WO1999018098A1

WO1999018098A1 - Pyrazole derivative

Info

Publication number: WO1999018098A1
Application number: PCT/JP1997/003607
Authority: WO
Inventors: Yoriyuki Takashima; Ichiro Nasuno; Hiroshi Yamamoto
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 1997-10-08
Filing date: 1997-10-08
Publication date: 1999-04-15
Also published as: AU4570997A

Abstract

A novel pyrazole derivative having a thiochroman ring bonded thereto through a carbonyl group; and herbicides containing the same as the active ingredient. The pyrazole derivative exhibits extremely excellent selectivity between crops and weeds in foliage treatment and soil treatment.

Description

l ^ Itoda Pyrazole derivative Technical field

The present invention relates to a virazole derivative and a herbicide containing the same as an active ingredient. Background art

It is essential to use herbicides to protect important crops such as rice, wheat, barley, corn, soybeans, potatoes and beets from weed damage and increase yield. Especially in recent years, in arable lands where these useful crops and weeds are mixed, even if the crops and weeds are treated simultaneously, they do not show phytotoxicity to the crops and selectively kill only weeds. There is a need for herbicides.

Conventionally, at the time of cultivation of corn and the like, the triazine herbicides atrazine and the acid anilide herbicides arachlor and metolachlor have been mainly used as soil treatments. It requires chemicals and causes environmental problems such as groundwater pollution.

In recent years, no-tillage cultivation for soil conservation has been encouraged. “No tillage cultivation” is a method of cultivating crops without cultivating the field, as opposed to normal tillage cultivation. In tillage cultivation, cultivation (cultivation) of the fields causes fertile topsoil to flow out due to rainwater, etc., which is a major agricultural problem and can also contribute to desertification. There is also a problem. On the other hand, in no-tillage cultivation, there is no problem of runoff of topsoil, but without cultivation, the soil becomes hard and the chemicals hardly seep into the soil, and the effectiveness of the soil treatment agent decreases. Therefore, there is a need for a herbicide that exhibits a high herbicidal effect at a low dose and that can be used as a single agent as a foliar treatment, especially in no-tillage cultivation, especially in soil treatment.

International Publication No. WO 93/18031 discloses a virazole derivative having a herbicidal activity and having a chiral mouth ring represented by the following structural formula.

(In the formula, R ¹ is an alkyl group. The description of other symbols is omitted. The representative compound (A) in the above-mentioned International Publication (Compound No. 66 in the International Publication) is shown below. .

The above compound (A) does not cause phytotoxicity when cultivated crops such as corn, wheat, barley and the like are subjected to foliage treatment at the 1-2 leaf stage, and exhibits excellent crop-weed selectivity. If foliage treatment is performed at the 4th leaf stage, the safety for crops is not sufficiently satisfactory.

In addition, International Publication WO 96/31507 discloses a virazole derivative having a herbicidal activity and having a chiochroman ring represented by the following structural formula.

(Wherein, R ¹ is - Ji ₆ haloalkyl group Flip having one or more halogen atoms. Explanation of the other symbols is saving.) Representative compounds disclosed in the above international publication (B) (International The compound No. 2) in the publication is shown below.

As shown in the representative compound (B), the international publication discloses only a compound having substantially one halogen atom.

Compounds having one such halogen atom show sufficient herbicidal activity against broadleaf and grass weeds even when treated at a low effective dose of 300 g per hectare. However, if the effective dose is further reduced, the effect on important weeds will be insufficient. Disclosure of the invention

INDUSTRIAL APPLICABILITY The present invention is a herbicide which is safe for cultivated crops such as corn, can control a wide range of weeds at a low dose, and has high selectivity for crops in foliage treatment, particularly foliage treatment in no-tillage cultivation. It is a first object of the present invention to provide a novel pyrazole derivative having activity.

A second object of the present invention is to provide a herbicide containing the novel pyrazole derivative as an active ingredient. '-The present inventors have conducted intensive studies to find a novel pyrazole derivative that can achieve the above object, and as a result, in the structural formula of the pyrazole derivative of the above-mentioned International Publication, those having two or more halogen atoms are foliage-treated. , Low in all soil treatments It has remarkably strong herbicidal activity against a wide range of weeds at a high dose, and has high safety against important crops such as wheat, barley, corn, soybeans, potatoes, beets, and rice. The present inventors have found that the present invention has high crop-weed selectivity and completed the present invention.

That is, a first object of the present invention is to provide a compound of the formula (I)

(Wherein, R ¹ is a Ci Cs haloalkyl group having two or more halogen atoms; RR ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group, a kill group or a halogen atom. ;

An alkyl group;

R ⁷ is a hydrogen atom or a Ci C alkyl group;

X is a C! C alkyl group, 〇! To 0. Roh, mouth alkyl group, a halogen atom, (^ ~ (^ § alkoxy group, (^ 04 C opening alkoxy group, C ₂ ~C ₄ alkoxyalkyl group, C! ~

C ₄ alkylthio group! ~. ! Haloalkylthio group, (^ ～〇 ₄ alkylsulfinyl group, c c alkylsulfonyl group, a nitro group or a nitrile group;

P is 0, 1 or 2;

Q is a hydrogen atom or one A-B;

Where A is one S 一₂ _, — (CH ₂ ) _k —CO— or one CR ⁸ R ⁹ —

(Where k is an integer of 0 to 3,

R ⁸ and R ⁹ are each independently a hydrogen atom or a C i -C ₄ alkyl group) B is an alkyl group, a C ₃ -C ₁₂ cycloalkyl group or a phenyl group which may be substituted with Ym

(Where Y is an alkyl group, a C ₁ -C ₄ alkoxy group, A kill group, a nitro group or a halogen atom,

m is an integer from 0 to 2)

n is 0, 1 or 2}

This is achieved by a pyrazole derivative represented by the formula:

Further, the second object of the present invention is achieved by a herbicide comprising a pyrazole derivative represented by the above formula (I) as an active ingredient. BEST MODE FOR CARRYING OUT THE INVENTION

A novel pyrazole derivative that achieves the first object of the present invention is a compound having a structure represented by the following formula (I).

