CA1288253C - Synergistic composition and method of selectively controlling weeds in cereals - Google Patents
Synergistic composition and method of selectively controlling weeds in cerealsInfo
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- CA1288253C CA1288253C CA000531189A CA531189A CA1288253C CA 1288253 C CA1288253 C CA 1288253C CA 000531189 A CA000531189 A CA 000531189A CA 531189 A CA531189 A CA 531189A CA 1288253 C CA1288253 C CA 1288253C
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
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- Pest Control & Pesticides (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
5-15782/+
Synergistic composition and method of selectively controlling weeds in cereals Abstract of the Disclosure Compositions which contain, as one active component, N-[2-(2-chloro-ethoxy)phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-ures of formula I
Synergistic composition and method of selectively controlling weeds in cereals Abstract of the Disclosure Compositions which contain, as one active component, N-[2-(2-chloro-ethoxy)phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-ures of formula I
Description
~ ~ifi~
5-157821+
Synergistic composition and method of selectively controllin~ weeds in cereals The present invention relates to a fiynergistic composition con-taining a combination of herbicides that is preeminently suitable for selectively controlling weeds in crops of cereals. The invention also relates to a method of controlling weeds in cereals, and to the use of the novel composition.
The most frequently encountered and most important weeds at the present time in cereals are species of the genera Avenua fatua (wild oat), Lolium (darr.el), Setaria (foxtail millet~, Sinapis (mustard), Stellaria (stichwort) and Veronica (speedwell).
An excellent selective herbicide against weeds in crops of cultivat-ed plants is N-~2-(2-chlnroethoxy)phenylsulfonyll-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea o~ formula I
SO2-NH-CO-NH--~ ~N (I) ~z- =.
O-CHz-CH2Cl \OCH3 This compound, together with the preparation and use thereof, is disclosed in published European patent application 44 808.
Compounds of the formulae II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII and XIX are also known selec-tive herbicides and some are commercially available.
The ~ollowing specl~ic comDounds in particular fall within the scope of formula Il R~ 0-~ NO2 (II) \Cl ~Z
wherein Rl is chlorine or trifluoromethyl and R2 is hydrogen, Cl-C4alkoxycarbonyl, Cl-C4alkoxy, -COONa, -COOK, -COOH, -CO-NH-S02CH~, -COO-CH(CH3)-COOC2Hs~ -C(CH3)=N-O-CHz-COOCH~ or -COO-CH2-COOC2Hs:
IIa: methyl 5-(2,4-dichlorphenoxy)-2-nitrobenzoate, known from the Pesticide Manual 7th Ed. (1983), 950, The British Crop Protec-tion Council, London;
IIb: 2,4-dichloro-(4-nitrophenoxy)benzene, known from the Pesticide Manual 7th Ed. (1983), 8950, The British Crop Protection Council, London;
IIc: 4-(2-chloro-4-trifluoromethylphenoxy)-2-ethoxynitrobenzene, - known from US patent 4,220,468;
IId: 4-(2,4-dichlorophenoxy)-2-methoxynitrobenzene, known from the Pesticide Manual 7th Ed. (1983), 4305, The British Crop Protection Council, London;
IIe: 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoic acid, known from the Pesticide Manual 7th Ed. (1983), 40, The British Crop Protection Council, London;
IIf: l-ethoxycarbonylethyl 5-~2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate, known from published European patent applica-tion 20 G52;
.
:
, X5.~
Ilg: 5-(2-ch-oro-4-trifluoromethy1phenoxy)-Z-nitrobenzoic ~cid methylslllfonylamlde, known from J. Agric. Food Chem. 25, 133g (l9~7);
IIh: 5-~2-chloro-4-trifluoromethylphenoxy)acetophenone oxime methoxycarbonylmethyl ether, known from German Offenlegungs-schrift 30 17 795; and IIi: ethoxycarbonylmethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate, known from published European patent applica-tion 20 052.
The following specific compounds fall within the scope of for- -mula III
N3C~ --OH (III) wherein R3 is bromine or iodine:
IlIa: 3,5-dibromo-4-hydroxybenzonitrile, known from the Pesticide Manual 7th Ed. (1983), 1410, The British Crop Protection Council, London; and IIIb: 3,5-diiodo-4-hydroxybenzonitrile, known from the Pesticide Manual 7th Ed. (1983), 7300, The British Crop Protection Council, London.
The following individual compounds in particular fall within the scope of formula IV
. _ .
Cl--~ ~--O-CH-COOH (IV) \R4 wherein R~ i~ chlorine or methyl and Rs is hydrogen or methyl:
IVa: 2,4-dichlorophenoxyacetic acid, known fro~ the Pesticide Manual 7th Ed. (1983), 3780, The ~ritish Crop Protection Council, London;
IVb: 4-chloro-2-methylphenoxyacetic acid, known from the Pesticide Manual 7th Ed. (1983), 7790, The British Crop Protection Council, London;
IVc: 2-(4-chloro-2-methylphenoxy)propionic acid, known from the Pesticide Manual 7th Ed. (1983), 7790, The British Crop Protection Council, London; and IVd: 2-(2,4-dichlorophenoxy)propionic acid, known from the Pesticide Manual 7th Ed. (1983), 4480, The British Crop Protection Council, London.
The following compounds in particular fall within the scope of formula V
~CH 3 ~b (v) R6-NH ~N NH-R7 wherein R~ is ethyl or methoxypropyl and R7 is isopropyl or tert-butyl:
Va: 2-ethylamino-4-tert-butylamino-6-methylthio-1,3,5-triazine, known from the Pesticide Manual 7th Ed. (1983), 11330, The British Crop Protection Council, London; and Vb: 2-isopropylamino-4-(3-methxoypropylamino)-6-methylthio-1,3,5-triazine, known from the Pesticide Manual 7th Ed. (1983), 8210, The British Crop Protection Council, London.
- s -The following compounds fall within the scope of ~ormula V1 H~N- ~ C4Hg-t (VI) RS _ S~
wherein R8 is methyl or ethyl:
VIa: 4-amino-6-tert-butyl-4,5-dihydro-3-ethylthio-1" ,4-triazin-5-one, known from '~S patent 3,671,523; and VIb: 4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one, known from the Pesticide Manual 7th Ed. (1983), 8580, The British Crop Protection Council, London.
The following individual substances fall within the scope of for-mula VII
,N--R9-SOz-NH-CO-~ N (VII) Rl~ N=~
\OCH3 wherein R9 is 2-methoxycarbonylphenyl or 2-methoxycarbonyltnien-3-yl and R1~ is hydrogen or methyl:
VIIa: N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, known from published European patent application 7 687;
VIIb: N-(2-methoxycarbonylthien-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, known from published European patent application 30 142; and VIIc: N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N'-methylurea, known from published European patent application 7 687.
. .
x~
The compounds of form~slae VIII, IX, X, Xl, XII, XIII, XIV, XV, XVI, XVII, .YVIII and XIX are illustrated by the following formulae:
7-chloro-3-methylquinoline-8-carboxylic acid of formula VIII
ICOOH
Cl\ ~
j il i (VIII) ~./ \.~ \CH3 known from German Offenlegungsschrift 32 33 089;
methyl 2-¦4-(2,4-dichlorophenoxy)phenoxy]propionate of formula IX
_ ~--O--~ ~---O-C~H-COOCH3 (IX) \Cl H3 known from the Pesticide Manual 7th Ed. (1983) 4520, The British Crop Protection Council, London;
N-benzoyl-N-(3-chloro-4-fluoropheny1)alanine isopropyl ester of formula X
Cl~
F~ -CH-COOC~H7-i (X) =' lo-.~
known from the Pesticide Manual 7th Ed. (1983) 6380, The British Crop Protection Council, London;
5-157821+
Synergistic composition and method of selectively controllin~ weeds in cereals The present invention relates to a fiynergistic composition con-taining a combination of herbicides that is preeminently suitable for selectively controlling weeds in crops of cereals. The invention also relates to a method of controlling weeds in cereals, and to the use of the novel composition.
The most frequently encountered and most important weeds at the present time in cereals are species of the genera Avenua fatua (wild oat), Lolium (darr.el), Setaria (foxtail millet~, Sinapis (mustard), Stellaria (stichwort) and Veronica (speedwell).
An excellent selective herbicide against weeds in crops of cultivat-ed plants is N-~2-(2-chlnroethoxy)phenylsulfonyll-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea o~ formula I
SO2-NH-CO-NH--~ ~N (I) ~z- =.
O-CHz-CH2Cl \OCH3 This compound, together with the preparation and use thereof, is disclosed in published European patent application 44 808.
Compounds of the formulae II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII and XIX are also known selec-tive herbicides and some are commercially available.
The ~ollowing specl~ic comDounds in particular fall within the scope of formula Il R~ 0-~ NO2 (II) \Cl ~Z
wherein Rl is chlorine or trifluoromethyl and R2 is hydrogen, Cl-C4alkoxycarbonyl, Cl-C4alkoxy, -COONa, -COOK, -COOH, -CO-NH-S02CH~, -COO-CH(CH3)-COOC2Hs~ -C(CH3)=N-O-CHz-COOCH~ or -COO-CH2-COOC2Hs:
IIa: methyl 5-(2,4-dichlorphenoxy)-2-nitrobenzoate, known from the Pesticide Manual 7th Ed. (1983), 950, The British Crop Protec-tion Council, London;
IIb: 2,4-dichloro-(4-nitrophenoxy)benzene, known from the Pesticide Manual 7th Ed. (1983), 8950, The British Crop Protection Council, London;
IIc: 4-(2-chloro-4-trifluoromethylphenoxy)-2-ethoxynitrobenzene, - known from US patent 4,220,468;
IId: 4-(2,4-dichlorophenoxy)-2-methoxynitrobenzene, known from the Pesticide Manual 7th Ed. (1983), 4305, The British Crop Protection Council, London;
IIe: 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoic acid, known from the Pesticide Manual 7th Ed. (1983), 40, The British Crop Protection Council, London;
IIf: l-ethoxycarbonylethyl 5-~2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate, known from published European patent applica-tion 20 G52;
.
:
, X5.~
Ilg: 5-(2-ch-oro-4-trifluoromethy1phenoxy)-Z-nitrobenzoic ~cid methylslllfonylamlde, known from J. Agric. Food Chem. 25, 133g (l9~7);
IIh: 5-~2-chloro-4-trifluoromethylphenoxy)acetophenone oxime methoxycarbonylmethyl ether, known from German Offenlegungs-schrift 30 17 795; and IIi: ethoxycarbonylmethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate, known from published European patent applica-tion 20 052.
