JPH04234875A - Substituted benzotriazole derivative, process for producing same and herbicidal composition containing same - Google Patents

Abstract

PURPOSE: To provide a new substituted benzotriazole derivative useful as selective herbicide for such as rice plant, wheat, soy bean, owing to weeding activity for various kinds of weed and selectivity to control plant of one seed.

CONSTITUTION: The objective compound of formula I, for example, ethyl- DL-2-[6-(1-methyl-5-trifluoromethyl-1-H-pyrazol-3-yloxy)benzotriazol-1- yl]propionate, is obtained by allowing the compound of formula II to react with the compound of formula III (Z is eliminative group) in the presence of base such as sodium hydride, preferably at 25-30°C in the organic solvent such as THF. In formula I, a dotted line shows double bonds arrayed so as to constitute condensated hetero aromatic ring series; Py is optionally substituted pyrazole ring; W is O, NR¹ (R¹ is H, lower alkyl); X is CH=CH, COCH₂, etc.; R², R³ are each H, alkyl, etc.; and R⁴ is CN, CSNH₂, etc.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to novel substituted benzotriazole derivatives, processes for their preparation, their use as herbicides and herbicidal compositions containing them.

0002

BACKGROUND OF THE INVENTION European Patent No. 178,708A describes certain benzoheterocyclic phenyl ether derivatives having herbicidal activity.

0003

[Contents of the invention] According to the present invention, formula (I):

[Image Omitted] (The dotted line in the formula indicates the presence of two double bonds arranged to constitute a fused heteroaromatic ring system; Py represents one pyrazole ring which may have a substituent. W is O or NR1 (R1 is a hydrogen atom or lower alkyl); X is (CH2)n, CH=CH, CH(OR5)
CH2, COCH2 (n is 0, 1 or 2); R2
or R3 is a hydrogen atom, alkyl, alkenyl or alkynyl which may have a substituent, halogen, NR6R7
or R2 and R3 together with the carbon to which they are attached form an optionally substituted alkenyl or cycloalkyl group; R4 is CO2R8
, CN, COR8, CH2OR8, CH(OH)R8,
CH(OR8)R9, CSNH2, COSR8, CSO
R8, CONHSO2R8, CONR10R11, CO
NHNR10R11, CONHN+R10R11R12
R14-, CO2-R15+ or COON=CR10R
11; R15+ is an agriculturally acceptable cation, and R14- is an agriculturally acceptable anion. R5, R8 and R9 are groups independently selected from a hydrogen atom, an alkyl, aryl, alkenyl or alkynyl group which may have a substituent; R6, R7, R10,
R11 and R12 are groups independently selected from a hydrogen atom or an alkyl, alkenyl, aryl, or alkynyl group that may have a substituent; or R6, R7, R1
Any two of R11 and R12 form a cycloalkyl or heterocycle together with the atoms to which they are bonded.

The term "alkyl" as used herein means a straight or branched chain containing up to 10 carbon atoms, preferably 1 to 6 carbon atoms. The terms "alkenyl" and "alkynyl" mean unsaturated straight or branched chains having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms. The term "cycloalkyl" means a ring containing 3 to 9 carbon atoms, preferably 3 to 6 carbon atoms. The term "alkoxy" means a straight or branched chain containing up to 10 carbon atoms, preferably 1 to 6 carbon atoms. "Used for alkyl, alkenyl or alkynyl groups"
The term "lower" refers to groups containing up to 3 carbon atoms.

"Haloalkyl" and "haloalkoxy"
The term refers to an alkyl group or an alkoxy group substituted by at least one halogen such as fluorine, chlorine or bromine, respectively. A particular haloalkyl group is trifluoromethyl. The term "heterocycle" is 1
It means a ring having up to 0 atoms, preferably up to 6 atoms, of which 3 are atoms selected from oxygen, nitrogen or sulfur. The term "halogen" means fluorine, chlorine, bromine or iodine.

Suitable substituents that the Py group may have include halogen (eg fluorine, chlorine, bromine or iodine);
a group Rx (Rx is the group defined previously for R8);
nitro; haloalkoxy (e.g. OCF3); group S
(O) up to 3 groups selected from mRy (m is 0, 1 or 2 and Ry is a group as previously defined for R8); or Rz (Rz is a group as previously defined for R4); can be mentioned.

A suitable pyrazole ring system Py which may have substituents has the formula (i)

(In the above formula, R16 is halogen, CN, haloalkyl, alkyl which may have a substituent, S(O)m
Ry (m and Ry are as defined above); R
17 is a hydrogen atom, halogen, CN, alkyl, haloalkyl, a group S(O)mRy (m and Ry are as defined above), nitro or the above group Rz, and R1
8 is alkyl, alkenyl or alkynyl which may have a substituent. Preferred R16 is haloalkyl, especially CF3. R17
is preferably a hydrogen atom, halogen, CN, alkyl, haloalkyl or nitro. In particular, R17 is a hydrogen atom,
Halogen, especially chlorine or methyl. R18 is preferably C1-6 alkyl, especially methyl.

R5, R6, R7, R as aryl group
8, R9, R10, R11, R12 and R13 may have suitable substituents such as halogen (fluorine, chlorine, bromine or iodine), lower alkyl, haloalkyl (e.g. CF
3), haloalkoxy (e.g. OCF3), nitro,
cyano, lower alkoxy (e.g. methoxy) or S(
O) qRW (q is 0, 1 or 2, RW is up to 5, preferably up to 3 groups selected from alkyl (eg thiomethyl, sulfinylmethyl and sulfonylmethyl groups).

R2, R3, R5, R6, R7, R8, R9, R1 as alkyl, alkenyl, alkynyl groups
Examples of substituents that R11 and R12 may have include halogen such as fluorine, chlorine or bromine; nitro; nitrile; aryl such as phenyl; CO2R19, NHC
OR19 or NHCH2CO2R19 (R19 is a hydrogen atom, C1-6 alkyl or an agriculturally acceptable cation); C1-6 alkoxy; oxo; S(O)qRW
(q and RW are as defined above; for example, thiomethyl, sulfinylmethyl and sulfonylmethyl), amino; mono- or di-C1-6 alkylamino;
CONR20R21 (R20 and R21 are each a hydrogen atom, C1-6 alkyl, C2-6 alkenyl or C2
-6 alkynyl, or R20 and R21 combine with each other to form a 7-membered ring, of which 3 members are selected from oxygen, nitrogen or sulfur). The following groups are mentioned. One example of a heterocyclic substituent is tetrahydrofuranyl.

Agriculturally acceptable cation R15+ or R
Examples of 19 include sodium, potassium or calcium ions, such as those of the formula S(O)fR10R11R12(f
is 0 or 1) sulfonium or sulfoxinium ion or formula N+R10R11R12R13 (R10, R1
1 and R12 are as defined above, and R13 is R10
Ammonium or tertiary ammonium ion (which is another group defined for ) is mentioned. Suitable substituents for alkyl, alkenyl and alkynyl groups in these cations include hydroxyl and phenyl. R10
, R11, R12 and R13 are alkyl which may have a substituent, it is suitable that these groups have 1 to 4 carbon atoms.

