JPH02200687A - Thiazole compound, its production and herbicide containing the compound as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R is H, 1-6C alkyl or phenyl; X and Y are H, 1-6C alkyl, 3-6C cycloalkyl or together with C bonded thereto form (methyl-substituted) 3-6C spirocycloalkyl]. EXAMPLE:3-Isopropyl-3-methyl-5H-imidazo-[1',2':1,2]pyrrolo[3,4-d]thiaz ole-2(2H),5- dione. USE:A selective herbicide. PREPARATION:The objective compound can be produced by reacting a thiazoledicarboxylic acid anhydride of formula II (e.g. thiazole-4,5-dicarboxylic acid anhydride) with a compound of formula III (e.g. 2-amino-2,3- dimethylbutylamide) and eliminating water from the resultant compound of formula IV with a dehydration agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to novel thiazole compounds, a method for producing the same, and a herbicide containing the same as an active ingredient.

[Prior Art] It has been reported in JP-A-54-64637 and JP-A-54-10506 that certain imidazolinyl derivatives have herbicidal activity.
No. 1, JP-A No. 57-24364, and other publications. These compounds are benzoic acid derivatives or nicotinic acid derivatives substituted with imidazolinyl groups, but they are not sufficient for use in field crops, and there are also problems with selectivity in important crops. .

[Problem to be solved by the invention] The present invention is a selective herbicide that is effective against a wide range of weed species at lower doses in most field crops and does not cause chemical damage to important crops. The goal is to provide a drug.

[Means and effects for solving the problem] The present inventors have conducted further research on imidazolinyl derivatives in order to obtain a herbicide that is more effective at a lower dosage than conventional herbicides and is free from phytotoxicity. As a result of our research, we discovered that thiazole compounds have extremely excellent characteristics as herbicides.

The thiazole compounds according to the present invention have the general formula (wherein,
R represents hydrogen, 01-C6 alkyl group, phenyl group,
X and Y are each independently hydrogen, C8-C, alkyl group,
A C8-C6 cycloalkyl group or a C8-C, spirocycloalkyl group, together with the carbon atom to which they are attached, is optionally substituted with a methyl group. ) is a new compound that has not been described in any literature.

The herbicide containing the thiazole compounds according to the present invention as an active ingredient is effective against noxious weeds that are a problem in most fields. For example, freckles, snail knotweed, purslane, chickweed, white grass,
Japanese radish, Japanese radish, white-bellied shepherd, shepherd's purse, American hornwort, Ebisugusa, Japanese commonweed, American gold deer, field pansy, Japanese morning glory, American morning glory, Maruba morning glory, Western bindweed, Hemlockweed, Hotokenoza, White-breasted butterfly,
Broad-leafed weeds such as Physalis japonica, Physcomitrella japonica, Japanese fir tree, sunflower, sycamore, corn marigold, etc.
Barnyard grass, golden millet, foxtail grass, crabgrass, sycamore, sycamore, oat, oat,
It is effective against weeds of the Poaceae family, such as Seiban sorghum, grasshopper, Japanese sorghum, and Cyperaceae, as well as weeds of the Cyperaceae family, such as Asiatic dayflower, and Cyperaceae, such as Cyperus spp. Furthermore, the herbicide according to the present invention exhibits a more rapid herbicidal effect on the above-mentioned weeds than conventional imidazolinyl derivatives. On the other hand, it causes little damage to important crops, especially soybeans, corn, wheat, rice, cotton, and sugar beets.

The herbicide according to the present invention is effective in all kinds of treatment methods such as hot water soil treatment, soil treatment, soil mixed layer treatment, and foliar spray treatment.

The thiazole compounds according to the present invention are produced by the following method.

That is, thiazole dicarboxylic acid anhydrides represented by general formula (II) (R is the same as above) and general formula (1) % formula % ([[) (X, Y are the same as above) A compound represented by the general formula (IV) (wherein R, X, and Y are the same as above) is produced by reacting the compound with can do.

