JPS61197580A - Imidazoline compound, production thereof, and herbicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [G is group of formula III (R<2> is H, 1-4C alkyl, alkoxyalkyl, 1-4C haloalkyl, etc.; R<3> is H, 1-4C alkyl, halogen, etc.; R<4> is H, di(lower alkyl)imino, 1-3C alkoxy, hydroxy, etc.), etc.; R is 1-4C alkyl; R<1> is 1-4C alkyl, 3-6C cycloalkyl, etc.] and its optical isomer. USE:Herbicide having selectivity to leguminous plants such as soybean and effective at a low dose because of its high herbicidal activity. PREPARATION:The compound of formula Ia (R<4> is Na,K, Mg, etc.) can be produced by heating the carboxylic acid amide derivative of formula IIa (R<4> is H) in 1-10 equivalent of an aqueous solution of NaOH, KOH, etc.

Description

[Detailed description of the invention] The present invention is.

[In the formula, G is R5 R2 is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group, a 10 to 10 alkyl group having 1 to 40 carbon atoms,
cycloalkyl group having 5 to 6 carbon atoms, benzyl group, substituted phenylalkyl group, acyl group, alkylsulfonyl group,
An arylsulfonyl group, or optionally a lower alkyl group having 1 to 4 carbon atoms, or a lower alkoxy group having 1 to 4 carbon atoms.

Represents a phenyl group or pyridyl group which may be substituted with a halogen atom, nitro group, cyan group or trifluoromethyl group.

R3 is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a halogen atom, a lower alkoxy group having 1 to 4 carbon atoms, a nitro group, an amine group, or optionally a lower alkyl group having 1 to 4 carbon atoms, or a lower alkyl group having 1 to 4 carbon atoms; -4 lower alkoxy group, 10-gen atom, nitro group.

Substituted with a cyano group or an alkylsulfonyl group "c"
May represent phenyl foundation.

R4 is a hydrogen atom, a di-lower alkylimino group, and R4 is a lower alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, a substituted phenyl group, a cycloalkyl group having 3 to 60 carbon atoms, a carboxyl group, a lower alkoxycarbonyl group , a lower alkyl group having 1 to 5 carbon atoms which may be substituted with a cyano group, a dialkylphosphonyl group or a tri-lower alkyl ammonium group, or a lower alkoxy group having 1 to 5 carbon atoms, a lower alkoxycarbonyl group or two Carbon number 1
A lower alkenyl group having 2 to 5 carbon atoms, which may be substituted with a lower alkoxy group having 5 to 5 carbon atoms, or a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, or an oxacycloalkyl group having 2 to 5 carbon atoms. mono-, di- or tri-heroalkenyl group, C2-C50-roalkynyl group, glycidyl group, alkylthioalkyl group.

Alternatively, it represents a cationic group selected from an alkali metal atom, an alkaline earth metal atom, ammonium, or organic ammonium.

R represents a lower alkyl group having 1 to 4 carbon atoms.

R1 is a lower alkyl group having 1 to 4 carbon atoms or a lower alkyl group having 3 to 4 carbon atoms
6 represents a cycloalkyl group.

Further, R1 and R2 can be combined to form a ring, and represent a cycloalkyl group having 5 to 6 carbon atoms which may be substituted with a lower alkyl group having 1 to 3 carbon atoms.

The present invention relates to an imidacillin compound represented by the above formula, an optical isomer of the compound, a method for producing the same, and a herbicide containing the compound and the optical isomer of the compound as active ingredients.

The compound of the present invention is a novel compound that has not been described in any literature, and has excellent physiological activity as a herbicide. Conventionally, when using herbicides, it has been generally pointed out that the economic cost of using herbicides is influenced by the amount of active ingredient treated per unit area, and high herbicidal effects can be achieved with low doses. Research has continued for many years on compounds that exhibit the following:

As a result of many years of research, the present inventors have found that many of the compounds of the present invention have significantly higher herbicidal effects than conventional herbicides.

It has been found that it has selectivity for certain crops, especially legumes9, such as soybeans, and is practically useful1.
The present invention has now been completed.

In other words, the compounds of the present invention can significantly reduce the amount of active ingredients applied per unit area compared to these conventionally known compounds, have extremely large economic effects compared to conventional herbicides, and can also reduce the amount of pesticides used. It can be said to be a revolutionary herbicide that can significantly reduce the risk of environmental pollution when applied.

