JPH0348635A - Substituted cyclohexadione derivative, its production and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound selected from a substituted cyclohexadione derivative of formula I [R<1> is alkyl, phenyl, aralkyl or heterocyclic group; Y is alkylene; (m) is 0 or 1; R<2> is H or alkyl; R<3> is halogen, cyano, alkyl, haloalkyl, phenyl, etc.; (n) is 0-5; Z<1> is W (W is halogen, etc.) or OR<9> (R<9> is alkyl); Z<2> is SR6 (R<6> is phenyl, etc.), OR<9> or Z<1> and Z<2> together form O, etc.], its salt, enamine or its analog, acylate, sulfonate, carbamate and ether derivative. EXAMPLE:5-(alpha-Chlorophenylthiomethyl)-2-(2-nitro-4-chlorobenzoyl)cy clohexane-1,3- dione. USE:A herbicide. PREPARATION:The compound of formula III (a compound of formula I wherein Z<1> and Z<2> are OR<9>) can be produced e.g. by selectively oxidizing a compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel substituted cyclohexadione derivative, a method for producing the same, and a herbicide containing the derivative as an active ingredient.

(Prior Art) Many herbicides have come to be used for weed control, which has required a great deal of labor, in the cultivation of jilt ornamental crops. However, the drug may be present in crops or remain in the environment.
Because of the risk of contamination, there is a desire to develop drugs that are more effective at lower doses and can be used safely.

Compounds similar to the compounds of the present invention are disclosed in JP-A-60-[17230, JP-A-00-87239, JP-A-61-1526'42, JP-A-61-1526/19.
, JP-A No. 61-155347, Special No. 1311, No. 62-12
3145, 1983-201152, 1983-10493
0, Sho 63-139146 is known.

(Problems to be Solved by the Invention) The purpose of the present invention is to provide a herbicide that can be industrially advantageously synthesized, is highly effective at a lower dosage, is highly safe, and has good IR selectivity with crops. It is.

(Means for Solving the Problems) The present invention provides -Noshiro [1] [wherein R1 represents lower alkyl, optionally substituted phenyl, optionally substituted aralkyl, or optionally substituted heterocycle] The number of it substituents represented is 0 to 5 in each case.

Y: Straight chain or branched lower alkylene m: 0
or I R2: Hydrogen or straight-chain or branched lower alkyl R3: Same or different halogen, cyano, alkyl, haloalkyl, cyanoalkyl, alkoxycarbonyl, optionally substituted phenyl n: 0. 1
．． 2.3.4.5z': w or OR" Z2: SR6 or OR'; or Zl, Z
2 together represent oxygen, CR'R', or Nr (where R4: hydrogen or alkyl; R5: hydrogen, alkyl,
Alketthio, alkenylthio, alkynylthio, heroanyl, alkoxyalkyl, alkylthioalkyl, optionally substituted phenyl; r: hydrogen, alkyl, alkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy:, W: halogen, SR', OR@
: R' is optionally substituted phenyl or heterocycle,
R7 and R@ are alkyl, optionally substituted phenyl or heterocycle; R9 is alkyl or two R together are alkylene)], or a salt thereof, enamine or similar thereof Compounds selected from compounds, acylates, sulfonates, carbamates, or ether derivatives, methods for producing the same, and herbicides.

Phenyl, aralkyl, and heterocycle of R1 above, R6
phenyl, R6 phenyl, R8 phenyl and heterocycle, 8 and R phenyl and heterocycle substituents are the same or different, halogen, hydroxy, nitro, cyano, alkyl, alkenyl, haloalkyl, Haloalkenyl, alkoxy, haloalkoxy, haloalkenyloxy, alkyllkylthio, herooalkenylthio, monoalkylamino, dialkylamino, alkoxyalkylthio, alkylthioalkylthio, alkoxycarbonyl, alkylcarbonylalkoxy, alkylcarbonyl, alkoxyamino, alkylsulfonyl, Alkenylsulfonyl, alkynylsulfonyl, alkoxyalkylsulfonyl, alkylthioalkylsulfonyl, alkylsulfonylalkylsulfonyl, haloalkylsulfonylalkoxycarbonylalkylthio, alkoxycarbonylalkylsulfinyl, alkoxycarbonylalkylsulfonyl, 1iTh 19 phenyl, It II may be Aralkyl, an optionally substituted heterocycle, and an alkyl group substituted with an optionally substituted heterocycle.

