JPH0257543B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel tetrahydrophthalimides and herbicides containing them as active ingredients. Conventionally, N-aryl-3,4,5,6-tetrahydrophthalimides have been known to have excellent herbicidal activity, but slight modifications to their structures (type, number, position of substituents, etc.) In many cases, the presence or absence of herbicidal activity, strength, or selectivity of a new compound differs significantly depending on the compound, and it is difficult to predict the herbicidal activity or selectivity of a new compound based on mere chemical structural similarity. The present inventors conducted intensive research to provide tetrahydrophthalimides with superior herbicidal activity and crop safety, and found that N-substituted aryl
Hydrogen atoms or halogen atoms at the 2nd and 6th positions,
Novel N-aryl-3, which is phenyl having a hydrogen atom, halogen atom, methyl group or methoxy group at the 4-position and a specific substituent at the 3-position.
We discovered that 4,5,6-tetrahydrophthalimides exhibit extremely excellent characteristics as herbicides,
We have arrived at the present invention. That is, the gist of the present invention is the general formula In the formula, A represents a hydrogen atom or a methyl group. X represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and Y and Z represent hydrogen atoms or halogen atoms which are the same or different from each other. U and V are hydrogen atoms that are the same or different from each other:

Group represented by [Formula]: Alkyl group optionally substituted with a substituent selected from a halogen atom, an alkoxy group, a cyano group, and an aryl group optionally substituted with a halogen atom: an alkoxycarbonyl group or a cyano group. Optionally substituted alkenyl group: Alkynyl group:

Indicates a group represented by the formula or an alkylsulfonyl group. In the above substituents, R ¹ represents a hydrogen atom, an alkyl group or a phenyl group, R ² represents a hydrogen atom or a methyl group,
n represents an integer of 1 to 6. B is −OR ³ , −SR ⁴ , or

Indicates a group represented by [Formula]. E is R ⁷ , OR ⁸ , SR ⁹ or

A group represented by the formula or an alkyl group optionally substituted with a halogen atom: an alkenyl group; an aryl group optionally substituted with a halogen atom or a hydrogen atom. Among the above substituents, R ³ is a hydrogen atom, an alkyl group, an alkenyl group,
Alkynyl group, cycloalkyl group, aryl group,
aralkyl group or

Indicates a group represented by [Formula]. R ⁴ represents an alkyl group. R ⁵ and R ⁶ are the same or different hydrogen atoms, alkyl groups, alkoxy groups, alkoxyalkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, cycloalkyl groups, alkylsulfonyl groups, or

It represents a group represented by the formula, or R ⁵ and R ⁶ represent a heterocyclic group which may contain an oxygen atom together with the nitrogen atom in the formula. R ⁷ represents an alkyl group optionally substituted with a halogen atom: an alkenyl group or an aryl group optionally substituted with a halogen atom. R ⁸ represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. R ⁹ represents an alkyl group or an aryl group. R ¹⁰ and R ¹¹ represent the same or different alkyl groups, alkoxy groups, or aryl groups which may be substituted with halogen. In the above substituents, R ¹² represents a hydrogen atom or an alkyl group. D is a hydroxyl group, an alkoxy group, or 1 or 2
represents an amino group which may be substituted with an alkyl group or an alkenyl group. However, X represents a chlorine atom, and Y and Z
When simultaneously represent a hydrogen atom, U and V do not represent the combinations shown in the table below.

【table】

[Table] Tetrahydrophthalimides and herbicides containing them as active ingredients. Next, the present invention will be explained using a specific example. The tetrahydrophthalimide used as a herbicide in the present invention is represented by the above general formula (). Preferably, it is represented by the above general formula () to general formula (). In the formula, A is a hydrogen atom,
3-methyl group or 4-methyl group, X represents a halogen atom such as a hydrogen atom, fluorine atom, chlorine atom, bromine atom, methyl group or methoxy group,
and Z is a hydrogen atom, a fluorine atom, a chlorine atom,
Represents a halogen atom such as a bromine atom, and U and V are hydrogen atoms that are the same or different from each other;

A group represented by [formula] [wherein R ¹ is a hydrogen atom, a C ₁ to _{C 12} alkyl group, preferably a C ₁ to _{C 8}
more preferably a C ₁ to _{C 6} alkyl group or a phenyl group, R ² represents a hydrogen atom or a methyl group, n represents an integer of 1 to 6, preferably an integer of 1 to 4, B is -OR ³ {wherein R ³ is a hydrogen atom, a C ₁ to C ₃₀ alkyl group, preferably a C ₁ to
_C20 alkyl group, more preferably _C1 - _C12 alkyl group, _C2 - _C6 alkenyl group, preferably _C3 - _C4
a _C2 - _C6 alkynyl group, preferably a _C3 - _C4 alkynyl group, a _C3 - _C8 cycloalkyl group, preferably a _C5 - _C7 cycloalkyl group,
Aryl group such as phenyl group, aralkyl group such as benzyl group, or

A group represented by the formula (wherein R ¹² is a hydrogen atom or a C ₁ to C ₆ alkyl group, preferably a C ₁ to C ₄ alkyl group, and D is a hydroxyl group or a C ₁ to _{C 4} alkoxy group) , or one or two _C1 - _C8 alkyl groups, preferably C1- _C8
represents an amino group optionally substituted with a C ₅ alkyl group or a C ₃ to C ₄ alkenyl group},
-SR ⁴ (wherein R ⁴ represents a C ₁ to C ₁₀ alkyl group, preferably a C ₂ to C ₅ alkyl group), or

