JPS5939871A - Cyclohexenylacetamide derivative, its preparation and herbicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is lower alkyl; m and n are 0-2; R<1> and R<2> are H or lower alkyl; Y is lower alkyl, lower alkoxy, halogen or nitro). EXAMPLE:N-(4,6-Dimethylpyridin-2-yl)-(cyclohexen-1-yl)acetamide. USE:Herbicide having broad herbicidal spectrum from the annual weeds (e.g. cockspur-grass) and perennial weeds (e.g. flatstage) in paddy field to the weeds in plowed land such as large crab-grass, etc. It exhibits high herbicidal effect especially by soil treatment, and can be used safely without damaging the main crops such as paddy rice plant, etc. It can be applied to the cultured land of various grains, vegetables, etc., orchard, lawn, pasture land, etc. PROCESS:The compound of formula I can be prepared in high yield and purity, by reacting the cyclohexenylacetic acid derivative of formula II or its reactive derivative with aminopyridine of formula III in an organic solvent in the presence of a reaction assistant such as triethylamine, etc. e.g. at room temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel cyclohexenyl acetamide derivatives, a method for producing the same, and a herbicide containing the derivative as an active ingredient.

More specifically, the first invention is based on the general formula (1): (wherein, X represents a lower alkyl group, 1m represents an integer of 0 to 2, and R1 and R2 represent a hydrogen atom or a lower alkyl group. , Y represents a lower alkyllkoxy group, a halogen atom or a nitro group, and n represents an integer of 0 to 2).

Further, the second invention has the general formula: l(1 (wherein, X., m, R' and 112 have the meanings described below)
A cyclohexenyl acetic acid visiting conductor or its reactive derivative represented by 1-1) is reacted with an aminopyridine represented by the general formula product): (wherein Y and n have the meanings given below). The general formula (
I): 1(1 (wherein, alkoxy group,
The gist of the present invention is a method for producing a cyclohexenyl acetamide derivative represented by a halogen atom or a nitro group, and n is an integer of 0 to 2.

Furthermore, the third aspect of the present invention provides a herbicide containing a cyclohexenylacetomide conductor represented by the general formula il+ as an active ingredient.

The present inventors succeeded in synthesizing a new compound represented by the general formula (Natsu 1). Water 01's perennial weeds are water cypress and urikawa.

It was discovered that it exhibits strong herbicidal activity against firefly, pine flycatcher, black bream, and other insects. It has also been found that the compound of the present invention has a herbicidal effect on upland weeds such as crabgrass and white loli. In this way, the compounds of the present invention have a broad killing spectrum when used as herbicides.

In order to effectively kill these weeds, the compound of the present invention is preferably applied to the soil or foliage in the cultivation area for mausoleum crops. Show effectiveness. In addition, conventional herbicides generally had low herbicidal effects against weeds of the Cyperaceae family, but
Among the compounds of the present invention, many compounds have been found to have particularly strong herbicidal activity against weeds of the Cyperaceae family. In addition, the compound of the present invention (a) has the excellent property that it does not cause phytotoxicity to major crops such as paddy rice and can be used safely. Not only can it be used effectively as a herbicide, but it can also be used on various grains,
In addition to cultivation areas such as vegetables, fruit orchards, 5 lawns, and meadows.

It can be widely used as a herbicide in tea gardens, mulberry gardens, rubber gardens, etc.

Known compounds similar to the compound of the present invention include "Journal of the Gummy Society", page 1080 (1915) and "Journal of the American Chemical Society", Vol. 1, Vol. 71, No. 521.
6 (1949) describes 1-cyclohexenyl acetanilide and balatluid. Also, “Chemical Abstracts” Volume 65, ID504d
describes 4-methyJL/-3-',/'/lohexenylacetanilide and 2-methyl-3-cyclohegysenylacetanilide. however,
There is no description of the herbicidal activity of these known compounds. Furthermore, as is clear from the test examples described later, these known compounds hardly exhibit any emasculating effect. Also, “Chemical γ
It is stated that a pyridyl group is used in the allyloxycarboxylic acid amide and that it has a high herbicidal effect.

In other words, it is a well-known fact that ζ, (!) is caused by the phytohormone fatty acid soap, and it is also an obvious fact that the herbicidal action has not been newly developed by using the pyridyl group. The compound of the present invention is essentially different from the compound of the present invention.Also, the compound of the present invention has an extremely weak herbicidal effect on weeds such as barnyard grass (7). It exhibits far superior herbicidal activity, and is superior in that it also exhibits an equivalent or superior herbicidal activity against broad-leaved weeds.