The following specific compounds fall within the scope of for- -mula III
N3C~ --OH (III) wherein R3 is bromine or iodine:
IlIa: 3,5-dibromo-4-hydroxybenzonitrile, known from the Pesticide Manual 7th Ed. (1983), 1410, The British Crop Protection Council, London; and IIIb: 3,5-diiodo-4-hydroxybenzonitrile, known from the Pesticide Manual 7th Ed. (1983), 7300, The British Crop Protection Council, London.
The following individual compounds in particular fall within the scope of formula IV
. _ .
Cl--~ ~--O-CH-COOH (IV) \R4 wherein R~ i~ chlorine or methyl and Rs is hydrogen or methyl:
IVa: 2,4-dichlorophenoxyacetic acid, known fro~ the Pesticide Manual 7th Ed. (1983), 3780, The ~ritish Crop Protection Council, London;
IVb: 4-chloro-2-methylphenoxyacetic acid, known from the Pesticide Manual 7th Ed. (1983), 7790, The British Crop Protection Council, London;
IVc: 2-(4-chloro-2-methylphenoxy)propionic acid, known from the Pesticide Manual 7th Ed. (1983), 7790, The British Crop Protection Council, London; and IVd: 2-(2,4-dichlorophenoxy)propionic acid, known from the Pesticide Manual 7th Ed. (1983), 4480, The British Crop Protection Council, London.
The following compounds in particular fall within the scope of formula V
~CH 3 ~b (v) R6-NH ~N NH-R7 wherein R~ is ethyl or methoxypropyl and R7 is isopropyl or tert-butyl:
Va: 2-ethylamino-4-tert-butylamino-6-methylthio-1,3,5-triazine, known from the Pesticide Manual 7th Ed. (1983), 11330, The British Crop Protection Council, London; and Vb: 2-isopropylamino-4-(3-methxoypropylamino)-6-methylthio-1,3,5-triazine, known from the Pesticide Manual 7th Ed. (1983), 8210, The British Crop Protection Council, London.
- s -The following compounds fall within the scope of ~ormula V1 H~N- ~ C4Hg-t (VI) RS _ S~
wherein R8 is methyl or ethyl:
VIa: 4-amino-6-tert-butyl-4,5-dihydro-3-ethylthio-1" ,4-triazin-5-one, known from '~S patent 3,671,523; and VIb: 4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one, known from the Pesticide Manual 7th Ed. (1983), 8580, The British Crop Protection Council, London.
The following individual substances fall within the scope of for-mula VII
,N--R9-SOz-NH-CO-~ N (VII) Rl~ N=~
\OCH3 wherein R9 is 2-methoxycarbonylphenyl or 2-methoxycarbonyltnien-3-yl and R1~ is hydrogen or methyl:
VIIa: N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, known from published European patent application 7 687;
VIIb: N-(2-methoxycarbonylthien-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, known from published European patent application 30 142; and VIIc: N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N'-methylurea, known from published European patent application 7 687.
. .
x~
The compounds of form~slae VIII, IX, X, Xl, XII, XIII, XIV, XV, XVI, XVII, .YVIII and XIX are illustrated by the following formulae:
7-chloro-3-methylquinoline-8-carboxylic acid of formula VIII
ICOOH
Cl\ ~
j il i (VIII) ~./ \.~ \CH3 known from German Offenlegungsschrift 32 33 089;
methyl 2-¦4-(2,4-dichlorophenoxy)phenoxy]propionate of formula IX
_ ~--O--~ ~---O-C~H-COOCH3 (IX) \Cl H3 known from the Pesticide Manual 7th Ed. (1983) 4520, The British Crop Protection Council, London;
N-benzoyl-N-(3-chloro-4-fluoropheny1)alanine isopropyl ester of formula X
Cl~
F~ -CH-COOC~H7-i (X) =' lo-.~
known from the Pesticide Manual 7th Ed. (1983) 6380, The British Crop Protection Council, London;
3,5-dibromo-4-hydroxybenzaldehyde oxime (2,4-dinitrophenyl) ether of formula XI
~, ~S~
~, HC~ CH=N-0-~ -N0~ (XI) Br N~2 known from the Pesticide Manual 7th Ed. (1983) 1360, The British Crop Protection Council, London;
N-(2,4-difluorophenyl)-2-(3-trifluoromethylphenoxy)nicotinic acid amide of formula XII
F~ (XII) ~N~ \0--~ ~-~ CF1 known from published European patent appllcation 53 011.
1-(2-benzothiazolyl)-1,3-dimethylurea of formula XIII
,~ \.~ \
~ -C0-NH-CH3 (XIII) known from the Pesticide Manual 7th Ed. (1983) 8050, The British Crop Protection Council, London;
(4-amino-3,5-dichloro-6-fluoropyridin-2-yloxy)acetic acid of formula XIV
N,2 ~Cl Cl-~ ~--O-CH2-COOH (XIV) F
nown from VS patent 4 110 104;
N~ ethylpropyl)-3,4-dlmethyl-2,6-dinitroaniline of formula XV
H3C~ -NH-C~ (XV) known from the Pesticide Manual 7th Ed. (1983) 9390, The British Crop Protection Council, London;
3,6-dichloro-2-methoxybenzoic acid of formula XVI
~Cl ~ -COOH (XVI) Cl OCH3 known from the Pesticide Manual 7th Ed. (1983) 4100, The British Crop Protection Council, London;
S-(2,3-dichloroallyl)diisopropylthiocarbamate of formula XVII
HClC=CC1-CH2-S-CO-N(C3Hz-i)2 (XVII) known from the Pesticide Manual 7th Ed. (1983) 3990, The British Crop Protection Council, London;
3,6-dichloropicolinic acid of formula XVIII
~ COOH ~XVIII) Cl/
known from the Pesticide Manual 5th Ed. (1977) 177, The British Crop Protection Council, London; and ethyl 2-[4-(6-chlorobenzoxazol-2-yloxy)phenoxy]propionate of for~ula XIX
~'J~ 5~
~ o--~ O-CH-COOC2Hs (XIX) known from the Pesticide Manual 7th Ed. (1983) 6160, The ~ritish Crop Protection Council, London.
Surprisingly, it has now been found that a combination of two compounds, in a variety of ratios, namely compound I and a compound selected from compound classes II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX, exerts a synergis-tic action that is able to control the majority of all important weeds in cereals without causing injury to the cereal crops. The principal weeds found in crops of cereals, e.g. species of the monocotyledenous genera Alopecurus, Avena and Setaria, as well as of the dicotyledenous genera Chrysanthemum, ~alium, Sinapis, Stellaria and Venturia, are controlled selectively by preemergence as well as postemergence treatment.
Accordingly, the present invention provides a novel synergistic composition for selectively controlling weeds that contains, as one active component, N-[2-(2-chloroethoxy)phenylsulfonyll-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea of formula I
SO2-NH-CO-NH-~
O-CH2-CH2Cl OCH3 and, as second active component, either a compound formula II
R~ -_0_~ NO2 (II) \Cl ~2 l~aa~
lo -~!herein Rl is chlorine or trifluoromethyl and R2 is hydrogen, Cl-C4alkoxycarbonyl, C~-C~lkoxy, -CCJONa, -COOK, -COOH, -CO-NH-SO2CH3, -COO-CH(CH3 )-COOC7Hs ~ -C(CH3)=N-O-CH2-CO-JCH3 or -COO-CH.-COOC2Hs, or a compound of formula III
N-eC~ -OH (III) \R3 wherein R3 is bromine or iodine, or a compound of formula (IV) Cl--~ O-CH-COOH (IV) .=.
wherein ~ is chlorine or methyl and Rs is hydrogen or methyl, or a compound of formula V
(V) R~-NH ~ ~ ~ H-R7 wherein R~ is ethyl or methoxypropyl and R7 is isopropyl or tert-butyl, or a compound of formula VI
R
H2N- ~ C4Hg-t ~VI) R8-S--~ ~
1~i8253 wherein R8 is methyl or ethyl, or a compound of formula VII
/c~3 R9-So2-NH-Co~ (VII) wherein R9 is 2-methoxycarbonylphenyl or 2-methoxycarbonylthien-3-yl and Rl is hydrogen or methyl, or the compound of formula VIII
C) 00~
Cl~ (VIII) ~./ \.~ \CH3 or the compound of formula IX
\ / O \ /~-O-~CH-COOCH3 (IX) or the compound of formula X
Cl~
F--~ H-COOC3H~-i (X) CO--~
or the compound of formula XI
Br\
HO--~ ~--CH=N-O--~ ~--NO2 (XI) Br N~2 or the compound of formula XII
1~82~3 NH~ F (XII) =--CF3 or the compound of formula XIII
CO-NH-CH3 (XIII) ~ H3 or the compound of formula XIV
N~2 ~Cl Cl~ --O-CH2-COOH (XIV) ~=
or the compound of formula XV
~NO2 ~--~ C2Hs H3C--~ ~--NH-C~ (XV) .=. C2Hs or the compound of formula XVI
~Cl ~ -COOH (XVI) Cl/ OCH3 or the compound of formula XVII
HClC=CCl-CH2-S-CO-~(C3H7-i)2 (XVII) or the compound of formula XVIII
1~38X'~:~
Cl COO~I ( XVI I I ) Cl~
or the compound of formula XIX
i i1 \--0~ --O-~H-COOC2Hs (XIX) in admixture with each other.
It is extremely surprising that the combination of the compound of formula I with a compound of formula II, III, I~, V, ~I, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX not only brings about an e~pected additive enhancement of the activity spectrum against the weeds customarily associated with cereals, but also has a synergistic effect that the potentiates the activity range of both components from two points of view.
On the one hand, the rates of application of the individual com-pounds I and II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XI~, XV, XVI, XVII, XYIII or XIX are markedly reduced with no reduction in the effectiveness of said compounds. On the other hand, the herbicidal combination also achieves a high degree of weed control where both individual components have become totally ineffective at too low rates of application. The consequence is a substantial broadening of the activity spectrum against weeds and an additlonal increase in the safety margin for application to cereals that i8 necessary and desirable in the event of unintentional overapplication.
The composition of this invention can be employed for selectively controlling weeds in crops of cereals such as oats, triticale, barley, rye and, in particular, wheat.
