JPS6340425B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () The present invention relates to a novel substituted phenylthionocarbamate represented by: and a herbicide containing the same as an active ingredient. However, in the above general formula (), X represents an oxygen atom, a sulfur atom, or a vinylene group. l and m
means an integer of 1 to 3, and n means an integer of 0 or 1. The number of members of the heterocycle formed by the nitrogen atom, two alkylene chains, and X is 4 to 7.
It is. From the viewpoint of herbicidal activity, the heterocycle of the substituted phenylthionocarbamate represented by the general formula () is preferably a 5-membered ring or a 6-membered ring. Y represents a halogen atom such as a chlorine atom, a bromine atom, an iodine atom, etc., and preferably a chlorine atom. R is a methyl group,
Ethyl group, propyl group, butyl group, pentyl group,
Alkyl groups optionally interrupted by one or more oxygen atoms such as hexyl, ethoxyethyl, ethoxyethoxyethyl; allyl, 2-chlorallyl, 3-chloroallyl, 2,3-dichloroallyl, 3 ,3-dichloroallyl group, 3,3
-dipromalyl group, crotyl group, 3-chloro-
Alkenyl groups optionally substituted with halogen atoms such as 2-methyl-2-propenyl group, methallyl group, prenyl group, 4-chloro-3-methyl-2-butenyl group, geranyl group; or propargyl group, 3- Represents an alkynyl group that may be substituted with a halogen atom, such as a chloropropargyl group, 2-butynyl group, 3-butyryl group, and 4-chloro-3-butyryl group. The substituted phenylthionocarbamate provided by the present invention has a halogen atom at the 4-position of the phenyl group and an alkoxy group whose alkyl moiety at the 3-position may be interrupted by one or more oxygen atoms. It is a compound characterized by having an alkenyloxy group or an alkynyloxy group that may be substituted with a halogen atom, and as described below, it is used as a herbicide or its It is useful as an active ingredient. It has been known that substituted phenylthionocarbamates such as 0-(4-chlorphenyl)1-pyrrolidinecarbothioate have herbicidal activity against upland weeds (U.S. Pat. No. 3,217,002).
However, these substituted phenylthionocarbamates cannot be put to practical use because their herbicidal activity is unsatisfactory and they are highly toxic to crops. The present inventors have conducted intensive research to create a compound with high herbicidal activity and low phytotoxicity to crops. As a result, the substituted phenylthionocarbamate represented by the general formula () has a high control rate against various weeds. It has been found that it has a significantly superior control effect against broad-leaved weeds compared to the above-mentioned known substituted phenylthionocarbamates, and also causes almost no phytotoxicity to useful crops such as paddy rice. , we have completed the present invention. Substituted phenylthionocarbamates represented by the general formula () are used for weeds that grow and flourish in undesired places such as rice paddies and fields, such as chickweed; ; Japanese dogweed; purslane;
Red-breasted moss, Tokiwa-goby, Purple-spotted moss;
Dicotyledonous weeds, such as chinensis, japonica; japonica; azalea; dicotyledonous weeds such as japonica, takasaburou, taucogi, American centangus, japonica, and cypress;
Asiatic sunflower; Japanese cyperus; Japanese cyperus; Japanese cyperus, Japanese cyperus, hinged cyperus, Japanese cyperus,
Water lily, Japanese cypress, Japanese cypress, Japanese cypress, Japanese cypress, Japanese cypress, Japanese firefly, Japanese cypress, Japanese cyperus, Japanese cypress, Japanese cypress; Golden violet, Japanese cypress, Japanese violet, Japanese violet, Japanese cypress, Japanese cypress,
It has a control effect against monocotyledonous weeds, such as foxtail grass and red foxtail, and there are many types of rice field weeds, and their occurrence density is extremely high.
It has a significantly high control effect against broad-leaved weeds that compete with paddy rice for space by stealing fertilizer throughout the entire growing period of paddy rice and causing ventilation problems. Among the substituted phenylthionocarbamates represented by the general formula (), especially the following general formula (-a) [In the formula, X, l, m and n have the same meanings as in the general formula (), and the number of members of the heterocycle formed by the nitrogen atom, two alkylene chains, and
~6. R' is an alkyl group having 1 to 4 carbon atoms or 3 to 4 carbon atoms which may be substituted with a chlorine atom
represents an alkenyl group or an alkynyl group. ] Compounds represented by these are preferred from the viewpoint of herbicidal activity against various weeds. Examples of typical substituted phenylthionocarbamates represented by the general formula () include the following.

