JPS6081169A - Indazole derivative and herbicide containing the same as active constituent - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R1 is H or halogen; R2 is CH3, halogen or cyano; R3 is OH, amino, 1-6C alkoxyl, lower alkynyloxy, lower alkylthio, lower alkenylamino, alkali (earth) metal salt or (alkyl)ammonium salt of OH; R5 is H or CH3; n is 3 or 4; R4 halogen, CH3, lower alkoxyl or -S(O)m R6 (R6 is lower alkyl; m is 0, 1 or 2)]. EXAMPLE:3-Chloro-2-( 4-chloro-3-isopropoxycarbonylphenyl )-4,5,6,7-tetrahydro-2H- indazole. USE:A herbicide capable of exhibiting a very powerful herbicidal activity with little phytotoxicity to crops. PREPARATION:An N-substituted pyrazolone expressed by formula III (R3 is OH, lower alkoxyl, lower alkyloxy or lower alkylthio) is reacted with a halogenating agent if necessary in an inert solvent under heating to afford the aimed compound expressed by formula I (R4 is halogen).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the formula (wherein 1 mo is a hydrogen atom or a halogen atom, 1 mo is a methyl group, 1 mo is a halogen atom or a cyan group, and 1 mo is a hydroxyl group, Amine group, (21-(T1.-lower alkoxy group, lower alkylthio group, lower alkylthio group, lower alkenylamino group or hydroxyl group) alkali metal salt, alkaline earth metal salt, ammonium salt or argylammonium salt , JC5 represents a hydrogen atom or a methyl group, 11
is 3 or 4, a4 is a halogen atom, methyl group, lower alkoxy group or -8 (01m R6, but 1
(, 6 is a lower alkyl group, m is not 0, 1 or 2) and a herbicide characterized by containing it as an active ingredient. .

It is known that some indazole derivatives have herbicidal activity. For example, JP-A-52-5136
5th prize is given.

As a result of various studies on N-substituted phenyl derivatives of indazole, the present inventors have found that the N-substituted phenyl derivatives of indazole have a halogen atom and a cyanogen group at the rose position, and a carboxyl group or a carboxyl group from it at the meta position, as shown in the above formula (1). It has been surprisingly found that derivatives having derived groups exhibit extremely strong herbicidal activity. Moreover, it was discovered that it can be used as a practical herbicide with little phytotoxicity to crops, leading to the completion of the present invention.

The compound of the present invention not only exhibits excellent herbicidal efficacy against barnyard grasses and broad-leaved weeds in paddy fields, but also exhibits excellent herbicidal efficacy at low doses.
It also shows a strong herbicidal effect against perennial weeds such as lily weed, firefly, water cypress, black eye, and pine weed, and it also shows excellent herbicidal effect in pre-emergence treatment and growing season treatment in field fields, especially in the barnyard grass family. It was discovered that it has an extremely excellent herbicidal effect against broad-leaved weeds such as Japanese knotweed and knotweed at a low dose. On the other hand, crops such as rice, wheat, oats, corn, cocos, soybeans, cotton, sunflowers, etc.
It is useful as a practical herbicide with little phytotoxicity.

In the present invention, the chlorine atom may be a chlorine atom, a bromine atom or a fluorine atom. C1-C
As the alkoxy group of 6 (J, methoxy group, methoxy group, 11-propoxy group, impropoxy group, 1]-butoxy group, 5ec-butoxy group, 1crl-butoxy group,
1]-pentyloxy group, isopentyloxy group, 1,
1-dimethylglobogysodistone, 1,2-dimethylpropoxy included (, +1-hexoloxy group, 1-methylpentyloxy group, 1,3-dimethylbutoxy group, I-ethylbutoxy group, 1]-'\butyloxy group, ■-ethylpentyloxy group, 1-ethyl-\quinoloxy group or +
:I: Examples include 2,2-cymef-4-methyl-pentyloxo group.

An alkynyloxynogyloxy group, a 2-butynyloxy7 group, a ]-methylpropargyloxy group, etc. can be added.

Examples of the lower alkylthio group include methylthio group, ethylthio group, n-propylthio group, inglovirthio group and Sec-butylthio group.

Examples of the lower alkenylamino group include an allyl-amino group, an allylmethylamino group, and a β,β-dichlorovinylamino group.

Alkali metal salts of hydroxyl groups include lithium, sodium or potassium salts, alkaline earth metal salts include calcium, magnesium or barium salts, and alkylammonium salts of hydroxyl groups include methylammonium, ethylammonium and propyl. ammonium, inglobil ammonium, butylammonium,
Examples include corinium or benzylammonium salts.

The novel indazole derivative represented by the formula (1) can be produced, for example, by the method shown below.

