Herbicide composition containing carboxylic-acid-amidothiolcarbamate derivatives

FIELD OF THE INVENTION
The invention relates to a herbicide composition which contains 10 to 80 percent by weight of a carboxylicacid-amido-thiolcarbamate derivative of formula (I) ##STR2## 10 to 90 percent be weight of a solid and/or liquid carrier as well as 1 to 30 percent by weight of an additive, suitably a surface-active agent.
In formula (I) the substituents have the following meanings:
R.sup.1 and R.sup.2 can be identical or different and can stand for hydrogen,
a C.sub.1-10 straight or branched alkyl group,
a C.sub.2-10 straight or branched alkenyl group,
a C.sub.5-6 cycloalkyl or phenyl group,
a phenyl radical mono or disubstituted by C.sub.1-3 alkyl, or by halogen;
but R.sup.1 and R.sup.2 can form together a hexamethylene group;
R.sup.3 can stand for a C.sub.1-5 straight or branched alkyl radical;
R.sup.4 can represent a C.sub.1-10 straight or branched alkyl group,
a C.sub.2-10 straight or branched alkenyl group,
a phenyl or a benzyl radical.
BACKGROUND OF THE INVENTION
An indispensable part of modern large-scale plant cultivation is chemical plant protection in which different parasites are prevented from destroying a significant part of the crop and reducing the crop, respectively.
In the past decades several plant protecting agents came into general use which protect the cultivated plants against weed. However, their use resulted in a modification of the weed flora on the one hand, on the other hand in developing resistance individual types of weeds and consequently it was necessary to search for further newer herbicides in order to enable agent rotation and to control the resisting weeds, respectively.
Subsequent to general use of the symmetrical triazines successfully used in the control of dicotyledonous weeds the weed flora shifted to the direction of the monocotyledonous plants and at the beginning of the sixties chloro-acet-anilide-derivatives were employed for protection against them (U.S. Pat. No. 2,863,752). However, the protection against all monocotyledonous weeds, particularly against the resisting Sorghum halepense, did not succeed with these compounds (Propachlor, Alachlor and so on).
In the second half of the sixties N,N-disubstituted thiocarbamic type herbicides (U.S. Pat. No. 2,913,327) began to be very much used because of their suitability for the control of several weeds resisting the chloro-acet-anilide-derivatives.
Their use, however, is accompanied by disadvantages because they harm most of the cultivated plants in a dose necessary for a safe weed control to a greater or lesser degree and cause deformed leaves and sprouts.
In order to eliminate this undesired phytotoxic effect combinations of the thiolcarbamates and compounds of so-called antidotal effect were elaborated.
To the thiolcarbamate herbicide some percents of a substance exerting an antidotal effect are admixed and thus the selectivity of the preparation is increased with an unchanged herbicidal effect (Hungarian Patent Specification No. 165,736). However, these substances exerting an antidotal effect do not ensure sufficient protection against the phytotoxic effect of the thiolcarbamates for all cultivated plants and for all types of the individual plants, respectively.
Japanese Patent Specification No. 53-148,530 discloses a thiocarbonyl-amino acid-derivative of a newer structure but these derivatives cannot be used as herbicides, they are suitable only for sterilization.
The glycinethiolcarbamate derivatives disclosed in Japanese Patent Specification No. 52-151,146 have a somewhat similar structure as the above derivatives but these preparations are used in rice cultivations, the phytotoxic effect exerted on other cultivated plant cultures, however, is not known.
All these facts make the research for further new plant protecting agents necessary by which the disadvantages of the agents already used could be eliminated and the agent rotation necessary for safe cultivation could be determined.
DESCRIPTION OF THE INVENTION
In the course of our research work we discovered that the known disadvantages of the thiolcarbamate herbicides can be eliminated if such an agent is used for weed control which contains 10 to 80 percent by weight of a compound of formula (I), 10 to 90 percent by weight of a solid and/or liquid diluting agent as well as 1 to 30 percent by weight of an additive.
The substituents are as defined as follows in the formula (I) of the carboxylic acid-amido-substituted-thiolcarbamate derivatives:
R.sup.1 and R.sup.2 can be identical or different and can stand for hydrogen, a C.sub.1-10 straight or branched alkyl group, a C.sub.2-10 straight or branched alkenyl group, a C.sub.5-6 cycloalkyl or phenyl group, a phenyl radical mono or disubstituted by C.sub.1-3 alkyl or halogen, or R.sup.1 and R.sup.2 together can form a hexamethylene group: R.sup.3 can stand for a C.sub.1-5 straight or branched alkyl radical, R.sup.4 can represent a C.sub.1-10 straight or branched alkyl group, a C.sub.2-10 straight or branched alkenyl group, a phenyl or benzyl radical.
The solid and/or liquid diluting agent preferably makes up between 20 and 90% of the composition by weight. Preferred liquid diluents include solvents not miscible with water, preferably aromatic or halogenated hydrocarbons. An artificial white oil fraction is a preferred liquid diluent. As preferred solid diluents preferably artificial amorphous silicic acid may be employed as well as minerals of the silicate, sulfate type.
The additive is present in an amount of 1 to 30% by weight of the composition and preferably is present in an amount of 1 to 15% by weight of the composition. The additive is preferably a surface active agent (e.g. a wetting or dispersing agent). Preferred surface active agents include anionic, cationic and non-ionic tensides.
The product of the invention can successfully be used for the control of mono- and dicotyledonous weeds, at the same time it does not exert a harmful effect on cultivated plants. In certain cases a stimulating effect on the green mass of cultivated plants was observed.
The present invention relates to a process for the preparation of carboxylic acid-amido-substituted-thiolcarbamates of formula (I). Accordingly one proceeds so that the N-substituted-amino-carboxylic acid-N,'N'-disubstituted-acid amide thereof of formula (II) ##STR3## wherein the substituents are as defined above--is reacted, optionally in a medium containing a solvent in the presence of an acid binding agent with the substituted chloro-formic acid-thiol-ester of formula (III) ##STR4## at a temperature of 20.degree. to 60.degree. C.

SPECIFIC EXAMPLES
The preparation of some compounds of formula (I) is illustrated with the aid of the following examples.
EXAMPLE 1
Into a round-bottom flask provided with a mixer, a thermometer and a feeder and a capacity of 500 ml of 21.4 g of N-ethyl-N-(N'-ethyl-acetanilide)-amine are weighed and under stirring dissolved in 150 ml of benzene. 16 ml of triethylamine are added, then keeping the temperature at 30.degree. to 40.degree. C., 13 g of chloro-formic acid-ethyl-thiolester are added within half an hour. After finishing the addition the reaction mixture is still stirred for half an hour, then 150 ml of distilled water are added. After stirring the organic phase is separated from the aqueous phase. The phase containing an organic solvent is washed at first with dilute hydrochloric acid, then with distilled water.
After the separation from the aqueous phase the phase containing the organic solvent is dried over sodium sulfate, the solvent is evaporated. 20.5 g of N-ethyl-N-(N'-ethyl-acet-anilido)-S-ethyl-thiolcarbamate are obtained in form of a transparent liquid, the refractive index of which is n.sub.D.sup.20 =1.5344.
Yield: 72%. Purity (gas chromatography): 94.8 Wt. %.
