EP0000351A1 - Phenoxy-phenyl-thio-alkanecarboxylic acid derivatives method for their preparation and their use as herbicides and plant growth regulators - Google Patents
Phenoxy-phenyl-thio-alkanecarboxylic acid derivatives method for their preparation and their use as herbicides and plant growth regulators Download PDFInfo
- Publication number
- EP0000351A1 EP0000351A1 EP78100270A EP78100270A EP0000351A1 EP 0000351 A1 EP0000351 A1 EP 0000351A1 EP 78100270 A EP78100270 A EP 78100270A EP 78100270 A EP78100270 A EP 78100270A EP 0000351 A1 EP0000351 A1 EP 0000351A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- halogen
- formula
- alkoxy
- alkyl
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
- A01N41/06—Sulfonic acid amides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
Definitions
- the present invention relates to new phenoxy-phenylthio-alkanecarboxylic acid derivatives which show herbicidal and plant growth-regulating activity, processes for the preparation of these derivatives, herbicidal and plant-growth-regulating agent which contain these derivatives as active compounds and the use of the new phenoxy-phenyl-thio-alkanecarboxylic acid derivatives or the compositions containing them as herbicides and / or for regulating plant growth.
- alkyl radicals in this formula can be branched or unbranched and contain the stated number of carbon atoms.
- the alkylene bridge can be the methylene bridge, the 1- or 2-ethylene bridge can be a straight or 1- or 2-methylethyl or 1,1-dimethyl-methylene branched propylene bridge, as well as a straight or correspondingly branched butylene bridge.
- the compounds of the present invention are not very toxic to warm-blooded animals and their application poses no problems. They are stable compounds which are soluble in the usual organic solvents, such as alcohols, ethers, ketones, dimethylformamide, dimethyl sulfoxide. Application rates between 0.1 and 5 kg per hectare are normally required.
- the new active compounds of the formula I according to the present invention have herbicidal activity in the case of pre- and post-emergence use and can be used as weed compositions in monocotyledonous and dicotyledonous crops.
- This diazo solution is added dropwise at 55-60 ° to a solution of 300 ml of water, 800 ml of toluene, 225 g of potassium methyl xanthate, 85 g of sodium carbonate and 75 ml of 30% sodium hydroxide solution.
- the toluene phase is separated off. This is washed with water and, after drying over sodium sulfate in 100 ml of triethylamine, added dropwise at 70 °. 2 hours reflux, then cool and add 200 ml of 30% sodium hydroxide solution. The organic phase is separated off and distilled. 160 g of 4-chloro-3-methylmercaptoanisole are obtained.
- the new active compounds of the formula I are stable compounds which are soluble in customary organic solvents, such as alcohols, ethers, ketones, dimethylformamide, dimethyl sulfoxide, etc.
- the active substance concentrations in the agents according to the invention are 1 to 80 percent by weight and, if appropriate, can also be present in low concentrations, such as 0.05 to 1%, when used.
- biocidal active substances or agents can be added to the agents according to the invention described.
- the active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin and then evaporated in vacuo.
- the specified active ingredient is applied to the appropriate carrier substances (kaolin and chalk) and then mixed and ground with the other ingredients. Spray powder of excellent wettability and suspension is obtained. From such wettable powders, suspensions of 0.1-80% active ingredient can be obtained by dilution with water, which are suitable for weed control in plant crops.
- the active ingredient is intimately mixed and ground with the additives in suitable devices.
- a paste is obtained, from which suspensions of any desired concentration can be prepared by dilution with water.
- the new 3-phenoxy-a-phenylthioalkanecarboxylic acid derivatives of the formula I and the compositions comprising them have an excellent selective herbicidal action against weeds in various, preferably monocotyledonous crops, and they also have a plant growth-regulating action.
- a particularly preferred area of application is the selective control of, above all, dicotyledon weeds in cereal crops, especially in rice.
- the new active ingredients are preferred as e.g. 25% wettable powder or e.g. 20% emulsifiable concentrates formulated and diluted with water, applied to the plant stands post-emergent.
- Various crops and weeds are grown from the seeds in pots in the greenhouse until they reach the 4 to 6 leaf stage. Then the plants are sprayed with aqueous active ingredient emulsions (obtained from a 20% emulsifiable concentrate) in various doses. The treated plants are then under optimal conditions of light, watering, temperature (22-25 ° C) and air humidity (50-70% relative) kept. The tests were evaluated 15 days after treatment.
- Rice plants that are 25 days old are transplanted into large rectangular eternit bowls in the greenhouse. Seeds of the weeds Echinochloa crus galli, Cyperus difformis, Ammania and Rotala which are found in rice crops are then sown between the rows of rice plants.
- the bowls are well watered and kept at a temperature of approx. 25 ° and high humidity. After 12 days, when the weeds have emerged and reached the 2-3 leaf stage, the earth in the bowl is covered with a 2.5 cm high layer of water.
- the active ingredient is then applied as an emulsion concentrate by means of a pipette between the rows of plants, the emulsion concentrate being diluted and applied in such a way that it corresponds to an application amount in the field of 2 and 1 kg of active ingredient per hectare.
- the experiment is evaluated after 4 weeks.
- the tested compounds according to the present invention showed pronounced contact herbicidal activity on some plants and growth arrest on many plants as a symptom of the growth-inhibiting properties.
- Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina and Dactylis glomerata were sown in plastic trays with soil-peat-sand mixture (6: 3: 1) and watered normally.
- the accumulated grasses were cut back to a height of 4 cm weekly and sprayed with aqueous spray liquors of an active ingredient of the formula I 40 days after sowing and 1 day after the last cut.
- the amount of active ingredient was the equivalent of 5 kg of active ingredient per hectare.
- the growth of the grasses was assessed 10 and 21 days after application.
- the active substances according to the invention cause a noticeable growth inhibition both in the grasses and in the cereals.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft neue Phenoxy-phenylthio-alkancarbonsäurederivate, welche herbizide und das Pflanzenwachstum regulierende Wirkung zeigen, Verfahren zur Herstellung dieser Derivate, herbizide und das Pflanzenwachstum regulierendes Mittel welche dieser Derivate als Wirkstoffe enthalten sowie die Verwendung der neuen Phenoxy-phenyl-thio-alkancarbonsäurederivate oder der sie enthaltenden Mittel als Herbizide und/oder zur Regulierung des Pflanzenwachstums.The present invention relates to new phenoxy-phenylthio-alkanecarboxylic acid derivatives which show herbicidal and plant growth-regulating activity, processes for the preparation of these derivatives, herbicidal and plant-growth-regulating agent which contain these derivatives as active compounds and the use of the new phenoxy-phenyl-thio-alkanecarboxylic acid derivatives or the compositions containing them as herbicides and / or for regulating plant growth.
Die neuen Phenoxy-phenylthio-alkancarbonsäurederivate entsprechen der Formel I
- worin A die Cyanogruppe oder einen Rest - COB
- B einen Rest -O-N=CR1R2, -OR3,-SR4 oder -NR5R6'
- C Wasserstoff, Halogen, Cyan, C1-C4 Alkyl oder C 1-C4 Alkoxy,
- D Wasserstoff, Halogen, Cyan, Nitro, Trifluormethyl,
- E Wasserstoff, Halogen, Cyan, Nitro, C1-C4 Alkyl, C1-C4 Alkoxy, Methylsulfonyl, Dimethylsulfamoyl,
- Hal Halogen
- n die Zahl 0, 1 oder 2,
- Q eine verzweigte oder unverzweigte C1-C4 Alkylenbrücke, die unsubstituiert oder durch Halogen, C1-C4 Alkoxy, C1-C4 Alkoxycarbonyl oder Cyan substituiert sein kann,
- R1 und R2 je C1-C4 Alkyl oder eines davon Wasserstoff,
- R3 und R4 je Wasserstoff oder das Kation einer Base
- M ein Alkali-, Erdalkali-Kation oder ein Fe, Cu-, Zn-, Mn-, Ni-Kation oder ein Ammonio-Rest
- m als ganze Zahl 1, 2 oder 3 die Wertigkeit des Kations berücksichtigt, während R , Rb, Rc a c und Rd unabhängig voneinander Wasserstoff, Benzyl oder einen gegebenenfalls durch -OH, -NH2 oder C1-C4 Alkoxy substituierten C1-C4 Alkylrest bedeuten,
- M ein Alkali-, Erdalkali-Kation oder ein Fe, Cu-, Zn-, Mn-, Ni-Kation oder ein Ammonio-Rest
- R3 und R4 weiter einen C1-C18 Alkylrest, der unsubstituiert oder durch Halogen, C1-C4 Alkoxy, C1-C4 Alkylthio, C3-C8 Cycloalkyl, Nitro-oder Cyano substituiert sein kann, einen C3-C18 Alkenylrest, der unsubstituiert oder durch Halogen substituiert sein kann, einen C3-C18 Alkinylrest, einen Phenyl- oder Benzylrest der unsubstituiert oder durch Halogen, C1-C4 Alkyl, C1-C4 Alkoxy, C1-C4- Alkylthio, eine Cyano-, Nitro- oder Trifluormethylgruppe substituiert sein kann,
- R5 und R6 unabhängig voneinander je Wasserstoff, C1-C6 Alkyl, das unsubstituiert oder C1-C4 Alkoxy, Halogen, Cyano, Hydroxyl oder C1-C4 Alkoxy substituiert sein kann oder
- R5 und R6 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen 5-6 gliedrigen heterocyclischen Ring, der auch noch Stickstoff, Sauerstoff oder Schwefel als zweites Heteroatom enthalten kann und der durch C1-C4 Alkyl oder Phenyl substituiert sein kann.
