JPH02202886A - Imidazolinylthiazole carboxylic acids, production thereof and herbicide containing the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:Compounds expressed by formula I (R represents H, 1-6C alkyl, 2-6C alkenyl, 2-6C alkynyl, benzyl, tetrahydrofurnanyl or furfuryl; R<1> represents H, 1-6C alkyl or phenyl; X and Y represent H, 1-6C alkyl, 3-6C cycloalkyl, etc.). EXAMPLE:2-Propyl 4-(5-isopropyl-5-methyl-4-oxo-2-imidazolinyl)-2-methylthiazole-5- carboxylate. USE:A selective herbicide. PREPARATION:A compound expressed by formula II is reacted with an alcohol expressed by the formula R-OH or an alkali metal alkoxide expressed by the formula R-OM (M represents alkali metal).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to novel imidazolinylthiazole carboxylic acids, 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, Japanese Unexamined Patent Publication No. 57-24364, etc., are already known.

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 aim to obtain a herbicide that is more effective at a lower dosage than conventional herbicides and has no chemical damage (further research on imidazolinyl derivatives). As a result of our research, we discovered that imidazolinylthiazole carboxylic acids have extremely excellent characteristics as herbicides.

The imidazolinylthiazole carboxylic acids according to the present invention have the general formula (I) (wherein R is hydrogen, C, -C6 alkyl group, C, -C6
Alkenyl group, 03-C6 alkynyl group, benzyl group,
Tetrahydrofuranyl group, furfuryl group, R1 represents hydrogen, C5-C6 alkyl group, phenyl group,
Y is each independently hydrogen, C, -C, alkyl group, 03
-C6 cycloalkyl group, or x2 and Y together with the carbon atom to which they are bonded, denotes a 03-C6 spirocycloalkyl group optionally substituted with a methyl group. ) is a new compound that has not been described in any literature.

The herbicide containing imidazolinylthiazole carboxylic acids as an active ingredient according to the present invention is effective against noxious weeds that are a problem in most fields. For example, buckwheat grass, snail knotweed, purslane,
Chickweed, Shiroza, Japanese radish, Japanese radish, Japanese radish, shepherd's purse, American hornwort, Ebisugusa, Japanese chickweed, American king deer, field pansy, Japanese violet, American morning glory, Maruba morning glory, St. convolvulus, Hemlockweed, Hotokenoza, White-breasted trumpet, Japanese Physalis, Japanese Physalis , broad-leaved weeds such as Japanese fir, sunflower, dogberry, and corn marigold; grass weeds such as Japanese barnyard grass, Japanese millet grass, foxtail grass, black grass, Japanese staghorn grass, oat, oat, Seiban sorghum, grass barley, Japanese chahiki, and Japanese sorghum; and dayflowers such as dayflower. It is effective against weeds of the Cyperaceae family, such as Cyperaceae, Cyperaceae, and Cyperaceae.

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, there is little phytotoxicity to important crops, especially soybeans, corn, wheat, rice, cotton, and sugar beet.

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

The imidazolinylthiazole carboxylic acids according to the present invention are produced by the following method.

That is, a compound represented by the general formula (IT) (wherein R1, X, and Y are the same as above) is converted into an alcohol represented by the general formula (I) R-OR(DI) (R is the same as above) Alternatively, it can be produced by reacting with an alkali metal alkoxide represented by ROM (R is the same as above).

-i The compound represented by formula (II) is represented by general formula (III)
or by heating in alcohol represented by R.O.
1 to 3 molar equivalents of an alkali metal alkoxide represented by ROM in an alcohol represented by H or in an inert solvent, or 1 to 5 molar equivalents in an alcohol represented by ROH or in an inert solvent. It can be produced by reacting with a catalytic amount of an alkali metal alkoxide represented by ROM in the presence of an alcohol represented by the general formula (I[[). Generally, the compound represented by the formula (I) can be produced by heating and refluxing the compound represented by the general formula (n) and the alcohol represented by the general formula (III), but the reaction is generally slow. - The reaction is completed within 15 minutes to 2 hours by adding a catalytic amount of ROM to the compound represented by formula (II) in the presence of an equivalent amount of ROM or an alcohol represented by equivalent amount of ROH. .