The term "heterocycle" refers to pyridyl, pyrimidyl, thienyl, furyl, pyrazolyl, pyrrolyl, imidazolyl, pyridazinyl, pyrazinyl, indolyl, and the like.

The compound of the present invention exhibits high herbicidal activity in both soil and foliage treatments under upland cultivation conditions.Especially in foliage spraying, it exhibits high efficacy against various field weeds such as crabgrass, cyperus, sedgeweed, and cornweed. It also contains compounds that are selective for crops such as , wheat, and soybeans.

In addition, the compound of the present invention can be applied to paddy field weeds such as novie
Contains compounds that have excellent herbicidal efficacy against weeds such as Omodaka and bulrushes, and are selective for rice.

Furthermore, the compounds of the present invention can be applied to control weeds in orchards, lawns, railroad tracks, vacant lots, etc.

The compound of the present invention can be produced by the following method.

Each process will be described in detail.

Reaction step (a) (wherein, R1, R2, R3, R4, R5, R9,
Y, m, and n have the same meanings as above, and Q means halogen, alkylcalsonyloxy, alkoxycal, I ] or [XV] can be obtained by reacting 1 mole of each non-compound or [Kari] with the compound [Kaoru] in the presence of 1 mole or perhydrogenated base, or by reacting 1 mole of each with the compound [Kaoru]. Compound [M] or C]
and compound [XX] with 1 mol or excess of DCC (dicyclohexylcarbodiimide).

The bases used are alkali metal hydroxides such as I(OIt, NaOH, etc.), alkaline earth metal hydroxides, tri(C+-Co alkyl)amines, pyridine, sulfur and lithium carbonates, and sulfur phosphates. etc., as the solvent: water, methylene chloride, toluene, ethyl acetate, dimethylformamide, T 11 F, dimethoxyethane,
The reaction mixture, in which acetonitrile or the like is used, is stirred at 0°C to 50°C until the reaction is complete.

As the solvent used in the reaction with DCC (dicyclohexylcarbodiimide), methylene chloride, toluene, ethyl acetate, dimethylformamide, THF, dimethoxyethane, acetonitrile, etc. are used. The reaction mixture is stirred at -50°C until the reaction is complete. The reaction mixture is worked up in a conventional manner.

The rearrangement reaction is carried out in the presence of a cyano compound and a mild base. A compound as mentioned above, for example 1 mol of the compound [■]
Alternatively, [XV] is reacted with 1 to 4 mol of base, preferably 2 mol of base, and 0.01 mol to 0.5 mol or more, preferably 0.1 mol of a cyano compound. As the base used here, any of the above-mentioned bases can be used. Further, as the cyano compound, potassium cyanide, acetone cyanohydrin, cyanide (hydrogen, a polymer holding potassium cyanide, etc.) are used.

Note that by adding a small amount of a phase transfer catalyst such as crown ether, the reaction can be completed in a shorter time. The reaction is 8
It is carried out at a temperature below 0°C, preferably between 20°C and 1L OoC. The solvent used is l.

These include 2-dichloroethane, toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, methyl isobutyl ketone, THF, dimethoxyethane, and the like.

Moreover, the compound [In ] or [fire] is the compound [X
1ffl or [4] and compound E'! ! ? ] can also be obtained by reacting in the presence of a base and a Lewis acid.
Ru.

Suitable bases are those mentioned above. Suitable Lewis acids are zinc chloride and aluminum trichloride, preferably zinc chloride.

The reaction is organic with acetonitrile or methylene chloride;
The process is carried out in 8 medium at a moderate temperature of -20°C to 40°C.

