JPH0655651B2 - Herbicide composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to novel herbicidal combinations which are effective in controlling unwanted vegetation, especially in transplanted paddy fields. In detail,
The present invention applies 3,5-pyridinedicarbothioic acid, 2- (difluoromethyl) -4-, applied individually or as a mixture.
(2-methylpropyl) -6- (trifluoromethyl)
-, S, S-dimethyl ester and benzoic acid, 2-
[[[[[(4,6-Dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl]-, for the use of methyl ester.

PRIOR ART Herbicidal pyridinedicarboxylate derivatives are immediately disclosed in the publication. For example, Japanese Patent Laid-Open No. 61-15
See 8,965 and JP-A-60-78,965.

Sulfonylurea compounds as herbicides are likewise known. See, for example, JP-A-59-1480.

[Problems and Means for Solving the Problems] The present inventors have mixed agents or 3,5-pyridinedithioic acid, 2-difluoromethyl-4- (2-methylpropyl) -6- (trifluoromethyl)-, each independently. , S,
S-dimethyl ester and benzoic acid, 2-[[[[[(4,6
It has been found that the application of -dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl]-, methyl ester is particularly effective in controlling undesired plants typically found in transplanted rice cultivation.
These compounds are used in proportions of about 5: 1 to about 1: 5, respectively, and for pyridinedicarbothioate compounds in the proportion of about 0.01 to about 0.28 Kg / ha and for sulfonium compounds about. 0.01 to about 0.2 kg / h
It is applied to the place where plants grow in the ratio of a. A particularly preferred ratio is about 0.04 to about 0.20 Kg / ha for pyridinedicarbothioate compounds and about 0.01 to about 0.15 Kg / ha for sulfonylurea compounds.
Is.

[Example] A method for producing each of these two types of compounds from a commercially available starting compound will be described below with reference to examples.

Example 1 3,5-Pyridinedicarbothioic acid, 2- (difluoromethyl) -4- (2-methylpropyl) -6- (trifluoromethyl)-, S, S-dimethyl ester Step A 3,5- Pyridinedicarbothioic acid, 1,4-dihydro-
4- (2-Methylpropyl) -2-, 6-bis (trifluoromethyl)-, dimethyl ester (2: 1 mixture)
Manufacture of Methyltrifluoroacetoacetate (MTFAA)
(178.9 g, 0.915 mol) and piperidine (0.
45.3 g (0.515 mol) of isovaleraldehyde were added to the mechanically stirred mixture of 44 g, 5.16 x 10 ^-3 mol in the course of 3 minutes. An exotherm occurred and the temperature rose to 108 ° C within 6 minutes. The reaction mixture was held at 108 ° C for 2 hours and then cooled to 60 ° C. Additional 4.45g
(0.051 mol) isovaleraldehyde was added and the mixture was held at 83 ° C for 1.5 hours. The reaction mixture was left overnight (12 hours) at room temperature, diluted with 80.4 g of toluene and then heated to 53 ° C. for 2 hours with stirring. Ammonia gas (16.2 g, 0.952 mol) was introduced into the reaction mixture for 1 hour and 40 minutes. The mixture was diluted with an additional 91 g of toluene and an additional 4.3 g (0.253
(Mol) ammonia was introduced during 25 minutes. The mixture was cooled to 5 ° C. in an ice bath while N ₂ was passed through for 20 minutes to remove excess NH ₃ . 40 g of sulfuric acid was added to the reaction mixture. Heat was generated and the temperature was raised to 45 ° C. After cooling to 35 ° C., an additional 301 g of sulfuric acid was added with stirring over a few minutes. The reaction mixture is stirred at 3 ° C. for 20 minutes and 1 Kg
Poured on ice. The mixture was stirred with 220 g toluene. The toluene layer was separated and the aqueous layer was extracted once with 280 g toluene and twice with 300 ml toluene. The combined toluene layers were washed with brine and concentrated under vacuum to give 182.2 g of oil. This oil was dissolved in 500 ml methylene chloride, washed successively with 200 ml saturated aqueous sodium hydrogen carbonate solution and 300 ml brine, dried (MgSO ₄ ) and concentrated in vacuo to give 179.4 g dihydropyridine as an oil. It was The product is 83% as a result of analysis.
Which corresponds to a yield from the starting material MTFAA of 83%.

