JPH05213970A - Condensed heterocyclic ring derivative and herbicide - Google Patents

Abstract

PURPOSE:To provide a novel compound which is useful as a herbicide of high selectivity, killing only weeds without exerting any adverse effect on the crop plants. CONSTITUTION:A compound of formula I [R is formula II (Y is H, F; R<1> is H, alkoxycarbonyl, alkoxycarbonylalkylthio, alkoxy); X is O, S; n is 3 to 5], for example, 8-(4-chloro-2-fluoro-5-ethoxy-carbonylmethylthiophenylimino)-7- thia-1,5-diazabicyclo[3.3.0]-octan-6-one. The compound of formula I is obtained by the reaction of phosgene with a compound of formula III in a solvent such as THF in the presence of a base such as triethylamine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fused heterocyclic derivative and a herbicide containing the derivative as an active ingredient.

[0002]

The present inventors have investigated thiadiazabicyclononane derivatives as fused heterocyclic derivatives and have found that they can be used as an active ingredient of herbicides. (Specification of JP-A-1-199978 and JP-A-2-45488)

[0003]

In recent years, there has been a strong demand for a herbicide having a selective action of killing only weeds without damaging the crops even when applied to useful crops and weeds at the same time. .. Further, in order to prevent excessive retention of the drug in the environment, there is a demand for the development of a drug capable of obtaining a complete effect with a low dose. However, the compounds described as the above-mentioned conventional techniques do not always completely satisfy these needs.

[0004]

[Means for Solving the Problems] In order to achieve the above-mentioned objects, the present inventors synthesized a large number of fused heterocyclic derivatives and studied variously their usefulness. as a result,
Substituted phenylimino group, substituted 2-benzothiazolone-5
8-ythia-1,6-diazabicyclo [4.3.0]-having an illimino group and a substituted 2H-1,4-benzoxazin-3-one-6-ylimino group as a substituent at the 9-position
The inventors have found that the 3-nonene derivative has excellent herbicidal activity and selectivity for the above purpose, and completed the present invention.

That is, the present invention has the general formula [I]

[0006]

[Chemical 4]

[In the formula, R is a chemical formula (2) wherein Y represents a hydrogen atom or a fluorine atom, R ¹ represents a hydrogen atom, an alkoxycarbonyl group, an alkoxycarbonylalkylthio group, a cycloalkoxycarbonylalkylthio group, an alkynyloxycarbonylalkylthio group. Group, alkenyloxycarbonylalkylthio group, unsubstituted or substituted benzyloxycarbonylalkylthio group, phenoxycarbonylalkylthio group, alkoxyalkoxycarbonylalkylthio group, haloalkoxycarbonylalkylthio group, alkoxycarbonylalkoxy group, alkoxyalkoxycarbonylalkoxy group, alkoxy group, alkynyl An oxy group or an alkenyloxy group) or a compound represented by the formula 3 (in the formula, Y represents a hydrogen atom or a fluorine atom, and R ² represents Represents an alkyl group, an alkenyl group or an alkynyl group, Z represents an oxymethylene group or a sulfur atom, X represents an oxygen atom or a sulfur atom, and n represents an integer of 3 to 5. .. } The condensed heterocyclic derivative represented by these, and a herbicide containing this.

The compounds of the present invention are illustrated in Tables 1A to 1D and Table 2. The compound numbers will be referred to in the following description.

[0009]

[Table 1A]

[0010]

[Table 1B]

[0011]

[Table 1C]

[0012]

[Table 1D]

[0013]

[Table 2]

The compound of the present invention can be produced, for example, by the following method.

[0015]

[Reaction formula 1]

(In the formula, R and n have the same meanings as described above.)