R10, R11, R12 in the above cation
Specific examples of and R13 are hydrogen, ethyl, isopropyl, 2-hydroxyethyl and benzyl. Examples of agriculturally acceptable anions R14- include halogens such as iodine. Suitable halo groups R2 and R3 include fluorine, chlorine or bromine. R6, R7, R1
Suitable heterocycles composed of two of 0, R11 and R12 and the atoms to which they are bonded include pyrrolidine, piperidine and morpholine. Preferred R2 is a hydrogen atom. Preferred R3 is a hydrogen atom or C1-3
Alkyl, especially methyl. Preferable R4 is CO2R
8 or CO2-R15+. A preferred example of R8 is C
1-6 alkyl, especially ethyl. Preferably, W is an oxygen atom. Preferable X is (CH2)n (n is 0
or 1, especially 0).

Formula (1) above includes tautomeric forms of the depicted structure, as well as physically distinct variations that can occur from the compound, such as various ways of arranging the molecules in a crystal lattice. or deformations resulting from the inability of one part of the molecule to freely rotate relative to the other, or deformations resulting from geometric isomerism, or from intramolecular or extramolecular hydrogen bonding. It is also intended to include modifications or otherwise occurring variations.

Some of the compounds of the invention can exist in enantiomeric forms. The invention includes both individual enantiomers and mixtures of the two enantiomers in any ratio. Specific examples of compounds of the invention are listed in Tables 1, 2 and 3 below.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

The compound of formula (I) is of formula (II):

[Chem.11
] (wherein Py and W are as defined for the compound of formula (I)) and a compound of formula (III):

embedded image (wherein X, R2, R3 and R4 are as defined for the compound of formula (I), and Z is a leaving group) optionally in the presence of a base. It can be prepared by reacting.

Suitable leaving groups Z include halogens such as fluorine, chlorine or bromine, and methanesulfonate and p-
Sulfonates such as toluenesulfonate are mentioned. Suitable bases for use in the reaction include bases such as sodium hydride and alkali metal carbonates and hydroxides or alkoxides. The reaction is dimethylformamide, dimethylsulfoxide, acetonitrile,
Preferably it is carried out in an organic solvent such as tetrahydrofuran, lower alkanol or lower alkyl ketone. It is suitable to use mild temperatures, for example temperatures between 20<0>C and 90<0>C. Conveniently, the reaction is carried out at 25°C to 30°C.

The compound of formula (II) is of formula (IV):

[Chemical 1
(wherein Py and W are as defined for the compound of formula (I), provided that W is not NH) in a suitable solvent such as, for example, aqueous acetic acid or aqueous hydrochloric acid. , for example, Campbell et al. ，
It can be prepared by diazotization with nitrous acid according to J Chem Soc, 1969, 742. The compound of formula (IV) is of formula (V):

It is prepared by reduction of the corresponding nitro compound in which Py and W are as defined for the compound of formula (I). A wide range of reducing agents can be used and can be selected from the chemical literature by one skilled in the art. The reduction reaction may be carried out using, for example, sodium dithionite, tin and hydrochloric acid, iron and hydrochloric acid, or hydrogen or a palladium on activated carbon catalyst with any suitable hydrogen donor such as sodium borohydride. I can do it. This reaction can be carried out in an organic solvent such as a lower alkyl alcohol, optionally mixed with water, at a temperature of 20°C to 90°C.

The compound of formula (V) is of formula (VI):

[Chem.15
] (wherein Ha1 is fluorine, chlorine, bromine or iodine) and a compound of formula (VII):

It can be prepared by reaction with a compound of (Py and W are as defined for the compound of formula (I)). This reaction is carried out using a suitable base such as sodium hydride, an alkali metal carbonate, and a hydroxide or alkoxide. This reaction is preferably carried out in an organic solvent such as dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, lower alkanols or ketones. Mild temperature, e.g. 15°C to 9°C
A temperature of 0°C is suitably used.

Another method of preparing compounds of formula (IV) is shown in the following formula, where R22 is lower alkyl, R23 is halogen, such as a fluorine atom, and Py is as defined for compounds of formula (I). ):

[Chemical formula 17]

The compounds of formulas (III), (VI) and (VII) are known compounds, or they can be prepared from known compounds by known methods. These reactions will give rise to a mixture of three isomers in which the group CR2R3XR4 is attached to the benzotriazole ring in its 1, 2 or 3 position. If appropriate, these isomers can be separated by conventional techniques, such as flash chromatography.

Another method for the preparation of compounds of formula (I) which will yield only one of the isomers in which the group CR2R3XR4 is attached to the 1 position of the benzotriazole ring is the formula (XIII)
:

[Chemical formula 18] (Py, W, X, R2, R3, R4 in the formula, W is NH
as defined for the compound of formula (I), except that it is not.

The compound of formula (XIII) can be prepared using the method shown in the following formula (in which R24
and R25 are each selected from halogen, Py, X, R1
, R2, R3 are as defined for compounds of formula (I); W is as defined for compounds of formula (I), with the proviso that W is not NH).

embedded image Suitable halide groups R24 and R25 include chlorine and fluorine.

Certain compounds of formula (XIII) are new and they constitute another aspect of the invention. These compounds have the formula (XIIIA):

embedded image wherein R2, R3 and X are as defined for the compound of formula (I), and R27 is R4 as defined for the compound of formula (I). These compounds can be prepared as described above for the preparation of compounds of formula (XIII).

Reduction of the compound of formula (XIV) can be carried out using a wide range of reducing agents selected from the chemical literature known to those skilled in the art. Reduction can be carried out using, for example, sodium dithionite or tin and hydrochloric acid, iron and hydrochloric acid or hydrogen or a palladium on activated carbon catalyst with any suitable hydrogen donor such as sodium borohydride. The reaction may be carried out in an organic solvent such as a lower alkyl alcohol, optionally mixed with water, at a suitable temperature between 20°C and 90°C.
The reaction with the compound can be carried out using a suitable base. Suitable bases for this reaction include alkali metal hydrides, carbonates and hydroxides or alkoxides. Preferably, the reaction is carried out in an organic solvent such as dimethylformamide, dimethylsulfoxide, lower alkanol or lower ketone. Mild temperature, e.g. 20℃~
A temperature of 90°C is suitably used. The reaction is carried out at 25°C to 30°C.
It is convenient to carry out at ℃.

The compound of formula (XV) is a dihalonitro compound (XVI) and the formula (III):

embedded image wherein R2, R3, R4 and X are as defined for the compound of formula (I). This reaction is carried out in the presence of a base if necessary. Suitable bases include tertiary amines, organic bases such as triethylamine, pyridine, dimethylaminopyridine, and alkali metal carbonates and alkoxides. This reaction is preferably carried out in an organic solvent such as dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, or lower ketone. Mild temperature, e.g. 20℃~9
A temperature of 0°C is suitably used. Reaction at 25℃~30℃
It is convenient to do so.

The compounds of formula (XVI) are known compounds, or these compounds can be prepared from known compounds by Crow
ther et al (JSC, 1949, 126
0-71); Van Dusen and Sc
hultz (J. Org. Chem. 1956, 21,
1326-9) and Fisher et al (J
．． Org. Chem, 1070, 35, 2240-2)
It can be prepared by the known method described in . The compound of formula (XIV) is of formula (XVII):

A compound of formula (XVIII) (wherein Py and W are as defined for the compound of formula (XIII)):

from a compound of the formula (wherein R2, R3, R4 and X are as defined for the compound of formula (I)), an organic It can be prepared by reacting in a solvent at a mild temperature, for example 0°C to 90°C, in the presence of a base. Suitable bases include tertiary amines, organic bases such as triethylamine, pyridine, dimethylaminopyridine, and alkali metal carbonates and alkoxides.