, 8~
- l4 -The herbicida~ combination employed ln the practice of this inven-tion contains a compou~ld of Formula I and a compound o~ formula 11, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XYIII or ~I~, in any ratio, but normally with an excess of the one component over the other. The ratio is of such little consequence that excesses of the component o~ formula I as well as of the component of formula II, III, IV, V, VI, YII, ~III, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX are tolerated. The preferred ratio of component I to the component of formula II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX is from 1:1 to 1:2000, in particular from 1:5 to 1:500. The herbicidal combinations of this invention have excellent activtty against weeds without noticeably affecting the crops of cereals in the conveni-ently employed rates of application of 0.005 to 3 kg, preferably 0.01 to 1 kg, per hectare.
Combinations of compound I with the following individual compounds have proved particularly effective synergistic herbicidal mixtures:
a) methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate [compound IIa3;
b~ ethoxycarbonylmethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate [compound IIi~;
c) 3,5-dibromo-4-hydroxybenzonitrile ~compound IIIa~; -d) 3,5-diiodo-4-hydroxybenzonitrile [compound IIIb3;
e~ 2,4-dichlorophenoxyacetic acid [compound Tval;
f) 4-chloro-2-methylphenoxyacetic acid ~compo~nd IVb];
g) 2-(4-chloro-2-methylphenoxy)propionic acid ~compound IYc];
h) 2-ethylamino-4-tert-butylamino-6-methylthio-1,3,5-triazine [compound Va3;
i) 2-isopropylamino-4-(3-methoxypropylamino)-6-methylthio-1,3,~-triazine [compound Vb]
j) 7-chloro-3-methylquinoline-8-carboxylic acid [compound VIII];
k) methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propionate [com-pound IX]; and l~a~s~
1) N-ben~oyl-N-(3-chloro-4-fluorophenyl)alanine isopropyl ester [compound ~].
Compounds IIi, IIIa and VIII are particularly preferred synergistic components.
The formulations, i.e. the compositions or preparations containing the mixture of herbicides of this invention and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds ~surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epo~idised ve~etable oils such as èpoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. To improve the physical properties ~t is also possible to add hlghly dispersed sil;cic acid OI highly dispersed absorbent polymers, Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suit~ble nonsorbent carriers are materials such as calcite or sand. In addition, a great nu~ber o~
pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues, e.g. cork powder or sawdust.
8~
Partioularly advantAgeous application promoting adjuvants which are able to reduce substantially the rate of application are also natural (animal or vegetable) or synthetic phospholipids of the ~eries of the cephalins and lecithins, e.g. phosphatidyl ethanol-amine, phosphatidyl serine, phosphatidyl choline, sphingomyeline, phosphatidyl inisotol, phosphatidyl glycerol, lysolecithin, plasmalogenes or cardiolipin, which can be obtained e.g. from animal or plant cells, in particular from the brain, heart, liver, egg yokes or soya beans. Examples of useful physical forms are phosphat-idyl choline mixtures. Examples of synthetic phospholipids are dioctanoylphosphatidyl choline and dipalmitoylphosphatidyl choline.
Suitable surface-active compounds are non-ionic, cationic and/or anionic sufactants having good emulsifying, dlspersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C1D_C2Z), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, espec~ally fatty sulfonates, fstty sulfates, s~lfo~ated ben~mid-azole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or sub-stltuted ammonium salts and contain a C8-Cz2alkyl radical which also includes the al~yl moiety oF acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a 2S~
mi~ture o~ fattY .~lcohol slJIfAtes obtalned from natural fatty acids.
These com~oun~s also comprise the salts of sulfuric acid esters and sulfonic aciAs of fatty alcohol/ethylene oxlde adducts. The sulfona-ted benximidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radlcal containing 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodiu~, calcium or tri-ethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic acid, or of a naphthalenesulfonic acidJformaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-phenol with 4 to 14 moles of ethylene oxide.
~on-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamino-polypropylene glycol and alkylpolypropylene glycol containing I to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene ~lycol unit.
Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/
polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e,g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
~88~53 Cationic surfacLants are preferably guaternary ammonium sa1ts which contain, as N-substituent, at least one C~-Cz%alkyl radical and, as f~1rther ~ubstituents, unsubstituted or halogenated lower alkyl, benzyl or hydro~y-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.~. stearyl-trimethylammoni~1m chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are dsscribed e.g. in "McCutcheon's Detergents and Emulsiflers Annual", MC Publishing Corp. Ridgewood, New Jersey, 1981; Helmut Stache "Tensid-Taschenbuch" (Surfactant Handbook) Carl Hanser Verlag, Munich/Vienna, 1981; M. and J. Ash: Encyclopaedia of surfactants, Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
The agrochemical compositions usually contain 0.1 to 95 %, p}efer-ably 0.1 to 80 %, of a mixture of herbicides of the formulae I
and II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.
Preferred formulations are composed in particular of the following constituents (% = percentage by weight):
Emulsifiable concentrates mixture of herbicides: 1 to 20 %, preferably 5 to 10 %
surfactant:5 to 30 %, preferably 10 to 20 %
liquid carrier:50 to 94 %~ preferably 70 to 85 %
Dusts mixture of herbicides: 0.1 to 10 %, preferably 0.1 to 1 %
solid carrier:99.9 to 90 %, preferably 99.9 to 99 %
1~88X5~
-- 1~3 --S~s~ension rc~_c~nt~at~
mi~ture o~ her~)icides:5 to 75 ~/0, preferably 10 to 50 ~/, water:94 to 25 %, preferably 90 to 30 ~/~
surfactant:1 to 40 %, preferably 2 to 30 %
Wettable powders mixture of herbicides: 0.5 to 90 %, preferably 1 to 80 %
surfactant: 0.~ to 20 %, preferably 1 to 15 %
solid carrier:S to 95 %, preferably 15 to 90 %
Granulates mixture of herbicides: 0.5 to 30 %, preferably 3 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %.
Whereas commercial products will be preferably formulated as concentrates, the end user will normally employ dilute formulations.
The formulations can be diluted to a concentration as low as O . 0~1 % .
The above described compositions can also be mixed with other biocides or biocidal compositions. Thus in addition to containing the cited compounds of the general formula I and of the formulae II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX, the novel compositions may contain e.g.
insecticides, fungicides, bacterici~es, fungistats, bacteriostats or nematicides in order to improve the activity spectrum.
The compositions of the invention can generally be formulated in accordance with the following Examples:
Formulation Examples Example F1: Formulation examples for syngistic mixtures of herbi-cides of the formulae I and II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX (throughout, percentages are by weight) lX~3825~
a) Wettab_e_~owd~rs a) b) c) d) compound ~ lO % 20 % 5 % 30 ~/~
compound I~, III, IV, V, Vl, VII, VIII, IX, X, XI~ XII, XIII, XIV, XV, ~VI, XVII, XVIII or XIX 10 r/~ 40 % 15 % 30 %
sodium li~nosulfonate 5 J~ 5 c/ 5 ~/v S ~/~
sodium laurylsulfate3 % - 3 %
sodium diisobutylnaphthalene-sulfonate - 6 % - 6 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 % - 2 %
highly dispersed silicic acid 5 % 27 % 5 % 27 %
kaolin 67 % - 67 %
The mixture of herbicides is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
b) Emulsifiable concentrates a) b) c) compound I 5 % 5 % l2 %
compound II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII
or XIX 5 % 20 % 13 %
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 % 3 % 3 %
calcium dodecylbenzenesulfonate 3 % 3 % 3 %
castor oil polyglycol ether (36 moles of ethylene oxide) 4 % 4 % 4 %
cyclohexanone 3a 2~ 3a 5~ 3~ ~
xy1ene mixt~e 50 % 35 ~o 35 %
Emulsions of any required concentration can be obtained from these concentrates by dilution with water.
~ ~8XS3 c) Du~ts a) b) c) d>
compound I 2 % 4 % 2 % 4 %
compound II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX 3 % 4 % 4 % 8 %
talcum 95 %~ % 94 % ~ %
kaolin - 92 % - 88 %
Ready for use dusts are obtained by mixing the mixture of herbicides with ~he carriers, and grinding the mixture in a suitable mill.
d) Extruder granulates a) b)c) compound I 5 % 3 % 5 %
compound II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX 5 % 7 % 15 %
sodium lignosulfonate 2 % 2 % 2 %
carboxymethylcellulose 1 % 1 % 1 %
kaolin 87 % 87 % 77 %
The mixture of herbicides is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. This mixture is extruded and then dried in a stream of air.
e) Coated granulates a) b) compound I l.5 % 3 %
compound II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII
or XIX 1.5 % 5 %
polyethylene gly^ol 200 3.0 % 3 %
kao~in 94.0 % 89 %
The finely ground mixture of herbicide is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
~; -'' 8~
-- 2 '~ --f) Su~l)en~1o~ ~ ~neetll!.?tes a) b) compo~lnd 1 20 % 20 ~, co~pound II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII~ XIV, XV, XVI, XVII, XVIIr or XIX 20 % 40 %
ethylene glycol 10 ~ 10 %
nonylphsnol polyethylene glycol ether (15 moles of ethylene oxide) 6 % 6 %
sodium lignosulfonate 10 %10.0 %
carboxymethylcellulose 1 % 1.0 %
37 % aqueous formaldehyde solution 0.2 % 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 0.8 %
water 32.0 % 12.0 %
The finely ground mixture of herbicides is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of any desi}ed concentration can be obtained by dilution with water.
Herbicides always have a synergistic effect if the herbicidal action of the combination of I and II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX is greater than the action to be expected when the individual herbicides are employed together.
The expected herbicidal activlty ~ for a gi~en combination of two herbicides call be calculated as follows (cf. COLBY, S.R., "Calculat-ing synergistic and antagonistic responses of herbicide composi-tions", Weeds 15, page~ 20-22, 1967).
E = X + Y (IoO-X) X = the percentage growth inhibition, compared with untreated controls (5 0 %), after treatment with a herbicide I at a rate of application of p kg per hectare, l~aa~s~
Y = the percellL~ge g1owth inhibition, compared wlth untreated controls, after treatment with a herblcide II, III~ IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XI~ at a rate of application of q kg per hectare, and E ~ the expected herbicidal activity (percentage growth inhibition compared with untreated controls) after treatment wlth the he}bicidal mixture of I and II, III, IY, V, VI, VII, ~III, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX at a rate of appllcation of p + q kg of active ingredient per hectare.
If the actually observed value is higher than the expected value E, then there is synergism.
The synergistic effect of the combinations of compounds I and II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX is demonstrated in the following Examples.