- where A is the cyano group or a residue - COB
- B a residue -ON = CR 1 R 2 , -OR 3 , -SR 4 or -NR 5 R 6 '
- C hydrogen, halogen, cyan, C 1 -C 4 alkyl or C 1 -C 4 alkoxy,
- D hydrogen, halogen, cyan, nitro, trifluoromethyl,
- E hydrogen, halogen, cyan, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, methylsulfonyl, dimethylsulfamoyl,
- Hal halogen
- n is the number 0, 1 or 2,
- Q is a branched or unbranched C 1 -C 4 alkylene bridge which may be unsubstituted or substituted by halogen, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl or cyano,
- R 1 and R 2 are each C 1 -C 4 alkyl or one of them hydrogen,
- R 3 and R 4 are each hydrogen or the cation of a base
- M is an alkali, alkaline earth cation or an Fe, Cu, Zn, Mn, Ni cation or an ammonio radical
- m takes into account the valence of the cation as an integer 1, 2 or 3, while R, R b , R c ac and R d independently of one another are hydrogen, benzyl or an optionally substituted by -OH, -NH 2 or C 1 -C 4 alkoxy Are C 1 -C 4 alkyl,
- M is an alkali, alkaline earth cation or an Fe, Cu, Zn, Mn, Ni cation or an ammonio radical
- R 3 and R 4 furthermore a C 1 -C 18 alkyl radical which may be unsubstituted or substituted by halogen, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 3 -C 8 cycloalkyl, nitro- or cyano C 3 -C 18 alkenyl radical which may be unsubstituted or substituted by halogen, a C 3 -C 18 alkynyl radical, a phenyl or benzyl radical which is unsubstituted or by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy , C 1 -C 4 - alkylthio, cyano, nitro or trifluoromethyl group may be substituted,
- R 5 and R 6 are each independently hydrogen, C 1 -C 6 alkyl which may be unsubstituted or C 1 -C 4 alkoxy, halogen, cyano, hydroxyl or C 1 -C 4 alkoxy or may be substituted
- R 5 and R 6 together with the nitrogen atom to which they are attached form a 5-6-membered heterocyclic ring which can also contain nitrogen, oxygen or sulfur as the second heteroatom and which are substituted by C 1 -C 4 alkyl or phenyl can.
Die Alkylreste in dieser Formel können verzweigt oder unverzweigt sein und enthalten die angegebene Anzahl Kohlenstoffatome.The alkyl radicals in this formula can be branched or unbranched and contain the stated number of carbon atoms.
Die Alkylenbrücke kann die Methylenbrücke, die 1- oder 2-Aethylenbrucke eine gerade oder als 1- oder 2-Methyläthyl oder 1,1-Dimethyl-methylen verzweigte Propylenbrücke, wie auch eine gerade oder entsprechend verzweigte ButylenbrUcke sein.The alkylene bridge can be the methylene bridge, the 1- or 2-ethylene bridge can be a straight or 1- or 2-methylethyl or 1,1-dimethyl-methylene branched propylene bridge, as well as a straight or correspondingly branched butylene bridge.
Als 5-6 gliedrige Heterocyclen, die Reste R5 und R6 zusammen mit dem Stickstoffatom, an das sie gebunden sind bilden können, kommen die Pyrrol, Pyrrolidin, Pyridin und Piperidin in Frage, falls noch ein zweites Heteroatom im Ring ist, auch die Pyrazol-, Piperazin-, Oxazol-, Thiazol-, Morpholino-und Thiomorpholino-Ringe. Diese Ringe können auch durch C1-C4 Alkyl substituiert sein, der Piperazin-Ring auch durch Phenyl.As 5-6-membered heterocycles, the radicals R 5 and R 6 together with the nitrogen atom to which they are attached, the pyrrole, pyrrolidine, pyridine and piperidine come into question, if there is also a second heteroatom in the ring, also the Pyrazole, piperazine, oxazole, thiazole, morpholino and thiomorpholino rings. These rings can also be substituted by C 1 -C 4 alkyl, the piperazine ring also by phenyl.
Die Verbindungen vorliegender Erfindung sind wenig giftig für Warmblüter und deren Applikation wirft keine Probleme auf. Sie sind stabile Verbindungen, welche in den üblichen organischen Lösungsmitteln, wie Alkoholen, Aethern, Ketonen, Dimethylformamid, Dimethylsulfoxid löslich sind. Normalerweise werden Aufwandmengen die zwischen 0,1 und 5 kg pro Hektar liegen benötigt.The compounds of the present invention are not very toxic to warm-blooded animals and their application poses no problems. They are stable compounds which are soluble in the usual organic solvents, such as alcohols, ethers, ketones, dimethylformamide, dimethyl sulfoxide. Application rates between 0.1 and 5 kg per hectare are normally required.
Die neuen Wirkstoffe der Formel I gemäss vorliegender Erfindung besitzen Herbizidwirkung bei pre- und post-emergenter Anwendung und können in mono-und dikotylen Kulturen als Unkrautmittel eingesetzt werden.The new active compounds of the formula I according to the present invention have herbicidal activity in the case of pre- and post-emergence use and can be used as weed compositions in monocotyledonous and dicotyledonous crops.
Ferner besitzen sie günstige wachstumsregulierende Effekte (Wuchshemmung). Insbesondere hemmen sie das Wachstum von dicotylen Pflanzen. Beispiele für die nutzbringende Anwendung der erfindungsgemässen Verbindungen sind z.B.
- - die Reduktion des vegetativen Wachstums bei Soja und ähnlichen Leguminosen, was zu einer Ertragssteigerung dieser Kultur führt;
- - die Hemmung des unerwünschten WachsLums von Geiztrieben bei Tabak, dessen Haupttrieb man geschnitten hat, was der Ausbildung grössere und schönere Blätter zugute kommt;
- - die Hemmung des Wachstums von Gras und dikotyledonen Pflanzen, wie Obstbäume, Zierbäume, Gebusche und Hecken, zwecks Einsparung an Schnittarbeit.
- - the reduction of vegetative growth in soybeans and similar legumes, which leads to an increase in the yield of this culture;
- - the inhibition of the undesirable wax-lice of stinging shoots in tobacco, the main shoot of which has been cut, which benefits the formation of larger and more beautiful leaves;
- - Inhibiting the growth of grass and dicot plants, such as fruit trees, ornamental trees, bushes and hedges, in order to save on cutting work.
Die Herstellung der neuen Verbindungen der Formel I erfolgt nach an sich bekannten Methoden und kann aus den folgenden Formelschema ersehen werden.
In diesen Formeln haben A, C, D, E, Hal, n und Q die unter Formel I gegebene Bedeutung.In these formulas, A, C, D, E, Hal, n and Q have the meaning given under formula I.
Einzelne dieser Ausgangsverbindungen und deren Herstellung sind bekannt und beschrieben z.B. in den DOS 2 130 919 oder 2 333 848.Some of these starting compounds and their preparation are known and described e.g. in DOS 2 130 919 or 2 333 848.
In den letzten Jahren ist eine reichhaltige Patentliteratur über herbizid wirksame, in verschiedener Weise substituierte Diphenyläther erschienen. Dabei sind vereinzelt auch substituierte Phenoxy-phenylthio-alkancarbonsäurederivate bekanntgeworden, vgl. DOS 2 223 894.In recent years, extensive patent literature on herbicidally active, variously substituted diphenyl ethers has appeared. Substituted phenoxy-phenylthio-alkane carboxylic acid derivatives have also become known, cf. DOS 2 223 894.
