NZ207519A - Herbicidal compositions containing 4-amino-6-t-butyl-3ethylthio-1,2,4-triazin-5(4h)-one - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £07519 2 0751 9 s * i Priority Date(s): Complete Specification Filed: (fl Class: Publication Date: [12 NOV 1986 P.O. Journal, No: .... ^iMg^TOFFlcH MAR ffi4 N.Z.No.

NEW ZEALAND NO DRAWIN8S Patents Act 1953 COMPLETE SPECIFICATION "Selective herbicidal agents based on a triazinone." We, BAYER AKTIENGESELLSCHAFT, a Company registered under the laws of the Federal Republic of Germany, of Leverkusen, Germany do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly o described in and by the following statement : - - 1 - (Followed by 1A.) 2075 1 9 - 1A" The present invention relates to the use of a known 1 ,2 ,4-t r i az i n-5-one for selectively combating weeds, and to new herbicidal agents which contain this triazinone derivative in combination with certain other 5 known herbicidal active compounds.

It has already been disclosed that certain 3,6-disubstituted 4-amino-1,2,4-triazin-5-(4H)-ones can be used as herbicides (compare, for example, U.S. patent Specifications 3,671,523 and 3,905,801). However, these 10 triazinones are not always satisfactory when they are employed for selectively combating weeds. Thus, in practice, most triazinones present difficulties when they are used for selectively combating dicotyledon weeds and graminaceous weeds in cereals. Of the group of triazin-15 ones described, 4-amino-6-1ert.-buty 1-3-methy11hio-1 ,2,4-triazin-5(4H)-one (A) has found acceptance in practice, and is used for selectively combating weeds in soya beans, potatoes, tomatoes and lucerne and, with severe limitations, in cereals. Its use in cereals is based chiefly 20 on post-emergence treatment. It is not possible to use it in cereals by the pre-emergence method for tolerance reasons. In addition, for reasons of phytotoxicity towards the cereal, its use is recommended only with certain varieties of cereal, and even in this case only 25 in a limited area.

It is furthermore already known that 4-amino-6-tert.-buty l-3-ethy11hio-1,2,4-1riazin-5(4H)-one (B) has general herbicidal properties (compare U.S. Patent Specification 3,671,523). However, particular properties of 30 this compound, in particular possibilities for selective use of this triazinone derivative in crops of useful plants, have not been disclosed.

It has now been found, surprisingly, that 4-amino-6-tert.-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one Le A 22 829 ,y. r°\ U / ij of the formula :rV> <CH3'3CY >-NH2 tB) SCjHc which is known, is particularly suitable for selectively combating monocotyledon and dicotyledon weeds in cereal 5 crops and leguminosae crops before and after emergence of the plants. The use of active compound (B) as a selective herbicide for cereals, chiefly in barley and wheat, is of particular importance.

It is particularly surprising that, in the case 10 of the active compound (B) to be used according to the invention - in contrast to the closely related active compound (A) - the difference between the effective herbicidal dose and the dose still tolerated by cereals and leguminosae is relatively large, so that the danger 15 of phytotoxic damage to the crop plants is very slight. In the case of use in cereals, it is furthermore surprising that the active compound (B), again in contrast to active compound (A), can be employed not only by the post-emergence method but also by the pre-emergence 2 0 method; moreover, active compound (B) can also be successfully used by the so-called pre-sowing incorpoi— ation method.

These particular properties of active compound (B) enable weeds to be combated in cereals using a 25 herbici dally active triazinone which, at the same time, is well tolerated by the crop plants. The active compound (B) which can be used according to the invention thus represents a great enrichment of selective herbicides in the cultivation of cereals and leguminosae. 30 By weeds, in the broadest sense, there are to be understood all plants which usually occur as contaminants Le A 22 829 of cereal crops or leguminosae crops. Examples which may be mentioned of weeds which are destroyed by the triazinone (B) to be used according to the invention and frequently occur in cereal crops and leguminosae crops 5 are: Picotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, 10 Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea. Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, 15 Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirups, Paspalum, Ischaemum, Sphenoclea, DactyIoctenium, Agrostis, Alopecurus and Apera.