Biological Examples Example B1: Preemergence test The test plants are sown in a greenho~se in plastic pots containing 0-5 & of sterilised garden soil. One day after sowing, the surface of the soil is sprayed with an aqueous dispersion of the combina-tion of herbicides. The concentration of herbicides is adjusted by suitably diluting the concentrate, and 50 ml of dispersion are sprayed per m2. The test plants are further cultivated in the greenhause at day te~perat~res o~ 18-22C, at night temperat~res of lO~ C, at a relative humidity of 6Q-7~a/o, and with daily watering.
Evaluation is made 2 to 4 weeks after sowing and application. The percentage growth inhibition in comparison with the untreated controls is registered. The following rating is employed:
100 % = plants perished 50 % = average activity O % = as untreated control 8~S3 The t:est results, together with the e~pected values computed in accordance with the Colby formula, are set forth in the tables in sections a, b, c, d, e, f and g. The respective concentrations employed and the tested cultivated plants and weeds are indicated.
Each of sections a, b, c, d, e, f and g contains three tables. The first two ta~les show the results obtained with the individual herbicides. The third table shows the expected values computed in accordance with the Colby formula, in contrast with the experimen-tally determined values.
a) Preemergence activity of mixtures of compound I and compound lIa.
Evaluation of percentage growth inhibition, compared with untreated controls, 22 days after application.
Compound I ~ 15 ~ 8 ~ 4 ~ 2 ~ 1 ~ 0 5 wheat "Probus" 0 0 0 0 0 0 Stellaria media 98 95 90 85 30 10 Sinapis alba 90 80 30 15 0 0 Compound IIa ¦ 1000 ¦ 500 ¦ 250 ~ 60 wheat "Probus" 0 0 0 0 0 Stellaria media 0 0 0 0 0 Sinapis alba 0 0 0 0 0 ~88Z53 Concentrations SLel1aria media Sinapis alba g a.i./ha Compound Compound Activity Expected Activity ~xpected I IIa found value foundvalue . _ 0.5 1000 40 10 0 0 . . .
0.5 500 30 10 _ 0 0 0.5 250 20 10 0 0 0.5 120 10 10 0 0 _ _ 8 60 ~00 95 90 80 1 60 50 30 ~0 0 0.5 60 20 10 --o b) Preeme~gence activity of mixtures of compound I and compound IVa.
Evaluation of percentage growth inhibition, compared with untreated controls, 22 days after application.
~825~
Compound I l5 a _ _ o . 5 . .. ___ _ _.
wheat "Probus" 0 0 0 0 0 0 Stellaria media98 95 90 85 30 10 Sinapis alba 90 80 30 15 0 0 Compound IYa 60 30 15 wheat "Probus" 0 0 0 Stellaria media0 0 0 Sinapis alba 0 0 0 Concentrations Stellaria media Sinapis alba g a.i./ha Compound Compound Activity Expected Activity Expected IVa foundvalue foundvalue 4 ~0 95 90 50 30 2 60 85 ô5 20 15 l 60 60 30 0 0 0.5 60 30 10 0 0 l 30 60 30 30 0 0.5 30 30 10 0 0 ___ 1 15 30 ~0 0 0 0.5 15 10 lO 0 0 c) Preemergence actlvity of mixtures of compound I and compound IVb.
Evaluation, compared with untreated controls, 17 days after applica-tlon.
lX88'~53 __ _ CnmpolJnd I l~ 8 ~ A.i.lh~ _ wheat "Problls" 0 () Avena fatua 20 5 ¦ Compound IVb ¦ 500¦ 250 ¦ 60 ¦ 15 ¦
.__ _ wheat "Probus" 0 0 0 0 Avena fatua 20 20 10 0 Compound I g a.i./ha 15 15 15 15 Compound IVb g a.i /ha 500 250 60 15 activity found 50 40 50 50 Avena i-atua - -- _ expected ~Talue 36 36 50 20 d) Preemergence activity of mixtures of compound I and compound Va.
Evaluation, compared with untreated controls, 21 days after applica-tion.
¦ Compound I ~ 2 ~ 1 ~ 0.5 wheat "Probus"0 0 0 Veronica persicaria 50 20 0 ¦ Compound Va~ 100 ~ 50 ¦
wheat "Probu~"0 0 Veronica persicaria 30 10 ~8l~253 Compound I g a.i,/ha 2 1 0.5 2 ._._ .
Compound Va g a.i.Jha 100 100 100 50 50 _ ........ .... _.. ___ _ Veronica act~vlty found 80 80 75 70 70 persicaria _ ~
expected value 65 44 30 55 28 e) Preemergence activity of mixtures of compound I and compound Yb, Evaluation, compared wlth untreated controls, 21 days after appli-cation.
.. _ .... .
g aPi /ha ~ 15 ~ 8 ~ 4 ~ 2 wheat "Probus" 0 0 0 0 0 Lolium perenne 70 60 20 0 0 g a i./ha 800 ~ 400 200 wheat "Probus" 20 10 0 Lolium perenne 20 10 0 1 Compound I g a.i./ha 15 8 4 2 1 4 2 1 4 2 Compound ~a g a.i.fha 800 800 800 800 800 400 400 400 20D 200 Lolium acti~ty found 85 80 70 S0 50 60 40 30 40 10 perenne expected value 76 68 36 20 20 28 10 10 20 0 f) Preemergence activity of mixtures of compound I and compound VIII
Evaluation, compared with untreated controls, 17 days after applica-tion.
1~8~53 ~ ~ 15 ~ 8 ~ -4 ~heat "Probus" 0 0 0 0 0 Setaria glauca 8580 70 20 lO
Compound Vb~ 1000 wheat "Probus" 0 Setarla glauca 50 Compound Ig a.i./ha 15 8 4 2 _ Compound VIII g a.i.lha lO00 1000 lO00 lO00 1000 activity found 85 85 70 50 30 Setaria glauca _ _ expected value 78 64 55 19 10 g) Preemergence activity of mixtures of compound I and compound IX.
Evaluation, compared with untreated controls, 22 days arter applica-tion.
g a.i lha 15 d 4 0.5 . . . _ _ wheat "Prob~s" D 0 0 0 0 Stellaria media9895 90 30 lO
Sinapis alba90 8030 0 0 - ~250l20 60 ._ wheat "Probus" 0 D 0 Stellaria media 0 0 0 Sinapis alba0 0 0 ~ ~8Z53 - 3~) -Corlcentratlons Stel3ar1a media Sinapis alba g a.i./ha Compound Compound Activity ~xpected Activity Expected rxfound VR lue foundvalue 8 250 98 95 85 sa 4 250 95 90 6~ 30 0.5 250 50 10 0 0 0.5 120 30 10 0 _ 8 60 98 95 90 oO
0.5 60 30 30 0 0 Example B2: Postemergence test The test plants are cul~ivated in plastic pots containing 0.5 % of sterilised garden soil. The plants are sprayed postemergence in the 2-3 leaf stage (c. 2 weeks after sowing) with an aqueous dispersion of the combinatlons of herbicides. The concentration of sp}ay mixture is 50 ml per m2. The concentration of herbicides is adjusted by suitably diluting the concentrate. The test plants are further cultivated in a greenhouse at day temperatures of 18-22~C, at night temperatures ~f 1~-12C, at a relative humidlty of 60-70 YD~ and with daily watering. Evaluation is made 2 to 4 weeks after appli-cation. The degree of iniury to the plants i9 determined in accor-dance with the same percentage rating as employed in the preemer-~ence test.
The test results, together with the expected values computed in accordance with the Colby formula, are set forth in the tables in the fol7cwing sections a, b, c, d, e and f. The respective concen-trations employed and the tested cultivated plants and weeds are ~ ~88253 indicated. Here too, each of sections a, b, c, d, e and f contains three tables. The flrst two tables show the results obtalned with the individual herbicides. The third table shows the expected values computed in accordance with the Colby formula, in contrast with the experimenta11y de~ermined values.
a) Postemergence activity of mixtures of compound I and com-pound IIIa.
Evaluation, c~mpared with untreated controls, 18 days after applica-tion.
Compound I 15 8 42 _ g a.i./ha _ _ _ wheat "Probus" 5 0 0 0 0 Stellaria media80 7050 50 40 Sinapis alba 8580 7070 60 Veronica persicaria 7020 10 0 0 Compoond IIIa¦ 250 ~ 120 wheat "Probus" 0 0 Stellaria media 10 0 Sinapis alba85 85 Veronica persicaria 30 30 ~ X88~3 . . . .. .. _ ~tl-00 O~tl-OO
, O> 3 1_ ~ ~ ~ r~ /` ~ t~
~I L
al,,~ ...._ 1~ ) U'~ U~ O O U~ O O O O O
o v :3 ~ O a~ t ~.; tJ O
;~
__ U Cl ~ t oo r` `D ~O `J
1~ cr~ O' o~
~ _ ~ ~ ~ ~ ~ ~ ~ oo oo ~ CO CO
~ .
U C~ ~ ~ U~ D O O O O O
Q, :~ ~ I_ U~ t 00 1- L~ t 6 ~Ll '' I~ _ _ U~ O O O O O
00 ~ CO ~0 00 a~ ~ o ¢ ~
~ .
: ~ ~ U~ o O O O U~ O O O O
.D ~
.._ . ._~ .__ ~7 ' :~ ~ O O O O O O O O O O
Q. ~ N C~ ~
~ . .
V ~0 ~ u~ u~
~ o . .
8~5~
b) Postemergence ACtiVity of mixtures of compound I and com-pound IIIb.
Evaluation, compared with untreated controls, 25 day~ after applica-tion.
Compoon I ~ 15 ~ 8 ~ 4 2 ~ 1 wheat "Probus" 0 0 0 0 0 Veron1ca persicaria 70 20 10 0 0 Compound IIIb250 ~ 60 wheat "P}obus" 0 0 Veronica persicaria 30 0 Concentrations Veronica persicaria g a.i./ha Compound Compound Activity Expected lIIb found value . . _ ..
c) Postemergence activity of mixtures of compound I and compound Va.
Evaluation, compared with untreated controls, 17 days after applica-tion.
Compound I ~ 8 ¦ ~ ~ 2 1 ~ O.S
wheat "Probus" 0 0 0 0 0 Lolium perenne 50 20 10 5 0 1~8~5~
Compound Va 400 200 g a.i.lha . ,_ _ wheat "Probus"10 10 Lolium perenne50 10 ConcentrationsWheat "Probus`' Lolium perenne g a.i./ha Compound Compound Activity Expected Activity Expected _ Vafound value foundvalue 0.5 400 10 10 60 50 0.5 20~ 10 10 40 10 d) Postemergence activi~y of mixtures of compound I and compound Vb.