EXAMPLE 2
Into a round-bottom flask provided with a mixer, a thermometer and a feed funnel 22.2 g of N-ethyl-N-(N'-isopropyl-acet-anilide)-amine are weighed, under stirring 150 ml of triethylamine are added. Then at a temperature of 30.degree. to 40.degree. C., 13 g of chloro-formic acid-ethyl-thiolester are dropped in under stirring within 30 minutes. After the addition the reaction mixture is still stirred at room temperature for 15 minutes, then 200 ml of water are added. After stirring the organic phase is separated from the aqueous phase, it is washed first with dilute hydrochloric acid, then with distilled water and taken up with 200 ml of benzene. After the evaporation of the solvent 16.5 g of crystalline N-ethyl-N-(N'-isopropyl-acet-anilido)-S-ethyl-thiolcarbamate are obtained which melts at a temperature of 72.degree.-73.5.degree. C.
Yield: 56%. Purity (gas chromatography): 98.2 wt %.
EXAMPLE 3
Into a round-bottom flask provided with a mixer, a thermometer, a dropping funnel and a capacity of 500 ml 10.3 g of N-isopropyl-N-(N'-methyl-acet-anilide)-amine are weighed, then dissolved in 100 ml of toluene. 7 g of chloroformic acid-n-amyl-thiolester are added to the solution under stirring at a temperature of 20.degree. to 40.degree. C. and the reaction mixture is stirred at room temperature for two hours. The reaction mixture is washed first with dilute hydrochloric acid, then with distilled water. The organic phase is separated and dehydrated with sodium sulfate, the toluene is distilled off. 15.2 g of liquid N-isopropyl-N-(N'-methyl-acet-anilido)-S-n-amyl-thiolcarbamate are obtained the refractive index of which is n.sub.D.sup.20 =1.5332.
Yield: 92%. Purity (gas chromatography) 94.5 Wt. %.
EXAMPLE 4
Into a round-bottom flask provided with a mixer, a thermometer and a dropping funnel and a capacity of 500 ml 21.9 g of N-ethyl-N-(2'-methyl-6'-ethyl-acet-anilide)-amine are weighed, then 120 ml of triethylamine are added. Under stirring 22.8 g of chloro-formic acid-n-octyl-thiolester are added to the mixture at a temperature of 20.degree.-25.degree. C., then it is stirred for another three hours. The precipitated solid crystalline material is separated by filtration, washed with n-pentane and dried. 28.5 g of solid, crystalline N-ethyl-N-(2'-methyl-6'-ethyl-acet-anilido)-S-n-octyl-thiolcarbamate are obtained, the melting point of which is 76.degree. to 78.5.degree. C.
Yield: 74%. Purity (gas chromatography): 95.4 Wt. %.
The physical constants of the derivatives of formula (I) prepared with the process according to the invention, similarly as described in Examples 1 to 4 are included in the following Table 1.
TABLE I__________________________________________________________________________substituent physical constantNr. R.sup.1 R.sup.2 R.sup.3 R.sup.4 m.p. .degree.C. n.sub.D.sup.201 2 3 4 5 6 7__________________________________________________________________________1 ethyl- phenyl- methyl- ethyl- -- 1.51272 i-propyl- phenyl- methyl- ethyl- 71-72 --3 methyl- phenyl- ethyl- ethyl- -- 1.52474 ethyl- phenyl- ethyl- ethyl- -- 1.53445 i-propyl- phenyl- ethyl- ethyl- 72-73.5 --6 methyl- phenyl- n-propyl- ethyl- -- 1.54157 ethyl- phenyl- n-propyl- ethyl- -- 1.52698 i-propyl- phenyl- n-propyl- ethyl- 81-83 --9 methyl- phenyl- i-propyl- ethyl- -- 1.542310 ethyl- phenyl- i-propyl- ethyl- -- 1.525911 i-propyl- phenyl- i-propyl- ethyl- 96-98 --12 methyl- phenyl- allyl- ethyl- -- 1.539713 ethyl- phenyl- allyl- ethyl- -- 1.530914 i-propyl- phenyl- allyl- ethyl- 77-78 --15 methyl- phenyl- n-butyl- ethyl- -- 1.529316 ethyl- phenyl- n-butyl- ethyl- -- 1.528417 i-propyl- phenyl- n-butyl- ethyl- 73.5-75 --18 methyl- phenyl- i-butyl- ethyl- -- 1.527619 ethyl- phenyl- i-butyl- ethyl- -- 1.523320 i-propyl- phenyl- i-butyl- ethyl- 98-99.5 --21 methyl- phenyl- s-butyl- ethyl- -- 1.536722 ethyl- phenyl- s-butyl- ethyl -- 1.528123 i-propyl- phenyl- s-butyl- ethyl- 79-81 --24 methyl- phenyl- t-butyl- ethyl- -- 1.518725 ethyl- phenyl- t-butyl- ethyl- -- 1.519826 i-propyl- phenyl- t-butyl- ethyl- 64.5-66 --27 methyl- phenyl- ethyl- n-propyl- -- 1.517728 ethyl- phenyl- ethyl- n-propyl- -- 1.535529 i-propyl- phenyl- ethyl- n-propyl- 65-67 --30 methyl- phenyl- n-propyl- n-propyl- -- 1.530731 ethyl- phenyl- n-propyl- n-propyl- -- 1.530132 i-propyl- phenyl- n-propyl- n-propyl- 61-64 --33 methyl- phenyl- i-propyl- n-propyl- -- 1.537334 ethyl- phenyl- i-propyl- n-propyl- -- 1.521935 i-propyl- phenyl- i-propyl- n-propyl- 69-71 --36 methyl- phenyl- allyl- n-propyl- -- 1.542637 ethyl- phenyl- allyl- n-propyl- -- 1.536338 i-propyl- phenyl- allyl- n-propyl- 64-66 --39 methyl- phenyl- n-butyl- n-propyl- -- 1.532340 ethyl- phenyl- n-butyl- n-propyl- -- 1.530441 i-propyl- phenyl- n-butyl- n-propyl 53-57 --42 methyl- phenyl- i-butyl- n-propyl- -- 1.534143 ethyl- phenyl- i-butyl- n-propyl- -- 1.528744 i-propyl- phenyl- i-butyl- n-propyl- 68-71 --45 methyl- phenyl- s-butyl- n-propyl- -- 1.536646 ethyl- phenyl- s-butyl- n-propyl- -- 1.528347 i-propyl- phenyl- s-butyl- n-propyl- -- 1.526848 methyl- phenyl- t-butyl- n-propyl- -- 1.535549 ethyl- phenyl- t-butyl- n-propyl- -- 1.517050 i-propyl- phenyl- t-butyl- n-propyl- -- 1.527851 ethyl- phenyl- ethyl- s-butyl- -- 1.523952 i-propyl- phenyl- ethyl- s-butyl- 68-70 --53 methyl- phenyl- n-propyl- s-butyl- -- 1.533454 ethyl- phenyl- n-propyl- s-butyl- 54-56 --55 i-propyl- phenyl- n-propyl- s-butyl- 101-103 --56 methyl- phenyl- i-propyl- s-butyl- -- 1.532357 ethyl- phenyl- i-propyl- s-butyl- -- 1.530358 i-propyl- phenyl- i-propyl- s-butyl- 