JPS6113458B2 - - Google Patents

Description

[Detailed description of the invention]

The subject of the invention is the general formula (In the above formula, R and R ₁ are halogen, (C ₁ -C ₄ )-halogenalkyl, (C ₁ -C ₄ )-alkyl, nitro, (C ₁ -
means the same or different substituents selected from the group consisting of C4)-alkoxy and ( _C1 - _C4 )-alkylthio, n _{and n1} represent integers from 0 to 3, and X is -O - or _-CH2- , Y means O or S, Z is a cyanoethyl group or a formula

means a residue represented by the formula, where A is -CH ₃ , -C ₂ H ₅ , -COCH ₃ as the case may be
a methylene group substituted by or by another residue of the formula -COOR ₃ or phenylene optionally mono- or di-substituted with (C ₁ -C ₄ )-alkyl, halogen and/or nitro; or a styryl group, and R ₃ is (C ₁ -C ₄ )-alkyl. Among the compounds represented by the general formula, preferred are those having chlorine and/or bromine for the halogen, 1 or 2 carbon atoms for the alkyl group, 1 or 2 for n, and n This is a compound where ₁ means 0 and Y means oxygen. Particularly preferable ones include (R) _o being 4-Cl, 2.4
-Cl, 4-Br, 2-Cl-4-Cl, or 4- _CF3
and n=1 or 2, n ₁ =0 and X and Y are oxygen. Z is preferably cyanoethyl or A= _-CH2
It is _a residue represented by the formula -A- _COOR3 having -, -CH( _CH3 )- or -CH( _C2H5 )-. The object of the present invention is furthermore to produce compounds represented by the general formula: (a) or (b) the general formula Compounds represented by the formula HYZ () or their alkali-
or an ammonium compound, and optionally in the presence of an acid binder.
Hal preferably means chlorine or bromine. The compound represented by the formula is a herbicide that exhibits excellent action against a wide range of weeds when used in pre- and post-emergence treatment methods. With the use of the substances according to the invention, it is possible to improve the production of grasses such as oats (Avena), Alopecurus, ryegrass (Lolium), Setaria, Echinocloa and Digitaria in crops of dicotyledonous plants. It is possible to control weeds belonging to . Some of the compounds according to the invention can be used to selectively control weeds also belonging to the Poaceae family in cereal crops. Even when applied in large amounts, soybeans, peanuts, kidney beans, broad beans, peas, Roussin, cabbage, rapeseed, cucumbers, sunflowers, tobacco, carrots, celery, and sugar beets are not harmed by the drug. Owing to their special action against weeds, inter alia oats, sylvestris, ryegrass and millet, these new herbicides are known, for example, by the compounds known under the following general names: Alachlor, Compared to some well-established herbicides like Monolinuron, Linuron, Pyrazon, Phenmedipham, Sodium Trichloracetate, Fluorodifen and Mecoprop, weed It is superior in its effectiveness when used in heavily infested fields. Furthermore, the amounts required to completely eradicate weeds may be much lower than in the case of the known herbicides mentioned above. The low toxicity of the compounds of the general formula to warm-blooded animals is also an advantage. Surprisingly, the compounds of the formula are also susceptible to molds and plant pathogens that damage commercially available materials, such as Piricularia
oryzae), rust fungus (Rostpilze), gray mold fungus (Botrytis cinerea), downy mildew fungus (Plasmopara
viticola), Phytophthora infestans,
Powdery mildew (EchteMehltau), damping-off fungus (Rhizoctonia solani), septoria blight (Rhizoctonia solani)
nodorum), Ustilago nuda, Phomabetae, Phithium
ultimum) and Hyminthosporium
gramineum). For use as fungicides for commercially available materials, the compounds according to the invention can be used, for example, as lacquer,