In the above formula (I), R ¹ has two or more halogen atoms

It is a lower alkyl group. This is because the herbicidal activity is relatively low when the compound has only one halogen atom. The C Ce alkyl group which forms the R ¹ backbone, a methyl group, El group, Pro / Les group, butyl group, hexyl group and the like pentyl and to, C ₃ or more alkyl groups may be linear, cyclic Alternatively, it may be branched. Of these, an ethyl group, a propyl group and an isopropyl group are preferred. Examples of the halogen atom to be substituted for the C ^ CeT alkyl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom is preferable. The halogen atom may be substituted with any hydrogen atom in the C i Ce alkyl group forming the skeleton of R ¹ , and the number of substitution is preferably 2 to 7, particularly preferably 2 to 4.

Specific examples of the C ₁ -C ₆ haloalkyl group include a Z— (CZ ₂ ) _{ql_} (CH ₂ ) _{q 2} — group (Z represents a halogen atom. The same applies hereinafter. 91 is an integer of 1 to 3, and 92 is 0 to 5 ), H- (CZ ₂ ) _q3 — (CH ₂ ) _q4 — ^ 3 is an integer from 1 to 5, q 4 is an integer from 0 to 5), (Z CH ₂ ) ₂ — CH— (CH ₂ ) _q5 —, (Z ₂ CH) ₂ — CH— (CH 2) _{q 5} —, (CZ ₃ ) ₂ -CH- (CH ₂ ) _{q 5} — (q 5 is an integer from 0 to 3), Z-(CZ ₂ ) _{q 6} — (CH ₂ ) _{q 7} -CH (CH ₃ ) one (q 6 is an integer from! To 4, q 7 is an integer from 0 to 3), H (CZ ₂ ) _q8 — (CH ₂ ) _q9 — CH (CH ₃ )-(q 8 is an integer from 1 to 4, q 9 is an integer from 0 to 3), (Z CH ₂ ) ₂ — CH— (CH ₂ ) _Ql . — CH (CH ₃ ) ―, (Z ₂ CH) ₂ -CH— (CH ₂ ) _{ql 0} CH (CH ₃ ) one, (CZ ₃ ) ₂ -CH— (CH ₂ ) _{ql 0} -CH (CH ₃ ) One (q10 is an integer of 0 to!).

Among these, linear, cyclic or branched alkyl groups of CiCA, such as —CH (CH ₂ F) ₂ groups, 1 CH ₂ —CF ₃ groups, —CH ₂ —CF ₂ —CF ₂ H groups but good preferred, one CH (CH _₂ F) ₂ group, one _{_{_{CH 2 - CF 2 - CF 2}}} H group is particularly preferred. In the above formula (I), R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a di-alkyl group, a C-di group, an alkyl group or a halogen atom.

Examples of the CiC alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group, and the propyl group and the butyl group may be linear, cyclic or branched. Also C ~. The ₄ Ha port alkyl group, of the hydrogen atoms contained in Ci C ₄ alkyl group from 1 to 9 hydrogen atoms are substituted with halogen atoms (eg if a fluorine atom, a chlorine atom, a bromine atom and an iodine atom) but, for example, - CF ₃ groups, -C ₂ F ₅ group, - C ₂ H ₄ F group one CH ₂ C 1 radical, one CHF ₂ group, - CC 1 ₃ group, - C ₂ H ₃ C 1 ₂ group, - C ₂ H ₃ F ₂ group, - C ₂ H ₂ F ₃ _{_{group, - C 2 H 2 C 1}} 3 group, _C ₃ H ₆ F group one C ₄ H ₈ F group, - CH ₂ B r group, one CH ₂ I group, —C ₃ H ₄ F ₃ group, one C ₄ H ₆ F ₃ group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among them, R ² , R ³ , R ⁴ and R ⁵ are preferably hydrogen atoms. In the above formula (I),! ¾ ⁶ ₁ to ₄ alkyl groups, of which methyl, propyl, isopropyl and ethyl groups are preferred, and especially ethyl Groups are preferred. R ⁷ is a hydrogen atom or C ^. 4 alkyl groups, of which a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable. Specific examples of C〗 ~ C ₄ alkyl group in R ^6, R ⁷ is the same as described above for R ^2.

Further, the above formula (I), X is C] -C ₄ alkyl group, Haroaru kill group, a halogen atom, Ci C alkoxy groups, Ci C Bruno, mouth alkoxy group, C -～ C ₄ alkoxyalkyl group, C " 〜C alkylthio, di-haloalkylthio, C―-C alkylsulfiel, C alkylsulfol, nitro and nitrile.

Here, examples of the CiC alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group, and the propyl group and the butyl group may be linear, cyclic, or branched. Good. Further, the CiC noroalkyl group has a structure in which 1 to 9 hydrogen atoms of the hydrogen atoms contained in the c alkyl group are substituted with halogen atoms (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom). and than, for example, - CF ₃ group, one C ₂ F ₅ group, one C ₂ H ₄ F group one CH ₂ C 1 radical, one CHF ₂ group, one CC 1 ₃ group, one C ₂ H ₃ C 1 ₂ group, -C ₂ H ₃ F ₂ group, _C ₂ H ₂ F ₃ group one C ₂ H ₂ C 1 ₃ group, - C ₃ H ₆ F group, - C ₄ H _S F group one CH ₂ B r group, —CH ₂ I group, —C ₃ H ₄ F ₃ group, one C ₄ H ₆ F ₃ group and the like.

Also, Jee ~. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and the propoxy group and the butoxy group may be any of a straight-chain, cyclic or branched one. . Also,

A lower alkoxy group is a hydrogen atom contained in a C i C alkoxy group in which 1 to 9 hydrogen atoms have been replaced with halogen atoms (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom). For example, one OCF _three , — OC ₂ F _five , — OC ₂ H ₄ F, — OC ₂ H ₄ Cl, — OCHF _two , — OCH ₂ F, — OCCl _three , — OC ₂ H ₃ Cl ₂ , — OC ₂ H ₃ F ₂ , — OCH ₂ Br, — OCH ₂ I, and the like. Further, a c „-c _d alkoxyalkyl group means that one of the hydrogen atoms contained in the alkyl group is a c ₁ -c ₃ alkoxy group (for example, a methoxy group, an ethoxy group, a propyloxy group or an i-propyloxy group) Such as one CH ₂₀ CH ₃ group, —CH ₂ OC ₂ H ₅ group, —CH ₂ OC ₃ H ₇ group, —C (CH ₃ ) ₂ OCH ₃ group, —C ( CH ₃ ) ₂ OC ₂ H ₅ groups, 1 CH ₂ CH ₂ OCH ₃ groups, 1 CH ₂ CH ₂ OC ₂ H ₅ groups, 1 CH ₂ C (CH ₃ ) ₂ 〇CH ₃ groups, 1 CH ₂ CH ₂ CH ₂ OCH _3. etc. Specific examples of the CiC alkylthio group include a methylthio group, an ethylthio group, a propylthio group and a butylthio group, and the propylthio group and the butylthio group are linear, cyclic or cyclic. It may be any of branched ones.

