DE3502629A1 - Phenoxybenzoic acid derivatives, their preparation, and their use in crop protection - Google Patents

Abstract

Compounds of the formula <IMAGE> in which R<1> and R<2> represent halogen or CF3, R<3> represents H or halogen, R<4> represents H, halogen, NO2 or CN, R<5> represents H or alkyl, R<6> represents H, alkyl or (if R<5> = H) an acyl, carboxylate, carbamoyl or (thio)phosphonate group, X represents, in particular, O or S and R<7> represents, in particular, alkyl, are effective selective herbicides.

Description

Phenoxybenzoic acid derivatives, process for their preparation

and their use in crop protection The present invention relates to new compounds of the general formula I wherein R FR2 independently of one another is F, C1, Br or CF3; R3 F, C1, Br or hydrogen, R4 hydrogen, halogen, CN or NO2, R5, R6 independently of one another hydrogen or (C1-C4) -alkyl; R6 also, if R5 = H, also the groups R7 is hydrogen, (C1-C4) -alkyl, optionally substituted once or twice by (C1-C4) -alkoxy, halogen or (Cl-C4) alkoxycarbonyl; furthermore (C3-C7) -cycloalkyl, (C3-C6) -alkenyl, (C3-C6) -alkynyl or benzyl, which is optionally substituted once or twice by halogen or (C1-C4) -alkyl; where, in the case of X = NR12, R7 and R12, together with the nitrogen atom, can form a pyrrolidyl, piperidyl, morpholinyl or N- (Cl-C4) alkyl-piperazinyl ring, R8 (Cl-C4) -alkyl, phenoxy (C1-C4 ) alkyl, where the phenyl radical can be substituted one to three times by halogen, CF3 or (Cl-C4) -alkyl; also C3-C6) alkenyl, (C3-C6) -alkynyl or phenyl, which is optionally substituted one to three times by halogen, CF3, NO2 or (C1-C4) -alkyl, R9, R1O (C1-C4) -alkyl or Phenyl, which is optionally substituted one to three times by halogen, CF3, NO2 or (Cl-C4) -alkyl, Rll (Cl-C4) -alkyl, X 0, S, NR12 Y 0, S and R12 hydrogen, (Cl- C6) -alkyl, (C3-C7) -cycloalkyl or benzyl, which is optionally substituted one to three times on the aromatic by halogen, CF3, NO2 or (C1-C4) -alkyl.

Preferred compounds of the general formula I are those in which X is oxygen or sulfur R1 chlorine R2 chlorine and in particular CF3 R3 hydrogen or chlorine R4 NO2 or hydrogen R5 hydrogen R6 hydrogen, R 7 denotes methyl, ethyl, benzyl.

The invention further provides a process for the preparation of the compounds of the general formula I, characterized in that compounds of the general formula II (Hal = halogen) in the presence of a base with compounds of the general formula III and if R5 and / or R6 = hydrogen, the compounds obtained are converted, if desired, in a manner known per se using alkylating or acylating agents into other compounds of the general formula I with R5 t hydrogen.

The compounds of the general formula II are known or are not known according to known methods, as they are, for. As described in US 4,395,570 or EP 21,692 will produce.

The compounds of the general formula III are also known or can be produced by known methods, such as those described, for. B. in DE-OS 23 58 904 are described.

The reactions are carried out in the presence of inorganic or organic Bases carried out, for example NaOH, K2CO3, NaHCO3, pyridine or triethylamine.

All solvents under the reaction conditions are suitable as solvents inert solvents, e.g. B. hydrocarbons or halogenated hydrocarbons, such as B. toluene, xylene or methylene chloride.

In the case of R5, R6 = hydrogen, the compounds of the general Formula III preferably in the form of its hydrochloric or sulfuric acid salts in the inventive Procedure used. In this case, the reaction is preferably carried out with alkali hydroxides carried out.

Working in the 2-phase system is particularly preferred. For in the case that methylene chloride is used as the solvent, the compound becomes of the general formula III in the form of its sulfuric acid salt in water / methylene chloride dissolved and the compound II added.

The reaction temperature is not critical, it is preferred between -100C and 350C chosen.

The compounds obtained can be if desired with the help of alkylating or acylating agents such as dimethyl sulfate, acid chlorides or Isocyanates in a known manner into other compounds of the formula I with R5 and, or R6 ç convert hydrogen.