The inert solvents mentioned here include tetrahydrofuran, dioxane, diethyl ether, diisopropyl ether,
, 2-dimethoxyethane, halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, and aromatic hydrocarbons such as benzene, toluene, and xylene. The reaction temperature is -1
It is possible from 0°C to the boiling point of the solvent, but preferably from 0°C to the boiling point of the solvent.
It is preferable to carry out the reaction at a temperature ranging from °C to room temperature. After completion of the reaction, the imidazolinylthiazole carboxylic acid represented by the -C formula (I) can be purified by carrying out a usual post-treatment and by column chromatography or recrystallization.

-C Of the imidazolinylthiazole carboxylic acids represented by formula (I), the compound in which R is hydrogen is an ester represented by general formula (1), or -form (If
) can be obtained by hydrolyzing the compound represented by the following formula using an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, or an alkaline earth metal hydroxide.

The compound represented by the formula (I[) (R1, X, and Y are the same as above) can be produced by the following method]2. That is, thiazoledicarboxylic anhydrides represented by the -C formula (IV) (R1 is the same as above) and the general formula (V) NH, -φ-CONHz (V) (χ,
Y is the same as above. ) in an inert solvent to produce a compound represented by -form (Vl) (2), which can be further produced by cyclization using a dehydrating agent.

In the reaction of -form (IV) and -form (V) to obtain -form (Vl), the inert solvent is tetrahydrofuran,
Ethers such as dioxane, diethyl ether, diisopropyl ether, and 1,2-dimethoxyethane, halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene, and xylene, acetonitrile, Examples include nitrites such as propionitrile, tertiary amines such as trimethylamine, triethylamine, trilopropylamine, pyridine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylpyrrolidine. Normal-C
The compound represented by formula (V) is used in an equivalent amount to the compound represented by general formula (IV). The reaction temperature is preferably from O''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. ,
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 general formula I) can be carried out by cyclization using a dehydrating agent in the presence of tertiary amines, or by cyclization using a dehydrating agent such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, etc. The cyclization can be carried out in an aqueous solution using an alkali metal hydroxide or an alkaline earth metal hydroxide, but 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 tertiary amines as a solvent, but in some cases it is carried out in an inert solvent using 2 to 10 molar equivalents of tertiary amines relative to the compound of -form (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 tertiary amines using 1 to 5 molar equivalents, preferably 2 to 3 molar equivalents, of thionyl chloride or phosphorus oxychloride relative to the compound of -form (Vl). 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 an exothermic reaction, and a dehydrating agent is added dropwise while cooling depending on the case. Generally, the reaction is often completed in a short time, and is completed within 20 minutes to 1 hour after the completion of dropping the dehydrating agent. After completion of the reaction, the compound represented by the -format (n) can be purified by column chromatography by carrying out usual post-treatments.

The starting materials, thiazole dicarboxylic acid anhydrides represented by the general formula (IV), are described in the Journal of the Chemical Society (J.

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

73B, 1240 (1949), Journal of the American Chemical Society (JAC3,
65, 2167 (1943))).

What should be understood here is that the imidazolylthiazole carboxylic acids of general formula (I) are tautomers. For convenience, they are shown as a single structure of the general formula (1), but they exist as any of the following isomeric forms: or (wherein R, R', X, Y are the same as above). -format CI) to denote imidazolylthiazole carboxylic acids in the cylindrical form.

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, and sugar beet. Further, the herbicide according to the present invention is effective in all kinds of treatment methods such as flooded soil treatment, soil treatment, soil mixed layer treatment, and foliage spraying treatment.

The compound represented by the general formula (T) according to the present invention thus obtained 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 inorganic materials such as clays, talc, bentonite, calcium carbonate, diatomaceous earth, silicic anhydride, etc.; vegetable materials such as wheat flour, soy flour, starch, and crystalline cellulose; petroleum resins, polyvinyl chloride, etc. , polyalkylene glycol, etc.; urea; 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. Preferred 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, alkyl sulfate ester salts (
Examples include sodium lauryl sulfonate, etc.), alkyl sulfonates (sodium 2-ethylhexene sulfonate, etc.), and aryl sulfonates (sodium lignosulfonate, sodium dodecylbenzenesulfonate, etc.).

The content of the compound represented by the general formula (T) in the herbicide according to the present invention varies depending on the formulation, but is usually 1 to 20% by weight for powders and 20 to 90% by weight for wettable powders.
For granules, the amount is 1 to 30% by weight; for agents, it is 1 to 50% by weight; for loable formulations, it is 10 to 50% by weight; and 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 weight percent.

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 can also be used in mixed preparations with these, and in some cases, synergistic effects may occur. You can also expect

[Example] Synthesis examples of imidazolinylthiazole carboxylic acids according to the present invention are shown below.