N-substituted virazolone (
In formula 1, , It2. L is also s, n is the same as in formula (1), I
Mo3 represents water v4, a lower alkoxy group, a lower alkynyloxy group, a lower alkylthio group) and a halogenating agent (21!11) and optionally an inert solvent such as chloroform, methylene chloride or toluene. By heating the reaction at 60°C to 180°C for 1 to 15 hours, formula (1) (in the formula, 1% □) can also be converted to 2.R3,I.
A compound represented by 5+n is the same as above, 1 and 4 each represent a halogen) can be obtained. In this case, dimethylformamide, pyridine, N,N-dialkylaniline, etc. can be added to promote the reaction. As the halogenating agent mentioned here, a general halogen compound or the like can be used, and phosphorus oxychloride or an oxyodor compound is preferable.

In formula (1), a compound in which R4 is a fluorine atom, an iodine atom, or a cyan group is a compound in which R4 is a chlorine atom, and a compound in which R4 is a chlorine atom may be substituted with an inorganic fluorine compound (e.g., sodium fluoride, potassium fluoride, cesium fluoride, etc.). , inorganic iodine compounds (e.g. sodium iodide, potassium iodide),
It can be obtained by heating cuprous cyanide in a solvent such as dimethyl sulfoxide, dimethylformamide, or N-methylpyrrolidone at 150 to 200°C for several hours to several days, but by the following method. We also manufacture vines.

(6) Heating ↓ A compound represented by formula (3) (wherein J, t, , n are the same as above) and formula (4) (wherein Itt , Ik ,
R3 is the same as in formula (1)) by reacting with hydrazine represented by formula (5) (in the formula, 1, 1, 1, 2.R3, I!
11 n is the same as above).

After obtaining the compound represented by the formula (6), diazotization is carried out by Scl+icm;+no) reaction using, for example, sodium scolding nitrate at -10'C to room temperature to obtain the borofluoride represented by formula (6).
flA (in the formula, R2, 1%sr n is the same as above)
This is thermally decomposed at 60 to 150°C to obtain a compound represented by formula (7) (in the formula LL, , ] is also 2.R,,])
5rnl (same as above) can be obtained. Further, the compound represented by formula (7) is preferably 1 to 1 in hydrofluoric acid.
After diazotizing the compound represented by formula (5) at 5°C by adding sodium nitrite, it is preferably heated at 30°C to 5°C.
It can also be removed by thermal decomposition at 0°C.

A compound represented by formula (8) in which J-R4 in formula (1) is a cyan group or an iodine atom (1't in the formula).

R2, R, R5, n are the same as above) is a compound of formula (5) which is diazotized in sananic acid, preferably at 06 to 25°C, and then converted into an inorganic iodo compound (e.g. cuprous iodide, potassium iodo) or an inorganic iodo compound. It can be obtained by reacting with an aqueous solution of a cyanide compound (for example, cuprous cyanide), preferably at 0 to 80°C.

A compound represented by the formula (9) or (10) potassium hydroxide, etc.), in the presence of an inert solvent such as water, tetrahydrofuran, dioxane, methylene chloride, i.e., toluene, or at temperatures ranging from 1 to 24°C at -20 to 100°C.
By reacting for a period of time, a compound represented by formula (11) (wherein [mo+, Rz, J(, 3, l and 5+') is obtained.

, n is as described above) can be obtained.

The compound represented by the formula (2) which is the raw stone is the formula (Eng.2)0
(4) (2) (1 in the formula (,, [] are the same as in formula (1), 1 moa does not indicate a lower argyl) and formula (4) (both 1.■ and 2.■ in the formula ,
is the same as Ail) in a suitable inert solvent (for example, methylene chloride, aliphatic or aromatic hydrocarbons such as toluene, alcohol or ethers, etc.), preferably 60 to 150℃
It can be obtained by dehydrating under reflux for 30 minutes to 30 hours.

In this case, the reaction can be completed under milder conditions (eg, between 5° C. and reflux temperature) by adding an appropriate base (eg, triethylamine, sodium hydroxide, alcolade, etc.) as necessary.

The 2-alkoxycyclohexanones represented by formula (12) can be prepared by known methods (Org, Syn, Colec
tiveVo1.2, 531.1943) QO Furthermore, substituted phenylhydrazines of formula (4) can be produced by formula (13)
Produced by reducing a diazonium salt obtained by diazotizing aniline represented by the formula (wherein rtl, rt2.几, are the same as above) with sodium nitrite, for example, with stannous chloride or sodium hydrogen sulfite. be able to.

A compound in which rt4 is a methyl group in formula (1) has the formula (
14) From a 2-acetylcycloalkanone represented by <14'5+ n is the same as above) and an f6-substituted phenylhydrazine represented by formula (4), a compound represented by formula (12) as described above is obtained. Represented by the compound and formula (4),
The compound represented by formula (2) can be obtained in the same manner as the compound represented by formula (2). At this time, the condensation reaction can be promoted by adding an acid catalyst (for example, p-)luenesulfonic acid, etc.).