That is, it can be produced by reacting the compound represented by the general formula [II] with phosgene. that time,
It does not matter whether or not there is a base. Here, as the base, aliphatic amines such as trimethylamine and triethylamine, tertiary amines such as pyridine, picoline and quinoline, or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate can be used. it can. Examples of the solvent include chlorine-containing hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, ethers such as diethyl ether, tetrahydrofuran and dioxane, hydrocarbons such as n-hexane, benzene and toluene, acetone, methyl ethyl ketone and the like. Can be used. The above reaction is -20
The temperature is in the range of ℃ to the boiling point of the solvent, and is completed in 1 to 24 hours. The target compound can be obtained from the reaction solution by a conventional method. Further, it can be purified by recrystallization or column chromatography, if necessary.

The compound represented by the general formula [II] as a raw material can be produced by the following method.

[0019]

[Reaction formula 2]

(In the formula, R and n have the same meanings as described above.)

It can be produced by reacting the compound represented by the general formula [III] with the compound represented by the general formula [IV] in the presence of a base. Here, as the base, use is made of aliphatic amines such as trimethylamine and triethylamine, tertiary amines such as pyridine, picoline and quinoline, or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. You can Examples of the solvent include chlorine-containing hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, ethers such as diethyl ether, tetrahydrofuran and dioxane,
Hydrocarbons such as n-hexane, benzene and toluene, or dimethisulfoxide, N, N-dimethylformamide and the like can be used. The above reaction is carried out in the temperature range of -20 ° C to the boiling point of the solvent, and is completed in 1 to 24 hours. The target compound can be extracted from the reaction solution by a conventional method.

Among the compounds represented by the general formula [IV], compounds having n = 3 are known in the literature [Poland Journal of Chemistry (Pol. J. Chem.) 198].
2,561,1131-8], where n = 5, can be produced by the following method.

[0023]

[Reaction formula 3]

That is, 1,2-diethoxycarbonylperhydro-1,2 described in Journal of Organic Chemistry (J. Org. Chem.) 1981, 46 (2), 323-7. It can be obtained by hydrolyzing diazepine with hydrochloric acid. The reaction can be carried out at room temperature to reflux temperature and is completed in 2 to 48 hours.

[0025]

INDUSTRIAL APPLICABILITY The compound of the present invention represented by the general formula [I] is a broad-leaved variety of weeds which are problematic in the field, such as Aubiyu, Shiroza, Chickweed, Stinkweed, Staghorn deer, Astragalus membranaceus, and Ona fir. Including weeds,
It exerts an excellent herbicidal effect over a wide range from the pre-emergence to the growing season of cyperaceae weeds such as Kogomegayatsu, cyperaceae, and grass weeds such as crabgrass and millet. Further, it is also possible to control annual weeds such as the northern grass, the eel, the pearl oyster, and the perennial weeds such as the firefly, the cypress, and the kurogwai, which occur in the paddy fields. On the other hand, the herbicide of the present invention is highly safe for crops, among which rice,
Highly safe against wheat, barley, corn, soybeans, turf, etc.

[0026]

EXAMPLES Next, the production method, formulation method and effects of the present invention will be specifically described with reference to examples. Production Example 1 8- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenylimino) -7-thia-1,5-
Synthesis of diazabicyclo [3.3.0] octane-6-one (Compound No. 4) Pyrazolidine hydrochloride 2.0 g (14 mmol) in a reaction flask.
And 20 ml of dichloromethane were added, and 2.8 g (28 mmol) of triethylamine was added dropwise under ice cooling. After the dropping, the mixture was stirred at room temperature for 30 minutes, 2.0 g (6.9 mmol) of 4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenylisothiocyanate was added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was washed with water, dried and then concentrated to obtain an intermediate 1- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenylaminothiocarbonyl) pyrazolidine. Then 1.2 g of this intermediate and pyridine
(15.1 mmol) was dissolved in 20 ml of dichloromethane, and 4.0 ml (8.0 mmo) of a 2N phosgene toluene solution under ice cooling.
l) was added dropwise. After dropping, the mixture was stirred at room temperature for 1 hour.
The reaction solution was washed with water, dried and then concentrated to obtain a crude product. This was purified by silica gel column chromatography to obtain 0.3 g (yield 11%) of the desired product having a melting point of 94-97 ° C.