General formula (I[) and general formula (I[[) form general formula (IV)
In the reaction to obtain , inert solvents include ethers such as tetrahydrofuran, dioxane, diethyl ether, diisopropyl ether, and 1,2-dimethoxyethane, halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, benzene, and toluene. , aromatic hydrocarbons such as xylene, nitriles such as acetonitrile and propionitrile, trimethylamine, triethylamine, trilopropylamine, pyridine, N,N-dimethylaniline, N,N-diethylaniline, N-methylpyrrolidine, etc. Tertiary amines can be mentioned. Usually, the compound represented by the general formula (I[[) is the general formula (II)
It is used in an equal amount to the compound represented by. The reaction temperature is 0
The reaction is preferably carried out at about 100°C to 100°C, preferably at room temperature. The obtained crude reaction product can be used as it is in the next reaction, but may be purified if necessary.

Furthermore, if the above-mentioned tertiary amines are used as a solvent in this reaction, the cyclization reaction can be carried out directly using the following dehydrating agent.

The cyclization reaction of the compound represented by the general formula (IV) is carried out in the third
cyclization using a dehydrating agent in the presence of grade amines, or using an alkali metal hydroxide or alkaline earth metal hydroxide such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, etc. Although the cyclization can be carried out in an aqueous solution, it is preferable to carry out the cyclization using a dehydrating agent in the presence of a tertiary amine. Examples of the tertiary amines include the above-mentioned tertiary amines.

Examples of the dehydrating agent include thionyl chloride, phosphorus oxychloride, acetyl chloride, acetic anhydride, etc., and preferably thionyl chloride and phosphorus oxychloride are used. usually,
The reaction can be carried out using a tertiary amine as a solvent, but in some cases it is carried out in an inert solvent using 2 to 10 molar equivalents of a tertiary amine relative to the compound of general formula (IV). be able to. The inert solvent mentioned here is
Tetrahydrofuran, dioxane, diethyl ether,
Ethers such as diisopropyl ether and 1,2-dimethoxyethane, halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene, and xylene, and esters such as ethyl acetate and butyl acetate. Examples include the following.

The reaction is carried out in the presence of a tertiary amine using 1 to 5 molar equivalents, preferably 2 to 3 molar equivalents of thionyl chloride or phosphorus oxychloride relative to the compound of general formula (IV). Ru. The reaction temperature can range from 0°C to the boiling point of the solvent, but it is preferable to drop thionyl chloride and phosphorus oxychloride at 40°C to 70°C.The reaction is exothermic, and in some cases, a dehydrating agent may be added while cooling. is added dropwise.The reaction is generally completed in a short time, within 20 minutes to 1 hour after the completion of dropping the dehydrating agent.After the reaction is completed, usual post-treatment is performed and column chromatography is carried out. - The compound represented by Funato (1) can be purified.

The starting materials, thiazole dicarboxylic acid anhydrides represented by the general formula (n) (R is the same as above), were published in the Journal of the Chemical Society (J.

Chem, Soc, 72.5221 (1950
)), Berichte (Ber,.

738, 1240 (1949)) Journal of
Chemical Society (J, Chem, Soc,
65.2167 (1943)) etc.

The compounds of the present invention thus obtained are effective against noxious weeds that are a problem in most fields, such as broad-leaved weeds, grass weeds, dayflower weeds, and cyperaceae weeds, and moreover exhibits a herbicidal effect quickly. . On the other hand, there is little phytotoxicity to important crops, especially soybeans, corn, wheat, rice, cotton, sugar beet, etc.

The compound represented by the general formula (1) according to the present invention obtained in this way may be used as it is for plants to be treated, but it is generally mixed with an inert liquid or solid carrier and treated as necessary. Add and mix other adjuvants as required, and prepare in commonly used formulations such as powders, granules, wettable powders, etc.
It is used as a herbicide in emulsions, flowable formulations, etc.

Solid carriers include clays, talc, bentonite,
Inorganic substances such as calcium carbonate, diatomaceous earth, silicic anhydride, etc.; Vegetable organic substances such as wheat flour, soybean flour, starch, crystalline cellulose; Polymer compounds such as petroleum resin, polyvinyl chloride, polyalkylene gelylcol, etc.; Urea; Examples include waxes and the like. Examples of liquid carriers include various oils, various organic solvents, and water.

As the auxiliary agent, for example, a wetting agent, a dispersing agent, a fixing agent, a spreading agent, etc. can be used alone or in combination as appropriate.