A compound in which 1 mo 4 in formula (1) is an alkylthio group can be obtained as follows. First, a known method (
TeLrahcdron LcLLcrs 43, 4
207.

1973), a cycloalkanone represented by the following formula (16) (in the formula, 10 is the same as above) and carbon disulfide are reacted in the presence of a base to produce a compound represented by the following formula (17) (in the formula) L5. n is the same as above), and then the following formula (18) (in the formula, 166 is a lower alkyl group, h
A compound represented by the following formula (19) (in the formula R5, R6, n
is the same as above) Substituting the compound represented by formula (19) with formula (4), 1. Hydrazine (in the formula (1) and (2) and (2) and ) (22), and then by adding an acid catalyst (for example, hydrogen chloride 9) and reacting for 1 to 10 hours at the room width to the reflux temperature of an inert solvent, a compound represented by formula (2'') ( 1+ in the formula,
, I too. , 1 too, , 1 too 5. J can also do li+I+ (same as above)'l (!). The compound represented by formula (22) (formula In, It,] et al.

[Mo32-cho'5 + R6+ rl is the same as above, 11
By reacting an alkylsulfinyl derivative of the formula (22) (wherein R,,I and 2.It3.I, 1 represents 1) at a relatively high temperature (room temperature to 150°C), 1
too. , 11 is the same as above, 111 does not represent 2) can be synthesized. In this case, the reaction will be an alkylsulfinyl derivative and then an alkylsulfonyl derivative, so in order to obtain both properly, check the progress of the reaction using thin layer chromatography or the like to determine the end point of the reaction. This is desirable.

Ma Puko, formula (in the formula ■, R2, I, 41F, and n are formula (1)
The compound represented by thionyl chloride or phosphorus oxychloride is reacted with a compound represented by (same as ) is obtained, and further added to this is formula 1 formula %
(25) (In the formula, It3 is the same as in formula (1). However, 1 and 3 do not represent an alkali metal salt of a hydroxyl group.) In an inert solvent, preferably in the presence of a base such as pyridine, -
The compound of formula (1) can be obtained by reacting at 5 to 100°C.

In addition, in formula (1), the compound in which 3 is an alkali metal salt of a hydroxyl group is the compound of formula (23) and Na Otl
.

Na2co3. It can be obtained by reacting with KOj-1 or &2 K2 CO3, etc., preferably in an aqueous solution by a turbulence method.

Examples of inert solvents used in the present invention include benzene, toluene,
Aromatic hydrocarbons such as xylene and chlorobenzene; [
Aliphatic hydrocarbons such as 1-1\xane, 1]-hebutane, and petroleum ether 4: Alicyclic hydrocarbons such as cyclohexane; Chloroform, carbon tetrachloride; ; acetone, methyl ethyl ketone 0'') ketones; ether angles such as ethyl ether, tetrahydrofuran, dioxane; methanol,
Alcohols such as ethanol; esters of acetic acid, ethyl ester, amides such as dimethylformamide, or water are used.

A specific example is shown next.

Synthesis example 1. (Compound Minami 2) ;3-chloro-2-(4-
chloro-3-impropoxycarbonylphenyl) -
Production of 4,5,6,7-thitrahydrol 2 Ll-indazole: 2-(4-chloro-3-impropoxycarbonylphenyl) -1,2,4,5,6,7--\xahydro-
311-indazol-3-one 9.25! ? (0
028 mol) and 3 me'r of phosphorus oxychloride, stir well, and add 11.7 mol of N,N-diethylaniline.
Add ml. Later, 130~1/IO°C
The product was heated for 5 hours, cooled, extracted with chloroform, and purified using a silica gel column to obtain 851 as a pale yellow oil (n'' 1.5741) (yield: 87.
4%) Elemental analysis value C101'lls C1□N2(J
□Calculated value C: 57.80115. I/II N near, 9
3 fruit 611] Value C: 57.8711: 5.16 Nia, Ri9 2-(4-chloro-3
-impropoxycarbonylphenyl) -1,2゜4
, 5.6.7-hemo;zahydro-311-indaso-
Lu-3-one was produced as follows.

20.07 (0.087 mol) of 4-chloro-3-ingrobolylphenylhydrazine and 2-carboethoxylated xanone 1/II P < 0.08:
3 mol) and 200 m6 of toluene and heated under reflux for 6 hours. Next, this is collapsed using Everbore Ku.

The resulting crystals were filtered, washed with a small amount of toluene, and 16g
・White crystals (melting point 177-8°C) were obtained.