Step B Preparation of 3,5-pyridinedicarboxylic acid, 2- (difluoromethyl) -4- (2-methylpropyl) -6- (trifluoromethyl)-, dimethyl ester 23.34 g (0.0514 mol) of the above A mixture of the compound obtained in step A, 11.11 g (0.0599 mol) of tributylamine and 50 ml of toluene was kept at reflux for 1 hour, cooled and diluted with 50 ml of toluene. Toluene solution with water (50 ml), 6N HCl
(2 × 100 ml), and brine (100 ml) successively, and concentrated in vacuo. 1 torr of residue
Kugelrohr was distilled. Initial fraction (0.25 g purity 74
% Of product), 19.17 g (86.2%) of 85.3% pure product was collected. Pot residue (po
t residue) (1.49g) dissolved in ether to 50m
It was extracted with 1 saturated aqueous sodium hydrogen carbonate solution. The aqueous layer was acidified with concentrated hydrochloric acid. The oily precipitate was extracted into ether. The ether extract is dried and concentrated under vacuum,
This gave 1.13 g of residue. This was reacted with 8.4 g methyl iodide and a solution containing 0.47 g K ₂ CO ₃ in 20 ml DMF to give 0.95 g (4.8%) of 96% pure product. The yield of product from MTFAA was 74%.

Step C Hydrolysis to diacid and conversion to diacid chloride 7192 g (57.68 mol) of 45% KOH in 22 flasks equipped with stirrer, condenser and heat controller.
The solution was charged with 4 H ₂ O, then 61
Charge 78 g (16.73 mol) of the compound obtained in Step B above and stir for about 5-10 minutes at 50 ° C.
Melted in. The mixture was heated to reflux (94 ° C.) and refluxed for 21 hours, substantially complete the hydrolysis. The reaction mixture was cooled to 45 ° C. and split in half (about 6 saline solutions for each half). The batch 1 was diluted with water 1 and stirred well for about 15 minutes, and then extracted with methylene chloride 5. The phases were separated and the basic aqueous phase was acidified with concentrated hydrochloric acid to a pH of about 2. The material was cooled to -4 ° C and the diacid was precipitated as a brown solid. The solid was washed with water. The overall yield was 88%.

22 flasks under N ₂ atmosphere with 4374.8 g (1
(2.82 mol) of the above 2 acid and 6 toluene were charged. Then 5737 g (3517 ml) (48.2 mol) of thionyl chloride were added stepwise over 15 hours at 15-26 ° C. The mixture is heated to boiling point and refluxed for about 40 hours, then cooled to about 65 ° C and cooled to 35 ° C for 2 hours.
Concentrated on a rotary evaporator at 0-30 Torr, finally 45 ° C, 0.2 Torr.

Finally, the product is treated with about 1 Kg of silica gel (60-200
It was purified by passing through a mesh. The column was moistened with hexane, the crude diacid chloride was dissolved in the minimum amount of hexane and the product was eluted with hexane.

Preparation of Step D Pyridine Carbothioate Twenty-two flasks were charged with 6 freshly removed reagent bottles of tetrahydrofuran and 1936.1 g (27.6 mol) of the methyl mercapton sodium salt under N ₂ . The solution was cooled to 0 ° C. and 4095.7.
g (11.36 mol) of the diacid chloride obtained in Step C was added keeping the temperature below 40 ° C. After 1 day the reaction was complete and the flask was cooled. 6 ethers, 1
12 N HCl and 4 water were added. The layers were separated and the organic phase was washed with 4 water, then once with 4 saturated brine. The solvent was removed under vacuum. The crude product was diluted 2 to 1 with hexane and eluted through hexane through a 6 inch long by 5 inch diameter silica gel column. The solvent was removed to give 4021.0 g (88%). The product was recrystallized from hexane to give a purified product 357 having a melting point of 57 to 62 ° C.
9.4 g (78.5%) was obtained.