The compounds of formula (XII) are new and therefore constitute another subject of the invention. These compounds have herbicidal activity in their own right. Formula (X
The compound of formula (VII) is prepared by combining the compound of formula (VII) and 3,4-dinitrofluorobenzene with dimethylformamide,
It can be prepared by reaction in an organic solvent such as dimethyl sulfoxide, acetonitrile, tetrahydrofuran or a lower alkyl ketone at a mild temperature, e.g. 20 DEG C. to 90 DEG C., in the presence of a suitable base. Suitable bases for this reaction include alkali metal hydrides, carbonates, hydroxides or alkoxides.

The compound of formula (XVIII) is a known compound or can be prepared from a known compound by a known method. Formula (where X is CH2 and R4 is CN, CHO or CO2R8 (R8 is lower alkyl)
The compound of formula (I) may also be a compound of formula (II) and a compound of formula (
XIX):

embedded image (wherein R2 and R3 are as defined for the compound of formula (I), and R28 is CN, CHO or COOR2
9 (R29 is lower alkyl)) in the presence of a base such as Triton B, an alkoxide or pyridine at 40-100°C using a Wiley
and Smith (JACS (1954), 76
．． It can also be prepared by reaction by Michael type addition as described in 4933).

The prepared esters are further modified by conventional techniques to give the corresponding acids, which are further modified to give the esters,
It can be hydrazide, hydrazinium, sulfonamide and other well known acid derivatives. Compound (XVII
) is a known compound or can be prepared from a known compound by a known method. If necessary, one or more of the following treatments can be carried out in any of these methods: i) If R4 is alkoxycarbonyl, hydrolysis to the corresponding acid. ii)
When R4 is COOH, esterify or salt;
Amide, sulfonamide, hydrazide or hydrazinium derivative. iii) When R4 is an alcohol, it is oxidized to the corresponding acid or aldehyde. iv) When R3 is alkoxycarbonyl, it is reduced to alcohol. v)
When R4 is an amide, it is dehydrogenated to the corresponding nitrile. vi) When R17 is a hydrogen atom, it is halogenated to, for example, chlorine or bromine. Treatments (i)-(vi) represent standard chemical variations or reactions. Suitable reactants and reaction conditions will be apparent to those skilled in the art from the literature. Examples of some of these modifications will be discussed below.

The compounds of formula (I) exhibit activity as herbicides and therefore, according to a further aspect of the invention, a method for treating weeds characterized in that an effective amount of a compound of formula (I) is applied to the weeds. To provide a method for severely damaging weeds or killing weeds. Compounds of formula (I) exhibit activity against a wide range of weeds, including monocotyledonous and dicotyledonous plants. These compounds also exhibit some degree of selectivity for certain plant species; these compounds can be used as selective herbicides in rice, soybean and wheat crops. formula(
The compounds of I) can be applied directly to the plants (post-emergence application) or to the soil before the plants germinate (pre-emergence application). These plants are particularly effective when used in post-emergence treatments. Although the compounds of formula (I) can be used on their own to inhibit plant growth or to severely damage or kill plants, they can be used together with a compound of the invention from a solid or liquid diluent. It is preferable to use it in the form of a composition comprising a carrier.

Accordingly, according to another aspect, the present invention comprises a compound of formula (I) as defined above and an inert carrier or diluent for inhibiting the growth of undesirable plants or for causing significant damage to undesirable plants. Compositions are provided that provide for the protection of plants or kill undesirable plants. Compositions containing compounds of formula (I) include both dilute compositions ready for use and concentrated compositions which usually require dilution with water before use. Preferably, the composition contains 0.01 to 90% by weight of active ingredient. Dilute compositions ready for use preferably contain from 0.01 to 2% by weight of active ingredient, while concentrated compositions may contain from 20 to 90% by weight, but not more than 20% by weight. ~70% by weight
It is usually preferred that

The solid compositions of the invention may be in the form of granules or may be prepared using a finely divided solid diluent, such as
It may be in the form of a powder in which active ingredients are mixed with kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, and gypsum. The solid compositions of the invention may also be in the form of dispersible powders or granules containing a wetting agent to facilitate dispersion of the powder or granules in a liquid. The solid composition in powder form can be applied as a foliar treatment dust. The liquid composition may consist of a solution or dispersion of the active ingredient dissolved or dispersed in water, optionally containing a surfactant, or the liquid composition may be comprised of a water-immiscible organic solvent. It may also consist of a solution or dispersion in which the active ingredient is dissolved or dispersed (which is dispersed as liquid particles in water).

The surfactant may be of the cationic, anionic or non-ionic type or a mixture thereof. Cationic activators are, for example, quaternary ammonium compounds (eg cetyltrimethylammonium bromide). Suitable anionic active agents are soaps; salts of aliphatic monoesters of sulfuric acid, such as sodium lauryl sulfate; salts of sulfonated aromatic compounds, such as sodium dodecylbenzenesulfonate, lignosulfonic acid or butylnaphthalenesulfonic acid. Sodium, potassium and ammonium salts, and mixtures of sodium diisopropylnaphthalenesulfonic acid and sodium salts of triisopropylnaphthalenesulfonic acid. Suitable non-ionic activators are:
Condensation products of ethylene oxide and aliphatic alcohols such as oleyl alcohol or cetyl alcohol, or ethylene oxide and alkylphenols such as octylphenol or nonylphenol (e.g. Agr.
aL90 (trade name) or a condensation product with octylcphenol. Other nonionic active agents are partial esters derived from long chain fatty acids and anhydrous hexitol, such as sorbitan monolaurate; condensation products of the above partial esters with ethylene oxide; and lecithins; silicone surfactants. (Water-soluble surfactants having a skeleton consisting of siloxane chains, such as Silwet L
77 (product name). A suitable mixture in mineral oil is Atp
lus 411F (product name).

The aqueous solution or dispersion of the active ingredient described above is
The active ingredient is dissolved in water or an organic solvent, optionally containing one or more wetting or dispersing agents, and then, if an organic solvent is used, the mixture obtained as described above is dissolved. may be prepared by addition to water, optionally containing one or more wetting agents or surfactants. Suitable organic solvents include, for example, ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylene and trichloroethylene. Compositions used in the form of aqueous solutions or dispersions are generally used in the form of concentrates containing a high proportion of the active ingredient, which concentrates are then diluted with water before use. This concentrate is usually required to withstand long-term storage and, after such storage, is an aqueous formulation that retains its homogeneity for a sufficient period of time to be diluted with water and applied with conventional spray equipment. It is required to be able to form Conveniently, the concentrate contains 20 to 90% by weight, preferably 20 to 70% by weight, of one or more active ingredients. Ready-to-use diluted preparations may contain 1
It may contain varying amounts of one or more active ingredients. 1
0.01% to 1% by weight of active ingredient or more
Amounts of 0.0% by weight, preferably 0.1% to 2% by weight are typically used.

The active ingredient is finely dispersed and is preferably in the form of a concentrated composition containing the active ingredient dispersed in water in the presence of a surfactant or suspending agent. Suitable suspending agents are hydrophilic colloids, such as polyvinylpyrrolidone and carboxymethylcellulose sodium salt,
and vegetable gums, such as gum acacia and gum tragacanth. Preferred suspending agents are those that impart thixotropic properties to the concentrate and increase the viscosity of the concentrate. Specific examples of preferred suspending agents include hydrated colloidal mineral silicates, such as montmolinite,
Mention may be made of beidellite, nontronite, hectorite, sapoite and sauconite. Bentonite is particularly preferred. Other suspending agents include cellulose derivatives and polyvinyl alcohol.