Example 12-Propynyl 4-(5-isopropyl-5
-Preparation of 2-methylthiazole-5-carboxylate (methyl-4-oxo-2-imidazolinyl) Add 3-isopropyl-3,7 to a solution of tetrahydrofuran (50 ml) and propargyl alcohol (3,5 g).
~dimethyl-5H-imidazo-(1'+2':1,2
) pyrrolo[3°4-d]thiazole-2(2H), 5-
After dissolving the dione (7.9 g), sodium hydride (abt, 60x, oily, 1 mg) was added at room temperature. The reaction solution was stirred at room temperature for 1 hour, then drained into water, and 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 (developing solvent: n-hexane:ethyl acetate-1:1) to obtain 2-propynyl 4-(5-isopropyl-5).
5.2 g of -methyl-4-oxo-2-imidazolinyl)-2-methylthiazole-5-carboxylate was obtained. m, p, 105-107°C'H-N Monthly R spectrum (CDCI 3) δ: 1.08, 1.16 (6
H,d.

J=7.0Hz), 1.72 (3H, s), 2.2~2
．． 6(LH,m), 2.47(11(.

t, J=2.4Hz), 2.71(311,s)
, 4.84 (2■, d, J=2.4■2) 7.8
8(LH, bs) Example 22-propynyl 4-(5-isopropyl-5
-Production of 2-methylthiazole-5-carboxylate (methyl-4-oxo-2-imidazolinyl) Sodium hydride (abt, 60χ, oily +1.2g)
After adding propargyl alcohol solution to a suspension of 3-isopropyl-3,7-dimethyl 5 in tetrahydrofuran (100 ml),
H-imidazo- [1”, 2’71.2) pyrrolo (
3,4-d) Thiazole-2(2H),5-dione(7
．． 9g) in tetrahydrofuran (30ml) was added at room temperature. The reaction solution was stirred at room temperature for 1 hour, then drained into water, and 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 subjected to silica gel chromatography (developing solvent: n-
Purification with hexane:ethyl acetate=1:1) gave 3.3 g of 2-propynyl 4-(5-isopropyl-5-methyl-4-oxo-2-imidazolinyl)-2-methyl-5-carboxylate). .

Example 3 Preparation of methyl 4-(5-isopropyl-5-methyl-4-oxo-2-imidazolinyl)-2-methylthiazole-5-carboxylate Methanol (1
00ml) to 3-isopropyl-3,7-dimethyl-5
H-imidazo-[1°, 2”:C2)pyrrolo(3,4-
d) Thiazole-2(2H), 5-dione (7,9g)
After melting sodium hydride (abt, 60χ,
Oily.

1 mg) was added at room temperature. After stirring the reaction solution for 1 hour at room temperature, the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (developing solvent: n-hexane:ethyl acetate = 1:1'') to give methyl 4-(5isopropyl-5-methyl-4-oxo-2-imidazolinyl)-2.
-4.9g of methylthiazole-5-carboxylate
Obtained.

'H-NMR spectrum (CDC13) δ: 1
．． 13, 1.23 (6o, d.

J=7.2Hz), 1.77(3H,s), 2.2~2
．． 7 (LH, m), 2.73 (3H.

s), 3.94 (38, s), 8.73 (IH, s) Example 4 Methyl 4-(5-isopropyl-5-methyl-4-oxo-2-imidazolinyl)-2-methylthiazole-5 - Preparation of carboxylate methanol (10
3-isopropyl-37-cymethyl-5H-
imidazo-(1',2':C2)pyrrolo(3,4-d)
After dissolving thiazole-2 (2H) and 5-dione (7.9 g), the reaction solution was stirred under heating and reflux for 15 hours.

After distilling off the solvent under reduced pressure, the residue was subjected to silica gel chromatography (developing solvent: n-hexane:ethyl acetate = i
:t) to produce methyl 4-(5-ituprovir-
5-Methyl-4-oxo-2-imidazolinyl)-2-
3.9 g of methylthiazole-5-carboxylate was obtained.