[Formula] {wherein R ⁵ and R ⁶ are the same or different hydrogen atoms, a C ₁ to _{C 30} alkyl group, preferably a C ₁ to C ₂₀ alkyl group, more preferably a C ₁ to C ₁₂ alkyl group, _C1 - _C12 alkoxy group preferably
_C1 - _C8 alkoxy group, more preferably _C1 - _C4 alkoxy group, _C2 - _C8 alkoxyalkyl group, preferably _C2 - _C6 alkoxyalkyl group, more preferably _C2 - _C4 alkoxy Alkyl group, _C2
~ _C8 alkenyl group, preferably _C3 ~ _C5 alkenyl group, _C2 ~ _C8 alkynyl group, preferably C3 _~
C5 alkyl group, aryl group such as phenyl group,
Aralkyl group such as benzyl group, _C3 - _C8 cycloalkyl group, preferably _C3 - _C6 cycloalkyl group, preferably _C1 - _C8 alkylsulfonyl group
_C1 - _C5 alkylsulfonyl group, or

represents a group represented by [Formula] (in the formula, R ¹² and D have the same meanings as above), or R ⁵
and R ⁶ represents a 5- to 7-membered multicyclic group, preferably a 5- to 7-membered saturated heterocyclic group, which may contain an oxygen atom together with the nitrogen atom in the formula]; a fluorine atom or a halogen atom such as a chlorine atom, preferably a chlorine atom, a _C1 to _C4 alkoxy group, a cyano group, and an aryl group optionally substituted with a halogen atom such as a chlorine atom, preferably a substituent such as a phenyl group C ₁ to C ₆ which may be
an alkyl group, preferably a C ₁ -C ₄ alkyl group;
_C2 optionally substituted with one or two _C2 - _C5 alkoxycarbonyl groups or cyano groups
~ _C6 alkenyl group, preferably _C2 ~ _C4 alkenyl group; _C2 ~ _C6 alkynyl group, preferably C3 _~
C4 alkynyl group;

A group represented by the formula [wherein E is -R ⁷ (wherein R ⁷ is a C ₁ to C ₅ group which may be substituted with 1 to 3 halogen atoms, preferably a fluorine atom or a chlorine atom)] Alkyl group, preferably a _C1 - _C3 alkyl group, a _C2 - _C5 alkenyl group, preferably a _C3 - _C4 alkenyl group, or an aryl group optionally substituted with a halogen atom such as a chlorine atom, preferably phenyl group), -OR ⁸
(In the formula, R ⁸ is a C ₁ to C ₁₂ alkyl group, preferably C _1
-C8 alkyl group, _C3 - _C8 cycloalkyl group, preferably _C5 - _C7 cycloalkyl group, _C7 - _C9
an aralkyl group, preferably a benzyl group or an aryl group such as a phenyl group), -SR ⁹ (in the formula,
R ⁹ represents a C ₁ to C ₆ alkyl group, preferably a C ₁ to _{C 4} alkyl group, or an aryl group such as a phenyl group), or

[Formula] (where R ¹⁰ and R ¹¹ are the same or different hydrogen atoms, a C ₁ to C ₄ alkyl group, preferably a C ₁ to _{C 2} alkyl group, a C ₁ to _{C 4} alkoxy group, preferably a C ₁ - _C2 alkoxy group,
or an aryl group optionally substituted with a halogen atom such as a chlorine atom, preferably a phenyl group] or a _C1 - _C4 alkylsulfonyl group, preferably a _C1 - _C2 alkylsulfonyl Indicates the group. However, X represents a chlorine atom, and Y and Z
When simultaneously represent a hydrogen atom, U and V do not represent the combinations shown in the table below.

【table】

[Table] The compound represented by the formula () of the present invention may exist in isomers such as optical isomers or diastereomers. In many cases, the isomers are obtained as a mixture containing all isomers. These isomers can be obtained by various known methods (e.g. asymmetric synthesis,
Each isomer is synthesized using a starting material having an asymmetric carbon source, optical resolution, recrystallization, or various chromatography methods such as column chromatography, thin layer chromatography, and high performance liquid chromatography). It is also possible to obtain
An example of separation of diastereomers is shown as Example No. 5. The compound represented by the formula () can be produced using various raw materials according to the reaction formula below. (In the above reaction formula, A, X, Y and Z have the same meanings as above) The above reduction reaction is carried out in a solvent such as acetic acid, ethanol, ethyl acetate, benzene, toluene, etc. in the presence of a catalyst such as palladium or Raney nickel, It is carried out at 0 to 150°C under normal pressure or increased pressure. In addition, the starting material N-(3-nitrophenyl)-3,4,
5,6-(Tetrahydrophthalimides are prepared by combining cyclohexene-1,2-dicarboxylic anhydride and nitroanilines without solvent or with acetic acid, methanol,
It can be easily obtained by reaction at 60 to 200° in a solvent such as toluene, dioxane, water, etc., and can also be subjected to the main reduction reaction without isolation. (In the reaction formula, A, , carried out at 60-200 °C in a solvent such as methanol, toluene, dioxane, water, etc. (In the above reaction formula, A, X, Y, Z, U and V have the same meanings as above, and V' and U' are hydrogen atoms:

Group represented by [Formula]: Alkyl group optionally substituted with a substituent selected from a halogen atom, an alkoxy group, a cyano group, and an aryl group optionally substituted with a halogen atom: Alkenyl group: Alkynyl group or alkyl group represents a sulfonyl group, provided that when X represents a chlorine atom and Y and Z simultaneously represent a hydrogen atom, U and V do not represent the combinations shown in the table below.

