Herbicidal agents containing photosynthesis-inhibiting herbicides in combination with carbamate derivatives

The present invention relates to new herbicidal synergistic active compound 
combinations consisting of known photosynthesis-inhibiting herbicides on 
the one hand and certain widely known carbamate derivatives on the other 
hand. 
It has already been disclosed that certain herbicides, such as, for 
example, 4-amino-6-tert.-butyl-3-methylthio-1,2,4-triazin-5-one; 
1-amino-3-(2,2-dimethylpropyl)-6-(ethylthio)-1,3,5-triazine-2,4-dione; 
6-chloro-2-ethylamino-4-isopropylamino-1,3,5-triazine or 
1-methoxy-1-methyl-3-(3,4-dichlorophenyl)-urea, have 
photosynthesis-inhibiting properties (compare, for example, Carl Fedtke, 
Biochemistry and Physiology of Herbicide Action, Springer Verlag, 1982). 
However, the disadvantage of these herbicidal compounds is that not always 
all of the broad-leaved and graminaceous weeds occurring are completely 
affected, or that some species of cropped plants are partially damaged 
when correspondingly high amounts are applied. 
It has been found that the new active compound combinations consisting of 
(a) a photosynthesis-inhibiting active compound (herbicide) and 
(b) a carbamate derivative of the general formula (II) (synergist) 
##STR2## 
in which R.sup.1 represents alkyl, halogenoalkyl, alkenyl, alkinyl or 
optionally substituted phenyl, 
R.sup.2 represents alkyl, halogenoalkyl, alkoxy, alkenyl, optionally 
substituted cycloalkyl or optionally substituted cycloalkylalkyl and 
R.sup.3 represents hydrogen or the grouping --CO--OR.sup.4, 
--CO--CO--OR.sup.5 or --CO--CO--NR.sup.6 R.sup.7, wherein 
R.sup.4 represents alkyl, alkenyl, alkinyl or optionally substituted 
phenyl, 
R.sup.5 represents alkyl, alkenyl or alkinyl and 
R.sup.6 and R.sup.7 are identical or different and represent hydrogen, 
alkyl or alkenyl, 
have a particularly high herbicidal activity. 
Surprisingly, the herbicidal activity of the active compound combinations 
according to the invention is substantially greater than the sum of the 
actions of the individual active compounds. In particular, the widely 
known carbamate derivatives of the general formula (II) do not have an 
intrinsic herbicidal action when the usual amounts are applied, but effect 
an increase in the herbicidal action of the photosynthesis-inhibiting 
active compounds. The synergistic effect found here is thus completely 
unexpected and surprising. 
Since the synergistic effect also concerns those weeds which are only 
insufficiently damaged or are not affected at all when the 
photosynthesis-inhibiting active compounds used are applied by themselves 
in the usual amounts, the synergistic active compound combinations 
according to the invention represent a valuable enrichment of the art. 
Photosynthesis-inhibiting active compounds which may be mentioned for the 
active compound combinations according to the invention are preferably the 
following of the general formulae (I-A) to (I-J): 
(A) triazinone derivatives of the formula 
##STR3## 
in which X.sup.1 represents amino, optionally substituted alkylideneamino 
or alkyl with 1 or 2 carbon atoms; 
X.sup.2 represents alkylthio with 1 or 2 carbon atoms, alkyl- or 
dialkyl-amino with in each case 1 or 2 carbon atoms in each alkyl part, or 
alkyl with 1 to 4 carbon atoms; and 
X.sup.3 represents tert.-butyl which is optionally substituted by halogen, 
or optionally substituted phenyl; 
(B) triazinedione derivatives of the formula 
##STR4## 
in which X.sup.4 represents amino, optionally substituted alkylideneamino 
or alkyl with 1 or 2 carbon atoms; 
X.sup.5 represents alkylthio with 1 or 2 carbon atoms, alkyl- and 
dialkylamino with in each case 1 or 2 carbon atoms in each alkyl part, or 
alkyl with 1 to 4 carbon atoms; and 
X.sup.6 represents alkyl with 1 to 6 carbon atoms or optionally substituted 
phenyl; 
(C) triazine derivatives of the formula 