The compound of the present invention has a chemical structure similar to that of the compound described in the above-mentioned literature, but has an excellent herbicidal effect and has a phytotoxic effect on useful crops such as paddy rice. It is significantly superior to similar known compounds in terms of its lack of resistance. The present invention was completed based on this new knowledge.

The method for producing the compound of the present invention, that is, the second method of the present invention, is carried out as follows. First, substituted pyridylamines represented by the general formula flll can be understood as a suitable organic solvent, such as benzene, toluene, xylene, chlorobenzene, dioxane, tetrahydrofuran, lumped methylene, acetone, chloroform, methyl alcohol, etc. To this, 1-cyclohexenyl LP+ or its reactive salt conductor represented by the general formula tUt is dissolved in an organic solvent such as benzene and added. Then, the reaction is carried out at room temperature or while heating or cooling as necessary. Also, the reactivity H of 1-cyclohexenyl acetic acid
As N conductors, acid anhydrides, acid salts, acid-smelling arsenic compounds,
There are carboxylic acid esters, etc., which can be easily obtained from these (1-Schiff 1]hexenyl acetic acids by applying known methods.Also, substituted pyridylamines and 1-Schiff 1-hexenyl trr, ht t ; 7= i For the purpose of reacting with the reactivity meter conductor, suitable reaction aids such as thionyl chloride, 11-crystalline chloride, phosphorus quinone, phosphorus oxychloride, pancyclohexylcarbodiimide, triethylamine can be used. , pyridine.

N-Methylmorpholine, Quino+1,-7, N,N-dimethylaniline, N,N-diethyl ayu111. lt2
Sodium chloride, potassium hydroxide, sodium methylate, etc. can be used. These reaction aids are preferably selected and used depending on the type of 1-cyclohexenyl acetic acid or its reaction 1-1 derivative.

After the reaction is complete, pass the reaction product through the cape or 1'f)
By removing the reaction aid by washing with water and distilling off the organic solvent used, the cyclohexenyl acetamide conductor of the general formula +Il of the present invention can be obtained with good purity and high yield. This compound 1''i can be further purified by recrystallizing it from acetone, methyl alcohol, ethyl alcohol, benzene, toluene, or chloroformate.

In addition, among the cyclohexenyl acetic acids with the general formula tU+ used in the method of the present invention, the method for producing 1-cyclohexenyl acetic acid is described in "1 Organic Reaction", Volume 1, No. 1.
7 are listed here. In addition, the method for producing 2-methyl-1-cycloI]hexenyl acetic acid is described in [Chemical γ-Bstract') J Vol. 25, 28 [1' (Journal of
The Chemical So →, Toyetei (193 (1st year) 22
17), and the method for producing 4-methyl-1-cyclohexenyl acetic acid is described in the same document, Chemical Abstracts, Vol. 19, 325.
' is also listed. Also, 5-methyl-1-cyclohexenyl acetic acid production method C, ``Chemical Reconstructions'' Volume 38 + 6624'' (Cnmpt, ren
d, Volume 214.

881 pages)', J6 and Volume 42, 1900a
(BIJII.

Snc, Chun, France (1947'
) m459u', entry 4 is written. In addition, the method for producing 2,6-dimethyl-1-cyclohexenyl acetic acid is described in "Chemical γ-Base Technology No. 185 B65 u (J,
Org, Cbem, Volume 32.

575 (1967)). Also 2
-(1-cyclohexenyl)-propionic acid, 2-(1
-cyclohexenyl)-butyric acid, 2-(1-cyclohexenyl)-caproic acid, etc.

1 Chim, France (Bul 1.5 (Ic, Chim, France)
) Written in 1948, Nos. 754-7.

In the present invention, the above compounds were produced by the methods described in these documents. It's amazing, the other compounds are new substances,
It can be manufactured by the method shown in the following formula.

<Next> Preparation examples of the starting compound 111 used in the method of the present invention will be specifically explained by reference examples, and examples of the production of the compound of the present invention will be specifically explained by examples.