C, C to C, and coalkylthio groups refer to the hydrogen atoms contained in C, C to C, and alkylthio groups in which 1 to 9 hydrogen atoms are halogen atoms (for example, a fluorine atom, a chlorine atom, a bromine atom). Atom and iodine atom), for example, _SCF ₃ groups, —SC ₂ F ₅ groups, 1 SC ₂ IF group, 1 SC ₂ H ₄ C 1 group, — SCHF ₂ groups, 1 S CH ₂ F group, _SCC 1 ₃ _{_{group, - SC 2 H 3 C 1}} 2 group, - SC _₂ H ₃ F ₂ group, one SCH ₂ B r groups, and the like one S CH ₂ I group.

Further, specific examples of the C, to C alkylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfyl group and a butynolesulfinyl group, and in the case of a propylsulfinyl group and a butylsulfinyl group, It may be linear, cyclic or branched, or misaligned.

Specific examples of C. to C <alkylsulfonyl groups include methylsulfonyl, ethylsulfonyl, propylsulfonyl and butylsulfonyl, and propylsulfonyl and butylsulfonyl are straight-chain It may be cyclic or branched.

Among these, X, c to c ₄ lay preferred alkyl group or a halogen atom, a methyl group or a chlorine atom is particularly preferred.

In the above formula (I), p represents the number of substitutions of X, and is an integer of 0, 1 or 2, particularly preferably 1 or 2, and particularly preferably 2.

In the above formula (I), n is an oxygen atom bonded to a sulfur atom of the chiochroman ring. Indicates the number of atoms, and is an integer of 0, 1 or 2. When n is 0, it represents a sulfide, when n is 1, it represents a sulfoxide, and when n is 2, it represents a sulfone. Among them, n == 2, that is, sulfone is preferable.

In the above formula (I), Q is a hydrogen atom or a group -AB.

A case of Q is Kiichi A- B _{is, _S0 2 -, - (CH} 2) k CO- or a CR ⁸ R ⁹ - is. Here, in the formula showing the embodiment of A, k is 0 or an integer of 1 to 3, and R ⁸ and R ⁹ are each independently a hydrogen atom or a C ₄ -C ₄ alkyl group.

When A is one (CH ₂ ) _k — CO—, a specific example is one CO— group (k = 0) and one CH. CO—group (k = l), one (CH ₂ ) ₂ CO— group (k = 2) and — (CH ₂ ) ₃ CO— (k = 3), among which one CO— group (k = 0 ) Or one CH ₂ CO group (k = l) is preferred.

When A is one CR ⁸ R ⁹ —, for example, one CH ₂ — group, one CH (CH ₃ ) one group, one C (CH ₃ ) ₂ — group, one CH (C ₂ H ₅₎ ) —, —C (C ₂ H ₅ ) ₂ —, and the like. Among them, one CH ₂ —, and —CH (CH ₃ ) — are preferable.

The A Among these, one S0 ₂ - group or a CO- group (k = 0) is favored arbitrary.

B where Q is Kiichi A- B is, Ci～C ₁₂ alkyl group, a C ₃ -C ₁₂ cycloalkyl Achill group or groups one P h- Ym.

Specific examples of the case where B is a C i to C, ₂ alkyl group, in addition to the compounds exemplified as C to C ₄ Al kills group above, a pentyl group, a hexyl group, a heptyl group, O corruptible group, Examples include a nonyl group, a decanyl group, a pendecanyl group, and a dodecanyl group. In the case of an alkyl group having 3 or more carbon atoms, the alkyl group may be linear or branched.

Specific examples of the case where B is a C ₃ ~ C _{t 2} cycloalkyl group, for example, cyclopropylcarbamoyl / Les group, Shikurobuchinore group, a cyclopentyl group, Kishinore group cyclohexylene, heptyl group cycloalkyl, Shikurookuchiru group, cyclononyl group, cyclodecyl Groups. When the carbon number of the cycloalkyl group is 4 or more, the cycloalkyl group may have a ring further substituted with an alkyl group. For example, when the carbon number is 4, And a chloropropyl group.

When B is a group P h — Y _m , P h in the formula represents a phenyl group, and Y is a C _t -C ₄ alkyl group, a di-alkoxy group, a C i -C ₄ haloalkyl group. , A nitro group or a halogen atom, and m is 0 or an integer of 1-2. Specific examples of the alkyl group, C ₁ -C ₄ alkoxy group, C ₁ -C ₆ , alkyl group and halogen atom are as already described for R ² in the formula (I). What is m = 0? Is not substituted with 丫, that is, it is an unsubstituted phenyl group. When m is an integer of 1 to 2, Y is substituted at one or two of the 2-, 3-, 4-, 5-, and 6-positions of Ph (phenyl group).

The B Among these, C, -C ₄ alkyl group, Ji ₃ ～〇 ₈ cycloalkyl group or a group one P h- Ym are preferred, Echiru group, n- propyl group, hexyl group, phenyl group (group cycloheteroalkyl in one P h- Ym, m is 0) or p- Toruiru group (group - in Ph- Y _m, Y is 4 one methyl group, m is 1) are particularly preferred.

Among them, Q is preferably a hydrogen atom or a group A-B consisting of the following combination of A and B.

That is, A is — S 0 ₂ — group, and B is C

The alkyl group is a combination of the groups P h —Ym. In this, A is one SO. In particular, a combination in which B is an ethyl group, an n-propyl group or a p-tolyl group (in the group Ph-Ym, Y is a 4-methyl group, and m is 1) is particularly preferable. Also, A gar (CH ₂₎ k- CO- a group, B is 〇 ₃ ～.Rei ₈ cycloalkyl group or a group - P h- Ym combination favored arbitrariness of. In this, A represents one CO— group (one (CH ₂ ) ,, — C 0, k = 0) or one CH ₂ CO— group (one (CH ₂ ) _k —CO—, k = l And B is particularly preferably a phenyl group (wherein m is 0 in the group Ph-Ym, or a combination of cyclohexyl groups).