Example 2 Step A Preparation of benzoic acid, 2- (chloromethyl)-, methyl ester Methanol (68g), 10% NaOH solution (48g,
480 ml) and CH ₂ Cl ₂ (1000 ml) with a thermometer,
Charge to 2 flasks equipped with stirrer and addition funnel. The mixture is cooled to about 10 ° C., and 2-chloromethyl benzoyl chloride (200 g, 150 ml) is added with stirring 1/2 while maintaining the temperature at 10 to 20 ° C.
Added dropwise over time. After the addition was complete, the mixture was warmed to room temperature and stirred for 21/2 hours until the reaction was complete. Aqueous phase and the organic phase was separated and the organic phase dried over MgSO _4. The solvent was removed on a rotary evaporator and the final traces of solvent were removed by Kugelrohr distillation at room temperature below 5 Torr to give 183.85 g of the methyl ester with a boiling point of 65.
Obtained as a colorless oil at ˜77 ° C.

Step B Preparation of benzoic acid [[(aminocarboximido) thio] -2-methyl], methyl ester, hydrochloride (1: 1) Step A material (175 g), thione (72.15).
g) and ethanol (950 ml) were charged to a flask of 2 and refluxed for 2 hours, then cooled to room temperature. The solvent was evaporated and the white residue was boiled with methanol (about 600 ml).
Dissolved in. The solution was cooled, filtered and vacuum dried to recover a white solid having a melting point of 198 ° C.

Step C Thiouronium salt of Step B (130.37 g) and 1
Was charged into a 3 round bottom flask equipped with stirrer, thermometer and gas outlet tube. Chlorine (106.37 g) was condensed at the temperature of dry ice and added to the flask in small portions over about 40 minutes so that the color disappeared during the addition. A thick white precipitate formed. The mixture was stirred for about 2 hours after the completion of chlorine addition. The white precipitate was then washed well with water and then dried overnight. Yield 241g.

Step D Preparation of benzoic acid, 2- (aminosulfonylmethyl)-, methyl ester The product of Step C is suspended in ether and the mixture is kept at 10 ° C.
Cooled to: While stirring the liquid ammonia, while maintaining the temperature at 10 to 15 ° C., it was added over about 15 minutes. The mixture was then stirred for about 1 hour while warming to room temperature. 100 ml of water were added and the phases were separated. Water phase 1
It is extracted twice with 50 ml of diethyl ether and the ether is extracted with M.
Dry over gSO ₄ , filter, evaporate the solvent and recrystallize with ethanol to give 55.88 g of a white solid, mp 75-78 ° C.

Step E The product of Step D (50 g) was charged to one flask equipped with an addition funnel, thermometer, reflux condenser and stirrer. 1,4-diazabicyclo [2.2.2] in a flask
Octane (0.5g), xylene (350ml) and n-
Butyl isocyanate (21.82 g) was added. The addition funnel was filled with dry ice and charged with 23.72 g of phosgene. Bring the flask to reflux (about 135
C) and phosgene was added in small portions over 3 hours. The flask was then cooled, producing a brown precipitate. The precipitate was filtered under a nitrogen atmosphere and the solvent was removed by Kugelrohr distillation. The product was recovered as 69.54 g brown oil.

Preparation of Step F Benzoic acid, 2-[[[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl]-, methyl ester In one flask with thermometer and stirrer 2-amino-4,6-dimethoxypyrimidine (28.6 g), acetonitrile (300 ml) and a small amount of 1,4-diazabicyclo [2.2.2] octane were charged. Step E
The isocyanate was added with stirring to produce a pale colored precipitate. The mixture was heated to 50-55 ° C for 1 hour and then left at room temperature overnight. The white solid was then filtered from the mixture, washed twice with acetonitrile and then dried under vacuum for 4 hours. White solid product (37.
55 g, melting point 179.5-183 ° C.) were recovered.