Evaluation, compared with untreated controls, 17 days after applica-tion.
g a i./ha 1; B4 2 1 wheat '`Probus" 100 0 0 0 Lolium perenne70 5020 10 5 Setaria glauca50 2010 ~
Avena fatua 30 100 0 0 g a i.~ha 400 wheat "Probus"30 Lolium perenne10 5etaria glauca20 Avena fatua .
.
~, ~S~
~, HC~ CH=N-0-~ -N0~ (XI) Br N~2 known from the Pesticide Manual 7th Ed. (1983) 1360, The British Crop Protection Council, London;
N-(2,4-difluorophenyl)-2-(3-trifluoromethylphenoxy)nicotinic acid amide of formula XII
F~ (XII) ~N~ \0--~ ~-~ CF1 known from published European patent appllcation 53 011.
1-(2-benzothiazolyl)-1,3-dimethylurea of formula XIII
,~ \.~ \
~ -C0-NH-CH3 (XIII) known from the Pesticide Manual 7th Ed. (1983) 8050, The British Crop Protection Council, London;
(4-amino-3,5-dichloro-6-fluoropyridin-2-yloxy)acetic acid of formula XIV
N,2 ~Cl Cl-~ ~--O-CH2-COOH (XIV) F
nown from VS patent 4 110 104;
N~ ethylpropyl)-3,4-dlmethyl-2,6-dinitroaniline of formula XV
H3C~ -NH-C~ (XV) known from the Pesticide Manual 7th Ed. (1983) 9390, The British Crop Protection Council, London;
3,6-dichloro-2-methoxybenzoic acid of formula XVI
~Cl ~ -COOH (XVI) Cl OCH3 known from the Pesticide Manual 7th Ed. (1983) 4100, The British Crop Protection Council, London;
S-(2,3-dichloroallyl)diisopropylthiocarbamate of formula XVII
HClC=CC1-CH2-S-CO-N(C3Hz-i)2 (XVII) known from the Pesticide Manual 7th Ed. (1983) 3990, The British Crop Protection Council, London;
3,6-dichloropicolinic acid of formula XVIII
~ COOH ~XVIII) Cl/
known from the Pesticide Manual 5th Ed. (1977) 177, The British Crop Protection Council, London; and ethyl 2-[4-(6-chlorobenzoxazol-2-yloxy)phenoxy]propionate of for~ula XIX
~'J~ 5~
~ o--~ O-CH-COOC2Hs (XIX) known from the Pesticide Manual 7th Ed. (1983) 6160, The ~ritish Crop Protection Council, London.
Surprisingly, it has now been found that a combination of two compounds, in a variety of ratios, namely compound I and a compound selected from compound classes II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX, exerts a synergis-tic action that is able to control the majority of all important weeds in cereals without causing injury to the cereal crops. The principal weeds found in crops of cereals, e.g. species of the monocotyledenous genera Alopecurus, Avena and Setaria, as well as of the dicotyledenous genera Chrysanthemum, ~alium, Sinapis, Stellaria and Venturia, are controlled selectively by preemergence as well as postemergence treatment.
Accordingly, the present invention provides a novel synergistic composition for selectively controlling weeds that contains, as one active component, N-[2-(2-chloroethoxy)phenylsulfonyll-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea of formula I
SO2-NH-CO-NH-~
O-CH2-CH2Cl OCH3 and, as second active component, either a compound formula II
R~ -_0_~ NO2 (II) \Cl ~2 l~aa~
lo -~!herein Rl is chlorine or trifluoromethyl and R2 is hydrogen, Cl-C4alkoxycarbonyl, C~-C~lkoxy, -CCJONa, -COOK, -COOH, -CO-NH-SO2CH3, -COO-CH(CH3 )-COOC7Hs ~ -C(CH3)=N-O-CH2-CO-JCH3 or -COO-CH.-COOC2Hs, or a compound of formula III
N-eC~ -OH (III) \R3 wherein R3 is bromine or iodine, or a compound of formula (IV) Cl--~ O-CH-COOH (IV) .=.
wherein ~ is chlorine or methyl and Rs is hydrogen or methyl, or a compound of formula V
(V) R~-NH ~ ~ ~ H-R7 wherein R~ is ethyl or methoxypropyl and R7 is isopropyl or tert-butyl, or a compound of formula VI
R
H2N- ~ C4Hg-t ~VI) R8-S--~ ~
1~i8253 wherein R8 is methyl or ethyl, or a compound of formula VII
/c~3 R9-So2-NH-Co~ (VII) wherein R9 is 2-methoxycarbonylphenyl or 2-methoxycarbonylthien-3-yl and Rl is hydrogen or methyl, or the compound of formula VIII
C) 00~
Cl~ (VIII) ~./ \.~ \CH3 or the compound of formula IX
\ / O \ /~-O-~CH-COOCH3 (IX) or the compound of formula X
Cl~
F--~ H-COOC3H~-i (X) CO--~
or the compound of formula XI
Br\
HO--~ ~--CH=N-O--~ ~--NO2 (XI) Br N~2 or the compound of formula XII
1~82~3 NH~ F (XII) =--CF3 or the compound of formula XIII
CO-NH-CH3 (XIII) ~ H3 or the compound of formula XIV
N~2 ~Cl Cl~ --O-CH2-COOH (XIV) ~=
or the compound of formula XV
~NO2 ~--~ C2Hs H3C--~ ~--NH-C~ (XV) .=. C2Hs or the compound of formula XVI
~Cl ~ -COOH (XVI) Cl/ OCH3 or the compound of formula XVII
HClC=CCl-CH2-S-CO-~(C3H7-i)2 (XVII) or the compound of formula XVIII
1~38X'~:~
Cl COO~I ( XVI I I ) Cl~
or the compound of formula XIX
i i1 \--0~ --O-~H-COOC2Hs (XIX) in admixture with each other.
It is extremely surprising that the combination of the compound of formula I with a compound of formula II, III, I~, V, ~I, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX not only brings about an e~pected additive enhancement of the activity spectrum against the weeds customarily associated with cereals, but also has a synergistic effect that the potentiates the activity range of both components from two points of view.
On the one hand, the rates of application of the individual com-pounds I and II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XI~, XV, XVI, XVII, XYIII or XIX are markedly reduced with no reduction in the effectiveness of said compounds. On the other hand, the herbicidal combination also achieves a high degree of weed control where both individual components have become totally ineffective at too low rates of application. The consequence is a substantial broadening of the activity spectrum against weeds and an additlonal increase in the safety margin for application to cereals that i8 necessary and desirable in the event of unintentional overapplication.
The composition of this invention can be employed for selectively controlling weeds in crops of cereals such as oats, triticale, barley, rye and, in particular, wheat.
, 8~
- l4 -The herbicida~ combination employed ln the practice of this inven-tion contains a compou~ld of Formula I and a compound o~ formula 11, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XYIII or ~I~, in any ratio, but normally with an excess of the one component over the other. The ratio is of such little consequence that excesses of the component o~ formula I as well as of the component of formula II, III, IV, V, VI, YII, ~III, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX are tolerated. The preferred ratio of component I to the component of formula II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX is from 1:1 to 1:2000, in particular from 1:5 to 1:500. The herbicidal combinations of this invention have excellent activtty against weeds without noticeably affecting the crops of cereals in the conveni-ently employed rates of application of 0.005 to 3 kg, preferably 0.01 to 1 kg, per hectare.
Combinations of compound I with the following individual compounds have proved particularly effective synergistic herbicidal mixtures:
a) methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate [compound IIa3;
b~ ethoxycarbonylmethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate [compound IIi~;
c) 3,5-dibromo-4-hydroxybenzonitrile ~compound IIIa~; -d) 3,5-diiodo-4-hydroxybenzonitrile [compound IIIb3;
e~ 2,4-dichlorophenoxyacetic acid [compound Tval;
f) 4-chloro-2-methylphenoxyacetic acid ~compo~nd IVb];
g) 2-(4-chloro-2-methylphenoxy)propionic acid ~compound IYc];
h) 2-ethylamino-4-tert-butylamino-6-methylthio-1,3,5-triazine [compound Va3;
i) 2-isopropylamino-4-(3-methoxypropylamino)-6-methylthio-1,3,~-triazine [compound Vb]
j) 7-chloro-3-methylquinoline-8-carboxylic acid [compound VIII];
k) methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propionate [com-pound IX]; and l~a~s~
1) N-ben~oyl-N-(3-chloro-4-fluorophenyl)alanine isopropyl ester [compound ~].
Compounds IIi, IIIa and VIII are particularly preferred synergistic components.
The formulations, i.e. the compositions or preparations containing the mixture of herbicides of this invention and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds ~surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epo~idised ve~etable oils such as èpoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. To improve the physical properties ~t is also possible to add hlghly dispersed sil;cic acid OI highly dispersed absorbent polymers, Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suit~ble nonsorbent carriers are materials such as calcite or sand. In addition, a great nu~ber o~
pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues, e.g. cork powder or sawdust.
8~
Partioularly advantAgeous application promoting adjuvants which are able to reduce substantially the rate of application are also natural (animal or vegetable) or synthetic phospholipids of the ~eries of the cephalins and lecithins, e.g. phosphatidyl ethanol-amine, phosphatidyl serine, phosphatidyl choline, sphingomyeline, phosphatidyl inisotol, phosphatidyl glycerol, lysolecithin, plasmalogenes or cardiolipin, which can be obtained e.g. from animal or plant cells, in particular from the brain, heart, liver, egg yokes or soya beans. Examples of useful physical forms are phosphat-idyl choline mixtures. Examples of synthetic phospholipids are dioctanoylphosphatidyl choline and dipalmitoylphosphatidyl choline.
Suitable surface-active compounds are non-ionic, cationic and/or anionic sufactants having good emulsifying, dlspersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C1D_C2Z), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, espec~ally fatty sulfonates, fstty sulfates, s~lfo~ated ben~mid-azole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or sub-stltuted ammonium salts and contain a C8-Cz2alkyl radical which also includes the al~yl moiety oF acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a 2S~
mi~ture o~ fattY .~lcohol slJIfAtes obtalned from natural fatty acids.
These com~oun~s also comprise the salts of sulfuric acid esters and sulfonic aciAs of fatty alcohol/ethylene oxlde adducts. The sulfona-ted benximidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radlcal containing 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodiu~, calcium or tri-ethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic acid, or of a naphthalenesulfonic acidJformaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-phenol with 4 to 14 moles of ethylene oxide.
