DE2628384A1 - HERBICIDES AND FUNGICIDES - Google Patents

Description

The invention relates to compounds of the general formula I in the

R, R [deep] 1 identical or different substituents from the group halogen,

(C [deep] 1-C [deep] 4) -haloalkyl, (C [deep] 1-C [deep] 4) -alkyl, nitro,

(C [deep] 1-C [deep] 4) -alkoxy or (C [deep] 1-C [deep] 4) -alkylthio,

n, n [deep] 1 whole numbers from 0 to 3,

X -0- or -CH [deep] 2-,

Y O, S, NH and

Z is a cyanoethyl group or a radical of the formula

A optionally by -CH [deep] 3, -C [deep] 2H [deep] 5, -COCH [deep] 3

or another radical of the formula -COOR [deep] 3 substituted

Methylene group or a phenylene radical which is optionally substituted once or twice by (C [deep] 1-C [deep] 4) alkyl, halogen and / or nitro, and

R [deep] 3 (C [deep] 1-C [deep] 4) alkyl

mean.

Preferred among the compounds of the formula I are those in which for halogen chlorine and / or bromine, as alkyl groups those with 1 to 2 carbon atoms, for n the numbers 1 or 2, for n [deep] 1 the number 0 and for Y are oxygen or sulfur.

Particularly preferred are compounds in which R is Cl, Br and / or CF [deep] 3 in the o- or p-position to X, n = 1 or 2, n [deep] 1 = 0 and X and Y = oxygen.

Z is preferably cyanoethyl or the radical of the formula -A-COOR [deep] 3 with A = -CH [deep] 2- or -CH (CH [deep] 3) -.

The invention also relates to a process for the preparation of the compounds of the formula I, which is characterized in that

a) Compounds of the general formula II or their alkali or ammonium salts with compounds of the formula III or

b) compounds of the general formula IV with compounds of formula V. or their alkali or ammonium compounds, if appropriate in the presence of an acid-binding agent, where Hal in the formulas II and III is preferably chlorine or bromine.

The compounds of the formula I are herbicides which, when used pre- and post-emergence, show good action against a broad spectrum of grass weeds. The substances according to the invention can be used to control grass-like weeds such as wild oats (Avena), field foxtail (Alopecurus), ryegrass (Lolium), bristle, chicken and blood millet (Setaria, Echinochloa, Digitaria) in dicotyledon cultures.

With some of the claimed compounds, even grass-like weeds in cereal crops can be selectively controlled.

Soybeans, peanuts, broad beans, field beans, peas, alfalfa, cabbage, rape, cucumber, sunflower, tobacco, carrots, celery and sugar beet are not damaged even in high doses.

Due to the special action against grass weeds, especially wild oats, foxtail, ryegrass and millet are the new of a number of proven herbicidal agents, such as the compounds known under the "common names" alachlor, monolinuron, linuron, pyrazone, phenmedipham, sodium trichloroacetate, fluorodifen and Mecoprop, which are superior in their effect when used in fields that are heavily infested with grass weeds.

In addition, the required application rates for the complete destruction of the grass weeds are far lower than for the above-mentioned known herbicides.

The favorable toxicity to warm-blooded animals of the compounds according to general formula I are also advantageous.

Surprisingly, the compounds of the formula I also show good activity against harmful fungi on industrial substrates and against phytopathogenic fungi such as Piricularia oryzae, rust fungi, Botrytis cinerea, Plasmopara viticola, Phytophthora infestans, powdery mildew species, Rhizoctonia solani, Septoria nodorum, Ustilago nuda, Phoma betae, Pythium ultimum and Helminthosporium gramineum.

For application as technical fungicides, the compounds are used, for example, as additives to lacquers, varnishes and paints.

For use as crop protection agents, they can be formulated as dusts, wettable powders, dispersions or emulsion concentrates. Their total active ingredient content is then generally 2-80% by weight, depending on the formulation. They also contain the usual adhesives, wetting agents, dispersants, fillers and carriers. They can also be mixed with other fungicides.

The invention therefore also relates to herbicidal and fungicidal compositions, characterized by their content of compounds of the formula I in addition to customary formulation auxiliaries and inert substances, and the use of compounds of the formula I for combating grass weeds and harmful fungi.