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[Table] The substituted phenylthionocarbamate represented by the general formula () can be easily produced by the following methods (i) to (iii). [In the above formula, X, l, m, n, Y and R have the same meanings as in the general formula (), and M represents an alkali metal. ] The above method (i) involves reacting the compound represented by the general formula () with thiophosgene in the presence of a base,
The reaction is then carried out by reacting the obtained compound represented by the general formula () with a cyclic amine represented by the general formula () in the presence of a base. As bases, aliphatic tertiary amines such as trimethylamine and triethylamine; pyridine, picoline,
Aromatic tertiary amines such as quinoline; tertiary anilines such as dimethylaniline and diethylaniline; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. are used. The amount of the base used in each condensation reaction is at least equivalent to the compound represented by the general formula () or the compound represented by the general formula () as a raw material,
Preferably it is equivalent to 3 times equivalent. In addition, in the condensation reaction between the compound represented by the general formula () and the cyclic amine represented by the general formula (), the latter can be used in an amount twice or more equivalent to the former, so that the cyclic amine also functions as a base. can. In addition,
These condensation reactions are preferably carried out in a solvent, such as ethers such as diethyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether; hydrocarbons such as n-hexane and benzene; aliphatic ketones such as acetone; Chlorine-containing hydrocarbons such as methylene, chloroform, and carbon tetrachloride; fatty acid esters such as methyl acetate and ethyl acetate; dimethyl sulfoxide, N,N-dimethylformamide, and the like can be used as the solvent. These condensation reactions are usually −50
The temperature is preferably 0 to 40°C. Method (ii) above can be carried out under similar conditions to method (i). However, in this case, the cyclic amine represented by the general formula (), which is the raw material for method (i), cannot be used as a base. In method (iii), a compound represented by the general formula () and a compound represented by the general formula () are preferably reacted in a solvent at a reaction temperature of −50 to
The reaction is carried out at 100°C, preferably from 0 to 40°C. As the solvent, the solvents listed in the explanation of method (i) above can be used. When the compound of the present invention is actually used, it can be used alone without adding other ingredients, but in order to make it easier to use as a herbicide, a carrier is added to form a preparation, which can be diluted as necessary. Generally, it is applied by For formulation, the compound of the invention is mixed with liquid or solid extender carriers (optionally with the addition of surfactants, emulsifiers and/or dispersants and/or A foaming agent may be used), thereby making it possible to form a dosage form such as a wettable powder, an emulsion, or a granule. Liquid carriers are mainly aromatic hydrocarbons,
For example xylene, toluene, benzene, alkylnaphthalenes; chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene,
methylene chloride; aliphatic or cycloaliphatic hydrocarbons such as cyclohexane, paraffins (e.g. mineral oil fractions); alcohols such as butanol, ethylene glycol and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone is appropriate. As solid carriers, ground natural minerals such as kaolin, clay, talc, bentonite, ziecrite, thioyoke, quartz, attapulgite, montmorillonite, diatomaceous earth; and ground synthetic minerals such as alumina, silicates, white carbon can be used. It is preferable to use Preferred examples of emulsifiers and saturants include nonionic and anionic emulsifiers, such as polyoxyethylene-aliphatic carboxylic acid esters; polyoxyethylene-aliphatic alcohol ethers, such as alkylaryl polyglycol ethers; alkyl sulfonates, alkyl sulfates. ate, aryl sulfonates and albumin hydrolysates. Preferred examples of dispersants include lignin sulfite waste liquor and methylcellulose. In preparing the herbicide of the present invention, it is also possible to express excellent herbicidal activity by using a combination of two or more substituted phenylthionocarbamates represented by the general formula (); It can also be applied in combination with fertilizers, insecticides, fungicides, herbicides or plant growth regulators applied in the same field. The formulation will generally contain at least 1x the compound of the invention.
