JPH0283359A - Hexahydrophthalic acid anilide derivative, its production and herbicide containing the same derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X<1> and X<2> are halogen; Y is O or S; R<1> is 1-6C straight-chain alkyl or cycloalkyl; R<2> is H or methyl; R<3> is cyano, 1-3C alkyl, 2-3C alkenyl, etc.). EXAMPLE:N-(4-chloro-2-fluoro-5-isopropoxyphenyl)-2-(2-methoxyethyl-oxy carbonyl) cylohexylcarboxylic acid amide. USE:A herbicide which can be extremely safely applied to crops such as rice, wheat and corn. PREPARATION:The compound of formula I can be produced by reacting an acid halide of formula II (X is halogen) with an anilide derivative of formula III in the presence of a base (e.g., thiethylamine or pyridine) at 0-150 deg.C, preferably 20-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] This invention relates to a novel hexahydrophthalic acid anilide derivative, a method for producing the same, and a herbicide containing the same as an active ingredient.

[Prior Art] The herbicidal activity of hexahydrophthalic acid anilide derivatives has been well known, for example, in JP-A-61-3315.
N-(4-chloro-2-fluoro-5-isopropoxyphenyl)-2-ethoxycarbonylcyclohexylcarboxylic acid amide disclosed in No. 4 and the like is known.

[Disadvantages of conventional technology] However, conventional hexahydrophthalic acid anilide derivatives do not necessarily have sufficient herbicidal activity or do not have sufficient selectivity between crops and weeds, and therefore have safety problems for one crop. .

[Problems to be Solved by the Invention] Therefore, the objects of the present invention are to provide a new compound which has high herbicidal activity and is highly safe for crops when used as a herbicide, a method for producing the same, and a novel compound using the compound as an active ingredient. The objective is to provide a herbicide that is effective.

[Means for solving the problem] As a result of intensive research, the present inventors have found that a novel hexahydrophthalic acid anilide derivative having a specific substituent at the 5-position of the ester moiety and the aryl moiety has extremely excellent herbicidal activity. This invention was completed based on the discovery that it has selectivity.

That is, this invention is based on the general formula [II is a cyano group, an alkyl group having 1 to 3 carbon atoms, and a group having 2 to 3 carbon atoms.
alkenyl group, alkynyl group having 2 to 4 carbon atoms, alkynyl group substituted with methoxy group having 3 to 6 carbon atoms, C0N
A hexahydrophthalic acid anilide derivative represented by HR'(R' represents an aromatic sulfonyl group or an azole heterocycle) is provided.

Also, this invention.

General formula [[r] (In the formula, ) [1, A chain or cyclic alkyl group, R2 is a hydrogen atom or a methyl group, R3 (
(wherein, X represents a halogen atom, and R1 represents a linear or cyclic alkyl group having 1 to 6 carbon atoms which may be substituted with oxygen) and an acid halide represented by the general formula [111] Y- (:14-R'' an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, an alkynyl group substituted with a methoxy group having 3 to 6 carbon atoms, C0NHR'(R' is aromatic sulfonyl The present invention provides a method for producing the compound of the present invention represented by the above general formula [I], which comprises reacting an anilide derivative represented by (representing a group) or an azole heterocycle in the presence of a base.

Furthermore, the present invention provides a herbicide containing the compound of the present invention represented by the above general formula [■] as an active ingredient.

[Effects of the Invention] The present invention provides a novel compound having excellent herbicidal activity and safety as a herbicide, and a method for producing the same.

Furthermore, the herbicide of the present invention containing the compound of the present invention as an active ingredient has a high herbicidal activity that can accurately exterminate a variety of weeds, as will become clear from the examples described later. It is highly safe and can be used extremely safely for various crops, especially rice and field crops such as wheat and corn.