More specifically, the compound of the present invention represented by the general formula (1) is represented by one of the following general formulas (Ia), (Ib), and (IC) (Id).

(Ia) (Ib) (Ic)
(Id) (In the formula, R, R, R, R and R4 represent the same meanings as above.) The compound of the present invention represented by the general formula (1) can be easily obtained from the following (reaction formula 1) iC. Can be manufactured. Compound of the present invention (I
Taking the production of a) as an example, it can be more specifically produced easily by (reaction formula 1a).

(Reaction formula 1a) (Blood) (Ia) (wherein, (), R, R', R2, R' and R4
has the same meaning as above. ) That is, the carboxylic acid amide derivative [ILa (R'=H
)] from room temperature in an aqueous solution of 1 to 10 equivalents of an alkali metal hydroxide or alkaline earth metal hydroxide such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, etc. at a concentration between 1 liter and 50%. The compound of the invention CIa (R' = Na
, K, Mg, etc.)] are obtained.

By neutralizing this with a mineral acid such as hydrochloric acid or sulfuric acid, the compound of the present invention (Ia (R'=H)) is obtained.

By treating this with ammonia and organic amine, 1
Compound of the present invention (Ia (R' = ammonium).

organic ammonium cation)] is obtained.

Compound of the present invention (Ia (R=H)) The compound of the present invention (Ia) can be obtained by esterification with various alcohols R'OI (corresponding to R4) in a t-e acid catalyst. Or 9 of the present invention The compound (Ia (R=CHs')) of the present invention is obtained by treating the compound (Ia (R=H)) with diazomethane in an inert solvent, and then transesterified with various R4K-corresponding alcohols R'OH. Compound (Ia) of the present invention can be obtained by carrying out the following steps.

Also, carboxylic acid amide derivatives (I[a(R'=CH,)
], using an inert solvent such as benzene, hexane, or ether if necessary, to phosphorus oxychloride.

The compound of the present invention [Ia (R=CH,) ] can be obtained by treatment with pentachloride 1) y, sodium hydride, or the like.

Raw material carboxylic acid amide derivative (I[a (R' = H
) ] can be synthesized according to the synthesis route of [Method A] below.

[Method A]

(■ri (lva) (va)
CVa(R5=H) )(va) [IIa(R'=H) ] [■a(R
'=H)) (in the formula, R, R', R2, Rs
R4 represents the same meaning, and R5 represents a hydrogen atom or an alkyl group. The enamine form (IVa) is obtained by heating to a temperature between ~80°C. The reaction temperature varies greatly depending on the basicity of aminopyrazole. Enamine form (IVa) is 5-aminopyrazole (IIa) and ogizaloacetate (R500CCH2COCOOR).
') can also be killed by synthesis. Enamine bodies (fVa)
and Wilsmeier's reagent (N, N-dimethylformamide-phosphorus oxychloride system, or other reagent system (see literature)) 'k 1° in chloroalkanes or chloroalkenes such as 2-dichloroethane, from room temperature to 100%
pyrazolo[s,4-b]] by reaction at temperatures between 70-80°C, more generally between 70-80°C.
Pyridine-5,6-dicarboxylic acid diester Va) is obtained.

References Adv, Heterocyclic Ch.
em, 51.207 (1982).

Adv, Org, Chem,, 3225-54
2 (1976).

The corresponding dicarboye form (CVa (R'=H)) is obtained by treating the diester form (Va) i with a water-alcohol solution containing 2 equivalents or more of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. . The corresponding acid anhydride (Ma) is obtained by heating this dicarboxylic acid with acetic anhydride, trifluoroacetic anhydride, etc. to a temperature between room temperature and reflux temperature, preferably between 60 and 100°C. A carboxylic acid amide derivative Cl1a(R,=H) can be obtained by reacting an acid anhydride (Ma) with an α-aminoamide in an inert solvent (eg, acetonitrile, acetone, methylene chloride, etc.). Isomers of carboxylic acid amide derivatives [Ma (R'=
H)] may be produced as a by-product. On the other hand, the carboxylic acid amide derivative CHa (R' = CH5)] is used in the following [Method B]
can be synthesized according to the synthesis route.