It is contained in an amount of 10 ^-7 % by weight, preferably 0.01 to 95% by weight, more preferably 0.1 to 80% by weight. The compounds of the present invention may be used in the form of the various types of preparations mentioned above, or these preparations may be further formulated into usage forms. The content of the compound of the present invention in the usage form can be appropriately selected within a very wide range such as 1 x 10 ^-7 to 100% by weight, but is preferably 1 x 10 ^-5 to 10% by weight. . The herbicides according to the invention are used in the customary manner appropriate to the particular use type. The dosage range of the compound of the present invention is 10 to 1000g/10a, preferably 25 to 10a.
The range is 250g/10a. Synthesis examples, formulation examples, and effect examples of the compounds of the present invention are shown below, but the present invention is not limited thereto. In addition, "parts" in the formulation examples mean parts by weight. Synthesis Example 1 Synthesis of 3-allyloxy-4-chlorophenol 4- Dissolve 40 g of chlorresorcin in 500 ml of dimethylformamide, add 13.3 g of oily sodium hydride (purity 50%) little by little to this solution.
The sodium salt of chlorresorcin was produced. 33.5 g of allyl bromide was added to this reaction solution, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was poured into ice water and extracted with diethyl ether. After washing the ether layer with water,
It was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The residual oil was separated and purified by silica gel column chromatography to obtain 25.6 g of 3-allyloxy-4-chlorophenol. O-(3-allyloxy-4-chlorophenyl)1-pyrrolidinecarbothioate [Compound
(1)] synthesis 3-allyloxy-4-chlorophenol
Dissolve 1.86g in 20ml of dimethylformamide and add oily sodium hydride (purity 50%) to this solution.
0.48 g was added to produce the sodium salt of 3-allyloxy-4-chlorophenol. 1-pyrrolidinethiocarbonyl chloride is added to this reaction solution.
1.94 g was added and the mixture was stirred for 20 hours. Ice water was added to the reaction mixture, and organic matter was extracted with diethyl ether. The solvent was distilled off from the ether layer, and the residue was purified by silica gel column chromatography to obtain 2.32 g of 0-(3-allyloxy-4-chlorophenyl)1-pyrrolidinecarbothioate [Compound (1)]. . Product melting point: 87.3~
91.1°C Compounds (5) to (21), (24) and (25) were obtained by the same method. Melting point (or properties) of each compound
is as described above. Synthesis Example 2 Synthesis of 0-(3-allyloxy-4-chlorophenyl)3-thiazolidinecarbothioate [Compound (2)] Add 3-allyloxy-4-chlorophenol to a solution of 7.7 g of sodium hydroxide dissolved in 30 ml of water.
Dissolve 35.0g and add 14.6ml of thiophosgene to this solution.
A solution of 55.0 ml of chloroform was added under stirring. After separating the resulting reaction solution, the chloroform layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. By distilling the residue under reduced pressure, 128~
Chlorothioformic acid 0 as a fraction at 129℃/0.4mmHg
-(3-allyloxy-4-chlorophenyl) ester was obtained in an amount of 33.0 g. Chlorothioformate 0-(3-allyloxy-4-
2.63 g of (chlorophenyl) ester was dissolved in 60 ml of diethyl ether, and 1.01 g of thiazolidine and 1.42 ml of triethylamine were added to this solution with stirring.
After stirring as it was for 4 hours, the reaction mixture was washed with water, and the solvent was distilled off from the ether layer. The obtained residue was recrystallized from methanol to obtain O-(3
2.1 g of -allyloxy-4-chlorophenyl)3-thiazolidinecarbothionate [Compound (2)] was obtained. Melting point of product: 103.6-105.6°C Synthesis Examples 3 and 4 0-[4-chloro-3-(3,3-dichloroallyloxy)phenyl]1-pyrrolidinecarbothioate [compound (3)] and 0 -[3-(3-
Synthesis of chlorpropargyloxy)-4-chlorphenyl1-pyrrolidinecarbothioate [compound (4)] 2.54 g of 4-chloro-3-(3,3-dichloroallyloxy)phenol was dissolved in dimethylformamide.
0.48 g of oily sodium hydride (purity 50%) was added to this solution. This reaction mixture contains 1
-1.94 g of pyrrolidinethiocarbonyl chloride was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into ice water and extracted with diethyl ether. The ether layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The residual oil was separated and purified by silica gel column chromatography to obtain 0-[4-chloro-3-(3,3-dichloroallyloxy)phenyl]1-pyrrolidinecarbothioate [compound (3)]. 1.2g and 0-
[3-(3-chloropropargyloxy)-4-
0.5 g of chlorphenyl 1-pyrrolidinecarbothioate [compound (4)] was obtained. of each product
The NMR spectrum and mass spectrometry values are shown below.

