JPS6127905A - Herbicide - Google Patents

Abstract

NEW MATERIAL:An arylsulfonylfatty acid amide derivative expressed by formula I [R represents H or lower alkyl; R<1> represents formula II (X represents lower alkyl, halogen atom, lower alkoxyl, trifluoromethyl, mono-lower alkylaminocarbonyloxy, etc.; n is 0 or an integer 1-3) or formula III (A represents C or N; Z represents Cl, methoxyl or methylthio; Q is 0, 1 or 2); R<2> represents H, lower alkyl or lower alkoxy lower alkyl]. EXAMPLE:N-(2,5-Dimethylphenyl)-4-methylphenylsulfonylacetamide. USE:Useful as a herbicide having an effect on annual weeds such as a barnyard grass and perennial weeds such as slender spikerush with no phytotoxicity on paddy rice, and further exhibiting effect in a dry field forming use with safety and no smell without any toxicity to humans, animals, fishes and shellfishes. PREPARATION:An amine derivative expressed by formula I is reacted with an arylsulfonylfatty acid expressed by formula IV in a solvent to obtain the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Object of the Invention Industrial Application Field The present invention relates to a herbicide containing a novel arylsulfonyl fatty acid amide derivative as an active ingredient. Therefore, the present invention can be effectively utilized in the fields of organic chemical industry and agricultural cooperative industry.

The following compounds are known as compounds similar to conventional arylsulfonyl fatty acid amide derivatives.

■ [Chem, Abstr, J Vol. 72 No. 790
26 f page (corresponding to Japanese Patent Publication No. 46-7104) X represents CJ, Br, CH3, CF5, NO2, parachlorophenoxy group, and n = 1 to 3. Although it is used as a raw material, there is no mention of its herbicidal activity.

■ [Chem, Abstr, J Vol. 88 No. 1207
Page 23b There is a report on germicidal activity, but there is no mention of herbicidal activity.

■ “Chem, Abstr, J Vol. 92 No. 6769
Although it is described as an intermediate for producing raw materials for color photographs on page 7a, there is no mention of its herbicidal activity.

■ [Chem, Abs tr, J Vol. 86 No. 13
Although it is described as a raw material for reacting with nitrostyrene to obtain an addition reaction product on page 9577m, there is no description of its herbicidal action.

■ “Chem, Abstr, J Vol. 82 No. 1645
In the formula on page 8c, X represents 4-CJ, 4-0 (3,4-NO2 or 4-CH3).It is only described as a raw material for reacting with various diazonium salts, and its herbicidal action is not described. do not have.

■ [Chem, Abstr, J Vol. 41 No. 6902
It is described that it exhibits a plant growth regulating effect on pages 1t to 3913C.

■ “Chem, Abstr, J Vol. 68 No. 3453
In the formula on page 67, X is f(, CH3, C1s, Br1NO2
(0-1m-1p-) or ○CH3. NMR data of X and the hydrogen atom on the ring are described, but there is no description of herbicidal activity.

■ “Chem, Abstr, J Vol. 71 No. 1014
On page 93j, there is a description that it exhibits herbicidal activity and plant growth regulating activity.

Problems to be Solved by the Invention Conventional arylsulfonyl fatty acid amide derivatives (the above [[
(e.g., compounds described in Chem, Abstr, J)
has little activity as a herbicide. The present invention provides a herbicide containing an arylsulfonyl fatty acid amide derivative as an active ingredient, which is a novel and highly practical herbicide in place of these conventional derivatives.

(2) Means for Solving the Constituent Problems of the Invention The present inventors synthesized a large number of novel arylsulfonyl fatty acid amide derivatives and conducted extensive research.

As a result, it was discovered that a series of compounds represented by general formula (1) are useful as herbicides.

In the formula, R represents a hydrogen atom or a lower alkyl group, a halogen atom, a lower alkoxy group, a trifluorotetramethyl group, a mono-lower alkylaminocarbonyloxy group, a di-lower alkylaminocarbonyloxy group, a lower alkoxycarbonyl group or a nitro group. and n is 0.1.2 or (in the formula, human represents a carbon atom or nitrogen atom, 2 represents a chlorine atom, methoxy group or methylthio group, and Q represents an integer of 0.1 or 2) R2 represents a hydrogen atom, a lower alkyl group, or a lower alkoxy lower alkyl group.