Used as an additive to varnishes and paints. For use as plant protection agents, these compounds are formulated as powders, wettable powders, dispersions or emulsions. The total content of active ingredients is generally from 2 to 80% by weight, depending on the respective preparation. Furthermore, they contain the customary adhesives, wetting agents, dispersing agents, fillers and carrier substances. They may be mixed with other fungicides. The subject of the invention is therefore also herbicides and fungicides, which are characterized in that they contain the compounds of the general formula together with customary formulation auxiliaries and inert substances, and which are also effective against grass weeds and harmful fungi. It is also the use of the compounds shown in the formula for the control of species. The agents according to the invention generally contain from 2 to 95% by weight of active ingredient of the formula. They can be used in the form of customary preparations as wettable powders, emulsions, spray solutions, powders or granules. Wettable powders are preparations that can be homogeneously dispersed in water, which contain, together with the active substance, diluents or inert substances and also wetting agents, such as polyoxyethylated alkylphenols, polyoxyethylated oleyls or stearylamines. an alkyl- or alkylphenyl sulfonate and a dispersant,
For example, sodium ligninsulfonate, 2.2-
Also included are sodium dinaphthylmethane-6,6'-disulfonate, or sodium oleylmethyl-taurate. Emulsions contain active substances in organic solvents such as butanol,
Obtained by dissolving in cyclohexanone, dimethylformamide, xylene or also high-boiling aromatic compounds. Powders are finely ground solid substances containing active substances.
For example, it is obtained by grinding with talc, naturally occurring clays such as kaolin, bentonite, pyrophyllite or diatomaceous earth. Spray solutions, which are often sold in spray containers, contain the active substance dissolved in an organic solvent and further contain, for example, mixtures of fluorochlorohydrocarbons and/or carbon dioxide as propellants. Granules are prepared by spraying the active substance onto an adsorbent granular inert material or by applying a carrier material such as sand, kaolinite or an adhesive onto the surface of the granular inert material. They can be produced, for example, by depositing concentrates of the active substance using polyvinyl alcohol, sodium polyacrylate or mineral oil. Alternatively, a suitable active ingredient may be added by a method customarily used for the production of granular fertilizers.
It can also be prepared in combination with fertilizers if desired. In the case of herbicides, the concentration of active ingredient may vary depending on the commercially available formulation. In wettable powders, the concentration of the active ingredient is, for example, about 10% to
It varies between 80% and the remainder consists of the formulation additives mentioned above. In the case of emulsions, the concentration of active ingredient is approximately 10
% to 80%. Powders usually contain 5-20% of active ingredient, spray solutions about 2-20%. In the case of granules, the content of active ingredient depends on whether the active ingredient is present in liquid or solid form and on what granulation aids, fillers, etc. are used. For application, commercially available concentrates are optionally diluted in the customary manner, for example with water in the case of wettable powders and emulsions. Powders and granules as well as sprays are no longer further diluted with inert substances before application. The amount required will vary depending on external conditions such as temperature, humidity, etc. It can vary within wide limits, for example between 0.1 and 10 Kg of active ingredient per hectare, but preferably between 0.1 and 3 Kg/ha.