However, the use of the active compound (B) accor-20 ding to the invention is in no way restricted to these genera, but also extends in the same manner to other p lants.

Active compound (B) is particularly suitable for combating weeds in the wheat, barley and maize varieties 25 of cereal and in the pea and soya bean varieties of leguminosae, the action being directed equally towards dicotyledon weeds <dicotyIedoneae) and towards graminaceous weeds (monocotyledoneae), in particular Avena fatua, Bromus, Alopecurus and Setaria.

It has also been found that new active compound combinations consisting of 4-amino-6-tert.-buty 1-3 -ethyIthio-1,2,4-triazin-5(4H)-one (B) and certain other known herbicidal active compounds have a particularly high herbicidal activity and are outstandingly suitable 35 for broadening the action spectrum and for extending the application range of the triazinone (B).

Le A 22 829 2 075 Thus, active compound combinations consisting of the triazinone (B) on the one hand and at Least one of the following compounds mentioned: (a) S-2,3,3-trich loro-allyl diisopropylthiolcarbamate (triallate), (b) S-2,3-5 dichloroallyl diisopropylthiolcarbamate (diallate) or Cc) 1-amino-6-ethylthi o-3-(2/.2-dimethylpropyl)-1,.3,5-tri-azine-2/4 (1H,3H)-dione (ametridione), on the other hand/ can be particularly successfully used by the pre-sowing incorporation method or by the pre-emergence method. 10 In the case of post-emergence treatment/ active compound combinations which consist of the triazinone (B) on the one hand and at least one of the following compounds mentioned: ( c) 1-amino-6-ethylthio-3-(2,2-di-methylpropyl)-1.,3,5-triaziri-2/4(1H,3H)-dione (ametridione) 15 (d) 4-amino-6-tert.-butyl-3-methyIthio-1 ,2/4-triazin-5-(4H)-one (A) (metribuzin), (e) 1,2-dimethy1-3,5-diphenyl-pyrazolium methyl-sulphate (difenzoquat), (f) ethyl N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate (benzoyl-prop-ethyl), (g) isopropyl N-benzoyl-N-(3-chloro-4-f luoro-20 pheny I)-2-aminopropionate (flampropisopropyL)/ (h) methyl N-benzoyl-N-(3-chloro-4-fluorophenyl)-2-aminopropionate (fI amprop-methy I), (i) methyl 2-C4-(2/4-dichlorophenoxy)-phenoxyD-propionate (dicLofop-methyI)/ (k) methyl-2-chloro-3-(4-chlorophenyl)-propionate (chlorofenprop-25 methyl), (I) 3/5-dibromo-4-hydroxy-benzonitrile (bromoxy-nil)/ (m) 3/5-diiodo-4-hydroxy-benzonitrile (ioxyniL)/ (n) 2/4-dichLorophenoxyacetic acid (2,4-D), (o) 2-(2,4-dichIorophenoxy)-propionic acid (2,4-DP), (p) 4-chloro-2-methyIphenoxyacetic acid (MCPA), (q) 2-(2-methyl-4-ch loro-30 phenoxy)-propionic acid (MCPP), (r) 1-(2-benzothiazolyl)-1 /3-dimethylurea (methabenzthiazuron) ,• (s) 3-(4-i sopropyl-phenyI)-1,1-dimethyIurea (isoproturon), (t) 3-(3-chloro-4-methyIphenyl)-1,1-dimethylurea (chlorotoluron) or (u) 3-isopropyl-2/1/3-benzo-thiadiazin-4-one 2/2-dioxide 35 (bentazon)/ on the other hand, are preferred.

The active compound combination consisting of the Le A 22 829 triazinones (B) + (A) is particularly preferred for post-emergence treatment (that is to say by the post-emergence method).

Surprisingly, the herbicidal activity of the active compound combinations mentioned is greater than the sum of the actions of the individual components, that is to say the active compound combinations exhibit a synergistic effect. The new active compound combinations thus likewise represent a valuable enrichment of the art.