【table】

[Table] Q represents a halogen atom or an alkoxy group such as mesylate, tosylate, methoxy group or ethoxy group, or Q represents an acid anhydride or mixed acid anhydride together with U) This reaction can be carried out without a solvent or with tetrahydrofuran, Dioxane, N,N-dimethylformamide, N,
N-dimethylacetamide, dimethylsulfoxide, sulfolane, benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride,
Sodium acetate, potassium hydrogen carbonate, in a solvent such as tricrene, ethyl acetate, acetone, ethyl methyl ketone, ether, diisopropyl ether, etc.
Sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, metallic lithium, metallic sodium, metallic potassium, sodium hydride, potassium hydride,
Sodium amide, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, zinc chloride, iron chloride (), iron chloride (), copper chloride (),
Copper chloride (), lithium iodide, sodium iodide,
Potassium iodide, potassium fluoride, cesium fluoride, cuprous oxide, calcium oxide, barium oxide, iron oxide (), iron oxide (), lead carbonate, pyridine, 4-dimethylaminopyridine, triethylamine, N,
N-diethylaniline, benzyltrimethylammonium chloride (bromide), benzyltriethylammonium chloride (bromide), tetra n-butylammonium bromide (iodide),
Crown ethers; -20 to 250°C, preferably 0 in the presence or absence of polyoxyethylenes, etc.
Performed at ~200°C. (In the above reaction formula, A, U and V have the same meanings as above, at least one of X, Y and Z represents a halogen atom, the others have the same meanings as above, X', Y' and
(At least one of Z' represents a hydrogen atom, and the others have the same meaning as the corresponding X, Y, and Z.) This reaction is performed in a solvent such as acetic acid, chloroform, carbon tetrachloride, benzene, chlorobenzene, etc., using chlorine, bromine, The reaction is carried out using a halogenating agent such as sulfuryl chloride, N-chlorosuccinimide, N-bromsuccinimide, etc. at -70 to 150°C, preferably -20 to 120°C. (In ^the above reaction formula ^, A, ³ , −SR ⁴ or

[Formula] and R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as above) The above hydrolysis reaction consists of (i) water, water-methanol,
In a solvent such as water-ethanol or water-dioxane, in the presence of an acid such as hydrochloric acid or sulfuric acid, at 0 to 120°C, or formic acid,
Performed at 80-180°C in a solvent such as acetic acid in the presence of methanesulfonic acid, p-toluenesulfonic acid, etc.:
(ii) N,N-dimethylformamide, N-methyl-
2-pyrrolidone, 2,4,6-collidine, 2,6
-Carried out at 100-200°C in a solvent such as lutidine or pyridine in the presence of lithium hydroxide, lithium bromide, lithium iodide, sodium iodide, etc.: (iii) Water, water-
methanol, water-ethanol, water-dioxane,
In a solvent such as water-acetone, sodium hydroxide,
In the presence of potassium hydroxide, barium hydroxide, etc. -20
After the reaction at ~150°C, the solvent was distilled off and the residue was diluted with acetic acid,
50~ in solvents such as dilute hydrochloric acid, dilute hydrochloric acid-dioxane, etc.
This is done by reacting at 200°C. (In ^the above reaction formula ^, A, ³ , −SR ⁴ or