[Detailed Description of the Invention] As mentioned above, the hexahydrophthalic acid anilide derivative of the present invention is represented by the above general formula [1]. General formula [
In 11, xl and x2 represent halogen atoms, and xI and x
2 may be the same or different. Preferred examples of xl and X2 include a fluorine atom and a chlorine atom. Y represents an oxygen atom or a sulfur atom [1 represents a linear or cyclic alkyl group having 1 to 6 carbon atoms which may be substituted with oxygen;

Preferred examples of 11 include alkoxylalkyl groups such as methoxyethyl group, ethoxyethyl group, methoxypropyl group, and ethoxypropyl group, and oxygen atom-containing heterocycles such as 2-tetrahydropyranylmethyl and 2-berhydropyranylmethyl. Examples include substituted alkyl groups. As a particularly preferred example, a methoxyethyl group, 2
-tetrahydrofuranylmethyl group, etc. R2 represents a hydrogen atom or a methyl group; R3 represents a cyano group, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, and a cyano group having 1 to 3 carbon atoms;
Alkynyl group substituted with methoxy group of 6, CON H
Preferred examples of R1, which represents R'(R' is an aromatic sulfonyl group) or an azole heterocycle such as oxasilyl, imidazolyl, pyrazolyl, thiazolyl, oxadiazolyl, and thiadiazolyl, are a cyano group, a methyl group, and an ethyl group.

Alkyl groups with 1 to 3 carbon atoms such as propyl group and isopropyl group, alkenyl groups such as vinyl group, propenyl group, butenyl group: ethynyl group, propynyl group, butynyl group, alkynyl group; 3-methoxypropynyl group, 4-methoxy Alkynyl group substituted with methoxy group such as butynyl group, 5-methoxypentynyl group; secondary amide group whose nitrogen atom is substituted with sulfonyl group such as tolylsulfonyl group, chlorophenylsulfonyl group, anisylsulfonyl group ;The number of carbon atoms in the 3rd position or methyl group, ethyl group, propyl group, etc.
Examples include azole heterocycles such as 5-(+,2,4-oxadiazolyl) groups substituted with ~3 alkyl groups.

Table 1 shows preferred specific examples of the present invention, but the compounds of the present invention are not limited thereto.

Table 1 x2, Y, R2 and R3 have the same meanings as above,
represents a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom.

The compound of the present invention represented by the above general formula has the above formula [II]
It can be produced from the acid halide represented by the formula [m] and the aniline derivative represented by the above formula [m] according to the following reaction formula. However, in the formula, x1, [+] R'' This reaction is carried out in the presence or absence of a reaction solvent, in the presence of a base, at 0°C to 150°C, preferably at 20°C to 100°C, for several minutes to 48 hours. The compound of the present invention can be obtained by the reaction.

Preferred examples of solvents used in the reaction include acetone,
Ketones such as methyl ethyl ketone; Aromatic hydrocarbons such as benzene, toluene, and xylene; Ethers such as ethyl ether, tetrahydrofuran, and dioxane; Halogenated hydrocarbons such as chlorobenzene, chloroform, carbon tetrachloride, dichloroethane, and dichloromethane; Triethylamine , tertiary amines such as pyridine and dimethylaniline; and polar solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, and hexamethyltriami-1-phosphate.

Examples of preferable bases used in the reaction include triethylamine, pyridine, l,8-diazabicyclo[5
, 4,0l-7-undecene, dimethylaniline, etc.; alkali hydroxides such as sodium hydroxide, potassium hydroxide; alkaline earth hydroxides such as calcium hydroxide: sodium carbonate, potassium carbonate, hydrogen carbonate. Examples include alkali carbonates such as sodium and potassium hydrogen carbonate, and metal hydrides such as sodium hydride.

The amount of reagents used in the reaction is usually 1 to 5 equivalents of the aniline derivative represented by the general formula [m] and 1 to 5 equivalents of the base per 1 equivalent of the acid halide represented by the general formula [1]. It is 10 equivalents.