The present compounds of the invention have excellent properties herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Also hard to control perennial root weeds are well covered by the active ingredients.

It does not matter whether the substances in pre-sowing, pre-emergence or post-emergence spraying.

If the compounds according to the invention are used before the germination of weed and crops applied to the surface of the earth will be used at higher dosages the emergence of the weed seedlings is completely prevented. When applying low Dosage does not completely suppress the emergence of the weeds. The plants grow to the cotyledon stage, but then stop growing and eventually die off after a few small volicas.

When applying the active ingredients to the green parts of the plant using the post-emergence method will soon after treatment the appearance of severe leaf necrosis and then rapid death of the weed plants is observed, so that in this way one Weed competition harmful to crops is eliminated early and sustainably can be. Although the compounds of the invention are an excellent herbicidal Cultivated plants become active against monocotyledon and dicotyledon weeds economically important cultures such as B. Wheat, barley, rye, rice, maize, Sugar beet, cotton and soy are only insignificantly damaged or not at all. The present For these reasons, compounds are very suitable for combating undesirable substances Plant growth in agricultural crops.

In addition, they have growth-regulatory properties Crops on. They have a regulating effect on the plant's own metabolism a and can thus to facilitate harvest such. B. by triggering desiccation, Abscission and stunted growth can be used.

Furthermore, they are also suitable for general control and inhibition of unwanted vegetative growth without killing the plants. One Inhibition of vegetative growth plays a role in many monocotyledon and dicotyledon crops plays an important role, as this reduces or completely prevents storage can.

The agents according to the invention can be emulsifiable as wettable powders Concentrates, sprayable solutions, dusts, dressings, dispersions, granulates or microgranules can be used in the usual preparations.

Wettable powders are preparations that can be dispersed evenly in water, those in addition to the active ingredient except, if appropriate, a diluent or inert substance nor wetting agents, e.g.

B. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkyl phenyl sulfonates and dispersants, e.g. B. sodium lignin sulfonic acid, Sodium 2,2'-dinaphthylmethane-6,6'-disulfonic acid, dibutylnaphthalenesulfonic acid Contain sodium or oleoylmethyltauric acid sodium. The production takes place in the usual way z. B. by grinding and mixing the components.

Emulsifiable concentrates can e.g. B. by dissolving the active ingredient in an inert organic solvent, e.g. B. butanol, cyclohexanone, dimethylformamide, Xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers are produced. In the case of liquid active ingredients, the solvent content is completely or partially omitted. As an emul- gators For example, the following can be used: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aryl polyglycol ethers, Fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, fatty alcohol-propylene oxide-ethylene oxide condensation products, Alkyl polyglycol ethers, sorbitan fatty acid esters, polyoxethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.

Dust can be removed by grinding the active ingredient with finely divided, solid materials, e.g. B. talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth.

Granules can either be sprayed onto adsorptive, Granulated inert material can be produced or by applying active ingredients by means of binders, e.g. B. polyvinyl alcohol, polyacrylic acid or sodium Mineral oils on the surface of carrier materials such as sand, kaolinite or granules Inert material. Suitable active ingredients can also be used for the production of fertilizer granules customary manner, if desired as a mixture with fertilizers, granulated.

In wettable powders, the active ingredient concentration is z.

B. about 10 to 90 wt .-%, the remainder to 100 wt .-% consists of usual Formulation ingredients. In the case of emulsifiable concentrates, the active ingredient concentration can be about 5 to 80 wt .-%. Dust-like formulations usually contain 5 up to 20% by weight of active ingredient, sprayable solutions about 2 to 20% by weight. With granules The active ingredient content depends in part on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used.

In addition, the active ingredient formulations mentioned may contain the usual adhesive, wetting, dispersing, emulsifying, penetrating, and solvents Fillers or carriers.

The concentrates available in commercially available form are used optionally diluted in the usual way, e.g. B. in wettable powders, emulsifiable Concentrates, dispersions and sometimes also with microgranulates using water. Dust-like and granulated preparations as well as sprayable solutions are before Usually no longer diluted with other inert substances after use.

With the external conditions such as temperature, humidity, etc. varies the required application rate. It can fluctuate within wide limits, e.g. B. between 0.005 and 10.0 kg / ha or more active substance, preferably it is but between 0.01 and 5 kg / ha.

Mixtures or mixed formulations with other active ingredients, such as B. insecticides, acaricides, herbicides, fertilizers, growth regulators or fungicides are optionally possible.