##STR5## 
in which X.sup.7 represents chlorine, alkoxy or alkylthio with in each 
case 1 or 2 carbon atoms; 
X.sup.8 represents alkylamino with 1 to 4 carbon atoms in the alkyl part; 
and 
X.sup.9 represents alkyl which has 1 to 4 carbon atoms and is optionally 
substituted by cyano; 
(D) urea derivatives of the formula 
##STR6## 
in which X.sup.10 represents optionally substituted phenyl, 
benzothiazolyl or optionally substituted thiadiazolyl; 
X.sup.11 represents hydrogen or methyl; 
X.sup.12 represents methyl; and 
X.sup.13 represents hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 
or 2 carbon atoms or alkinyl with 2 to 4 carbon atoms; 
(E) carboxanilide derivatives of the formula 
EQU X.sup.14 --CO--NH--X.sup.15 (I-E) 
in which 
X.sup.14 represents alkyl with up to 6 carbon atoms, alkoxy with 1 to 4 
carbon atoms, alkenyl with 2 to 4 carbon atoms or cycloalkyl with 3 to 6 
carbon atoms; and 
X.sup.15 represents optionally substituted phenyl; 
(F) uracil derivatives of the formula 
##STR7## 
in which X.sup.16 represents alkyl with 1 to 6 carbon atoms or cycloalkyl 
with 5 to 7 carbon atoms; 
X.sup.17 represents halogen; and 
X.sup.18 represents alkyl with 1 or 2 carbon atoms, or 
X.sup.17 and X.sup.18 together represent an optionally substituted alkylene 
chain or an optionally substituted fused-on benzene ring; and 
X.sup.19 represents the --CO-- or --SO.sub.2 -- group; 
(G) biscarbamate derivatives of the formula 
##STR8## 
in which X.sup.20 represents alkyl with 1 to 4 carbon atoms or optionally 
substituted phenyl; and 
X.sup.21 represents alkoxy with 1 to 4 carbon atoms or dialkylamino with 1 
or 2 carbon atoms in each alkyl part; 
(H) pyridiazinone derivatives of the formula 
##STR9## 
in which X.sup.22 represents optionally substituted phenyl; 
X.sup.23 represents amino or alkylamino or dialkylamino with in each case 1 
or 2 carbon atoms in each alkyl part; and 
X.sup.24 represents halogen; 
(J) hydroxybenzonitrile derivatives of the formula 
##STR10## 
in which X.sup.25 represents halogen; and 
X.sup.26 represents halogen. 
The following photosynthesis-inhibiting active compounds of the general 
formulae (I-A) to (I-J) are particularly preferred: 
(A) triazinone derivatives of the formulae 
##STR11## 
The photosynthesis-inhibiting active compounds of the formulae (I-A to I-J) 
are known (compare, for example, Carl Fedtke, Biochemistry and Physiology 
of Herbicide Action, Springer-Verlag, 1982). 
Formula (II) provides a general definition of the carbamate derivatives 
also to be used as components in the mixture. Preferably, in this formula, 
R.sup.1 represents straight-chain or branched alkyl with 1 to 8 carbon 
atoms, halogenoalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms 
(such as, in particular, fluorine and chlorine atoms), alkenyl or alkinyl 
with in each case 3 to 6 carbon atoms or phenyl; 
R.sup.2 represents straight-chain or branched alkyl with 1 to 8 carbon 
atoms, halogenoalkyl with 1 to 5 carbon atoms and 1 to 3 halogen atoms 
(such as, in particular, fluorine and chlorine atoms), alkoxy with 1 to 4 
carbon atoms, or cycloalkyl or cycloalkylalkyl with in each case 3 to 6 
carbon atoms in the alkyl part and in each case optionally substituted by 
alkyl with 1 to 4 carbon atoms; 
R.sup.3 represents hydrogen or the grouping --CO--OR.sup.4, 
--CO--CO--OR.sup.5 or --CO--CO--NR.sup.6 R.sup.7 ; 
R.sup.4 represents straight-chain or branched alkyl with 1 to 4 carbon 
atoms, alkenyl or alkinyl with in each case 3 to 4 carbon atoms, or phenyl 
which is optionally substituted by halogen and/or alkyl with 1 or 2 carbon 
atoms; 
R.sup.5 represents straight-chain or branched alkyl with 1 to 4 carbon 
atoms, or alkenyl or alkinyl with in each case 3 or 4 carbon atoms; and 
R.sup.6 and R.sup.7, which are identical or different, represent hydrogen, 
straight-chain or branched alkyl with 1 to 6 carbon atoms or alkenyl with 
3 to 4 carbon atoms. 