It is. The active ingredients according to the invention can be combined with other herbicides and soil pesticides. Production Example Example 1 2-[4′-(4″-chlorophenoxy)-phenoxy]-propionyl lactic acid methyl ester In 160 ml of acetone, 81 g of 2-[4′-(4″-chlorophenoxy)-phenoxy]-propionic acid and 2- A solution of 48 g of promopropionic acid methyl ester is heated and boiled with 40 g of potassium carbonate for 8 hours while stirring. After cooling to 20°C, the inorganic salts are separated. Acetone is distilled off from the liquid, and the residue is distilled under reduced pressure. bp _0.1 : 91 _g (87.0% of theory) of the following compound at 190 DEG -191 DEG C. are obtained. Example 2 2-[4′-(2″・4″-dichlorophenoxy)-phenoxy]-propionylglycolic acid methyl ester 2-[4′-(2″・4″-dichlorophenoxy)-phenoxy] - 61 g of propionic acid and 24 g of methyl chloroacetate are dissolved in 200 ml of butanone. After adding 29 g of potassium carbonate, the mixture is heated and boiled for 8 hours while stirring. The reaction mixture is cooled to 20°C and the inorganic salts are separated off. Butanone in the liquid is distilled off, and the resulting ester is purified by vacuum distillation. bp _0.05 : 67 g ₍ 90.0% of theory) of the following compound at 207°-208°C are obtained. Example 3 2-[4'-(2''·4''-dichlorophenoxy)-phenoxy]-propionyl-thioglycolic acid methyl ester 48 g of methyl ethyl thioglycolate are dissolved in 200 ml of toluene. 2-[4'-(2''·4''-dichlorophenoxy)- dissolved in 150 ml of toluene
156 g of phenoxy]-propionic acid chloride and 48 g of dry triethylamine dissolved in 50 ml of toluene are added dropwise simultaneously at 20 DEG -40 DEG C. The mixture is then stirred for 2 hours at 40°C. The triethylamine hydrochloride formed is suctioned off. The toluene in the liquid is distilled off, and the residue is purified by distillation at 0.2 mmHg. bp _0.2 : 180 g (96% of theory) of the following compound having _a temperature of 230° to 232° C. is obtained. Example 4 2-[4′-(4″-bromophenoxy)-phenoxy]-propionic acid-(2-cyanoethyl)-ester 30 g of 3-oxypropionic acid nitrile are dissolved in 150 ml of toluene. 2-[4′-(4″-bromophenoxy)-phenoxy]-propionic acid chloride 40 g dissolved in 143 g and 50 ml toluene
g simultaneously dropwise at 20° to 40°C. The mixture is stirred for a further 2 hours at 40°C, cooled to 20°C, filtered with suction and the toluene in the liquid is distilled off.
151 g of residue is obtained. After distillation of the _residue , bp _0.1 : 208°
138 g (8.8% of theory) of the following compound are obtained at ~210°C. Example 5 2-[4′-(4″-trifluoromethylphenoxy)-phenoxy]-propionic acid-(4-carbomethoxyphenyl)-ester 23 g of 4-oxybenzoic acid methyl ester and 17 g of dry triethylamine were added to toluene. Dissolve in 120 ml of toluene and 2-[4′-(4″-
trifluoromethylphenoxy)-phenoxy]-
A solution of 52 g of propionic acid chloride is added dropwise at 20-40°C. After stirring the mixture at 40° C. for 2 hours, it is cooled to 20° C., the triethylamine hydrochloride is suctioned off, and the toluene is distilled off from the liquid. The oil obtained is recrystallized from n-hexane. 64g of the following compound with a melting point of 78° to 79°C (theoretical amount of 92
%) is obtained. Example 6 2-[4′-(2″・4″-dichlorophenoxy)-phenoxy]-propionyl-(2-acetoacetic acid-
Methyl ester) 70 g of sodium 2-[4'-(2''·4''-dichlorophenoxy)-phenoxy]-propionate are suspended in 300 ml of benzene and 32 g of 2-chloroacetoacetic acid methyl ester are added. 8 at 80℃
Stir for an hour, cool and remove the sodium chloride. Distill toluene. 76 g of a yellow oil with a refractive index of n ²⁵ _D = 1.5593
is obtained. Further compounds listed in the table below were prepared according to the methods described in Examples 1-6.