[Formula] and R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as above) The above reaction can be carried out without solvent or using benzene, toluene, methylene chloride, chloroform, carbon tetrachloride,
Hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, thionyl chloride, phosphorus oxychloride, methyl chlorocarbonate, chlorocarbonate in a solvent such as tetrahydrofuran, dioxane, ether, acetonitrile, pyridine, N,N-dimethylformamide, etc. In the presence of ethyl, N,N'-dicyclohexylcarbodiimide, etc., sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate,
Sodium hydroxide, potassium hydroxide, pyridine,
The reaction is carried out at -20 to 150° in the presence or absence of a base such as triethylamine or N,N-diethylaniline. In this condensation reaction, carboxylic acids, which are the starting materials, form various intermediates such as acid chlorides, acid anhydrides, and mixed acid anhydrides, depending on the case, and react with various alcohols, mercaptans, amines, etc. In particular, the target compound is produced. It is also possible to isolate and use these intermediates in some cases. (In the above reaction formula, A, X, Y, Z, R ¹ , R ² , n
and R ³ have the same meanings as above, U and V represent a hydrogen atom or an alkyl group, and Q represents a halogen atom such as chlorine, bromine, iodine, mesylate, tosylate, etc.) ,
Acetonitrile, benzene, toluene, N,N-
Sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, metallic sodium, metallic potassium, sodium hydride, in a solvent such as dimethylformamide, tetrahydrofuran, dioxane, etc.
In the presence of potassium fluoride, cesium fluoride, etc., 0-
It is carried out at 180℃. The compound of the present invention thus obtained can be used as a herbicide as it is, but it is usually mixed with an inert liquid carrier or solid, and a suitable surfactant is added thereto to form an emulsion, powder, granule, tablet, etc. Used in the form of hydrating powders, etc. Liquid carriers include toluene, xylene, methylnaphthalene, cyclohexane, butanol, glycol, dimethyl sulfoxide, dimethyl formamide, acetone, methyl isobutyl ketone,
Animal and vegetable oils, fatty acids, fatty acid esters, water, etc., and solid carriers include clay, kaolin clay, talc, bentonite, diatomaceous earth, silica, calcium carbonate, and vegetable powders such as soy flour and wheat flour. It will be done. If you need more,
It may also be used in admixture with other active ingredients such as agricultural fungicides, insecticides, nematicides or other herbicides, plant growth regulators, soil amendments and fertilizers. Further, in order to obtain a reliable herbicidal effect, auxiliary agents such as a spreading agent, an emulsifier, a wetting agent, and a fixing agent may be appropriately mixed. The application amount of the herbicide of the present invention naturally varies depending on the type of compound selected, the target weed, the treatment time, the treatment method, the nature of the soil, etc., but it is usually 0.1 to 80g per are as the active ingredient, preferably A range of 0.5 to 20gr is appropriate. The herbicide of the present invention can be used in either pre-emergence flooded soil treatment or growing season treatment in transplanted rice fields, and exhibits high herbicidal activity against annual and perennial weeds. It has the characteristic that it has extremely favorable properties as a herbicide for paddy fields, with extremely little impact. In addition, pre-emergence soil treatment and foliage and soil treatment in field crops show excellent herbicidal activity and sufficient residual efficacy against annual and perennial weeds, and even when treated at high concentrations, they are effective against crops. It has the excellent feature of having extremely minimal impact. In particular, it is unique in that it is as effective as other weeds, such as wild morning glory, Japanese morning glory, and common weed, which have been considered difficult to control with existing herbicides. The compounds of the present invention can be used, for example, to control the following weeds. Weeds that are dicots, such as wild morning glory,
Shiroza, Japanese knotweed, Japanese morning glory, Ichibi, Yaemugura, white mustard, wild mustard,
Chickweed, leafminer, squeak, dogweed, ragweed, stagweed, chamomile, kikashigusa, azaena, hawkweed, trumpetweed, abnome, chickweed, swamp buckwheat. Weeds that are monocotyledonous plants, such as black-and-white grass, black-and-white grass, black-and-white grass, black-and-white grass, black-and-white grass, grasshopper, silver grass, grasshopper, Japanese cyperus, Japanese cyperus, black grass,
Pinus vulgaris, firefly, water cypera, kouki tita, kosanagi, urikawa, yellow-tailed butterfly, and white-tailed butterfly. The compounds of the invention can be used as selective herbicides, for example in the cultivation of the following crops: Cultivated crops that are dicotyledons: soybeans, cotton, sugar beets, sunflowers, peas, potatoes, and cucumbers. Cultivated crops that are monocots: rice, wheat, barley, oats, rye, corn,
sugar cane. The scope of application of the compound of the present invention is not limited to the above-mentioned types of plants, and can be used for other plants by the same application method. Next, the present invention will be described in more detail with reference to examples, but the present invention will not exceed the gist thereof.
The present invention is not limited to the following examples. Example 1 Production of N-(5-amino-4-chloro-2-fluorophenyl)-3,4,5,6-tetrahydrophthalimide Cyclohexane-1,2-dicarboxylic anhydride and 4-chloro-2- N-(4-
Chlor-2-fluoro-5-nitrophenyl)-
A mixture of 60.0 g of 3,4,5,6-tetrahydrophthalimide (mp. 136-138°C) and 250 ml of benzene was subjected to catalytic reduction at 55°C in the presence of 5% palladium/carbon. After reduction, the catalyst was separated and the solvent was distilled off to obtain crystals. This is benzene
Recrystallized from n-hexane, the compound listed in Table 1 (No.
277) Obtained 50.8g. Example 2 N-(3-amino-4-chlorophenyl)-3,
Production of 4,5,6-tetrahydrophthalimide Cyclohexene-1,2-dicarboxylic anhydride
16.0g, 4-chloro-m-phenylenediamine
A mixture of 14.3 g and 200 ml of water was heated to 100°C with stirring.
The reaction was carried out for 9 hours. After cooling, the precipitated crystals were collected to obtain 26.8 g of the compound (No. 270) listed in Table 1. Example 3 Preparation of N-[2-fluoro-5-[1-(1-methylpropylcarbamoyl)ethyl]aminophenyl]-3,4,5,6-tetrahydrophthalimides 2-(4-fluoro-3-nitro After catalytic reduction of 7.86 g of (phenylamino)-N-(1-methylpropyl)propionamide in the presence of 5% palladium on carbon in 35 ml of acetic acid, the catalyst was separated off. Cyclohexene-
4.21 g of 1,2-dicarboxylic anhydride was added, and the mixture was heated under reflux with stirring for 2 hours, and then the solvent was distilled off. After adding 50 ml of ethyl acetate, washing with water and drying with Glauber's salt, the solvent was distilled off, and the residue was purified with a silica gel column (developing solvent: ethyl acetate-n-hexane 3:2) to form the compound listed in Table 1 (No. 51). Obtained 8.30g. In addition, 2-(4-fluoro-3 used as a raw material)
-Nitrophenyl)amino-N-(1-methylpropyl)propionamide was prepared as follows. That is, 4-fluoro-3-nitroaniline
5.20g, N-(1-methylpropyl)-2-bromopropionamide and sodium bicarbonate
After heating 3.05 g of the mixture at 160°C for 1 hour, it was purified using a silica gel column (developing solvent: ethyl acetate-n-hexane 1:1) to obtain 9.19g (mp. 101-102°C) of the above propionamide derivative. Obtained. Example 4 Production of N-[4-chloro-3-[1-(1-methylpropyl)carbamoylpropyl]aminophenyl]-3,4,5,6-tetrahydrophthalimide N-(3-amino-4-chlorophenyl) -3,
2.77g of 4,5,6-tetrahydrophthalimide,