In the formula (I), a pyrazole derivative wherein Q is a hydrogen atom, that is, a formula (la)

(In the formula, each symbol is as defined in formula (I).)

When the pyrazole derivative is represented by the formula

(lb), the structure represented by the formula (Ic) and the formula (Id). The pyrazole derivative of the present invention also includes all these isomer compounds and mixtures thereof.

(I c) (I d)

(In the formula, each symbol is as defined in formula (I).)

Further, the pyrazole derivative represented by the formula (la) is an acidic substance, and can be easily converted into a salt by treating with various bases. — Included in the phenol derivative.

Here, the base is not particularly limited as long as it is a known base, and examples thereof include organic bases such as amines and anilines, and inorganic bases such as sodium compounds and potassium compounds. Examples of amines include monoalkylamine, dialkylamine, and trialkylamine. Alkyl group in the alkyl amines are usually 〇 to c _4. Examples of anilines include aniline, monoalkylaniline, and dialkylaniline. The alkyl group in the alkylanilines is usually a CiC alkyl group. Examples of sodium compounds include sodium hydroxide and sodium carbonate, and examples of potassium compounds include potassium hydroxide and lithium carbonate.

Further, the virazole derivative represented by the formula (I) has an asymmetric carbon and various isomers, and the birazol derivative of the present invention contains all the isomers and a mixture thereof. Is what you do.

The herbicide of the present invention contains, as an active ingredient, the novel pyrazolyl derivative of the present invention represented by the formula (I) and / or a salt thereof as an active ingredient. It can be mixed with a solid carrier such as mineral fine powder and formulated into wettable powders, emulsions, powders, granules and the like. A surfactant may be added in order to impart emulsifiability, dispersibility, spreadability and the like during formulation.

When the herbicide of the present invention is used as a wettable powder, the pyrazole derivative of the present invention and

Z or its salt is blended at a ratio of 10 to 55% by weight, a solid carrier at 40 to 88% by weight, and a surfactant at a ratio of 2 to 5% by weight. When used in the form of an emulsion, usually, 20 to 50% by weight of the pyrazole derivative and / or its salt of the present invention, 35 to 75% by weight of a solvent and 5 to 15% by weight of a surfactant are used. Mix in proportions. When used in the form of a powder, the pyrazolyl derivative of the present invention and / or a salt thereof is usually 1 to 15 weight. / ₀ , solid carrier 80-97 weight. / ₀ and surfactant 2 to 5% by weight. Further, when used in the form of granules, the virazole derivative of the present invention and / or a salt thereof is 1 to 15% by weight. /. 80-97% by weight of solid carrier and 2-5% by weight of surfactant. /. Mix in the ratio of Here, the solid carrier is usually a fine powder of a mineral substance, for example, oxides such as diatomaceous earth, slaked lime, phosphates such as apatite, sulfates such as gypsum, talc, ferrite, clay, kaolin, and kaolin. Bentonite, acid clay, white carbon, quartz powder, and silicates such as calcium stone powder are used.

The solvent is usually an organic solvent, specifically, an aromatic hydrocarbon such as benzene, toluene, or xylene, a chlorinated hydrocarbon such as o-chlorotoluene, trichloroethane, or trichloroethylene, or cyclohexanol. Ketones such as amyl alcohol, ethylene glycol, etc., isophorone, cyclohexanone, cyclohexanone, cyclohexenyl-cyclohexanone, and ethers such as butinoreseroso / rev, getinol ether, methylethyl ether Esters such as isopropyl acetate, benzyl acetate and methyl phthalate, amides such as dimethylformamide and mixtures thereof are used.

Further, as the surfactant, any of an anionic type, a nonionic type, a cationic type and a zwitterionic type (amino acid, petaine, etc.) can be used. The herbicide of the present invention may contain, if necessary, other herbicidal active ingredients, together with the pyrazole derivative represented by the above general formula (I) and / or a salt thereof as an active ingredient. Examples of such other herbicidal active ingredients include conventionally known herbicides, for example, phenoxy, diphenyl ether, triazine, urea, force bamboo, thiol carbamate, and acid anilide. And pyrazolyl, phosphate, sulfonylurea, and oxadiazonones. These herbicides may be appropriately selected and used according to the herbicidal effect and weed selectivity.

Further, the herbicide of the present invention can be mixed with an insecticide, a bactericide, a plant growth regulator, a luster, etc., if necessary.

The compound of the present invention can be used as a herbicide for field action in any of soil treatment, soil admixture treatment and foliage treatment. The field weeds (Cropland weeds) targeted by the compound of the present invention include, for example, solanaceae weeds, Abutilon theophrasti, and solanaceae weeds represented by, for example, rosewood (Solanum nigrum) and Datura stramonium. Malvaceae weeds, represented by the American spiny deer (Side spinosa), etc., and Malva morning glory (Ipomoea purpurea) Amaranthaceae weeds, Amaranthaceae weeds represented by convolvulaceae weeds such as morning glory (Ipomoea spps.) And convolvulaceae (Calystegia spps.) And Amaranthaceae weeds represented by inambu (Amaranthus lividus) ), Fakkusa (Ambrosia artemisiaefoliaj ^ Helian thus annus), Nozukida megiku (Galinsoga ciliata), Crabs crab (Cirsium arvense), Soiled crab (Senecio vulgaris), Himejon (represented by Eriger on annus) Asteraceae

(Compositae) Brassicaceae represented by weeds, crows (Rorippa indica), wild squirrels (Sinapis arvensis), napsuna (Capsella bursa-pastoris), etc.

(Cruciferae) miscellaneous, Polygonum blumei, Polygonum convolvulus, etc., Polygonaceae weed, Portulaca oleracea (Portulaca oleracea), etc.