Die herbizide Wirksamkeit der bekannten Phenoxyphenyl-thio-alkancarbonsäurederivate ist jedoch - insbesondere bei niedrigen Aufwandmengen - nicht befriedigend.However, the herbicidal activity of the known phenoxyphenyl-thio-alkanecarboxylic acid derivatives is unsatisfactory, especially at low application rates.
Es wurde nun überraschenderweise gefunden, dass die neuen Verbindungen der Formeln I starke herbizide Eigenschaften, insbesondere auch selektiv herbizide Wirksamkeit besitzen.It has now surprisingly been found that the new compounds of the formulas I have strong herbicidal properties, in particular also selective herbicidal activity.
Die nachfolgenden Beispiele veranschaulichen diese Herstellungsverfahren näher. Weitere in entsprechender Weise hergestellte Wirkstoffe sind in den anschliessenden Tabellen aufgeführt. Temperaturangaben beziehen sich jeweils auf Celsius-Grade, Prozentangaben auf das Gewicht.The following examples illustrate these manufacturing processes in more detail. Further active substances produced in a corresponding manner are listed in the tables below. Temperatures refer to degrees Celsius, percentages relate to weight.
- a) 12 g 4-Chlor-2-methylmerkapto-nitrobenzol werden in 50 ml Dimethylsulfoxyd mit 10 g 2,4-Dichlorphenol und 2,5 g Natriumhydroxyd auf 160° erhitzt. Nach zwei Stunden giesst man den Ansatz auf Eis und extrahiert mit Essigester.Die organische Lösung wird eingedampft und der Rückstand aus Toluol/Hexan umkristallisiert. Man erhält 16 g 2,4-Dichlor-3'-methylmerkapto-4'-nitrodiphenyläther vom Schmelzpunkt 120-122°. Die katalytische Reduktion in Dioxan mit Raney-Nickel ergibt daraus in nahezu quantitativer Ausbeute 2,4-Dichlor-3'-methylmerkapto-4'-amino-diphenyläther. Smp. 40-43°a) 12 g of 4-chloro-2-methylmerkapto-nitrobenzene are heated to 160 ° in 50 ml of dimethyl sulfoxide with 10 g of 2,4-dichlorophenol and 2.5 g of sodium hydroxide. After two hours, the mixture is poured onto ice and extracted with ethyl acetate. The organic solution is evaporated and the residue is recrystallized from toluene / hexane. 16 g of 2,4-dichloro-3'-methylmerkapto-4'-nitrodiphenyl ether of melting point 120-122 ° are obtained. The catalytic reduction in dioxane with Raney nickel gives 2,4-dichloro-3'-methylmerkapto-4'-amino-diphenyl ether in almost quantitative yield. Mp 40-43 °
- b) 65 g dieser Verbindung werden mit 300 ml Wasser und 144 ml konz. Schwefelsäure vermischt und auf 0° gekühlt. Durch Umsatz mit.einer 5%-iger Natriumnitritlösung bei 0-5° bereitet man eine Diazoniumsalzlösung, in die nach einer Stunde bei 0° eine Lösung von 39,5 g Kaliumjodid in 370 ml Wasser eingetropft wird. Es bildet sich ein klebriger Niederschlag, der nach 2 Stunden durch Zugabe von Methylenchlorid gelöst wird. Die organische Phase wird abgetrennt und eingedampft. Der Rückstand wird mehrmals mit warmem Hexan extrahiert und die vereinigten Hexanextrakte eingeengt und abgekühlt. Durch Kristallisation erhält man 67 g 2,4-Dichlor-3'-methylmerkapto-4-jod- diphenyläther.b) 65 g of this compound are concentrated with 300 ml of water and 144 ml. Mixed sulfuric acid and cooled to 0 °. By reacting with a 5% sodium nitrite solution at 0-5 °, a diazonium salt solution is prepared, into which a solution is obtained after one hour at 0 ° of 39.5 g of potassium iodide is dropped in 370 ml of water. A sticky precipitate forms, which is dissolved after 2 hours by adding methylene chloride. The organic phase is separated off and evaporated. The residue is extracted several times with warm hexane and the combined hexane extracts are concentrated and cooled. Crystallization gives 67 g of 2,4-dichloro-3'-methylmerkapto-4-iododiphenyl ether.
- c) 15 g dieser Verbindung werden in 50 ml N-Methyl-2-pyrrolidon unter Stickstoff mit 3,5 g Kupfer-I-cyanid bei 140° verrührt. Nach 3 Stunden kühlt man ab und verrührt mit 500 ml Wasser und 20 ml konz. Ammoniak. Der Niederschlag wird gesammelt, getrocknet und aus Toluol/Hexan umkristallisiert. Man erhält 10 g 2,4-Dichlor-3'-methylmerkapto-4'-cyan-diphenyläther. Smp. 84°c) 15 g of this compound are stirred in 50 ml of N-methyl-2-pyrrolidone under nitrogen with 3.5 g of copper-I-cyanide at 140 °. After 3 hours, the mixture is cooled and stirred with 500 ml of water and 20 ml of conc. Ammonia. The precipitate is collected, dried and recrystallized from toluene / hexane. 10 g of 2,4-dichloro-3'-methylmerkapto-4'-cyanodiphenyl ether are obtained. Mp 84 °
- d) 5 g dieser Verbindung werden in 20 ml Bromessigsäure- methylester am Rückfluss erhitzt. Nach 8 Stunden wird der Bromessigsäuremethylester abdestilliert und der Ruckstand chromatographisch gereinigt. Man erhält neben unverändertem Ausgangsprodukt die Titelverbindung mit Schmelzpunkt 95°.d) 5 g of this compound are refluxed in 20 ml of methyl bromoacetate. After 8 hours, the methyl bromoacetate is distilled off and the residue is purified by chromatography. In addition to the unchanged starting product, the title compound with a melting point of 95 ° is obtained.
- a) Eine Lösung von 400 g 2,4-Di-(2',4'-dichlorphenoxy)-nitrobenzol, 64 g 85%-igem Kaliumhydroxyd und 700 ml Dioxan wird mit 45 g Methylenmerkaptan bei 50-70° versetzt. Nach einer Stunde wird das Lösungsmittel am Vakuum abgezogen und der Rückstand mit Toluol aufgenommen. Die durch Waschen der Lösung mit verdünnter Natronlauge vom entstandenen 2,4-Dichlorphenol befreite Lösung wird zu einer siedenden Mischung von 500 g Eisenpulver, 500 g Alkohol und 50 ml konz. Salzsäure getropft. Nach 15 Stunden RUckfluss wird abgekühlt, alkalisch gemacht mit 30%-iger Natronlauge, vom Eisenlamm abgesaugt und der Filterkuchen mit Toluol gewaschen. Die organische Phase des Filtrats wird eingedampft und destilliert. Man erhält 192,5 g der Verbindung Beispiel la, Sdp. 170°/0,1a) A solution of 400 g of 2,4-di- (2 ', 4'-dichlorophenoxy) nitrobenzene, 64 g of 85% potassium hydroxide and 700 ml of dioxane is mixed with 45 g of methylene mercaptan at 50-70 °. After one hour the solvent is removed in vacuo and the residue is taken up in toluene. The solution freed from the resulting 2,4-dichlorophenol by washing the solution with dilute sodium hydroxide solution is concentrated to a boiling mixture of 500 g iron powder, 500 g alcohol and 50 ml. Dropped hydrochloric acid. After 15 hours of reflux, the mixture is cooled, made alkaline with 30% sodium hydroxide solution, suction filtered from the iron lamb and the filter cake is washed with toluene. The organic phase of the filtrate is evaporated and distilled. 192.5 g of the compound Example la, bp 170 ° / 0.1 are obtained
- b) 180 g der Verbindung Beispiel 3a werden in 1,5 Liter Eisessig gelöst und mit 153 ml konz. Salzsäure versetzt. Durch Eintropfen einer Lösung von 41,5 g Natriumnitrit in 100 ml Wasser bei 5° wird eine Dixanlösung hergestellt, die nach dem Zerstören des Nitritüberschusses mit Sulfaminsäure bei 75-90° in 2 Liter einer 1°%-iger Salzsäure und 118 g Kupfer (I)chlorid getropft wird. Nach 1 Stunde extrahiert man mit Toluol, dampft die organische Phase ein und destilliert den Rückstand. Man erhält 172 g 3-(2',4'-Dichlorphenoxy)-6-chlormethylmerkaptobenzol Sdp. 158° /0,05 .b) 180 g of the compound Example 3a are dissolved in 1.5 liters of glacial acetic acid and concentrated with 153 ml. Hydrochloric acid added. A solution of 41.5 g of sodium nitrite in 100 ml of water at 5 ° is added dropwise to produce a dixan solution which, after destroying the excess nitrite with sulfamic acid at 75-90 ° in 2 liters of 1% hydrochloric acid and 118 g of copper ( I) chloride is dropped. After 1 hour, the mixture is extracted with toluene, the organic phase is evaporated and the residue is distilled. 172 g of 3- (2 ', 4'-dichlorophenoxy) -6-chloromethylmercaptobenzene, bp 158 ° / 0.05, are obtained.
