R6 is H, C1.
4alkyl or aryl optionally substituted by 1-3 groups R21.
10 8. The composition according to claim 7, wherein R21 is halogen, C1.2alkyl or C1.
2haloalkyl.
9. The composition according to any one of claims 1 to 5, wherein R5 and R6 together
form a C2.5alkylene chain.
10. The composition according to any one of the preceding claims, wherein R8 is H,
15 halogen or C1.2alkyl.
1 1. The composition according to any one of the preceding claims, wherein R9 is H,
halogen, C1.2alkyl or Claalkylthio.
12. The composition according to any one of the preceding claims, wherein R1° is H, C1.
2alkyl or C1.4alkoxycarbonyl.
20 13. The composition according to any one of the preceding claims, wherein the safener is
N-(2-methoxybenzoy1)-4-[ (methylaminocarbonyl)amino]b enzenesulfonamide.
14. The composition according to any one of claims 1 to 12, wherein the safener is
cloquintocet-mexyl.
15. A method for protecting crops of usehl plants from the harmful effects of a herbicide
25 of formula (I) as defined in any one of claims 1 to 12, which comprises applying to the
locus of the usehl plants at least one safener selected from the group consisting of
benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of cyometrinil,
cyprosulfamide (CAS RN 22 1667-3 1 -8), dichlormid, fenchlorazole-ethyl, fenclorim,
flurazole, fluxofenirn, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic anhydride (CAS
RN 8 1 -84-5), oxabetrinil, N-(2-methoxybenzoy1)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R-29 148 (CAS RN
52836-3 1-4) or a 2,2,4,5-tetrasubstituted 3-dichloroacetyl- l,3-oxazolidine.
16. A method for combating weeds in crops of usefbl plants, which comprises treating the
useful plants, seeds or cuttings thereof or the locus of the useful plants simultaneously
or at separate times with a herbicidally active amount of a compound of formula (I) as
defined in any one of claims 1 to 12 and at least one safener selected from the group
consisting of benoxacor, cloquintocet-mexyl, cyometrinil, the (Z) isomer of
cyometrinil, cyprosulfamide (CAS RN 221667-3 1-8), dichlormid, fenchlorazole-ethyl,
fenclorim, flurazole, fluxofenim, isoxadifen-ethyl, mefenpyr-diethyl, naphthalic
anhydride (CAS RN 8 1-84-5), oxabetrinil, N-(2-methoxybenzoy1)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide, an oxylipin A, R-29 148 (CAS RN
52836-3 1-4) or a 2,2,4,5-tetrasubstituted 3-dichloroacetyl- l,3-oxazolidine.