Some formulation examples are given below: A dusting agent is obtained by adding 10 parts by weight of active ingredient and 90 parts by weight of talc or mixes inert substance and comminutes in a hammer mill.

A wettable powder which is easily dispersible in water is obtained, by adding 25 parts by weight of active ingredient, 64 parts by weight of kaolin-containing quartz as Inert, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyltauric acid Mixes sodium as a wetting and dispersing agent and grinds it in a pin mill.

A dispersion concentrate which is easily dispersible in water is obtained, by 20 parts by weight of active ingredient with 6 parts by weight of alkylphenol polyglycol ether (Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 AeO) and 71 parts by weight paraffinic mineral oil (boiling range e.g. approx. 255 to over 377 OC) and ground in an attritor ball mill to a fineness of less than 5 microns.

An emulsifiable concentrate is obtained from 15 parts by weight of active ingredient, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated Nonylphenol (10 AeO) as an emulsifier.

A. Preparation Examples Example 1 N- [5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoYll-O-methylisourea 6.7 g (55 mmol) of O-methyl isourea sulfate are dissolved in 50 ml of water and 100 ml of methylene chloride dissolved and cooled to 0 ° C. At the same time, 8 g of 50% strength sodium hydroxide solution are added dropwise at 0 ° C (100 mmol) and 19 g (50 mmol) 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoyl chloride, dissolved in 30 ml of methylene chloride, too. The mixture is subsequently stirred at 0 ° C. for 1 hour and at 30 ° C. for 2 hours. The organic phase is separated off and washed twice with 100 ml of water each time. To Drying over sodium sulfate, the solvent is distilled off under reduced pressure.

The residue obtained is 16.3 g (78% of theory) of N- [5- (2-chloro-4-trifluoromethylphenoxy) -2- nitro-benzoyl] -O-methyl-isourea in the form of a viscous light brown oil. The identification done by 1H-NMR.

Example 2 N-r5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoyl] -N '- (4-chloro-phenoxyacetyl) -0-methyl-isourea 12.1 g (50 mmol) of N- (4-chloro-phenoxyacetyl) -0-methylisourea and 5 g of triethylamine are dissolved in 120 ml of methylene chloride. 19 g (50%) are added dropwise at room temperature mmol) 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoyl chloride, dissolved in 30 ml of methylene chloride, within 15 min. The mixture is stirred for 30 min at RT and for 4 h 35 OC after. After vacuuming the failed Triethylamine hydrochloride the methylene chloride solution is washed twice with water. After drying over Sodium sulfate, the solvent is distilled off under reduced pressure. Man receives 24 g (87% of theory) N- [5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-benzoyl] -N '- (4-chlorophenoxyacetyl) -O-methyl-isourea in the form of a tough brown oil. Identification was carried out by 1H-NMR.

Example 3 N- [5- (2-chloro-4-trifluoromethXl-phenoxy) -2-nitro-benzOyl] -N '- (3-chloro-4-methyl-phenylcarbamoyl) -0-methyl-isourea 12.1 g (50 mmol) of N- (3-chloro-4-methyl-phenylcarbamoyl) -0-methyl-isourea are dissolved and 4 g (51 mmol) of pyridine in 160 ml of toluene and a solution of 19 is added dropwise at RT g (50 mmol) 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoyl chloride in 40 ml Methylene chloride too. The mixture is stirred for 5 hours at 35 ° C. and the precipitate formed is filtered off with suction and washes the mother liquor 3 times with 100 ml of water. After drying over sodium sulfate the solvent is distilled off under reduced pressure. 30.2 g are obtained (97% of theory) N- [5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzOyl] -N '- (3-chloro-4-methyl-phenylcarbamoyl) -0-methylisourea as a light brown resin. Identification was carried out by 1H-NMR.

Example 4 N- [5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoyl] ~ N'-acetyl-S-methyl-isothiurea 6.6 g (50 mmol) of N-acetyl-S-methyl-isothiourea are dissolved and 4 g (51 mmol) of pyridine in 100 ml of toluene and a solution is added dropwise at room temperature. of 29 g (50 mmol) of 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoyl chloride in 40 ml of methylene chloride. After stirring for 4 hours at 35 ° C., the precipitate formed is removed aLgqsucks. The toluene phase is washed 3 times with 100 ml of water and over sodium sulfate dried. After distilling off the solvent under reduced pressure 19.5 g (82% of theory) of N- [5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoyl] -N'-acetyl-S-methyl-isothiourea are obtained as brown oil. The identification was carried out by 1 H-NMR.