The insect repellent of the present invention containing the above-mentioned compound of the present invention as an active ingredient is suitable for use against various weeds that are problematic in the flooding treatment of rice fields, such as grass weeds such as Japanese millet, broad-leaved weeds such as azalea, azalea, chickweed, and Japanese chickweed. It has a herbicidal activity against weeds of the Cyperaceae family, such as Cyperus japonica, Cyperus japonica, and Cyperus japonica, and has particularly excellent herbicidal activity against broad-leaved weeds in upland areas. Such weeds include, for example, mustard greens, soybean shepherd's shepherd's purse, japonica japonica, goldenrod, chickweed, pigweed, stinging nettle, bushweed, green grass,
Examples include Onamomi, Japanese knotweed, Japanese knotweed, and Ichibi. Furthermore, the herbicide of the present invention causes almost no phytotoxicity to grass crops such as corn, rice, and wheat, and is highly safe.

The herbicide of the present invention is an emulsion formulated by a method commonly used for pesticide formulations, using the above-described active ingredient, which is the compound of the present invention, and a pesticide adjuvant commonly used in this field. It is available in formulations such as , wettable powders, and single oil tablets. In actual use, these various preparations can be used as is or diluted with water to a predetermined concentration.

Examples of pesticide adjuvants include diluents, surfactants, stabilizers, fixing agents, aerosol sprays, synergists, fillers, solid carriers, efficacy extenders, dispersion stabilizers, and the like. Examples of diluents include water, hydrocarbons, alcohols,
Mention may be made of ethers, alcohol ethers, ketones, esters, amides, and sulfoxides.

In addition, as fillers and solid carriers, inorganic powder 1 such as quicklime, magnesium lime, gypsum, calcium carbonate, ridged earth, perlite, pumice, diatomaceous earth, alumina, zeolite,
clay minerals (talc, vermiculite, kaolinite),
Examples include plant powder (for example, starch, flour, glucose), synthetic resin powder (for example, phenol resin, carbon resin, vinyl chloride resin), and the like. As a surfactant.

Anionic surfactants (e.g. alkyl sulfates,
Aryl sulfonic acids, succinates, polyethylene glycol alkyl aryl ether sulfates), cationic surfactants (e.g. alkylamines, polyoxyethylene alkyl amines), nonionic surfactants (e.g. polyoxyethylene glycol ethers, polyethylene glycol ethers, (oxyethylene glycol esters, polyhydric alcohol esters), amphoteric surfactants, and the like.

Examples of specific formulations are shown below.

Formulation example l (emulsion) 20 parts by weight of active ingredient, 60 parts by weight of xylene, and Tsurpol 2805B (Product name: Surfactant manufactured by Toho Chemical Industries)
20 parts by weight were uniformly stirred and mixed to form an emulsion.

Formulation example 2 (hydrating powder) 10 parts by weight of active ingredient, 87 parts by weight of Zikrite, Neoplex powder (product name: manufactured by Kako Co., Ltd.) and Tsurupol 800A (product name: surfactant manufactured by Toho Chemical Co., Ltd.) 1.5 parts by weight are mixed and ground to prepare a wettable powder.

The herbicide of the present invention can be used in the same manner as conventional herbicides, and can be used, for example, to treat soil before or in the early stages of germination of upland weeds. In addition, for paddy field weeds, for example, the herbicide of the present invention can be used to treat soil before or immediately after the weeds emerge after the rice transplants have taken root.

The application amount of the herbicide of the present invention can be appropriately selected depending on the application method, purpose, timing, and weed growth situation.
Usually, the amount of active ingredient per hectare is from 0.0 kg to 10 kg, preferably from 0.05 kg to 5 kg.

The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples only.

[Example] 1-diluted N-(4-chloro-2-fluoro-5-isopropoxyphenyl)-2-(2-methoxyethyloxycarbonyl)cyclohexylcarboxylic acid amide (compound number l
(See Table 1)) Production of 1.2,3,4,5.6-hexahydrophthalic acid 2-
0.69 g of methoxyethyl ester and 20 g of methylene chloride
Dissolved in ml, pyridine 0.24ml, thionyl chloride 0
．． 22+sl was added and stirred at room temperature. 4 after 1 hour
- Added 0.57 g of chloro-2-fluoro-5-isopropoxyaniline and 0.42+*I of triethylamine and stirred at room temperature for 1.5 hours.
% aqueous hydrochloric acid solution was added to make the mixture acidic, and the mixture was extracted twice with methylene chloride. The extract was washed with a saturated aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography (carrier Nijiri gel, developing solvent: hexane/ethyl acetate-1/1 (V/V
)) It was purified to obtain 0.59 g of a solid.