Reference Example 1 Synthesis of 1113.5-dimethyl-1-hydroxycyclohegysyl acetic acid ethyl ester Metal zinc 13y (0.2 mol) in the form of chips was placed in a 1α reaction flask. Separately, bromoacetic acid ethyl ester 33.4y (02
mol), 3.5-dimesalcyclohexanone 25.39
(0.2 mol)% toluene 7Qml, benzene 70
ml and put into a dropping funnel, put 30Ilt into a reaction flask, and add 0.0ml of iodine. Add IP. When heated while stirring, a violent reaction occurs and reflux begins. Dripping is started from the dropping funnel, and the reaction is carried out while adjusting the dropping rate to maintain a reflux state. After the dropwise addition is completed, the reaction is allowed to take place at 85-900°C for 2 hours, and the zinc disappears, confirming the completion of the reaction. This reaction solution was cooled and returned to room temperature, and 10% sulfuric acid aqueous solution 105 ml was added thereto and stirred, then transferred to a 500,111 volume separatory funnel and allowed to stand to separate into two layers. Remove the lower layer of water, add water 1
Wash twice with 00@Z and 50 mt, sprinkle with 5F of Glauber's Salt, dehydrate and dry, and filter. Benzene and toluene in liquid P are distilled off under reduced pressure, and then vacuum heat M is applied in G);
Konau boiling point 84-86'0/2rn+T(g
Then, 3,5-dimethyl-1-hydroxycyclohexyl acetic acid ethyl ester represented by the following formula: is obtained as a colorless transparent liquid. Yield 60.7F, yield 71.6%.

Elemental analysis value (as C+tHttO□) Actual 11111 value C67, 23%, Hlo, 32%.

022.45% Rt n (VL C67,25%, I4'
10.35%.

022.40% Synthesis of 213,5-dimethyl-1-cyclohexenyl acetate ethyl ester In a 500 Ilt capacity reaction flask equipped with a stirrer, a thermometer, and a reflux condenser with a 1-rim tube of calcichloride.

Dehydrated benzene 280. mt, phosphorus pentoxide 80F (0,
56 mol) and the previously synthesized 6,5-dimethyl-1-
Hydroxycyclohexyl acetic acid ethyl ester 30y (
0.14 mol) and heated under reflux for 6 hours while stirring vigorously. This reaction lfk is cooled to room temperature,
Collect the benzene layer by decanting, wash with water, dry with Glauber's salt, and filter. If the benzene in the P liquid is distilled off under reduced pressure and the remaining liquid is vacuum distilled, the boiling point will be 53-55°0 / 0.5°11
5,5-dimethyl-1-cyclohexenyl acetic acid ethyl ester represented by the following formula is obtained as a colorless transparent liquid. Yield 1i21.7F, yield 78.97%.

Elemental analysis value (as Ctt H2゜0.) Actual value C7
3,46%, Hlo, 25%, 016.29% calculated value
C73, 43%, Hlo, 27%, oi6.3o% The position of the double bond is within the ring, which is proven by nuclear magnetic resonance +1111 constant observation that 2H of the acetate group is 2.80 ppm. Ru.

131 5.5-') Synthesis of 1-methyl-1-cyclohexenyl acetic acid Into a 500-capacity reaction flask equipped with a stirrer, a thermometer, and a reflux condenser, add 100 parts of ethyl alcohol, 1 t of water, 20 t of water.
0-1 potassium hydroxide 1 rim 7y (0,13 mol) and 6
,5-dimethyl-1-cyclohexenyl acetic acid ethyl ester 20F (0.10 mol) and stirred
The mixture was heated to reflux for an hour. Next, vacuum distillation was carried out to concentrate the content to 100 ml of liquid, which was then cooled to return to room temperature.

This was placed in a separatory funnel, ether 50% was added thereto, and the mixture was well shaken to separate the liquids. The aqueous layer is taken, neutralized with a 10% aqueous sulfuric acid solution to make it acidic to pH 2, and extracted with 70% methylene chloride. Extract two more times using 70% of methylene chloride for a total of three extractions.

Add 5F of Glauber's Salt to the methylene chloride layer and shake well.

After dehydration and drying, it was filtered. When the methylene chloride in the P solution is distilled off and left in a cool place, 3,5-dimethyl-1-cyclohexenyl acetic acid represented by the following formula is obtained as white crystals. Melting point 44-46°0, yield 16.7jE0 Various other cyclohexenyl acetic acids represented by the general formula ([1) can be produced in the same manner as in the above reference example,
This was used for the production of cyclohegysenylacetamide derivative 4 of 1).