58-62 --59 methyl- phenyl- allyl- s-butyl- -- 1.540060 ethyl- phenyl- allyl- s-butyl- -- 1.536161 i-propyl- phenyl- allyl- s-butyl- 72-75 --62 methyl- phenyl- n-butyl- s-butyl- -- 1.530863 ethyl- phenyl- n-butyl- s-butyl- -- 1.525564 i-propyl- phenyl- n-butyl- s-butyl- 77-78 --65 ethyl- phenyl- s-butyl- s-butyl- -- 1.527366 methyl- phenyl- t-butyl- s-butyl- -- 1.528767 ethyl- phenyl- t-butyl- s-butyl- -- 1.523168 i-propyl- phenyl- t-butyl- s-butyl- -- 1.521369 methyl- phenyl- n-propyl- n-amyl- -- 1.530270 ethyl- phenyl- n-propyl- n-amyl- -- 1.525871 i-propyl- phenyl- n-propyl- n-amyl- 58-61 --72 methyl- phenyl- i-propyl- n-amyl- -- 1.533273 ethyl- phenyl- i-propyl- n-amyl- -- 1.527074 i-propyl- phenyl- i-propyl- n-amyl- -- 1.524275 methyl- phenyl- allyl- n-amyl- -- 1.538476 ethyl- phenyl- allyl- n-amyl- -- 1.532877 i-propyl- phenyl- allyl- n-amyl- -- 1.529378 methyl- phenyl- n-butyl- n-amyl- -- 1.527079 ethyl- phenyl- n-butyl- n-amyl- -- 1.523480 i-propyl- phenyl- n-butyl- n-amyl- 38-40 --81 ethyl- phenyl- i-butyl- n-amyl- -- 1.526882 methyl- phenyl- t-butyl- n-amyl- -- 1.524883 ethyl- phenyl- ethyl- n-amyl- -- 1.528184 i-propyl- phenyl- i-butyl- n-amyl- -- 1.519085 methyl- phenyl- n-propyl- i-amyl- -- 1.530886 ethyl- phenyl- n-propyl- i-amyl- -- 1.526287 i-propyl- phenyl- n-propyl- i-amyl- 61-64 --88 methyl- phenyl- i-propyl- i-amyl- -- 1.532989 ethyl- phenyl- i-propyl- i-amyl- -- 1.527990 i-propyl- phenyl- i-propyl- i-amyl- -- 1.524491 methyl- phenyl- allyl- i-amyl- -- 1.537592 ethyl- phenyl- allyl- i-amyl- -- 1.532293 i-propyl- phenyl- allyl- i-amyl- -- 1.529094 methyl- phenyl- n-butyl- i-amyl- -- 1.525295 ethyl- phenyl- n-butyl- i-amyl- -- 1.523596 i-propyl- phenyl- n-butyl- i-amyl- -- 1.520497 ethyl- phenyl- t-butyl- i-amyl- -- 1.522798 methyl- phenyl- t-butyl- i-amyl- -- 1.526799 ethyl- phenyl- ethyl- i-amyl- -- 1.5258100 i-propyl- phenyl- t-butyl- i-amyl- -- 1.5200101 hydrogen 2,6-dimethyl-phenyl- ethyl- ethyl- 107-110 --102 hydrogen 2,6-dimethyl-phenyl- n-propyl- ethyl- 82-85 --103 hydrogen 2,6-dimethyl-phenyl- i-propyl- ethyl- 126-128 --104 hydrogen 2,6-dimethyl-phenyl- allyl- ethyl- 103-104.5 --105 hydrogen 2,6-dimethyl-phenyl- n-butyl- ethyl- 92-96 --106 hydrogen 2,6-dimethyl-phenyl- s-butyl- ethyl- 112-114.5 --107 hydrogen 2,6-dimethyl-phenyl- t-butyl- ethyl- 194.5-196 --108 hydrogen 2,6-dimethyl-phenyl- ethyl- n-propyl 91-93 --109 hydrogen 2,6-dimethyl-phenyl- n-propyl- n-propyl 59-63 --110 hydrogen 2,6-dimethyl-phenyl- i-propyl- n-propyl- 113-114 --111 hydrogen 2,6-dimethyl-phenyl- allyl- n-propyl- 111-112,5 --112 hydrogen 2,6-dimethyl-phenyl- n-butyl- n-propyl- 82-84 --113 hydrogen 2,6-dimethyl-phenyl- s-butyl- n-propyl- 71-74 --114 hydrogen 2,6-dimethyl-phenyl- t-butyl- n-propyl- 164-167 --115 hydrogen 2,6-dimethyl-phenyl- ethyl- n-octyl- 65-69 --116 hydrogen 2,6-dimethyl-phenyl- n-propyl- n-octyl- 57-61 --117 hydrogen 2,6-dimethyl-phenyl- i-propyl- n-octyl- 53-57,5 --118 hydrogen 2,6-dimethyl-phenyl- allyl- n-octyl- 69-72 --119 hydrogen 2,6-dimethyl-phenyl- n-butyl- n-octyl- 68-70 --120 hydrogen 2,6-dimethyl-phenyl- s-butyl- n-octyl- -- 1.5198121 hydrogen 2,6-dimethyl-phenyl- t-butyl- n-octyl- 59-63 --122 hydrogen 2,6-diethyl-phenyl- ethyl- ethyl- 110-114 --123 hydrogen 2,6-diethyl-phenyl- n-propyl- ethyl- 104-108 --124 hydrogen 2,6-diethyl-phenyl- i-propyl- ethyl- 130-135 --125 hydrogen 2,6-diethyl-phenyl- allyl- ethyl- 125-129 --126 hydrogen 2,6-diethyl-phenyl- n-butyl- ethyl- 105-108 --127 hydrogen 2,6-diethyl-phenyl- s-butyl- ethyl- 78-82 --128 hydrogen 2,6-diethyl-phenyl- t-butyl- ethyl- 200-205 --129 hydrogen 2,6-diethyl-phenyl- ethyl- n-propyl- 82-84.5 --130 hydrogen 2,6-diethyl-phenyl- n-propyl- n-propyl- 108-112 --131 hydrogen 2,6-diethyl-phenyl- i-propyl- n-propyl- 107-109 --132 hydrogen 2,6-diethyl-phenyl- allyl- n-propyl- 105-108 --133 hydrogen 2,6-diethyl-phenyl- n-butyl- n-propyl- 98-102 --134 hydrogen 2,6-diethyl-phenyl- s-butyl- n-propyl- 73-76 --135 hydrogen 2,6-diethyl-phenyl- t-butyl- n-propyl- 191-194 --136 hydrogen 2,6-diethyl-phenyl- ethyl- n-octyl- 74-76.5 --137 hydrogen 2,6-diethyl-phenyl- n-propyl- n-octyl- 61-64 --138 hydrogen 2,6-diethyl-phenyl- i-propyl- n-octyl- 63.5-65 --139 hydrogen 2,6-diethyl-phenyl- allyl- n-octyl- 70.5-72 --140 hydrogen 2,6-diethyl-phenyl- n-butyl- n-octyl- 64-67 --141 hydrogen 2,6-diethyl-phenyl- s-butyl- n-octyl- -- 1.5192142 hydrogen 2,6-diethyl-phenyl- t-butyl- n-octyl- 62-65.5 --143 hydrogen 2-methyl-6-ethyl-phenyl- ethyl- ethyl- 88-92 --144 hydrogen 2-methyl-6-ethyl-phenyl- n-propyl- ethyl- 94-96 --145 hydrogen 2-methyl-6-ethyl-phenyl- i-propyl ethyl- 99-100.5 --146 hydrogen 2-methyl-6-ethyl-phenyl- allyl- ethyl- 118.5-120 --147 hydrogen 2-methyl-6-ethyl-phenyl- n-butyl- ethyl- 85-90 --148 hydrogen 2-methyl-6-ethyl-phenyl- s-butyl- ethyl- -- 1.5357149 hydrogen 2-methyl-6-ethyl-phenyl- t-butyl- ethyl- 190-193.5 --150 hydrogen 2-methyl-6-ethyl-phenyl- ethyl- n-propyl- 60-64 --151 hydrogen 2-methyl-6-ethyl-phenyl- n-propyl- n-propyl- 91.5-94 --152 hydrogen 2-methyl-6-ethyl-phenyl- i-propyl- n-propyl- 84-87 --153 hydrogen 2-methyl-6-ethyl-phenyl- allyl- n-propyl- 104-106 --154 hydrogen 2-methyl-6-ethyl-phenyl- n-butyl- n-propyl- 97-99.5 --155 hydrogen 2-methyl-6-ethyl-phenyl- s-butyl- n-propyl- -- 1.5330156 hydrogen 2-methyl-6-ethyl-phenyl- t-butyl- n-propyl- 121-125 --157 hydrogen 2-methyl-6-ethyl-phenyl- ethyl- n-octyl- 73.5-75 --158 hydrogen 2-methyl-6-ethyl-phenyl- n-propyl- n-octyl- 60-64 --159 hydrogen 2-methyl-6-ethyl-phenyl- i-propyl- n-octyl- -- 