(Chenopodium album; Chenopodium ficifolium, Kochia scop aria) and other species (Chenopodiaceae) weeds, and Cary ophyllaceae (Cary ophyllaceae) weeds such as Stellaria media. Veronica persica) and other species such as Scrophulariaceae and communis, and communis (Commelinaceae) weeds and communis (Commelinaceae) and weeds (Lamium amplexicaule and Lamium purpureum, respectively). Weeds, Labiatae weeds, Euphorbia supina, Euphorbia maculata, and other Euphorbiaceae weeds; Galium spurium, Galium sp. Rubia akane)

(Rubiaceae) weeds, broadleaf weeds such as violets (Violaceae) weeds represented by violets (iola arvensis), broadleaf weeds such as leguminous weeds represented by Sesbania exaltata and Cassia obtusifolia

(Broad-leaved weeds), wild sorghum (Sorgham bicolor),

(Panicum dichotomiflorum), Shillongseongkhus (Sorgnam ha epense), Inu Hee (Echinochloa crus-galli), Meshihino (Digitaria adscendens), Cafsum

(Avena fatua), Oshihinoku (Eleusine indica), Enoko mouth gusa (Setaria viridis), Sparrow Note (Alopecurus ae ^ ualis, etc.) weeds) Weeds and Cyperaceous weeds weeds, such as Cyperus rotundus and Cyperus esculentus.

Further, the compound of the present invention can be used as a herbicide for paddy fields in both foliage treatment and soil treatment under flooding. Examples of paddy weeds (Paddy weeds) include Omodaka (Almoda canaliculatum), Omodaka (Sagittaria trifoUa), and Persimmon (Sagittaria pygmaea).

(Alismataceae) Weeds, Cyperus difformis, Cyperus serotinus, scallopus juncoides, black croak, 'Wai (Eleochans kuroguwai li), and other weeds such as Cyperacea (Cyperaceae), inhabitants such as Cyperaceae (in. Scrothulariaceae weeds, and Pondenderiaceae weeds, such as Monochoria vaginalis, weeds

(Potamogeton distinctus), etc. (Potamogetonaceae) weeds, (Rotala indica), etc. (Lythraceae) weeds, and rice grasses (Echinochloa crus-galli), etc. Gramineae) Weeds and the like.

In addition, the compound of the present invention can be applied to the control of various weeds in non-agricultural lands such as athletic fields, open lands, track ends, in addition to agricultural and horticultural fields such as fields, paddy fields and orchards. The novel pyrazole derivative represented by the formula (I) of the present invention can be synthesized by various methods, but is produced by the following method.

(III)

(In the formula, each symbol is as defined in formula (I), and Ha 1 represents a halogen atom.) In the pyrazole derivative of the formula (I), a compound in which Q is a hydrogen atom (a pyrazole derivative of the formula (Ih)) is obtained by combining a carboxylic acid of the formula (Π) with a pyrazole compound of the formula (ΠΙ) , An ester condensation step 1a and a step 1b of rearranging the condensed ester (Ig). In addition, the compound in which Q is a group A-B (a pyrazole derivative of the formula (I.)) is obtained by introducing a group A-B into the hydroxyl group of the pyrazole derivative obtained in the step I. Manufactured by Hereinafter, each step will be described in detail. Step 1—a

A compound of formula (Π) and a compound of formula (ΙΠ) are dehydrated, for example, DC C (N, N-dicyclohexylcarbodiimide), CD I (1,1'-carbonyldiimidazole), The reaction is carried out in an inert solvent, preferably in the presence of DDC, such as EDC (1- (3-dimethylaminopropyl) -13-ethylcarbodiimide), to produce a pyrazole ester.

In this reaction, the compound of formula (m) is 1.o ~

It is preferable to use three times the molar equivalent. The dehydrating agent is preferably used in an amount of 1.0 to 1.5 times the molar equivalent of the compound of the formula (Π). The inert solvent is not particularly limited as long as it is inert to the reaction. Secondary or tertiary alcohols such as t-butyl alcohol, t-amyl alcohol, 2-propanol, dichloromethane, 1,2-dichloroethane, Preference is given to solvents such as chlorophonolem and benzene benzene, logen solvents and ether solvents such as diethyl ether, tetrahydrofuran, dioxane and 1,2′-dimethoxetane. The reaction temperature is usually from 120 ° C to the boiling point of the solvent, preferably around room temperature (10 ° C to 30 ° C).

Alternatively, a compound of the formula (II) is reacted with a halogenating agent such as thionyl chloride, phosphorus oxychloride, phosphorus tribromide or the like in an inert solvent to convert the compound into the corresponding acid halide, The compound of m) may be reacted with an inert solvent in the presence of a base to produce a pyrazole ester (Ig).

In this reaction, it is preferable to use the halogenating agent in a molar equivalent of at least 1.0 times the amount of the compound of the formula (II). Inert solvents include those inert to the reaction. There is no particular limitation as long as it is not limited. For example, halogen-based solvents such as dichloromethane, 1,2-dichloroethane, carbon tetrachloride, and chlorobenzene, and aromatic hydrocarbons such as benzene, toluene, and xylene are preferable.

If the halogenating agent to be used is a liquid such as thionyl chloride, an excess amount of the halogenating agent can be used as a solvent. The reaction temperature is from room temperature to the boiling point of the solvent, preferably 50 to 100 ° C.

The compound of the formula (II) is preferably used in an amount of 1.0 to 3.0 times molar equivalent to the acid halide. The base is not particularly limited, but it is preferable to use an organic base such as triethylamine, pyridine and the like, and an inorganic base such as sodium carbonate and potassium carbonate in an amount of 1.0 to 3.0 times molar equivalent to the acid halide. The inert solvent used at this time is not particularly limited as long as it is inert to the reaction, but halogen solvents such as dichloromethane, 1,2-dichloroethane, chloroform and benzene are preferred. The reaction temperature is from −20 ° C. to the boiling point of the solvent, preferably from −20 to 20 ° C. Step 1 b

A pyrazole derivative represented by the formula (Ih) is produced by reacting a pyrazole ester represented by the formula (Ig) in an inert solvent in the presence of a base. At this time, by coexisting a so-called “cyanide source” in the reaction system, the reaction can proceed under milder conditions. The “cyanide source” is a compound capable of generating cyan ions in the reaction system, and includes, for example, an organic cyanohydrin compound such as acetone cyanohydrin. Alternatively, an organic solvent can be prepared by using an inorganic cyanide compound such as sodium cyanate or potassium cyanate together with a metal ion inclusion phase transfer catalyst such as 18-crown-16 and benzo-18-crown-6. Cyan ions can be generated therein. When a "cyanide source" is used, it is preferably used in a molar equivalent of 0.01 to 0.2 times the pyrazole ester.