Example 1 1,000 onyl chloride 189 (152 mmol) was added to 1-cyclohexenyl acetic acid 7y (50 mmol).

The mixture was heated under reflux for 2 hours. Excess thionyl chloride was distilled off under reduced pressure, and 1-cyclohexenyl acetate chloride 7,9 jl
(100% yield) was obtained as a yellow oil.

Next, this 1-cyclohexenyl acetic acid chloride 06(3
10 w, t of a benzene solution containing 2-amino-4,6-dimethylpyridine (4,0 mmol) and triethylamine [140F (4,0 mmol) were added to 20 ml of a benzene solution containing 2-amino-4,6-dimethylpyridine (4,0 mmol) at room temperature. dripped. After the addition, the mixture was heated under reflux for 2 hours.

After cooling this reaction solution to room temperature, it was transferred to a dispersion funnel and washed with 10-distilled water, and after removing the aqueous layer, 5-y of sodium sulfate was added to the benzene layer, mixed well, and allowed to stand to dry. It was then filtered. The content of benzene in this p liquid is 5
After concentrating by distillation under reduced pressure until it becomes stl, develop Ak
Using a mixed solution of i and n-hexane and ethyl acetate, the
It took. N-(4,6-dimethylpyridin-2-yl)
-(cyclohexen-1-yl)-doset γmide 0.7
3y (yield 78%) was obtained as white crystals. The melting point and elemental analysis results of this compound are shown below.

Melting point: 109-110℃ Elemental analysis: Actual 11111 (direct: C73,72%, H8,26%
, N11.49%.

0653% Calculated value, C73, 74%, 118.25%, N11.4
7% 0655% Example 2 H3yt1B 3.5-dimethyl-1-cyclohexenyl acetate 8,49
(50 mmol) to thionyl chloride 18y (j 52
mol) was added thereto, and the mixture was heated under reflux for 2 hours.

The excess thionyl IL compound was distilled off under pressure, and the 6,5-
Dimethyl-1-cyclohexenyl acetic acid chloride 93 (
Yield 100'%) was obtained as a yellow oil.

Next, a solution of 0.65 fl (3,48 mmol) of this 3,5-dimethyl-1-cyclohexenyl acetate in benzene is added to 0.45 y of 2-amino-4,6-dimethylpyridine. (3.63 mmol) and triethylamine/0.37 mmol (363 mmol) were added dropwise to a 20-liter benzene solution surface at room temperature.

After the addition, the mixture was heated under reflux for 2 hours. After the reaction solution was cooled to room temperature, it was transferred to a separatory funnel, and 10 mL of distilled water was added thereto, thoroughly shaken, washed with water, and the aqueous layer was separated. Add 3 Y of Glauber's Salt to the organic layer, shake well and leave to dry.
It was then filtered. o) Benzene with a content of 5
The product was concentrated by distillation under reduced pressure until it reached .g, and #II was prepared by column chromatography using a mixed solution of n-hexane and acetic acid ethyl ester. N-(4,
6-dimethylpyridin-2-yl)”(3,5-dimethylcyclohexen-1-yl)-γcetoγmide 0,72
F (yield 76%) was obtained as white crystals.

The melting point and elemental analysis results of this compound are shown below.

Melting point 62.5-63.5℃ Elemental analysis value (C5tH24N20) Actual value: C74
, 99%, HF 2.89%, N 10.27%.

0585% Calculated value 2C74,96%, H8,88%, N10.29
%.

05.87% Example 3 2-(1-cyclohexenyl)-butyric acid 8.4y(499
Milli-E Le) IC Thioni Chloride J+/18 P(1
52 mmol) was added thereto, and the mixture was heated under reflux for 2 hours. Excess thionyl chloride was distilled off under reduced pressure to obtain 93 pieces of 2-(1-cyclohegycenyl)-butyric acid chloride (yield 100%) as an oil. Next I here 2-(1-cyclohexenyl)
- A solution of 0.70y (3.75 mmol) of butyric acid chloride in monochlorobenzene containing 0.48y (3.96 mmol) of 2-amino-4,6-dimethylpyridine and 0.40F (3.96 mmol) of triethylamine was added. t
The solution was added dropwise to r-monochlorobenzene solution a 20 st at room temperature, and after the dropwise addition, the mixture was heated to 70° C. with stirring for 1.5 hours. After cooling this reaction solution to room temperature, transfer it to a separating funnel, add 10 ml of distilled water, shake well, and wash with water.
The layers were separated and the aqueous layer was removed. 4 y of Glauber's Salt was added to the organic layer, shaken, allowed to stand to dry, and then filtered. The monochlorobenzene in this PM was concentrated by distillation under reduced pressure until the content became 5 sj, and purified by column chromatography using a mixed solution of n-hexane and ethyl acetate as a developing solution. N-(4,6-dimethylpyridine-2
-yl)-2-(cyclohegysen-1-yl)-butyric acid compound 075 (yield 74%) was obtained as white crystals. The melting point and elemental analysis results of this compound are shown below.