(Yield 593%) Elemental analysis value Ca7I' (1, cl, N2 Q: +F
i'l calculated value C: 60.9911: 5.72 N: 8. :
37 real 41 real Value C: 61.20 1-I: 5.7
4N:8. /II11 synthesis, (compound production 39) 3-
chloro-2-<4-chloro-3-carbogysiphenyl)
-4゜5,6.7-Tetrahydro-211-indazole production: : Uichloro2-(/I-ri[gor7-3-isoglobogysiluponylphenyl)-4,'5.6.7- Citrahydro2, l-1-indazole 8.05 y・
<0.023 mol) and 50 rrL/+ of alcohol are mixed, and a solution of sodium hydroxide t, 5y (o, o 37 mol) dissolved in 5 me of water is added. Warm to 40℃ in a hot water bath, stir for 5 minutes, acidify with dilute hydrochloric acid, and dilute water to 10℃.
0ml! In addition, the resulting crystals are filtered and dried,
White crystals of 6.16P (melting point 189-90°C) were obtained.

(Yield 930%) Elemental analysis value C,, I-1, □CI. N2O2 calculation value C
:54.04 I-1:3.89 N:9. OO actual measurement value C: 54.01 1-1: 3.92 N: 9.1
0 Synthesis Example 3.2-C4-chloroa-2-fluoro-5=
isopropoxycarbonylphenyl) -1,2゜4,
5.6. Preparation of 7-hexahydro-5-methyl-3F1-indazol-3-one: 29.3 v (o, 12 mol) of 4-chloro-2-fluoro-3-ingloboxycarponylphenylhydrazine and 4- Methyl-2-carboethoxycyclohexanone 22.5y-Co, 12 mol) totoluene 100m7!
Mix and heat under reflux for 3 hours. The reaction solution was concentrated, the resulting crystals were filtered, washed with a small amount of ether, and
White crystals of P (melting point 191-2°C) were obtained. (yield 3
8%) Elemental analysis value Cl1l 1-120 CI, F1N2
03 Calculated value C: 58.94 H: 5.50 N near, 6
4 Actual measurement value C: 58.89 Jl:s. 53 Nia, 70 Synthesis Example 4 (Compound N[131) 3-chloro-
Preparation of 2-(4-10o-2-fluoro-5-isopropoxycarbonylphenyl)-4,5,6,7-tetrahydro-5-methyl-2H-indazole: 2-<4-chloro-2-fluoro- 5-1 sopropoxycarponylphenyl) -1,2,/1.5.6.7-
hexahydro-5-methyl-311-indazole-;
Add 3-off 13457 (0,037 moles) and 4.0 me phosphorus oxychloride, stir, and add 6,3 me tg N,N-dimethylaniline. Later J: 30~
The mixture was stirred and heated at 140°C for 4 hours, then cooled, extracted with ethyl acetate, washed with a dilute hydrochloric acid aqueous solution, then a thorium hydrogen carbonate aqueous solution, and water. Separate and purify with silica gel column 5
．． White crystals of 51 (melting point 65-6°C) were obtained. (yield 3
9.1%) Elemental analysis value Cls) IB cl□F, N20□ Calculation Direct C: 56. ] 211: 4.97N core 27 Actual measurement value C: 56.04 17491N near, 35 Synthesis example 5. (32 to compound 1') 2-(4-chloro-2-
fluoro-5-isopropoxycarbonylphenyl)
Preparation of -4,5,6,7-tetrahydro-5-methyl-3-methoxy-211-indazole 2-(4-chloro-
2-Fluoro-5-isopropoxycarbonylphenyl)-1,2,4,5,6,7-hexahydro-5-methyl-30-interso/C3-one 18.34
! i' (0.05 mol) in tetrahydrofuran 160
mg, add 6.6 ml of dimethyl sulfate, and add 34 ml of 10% sodium hydroxide aqueous solution to this solution.
．． Add 0P slowly. Then, the mixture was stirred for 111 hours, extracted with ether, washed with water until neutral, dried with anhydrous sulfuric acid, concentrated, and purified using a silica gel column to obtain a yellow oil of 1,33 ii'- (
n, "1.5512) '('I4iko.