~on-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamino-polypropylene glycol and alkylpolypropylene glycol containing I to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene ~lycol unit.
Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/
polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e,g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
~88~53 Cationic surfacLants are preferably guaternary ammonium sa1ts which contain, as N-substituent, at least one C~-Cz%alkyl radical and, as f~1rther ~ubstituents, unsubstituted or halogenated lower alkyl, benzyl or hydro~y-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.~. stearyl-trimethylammoni~1m chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are dsscribed e.g. in "McCutcheon's Detergents and Emulsiflers Annual", MC Publishing Corp. Ridgewood, New Jersey, 1981; Helmut Stache "Tensid-Taschenbuch" (Surfactant Handbook) Carl Hanser Verlag, Munich/Vienna, 1981; M. and J. Ash: Encyclopaedia of surfactants, Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
The agrochemical compositions usually contain 0.1 to 95 %, p}efer-ably 0.1 to 80 %, of a mixture of herbicides of the formulae I
and II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.
Preferred formulations are composed in particular of the following constituents (% = percentage by weight):
Emulsifiable concentrates mixture of herbicides: 1 to 20 %, preferably 5 to 10 %
surfactant:5 to 30 %, preferably 10 to 20 %
liquid carrier:50 to 94 %~ preferably 70 to 85 %
Dusts mixture of herbicides: 0.1 to 10 %, preferably 0.1 to 1 %
solid carrier:99.9 to 90 %, preferably 99.9 to 99 %
1~88X5~
-- 1~3 --S~s~ension rc~_c~nt~at~
mi~ture o~ her~)icides:5 to 75 ~/0, preferably 10 to 50 ~/, water:94 to 25 %, preferably 90 to 30 ~/~
surfactant:1 to 40 %, preferably 2 to 30 %
Wettable powders mixture of herbicides: 0.5 to 90 %, preferably 1 to 80 %
surfactant: 0.~ to 20 %, preferably 1 to 15 %
solid carrier:S to 95 %, preferably 15 to 90 %
Granulates mixture of herbicides: 0.5 to 30 %, preferably 3 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %.
Whereas commercial products will be preferably formulated as concentrates, the end user will normally employ dilute formulations.
The formulations can be diluted to a concentration as low as O . 0~1 % .
The above described compositions can also be mixed with other biocides or biocidal compositions. Thus in addition to containing the cited compounds of the general formula I and of the formulae II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX, the novel compositions may contain e.g.
insecticides, fungicides, bacterici~es, fungistats, bacteriostats or nematicides in order to improve the activity spectrum.
The compositions of the invention can generally be formulated in accordance with the following Examples:
Formulation Examples Example F1: Formulation examples for syngistic mixtures of herbi-cides of the formulae I and II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX (throughout, percentages are by weight) lX~3825~
a) Wettab_e_~owd~rs a) b) c) d) compound ~ lO % 20 % 5 % 30 ~/~
compound I~, III, IV, V, Vl, VII, VIII, IX, X, XI~ XII, XIII, XIV, XV, ~VI, XVII, XVIII or XIX 10 r/~ 40 % 15 % 30 %
sodium li~nosulfonate 5 J~ 5 c/ 5 ~/v S ~/~
sodium laurylsulfate3 % - 3 %
sodium diisobutylnaphthalene-sulfonate - 6 % - 6 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 % - 2 %
highly dispersed silicic acid 5 % 27 % 5 % 27 %
kaolin 67 % - 67 %
The mixture of herbicides is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
b) Emulsifiable concentrates a) b) c) compound I 5 % 5 % l2 %
compound II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII
or XIX 5 % 20 % 13 %
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 % 3 % 3 %
calcium dodecylbenzenesulfonate 3 % 3 % 3 %
castor oil polyglycol ether (36 moles of ethylene oxide) 4 % 4 % 4 %
cyclohexanone 3a 2~ 3a 5~ 3~ ~
xy1ene mixt~e 50 % 35 ~o 35 %
Emulsions of any required concentration can be obtained from these concentrates by dilution with water.
~ ~8XS3 c) Du~ts a) b) c) d>
compound I 2 % 4 % 2 % 4 %
compound II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX 3 % 4 % 4 % 8 %
talcum 95 %~ % 94 % ~ %
kaolin - 92 % - 88 %
Ready for use dusts are obtained by mixing the mixture of herbicides with ~he carriers, and grinding the mixture in a suitable mill.
d) Extruder granulates a) b)c) compound I 5 % 3 % 5 %
compound II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX 5 % 7 % 15 %
sodium lignosulfonate 2 % 2 % 2 %
carboxymethylcellulose 1 % 1 % 1 %
kaolin 87 % 87 % 77 %
The mixture of herbicides is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. This mixture is extruded and then dried in a stream of air.
e) Coated granulates a) b) compound I l.5 % 3 %
compound II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII
or XIX 1.5 % 5 %
polyethylene gly^ol 200 3.0 % 3 %
kao~in 94.0 % 89 %
The finely ground mixture of herbicide is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
~; -'' 8~
-- 2 '~ --f) Su~l)en~1o~ ~ ~neetll!.?tes a) b) compo~lnd 1 20 % 20 ~, co~pound II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII~ XIV, XV, XVI, XVII, XVIIr or XIX 20 % 40 %
ethylene glycol 10 ~ 10 %
nonylphsnol polyethylene glycol ether (15 moles of ethylene oxide) 6 % 6 %
sodium lignosulfonate 10 %10.0 %
carboxymethylcellulose 1 % 1.0 %
37 % aqueous formaldehyde solution 0.2 % 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 0.8 %
water 32.0 % 12.0 %
The finely ground mixture of herbicides is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of any desi}ed concentration can be obtained by dilution with water.
Herbicides always have a synergistic effect if the herbicidal action of the combination of I and II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX is greater than the action to be expected when the individual herbicides are employed together.
The expected herbicidal activlty ~ for a gi~en combination of two herbicides call be calculated as follows (cf. COLBY, S.R., "Calculat-ing synergistic and antagonistic responses of herbicide composi-tions", Weeds 15, page~ 20-22, 1967).
E = X + Y (IoO-X) X = the percentage growth inhibition, compared with untreated controls (5 0 %), after treatment with a herbicide I at a rate of application of p kg per hectare, l~aa~s~
Y = the percellL~ge g1owth inhibition, compared wlth untreated controls, after treatment with a herblcide II, III~ IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XI~ at a rate of application of q kg per hectare, and E ~ the expected herbicidal activity (percentage growth inhibition compared with untreated controls) after treatment wlth the he}bicidal mixture of I and II, III, IY, V, VI, VII, ~III, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX at a rate of appllcation of p + q kg of active ingredient per hectare.
If the actually observed value is higher than the expected value E, then there is synergism.
The synergistic effect of the combinations of compounds I and II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX is demonstrated in the following Examples.
Biological Examples Example B1: Preemergence test The test plants are sown in a greenho~se in plastic pots containing 0-5 & of sterilised garden soil. One day after sowing, the surface of the soil is sprayed with an aqueous dispersion of the combina-tion of herbicides. The concentration of herbicides is adjusted by suitably diluting the concentrate, and 50 ml of dispersion are sprayed per m2. The test plants are further cultivated in the greenhause at day te~perat~res o~ 18-22C, at night temperat~res of lO~ C, at a relative humidity of 6Q-7~a/o, and with daily watering.
Evaluation is made 2 to 4 weeks after sowing and application. The percentage growth inhibition in comparison with the untreated controls is registered. The following rating is employed:
100 % = plants perished 50 % = average activity O % = as untreated control 8~S3 The t:est results, together with the e~pected values computed in accordance with the Colby formula, are set forth in the tables in sections a, b, c, d, e, f and g. The respective concentrations employed and the tested cultivated plants and weeds are indicated.
Each of sections a, b, c, d, e, f and g contains three tables. The first two ta~les show the results obtained with the individual herbicides. The third table shows the expected values computed in accordance with the Colby formula, in contrast with the experimen-tally determined values.
a) Preemergence activity of mixtures of compound I and compound lIa.
Evaluation of percentage growth inhibition, compared with untreated controls, 22 days after application.
Compound I ~ 15 ~ 8 ~ 4 ~ 2 ~ 1 ~ 0 5 wheat "Probus" 0 0 0 0 0 0 Stellaria media 98 95 90 85 30 10 Sinapis alba 90 80 30 15 0 0 Compound IIa ¦ 1000 ¦ 500 ¦ 250 ~ 60 wheat "Probus" 0 0 0 0 0 Stellaria media 0 0 0 0 0 Sinapis alba 0 0 0 0 0 ~88Z53 Concentrations SLel1aria media Sinapis alba g a.i./ha Compound Compound Activity Expected Activity ~xpected I IIa found value foundvalue . _ 0.5 1000 40 10 0 0 . . .
0.5 500 30 10 _ 0 0 0.5 250 20 10 0 0 0.5 120 10 10 0 0 _ _ 8 60 ~00 95 90 80 1 60 50 30 ~0 0 0.5 60 20 10 --o b) Preeme~gence activity of mixtures of compound I and compound IVa.
Evaluation of percentage growth inhibition, compared with untreated controls, 22 days after application.
~825~
Compound I l5 a _ _ o . 5 . .. ___ _ _.
wheat "Probus" 0 0 0 0 0 0 Stellaria media98 95 90 85 30 10 Sinapis alba 90 80 30 15 0 0 Compound IYa 60 30 15 wheat "Probus" 0 0 0 Stellaria media0 0 0 Sinapis alba 0 0 0 Concentrations Stellaria media Sinapis alba g a.i./ha Compound Compound Activity Expected Activity Expected IVa foundvalue foundvalue 4 ~0 95 90 50 30 2 60 85 ô5 20 15 l 60 60 30 0 0 0.5 60 30 10 0 0 l 30 60 30 30 0 0.5 30 30 10 0 0 ___ 1 15 30 ~0 0 0 0.5 15 10 lO 0 0 c) Preemergence actlvity of mixtures of compound I and compound IVb.
Evaluation, compared with untreated controls, 17 days after applica-tlon.
lX88'~53 __ _ CnmpolJnd I l~ 8 ~ A.i.lh~ _ wheat "Problls" 0 () Avena fatua 20 5 ¦ Compound IVb ¦ 500¦ 250 ¦ 60 ¦ 15 ¦
.__ _ wheat "Probus" 0 0 0 0 Avena fatua 20 20 10 0 Compound I g a.i./ha 15 15 15 15 Compound IVb g a.i /ha 500 250 60 15 activity found 50 40 50 50 Avena i-atua - -- _ expected ~Talue 36 36 50 20 d) Preemergence activity of mixtures of compound I and compound Va.