A mixture of 4.44 g of 2-bromo-N-(1-methylpropyl)butyric acid amide and 0.41 g of zinc oxide was heated at 160°C.
After stirring for 5 hours at room temperature, the mixture was cooled to room temperature, 30 ml of ethyl acetate was added, and the insoluble portion was separated. After concentrating the liquid under reduced pressure, the residue was transferred to a silica gel column (developing solvent: ethyl acetate).
The product was purified with n-hexane (1:2) to obtain 2.72 g of the compound (No. 151) listed in Table 1. Example 5 N-[4-chloro-3-[1-(methylhexyl)
Carbamoylethyl]aminophenyl]-3,
Production of 4,5,6-tetrahydrophthalimide and separation of generated diastereoisomers N-(3-amino-4-chlorophenyl)-3,
2.77g of 4,5,6-tetrahydrophthalimide,
A mixture of 6.00 g of 2-bromo-N-(1-methylhexyl)propionamide and sodium hydrogen carbonate was stirred at 160° C. for 2.5 hours, cooled to room temperature, added with 30 ml of ethyl acetate, washed with water, and dried with mirabilite. Silica gel thin layer chromatography (developing solvent: ethyl acetate-n-hexane 1:2) of this product showed R _f 0.33.
and 0.28 showed two types of products. After distilling off the solvent, the residue was separated using a silica gel column (developing solvent: chloroform), and the compounds listed in Table 1 (No.
0.92 g (No. 77, with high R _f value), 0.93 g (No. 78, with low R _f value) and 0.90 g of their mixture were obtained. Example 6 Preparation of N-[5-[1-(allylcarbamoyl)propyl]amino-4-chloro-2-fluorophenyl]-3,4,5,6-tetrahydrophthalimide N-(5-amino-4 A mixture of 2.77 g of -chloro-2-fluorophenyl)-3,4,5,6-tetrahydrophthalimide, 4.12 g of N-allyl-2-bromobutyric acid amide, and 1.01 g of sodium hydrogen carbonate was stirred at 150°C for 2 hours. After that, the mixture was cooled to room temperature, 0 ml of ethyl acetate was added, washed with water, dried with sodium sulfate, and the solvent was distilled off. The residue was purified using a silica gel column (developing solvent system: ethyl acetate-n-hexane 1:2) and shown in Table 1.
2.30 g of the described compound (No. 175) was obtained. Example 7 N-[4-chloro-3-[1-(2-methylbutylcarbamoyl)propyl]aminophenyl]
-Production of 3,4,5,6-tetrahydrophthalimide N-(3-amino-4-chlorophenyl)-3,
2.77g of 4,5,6-tetrahydrophthalimide,
N-(2-methylbutyl)-2-bromobutyric acid amide
4.60g, sodium bicarbonate 1.01g, potassium iodide
A mixture of 0.38 g and 5 ml of sulfolane was stirred at 160° C. for 3 hours, cooled to room temperature, added with 30 ml of ethyl acetate, washed with water, dried with sodium sulfate, and then the solvent was distilled off. The residue was purified using a silica gel column (developing solvent: ethyl acetate-n-hexane 1:3) to produce the compounds listed in Table 1 (No.
166) Obtained 1.90g. Example 8 N-[2,4-dibromo-5-fluoro3-[1
-(1-methylpropyl)carbamoylethyl]
Production of aminophenyl]-3,4,5,6-tetrahydrophthalimide N-[2-fluoro-5-[1-(1-methylpropyl)carbamoylethyl]aminophenyl]
-3,4,5,6-tetrahydrophthalimide
1.60 g of bromine was added dropwise to a solution of 1.93 g and 5 ml of acetic acid at room temperature with stirring. After 0.5 hours ethyl acetate 20
After washing with water and drying the solution with sodium sulfate, the solvent was distilled off. The residue was purified using a silica gel column (developing solvent: ethyl acetate-n-hexane 1:1) to obtain 3.10 g of the compound (No. 55) listed in Table 1. Example 9 N-[2-chloro-3-(1-ethoxycarbonylpropyl)amino-6-fluorophenyl]
-Production of 3,4,5,6-tetrahydrophthalimide N-[5-(1-ethoxycarbonylpropyl)
Amino-2-fluorophenyl]-3,4,5,
0.70 g of sulfuryl chloride was added dropwise to a stirred solution of 1.87 g of 6-tetrahydrophthalimide and 20 ml of benzene at 10°C. After 1 hour, the solvent was distilled off and the residue was purified using a silica gel column (developing solvent: ethyl acetate-n-hexane 1:2) to obtain 0.95 g of the compound (No. 135) listed in Table 1. Example 10 N-[3-(1-carboxyethyl)amino-4
Preparation of -methylphenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(1-ethoxycarbonylethyl)amino-4-methylphenyl]-3,4,5,6-
A mixture of 24.0 g of tetrahydrophthalimide, 8.9 g of sodium hydroxide, 15 ml of water and 80 ml of methanol was stirred at 80° C. for 1 hour, and then the solvent was distilled off. Cyclohexene-1,2-dicarboxylic anhydride in the residue
After adding 2.1 g and 80 ml of acetic acid and heating under reflux for 3 hours with stirring, the solvent was distilled off again, and 120 ml of ethyl acetate was added.
After washing with water and drying the solution with sodium sulfate, the solvent was distilled off. The residue was recrystallized from ethyl acetate-n-hexane to obtain 15.7 g of the compound (No. 9) listed in Table 1. Example 11 N-[4-chloro-3-[1-(N-methoxy-
Production of N-methylcarbamoyl)butyl]aminophenyl]-3,4,5,6-tetrahydrophthalimide N-[4-chloro-3-(1-carboxybutyl)aminophenyl]-3,4,5,6-tetrahydrophthalimide A solution of 0.65 g of thionyl chloride dissolved in 1 ml of dichloromethane was added dropwise to a mixture of 1.88 g of thionyl chloride, 0.99 g of pyridine, and 15 ml of dichloromethane at 7°C with stirring, and the mixture was stirred for 20 minutes. To this, 0.39 g of N,O-dimethylhydroxylamine,
Triethylamine 0.56g and dichloromethane 3
ml of the mixture was added dropwise, and after further stirring at room temperature for 1.5 hours, the reaction solution was washed successively with 2N hydrochloric acid and water.
After drying the organic layer with sodium sulfate, the solvent was distilled off, and the residue was purified using a silica gel column (developing solvent: ethyl acetate-n-hexane 4:7) to form the compounds listed in Table 1 (No.
208) Obtained 1.85g. Example 12 Preparation of N-[4-chloro-3-[1-(1-ethoxycarbonylbutyloxycarbonyl)ethyl]aminophenyl]-3,4,5,6-tetrahydrophthalimide N-[4-chloro-3- A mixture of 1.74 g of (1-carboxyethyl)aminophenyl]-3,4,5,6-tetrahydrophthalimide, 1.15 g of 2-bromovaleric acid ethyl ester, 0.64 g of potassium fluoride, and 10 ml of acetonitrile was heated under reflux for 30 hours with stirring. After that, the solvent was distilled off. Add 20 ethyl acetate to this
ml was added, washed with water, dried repeatedly with sodium sulfate, the solvent was distilled off, and the residue was transferred to a silica gel column (developing solvent: ethyl acetate-n-
Hexane 4:7) was used to purify the compound listed in Table 1 (No.
25) Obtained 1.85g. Example 13 N-[4-chloro-3-(N-ethoxycarbonyl-N-propyl)aminophenyl]-3,4,
Production of 5,6-tetrahydrophthalimide N-(4-chloro-3-propylaminophenyl)-3,4,5,6-tetrahydrophthalimide 1.50g, ethyl chlorocarbonate 0.56g, pyridine 0.45g
A mixture of 20 ml of anhydrous tetrahydrofuran and 20 ml of anhydrous tetrahydrofuran was heated under reflux for 2 hours with stirring, and then the solvent was distilled off. The residue was extracted with ethyl acetate, washed with water, dried with sodium sulfate, and then the solvent was distilled off. The residue was purified with a silica gel column (developing solvent: ethyl acetate-n-hexane 1:3) to obtain the compounds listed in Table 1. (No.243) 1.25g was obtained. Example 16 N-[4-chloro-3-(N-methoxy-N-methylcarbamoyl)aminophenyl]-3,4,
Production of 5,6-tetrahydrophthalimide N-(3-amino-4-chlorophenyl)-3,
2.77g of 4,5,6-tetrahydrophthalimide,
N-methoxy-N-methylcarbamoyl chloride
A mixture of 1.19 g and 10 ml of pyridine at room temperature
After standing for a period of time, 30 ml of water was added. The precipitated crystals were collected, washed with water, dried, and recrystallized from ethyl acetate-n-hexane to obtain 1.99 g of the compound (No. 265) listed in Table 1. Other compounds included in the above general formula were also prepared by any of the methods described above. The manufacturing method is shown in the Example No. column of Table 1 below. All the compounds listed in Table 1 were confirmed by IR spectrum and/or ¹ H-NMR spectrum.