(Yield 7.0%) Elemental analysis value C19I12゜cl, l'+ N2 (
J3 calculation value C: 59.9211: 5.82 N near, 3
5 Actual measurement value C: 59.84 Jl: 5.87 N near, 40 Synthesis example 6 (compound Nu9) 3-rioo-2 (4
-Chloro-2-fluoro-5-isoprophoxydicarbonylphenyl) = 4.5.6.7-titrahito r' -2
Production of J-1-indazole: 2-(4-chloro-2-
fluoro-5-isoprophoxydicarbonylphenyl)
-1,2,4,5,6,7-hexahydro-31-1-
1.85 ml of phosphorus oxychloride in indazol-3-one 6P (0,017 mol)! and slowly add 2.9 ml of N-dimethylaniline to the mixture. Then, heat and stir at 130/IO'C for 5 hours,
This was cooled, extracted with ethyl acetate, washed with a dilute aqueous hydrochloric acid solution, a dilute aqueous sodium hydrochloric acid solution, and then water.
After drying with IJum (100 ml of water and sulfuric acid), the residue was concentrated and purified several times using a silica gel column to obtain a 3.5P pale yellow oil (n: 51.5578). (Yield rate 55,6
%) Elemental analysis value CI71 (+7 CI2 FI N2O2 division value C: 55.00 H: 4.62 N47.5
4 Actual measurement value C: 55.22 11: 4.65 N:
, 7.60 Synthesis Example 7. (Compound 1'b26) 2-(4
-promo 2-7 /I/ , t o -5-isopropoxydicarbonylphenyl) - Production of -4,5,6,7-tetrahydro-3-methoxy-2r-i-indazole: 2-(4-promo 2 -fluoro-5-impropoxycarbonylphenyl) -1,2,4,5,6,7
-hexahydro-3l-1-indazol-3-one 3
3F-(0,083%) was dissolved in tetrahydrofuran, 10.8 m/4 of dimethyl sulfuric acid was added thereto, and 10% aqueous sodium hydroxide solution 5561 was dissolved in 7 to 9 m/4 of dimethyl sulfuric acid.
Add while maintaining the temperature. Afterwards, the mixture is stirred at 7-9°C for 2 hours.

The extract was extracted with ether, washed with water until neutral, dried over anhydrous sodium sulfate, concentrated, and separated and purified using a silica gel column to obtain pale brown crystals of 5.51 (melting point: 8:3-4°C). (Yield 161%) Elemental analysis value CI8 l-120B
r, FIN203 calculated value C: 52.5711:4.
90 N: 6.81 Actual 6 (1j value C: 52.44
f-1: 4.93 N: 6.90 Synthesis example 8. (Compound 11kl'2) 2-(4-chloro-2-fluoro-5
-isoprophoxydicarbonylphenyl) -4,5,6
, 7-tetrahydro-3-methylthio-2[1-indazole production = 4-1'lolo-6-fluoro-5-isoprophoxydicarbonylphenylhydrazine 36.4 F
I- (0,145 mol) and α-bismethylthiomethylenecyclohexanone 21.7 (0,12 mol) toinglobanol 200ml11! Mix and warm in a hot water bath,
Stir and reflux for an hour. Next, 100ml of water and 20ml of salt-made acid were added, and the mixture was stirred at 70"C for 3 hours.