The weight ratios of the active compounds in the active compound combinations can vary within relatively wide limits. In general, 0.0E to 10 parts by weight of the mixing partner mentioned, preferably 0.05 to 4 parts by weight, are present per part by weight of the triazinone (B).

The active compound combinations according to the invention can be used for the same plants as the active compound (B).

The triazinone (B) and the new active compound combinations mentioned 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 naphthalenes, chlorinated aromatics or Le A 22 829 ' ■ - - -V- I ■ N ■ ■ 2075 1 chlorinated aliphatic hydrocarbons/ such as chloroben-zenes/ chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol 5 or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or eyelohexanone, 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, chalk, quartz, attapulgite, montmori I lonite or diatoma-ceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; 15 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, coco-20 nut shells, maize cobs and tobacco stalks; as emulsify-ing and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as poly-oxyethy I ene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, 25 a IkyIsuIphonates, a Iky I su Iphates, aryIsuIphonates as well as albumin hydro lysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethy I ce11ulose and 30 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.

It is possible to use colorants such as inorganic 35 pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin Le A 22 829 I* 1 2 r"\ 7?~ '• i I "1 I.--' / dyestuffs, azo dyestuffs and metal phtha locyanine dye-stuffs, and furthermore trace nutrients such as salts of iron/ manganese/ boron/ copper/ cobalt/ molybdenum and zinc/ as further additives in the formulations. 5 The formulations in general contain between 0.1 and 95 per cent by weight of active compound or 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 10 formulations. However/ the active compounds contained in the active compound combinations can also be mixed as individual formulations when used/ that is to say they can be used in the form of tank mixtures.

The active compound (B) and the new active com-15 pound combinations/ as such or in the form of their formulations/ can also be used as mixtures with other known herbicides for cereals and leguminosae/ finished formulations or tank mixing again being possible. Mixtures with other known active compounds/ such as fungicides/ 20 insecticides/ acaricides/ nematicides/ bird repellents/ growth factors/ plant nutrients and agents which improve soil structure/ are also possible.

The active compound (B) and the new active compound combinations can be used as such/ in the form of 25 their formulations or in the use forms prepared therefrom by further dilution/ such as ready-to-use solutions/ suspensions/ emulsions/ powders/ pastes and granules.

They are used in the customary manner/ for example by watering, spraying, atomising/ dusting or scattering. 30 Whilst the triazinone (A) can be applied to cereals only by the "post-emergence" method/ and even then only with the further limitations mentioned/ it is possible to apply the triazinone (B) and the above-mentioned new active compound combinations to cereals 35 both by the "post-emergence" method and by the "pre-emergence" method. The triazinone (B) and the new Le A 22 829 ,.,v— active compound combinations can also be incorporated into the soil before sowing.

The amount of active compound applied can vary within a substantial range, and depends, inter alia, on 5 the weather and on soil factors. In general, the amounts applied are between 0.01 and 5 kg of active compound (B) or active compound combinations per ha, preferably between 0.1 and 3 kg/ha.

The following examples serve to further illustrate 10 the invention.

Preparation Examples 1. 4-Ami no-6-te rt.-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (B) ml of an alkylaryl polyglycol ether, as an 15 emulsifier, and 572 g (5.25 mols) of ethyl bromide are added to a solution of 1,000 g (5 mols) of 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5(4H)-one (compare U.S. Patent Specification 3,671,523) in 5,250 ml of 1 N sodium hydroxide solution. The mixture is stirred vigoi— 20 ously at 50°C until the pH value of the aqueous phase has fallen to 7 - 8 (10 - 12 hours). After cooling the mixture to 20°C, the reaction product which has crystallised out is filtered off, washed several times with water and dried at 50°C. 1,050 g (92% of theory) of an iso-25 mer mixture which has a melting point of 77 - 82°C and the following composition, determined by gas chromatography, are obtained: O 81% of 4-amino-6-tert .-buty 1-3- ^ J i ^ et hy It h i o-1,2,4-t ri az i n- 2 5 5 (4H)-one (B) 19% of (CHj^4-amino-6-tert.-buty 1-2- 'Nt N~K"2 ethy 1-1 ,2,4-t ri az i n-5 (4H)' N ® one-3(2H)-thione (C) Le A 22 829 The pure 3-ethylthio derivative (B) with a melting point of 95°C can easily be separated off by re-crystallising the isomer mixture from cyclohexane.