- c) 140 g der Verbindung aus Beispiel 3b werden mit 105 ml 2-Brompropionsäuremethylester und einem Kristall Kaliumjodid 16 Stunden am RUckfluss gekocht. Die anschliessende Destillation ergibt 150 g der Titelverbindung. Sdp. 186°/0,09c) 140 g of the compound from Example 3b are refluxed for 16 hours with 105 ml of methyl 2-bromopropionate and a crystal of potassium iodide. The subsequent distillation gives 150 g of the title compound. Bp. 186 ° / 0.09
a) 241 g 2-Chlor-5-methoxy-anilin werden unter starkem Rühren zu 310 ml Wasser und 385 ml konz. Salzsäure gegeben, gefolgt von 750 g Eis. Man kühlt die Mischung auf 10° und gibt auf ein Mal eine Lösung von 111 g Natriumnitrit in 150 ml Wasser dazu, dabei steigt die Temperatur rasch auf 10°. Nach 30 Minuten wird der Nitritüberschuss mit Sulfaminsäure entfernt und die Lösung durch Filtration gelöst.a) 241 g of 2-chloro-5-methoxy-aniline are concentrated to 310 ml of water and 385 ml of conc. Hydrochloric acid, followed by 750 g of ice. The mixture is cooled to 10 ° and a solution of 111 g is added all at once Sodium nitrite in 150 ml of water, the temperature quickly rises to 10 °. After 30 minutes, the excess nitrite is removed with sulfamic acid and the solution is dissolved by filtration.
Diese Diazolösung wird bei 55-60° zu einer Lösung von 300 ml Wasser, 800 ml Toluol, 225 g Kaliummethylxanthogenat, 85 g Natriumcarbonat und 75 ml 30% Natronlauge getropft. Nach beendeter, sehr lebhafter Gasentwicklung trennt man die toluolische Phase ab. Diese wird mit Wasser gewaschen und nach dem Trocknen über Natriumsulfat in 100 ml Triäthylamin bei 70° getropft. 2 Stunden Rückfluss, dann abkühlen und Zugabe von 200 ml 30%-iger Natronlauge. Die organische Phase wird abgetrennt und destilliert. Man erhält 160 g 4-Chlor-3-methylmercaptoanisol. Sdp. 138-145°/11This diazo solution is added dropwise at 55-60 ° to a solution of 300 ml of water, 800 ml of toluene, 225 g of potassium methyl xanthate, 85 g of sodium carbonate and 75 ml of 30% sodium hydroxide solution. After the very vigorous evolution of gas has ended, the toluene phase is separated off. This is washed with water and, after drying over sodium sulfate in 100 ml of triethylamine, added dropwise at 70 °. 2 hours reflux, then cool and add 200 ml of 30% sodium hydroxide solution. The organic phase is separated off and distilled. 160 g of 4-chloro-3-methylmercaptoanisole are obtained. Bp 138-145 ° / 11
152,5 g dieser Verbindung werden analog J.Am.Chem. Soc. 79,720 zu 110 g 4-Chlor-3-methylmerkaptophenol verseift. Sdp. 117-121°/0,03152.5 g of this compound are analogous to J.Am.Chem. Soc. 79.720 to 110 g of 4-chloro-3-methylmercaptophenol saponified. Bp 117-121 ° / 0.03
b) 50 g 4-Chlor-3-methylmercaptophenol, 62 g 3,4-Dichlorbenzotrifluorid und 12 g Natriumhydroxyd werden in 150 ml Dimethylsulfoxyd 6 Stunden bei 142° verrührt. Dann giesst man das Reaktionsgemisch auf Eis, extrahiert mit Toluol und destilliert die organ. Phase. Man erhält 81 g 3-(2'-Chlor-4-trifluormethyl- phenoxy)-6-chlor-thioanisol vom Sdp. 158°/0,4b) 50 g of 4-chloro-3-methylmercaptophenol, 62 g of 3,4-dichlorobenzotrifluoride and 12 g of sodium hydroxide are stirred in 150 ml of dimethyl sulfoxide at 142 ° for 6 hours. Then the reaction mixture is poured onto ice, extracted with toluene and the organ is distilled. Phase. 81 g of 3- (2'-chloro-4-trifluoromethyl-phenoxy) -6-chloro-thioanisole are obtained, boiling at 158 ° / 0.4
c) 20 g dieser Verbindung aus Beispiel 4 b werden mit 30 ml 2-Brompropionsäuremethylester bei 190° 20 Stunden verrührt, dann erfolgt Destilliation im Kugelrohr. Man erhält 21 g der Titelverbindung. Sdp. 200°/0,13c) 20 g of this compound from Example 4 b are stirred with 30 ml of 2-bromopropionic acid methyl ester at 190 ° for 20 hours, followed by distillation in a Kugelrohr. 21 g of the title compound are obtained. Bp 200 ° / 0.13
- a) 187 g Hydrochinonmonomethyläther, 324 g 3,4-dichlorbenzotrifluorid und 60 g Natriumhydroxyd werden in 500 ml Dimethylsulfoxyd 5 Stunden bei 140° verrührt. Man gibt die Reaktionslösung auf Eis und sammelt den gebildeten 2-Chlor-4-trifluormethyl-4'-methoxy-diphenyläther durch Nutschen. 315 g dieser Verbindung (Smp. 60-63°) werden in 1 Liter Eisessig mit 170 g einer Mischsäure aus 67 g rauchender Salpetersäure und 103 g konz. Schwefelsäure bei 10° tropfenweise versetzt. Man lässt noch 3 Stunden nachrUhren, dann sammelt man den Niederchlag durch Nutschen. Man erhält nach dem Trocknen 291 g 4-(2'-Chlor-4-trifluormethyl- phenoxy)-2-nitro-anisol. Smp. 90-92°.a) 187 g of hydroquinone monomethyl ether, 324 g of 3,4-dichlorobenzotrifluoride and 60 g of sodium hydroxide are stirred in 500 ml of dimethyl sulfoxide at 140 ° for 5 hours. The reaction solution is poured onto ice and the 2-chloro-4-trifluoromethyl-4'-methoxy-diphenyl ether formed is collected by suction filtering. 315 g of this compound (mp. 60-63 °) in 1 liter of glacial acetic acid with 170 g of a mixed acid from 67 g of smoking nitric acid and 103 g of conc. Sulfuric acid added dropwise at 10 °. You have to stir for another 3 hours, then you collect the precipitate by suction. After drying, 291 g of 4- (2'-chloro-4-trifluoromethylphenoxy) -2-nitro-anisole are obtained. Mp 90-92 °.
- b) 318 g der Verbindung Beispiel 5a werden in Dioxan mit Nickel als Katalysator hydriert. Durch Abtrennen des Katalysators und Eindampfen der Reaktionslösung erhält man 300 g 4-(2'-Chlor-4'-trifluormethyl-phenoxy)-2-amino-anisol. Sdp. 185°/0,4 (Kugelrohr), Smp. 36-38°.b) 318 g of the compound Example 5a are hydrogenated in dioxane with nickel as a catalyst. By separating the catalyst and evaporating the reaction solution, 300 g of 4- (2'-chloro-4'-trifluoromethyl-phenoxy) -2-amino-anisole are obtained. Bp 185 ° / 0.4 (Kugelrohr), mp 36-38 °.