After cooling, it was extracted with ethyl acetate, washed until neutral, dried over anhydrous sodium sulfate, concentrated, and separated and purified using column chromatography to obtain a 29.3P yellow oil (n
, :51.5785) was obtained. (Yield 65%) Elemental analysis values Cu+ t12o c+, lj', N202
S1 calculated value C: 56. /17115.27 Nia,
32 Actual measurement value C: 56.61 1-15.30 N
Nia, 51 Synthesis Example 9.2-(4-chloro-2-fluoro-5-isopropoxycarbonylphenyl) -4,5
゜6.7-tetrahydro-3-methylsulfinyl-2
Preparation of II-indazole: 2-(4-chloro-2-fluoro-5-isoprophoxydicarbonylphenyl)-4,,5,6,7-f)dihydro-3-methylthio-21-1-indazole 55
Dissolve g in 100 ml of acetic acid, add 2.0 g of hydrogen peroxide (35%) to this, stir at 50°C for 2 hours, cool, then pour into a large amount of ice water to dissolve ethyl acetate. After extraction, separation and purification using silica gel column chromatography resulted in 53
Yellow crystals of No. 1 (melting point 105-7°C) were obtained. (Yield 92
．． 7%) Elemental analysis value C+s l-1zo C1l 1! “I
N203 Sl calculated value C: 54.20 I-1: 5.0
5 N near, 02 actual measurement value C: 54.3211: 5.11
Nia, 12 Synthesis Example 10. (Compound Nc51) 2-
(4-chloro-2-fluoro-5-isopropoxycarbonylphenyl) -4,5,6,7-titrahydro: 3-methylsulfonyl-2l-1-indazole (a) Production: 2-(4-chloro-2 -Fluoro-5-isoprophoxydicarbonylphenyl) -4,5,6,7-tetrahydro-3-methylthio-21-1-indazole (5.51 m) was dissolved in 100 m6 of acetic acid, and 421 m6 of 35% hydrogen peroxide was added thereto. In addition, the mixture was heated and stirred at 70°C for 4 hours, cooled, poured into a large amount of ice water, extracted with ethyl acetate, and separated and purified using Norica gel column chromatography.
- pale yellow crystals (melting point 130-3'C) were obtained. (Yield 95.8%) Elemental analysis value CIRL12o C1,I
's N20s Sr calculated value C:52.111-1:4
．． 86 N: 6.75 Actual side value C: 52.23 H
:4.81 N:6.80/ Synthesis Example 11. (Compound N7) 3-chloro-2=(4-
1'lolo-3-methoxycarbonylphenyl) -4,
Production of 5,6,7-tetrahydro-21-■-indazole: 3-chloro-2-(4-chloro-3-carboxyphenyl)-4,5,6,7-titrahydro2t-i
-indazole 4.19- (0,013 mol) and thionyl chloride 1.8 me tocucroform 20rne'a
: Mix, heat under reflux for 3 hours, and distill off the solvent. Add 5 ml of methanol to this and add 2.5 ml of triethylamine. x
me* Add slowly. Afterwards, it was extracted with ethyl acetate, washed with water until neutral, dried over anhydrous sodium sulfate, and concentrated.
It was separated and purified using a silica gel column to obtain 4.15' white crystals (melting point 93-4°C). (Yield 97%) Elemental analysis value C's Ll+4C1□N20□Calculated value C: 55.4
01-1: 4.34 N: 8.61 Actual value C: 55.4
51-1:4.38 N:8.70 Synthesis Example 12. (Compound 1'1&138) 3-chloro-2-(4-chloro-
2-fluoro-5-allylaminocarbonylphenyl)
-Production of 4,5,6,7-titrahydro-21-1-indazole: 3-chloro-2-(4-chloro-2-fluoro-5-chlorocarbonylphenyl) -4,5,
6,7-tetrahydro-2H-indazole 4.2 P
(0,012 mol) and toluene 100rn/! Mix allylamine 1.645"a while cooling and stirring.
'Add. Thereafter, it was extracted with ethyl acetate, washed until neutral, and separated and purified using silica gel chromatography to obtain 3.6 J of a colorless oil (n: 51.5582). (Yield 90%) Elemental analysis value C1□I-L16 C1□F, N, 0, calculated value C: 55.45 H: 4.38 N: 11.41 Actual value C: 55.51 1-1 :4.40 N:I
l, 53 Synthesis Example 13. (Compound ~λ30) Synthesis of 3-chloro-2-(4-bromo-2-fluoro-5-ethylthiocarbonylphenyl)-4,5,6,7-titrahydro2l-1-indazole: 3-chloro- 2-
(4-Bromo-2-fluoro-5-carboxyphenyl) -/1.5.6.7-teI dihydro-211-indazole 4Ai P (0,0123 mol) thionyl chloride 1.8 me and chloroform 20 me was heated under reflux for 3 hours, the solvent was distilled off, then 50ml of toluene (1%) was added, cooled, and ethyl mercaptan (1,2 m, e) was added, and while stirring, triethylamine (2.1 m) was added.
Add tc slowly. The extract was extracted with ethyl acetate, washed with water until neutral, dried over anhydrous sodium sulfate, concentrated, and separated and purified using a silica gel column to obtain a colorless oil (n451.6100) of 4.81. (Yield 93.4%) Elemental analysis value c, 6i-■,, 13x□C1,II",
N201S1 total value C: 46.011131i2 N
:6.71 Actual value C:46.07 1:l:3.
(i8 N: 6.92) An example of the compound represented by the formula obtained by the method described in 1 is shown in Table 1.

When using the herbicide of the present invention, depending on the purpose of use, it can be used as it is, or mixed with pesticide adjuvants to enhance or stabilize the effect, and can be used as a powder, fine powder, etc., according to methods commonly used in the field of pesticide manufacturing. It can be used in the form of granules, granules, wettable powders, flowable preparations, emulsions, and the like.

These various formulations can be used directly as they are, or mixed with water to the desired degree and other auxiliary agents, such as spreading agents, emulsifiers, wetting agents, dispersants, fixing agents, and disintegrants. etc. can be given.

Examples of liquid carriers include toluene, xylene-based aromatic hydrocarbons, aliphatic hydrocarbons such as ligroin and grox, alcohols such as methanol, butanol, and glycol, ketones such as acetone, amides such as dimethylformamide, dimethyl sulfoxide, etc. sulfoxides, methylnaphthalene, cyclohexane, animal and vegetable oils, fatty acids, fatty acid esters, etc.

Solid carriers include clay, kaolin, talc, diatomaceous earth,
Examples include silica, calcium carbonate, montmorillonite, hentonite, feldspar, quartz, alumina, and sawdust.

In addition, surfactants are usually used as emulsifiers or dispersants, such as anionic agents such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, and lauryl betaine, and cationic agents. Surfactants, nonionic surfactants, and zwitterionic surfactants are available.