Both zinc chloride and the base are combined into the compound ['fA] or [cold]
It is appropriate to use a slight excess of .

Reaction step (b) (wherein, R1, R2, R3, R6, R9, X%Y
.

m and n have the same meanings as above) reaction step (b)
Compound [V] can be obtained by hydrolyzing compound [1''/] in a water-containing solvent in the presence of a base or silica gel at room temperature.
In some cases, it can be obtained by slightly heating it.

The bases used are l(011, alkali metal hydroxides such as NaOH, alkaline earth metal hydroxides, tri(C+-Ca alkyl)amines, pyridine, sodium hydrogen carbonate, thorium carbonate, potassium carbonate. , sodium phosphate, etc., preferably potassium carbonate. Silica gel can achieve the purpose by using a small amount of adsorbent for the column. As a solvent, hydrous acetone, hydrous dioxane, hydrous alcohol, hydrous Dimethoxyethane, hydrous acetonitrile, etc. are used.The water content is 30-60%, preferably 30%.The reaction mixture is stirred at 0°C-60°C until the reaction is complete. In some cases, the desired product can be obtained in a short time when heated to 60°C.

In addition, the hydrolysis conditions used for the synthesis of compound [V] from compound [l■] can be similar to the conventional hydrolysis conditions for acetal and kekuhl. The reaction that yields the compound proceeds quickly at room temperature or, in some cases, with slight warming.
The solvent used is hydrous alcohol, hydrous acetone, or the like.

In addition, in the oxidation reaction used for the synthesis of compound [V] from compound [111], aldehyde,
Oxidizing agents used in the conversion of ketones can be applied.
I! II, ChromiuII Trioxid
e-Pyridine Complex (e.g., C
Oxidation with chromic acid or activated DMSO (e.g., DMSO and Oxalins reagent)
5 by VF4 (made from yl chloride)
uerr+l! l! i conversion etc. are used. In the case of chromic acid oxidation, the oxidizing agent is reacted with 2 to 10+a moles, preferably 6 times the mole of the raw material, of the oxidizing agent at room temperature. The solvent used is 1,2-dichloroethane, methylene chloride, etc. In addition, activated DMSO can be prepared by various methods, but due to its reactivity, yield, etc., the above-mentioned Swe
The rn reagent is the preferred oxidizing agent.
-60°C, preferably 1 mol of compound [1 at -60°C
1] with 1 to 2 moles of an oxidizing agent, as described in the literature (J,
Org, Cbem, Vol, 44. No, 23.4
The desired compound [Vco] can be obtained by treating the reaction intermediate with a base such as triethylamine according to the method described in Section 8.1979). Solvents used include toluene, 1,2-dichloroethane, methylene chloride, acetonitrile, acetone, hexane-methylene chloride (9:1 V/V), and the like.

Reaction step (c) (However, in the formula, R-2R2, R3, r, Y, rn
, and n have the same meanings as above) In the reaction step (c), the compound [■] is the compound [V]
and compound [VI] in the presence or absence of a base.

Suitable bases are conventional bases such as triethylamine.

The reaction consists of toluene, 1,2-dichloroethane, methylene chloride, ace!・Nitrile, acetone, THE
, -20 in an organic solvent such as dimethoxyethane.
It is carried out at a moderate temperature between 0C and 40'C, preferably at room temperature.

Reaction step (d) (wherein, R1, R2, R3, R6, R7, R.
X.

In reaction step (d) (Y, m, and n have the same meanings as above), compound [■] can be easily obtained from compound ['fA] using a halogenating agent such as sulfuryl chloride. For example, 1 mol of compound [XXl] and
The desired product can be obtained almost quantitatively by simply reacting equimolar, preferably slightly excess, sulfuryl chloride at room temperature and distilling off the solvent after the reaction is complete. Solvents used include toluene, 1,2-dichloroethane, methylene chloride, and the like.

Compound [XI] or compound [XI] is compound [IV]
and compound R? By reacting SH[[] or the compound RaOH[:Xl in the presence or absence of a base! ! can be built.