The agents according to the invention generally contain 2 to 95% by weight of the active ingredients of the formula I. They can be used in the customary preparations as wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules.

Wettable powders are preparations that are uniformly dispersible in water, which, in addition to the active ingredient, contain a diluent or inert substance, wetting agents, e.g. polyoxyethylated alkylphenols, polyoxyethylated oleyl or stearylamines, alkyl or alkylphenyl sulfonates, and dispersants, e.g. sodium lignin sulfonic acid, 2,2 ' -dinaphthylmethane-6,6'-disulphonic acid sodium, or oleoylmethyl-tauric acid sodium.

Emulsifiable concentrates are obtained by dissolving the active ingredient in an organic solvent, e.g. butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics.

Dusting agents are obtained by grinding the active ingredient with finely divided, solid substances, e.g. talc, natural clays such as kaolin, bentonite, pyrophyllite or diatomaceous earth.

Sprayable solutions, as they are often traded in spray cans, contain the active ingredient dissolved in an organic solvent, alongside a mixture of chlorofluorocarbons and / or carbon dioxide, for example, as a propellant.

Granules can be produced either by spraying the active ingredient onto adsorptive, granulated inert material or by applying active ingredient concentrates using adhesives, e.g. polyvinyl alcohol, sodium polyacrylic acid or mineral oils, to the surface of carrier materials such as sand, kaolinite, or granulated inert material. Suitable active ingredients can also be produced in the manner customary for the production of fertilizer granules - if desired in a mixture with fertilizers.

In the case of herbicidal agents, the concentrations of the active ingredients in the commercially available formulations can be different.

In wettable powders, the active ingredient concentration varies e.g. between about 10% and 80%, the remainder consists of the formulation additives given above. In the case of emulsifiable concentrates, the active ingredient concentration is around 10% to 80%. Dust-like formulations usually contain 5 - 20% active ingredient, sprayable solutions around 2 - 20%. In the case of granules, the active ingredient content partly depends on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used.

For use, the commercially available concentrates are diluted in the usual way if necessary, e.g. in the case of wettable powders and emulsifiable concentrates with water. Dust-like and granulated preparations as well as sprayable solutions are no longer diluted with other inert substances before use. The required application rate varies with the external conditions such as temperature, humidity, etc. she can vary within wide limits, e.g. between 0.1 kg / ha and 10 kg / ha of active substance, but is preferably between 0.1 and 3 kg / ha. The active compounds according to the invention can be combined with other herbicides and soil insecticides.

Manufacturing examples

Example 1:

2- [4'- (4 "-Chlorophenoxy) -phenoxy] -propionyllactic acid methyl ester

A solution of 81 g of 2- [4'- (4 "-chlorophenoxy) phenoxy] propionic acid and 48 g of methyl 2-bromopropionate in 160 ml of acetone is heated to boiling with 40 g of potassium carbonate while stirring for 8 hours The inorganic salts are filtered off, the acetone is distilled off from the filtrate and the residue is distilled in vacuo.

91 g = 87.0% of theory are obtained. Th. Of bp [low] o, [low] 1: 190 ° - 191 ° C

Example 2:

2- [4 '- (2 ", 4" -Dichlorophenoxy) -phenoxy] -propionylglycolic acid methyl ester

61 g of 2- [4'- (2 ", 4" -dichlorophenoxy) phenoxy] propionic acid and 24 g of methyl chloroacetate are dissolved in 200 ml of butanone. After adding 26 g of potassium carbonate, the mixture is heated to boiling with stirring for 8 hours. The reaction mixture is cooled to 20 ° C. and the inorganic salts are filtered off. The butanone of the filtrate is distilled off and the ester formed is purified by vacuum distillation.

67 g = 90.0% of theory are obtained. Th. From Kp [low] o, [low] 05: 207 ° - 208 ° C

Example 3:

2- [4 '- (2 ", 4" -Dichlorophenoxy) -phenoxy] -propionyl-thioglycolic acid methyl ester

48 g of methyl thioglycolate are dissolved in 200 ml of toluene. At 20 ° - 40 ° C, 156 g of 2- [4´- (2 ", 4" -Dichlorphenoxy) -phenoxy] -propionic acid chloride, dissolved in 150 ml of toluene, and 48 g of dry triethylamine, dissolved in 50 ml of toluene, are added at the same time. added dropwise. The mixture is then stirred at 40 ° C. for 2 hours. The triethylamine chlorohydrate formed is filtered off with suction. The toluene of the filtrate is distilled off and the residue is purified by distillation at 0.2 torr.