[Method B]

(Ka) (wherein R, R', R2, R5, R' and R
5 represents the same meaning as above. ) Hafester compound [Ma (R' = CH,)] can be synthesized by semi-hydrolysis reaction of the corresponding diester compound (Va (R' = CH,)) or methanol decomposition of acid anhydride (Ma). Compound [Ma (R'=CH5) ] @
The compound (I[a(R'
=CH, ) ) can be obtained. Alternatively, the compound (Ka) can be obtained by reacting the acid anhydride (Ma) with α-aminonitrile in an inert solvent, removing the solvent, and heating in an acetic anhydride solvent in the presence of catalytic amounts of sodium acetate and potassium acetate. can get.

Compound (Xa) is then obtained by treatment with a strong acid such as sulfuric acid, and if necessary in a halogenated hydrocarbon solvent such as chloroform, methylene chloride, carbon tetrachloride. Compound (Xa) obtained in this way can be treated with methoxide anion in methanol solvent to form compound CI
Ia (R'=CH3) ] is obtained.

Pyrazolopyridine dicarboxylic acid ester (V), which is an important intermediate in the present invention, can be synthesized from the corresponding aminopyrazole (b) via the Willsmeier reaction in the same manner as in the CA method).

(mb) (Vb) (lIIc) (Vc) (Vb), (
From Vc) and (Vd), the corresponding compounds of the present invention (Ib), (Ic) and (Id) are prepared in the same manner as in [Method A].
t-can be synthesized.

The raw material aminopyrazole (2) can be synthesized in the same manner as in the following known literature or by a similar method.

USP 5,414,580, USP! 1,6
86,171.

J8Med, Chem, 27.1596 (1
984).

J, Heterocyclic Chem, Yu1
5 (15 (1975).

1bid,, 15.1447 (197B), 1b
id,, 16. N41 (1979), 1bid,
, 689 (1984) Beil, 25N,
202B-2054J-Am, chem, Soc,
, 81.2456 (1959) Compound of the present invention (1)
For example, the compound (Ia) of the present invention kQ shown below (reaction formula 2a
) can be easily manufactured.

(Reaction formula 2a) (XIa) (Engineering a) (wherein,
R, R', R2, R' and R4 have the same meanings as above. ) That is, the tetracyclic compound (Xla) is prepared in an inert aprotic solvent such as tetrahydrofuran.

Dioxane etc. 9 R'OH gold reaction temperature corresponding to various R4 At a temperature between about 20-50°C, if necessary, an inorganic base such as sodium hydride or an organic base such as triethylamine is added as a catalyst. The compound (Ia) of the present invention can be obtained by carrying out the reaction.

The starting material, the tetracyclic compound (XIa), can be synthesized according to the synthesis route of [Method C] below.

[C method]

(Xa) (XIa) (XI[a) (In the formula, R, R', R2 and R3 represent the same meanings as above.) Amide (Xa)'t Aromatic carbonization of benzene, toluene, xylene, etc. In a hydrogen solvent, an alkali metal hydride such as sodium hydride, an organic base such as DBU, or p-
) A ditetracyclic compound (Xla) can be synthesized by treatment with an In-containing compound such as luenesulfonic acid.

Although a small amount of isomer tetrafunctional compound (XIIa) may be produced as a by-product, it can be removed by separation means such as column chromatography. Alternatively, even if the isomer mixture of (XIa) and (XIIa) is used in the next reaction (see Reaction Scheme 2a), the compound (Ia) of the present invention can be easily separated and purified from the reaction crude product.

This will be specifically explained using the following synthesis example.

5-Amino-4-ethoxycarbonyl-1-methylpyrazole 509 (0.3 mol) and 500 mtf of concentrated hydrochloric acid were mixed and heated at reflux temperature for 10 hours. Water was distilled off under reduced pressure to obtain 5-amino-1-methylpyrazole hydrochloride. The hydrochloride salt was redissolved in water, powdered sodium bicarbonate was added to bring the aqueous solution to pH 8, and then water was completely distilled off under reduced pressure. After dissolving the crystalline residue in ethanol and separating it from insoluble inorganic substances, the ethanol is distilled off to form 5-amino-1-methylpyrazole Offa (R2=
CH,, R'=H)] was obtained. The 5-amino compound was dissolved in 200 g of methanol without purification, and 29.4 f (0.21 mol) of acetylene dicarboxylic acid dimethyl ester was added dropwise over 1 hour while cooling with water, and the methanol was distilled off under reduced pressure. I left. The dark red oil was dissolved in chloroform, washed with water, dried, and distilled off. 48.6 ft of the oil obtained was purified by column chromatography to form a yellow oil enamine [process va (R2=R
5=CH,, R'=H) ] 27.8 f (0,1
2 mol) t-obtained.