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[Table] Formulation example 1 Manufacturing method of wettable powder 50 parts of the compound listed in Table 1 or comparative agent (all parts below indicate parts by weight), White Clay Carplex #80
(Shionogi & Co., Ltd. trademark) 15 parts, N,N kaolin clay (Tsuchiya Kaolin Co., Ltd. trademark) 30 parts and higher alcohol sulfate Esthes surfactant Solbol 8070
(Trademark of Toho Chemical Co., Ltd.) 5 parts were mixed and pulverized uniformly to obtain a wettable powder containing 50% of the active ingredient. Formulation example 2 Manufacturing method of granules 5 parts of the compound listed in Table 1 or comparative agent (all parts below indicate parts by weight), 38 parts of clay (manufactured by Nippon Talc Co., Ltd.), 55 parts of bentonite (manufactured by Hojun Yoko Co., Ltd.) Department,
Two parts of the succinate surfactant Airol CT-1 (trademark of Toho Chemical Co., Ltd.) are mixed, water is added, the mixture is kneaded, and the mixture is granulated using a granulator. Next, this was dried at 60° C. for 2 hours to obtain granules containing 5% of the active ingredient. Formulation Example 3 Emulsion Manufacturing Method 30 parts of the compound listed in Table 1 or the comparative agent (all parts below indicate parts by weight) were dissolved in a mixed solvent consisting of 30 parts of xylene and 25 parts of dimethylformamide,
Furthermore, the polyoxyethylene surfactant Solpol
Add 15 parts of 3005X (trademark of Toho Chemical Co., Ltd.) to the active ingredient
An emulsion containing 30% was obtained. Example 17 Upland soil treatment test A 1/2500 are resin vat was filled with upland Kuroboku soil, and after fertilization, each seed of corn, wheat, and barley was sown and covered with 2.5 cm of soil. . After mixing various weed seeds shown in Table 2 into the soil surface layer, 3-(3',4'-dichlorophenyl)- 1-methoxy-1-methylurea (hereinafter abbreviated as comparative agent A), 2,4-dichlorophenyl-4'-nitrophenyl ether (hereinafter abbreviated as comparative agent B) or N-methoxymethyl-2,6 - A wettable powder or emulsion containing diethyl-α-chloroacetanilide (hereinafter abbreviated as Comparative Agent C) as an active ingredient was diluted with water, and the amount of active ingredient was 3.125, 6.25, 12.5, and 25g per are. It was evenly spread over the soil surface using a small powered pressurized sprayer. The herbicidal effect was investigated 30 days after the chemical was sprayed, and at the same time, the chemical damage to each crop was also investigated. The results are shown in Table 2. In addition, the evaluation of herbicidal power is (1 - above-ground fresh weight of weeds in treated area / above-ground fresh weight of weeds in non-treated area) x 100 = Y (
%) was determined and expressed as a herbicidal effectiveness coefficient based on the following criteria.