Action The compound of the general formula (T) has no phytotoxic effects on paddy rice, and is effective against annual weeds in paddy fields, such as Japanese field weed, Japanese cypress, Japanese cypress, Japanese snail, and perennial weeds that have become a problem in recent years, such as Japanese cypress, Japanese cypress, Japanese cypress, Japanese black grass, etc. It shows strong herbicidal action against. Also, crabgrass,
It is also effective against grasshoppers, knotweed, goldenweed, black-and-white snail, purslane, black-and-white grass, whitewort, Japanese knotweed, bindweed, black-and-white grass, black-and-white grass, sycamore, sycamore, shepherd's purse, hackberry, etc. Therefore, in addition to being particularly effective as a herbicide for paddy rice, it is also useful as a herbicide for field crops and other arable and non-agricultural lands, and these effects can be expressed through soil treatment or foliage treatment. Furthermore, the compound of the general formula (D) is not toxic to humans, livestock or fish and shellfish, and does not have a bad odor, so it can be used safely.

Next, a method for producing the compound of general formula (I) of the present invention will be specifically described.

reaction formula %formula%( In the formula, R, R' and R2 have the same meanings as above.

To produce the compound of the present invention, first, the amine derivative represented by the general formula (I) is mixed with a suitable reaction solvent such as benzene, toluene, xylene, chlorobenzene, dioxane,
It is dissolved in tetrahydrofuran, methylene chloride, acetone, methyl alcohol, etc., and an equivalent amount of the arylsulfonyl fatty acid represented by the general formula (1) or its reactive derivative is added thereto either as it is or dissolved in the above-mentioned organic solvent. Then, the reaction is carried out at room temperature or while cooling or heating as necessary. The reaction time is preferably 1 to 5 hours. Reactive derivatives of arylsulfonyl fatty acids include acid anhydrides, acid chlorides, acid bromides, and carboxylic acid esters, which can be easily obtained from arylsulfonyl fatty acids by applying known methods. Also, general formula (2)
When reacting the amine derivative of formula (M) with the arylsulfonyl fatty acid of general formula (M) or a reactive derivative thereof, a suitable reaction aid such as thionyl chloride, trivalent silicon,
Phosphorus pentachloride, phosphorus oxychloride, dicyclohexylcarbodiimirr1 triethylamine, pyridine, N-methylsorforin, N, N-'; ethylaniline% sodium dihydride, sodium methylate, sodium carbonate, potassium carbonate, etc. Can be used. These reaction aids are preferably selected and used depending on the type of arylsulfonyl fatty acid or its reactive derivative.

After the reaction, the reaction product is filtered or washed with water to remove the reaction aid, and the organic solvent used is distilled off to ensure the purity of the arylsulfonyl fatty acid amide derivative represented by the general formula (1). It can be obtained easily and in high yield. These compounds can be further purified by recrystallization from acetate/methyl alcohol, benzene, toluene, chloroform, etc.

Examples will be shown next, but the present invention is not limited to the methods disclosed in the following examples.

Example 1 2.6-dimethylaniline1. ! M (10 mmol) and potassium carbonate 1.5 F (10.9 mmol) are placed in a round neck flask and acetone 25- is added. Keep the internal temperature at 5 to 10°C in an ice water bath and add 4-methylphenylsulfonylacetic acid chloride 2.32.
A solution of 9 (10 mmol) dissolved in acetone 5-
The mixture was added dropwise over 0 minutes, and then heated under reflux for 30 minutes. Next, 20% of acetone was distilled off, the temperature was returned to room temperature, and 150% of water was distilled off.
Add and stir, then add 100% of ethyl acetate, stir, and transfer to a separatory funnel. After standing, the mixture is separated and the aqueous layer is removed. The mixture is washed with a 5% hydrochloric acid aqueous solution, a 5% sodium carbonate aqueous solution, and water in this order, and 5 g of Glauber's salt is added, mixed with a lid, dried, and filtered. When ethyl acetate in solution F was distilled off, N-(2,5
-Dimethylphenyl)-4-methylphenylacetic acid amide (5.19C yield: 90%) was obtained, with a melting point of 178-1795°C.