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[Table] Example 88 2-[4′-(2″・4″-dichlorobenzyl)-phenoxy]-propionyl lactic acid-methyl ester 2-[4′-(2″・4″-dichlorobenzyl)-phenoxy ]-44 g of propionic acid, 27 g of 2-promopropionic acid methyl ester, 21 g of anhydrous calcium carbonate and 100 ml of acetone are stirred at 60°C for 8 hours. After cooling to 20°C, the inorganic salts are separated. Acetone is distilled off from the liquid, and the residue is distilled under reduced pressure. bp _0.5 : 51 g (91.6% of theory) of the following compound having _a temperature of 165° to 166°C are obtained. Example 89 2-[4′-(4″-chlorophenoxy)-phenoxy]-propionyl-tartronic acid diethyl ester 2-[4′-(4″-chlorophenoxy)-phenoxy]-propionic acid sodium salt 32 g, brommalonic acid 27 g of diethyl ester, 1 ml of dimethylformamide and 150 ml of toluene at 80°C
Stir for 18 hours. After suctioning sodium bromide,
Toluene and excess brommalonic acid diethyl ester are distilled off from the liquid. ^n25D : 43g of _the following compound having a refractive index of 1.5300
(96.0% of theory) is obtained as a pale yellow oil. Example 90 2-[4′-(2″・4″-dichlorophenoxy)-phenoxy]-propionyl-tartronic acid-diethyl ester 2-[4′-(2″・4″-dichlorophenoxy)- Phenoxy]-propionic acid-sodium salt 35g,
27 g of brommalonic acid diethyl ester, 1 ml of dimethylformamide and 150 ml of toluene are stirred at 80° C. for 18 hours. After cooling to 20°C and suctioning off the sodium bromide, toluene and excess brommalonic acid diethyl ester are distilled off from the liquid. 47 g (97% of theory) of a pale yellow oil are obtained. ^n26D _: 1.5337 Example 91 (Reference example) 2-[4′-(2″・4″-dichlorophenoxy)-phenoxy]-propionyl-glycine methyl ester 14 g of glycine ester newly released from glycine methyl ester chlorhydrate
(0.152 mol) dissolved in 80 ml of toluene,
2-[4′-(2″・4″-dichlorophenoxy)-phenoxy]-propionic acid chloride in 40 ml of toluene
24g (0.076mol) solution at 10° to 15°C
Add dropwise over 30 minutes. The mixture is then heated between 15° and 22°
Stir for 2 hours at °C. The resulting glycine methyl ester chlorohydrate is filtered off with suction. Toluene is distilled off from the liquid under reduced pressure. 30 g of a pale yellow oil with n ²⁵ _D of 1.5652 are obtained. Biological Test Examples Herbicide Examples 1 Pre-emergence Treatment Seeds of various grasses were sown in pots and the compounds according to the invention formulated as wettable powders or emulsions were sprayed onto the soil surface at various tortuosity levels. The above pots were then placed in a greenhouse for 4 weeks, and the results of the treatment were judged according to Bolle's evaluation criteria (see the evaluation criteria table below) in the same manner as in the following examples. The compounds according to the invention listed in Table 1 have a very good effect against weeds, with an effect of 0.15 active ingredients per ha for most species.
It was still effective even at the lowest application rate of Kg. Comparative drugs Fluorodifen and Mecoprop had substantially weaker effects on grasses. Example: Post-germination treatment Seeds of various grasses were sown in pots and cultured in a greenhouse. Three weeks after sowing, the plants were sprayed with various application rates of the compounds according to the invention, formulated as powders or emulsions, and the action of these compounds was determined after 4 weeks in the greenhouse. The compounds according to the invention listed in Table 1 show a good to very good action against grass weeds and are superior to the comparative drugs phlorodifen and mecoprop. Example: In another test using the same method as in Example (post-emergence treatment), various cultivated plants were sprayed with suspensions or emulsions of the compounds according to the invention mentioned in Example and. Even at a high application rate of 2.5Kg/ha, soybeans, peanuts, fava beans, kidney beans, peas, russin,
Linus, cabbage, rapeseed, cucumber, sunflower,
Tobacco, carrot, celery and sugar beet are
There was no drug damage. Barley and wheat are
There was no reaction to the drugs according to Examples 1, 2, 8, 11, 37, 38, 43, 47, 53, 56 and 57. Similar results were obtained when these compounds were sprayed onto the soil surface in a pre-emergence treatment method. Evaluation criteria table Bolle (Nachrichtenblatt des
Deutschen, Pflanzenschutzdienstes 16 ,
(1964, 92-94)