Herbicidal effect Future problem weeds in paddy fields have been evaluated by many Japanese researchers. The consensus is that weeds of four species are listed as the most important weeds in the future. These are Hie (1st year grass weed), Konagi (1st year broadleaf weed), Mizuka and Tsuri and Firefly (perennial weed). These are selected mainly because they have strong regenerative power in paddy fields. Other presently problematic weeds, such as seaweed, main or kuroguro, only propagate through the tubers of the plant. Therefore, it is expected that once a good herbicide for these is developed, its population will drop significantly in the short term. However, it is very difficult to completely control the above-mentioned 4 types of main weeds, and even if one plant remains in the paddy field, the population of the next year will explode and the herbicide application will increase. Is absolutely necessary. Several weeds other than the four major weeds are also problem weeds and current and new herbicides are needed to control them. However, these new herbicides must control these four types of weeds. In other words, these four types of weeds are the smallest weeds that cannot be ignored because they are controlled by new commercial herbicides.

The current situation regarding the development of new herbicides suggests that agents that can control the elbow have great commercial potential as a component of admixtures with herbicides that control major nonweed weeds. is doing.

There is currently growing environmental concern about the use of herbicides, and one of the major concerns is the contamination of rivers and drinking water with herbicides. It is said that the way to reduce the contamination of water with herbicides is to reduce the proportion of herbicides so that the herbicides can move only a small amount in the soil. Therefore, agents with high unit activity, low water solubility and high soil absorbency can be effective herbicides for paddy rice while solving or alleviating this problem.

As mentioned above, the herbicide combinations according to the invention are particularly effective in controlling plants which are not desired for transplanted rice. One of the pyridine-based herbicides according to the present invention, like Monochoria, satisfactorily controls weeds of the family Gramineae (Hie, Mehishiba),
The other component, the sulfonylurea component, is remarkably effective in controlling broad-leaved weeds of Cyperus and Scirpus species and perennials. Thus, the combinations according to the invention are capable of controlling a wide range of highly harmful undesired plants effectively.

To illustrate the control of these undesired plants, the pyridine and sulfonylurea compounds of the invention were individually tested for weed control in a small-scale field trial, while also testing combinations of these compounds. did. In the following tests, weed species are designated by the following code letters.

A-Hie (seeding) B-Konagi (seeding) C-Cyperus difformis (seeding) D-Firefly (seeding) E-Mizukayatsuri (tuber planting) F-Mainaka (tuber planting) G-Kurogai (tuber) Implantation H-Urikawa I-Kikashigusa J-Matsubae K-Himemisohagi L-Ajina Herbicidal effects were tested as follows. Transplanted paddy rice (Nihonbare). Different weed species were mixed with soil, sown in the case of sowing weeds, and tubers were randomly planted in test plots in the case of weeds propagated by tubers.

After transplanting paddy rice and sowing weeds, each test plot was treated with the pyridine herbicide of the present invention, the sulfonylurea of the present invention, or a combination of the above two. There were 3 replicates per test. The control% shown in the table below is the average value of 3 subdivisions.

Details regarding the test site, soil properties, and other conditions are as follows.

As is evident from the above data, the admixture according to the invention appears to be relatively safe for transplanted rice and thus can be used for the selective control of weeds in this crop.

The herbicidal compositions of the present invention also include concentrated formulations which require dilution prior to application and may contain adjuncts and active ingredients in liquid or solid form. This composition is mixed with a diluent, filler, carrier, and various auxiliaries for formulating the composition in the form of finely divided finely divided solids, granules, pellets, solutions, dispersions or emulsions. The active ingredients can be prepared by applying, or the two active ingredients can be applied individually in the form of liquids, solids and the like. Thus, the active ingredient is one that can be used with adjuvants such as finely divided solids, liquids of organic origin, water, wetting agents, dispersing agents, emulsifying agents or any suitable combination thereof.