180 g = 96% of theory are obtained. Th. Of bp [low] o, [low] 2: 230 ° - 232 ° C

Example 4:

2- [4'- (4 "-Bromophenoxy) phenoxy] propionic acid (2-cyanoethyl) ester

30 g of 3-oxypropiononitrile are dissolved in 150 ml of toluene. At the same time, 143 g of 2- [4'- (4 "-Bromophenoxy) phenoxy] propionic acid chloride, dissolved in 100 ml of toluene, and 40 g of dry triethylamine, dissolved in 50 ml of toluene, are added dropwise at 20 ° -40 ° C. 2 Hours of stirring at 40 ° C., cooled to 20 ° C., filtered off with suction and the toluene distilled off from the filtrate, 151 g of residue are obtained. After distillation of the residue, 138 g = 88% of theory of boiling point o, [low] 1: 208 ° - 210 ° C obtained.

Example 5:

2- [4- (4 "-Trifluoromethylphenoxy) phenoxy] propionic acid (4-carbomethoxyphenyl) ester

23 g of methyl 4-oxybenzoate and 17 g of dried triethylamine are dissolved in 120 ml of toluene. To this end, a solution of 52 g of 2- [4'- (4 "-trifluoromethylphenoxy) phenoxy] propionic acid chloride in 80 ml of toluene is added dropwise at 20 ° -40 ° C. After the mixture has been stirred at 40 ° C. for 2 hours, the mixture is increased The mixture was cooled to 20 ° C., triethylamine chlorohydrate was filtered off with suction and the toluene was distilled off from the filtrate, and the oil obtained was recrystallized from n-hexane.

64 g = 92% of theory are obtained. Th. From m.p. 78 ° - 79 ° C.

Example 6:

2- [4´- (2 ", 4" -Dichlorphenoxy) -phenoxy] -propionyl- (2-acetic acid methyl ester)

70 g of sodium 2- [4'- (2 ", 4" -dichlorophenoxy) phenoxy] propionic acid are suspended in 300 ml of benzene and 32 g of methyl 2-chloroacetoacetate are added. The mixture is stirred at 80 ° C. for 8 hours, cooled and the sodium chloride is filtered off. The toluene is distilled off.

76 g of yellow oil with a refractive index n [low] d [high] 25 = 1.5593 are obtained.

The other compounds listed in the tables below were prepared by the methods of Examples 1-6.

Table 1:

Table 1 (continued) <Table> Table 1 (continued) <Table>

Table 2:

Table 3:

Table 4:

Example 89:

2- [4'- (2 ", 4" -Dichlorobenzyl) phenoxy] propionyllactic acid methyl ester

44 g of 2- [4'- (2 ", 4" -dichlorobenzyl) phenoxy] propionic acid, 27 g of methyl 2-bromopropionate, 21 g of anhydrous potassium carbonate and 100 ml of acetone are stirred at 60 ° C. for 8 hours. After cooling to 20 ° C., the inorganic salts are filtered off. The acetone is distilled off from the filtrate and the residue is distilled in vacuo.

51 g = 91.6% of theory are obtained. Th. Of bp [low] o, [low] 05: 165 ° - 166 ° C

Example 90:

2- [4'- (4 "-Chlorophenoxy) -phenoxy] -propionyl-tartronic acid diethyl ester

32 g of 2- [4'- (4 "-chlorophenoxy) -phenoxy] -propionic acid sodium salt, 27 g of bromomalonic acid diethyl ester, 1 ml of dimethylformamide and 150 ml of toluene are stirred for 18 hours at 80 ° C. After the sodium bromide has been suctioned off, the filtrate is removed the toluene and the excess of diethyl bromomalonate are distilled off.