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[Table] In addition, the evaluation of chemical damage is as follows: (1 - above-ground fresh weight of crops in treated area / above-ground fresh weight of crops in non-treated area) x 100 = Y (
%) was calculated and expressed as a drug toxicity coefficient according to the following criteria.

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[Table] Example 18 Stem and leaf treatment test After filling small polyethylene pots with upland black soil and fertilizing, edible millet, crabgrass, radish,
Seeds of Japanese knotweed, wheat, corn, and rice were sown. Cultivation management continued in the greenhouse, and the growth levels of the test plants were as follows: edible millet at the 2-leaf stage, crabgrass at the 3-leaf stage, radish at the 1st true leaf stage, Japanese knotweed at the 2.5-leaf stage,
When wheat reached the 2-leaf stage, corn the 2.5-leaf stage, and rice the 3-leaf stage, the emulsion of each drug prepared according to Formulation Example 3 and the comparative agent 3,4-dichloropropionic acid anilide (hereinafter referred to as the comparative agent) (Abbreviated as D)
The emulsion containing the active ingredient is diluted with water, and each prepared liquid obtained by adjusting the active ingredient concentration to 0.0625, 0.125, and 0.25% is heated using a small power source so that the liquid volume is 10 liters per are. Spraying treatment was carried out using a pressurized sprayer. Afterwards, observations were continued in the greenhouse, and on the 15th day after spraying, we investigated herbicidal effects and chemical damage. The results are shown in Table 3. The evaluation of herbicidal power and phytotoxicity was expressed in the same manner as in Test Example 1.

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[Table] Example 19 Flooded soil treatment test before weed emergence in paddy fields Paddy alluvial clay loam was filled in a 1/2500 are vat, and after fertilization, seeds of Japanese millet, Kikashigusa, Firefly, and Helaomodaka were sown. On the other hand, 3-leaf stage paddy rice seedlings (variety: Sasanishiki, plant height: 15 cm, seedling quality: good) were inserted into each pot with 2 plants and then planted at a shallow depth of approximately 2 cm. A water depth of 3 cm was maintained, and the next day after transplantation, granules prepared according to Formulation Example 2 and S-(4-chlorobenzyl)-N,N-diethyl-thiol carbamate (hereinafter abbreviated as Comparative Agent E) were added. Predetermined amounts of granules as ingredients were dropped onto the flooded surface so that the amount of active ingredient was 6.25, 12.5, and 25 g per are. 3cm/3 days after treatment
After that, the plants were kept in a greenhouse, and the herbicidal effects and damage were investigated on the 21st day after the chemical treatment. The results are shown in Table 4. The evaluation of herbicidal power and phytotoxicity was expressed in the same manner as in Test Example 1.