Production Example 2 10- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenylimino) -9-thia-1,7
-Synthesis of diazabicyclo [5.3.0] decan-8-one (Compound No. 42) To a reaction flask were added 2.0 g (11.6 mmol) of perhydro-1,2-diazepine hydrochloride and 20 ml of dichloromethane, and the mixture was cooled with ice. Then, 2.4 g (24 mmol) of triethylamine was added dropwise. After the dropping, the mixture was stirred at room temperature for 30 minutes, and 4-chloro-
2.0 g (6.9 mmol) of 2-fluoro-5-methoxycarbonylmethylthiophenyl isothiocyanate was added,
The mixture was stirred at room temperature for 1 hour. The reaction solution was washed with water, dried and then concentrated to obtain the intermediate 1- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenylaminothiocarbonyl) perhydro-1,2-diazepine. Next, this intermediate and pyridine 1.2 g (15.1 mmo)
l) was dissolved in 20 ml of dichloromethane, and 4.0 ml (8.0 mmol) of a 2N phosgene toluene solution was added dropwise under ice cooling. After dropping, the mixture was stirred at room temperature for 1 hour. The reaction solution was washed with water, dried and then concentrated to obtain a crude product. This was purified by silica gel column chromatography, and the refractive index was 1.
Thus, 0.49 g (yield: 14%) of the desired product of 5927 was obtained.

Production Example 3 10- {7-Fluoro-3-oxo-4- (2-propenyl) -3,4-dihydro-2H-1,4-benzoxazin-6-ylimino} -9-thia-1 , 7-diazabicyclo [5.3.0] decan-8-one (Compound No. 8
Synthesis of 5) 2.0 g (11.6 mmol) of perhydro-1,2-diazepine hydrochloride and 20 ml of dichloromethane were placed in a reaction flask, and 2.4 g (24 mmol) of triethylamine was added dropwise under ice cooling. After the dropping, the mixture was stirred at room temperature for 30 minutes, and 1.8 g of 7-fluoro-3-oxo-4- (2-propenyl) -3,4-dihydro-2H-1,4-benzoxazin-6-ylisothiocyanate ( 6.9 mmol) and added at room temperature to 1
Stir for time. The reaction mixture was washed with water, dried, and concentrated to give the intermediate 1- {7-fluoro-3-oxo-4-.
(2-Propenyl) -3,4-dihydro-2H-1,4-
Benzoxazin-6-ylaminothiocarbonyl} perhydro-1,2-diazepine was obtained. Next, 1.2 g (15.1 mmol) of this intermediate and pyridine were dissolved in 20 ml of dichloromethane, and 4.0 ml (8.0 mmol) of a 2N phosgene toluene solution was added dropwise under ice cooling. 1 at room temperature after dropping
Stir for time. The reaction solution was washed with water, dried and then concentrated to obtain a crude product. This was purified by silica gel column chromatography to obtain 0.5 g (yield 18.6%) of the desired product having a melting point of 122-125 ° C.

Reference Example Synthesis of Perhydro-1,2-diazepine dihydrochloride 24.4 g of 1,2-diethoxycarbonylperhydro-1,2-diazepine in a reaction flask equipped with a Dimroth.
(100 mmol) and 200 ml of concentrated hydrochloric acid were added, and the mixture was refluxed for 20 hours. The reaction solution was concentrated and toluene was added to the residue for washing to obtain 10.3 g of the desired product (yield 63%). This hydrochloride salt was used in the next reaction without purification.

The herbicide of the present invention comprises a fused heterocyclic derivative represented by the general formula [I] as an active ingredient. When the compound of the present invention is used as a herbicide, the compound of the present invention may be used as it is, but it is a carrier generally used for formulation,
Mixing a surfactant, dispersant or auxiliary agent, etc., powder,
It can also be used by formulating it into a wettable powder, an emulsion, a fine granule or a granule.