If, instead of ethyl bromide, the equivalent 5 amount of ethyl iodide is used, the two isomers (B) and (C) are formed in a ratio of 90:10. 2. Formulation Example: A 60% strength wettable powder is prepared by the following procedure: 60 parts by weight of the tri-10 azinone (B), consisting of technical grade active compound, 3 parts by weight of an ary1 a IkyIsuIphonate, 3 parts by weight of sulphite waste liquor (spray-dried), 5 parts by weight of a formaIdehyde/cyclohex anone/Na bisulphite condensate, 10 parts by weight of highly dis-15 persed silicic acid and alumina (as the remainder to make up to 100 parts by weight) are mixed in a Lodiger mixer and the mixture is then ground via an 8 inch jet mill.

The formulation thus prepared can be suspended in water and is used for the preparation of a ready-to-20 use spray formulation.

Use Examples In all the examples: (A) = 4-amino-6-tert.-buty1-3-methyIthio-1,2,4-triazin-5(4H)-one (B) = 4-amino-6-tert.-butyl-3-ethyIthio-1,2,4-triazin-5(4H)-one Explanation of the abbreviations: PANMI = Panicum miliaceum SINAL = Sinapis alba 30 GASPA = Galinsogaparvi flora STEME = Stellaria media CHEAL = Chenopodium album LAMSS = Lamium spec.