Auxiliary agents used for the purposes of wetting, dispersing, spreading, stabilizing ingredients, stabilizing physical properties, etc. include various surfactants or polymers such as gelatin, albumin, sodium alginate, methyl cellulose, polyvinyl alcohol, xanthan gum, etc. Compounds or other adjuvants may be mentioned. Further, for antibacterial and anti-mold purposes, an industrial disinfectant or an anti-bacterial and anti-mold agent may be added depending on the case.

As the surfactant, nonionic, anionic, cationic and amphoteric surfactants can be used as appropriate. Strange examples include alkyl phenols, higher alcohols, alkyl naphthols, higher fatty acids, fatty acid esters, dialkyl phosphate amines, etc., polymerized with ethylene oxide and propylene oxide, and alkyl sulfate ester salts (
sodium lauryl sulfate, etc.), alkylsul is an acid salt (2
(sodium ethylhexene sulfonate, etc.), aryl sulfonates (sodium lignosulfonate, sodium dodecylbenzenesulfonate, etc.).

The content of the compound represented by general formula ('I) in the herbicide according to the present invention varies depending on the formulation form, but
Usually 1-20% by weight for powders, 20-90% by weight for wettable powders, 1-30% for granules, 1-50% for emulsions, 10-50% by weight for flowable formulations, and 10-50% by weight for dry flowable formulations. It is 20 to 70% by weight. The content of the adjuvant is 0 to 80% by weight, and the content of the carrier is the amount obtained by subtracting the content of the active ingredient compound and the adjuvant from 100% by weight.

The herbicide of the present invention includes one or more other herbicides,
Not only can it be used in combination with agricultural chemicals such as insecticides and plant growth regulators, soil conditioners, or fertilizing substances, but it is also possible to create a mixed formulation with these, and in some cases, a synergistic effect may occur. You can also expect

[Example] Synthesis examples of thiazole compounds according to the present invention are shown below.

Practical Mi Example 1 3-isopropyl-3-methyl-5H-imidazo-[1'+2':L2]pyrrolo[3,4-d
]] Thiazole-22) 1) Production of 5-' dione 20
Thiazole-45- in 0 ml of tetrahydrofuran
Dicarboxylic anhydride (8,5 g) and 2-amino-2,3
A mixture of dimethylbutyramide (6.5 g) was added at room temperature to
Stir for hours. The reaction mixture was concentrated under reduced pressure to 14.0
g of crude organism was obtained. The crude product was slushed with a mixed solvent of acetone and isopropyl ether to obtain N-(1-carbamoyl-1,2-dimethylpropyl)thiazole-
11.5 g of 4,5-dicarboxylic acid-4-monoamide was obtained. m, p, 132-134°CN-(1-rubamoyl-1,2-dimethylpropyl)thiazole-4,5
-Dicarboxylic acid-4-monoamide (8.6g) in pyridine (30ml)? After dissolving, phosphorus oxychloride (6.0 ml) was added dropwise at 50°C over 5 minutes. At this time, the reaction temperature rose to 85°C. After stirring the reaction mixture for 30 minutes, the solvent was distilled off under reduced pressure.

Dilute hydrochloric acid was added to the residue, insoluble matter was filtered, and the filtrate was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off. The residue was purified by silica gel chromatography (Development: HX; n-hexane:ethyl acetate-2:1), and 3-isopropyl-3
-Methyl-5H-imidazo[1',2'':1,2]pyrrolo[3,4-d]]thiazole-22H), 4.4 g of 5-dione was obtained.