Example 5 Preparation of 2-butynyl 4-(5-isopropyl-5methyl-4-oxo-2-imidazolinyl)-2-methylthiazole-5-carboxylate Tetrahydrofuran (50 ml), 2-butyn-1-
3-isopropyl-7-methyl-5H imidazo-[1'',2':1.2)pyrrolo(3,4-d)thiazole-2(2H),5-dione(
After melting 7.9 g of sodium hydride (abt
, 60χ, oily, 1 mg) was added at room temperature. The reaction solution was stirred at room temperature for 1 hour, then drained into water, and 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 (developing solvent: n-hexane:ethyl acetate = 1:1) to give 2-butynyl 4-(5-isopropyl-5-methyl-4-oxy2-imidazolinyl)-2-methyl. Thiazole-5-carboxylate 4
．． 3g was obtained.

m, p, 124-125.5°C'H-NMR spectrum (CDC13) δ: 1
．． 14, 1.16 (6H, d.

J=7.2Hz), 1.88(3H,t, J=2.4H
z), 2. (1-2.4 (1B, m).

2,74 (3H,s), 4.86 (2H,Q,
J=2.4Hz), 5.97 (IH, dd,
J = 10.2, 8.0Hz), 8.89 (IH, bd,
J=8.0Hz))Jl]6 4-(5-isopropyl-5-methyl-4-oxy-2-imidazolinyl)-2
-Production of methylthiazole-5-carboxylic acid 2-propynyloxy 4-(5-isopropyl-5-methyl-
4-oxo-2-imidazolinyl)-2-methyl-5-
carboxylate (3.2 g) in methanol (10 ml)
) solution was added at room temperature and stirred for 10 hours. The mixture was made acidic by adding concentrated hydrochloric acid, and the precipitated solid was collected by filtration. Wash with water, dry and add 2.5 g of 4-(5-isopropyl-5-methyl-4).
-Oxo-2-imidazolinyl)-2-methylthiazole-5-carboxylic acid was obtained. m, p, 162.5~1
64'C'H-IJMR spectrum (DMSO-d6
) δ: 1.00, 1.04 (611°d, J=7
．． 6Hz)+1.58(3H+s)+2.2~2.6(
IH, m), 2.72 (3H, s), 9.02 (IH,
s) Example 7 4-(5-isopropyl-5-methyl-4-
Preparation of oxo-2-imidazolinyl)-2-methylthiazole-5-carboxylic acid 3-isopropyl-3,7-dimethyl-5H-imidazo-(1
',2':C2)pyrrolo(3,4-d)thiazole-2
(2) 1), 5-dione (2,6 g) in methanol (1
0ml) solution was added at room temperature and stirred for 10 hours. The mixture was made acidic by adding concentrated hydrochloric acid, and the precipitated solid was collected by filtration. Wash with water,
After drying, 2.2 g of 4-(5-isopropyl-5-methyl-4-oxo-2-imidasilinyl)-2-methylthiazole-5-carboxylic acid was obtained.

Next, as a reference example, a synthesis example of an intermediate compound represented by general formula (II) will be shown.

Reference Example 13-Isopropyl-3-methyl-5H-imidazo-[1”,2”:1,2)pyrrolo(3,4-d)
Production of thiazole-2 (2H), 5-dione 200ml
A mixture of thiazole-4°5-dicarboxylic anhydride (8.5 g) and 2-amino-2,3-dimethylbutyramide (6.5 g) in tetrahydrofuran was stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure to give 14.0 g.
A 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-4.
, 11.5 g of 5-dicarboxylic acid-5-monoamide was obtained. m, p, 132-134°CN-(1-carbamoyl-1,2-dimethylpropyl)thiazole-4,5-
After dissolving dicarboxylic acid-5-monoamide (8.6 g) in pyridine (30n+1), 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 (developing solvent: n-hexane:ethyl acetate-2=1) to give 3-isopropyl-3-methyl-5H-imidazo-(1',2'':1,2)pyrrolo(3). , 4-d) 4.4 g of thiazole-2(2H), 5-dione was obtained.

