JPH04145087A - Condensed heterocyclic derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R is group shown by formula II (Y is H or F; R<1> is alkoxycarbonylalkylthio, alkoxycarbonyl, alkynyloxy, alkoxy, etc.) or formula III (Y<1> is H or F; R<2> is alkyl, alkenyl or alkynyl; Z is oxymethylene or S); X is O or S]. EXAMPLE:9-(4-Chloro-2-fluoro-5-methoxycarbonylmethylthiophenylimino)-8 -thia-1,6- diazabicyclo[4,3,0]-3-nonen-7-one. USE:A herbicide having excellent herbicidal activity and selectivity. PREPARATION:A compound shown by formula IV is reacted with phosgene or thiophosgene optionally in the presence of a base (e.g. trimethylamine) in a solvent such as dichloromethane.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel fused heterocyclic derivative and a herbicide containing the same as an active ingredient.

[Prior Art] Until now, JP-A-1-250388 has described that fused heterocyclic derivatives can be used as active ingredients of herbicides.

[Problems to be Solved by the Invention] However, these compounds are not necessarily satisfactory because they have insufficient herbicidal activity or poor selectivity between crops and weeds.

In recent years, there has been a strong demand for herbicides that have a selective action that kills only weeds without harming the crops, even when applied to useful crops and weeds at the same time. Furthermore, in order to prevent excessive residual of drugs in the environment, there is a desire to develop drugs that can be fully effective at low doses.

[Means for Solving the Problems] In order to achieve the above object, the present inventors synthesized a number of fused heterocyclic derivatives and conducted various studies on their usefulness. As a result, a substituted phenylimino group, a substituted 2-
Benzothiazolone-5-ylimino group and substituted 2H-
An 8-thia-1,6-diazabicyclo[4,3,0]-3-nonene derivative having a 1,4-benzoxazin-3-one-6-ylimino group as a substituent at the 9-position meets the above purpose. It was discovered that it has excellent herbicidal activity and selectivity, and the present invention was completed. That is, the present invention relates to the general formula carbonylalkylthio group, alkoxycarbonyl group,
Alkoxyalkoxycarbonylalkoxy group, alkynyloxy group, alkoxy group, cycloalkoxycarbonylalkylthio group, alkoxyalkoxycarbonylalkylthio group, alkoxycarbonylalkoxycarbonylalkylthio group, alkynyloxycarbonylalkylthio group, alkenyloxycarbonylalkylthio group, benzyloxycarbonylalkylthio group, It represents a phenyloxycarbonylalkylthio group, an alkylthiocarbonylalkylthio group, a phenethyloxycarbonylalkylthio group, or a haloalkoxycarbonylalkylthio group. ) in the table (wherein, Y'' represents a hydrogen atom or a fluorine atom, R'' represents an alkyl group, alkenyl group, or alkynyl group, and Z represents an oxymethylene group or a sulfur atom). and X represents an oxygen atom or a sulfur atom).

Next, specific examples of the compounds of the present invention are shown in Tables 1 and 2. Compound numbers are referenced in the description below.

(Margin below) Table 1 continued (Margin below) Compound of the present invention [■] teeth, Manufactured by the following method can do.

Enter [nl [1]
(In the formula, R and X have the same meanings as above.) That is, the reaction is carried out by reacting a compound represented by the general formula [nl with phosgene or thiophosgene in the presence or absence of a base.

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.

Examples of solvents 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, and fats such as acetone and methyl ethyl ketone. Ketones and the like can be used. The above reaction is -20
It is carried out at a temperature ranging from °C 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.

Note that the raw material [II] can be produced by the following method.

[I11] [rV]
[Il] (wherein R has the same meaning as above) is carried out by reacting a compound represented by the general formula [m] with a compound represented by the general formula [1't'].

Examples of solvents 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 dimethysulfoxide, N, N, - Dimethylformamide etc. can be used. The above reaction is -20
It is carried out at a temperature ranging from °C to the boiling point of the solvent, and is completed in 1 to 24 hours. The target compound can be taken out from the reaction solution by a conventional method. In addition, the compound represented by the general formula [m] is manufactured by Biltier Société Chemis Français (Bull,
Soc, Chim, France), 704-708 (
1957).

Next, production examples of the compounds of the present invention will be shown.