The following compounds can be prepared in an analogous manner. n cJ ot \ o U cr IN a3k a aJ Ma> u \ co 1 O = t1 0 t I. XOOOOORZOOOO X h ha, x c xna, CI h (U oa 7 Cl X 1 auco I Cl HH 0 Del kf O O c, n 1 9 1 NO2 IN IH CH3 H 5 -; ft UO 11 H <HH NH 158-162 NHNNN UUU z II 13 O = t =) O = (») H = t) IIIIIII II 14 H, C-CH2- (4-0F3-phenyl) 0 ss IXIX , ~ INI. NI 15 Cl O = = -C-CH2- (4-Cl-2-CH3-phenyl) O l NNN “OOO 1t IZZIZ - = t = = 15th IX ~ HH < 11: IIO () OIIIII t) QO vI N rN x uo sg fw a tD MoCl 0 resin 0 II 17 H, -C-CH2 (4-C1-phenyl) 5 0 II xo H zz ,, vl ro v) v3 ZZ 5 - '1 P k 20 HF; V 21 H a) O v sr NN v 22 cc H2-pheny1; e (4l-phenyi) 5 II hl YY UUO -H COCH2 (2,4dil-'henyl) NH O = U 0 = O 0 = O 25 H 1r OH2 (4l-phenyl) 1 NH NN n III =) C) ., (~ SN t'S CS LA Example R3 R4 R7 z XFp [0C3 26 Cl NO2 -C2H5 -cO- (4-Cl-phenyl) ll 10 z po . ~ 29 o NO2 0 ZO tß tß O 5 30 H NO2 -H -CO-CH3 NH 31 H NO2 -CH3 -CO-0-phenyl 0 Ah rl rl E: 32 H <-C2H5 -CO-OCH3 5 C a, a, aa QI CCII ap, ri ri ri a I m 1 uu I en 2 33 Cl NO2 <p @ tt ~ 5 N rl Cr <Erl 1 a, jl h UUUU 6 m Y mm III ma 3: 1 1 3: TH wuooz æ o -CH3 -CO-NH- (4-Cl-phenyl) 0 IIIIII - c 35 H uu ° IIIIIIA ° l nnu, = na N > uuu U: nuuuuuu X l N b1 NNNN fQ v OOOOOOOOO X æ = = æ zzzzzzz n <H < co uu: u = 2 H @ ffi XD> oD 08 0 <N ns -1 fS N o4 N mnennne @ m B. Biological Examples The damage to the weed plants or the crop plant tolerance was rated according to a key in which the effectiveness is expressed by values from 0-5. This means: O = no effect or damage 1 = 0 - 20% effect or damage 2 = 20 - 40% effect or damage 3 = 40 - 60% effect or damage 4 = 60 - 80% effect or damage 5 = 80-100% effect or damage 1. Weed effect in pre-emergence Seeds or pieces of rhizome from monocotyledon and dicotyledon weed plants were placed in sandy loam soil in plastic pots and covered with soil. The compounds according to the invention, formulated in the form of wettable powders or emulsion concentrates, were then applied to the surface of the covering soil as aqueous suspensions or emulsions with a water application rate of the equivalent of 600 l / ha.

After the treatment, the pots were placed in the greenhouse and kept under good growing conditions for the weed plant (temperature 23c relative humidity 60 - 80%).

The visual assessment of the damage to plants or emergence was carried out after the emergence of the test plants after a test period of 3 - 4 weeks in comparison to untreated controls.

As the rating values in Table 1 show, the inventive Compounds have good herbicidal pre-emergence activity against a broad spectrum from Weed grasses and weeds.

2. Weed effect in post-emergence seeds or rhizome pieces of mono- and dicotyledon weeds were placed in plastic pots (9 cm) in sandy loam soil, covered with soil and grown in the greenhouse under good growing conditions. Three weeks after sowing, the test plants were treated at the three-leaf stage.

The formulated as wettable powders or as emulsion concentrates according to the invention Compounds were administered in various dosages with a water dose of The equivalent of 600 l / ha is sprayed onto the green parts of the plant and after approx. 3 - 4 weeks Service life of the test plants in the greenhouse under optimal growth conditions (Temperature 23 plus / minus 1 ° C, relative humidity 60 - 80%) the effect of the Preparations rated visually in comparison to untreated controls.