1.5192160 hydrogen 2-methyl-6-ethyl-phenyl- allyl- n-octyl- 60.5-63.5 --161 hydrogen 2-methyl-6-ethyl-phenyl- n-butyl- n-octyl- 59-62 --162 hydrogen 2-methyl-6-ethyl-phenyl- s-butyl- n-octyl- -- 1.5205163 hydrogen 2-methyl-6-ethyl-phenyl- t-butyl- n-octyl- -- 1.5157164 methyl- phenyl- methyl- ethyl- -- 1.5120165 ethyl- phenyl- ethyl- n-octyl- -- 1.5083166 methyl- phenyl- ethyl- n-octyl- -- 1.5028167 ethyl- phenyl- methyl- n-propyl- -- 1.5400168 methyl- phenyl- methyl- n-propyl- -- 1.5513169 ethyl- phenyl- ethyl- allyl- -- 1.5497170 ethyl- phenyl- ethyl- benzyl- -- 1.5612171 ethyl- phenyl- ethyl- phenyl- -- 1.5664172 hydrogen phenyl- ethyl- ethyl- -- 1.5697173 hydrogen 3-chloro-phenyl- ethyl- ethyl- -- 1.5716174 hydrogen 3-methyl-phenyl- ethyl- ethyl- -- 1.5675175 hydrogen cyclohexyl- ethyl- ethyl- 85-88 --176 methyl- cyclohexyl- ethyl- ethyl- -- 1.5191177 ethyl- cyclohexyl- ethyl- ethyl- -- 1.5154178 hexamethylene ethyl- ethyl- 38-42 --179 hexamethylene ethyl- n-propyl- -- 1.5221180 methyl- methyl- ethyl- ethyl- -- 1.4980181 ethyl- ethyl- ethyl- ethyl- -- 1.5015182 ethyl- ethyl- ethyl- n-propyl- -- 1.4987183 n-propyl- n-propyl- ethyl- ethyl- 36.5-38.5 --184 allyl- allyl- ethyl- ethyl- -- 1.5146185 allyl- allyl- ethyl- n-propyl- -- 1.5119186 i-butyl- i-butyl- ethyl- ethyl- 58-61 --187 i-butyl- i-butyl- i-propyl- ethyl- 42-45 --__________________________________________________________________________
The herbicide according to the invention can be used in form of an emulsion-concentrate, a wettable powder, a granulate, an aqueous or oily suspension in plant protection. The preparation of the product is illustrated by the following examples.
EXAMPLE 5
Into a round-bottom flask provided with a mixer and with a capacity of 500 ml. 50 parts by weight of N-ethyl-N-(N'-ethyl-acet-anilido)-S-ethyl-thiolcarbamate are weighed, 40 parts by weight of kerosine, 5 parts by weight of octyl-phenol-polyglycol-ether (Tensiofix AS) and 5 parts by weight of nonyl-phenyl-polyglycol-ether (Tensiofix IS) emulsifier are added. The stirring is continued until dissolving is finished, thus a 50 Wt.% emulsion concentrate is obtained.
Table II includes the composition data of the emulsifiable concentrates prepared from derivatives of formula (I), similarly as described in Example 5.
TABLE II__________________________________________________________________________Components in parts by weightNumber compoundaccording according methylene Tensiofix Tensiofixto Table I to Table I kerosine xylene chloride phenol AS IS Product1 2 3 4 5 6 7 8 9__________________________________________________________________________ 1 50 40 -- -- -- 5 5 50 EC 2 30 -- 60 -- -- 5 5 30 EC 3 50 40 -- -- -- 5 5 50 EC 4 50 40 -- -- -- 5 5 50 EC 5 30 -- 60 -- -- 5 5 30 EC 6 50 40 -- -- -- 5 5 50 EC 7 50 -- 30 10 -- 5 5 50 EC 8 50 -- 30 10 -- 5 5 50 EC 9 50 40 -- -- -- 5 5 50 EC10 50 40 -- -- -- 5 5 50 EC11 20 -- 52.5 17.5 -- 5 5 20 EC12 50 40 -- -- -- 5 5 50 EC13 50 40 -- -- -- 5 5 50 EC14 20 -- 52.5 17.5 -- 5 5 20 EC15 50 40 -- -- -- 5 5 50 EC16 50 40 -- -- -- 5 5 50 EC18 50 40 -- -- -- 5 5 50 EC19 50 40 -- -- -- 5 5 50 EC21 50 40 -- -- -- 5 5 50 EC22 50 40 -- -- -- 5 5 50 EC23 50 40 -- -- -- 5 5 50 EC24 40 -- 37.5 12.5 -- 5 5 40 EC25 50 40 -- -- -- 5 5 50 EC27 50 40 -- -- -- 5 5 50 EC28 50 40 -- -- -- 5 5 50 EC30 50 40 -- -- -- 5 5 50 EC31 50 40 -- -- -- 5 5 50 EC33 50 40 -- -- -- 5 5 50 EC34 50 -- 30 10 -- 5 5 50 EC35 50 -- 20 -- 20 5 5 50 EC36 50 40 -- -- -- 5 5 50 EC37 50 40 -- -- -- 5 5 50 EC39 50 -- 30 10 -- 5 5 50 EC40 50 40 -- -- -- 5 5 50 EC42 50 -- 30 10 -- 5 5 50 EC43 50 -- 30 10 -- 5 5 50 EC45 50 40 -- -- -- 5 5 50 EC46 30 -- 40.5 15 4.5 5 5 30 EC47 50 40 -- -- -- 5 5 50 EC48 50 40 -- -- -- 5 5 50 EC49 30 -- 45 15 -- 5 5 30 EC50 40 -- 37.5 12.5 -- 5 5 40 EC51 50 40 -- -- -- 5 5 50 EC52 40 -- 22.5 25 2.5 5 5 40 EC53 50 40 -- -- -- 5 5 50 EC54 40 -- 22.5 25 2.5 5 5 40 EC56 50 40 -- -- -- 5 5 50 EC57 50 -- 30 10 -- 5 5 50 EC58 40 -- 22.5 25 2.5 5 5 40 EC59 50 40 -- -- -- 5 5 50 EC60 50 40 -- -- -- 5 5 50 EC62 50 40 -- -- -- 5 5 50 EC63 50 -- 30 10 -- 5 5 50 EC65 50 40 -- -- -- 5 5 50 EC66 50 40 -- -- -- 5 5 50 EC67 50 40 -- -- -- 5 5 50 EC68 50 40 -- -- -- 5 5 50 EC69 50 40 -- -- -- 5 5 50 EC70 50 40 -- -- -- 5 5 50 EC72 50 40 -- -- -- 5 5 50 EC73 50 40 -- -- -- 5 5 50 EC74 50 40 -- -- -- 5 5 50 EC75 50 40 -- -- -- 5 5 50 EC76 50 40 -- -- -- 5 5 50 EC77 50 40 -- -- -- 5 5 50 EC78 50 40 -- -- -- 5 5 50 EC79 50 40 -- -- -- 5 5 50 EC81 50 40 -- -- -- 5 5 50 EC82 50 40 -- -- -- 5 5 50 EC83 50 40 -- -- -- 5 5 50 EC84 50 40 -- -- -- 5 5 50 EC85 50 40 -- -- -- 5 5 50 EC86 50 40 -- -- -- 5 5 50 EC88 50 40 -- -- -- 5 5 50 EC89 50 40 -- -- -- 5 5 50 EC90 50 40 -- -- -- 5 5 50 EC91 50 40 -- -- -- 5 5 50 EC92 50 40 -- -- -- 5 5 50 EC93 50 40 -- -- -- 5 5 50 EC94 50 40 -- -- -- 5 5 50 EC95 50 40 -- -- -- 5 5 50 EC96 50 -- 30 10 -- 5 5 50 EC97 50 40 -- -- -- 5 5 50 EC98 50 40 -- -- -- 5 5 50 EC99 50 40 -- -- -- 5 5 50 EC100 50 40 -- -- -- 5 5 50 EC__________________________________________________________________________
EXAMPLE 6
50 parts by weight of N-ethyl-N-(N'-isopropyl-acet-anilido)-S-ethyl-thiolcarbamate, 40 parts by weight of a synthetic amorphous silicic acid grist (Zeolex 444), 4 parts by weight of sulfite waste liquor powder, 2 parts by weight of alkyl-sulfonic acid-sodium (Nettzer IS) wetting agent and 4 parts by weight of sodium-lignin-sulfonate (Hoes 1494) dispersing agent are weighed into a powder mixer, the mixture is ground in an air-flow mill and then homogenized.
