JPS60152464A - Tetrahydrophthalimide and herbicide containing the same - Google Patents

Abstract

NEW MATERIAL:A tetrahydrophthalimide of formula I (X is halogen; Y is H, halogen; R is alkyl, alkenyl, alkinyl, cycloalkyl). EXAMPLE:N-[4-Chloro-5-(ethylthio)-2-fluorophenyl]-3,4,5,6-tetrahydroph thalimide. USE:It is used as a herbicide. It can be used in both cases of pre-emergence soil treatment after flooding and of treatment in growth periods. Further, it can be used in crop fields, for pre-emergence treatment and foliage and soil treatment. It shows high heribicidal action on annual and perennial weeds in paddy and crop fields, but exerts little influence on soybean, cotton, cucumber, rice plant, wheat and other crop plants. PREPARATION:For example, the reaction of a compound of formula II with a compound of R-Z (R is halogen) is carried out in an appropriate solvent in the presence of a base to give the compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel tetrahydro-7-talimides and herbicides containing them as active ingredients.

Conventionally, N-aryl-3,5,6-titrahydrophthalimides have been known to have excellent herbicidal activity, but slight modifications of their chemical structures (types of substituents,
The presence or absence of herbicidal activity, strength, and selectivity often vary significantly depending on the number, position, etc., and it is difficult to predict the herbicidal activity of a new compound based on mere chemical structure similarity.

As a result of intensive research into herbicides containing tetrahydrophthalimides as active ingredients, the present inventors found that N-aryl has a hydrogen atom or a halogen atom at the 2nd position, a halogen atom at the 3rd position, and a specific type of herbicide at the 3rd position. A novel N-aryl-, which is a phenyl group having a substituent, ? , 4Z, j,
The inventors have discovered that &-tetrahydrophthalimides have extremely excellent herbicidal activity and selectivity, and have arrived at the present invention.

That is, the gist of the present invention is represented by the general formula (wherein, X represents a halogen atom, Y represents a hydrogen atom or a halogen atom, and R represents an alkyl group, an alkenyl group, an alkynyl group, or a cycloalkyl group). Tetrahydrophthalimides and herbicides containing them as active ingredients.

Next, the present invention will be explained in more detail.

The compound used as a herbicide in the present invention is represented by the above general formula (1).

In the general formula (1), or a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom. Y represents a hydrogen atom or a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, etc., preferably a hydrogen atom or a fluorine atom.

R may be a straight chain or branched chain having 7 to g carbon atoms 1/)7
jlzKyl group, alkenyl group with a carbon number of Co to S, a carbon number of 3
~! represents an alkynyl group or a cycloalkyl group having 3 to 7 carbon atoms. Preferably, R represents an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 3 to 3 carbon atoms, a propargyl group, or a cycloalkyl group having 5 to 5 carbon atoms.

The compound represented by formula (1) can be produced using various raw materials, for example, according to reaction formula (1) or (2) below.

(1) (Old (1) (In the above reaction formula, 2 represents a halogen atom such as chlorine, bromine, iodine, etc., and X, Y, and R have the same meanings as above.) The above reaction can be performed without a solvent or with acetone, ethyl Ketones such as methyl ketone, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as diethyl, ether, tetrahydrofuran, and dioxane, and esters such as ethyl acetate and butyl acetate.Acetonitrile, N, N-
Aprotic compounds such as dimethylformamide, N-methyl-ruvirolidone, dimethyl sulfoxide, and sulfolane;
In a solvent such as a polar solvent, in the presence of a base such as an organic base such as sodium carbonate, potassium carbonate, carbonaceous ethylamine, pyridine, N,N-dimethylaniline, etc., or in the presence of an iodide such as sodium iodide or potassium iodide. Alternatively, it is carried out at -10 to /60''Q in the absence of oxidation.

The thiophenol derivative represented by the general formula (II), which is a raw material for the above reaction, is, for example, the aminothiophenol derivative represented by the general formula (1) as shown in the reaction formula below, and 3.
/, t, 5. It can be synthesized by reacting with 6-titrahydrophthalic anhydride.