Example 2 2-amino-4,6-dimethylpyridine 121 (10 mmol) and triethylamine 1.1! ! (10,9
mmol) into a round neck flask and add benzene 3
Add 0go. Keep the internal temperature at 5 to 10°C in an ice water bath and stir without stirring.
)' 2.32F (10 mmol) in benzene 5-
The solution was added dropwise over 10 minutes, followed by heating under reflux for 30 minutes.

This is returned to room temperature, filtered to remove triethylamine hydrochloride, and the benzene in the tear fluid is distilled off to obtain white crude crystals. When this crude crystal was purified by silica gel column chromatography, N-(4,6-dimethylpyridine-2-
2.8.9 (yield: 88%) of white crystals of -4-methylphenylsulfonylacetic acid amide were obtained, with a melting point of 1.
The temperature was 56-157.5°C.

Example 6 2-methylthio-4-amino-6-chloropyrimidyt
76I! (10 mmol) and dimethylaniline 1.
221! (10 mmol) into a neck round bottom flask and add 30 mmol of ethyl acetate. Reduce the internal temperature to 5 in an ice water bath.
A solution of 2.32.9 (10 m) of 4-methylphenylsulfonylacetic acid chloride dissolved in 5-ethyl acetate was added dropwise to the mixture over 10 minutes while stirring, and the mixture was heated to reflux for 30 minutes. This is returned to room temperature, filtered to remove dimethylaniline hydrochloride, and ethyl acetate from the filtrate is distilled off to obtain white crude crystals. When this crude crystal was purified by silica gel column chromatography, N-(2-methylthio-4-chloropyrimidin-6-yl)-4-,,'
Tylphenylsulfonylacetic acid amide &2g (yield 86%)
) was obtained as white crystals, melting point 184.5-185.
It showed 5°C.

Examples of compounds produced by the method of the present invention are shown in Table 1.

1st elemental analysis value (upper row: calculated value, lower row: actual measured value) 55.64
4.36 10.95 4.33 14.82
9.9055.62 4.37 10.97 4.
')6 14.82 9. B2S3.64 4.3
6 1α95 4.33 14.82 9.9055
．． 66 4.33 10.94 4.32 14
．． 83 9.9250.29 5.66 19.7
9 3.91 13.40 8.9550.31
3.64 19.77 3.94 1i99
B, 9650.29 5.66 19.79 3
．． 91 13.40 a9550.27 3.6
719.80 3.92 13.38 B9.
650.29 3.66 19.79 3.91
+3.40 8.9550.31 3.68
19.77 3.90 13.40 8.9450
．． 29 3.66 19.79 3.91 13.
40 8.9550.27 5.64 19.78
3.93 13.44 8.94 Compound elemental analysis values (upper row: two calculated values, lower row: actual measured values).