[Table] Formulation example 1 Emulsion Prepare 30 parts each of compounds (1) to (25), add 60 parts each of an equal mixture of xylene and isophorone,
10 parts of surfactant Solpol 800A (trade name, manufactured by Toho Chemical Industry Co., Ltd.) was added and the mixture was thoroughly stirred and mixed to obtain each emulsion. Formulation example 2 Wettable powder Prepare 50 parts each of compounds (1) to (25) and add surfactant Solpol 800A (same as above) to each of them.
5 parts were thoroughly mixed, 45 parts of a mixture of equal amounts of talc and bentonite was added, and the mixture was sufficiently stirred and mixed in a grinder to obtain each wettable powder. Formulation example 3 Granules 10 parts each of compounds (1) to (25), 80 parts of an extender made by mixing talc and bentonite at a ratio of 1:3, 5 parts of white carbon, surfactant Solpol
Add 10 parts of water to 5 parts of 800A (same as above), mix well to make a paste, extrude it through a sieve hole with a diameter of 0.7 mm, and after drying, cut it into lengths of 1 to 2 mm.
Each 10% granule was obtained. 5% each by the same method as above except using 5 parts each of compounds (1) to (25) and 85 parts of filler.
Granules were obtained. Effect Example 1 Flooded Soil Treatment Effect Test Paddy soil was placed in a pot with a diameter of 12 cm, and seeded with Japanese wild grass, bulrush, cypress, Japanese cypress, and 2.5-leaf stage paddy rice seedlings were transplanted. Three days later, the area was flooded with 3 cm of water. A hydrating powder of a test compound obtained in the same manner as in Formulation Example 2 was diluted with water to prepare a drug solution with a predetermined concentration. This chemical solution was dropped onto the above water surface, and 14 days later, the herbicidal effect and paddy rice damage were judged based on the following criteria. The results are summarized in Table 1. Weeding effect judgment criteria 5: Weed suppression rate or weed death rate compared to no treatment
80-100% 4: 〃 60-less than 80% 3: 〃 40-less than 60% 2: 〃 20-less than 40% 1: 〃 〃-less than 20% 0: 〃 0% Paddy rice chemical damage judgment criteria: Browning of aboveground parts Extremely large. : 〃 Moderate. +: 〃 It is small. ±: 〃 Very small. −: 〃 Not at all.