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Claims (1)

[Claims] 1. General formula In the formula, A represents a hydrogen atom or a methyl group. X represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and Y and Z represent hydrogen atoms or halogen atoms which are the same or different from each other. U and V are hydrogen atoms that are the same or different from each other: a group represented by the formula: substituted with a substituent selected from a halogen atom, an alkoxy group, a cyano group, and an aryl group optionally substituted with a halogen atom; Alkyl group: Alkenyl group optionally substituted with an alkoxycarbonyl group or cyano group: Alkynyl group: Indicates a group represented by the formula or an alkylsulfonyl group. In the above substituents, R ¹ represents a hydrogen atom, an alkyl group or a phenyl group, R ² represents a hydrogen atom or a methyl group,
n represents an integer of 1 to 6. B represents -OR ³ , -SR ⁴ or a group represented by [Formula]. E represents a hydrogen atom, R ⁷ , OR ⁸ , SR ⁹ or a group represented by [Formula]. Among the above substituents, R ³ is a hydrogen atom, an alkyl group, an alkenyl group,
Alkynyl group, cycloalkyl group, aryl group,
Indicates an aralkyl group or a group represented by [Formula]. R ⁴ represents an alkyl group. R ⁵ and R ⁶ are the same or different hydrogen atoms, alkyl groups, alkoxy groups, alkoxyalkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, cycloalkyl groups, alkylsulfonyl groups, or represented by [Formula] R ⁵ and R ⁶ represent a heterocyclic group which may contain an oxygen atom together with the nitrogen atom in the formula. R ⁷ represents an alkyl group optionally substituted with a halogen atom: an alkenyl group or an aryl group optionally substituted with a halogen atom. R ⁸ represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. R ⁹ represents an alkyl group or an aryl group. R ¹⁰ and R ¹¹ represent the same or different alkyl groups, alkoxy groups, or aryl groups which may be substituted with halogen. In the above substituents, R ¹² represents a hydrogen atom or an alkyl group. D is hydroxyl group: alkoxy group: or 1 to 2
represents an amino group which may be substituted with an alkyl group or an alkenyl group. However, X represents a chlorine atom, and Y and Z
When simultaneously represent a hydrogen atom, U and V do not represent the combinations shown in the table below. [Table] Tetrahydrophthalimides represented by [Table]. 2 General formula In the formula, A, X, Y, Z, R ¹ , R ² , n and B have the same meanings as above, and V is a hydrogen atom, an alkyl group,
Represents a group represented by [Formula] (in the formula, R ⁷ represents an alkyl group optionally substituted with a halogen atom) or a group represented by [formula] (in the formula, R ⁸ represents an alkyl group) . Tetrahydrophthalimide according to claim 1, which is represented by: 3 General formula In the formula, U is an alkyl group optionally substituted with a substituent selected from a halogen atom, an alkoxy group, a cyano group, and an aryl group optionally substituted with a halogen atom: an alkyl group substituted with an alkoxycarbonyl group or a cyano group. An optional alkenyl group: Alkynyl group: represents a group represented by the formula (wherein E has the same meaning as above) or an alkylsulfonyl group, and V represents a hydrogen atom or an alkyl group. Tetrahydrophthalimide according to claim 1, which is represented by: 4 General formula In the formula, U represents an alkyl group, an alkenyl group, or an alkynyl group which may be substituted with an alkoxy group or a cyano group, and V represents a hydrogen atom or an alkyl group. Tetrahydrophthalimide according to claim 1, which is represented by: 5 General formula In the formula, U represents a group represented by [formula] (in which R ⁸ has the same meaning as above) or a group represented by [formula] (wherein R ⁹ shows the same meaning as above), and V represents an alkyl group. Tetrahydrophthalimide according to claim 1, which is represented by: 6 General formula In the formula, A, X, Y and Z have the same meanings as above. Tetrahydrophthalimide according to claim 1, which is represented by: 7 General formula In the formula, A represents a hydrogen atom or a methyl group. X represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and Y and Z represent hydrogen atoms or halogen atoms which are the same or different from each other. U and V are hydrogen atoms that are the same or different from each other: a group represented by the formula: substituted with a substituent selected from a halogen atom, an alkoxy group, a cyano group, and an aryl group optionally substituted with a halogen atom; Alkyl group: Alkenyl group optionally substituted with an alkoxycarbonyl group or cyano group: Alkynyl group: Indicates a group represented by the formula or an alkylsulfonyl group. In the above substituents, R ¹ represents a hydrogen atom, an alkyl group or a phenyl group, R ² represents a hydrogen atom or a methyl group,
n represents an integer of 1 to 6. B represents -OR ³ , -SR ⁴ or a group represented by [Formula]. E represents a hydrogen atom, R ⁷ , OR ⁸ , SR ⁹ or a group represented by [Formula]. Among the above substituents, R ³ is a hydrogen atom, an alkyl group, an alkenyl group,
Alkynyl group, cycloalkyl group, aryl group,
Indicates an aralkyl group or a group represented by [Formula]. R ⁴ represents an alkyl group. R ⁵ and R ⁶ are the same or different hydrogen atoms, alkyl groups, alkoxy groups, alkoxyalkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, cycloalkyl groups, alkylsulfonyl groups, or represented by [Formula] R ⁵ and R ⁶ represent a heterocyclic group which may contain an oxygen atom together with the nitrogen atom in the formula. R ⁷ represents an alkyl group optionally substituted with a halogen atom: an alkenyl group or an aryl group optionally substituted with a halogen atom. R ⁸ represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. R ⁹ represents an alkyl group or an aryl group. R ¹⁰ and R ¹¹ represent the same or different alkyl groups, alkoxy groups, or aryl groups which may be substituted with halogen. In the above substituents, R ¹² represents a hydrogen atom or an alkyl group. D is hydroxyl group: alkoxy group: or 1 to 2
represents an amino group which may be substituted with an alkyl group or an alkenyl group. However, X represents a chlorine atom, and Y and Z
When both represent a hydrogen atom, U and V do not represent the combinations shown in the table below. [Table] [Table] Herbicides containing tetrahydrophthalimides as active ingredients.