The application rate of the compounds of the invention depends, for example, on the compound selected for use, the type of plant whose growth is to be inhibited, the formulation selected for use, as well as the uptake of the compound. It will depend on many factors, including whether it should be applied as root uptake or not. However, as a general guideline, an application rate of 0.01 to 20 kg of active ingredient per hectare is appropriate, although an application rate of 0.025 to 10 kg of active ingredient per hectare is preferred. obtain. Compositions of the invention may contain, in addition to one or more of the compounds of the invention, one or more compounds that are not compounds of the invention but have biological activity. Therefore, according to a further aspect of the invention, the formula (I
) and at least one other herbicide are further provided.

The other herbicides mentioned above may be herbicides not having the above formula (I). It can generally be a herbicide with complementary action in certain applications. Examples of useful supplemental herbicides include the following herbicides: A. Benzo 2,1,3-thiadiazin-4-one-2
, 2-dioxides such as bentazone; B. Hormonal herbicides, especially phenoxyalkanes, such as MC
PA, MCPA-thioethyl, dichloroprop, 2,
4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, triclopyr, clopyralid (Clopy
C. ralids) and their derivatives (e.g. salts, esters and amides); C. 1,8-dimethylpyrazole derivatives such as pyrazoxifene, pyrazolate and benzofenap;

[
D. Dinitrophenols and their derivatives (e.g. ethyl acetate), e.g. dinoterb, dinoceb and its esters, dinoceb acetate; E. Dinitroaniline herbicides, such as dinitramine, trifluralin, etalfluroline, pendimethalin, oryzalin; F. Aryl urea herbicides, diuron, fluometuron, methoxuron, nebulon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromulon, daimuron, metabenzthiazuron; G. Phenylcarbamoyloxyphenylcarbamates, such as femedipham and desmedipham;
H. 2-phenylpyridazin-3-ones such as chloritazone and norflurazone; I. Uracil herbicides such as Renacil, Bromacil and Turbacil; J. Triazine herbicides such as atrazine, simazine, aziprothrin, cyanazine, promethrin, dimethamethrin, cymetrine and terbutryn; K. Phosphorothioate herbicides, such as piperophos, bensuride and butamiphos;

[0037]L. Thiol carbamate herbicides, such as cycloate, vernolate, molinate, thiobencarb, butyrate*, EPTC*, trialate,
dialate, esprocarb, thiocarbasil, pyridate and dimepiperate; M. 1,2,4-triazin-5-one herbicides such as metamitrone and metribuzin;N. Benzoic acid herbicides, such as 2,3,6-TBA,
Dicamba and chloramben; O. Anilide herbicides such as pretilachlor, butachlor, alachlor, propachlor, propanil, metazachlor, metolachlor, acetochlor and dimethachlor; P. Dihalobenzonitrile herbicides, such as dichlobenil, bromoxynil and ioxynil;

[0035]
Q. Haloalkane herbicides, such as Darapon, TCA
and salts thereof; R. Diphenyl ether herbicides, such as lactofen, fluroglycofen or their or esters, nitrofen, bifenox, acifluorfen and salts or esters thereof, oxyfluorfen, fomesafen, chlornitrophen and clomethoxyfen; S. Phenoxyphenoxypropionate herbicides, such as diclofop and its esters, such as methyl ester, fluazifop and its esters, haloxyfop and its esters, quizalofop and its esters,
and fenoxaprop and their esters such as methyl esters; T. Cyclohexanedione herbicides such as alloxydim and its salts, sethoxydim, cycloxydim, tralkoxydim and cresodim; U. Sulfonylurea herbicides, such as chlorsulfuron, sulfometuron, metsulfuron and its esters, benzsulfuron and its esters, such as DP
X-M6313, chlorimuron and its esters such as ethyl ester, pyrimisulfuron and its esters such as methyl ester, 2-{3-(4-methoxy-
6-methyl-1,3,5-triazin-2-yl)-3
-methylureidosulfonyl)benzoic acid esters, such as methyl ester (DPX-LS300) and pyrazosulfuron;

[0039]V. Imidazolidinone herbicides, e.g.
imazaquin, imazametabenz, imazapyr and its isopropylammonium salt, imazethapyr; W. Arylanilide herbicides such as flamprop and its esters, benzoylprop-ethyl, diphenican; X. Amino acid herbicides such as glyphosate and glufosinate and their salts and esters, sulfosate, and bialaphos; Y. Organic arsenic herbicides, such as sodium methanarsonate (MSMA); Z. Herbicidal amide derivatives, such as napropamide,
propyzamide, carbetamide, tebutam, bromotide,
isoxaben, naproanilide and naptalam;

00
40] AA. Other herbicides, such as etofumesate, synmethyline, difenzocort and its salts, such as methyl salute salt, clomazone, oxadiazone, bromophenoxime, barban, tridifan, fluorochloridone, quinclorac, dithiopyr, and mefenacet; BB. Examples of useful catalytic herbicides include: bipyridylium herbicides, such as those in which the active moiety is paraquat and those in which the active moiety is diquat. The above-mentioned compounds marked with * are preferably used in combination with an antidote, for example dichloramide.

Example 1 This example describes the preparation of compounds 1, 4 and 6:
Step A 5-trifluoromethyl-3-hydroxy-1-methylpyrazole (3.94g), 5-fluoro-2-nitroaniline (3.7g) and potassium carbonate (3.27g)
was dissolved in dimethyl sulfoxide (30 cm3) and the reaction mixture was stirred at 80°C for 16 hours. After cooling, the mixture was poured into ice/water and the precipitated solid was filtered and dried. The resulting yellow solid was triturated with hexane and then dried to give 5-(1-methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)-2-nitroaniline (3.68 g, m.p. .91-2°C) was obtained.

Step B The nitroaniline obtained in Step A (2 g, 6.6 mmol) was dissolved in 50% aqueous ethanol (100 cm2) and sodium dithionite (4.61 g, 26.5 mmol) was stirred. After the added amount was dissolved, the next amount was added little by little and dissolved. . The reaction mixture was heated under reflux with stirring for 1.5 h and, after cooling, water (5
0 cm3) and, after neutralization with aqueous sodium bicarbonate, extracted with ethyl acetate (2 x 100 cm3). The combined extracts were dried (MgSO4) and the solvent removed in vacuo to give a tan solid. This was triturated with hexane, filtered and dried to produce 4-(1-methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy).
-o-phenylenediamine (m.p. 109-111°C
) was obtained.

Step C The o-phenylenediamine (1.0 g, 3.7 mmol) obtained in Step B in water (20 cm3) was heated at room temperature with concentrated hydrochloric acid (
1.7 cm3). After stirring for 15 minutes, add water (1
0 cm3) was added and the mixture was cooled to approximately 0°C in an ice/salt bath. Sodium nitrite (0.5 cm3) in water (5.5 cm3)
544 cm3, 7.9 mmol) was added dropwise with stirring while maintaining the temperature below 0°C. Once the addition was complete, the reaction mixture was stirred at 0° C. for 30 minutes and then at room temperature for an additional 2 hours. The mixture was extracted several times with ethyl acetate, the combined extracts were washed with water, dried (MgSO4) and the solvent was evaporated.
Methyl-5-trifluoromethyl-1H-pyrazole-
3-yloxy)benzotriazole as a pale yellow solid (m
．． p. 129-131°C).