The agents according to the invention also exhibit good post-emergence herbicidal activity against a broad spectrum of economically important grass weeds and weeds (Table 2).

3. Compatibility with crop plants In further experiments in the greenhouse seeds of a large number of crops were grown in pots in sandy loam soil laid out and covered with earth.

Some of the pots were treated immediately as described under 1.; the rest were placed in the greenhouse until the plants two or three real ones Sheets had developed and then with the substances according to the invention in different Dosages like described under 2., sprayed.

Four to five weeks after application and standing in the greenhouse it was found by means of optical evaluation that the compounds according to the invention dicotyledonous cultures such as B. soy, cotton, rapeseed, sugar beet and potatoes undamaged in the pre- and post-emergence process even with high doses of active ingredient let. In addition, some substances also spared Gramineae cultures such as B. barley, sorghum, corn, wheat or rice. The compounds of formula I have thus a high selectivity when used to control unwanted vegetation in agriculturally important crops.

Table 1 Herbicidal activity of the compounds according to the invention in Pre-emergence e.g. dose of herbicidal effect kg a.i./ha CFRS SIA LOM ECG 1 2.5 5 5 5 5 10 2.5 5 4 3 4 3 2.5 5 3 3 5 11 2.5 5 5 5 4 2 2.5 5 5 5 5 4 2.5 5 5 3 5 Tabel 2 Post-emergence herbicidal effect of the compounds according to the invention, e.g. dose herbicidal activity kg a.i./ha CRS SIA LOM ECG 1 2.5 5 5 3 5 10 2.5 3 5 0 2 3 2.5 3 4 2 2 11 2.5 4 5 3 3 2 2.5 5 5 5 5 4 2.5 5 5 2 2 Abbreviations: CFRS = Chrysanthemum segetum SIA = Sinapis arvensis LOM = Lolium multiflorum ECG = Echinochloa crus-galli

Claims (1)

Claims 1. Compounds of the general formula I wherein R¹, R², independently of one another, are F, C1, Br. or CF3; R³ is F, Cl, Br or hydrogen, R4 is H, halogen, CN or NO2; R5, R6 independently of one another are hydrogen or (C1-C4) -alkyl; R6 also, if R5 = H, also the groups R7 is hydrogen, (C, -C4) -alkyl, optionally substituted once or twice by (C1-C4) -alkoxy, halogen or (Cl-C4) alkoxycarbonyl; furthermore (C3-C7L cycloalkyl, (C3-C6) -alkenyl, (C3-C6) -alkynyl or benzyl, which is optionally substituted once or twice by halogen or (C1-C4) -alkyl; where in the case X = NR12 R7 and R together with the nitrogen atom can form a pyrrolidyl, piperidyl, morpholinyl or N- (C1-C4) alkyl-piperazinyl ring. R8 (C1-C4) -alkyl, phenoxy (C1-C4 alkyl, where the phenyl radical is one to can be trisubstituted by halogen CF3 or (C1-C4) -alkyl; also C3-C6) alkenyl, (C3-C6) -alkynyl or phenyl, which is optionally substituted one to three times by halogen, CF3, NO2 or (Cl-C4) -alkyl is substituted. R9, R10 (Cl-C4) -alkyl or phenyl, optionally one to three times is substituted by halogen, CF3, NO2 or (Cl-C4) -alkyl, Rll (Cl-C4) -alkyl, X O, S, NR12, y 0, S and R12 are hydrogen, (Cl-C6) -alkyl, (C3-C7) -cycloalkyl or Benzyl, which can optionally be substituted one to three times on the aromatic by halogen, CF3, NO2 or (Cl-C4) -alkyl is substituted. Process for the preparation of the compounds according to Claim 1, characterized in that compounds of the general formula II (Hal = halogen) in the presence of bases with compounds of the general formula III and, if R5 and / or R6 = hydrogen, the compounds obtained are converted, if desired, in a manner known per se using alkylating or acylating agents into other compounds of the general formula I with R5 r hydrogen. 3. Use of compounds according to claim 1 for combating undesirable Plant growth or for growth regulation. 4. Herbicides and growth regulators, characterized by a content of compounds according to claim 1. 5. Method of combating undesired vegetation or for Growth regulation, characterized in that one acts on the areas to be treated or plants applying an effective amount of a compound according to claim 1.