- c) 97 g der Verbindung Beispiel 5b werden in 100 ml Dimethylformamid, 100 ml konz. Salzsäure und 100 ml Wasser mit Natriumnitrit nach Beispiel 4a diazotiert und mit Kaliummethylxanthogenat zu 4-(2'-Chlor-4'-trifluormethyl-phenoxy)-2-methyl- mercapto-anisol umgesetzt. Sdp. 150-155°/0,01c) 97 g of the compound Example 5b are concentrated in 100 ml of dimethylformamide, 100 ml. Hydrochloric acid and 100 ml of water diazotized with sodium nitrite according to Example 4a and reacted with potassium methyl xanthate to give 4- (2'-chloro-4'-trifluoromethyl-phenoxy) -2-methyl-mercapto-anisole. Bp 150-155 ° / 0.01
-
d) 8 g der Verbindung Beispiel 5c mit 2-Brompropionsäureäthylester analog Beispiel 3c umgesetzt ergeben die Titelverbindung. Sdp. 190°/0,001 (Kugelrohr )
Die neuen Wirkstoffe der Formel I sind stabile Verbindungen, welche in üblichen organischen Lösungsmitteln, wie Alkoholen, Aethern, Ketonen, Dimethylformamid, Dimethylsulfoxyd etc. löslich sind.The new active compounds of the formula I are stable compounds which are soluble in customary organic solvents, such as alcohols, ethers, ketones, dimethylformamide, dimethyl sulfoxide, etc.
Die Herstellung erfindungsgemässer Mittel erfolgt in an sich bekannter Weise durch inniges Vermischen und Vermahlen von Wirkstoffen der allgemeinen Formel I mit geeigneten Trägerstoffen und/oder Verteilungsmitteln, gegebenenfalls unter Zusatz von gegenüber den Wirkstoffen inerten Antischaum-, Netz-, Dispersions- und/ oder Lösungsmitteln, Dfe Wirkstoffe können in den folgenden Aufarbeitungsformen vorliegen und angewendet werden:
- Feste Aufarbeitungsformen: Stäubemittel, Streumittel, Granulate, Umhüllungsgranulate, Imprägnierungsgranulate und Homogengranulate;
- In Wasser Dispergierbare Wirkstoffkonzentrate: Spritzpulver (wettable powder), Paste, Emulsionen; Emulsionskonzentrate
- Flüssige Aufarbeitungsformen: Lösungen
- Solid processing forms: dusts, scattering agents, granules, coating granules, impregnation granules and homogeneous granules;
- Active ingredient concentrates dispersible in water: wettable powder, paste, emulsions; Emulsion concentrates
- Liquid processing forms: solutions
Die Wirkstoffkonzentrationen betragen in den erfindungsgemässen Mitteln 1 bis 80 Gewichtsprozent und können gegebenenfalls bei der Anwendung auch in geringen Konzentrationen wie etwa 0,05 bis 1% vorliegen.The active substance concentrations in the agents according to the invention are 1 to 80 percent by weight and, if appropriate, can also be present in low concentrations, such as 0.05 to 1%, when used.
Den beschriebenen erfindungsgemässen Mitteln lassen sich andere biozide Wirkstoffe oder Mittel beimischen.Other biocidal active substances or agents can be added to the agents according to the invention described.
Die folgenden Formulierungsbeispiele sollen die Herstellung von festen und flüssigen Aufbereitungsformen näher erläutern.The following formulation examples are intended to explain the production of solid and liquid preparation forms in more detail.
Zur Herstellung eines 25%igen Emulsionskonzentrates werden
- 25 Teile eines Wirkstoffes der Formel I,
- 5 Teile einer Mischung von Nonylphenolpolyoxyäthylen oder Calciumdodecylbenzolsulfat,
- 15 Teile Cyclohexanon,
- 55 Teile Xylol
miteinander vermischt. Dieses Konzentrat kann mit Wasser zu Emulsionen auf geeigneten Konzentrationen von z.B. 0,1 bis 10% verdünnt werden. Solche Emulsionen eigenen sich zur Bekämpfung von Unkräutern in Kulturpflanzungen.To prepare a 25% emulsion concentrate
- 25 parts of an active ingredient of the formula I,
- 5 parts of a mixture of nonylphenol polyoxyethylene or calcium dodecylbenzenesulfate,
- 15 parts of cyclohexanone,
- 55 parts of xylene
mixed together. This concentrate can be diluted with water to emulsions to suitable concentrations of, for example, 0.1 to 10%. Such emulsions are suitable for controlling weeds in crops.
Zur Herstellung eines 5%igen Granulates werden die folgenden Stoffe verwendet:
- 5 Teile eines der Wirkstoffe der Formel I,
- 0,25 Teile Epichlorhydrin,
- 0,25 Teile Cetylpolyglykoläther,
- 3,50 Teile Polyäthylengylkol,
- 91 Teile Kaolin (Korngrösse: 0,3-08 mm).
- 5 parts of one of the active ingredients of the formula I,
- 0.25 parts epichlorohydrin,
- 0.25 parts of cetyl polyglycol ether,
- 3.50 parts of polyethylene glycol,
- 91 parts of kaolin (grain size: 0.3-08 mm).
Die Aktivsubstanz wird mit Epichlorhydrin vermischt und in 6 Teilen Aceton gelöst, hierauf wird Polyäthylenglykol und Cetylpolyglykoläther zugesetzt. Die so erhaltene Lösung wird auf Kaolin aufgesprüht und anschliessend im Vacuum verdampft.The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin and then evaporated in vacuo.
Zur Herstellung eines a) 70%igen und b) 10%igen Spritzpulvers werden folgende Bestandteile verwendet:
- a) 70 Teile eines Wirkstoffes der Formel I, 5 Teile Natriumdibutylnaphtylsulfonat, 3 Teile Naphthalinsulfonsäuren-Phenolsulfonsäuren-Formaldehyd-Kondensat 3:2:1, 10 Teile Kaolin, 12 Teile Champagne-Kreide;
- b) 10 Teile eines Wirkstoffes der Formel I, 3 Teile Gemisch der Natriumsalze von gesättigten Fettalkoholsulfaten, 5 Teile Naphthalinsulfonsäuren-Formaldehyd-Kondensat, 82 Teile Kaolin.
- a) 70 parts of an active ingredient of the formula I, 5 parts of sodium dibutyl naphthyl sulfonate, 3 parts of naphthalenesulfonic acid-phenolsulfonic acid-formaldehyde condensate 3: 2: 1, 10 parts of kaolin, 12 parts of champagne chalk;
- b) 10 parts of an active ingredient of the formula I, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulfates, 5 parts of naphthalenesulfonic acid-formaldehyde condensate, 82 parts of kaolin.
Der angegebene Wirkstoff wird auf die entsprechenden Trägerstoffe (Kaolin und Kreide) aufgezogen und anschliessend mit den Übrigen Bestandteilen vermischt und vermahlen. Man erhält Spritzpulver von vorzüglicher Benetzbarkeit und Schwebefähigkeit. Aus solchen Spritzpulvern können durch Verdünnen mit Wasser Suspensionen von 0,1-80% Wirkstoff erhalten werden, die sich zur Unkrautbekämpfung in Pflanzenkulturen eignen.The specified active ingredient is applied to the appropriate carrier substances (kaolin and chalk) and then mixed and ground with the other ingredients. Spray powder of excellent wettability and suspension is obtained. From such wettable powders, suspensions of 0.1-80% active ingredient can be obtained by dilution with water, which are suitable for weed control in plant crops.
Zur Herstellung einer 45%igen Paste werden folgende Stoffe verwendet:
- 45 Teile eines Wirkstoffes der Formel I,
- 5 Teile Natriumaluminiumsilikat,
- 14 Teile Cetylpolyglykoläther mit 8 Mol Aethylenoxid,
- 1 Teil Oleylpolyglykoläther mit 5 Mol Aethylenoxid,
- 2 Teile Spindeloel,
- 10 Teile Polyäthynglykol,
- 23 Teile Wasser.
- 45 parts of an active ingredient of the formula I,
- 5 parts of sodium aluminum silicate,
- 14 parts of cetyl polyglycol ether with 8 moles of ethylene oxide,
- 1 part of oleyl polyglycol ether with 5 moles of ethylene oxide,
- 2 parts spindle oil,
- 10 parts of polyethylene glycol,
- 23 parts of water.
Der Wirkstoff wird mit den Zuschlagstoffen in dazu geeigneten Geräten innig vermischt und vermahlen. Man erhält eine Paste, aus der sich durch Verdünnen mit Wasser Suspensionen jeder gewünschten Konzentration herstellen lassen.The active ingredient is intimately mixed and ground with the additives in suitable devices. A paste is obtained, from which suspensions of any desired concentration can be prepared by dilution with water.