'H-NMR spectrum (CDCI 3) δ:
1.14 (68, d, J=6.8Hz), 2.10 (
38,s), 2.6-3.0(IH,m), 9.2
8 (Ill, s) Reference example 23-isopropyl-3,7-
Preparation of dimethyl-5H imidazo-(1',2':1,2)pyrrolo(3,4-d)thiazole-2(2H),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. The crude organism was dissolved in pyridine (50 ml) and then heated at 50 C.
Then thionyl chloride (7.5ml) was added dropwise over 10 minutes. At this time, the reaction temperature rose to 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. The organic layer was washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off. The residue was purified using silica gel chromatography (developing solvent; n-hexane:ethyl acetate = t:1) to give 3-isopropyl-3,7-dimethyl-5H-imidazo-(1',2':1,2]pyrrolo(3). , 4-d) Thiazole-2 (2H), 8.2 g of 5-dione was obtained. m, p, 127-129°C'H-
NMR spectrum (CDCI+) δ: 1.10
(6H, d, J=6.8Hz), 2.02 (3H, s
), 2.6-3.0 (IH, m), 2.89 (3H
,s) Reference example 33-ethyl-3,7-dimethyl-5H-
imidazo-(1',2':1,2)pyrrolo(3,4-
d) Production of thiazole-2(2H), 5-dione 100
A mixture of 2-methylthiazole-4°5-dicarboxylic anhydride (8.5 g) and 2-amino-2-methylbutyramide (5.8 g) in ml of pyridine was stirred at room temperature for 1 hour. Next, the temperature of the reaction mixture was raised to 50°C, and thionyl chloride (7.5ml) was added dropwise over 10 minutes. At this time, the reaction temperature rose to 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. The organic layer was washed with water, 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 hexane:ethyl acetate=i:i) and purified with 3-ethyl-3,7-dimethyl-5H-imidazo-(1',2')
:1.2) pyrrolo(3,4-d)thiazole-2(2
H), 6.9 g of 5 dione was obtained. In, p, 75~
78°C'II-NMR spectrum (CDCI+)
δ: 1.12 (3■, t, J=7.6Hz), 2
．． 03 (38, s), 2.0-2.8 (2H, m),
2.95(311,s) General formula (1) according to the present invention
The compounds represented by (II) and their physical properties are listed in Tables 1 and 2. The active ingredient compounds in the following formulation examples and test examples are indicated by the compound numbers listed in Table 1.

Next, formulation examples and herbicidal activity test examples of the herbicide according to the present invention will be shown.

Formulation Example 1 (Wettable powder) Compound of the present invention (6): 20 parts by weight, sodium alkylbenzenesulfonate: 2 parts by weight, polyoxyethylene alkyl phenyl ether: 2 parts by weight, and dicrite:
76 parts by weight were ground and mixed to obtain a wettable powder.

Formulation example 2 (hydrating powder) Compound (6) of the present invention: SO parts by weight, white carbon:
A wettable powder was obtained by thoroughly pulverizing and mixing 5 parts by weight of polyoxyethylene alkylphenyl ether ammonium sulfate salt, 4 parts by weight of sodium ligninsulfonate, and 39 parts by weight of diatomaceous earth.

Formulation Example 3 (Flowable agent) Compound of the present invention (20): 20 parts by weight, sodium ligninsulfonate: 2 parts by weight, xanthan gum: 0.3
After adding 6.7 parts by weight of water to 21 parts by weight of polyoxyethylene alkylaryl ether and mixing,
It was finely ground using a sand grinder to obtain a flowable agent.

Formulation Example 4 (Powder) Compound of the present invention (1): 3 parts by weight, sodium ligninsulfonate: 3I! 2 parts by weight of polyoxyethylene alkylaryl ether and 92 parts by weight of clay were mixed and pulverized to obtain a powder.

Formulation Example 5 (Dry Flowable Agent) 60 parts by weight of the compound of the present invention (21), 5 parts by weight of sodium alkylbenzenesulfonate, and 35 parts by weight of polypropylene glycol polyethylene glycol ether were mixed, and the mixture was mixed using a Jet-0-mizer. It was crushed to obtain a dry flowable agent.

Formulation Example 6 (Granules) Finely ground compound of the present invention (6): 5 parts by weight, Gosenol GL-05s (Nippon Gosei)
After thoroughly mixing 2 parts by weight of Sunextract P-252 (sodium lignin sulfonate manufactured by Dezumi Kokusaku Pulp Co., Ltd.) and 91 parts by weight of Clay Ni, an appropriate amount of water was added. The mixture was moistened using an injection molding machine, and then extruded and granulated using an injection molding machine. This was air-dried at 60 to 90°C, crushed, and then sized to a size of 0.3 to 1 mm using a sizing machine to obtain granules.

Formulation Example 7 (Emulsion) Compound of the present invention (6): 10 parts by weight, Tsurupol 800A
(Toho Chemical Co., Ltd. product name: mixture of nonionic surfactant and anionic surfactant): 10 parts by weight and 80 parts by weight of 0-xylene were mixed and dissolved to obtain an emulsion.