Reference example 1 1-(N-(4-chloro-2-fluoro-5
-Methoxycarbonylmethylthiophenyl)thiocarbamoyl)-1゜Production of 2.3.6-titrahydropyridazine In a reaction flask, add 0.5 g (6.0 mmo 1) of 1.2,3.6-titrahydropyridazine and dichloromethane. Add 20mQ of 4-chloro-2-fluoro-
1.2 g (4.1 mm01) of 5-methoxycarbonylmethylthiophenylthioisocyanate was added, and the reaction was further stirred at room temperature for 2 hours to complete the reaction. Next, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain a composition. This composition was washed with a hexane/ethanol mixture to obtain 1.3 g of the target compound as white crystals (
A yield of 84% was obtained. Melting point 155-158°C.

Example 19-(4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenylimino)-8-thia-1,6-diazabicyclo[4,3,0-3-nonen-7-one (
Preparation of Compound 1) 1-(N-(4) prepared according to Reference Example 1 was placed in a reaction flask.
-chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl)thiocarbamoyl) -1,2,3,
6-titrahydroviridazine 1.6 g (4.2 mm
o 1), pyridine 1.0g (13mmo 1) and dichloromethane 20mQ, and cooled with ice water.
3 mρ (6 mmol) of N phosgene toluene solution was added dropwise. After the dropwise addition, stirring was further performed at room temperature for 2 hours to complete the reaction. Next, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain a composition. This composition was purified using a column to obtain 0.9 g of the target compound in the form of light brown crystals (
A yield of 53% was obtained. Melting point 90-92°C.

Example 29-(4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenylimino)-8-thia-1,6-diazabicyclo[4,3,0]-3-nonene-7-thione (compound 16) 1-(N-(4
-chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl)thiocarbamoyl) -1,2,3,
6-titrahydroviridazine 1.1 g (2.8 mm
o ]), pyridine 1. Ig (14 mmol) and 20 mQ of dichloromethane were added, and 0.8 g (7.0 mmol) of thiophosgene was added dropwise while cooling with ice water. After the dropwise addition, stirring was further performed at room temperature for 2 hours to complete the reaction.

Next, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain a composition. This composition was washed with an isopropyl ether/ethanol mixture to obtain 0.7 g (yield: 60%) of the target compound as white crystals.

Melting point 123-126°C.

Example 39-(6-fluoro-3-propargylbenzothiazol-2-one-5-ylimino)-8-thia-1,6-diazabicyclo[4,3,0]-3-nonen-7-one (
Preparation of Compound 35) 1-(N-(6-fluoro-3propargylbenzothiazol-2-one-5-yl)thiocarbamoyl)-1,2,3,6-titrahydroviridazine 1. 3g (3.7mmol), pyridine 0.9g
(11,0mmo ]) ,] digloromethane 20m
was added, and 2.5 mQ (5.0 mmol 1) of 2N phosgene toluene solution was added dropwise while cooling with ice water. After the dropwise addition, stirring was further performed at room temperature for 1 hour to complete the reaction. Next, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain a composition. This composition was purified by column to obtain 1.0 g (yield 72%) of the target compound as white crystals.

Melting point 204-208°C.

Example 49-(7-fluoro-4-propargyl-2H-
Preparation of 1,4-benzoxazin-3-one-6-ylimino)-8-thia-1,6-diazabicyclo[4,3゜0co-3-nonen-7-one (compound 37) 1- (N-(7-fluoro-4-propargyl-28-1,4-benzoxazin-3-one-
6-yl)thiocarbamoyl)-1゜2.3.6-titrahydropyridazine 1.7 g (4゜9 mmol),
Pyridine 0.9g (11,0mm.

1) Add 20rnQ of dichloromethane and add 3.2mΩ (6.4mΩ) of 2N phosgene toluene solution while cooling with ice water.
mo 1) was added dropwise. After the dropwise addition, stirring was further performed at room temperature for 1 hour to complete the reaction. Then, the reaction solution was washed with water,
After drying with magnesium sulfate, the solvent was distilled off to obtain a composition. This composition was washed with isopropyl ether,
1.2 g (yield: 66%) of the target compound as white crystals was obtained. Melting point: 175-178°C.

The herbicide of the present invention contains a fused heterocyclic derivative represented by the general formula [T] as an active ingredient.

When the compound of the present invention is used as a herbicide in rice fields, fields, orchards, non-agricultural lands, etc., the active ingredient can be used in an appropriate dosage form depending on the purpose.