As the carrier used for formulation,
For example Sieglite, talc, bentonite, clay,
Examples thereof include solid carriers such as kaolin, diatomaceous earth, white carbon, vermiculite, calcium carbonate, slaked lime, silica sand, ammonium sulfate and urea, and liquid carriers such as isopropyl alcohol, xylene, cyclohexane and methylnaphthalene. Examples of the surfactants and dispersants include alkylbenzene sulfonic acid metal salts, dinaphthylmethane disulfonic acid metal salts, alcohol sulfate ester salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkyls. Examples include aryl ethers and polyoxyethylene sorbitan monoalkylates. Examples of the auxiliary agent include carboxymethyl cellulose, polyethylene glycol, gum arabic and the like. When using, dilute to an appropriate concentration and spray or apply directly.

The herbicide of the present invention can be used by foliage application, soil application or water surface application. The blending ratio of the active ingredient is appropriately selected according to need, but in the case of powder or granule, it is appropriately selected from the range of 0.01 to 10% (weight), preferably 0.05 to 5% (weight). Is good. When used as an emulsion or wettable powder, 1-50%
(Weight), preferably 5 to 30% (weight).

The application rate of the herbicide of the present invention varies depending on the kind of compound used, target weeds, development tendency, environmental conditions and dosage form used, but when it is used as it is as in powder and granules, The active ingredient may be appropriately selected from the range of 0.1 g to 5 kg, preferably 1 g to 1 kg per 10 ares. When it is used in a liquid state such as an emulsion or a wettable powder, it is appropriately selected from the range of 0.1 to 50,000 ppm, preferably 10 to 10,000 ppm.

If desired, the compound of the present invention may be mixed with insecticides, fungicides, other herbicides, plant growth regulators, fertilizers and the like. Next, the formulation method will be specifically described with reference to typical formulation examples. The types and compounding ratios of the compounds and additives are not limited to these, and can be changed in a wide range. In the following description, “part” means part by weight.

Formulation Example 1 Wettable powder 10 parts of compound (4), 0.5 part of polyoxyethylene octyl phenyl ether, 0.5 part of sodium salt of β-naphthalenesulfonic acid formalin condensate, 2 parts of diatomaceous earth.
0 parts and 69 parts of clay are mixed and ground to obtain a wettable powder.

Formulation Example 2 Wettable powder 10 parts of compound (17), 0.5 part of polyoxyethylene octyl phenyl ether, 0.5 part of sodium salt of β-naphthalenesulfonic acid formalin condensate, 20 parts of diatomaceous earth, 5 parts of white carbon and 64 parts of clay are mixed and ground to obtain a wettable powder.

Formulation Example 3 Wettable Powder To 10 parts of the compound (40), 0.5 part of β-naphthalenesulfonic acid formalin condensate sodium salt, 0.5 part of sodium lauryl sulfate, 20 parts of diatomaceous earth, and white carbon. 5 parts and 64 parts of calcium carbonate are mixed and ground to obtain a wettable powder.

Formulation Example 4 Emulsion Emulsion 10 parts of compound (42) in 80 parts of an equal mixture of xylene and isophorone, 10 parts of a mixture of surfactant polyoxyethylene sorbitan alkylate, polyoxyethylene alkylaryl polymer and alkylaryl sulfonate. Is added, and these are well stirred to obtain an emulsion.

Formulation Example 5 Granules 3 parts of compound (55), talc and bentonite 1: 3
77 parts of the mixed extender, 5 parts of the white carbon, 5 parts of the mixture of the surfactant polyoxyethylene sorbitan alkylate, the polyoxyethylene alkylaryl polymer and the alkylaryl sulfonate and 10 parts of water, The kneaded paste is extruded through a sieve hole with a diameter of 0.7 mm and dried to 0.5-0.5
Cut into 1 mm length to obtain granules.

Next, the effects of the compound of the present invention will be described with reference to test examples. Test Example 1 (Test of herbicidal effect by paddy soil treatment) A 100 cm ² plastic pot was filled with paddy soil,
After scratching, Tainubie (Eo), Konagi (Mo) and Firefly (Sc)
Each seedling was sown and flooded to a depth of 3 cm. The next day, the wettable powder prepared according to Formulation Example 1 was diluted with water and added dropwise to the water surface. The application rate was 100 g per 10 ares of the active ingredient. Then, the plants were grown in a greenhouse, and 21 days after the treatment, the herbicidal effect was investigated according to the criteria shown in Table 3. The results are shown in Table 4.