Compound [■] and compound [Xl] can be used in excess and also serve as a solvent.

A suitable base is an organic base such as triethylamine.

The reaction is as follows: Toluene, 1. 2-dichloroethane, methylene chloride, acetonitrile, acetone, THE,
-20°C in a solvent such as dimethoxyethane
It is carried out at a moderate temperature of ~40°C, preferably in a room at room temperature.

The raw material compound and the compound [1] of the present invention have many tautomeric forms, for example, (wherein the formula: R1, R2, R3, y, z', 7.'
, m, and n have the same meanings as above).

All such forms are within the scope of this invention.

If the compound [11] contains a free hydroxyl group in the above-mentioned manner, salts thereof, in particular a horticulturally acceptable salt, an enamine or analogue thereof, an acrylate, a sulbonate, a carbamate or Ether can be derived.

Suitable agriculturally and horticulturally acceptable salts include sodium;
Salts such as potassium, calcium and ammonium salts may be mentioned.

An example of an ammonium salt is the formula = N″R”RbR'R
'(wherein R'', R'', R', and Rd are each,
Mention may be made of salts with ions of hydrogen and optionally selected from C-10 alkyl groups substituted, for example, by hydroxyl groups. R”, R”% ROl and R6
If any of these are optionally substituted alkyl groups, they desirably contain 1 to 4 carbon atoms.

Suitable enamines or analogs thereof are such that the OH moiety is
Formula: -NR'R' (R. is, for example, an alkyl IJ - M with a carbon number of 1 to 6, optionally with one moxibustion device),
For example, phenyl group. Also, in the case of R'l, when the element or example number is 1 to 6;
saletaalkyl or aryl group, e.g. phenyl 7
M is a compound that has been converted to a halogen or SRQ.

Suitable acrylate or ether derivatives are those in which the O 11 moiety has the formula: -OCORh or -OR'(R"
is the same as the above-mentioned group R0).

Suitable carbamate derivatives have the O H RfII component of the formula niQC (0)NR'r(i, where R1 and RI
Ha, each/? , hydrogen or the same as the group R0 above).

These derivatives can be prepared by the method for +n.

The structure of the compound of the present invention was determined from lrl, NMR, MS, etc.

(Examples - Compounds) Next, the compounds of the present invention will be explained in further detail with reference to Examples.

Example 1 5-(α-chlorophenylthiomethino)-2-(2-
didro-4-chlorobenzoyl)cyclohexane-1,
3-dione (compound number: I-165-phenylthiomethyl-2-(2-nitro-4-chlorobenzoyl)cyclobeki1nan-1.3-dione n., t7g (1
0 to 1 nmol) was dissolved in 50 ml of J Basin I Himethylene,
Sulfuryl chloride 1.5 while cooling with ice water and stirring.
g (11 mmol) was added. After returning to room temperature, the mixture was stirred for 2 hours and 4 hours. After the reaction was completed, the solvent was distilled off, and the residue was purified using Shibuno gel column chromatography (
Elution time: 1 non-methylene chloride 1:1) L/,
One drop of crystalline $5) powder.

Purpose of purification from hexane-methylene chloride mixed solvent ζ. Things a. o7g (yield 90%), mp12B-1
The temperature was 30℃.

Example 2 5-formyl-2-(2-nitro-4-chlorobenzoyl)cyclohexane-1,3-dione (compound number:
1-139), add 200 ml of ethyl acetate and 50 ml of water to
It was dissolved using J++. Dilute 13 acid was added until the aqueous layer became acidic, and the organic layer was washed with saturated brine and dried over magnesium sulfate. The residue obtained by distilling off the solvent was purified using solica gel column chromatography (exit i'21) α hexane-methylene chloride 1:1), sticky y+” target product 2.4 g (yield 74.2%).