P0LC0 = Polygonum convolvulus 35 P0LLA = Polygonum lapathifoIium VI0TR= Viola tricolor Le A 22 829 u/ RAPRA = Raphanus raphanistrum GALAP = Galium aparine POLAV = Polygonum aviculare Example A 5 Post-emergence test / greenhouse Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-10 pound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Test plants which have a height of 5 - 15 cm are 15 sprayed with the preparation of the active compound in such a way as to apply the amounts of active compound per unit area which are indicated in the table. The concentration of the spray liquor is so chosen that the amounts of active compound shown in the table a re applied 20 in 2,000 Litres of water/ha. After three weeks, the degree of damage to the plants is rated in % damage in comparison with the development of the untreated control. The figures denote: 0% = no action (like untreated control) 25 100% = total destruction The active compounds, amounts applied and results can be seen from the following Table A: Le A 22 829 Table A Post-emergence test / greenhouse Active Amount of PANMI SINAL compound active compound applied kg/ha (A) 1.0 0,5 0,25 100 100 100 100 100 100 (B) ■1,0 0,5 0,25 100 100 95 100 100 100 ~) GASPA STEME Wheat Maize 100 100 100 90 100 100 90 90 100 100 90 70 100 100 80 100 100 0 100 90 0 0 NJ O Nl C/l vO o r\ *- •cO/0 E xampLe B Post-emergence test / open air In a muIti-variety test/ summer .wheat/ summer barley and peas were sown on sandy Loam with a medium 5 humus content. Sowing took place on the 8th Hay. Treatment with the herbicide was carried out after 33 days, on the 10th June/ that is to say by the post-emergence method. At the time of treatment/ the weeds were in the 4-6 leaf stage. The amounts of active 10 compound indicated were applied in 500 liters of water/ha. The active compounds were triazinone (A)/ formulated as a 70 Z strength wettable powder/ and triazinone (B), formulated as a 60 % strength wettable powder. The plot size was 10 m^. The herbicidal action was measured on 15 the naturally occurring weed population. The action on the weeds and crops was determined in percentage damage in comparison with the untreated control and is summarised in the following Table B: Le A 22 829 0 o Table B Post-emergence test / open air r* n> Amount of active Active compound CHEAL RAPRA GALAP ^ compound applied ro kg/ha (A) 2.0 100 100 90 1 .5 100 100 85 1 .0 100 100 80 0.5 100 100 75 (B) 2.0 100 100 100 1 .5 100 100 95 1 .0 100 100 90 0.5 100 100 80 . ) <) POLCO POLAV Summer Summer Peas barley wheat 100 100 95 70 70 100 100 90 50 50 100 100 85 100 100 100 100 0 100 100 0 100 100 0 0 100 100 0 0 0 ho o N Ul vO \— - ' " u 2075 1 Examp Le C Pre-emergence test / greenhouse In a greenhouse test, the reaction of various varieties of cereal towards herbicides was examined in 5 seed dishes. Seed dishes (20 x 20 cm in size) were filled with sandy loam with a humus content of 2.2 X. After sowing the various varieties of cereal, spraying took place in a spray booth on the same day, that is to say by the pre-emergence method. The amount of active 10 compound was applied in 420 litres of water/ha. Evaluation took place 4 weeks after sowing. The action was rated as percentage damage in comparison with the untreated control and is summarised in the following Tab le C: u Le A 22 829 Table C Pre-emergence test / greenhouse Active compound Amount of active compound applied k^/ha Wheat Neepawa Triumph (A) 0.5 87 100 0.25 17 60 0.125 0 2 (B) 0-5 0.25 0.125 0 0 0 2 0 0 1 Wascana Barley Larker I Bonanza Gait 100 63 10 18 10 2 100 25 3 3 0 0 97 10 2 8 0 0 100 17 8 12 10 0 VI I vO 2^ -T» jr— '*J J .J j Example D Pre-emergence test / open-air In a muIti-variety test, summer wheat, summer barley and peas were sown on sandy loam with a medium 5 humus content. Sowing took place on 8th May. Treatment with the herbicide took place the same day, that is to say by the pre-emergence method. The amounts of active compound indicated were applied in 500 litres of water/ha The active compounds were triazinone (A), formulated as 10 a 70 % strength wettable powder, and triazinone (B), formulated as a 60 % strength wettable powder. The plot size was 10 m^. The herbicidal action was measured on the naturally occurring weed population. The action on weeds and crops was determined in percentage damage in 15 comparison with the untreated control and is summarised in the following Table D: Le A 22 829 Table D Pre-emergence test / open-air Amount of active Active compound CIIEAL compound applied kg/ha (A) 2,0 100 1,5 100 1,0 100 0,5 95 (B) 2,0 95 1,5 90 1,0 85 0,5 75 1 LAMSS POLCO Summer Summer Peas barley wheat 100 100 50 70 100 100 50 95 100 90 95 0 100 100 100 100 0 0 0 95 95 0 0 0 80 90 0 0 0 to O (Ji sO Example E Pre-emergence test / open-air In a multi-variety test, summer wheat, summer barley and peas were sown on sandy loam with a medium 5 humus content. Sowing took place on 20th May and treatment with the herbicide was carried out on the following day, that is to say by the pre-emergence method. The amounts of active compound indicated were applied in 500 litres of water/ha. The active compounds were tri-10 azinone (A), formulated as a 70 % strength wettable powder, and triazinone (B), formulated as a 60 % strength wettable powder. The plot size was 10 m^. The herbicidal action was measured on the naturally occurring weed population. The action on weeds and crops was determined in percent-15 age damage in comparison with the untreated control and is summarised in the following Table E: Le A 22 829 Table E Pre-emergence test / open-air Amount of active Active compound POLLA VIOTR LAMSS compound applied kg/ha (A) 2,0 100 100 100 1r5 98 100 100 1.0 95 98 95 0,5 85 95 90 <B> 2,0 100 100 100 1,5 100 95 100 1,0 95 90 95 0,5 85 70 85 POLCO Summer Summer Peas barley wheat 100 95 90 85 100 95 90 80 50 20 10 5 0 0 0 0 50 30 20 10 0 0 0 0 0 0 0 0 0 0 0 « i NJ O (J1 2075 1 Example F Pre-sowing incorporation / greenhouse In a greenhouse test, the reaction of various varieties of cereal towards herbicides was examined in seed dishes. Seed dishes (20 x 20 cm in size) were filled with sandy loam with a humus content of 2.2 %. Spraying took place in a spray booth. The amounts of active compound were applied in 420 litres of water/ha. After the spraying, the active compound was incorporated into the soil and the various varieties of cereal were then sown. Application thus took place by the pre-sowing incorporation method. Evaluation took place 4 weeks after sowing. The action was rated as percentage damage in comparison with the untreated control and is summarised in the following Table F: Le A 22 829 Table F Pre-sowing incorporation / greenhouse Active compound Amount of active compound applied kg/ha Neepawa Wheat Triumph (A) 0,5 0,25 0,125 100 25 3 100 57 15 (B) 0,5 0,25 0,125 8 3 0 5 0 Wascana Barley Larker Bonanza Gait 100 90 27 100 75 12 100 63 17 100 17 8 i IN) 8 0 0 3 0 0 8 0 0 12 10 0 ro 0 -Nl 01 sD 20751 9' r< Example G Individual field plots were treated with the herbicides(A) and (b), respectively, 4-amino-6-tert.-butyl-3-methylthio-1,2,4-triazin-5(4H)-one and its 3-ethylthio hromologue, by 5 applying them broadcasting over the soil surface at various kg/hectare rates and immediately rototilling them in to a depth of approximately 4 inches. On the same day, wheat and barley were planted row-wise into the plots.