Melting point: 58-60°C Elemental analysis value Elemental analysis value NMR ((: DCl, δpp+w) 1.15
-2.55 (14H, m), 2.60-3.16 (2H
,■)127(3H,s), :1lO-3,70(21
, s) 4.15-4.70 (3H, s), 7.05 (I
ll, d, J=10Hz)7, fi7(IH,br),
8.16 (d, III, J=7Hz) Example 2 5-allylthio-4-chloro-2 as aniline derivative
The same operation as in Example 1 was performed except for using -fluoroaniline to obtain compound No. 2 (see Table 1).

Refractive index n" 1.5587 N M R (CDCI2 δpp@) 1, I5-2
．． 62 (88, ■), 2.65-3.17 (2H, ■)
3.30 (3H, s), 3.40-3.65 (48
, *) 4.15-4.38 (2H, m), 4.95-6
．． 20 (3H, s) 7.09 (IH, d, J = 10),
7.67 (IH, br).

g, +5 (IH, d, J-8) Example 3 4-chloro-2-fluoro-5- as aniline derivative
Example 1 except using propargyloxyaniline
The same operation as above was performed to obtain compound No. 3 (see Table 1).

Melting point: 92-93°C Elemental analysis value Elemental analysis value NMR (CDCIz δpp ■) 1.15-2
．． 42 (8H, m), 2.56 (lH, t, J=2)2
．． 65-3.15 (211, m), 3.30 (:l) I
, s) 3.35-165 (2H, +s), 4.06-4
．． : 18 (2H, m) 4.72 (2H, d, J-2),
7.12 (Ill, d, J-10) 7.76 (IH
, br), 8.12 (IH, d, j = 7) Example 4 4-chloro-2-fluoro-5- as an aniline derivative
The same operation as in Example 1 was performed except that (1-methylpropargyloxy)aniline was used to obtain compound No. 4 (see Table 1).

Melting point = 68-70°C NMR (CDCh δppm) 1.15-2.
40 (118, s), 2.50 (IH, d, J-2
)2.60-:1.20(211,m), 3.25
(311, s) 3.40-3.65 (211, m),
4.10-4.35 (2H, m) 4.90 (Hl, -
dq, J-2,5), 7.08(l) I, d, J=
10) 7.65 (IH, br), 8.20 (IH, +s
) Example 5 The same operation as in Example 1 was performed except for using 5-(l-methyl-3-butynyloxy)-4-chloro-2-fluoroaniline as the aniline derivative, and compound No.
The compound (see Table 1) was obtained.

Refractive index: τ+” 1.5330 Elemental analysis value NMR ((:DC1□ δppm) 1.1s-3
, 15 (16H, m), 3.28 (311,5) 132
-3.62 (2H, +s), 4.00-4.55 (
:Iff, layer) 7.02 (IH, d, J=IO), 7.
60 (IH, br) 8.02 (Ill, d, J-7) 4-chloro-2-fluoro-5-
The same operation as in Example 1 was performed except for using (4-methoxy-2-butynyloxy)aniline to obtain compound No. 6 (see Table 1).

Refractive index: n% 51.53:19 NMR (CDCI: + δppm) 1.15-
2.50 (8H, m), 2.55-3゜08 (2H
,+*)3.15-3.68(8H,+s), :1
．． 95-4. :10(4H,m)4.72(2H,t,
J-1), 7.02 (IH, d, J-10) 7.6
5 (IH, br), 8.12 (IH, d, J1=7
) Example 7 4-chloro-2-fluoro-5- as aniline derivative
The same operation as in Example 1 was performed except for using propargylthioaniline to obtain compound No. 7 (see Table 1).