Example 3 5-formyl-2-(2-di)rho-4-chlorobenzoyl)cyclohexane-1. 3-dione (compound number: I-139) 6-(α-chloro(4-chlorophenyl))thiomethyl-2-(2-nitro-4-chlorobenzoyl)cyclohexane-1,,3-dione 4.52 g (10 mmol)
was dissolved in 100 ml of 50% acetone water, 2.76 g (20 mmol) of potassium carbonate was added to the solution, and the mixture was stirred at room temperature for 100 ms. After the reaction is completed, the solvent is distilled off,
1 0.78 g of residual oxalyl chloride (QC) given
(6.

A methylene chloride solution (10 ml) of -6
Cool to 0°C and add DMSOo. 40g ((3.1
4 mmol) salt 1 himethylene solution 1α (10 m
1) was added dropwise under pressure II and stirred for 118 minutes.

This solution ζ is a methylene chloride solution (2
0 ml> was lubricated with oil at the same temperature and stirred for 4 hours. After the reaction was completed, the reaction mixture was lubricated with a methylene chloride solution (10 ml) containing 1.24 g (12° 28 mmol) of triethylamine at the same temperature, and poured into ice water. Then, methylene chloride was added for extraction, and the organic layer was washed with water. Then, the i8 medium was removed by drying with magnesium sulfate, and the resulting residue was subjected to silica gel column chroma! Purification (eluent: hexane-methylene chloride I:I) L/, yielded 0.6 g (yield 60.4%) of the same target product as in Example 2.

Example 4 5-ethoxyiminomethyl-2-(2-nitro-4-chlorobenzoyl)cyclohexane-1°3-dione (compound number: l-147), 100H 5-formyl-2-(2-21)・Rho-4-chlorobenzoyl)cyclohexane-1,3-dione 1.2g (3,
71 mmol) was dissolved in 30 ml of methylene chloride, and 0.23 g (3.77 mmol) of ethoxyamine was added.
After the reaction was completed by stirring at room temperature for 3 hours, dilute hydrochloric acid was added to make the aqueous layer acidic, and the organic layer was separated, and then the organic layer was washed with saturated brine. After drying with magnesium sulfate,
The solvent was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography (elution: α hexane-methylene chloride 7:3) to obtain 129 g of the desired product (yield: 95%).
) was obtained. nD2551.584 Example 5 5-propenyl-2-(2-nitro-4-chlorobenzoyl)cyclohexane-1,3-dione (1 compound number: l-149) 5-propenyl-cyclohexane-1,3- Zeon 0
．． 4 g (2.63 mmol) was dissolved in 10 ml of methylene chloride, and 0.23 g (2.89 mmol) of pyridine was added. This solution) α was lubricated with 5 ml of a methylene chloride solution containing 0.58 g (2.63 mmol) of 2-nitrochlorobenzoyl chloride at room temperature, and stirred at room temperature for 1 hour. After the reaction was completed, the methylene chloride solution Wash with water, then
The residue obtained by distilling off the am medium dried over magnesium sulfate was dissolved in 15 ml of acetonitrile, and 0.0 ml of triethylamine was added. Add 20 g (2,57 mmol),
Then 0.046 g (0.7 mmol) of potassium cyanide was added. After stirring at room temperature for 18 hours, i″(7
The medium was distilled off, and then ethyl acetate and diluted hydrochloric acid were added to the resulting residue; it was dissolved. 4ffil was washed with saturated brine, dried over magnesium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluent: hexane-methylene chloride 0:2), and then crystallized from methanol to obtain 0.7 g of the desired product (yield: 8).
7.5%).

Example 6 5-(2-(2-methyl-1,3-dioxalanyl)
)-2-(2-di)-rho-4-chlorobenzoyl)cyclohexane-1,3-dione (compound number: l-1
62) 5-(2-(2-methyl-1,3-dioxalanyl)
) cyclohexane-1,3-dione 8 g < 40.4 mmol) and 2-2! - Mouth ~ 4-chlorobenzoyl chloride 0. 08 g (40,4 mmol) of salt (hymethylene i
'8) Add 0 triethylamine to α100ml under water cooling.
．． The reaction mixture to which 15 g (On, 8 mmol) was added was stirred at room temperature for 2 hours.