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[Table] Biological test example: Fungicide example: Barley seeds (infestation rate 15%) infected with the fungus Ustilago nuda are soaked in the compound according to the invention at the concentration shown in the table and placed in a pot. and cultivated in a greenhouse first at a lower temperature and then at a higher temperature (20°C). 10～12
After a week, healthy stems and naked smut fungus (Ustilago
The number of infected stems was counted, the degree of infestation was determined in each case, and finally the degree of effect was calculated. In this and the following examples, the letters A to E refer to the following comparative drugs: A = 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxyanilide and methoxyethyl-Hg - combination with silicate B=manganese-ethylene-1,2-bis-dithiocarbamate D=tetramethylthiuram-disulfide (TMTD) E=S-ethyl-N-(3-dimethylaminopropyl)-thiolcarbamate-hydrochloride (Prothiocarb)

[Table] It is clear from the table that the effect of the compounds according to the invention against Ustilago nuda is superior to that of comparative drug A. Example Helminthosporium gramineum
Seeds of summer barley naturally infested with an infestation of 24% were soaked in the compound according to the invention (50% soaking agent) at the concentrations listed in the table. The seeds were sown in dishes, which were then placed in a greenhouse. Afterward, count the number of plants affected by the leaf spot fungus and healthy plants, measure the degree of infestation in each case,
Finally, the degree of effect was calculated (Table 1).

[Table] The results in Table 1 demonstrate the excellent efficacy of the compound according to the present invention against the leaf spot fungus and the mercury-free compound of this mercury-free comparative drug B.
It also shows superiority over Comparative Drug A containing mercury. EXAMPLE Sugar beet seeds naturally infected by Phoma betae with an infestation of about 60% are soaked in a compound according to the invention, sown in dishes and grown in a greenhouse.
Cultivated at 20℃. Three weeks after sowing, the degree of spread of sugar beet by Janome disease fungi was examined.
The effectiveness of the compounds according to the invention was determined.

[Table] Example A compound according to the invention was uniformly mixed and distributed in soil that was uniformly and strongly infected with the white rot fungus (Pythium ultimum). Fill plastic pots with soil treated in this way, then fill each pot with
Ten pea seeds were sown. sowing 8
After ~10 days, the test was evaluated by counting the number of germinated healthy plants and calculating the degree of effectiveness of the compounds according to the invention. As a control sample, pots infected with the fungus but untreated were used.

TABLE 1 From Table 1 and Table 1, the superior fungicidal action of the compounds according to the invention compared to the comparative drugs D and E is clearly seen.

Claims (1)