A 50 Wt.% wettable powder mixture is obtained.
A wettable powder product can be prepared from the derivatives provided in Table III in a similar way.
TABLE III______________________________________components in parts by weight com-Number pound sulfiteaccord- accord- waste-ing to ing to Zeolex liquor Nettzer HoesTable I Table I 444 powder IS 1494 product______________________________________17 50 40 4 2 4 50 WP20 50 40 4 2 4 50 WP26 50 40 4 2 4 50 WP29 50 40 4 2 4 50 WP32 50 40 4 2 4 50 WP38 50 40 4 2 4 50 WP41 50 40 4 2 4 50 WP44 50 40 4 2 4 50 WP55 50 40 4 2 4 50 WP61 50 40 4 2 4 50 WP64 50 40 4 2 4 50 WP71 50 40 4 2 4 50 WP80 50 40 4 2 4 50 WP87 50 40 4 2 4 50 WP______________________________________
EXAMPLE 7
80 g of active agent No. 20 of Table I are homogenized with 10 g of synthetic amorphous silicic acid grist, 2 g of an alkyl-sulfonic acid-sodium wetting agent as well as 3 g of cresol-formaldehyde condensate and 5 g of a sodium-lignin-sulfonate dispersing agent. The mixture is preground in a laboratory ball mill for 1 hour, then follows fine grinding with steady addition in a contraplex laboratory rod mill. 100 g of a wettable powder product containing 80 Wt.% of an active agent are obtained.
Floatability (after half an hour): 84%
Wet sieve residue (on a 50.mu. sieve): 1.4 Wt.%
Bulk density: 0.36 g/cm.sup.3.
EXAMPLE 8
65 g of active agent No. 52 of Table I, 10 g of a synthetic amorphous silicic acid grist and 15 g of a mineral kieselguhr carrier, 2 g of an alkyl-sulfonic acid-sodium wetting agent as well as 4 g of cresol-formaldehyde-condensate and 5 g of sodium-lignin-sulfonate dispersing agent are together homogenized. The mixture is preground in a laboratory ball mill for 1 hour, then fine grinding is carried out in an ultraplex beater-disc laboratory mill with steady addition.
100 g of a wettable powder product containing 65 Wt.% of an active agent are obtained.
Floatability: (after half an hour): 86%
Wet sieve residue (on a 50.mu. sieve): 1.2 Wt.%
Bulk density: 0.32 g/cm.sup.3.
EXAMPLE 9
10 g of active agent No. 115 of Table I are thoroughly admixed with 10 g of synthetic amorphous silicic acid grist and 70 g of a mineral kieselguhr carrier, 2 g of an alkyl-sulfonic acid-sodium wetting agent, 4 g of cresol-formaldehyde condensate and 5 g of a sodium-lignin-sulfonate dispersing agent. This mixture is preground in a laboratory ball mill for 1 hour, then fine grinding is performed in an ultraplex beater-disc mill with steady addition.
The obtained wettable powder product containing 10 Wt.% of an active agent has a
Floatability (after half an hour): of 92%
Wet sieve residue (on a 50.mu. sieve): 0.65 Wt.%
Bulk density: 0.26 g/cm.sup.3.
EXAMPLE 10
30 g of active agent No. 4 of Table I are admixed with 30 g of xylene by 5 minutes of stirring. The mixture is sprayed on 30 g of ground synthetic amorphous silicic acid carrier (max. corn size: 20.mu.) in a shaker. 2 g of an alkyl-sulfonic acid-sodium wetting agent, 3 g of cresol-formaldehyde-condensate and 5 g of sodium-lignin-sulfonate dispersing agent are added.
The mixture is homogenized and ground in a laboratory ball mill for 1 hour. A wettable powder product containing 30 Wt.% of an active agent is obtained.
Floatability (after half an hour): 88%
Wet sieve residue (on a 50.mu. sieve): 0.1 Wt.%
Bulk density: 0.21 g/cm.sup.3.
EXAMPLE 11
80 g of active agent No. 4 of Table I, 14 g of kerosine as well as an emulsifier containing the mixture of 6 g of dodecyl-benzene-sulfonic acid-calcium and polyoxy-ethylene-alkyl-phenyl are homogenized with a laboratory mixer for 15 minutes, then filtered on a folder filter. An emulsion concentrate containing 80 Wt.% of an active agent is obtained.
Density: 1.07 g/cm.sup.3
Emulsion stability, after 2 and 24 hours some reversible precipitation.
EXAMPLE 12
10 g of active agent No. 11 of Table I are dissolved under stirring in the mixture of 50 g of xylene and 30 g of methylene-chloride. An emulsifier containing the mixture of 10 g of dodecyl-benzene-sulfonic acid-calcium and polyoxy-ethylene-alkyl-phenol is added, the solution is homogenized by stirring for 15 minutes and finally filtered on a folder filter.
An emulsion concentraate containing 10 Wt.% of an active agent is obtained.
Density: 1.02 g/cm.sup.3
Emulsion stability: (1 percent concentration, in water of 19.2.degree. GH), after 2 hours stable, after 24 hours min. reversible precipitation.
EXAMPLE 13
20 g of active agent No. 130 of Table I and 20 g of mineral kieselguhr grist are homogenized, then ground in an ultraplex beater-disc mill under a corn size of 40.mu.. The powder mixture is homogenized with 49 g of gypsum binding agent and pulped with 11 g of a 0.4 Wt.% methyl-cellulose solution. The thick pulp is poured into vaseline oil containing 2000 g of a 0.5 Wt.% polyoxy-ethylene-sorbitane-monooleate wetting agent and granulated under intense stirring. In the course of a 2 hour stirring the binding agent solidifies. The granulate is filtered off the oil, the residual oil is washed off and dried at 50.degree. C. 100 g of a granulate containing 20 Wt.% of an active agent are obtained.
Corn size: 90% between 0.4 and 1.0 mm.