Step D: Benzotriazole obtained in Step C (3 g, 10.6
Sulfuryl chloride (1.5 mmol) is dissolved in acetonitrile (20 cm
8 g, 11.7 mmol) was added dropwise. After the addition was complete, the mixture was stirred for a further 20 minutes and then water (75 cm3
) into a solution of sodium bicarbonate (2 g) in The aqueous solution was extracted with diethyl ether and the extracts were washed with brine and dried (MgSO4). The solvent was removed to give 6-(4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)benzotriazole as a light brown solid (m.p. 195°C (decomposition)).
obtained as.

Step E The benzotriazole (1.59 g, 5 mmol) obtained in step D in dimethylformamide (25 cm3) was dissolved in a suspension of sodium hydride (50% in mineral oil, 120 m
g, 5 mmol) was added dropwise into this while stirring, and 3
Stirring was continued for 0 minutes. Dimethylformamide (25cm
3) DL ethyl-2-bromopropionate (0.
9 g, 5 mmol) was added dropwise and the resulting mixture was stirred at room temperature overnight. The reaction mixture was carefully poured into ice/water (1
00 cm3) and extracted several times with ethyl acetate. The combined extracts were washed with brine and dried (MgSO4), then the solvent was removed in vacuo to give an orange solid. The reaction mixture was further purified using column chromatography on silica gel eluting with hexane/ethyl acetate (2:1) to yield compound 1, namely DL ethyl 2-[6-(4-chloro-1-methyl-5- Trifluoromethyl-1H-pyrazol-3-yloxy)benzotriazol-2-yl]propionate and the corresponding benzotriazole-
A mixture of 1-yl and benzotriazol-32-yl, compounds 6 and 4, respectively, was obtained.

Example 2 This example describes the preparation of compound 7: Step A Ethyl DL2-(5
-fluoro-2-nitrophenylamino)propionate (11.35 g, 44 mmol) was added to 3-hydroxy-1-methyl-5-trifluoromethylpyrazole (7
．． 36 g, 44 mmol) and acetonitrile (40 c
Potassium carbonate (6.07 g, 44 mmol) in m3)
added to the mixture. The resulting mixture was heated under reflux for 3 hours, allowed to cool and poured into water. This aqueous mixture was extracted several times with ethyl acetate, and the extracts were combined and dried (Mg
SO4) and then the solvent was removed under reduced pressure to obtain an orange viscous gum. The product was purified using column chromatography on silica gel using hexane/ethyl acetate (3:
1). DL-ethyl (5-(1-methyl-5
-trifluoromethyl-1H-pyrazol-3-yloxy)-2-nitrophenylamino)-2-propionate was obtained as a gum.

Step B Propionate obtained in Step A (5.25 g, 13.
1 mmol) was dissolved in tetrahydrofuran (25 cm3) and isopropyl alcohol (60 cm3) was added. This solution was mixed with caustic soda (0.5 cm3) in water (6 cm3).
76 g, 14.4 mmol) and then 3
Stir for hours. The solvent was removed in vacuo to give DL-(5-(
1-Methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy-2-nitrophenylamino)-2
- Sodium salt of propionate as a stirrup red solid (5.
33g) and used without further purification.

Step C The sodium salt obtained in step B (2.95 g, 7.9 mmol) in 2M caustic soda (60 cm3) was dissolved under a stream of nitrogen for 10 minutes on activated carbon in water (30 cm3).
Added dropwise into a suspension of 0% palladium (100 mg) and sodium borohydride (726 mg, 15.8 mmol). The reaction mixture was stirred at room temperature for 3 hours and filtered through Celite to give a light brown aqueous solution. The filtrate was cooled to below 0°C in an ice/salt bath for 20
% hydrochloric acid. A solution of sodium nitrite (1.09 g, 15.8 mmol) in water (11 cm3) was added dropwise with stirring to keep the temperature below 0°C. After the addition was complete, the mixture was warmed to room temperature and extracted several times with ethyl acetate. The combined extracts were dried (MgSO4) and the solvent removed in vacuo to give a tan solid.

The above solid (1.9 g) was dissolved in dichloroethane (
40 cm3) and ethanol (270 mg,
5.9 mmol) and 4-dimethylaminopyridine (6
0 mg 0.5 mmol) was added and the mixture was cooled in an ice bath. Dicyclohexylcarbodiimide (1.1g, 4
(mmol) was added portionwise and the mixture was stirred at room temperature overnight. A further small amount of ethanol (5 cm3) was added and the mixture was heated under reflux for 3 hours before being poured into water and extracted with chloroflume. Dry the organic extract (MgS
O4) and evaporation of the solvent gave a brown solid (2.35). This was dissolved in hexane/ethyl acetate (2:1) and filtered. The filtrate was evaporated to give an orange solid (1.21g
) was obtained. This was purified using column chromatography on silica gel using hexane/ethyl acetate (2:1). Compound 7, namely ethyl DL-2-[6-(1
-Methyl-5-trifluoromethyl-1-H-pyrazol-3-yloxy)benzotriazol-1-yl]
Propionate was obtained as an orange gum (320mg).

Example 3 This example describes the preparation of compound 6: pyrazole (400 mg, 1.05 mmol) obtained in Example 2.
was dissolved in acetonitrile (10 cm3) and sulfuryl chloride (154 m3) was added while maintaining the temperature below 25°C.
g, 0.1 cm3, 1.14 mmol) were added. After stirring for 1 hour at room temperature, the reaction mixture was poured into sodium bicarbonate solution and extracted with ether. Dry the extract (MgS
O4) and evaporate the solvent to give ethyl DL-2-[6-(4
-chloro-1-methyl-5-trifluoromethyl-1H
-pyrazol-3-yloxy)benzotriazole-
1-yl]propionate as a yellowish brown viscous rubber (
350 mg).

Example 4 This example describes the preparation of compounds 2, 5 and 7:
The benzotriazole (2.00 g, 7.1 mmol) obtained in step C of Example 1 in dimethylformamide (30 cm3) was dissolved in sodium hydride (60% in mineral oil, 339 mg, 8
．． 5 mmol) dropwise into a stirring suspension and stirring was continued for 5 minutes. DL-ethyl bromopropionate (0.92 g, 10.6 mmol) was added dropwise and the mixture was stirred at room temperature for 3 hours. The mixture was mixed with water (
100 g) and diethyl ether (3 x 100
cm3). The organic extracts were collected and dried (MgS
O4), filtered and the filtrate was evaporated. The evaporation residue was purified using flash column chromatography on silica gel eluting with diethyl ether/hexane (1:1) to yield compound 2, namely DL ethyl 2-[6-(1-methieu-5-trifluoro). Methyl-1H-pyrazole-
3-yloxy)benzotriazol-2-yl]propionate (0.64 g) (colorless oil) and the corresponding benzotriazol-1-yl and benzotriazol-3-yl isomers (1.15 g), i.e. the compound A mixture of 7 and 5 (oil) was obtained, respectively.