43 g of light yellow oil = 96.0% of theory are obtained. Th. N [low] D [high] 25: 1.5300

Example 91:

2- [4'- (2 ", 4" -Dichlorophenoxy) -phenoxy] -propionyl-tartronic acid diethyl ester

35 g of 2- [4'- (2 ", 4" -dichlorophenoxy) phenoxy] propionic acid sodium salt, 27 g of diethyl bromomalonate, 1 ml of dimethylformamide and 150 ml of toluene are stirred at 80 ° C. for 18 hours. After cooling to 20 ° C. and suction of the sodium bromide, the toluene and the excess diethyl bromomalonate are distilled off from the filtrate.

47 g of light yellow oil = 97% of theory are obtained. Th. N [low] D [high] 25: 1.5337

Example 92:

2- [4 '- (2 ", 4" -Dichlorophenoxy) -phenoxy] -propionyl-glycine methyl ester

To 14 g (0.152 mol) of glycine ester released freshly from the glycine methyl ester chlorohydrate dissolved in 80 ml of toluene, a solution of 24 g (0.076 mol) of 2- [4´- (2 ", 4" -dichlorophenoxy) is added at 10 ° - 15 ° C. -phenoxy] -propionic acid chloride in 40 ml of toluene was added dropwise in 30 min. The mixture is then stirred at 15.degree.-22.degree. C. for 2 hours. The resulting glycine methyl ester chlorohydrate is filtered off with suction. The toluene is distilled off from the filtrate in vacuo.

30 g of pale yellow oil n [low] D [high] 25: 1.5652 are obtained

Biological examples: herbicides

Example I: Pre-emergence treatment

Grass seeds were sown in pots and the preparations according to the invention, formulated as wettable powders or emulsion concentrates, were sprayed in various doses onto the surface of the earth. The pots were then placed in a greenhouse for 4 weeks and the result of the treatment (as in the following examples) was recorded by rating according to the Bolle scheme (see rating scheme).

The preparations according to the invention listed in Table I show a very good action against grass weeds, which is still present in most species even at the lowest dose of 0.15 kg of active substance / ha. The comparative preparations Fluorodifen and Mecoprop were much weaker in their action against grasses. The following preparations according to the invention according to Examples No. 1, 10, 11, 13, 26, 37, 38, 41, 43, 44, 47, 54 and 57 also showed similarly good activity against grasses.

Example II: Post-emergence treatment

Grass seeds were sown in pots and grown in the greenhouse. 3 weeks after sowing, the preparations according to the invention, formulated as wettable powders or emulsion concentrates, were sprayed onto the plants in various doses and, after standing in the greenhouse for 4 weeks, the effect of the preparations was rated.

The preparations according to the invention listed in Table II show a good to very good action against grass weeds and are superior to the comparison agents Fluorodifen and Mecoprop. place. The following preparations according to the invention according to Examples No. 1, 10, 11, 13, 26, 37, 38, 41, 43, 44, 47, 54 and 57 also showed similarly good activity against grasses.

Example III:

In a further experiment using the same methodology as in Example II (post-emergence treatment), various crop plants were sprayed with suspensions or emulsions of the substances according to the invention mentioned in Examples I and II. Soybeans, peanuts, French beans, field beans, peas, alfalfa, flax, cabbage, rape, cucumber, sunflower, tobacco, carrots, celery and sugar beet showed no damage even in the high dosage of 2.5 kg / ha. Barley and wheat showed no reaction to the preparations according to Examples 2, 8, 11, 38, 47, 56 and 57.

Similar results are obtained if the substances are sprayed onto the soil surface using the pre-emergence method.

So you can use substances according to the invention to combat grass-like weeds such as wild oats (Avena), field foxtail (Alopercurus), reygrass (Lolium), bristle, chicken and blood millet (Setaria, Echinochloa, Digitaria) in dicotyledon cultures. With some of the claimed substances, it is even possible to selectively control grass-like weeds in cereal crops, which are also known to be grasses.

Example IV:

In an experiment in which they were sprayed after emergence, compounds according to the invention were extremely effective against Alopercurus and Setaria and at the same time were gentle on barley and wheat (Table IV). The preparations from Example Nos. 43 and 53 had a similar effect.