EXAMPLE 14
80 g of active agent No. 144 of Table I, 6 g of a synthetic amorphous silicic acid carrier, 20 g of ethylene-glycol anti-freezer, tenside containing the mixture of 20 g of nonyl-phenol-polyglycol-ether and sodium-oleoyl-methyl-tauride and 74 g of water are weighed into a laboratory pearl mill with a capacity of 0.5 l and 300 g of a glass pearl charge (diameter 1.0 to 1.5 mm) are added. The suspension is ground with a speed of 1000 r.p.m. for 1 hour. The charge is separated from the product on a sieve.
An aqueous suspension concentrate containing 40 Wt.% of an active agent is obtained.
Density: 1.12 g/cm.sup.3
Floatability: 95%
Cold resistance: at 0.degree. C. no change within 48 hours.
EXAMPLE 15
40 g of active agent No. 71 of Table I, 140 g of technical vaseline oil and tenside containing the mixture of 20 g of dodecyl-benzene-sulfonic acid-calcium and polyoxy-ethylene-alcohol are weighed into a laboratory pearl mill with a capacity of 0.5 l and 300 g of glass pearl charge with a diameter of 1.0 to 1.5 mm are added. The suspension is ground at a speed of 1000 r.p.m. for 1 hour, then the product is separated from the charge on a sieve. An oily suspension concentrate is obtained. 20 Wt.%.
Density: 0.97 g/cm.sup.3
Floatability: (in a 3 percent concentration, after 30 minutes): 98%.
The essence of the recognition of the invention resides in the fact that the mono- and dicotyledonous weeds can be successfully controlled by products containing 10 to 90 Wt.% of a liquid and/or solid diluting agent(s), 10 to 30 Wt.% of an additive(s) and 10 to 80 Wt.% of carboxylic acid-amido-substituted-thiolcarbamates derivatives of formula (I), at the same time the product does not exert any harmful effect on cultivated plants.
The following examples illustrate biological tests carried out with the product according to the invention.
EXAMPLE 16
The test series were carried out in jars with a surface of 120 cm.sup.2 and were repeated in parallel four times. 400 g of air-dry sand were weighed into the jars and the seeds of the test plants were sown into the jars.
MvTC-596 maize (Zea mays): 15 corns
Ireger striped sunflower (Helianthus annuus): 15 corns
K. Jubileum tomato (Solonum lysopersicum): 15 corns
crowfoot grass (Echinocloa-crus-galli): 1 g.
The seeds were covered with 200 g of sand and the soil was treated chemically by spraying. The products according to the invention were used in formulation 50 EC (emulsion concentrate) and 50 WP (wettable powder). For the purpose of comparison treatments were performed with the product 78 EC of EPTC thiolcarbamate and the product 80 Ec containing EPTC as well as the antidote N-dichloro-acetyl-1-oxa-4-aza-spiro-4,5-decane (code AD-67), too.
The dose of every treatment corresponds to an addition of 3 kg of active agent/ha.
After the treatment 100 g of sand were weighed into the jars, the soil was watered up to a water capacity of 65% and in the cours of cultivation a uniform soil wetness was ensured by repeated watering. The plants were cultivated in a glass-house under 400 W daylight lamps of type HgMI/D in a 16 hour lighting period. The daily average temperature was 26.6.degree. C. (min. 24.degree. C., max. 29.2.degree. C.) while the average relative humidity was 73.6%.
For the evaluation of the tests untreated control plants were grown the data of which measured at the evaluation were taken as 100%.
The evaluation was performed in the case of maize, sunflower and crowfoot grass on the 14th day after the treatment, for potatoes on the 19th day by measuring the green mass of the plants. Besides in the case of maize the length of the sprouts was measured, too.
The results of the tests carried out with the products Nos. 1 to 26 according to Tables II and III are shown in Table IV.
TABLE IV______________________________________ Maize (zea mays) Sun- length flower Tomato Echino- of green green green clea sprout weight weight weight sp greenTreatments % % % % weight %1 2 3 4 5 6______________________________________Untreated 100 100 100 100 100controlEPTC + AD-67 96 97 85 13 0antid. 80ECEPTC 78EC 57 84 77 11 0Number accord-ing to Table I1 109 91 73 0 02 104 94 93 0 183 103 91 97 0 04 103 91 95 0 05 103 95 80 0 316 108 97 80 47 07 101 83 92 0 08 105 88 90 40 369 110 101 109 74 210 112 101 106 64 211 94 94 122 90 3112 88 84 122 44 413 82 82 124 46 014 91 92 94 69 4815 96 101 124 54 616 86 86 118 79 717 97 97 93 102 5018 109 123 86 82 019 85 82 126 91 420 108 114 104 87 3021 106 107 99 65 022 114 120 107 77 323 107 115 103 105 424 99 101 114 87 725 117 129 107 73 226 108 116 120 87 21______________________________________
From the data of the tests it is clear, that the products of the invention successfully control the crowfoot grass, at the same time they do not harm maize and sunflower, even exert a stimulating effect in most of the cases. Though in the case of tomato individual derivatives reduced the green mass, at the same time other ones showed a stimulating effect, too.
EXAMPLE 17
The effect of products Nos. 27 to 45 of Tables II and III as well as of products containing active agents Nos. 111 to 160 and 164 to 187 of Table I was examined with the test methods described in the previous example with the difference that Hungarian grass (Setaria sp was used as test plant.)
The result of the tests are summarized in Table V.