The base used in this reaction is not particularly limited.For example, an organic base such as triethylamine or pyridine, or an inorganic base such as sodium carbonate or potassium carbonate is used in an amount of 1.0 to 3.0 times the molar amount of the pyrazole ester. Preferred to use equivalent Les ,. The inert solvent is not particularly limited as long as it is inert to the reaction, but dioxanacetonitrile is preferred. The reaction temperature is preferably around room temperature when a “cyanide source” is allowed to coexist, and is preferably 50 to 130 ° C. when not coexisting. As a reaction condition, when a “cyanide source” is used, triethylamine is used as a base, and the reaction is performed in acetonitrile at around room temperature (10 to 25 ° C.).

When a “cyanide source” is not used, it is preferable to carry out the reaction at a boiling point of a solvent in dioxane (101 ° C.) using potassium carbonate as a base. Step 1 a b

By selecting suitable reaction reagents and conditions in step 1a and step 1b in the above reaction scheme, the isolation of the formula (Ig) in one reaction can be carried out without isolating the intermediate benzoyl ester (Ig). The pyrazole derivative of Ih) can also be produced. For example, a case where DC C is used as a dehydrating agent in step 1a, and a compound of the formula (ΠΙ) and a compound of the formula (Π) are reacted in an inert solvent in the presence of a base. In this reaction, the compound of the formula (m) is 1.o to 3.

The molar ratio of DCC is preferably 1.0 to 1.5 times that of the compound of the formula (II). As the base, potassium carbonate, sodium carbonate and the like are preferred, and the base is usually used in a molar amount of 0.5 to 2.0 times that of the compound of the formula (Π). The inert solvent is preferably t-butyl alcohol / recohol, t-amino alcohol, i-propyl alcohol, and the reaction temperature is preferably from room temperature to the boiling point of the solvent, and is 50 to 100 °. C is particularly preferred.

Further, the carboxylic acid derivative represented by the formula (Π) can be synthesized by the method described in International Publication No. WOZ966NO3507. Hereinafter, the present invention will be described specifically with reference to Production Reference Examples, Production Examples, and Herbicide Examples, but the invention is not limited thereto.

(Production Reference Example) Synthesis of Carboxylic Acid Derivative of Formula (II)

(1) Etherification process

6-Ethoxy power / Repo-ninore 4-Hydroxy-I-5,8-Dimethinoretiochroman 3. To 100 g (10.4 mmo 1), 9 ml of 1,3-dichloro-1-propanol and 1 drop of concentrated sulfuric acid were added, and the mixture was reacted under heating and reflux for 10 minutes. After cooling, the reaction mixture was poured into an ice bath and extracted with ethyl acetate. The obtained organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified by column chromatography (silica gel; hexane: ethyl acetate = 20: 1 to 5: 1). Thus, 2.2 g (61% yield) of 4- (1,3-difluoro-2-propoxy) -16-ethoxycarbonyl-15,8-dimethylthiochroman was obtained.

(2) Oxidation process

Acetic acid was added to 2.2 g (6.39 mmo 1) of the 4- (1,3-difluoro-2-propoxy) -16-ethoxycarbonyl-2,8-dimethylthiochroman obtained in the above (1). 2 ml and 2.17 g (19.2 mmo 1) of 30% aqueous hydrogen peroxide as an oxidizing agent were added, and the mixture was reacted at 80 ⁼ C for 1 hour. After cooling, excess hydrogen peroxide was decomposed by adding a 2% aqueous sodium bisulfite solution to the reaction mixture, and extracted with ethyl acetate. The obtained organic layer was washed with a saturated saline solution and dried over anhydrous sodium sulfate to obtain 4- (1,3-difluoro-2-propoxy) -16-ethoxycarbonyl-1,5,8-dimethylthiochroman-1,1. 2.4 g (100% yield) of a crude product of 1-dioxide was obtained.

(3) Hydrolysis step

2.4 g of the crude 4- (1,3-difluoro-2-propoxy) -1,6-ethoxycarbonyl-5,8-dimethylthiochroman-1,1-dioxide obtained in (2) above (6. 0.47 g of potassium hydroxide, 8 ml of ethanol and 2.7 ml of water were added to 39 mm o 1), and the mixture was stirred at room temperature for 3 days. After completion of the reaction, the solvent was distilled off, 5 ml of water was added, and 5% hydrochloric acid was added to adjust the pH to 1. Subsequently, the mixture was extracted with ethyl acetate, and the organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 4- (1,3-difluoro-2-propoxy) -16-carboxy-1. 1.84 g (83% yield) of methylthiochroman-1,1-dioxide was obtained. Other carboxylic acids (II) were synthesized by the same reaction as in Production Reference Examples (1) to (3). Table 1 shows the structure and physical properties of the obtained carboxylic acid.

(Production Example 1)

4- (1,3-difluoro-2-propoxy) -1,5,8-dimethyl-1-6— (1-ethyl / re-5-hydroxypyrazole-4-inole) carbylthiochroman-1,1-dioxide (compound No. 1)

4- (1,3-difluoro-2-propoxy) -1-6-carboxy-5,8-dimethylthiochroman-1,1-dioxide (corresponding to the carboxylic acid of the formula (Π)) 1.84 g (5.28 0.5 ml of thionyl chloride (6.886 mmo 1) and 1 drop of dimethylformamide were added to a solution of 10 ml of dichloroethane in 10 ml of mmo 1), and the mixture was stirred at 50 ° C. for 1 hour. After distilling off the solvent and excess thionyl chloride under reduced pressure, dissolve it in 4.5 ml of acetonitrile solution, and add 1-ethyl virazole (corresponding to the virazole of the formula (ΠΙ)). g (5.80 ml) and 0.81 ml of triethylamine (5.80 mmo 1) were added, and the mixture was stirred at room temperature for 1 hour. To this mixture, 0.81 ml of triethylamine and 3 drops of acetone cyanohydrin were added, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off under reduced pressure, and the residue was dissolved with a 3% sodium carbonate solution, and washed with ethyl acetate. The resulting aqueous layer was acidified by adding 5% hydrochloric acid, and the resulting oil was extracted with ethyl acetate. Ethyl acetate was distilled off under reduced pressure to obtain 1.56 g (yield 67%) of the title compound.