Particularly preferred compounds of the formula (II) are those in which 
R.sup.1 represents straight-chain or branched alkyl with 1 to 5 carbon 
atoms, such as, in particular, methyl; or furthermore represents 
chloroethyl, fluoroethyl, trifluoroethyl or trichloroethyl; or represents 
alkyl, propargyl, 3-butin-2-yl or phenyl; 
R.sup.2 represents straight-chain or branched alkyl with 1 to 8 carbon 
atoms; or represents chloroethyl, fluoroethyl, trifluoroethyl or 
trichloroethyl, or tert.-butyl or neopentyl, each of which is mono-, di- 
or tri-substituted by fluorine or chlorine; or furthermore represents 
cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclopentylmethyl cyclohexyl 
or cyclohexylmethyl, each of which is optionally substituted by methyl; or 
represents alkoxy with 1 to 4 carbon atoms, allyl or propargyl; 
R.sup.3 represents hydrogen or the grouping --CO--OR.sup.4, 
--CO--CO--OR.sup.5 or --CO--CO--NR.sup.6 R.sup.7 ; 
R.sup.4 represents methyl, allyl, propargyl or phenyl; 
R.sup.5 represents straight-chain or branched alkyl with 1 to 4 carbon 
atoms, such as, in particular, methyl; or represents allyl or propargyl; 
and 
R.sup.6 and R.sup.7 are identical or different and represent hydrogen, 
straight-chain or branched alkyl with 1 to 5 carbon atoms, allyl or 
propargyl. 
The carbamate derivates of the formula (IL) are known (compare, for 
example, German Offenlegungsschriften [German Published Specification] 
Nos. 3,035,392, 3,035,393, 3,230,294 and 3,230,295; or they are the 
subject of commonly assigned pending applications (compare German Patent 
Application Nos. P 33 12 498 of Apr. 7, 1983 and P 33 26 145 of July 20, 
1983; or they can be obtained in the customary manner by processes 
described in these references, for example by reacting amines, if 
appropriate in the form of their hydrosalts, with carbonic acid 
ester-halides; or by reacting isocyanates with alcohols in the presence of 
a catalyst; or by reacting chlorooxalylcarbamic acid esters with alcohols 
or amines (in this context, compare also the preparation examples). 
The weight ratios of the active compounds in the new active compound 
combinations can vary within relatively wide limits. In general, 0.25 to 
100, preferably 5 to 50 and in particular 10 to 20, parts by weight of 
carbamate derivative of the formula (II) (synergist) are present per part 
by weight of photosynthesis-inhibiting active compound (herbicidal active 
compound). 
The photosynthesis-inhibiting active compounds exhibit powerful herbicidal 
actions. Nevertheless, against some broad-leaved weeds, such as, for 
example, Galium aparine, Ipomoea hederacea, Datura stramonium, Cirsium 
arvense, Convolvulus arvensis or Solanum nigrum, and some gramineous 
weeds, such as, for example, Agropyron repens, Avena fatua, Cynodon 
dactylon, Cyperus ssp. and Lolium rigidum, they have an action which is 
not always adequate. The active compound combinations according to the 
invention extend the action spectrum of the compounds of the formulae (I-A 
to 1-J) and thereby enable these weeds which can be controlled only with 
difficulty or not at all by the herbicidal active compounds by themselves 
to be combated. 
The active compound combinations according to the invention can be used, 
for example, in connection with the following plants: 
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, 
Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, 
Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, 
Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, 
Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea. 
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, 
Phaseolus, Pisum, Solanum, Linum, Vicia, Nicotiana, Lycopersicon, Arachis, 
Brassica, Lactuca, Cucumis and Cucurbita. 
Monocotyledon weeds of the genera: Echinochloa, Setaria, Brachiaria, 
Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, 
Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, 
Sphenoclea, Dactyloctenium, Agrotis, Alopecurus and Apera. 
Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, 
Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium. 
However, the use of the active compound combinations according to the 
invention is in no way restricted to these genera, but also extends in the 
same manner to other plants. 