Abbreviat ion Botanical Name Common Name AMARE Amaranthus retroflexus Red Root Pig Weed AMBEL Ambrosia artemisiifolia Rag Weed AVE FA Avena fatua Wild Oat BRAPI Brachiaria piligera None CHEAL Chenopodium album Lambs Quarters DATST Datura stramonium Jimson Weed DIGS A Digitaria sanguinalis Large Crab Grass ECHCG Echinochloa crus-galli Barnyardgras s GAETE Galeopsis tetrahit Hemp nettle HELAN Helianthus annuus Sunflower POLPE Polygonum persicaria Redshank POLSC Polygonum scabrum moench Green Smartweed SETVI Setaria viridis Green Foxtail Le A 22 829 20751 9 Four weeks later evaluations were made visually in comparison to adjacent untreated CHECK plots with respect to the amount of damage. Each weed evaluation was based on four combined plots receiving the same concentration of herbicide. For 5 each crop there was determined that concentration of herbicide which produced at most 15% damage. For each weed there was determined that concentration of herbicide which produced at least 80% control.

Tables G and H present the results for each herbicide 10 with respect to both crops and weeds. The vertical lines represent the acceptable concentration for each crop and "X" to the right of such line for any given weed means the weed is not controlled at a concentration suitable for that crop. If "X" is to the left of the vertical, it means the weed is 15 controlled .

The longer the horizontal line is to the left of the vertical line, the greater is the margin of safety in using the particular herbicide.

These tables show that the 3-ethylthio homologue with 20 these crops is superior to the 3-methylthio homologue. & ' i* v 0 Le A 22 829 2075 1 9 - 24 -Table G Wheat Rate of Herbicide (B) at pre-emergent application (kg/ha) Weed Herbicide (B) e.« o.i»s' om i i.o 1 uri i.<; i i.o \ vo | »..« AVEFA SETVT AMARE GffiAL V X v , , AVEFA AMARE CHEAL POLSC CGAETE) X > X ? , , X AVEFA BRAPI (DIGSA) (ECHCG) AMARE AMBEL CHEAL DAIST HELAN -2L •X .

JL _ ..

. . X. . ....

AVEFA SETVI CHEAL X X '* AVEFA AMARE CHEAL POLSC X X * AVEFA POLPE AVEFA SETVT POLPE X * 1 x > Le A 22 829 Table G - Continued Wheat / Comparison Test Rate of Herbicide (A) at pre-emergent application (kg/ha) Weed Herbicide (A) 0.1 |«.« 10.2 ftis |O.J>4|0.S |<»S | f\.0 AVEFA SEIVI AMf\RE CHEAL - X- x AVEFA AMARE CHEAL POLSC (GAETE) x— - — - - — _x ...I77..7777_T.'_.