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 is 5I per are! ,. 10 days after chemical spraying
The effects on the IC, crops, and weeds were observed and investigated, and the results are shown in Table 3. 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 (Quality) 11-40 (Nakayori) 41-70 (Small) 71-90 (Minor Harm) 91-100 (Harmless) In this test, the compounds according to the present invention were compared to the control compound. Compared to A and B, it exhibited high activity against upland weeds and exhibited excellent selectivity against corn and wheat.

Control compound (compound described in JP-A No. 57-24364) [Effect of the invention] The herbicide containing the compound represented by the general formula (I) according to the present invention is rapidly effective against weed species that are problematic in agriculture. It shows remarkable herbicidal activity and has a herbicidal spectrum. On the other hand, useful crops, especially soybean, trasum, wheat,
It can be safely used on rice, cotton, sugar beet, etc., and has performance superior to comparative drugs or other known compounds.

Claims (5)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is hydrogen, C_1 to C_6 alkyl group, C_3
~C_6 alkenyl group, C_3-C_6 alkynyl group,
Represents a benzyl group, a tetrahydrofuranyl group, or a furfuryl group, R^1 represents hydrogen, a C_1-C_6 alkyl group, or a phenyl group, and X and Y each independently represent hydrogen, C_1-
C_6 alkyl group, C_3 to C_6 cycloalkyl group,
Alternatively, X and Y together with the carbon atoms to which they are attached, optionally substituted with a methyl group, C_
3-C_6 means a spirocycloalkyl group. ) imidazolinylthiazole carboxylic acids. (2) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is a C_1 to C_6 alkyl group, C_3 to C_
6 alkenyl group, C_3 to C_6 alkynyl group, benzyl group, tetrahydrofuranyl group, furfuryl group,
R^1 represents hydrogen, C_1 to C_6 alkyl group, or phenyl group, and X and Y each independently represent hydrogen, C_1 to C_6
Alkyl group, C_3-C_6 cycloalkyl group, or
_6 means spirocycloalkyl group. ) In the production of imidazolinylthiazole carboxylic acids represented by general formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R^1, X, and Y are the same as above.) A compound represented by the formula (III) is reacted with an alcohol represented by R-OH(III) (R is the same as above) or an alkali metal alkoxide ROM (M represents an alkali metal atom and R is the same as above). General formula (I) characterized by
A method for producing a compound represented by (3) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is hydrogen, R^1 is hydrogen, C_1 to C_6 alkyl group, phenyl group, and X and Y are each independently hydrogen, C_1-C_6 alkyl group, C_3-C_6 cycloalkyl group, or In the production of imidazolinylthiazole carboxylic acids represented by the general formula (I) ▲mathematical formulas, chemical formulas, tables, etc.▼(I) (in the formula, R is a C_1 to C_6 alkyl group). ,C_3~C_
6 alkenyl group, C_3 to C_6 alkynyl group, benzyl group, tetrahydrofuranyl group, furfuryl group,
R^1 represents hydrogen, C_1 to C_6 alkyl group, or phenyl group, and X and Y each independently represent hydrogen, C_1 to C_6
Alkyl group, C_3-C_6 cycloalkyl group, or
_6 means spirocycloalkyl group. ) A method for producing a compound represented by general formula (I), which comprises hydrolyzing an imidazolinylthiazole carboxylic acid ester represented by formula (I) using an alkali metal hydroxide or an alkaline earth metal hydroxide. (4) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is hydrogen, R^1 is hydrogen, C_1 to C_6 alkyl group, phenyl group, and X and Y are Each independently hydrogen, C_1-C_6 alkyl group, C_3-C_6 cycloalkyl group, or In the production of imidazolinylthiazole carboxylic acids represented by cycloalkyl group, general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1, X, Y is the same as above.) A method for producing a compound represented by formula (I), which comprises hydrolyzing the compound represented by formula (I) using an alkali metal hydroxide or an alkaline earth metal hydroxide. (5) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is hydrogen, C_1 to C_6 alkyl group, C_3
~C_6 alkenyl group, C_3-C_6 alkynyl group,
It represents a benzyl group, a tetrahydrofuranyl group, a furfuryl group, R_1 represents hydrogen, a C_1-C_6 alkyl group, a phenyl group, and X and Y each independently represent hydrogen, C_1-
C_6 alkyl group, C_3 to C_6 cycloalkyl group,
Alternatively, X and Y together with the carbon atoms to which they are attached, optionally substituted with a methyl group, C_
3-C_6 means a spirocycloalkyl group. ) A herbicide characterized by containing an imidazolinylthiazole carboxylic acid represented by the following as an active ingredient.