Melting point 72-74°0 Elemental analysis value (C+tlh4N20) Actual value, C74, 98%, 118.85%, N10.2
8%.

05.89% Calculated value: C74, 96%, H8,8f3%, N10.2
9%.

Example 4 10 ml of an acetone solution of 1-cyclohexenyl acetate chloride (3.8 mmol) was mixed with 0.519 (4.0 mmol) of 2-chloro-5-aminopyridine and 0.409 mmol of triethylamine. (4,0::11 mol)
It was added dropwise to an acetone solution containing 20% of the mixture at room temperature. After the dropwise addition, the mixture was heated under reflux for 1 hour. The acetone in this reaction solution was distilled off under reduced pressure, and 60 grams of benzene and 10 grams of distilled water were added, stirred well, and transferred to a separating funnel. The aqueous layer was removed, and 4 parts of Glauber's salt was added to the organic layer, mixed, allowed to stand, dried, and then filtered. The benzene content of the FD is 5*
The mixture was distilled under reduced pressure to sacrifice it to 100% acetate, and purified by silica gel column chromatography using a mixed solution of n-hexane and ethyl acetate as a developing solution.

N-(2-chloropyridin-5-yl)-2-(cyclohexen-1-yl)-γcetamide o, 78 y
(yield 78%) was obtained as white crystals.

The results of the melting point and elemental analysis of this f-hybrid are shown below.

Melting point: 127-128°C Urine analysis (C+aH1BN10C) Actual 6111 value,
C62, 25%, ! -16,0-5%, N11.18
%.

06, 36%, (114,16% Fj′i calculated value, C62,27%, H6,03%, N1
1.17%.

06, 58%, C) 14.14% Example fII5 10 ml of 1 (r 1-cyclohexenyl acetic acid chloride 0.6) (3.8 mmol) of benzenoic acid a was added to 2-γ minnow 3.
5-dibromopyridine 1. It was added dropwise at room temperature to 20 ml of K benzenoic acid containing OIf (4.0 mmol) and 0.4 y (4.0 mmol) of triethylamine. The mixture was added dropwise and heated under reflux for 2 hours. After cooling the reaction solution to room temperature, it was transferred to a separatory funnel and washed with 10 parts of distilled water. After removing the aqueous layer, 4 parts of sodium sulfate was added to the benzene layer, mixed well, and allowed to stand to dry. , then filtered.

This benzene due to P was concentrated by distillation under reduced pressure until the internal density became 5 Ilt, and then purified by silica gel column chromatography using a mixed solution of n-hexane and acetic acid ethyl ester as a developing solution. N-(5,5-dibromopyridyl-2-yl)-2-(cyclohexene-
1-yl)-acetamide 0.951 (yield 67%)
was obtained as white crystals. The melting point and elemental analysis values of this compound are shown below.

Melting point: 1555. ~156.5'.

Elemental analysis value (C+sH++N20Br2) fruit d4sf
Straight: C41.72%, H5.79%, N7.48
%.

04.27%, Br42.74% Calculated value: C41.74%, )13.77%, N749%
.

04.28%, Br42.72% Example 6 10 tons of a benzene solution of 0.701' (5.73 mmol) of 2-(1-cyclohexenyl)-2-methylpropionic acid chloride was mixed with 2-aminoyl/ -4,6-dimethylpyridine (0.48 P C3,96 mmol) and triethylamine 0.40 F (3,96 mmol) were added dropwise at room temperature to a benzene solution containing 20 Mt.
The mixture was heated to reflux for an hour. The reaction solution was cooled to room temperature and transferred to a dispersion funnel, 10 liters of distilled water was added and mixed, the aqueous layer was removed, and 4 Y of Glauber's Salt was added to the benzene layer, mixed well and allowed to stand to dry.