In normal cases, the active ingredient is diluted with an inert liquid or solid carrier, and if necessary, surfactants, dispersants, adjuvants, etc. are added to form powders, wettable powders, emulsions, granules, etc. It can be formulated and used in various forms. Examples of carriers used in formulation include solid carriers such as dicrite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea, isopropyl alcohol, xylene, cyclohexanone, and methylnaphthalene. Examples include liquid carriers such as . Examples of surfactants and dispersants include alcohol sulfate salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, and polyoxyethylene sorbitan monoalkylates. . Examples of the adjuvant include carboxymethyl cellulose, polyethylene glycol, gum arabic, and the like. When using it, it can be diluted to an appropriate concentration and sprayed, or it can be applied directly. The amount of application varies depending on the occasion and timing of application, application method, cultivated crops, etc., but in general, the amount of active ingredient of the compound of the present invention is 0.1 g to 1 kg per 10 ares.

Next, the formulation method will be specifically explained using typical formulation examples. In the following description, "part" means part by weight.

Formulation Example 1 10 parts of wettable powder compound (1), 0.5 part of Emulgen (registered trademark of Kao Corporation) 810, 0.5 part of Demol (registered trademark of Kao Corporation) N, Kunilite (Kunimine 20 copies of 201 (registered trademark of Kogyo Co., Ltd.), Zeekrite (
69 parts of CA (registered trademark of Zeekrite Co., Ltd.) are mixed and ground to obtain a wettable powder.

Formulation Example 2 10 parts of wettable powder compound (35), 0.5 part of Emulgen 810, 0.5 part of Demol N, 20 parts of Kunilite 201,
5 parts of Carplex 80 and 64 parts of Zikrite CA are mixed and ground to obtain a wettable powder.

Formulation Example 3 By adding 80 parts of xylene, 5 parts of dimethyl sulfoxide, and 10 parts of the surfactant Tsurupol (registered trademark of Toho Chemical Industry Co., Ltd.) 800A to 5 parts of the emulsion compound (), and stirring these thoroughly. Obtain emulsion.

Formulation Example 4 10 parts of granule compound (11), 1 = talc and bentonite
80 parts of bulking agent mixed in the ratio of 3 parts, 5 parts of white carbon, 5 parts of surfactant Tsurupol 800A, and 10 parts of water.
0.0 mm, knead well to make a paste, and make a paste with a diameter of 0.
After extruding through a 7mm sieve hole and drying, 0.5
Cut into lengths of ~1 mm to obtain granules.

[Effects of the Invention] The compound of the present invention represented by the general formula [1] is effective against annual fibers such as barnyard grass, Japanese cypress, Japanese cypress, Japanese azalea, and azalea that occur in rice fields, and perennial weeds such as bulrush, Japanese cypress, and water cyperus. It exhibits an excellent weeding effect at an extremely low dose over a wide range from the time of germination to the growing season, and at the same time is highly safe for paddy rice. In addition, various weeds that cause problems in fields, such as polygonum,
Highly effective weed control with soil treatment or foliage treatment for broad-leaved weeds such as bluegrass, whiteweed, and croaker, as well as Cyperaceae weeds such as cyperus cyperus and cyperus, and grasses such as barnyard grass, silver grass, foxtail grass, johnson grass, and grasshopper. In addition to being effective, it is also highly safe for soybeans, cotton, corn, turgsum, upland rice, wheat, etc. It can also be used in orchards, pastures, lawns, non-agricultural lands, etc.

Next, the effects of the compounds of the present invention will be explained by giving test examples.

Test example 1 (herbicidal effect test by paddy soil treatment) 100
A cm' plastic pot was filled with paddy soil, and after puddling, seeds of Japanese millet, Japanese cypress, Japanese cypress, and bulrush were sown, and the pot was submerged in water to a depth of 3 cm. The next day, the wettable powder prepared according to Formulation Example 1 was diluted with water and dropped onto the water surface. The application amount is 100g of active ingredient per 10 ares.
And so. Thereafter, they were grown in a greenhouse, and on the 21st day after treatment, the unveiling effect was investigated according to the standards in Table 3. The results are shown in Table 4.

Table 3 Test Example 2 (Herbicidal effect test by field soil foliage treatment) 120c
m' Plastic pots were filled with field soil, and seeds of Japanese knotweed, Japanese violet, Japanese cypress, and Japanese cypress were sown and grown in a greenhouse for two weeks. Dilute the wettable powder prepared according to Formulation Example 1 with water, and apply it to the whole plant from above using a small sprayer so that the active ingredient per 10 ares is 100 g and the amount of water sprayed per 10 ares is 100 Q. Sprayed. Thereafter, they were grown in a greenhouse, and the unveiling effect was investigated 21 days after treatment according to the standards in Table 3.

The results are shown in Table 5.