[0041]

[Table 3]

[0042]

[Table 4]

Test Example 2 (Herbicidal effect test by treatment of upland soil) A 120 cm ² plastic pot was filled with upland soil, and various seeds of Meshishiba (Di), Aobiyu (Am), Shiroza (Ch) and Kogomegayatsuri (Ci) were sown. And covered the soil. A wettable powder prepared according to Formulation Example 1 was diluted with water, and 100 liters per 10 ares were evenly sprayed on the soil surface so that the active ingredient was 100 g per 10 ares. Then, it was grown in a greenhouse, and the herbicidal effect was investigated on the 21st day of the treatment according to the criteria in Table 3. The results are shown in Table 5.

[0044]

[Table 5]

Test Example 3 (Herbicidal effect test by foliar treatment of upland field) A 120 cm ² plastic pot was filled with upland field soil, and edible millet (Ec), Mexican herb (Di), Aobiyu (Am), and Shiroza (C)
h), sowing various larvae of Kogomegaya (Ci), and place them in a greenhouse for 2
After growing for a week, the wettable powder prepared according to Formulation Example 1 was diluted with water so that the active ingredient was 100 g per 10 are.
100 liters per 10 ares were foliage sprayed over the whole plant with a small sprayer. After that, grow in the greenhouse,
On the 14th day of the treatment, the herbicidal effect was investigated according to the criteria shown in Table 3. The results are shown in Table 6.

[0046]

[Table 6]

[0047]

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[Procedure amendment]

[Submission date] May 8, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

[0009]

[Table 1A]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

Formulation Example 5 Granules 3 parts of compound (55), talc and bentonite 1: 3
In an amount of 87 parts of the mixed extender, 5 parts of white carbon, 5 parts of the mixture of surfactant polyoxyethylene sorbitan alkylate, polyoxyethylene alkylaryl polymer and alkylaryl sulfonate, add 10 parts of water, The kneaded paste was extruded from a sieve hole having a diameter of 0.7 mm, dried, and then dried.
Cut into a length of 5 to 1 mm to obtain granules.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display area C07D 231: 00 285: 00) (C07D 513/04 237: 00 285: 00) (C07D 513/04 243: 00) 285: 00) (72) Inventor Shigehiko Tachikawa 3-57 Anzai, Shizuoka City, Shizuoka Prefecture (72) Inventor Takeshige Miyazawa 9 of 1205 Iwaname, Daito Town, Ogasa County, Shizuoka Prefecture

Claims (2)

[Claims] 1. A general formula: {Wherein R is the formula (In the formula, Y represents a hydrogen atom or a fluorine atom, R ¹ represents a hydrogen atom, an alkoxycarbonyl group, an alkoxycarbonylalkylthio group, a cycloalkoxycarbonylalkylthio group, an alkynyloxycarbonylalkylthio group, an alkenyloxycarbonylalkylthio group, an unsubstituted or A substituted benzyloxycarbonylalkylthio group, a phenoxycarbonylalkylthio group, an alkoxyalkoxycarbonylalkylthio group, a haloalkoxycarbonylalkylthio group, an alkoxycarbonylalkoxy group, an alkoxyalkoxycarbonylalkoxy group, an alkoxy group, an alkynyloxy group or an alkenyloxy group). A group or formula represented: (In the formula, Y represents a hydrogen atom or a fluorine atom, R ² represents an alkyl group, an alkenyl group or an alkynyl group,
Z represents an oxymethylene group or a sulfur atom. ), X represents an oxygen atom or a sulfur atom, and n
Represents an integer of 3 to 5. } The condensed heterocyclic derivative represented by these. 2. A herbicide containing the fused heterocyclic derivative according to claim 1 as an active ingredient.