N, N-dimethylformamide 8.549 (0,1
14 mol) and 12-dichloroethane 200 d17) 4
The mixture was cooled and 17.5 r (1114 moles) of phosphorous oxychloride! The mixture was added dropwise, stirred for 1 hour at room temperature, and then cooled with water. Next, the enamine body (IVa (R2=R'
=CH,,R'=)()] 27.5? (0,11
A solution of 4 moles of 1,2-dichloroethane dissolved in 40 moles of 1,2-dichloroethane was added dropwise over 30 minutes, and the mixture was further heated at reflux temperature for 5 hours. Add drained water that has been cooled to room temperature and stir.

The organic layer was completely separated, dried, and evaporated under reduced pressure, and the obtained crude product was purified by column chromatography to obtain the title dicarboxylic acid ester (Va (R' = R' = CH, , R''
7.5 f (Q, O' 50 mol) of white crystals were obtained.

(mp 141-145°C: NMR (CDCj!,
): 3.95 (s, 3H).

4.04 (p, 5H), 4.18 (s, 5H),
8.18 (S, +H), 8.75 (S.

IH); Mass (m/z): 249 (M”, 78%
), 21B(100).

190(70), 155(40)] j1 upper methyl ester C, Va (R2=R' =R5=
CH, )] 17.0f (0,0646 mol), hydric soda 5.699 (0,142 mol), water 50 and ethanol 500 d was stirred and heated under reflux (5 hours).
. The precipitated white crystalline disodium salt [Va (R2=R'
=CH,.

R'-Na))k was cut into pieces, redissolved in water, and made strongly acidic with concentrated hydrochloric acid to precipitate white crystals. Split your mouth.

When dried, white crystals of the title compound 13. Of (0
, O553 mol) was obtained.

(mp 255°C (decomposition); NMR (DMSO-d
6): 2.54 (s, 5H).

4.02 (s, 5H), 9.64 (S, IH),
11.5-. 12.5(b, 2H)] Kandanjo dicarboxylic acid [Va (R2=CH,, R'=C,H,
, R5=H) 312.5f (10421 mol) and acetic anhydride were heated and stirred at t-9O-100°C for 8 hours. After the heating reaction was completed, the mixture was cooled and the precipitated pale green crystals were cut into pieces. Marked object 11129 (Q, 0566 so) 1
-I got it.

(mp 27B-280°C; NMR (DMSO-d6
): 4.29 (S, AH).

7.5-7.7 (m, 5H), 8.0-8.2 (m, 2
H), 9.50 (s, IH)] (Va) and (Va) shown in Table 1 can be synthesized using the same polarity as Synthesis Examples 1 to 6.

In Table 1, p-Tol+ represents 4-CH, C6H4 group, and N
MR data represent δ values (CDC/, 3).

Synthesis Example 4 [IIa(R='=CH5, R'=i-pr, R'=
R'=H)]pyrazolo(s, 4-1))pyridine-5,6-dicarboxylic anhydride [Va(R2=CHs,
R'=H)) 4. Ot (20 mmol), 2-
Amino-2,5-dimethylbutanamide 2.56r(2
A mixture of 0 mmol) and 10 mmol of acetonitrile was stirred vigorously at room temperature for 2 days. The precipitated white crystals were
Separated. (5,09 (15 mmol), mp215-2
From the HPLC and NMR analysis results, the title 5-carboxylic acid [I[a(R=R2=CH, #
R'=i-pr, R'=R'=H) Contains E as the main product.

6-carboxylic acid body which is an isomer [Va(R2R2=CH
,.

It was found that R':i-pr I R' = R':H) was contained as a by-product. It was difficult to separate both isomers, so they were used in the next reaction without being separated.

Synthesis Example 5 Pyrazolo(5,4-b)pyridine-5,6-dicarboxylic anhydride (Va(R2=R'=CE(,)39.50
A mixture of F (45 mmol), 5.049 g (45 mmol) of 2-amino-2,3-dimethylbutanenitrile and 100 g of acetonitrile was heated under reflux for 2 hours.

After heating, acetonitrile was distilled off.

100ml of acetic anhydride and 11ml of acetic anhydride
was added and heated at 120-150°C for 4 hours.