Die neuen 3-Phenoxy-a-phenylthioalkancarbonsäurederivate der Formel I sowie die sie enthaltenden Mittel besitzen eine ausgezeichnete selektiv-herbizide Wirkung gegen Unkräuter in verschiedenen, vorzugsweise monokotylen Kulturpflanzenbeständen, ferner üben sie eine das Pflanzenwachstum regulierende Wirkung aus.The new 3-phenoxy-a-phenylthioalkanecarboxylic acid derivatives of the formula I and the compositions comprising them have an excellent selective herbicidal action against weeds in various, preferably monocotyledonous crops, and they also have a plant growth-regulating action.
Ein besonders bevorzugtes Einsatzgebiet ist die selektive Bekämpfung von vor allem dikotylen Unkräutern in Getreidekulturen, speziell in Reis.A particularly preferred area of application is the selective control of, above all, dicotyledon weeds in cereal crops, especially in rice.
Obwohl die neuen Wirkstoffe der Formel I bei pre-und post-emergenter Anwendung wirksam sind, scheint die post-emergente Applikation als Kontaktherbizide den Vorzug zu verdienen, obwohl auch der pre-emergente Einsatz von Interesse ist.Although the new active ingredients of formula I are effective in pre- and post-emergent use, post-emergent application as contact herbicides seems to deserve preference, although pre-emergent use is also of interest.
Bevorzugt werden die neuen Wirkstoffe als z.B. 25%ige Spritzpulver oder z.B. 20%ige emulgierbare Konzentrate formuliert und mit Wasser verdünnt, auf die Pflanzenbestände post-emergent appliziert.The new active ingredients are preferred as e.g. 25% wettable powder or e.g. 20% emulsifiable concentrates formulated and diluted with water, applied to the plant stands post-emergent.
Herbizide Wirkung bei Applikation der Wirkstoffe nach dem Auflaufen der Pflanzen (post-emergent.)Herbicidal effect when the active ingredients are applied after the plants have emerged (post-emergent.)
Verschiedene Kulturpflanzen und Unkräuter werden aus den Samen in Töpfe im Gewächshaus aufgezogen, bis sie das 4- bis 6-Blatt-Stadium erreicht haben. Dann werden die Pflanzen mit wässerigen Wirkstoffemulsionen (erhalten aus einem 20%-igen emulgierbaren Konzentrat) in verschiedenen Dosierungen gespritzt. Die behandelten Pflanzen werden dann bei optimalen Bedingungen von Licht, Begiessung, Temperatur (22-25°C) und Luftfeuchtigkeit (50-70% relativ) gehalten. 15 Tage nach Behandlung werfolgte die Auswertung der Versuche.Various crops and weeds are grown from the seeds in pots in the greenhouse until they reach the 4 to 6 leaf stage. Then the plants are sprayed with aqueous active ingredient emulsions (obtained from a 20% emulsifiable concentrate) in various doses. The treated plants are then under optimal conditions of light, watering, temperature (22-25 ° C) and air humidity (50-70% relative) kept. The tests were evaluated 15 days after treatment.
In diesem Versuch hat die Verbindung No. 1 sämtliche getestete dikotylen Pflanzen und Unkräuter stark geschädigt. Die monokotylen Kulturen wurden grösstenteils geschont während die Ungräser nur leicht bis mittelstark geschädigt wurden.In this experiment, compound no. 1 All dicotyledonous plants and weeds tested were severely damaged. The monocot crops were largely spared while the grasses were only slightly to moderately damaged.
Reispflänzchen, welche 25 Tage alt sind, werden im Gewächshaus in grosse rechteckige Eternitschalen verpflanzt. Zwischen die Reihen der Reispflanzen werden dann Samen der in Reiskulturen vorkommenden Unkräuter Echinochloa crus galli, Cyperus difformis, Ammania und Rotala gesät. Die Schalen werden gut bewässert und bei einer Temperatur von ca. 25° und hoher Luftfeuchtigkeit gehalten. Nach 12 Tagen, wenn die Unkräuter aufgelaufen sind und das 2-3 Blattstadium erreicht haben, wird die Erde in der Schale mit einer 2,5 cm hohen Schicht Wasser bedeckt. Der Wirkstoff wird dann als Emulsionenskonzentrat mittels einer Pipette zwischen die Pflanzenreihen appliziert, wobei man das Emulsionskonzentrat so verdünnt und aufträgt, dass es einer Applikationsmenge im Feld von 2 und 1 kg Wirkstoff pro Hektar entspricht. Der Versuch wird nach 4 Wochen ausgewertet.Rice plants that are 25 days old are transplanted into large rectangular eternit bowls in the greenhouse. Seeds of the weeds Echinochloa crus galli, Cyperus difformis, Ammania and Rotala which are found in rice crops are then sown between the rows of rice plants. The bowls are well watered and kept at a temperature of approx. 25 ° and high humidity. After 12 days, when the weeds have emerged and reached the 2-3 leaf stage, the earth in the bowl is covered with a 2.5 cm high layer of water. The active ingredient is then applied as an emulsion concentrate by means of a pipette between the rows of plants, the emulsion concentrate being diluted and applied in such a way that it corresponds to an application amount in the field of 2 and 1 kg of active ingredient per hectare. The experiment is evaluated after 4 weeks.
In diesem Versuch hat die Verbindung No. 1 die dikotylen Unkräuter Ammania und Rotala schwer sowie das Gras Cyperus difformis merklich geschädigt. Der Reis blieb ungeschädigt.In this experiment, compound no. 1 the dicotyledon weeds Ammania and Rotala heavily damaged and the grass Cyperus difformis noticeably damaged. The rice remained undamaged.
Die geprUften Verbindungen gemäss vorliegender Erfindung zeigten auf einigen Pflanzen ausgeprägte kontaktherbizide Wirkung und auf vielen Pflanzen Wachstumsstillstand als Symptom der wachstumshemmenden Eigenschaften.The tested compounds according to the present invention showed pronounced contact herbicidal activity on some plants and growth arrest on many plants as a symptom of the growth-inhibiting properties.
In Kunststoffschalen mit Erde-Torf-Sand-Gemisch (6:3:1) wurden Samen der Gräser Lolium perenne, Poa pratensis, Festuca ovina und Dactylis glomerata ausgesät und normal bewässert. Die aufgelaufenen Gräser wurden wöchentlich bis auf 4 cm Höhe zuruckgeschnitten und 40 Tage nach der Aussaat und 1 Tag nach dem letzten Schnitt mit wässerigen SpritzbrUhen eines Wirkstoffs der Formel I bespritzt. Die Wirkstoffmenge betrug umgerechnet 5 kg Aktivsubstanz pro Hektar. 10 und 21 Tage nach Applikation wurde das Wachstum der Gräser beurteilt.Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina and Dactylis glomerata were sown in plastic trays with soil-peat-sand mixture (6: 3: 1) and watered normally. The accumulated grasses were cut back to a height of 4 cm weekly and sprayed with aqueous spray liquors of an active ingredient of the formula I 40 days after sowing and 1 day after the last cut. The amount of active ingredient was the equivalent of 5 kg of active ingredient per hectare. The growth of the grasses was assessed 10 and 21 days after application.
In Kunststoffbechern wurde Sommerweizen (Triticum aestivum), Sommergerste (Hordeum vulgare) und Roggen (Secale) in sterilisierter Erde angesät und im Gewächshaus gezogen. Die Getreidesprösslinge werden 5 Tage nach Aussaat mit einer Spritzbrühe des Wirkstoffs behandelt. Die Blattapplikation entsprach 6 kg Wirkstoff pro Hektar. Die Auswertung erfolgt nach 21 Tage.Summer wheat (Triticum aestivum), spring barley (Hordeum vulgare) and rye (Secale) were sown in sterilized soil in plastic cups and grown in the greenhouse. The grain sprouts are treated with a spray mixture of the active ingredient 5 days after sowing. The leaf application corresponded to 6 kg of active ingredient per hectare. The evaluation takes place after 21 days.
Die erfindungsgemässen Wirkstoffe bewirken eine merkliche Wuchshemmung sowohl bei den Gräsern wie beim Getreide.The active substances according to the invention cause a noticeable growth inhibition both in the grasses and in the cereals.