Spreading agents include polyogyzoethylene nonylphenyl ether and polyoxyethylene diuryl ether; wetting agents include dialkyl sulfosuccinate,
Polyoxyethylene nonylphenyl ether, etc., as a fixing agent, dimethyl cellulose or polyvinyl alcohol, and as a disintegrant, sodium chloride sulfonate, sodium lauryl sulfate, etc. can be mentioned.

All formulations can be used not only alone, but also in combination with fungicides, insecticides, 41μ growth regulators, acaricides, agricultural and horticultural fungicides, soil fungicides, soil conditioners, or nematicides. It can also be used in combination with fertilizers and other herbicides.

The active ingredient compound M1 in the herbicide of the present invention varies depending on the formulation form, application method, and other conditions.
In some cases, only the active ingredient compound may be used, but usually it is 0.
It ranges from 5 to 95% (by weight), preferably from 2 to 50% (by weight).

In addition, when weeding with the herbicide of the present invention, the amount used varies depending on the compound used and the place of application, but usually the active ingredient compound is 0.1 to 100 J per are, preferably 1 to 100 J.
It is used in a range of 10g.

Next, formulation examples of the present invention will be explained in more detail.
The types and mixing ratios of additives are not limited to these (they can be used in a wide range). Note that "part" means "fi", and "-?i" means "part".

Formulation example 1. Add and dissolve 35 parts of a mixture of xylene and methylnaphthalene (1:1) to 50 parts of emulsion compound No. 9, and add 15 parts of a mixture of polyoxyethylene alkylphenyl ether and calcium alkylbenzenesulfonate (8:2) to the slurry. An emulsion is obtained by mixing with. To use it, dilute it with water to a concentration of 0.01 to 1%.

Formulation example 2. A powder is obtained by adding 95 parts of clay to 5 parts of powder compound No. 15, mixing and pulverizing the mixture. This is used for direct spraying.

Formulation example 3. Irrigation agent compound number 25050 parts, diatom ±10 parts, kaolin 32 parts
8 parts of a mixture of sodium lauryl 4A 61/sodium and 2,2'-dinaphthylmethanesulfonate were mixed in a uniform solution, and the mixture was pulverized to obtain a wettable powder as a fine powder. Motoichi is diluted to a concentration of 0.01 to 2% and used as a suspension.

Formulation Example 4 Granules Using an appropriate mixer, spread 5 parts of a fine powder of 9K material No. 26 onto 94.5 parts of silica grains (16-32 mesoyu) and a mechnol solution containing 0.5 parts of polyvinyl acetate as a binder. Granules are obtained by coating. This is directly dispersed into the soil and rice fields.

Formulation Example 5 40 parts of fine powder of flowable agent Compound No. 39 was mixed with 3 parts of sodium ligninsulfonate, 0.5 parts of silicone thread antifoaming agent, 5 parts of Acrisol FL1041i' (manufactured by Kakosoup Co., Ltd.), and 51 parts of water.
Add 0.5% of formaldehyde to the mixed solution while stirring with a homogenizer to completely disperse it.
A flowable agent is obtained by adding parts and mixing. Motoichi uses it after diluting it with water to a concentration of 0.01 to 2%.

Does the active ingredient compound of the present invention have excellent weed control properties? f-柘る壬l イ) ム〉RUTA Il さいい 11π SAT h MIJ
, lU4-1-h.

All experiments were conducted in duplicate, and the results are shown as the average value of each.

Experimental example 1. Paddy field weed pre-emergence submergence treatment A Wagner bonoto of 115,000 are was filled with a certain amount of water [l] soil j″X, and a certain amount of seeds of Japanese millet, Japanese cabbage, Japanese staghorn, azalea, Japanese chickweed, and Japanese cypress were sown. Furthermore, 93 tubers of Urikawa were buried at a depth of 17771 below the surface layer of the soil fracture, and after being flushed with fresh water to a depth of 3 crn, the active ingredient compound of the present invention was added to a concentration of 0.4 to 25 g per are. The prepared diluted solution was dropped into the flooded water. Three days later, paddy rice 1'J' at the 2.5 leaf stage was treated.
(Bombare) were transplanted. Thirty days after chemical treatment, the herbicidal effect and the presence or absence of chemical damage to paddy rice were determined. The investigation was conducted based on the following criteria and the results shown in Table 2 were obtained.