Rating scheme

according to Bolle (newsletter of the German Plant Protection Service 16, 1964, 92 - 94)

Table I:

Weed rating figures for pre-emergence treatment

Table II:

Weed rating figures for post-emergence treatment

Table IV:

Weed and cultivated plants rating numbers for post-emergence treatment

Biological examples: fungicides

Example V:

Ustilago nuda-infected gesture seed (degree of infestation 15%) was dressed with compounds according to the invention in the use concentrations given in Table V, sown in pots and grown in a greenhouse initially at low and later at higher temperatures (20 ° C.). 10-12 weeks later, the healthy stalks and those infected with Ustilago nuda were counted, the respective degree of infection was determined and finally the degree of effectiveness was calculated.

In this and the following examples, the letters A to E stand for the comparison agents mentioned below:

A = Combination preparation of 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide and methoxyethyl-Hg-silicate

B = manganese-ethylene-1,2-bis-dithiocarbamate

D = tetramethylthiuram disulfide (TMTD)

E = S-ethyl-N- (3-dimethylaminopropyl) thiol carbamate hydrochloride (prothiocarb).

Table V:

Table V shows the excellent action of the claimed compounds against Ustilago nuda, which is superior to comparative agent A.

Example VI:

Spring barley seeds naturally infected with Helminthosporium gramineum with an infestation level of 24% were dressed with claimed compounds (50% dressing agents) in the concentrations given in Table VI. The seeds were sown in trays, which were then placed in a greenhouse. Later both the plants infected with Helminthosporium gramineum and the healthy plants were counted, the respective degree of infection was determined and finally the degree of effectiveness was calculated (Table VI).

Table VI:

The results in Table VI show the excellent Helminthosporium activity of the claimed compound and the superiority of this mercury-free compound over both the mercury-free comparative agent B and the mercury-containing comparative agent A.

Example VII:

Sugar beet seed naturally contaminated with Phoma betae with an infestation level of approx. 60% was pickled with the claimed compound, laid out in bowls and grown in a greenhouse at 20 ° C. 3 weeks after sowing, the sugar beet plants were examined for infestation with Phoma betae and the degree of effectiveness of the compound claimed was determined.

Table VII:

Example VIII:

In a soil that was evenly and heavily contaminated with Pythium ultimum, the stressed compound was evenly mixed in and distributed. The soil treated in this way was filled into plastic pots and each pot was then sown with 10 pea seeds. The tests were evaluated 8-10 days after sowing by determining the number of healthy plants that had emerged and calculating the degree of effectiveness of the compound claimed. Pots with infected, untreated soil were used as controls.

Table VIII:

Tables VII and VIII show the excellent fungicidal action of the claimed compound, which is superior to the comparative agents D and E.

Claims (6)

1. Compounds of the general formula I in the R, R [deep] 1 identical or different substituents from the group halogen, (C [deep] 1-C [deep] 4) -haloalkyl, (C [deep] 1-C [deep] 4) -alkyl, nitro, (C [deep] 1-C [deep] 4) -alkoxy or (C [deep] 1-C [deep] 4) -alkylthio, n, n [deep] 1 whole numbers from 0 to 3, X -0- or -CH [deep] 2-, Y O, S, NH and Z is a cyanoethyl group or a radical of the formula A optionally by -CH [deep] 3, -C [deep] 2H [deep] 5, -COCH [deep] 3 or another radical of the formula -COOR [deep] 3 substituted Methylene group or a phenylene radical which is optionally substituted once or twice by (C [deep] 1-C [deep] 4) alkyl, halogen and / or nitro, and R [deep] 3 (C [deep] 1-C [deep] 4) alkyl mean. 2. Process for the preparation of the compounds of the formula I, characterized in that either in a manner known per se a) Compounds of the general formula II or their alkali or ammonium salts with compounds of the formula III or b) compounds of the general formula IV with compounds of formula V. or their alkali or ammonium compounds, optionally in the presence of an acid-binding agent. 3. Herbicidal agents, characterized in that they contain compounds of the formula I. 4. Fungicidal agents, characterized in that they contain compounds of the formula I. 5. Use of the compounds of the formula I for combating grass weeds. 6. Use of the compounds of the formula I for combating harmful fungi.