(Production Examples 2 to 4)

In place of the 4- (1,3-difluoro-2-propoxy) -1-6-carboxy-5,8-dimethylthiochroman-1,1-dioxide corresponding to the carboxylic acid (Π) as the starting material in Production Example 1, Table 1 Compounds Nos. 2 to 4 corresponding to the formula (lh) were obtained in the same manner as in Production Example 1 except that the starting material shown in (1) was used (corresponding to the carboxylic acid of the formula (Π)). . Table 2 shows the starting materials, the structures and yields of the obtained compounds, and Table 4 shows the physical properties of the obtained compounds.

(Production Example 5)

4- (1,3-difluoro-2-propoxy) -1,5,8-dimethyl-6- (1-ethyl-5-n-prononsulfonyloxypyrazol-1-yl 41-yl) carbonyl Synthesis of Thiochroman-1, 1-dioxide (Compound No. 5)

4- (1,3-Difluoro-2-propoxy) -5,8-dimethyl-6- (1-ethynole-5-hydroxypyrazol-1-ru-4-yl) carbonyl thiochroman-1 obtained in Production Example 1 0.63 g (1.6 mmol) of 1,1-dioxide (corresponding to the pyrazole derivative of the formula (Ih)) was dissolved in 5 ml of dichloroethane. 0.40 g (2.93 mmo 1) of potassium carbonate was dissolved in 5 ml of water and added. To this mixed solution, 0.25 g (1.75 mmol) of n-propanesulfonyl chloride (corresponding to the compound of the formula (IV)) was added as a reaction reagent, and benzyltriethylammonium chloride as a phase transfer catalyst was further added. 0.05 g (0.2 mmo 1) of muchloride was added and reacted at room temperature for 1 hour. After completion of the reaction, water and dichloromethane were added to carry out liquid separation. The resulting organic layer was dried over anhydrous sodium sulfate, concentrated, and purified by flash column chromatography (silica gel; hexane: ethyl acetate = 1: 1) to give 0.53 g of the title compound (yield 85%).

(Production Example 6)

In Production Example 6, 4- (1,3-difluoro-2-propoxy) -5,8-dimethinole_6— (1-ethynole-5-hydroxypyrazo-one 4-isle) canoleboninolethiochroman-1,1- 4- (2,2,3,3-tetrafluoro-1-propoxy) -1,8-dimethyl-1-6- (1-ethyl-5-hydroxypyrazole-1-4-yl) carboxylthiochromane instead of dioxide Except that 0.63 g (1.6 mmo 1) of 1,1-dioxide was used, the same operation as in Production Example 5 was carried out to obtain a compound No. 6 corresponding to the formula (I) (yield 43%). I got

Table 3 shows the starting materials, structures and yields of the obtained compounds, and Table 4 shows physical properties. Table 2

Table 3

Table 4 Compounds (p

Dimension O DC 13

Dimension * -'MR p m), C

'· I R (c m— Melting point (° c) t ίΙ

IN

Internal standard: L---J

Fu no fu no

1 1.46 O Q

t (3,,-/. driz 7J fish shell size oH

2.44 (3 boH, s 丄 b0U,

3.1-3.4 (1 QO

mj 丄 1 丄

2H, m ヽ) 5.0—5.1 (Hi, m,)

7.33 (2H, s)

2 1.46 (3H, t, J = 17.4Hz)

Sword Nose tool

2.37 (3H, s) 2.5—2.9 (2H, m) lb 154U

2.78 (3H, s) 1300, lldU

1H, m) 3.6—4.2 (3H, m) 1100

3H, m)

(tt, J = 5 and 54Hz)

7.32 (1H, s) 7.36 (1H, s)

3 1.46 (3H, t) 2.5—2.9 (H, m) 3450, 2990 Cuffs ®

1H, m) 3.8—4.5 (6H, m) 1640, 1590

ヽ

2H, m) 5.1—5.3 (1H, m) 153 r5 f, 1215

7.34 (IH, s) 7.64 (IH, a) ヽ) 116U, 1135

8.00 (1H ヽ

, A)

4 1.46 (3H, t) 2.6—2.9 (2H, m) 95U

3.1-3.4 IH, m) 3.7-4.3 (/ 5 "H, m) 1530, 1290

5.04 (IH, m) 7.33 (IH, s) 1160, 1135

7.65 (1H, a) 8.01 (1H, a) 丄 U U

"

5 1.17 (3H, t, J = 7.4Hz) 丄 bb i J ^^ m.

1.52 (3H, -f,

t, J = 7.4Hz) 1540, ldoU

1.9-2.3, 2H, m,) .όΊ dH, s) H U

2.5-2.8 ―, / our 1

3.1—3.4 f,

, 丄, mj d.0—4.4 oH, mj

rl, m .y 0. 丄丄丄 1, mj

7.25 (ΙΗ '

1.17 (3H, t, J— 7.4rlz 丄 bbU sword Nosuma Λ "W

1.52 (3H, Ariz)

1.9-2.3 1 丄 QOn, 1 丄丄 1 ¾n

2.30 (3H, s) 1130, 1100

2.5-2.9 (2H, m) 2.77 (3H, s)

(IH, m) 3.5-4.0 is H, m)

4.22 (2H, q, J = 7.4Hz)

4.7-4.9 (1H, m)

5.88 (IH, tt, J = 4.4 and 54Hz)

7.28 (IH s)

7.50 (IH s) (Example of herbicide)

(1) Herbicide adjustment

Talc (trade name: G-Cryte, manufactured by G-Cryte Industries, Ltd.) 97 parts by weight, alkyl aryl sulfonate as a surfactant (trade name: Neoperex, Kao Atlas Co., Ltd.) 1.5 parts by weight and nonionic and anion type surfactants (trade name: Solpol 800A, manufactured by Toho Chemical Industry Co., Ltd.) An agent carrier was obtained.

90 parts by weight of this carrier for wettable powders and 10 parts by weight of the compound of the present invention obtained in the above Production Example were uniformly ground and mixed to obtain respective herbicides.