5cL29 166 19.79 391 13.
40 a9550.28 3.69 19.77
3.9[] 13.38 a9850.29
3.66 19.79 &91 15.40
8.9550.28 3.68 19.78 3.9
2 13.38 8.9663.34 5. (554
,6215,8210,5763,365,624,6
315,8410,5564,336,054,411
5,1210,1064356,[114,4315,
1310,0864336,034,4115,121
0,10+54.315 6.02 4.4
2 15.10 10.1065.23 6.59
4.23 14.48 9.6765.20
6.3B 4.25 14.49 9
．． 6B64.53 6.034.41 15.12
10.1064.1 6.05 4.42
15.11 10.12 Compound C2) (5 Elemental analysis value (upper row: calculated value, lower row: measured value) 64.33
6.03 4.41 15.12 10
．． 1064.35 6.00 4.42 1
5.12 10.1164.33 6.03
4.41 15.12 10.1064.31 6
．． 01 4.43 15.15 10.10
66.06 6.71 4.05 1'5.
89 9.2866.04 6.75 4
02 1&92 9.2765.23 6.39
4.23 14.48 9.6765.25
6.37 4.22 14.50
9.6656.88 4.77 10.50 4.
15 14.21 9.4956.89 4.75
1 (L55 4.16 14.22 9.4556.
88 477 1 (1504, 1514, 219, 49
56,854,791α53 4.18 14.21
? , 446α17 5.37 4.59
2α04 10.046α19 5.55
4.36 2f104 10.06 compound + a'3 60.17 5.37 4.39
20.04 IQ, 046α15 5.56
4.42 2Q, 02 10.055
4.31 4.56 1α02 196 1a
09 9.0 (S54.34 4.54 H
l, 05 193 1a11 9.0562.2
3 6.09 4.03 1&42
9.2362.25 &07
4.06 1&42 9.2057.435.
315 7.44 21.25
115257.42 5.38 24
1 21.29 8.5059.59 5.9
86.95 19.78 7.9559.38
5.97 &94 19.81
7.905378′! h, 95
i92 1A45 &97 15.955&
79 i96 A90 1A46
a96 15.9349.05 '5.5
4 9.05 3.58 12.25
a18 14.5549, 02 &56 9
．． 07 &54 12.28 &16
14.57 Compound elemental analysis value (upper row: calculated value, lower row: actual measured value) 53.88
4.22 a38 2593
9.595589 4.24
&37 2 to 91 9.595a78
4.93 4.03 23.03
9.235, a75 4.95
4.02 2KO49,2459,825,3
0588 22.13 &8759.85
5.29 5B6 22.14
a8659.82 5.30
3.88 22.13 8.8759.8
1 5.33 5B6 22.
11 8.89+51.24 5.74
4.20 19.20 9.626
1.27 5.72 4.21
19.15 9.6564.75 6.99
K60 16.43 &23
64.75 6.96 &63
16.48 &2065.25 6.3
9 4.23 14.48 9
．． 6765.25 6.57 4
24 14.49 9.65 Compound elemental analysis value (upper row: calculated value, lower row: measured value) 0% H
% Cj* N% 0% 8% F%6
7.24 5.05 4.13 14.1
4 9.4567.22 5.08 4
．． 16 14.11 9.4357.91 4.8
6 9.65 16.53 11.0457
．． 95 4.88 9.63 16.54
11.0257.91 4.86 9.
65 16.53 11.0457.90 4.84
9.68 16.51 11.0760.
36 5.70 &80 15.08
10.076a34 5.72a82
15.03 10.0956.24 5.03
&74 19.98 10.0156.26
5.01 &73 19.98 10
．． 0255.07 4.95 13.76
15.72 1α5055.05 4.98
i&77 15.70 1a5049.48
4.15 1α43 12.37 14.13 9
．． 4449.45 4.17 1a, 42 12.3
9 14. L6 9.41 Compound elemental analysis value (upper row: calculated value, lower row: actual measured value) 45.22
3.79 9.53 11.1 12.91 1
72545.24 3.78 9.52 11.3
2 12.91 17.23! M+, 41 5.37
13.1615.0! +10.045
6.41 5.35 13.19 15.
02 10.0355.64 4.56 10.95
4.33 14.82 9.9055.66
4.33 10.96 4.52 14.81 9
．． 9255.64 4.56 10.95 4.3
3 14.82 9.9055%3 4.38 1
0.93 4.3614.82 9.8850.2
9 3.66 19.79 3.91 13.40
8.9550.27 &69 19.78
3.90 13.39. 8.9756.88 4.
77 10.50 4.15 14.21 9.4
956, B9 4.75 10.55 4.161
4.19 9.4859.80 5.02
4.3614.94 9.98 5.9+59
．． 82 5.01 4.35 14.91
．． 9.99 -5.92 Compound 2H5 Elemental analysis value (upper row: calculated value, lower row: measured value) -53
,783,953,9213,438,9715,95
53,753,963,9413,428,9715,
9656,8B 4.77 10.50 4.1
5 14.21 9.4956.87 4.79
10.52 4.13 14.21 9.4851
．． 62 4.06 19.05 'h76 12
．． 89 &6151.65 4.06 19.0
'2 3.74 12.91 B, 6265.2
36,39 4.23 14.48 9.
6765.22 6.57, 4.26
14.50 9.6558.03 5.1610
．． 0B 3.98 13,64 9.11
5a05 5. i4 10.05 3.99
1&6:6 9.1454.98 4,3
4 3.77 12.92 8
．． 63 15.3554.95 4.56
3.78 12.93 &64
15.3465.97 6.71
3.73 17.04 a5465.96
6.73 3.75 17.
04 a52 When using the compound of the present invention as a herbicide, the compound of the present invention may be sprayed as it is on the soil or foliage of crop cultivation areas, but the herbicidal action of the compound of the present invention may be sufficiently exerted. To achieve this effect, the compound of the present invention is mixed with a suitable carrier and auxiliary agents such as surfactants, binders, stabilizers, etc., and prepared as an aquarium, emulsion, etc. by a conventional method.
It is preferable to use the preparation in the form of an aqueous solution, an oil suspension, a powder, a fine granule, a coarse powder, or the like.