Refractive index: n'' 1.5612 Elemental analysis value NMR (CDC1, δppm) 1.2O-160 (9H, m), 2.70-3.25 (
2H,i) 3.32(311,s), 3.34-:1.
80 (4H, m) 4.10-4.45 (2H, m), 7
．． 20 (Iff, d, J-10) 7.113 (II, b
r), 8.48 (IH, d, J = 7) Example 8 Same as Example 1 except that 2,4-dichloro-5-(1-methyl-propargyloxy)aniline was used as the aniline derivative. The operation was carried out to obtain compound No. 8 (see Table 1).

Refractive index: n" 1.54:17 ■ NMR (CDC1ff δppm) 1.15-2
．． 37 (1111, s), 2.50 (11, d, J
= 2) 2.60-3.1:1 (2H, m), 124 (3
H, s) 3,: 10-3.53 (211, m), 4
．． 05-4.32 (2fl, ■) 4.90 (IH, dq
, J-11,7), 7.25(IH,s), 7
．． 85 (IH, br) 8.28 (IH, d, Jco 2) Example 9 4-chloro-2-fluoro-5- as acid halide
The same operation as in Example 4 was performed except for using (l-methyl-propargyloxy)aniline to obtain compound No. 9 (see Table 1).

Melting point: 101-102°C Elemental analysis value NMR (CDCI3 δppm) 1.15-2
15 (15H, ■), 2.50 (II (, d, J=
2) 2.57-3.20 (2) 1. m), 3.50
-4.35 (5tl, m) 4.85 (IH, dq, J-
2,6), 7.12 (Ill, d, J=IO) 7.73
(IN, br), 8.20 (IH, dd, J=2.7)
Example 10 4-chloro-2-fluoro-5- as aniline derivative
The same operation as in Example 1 was performed except for using (1-cyanoethoxy)aniline to obtain compound No. 10 (see Table 1).

Melting point = 79-82°C NMR (CDCI z δpp ■) 1.20-
2.50 (IIH, m), 2.60-3.10 (2H,
Seal) 3.15-3.70 (58, shoes), 4.08-
4.38 (2H, m) 4.92 (IH, Q, J-7))
, 7.12 (Ill, d, J-10) 7.74 (IH,
br), 8.24 (IH, d, J=7) Example 11 4-chloro-2-771, as an aniline derivative, was converted into rho-5-(1-(3-methyl-1,2,4-oxadiazole) The same operation as in Example 1 was performed except that -5-yl)ethoxy)aniline was used to obtain compound Th8 No. 11 (see Table 1).

Refractive index: n” 1.5:100 Elemental analysis value Elemental analysis value NMR (CDC11δppm) 1.20-2.20 (1111, s), 2.]5
(38, s) 2.65-3.10 (2H, @), 3.2
5 (3H, s): 1.30-3.60 (2H, m), 4
．． 30-4.40 (2H111) 5.45 (IH, q,
J=7), 7.03 (IH, d, O120) 7.5
8 (III, br), 8.05 (IH, d, J=7) Example 12 4-chloro-2-fluoro-5- as aniline derivative
Example 1 except using (1-(4-methoxybenzenesulfonylaminocarbonyl)ethoxy)aniline
Compound number 1, which is a viscous substance, is obtained by performing the same operation as
Compound 2 (see Table 1) was obtained.