Example 5 This example describes the preparation of compound 3 in Table 1: Compound 2 (0.43 g, 1.1 mmol) prepared in Example 4 was dissolved in ethanol (20 cm 3 ) and water (10 cm 3 ). Sodium carbonate (0.24 g, 2
．． 2 mmol) was added and the mixture was stirred at room temperature for 17 hours. The ethanol was removed under reduced pressure and the aqueous solution was diluted with 2N
Acidified with hydrochloric acid, then ethyl acetate (3 x 50 cm3)
Extracted with. Combine the organic extracts and dry (MgSO4)
filtration and evaporation of the filtrate to give a colorless oil. Further purification by flash column chromatography on silica gel eluting with methanol/dichloromethane (1:4) yielded compound 3, namely DL2-[6-(4-chloro-1
-Methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)benzotriazol-2-yl]propionic acid (0.30 g) as a colorless solid (m.p.
7°C (decomposition)).

Example 6 This example describes the preparation of compound 9 in Table 3: Step A 4-chloro-3-hydroxy-1-methyl-5-trifluoromethylpyrazole (20.1 g, 0.1 mmol ) and potassium carbonate (13.8 g, 0.1 mmol) were stirred in acetonitrile (200 cm3) at room temperature for 30 minutes. 3,4- in acetonitrile (100 cm3)
A solution of dinitrofluorobenzene (18.6 g, 0.1 mmol) was added dropwise maintaining the internal temperature below 30 °C and the reaction mixture was stirred at room temperature for 19 h and then at 70 °C for 4 h. . Add the above mixture to water (600c
m3) and extracted with ethyl acetate (2 x 600 cm3). Combine the organic extracts and dry (MgSO4)
filtered, and concentrated to give a brown solid. Recrystallization (
4-(4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazole-3) (ethyl acetate/hexane)
-yloxy)-o-dinitrobenzene (23.8g)
was obtained as a colorless solid (m.p. 139-140°C).

Step B Dinitrobenzene obtained in Step A (10.0 g, 27
．． 3 mmol) in dimethylformamide (40 cm3)
dissolved in it. Triethylamine (4.6cm3, 32
．． 7 mmol) and DL2-aminopropanol (2.6
cm3, 32.7 mmol) was added and the mixture was stirred at room temperature for 17 hours and then at 50° C. for 4 hours. The mixture was cooled to room temperature and diluted with diethyl ether (200 cm3
) and washed with water (3 x 200 cm3). The ether phase was collected, dried (MgSO4), filtered and the solvent removed under reduced pressure to give a waxy yellow solid. Recrystallize (ethyl acetate/hexane) to obtain DL-2-[5-(
4-chloro-1-methyl-5-trifluoromethyl-1
H-pyrazol-3-yloxy)-2-nitrophenylamino]propan-1-ol (8.71 g) was obtained as an orange solid (m.p. 118-120<0>C).

Step C Nitrobenzene (2.55 g, 6.5 mmol) obtained in Step B was dissolved in a mixture of tetrahydrofuran (10 cm3) and methanol (20 cm3),
It was added dropwise to a mixture of 0% palladium (0.1 g) and sodium borohydride (0.49 g, 12.9 mmol) in water (15 cm3) and the reaction mixture was mixed for 1 hour at room temperature. Filter off the solids and dilute the filtrate with 2N
It was acidified with hydrochloric acid and the solvent was removed by evaporation under reduced pressure. The residue was taken up in water (100 cm3) and diluted with ethyl acetate (3
x 100 cm3). The combined organic extracts were dried (MgSO4), filtered and the solvent was removed under reduced pressure. The residue was purified using flash column chromatography on silica gel eluting with ethyl acetate to give DL-2.
-[2-amino-5-(4-chloro-1-methyl-5-
Trifluoromethyl-1H-pyrazol-3-yloxy)phenylamino]propan-1-ol (1.33
g) was obtained as an off-white solid (m.p. 110-112°C).

Step D The diamine (1.08 g) obtained in Step C was mixed with glacial acetic acid (20 c
m3) and water (2 cm3) and incubated at 5 °C in an ice/salt bath.
Cooled below. A solution of sodium nitrite (0.41 g, 5.9 mmol) in water (5 cm3) was added dropwise at such a rate that the internal temperature was maintained below 5°C and the reaction mixture was allowed to stand for 4 hours after the addition was complete. Stir while warming to room temperature. The mixture was poured into ethyl acetate (100 cm3) and
It was washed successively with water (2 x 100 cm3) and saturated aqueous sodium bicarbonate solution (100 cm3). The organic phase was dried (MgSO4), filtered and the filtrate was evaporated under reduced pressure. The remaining solid was further purified by flash column chromatography on silica gel eluting with diethyl ether to yield compound 9, namely DL2-[6-(4-chloro-
1-Methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)benzotriazol-1-yl]
- Propan-1-ol (0.90 g) was added as an off-white solid (
m. p. 153-154°C). Compound 8 and compound 17 of Table III were prepared in a similar manner from the appropriate starting materials.

Example 7 This example describes the preparation of compound 11 in Table 3:
Jones reagent with Organic Sh
(1965), 45, 28. That is, chromium trioxide (6.7 g) was mixed with water (13 cm
3), concentrated sulfuric acid (5.8 cm3) was added thereto, and the precipitated salt was redissolved in water (5 cm3). Compound 9 prepared in Example 6 (0.62 g, 1.7 mmol)
A solution of was dissolved in acetone (20 cm3) and cooled in an ice/water bath. Add a small amount (0
．． 3 cm3) for a total of 2.1 cm3. After the addition was complete, the mixture was stirred at room temperature for 17 hours. Isopropyl alcohol (5 cm3) was added and the precipitated salts were removed by filtration. The filtrate was concentrated under reduced pressure and the mixture was taken up in ethyl acetate (100 cm3) and water (3 x 100 cm3).
). The organic phase was dried (MgSO4), filtered and concentrated to give a colorless solid. Trituration with diethyl ether gave compound 12, namely DL2-[6-(4-chloro-
1-Methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)benzotriazol-1-yl]
-Propionic acid (0.36 g) as a colorless solid (m.p.
209-211°C). Compound 10 in Table 3,
20 and 24 were prepared in a similar manner from appropriate starting materials.

Example 8 This example describes the preparation of compound 6 in Table 3: The acid prepared in Example 7 (0.36 g, 0.9 mmol) was dissolved in 1,2-dichloroethane (10 cm3). suspend,
Cooled in an ice bath. Ethanol (0.5cm3, excess)
and 4-dimethylaminopyridine (0.14 g, 1.1 mmol) were added followed by dicyclohexylcarbodiimide (0.28 g, 1.4 mmol) and the reaction mixture was stirred for 23 hours. The mixture was filtered and the filtrate was evaporated under reduced pressure. The residue was purified using flash column chromatography on silica gel eluting with diethyl ether/hexane (1:1) to yield compound 7, i.e. DL
Ethyl 2-[6-(4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)
benzotriazol-1-yl]propionate (0.
29g) was obtained as a colorless oil. Compound 1 in Table 3
2, 13, 14, 21, 22, 25, 26 and 27 were prepared in a similar manner from appropriate starting materials.

Example 9 This example describes the preparation of compound 15 in Table 3:
The acid prepared in Example 7 (0.3 g, 0.8 mmol) was suspended in dichloroethane (3 cm3). Oxalyl chloride (168 μl, 1.9 mmol) was added followed by 1 drop of dimethylformamide and the reaction mixture was stirred at room temperature for 18 hours. The solvent was evaporated under reduced pressure and the residue was dissolved in diethyl ether (5 cm3) and methylmelamine (40% aqueous solution, 1 cm3) was added. The mixture was stirred at room temperature for 3 hours and ethyl acetate (5
0 cm3) and washed with water (50 cm3). The aqueous phase was extracted with ethyl acetate (2 x 25 cm3). The combined organic extracts were dried (MgSO4), filtered,
And the filtrate was concentrated under reduced pressure. The concentrate was purified by flash column chromatography on silica gel eluting with diethyl ether to yield compound 15, namely DL methyl-2[
6-(4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)benzotriazol-2-yl]propionamide (0.21 g) was dissolved as a colorless solid (m.p. 190- 192°C) was obtained. Table 3
Compound 16 was prepared in a similar manner from appropriate starting materials.