In the above, the carrier can be either solid or liquid as long as it is commonly used for agricultural and horticultural chemicals.
It is not limited to a specific thing. Examples of solid carriers include mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, alamite, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.), and vegetable matter. Powder (soybean flour, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), polymer compounds (petroleum resin, polyvinyl chloride, ketone resin, dammar gum, etc.), alumina,
Examples include silicates, sugar chamber coalescence, highly dispersed silicic acid, and waxes. Liquid carriers include water, alcohols (methyl alcohol, ethyl alcohol, n-i lobil alcohol, 1so-10 methyl alcohol, phthanol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.). , ethylbenzene, chlorobenzene, cumene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane, chloroether, trichlorofluoromethane, dichlorodifluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane, (tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.), acid amides (dimethylformamide, dimethylacetamide, etc.) , nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, industrial gasoline (petroleum ether, solvent naphtha, etc.),
Examples include petroleum fractions (paraffins, kerosene, light oil, etc.).

Furthermore, surfactants (or emulsifiers) are used for the purposes of emulsification, dispersion, solubilization, wetting, foaming, and expansion of lubrication when preparing formulations such as emulsions, aqueous preparations, and flowable preparations. Examples of such surfactants include nonionic types (polyoxyethylene alkyl ethers, phoroxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, sorbitan alkyl esters), anionic types (alkylbenzene sulfonates, alkyl sulfosuccinates, (alkyl sulfate, holoxyethylene alkyl sulfate, aryl sulfonate, etc.), cationic type [alkylamines (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, etc.)], polyoxyethylene alkylamines], amphoteric type [ Examples include carboxylic acids (betaine type), sulfuric ester salts, etc., but are not limited to these examples only.
In addition to these, polyvinyl alcohol, carboxymethyl cellulose, gum arabic, polyvinyl acetate,
Various adjuvants such as gelatin, casein, sodium alginate, gum tragacanth, etc. can be used.

Furthermore, the compound of the present invention can be used in combination with other herbicides to improve herbicidal efficacy or to expect a synergistic herbicidal effect. Examples of this include phenoxy herbicides (2,4-dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxybutyric acid and their esters, thioester a, salt a, 2-(4-
(5-) Lifluorotetramethyl-2-biridyloxine phenoxyp-n-butyl pionate]).