MR (CDCI, δpp garden) 1.05-2.50 (til+, ■), 2.58-3.
12 (211, a) 1.28 (38, s), : 1.40
-3.68 (2B4), 3.82 (3H, s) 4.10
-4.40 (2H, m), 4.67 (IH, q, J=7
)6.80-7.20 (4+1.Otori), 7.60-
8.15 (4+1.Otori) Example 13 Soil treatment test on transplanted paddy rice A 60c■2 plastic pot was filled with paddy soil, and after plowing, seeds of weeds shown in Table 2 below were sown, and then two-leaf stage paddy rice (variety : Yamahoshi) was transplanted,
It was managed in a flooded state of about 30 meters. At the early stage of the emergence of wild grass and broad-leaved weeds, the herbicide of the present invention formulated according to Formulation Example 2 above was diluted with a predetermined amount of water, and the amount shown in Table 2 was uniformly applied to the water surface. In addition, as a control compound, JP-A-61-331
N-(4-chloro-2-fluoro-5-isopropoxyphenyl)-2-ethoxycarbonylcyclohexylcarboxylic acid ethyl ester disclosed in No. 54 and the like was used. The growth conditions of weeds and crops were observed 20 days after the chemical treatment, and the results shown in Table 1 and Table 2 were obtained. The herbicidal efficacy was evaluated using a number from 0 to 5 as shown below.

In addition, phytotoxicity to crops was also shown using the same criteria as herbicidal efficacy.

O... L... 2... 3, ψ 4, Life 5... 0-9% 10-29% 30-49% 50-69% 70-89% 90-100% ・Weed suppression rate・Weed suppression rate・Suppression Weed rate / Weed control rate / Weed control rate / Weed control rate Flame Mugoyu A Stem and leaf treatment test Pack field soil into a 22cm x 16cm plastic vat, sow a certain amount of wheat, corn, and dice seeds, and then weed grass, grass, and grass on top. , Aobiyu.

The soil was covered with soil containing weed seeds such as Japanese fir tree to a thickness of about 1 cm. When the wild animals reached the 2 to 2.5 i stage, the above-mentioned compound of the present invention was sprayed in the amount shown in Table 3 below. The growth status of weeds and crops was observed 14 days after spraying, and the results shown in Table 3 were obtained.

The same control compound as in Example 13 was used, and the herbicidal effect and phytotoxicity evaluation were conducted in the same manner as in Example 13.

Claims (7)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, X^1 and X^2 are the same or different halogen atoms, Y is an oxygen atom or a sulfur atom, and R^1 is substituted with oxygen. a linear or cyclic alkyl group having 1 to 6 carbon atoms, which may be a straight chain or cyclic alkyl group having 1 to 6 carbon atoms; R^2 is a hydrogen atom or a methyl group; R^3 is a cyano group; an alkyl group having 1 to 3 carbon atoms; alkenyl group, alkynyl group having 2 to 4 carbon atoms, 3 to 4 carbon atoms
6 alkynyl group substituted with methoxy group, CONHR
A hexahydrophthalic acid anilide derivative represented by ^4 (R^4 represents an aromatic sulfonyl group or an azole heterocycle). (2) The hexahydrophthalic acid anilide derivative according to claim 1, wherein X^1 and X^2 are fluorine atoms or chlorine atoms. (3) The hexahydrophthalic acid anilide derivative according to claim 2, wherein R^1 is a methoxyethyl group or a 2-tetrahydrofuranylmethyl group. (4) The hexahydrophthalic acid anilide derivative according to claim 2, wherein the azole heterocyclic substituent R^3 is a 1,2,4-oxadiazolyl group substituted with an alkyl group having 1 to 3 carbon atoms at the 3-position. . (5) The hexahydrophthalic acid anilide derivative according to claim 2, wherein R^4 is anisylsulfonyl group. (6) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, X represents a halogen atom, and R^1 represents a linear or (represents a cyclic alkyl group) and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, X^1, X^2 are the same or different halogen atoms, Y is an oxygen atom or Sulfur atom, R^2 is a hydrogen atom or a methyl group, R^3 is a cyano group, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, a carbon number 2 to 4
an alkynyl group, an alkynyl group substituted with a methoxy group having 3 to 6 carbon atoms, an anilide derivative represented by CONHR^4 (R^4 represents an aromatic sulfonyl group or an azole heterocycle) in the presence of a base. 2. The method for producing a hexahydrophthalic acid anilide derivative according to claim 1, wherein the reaction is carried out using: (7) A herbicide containing the hexahydrophthalic acid anilide derivative according to any one of claims 1 to 5 as an active ingredient.