[.X.„ AVEFA BRAPI (DIGSA) (ECHCG) AMARE AMBEL CHEAL DAIST HELAN * "X n™™ x X Y x AVEFA SEIVI CHEAL _ AVEFA AMARE CHEAL POLSC * x " : x _ x _ AVEFA POLPE 1 ■ -i-EizEilE AVEFA SEIVI POLPE . .TlZTX'" X — J...... -x Le A 22 829 A.. ■;y - 2075 1 Remarks on Table G: The vertical line indicates the rate at which damage to the crops u/as within acceptable limits, i.e. no more than 10-15 K.

"X" indicates the rate at which each individual weed was controlled to a commercially acceptable degree, i.e. about 80 %.

If the letter "X" is on the vertical line, commercial control of that weed was achieved at the highest, still 10 tolerable rate. If the letter "X" appears to the left of the vertical line, weed control was achieved at a lower rate than the crop tolerance limit. The horizontal connecting line between "X" and the vertical indicates selective weed control, and the length of 15 the line reflects the margin of safety. o Le A 22 829 \r —v.- r". J 2 0 75 1 9 Table H Barley Rate of Herbicide (B) at pre-emergent application (kg/ha) Weed Herbicide (B) ojs lo.ns'o.S le/tt- 1 -o i.<; I ao i vo I AVEFA SEIVI AMARE CHEAL X X * AVEFA __ .AMARE .CHEAL Y .

X A F0I.SC- X GAEIE— * (AVEFA) (SEIVI) CHEAL X X X AVEFA AMARE CHEAL . POLSC.

X T x1 ■■ • . • .

► AVEFA POLPE X I X I AVEFA (SEIVI) POLPE X . - •> G Le A 22 829 Table H - Continued Barley / Comparison Test Rate of Herbicide (A) at pre-emergent application (kg/ha) Weed Herbicide (A) 6A [ ais I C.2. OJS |O.V>S | c.£ IC/IS | t.O ) 1.1* is AVEFA SEIVI AMARE CHEAL ... » - > X AVEFA . AMARE .CHEAL .POLSC GAETE-— X , .

A • X X ■ 7 (AVEFA) (SEIVI) CHEAL x - AVEFA AMARE . CHEAL . POLSC. - - -• . — 3T 1 / AVEFA POLPE AVEFA (SEIVI) POLPE .... — X Le A 22 829

Claims (11)

2075 1 - 29 - Remarks on Table H: The vertical line indicates the rate at which damage to the crop u/as within acceptable limits (no more than 10-15 80- "X" indicates the rates at u/hich each individual weed was controlled to a commercially acceptable degree (about 80 %). If the letter "X" is on the vertical line, commercial control of that weed was achieved at the highest, still tolerable rate. If the letter "X" appears to the left of the vertical line, weed control was achieved at a lower rate than the tolerance limit. The horizontal connecting line between "X" and the vertical is then indicative for selective weed control, and the length of the line reflects the margin of safety. Le A 22 829 207519 - 30 - WHAT WE CLAIM I§:

1. A method for selectively combating monocotyledon and dicotyledon weeds in cereal crops and leguminosae crops which comprises applying to such crops or a crop growing area before or after emergence of the plants, a herbicidally effective amount of 4-amino-6-tert.-butyl-3-ethylthio-l,2,4-triazin-5(4H)-one of the formula V (CH3)3C ' 1 2 n>N^SC«H NH2 (B) 2H5

2. A method according to claim 1 wherein the compound of formula (B) is applied in amounts of between 0.01 and 5 kg/ha.

3. A process according to claim 1 wherein the compound of formula (B) is applied in amounts between 0.1 and 3 kg/ha.

4. Selective herbicidal agents for use by the pre-emergence method and for pre-sowing incorporation, characterised in that they contain an active compound combination consisting of (1) 4-ami no-6-te rt.-butyl-3- ethy 11hio-1,2,4-triazin-5(4H>-one and (2) at least one of the foilowing compounds mentioned: (a) S-2,3,3-trichloro-allyl diisopropyl-thiolcarbamate (triallate); Cb) S-2,3-dich I oroa11 yI diisopropylthiolcarbamate (diallate) or (c) 1-amino-6-ethylthi o-3-C2,2-di methyLpropyl)-1,3,5-triazine-2,4MH,3H)-dione (ametridione) .