(In the above reaction formula, X and yH have the same meanings as above.) The aminothiophenol derivative (Ill) is, for example, a dithiocarbonate derivative represented by the general formula (1v) or a general formula (l) as shown in the reaction formula below. (In the above reaction formula, R1 and Crow represent a lower alkyl group, and X and Y have the same meanings as above.) Compounds represented by general formulas (IV) and (V) can be obtained by, for example, It can be synthesized via the diazonium salt obtained from the aniline derivative represented by (Vl).Compounds (IV) and (V) can be led to compound 01) in one step, for example, by hydrolysis. By converting either one of the acylamino group in compounds (IV) and ff), the alkoxy (thiocarbonyl cothio group in compound (IV), and the thiocyanato group in compound (V)), and then converting the other. It is also possible to lead to compound (1).

21 (In the above reaction formula, X, Y and Ri have the same meanings as above.) The above reaction can be carried out without solvent or with water, carbonic acids such as acetic acid, ethers such as tetrahydrofuran and dioxane,
It is carried out in a solvent such as alcohols such as methanol, ethanol, and globanol, and aromatic hydrocarbons such as benzene, toluene, xylene, and pyridine at a temperature of 60 to -00°C.

The aniline derivative represented by the general formula (■) can be synthesized, for example, from the above-mentioned thiocyanate derivative (V) according to the reaction formula below.

(V) (Vll) ([) (In the above reaction formula, X, Y, Z, R and R have the same meanings as above.) The compound of the present invention represented by the general formula (1) can be used as a herbicidal herbicidal compound as is. It can be used as an aqueous agent, but it is usually mixed with an inert liquid carrier or solid carrier, and an appropriate surfactant is added thereto, and used in the form of an aqueous solution, granule, emulsion, tablet, powder, flowable agent, 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, silica, silica, and calcium carbonate. and soy flour,
Examples include vegetable powders such as wheat flour. If you feel more confident, you can mix it with other active ingredients, such as agricultural fungicides, insecticides, nematicides, or other herbicides, plant growth leg-articulating agents, ring-locking improvers, and fertilizer P+. You can also do that. In addition, in order to obtain a reliable herbicidal effect, we use spreading agents, emulsifiers,
Auxiliary agents such as wetting agents and fixing agents may be appropriately mixed.

The application site of the herbicide of the present invention varies depending on the type of compound used, the target weed, the treatment time, the treatment method, the nature of the soil, etc., but usually the active ingredient is L.
o, os-g□9r foot, preferably θ, 7~sIr
A range of is appropriate.

The herbicide of the present invention can be used for either pre-emergence submerged soil treatment or growing-season treatment for weeds in transplanted rice, and exhibits high herbicidal activity against annual and perennial weeds. It has an extremely favorable property as a herbicide for paddy fields, as it has very little effect on herbicides.

In addition, in pre-emergence soil treatment and foliage and soil treatment in field crops, it shows excellent pasture activity and sufficient residual efficacy against annual and perennial weeds, and even when treated at high concentrations, it is effective against crops. It has the excellent feature of having extremely minimal impact.

The herbicide of the present invention is effective for controlling, for example, the following weeds.

Weeds that are dicotyledonous plants, such as wild morning glory, japonica, chickweed, leafweed, pigweed, whiteweed, and
Wild mustard, shepherd's purse, snail, knotweed, purslane,
Dogweed, Pigweed, Kikashigusa, Azena, Takasaburou, Tau Kyogi, Abdominal stinging plant, Mizochickweed, Mizosoba.

Weeds that are monocotyledonous plants, such as grasshopper, grasshopper, grasshopper, foxtail grass, sycamore, grasshopper, grasshopper, cyperus, cyperus cyperus, cyperus cyperus, cyperus cyperus, cyperus cyperus, cyperus japonica, cyperus japonica, Japanese cyperus, water hyacinth, black-and-white chickadee, konagi, urikawa, staghorn grass, omodaka.

The herbicide of the present invention can also be used as a selective herbicide in the cultivation of, for example, the following crops:

Cultivated crops that are dicotyledons include soybean, cotton, sugar beet, sunflower, pea, potato, cucumber, etc. Cultivated crops that are monocots include rice, wheat, barley, oats, rye, corn, etc.
Examples include sugarcane, etc., but the scope of application of the herbicide of the present invention is not limited to plants of the above-mentioned species,
It can also be used on other plants using similar application methods.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 9NI N-[y-chloro-5-(ethylthi, t)
-1-fluorophenyl]-,7,Q.