It was then filtered. Is this Pi'iM's benzene inside? i
After concentrating by distillation under reduced pressure until t is 5 ml, a mixture of n-hexane and ethyl acetate was added to the developing solution.
It was purified by silica gel column chromatography using. N-<4.6-dimethylpyridyl-2-yl)
-2-(cyclohexen-1-yl)-2-methylpropionamide 082F (yield 80%) was obtained as white crystals. The refractive index and elemental analysis values of this compound are shown below.

n D' 1.5355 Elemental analysis value (017824N20) Actual 611j value, C74, 98%, H8, 87%, N1
0.26%.

05.89% Calculated value: C74, 96%, H8, 88%, N10.29
%.

05.87% Specific examples of compounds of the general formula fl+ of the present invention are shown in Table 1 below. However, many other compounds included in general formula (1) can also be used effectively in the same way as the exemplified compounds.

In addition, the compound information is also referred to in the Examples and Formulation Examples under JSO.

When actually using the compounds of the present invention as herbicides, the compounds of the present invention may be sprayed as they are on the soil or foliage of crop cultivation areas.

ζ that fully exerts the herbicidal action of the compound of the present invention is
The compound of the present invention is mixed with a suitable carrier and auxiliary agent 1, such as a surfactant, a binder, a stabilizer, etc., and prepared by a conventional method to form a wettable powder, an emulsion, an aqueous solution, an oil suspension, or a powder. , fine granules,
It is preferable to strain and use the formulation in the form of a coarse powder.

In the above step (d), the carrier may be either solid or liquid, as long as it is commonly used in agricultural and horticultural mulberry preparations, and is not limited to any particular carrier. For example, solid carriers include mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.), vegetable matter, etc. Powder (soybean flour, wheat flour, wood flour, tobacco powder, starch, crystalline cellulose, etc.), polymer compounds (petroleum resin, polyvinyl chloride, ketone ceramic resin, dammargum, etc.)
, aluminum ten, silicate, sugar polymer.

Examples include highly dispersed silicic acid and waxes.

In addition, liquid carriers include water, alcohols (methyl alcohol, ethyl alcohol, n-7' alcohol, isr+-furobyl alcohol, phthanol, ethylene glycol, benzyl alcohol, etc.), aromatic stratiform hydrogens (toluene, etc.). , benzene, xylene, ethylbenzene, chlorobenzene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroborum, carbon tetrachloride, dichloromethane, etc.).

chloroethylene, monochlorobenzene, trichlorofluoromethane, dichlorodifluoromethane), ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.), intermediates (dimethylformamide, dimethylacetamide, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethylsulfoxide, etc.) )-gamma alcohol ethers (1-ethylene glycol 7-methyl ether, ethylene glycol monoethyl ether, etc.), aliphatic or alicyclic hydrocarbons [n-hegisan, cyclohexane → J-n, industrial kalin (petroleum ether, solvent naphtha, etc.) and petroleum distillates (paraffins, kerosene, light oil, etc.).

Furthermore, in the preparation of emulsions, wettable powders, flowable preparations, and the like, surfactants (or emulsions) are used for the purposes of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading, and the like. Such surfactants include nonionic types (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan gamma alkyl ester, sorbitan alkyl ester, etc.) and anionic types (alkylbenzene sulfonate, argyl sulfosuccinate, etc.). nate, argyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate, etc.),
Positive/r-on type alkylamines (laurylamine, ester trimethyl chloride 11 chloride, γ-alkyldimethylbenzyl ammonium chloride, etc.) polyoxyethylene alkylamines] 1 and 1 raw type [carboxylic acid (betaine type) , αC acid ester 1, etc.], but the present invention is not limited to these examples. In addition to these, polyvinyl alcohol.

Various yuzu extraction aids such as carpogysimethylcellulose, beer gum, polyvinyl acetate, gelatin, casein, alkinoic acid sorta, gum arabic, and gum tragacanth can be used.