Claims (13)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH8426/77 | 1977-07-07 | ||
CH842677 | 1977-07-07 | ||
CH92978 | 1978-01-27 | ||
CH929/78 | 1978-01-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0000351A1 true EP0000351A1 (en) | 1979-01-24 |
Family
ID=25686139
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100270A Ceased EP0000351A1 (en) | 1977-07-07 | 1978-06-29 | Phenoxy-phenyl-thio-alkanecarboxylic acid derivatives method for their preparation and their use as herbicides and plant growth regulators |
Country Status (15)
Country | Link |
---|---|
US (1) | US4349377A (en) |
EP (1) | EP0000351A1 (en) |
JP (1) | JPS5416438A (en) |
AR (1) | AR221487A1 (en) |
AT (1) | AT358557B (en) |
AU (1) | AU522170B2 (en) |
BR (1) | BR7804382A (en) |
CA (1) | CA1108172A (en) |
CS (1) | CS222267B2 (en) |
DD (1) | DD138142A5 (en) |
ES (1) | ES471526A1 (en) |
HU (1) | HU182473B (en) |
IL (1) | IL55085A (en) |
IT (1) | IT1096916B (en) |
TR (1) | TR20047A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0025773A1 (en) * | 1979-09-13 | 1981-03-25 | Ciba-Geigy Ag | Alkylcarboxylic acid derivatives that contain sulphur and that show a herbicidal and plant growth controlling activity, their preparation and use |
EP0089573A1 (en) * | 1982-03-20 | 1983-09-28 | BASF Aktiengesellschaft | Silylalkyl esters of mercaptalkyl acids, process for their preparation and their application to combating undesired plant growth |
EP0033885B1 (en) * | 1980-02-08 | 1984-03-21 | Bayer Ag | Process for the preparation of (2-chloro-4-trifluormethyl-phenyl)-(3-methoxy-phenyl)-ether |
Families Citing this family (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4419123A (en) * | 1981-10-19 | 1983-12-06 | Rohm And Haas Company | Herbicidal 4-trifluoromethyl-3'-carbon-substituted-4'-substituted diphenyl ethers |
AU557324B2 (en) * | 1981-12-25 | 1986-12-18 | Sumitomo Chemical Company, Limited | Tetrahydro phthalimide compounds |
JPS59212472A (en) * | 1983-05-16 | 1984-12-01 | Sumitomo Chem Co Ltd | 4,5,6,7-tetrahydro-2h-isoindole-1,3-dione derivative, its production and herbicide containing the same as active constituent |
US4902832A (en) * | 1983-08-31 | 1990-02-20 | Sumitomo Chemical Company, Limited | 2-Substituted phenyl-4,5,6,7-tetrahydro-2H-isoindole-1,3-diones, and their production and use |
JPS6054362A (en) * | 1983-08-31 | 1985-03-28 | Sumitomo Chem Co Ltd | Tetrahydrophthalimide derivative, its preparation and herbicide containing said derivative as active component |
US4600432A (en) * | 1984-07-25 | 1986-07-15 | Agro-Kanesho Co., Ltd. | Propionic acid derivatives and herbicides employing them |
EP0302203B1 (en) * | 1987-08-05 | 1992-10-28 | Dowelanco | Herbicidal fluorophenoxyphenoxyalkanoic acids and derivatives thereof |
DE3928988A1 (en) * | 1989-09-01 | 1991-03-07 | Bayer Ag | ARYLOXYNAPHTHALINE DERIVATIVES |
EP2654433B1 (en) | 2010-12-21 | 2017-08-30 | Bayer Cropscience LP | Sandpaper mutants of bacillus and methods of their use to enhance plant growth, promote plant health and control diseases and pests |
BR112014005654A2 (en) | 2011-09-12 | 2017-03-28 | Bayer Cropscience Lp | methods to improve health and promote plant growth and / or fruit ripening |
US11957072B2 (en) | 2020-02-06 | 2024-04-16 | Deere & Company | Pre-emergence weed detection and mitigation system |
US11079725B2 (en) | 2019-04-10 | 2021-08-03 | Deere & Company | Machine control using real-time model |
US11672203B2 (en) | 2018-10-26 | 2023-06-13 | Deere & Company | Predictive map generation and control |
US11589509B2 (en) | 2018-10-26 | 2023-02-28 | Deere & Company | Predictive machine characteristic map generation and control system |
US11240961B2 (en) | 2018-10-26 | 2022-02-08 | Deere & Company | Controlling a harvesting machine based on a geo-spatial representation indicating where the harvesting machine is likely to reach capacity |
US11641800B2 (en) | 2020-02-06 | 2023-05-09 | Deere & Company | Agricultural harvesting machine with pre-emergence weed detection and mitigation system |
US11653588B2 (en) | 2018-10-26 | 2023-05-23 | Deere & Company | Yield map generation and control system |
US11178818B2 (en) | 2018-10-26 | 2021-11-23 | Deere & Company | Harvesting machine control system with fill level processing based on yield data |
US11467605B2 (en) | 2019-04-10 | 2022-10-11 | Deere & Company | Zonal machine control |
US11778945B2 (en) | 2019-04-10 | 2023-10-10 | Deere & Company | Machine control using real-time model |
US11234366B2 (en) | 2019-04-10 | 2022-02-01 | Deere & Company | Image selection for machine control |
US11477940B2 (en) | 2020-03-26 | 2022-10-25 | Deere & Company | Mobile work machine control based on zone parameter modification |
US11592822B2 (en) | 2020-10-09 | 2023-02-28 | Deere & Company | Machine control using a predictive map |
US11946747B2 (en) | 2020-10-09 | 2024-04-02 | Deere & Company | Crop constituent map generation and control system |
US11845449B2 (en) | 2020-10-09 | 2023-12-19 | Deere & Company | Map generation and control system |
US11871697B2 (en) | 2020-10-09 | 2024-01-16 | Deere & Company | Crop moisture map generation and control system |
US11675354B2 (en) | 2020-10-09 | 2023-06-13 | Deere & Company | Machine control using a predictive map |
US11927459B2 (en) | 2020-10-09 | 2024-03-12 | Deere & Company | Machine control using a predictive map |
US11825768B2 (en) | 2020-10-09 | 2023-11-28 | Deere & Company | Machine control using a predictive map |
US11474523B2 (en) | 2020-10-09 | 2022-10-18 | Deere & Company | Machine control using a predictive speed map |
US11635765B2 (en) | 2020-10-09 | 2023-04-25 | Deere & Company | Crop state map generation and control system |
US11983009B2 (en) | 2020-10-09 | 2024-05-14 | Deere & Company | Map generation and control system |
US12013245B2 (en) | 2020-10-09 | 2024-06-18 | Deere & Company | Predictive map generation and control system |
US11650587B2 (en) | 2020-10-09 | 2023-05-16 | Deere & Company | Predictive power map generation and control system |
US11889788B2 (en) | 2020-10-09 | 2024-02-06 | Deere & Company | Predictive biomass map generation and control |
US11727680B2 (en) | 2020-10-09 | 2023-08-15 | Deere & Company | Predictive map generation based on seeding characteristics and control |
US11895948B2 (en) | 2020-10-09 | 2024-02-13 | Deere & Company | Predictive map generation and control based on soil properties |
US11849672B2 (en) | 2020-10-09 | 2023-12-26 | Deere & Company | Machine control using a predictive map |
US11711995B2 (en) | 2020-10-09 | 2023-08-01 | Deere & Company | Machine control using a predictive map |
US11874669B2 (en) | 2020-10-09 | 2024-01-16 | Deere & Company | Map generation and control system |
US11849671B2 (en) | 2020-10-09 | 2023-12-26 | Deere & Company | Crop state map generation and control system |
US11844311B2 (en) | 2020-10-09 | 2023-12-19 | Deere & Company | Machine control using a predictive map |
US11889787B2 (en) | 2020-10-09 | 2024-02-06 | Deere & Company | Predictive speed map generation and control system |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH424761A (en) * | 1963-06-28 | 1966-11-30 | Sandoz Ag | Process for the production of new thiol carboxylic acid esters |