Excess acetic anhydride and low-boiling products were completely distilled off under reduced pressure, and the residue was washed with 300% chloroform. When the chloroform layer was treated with activated carbon and chloroform was distilled off, the title target imide (Ka(R=R2=R'=CH5l
R' = i - Pr )3 white crystal 12.0f (59
mmol) was obtained.

[mp 24 days - 252°C; NMR (CDCJS):
t15 (d, 6H), 2.11 (s.

3H), 2.68 (s, 5H), 500 (qq, IH
), 4.20(s, 5H), 8.48(s
.

1H)] Synthesis Example 6 The imide synthesized in Synthesis Example 5 (Ka(R=R2=R'=
CH,, R'=i-Pr)) 12. Powder of Or (59 mmol) was added portionwise to ice-cold concentrated sulfuric acid 809.

Once the solution became homogeneous, it was left at room temperature overnight. When the concentrated sulfuric acid reaction solution was carefully added to ice water, white crystals were formed. 7
After separating, it was thoroughly washed with water and an aqueous sodium bicarbonate solution, and then air-dried. 10.0v (50 mmol) of white crystals were obtained.

[mp 27FI-281°C; NMR (DMSO-d6
): 0.86(d, 5H), i, []6(d.

5H), t75(s, 5H), 2.57(s
, 5H), 2.75 (qq, IH), 4.0
8 (s, 3H).

6.7-7.5 (b, 2H), 8.70 (S, IH)
]-gold i 1 Amide synthesized in Synthesis Example 6 (Xa (R-R2=R'
=CH! .

R'=i-Pr)] 10.29 (51 mmol),
A mixture of 193f (40 mmol) of so% sodium hydride and 400d of dry toluene was heated at reflux temperature for 42 hours. The reaction solution was passed through a Celite 545 filter while hot, and the 9-mouth liquid was distilled off under reduced pressure to give 5.5 pale yellow crystals. Of
't-Tokuen. (m, p, 205°C (decomposition)) The crude product contained the title tetracyclic compound [X1a (R=R2
=R'=CH,,R'=i-pr)][NMR(DM
SO-d6): 0.95 (d, 6H), 115 (d
, 5H), t69(s, 5H), 2.3
5(qq, IE().

2.68 (s, 5H), 4.20 (s, 5H), 8.7
0(s, IH)] f, and as a by-product an isomeric tetracyclic compound [XI[a(R=R2=R'=CH, l R'
=i −Pr )] 'i Contains a small amount of NMFI
This was confirmed from the measurement results. Both isomers were used in the next reaction without separation.

The compound of the present invention represented by general formula (I) can be synthesized by either the method of (Reaction formula 1) or (Reaction formula 2) described in @. Specific examples thereof are listed in Table 2. However, 9 compounds of the present invention.

It is not limited only to these.

Synthesis Example B Amide synthesized in Synthesis Example 4 [11a (R=R2=C
H.S.

R'=i-Pr, R'=R'=:E() ] 5
．． 0r(15mm k>'fr.

Sodium hydroxide 2.49 (60 mmol) 1! - mix with an aqueous solution containing 20 g and at a temperature of 70-80 ° C.
Heat for 5 hours and enjoy. After cooling, insoluble materials were removed and acetic acid was added to make the mixture acidic, and crystals were precipitated.

The separated crystals were completely dried to obtain 2.2 f (7 mmol) of white crystals of the present compound Swallow 1.

[mp 260-262℃ (decomposition); Mass (m
/z): 515 (M, 4chi), 297 (45), 2;N
(55), 228 (I DO)] Synthesis Example (Compound of the Present Invention &2) A mixture of the compound of the present invention Alt900'A synthesized in Synthesis Example 8, 100 tons of ethanol, and 3111 t of concentrated sulfuric acid was heated at reflux temperature for 5 days. After distilling off the alcohol, water was added, extracted with chloroform, and dried in a chloroform tube.
The gold in chloroform was then distilled off under reduced pressure to yield a pale yellow oil.

The mixture was separated and purified using a column chromatogram 2 feed (distillate: chloroform/methanol 2'00/10 V/V) to obtain 470 da of white crystals of 9 compounds of the present invention M2. (mp2f5-220′C] Tetrafunctional compound CXra synthesized in Synthesis Example 7 (R=R”=
R'=CH5, R'=i-Pr) 393015! (5
mmol)′lk.