Test Example 3 (Herbicidal effect test by field soil treatment) 120
cm'' plastic pots are filled with field soil, and barnyard millet,
Seeds of crabgrass, Japanese knotweed, Japanese knotweed, blueberry, whiteberry, and cypress were sown and covered with soil. A wettable powder prepared according to Formulation Example 1 was diluted with water, and 100Q per 10 ares was uniformly sprayed on the soil surface using a small sprayer so that the active ingredient was 100 g per 10 ares. Thereafter, the plants were grown in a greenhouse, and the herbicidal effect was investigated 21 days after treatment according to the criteria in Table 3. The results are shown in Table 6.

Table 6 Test Example 4 (Medical efficacy and phytotoxicity test by paddy soil treatment) 1
/ 5000a Wagner pot filled with paddy soil,
After watering and puddling, seeds of Japanese barnyard grass, Japanese grasshopper, and firefly were sown, and two plants of rice at the 2.5-leaf stage were transplanted to a transplant depth of 2 cm, and then flooded to a water depth of 3 cffl. The next day, a predetermined amount of the active ingredient of a wettable powder prepared according to Formulation Example 1 was diluted with water and dropped onto the water surface.

Thereafter, the plants were grown in a greenhouse, and 30 days after treatment, the herbicidal effect and phytotoxicity were investigated according to the standards in Table 3.

The results are shown in Table 7.

Table 7 continued Test example 5 (crop selectivity test in field stem and foliage treatment) 60
Fill each 0cm' plastic pot with upland soil,
A+ Corn, Japanese knotweed, Japanese knotweed, and Johnson grass were sown; B: Dice, Japanese knotweed, Japanese knotweed, and Japanese fir tree were sown.

Water was absorbed from the bottom of the pot, and the plants were grown in a greenhouse until the dice reached the one-leaf stage and the corn reached the three-leaf stage. Formulation example 1
A predetermined amount of the active ingredient of a hydrating powder prepared according to the method was diluted with 100 Ω water per 10 ares, and the mixture was sprayed onto the soil surface using a small sprayer. After that, it was grown again in the greenhouse and 21 days after treatment.
Herbicidal effects and phytotoxicity were investigated according to the standards in Table 3 of the daily schedule. The results are shown in Table 8-A and Table 8-B.

In addition, the following compound described in the specification of JP-A-1-250388 was used as a control drug.

8th Table A continued (Margin below) Table 8-B Patent applicant Kumiai Chemical Industry Co., Ltd. Ihara Chemical Industry Co., Ltd.

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ {In the formula, R is the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Y represents a hydrogen atom or a fluorine atom, and R^1 Alkoxycarbonylalkylthio group, alkoxycarbonyl group, alkoxyalkoxycarbonylalkoxy group, alkynyloxy group, alkoxy group, cycloalkoxycarbonylalkylthio group, alkoxyalkoxycarbonylalkylthio group, alkoxycarbonylalkoxycarbonylalkylthio group, alkynyloxycarbonylalkylthio group, alkenyloxycarbonyl alkylthio group, benzyloxycarbonylalkylthio group, phenyloxycarbonylalkylthio group, alkylthiocarbonylalkylthio group, phenethyloxycarbonylalkylthio group, or haloalkoxycarbonylalkylthio group. ▼ (In the formula, Y^1 represents a hydrogen atom or a fluorine atom, and R
^2 represents an alkyl group, alkenyl group or alkynyl group, and Z represents an oxymethylene group or a sulfur atom. )
represents a group represented by, and X represents an oxygen atom or a sulfur atom. } A fused heterocyclic derivative represented by. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ {In the formula, R is the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Y represents a hydrogen atom or a fluorine atom, and R^1 Alkoxycarbonylalkylthio group, alkoxycarbonyl group, alkoxyalkoxycarbonylalkoxy group, alkynyloxy group, alkoxy group, cycloalkoxycarbonylalkylthio group, alkoxyalkoxycarbonylalkylthio group, alkoxycarbonylalkoxycarbonylalkylthio group, alkynyloxycarbonylalkylthio group, alkenyloxycarbonyl alkylthio group, benzyloxycarbonylalkylthio group, phenyloxycarbonylalkylthio group, alkylthiocarbonylalkylthio group, phenethyloxycarbonylalkylthio group, or haloalkoxycarbonylalkylthio group. ▼ (R^2 represents an alkyl group, alkenyl group, or alkynyl group, Z represents an oxymethylene group or a sulfur atom), and X represents an oxygen atom or a sulfur atom. A herbicide containing a fused heterocyclic derivative represented by } as an active ingredient.