Reaction j? After completion, the reaction solution was washed with water, and then the organic layer was dried over magnesium sulfate. The solvent was distilled off to obtain a crystalline product. After adding and dissolving 150 ml of acetonitrile to this crude product, triethylamine 4. 1 &
(40,4 mmol), l(CN 0゜3g(4,(3
mmol) and 18-crown-60, 1 g,
The mixture was stirred at room temperature for 18 hours.

After the reaction was completed, the solvent was distilled off, and 200 ml of ethyl acetate and 50 ml of water were added to the resulting residue for 18 hours. The aqueous layer was made acidic using dilute hydrochloric acid. The resulting crystal is 0
Separation gave fII crystals. The organic layer was washed twice with 20ml of diluted hydrochloric acid, and then with saturated saline. Ahead, I dried it with sulfur, magun, and sium. After distilling off the solvent, combine the residue obtained from the above 1.1 and the crystals and recrystallize with methanol.
I got 15.

Fruit 1 no 151 glyph 5-(α-methoxyphenylthiomethyl)-2-(2-
Nitro-4-chlorobenzoyl)cyclohexane-1,
3-dione (compound number: J-IGI) 5-(α-chlorophenylthiomethyl)-2-(2-nitro-4-chlorobenzoyl)cyclohexane-1,3
-4.52 g (10 mmol) of dione in 20 methanol
ml and stirred at room temperature for 18 hours. After the reaction was completed, the solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (F6 eluent: hexane-methydine chloride 8:2), and the target product was obtained as a sticky oil. , 4
．． 02g was obtained.

Representative η of the compounds of the present invention, including the above-mentioned implementation ηI]
- Shown in Table 3. However, in the table, R8, R, and R2 represent the following substituents.

Table 1 Mizozo formula Table 3 (Means for solving the problem - Herbicide) The herbicide of the present invention contains as an active ingredient one or more of the compounds represented by Noshiro [I] above, and usually It has a form similar to that of the drug. That is, the active ingredient compound is generally mixed with a suitable carrier and formulated into a wettable powder, emulsion, granule, aqueous solution, flowable preparation, etc.The solid carriers include talc,
white carbon (silica), bentonite, clay,
Liquid carriers include water, alcohol, benzene, xylene, kerosene, mineral oil,
Cyclohexane, cyclohexanone, dimethylformamide, etc. are used. In these preparations, a surfactant may be added if necessary in order to obtain a uniform and stable form.

The concentration of the active ingredient in the herbicide of the present invention varies depending on the form of the formulation mentioned above, but for example,
In wettable powders, 5 to 70%, preferably 10 to 30%
%: In emulsions, 3-70%, preferably 5-2
0%: In granules, 0.01 to 30%, preferably 0.05 to 10% is used.

The wettable powders and emulsions thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion), and the granules are directly sprayed on soil before or after weed germination or Processed by admixture. When actually applying the herbicide of the present invention, an appropriate amount of 1 g or more of the active ingredient is applied per 10 ares.

In addition, the herbicide of the present invention can be used with known seedlings, insecticides, acaricides,
It can also be used in combination with herbicides, plant growth regulators, etc. In particular, by using it in combination with a herbicide, it is possible to reduce the amount of the drug used. In addition to saving labor, it can also be expected to have even higher effects due to the synergistic action of the mixed drugs.