The mixture was added to a tetrahydro7ran 50ad solution containing globargyl alcohol 555Q (6 mmol) and 50% sodium hydride 144W (5 mmol), and stirred at room temperature overnight. After making the mixture acidic by adding acetic acid, the solvent and the like were distilled off under reduced pressure, and water was added to the resulting residue to precipitate crystals. After drying the precipitated crystals, the crude product (780W
IP) was purified by column chromatography to obtain 520 jllp (α87 mmol) of white crystals of the compound of the present invention 5.
I got it. (mp211-213℃ (decomposition)) (Reaction formula 1
) or (Reaction Formula 2), the compounds (I) of the present invention shown in Tables 6 to 6 can be synthesized.

In Table 5, Me is CH, group et Et is C2H5 group *
1-Pr represents (CH5)2CH.

Table 4 In the table, Me is CH, group 'i, and Et is C2H5 group.

1-Pr represents a (CH3)2CH group.

In the table, Me is CH, group 'i, Et is c2H5 group 't+
1-Pr represents a 2CH group.

In Table 6, Me is CH, group '1. Et is a C2H5 group, 1
-Pr represents a (CHS)2CH group.

When the compounds of the present invention are applied as herbicides or plant growth regulators, suitable carriers are generally used.

Examples include solid carriers such as phlegm, talc, bentonite, diatoms, or water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons.

Ethers, ketones, esters (ethyl acetate, etc.),
It can be applied in combination with a liquid carrier such as acid amides (dimethylformamide, etc.), and if desired, emulsifiers, suspending agents, penetrating agents, spreading agents, stabilizers, etc. can be added.
Solutions, emulsions, hydrated M11.

It can be put into practical use in any desired dosage form, such as a 9-grain powder or a flowable tablet. The content of the active ingredient compound in these preparations is not particularly limited, but is generally desirably in the range of 1.0 to 90.0 parts by weight. Further, if necessary, it may be mixed with other herbicides, various insecticides, fungicides, plant growth regulators, synergists, etc. at the time of formulation or spraying. Types of herbicides to be mixed include 9. For example, Farm Chemicals + Handbook (Farm Ch
There are 10 compounds described in the 70th edition (19F14) of the Chemicals Hand-book).

9. The compound of the present invention can be applied to control various weeds in agricultural and horticultural fields such as fields, paddy fields, and orchards, as well as in non-agricultural fields such as playgrounds, vacant lots, and railway edges, and the amount of the applied drug depends on the application situation. There are differences depending on the application time, application method, target grass species, cultivated crops, etc., but in general, the appropriate amount of active ingredient is about 0,005 to 10 Kp per hectare.

Next, all formulation examples of herbicides and plant growth regulators as active ingredients of the compounds of the present invention are not limited to these. In addition, in the following formulation examples, the phrase "means parts by weight."

Formulation Example 1 Wettable powder The above ingredients are uniformly mixed and pulverized to form a wettable powder. When using, the above-mentioned hydrating agent is diluted 50-to, ooo times so that the amount of active ingredient per hectare II) o, OD 5 KP
Spray at ~10KPVc.

Combination example 2! ]' L agent 1 compound of the present invention ya 2 ゛°゛°°“°°゛°°”°°°
°°°°゛“−°°＋ 0-part compound: Toho Chemical Industry Co., Ltd.
Product name) Mix the above ingredients uniformly to make an emulsion. When used, the above emulsion is diluted 50 to 00 times and applied so that the amount of active ingredient is O.OO5 kg to +oxPic per hectare.

Formulation Example 6 Granules The above ingredients are uniformly mixed and pulverized, a small amount of water is added, the mixture is stirred, the mixture is granulated using an extrusion granulator, and the mixture is dried to form granules. When using the above granules, the active ingredient 1 is 0.00% per hectare.
05 to P to 10.

Formulation example 470 Apple agent Tsurupol 3353. Lunox 1000C and 1 tisansan gum water soluble [- homogeneously dissolved in water.

Next, Invention Hardware Store 1 was added and stirred thoroughly.

A flowable agent is obtained by wet grinding in a sand mill.

When using, the above flowable agent r, (so ~ 1, 0
The amount of active ingredient is 0.0 per hectare when diluted 0.0 times.
05 Spray on K9-10 so that it becomes 2.

- Hydrating agent Compound of the present invention &6・・・・・・・・・・・・・・・
・・・・・・・・・ 50 part test "1 肚 2" - Weeding effect test by soil destruction treatment 50t% vertically, 221% horizontally. Depth 6cy! L
Put sterilized alluvial soil mt- in a plastic box, rice,
Nobie, foxtail grass, cyperus grass, and cyperus grass.