[Claims] 1. General formula (In the above formula, R and R ₁ are halogen, (C ₁ -C ₄ )-halogenalkyl, (C ₁ -C ₄ )-alkyl, nitro, (C ₁ -
means the same or different substituents selected from the group consisting of C4)-alkoxy and ( _C1 - _C4 )-alkylthio, n _{and n1} represent integers from 0 to 3, and X represents -O - or -CH ₂ -, Y means O or S, and Z means a cyanoethyl group or a residue of the formula where A is -CH ₃ as the case may be; , −C ₂ H ₅ , −COCH ₃
a methylene group substituted by or by another residue of the formula -COOR ₃ or phenylene optionally mono- or di-substituted with (C ₁ -C ₄ )-alkyl, halogen and/or nitro; or a styryl group, and _R3 means ( _C1 - _C4 )-alkyl). 2 formulas The compound according to claim 1, which is a compound represented by: 3 formulas The compound according to claim 1, which is a compound represented by: 4 formula The compound according to claim 1, which is a compound represented by: 5 formula The compound according to claim 1, which is a compound represented by: 6 formula The compound according to claim 1, which is a compound represented by: 7 formula The compound according to claim 1, which is a compound represented by: 8 formula The compound according to claim 1, which is a compound represented by: 9 formula The compound according to claim 1, which is a compound represented by: 10 formula The compound according to claim 1, which is a compound represented by: 11 formula The compound according to claim 1, which is a compound represented by: 12 formula The compound according to claim 1, which is a compound represented by: 13 formula The compound according to claim 1, which is a compound represented by: 14 General formula (In the above formula, R and R ₁ are halogen, (C ₁ -C ₄ )-halogenalkyl, (C ₁ -C ₄ )-alkyl, nitro, (C ₁ -
means the same or different substituents selected from the group consisting of C4)-alkoxy and ( _C1 - _C4 )-alkylthio, n _{and n1} represent integers from 0 to 3, and X is -O - or -CH ₂ -, Y means O or S, and Z means a cyanoethyl group or a residue of the formula where A is -CH ₃ as the case may be; , −C ₂ H ₅ , −COCH ₃
a methylene group substituted by or by another residue of the formula -COOR ₃ or phenylene optionally mono- or di-substituted with (C ₁ -C ₄ )-alkyl, halogen and/or nitro; or a styryl group, and R ₃ is (C ₁ -C ₄ )-alkyl). A method for producing a compound represented by the above general formula, which comprises reacting a compound represented by the formula or an alkali salt or ammonium salt thereof with a compound represented by the formula Hal-Z (). 15 General formula (In the above formula, R and R ₁ are halogen, (C ₁ -C ₄ )-halogenalkyl, (C ₁ -C ₄ )-alkyl, nitro, (C ₁ -
means the same or different substituents selected from the group consisting of C4)-alkoxy and ( _C1 - _C4 )-alkylthio, n _{and n1} represent integers from 0 to 3, and X is -O - or -CH ₂ -, Y means O or S, and Z means a cyanoethyl group or a residue of the formula where A is -CH ₃ as the case may be; , −C ₂ H ₅ , −COCH ₃
a methylene group substituted by or by another residue of the formula -COOR ₃ or phenylene optionally mono- or di-substituted with (C ₁ -C ₄ )-alkyl, halogen and/or nitro; or a styryl group, and R ₃ is a (C ₁ -C ₄ )-alkyl group), by a method known per se, the compound represented by the general formula A compound represented by the above general formula, which is characterized by reacting the compound represented by the formula HYZ () with a compound represented by the formula HYZ () or an alkali or ammonium compound thereof, optionally in the presence of an acid binder. manufacturing method. 16 General formula (In the above formula, R and R ₁ are halogen, (C ₁ -C ₄ )-halogenalkyl, (C ₁ -C ₄ )-alkyl, nitro, (C ₁ -
means the same or different substituents selected from the group consisting of C4)-alkoxy and ( _C1 - _C4 )-alkylthio, n _{and n1} represent integers from 0 to 3, and X is -O - or -CH ₂ -, Y means O or S, and Z means a cyanoethyl group or a residue of the formula where A is -CH ₃ as the case may be; , −C ₂ H ₅ , −COCH ₃
a methylene group substituted by or by another residue of the formula -COOR ₃ or phenylene optionally mono- or di-substituted with (C ₁ -C ₄ )-alkyl, halogen and/or nitro; or a styryl group, and _R3 means ( _C1 - _C4 )-alkyl. 17 General formula (In the above formula, R and R ₁ are halogen, (C ₁ -C ₄ )-halogenalkyl (C ₁ -C ₄ )-alkyl, nitro, (C ₁ -
means the same or different substituents selected from the group consisting of C4)-alkoxy and ( _C1 - _C4 )-alkylthio, n _{and n1} represent integers from 0 to 3, and X is -O - or -CH ₂ -, Y means O or S, and Z means a cyanoethyl group or a residue of the formula where A is -CH ₃ as the case may be; , −C ₂ H ₅ , −COCH ₃
a methylene group substituted by or by another residue of the formula COOR ₃ or phenylene optionally mono- or di-substituted with (C ₁ -C ₄ )-alkyl, halogen and/or nitro or 1. A fungicide characterized by containing a compound represented by the following formula: a styryl group, and _R3 means ( _C1 - _C4 )-alkyl.