Example 10 This example describes the preparation of compound 18 in Table 3:
DL2-[6-(4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)benzotriazol-1-yl]propionamide (0.
18 g, 0.46 mmol) dichloromecne (10 c
m3) and triethylamine (0.13 cm3) and the mixture was cooled in an ice bath. Trichloroacetyl chloride (0.08cm2, 0.69
mmol) was added and the mixture was stirred for 1 hour. The solution was diluted with dichloromethane (10 cm3) and water (20 cm3) was diluted with dichloromethane (10 cm3).
cm3). The aqueous phase was extracted with dichloromethane. The combined organic extracts were dried (MgSO4), filtered and the solvent was evaporated under reduced pressure. The residue was purified by flash column chromatography on silica gel eluting with diethyl ether/hexane (3:1) to yield compound 18, namely DL2-[6-(4-chloro-1-methyl-5-trifluoromethyl-1H- Pyrazol-3-yloxy)-benzotriazol-1-yl]propionitrile (0.07 g) was dissolved as a colorless solid (m.p. 147
-150°C).

Example 11 This example describes the preparation of compounds 19 and 23 in Table 3: Step A 4-(1-Methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)-o- Dinitrobenzene (
17.7 g, 54.9 mmol) in glacial acetic acid (90 cm
3) and acetic anhydride (10 cm3),
The solution was warmed to 80°C. N-promosuccinimide (14.7 g, 82.4 mmol) was added and the mixture was stirred at 80° C. for 1 hour, then cooled to room temperature. The precipitate was collected and washed with water and taken up in ethyl acetate (500 cm3). This solution was dissolved in saturated sodium bicarbonate solution (2
x 300 cm3), dried (MgSO4), filtered and evaporated under reduced pressure to 4-(4-bromo-1-methyl-5-trifluoromethyl-1H-pyrazole-3-
yloxy)-0-dinitrobenzene (17.5 g) was obtained as a colorless solid (m.p. 152-153°C).

Step B: Dinitrobenzene obtained in Step A (10.0 g, 24
．． 3 mmol) in N,N-dimethylformamide (60
cm3). Triethylamine (5.1cm
3, 36.5 mmol) and DL2-aminopropanol (2.9 cm3, 36.5 mmol) were added and the mixture was stirred at room temperature for 21 hours and then at 70°C for 3 hours. The mixture was cooled to room temperature and diluted with diethyl ether (50
0 cm3) and washed with water (3 x 300 cm3). The organic phase was dried (MgSO4), filtered and the solvent removed under reduced pressure to give DL2-[5-(4-bromo-1-methyl-5-trifluoromethyl-1H-pyrazole-3).
-yloxy))-2-nitrophenylamino]propan-1-ol (10.15 g) as an orange solid (m.p.
．． 116-110°C).

Step C Nitrobenzene (10.15 g, 23.1 mmol) obtained above was dissolved in a mixture of tetrahydrofuran (30 cm3) and methanol (60 cm3) and mixed with 10% palladium on activated carbon (0.75 g). Sodium borohydride (1.76 g, 46.2 g in water (45 cm3)
(mmol) dropwise at room temperature and the reaction mixture was mixed for 30 minutes at room temperature. The solids were filtered off, the filtrate was acidified with 2N hydrochloric acid and the solvent was removed by evaporation under reduced pressure. The residue was partitioned between ethyl acetate (400 cm3) and water (400 cm3), the organic extracts were dried (MgSO4), filtered and the solvent was removed under reduced pressure to give a dark brown residue. . The residue obtained above was dissolved in glacial acetic acid (1
00 cm3) in water (10 cm3) and the mixture was cooled in an ice bath. A solution of sodium nitrite (3.19 g, 46.2 mmol) in water (10 cm3) was added dropwise and the reaction mixture was stirred for 30 minutes after the addition was complete. The reaction mixture was diluted with ethyl acetate (300 cm3) and washed successively with water (3x300 cm3) and saturated aqueous sodium bicarbonate solution. The organic phase was dried (MgSO4), filtered and evaporated under reduced pressure. The residue was further purified using flash column chromatography on silica gel eluting with diethyl ether and recrystallized (ethyl acetate/hexanes) to yield compound 19, i.e. DL2-[
6-(4-bromo-1-methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)benzotriazol-1-yl]-propan-1-ol (4.89
g) was obtained as a pale brown solid (m.p. 142-144°C).

Step D The alcohol obtained in Step C (3.76 g, 8.95 mmol) was dissolved in N,N-dimethylformamide (30 cm3), and imidazole (0.73 g, 10.74) and tert-butyl Dimethylsilyl chloride (1.62
g, 10.74 mmol) was added. The reaction mixture was stirred at room temperature for 4 hours and then diluted with diethyl ether (150 cm
3) Injected into the inside. The solution was dried (MgSO4), filtered and the filtrate was evaporated under reduced pressure. The remaining solid was purified by flash column chromatography on silica gel eluting with diethyl ether/hexane (2:3) to DL2.
-[6-(4-Bromo-1-methyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)benzotriazol-1-yl]-tert-butyldimethylsiloxypropane (4.27 g) was mixed with an off-white solid ( m.p.
84-86°C).

Step E The silyl ether obtained in Step D (4.12 g, 7.71 mmol) was dissolved in diethyl ether (80 cm@3) and the solution was cooled to below -70.degree. C. in a nitrogen stream. N-butyllithium (1.6M solution in hexane, 5.
8 cm3, 9.25 mmol) were added dropwise and the reaction mixture was stirred for 15 minutes after the addition was complete. Methyl iodide (1.4 cm3, 23.1 mmol) was added and the reaction mixture was stirred for 1 hour, then the cooling bath was removed and stirring continued for an additional 2 hours. The reaction mixture was separated by pouring it into water (100 cm3) and the precipitate and aqueous phase were dissolved in diethyl ether (3 x 50 cm3).
m3). Combine the organic extracts and dry (Mg
SO4), filtered and the filtrate was evaporated under reduced pressure. The residue was taken up in tetrahydrofuran (30 cm3) and tetra n-butylammonium fluoride (1.0M solution in tetrahydrofuran, 10.9 cm3, 10.9
mmol) was added. The reaction mixture was stirred at room temperature for 5 hours. The solvent was evaporated under reduced pressure and the residue was dissolved in ethyl acetate (8
0 cm3) and water (80 cm3). The aqueous phase was extracted with ethyl acetate, the organic extracts were combined and dried (
MgSO4), filtered and the filtrate was evaporated under reduced pressure. The residue was purified using flash column chromatography on silica gel eluting with ethyl acetate/hexanes (2:1) to give a colorless solid (2.15 g). Recrystallization (ethyl acetate/hexane) yielded compound 23, i.e. DL2-[6
-(1,4-dimethyl-5-trifluoromethyl-1H
-pyrazol-3-yloxy]benzotriazole-
1-yl]-propan-1-ol as a colorless solid (m.
p. 114-117°C).