Dogfish, Imegarashi, Onamomi, and Ichibi.

Golden deer, corn, wheat, soybean, cotton, leafminer, and morning glory were sown, and after covering the soil for about 15 minutes, the amount of the active ingredient was uniformly spread over the soil surface at a predetermined ratio. The chemical solution used for spraying was the wettable powder, emulsion or flowable powder of the formulation example described above diluted with water and sprayed over the entire surface with a small sprayer. Three weeks after spraying the chemical solution, the herbicidal effect on various weeds was investigated according to the following criteria.

Judgment Criterion 5: Weed killing rate of 90% or more (almost complete death) 4...
・Weed killing rate 70 to 90% 3... Weed killing rate 40 to 70% 2... Weed killing rate 20 to 4 degrees...Weed killing rate 5 to 20 degrees 0.°゛Weed killing rate 5% or less (mostly effective) (None) However, the above-mentioned weed killing rate was determined by the following formula by measuring the above-ground fresh grass weight in the chemically treated plot and the above-ground fresh grass weight in the non-treated plot.

In addition, phytotoxicity to various crops was investigated according to the following criteria. The results are shown in Table 7.

Criterion 5: The crop is almost completely dead 4: The phytotoxicity to the crop is significant 5: The phytotoxicity to the crop is observed 2: Some phytotoxicity to the crop is observed 1: The phytotoxicity to the crop is almost not observed No 0... No chemical damage to crops is observed Test example - 2 Herbicidal effect test result by foliar treatment In May, sterilized diluvial soil was placed in a plastic box measuring 22 mm wide and 61 mm deep, and rice and wildflowers were grown. .

Foxtail grass, johnson grass, cyperus grass.

Dogfish, Doggarashi, Onamomi, and Ichibi.

Seeds of golden deer, leafminer, morning glory, corn, wheat, soybean, cotton, and beet were sown in spots, and the soil was covered with about 15 m of soil. 2 various plants
When the plant reached the ~3-leaf stage, the active ingredients were uniformly sprayed onto the stems and leaves at a predetermined ratio.

The chemical solution used for spraying is the above-mentioned water concentrator, emulsion, or flowable agent diluted with water and sprayed with a small sprayer over the entire surface of the stems and leaves of various weeds and crops.The herbicidal effect on various weeds is confirmed 4 weeks after spraying the pill solution. In addition, phytotoxicity to various crops was investigated according to the criteria of Test Example-1. The results are shown in the WJB table.

Table 7 Table 8 "Comparative compounds in Table 8" [Acifluorfen (Ac
The structural formula of ifluorfen-8odium) is.

Claims (3)