TABLE V__________________________________________________________________________ Sunflower Tomato Maize (Zea mays) (Heli- (Solanum Hungarian Grass length green anthus an) lysp.) (Setarin sp) of sprout weight green weight green weight green weightTreatments % % % % %1 2 3 4 5 6__________________________________________________________________________Untreated 100 100 100 100 100controlEPTC + AD-67 94 87 89.1 32.7 3.880 ECEPTC 78EC 28.6 46.9 94.8 63.6 34.6Number accord-ing to Table I27 93.8 84.5 85.7 98.2 18.628 87.0 76.9 103.3 107.3 0.029 81.9 65.2 95.1 116.4 21.330 97.5 97.2 95.5 100.0 58.331 91.1 87.3 88.4 110.9 27.332 91.9 90.9 90.1 129.1 42.333 90.4 85.3 88.0 96.4 33.234 95.8 92.2 88.5 74.5 19.835 101.7 97.8 92.3 81.8 26.336 102.5 95.4 90.7 100.0 24.537 89.0 80.8 96.0 103.6 29.138 89.2 77.1 108.6 98.2 28.739 96.2 95.4 104.6 96.4 39.140 97.0 88.8 96.2 94.5 22.741 94.3 89.9 90.8 125.5 21.542 97.1 93.3 86.0 118.2 26.643 96.7 92.4 90.2 118.2 70.044 92.1 80.7 84.7 121.8 82.845 94.5 90.5 82.6 100.0 45.1111 118.6 137.9 124.2 154.4 127.3112 99.8 101.4 118.9 175.4 91.2113 108.7 131.2 127.4 145.1 93.2114 121.2 139.7 141.5 175.7 102.7115 99.5 102.5 131.4 138.4 130.6116 113.3 111.9 121.2 147.4 97.5117 118.9 136.0 126.2 109.6 131.8118 125.4 132.9 130.0 127.7 119.9119 116.3 129.4 126.1 115.8 85.6120 92.1 90.7 124.0 134.3 94.0121 101.7 108.1 131.3 100.0 125.0122 117.5 143.7 123.0 149.9 118.0123 102.5 98.6 115.7 153.6 85.0124 110.6 100.8 109.9 134.2 116.0125 111.8 118.0 123.4 134.3 92.4126 98.6 91.4 121.2 128.5 100.8127 96.6 95.1 119.4 110.6 94.5128 114.3 106.2 124.8 131.0 115.8129 129.9 125.4 128.9 168.5 136.5130 114.5 121.9 130.4 124.5 103.9131 108.1 114.1 109.6 95.0 110.1132 120.7 116.1 126.6 122.9 119.9133 111.3 118.9 115.5 104.8 110.1134 102.7 108.6 116.9 144.1 92.9135 111.3 110.9 154.5 145.7 97.1136 113.2 128.7 139.0 158.9 143.1137 124.6 143.9 116.1 154.4 97.5138 114.7 134.3 115.3 147.4 105.7139 120.8 140.0 128.3 140.9 119.3140 116.7 148.0 113.4 136.9 127.9141 121.4 139.2 129.6 164.4 86.4142 98.6 113.6 115.5 101.8 122.4143 102.8 109.8 136.1 134.3 93.8144 98.2 111.2 119.4 145.8 112.7145 108.3 130.6 139.2 96.5 68.4146 96.3 96.5 113.3 103.9 126.9147 102.1 112.9 118.6 100.0 127.5148 110.6 126.9 111.9 107.1 97.5149 108.3 110.9 120.9 111.1 138.6150 120.8 139.8 126.4 84.2 102.0151 104.3 123.1 117.6 90.7 125.2152 82.0 108.0 103.4 79.0 101.4153 117.1 137.9 96.4 92.1 100.0154 103.9 101.2 117.1 89.5 132.2155 103.9 100.9 116.4 126.1 144.4156 114.9 102.7 109.4 91.6 134.1157 106.7 107.7 115.1 83.5 128.7158 110.2 126.2 107.0 93.0 97.5159 88.2 92.6 93.0 98.3 87.3160 104.5 102.4 118.9 116.3 100.4164 100.3 85.9 84.1 98.3 118.3165 102.1 77.7 92.7 -- 109.7166 102.4 83.8 90.8 -- 68.5167 91.2 74.2 86.6 108.1 105.8168 95.9 99.2 80.9 102.9 80.9169 104.4 155.0 94.1 74.6 89.3170 104.7 98.4 94.9 103.6 106.2171 105.3 98.3 100.1 97.8 64.5172 98.9 96.0 96.1 108.5 139.4173 104.0 107.6 88.8 108.2 137.3174 103.5 100.8 92.1 118.2 137.9175 95.7 90.5 84.5 144.1 134.3176 95.0 84.3 94.5 169.5 121.0177 107.1 98.6 90.4 97.3 74.0178 98.4 85.7 86.8 111.1 76.5179 92.7 81.0 92.2 124.3 35.2180 92.7 80.7 97.1 114.0 111.9181 88.5 79.6 90.1 109.7 92.6182 92.2 63.2 92.4 112.8 30.8183 98.7 84.5 81.2 100.3 98.8184 105.1 93.4 81.3 133.1 76.3185 89.2 76.3 86.4 100.0 10.9186 106.7 78.3 92.2 95.9 132.5187 100.5 85.3 89.2 107.7 98.7__________________________________________________________________________
EXAMPLE 18
The effect of products Nos. 46 to 100 according to Tables II and III as well as products containing active agents Nos. 101 to 110 of Table I was examined with the test method described in Example 16 with the difference that Hungarian grass (Setaria sp) was used as test plant and that the treatments were performed with a dose of 2 kg/ha.
The test results are included in Table VI.
TABLE VI__________________________________________________________________________ Sunflower Tomato Maize (Zea mays) (Heli- (Solanum Hungarian grass length green anthus an) lysp) (Setaria sp) of sprout weight green weight green weight green weightTreatments % % % % %1 2 3 4 5 6__________________________________________________________________________Untreated 100 100 100 100 100controlEPTC + AD-6780 EC 109.3 95 92.2 68.2 16.5EPTC 78 EC 79.7 92.4 96.9 93.2 11.5Number accord-ing to Table I46 108.1 116.2 103.8 113.2 101.147 111.0 120.9 99.2 105.0 83.148 109.7 115.5 91.2 101.8 92.649 99.6 109.3 90.0 125.0 78.350 111.4 120.4 98.3 105.0 111.751 94.1 92.1 92.0 125.0 91.452 109.7 120.8 104.8 101.8 94.853 111.4 124.7 97.9 116.8 90.354 108.9 129.9 95.1 90.0 77.455 107.6 107.9 98.1 87.5 71.356 107.6 117.9 95.6 96.8 71.157 105.5 108.9 96.9 108.2 91.458 117.8 138.7 97.6 116.8 70.059 101.3 104.4 99.2 120.0 102.760 106.3 106.9 87.7 94.8 97.161 99.6 93.7 91.2 91.0 79.562 112.3 130.6 90.5 112.5 60.563 97.5 94.3 95.5 115.0 90.364 108.5 115.0 109.5 117.8 69.165 109.7 126.6 98.3 105.2 58.066 100.8 100.5 93.4 90.0 71.167 95.3 103.3 98.6 116.8 73.168 106.3 115.3 94.4 105.0 81.769 106.3 113.3 95.6 100.0 83.170 107.6 118.5 93.0 118.2 98.471 107.2 116.9 97.2 100.0 105.072 113.6 122.0 90.3 103.5 113.173 113.1 127.5 92.8 100.0 81.374 98.3 93.3 99.7 111.5 82.475 109.3 112.5 90.0 106.8 74.076 103.0 104.0 95.4 109.5 106.177 114.0 124.9 96.7 118.2 84.778 106.8 99.7 107.3 108.2 102.379 111.4 122.8 102.1 111.5 76.780 101.3 98.7 94.6 85.0 107.981 109.3 121.6 87.4 100.0 105.982 123.3 142.1 104.7 100.0 112.983 108.9 119.7 95.1 101.8 109.584 113.1 115.9 107.1 80.8 23.785 105.9 103.0 89.8 91.0 58.986 106.8 110.5 95.8 95.0 56.487 105.5 115.0 89.8 86.8 73.888 97.0 97.4 81.5 105.0 84.289 105.1 110.3 82.7 97.2 67.790 99.2 92.7 100.3 95.0 61.991 108.9 100.3 80.1 91.0 72.792 106.3 113.6 100.4 100.0 54.993 99.6 89.6 80.8 85.5 71.894 105.5 101.3 94.6 96.5 84.795 98.7 101.5 93.6 91.8 70.496 108.9 120.6 92.2 100.2 76.397 101.3 96.0 96.9 85.0 67.798 112.3 127.3 92.8 82.2 31.299 109.3 124.6 94.3 91.0 58.2100 110.2 116.5 85.9 88.5 73.6101 103.9 109.8 91.1 -- 83.3102 104.8 103.1 97.6 -- 64.0103 107.9 111.7 95.8 -- 78.3104 113.7 115.4 111.1 -- 114.9105 102.6 104.7 85.2 -- 81.8106 114.5 126.9 106.4 -- 48.5107 105.3 109.9 92.2 -- 79.2108 120.2 119.3 106.1 -- 102.9109 117.2 113.0 107.7 -- 113.6110 118.1 123.9 92.2 -- 102.7__________________________________________________________________________
EXAMPLE 19
Examination of the dose effect
The effect of the different doses of those compounds of formula (I) was examined which showed better results in the previous tests.
The test was carried out in jars with a surface of 120 cm.sup.2. A mixture of plowed-land surface soil (humus %=1.82; pH.sub.H.sbsb.2.sub.O =6.72; pH.sub.KCl =6.69; K.sub.A =41.2) as well as sand was used for the test in a ratio of 1:1.
At first 500 g each of the mixture were weighed into the jars, then the seeds of the test plants were sown onto the soil.
maize (Zea mays, L) NK-PX-15: 15 corns/jar
sunflower (Helianthus annuus): 15 corns/jar
Hungarian grass (Setaria sp): 1 g/jar
crowfoot grass (Echinocloa crus-galli): 1 g/jar.