Example 12 This example describes the preparation of compound 28: Sodium methoxide (0.032 g, 0.60 mmol) was dissolved in DL2-[6-(1,4-
Added to a solution of dimethyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)benzotriazol-1-yl]propionic acid (0.22 g, 0.60 mmol) and stirred the reaction mixture at room temperature for 30 minutes. did. Evaporation of the solvent yielded compound 28, i.e. DL2-[6-(1,4
Sodium -dimethyl-5-trifluoromethyl-1H-pyrazol-3-yloxy)-benzotriazol-1-yl]propionate (0.22 g) was obtained as a colorless solid (m.p. 235-237°C). .

Biological Data The herbicidal activity of the compounds of the invention was tested as follows:
78.2 g of each compound according to the final spray volume
/liter Tween 20 and 21.8
Span 80 g/liter and adjusted to 1 liter with methylcyclohexane. Tween 20 is a trademark for a surfactant consisting of a condensate of ethylene oxide and sorbitan laurate in a 20 molar ratio. Span 80 is a trademark for a surfactant consisting of sorbitan mono-laurate. If the compound did not dissolve, the volume was made up to 5 ml with water, glass beads were added, the mixture was shaken to dissolve or suspend the compound, and the beads were then removed. The mixture was then diluted with water in all cases to the desired spray volume. 25c for pre-emergence and post-emergence tests when sprayed individually.
A volume of m3 and 30 cm3 was required respectively; in the case of joint spraying 45 cm3 was required. The sprayed aqueous emulsion contained a 4% solvent/surfactant stock mixture and the appropriate concentration of the test compound.

The spray formulation prepared as described above was sprayed onto young potted plants in an amount corresponding to 1,000 liters per hectare (post-emergence test). Damage to plants was assessed 13 days after spraying and compared to unsprayed plants. The evaluation standard is 0-9, where 0 is a damage rate of 0%, 1 is a damage rate of 1-5%, 2 is a damage rate of 6-15%, and 3 is a damage rate of 16%.
-25%, 4 has a damage rate of 26-35%, 5 has a damage rate of 36-
59%, 6 has a damage rate of 60-69%, 7 has a damage rate of 70-7
9%, 8 has a damage rate of 80-89% and 9 has a damage rate of 90-
It was set as 100%. In tests conducted to determine pre-emergence herbicide activity, crop species (i.e. Sb, Ct, Rp, Ww
, Mz, Rc, Sy) to a depth of 2 cm below the compost and weed seeds to a depth of 1 cm, and the above formulation was sprayed at a rate of 1,000 liters per hectare. After 20 days of spraying, the seedlings in the sprayed plastic trays were compared to the seedlings in the unsprayed control trays and damage was evaluated using the same 1-9 scale as above. The results of the test are shown in Table 4 below.

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

Claims (13)

[Claims] Claim 1: Formula (I): [Image Omitted] (The dotted line in the formula indicates the presence of two double bonds arranged to constitute a fused heteroaromatic ring system; Py has a substituent. is an optionally pyrazole ring: W is O or NR
1 (R1 is a hydrogen atom or lower alkyl) and:
X is (CH2)n, CH=CH, CH(OR5)CH2
, COCH2 (n is O, 1 or 2): R2 and R
3 each represents a hydrogen atom, an alkyl which may have a substituent, alkenyl or alkynyl, halogen, NR6R
7, or R2 and R3, together with the carbon to which they are bonded, form an optionally substituted alkenyl or cycloalkyl group; R4 is CO2R
8, CN, COR8, CH2OR8, CH(OH)R8
, CH(OR8)R9, CSNH2, COSR8, CS
OR8, CONHSO2R8, CONR10R11, C
ONHR10R11, CONHN+R10R11R12
R14-, CO2-R15+ or COON=CR10R
11: R15+ is an agriculturally acceptable cation; R14- is an agriculturally acceptable anion; R5
, R8 and R9 are each a group selected from a hydrogen atom or an alkyl, aryl, alkenyl or alkynyl group which may have a substituent: R6, R7, R10, R1
1 and R12 are each a group selected from a hydrogen atom or an alkyl, alkenyl, aryl, or alkynyl group that may have a substituent; or R6, R7, R10
, any two of R11 and R12 form a cycloalkyl or a heterocycle together with the atoms to which they are bonded. [Claim 2] Py has the formula (i) [Formula 2] (In the above formula, R16 is halogen, CN, haloalkyl, alkyl which may have a substituent, S(O)m
Ry (m is 0, 1 or 2 and Py is claim 1
) is the group defined for R8 in: R1
7 is a hydrogen atom, halogen, CN, alkyl, haloalkyl, nitro, S(O)mRy (m and Ry are as defined above); or group Rz (Rz is R in claim 1);
4): and R18 is an optionally substituted alkyl, alkenyl or alkynyl. [Claim 3]Claim 2, wherein R16 is haloalkyl.
Compounds described in. 4. The compound according to claim 2, wherein R17 is a hydrogen atom, halogen or methyl. 5. The compound according to claim 2, wherein R18 is C1-6 alkyl. 6. R4 is a group CO2R8, CN, CH2O
R8, CONR10R11, COON=CR10R11
or CONHN+R10R11R12R14-(R8,
A compound according to any one of the preceding claims, wherein R10, R11, R12 and R14- are as defined in claim 1. 7. R4 is a group CO2R8 (R8 is C1-6
5. The compound according to claim 4, which is alkyl. 8. A compound according to any one of the preceding claims, wherein X is (CH2)n, where n is O or 1. 9. A compound according to claim 1, wherein W is oxygen. Claim 10: (a) Formula (II): [Claim 3] (Py and W in the formula are as defined in claim 1)
is reacted with a compound of formula (III): wherein R2, R3, R4 and X are as defined in claim 1 and Z is a leaving group. or (b) X is CH2 and R4 is CN
, CHO or CO2R8 (R8 is lower alkyl)
, the compound of the formula (II)) and the formula (X
IX): [Formula 5] (wherein R2 and R3 are as defined in claim 1, R28 is CN, CHO or CO2R29 (R29 is lower alkyl)) in the presence of a base. or W is other than NH and CR7R3XR
When 4 is in position 1 of the benzotriazole ring, the formula (
XIII): embedded image (in which Py, X, R2, R3 and R4 are as defined in claim 1, and W is as defined in claim 1 but not NH) consisting of diazotizing the compound, followed by, if necessary, the following steps i) to vi.
); i) if R4 is alkoxycarbonyl, hydrolyzing to the corresponding acid; ii) if R4 is COOH, esterifying or forming a salt, amide, sulfonamide, hydrazide or hydrazinium derivative iii) When R4 is an alcohol, oxidizing it to the corresponding acid or aldehyde; iv) When R3 is an alkoxycarbonyl, reducing it to an alcohol; v) When R4 is an amide, dehydrating it to the corresponding nitrile; and vi) when R17 is a hydrogen atom, halogenation, for example to chlorine or bromine. 11. A herbicide comprising a compound of formula (I) according to claim 1, a carrier or a diluent, and optionally another herbicide other than the compound of formula (I). Herbicide composition. 12. A method for inhibiting or controlling the growth of unwanted plants, which comprises applying an effective amount of the compound of formula (I) according to claim 1 to a plant or a place where the plant is growing. [Claim 13] Formula (XIIIA): [Formula 7] (wherein Py, W, R2, R3 and X are as defined in claim 1, and R27 is a group as defined for the compound of formula (I) or a compound of formula (XVII):
A compound of the formula (wherein Py and W are as defined in claim 1).