Diphenyl ether herbicides (2,4-dichlorophenyl-47-nitrophenyl ether, 2.4.6-dichlorophenyl-4'-nitrophenyl ether, 2-
Chloro-4-)'J fluoromethyl-3'-ethoxy-
4'-nitrophenyl ether, 2,4-dichlorophenyl-4'-nitro-3'-methoxyphenyl ether, 2,4-dichlorophenyl-3'-methoxycarbonyl-4'-nitrophenyl ether, etc.), triazine-based herbicides agent (2-chloro-4,6-pisethylamino-1
, 3.5-triazine, 2-chloro-4-ethylamino-6-itupropylamino-1,5.5-) rear 9
y, 2-methylthio-4,6-bisethylamino-1゜6.5-triazine, 2-methylthio-4,6-pisisopropylamino-1,3.5-triazine, etc.), urea herbicides ( 3-(3,4-dichlorophenyl) -1
, 1-dimethylurea, 3-(5,4-dichlorophenyl)-1-methoxy-1-methylurea, 1-(2,2-dimethylbenzyl)-3-p-)lylurea], carbamate herbicides [ isopropyl-N-(5-chlorophenyl)carbamate, methyl-N-(3,4-dichlorophenyl)carbamate], thiol carbamate herbicide (S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate, S -ethyl-N,N-hexamethylenethiol carbamate], acid aniline, de-based herbicide [
3,4-dichloropropionanilide, N-methoxymethyl-2,6-diethyl-α-chloroacetanilide,
2-chloro+ 2/,6/-diethyl-N-butoxymethyl-acetanilide, 2-chloro-2,6-dinithyl-N-(n-propoxyethyl)-acetanilide, N
-chloroacetyl-N-(2,6-dinitylphenyl)
-ri 17 ethyl ester], uracil herbicide (
5-bromo-6-sec-butyl-6-methyluracil,
3-cyclohexyl-5,6-trimethylenecracil, etc.), pyridinium chlorine herbicides (1,1'-dimethyl-4,4'-bispyridinium chloride, etc.), cin-based herbicides [N-(phosphonomethyl)] Chrysin, 0-ethyl-〇-(2-nitro-5-methylphenyl-N-sec-butylphosphoramidothioate, 5-(2-methyl-
1-piperidylcarbonylmethyl) -0,0-')
-n-i lopyldithiophos7ate, 5-(2-methyl-1-pilysylcarbonylmethyl)-0,0-diphenyldithiophosphate, ammonium-(3-aminocarboxyptetrapyru)-methylphosphinate,
2-amino-4-methylphosphinobutylalanylalanine], toluidine herbicides (α, α, α-trifluoro-2,6-sinitro-N,N-dipropyl-p-)luidine, etc.), others [5- tertiary butyl-3-(2,
4-dichloro-5-isopropoxyphenyl) -1,
3,4-oxadiazolin-2-one, 3-inpropyl-IH-2,1,3-benzothiadiazine-(4)
-5'H-one-2,2-dioxide, α-(β-naphthoxy)-propionanilide, 4-(2,4-dichlorobenzoyl)-'1,5-dimethylpyrazole-5-
yl-p-)luenesulfonate, 2-(: (4,
6-Simethoxypyrimidin-2-yl)aminocarbonylaminosulfonylmethylbenzoic acid methyl ester
These include, but are not limited to.

In addition, the compound of the present invention may be used as an insecticide, nematocide, fungicide, water-applied insecticide or fungicide, soil-applied fungicide or insecticide, if necessary.
It can also be used in combination with a plant growth regulator or fertilizer.

The application amount of the compound of the present invention represented by general formula (1) varies depending on the type of specific compound to be used, the type of weeds to be weeded, etc., but is generally 0.02 to 2 kg per 10 ares.
It is good that it is within the range of .

Examples of uninvented herbicides are shown next, but the proportions of active ingredients, carriers and adjuvants, as well as their types, are not limited to the following examples. In the Examples, all parts refer to parts by weight.

Example 4 30 parts of wettable powder compound A2, 2 parts of lignin sulfonic acid calcium salt, 6 parts of dodecylbenzenesulfonic acid sodium salt and 65 parts of diatomaceous earth are thoroughly ground and mixed to obtain an irrigation agent.

Example 5 Granules 7 parts of compound A8, 2 parts of white carbon, 5 parts of calcium lignin sulfonate salt and 88 parts of clay were thoroughly ground and mixed, water was added and the mixture was thoroughly kneaded, then granulated and dried to form granules. get the agent.

Example 6 60 parts of agent clay, 35 parts of bentonite and 5 parts of hylignin sulfonic acid calcium salt are pulverized and mixed, water is added and the mixture is mixed and granulated and dried to produce granules containing no active ingredient. Granules are obtained by impregnating 95 parts of the granules with 5 parts of compound compound 35.

Example 7 Particles of bentonite sieved to 300-850 microns
part is impregnated with 4 parts of compound &47 to obtain granules.