＼ In addition, it is intended to improve the herbicidal efficacy of the compound c4 of the present invention,
Since a synergistic herbicide effect is expected, it can be used in combination with other herbicides. Examples of this include phenoxy herbicides (2,4-dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid,
-41
-nitrophenyl ether, 2,4.6-)dichlorophenyl-41-nitrophenyl ether, 2-1'-4-trifluoromethyl-3'-ethoxy-4'-nitrophenyl ether, 2,4-')'lllowaenyl-4'-nitro-3'-methoxyphenyl ether, 2
．． A-di'IOrophenyl-3'-methoxycarbonyl-4'-nitrophenyl ethernato)% triazine herbicide (2-chloro-4,6-bisethylamino-1,
3,5-) Riryojin, 2-chloro-4-ethylamino-
6-Imbropylamino1.3.5-) riazine, 2
-Methylthio-4,6-bisethylamino-1,3,5
-) riazine, 2-methylthio-! 1.6-pisisopropyl 7°mino-+, 3.5-)suγdine, etc.), urea-based herbicides (3-(3,4-dichloro1cowenino1/)-
1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea, 1-(2,
2-dimethylbenzyl)-3-p-), carbamate herbicides (-rsobroL'-N-(3-chlorophenyl)cart<l-).

Methyl-N-(3,4-dichlorophenyl)-carbamate), thiol-octamate herbicide (s-(4-
chlorobenzyl) N, N-') ethylthiol carbamate, S-ethyl-N, N-hexamethylenethiol carbamate)), acid anilide herbicide (3,4-
Dichloroglopionani 11, N-methoxymethoxy, 2,6-dinithyyl, α-chloroacetate, 21)
,2-'/口o-2',6'-diethyl-N-butoxymethyl)-RosetoRyoji1! do,2-chloro-2,6
-Dinityl N-'(n-propoxyethyl)-γ
Cetolynilide, N-riOroacetyl-N-<2.6-dinitylphenyl)-glycine ethyl ester, etc.), uracil herbicides (5-bromo-3-5ec-butyl-6
-methyluracil, 6-cyclohexyl-5,6-drimethyleneuracil, etc.), pyridinium chlorine herbicides (
1,1'-dimethyl-4,4'-bispyridinium chloride, etc.), 11-thread herbicides (N,N-bis(phosphonomethyl)-glycine, 0-ethyl-0-(2-nitro-
5-methylphenyl)-N-secondary-butylphosphoroamide thioate, 5-(2-methyl-1-piperidylcarbonylmethyl)-0,0-di-n-propyldithiophosphate, S'-(2-methyl -1-piperidylcarbonylmethyl)0. O-diphenyldithiophosphate, etc.), toluidine herbicides (α,α,α-trifluoro-2,6-sinitro-N,N-dipropyl-p-
) luidine, etc.), others (5-tert-butyl-
3-(2,4-dichloro-5-impropoxyphenyl)-1,3,4-oxadiazolin-2-one, 6-ituprobyl-IH-2.1.3-penzotiγdiγdine-
(4) -3H-one-2,2-dioxide, α-(β-
naphthoxy)-propionanilide, 4-(2,4-dichlorobenzoyl)-1,+-dimethylpyrazole-5
-yl-p-toluenesulfonate), but are not limited to these.

The compound of the present invention may also be used as an insecticide if necessary.

It can also be used in combination with nematicides, fungicides, water-applied insecticides and fungicides, soil-applied fungicides and insecticides, plant growth regulators, fertilizers, and the like.

The application rate of the compound of the present invention of general formula +11 varies depending on the type of specific compound to be used, the type of weeds to be weeded, etc., but in general, it is 0.02 K per 10 γ-L,
- to 2K.

Next, the formulation fil of the herbicide of the present invention is shown.
The proportions and types of carriers and auxiliary agents are not limited to the following examples.

In addition, all parts in the formulation examples indicate parts by weight.

Formulation Example 1 Wettable powder 30 parts of compound Na 8, 2 parts of Regenin Sulpon fil J Lucium Tan, 6 parts of dodecylbenzenesulfonic acid sodium salt and 65 parts of diatom are thoroughly ground and mixed to obtain an irrigation agent.

Formulation Example 2 Granules: 5 parts of compound Na29, 2 parts of white carbon,
. .

5 parts of lignin sulfonic acid calcium salt and lily (
088 parts were thoroughly ground and mixed, water was added and the mixture was thoroughly kneaded, granulated, and dried to form granules.

Formulation Example 6 Granules 60 parts of clay, 35 parts of bentonite, and 5 parts of lignin sulfonic acid calcium salt are pulverized and mixed, water is added, kneaded, and granulated and dried to produce granules Ik containing no active ingredient. Granules are obtained by impregnating 95 parts of the granules with 5 parts of the compound Nα13.