As a comparative example, a herbicide using the compound (B) was prepared by the same method.

(2) Criteria for herbicidal effect and crop damage

Based on the biological test results shown below,

Untreated ratio of residual grass weight = (Residual weight of treated area / remaining weight of untreated area) X "100" I asked. Herbicidal effect No treatment ratio of residual grass [%]

0 8 1 to 1 0 0

6 1 ~ 8 0

2 4 1 to 6 0

3 2 1 ~ 4 0

4 1 ~ 2 0

5 0 Crop injury Residue weight untreated ratio [%]

1 0 0

Sat 9 5 ~ 9 9

+ 90-94

++ 80 to 8 9

+++ 0-7 9

(3) Biological test (field foliage treatment test)

Weed seeds of ibis, ragweed, and ginkgo biloba are sown in a 1Z500 w arener pot filled with field soil, and after covering the soil, they are grown in a greenhouse.These plants have 3 to 4 leaves.) A predetermined amount of the herbicide obtained in the above (1) was suspended in water, and the solution was uniformly spray-sprayed on the foliage at a liquid volume of 20 () 0 liters Z hectares. Thereafter, the plants were grown in a greenhouse, and on the 30th day after the treatment, the herbicidal effect and the phytotoxicity to the crops were determined according to the criteria of (2). Table 5 shows the results.

Table 5 Compounds Herbicidal effect Crop damage

N o. G Z h a Ichibi Ragweed Enokorogusa Tumokoshi

1 1 0 0 5 5 5 ―

2 1 0 0 4 5 5 ―

3 1 0 0 4 5 5 ―

4 1 0 0 4 5 5

5 1 0 0 5 5 5

6 1 0 0 5 5 5

A 1 0 0 2 2 1

From the results in Table 5, it was confirmed that the herbicide of the present invention does not cause harm to corn and can selectively control important field weeds at an extremely low dose. In addition, the effect is superior to the compound (A) described in International Publication WO966 / 31507.

Claims

Scope of word blue

1. Formula (I)

{Wherein, R ¹ is a C, to C ₆ haloalkyl group having two or more halogen atoms; R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, C, to C ₄ An alkyl group, 〇 [-〇, an alkyl group or a halogen atom;

R ⁶ is a C, -C ₄ alkyl group;

R ⁷ is a hydrogen atom or a C, -C ₄ alkyl group;

X is, Ci～C ₄ alkyl group, (^ - (^ Nono Roarukiru group, a halogen atom, C _l -C ₄ 7 alkoxy group, _Ci to c ₄ c port alkoxy group, C ₂ -C ₄ alkoxyalkyl group, Ci ~

A C ₄ alkylthio group, a C ₁ -C ₄ haloalkylthio group, a C, -C ₄ alkylsulfuryl group, a CiC alkylsulfonyl group, a nitro group or a nitrile group; p is 0, 1 or 2 Yes;

Q is a hydrogen atom—or one A—B;

Wherein A is one S〇 ₂ —, one (CH ₂ ) _k one CO— or one CR ⁸ R ⁹ —

(Where k is an integer of 0 to 3,

R ⁸ and R ^9, a is) B are each independently hydrogen atom or C ^ C alkyl group, is ～〇 ₁₂ alkyl group, C ₃ ~ C ₁₂ which may phenyl group substituted with a cycloalkyl group or Ym -

(Wherein, Y is an alkyl group, C, -C ₄ alkoxy groups,. ₁ ~ Ji ₄ Ha port al Kill group, a nitro group or a halogen atom,

m is an integer from 0 to 2)

n is 0, 1 or 2} A virazole derivative represented by the formula:

2. The pyrazole derivative according to claim 1, wherein R ¹ is —CH (CH ₂ F) ₂ , —CH ₂ CF ₃ , or one CH ₂ CF ₂ CF ₂ H.

3. R ¹ is —CH (CH ₂ F) ₂ , —CH ₂ CF ₃ , —CH ₂ CF ₂ CF ₂ H, and R ² , RR ⁴ and R ⁵ are hydrogen atoms;

R ⁶ is an alkyl group

R ⁷ is a hydrogen atom or a Ci-C ₄ alkyl group;

X is an alkyl group or a halogen atom,

Mosquito 1 or 2,

Q is a hydrogen atom or — A— B,

A is — S〇 ₂ — and

B, J!じ is an alkyl group,

2. The pyrazolyl derivative according to claim 1, wherein n is 0, 1 or 2.

4. The benzoyl derivative is 4- (1,3-difluoro-2-propoxy) -1,5,8-dimethyl-16- (1-ethyl-15-hydroxypyrazole-14-yl) carbonyl 2. The pyrazole derivative according to claim 1, which is luthiochroman-1,1-dioxide.

5. The pyrazole derivative is 4- (2,2,3,3-tetrafluoro-1-propoxy) -1,5,8-dimethyl-6- (1-ethyl-1-5-hydroxypyrazol-1-4- 2. The pyrazole derivative according to claim 1, wherein the pyrazole derivative is carbonylthiochroman-1,1-dioxide.

6. The virazole derivative is 4- (1,3-difluoro-2-propoxy) — 5 1-6 1- (1-Echinol-5-hydroxypyrazonol-1 4-inole) The pyrazolyl derivative according to claim 1, which is luthiochroman 1,1-dioxide.

7. The pyrazole derivative is 4- (2,2,2-trifluoroethoxy) -1-5-chloro-6- (1-ethynole-5-hydroxypyrazonole-1-4-inole) canoleboninole chiochroman 2. The pyrazole derivative according to claim 1, which is 1,1-dioxide.

8. The pyrazole derivative is 4- (1,3-difluoro-2-propoxy) -1,5,8-dimethyl-16- (1-ethyl-1-5-n-propanesulfonyloxypyrazol 4-yl) 3. The pyrazole derivative according to claim 1, which is carboxythiochroman-1,1-dioxide.

9. The villazole derivative is 4- (2,2,3,3-tetrafluoro-1-propoxy) -1,5,8-dimethinole-6- (1-ethynole_5—n-prono ヽ⁰ The pyrazolyl derivative according to claim 1, which is a carboxythiochroman 1,1-dioxide.

10. A herbicide comprising the pyrazol derivative according to any one of claims 1 to 10 as an active ingredient.