Besides a good action against graminaceous weeds, the active compound 
combinations according to the invention also exhibit a good herbicidal 
action on broad-leaved weeds. 
The active compound combinations according to the invention can be 
converted to the customary formulations, such as solutions, emulsions, 
wettable powders, suspensions, powders, dusting agents, pastes, soluble 
powders, granules, suspension-emulsion concentrates, natural and synthetic 
materials impregnated with active compound, and very fine capsules in 
polymeric substances. 
These formulations are produced in known manner, for example by mixing the 
active compounds with extenders, that is liquid solvents and/or solid 
carriers, optionally with the use of surface-active agents, that is 
emulsifying agents and/or dispersing agents and/or foam-forming agents. 
In the case of the use of water as an extender, organic solvents can, for 
example, also be used as auxiliary solvents. As liquid solvents, there are 
suitable in the main; aromatics, such as xylene, toluene or alkyl 
napthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, 
such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic 
hydrocarbons, such as cyclohexane or paraffins, for example petroleum 
fractions, alcohols, such as butanol or glycol as well as their ethers and 
esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl 
ketone or cyclohexanone, strongly polar solvents, such as 
dimethylformamide and dimethylsulphoxide, as well as water. 
As solid carriers there are suitable: for example ground natural minerals, 
such as kaolins, clays, talc, quartz, attapulgite, montmorillonite or 
diatomaceous earth, and ground synthetic minerals, such as highly disperse 
silicic acid, alumina and silicates, as solid carriers for granules there 
are suitable: for example crushed and fractionated natural rocks such as 
calcite, marble, pumice, sepiolite and dolomite, as well as synthetic 
granules of inorganic and organic meals, and granules of organic material 
such as sawdust, coconut shells, corn cobs and tobacco stalks; as 
emulsifying and/or foam-forming agents there are suitable: for example 
non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid 
esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl 
polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as 
well as albumin hydrolysis products; as dispersing agents there are 
suitable: for example lignin-sulphite waste liquors and methylcellulose. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, can be used in the formulations. 
The formulations can contain, as further additives, colorants such as 
inorganic pigments, for example iron oxide, titanium oxide and Prussian 
Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and 
metal phthalocyanine dyestuffs, and moreover trace nutrients such as salts 
of iron, manganese, boron, copper, cobalt, molybdenum and zinc. 
The formulations in general contain between 0.1 and 95 percent by weight of 
active compound combination, preferably between 0.5 and 90%. 
The active compound combinations according to the invention are in general 
used in the form of finished formulations. However, the active compounds 
contained in the active compound combinations can also be mixed as 
individual formulations when used, that is to say can be applied in the 
form of tank mixes. 
The new active compound combinations, as such or in the form of their 
formulations, can furthermore also be used as mixtures with other known 
herbicides, finished formulations or tank mixes again being possible. 
Mixtures with other known active compounds, such as fungicides, 
insecticides, acaricides, nematicides, bird repellents, growth factors, 
plant nutrients and agents which improve soil structure, are also 
possible. 
The new active compound combinations can be used as such, in the form of 
their formulations or in the use forms prepared therefrom by further 
dilutions, such as ready-to-use solutions, suspensions, emulsions, 
powders, pastes and granules. They are used in the customary manner, for 
example by watering, spraying, atomizing, dusting or scattering. 
The active compound combinations according to the invention can be applied 
either before or after sowing as well as after emergence of the plants, 
together or in separate applications. The sequence of applications is of 
no importance here. 
When the synergists according to the invention are used, the customary 
application amount of the herbicides of the formulae (I-A to I-J) can be 
reduced. The amount of herbicidal photosynthesis-inhibiting active 
compound applied in the case of surface treatment is between 0.01 and 3.0 
kg/ha, preferably between 0.05 and 2.0 kg/ha. 
The amount of synergistic carbamate derivative (II) applied in the case of 
surface treatment is between 0.1 and 10 kg/ha, preferably between 0.05 and 
3 kg/ha. 
The good herbicidal action of the active compound combinations according to 
the invention can be seen from the following examples. While the 
individual active compounds show weaknesses in herbicidal action, the 
combinations according to the invention exhibit a herbicidal action which 
goes beyond a simple summation of the actions. 
A synergistic effect is always present with herbicides if the herbicidal 
action of the active compound combination is greater than the sum of the 
actions of the active compounds applied.