Example 8 Powder 3 parts of Compound A49, 56 parts of clay, 60 parts of Merck and 1 part of isopropyl phosphate are added and mixed by pulverization in an atomizer at a rotational speed of 12.00 Orpm to obtain a powder.

3030 parts of the compound As, 60 parts of xylene, and 1 part of Tsurpol 5M100 (mixture of nonionic surfactant and anionic surfactant, product of Toho Chemical Industry Co., Ltd.)
0 parts are mixed and dissolved to obtain an emulsion.

(3) Effects of the invention Next, the herbicidal effects of the compounds of the present invention will be shown in test examples.

Test Example 1 Flooded soil treatment herbicidal test Paddy soil was packed in a porcelain pot of 1/15,500 are, and seeds of wild grass, firefly, Japanese cypress, Japanese cypress, and Kikashigusa were uniformly sown on the surface layer, and the seeds were placed at a depth of 2 cR. After flooding the soil, two paddy rice seedlings (variety Nihonbare) at the two-leaf stage were transplanted. One day later, a predetermined amount of the diluted water solution obtained according to Example 4 was uniformly dropped onto the water surface for treatment. Thereafter, the pots were kept in a greenhouse and watered from time to time. Twenty days after the chemical solution treatment, the herbicidal effect and the degree of chemical damage to paddy rice were investigated using the following criteria. This test example was conducted using a 3-pot system with one drug dose, and the average value was determined. The results are shown in Table 2.

Weeding effect 5: Weed killing rate 95% or more - complete death 4: Weed killing rate 80% or more - less than 95% 3: Weed killing rate 50% or more - less than 80% 2: Weed killing rate 30% or more - less than 50% 1: Weed killing rate 10 % or more - less than 30% 0: Weed killing rate less than 10% Phytotoxicity degree 1: Harmless ±: Slight damage (withering of leaf tips) +: Moderate damage (withering of leaves) Ox: Severe damage (growth suppression) m: Severe damage (withering) 2nd Table 25-3 4 4 5ζ5 10 50-5.4. 3 5 5 12 50-5 5 j 3 4 25-343'44 21 50-5'5 3 4 5 28 50 - 4. 5
4 4 529 50 -
．． 5 5 3 5 425
- 3'4 2 4 3 Comparative drug 50 - 0 3 1 1
1A25-02000 B25-01001 Comparative drug 50 - 1 2 0
1 2C25-02001 Comparative drug 50 - 1 2 0
1 1D25-01000 Comparative drug 50 - 2 2 1
3 3E25-12012 Comparative alignment J50-23133 F25-12022 Comparative drug 50 - 1 2 0
2 2G25-01011 Comparative drug 50 - 2 6 0 2 2
H25-02011 Comparative drug 50 - 1 2 0
2 2I 25 °-01011 Comparative drug 50 - 1 2 0
2 3J 25-0.1 0
1 2 Untreated area -oooo.

-oooo.

Comparative drugs had the following chemical structures, and were formulated and tested in the same manner as the compounds of the present invention.

(Chem, Abstr, J Vol. 82, No. 164'
Compounds described on page 58C) ([Chem, Abstr, J Vol. 88, No. 12072
Compounds described on page 3b) (Chem, Abstr, J Vol. 68, No. 34536)
Compounds described on page y) ([Chem, Abstr, J Vol. 41, No. 3902
．． Compounds described on pages 7-3913c) ([chem, Abstr, J Vol. 71, No. 10149
Compound described on page 3j) Patent applicant Hokuko Chemical Industry Co., Ltd. Agent Patent attorney Yamashita Haku procedural amendment August 29, 1980

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a hydrogen atom or a lower alkyl group,
^1 is a formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is a lower alkyl group, halogen atom, lower alkoxy group, trifluoromethyl group, mono-lower alkylaminocarbonyloxy group, di-lower alkylaminocarbonyloxy group , lower alkoxycarbonyl group or nitro group, and n is an integer of 0, 1, 2 or 3)
represents a carbon atom or a nitrogen atom, Z represents a chlorine atom, a methoxy group or a methylthio group, and Q represents an integer of 0, 1 or 2), and R^2
represents a hydrogen atom, a lower alkyl group, or a lower alkoxy lower alkyl group) as an active ingredient.