'H-N gate R spectrum (CDC13) δ: 1
．． 14 (68, d, J=6.8Hz), 2.10 (3
H, s), 2.6-3.0 (18, m), 9.28
(IH,s) Example 23-isopropyl-3,7-dimethyl-5H-imidazo-[1',2':1,2]pyrrolo[3,4-d]thiazole-2(21(),5-dione In 200 ml of tetrahydrofuran, 2-methylthiazole-4,5-dicarboxylic anhydride (8.5 g
) and 2-amino-2,3-dimethylbutyramide (6,
5g) was stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure to obtain 15.2 g of crude product. After dissolving the crude product in pyridine (50 ml), thionyl chloride (7.5 ml) was added dropwise over 10 minutes at 50"C. At this time, the reaction temperature rose to 80°C. The reaction mixture was left to stir for 30 minutes. Afterwards, the solvent was distilled off under reduced pressure. Dilute hydrochloric acid was added to the residue, insoluble matter was filtered, and the filtrate was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate, and then the solvent was evaporated. The residue was purified by silica gel chromatography (developing solvent: n-hexane:ethyl acetate = 4:1) to give 3-isopropyl-3,7-dimethyl-5■-imidazo-[1',2' :
1+2]pyrrolo[3,4-d cothiazole-2(2H)
, 8.2g of 5-dione was obtained. m, p, 127-12
9°C'H-NMR spectrum (CDC) a) δ:
1.10 (6H, dJ=6.8Hz), 2.
02 (3B, s), 2.6-3.0 (11 (, m),
2.89(3H,s) Example 33-ethyl-3,7-
Cymethyl-5H-imidazo-[1”,2':1,2]
Preparation of pyrrolo[3,4-d]thiazole-2 (211L5-dione) In 100 ml of pyridine, 2-methylthiazole-4,5 dicarboxylic anhydride (8.5 g) and 2-amino-2-methylbutyramide ( 5.8g) was stirred at room temperature for 1 hour.Then, the reaction mixture was heated to 50'C, and thionyl chloride (7,5n+1) was added dropwise over 10 minutes.At this time, the reaction temperature was 80°C. After stirring the reaction mixture for 30 minutes, the solvent was distilled off under reduced pressure. Dilute hydrochloric acid was added to the residue, insoluble matter was filtered, and the filtrate was extracted with ethyl acetate. It was dried over anhydrous sodium sulfate, and then the solvent was distilled off.

The residue was subjected to silica gel chromatography (developing solvent: n-
Purified with 3-ethyl-3,7-dimethyl-5H-imidazo-[1",2"
:1.2]pyrrolo[3,4-dlthiazole-2(21
( ), 6.9 g of 5-dione was obtained. m, p, 75-7
8'C1(-NMR spectrum (CDC13) δ:
1.12 (3H, t, J=7.6Hz), 2.0
3 (3H, s), 2.0-2.8 (2H, m), 2
．． 95(3H,s) Compounds represented by formula (1) according to the present invention and their physical properties are listed in Table 1. The active ingredient compounds in the following formulation examples and test examples are indicated by the compound numbers listed in Table 1.

1 day Table 1 Next, formulation examples and herbicidal activity test examples of the herbicide according to the present invention are shown.

Formulation Example 1 (Aqueous phase agent) Compound 2 of the present invention: 20 parts by weight, sodium alkylbenzene sulfonate = 2 parts by weight, polyoxyethylene alkylphenyl ether 22 parts by weight, and Dicrite: 76 parts by weight
Parts by weight were thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 (Aqueous phase agent) Compound 4 of the present invention: 50 parts by weight, white carbon: 5 parts by weight, polyoxyethylene alkylphenyl ether ammonium sulfate salt: 1 part by weight of 4 parts, sodium lignin sulfonate 99,122 parts by weight, and diatomaceous earth = 39 Parts by weight were thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 3 (Flowable agent) Compound 2 of the present invention: 20 parts by weight, lignin sulfonate sodium 99,122 parts by weight, xanthan gum: 0.3 parts by weight, polyoxyethylene alkylaryl ether: 1 part by weight, water: 76.7 parts by weight. After mixing, the mixture was finely ground using a sand grinder to obtain a flowable agent.

Formulation Example 4 (Powder) 3 parts by weight of the compound of the present invention 8, 23 parts by weight of sodium ligninsulfonate, 2 parts by weight of polyoxyethylene alkylaryl ether, and 92 parts by weight of clay were mixed and ground to obtain a powder.

Formulation Example 5 (Dry Flowable Agent) 60 parts by weight of the compound of the present invention 2, 5 parts by weight of sodium alkylbenzenesulfonate, and 35 parts by weight of polypropylene glycol polyethylene glycol ether were mixed and pulverized using a Jet-0-mizer. A dry flowable agent was obtained.