Evaluation, compared with untreated controls, 21 days after applica-tion.
¦ Compound I ~ 2 ~ 1 ~ 0.5 wheat "Probus"0 0 0 Veronica persicaria 50 20 0 ¦ Compound Va~ 100 ~ 50 ¦
wheat "Probu~"0 0 Veronica persicaria 30 10 ~8l~253 Compound I g a.i,/ha 2 1 0.5 2 ._._ .
Compound Va g a.i.Jha 100 100 100 50 50 _ ........ .... _.. ___ _ Veronica act~vlty found 80 80 75 70 70 persicaria _ ~
expected value 65 44 30 55 28 e) Preemergence activity of mixtures of compound I and compound Yb, Evaluation, compared wlth untreated controls, 21 days after appli-cation.
.. _ .... .
g aPi /ha ~ 15 ~ 8 ~ 4 ~ 2 wheat "Probus" 0 0 0 0 0 Lolium perenne 70 60 20 0 0 g a i./ha 800 ~ 400 200 wheat "Probus" 20 10 0 Lolium perenne 20 10 0 1 Compound I g a.i./ha 15 8 4 2 1 4 2 1 4 2 Compound ~a g a.i.fha 800 800 800 800 800 400 400 400 20D 200 Lolium acti~ty found 85 80 70 S0 50 60 40 30 40 10 perenne expected value 76 68 36 20 20 28 10 10 20 0 f) Preemergence activity of mixtures of compound I and compound VIII
Evaluation, compared with untreated controls, 17 days after applica-tion.
1~8~53 ~ ~ 15 ~ 8 ~ -4 ~heat "Probus" 0 0 0 0 0 Setaria glauca 8580 70 20 lO
Compound Vb~ 1000 wheat "Probus" 0 Setarla glauca 50 Compound Ig a.i./ha 15 8 4 2 _ Compound VIII g a.i.lha lO00 1000 lO00 lO00 1000 activity found 85 85 70 50 30 Setaria glauca _ _ expected value 78 64 55 19 10 g) Preemergence activity of mixtures of compound I and compound IX.
Evaluation, compared with untreated controls, 22 days arter applica-tion.
g a.i lha 15 d 4 0.5 . . . _ _ wheat "Prob~s" D 0 0 0 0 Stellaria media9895 90 30 lO
Sinapis alba90 8030 0 0 - ~250l20 60 ._ wheat "Probus" 0 D 0 Stellaria media 0 0 0 Sinapis alba0 0 0 ~ ~8Z53 - 3~) -Corlcentratlons Stel3ar1a media Sinapis alba g a.i./ha Compound Compound Activity ~xpected Activity Expected rxfound VR lue foundvalue 8 250 98 95 85 sa 4 250 95 90 6~ 30 0.5 250 50 10 0 0 0.5 120 30 10 0 _ 8 60 98 95 90 oO
0.5 60 30 30 0 0 Example B2: Postemergence test The test plants are cul~ivated in plastic pots containing 0.5 % of sterilised garden soil. The plants are sprayed postemergence in the 2-3 leaf stage (c. 2 weeks after sowing) with an aqueous dispersion of the combinatlons of herbicides. The concentration of sp}ay mixture is 50 ml per m2. The concentration of herbicides is adjusted by suitably diluting the concentrate. The test plants are further cultivated in a greenhouse at day temperatures of 18-22~C, at night temperatures ~f 1~-12C, at a relative humidlty of 60-70 YD~ and with daily watering. Evaluation is made 2 to 4 weeks after appli-cation. The degree of iniury to the plants i9 determined in accor-dance with the same percentage rating as employed in the preemer-~ence test.
The test results, together with the expected values computed in accordance with the Colby formula, are set forth in the tables in the fol7cwing sections a, b, c, d, e and f. The respective concen-trations employed and the tested cultivated plants and weeds are ~ ~88253 indicated. Here too, each of sections a, b, c, d, e and f contains three tables. The flrst two tables show the results obtalned with the individual herbicides. The third table shows the expected values computed in accordance with the Colby formula, in contrast with the experimenta11y de~ermined values.
a) Postemergence activity of mixtures of compound I and com-pound IIIa.
Evaluation, c~mpared with untreated controls, 18 days after applica-tion.
Compound I 15 8 42 _ g a.i./ha _ _ _ wheat "Probus" 5 0 0 0 0 Stellaria media80 7050 50 40 Sinapis alba 8580 7070 60 Veronica persicaria 7020 10 0 0 Compoond IIIa¦ 250 ~ 120 wheat "Probus" 0 0 Stellaria media 10 0 Sinapis alba85 85 Veronica persicaria 30 30 ~ X88~3 . . . .. .. _ ~tl-00 O~tl-OO
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al,,~ ...._ 1~ ) U'~ U~ O O U~ O O O O O
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~ .
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Q, :~ ~ I_ U~ t 00 1- L~ t 6 ~Ll '' I~ _ _ U~ O O O O O
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b) Postemergence ACtiVity of mixtures of compound I and com-pound IIIb.
Evaluation, compared with untreated controls, 25 day~ after applica-tion.
Compoon I ~ 15 ~ 8 ~ 4 2 ~ 1 wheat "Probus" 0 0 0 0 0 Veron1ca persicaria 70 20 10 0 0 Compound IIIb250 ~ 60 wheat "P}obus" 0 0 Veronica persicaria 30 0 Concentrations Veronica persicaria g a.i./ha Compound Compound Activity Expected lIIb found value . . _ ..
c) Postemergence activity of mixtures of compound I and compound Va.
Evaluation, compared with untreated controls, 17 days after applica-tion.
Compound I ~ 8 ¦ ~ ~ 2 1 ~ O.S
wheat "Probus" 0 0 0 0 0 Lolium perenne 50 20 10 5 0 1~8~5~
Compound Va 400 200 g a.i.lha . ,_ _ wheat "Probus"10 10 Lolium perenne50 10 ConcentrationsWheat "Probus`' Lolium perenne g a.i./ha Compound Compound Activity Expected Activity Expected _ Vafound value foundvalue 0.5 400 10 10 60 50 0.5 20~ 10 10 40 10 d) Postemergence activi~y of mixtures of compound I and compound Vb.
Evaluation, compared with untreated controls, 17 days after applica-tion.
g a i./ha 1; B4 2 1 wheat '`Probus" 100 0 0 0 Lolium perenne70 5020 10 5 Setaria glauca50 2010 ~
Avena fatua 30 100 0 0 g a i.~ha 400 wheat "Probus"30 Lolium perenne10 5etaria glauca20 Avena fatua .
.
5~
Compound I r a.i./ha 15 _ 4 2 _ Compound Vb g a i.lha400 400 400400 400 activlty found30 20 25 30 30 wheat "Probus" - _ _ expected value37 30 3030 30 activity found80 70 7070 40 Lolium perenne _ _ expected value73 55 2819 15 . __ . _ _ activity found80 70 8040 30 Setaria glauca _ expected value60 36 2820 20 activity found98 98 9898 98 Avena fatua _ _ _ expected value86 82 80 80 80 e) Postemergence activity of mixtures of compound I and com-pound VIII.
Evaluation, compared with untreated controls, 14 days after applica-tion.
- ~ 8 ¦ 4 ~ 2 ~ l wheat "Probus"0 0 0 0 Stellaria medla 85 80 70 60 Compottnd VIII1000 500 250 g a,i.lha _ wheat "Probus"0 0 0 Stsllaria msdia 10 0 ~8Z5;~
Concentrations Stellaria media g a.i./ha Compo~lnd Compound Activity Expected I IIIbfound value _ _ _ .
1- _ .250 65 60 f) Postemergence activity of mixtures of compound I and compound X.
Evaluation, compared with untreated controls, 14 days after applica-tion.
Compound I ~~`-~~-~-wheat "Probus" 5 0 Lolium perenne 60 15 ompound X ~ ¦ - L - 1 wheat "Probus" 10 0 0 Lolium perenne . 0 , Concentratiorls Wheat "Probus" Lolium perenne g a.i.lha Compound Compound Activlty Expected Activity Expected _ f ound va lue foundvalue 8 2000 10 10 60 l5 8 1000 5 0 40 lS
8 500 0 o --- 50 15
Compound I r a.i./ha 15 _ 4 2 _ Compound Vb g a i.lha400 400 400400 400 activlty found30 20 25 30 30 wheat "Probus" - _ _ expected value37 30 3030 30 activity found80 70 7070 40 Lolium perenne _ _ expected value73 55 2819 15 . __ . _ _ activity found80 70 8040 30 Setaria glauca _ expected value60 36 2820 20 activity found98 98 9898 98 Avena fatua _ _ _ expected value86 82 80 80 80 e) Postemergence activity of mixtures of compound I and com-pound VIII.
Evaluation, compared with untreated controls, 14 days after applica-tion.
- ~ 8 ¦ 4 ~ 2 ~ l wheat "Probus"0 0 0 0 Stellaria medla 85 80 70 60 Compottnd VIII1000 500 250 g a,i.lha _ wheat "Probus"0 0 0 Stsllaria msdia 10 0 ~8Z5;~
Concentrations Stellaria media g a.i./ha Compo~lnd Compound Activity Expected I IIIbfound value _ _ _ .
1- _ .250 65 60 f) Postemergence activity of mixtures of compound I and compound X.
Evaluation, compared with untreated controls, 14 days after applica-tion.