5. Synthesis of 6-tetrahydrophthalimide N-(4/-chloro-twofluoro-5-mercaptophenyl)-3
,4! , &, 6-tetrahydrophthalimide/,0
91/, ethyl iodide 0.6&li.

A mixture of potassium carbonate, sgi and acetone was heated to reflux for 1 hour with stirring. After cooling, the insoluble matter was separated, the P solution was concentrated, and the residue was subjected to silica gel column chromatography (developing solvent: ethyl acetate-n-hexane).
The compound (A)/,Q shown in Table-/
/17 was obtained.

Example: Synthesis of 2N-(&-(θeC-butylthio)-cuchlorocofluorophenyl] -, ?, name t, A-tetrahydrophthalimide N-(4t-chloro-twofluoro-5-mercaptophenyl)- 3, II, 3.&-tetrahydrophthalimide/, 09g, θec-butyl bromide o, sgi, potassium carbonate o, s A' y, potassium iodide 0.
/All and acetone/3'ml was heated to reflux for 1 hour with stirring.

After cooling, the unbathed materials were separated by f, and the liquid e was condensed. The residue was purified by silica gel column chromatography (&M solvent: ethyl acetate/n-hexane/2 g) to obtain the compounds listed in Table 1. (A7)/, 0! ; g was obtained.

Example M, 7 N-44'-chlorocofluoro-5-
Synthesis of (isopropylthio)phenyl]-3,lI,t,g-tetrahydro-7talimide Dark chloroconfluoro-j-(ia7'ropylthio)aniline 6,j 9.1.3%4,l,- Tetrahydrophthalic anhydride s, oag and acetic acid 30ml
The mixture was heated to reflux with stirring overnight.

The reaction mixture was poured into water and extracted with benzene.

After washing with water and drying with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate-n-hexane) to obtain the compounds listed in Table 1. (&da) g, 69,
! I got i'.

Similarly, compounds A/, j, j, & and g~/S listed in Table 7 were obtained according to the synthesis method listed in Table 7.

The structures of the compounds listed in Table 1 are all clearly determined by IR spectra and NMR spectra, and formulation examples using the compounds of the present invention are described. In addition, below, "department", "
``chi'' means ``parts by weight'' and ``parts by weight'', respectively.

Formulation Example 1 (Wettable powder) lIo parts of the compounds of the present invention shown in Table 7, Carplex #gθ (Shionogi & Co., trade name) 20 parts% N
, N kaolin clay (Ueya Kaolin Co., Ltd.).

Trademark name) 3! r part and 95 parts of a higher alcohol sulfate ester surfactant Tsurunei Goto (Toho Kagaku Co., Ltd., trade name) were mixed and pulverized uniformly to obtain an irrigation agent containing 170% of the active ingredient.

Formulation Example (Granules) One part of the compound of the present invention shown in Table 7, 7 parts of clay (manufactured by Nippon Talc Co., Ltd.), and bentonite (manufactured by Toyojun Yoko Co., Ltd.)
SS part, succinate surfactant Airol OT-/
(Toho Chemical Co., Ltd., trade name). After mixing and pulverizing a part, add 19 parts of water and stir uniformly. Using a kneading granulator, extrude it through the sieve hole of a diameter After drying at 60 DEG C. for one hour, the mixture was cut into lengths of /-- to obtain granules containing the active ingredient λ.

Formulation Example 3 (Emulsion) 30 parts of the compounds of the present invention shown in Table 1 and 3 parts of xylene
It is dissolved in a mixed bath medium consisting of 0 parts of dimethylformamide and 5 parts of dimethylformamide, and the polyoxyethylene surfactant Tsurupol 300! ; X (Toho Kagaku Co., Ltd., trade name)/j part was added to obtain an emulsion containing active ingredient 3096.

Test example/Flooded soil treatment test 4! Paddy alluvial clay loam was filled in a resin vat with a diameter of 0.00 liters, and after fertilization, an appropriate amount of water was added and raked. Seeds of Japanese millet, Kikashigusa, and Firefly were mixed into the θ and left α layers from the soil surface, and individual tubers of Urikawa and Kizugaya were transplanted.