Suitable wetting agents are sulfonates of alkylbenzenes and alkylnaphthalenes, sulfated fatty alcohols, amines or acid amides, long-chain acid esters of sodium isothionate,
Monoester of sodium sulfosuccinate ester, sulfated or sulfonated fatty acid ester, petroleum sulfonate, sulfonated vegetable oil, diter-sialyacetylene glycol, polyoxyethylene derivative of alkylphenol (especially isooctylphenol and nonylphenol) and hexitol anhydride. Includes polyoxyethylene derivatives of higher fatty acid esters (eg sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonate, polymeric alkylnaphthalene sulfonates, sodium naphthalene sulfonate, and polymethylene bisnaphthalene sulfonate.

Wettable powders are water dispersible compositions containing an active ingredient, an inert solid extender and one or more lubricants and dispersants. The inert solid extenders are usually of mineral origin, such as natural clay, diatomaceous earth and silica derived synthetic minerals. Examples of said extenders include kaolinite, attapulgite and synthetic magnesium silicate. The wettable powder of the present invention is usually about 0.5 to 60 parts (preferably 5 to 20 parts).
Active ingredient, about 0.25 to 25 parts (preferably 1 to 15)
Part) wetting agent, about 0.25 to 25 parts (preferably 1.0).
~ 15 parts) and 5 to about 95 parts (preferably 5 to 5 parts).
50 parts) of an inert solid extender. All parts are parts by weight with respect to the total composition. If necessary, about 0.1-2.
0 parts of solid inert extender can be replaced by corrosion inhibitors or antifoaming agents or both.

Alternative formulations include powder concentrates containing 0.1 to 60 parts by weight of the active ingredient on a suitable filler. These powders can be diluted to a concentration in the range of about 0.1-10% by weight for application.

Aqueous suspensions are prepared by dispersing the water-insoluble active ingredient in water with a dispersant under high shear stirring to produce a stable suspension of very finely ground particles. it can. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, which allows for very uniform processing when diluted and sprayed. Suitable concentrations of the preparations contain about 0.1-60%, preferably 5-50% active ingredient.

Emulsions can be made by stirring a non-aqueous solution of a water-insoluble active ingredient and an emulsifier with water until homogeneous and then homogenizing to give a safe emulsion of very fine non-aqueous particles. Appropriate concentrations of these formulations are about 0.1-6
It contains 0%, preferably 10 to 50% by weight of active ingredient. The upper limit is determined by the solubility limit of the active ingredient in the solvent and the packing density of emulsion particles in water.

A concentrated emulsion is a solution of the active ingredient dissolved together with an emulsifier in a water-immiscible or partially water-immiscible solvent. Suitable solvents for the active ingredient according to the invention include dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons and water-immiscible ethers, esters or ketones. However, other highly concentrated liquid concentrate formulations can be formulated by dissolving the active ingredient in a solvent and then diluting to a spray concentration, for example with kerosene. Concentrated compositions generally contain from about 0.1 to 95 parts (preferably 5 to 60 parts) of active ingredient, about 0.25 to 5 parts.
It contains 0 parts (preferably 1 to 25 parts) of surfactant and, if necessary, about 4 to 94 parts of solvent. All parts are parts by weight based on the total weight of emulsifiable oil.

Granules are inert, physically stable, granular compositions containing the active ingredient attached to or distributed in the basic matrix of the finely ground particulate extender. Surfactants, such as those mentioned above, may be present in the composition to aid in leaching the active ingredient from the particulate extender. Natural clays, pyrophyllites, illites and vermicillites are examples of viable classes of particulate mineral extenders. Preferred extenders are porous, absorbent, pre-formed particles such as pre-formed and sieved granular attapulgite or thermally expanded granular vermiculite and finely divided clays such as Kaolin, hydrated attapulgite or bentonite.