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[Table] Effect example 2 Flooded soil treatment effect test Paddy soil was placed in a pot with a diameter of 12 cm, and seeds of wild grass, bulrush, Japanese grass, Japanese cypress, and water cypress were sown therein, and after 3 days, the pot was flooded with water to a depth of 3 cm. An emulsion of the test compound obtained in the same manner as in Formulation Example 1 was diluted with water to prepare a drug solution with a predetermined concentration. This chemical solution was dropped onto the above water surface, and the herbicidal effect was determined 14 days later using the criteria shown in Effect Example 1. The results are shown in Table 2.

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[Table] Effect example 3 Flooded soil treatment effect test Paddy soil was placed in a 12 cm diameter pot, and seeded with wild grass, firefly, and broad-leaved weeds (Kikashigusa, Konagi), and then paddy rice seedlings at the 2.5 leaf stage were transplanted. . It was flooded with 2cm of water. A hydrating powder of a test compound obtained in the same manner as in Formulation Example 2 was diluted with water to prepare a drug solution with a predetermined concentration. This chemical solution was dropped onto the above water surface, and the herbicidal effect and paddy rice damage were determined two weeks later using the criteria shown in Effect Example 1. The results are shown in Table 3.

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[Table] Effect example 4 Field soil treatment effect test A 20 cm x 15 cm polyethylene bucket was filled with sieved field soil, seeds of various plants were sown in it, and 1
cm of soil was covered. One day later, a predetermined amount of a hydrating powder of compound (10) prepared in the same manner as in Formulation Example 2 was added.
The soil was treated with a water amount of 200/10a. The herbicidal effect and crop damage after 15 days were determined according to the criteria shown in Effect Example 1, and the results are shown in Table 4.

[Table] Effect example 5 Field vat test (wettable powder treatment) Paddy soil was put into a vat of ^800cm2 , and wild grass, bulrush, and broad-leaved weeds (Kikashigusa, Konagi) were added to it.
were sown, and Urikawa tubers were also buried in the soil. 3cm
After flooding, predetermined amounts of hydrating powders of Compound (1), Compound (10), and MO prepared by the same method as in Formulation Example 2 were diluted with water and applied to the water surface. The herbicidal effect after 15 days was determined according to the criteria shown in Effect Example 1, and the results are shown in Table 5.

[Table] Effect example 6 Field vat test (granule treatment) Paddy soil was placed in a vat of 675 cm ² , and it was filled with wild grass, bulrush, broad-leaved weeds (Kikashigusa, Konagi), etc.
Seeds of Japanese cypress were sown and Urikawa tubers were buried in the soil. After immersion in water for 2 cm, 5% granules of each of Compound (1) and Compound (10) prepared in the same manner as in Formulation Example 3 were sprinkled on the water surface. The herbicidal effect after 20 days was determined according to the criteria shown in Effect Example 1, and the results are shown in Table 6.

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Claims (1)

[Claims] 1. General formula (In the formula, X represents an oxygen atom, a sulfur atom, or a vinylene group, l and m mean an integer of 1 to 3, and n
means an integer of 0 or 1. In addition, the number of members of the heterocycle formed by the nitrogen atom, two alkylene chains, and X is 4 to 7. Y represents a halogen atom, and R represents an alkyl group which may be interrupted by one or more oxygen atoms, or an alkenyl group or an alkynyl group which may be substituted with a halogen atom. ) Substituted phenylthionocarbamate. 2 General formula (In the formula, X represents an oxygen atom, a sulfur atom, or a vinylene group, l and m mean an integer of 1 to 3, and n
means an integer of 0 or 1. In addition, the number of members of the heterocycle formed by the nitrogen atom, two alkylene chains, and X is 4 to 7. Y represents a halogen atom, and R represents an alkyl group which may be interrupted by one or more oxygen atoms, or an alkenyl group or an alkynyl group which may be substituted with a halogen atom. ) A herbicide containing a substituted phenylthionocarbamate as an active ingredient.