In that case, combinations with multiple public herbicides are also possible. Examples of chemicals suitable for use in combination with the herbicide of the present invention include bentiocarb, molinate, and MY-93 (S
-(2,2-dimethylbenzyl)l-biverizine-rubocete], thiocarbamate herbicides, acid amide herbicides such as butachlor, pretilachlor, mefenacet, diphenyl ethers such as chromethoxynil, bifenox, etc. Herbicides, triazine herbicides such as atrazine and cyanazine, sulfonylurea herbicides such as chlorsulfuron and sulfometuron-methyl, phenoxyalkanecarboxylic acid herbicides such as MCP and MCPB, and phenoxyphenoxypropion such as diclofop-methyl. Acid herbicides, pyridyloxyphenoxypropionic acid herbicides such as fluadipopbutyl, benzoylaminopropionic acid herbicides such as benzoylprop-ethyl and furanprop-ethyl, and others such as Viverophos, Daimeron, Pentacin, Daifuenzoco-1・, Nabroanilide, HW-52 (
4-ethoxymethoxybenz-2,3-cycloanilide), I(NW-242(1-(3·-methylphenyl)-5-phenyl-IH-1,2°4-triazole-3-carboxamide) , Ki, Nclorac (3,7-
dichloro-8-quinolinecarboxylic acid), herbicides such as setogishidim and alloxydim-sodium, and lohexanedione-based herbicides. Moreover, it is also possible to add plant ura and melody seeds to these mixtures.

(Example - Herbicide) Next, some examples of herbicides related to the herbicide of the present invention are shown, but the active ingredient compounds, additives, and addition ratios are not limited to those in this example, and may be changed at various times. It is possible.

Example Day Wettable powder Compound of the present invention 20 parts White carbon 20 parts Diatom ± 52 parts Sodium alkyl sulfate 8 parts or more were uniformly crushed into 131H f5) to obtain a wettable powder containing 20% of the active ingredient. Ta.

Example 9 Emulsion Compound of the present invention 20 parts xylene 55 parts dimethylform 7mide 15 parts polyethylene phenyl ether 10 parts or more were mixed. '2+ analysis to obtain an emulsion containing 20% of the active ingredient.

Example 10 Granules Compound of the present invention 5 parts Talc 40 parts Clay
38 cities bentonite
10 parts Sodium alkyl sulfate 7 parts or more are mixed uniformly and finely ground to a diameter of 0°5 to 1.
The product was granulated into granules containing 5% of the active ingredient.

(Effect of the invention) Next, test examples regarding the effect of the herbicide of the present invention will be shown.

Test 1511 1 Stalk and foliage spraying treatment A 200 cd pot was filled with soil, and each seed, such as cypress, cyperus, cyperus, and ichi, was added to the surface layer II! The plants were grown in a greenhouse after being lightly covered with soil. When each fi grass grew to a height of 5 to 10 cm, an emulsion of each test compound was diluted with water to prepare 1000
The ratio of drug B 1α to I OOQ / 10a (10a
(equivalent to 100 g per portion) was sprayed on the stems and leaves of weeds using a small sprayer. After 3a, the herbicidal effect on weeds was investigated according to the following investigation criteria, and the results are shown in Table 4.

Research standard killing grass $ tier grass
Index 0% 0 20-29% 2 40-49% 4 60-69% 6 80-89% 8 100% 10 Also, the numerical values of 1.3.5.7.9 are 0 and 2.2, respectively. 4
．． It shows a value between 4, 6.6, 8.8 and 10.

Above-ground grass melon in untreated area Above-ground grass weight in one treatment area Weed killing rate (%) = × 100 Above-ground grass weight in untreated area 0 shots Akira person Protection Slope Hide husband 345 Yanagimachi, Takada, Odawara City, Kanagawa Prefecture Inside the Hara Institute Nippon Soda Co., Ltd. Oda