* Weeding effect index 5: Complete weeding 4: Weeding around 80% 3: 60% 2: 40% 1: Weeding around 20% 0: No effect ※※Phytotoxicity index 12 No Harm 12 Slightly harmful Ox: Minor damage 11: Medium Harm: Severe damage A certain amount of seeds of Japanese cabbage, Japanese cabbage, Kikashigusa, Japanese azalea, Mizono kobe, Japanese cypress, and firefly were sown. Furthermore, 3 tubers of Urikawa per bond were buried at a depth of 1 crn from the soil surface layer, and 25
Three paddy rice seedlings (Nihonbare) of Haho were transplanted. 3Crn
The plants were flooded with water to a depth of When the weeds grew to the 2nd to 3rd leaf stage, a diluted solution adjusted to contain 15 to 25 g of the active ingredient compound of the present invention per are was dropped into the flooded water.

Thirty days after the chemical treatment, the herbicidal effect was investigated and the results shown in Table 3 were obtained. The criteria for the investigation were Experimental Example 1 and (Ill.

Table 3: Rice paddy weed growing season Treatment notes Control agent As seen in the results of Experimental Examples 1 and 2, the compound of the present invention was applied to the main weeds of perennial and perennial plants in 11% of water by 7.1%.
It showed excellent herbicidal efficacy in pre- and post-emergence treatments and in growing season treatments. Moreover, it was found to be highly safe for paddy rice when treated before and after transplantation.

Next, we will show an example of an experiment conducted in a field.

Experimental Example 3 A circular plastic case measuring 80° in diameter and 80° in depth was covered with soil. Immediately, the soil surface was treated with a diluted solution containing a preparation containing the active ingredient compound of the present invention so that the amount of active ingredient per area was 0.8 to 2501. After treatment, growth was controlled in a greenhouse, and the herbicidal effect was investigated on the 20th. The experiment was conducted in duplicate, and the average value for each was calculated. Furthermore, para
The testing criteria were the same as in Experimental Example 1, and the results shown in Table 4 were obtained.

Table-4 Soil treatment before germination of field weeds Notes Known compound 1 Same experimental example 4 as above CtX 23 crt, width 45 cm, depth j2, 5z
A certain amount of field soil was filled in a plastic bunt, and seeds of dice, cotton, corn, wheat, peanut, and rice were sown in a certain amount, and the soil was covered with about 3 cm of soil.

6. Immediately administer the preparation containing the active ingredient compound of the present invention with the active ingredient per area. : 20 ml of diluted solution adjusted to 3-50 J per vat! was applied to the soil surface using a small sprayer. After treatment, growth is managed in a greenhouse,
The criteria for investigating the extent of chemical damage to each crop on day 20 was the same as in Experimental Example 1, and the results shown in Table 5 were obtained.

Table 5 Effects on crops (pre-germination soil treatment) Experimental example 5 Fill a circular plastic case with a diameter of 13 cm and a depth of 8σ with a certain amount of field soil, and sow certain amounts of seeds of hackberry and snail, respectively, and grow them for 3 to 30 minutes. When the plants had grown to the four-leaf stage, a diluted water solution containing the active ingredient compound of the present invention with the active ingredient per area of 12.5 and 25 g was sprinkled on the plants.

The experiment was conducted in duplicate. On the 20th day after the drug treatment, an investigation was conducted using the same investigation criteria as in Experimental Example 1, and the results shown in Table 6 were obtained.

Table 6: Field weed growth season foliar treatment ηIJ As is clear from the results of Experimental Examples 3 and 5, the compound of the present invention exhibits an extremely excellent debt elimination effect on major weeds in the field when pre-germinated and grown. It turns out that there is something. Furthermore, as is clear from the results of Experimental Example 4, it does not cause any phytotoxicity to crops and is suitable as a herbicide for upland fields.

Special gamma Ding applicant E1 Honka Yakuju Type Company

Claims (2)

[Claims] (1) Formula (in the formula, 几l is the hydrogen atom size or... rogen atom, 'I
t is a methyl group, a halogen atom, or a cyan group, and the border is a hydroxyl group, an amino group, a C, to C6-alkoxy group, a lower alkynyloxy group, a lower alkylthio group, a lower alkenylamino group, or an alkali metal of the hydroxyl group. Salts, alkaline earth metal salts, ammonium or alkylammonium salts? , L is a hydrogen atom or a methyl group, n is 3 or 4, and 4 is a J atom, a methyl group, a lower alkoxy group or -8 (olm rt., where 几6 is a lower an indazole derivative represented by an alkyl group (111 represents 0, 1 or 2) (2) Formula (where 1(, l represents a hydrogen atom or halogen 7,
Mo2 is a methyl group, halogen atom is a cyan group, IL
3 is a hydroxyl group, an amino group, a C] to Co alkoxy group, a lower alkynyloxy group, a lower alkylthio group, a lower alkenylamine group, or an alkali metal salt, alkaline earth metal salt, ammonium salt or alkylammonium salt of a hydroxyl group, 5 is a hydrogen atom or a methyl group, 1] is 3 or 4,
,. is a lower alkyl group, m is 0.1 or 2) A herbicide containing an indazole derivative as an active ingredient.