5. Selective herbicidal agents for use by the post-emergence method, characterised in that they contain an active compound combination consisting of (1) 4-amino-6-tert.-butyl-3-ethy 11hio-1,2,4-triazin-5(4H)-one and (2) at least one of the following compounds mentioned: (c) 1-amino-6-ethylthio-3-(2/2-dimethylpropyl)-1,3,5-triazin-2,4 (1 H,3H)-di one (ametridione), (d) 4-amino-6-tert.-butyl~ 3-methylthio-1,2,4-triazin-5(4H)-one (A) (metribuzin), (e) 1,2-dimethyl-3,5-diphenyl-pyrazolium methylsulphate (difen2oquat), (f) ethyl N-benzoy l-N-(3,4-dich loropheny l>- 2-amino-propionate (benzoyIprop-ethy I), (g> isopropyl Le A 22 829 207S19 - 31 - N-benzoyl-N-(3-chloro-4-fluorophenyl)-2-amino-propionate Cflamprop-isopropyL), (h) methyl N-benzoyl-N-(3-chloro-4-fluorophenyl)-2-amino-propionate (flamprop-methyl), (i) methyl 2-C4-(2,4-dich lorophenoxy)-phenoxy3-propionate (dic lofopmethyI), (k) methyl 2-ch loro-3-(4-chlorophenyI)-propionate (chlorprop-methy I), (I) 3,5-dibromo-4-hydroxy-benzonitrile (bromoxyni I), Cm) 3,5-diiodo-4-hydroxy-benzonitrile (ioxynil), (n) 2,4-dichlorophenoxyacetic acid (2,4-D), (o) 2-(2,4-dichlorophenoxy)-propionic acid (2,4-DP), <p) 4-ch loro-2-methyIphenoxyacetic acid (MCPA), ( q ) 2-(2-methyl-4-chlorophenoxy)-propionic acid ( M C P P > , (r) 1 -(2-benzothiazolyI>-1,3-dimethy lurea (methabenzthi-azuron), (s) 3-<4-isop ropy Ipheny 1)-1,1-dimethyLurea (i soproturon) , (t) 3-(3-ch Ioro-4-met hy Ipheny I)-1, 1 -di-methylurea (chIorto I uron) or (u) 3-isop ropy 1-2,1,3-benzo-thiadiazin-4-one 2,2-dioxide (bentazon).

6. Selective herbicidal agents for combating weeds in cereal crops and Leguminosae crops, characterised in that they contain an active compound combination consisting of (1) 4-amino-6-tert.-buty l-3-ethy11hio-1,2,4-tri-azin-5(4H)-one and (2) 4-amino-6-tert.-butyl-3-methyl-thio-1,2,4-triazin-5(4H)-one. any Qne Qf^

7. Herbicidal agents according to ^Claims 3, 4 and 5, characterised in that the weight ratio of component (1) to component (2) in the active compound combination is between 1:0.02 and 1:10.

8. Herbicidal agents according to Claim 6, characterised in that the weight ratio of component (1) to component (2) in the active compound combination is between 1:0.05 and 1:4.

9. A method for selectively combating monocotyledon and dicotyledon weeds in cereal crops and leguminosae crops which comprises applying to such crops or a crop growing area before or after emergence of the plants, a herbicidally effective amount of active compound combinations according to claims 3, 4, 5, 6 or 7.

10. Process for the preparation of herbicidal agents, characterised in that an active compound combination according to Claim 3, 4, 5, 6 or 7 is mixed with extenders and/or surface-active agents. Le A 22 829 207*13 - 3a. i.

11. A herbicidal agent according to claim 3,4 or 5 substantially as hereih described or exemplified. . BAYER AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By: