HERBICIDAL COMPOSITIONS FOR KILLING MONOCOTYLEDONOUS AND DICOTYLEDONOUS WEEDS IN MAIZE

Abstract: A herbicidal composition and a method of treatment for killing mono- and dicotyledonous weeds in maize. The composition contains as active ingredient a chloro acetanilide derivative of general formula (I) as herbicide, wherein independently of each other R1 stands for hydrogen or C1-4 alkyl, R2 stands for hydrogen or C1-4 alkyl, R3 stands for propyl, iso-propyl, methoxy-methyl, methoxy ethyl, ethoxy methyl, R4 stands for chloro acetyl, and a thiol carbamate derivative of general formula (II) as a further herbicide, wherein independently of each other R5 stands for straight or branched chained C1-5 alkyl, R6 stands for straight or branched chained C1-5 alkyl, R7 stands for straight or branched chained C1-5 alkyl, and the weight ratio of chloro acetanilide derivatives of general formula (I) to the thiol carbamate derivatives of general formula (II) is 1.2-1:3-1.

Description: HERBICIDAL COMPOSITIONS FOR KILLING MONOCOTYLEBONOUS AND DICOTYLEDONOUS WEEDS IN MAIZE The present invention is related to herbicidal compositions for killing monocotyledonous and dicoty¬ ledonous weeds in maize and a method for killing said weeds. We have now found that a mixture containing a compound of the general formula - wherein R, . stands for hydrogen or C,_ z , straight or branched chained alkyl, R stands for hydrogen or C, ^ straight or branched chained alkyl, - 2 stands for propyl, isopropyl, methoxy methyl, methoxy ethyl, ethoxy methyl, R stands for chloro acetyl - and a compound of the general formula 0 - wherein Re, Rg, Rr- represent a straight or branched chained alkyl containing 1 to 5 carbon atoms - and optionally an antidote, such as N-/dichloro acetyl/- -l-oxa- -aza-spiro-/-l-.5/-decane or 2-/dichloro-methyl/- -2-methyl- —ethyl-l,3-dioxolane cr 2-/dichloro-methyl/-2-met -1,5-dioxolane - the compounds of the general formulae /I/ and /II/ being known- monccctyledonous herbicides - show apart from the strong monocctyledonous weed killing effect a surprisingly good dicotyledonous weed killing activity. The active ingredients of the mixture and the preparation thereof as well as their herbicidal activity are disclosed in the following Patent Specifications: the preparation of substituted acetanilides and their use as herbicides was disclosed in US-PS Nos. 3•-^2•9-4*5 and 3.5-1-7 • 620, herbicides containing thiol carbamates are disclosed in US-PS 2.913-327, the known N-/dichloro- -acetyl/-l-oxa---!--aza-spiro-/ ,5/- < iecane " antidote is dis¬ closed in HU-PS 176 7S-4-, whereas 2-/dichloro-methyl/- -2-methy1-4-ethyl-__,3- __cκo3βne aid2-/dichloro-methyl/-2- -methyl-l,3-dioxolane antidotes are referred to in European Patent Application No. 8 111 0371.2. In Tables I and II the trivial and chemical names of those herbicides and antidotes are enumerated which are mentioned throughout the specification. Table I Herbicides of acetanilide type Trivial name Chemical name PROPACHLOR N-isopropyl-alpha-chloro-acetanili ACETOCΞLOR 2-methyl-6-ethyl-N-/ethoxy-methyl/ -chloro-ac etanilide ALACHLOR 2,6-diethyl-N-/me hoxy-methyl/- -chloro-acetanilide Table II.A Herbicides of thiol carbamate type Trivial name Chemical name EPTC S-ethyl-N,N-dipropyl-thiol carbamat VERNOLATE S-propyl-N,N-dipropyl-thiol carbama BUTYLATE S-ethyl- ,N-di-isobutyl-thiol carbamate Table II.B Letter-index Name Manufacturer Active ingredient content a Acenit 50 EC Nitrokemia Ipartelepek Acetochlor 50 % by vol. b Nip an 80 EC Nitrokemia Ipartelepek EPTC 80 % by volume c Eradicane 6 E S auffer Co. EPTC 72 % by volume d Aktikon Nitrokemia' Ipartelepek Atrazin 0 % by weight e Penuron 50 WP Nitrokemia Ipartelepek Fenuron 50 by weight 10 f Banvel 480 Chemie Linz Dica ba 480 g/1 i Niticid 65 WP Nitrokemia Ipartelepek Propachlor 65 by vol. _ Acenit A 500 EC Nitrokemia Ipartelepek Acetochlor 500 g/1, AD-67 antidote 50 g/1 k Maloran 50 WP Ciba-Geigy Chlorbromuron 50 % by w. 15 1 Lasso Monsanto Co. Alachlor 480 g/1 Table III Antidotes Trivial name Chemical name AD-67 N-dichloro-acetyl/-l-oxa-4-aza- -spiro-/4,5/-decane MG-191 2-/dichloro-methyl/-2-methyl- -1,3-dioxolane MG-235 2-/dichloro-methyl/-2-methyl- -4-ethyl-l,3-dioxolane Table IV Other herbicides Trivial name Chemical name Atrazin 2-chloro-4,6-bis-/ethyl-amino/-s- -triazine Dicamba 2-methoxy-3,6-dichloro-benzoic acid Chlorobromuron N-/4-bromo-3-chloro-phenyl/-N'- -methoxy- • -methyl-urea Fenuron N,N-dimethyl-N'-phenyl-urea ' In agriculture S-ethyl-N,N-dipropyl thiol carbamate is applied into the soil combined with an antidote as a pre-sowing herbicide. Acetochlor is used . for weed-killing in maize per se or combined with N- -/dichloro-acetyl/-l-oxa-4-aza-spiro-/4,5/-decane anti- dote as a pre-emergent herbicide by spraying it on the soil. Both herbicides are typical monocotyledonous weed- killing agents. - In maize cultivation the following problems arise: - In spite of the widespread use of graminicides the tendency of increased growth of monocotyledonous un- desired plants can be still observed. This phenomenon particularly appears in maize grown in two-three years old mono-cultures. - Next to the dominance of monocotyledonous weeds the spreading ■ of dicotyledonous weeds is still a great problem, particularly the Amaranthus species which are resistant to atrazine represent a great problem. - Part of the used herbicides does not act optimally under humid soil conditions /thiol carbamates/ and another part under dry conditions /such as chloro acetanilides, triazines, ureas/. - There is no herbicide in maize, which acts as a good herbicide independently of the humus content of the soil and of its physical heaviness. - In order to obtain a completely effective soil herbi- cide out of the presently applied herbicides the demands on the cultivation conditions of the soil are extremely high, a soil surface which is cloddy and contaminated with stubble residues can considerably reduce the acti¬ vity of the herbicides. The aim of the present invention was to elaborat a plant protecting agent which is suitable for - the effective weed-killing in case of dicotyledonous undesired plants next to monocotyledonous undesired plants, - acting without any significant fluctuation both during dry periods and periods of rainfalls, - giving a good herbicide activity independently of the type of the soil and of culture condition. This aim could be achieved by elaborating a herbicide combination consisting of a thiol carbamate type herbicide, an acetanilide type herbicide and optionally an antidote and solid/or liquid carriers and surfactants. The mentioned typical monocotyledonous weed killing agents unexpectedly show an excellent dicotyle¬ donous weed killing activity and this activity is parti¬ cularly advantageous against undesired plant species which are resistant to atrazine, such as the species Amaranthus and Chenopodium. We have also found that when applying the active ingredients in combination according to the invention the activity on monocotyle¬ donous undesired sprouting plants is more intensive than when applied separately. This increased activity can also be observed against such monocotyledonous weeds difficult to combat - as Panicum spp., and sprout¬ ing Sorgum halepense. A further unexpected effect occured, i.e. the activity of the herbicide combination was independent of soil type, the quality of the soil preparation and of the precipitation conditions. The present invention is directed to herbicidal compositions suitable for monocotyledonous and dicotyle- donous weed killing in maize containing as active in¬ gredient a chloro acetanilide derivative of the general formula wherein independently of each other R-, stands for hydrogen or C, . alkyl stands for hydrogen of C-, . alkyl R-z stands for propyl, iso-propyl, methoxy methyl, methoxy ethyl, ethoxy methyl R^ stands for chloro acetyl and a herbicide of thiol carbamate. type of the general formula - wherein independently of each other R e stands for C,_-. straight or branched chained alkyl R,- stands for C, ,- straight or branched chained alkyl R-, stands for C-, -. straight or branched chained alkyl ( 1-5 ° and optionally as antidote N-/dichloro-acetyl/-l-oxa- -4-aza-spiro-/4,5/-decane of the formula C = 0 /III/ CH - 01 I Cl or 2-/dichloro-methyl/-2-methyl-4-ethyl-l,3-dioxolane of the formula or 2-/dichloro-methyl/-2-methyl-l,3-dioxolane of the formu The compositions may contain any other antidote as well. Related to the total weight of the composition it contains 0.5 to 95 % by weight of liquid carrier, e.g. 7 to 70 of aromatic solvents, particularly xylene, as solvent transmitter 5 to 40 # aliphatic alcohols con¬ taining 1 to 4 carbon atoms or aliphatic ketones contain¬ ing 1 to 6 carbon atoms, dimethyl formamide, as emulsifier 5 to 30 % by weight of ionogenic and non-ionogenic tenside or a mixture thereof. - 8 - The weight ratio of the chloro acetanilide derivative of the general formula /I/ and the thiol carbamate derivative of the general formula /II/ as well as the antidote may be in the range from 1.2-1:3-1*' 1-0.2. The present invention further provides a method of treatment of maize for combatting undesired mono- and dicotyledonous plants comprising applying to the soil on the sowing area a chloro acetanilide of the general formula /I/ as herbicide at a rate of 1.0-7.0 kg/ha, preferably 1.0-4.5 kg/ha and a thiol carbamate derivative of the general formula /II/ as herbicide at a rate of 1.0-10.0 kg/ha, preferably 1.0-8.0 kg/ha and optionally an antidote, preferably a compound of the formula /III/, • /IV " / or /V/ at a rate of 0.1-4 kg/ha, preferably 0.3-3.0 kg/ha. before sowing simultaneously or separately in finely divided form. The herbicides and antidotes' according to the invention can be formulated to liquid compositions by methods known per se. When formulating emulsifiable concentrates as solvents mainly aromatic solvents, and as solvent transmitters C, ^ aliphatic alcohols or C, g aliphatic ketones, optionally dimethyl ' formamide may be used. As emulsifying agent a mixture of ionogenic and/or non-ionogenic tensides is used, such as Berol 930, Berol 938, Tensiofix 7438, Tensiofix 7^53 /Berol is manufactured by the Swedish firm Kemi AB and Tensiofix by the Belgian firm Tensia SA/. As solvent transmitters ethanol, ethanol, acetone and methyl ethyl ketone may be used. The following ionic and non-ionic tensides are preferred: - alkyl-phenoxy-polyethoxy ethanols, - poly/oxy-ethyl/ated vegetable oils, - poly/oxy-ethyl/ated fatty alcohols, - poly/oxy-ethylene/glycerol fatty acid esters, - aryl alkyl sulfonic acid salts, - alkoxy-polyethoxy-ethanol phosphates. The following Examples illustrate the composi¬ tions according to the invention in the form of emulsifi¬ able concentrates: Example 1 Emulsifiable concentrates 1.1 Composition 1.2 Composition Acetochlor 200 1 s Acetochlor 200 g AD-67 antidote 60 1 s AD-67 antidote 90 g Berol 930 5C 1 s Tensiofix 7-1-3840 g Berol 938 5C 1 g Tensiofix 7-1-53 60 g Xylene 28C 1 s Xylene 250 g 1.3 Composition 1.4 Composition EPTC 360 s EPTC 360 g Alachlor 240 s Alachlor 240 g • AD-67 antidote 60 g AD-67 antidote 90 g Berol 930 50 g Berol 930 50 g Berol 938 50 oo* Berol 938 50 g Methyl-ethyl- Methyl-ethyl- ketone 100 s ketone 100 g Xylene 140 s Xylene 110 g 1.5 Composition 1.6 Composition Butylate 360 o a- Butylate 360 g Acetochlor 200 σ* Acetochlor 200 g AD-67 antidote 60 s AD-67 antidote 90 g Tensiofix 7438 60 s Berol 950 50 g Tensiofix 7453 40 s Berol 938 50 g Xylene 280 s Xylene 250 g -Φ 1.7 Composition 1.8 Composition Butylate 360 g Butylate 360 g Alachlor 240 g Alachlor 240 g AD-67 . antidoe 60 g AD-67 antidote 90 g Berol 950 50 g Tensiofix 7-^38 40 g Berol 958 50 g Tensiofix 7-H5 40 g Xylene 140 g Xylene 110 g Methyl-ethy1- ketone 100 g 1.9 Composition 1.10.Composition Butylate 250 g . Propachlor 250 g Propachlor 250 g EPTC 250 g AD-67 antidote 50 g AD-67 antidote 50 g Berol 950 5 g Tensiofix 7-1-38 50 g Berol 958 • 5 g Tensiofix 7-1-53 50 g Dimethyl- Dimethyl- formamide 160 g formamide 90 g Xylene 240 g Xylene 260 g In the following biological examples the activi -y of the combination according to the invention was tested under various soil, precipitation and temperature condi¬ tions and by various herbicidal application methods. The following mono- and dicotyledonous plants occured on the test area in the Examples. Table V Monocotyledonous plants Abbreviated International English name name name ECHCR Echinochloa crus-galli barnyard grass PANMI Panicum miliaceum SETGL Setaria glauca bristle grass SETVI Se aria viridis green bristle grass SORHA Sorgum halepense Table VI Dicotyledonous plants Abbreviated International name English name name AMAAL Amaranthus albus AMABL Amaranthus blithoides AMACH Amaranthus chlorostachys AMARE Amaranthus retroflexus pig weed CANSA Cannabis sativa CHEAL Chenopodium album fat hen CHENY Chenopodium hybridum CIRAR Cirsium arvense creeping thistle HBTR Hibiscus trionum LATTU Lathyrus tuberosus MERAN Mercurialis annus dog's mercury POLLA Polygonum lapathifolium RESLU Reseda lutea wild mignonette SINAR Sinapis arvensis yellow charlock STAAN Stachys annua annμal woundwort EQUAR Ξquisetum arvense common horsetail The effect of the combination according to the invention, of .the control and of the comparative mono- and dicotyledonous weed killers upon maize and upon weeds was evaluated on the basis of the EWRC value. Table 1 i/ I Explanation of EWRC scale Weed killing General Value of Phytotoxic activity impression EWRC scale symptoms on the domesticated plant 100 excellent l " none 98 very good 2 very slight symptoms 95 good 3 slight symptoms 90 satisfactory 4 strong, but pro¬ bably transient symptoms, no crop decrease is * pro.bable 82 doubtful 5 symptoms of un¬ known effect 70 not satisfactory 6 damaging symptoms can be observed 55 bad 7 symptoms of bad damage 30 very bad 8 symptoms of very bad damage 0 cannot be used 9 total killing Example 2 Biological test results Soil conditions: - Type of soil: chernozem brown forest soil - Humus: 2.9 # - Cledgyness /Arany/: 43 - pH value: 6.2 Sowing time of maize: 23.04 Art: Pi 3780 Weeds: Piece/ on the control area Setaria glauca 21 Echinochloa crus-galli 14 Amaranthus retroflexus 8 The average weed killing of the control areas was 80 % at the end of the cultivation period. Test conditions: Parcel size: 0.5 ha /20 x 250 m/ Control: 4 x 4 m covered control " Spray liquid: 300 1/ha Day of treatments: 17. 04. /presowing/ 26. 04. /preemergence/ Precipitation conditions: Within 7 days after the presowing treatment: 12 mm Within 7 days after pree ergent treatment: 19 mm Table VIII Method of treatment Active Application Time of Weed killing Phyto- ingredient method evalu- effect toxic dose ation EWRC values effect AMARE SETGL ECHCR 1. Control/untreated 1 9 9 9 1 10 2. Acetochlor a 2.0 pre 1 4 4 4 1 2 5 4 4 1 3 6 4 5 1 3- EPTC + . 1 5 3 3 1 AD-67 antidote 5 0.3 PPi 2 6 3 3 1 15 4. EPTC + 3.0 1 1 2 2 1 AD-67 antidote b + 0.3 ppi 2 1 2 2 1 acetochlor 1.5 pre 5- EPTC + 4.5 1 2 2 2 1 R-25788 antidote* 3 + 0.48 pp 2 2 2 2 1 atrazin- 1.2 pre 3 2 2 2 1 6. Acetochlor + 2.0 1 2 4 4 1 a _t.razm• d 1.0 2 3 4 4 1 3 3 4 5 1 Time of evaluation: 1. 05. 06. 2. 27. 07. 3. 01. 10. ppi = applied to the soil presowing pre = applied after sowing before emergence Table VIII shows that Acenit 50 EC /No. 2/ applied alone and the combination of EPTC /No. 3/ used -alone and AD-67 antidote /Niptan 80 EC/ was ineffective against the dicotyledonous Amaranthus retroflexus, whereas against the monocotyledonous Echinochloa crusgalli the activity proved to be good and satisfactory. In test No. 4 EPTC + AD-67 antidote was applied -on the sowing area ppi and the acetochlor was applied on the same area pre. The table shows that these two active ingredients killing mono-cotyledons excellently kill the dicotyledonous Amaranthus next to monocotyledons. In tests 5 and 6 two combinations are shown, which combat usual, mono- and di¬ cotyledons, where next to the monocotyledonous weed killing agents: antidoted EPTC and Acetochlor atrazine was used against dicotyledons. The table shows that the combination according to the invention used in test No. 4 was more effective ■ against the dicotyledonous Amaranthus retroflexus than the known compositions, and at the same time its activity against monocotyledonous weeds is equal or even better than that of the known compositions. It should be noted, that the active ingredients in the known compositions are applied at a higher rate than in the combinations ' according to the invention and even so they do not achieve the effect of the combinations according to the invention. The test series show unambigously that when spraying the active ingredients according to the in¬ vention subsequently on the sowing area the active in¬ gredients act synergistically on each other resulting thus a broader spectrum of activity and an increased specific activity. Example 3 Soil conditions: - Type of soil: lime-deposit chernozem - Humus: 2.1 - Heaviness /Arany/: 39 - pH-value: 7-3 Heaviness number /Arany/ indicates the of the amount of water related to the weight of soil, needed to achieve the necessary plasticity. Sowing time of maize: 02.05., 05.05., 06.05. Art: Pi 3780 MSC Weeds: The test area is covered mainly by monocotyledonous weeds mainly ECHCR, SETGL, dicotyledonous weeds occur only -moderately /mainly CHEA , AMARE, AMABL, AMACH/.. The average coverage of the control areas, /frequency / is shown below the EWRC value tables. Test conditions: • Parcel size: 4 x 10 m Number of replicates: 4 Control: 4 x 10 m between the treated parcels, 3 per replicates Spray liquid: 3001/ha Time of treatments: ppi: 28.04, 18.05. Precipitation conditions: Within 7 days after presowing treatment: 4-5 mm Within 7 days after pre-emergent treatment: 22 mm An outstanding result was obtained in the test by using EPTC-360 g/1 + acetochlor-200 g/1 + AD-67-15 %. The monocotyledonous weed killing was excellent or good starting from the treatment until the end evalu- ation resp. during the whole vegetation period. At the same time as expected as a result of the treatment all parcels treated with the combination according to the invention were entirely weed-free during the whole period of cultivation. EPTC and acetochlor active ingredients when sprayed separately showed a somewhat lower mono¬ cotyledonous weed killing effect /by 1-2 EWRC values/. Said two active ingredients when sprayed separately showed also a weaker effect on the dicotyledonous weeds. The synergistic activity of EPTC and acetochlor used together according to the invention is proved by this Example both as to the increased activity and to the broadened spectrum of activity. The rates of 121/ha and 24 " 1/ha were applied in order to evaluate phyto- toxicity: no phytotoxic symptoms were observed in case of the higher rates /121/ha, 241/ha/ of the composition according to the invention with lower antidote content. Table IX/A Test results Time of the first evaluation: 24. 05. Active ingredient Dose Application e e d s Phytotoxic kg/ha method EWRC values activity ECHCR SETGL CHEAL AMACH AMARE 1.2.3 10 1.2.3 1.2.3 1.2.3 1.2.3 1.2.3 1. Acetochlor + 2.1 pre 44 3 44 3 3 3 3 1 1 1 atrazi ■nd 1.4 0 Acetochlor + 2.1 pre 5 5 3 5 5 3 3 3 3 1 1 1 15 enuron 1.05 3. Acetochlor + 2.0 ppi 1 1 1 1 2 1 1 1 EPTC + 3.6 AD-67 0.9 /Composition according to Example- 1.2 10 1/ha/ 20 4. Acetochlor + 2.4 ppi 2 1 2 1 1 1 1 1 1 /Composition according to Examples 1.2 12 1/ha/ 5. Acetochlor + 4.8 ppi 1 1 1 1 1 1 1 1 1 25 EPTC + 8.64 AD-67 2.16 /Composition according to Examples 1.2 24 1/ha/ Continuation of Table IX/A Active ingredient Dose Application e e d s Phytotoxic kg/ha method EWRC values activity ECHCR SETGL CHEAL AMACH AMARE 1.2.3 1.2.3 1.2.3 1.2.3 1.2.3 1.2.3 6. Acetochlor + 2.0 ppi 1 1 2 1 12 3 3 3 1 1 1 10 EPTC + 3.-6 AD-67 0.6 /Composition according to Example 1.1 10 1/ha/ 7. Acetochlor + 2.4 ■ ppi 1 22 1 1 1 1 EPTC + 3.6 15 AD-67 0.72 /Composition according to Example 1.1 121/ha/ 8. Acetochlor + 4.8 pp 1 1 1 1 1 3 33 1 1 1 EPTC + 8.64 AD-67 1.44 20 /Composition according to Example 1.1 241/ha/ 9. EPTC 3.75 ppi 22 2 21 1 2 3 3 3 3 3 1 1 1 Acetochlor a 2.0 pre 10.Acetochlor a 2.5 pre 33 3 443 333 1 1 1 f Dicamba 0,268 post 25 Control frequency 46 38 8 8 Note: EWRC values were shown separately according to sowing time for each evaluation. 1. 02.05. values related to ms.ize sown on ) 2. 05.05. 3. 16.05. Table IX/B Test results Time of second evaluation: 08.07. Active ingredient Dose Application Weeds Phytotoxic kg/ha method EWRC values activity ECHCR SETGL CHEAL AMACH, AMARE 1.2.3 10 ' l.2.3 1.2.3 1.2.3 1.2.3 1.2.3 1. Acetochlor + 2.1 pre 45 3 ^ 3 3 1 1 1 atrazin 1.4 2. Acetochlor + 2.1 pre 654 653 2 2 1 1 1 15 fenuron 1.O5 3. Acetochlor + 2.0 ppi 2 2 2 2 2 2 444 1 1 1 EPTC + 3.6 AD-67 0.9 /Composition according to Example 1.2 10 1/ha/ 20 4. Acetochlor + 4.8 ppi 2 2 1 1 1 1 1 1 1 EPTC + 4.32 5. Acetochlor + 4.8 ppi 222 1 1 1 1 1 1 25 EPTC + 8.6 AD-67 2.16 /Composition according to Example 1.2 24 1/ha/ Continuation of Table IX/B Active ingredient Dose Application Weeds Phytotoxic kg/ha method ' EWRC values activity ECHCR SΞTGL CHEAL AMACH AMARE 1.2.3 1.2.3 1.2.3 1.2.3 1.2.3 1.2.3 6. Acetochlor + 2.0 ppi 2 2 2 2 2 2 3 3 3 3 3 3 1 1 1 EPTC 3.5 10 AD-67 0.6 /Composition according to Example 1.1 101/ha/ 7. Acetochlor + 2.4 ppi 1 2 2 1 1 2 1 1 1 EPTC + 3.6 AD-67 0.72 15 /Composition according to Example 1.1 121/ha/ 8. Acetochlor + . 4.8 ppi 1 1 2 1 2 1 3 3 3 1 1 1 EPTC + AD-67 1.-> • -» • /Composition according to Example 1.1 24 1/ha/ 20 9. EPTC b 3.75 Ppi 2 2 3 22 2 3 3 3 4 3 3 1 1 1 Acetochlor 2.0 pre 10. Acetochlor a 2.5 pre 44 3 44 J 34 3 1 1 1 f Dicamba ' 0.268 post Control frequency # 52 54 8 Table IX/C Test results ' Time of the third evaluation: 29.07. Active ingredient Dose Application Weeds Phytotoxic kg/ha method EWRC values activity ECHCR- SETGL CHEAL AMACH AMARE 1.2.3 1.2.3 1.2.3 1.2.3 1.2.3 1.2.3 1. Acetochlora + 2.1 pre 553 553 333 1 1 1 10 atrazin 1.4 2. Acetochlor + 2.1 pre 664 6 6 3 3 3 1 1 1 fenuron 1.05 3. Acetochlor + 2.0 ppi 3 3 2 3 3 2 3 3 1 1 1 EPTC 3.6 15 AD-67 0.9 /Composition according to Example 1.2 10 1/ha/ 4. Acetochlor + 4.8 ppi 2 2 2 2 2 2 1 1 1 EPTC + 4.32 AD-67 1.08 20 /Composition according to Example 1.2 12 1/ha/ 5. /Composition according to Example 1.2 24 1/ha/ Continuation of Table IX/C Active ingredient Dose Application Weeds Phytotoxic kg/ha method EWRC values activity ECHCR SETGL CHEAL AMACH AMARE 1.2.3 1.2.3 1.2.3 1.2.3 1.2.3 1.2.3 6. Acetochlor + 2.0 pp 2 3 2 2 22 3 3 3 3 3 3 1 1 1 EPTC + 3.5 AD-67 0.6 10 /Composition according to Example 1.1 101/ha/ 7. Acetochlor + 2.4 ppi 222 1 12 1 1 1 EPTC + 3.6 AD-67 0.72 /Composition according to Example 1.1 1.2 1/ha/ 15 8. Acetochlor + 4.8 ppi 222 121 3 3 3 1 1 1 EPTC + 8.64 AD-67 1.44 /Composition according to Example 1.1 24 1/ha/ 9. EPTC 3.75 ppi 3 3 3 3 22 43 5 3 33 1 1 1 20 Acetochlor a 2.0 pre 10. Acetochlor a 2.5 pre 566 "665 3 3 1 1 1 Dicamba f ' 0.268 post Control frequency %■ 38 42 10 10 Examϋ - le 4 Test conditions: Soil conditions Type of soil: lime deposit brown forest soil Humus: 2.84 % Heaviness /Arany/: 43 pH /KCl/ : 7*8 Time of maize sowing: 05.05. Art: Pi 3732 MSC Weeds: The area is mainly covered by dicotyledonous weeds, and is moderately infected by monocotyledons. Total weed covering: 25 % CΞEAL 18.75 # AMABL 2.12 % AMBEL 0.62 % ECHCR 0.62 BILCO 0.62 % SINAR 0.10 % DIPMU 0.10 % . The data of weed covering refer to the beginning of the cultivation period. Time of oonitation: 01.06. Further test conditions: Parcel size: 4 x 10 m Number of replicates: 4 Control: 4 x 10 m untreated parcel between the treated parcels, 3 per replicates Spray liquid: 300 1/ha Term of treatments: O3.O5. presowing 15.05. pre-emergence Precipitation conditions: Within 7 days after the presowing treatment: 20 mm Within 7 days after the pre-emergent treatment: 25 mm In spring and at the beginning of summer there were considerably more rainfalls than usually: April: 46 mm May: 90 mm June 55 mm On the test area infection caused by dicotyledonous plants, mainly CHEAL and AMACL were typical. The soil was in about 15-20 cloddy and covered with stock residues at the time of the treatment. The combinations of the invention showed even under such circumstances an expressively good weed killing effect /Table X. treatments Nos: 1-6 and 8-12/. against dicotyledonous plants mentioned above. This result unambigously proves the synergistic activity of the active ingredients according to the invention as a consequence of which two herbicides effective against monocotyledons act in a combination according to the invention against dicotyledonous weeds too. Table X Time of evaluation: 01.06. Active Dose Application Weed killing Phyto- activity ingredient 1 kg/ha method. EWRC values toxic AMCL CHEAL activity .2.3.4 1.2.3.4 1.2.3.4 1. EPTC + 3-6 ppi 1 1 1 1 3322 2223 acetochlor+ 2.0 AD-67 0.6 /Composition according to Example 1.1 10 1/ha/ 2. EPTC+AD-67 3-75 + 0.375 ppi 1 1 1 1 1 1 1 1 2222 Acetochlor a 2.0 pre AD-67 0,2 3. Butylate + 3-6 ppi 1 1 1 1 2 1 1 1 2222 acetochlor 2.0 AD-67 0.6 /Composition according to Example 1.510 1/ha/ 4. Butylate 4.0 ppi 1 1 1 1 1 1 1 1 2222 Acetochlor-** 2.0 pre AD-67 '" 0.2 /Continuation of Table X/ Active Dose Application Weed killing Phyto- ingredient 1 kg/ha method EWRC values toxic AMCL CHEAL activity 1.2.3.4 1.2.3.4 1.2.3.4 5. EPTC + 3.6 ppi 1 1 1 1 3 2 1 2 3 2 1 1 alachlor + 2.4 AD-67 0.6 /Composition according to Example 1.5 10 1/ha/ 6. EPTC+AD-67 33.-7755 +0.375 ppi 1 1 1 1 1 1 1 1 1 1 1 1 Alachlor 6 2.5 pre 7. Control 8. Butylate + 3-6 1 1 1 1 1 2 1 2 1 1 1 1 alachlor + 2.4 ppi .AD-67 0.6 /Composition according to Example 1.7 10 1/ha/ 9. EPTC + 3-75 PPi 1 1 1 1 2 2 2 2 1 1 1 1 AD-67 + 0.375 propachlor 3 * 75 /Composition according to Example 1.10 15 1/ha/ 10. _-PTC+AD-67 3-75+0.375 ppi 1 1 1 1 2 2 1 1 1 1 1 Propachlor 3.25 pre 11. Butylate + 4.0 ppi 1 1 1 1 3 3 3 2 1 1 1 1 propachlor + 4.0 AD-67 0.8 /Composition according to Example 1.9 16 1/ha/ 12. Butylate 5 _ 4.0 ppi 1 1 1 1 22 3 3 1 1 1 1 Propachlor 1 3.25 pre 13. Control 14. EPTC+AD-67 b 4.5+0.45 ppi 1 155.. B Buuttyyllaattee 8 - 5 - 4 4..00 p PpPii 1 1 1 1 1 1 1 1 1 1 1 1 Atrazin 1.35 16. Acetochlor 0" 1.8 pre 1 1 1 1 1 1 1 1 1 1 1 1 Atrazin ' 1.2 /Continuation of Table X/ Active Dose Application Weed killing Phyto- ingredieήt 1 kg/ha method EWRC values toxic AMCL CHEAL activity 1.2.3.4 1.2.3.4. 1.2.3.4 17. Alachlor 3-0 pre 1 1 1 1 1 1 1 1 Atrazin 1:35 18. Fropachlor 4.55 pre 1 1 1 1 1 1 1 1 1 1 1 1 19. Control Example 5 Test conditions: Soil conditions: - Type of soil: meadow soil Humus: 3.34 < $> Heaviness /Arany/: 39.9 pH /KCl/ : 7*9 Green-crop: 1. year maize 2. year sunflower 3. year winter wheat Sowing of maize: 4. year 26.04. Art: Pi 3732 MSC Weeds: The area is characterized by intensive mono- and di¬ cotyledonous weed coverage. On the control areas the total weed coverage amounted to 37 * 5 > at the. first evaluation, on 03. 06. CHEAL 18.75 ΞCHCR 15.62 AMBEL 3.12 ANAAR 0.10 ΞUPFA 0.10 CHΞHY 0.10 CONAR 0_36 - 29 - CONAR 0.36 STAAN 0.10 SYNAR 0.36 DPMU 0.36 SONAS 0.36 Test conditions: Parcel size: 4 x 10 m Replicates: 4 Control: 4 x 10 m untreated parcel between the treated parcels, 3 per replicates Amount of spray liquid: 300 1/ha Time of treatment: 25.04. /presewing/ 02.05. /pre-eπergent/ Precipitation conditions: On 30. April after the presov/ing treatment 10.5 mm of precipitation was falling. Subsequently in May 91.9 mm and in June 108.4 mm and within 7 days after the ' pre- emergent treatment 18.0 mm rainfall followed. Spring and the beginning of summer was characterized by exceptionally much rainfall. After the 14th day after the preemergent treatment 45 mm. of precipitation was raining on the test area. Daily precipitation following the treatments: On 30. April 10.5 mm 05. May 7-6 mm 08. 4.2 mm 09. 7.0 mm 10. 15.7 mm 13. 0.7 mm 16. 13.1 mm /plant average/ 19. 4.2 mm 20. 6.8 τ.m 21. 0.3 mm 22. 0.6 .mm 23- 10.7 πm 24. 6.0 mm 2^. c • •— mm α 7 z rr,r- 31 2.5 mm 91.9 mm On 04. June 0.6 mm 06. - 1.8 mm 07. 11.1 mm 08. 3.0 mm 15. 14.2 mm 18. 1.0 mm 22. 22.0 mm 23. 45.0 mm 24. 4.1 mm 27. 2.4 mm 29. 15.5 mm 30. 8.7 mm 108.4 mm Table XI Active Dose Application Weed killing Phyto- ingredient 1 kg/ha method effect - toxic EWRC values effect ECHCR CHEAL 1.2.3.4 1.2.3.4 1.2.3-4 1. EPTC + 3-6 ppi 2 22 2 2 2 2 2 1 1 1 1 acetochlor 2.0 AD-67 0.6 /Composition according to Example 1.1/ 2. EPTC+AD-67 3-6+0.36 ppi 1 1 1 1 1 1 21 221 1 Acetochlor+ pre AD-67- 0.2 3. Butylate + 3-6 acetochlor + 2.0 ppi 1 1 3 2 1 1 22 2222 AD-67 0.6 /Composition according to Example 1.5/ 4. Butylate 5 3.6 ppi 1 1 1 1 1 1 1 1 2221 Acetochlor- 2.0 pre AD-67 0.6 Continuation of Table XI Active Dose Application Weed killing Phyto- ingredient 1 kg/ha method EWRCValues toxic ECHCR CHEAL effect 1.2.3.4 1.2.3.4 1.2.3.4 5. EPTC + 3.6 Alachlor 2.4 ppi 1 1 1 2 1 1 1 1 2 2 2 1 AD-67 0.6 /Composition according to Example 1.3/ 6. EPTC+AD-67 b 3.75+0.37 PPi 1 1 1 1 1 1 1 1 2 2 2 2 Alachlor 2.5 pre 7. Control 8. Acetochlor- 2.4 pre 1 1 1 1 1 1 1 1 6 3 3 3 AD-67 + 0.2 chlorobromuron 1.5 9. Butylate 5 4.0 ppi 1 1 1 1 1 1 1 1 1 1 1 1 Alachlor 2.5 pre 10. EPTC+AD-67 b 3-75+0.375 PPi 3 3 442 2 3 3 1 1 1 1 Propachlor 1 3-25 11. EPTC+AD-67 3.75+0.37 ppi 1 1 1 3 22 2 2 1 1 1 1 Propachlor 1" 3 * 25 pre 12. Butylate + 4.0 ppi 2 3 3 3 3 2 2 2 1 1 1 1 propachlor+ 4.0 AD-67 0.8 /Composition according to Example 1.9 16 1/ha/ 13. Butylate 5 4.0 ppi 222221 2 2 1 1 21 Propachlor 1 3.25 pre 14. Control 15. EPTC+AD-67 4.5+0.45 ppi 44 3 2 1 1 1 1 1 1 1 1 Atrazin 1.35 16. Butylate 5 4.0 ppi 44 3 2 1 1 1 1 1 1 1 1 Atrazin 1.35 17- Propachlor 1 4.55 pre 2 2 1 1 1 1 1 1 1 1 1 1 Atrazin 1-35 18. Acetochlor a 1.8 pre 1 1 1 1 1 1 1 1 3 2 24 Atrazin d 1.2 19. Alachlor 1 3-0 pre 1 1 1 1 1 1 1 1 1 2 2 2 On the test area ECHCR and CHEAL infection is critical. The combinations according to the invention showed a very .good result against dicotyledonous plants inspite of the fact that the combination does not contain any component being active against dicotyledons. Con¬ sequently a synergistic effect occurs between the active ingredients according to the invention. The combinations according to the invention act on the sowing area as excellent mono- and dicotyledonous weed killing agents during the whole vegetation period of maize without containing dicotyledonous weed killers, and they even surpass the activity of known mono- and dicotyledonous weed killing combinations. By using the combinations according to the invention the so far used two weed killing steps in the agriculture /ppi and pre/ can be replaced by one weed killing step /ppi/ resulting in considerable decrease of the weed killing costs.

Claims: C L A I M S 1. Herbicidal composition for killing mono- and dicotyledonous weeds in maize comprising as active ingredient a chloro acetanilide derivative of the general formula as herbicide ' - wherein independently of each other R, stands for hydrogen or C, ^ alkyl 2 stands for hydrogen or C, . alkyl R, stands for propyl, iso-propyl, methoxy-methyl, methoxy ethyl, ethoxy methyl R. stands for chloro acetyl and a thiol carbamate derivative of the general formula 0 as a further herbicide wherein independently of each other e 'stands for straight or branched chained C, ,- alkyl Rg stands for straight or branched chained C-,_- alkyl E- stands for straight or branched chained C, -- alkyl and the weight ratio of chloro acetanilide derivatives of the general formula /I/ to the thiol carbamate deriva¬ tives of the general formula /II/ is 1.2-1:3-1- - 2. A composition as claimed in claim 1 comprising next to the active ingredients a known antidote decreasing phytotoxicity of chloro acetanilide and thiol carbamate and the weight ratio of the chloro acetanilide deriva¬ tive of the general formula /I/ and the thiol carbamate derivative of the general formula /II/ and the antidotes amounts to 1.2-1:3-1"•1-0.2. 3. A composition as claimed in any of claims 1 to 2 comprising as an antidote N-/dichloro-acetyl/-l- -oxa-4-aza-spito-/4,5/-decane of the formula /in/ C = 0 CH ■ - Cl Cl or 2-/dichloro-methyl/-2-methyl-4-ethyl-l,3-dioxolane of the formula or 2-/dichloro-methyl/-2-methyl-l ,3-dioxolane of the formula CH . 0 CH. A/ \ Jl CH - 0 CH, . 4. A method of treatment of maize for combatting undesired mono- and dicotyledonous plants comprising applying into the soil on the sowing area a chloro acetanilide derivative of the general formula /I/ as herbicide at a rate of 1.0-7-1 kg/ha, preferably 1.0-4.5 kg/ha, a thiol carbamate derivative herbicide of the general formula /II/ at a rate of 1.0-10 kg/ha, preferably 1.0-8.0 kg/ha and optionally a known anti¬ dote at a rate of 0.1-4.0 kg/ha, preferably 0.3-3.0 kg/ha before sowing simultaneously or separately in a finely divided form.

Inventors: CSIBOR ISTVAN, CZEKMANY ARNOLD, FODOR FERENC, HENGER KAROLY, HORVATH AKOS, HORVATH ANDRAS, IGARI ZSUZSANNA, KALLO SANDOR, OERDOEG ATTILA, PAMUK GYULA, REISINGER KATALIN, SZELL ENDRE, TOEMOERDI ELEMER, CSIBOR, ISTVAN, CZEKMANY, ARNOLD, FODOR, FERENC, HENGER, KAROLY, HORVATH, AKOS, HORVATH, ANDRAS, IGARI, ZSUZSANNA, KALLO, SANDOR, OERDOEG, ATTILA, PAMUK, GYULA, REISINGER, KATALIN, SZELL, ENDRE, TOEMOERDI, ELEMER
Applicants: KSZE NOEVENYTERMELESI RENDSZER, NITROKEMIA IPARTELEPEK
Application year: 1985
Main classification: A01N47
IPC codes: A01N47