On the other hand, paddy rice seedlings (variety: Akinishiki, plant height = 7cm - 7cm, seedling quality: good) with 2.3 part leaves M were piled up at an insertion depth of about 1 cTL using 93 to 1 seedlings per bat. After that, about 3. !
;Maintain the water depth of C1n and use the formulation example on the next day after transplantation.
It was obtained in the same manner as in the example of granule and sand preparations containing compound points 1 to 15 of the obtained compound of the present invention as active ingredients. N-[<(
-(methylthio)phenyl]-3,lI, 5. A-
Granules containing tetrahydrophthalimide (hereinafter abbreviated as Comparative Agent A) and S-(-2-chlorobenzyl)-N,N-diethyl-thiol carbamate (hereinafter abbreviated as Comparative Agent C) as active ingredients. A predetermined amount of the agent was dropped onto the flooded surface so that the active ingredient amount was 8-2j, 5, and 5.

After treatment, the plants were given a water reduction method of 3 cm per day for 1 day, and the plants were cultivated in a recondensing greenhouse, and the weeding effect and herbiological damage were investigated every day after chemical treatment.

The results are shown in Table 2. Furthermore, the evaluation of the herbicidal effect is was expressed as a herbicidal effect coefficient based on the following criteria.

Also, the evaluation of drug damage is was expressed as a phytotoxicity coefficient according to the following criteria.

- × Comparative agent A Test example of compound described in % Kaisho/Is-15-1S Field soil treatment test Field field soil was filled into a resin vat with a ratio of 1/3 of goo, and after fertilization, wheat, corn, Each cotton seed was sown (covered with soil of 7 cm to 3 cm).

After sowing and mixing the seeds of crabgrass, Japanese knotweed, and white grass in the surface layer of the soil, Formulation Example/Irrigation agent and Formulation Example containing Compounds A/ to/Left of the compounds of the present invention obtained as active ingredients/ obtained in the same manner as eN-(4'-chloro-twofluoro-3-ingropoquinphenyl) J+ lIs
'+6-titrahydrophthalimide (hereinafter abbreviated as comparative agent B) and ? -(3',G'-dichlorophenyl)-/,/-Dimethylurea (hereinafter abbreviated as comparative agent) was diluted with water and prepared with water, and the active ingredient 1 was 1 liter. It was evenly sprayed on the soil surface using a J"l type power pressurized jet rock so that the amount of herbicidal agents per area was 0, S%s, iog. We also investigated chemical damage to crops.

The results are shown in Table-3. The herbicidal effect and phytotoxicity were evaluated in the same manner as in Test Example 1.

Table-3 * Comparative agent B Tokkai Sho! ;7-/l,? J6! Compound Test Example 3 Stalk and Leaves Treatment Test G, G So Min/R small polyethylene pots were filled with upland Kuroboku soil, and after fertilization, edible daikon and radish seeds were sown in each pot.

Cultivation management was continued in the greenhouse, and when the growth level of the test plants reached the single-leaf stage for edible daikon radish and the first true leaf stage for radish, Compound A of the present compound obtained according to Formulation Example 3 was added. Comparative agents A and B obtained in the same manner as emulsion containing 15 as an active ingredient and Formulation Example 3, and 3. An emulsion containing kudichloropropionic acid anilide (hereinafter abbreviated as comparative agent E) as an active ingredient was diluted with water so that the active ingredient concentration was o, os, O1/, 0.2. Spraying was carried out using a small power pressurized music machine in an amount equivalent to 1 Qll of spray liquid per lid. Afterwards, observations were continued in the greenhouse, and the herbicidal effect was investigated after spraying the chemicals and in the evening sun.

The results are shown in Table D. The herbicidal effect was evaluated using the same criteria as in Test Example.

table-da

Claims (2)

[Claims] (1) Tetrahydrophthalimides represented by the general formula (wherein, Y represents a hydrogen atom or a halogen atom, and R represents an alkyl group, an alkenyl group, an alkynyl group, or a cycloalkyl group). (2) Tetrahydrocttalimides represented by the general formula (wherein, X/li represents a halogen atom, Y represents a hydrogen atom or a halogen atom, and R represents an alkyl group, an alkenyl group, an alkynyl group, or a cycloalkyl group) Herbicide with active ingredient.