Claims (9)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R^1 is lower alkyl, optionally substituted phenyl, optionally substituted aralkyl, or substituted represents a good heterocycle. The number of substituents is 0 to 5 in each case. Y: Straight chain or branched lower alkylene m: 0 or 1 R^2: Hydrogen or straight chain or branched lower alkyl R^3: Same or different halogen, cyano, alkyl, haloalkyl, cyanoalkyl, alkoxy Carbonyl, optionally substituted phenyl group n: 0, 1, 2, 3
, 4, 5 Z^1: W or OR^9 Z^2: SR^6 or OR^9; or Z^1, Z^
2 together form oxygen, CR^4R^6, or N-r(
However, R^4: hydrogen or alkyl; R^5: hydrogen, alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, optionally substituted phenyl; r: hydrogen, alkyl, alkoxy, haloalkoxy, alkenyloxy,
Haloalkenyloxy; W: halogen, SR^7, OR
^8; R^6 is optionally substituted phenyl or heterocycle; R^7 and R^8 are alkyl, optionally substituted phenyl or heterocycle; R^9 is alkyl, or two R^9 are A compound selected from substituted cyclohexadione derivatives, or salts thereof, enamines or analogs thereof, acylates, sulfonates, carbamates, or ether derivatives; (2) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (However, in the formula, R^1, R^2, R^3, Y, m, and n
has the same meaning as above); or the general formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] (However, in the formula, R^1, R^2 , R^3, R^9, Y, m
, and n have the same meanings as above) in the presence of an acid; or general formula [IV] ▲ Numerical formula, chemical formula, table, etc. ▼ [IV] (However, in the formula, R ^1, R^2, R^3, R^6, Y, m
, and n have the same meanings as above, and X means halogen) is hydrolyzed in the presence of a base or in the presence of silica gel, with the general formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc.▼[V] (However, in the formula, R^1, R^2, R^3, Y, m, and n
has the same meaning as above). (3) General formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [V] (However, in the formula, R^1, R^2, R^3, Y, m, and n
has the above meaning) and a compound of the general formula [VI]H_2N-r[VI] (wherein r has the same meaning as above) in the presence or absence of a base. General formula [VII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [VII] (However, in the formula, R^1, R^2, R^3, Y, m, n, and r have the same meanings as above). (4) General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IV] (However, in the formula, R^1, R^2, R^3, R^6, X, Y
, m, and n have the same meanings as above);
General formula [VIII] R^7SH [VIII] (However, in the formula, R^7
has the same meaning as above) General formula [IX] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IX] (However, in the formula, R^1, R^2 , R^3, R^6, R^7
, Y, m, and n have the same meanings as above). (5) General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IV] (However, in the formula, R^1, R^2, R^3, R^6, X, Y
, m, and n have the same meanings as above);
General formula [X I ] ▲ Numerical formula, chemical formula, There are tables, etc. ▼ [X I ] (However, in the formula, R^1, R^2, R^3, R^6, R^8
, Y, m, and n have the same meanings as above). (6) General formula [XII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [XII] (However, in the formula, R^1, R^2, R^3, R^6, Y, m
, and n have the same meanings as above) and a halogenating agent.General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[IV] (However, in the formula, R^1, R^2, R^3, R^6, X, Y
, m, and n have the same meanings as above). (7) General formula [XIII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [XIII] (However, in the formula, R^2, R^3, R^4, R^5, Y, m
, and n have the same meanings as above) and a compound of the general formula [XIV]R^1COCN[XIV] (wherein R^1 has the same meanings as above) are combined with a base and a Lewis acid. or general formula [XV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [XV] (However, in the formula, R^1, R^2, R^3, R^4, R^5
, Y, m, and n have the same meanings as above) in the presence of a cyano compound and a base, the general formula [XVI] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [XVI] (However, in the formula, R^1, R^2, R^3, R^4, R^5
, Y, m, and n have the same meanings as above). (8) General formula [XVII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [XVII] (However, in the formula, R^2, R^3, R^9, Y, m, and n
has the same meaning as above) and a compound of general formula [XIV]R^ICOCN[XIV] (wherein R^1 has the same meaning as above) in the presence of a base and a Lewis acid. or general formula [XVII] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [XVII] (However, in the formula, R^1, R^2, R^3, R^9, Y, m
, and n have the same meanings as above) in the presence of a cyano compound and a base, the general formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] ( However, in the formula, R^1, R^2, R^3, R^9, Y, m
, and n have the same meanings as above). (9) General formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (However, in the formula, R^1, R^2, R^3, Y, Z^1, Z
^2, m, and n have the same meanings as above) A herbicide characterized by containing one or more compounds as an active ingredient.