DE2130919A1 (en) * | 1970-06-22 | 1971-12-30 | Nippon Kayaku Kk | Substituted diphenyl ethers, process for their preparation and their use as herbicides |
DE2223894A1 (en) * | 1972-05-17 | 1973-12-13 | Hoechst Ag | HERBICIDAL AGENTS |
DE2333848A1 (en) * | 1973-07-03 | 1975-01-16 | Bayer Ag | HALOGENATED 4-TRIFLUOROMETHYL DIPHENYL (THIO) ETHER, PROCESS FOR THEIR PRODUCTION AND USE AS HERBICIDES |
FR2285861A1 (en) * | 1974-09-30 | 1976-04-23 | Lafon Labor | DIARYL SULFUR AND DIARYL OXYGEN COMPOUNDS |
FR2325638A1 (en) * | 1975-09-27 | 1977-04-22 | Ishihara Mining & Chemical Co | PHENOXY PHENOXY ALKANE CARBOXYLIC ACID HERBICIDES |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3784635A (en) * | 1969-04-25 | 1974-01-08 | Mobil Oil Corp | Substituted phenoxybenzoic acids and esters thereof |
-
1978
- 1978-06-29 EP EP78100270A patent/EP0000351A1/en not_active Ceased
- 1978-07-05 IL IL55085A patent/IL55085A/en unknown
- 1978-07-05 AR AR272847A patent/AR221487A1/en active
- 1978-07-05 DD DD78206536A patent/DD138142A5/en unknown
- 1978-07-06 IT IT25415/78A patent/IT1096916B/en active
- 1978-07-06 TR TR20047A patent/TR20047A/en unknown
- 1978-07-06 AU AU37824/78A patent/AU522170B2/en not_active Expired
- 1978-07-06 ES ES471526A patent/ES471526A1/en not_active Expired
- 1978-07-06 CA CA306,928A patent/CA1108172A/en not_active Expired
- 1978-07-06 AT AT491978A patent/AT358557B/en not_active IP Right Cessation
- 1978-07-06 HU HU78CI1838A patent/HU182473B/en unknown
- 1978-07-07 JP JP8281778A patent/JPS5416438A/en active Granted
- 1978-07-07 BR BR7804382A patent/BR7804382A/en unknown
- 1978-07-07 CS CS784551A patent/CS222267B2/en unknown
-
1980
- 1980-09-05 US US06/184,608 patent/US4349377A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH424761A (en) * | 1963-06-28 | 1966-11-30 | Sandoz Ag | Process for the production of new thiol carboxylic acid esters |
DE2130919A1 (en) * | 1970-06-22 | 1971-12-30 | Nippon Kayaku Kk | Substituted diphenyl ethers, process for their preparation and their use as herbicides |
DE2223894A1 (en) * | 1972-05-17 | 1973-12-13 | Hoechst Ag | HERBICIDAL AGENTS |
DE2333848A1 (en) * | 1973-07-03 | 1975-01-16 | Bayer Ag | HALOGENATED 4-TRIFLUOROMETHYL DIPHENYL (THIO) ETHER, PROCESS FOR THEIR PRODUCTION AND USE AS HERBICIDES |
FR2285861A1 (en) * | 1974-09-30 | 1976-04-23 | Lafon Labor | DIARYL SULFUR AND DIARYL OXYGEN COMPOUNDS |
FR2325638A1 (en) * | 1975-09-27 | 1977-04-22 | Ishihara Mining & Chemical Co | PHENOXY PHENOXY ALKANE CARBOXYLIC ACID HERBICIDES |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0025773A1 (en) * | 1979-09-13 | 1981-03-25 | Ciba-Geigy Ag | Alkylcarboxylic acid derivatives that contain sulphur and that show a herbicidal and plant growth controlling activity, their preparation and use |
EP0033885B1 (en) * | 1980-02-08 | 1984-03-21 | Bayer Ag | Process for the preparation of (2-chloro-4-trifluormethyl-phenyl)-(3-methoxy-phenyl)-ether |
US4450308A (en) * | 1980-02-08 | 1984-05-22 | Bayer Aktiengesellschaft | Process for the preparation of trifluoromethylphenyl oxyphenyl ether compounds |
EP0089573A1 (en) * | 1982-03-20 | 1983-09-28 | BASF Aktiengesellschaft | Silylalkyl esters of mercaptalkyl acids, process for their preparation and their application to combating undesired plant growth |
Also Published As
Publication number | Publication date |
---|---|
ES471526A1 (en) | 1979-01-16 |
IL55085A0 (en) | 1978-09-29 |
AU522170B2 (en) | 1982-05-20 |
JPS5416438A (en) | 1979-02-07 |
US4349377A (en) | 1982-09-14 |
AT358557B (en) | 1980-09-25 |
JPS6230184B2 (en) | 1987-07-01 |
IT1096916B (en) | 1985-08-26 |
HU182473B (en) | 1984-01-30 |
BR7804382A (en) | 1979-03-06 |
DD138142A5 (en) | 1979-10-17 |
IT7825415A0 (en) | 1978-07-06 |
ATA491978A (en) | 1980-02-15 |
IL55085A (en) | 1983-02-23 |
TR20047A (en) | 1980-07-02 |
CS222267B2 (en) | 1983-06-24 |
CA1108172A (en) | 1981-09-01 |
AR221487A1 (en) | 1981-02-13 |
AU3782478A (en) | 1980-01-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0000351A1 (en) | Phenoxy-phenyl-thio-alkanecarboxylic acid derivatives method for their preparation and their use as herbicides and plant growth regulators | |
DE2732846C2 (en) | ||
EP0003114A1 (en) | Herbicidal active unsaturated esters of 4- (3',5'-dihalogenpyridyl-(2')-oxy)-alpha-phenoxy propionic acids, process for their preparation, herbicidal compositions containing them and their use | |
EP0004317A2 (en) | Derivatives of phenoxy-alkanecarboxylic acids, their preparation, weed-killing products containing them and their use | |
EP0014684A2 (en) | 2-Substituted 5-phenoxy-phenylphosphonic acid derivatives, process for preparing them and their use as herbicides | |
US4394327A (en) | Herbicidally active phenoxy-α-phenoxy-alkanecarboxylic acid derivatives | |
EP0003295B1 (en) | Phenoxy-phenoxy-alkylcarboxylic acid derivatives with herbicidal activity, their preparation, compositions containing them and their use | |
EP0148119B1 (en) | Amides of 2-phenoxypropionic acid | |
EP0036390B1 (en) | Diphenyl ether ureas with herbicidal activity | |
EP0211805A2 (en) | N-(2-fluorophenyl)azolidines | |
EP0008624A1 (en) | O-(Pyridyloxy-phenyl)-lactic acid esters, process for their preparation and their use as herbicides and plant growth regulants | |
CH623725A5 (en) | Herbicide containing, as active substance, novel phenoxy-alpha-phenoxyalkanecarboxylic acid derivatives | |
EP0058639B1 (en) | 2-(4-(6-halogen-quinoxalinyl-2-oxy)-phenoxy)-propionic-acid esters, processes for their preparation and their application as herbicides and plant growth regulators | |
EP0003297B1 (en) | Phenoxy-alkyl-oxazolines, their preparation, herbicide compositions containing them, and their application | |
DE2615878A1 (en) | POLYCYCLIC NITROGEN COMPOUNDS | |
EP0259265B1 (en) | 3-methyl phthalimides | |
DE2730591A1 (en) | NEW HERBICIDALLY EFFECTIVE, CORE SUBSTITUTED PHENOXY-PHENOXY-ALKANCARBONIC ACID DERIVATIVES AND THEIR USE FOR COMBATING UNGRAES | |
EP0001641A1 (en) | 2-(2'-Nitro-5-(2"-chloro-4"-trifluoromethylphenoxy)-phenoxy)-propionic acid-methoxyethyester, a composition containing this ester as active ingredient and its use as a herbicide. | |
EP0034120B1 (en) | Derivatives of phenoxy-phenoxy-carboxylic acids | |
EP0098440B1 (en) | 3,7-dichloroquinoline derivatives, process for their preparation and their use to prevent undesired plant growth | |
DE2742034A1 (en) | POLYCYCLIC NITROGEN COMPOUNDS | |
EP0000359B1 (en) | Phenoxy-phenylsulfinyl-and-sulfonylalkanecarboxylic acid derivatives, method for their preparation and their use as herbicides and plant growth regulators. | |
EP0249858B1 (en) | Fluoralkylsubstituted quinoline derivatives, their synthesis and use against unwanted plant growth | |
KR820000627B1 (en) | Process for the preparation of phenoxy phenylthio alkane carboxylic acid derivatives | |
EP0107123A1 (en) | Aniline derivatives, process for their preparation and their use in combating undesired plant growth |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): BE CH DE FR GB NL |
|
17P | Request for examination filed | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
18R | Application refused |
Effective date: 19810804 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: ROHR, OTTO, DR. Inventor name: DUERR, DIETER, DR. Inventor name: BOEHNER, BEAT, DR. Inventor name: PISSIOTAS, GEORG, DR. |