Then the seeds were covered with 200 g each of a soil mixture, the chemical treatments were performed in different doses on the soil by spraying. The products of the invention were used in formulation 10 EC (emulsion concentrate). As comparison EPTC as well as product 80 EC containing antidote AD-67 were used for the treatment of the test plants.
After spraying still 100 g each of soil were weighed, then the soil was watered up to a water capacity of 60% and in the course of the cultivation the evaporated water was supplemented by watering on the basis of weight measurement.
The plants were cultivated under 400 W daylight lamps of type HgMI/D. The daily average temperature was 25.8.degree. C. (min. 22.8.degree. C., max. 28.8.degree. C.), the relative humidity 60.7%.
The evaluation was performed by measuring the green mass of the plants as well as the length of sprouts in the case of maize on the 11th day after the treatment.
The test results are set forth in Tables VII and VIII.
TABLE VII__________________________________________________________________________Examination of the dose effect on the sprout length and green weight ofmaize Maize sprout length in percent Maize green weight in percent Dose kg/ha active agent Dose kg/ha active agentCompounds 0 1 2 4 8 16 0 1 2 4 8 16__________________________________________________________________________Number accord-ing to Table INo. 3 100 95.7 103.9 102.2 97.4 92.6 100 95.5 110.0 100.4 100.6 92.4 4 100 103.5 103.5 97.4 59.7 46.3 100 108.5 109.6 102.7 56.9 46.827 100 99.1 97.0 92.6 82.3 55.8 100 94.9 110.5 96.9 76.9 56.528 100 97.0 93.9 81.0 75.3 41.6 100 99.4 100.5 82.4 74.0 41.9164 100 90.5 70.6 96.1 93.1 92.6 100 91.5 84.7 94.4 101.1 90.0EPTC + AD-67 100 95.2 90.9 96.1 95.2 81.0 100 98.0 94.2 92.7 99.3 80.1__________________________________________________________________________
TABLE VIII__________________________________________________________________________Examination of the dose effect on the green weight of sunflowers,crowfoot grass and Hungarian grass Sunflower green weight Crowfoot grass green Hungarian grass green in percent weight in percent weight in percentCom- dose kg/ha active agent dose kg/ha active agent dose kg/ha active agentpounds 0 1 2 4 8 16 0 1 2 4 8 16 0 1 2 4 8 16__________________________________________________________________________No. accord-ing toTable I 3 100 94.2 119.1 114.2 96.6 83.8 100 225.0 25.0 -- -- -- 100 127.0 103.3 51.2 15.6 -- 4 100 89.0 116.1 97.4 106.0 100.2 100 200.0 25.0 -- -- -- 100 64.0 74.9 4.7 -- --27 100 108.6 92.3 88.1 89.7 94.2 100 150.0 125.0 60.0 10.0 -- 100 55.5 15.2 -- -- --28 100 100.5 87.3 91.4 90.5 86.4 100 275.0 75.0 25.0 -- -- 100 74.4 47.4 -- -- --164 100 97.8 95.9 96.8 92.2 88.5 100 300.0 100.0 40.0 -- -- 100 2.4 1.4 1.0 -- --EPTC + AD-67 100 80.5 84.8 94.1 86.6 76.6 100 50.0 -- -- -- -- 100 -- -- -- -- --80 EC__________________________________________________________________________
From tha results of the tests it comes clear that except compound No. 3 of Table I all other compounds control the monocotyledonous weeds even in a dose of 4-8 kg/ha active agent and do not cause harm to maize and sunflowers.
EXAMPLE 20
A test was performed with compounds Now. 1, 3, 4, 13, 27 and 28 according to Table I at 14 different plants. Jars with a surface of 120 cm.sup.2 were used in the test series.
For the test carried out in jars plough-land surface soil passed through a sieve with a mesh size of 2 mm (humus %=1.82; pH.sub.H.sbsb.2.sub.O =6.72; pH.sub.KCl =6.69; K.sub.A =41.2) was weighed in a quantity of 400 g per jar, then the seeds of the test plants were sown.
______________________________________1. Winter wheat (Triticum aestivum) 50 corns/jar2. Sugar-beet (Beta vulgaris) 30 "3. Rice (Oryze sativa) 50 "4. Pea (Pisum sativum) 15 "5. Bean (Phosealus vulgaris) 15 "6. Pumpkin (cucurbita pepo) 10 "7. Melon (citrullus lanatus) 15 "8. Millet (Panikum miliaceum) 0.5 g/jar9. Sorghum (Sorghum bicolor) 0.5 "10. Abutilon (Abutilon sp) 0.5 "11. Flax (Linum usitatissimum) 50 corns/jar12. Cheese-rennet (Galium aparina) 50 "13. Rape (Brassica napus) 50 "14. Heckle-mustard (Raphanus raphanistrum) 50 "______________________________________
The seeds are covered with 200 g each of soil, then they were chemically treated with a dose of 3 kg/ha of the indicated compounds as well as product 80 EC containing the EPTC and antidote AD-67. Then still 100 g each of soil were weighed immediately and the soil was watered up to a water capacity of 60% and the uniform soil wetness was ensured by repeated watering in the course of the cultivation.
The plants were cultivated under 400 W daylight lamps of type HgMI/D. The daily average temperature was 24.7.degree. C. (min. 21.5.degree. C., max. 27.7.degree. C.) and the relative humidity 63.1%.
The evaluation was performed by measuring the green weight of the plants on the 13th day after the treatment when the results were related to the untreated control the value of which was taken as 100%.
The test results are set forth in Tables IX and X.
TABLE IX__________________________________________________________________________Selectivity concerning cultivated plants Compounds according to Table I EPTC + AD-67Plants 1 3 4 13 27 28 EC__________________________________________________________________________winter wheat 69.9 71.8 66.0 90.3 35.9 62.1 --sugar-beet 88.1 92.1 17.8 90.1 92.1 92.1 83.2rice 73.9 82.6 65.2 65.2 78.2 56.5 --pea 39.1 50.8 112.3 107.7 145.5 144.0 24.0bean 83.2 98.4 78.8 102.7 79.9 89.1 85.9pumpkin 74.6 85.4 87.8 81.9 110.3 87.7 79.5melon 102.7 85.7 90.2 109.2 95.3 80.9 38.5__________________________________________________________________________
TABLE X__________________________________________________________________________Selectivity concerning weeds Compounds according to Table I EPTC + AD-67Plants 1 3 4 13 27 28 80 EC__________________________________________________________________________millet 142.5 -- 10.3 47.3 -- -- --sorghum 22.7 20.3 12.5 67.2 -- 13.3 6.2abutilon 100.9 77.4 66.9 97.2 168.0 72.6 24.5flax 89.9 84.8 94.9 97.5 110.1 58.2 52.0cheese- 233.0 -- 133.0 100.0 66.7 106.7 --rennetrape 84.6 83.3 62.8 137.2 80.8 92.3 --heckle-mustard -- -- -- -- -- -- --__________________________________________________________________________
From our tests we determined that successful weed-control can be performed with the products according to the invention without causing any harm to cultivated plants.

Number	Name	Date
3493360	Fancher et al.	Feb 1970
3897474	Pissioris	Jul 1975
4108885	Hoyer et al.	Aug 1978

Number	Date	Country
52-151146	Dec 1977	JPX
53-148530	Dec 1978	JPX

Herbicide composition containing carboxylic-acid-amidothiolcarbamate derivatives

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Chem. Abstracts 89:75452V, (Japanese Patent Application 52 151146) (1978).
Chem. Abstracts 90:181578W, (Japanese Patent Application 53 148530) (1979).