The granules of the present invention are about 0.1 to about 30 per 100 parts by weight of clay.
It may contain from 0 to about 5 parts by weight of surfactant per 100 parts by weight of the active ingredient and 100 parts by weight of the granular clay.

The compositions of the present invention may also contain other additives, such as fertilizers, other herbicides, other insecticides, safeners, etc., used as an adjunct or in combination with any of the adjuncts described above. Agents useful in combination with the active ingredients of the present invention include, for example, triazine, urea, dinitroaniline,
Carbamate, acetamide, acetanilide, uracil, acetic acid or phenol derivative, thiocarbamate, triazole, benzoic acid, nitrile, biphenyl ether herbicide and the like are included.

Fertilizers useful for use in combination with the active ingredients include, for example, ammonium nitrate, urea, potassium and superphosphate. Other useful additives include materials on which plant organisms are rooted and grown, such as compost, manure, mulch, sand and the like.

The formulation of herbicides of the type described above is illustrated in the following several illustrative embodiments.

I. emulsifier II. Flowables III. Wettable powder IV. Powder V. Granule When practiced according to the invention, an effective amount of a compound of the invention is applied to the soil containing seeds or plant tubers, or
Alternatively, it is mixed into the soil medium by any convenient method.
Application of liquid and particulate solid compositions to soil can be carried out by conventional methods, such as power spreaders, booms and manual sprayers and spray spreaders. The composition can also be applied by air as a powder or spray as it is effective at low application rates.

The exact amount of active ingredient used depends on various factors, including the species of the plant and its stage of development, soil type and condition, rainfall and the amount of the particular compound used. About 0.02 in selective pre-emergence application to soil
To about 3.0 kg / ha, preferably about 0.1 to about 1.0 kg / ha
Generally, an amount of all active ingredients of the invention is used. In some cases lower or higher rates are required.
One skilled in the art can readily determine the optimum rate to apply in any particular case from this specification, including the examples above.

The term "soil" is used in its broadest sense, including all conventional "soils" as defined in the Webster New International Dictionary, Second Edition, Encyclopedia (1961). Thus, the term applies to any substance or medium on which a plant has roots and grows, and is not only soil, but compost, manure, dung, mulch, loam, silt, tailored to support plant growth.
Also includes mud, clay, sand, etc.

Although the present invention has been described with the above embodiments, the present invention, of course, should not be construed as limited thereby.

Claims (5)

[Claims] 1. 3,5-Pyridinedicarbothioic acid, 2-difluoromethyl-4- (2-methylpropyl) -6-
(Trifluoromethyl)-, S, S-dimethyl ester and benzoic acid, 2-[[[[[(4,6-dimethoxy-2
-Pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl]-, a herbicide composition containing a mixture of methyl esters. 2. The composition according to claim 1, wherein the weight ratio of pyridinedicarbothioic acid diester to sulfonylurea is 1: 5 to 10: 1. 3. A method for suppressing undesired plant growth in transplanted rice, which comprises applying the composition according to claim 1 to a place where plants grow. 4. A pyridinedicarbothioic acid diester of 0.01
~ 0.28kg / ha and sulfonylurea 0.01%
The method according to claim 3, wherein the method is applied at a rate of 0.2 kg / ha. 5. 0.01-0.2 kg / ha 3,5-pyridinedicarbothioic acid, 2-difluoromethyl-4- (2-methylpropyl) -6- (trifluoromethyl)-, S, S-dimethyl Ester and 0.01-0.2 kg / ha benzoic acid, 2-
[[[[[(4,6-dimethoxy-2-pyrimidinyl)
Amino] carbonyl] amino] sulfonyl] methyl]
A method for suppressing unwanted plant growth in transplanted paddy rice, which comprises applying methyl ester to a place where the plant grows.