Formulation Example 6 (Granules) Finely pulverized compound of the present invention 2: 5 parts by weight, gohsenol (
Gosenol) GL-05s (Nippon Gosen Kagaku Co., Ltd.)
pv8) = 2 parts by weight, Sunextract P-252 (Desumi Kokusaku Pulp Co., Ltd. class lignin sulfonic acid sodium): 2 parts by weight, and clay: 91 parts by weight were mixed well, and then an appropriate amount of water was added. It was moistened and then extruded and granulated in an injection molding machine. After air-drying and crushing this at 60-90℃, it is
．． The granules were sized to 3 to III+ to obtain granules.

Formulation Example 7 (Emulsion) Compound 2 of the present invention: 10 parts by weight, Trupol 800A (trade name, manufactured by Toho Chemical Co., Ltd.: mixture of nonionic surfactant and anionic surfactant): 10 parts by weight, and 0-xylene. An emulsion was obtained by mixing and dissolving 280 parts by weight.

Test Example 1 Field Soil Treatment Test Field soil was filled into a 1/10,000 are resin pot, and morning glory, giant knotweed, chickweed, white locust, and
One species each of golden millet, crabgrass, corn, and wheat were sown and grown in a greenhouse.

When each plant has 2 to 3 leaves, a predetermined amount of the test compound is diluted with water in an emulsion prepared according to the method described in Formulation Example 7, and a predetermined amount is applied using a pressurized microsprayer. Spread. The amount of spraying was 51 per area. On the 10th and 30th day after the chemical spraying, the effects on crops and weeds were observed and investigated, and the results are shown in Table 2. In the table, the degree of damage to the test plants and the degree of phytotoxicity to the crops are expressed by comparing the growth state of the plants with that of the untreated air-dried type using the following criteria.

Growth rate (χ) shown by air dry weight ratio vs. untreated area 0-5
(Death) 6-10 (Infestation) 11-40 (Virtual damage) 41-70 (Small damage) 71-90 (Minor damage) 91-100 (Harmless) In this test, the compounds related to the present invention were compared to the control compound Compared to A and B, it showed high immediate activity against the upland weeds tested, and also showed excellent selectivity against corn and wheat.

[Effect of the invention] As is clear from the test results, the formula 1 (i) according to the present invention
Herbicides containing the compound represented by 1) exhibit rapid and significant herbicidal activity against weed species that are problematic in agriculture, and have a herbicidal spectrum. On the other hand, it can be safely used for useful crops, especially soybeans, corn, wheat, rice, cotton, sugar beet, etc., and has performance superior to comparative drugs or other known compounds.

Claims (3)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents hydrogen, a C_1 to C_6 alkyl group, or a phenyl group, and X and Y each independently represent hydrogen, C_1 ~C
_6 alkyl group, C_3-C_6 cycloalkyl group, or C_3 where X and Y together with the carbon atoms to which they are attached are optionally substituted with a methyl group
~C_6 means a spirocycloalkyl group. ) Thiazole compounds represented by (2) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents hydrogen, a C_1 to C_6 alkyl group, or a phenyl group, and X and Y each independently represent hydrogen, C_1 ~C
_6 alkyl group, C_3-C_6 cycloalkyl group, or C_3 where X and Y together with the carbon atoms to which they are attached are optionally substituted with a methyl group
~C_6 means a spirocycloalkyl group. ) In order to produce thiazole compounds represented by the formula (II), there are mathematical formulas, chemical formulas, tables, etc. (II) (wherein, R is the same as above). and general formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, X and Y are the same as above.) By reacting the compound represented by general formula (IV) ▲ mathematical formula, chemical formula, There are tables, etc. ▼ (IV) (In the formula, R, General formula ( I
) A method for producing a compound represented by (3) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents hydrogen, a C_1 to C_6 alkyl group, or a phenyl group, and X and Y each independently represent hydrogen, C_1 ~C
_6 alkyl group, C_3-C_6 cycloalkyl group, or C_3 where X and Y together with the carbon atoms to which they are attached are optionally substituted with a methyl group
~C_6 means a spirocycloalkyl group. A herbicide characterized by containing a thiazole compound represented by ) as an active ingredient.