Blend Example 4 Particles Bentonite 96 sieved to 500-850 microns
1 part is soaked with 4 parts of compound Na12 to obtain granules.

Formulation Example 5 Add 3 parts of powder compound M4, 36 parts of clay (○), 60 parts of Merck and 1 part of isopropyl phosphate, and reduce the number of rotations to 2. A powder is obtained by pulverizing and mixing with an atomizer of OD rprn.

Arrangement example 6 Emulsion compound Nu150) 60 parts of 50-tone L xylene, Tsurupol 5M100 (a surfactant product manufactured by Toho Chemical Industry Co., Ltd. containing a mixture of a nonionic surfactant and an anionic surfactant) An emulsion is obtained by mixing and dissolving 10 parts of the following ingredients.

Next, the herbicidal effects of the compounds of the present invention will be shown in Examples.

Example 7 Flooded soil treatment herbicidal test 1715.5 f] Paddy soil was filled in an Oγ-I porcelain pot, and the surface layer of the pot was filled with wild grass, firefly, and snail 1
1. Uniformly sow the seeds of Konagi and Kikashigusa, 2 c.
After flooding to a depth of m, paddy rice seedlings at the two-leaf stage
'#) were transplanted. When the weeds germinated, a predetermined amount of the diluted solution of the irrigation agent prepared in accordance with Formulation Example 1 was uniformly dropped onto the water surface for treatment. Thereafter, the pots were kept in a greenhouse and watered from time to time. After 20 days of chemical treatment, the herbicidal effect and degree of chemical damage to paddy rice were investigated using the following criteria.

This test was conducted using the 1'114ji'3boi7) system, 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% Level of chemical damage m: Harmless M: Slight damage (leaf tip blight) +: Moderate damage (leaf blight) R: Severe damage (growth suppression) (Death) Comparative drugs A and B in Table 2 have the following chemical structures, and were formulated and tested in the same manner as the compounds of the present invention.

(Journal of the Chemical Society, p. 1080 and Journal of the American
Chemical Society 1, Volume 71.

Compound described on page 3216) C) (Same as above) 1982
June 6, 2017 Mr. Commissioner of the Japan Patent Office1, Indication of the case Patent Application No. 149179 of 19822, Title of the invention3, Relationship with the person making the amendment Patent No. 8'I applicant address Nihonbashi, Chuo-ku, Tokyo Honseki-cho 4-2 Bussan Building Annex Telephone (
591) 0261 Contents of correction in the detailed description of the invention in the specification subject to the left amendment (11th specification, page 15, line 10 "Cl2H2□0
3 Correct J to "Cl2H2□03".

(2) Insert l'-(as C,6H2oN20) next to "Elemental analysis value" on page 20, line 10. Pyridine” is corrected.

(4) "White crystals" on page 28, line 14 of the same document is corrected to "oily substance."

(5) Same, Table on page 35 (Continuation of Table 1, Compound 4
Delete 26-29) and insert the attached 84th edition table (continuation of Table 1, compounds &26-37) in its place.

+6J Same, the table on page 51 (Continuation of Table 2, Compound 29, Comparative drugs A, B'', untreated area) was deleted and replaced with the table in Appendix 85 (Continuation of Table 2, Compound &29~37.
Insert comparative drugs A, B, and untreated group).

Claims (1)

[Claims] 1. General formula (wherein, X represents a lower alkyl group, m represents an integer of 0 to 2, R' and R2 represent a hydrogen atom or a lower alkyl group, and Y represents a lower alkyl group) group, lower γ-alkoxy group, halogen atom or nitro group, n is an integer of 0 to 2). 2 A cyclohexenyl acetate cotton conductor or its reactive conductor represented by the general formula (in the formula, b X s rn, R1 and R2 have the meanings given below) and the general formula: (wherein Y and n have the meanings given below) General formula characterized by reacting with γminopyridine represented by group, Y is a lower alkyl group, a lower alkoxy group,
a halogen atom or a nitro group, and n is an integer of 0 to 2). 5 general formula: (wherein, A herbicide containing as an active ingredient a cyclohexenylaceto γmide derivative represented by the following formula (representing a group, a halogen atom, or a nitro group, and n is an integer of 0 to 2).