Compound I ~~`-~~-~-wheat "Probus" 5 0 Lolium perenne 60 15 ompound X ~ ¦ - L - 1 wheat "Probus" 10 0 0 Lolium perenne . 0 , Concentratiorls Wheat "Probus" Lolium perenne g a.i.lha Compound Compound Activlty Expected Activity Expected _ f ound va lue foundvalue 8 2000 10 10 60 l5 8 1000 5 0 40 lS
8 500 0 o --- 50 15
Claims (11)
1. A synergistic composition for selectively controlling weeds that contains, as one active component, N-[2-(2-chloroethoxy)phenyl-sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea of for-mula I
(I) and, as second active component, either a compound formula II
(II) wherein R1 is chlorine or trifluoromethyl and R2 is hydrogen, C1-C4alkoxycarbonyl, C1-C4alkoxy, -COONa, -COOK, -COOH, -CO-NH-SO2CH3, -COO-CH(CH3)-COOC2H5, -C(CH3)=N-O-CH2-COOCH3 or -COO-CH2-COOC2H5, or a compound of formula III
(III) wherein R3 is bromine or iodine, or a compound of formula (IV) ( IV) wherein R4 is chlorine or methyl and R5 is hydrogen or methyl, or a compound of formula V
(V) wherein R6 is ethyl or methoxypropyl and R7 is isopropyl or tert-butyl, or a compound of formula VI
(VI) wherein R8 is methyl or ethyl, or a compound of formula VII
(VII) wherein R9 is 2-methoxycarbonylphenyl or 2-methoxycarbonylthien-3-yl and R10 is hydrogen or methyl, or the compound of formula VIII
(VIII) or the compound or formula IX
(IX) or the compound of formula X
(X) or the compound of formula XI
(XI) or the compound of formula XII
(XII) or the compound of formula XIII
(XIII) or the compound of formula XIV
(XIV) of the compound of formula XV
(XV) or the compound of formula XVI
(XVI) or the compound of formula XVII
HClC=CCl-CH2-S-CO-N(C3H7-i)2 (XVII) or the compound of formula XVIII
(XVIII) or the compound of formula XIX
(XIX) in admixture with each other, together with carriers and/or other adjuvants.
(I) and, as second active component, either a compound formula II
(II) wherein R1 is chlorine or trifluoromethyl and R2 is hydrogen, C1-C4alkoxycarbonyl, C1-C4alkoxy, -COONa, -COOK, -COOH, -CO-NH-SO2CH3, -COO-CH(CH3)-COOC2H5, -C(CH3)=N-O-CH2-COOCH3 or -COO-CH2-COOC2H5, or a compound of formula III
(III) wherein R3 is bromine or iodine, or a compound of formula (IV) ( IV) wherein R4 is chlorine or methyl and R5 is hydrogen or methyl, or a compound of formula V
(V) wherein R6 is ethyl or methoxypropyl and R7 is isopropyl or tert-butyl, or a compound of formula VI
(VI) wherein R8 is methyl or ethyl, or a compound of formula VII
(VII) wherein R9 is 2-methoxycarbonylphenyl or 2-methoxycarbonylthien-3-yl and R10 is hydrogen or methyl, or the compound of formula VIII
(VIII) or the compound or formula IX
(IX) or the compound of formula X
(X) or the compound of formula XI
(XI) or the compound of formula XII
(XII) or the compound of formula XIII
(XIII) or the compound of formula XIV
(XIV) of the compound of formula XV
(XV) or the compound of formula XVI
(XVI) or the compound of formula XVII
HClC=CCl-CH2-S-CO-N(C3H7-i)2 (XVII) or the compound of formula XVIII
(XVIII) or the compound of formula XIX
(XIX) in admixture with each other, together with carriers and/or other adjuvants.
2. A composition according to claim 1, which contains either methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate or ethoxycarbonylmethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-benzoate or
3,5-dibromo-4-hydroxybenzonitrile or 3,5-diiodo-4-hydroxybenzonltrile or 2,4-dichlorophenoxyacetic acid or
4-chloro-2-methylphenoxyacetic acid or 2-(4-chloro-2-methylphenoxy)propionic acid or 2-ethylamino-4-tert-butylamino-6-methylthio-1,3,5-triazine or 2-isopropylamino-4-(3-methoxypropylamino)-6-methylthio-1,3,5-triazine or 7-chloro-3-methylquinoline-8-carboxylic acid or methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propionate or N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine isopropyl ester as second component in addition to the compound of formula I.
3. A composition according to claim 1, which contains ethoxy-carbonylmethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate as second component in addition to the compound of formula I.
4. A composition according to claim 1, which contains 3,5-dibromo-4-hydroxybenzonitrile as second component in addition to the compound of formula 1.
3. A composition according to claim 1, which contains ethoxy-carbonylmethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate as second component in addition to the compound of formula I.
4. A composition according to claim 1, which contains 3,5-dibromo-4-hydroxybenzonitrile as second component in addition to the compound of formula 1.
5. A composition according to claim 1, which contains 7-chloro-3-methylquinoline-8-carboxylic acid as second component in addition to the compound of formula I.
6. A composition according to claim 1, wherein the weight ratio of component I to the second component of formula II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX is from 1:1 to 1:2000.
7. A composition according to claim 6, wherein the weight ratio of component I to the second component of formula II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII or XIX is from 1:5 to 1:500.
8. A method of selectively controlling weeds in cereals, which comprises treating weed-infested crops of cereals pre- or post-emergence with a herbicidally effective amount of a composition as claimed in claim 1.
9. A method according to claim 8, wherein the weeds to be con-trolled are monocotyledons of the genera Avena, Lolium or Setaria and dicotyledons of the genera Stellaria or Veronica.
10. A method according to claim 8, which comprises treating the crops of cereals with the composition at rates of application corresponding to 0.005 to 3 kg, preferably 0.01 to 1 kg, of total active ingredient per hectare.
11. Use of a herbicidally effective amount of a composition as claimed in claim 1 for selectively controlling weeds pre- and postemergence in crops of cereals.
FO 7.5/CW/cc*
FO 7.5/CW/cc*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH93686 | 1986-03-07 | ||
| CH936/86-5 | 1986-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1288253C true CA1288253C (en) | 1991-09-03 |
Family
ID=4198623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000531189A Expired - Lifetime CA1288253C (en) | 1986-03-07 | 1987-03-05 | Synergistic composition and method of selectively controlling weeds in cereals |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0236273B1 (en) |
| AT (1) | ATE55215T1 (en) |
| AU (1) | AU590824B2 (en) |
| BR (1) | BR8701059A (en) |
| CA (1) | CA1288253C (en) |
| DE (1) | DE3764118D1 (en) |
| ES (1) | ES2016859B3 (en) |
| GR (1) | GR3000704T3 (en) |
| IL (1) | IL81788A (en) |
| ZA (1) | ZA871626B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8883680B2 (en) | 2006-11-13 | 2014-11-11 | Bayer Cropscience Ag | Herbicide combinations with particular sulphonyl ureas |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5231071A (en) * | 1987-07-10 | 1993-07-27 | Hoechst Aktiengesellschaft | Herbicidial agents |
| EP0298901B1 (en) * | 1987-07-10 | 1992-01-15 | Hoechst Aktiengesellschaft | Herbicidal agents |
| CH672711A5 (en) * | 1987-08-14 | 1989-12-29 | Ciba Geigy Ag | |
| SI8812129A (en) * | 1987-11-27 | 1996-10-31 | Ciba Geigy Ag | Herbicide with synergistic effect and its preparation |
| FR2625647B1 (en) * | 1988-01-12 | 1990-05-18 | Rhone Poulenc Agrochimie | SYNERGISTIC HERBICIDE COMBINATION OF BIFENOX AND SULFONAMIDES |
| DE3926057A1 (en) * | 1989-08-07 | 1991-02-14 | Basf Ag | SYNERGISTIC MIXTURE OF A UREA AND A DIPHENYL ETHER DERIVATIVE FOR ABSCISSION OF PLANT PARTS |
| DE3926055A1 (en) * | 1989-08-07 | 1991-02-14 | Basf Ag | USE OF DIPHENYLETHER DERIVATIVES FOR DESICCATION AND ABSCISSION OF PLANT ORGANS |
| RO117587B1 (en) * | 1991-07-12 | 2002-05-30 | Hoechst Ag | Herbicidal composition, preparation process and weed control method |
| DK0639050T3 (en) * | 1992-05-06 | 2001-04-23 | Novartis Ag | Synergistic agent and method for selective weed control |
| US6017851A (en) * | 1992-05-06 | 2000-01-25 | Novartis Corp. | Synergistic composition and process for selective weed control |
| RU2040180C1 (en) * | 1992-09-04 | 1995-07-25 | Латвийская фирма "КАРЕ" | Herbicide synergistic composition |
| AU3387395A (en) * | 1994-09-06 | 1996-03-29 | Novartis Ag | Herbicidal synergistic composition and method of weed conrol |
| WO1996008165A1 (en) * | 1994-09-13 | 1996-03-21 | Wm. Wrigley Jr. Company | Continuous chewing gum manufacture from base concentrate |
| ATE324042T1 (en) * | 1994-12-22 | 2006-05-15 | Monsanto Technology Llc | HERBICIDAL COMPOSITIONS CONTAINING A SULFONYL UREA AND A UREA DERIVATIVE |
| EP2052607A1 (en) * | 2007-10-24 | 2009-04-29 | Bayer CropScience AG | Herbicide combination |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3416201A1 (en) * | 1984-05-02 | 1985-11-07 | Hoechst Ag, 6230 Frankfurt | HERBICIDAL AGENTS |
| ES2028823T3 (en) * | 1986-05-09 | 1992-07-16 | Hoechst Aktiengesellschaft | HERBICIDE AGENTS. |
-
1987
- 1987-03-02 AT AT87810117T patent/ATE55215T1/en not_active IP Right Cessation
- 1987-03-02 DE DE8787810117T patent/DE3764118D1/en not_active Expired - Lifetime
- 1987-03-02 ES ES87810117T patent/ES2016859B3/en not_active Expired - Lifetime
- 1987-03-02 EP EP87810117A patent/EP0236273B1/en not_active Expired - Lifetime
- 1987-03-05 CA CA000531189A patent/CA1288253C/en not_active Expired - Lifetime
- 1987-03-05 IL IL81788A patent/IL81788A/en not_active IP Right Cessation
- 1987-03-06 ZA ZA871626A patent/ZA871626B/en unknown
- 1987-03-06 BR BR8701059A patent/BR8701059A/en not_active IP Right Cessation
- 1987-03-06 AU AU69770/87A patent/AU590824B2/en not_active Expired
-
1990
- 1990-08-09 GR GR90400348T patent/GR3000704T3/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8883680B2 (en) | 2006-11-13 | 2014-11-11 | Bayer Cropscience Ag | Herbicide combinations with particular sulphonyl ureas |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6977087A (en) | 1987-09-10 |
| ATE55215T1 (en) | 1990-08-15 |
| EP0236273A2 (en) | 1987-09-09 |
| IL81788A (en) | 1992-03-29 |
| BR8701059A (en) | 1987-12-22 |
| ES2016859B3 (en) | 1990-12-01 |
| GR3000704T3 (en) | 1991-10-10 |
| AU590824B2 (en) | 1989-11-16 |
| DE3764118D1 (en) | 1990-09-13 |
| EP0236273B1 (en) | 1990-08-08 |
| ZA871626B (en) | 1987-11-25 |
| EP0236273A3 (en) | 1987-11-19 |
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