[Claims] (1) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, G is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. R^2 is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group, a haloalkyl group having 1 to 4 carbon atoms,
cycloalkyl group having 5 to 6 carbon atoms, benzyl group, substituted phenylalkyl group, acyl group, alkylsulfonyl group,
An arylsulfonyl group, or a phenyl group optionally substituted with a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, or a trifluoromethyl group, or Represents a pyridyl group. R^3 is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a halogen atom, a lower alkoxy group having 1 to 4 carbon atoms, a nitro group, an amino group, or optionally a lower alkyl group having 1 to 4 carbon atoms, carbon Represents a phenyl group optionally substituted with a lower alkoxy group of numbers 1 to 4, a halogen atom, a nitro group, a cyano group, or an alkylsulfonyl group. R^4 is a hydrogen atom, a di-lower alkylimino group, a lower alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, a substituted phenyl group, a halocycloalkyl group having 5 to 6 carbon atoms, a carboxyl group, a lower alkoxycarbonyl group, A lower alkyl group having 1 to 5 carbon atoms, which may be substituted with a cyano group, a dialkylphosphonyl group, or a tri-lower alkyl ammonium group, or a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, or a 2-carbon Number 1
A lower alkenyl group having 2 to 5 carbon atoms, which may be substituted with a lower alkoxy group having 5 to 5 carbon atoms, or a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, or an oxacycloalkyl group having 2 to 5 carbon atoms. mono-, di- or trihaloalkenyl group, haloalkynyl group having 2 to 5 carbon atoms, glycidyl group,
It represents an alkylthioalkyl group or a cationic group selected from alkali metal atoms, alkaline earth metal atoms, ammonium or organic ammonium. R represents a lower alkyl group having 1 to 4 carbon atoms. R^1 is a lower alkyl group having 1 to 4 carbon atoms or 5 carbon atoms
~6 cycloalkyl group. Moreover, R and R^1 can be combined to form a ring, and represent a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with a lower alkyl group having 1 to 5 carbon atoms. ] and optical isomers of the compound. (2) General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, G is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. R^2 is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group, a haloalkyl group having 1 to 4 carbon atoms,
Cycloalkyl group having 5 to 6 carbon atoms, benzyl group, substituted phenylalkyl group 3 Acyl group, alkylsulfonyl group 3
An arylsulfonyl group, or a phenyl group optionally substituted with a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, or a trifluoromethyl group, or Represents a pyridyl group. R^3 is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a halogen atom, a lower alkoxy group having 1 to 4 carbon atoms, a nitro group, an amino group, or optionally a lower alkyl group having 1 to 4 carbon atoms, carbon Represents a phenyl group optionally substituted with a lower alkoxy group of numbers 1 to 4, a halogen atom, a nitro group, a cyano group, or an alkylsulfonyl group. R^4 is a hydrogen atom, a di-lower alkylimino group, a lower alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a substituted phenyl group, a halocycloalkyl group having 5 to 6 carbon atoms, a carboxyl group, a lower alkoxycarbonyl group, A lower alkyl group having 1 to 5 carbon atoms, which may be substituted with a cyano group, a dialkylphosphonyl group, or a tri-lower alkyl ammonium group, or a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, or a 2-carbon Number 1
A lower alkenyl group having 2 to 5 carbon atoms, which may be substituted with a lower alkoxy group having 5 to 5 carbon atoms, or a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, or an oxacycloalkyl group having 2 to 5 carbon atoms. mono-, di- or trihaloalkenyl group, haloalkynyl group having 2 to 5 carbon atoms, glycidyl group,
It represents an alkylthioalkyl group or a cationic group selected from alkali metal atoms, alkaline earth metal atoms, ammonium or organic ammonium. R represents a lower alkyl group having 1 to 4 carbon atoms. R^1 is a lower alkyl group having 1 to 4 carbon atoms or 3 carbon atoms
~6 cycloalkyl group. Furthermore, R^1 and R^2 can be combined to form a ring, and represent a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with a lower alkyl group having 1 to 3 carbon atoms. . ] in an aqueous solution of an alkali metal hydroxide or an alkaline earth metal hydroxide, or by cyclizing a carboxylic acid amide derivative represented by cyclization in the presence of an alkaline earth metal, or using a dehydrating reagent such as dichlorohexylcarbodiimide, or in some cases, esterifying the cyclized product with diazomethane, or R^
General formula (I) characterized by esterification or transesterification with alcohol R^4OH corresponding to 4: ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (In the formula, G, R, R^1 , R^2, R^3 and R^4
has the same meaning as above. ) and a method for producing an optical isomer of the compound. (3) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, G is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. R^2 is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group, a haloalkyl group having 1 to 4 carbon atoms,
cycloalkyl group having 5 to 6 carbon atoms, benzyl group, substituted phenylalkyl group, acyl group, alkylsulfonyl group,
An arylsulfonyl group, or a phenyl group optionally substituted with a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, or a trifluoromethyl group, or Represents a pyridyl group. R^3 is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a halogen atom, a lower alkoxy group having 1 to 4 carbon atoms, a nitro group, an amino group, or optionally a lower alkyl group having 1 to 4 carbon atoms, carbon Represents a phenyl group optionally substituted with a lower alkoxy group of numbers 1 to 4, a halogen atom, a nitro group, a cyano group, or an alkylsulfonyl group. R^4 is a hydrogen atom, a di-lower alkylimino group, a lower alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, a substituted phenyl group, a halocycloalkyl group having 3 to 6 carbon atoms, a carboxyl group, a lower alkoxycarbonyl group, A lower alkyl group having 1 to 5 carbon atoms, which may be substituted with a cyano group, a dialkylphosphonyl group, or a tri-lower alkyl ammonium group, or a lower alkoxy group having 1 to 5 carbon atoms, a lower alkoxycarbonyl group, or a lower alkoxycarbonyl group having 2 carbon atoms. Number 1
A lower alkenyl group having 2 to 5 carbon atoms, which may be substituted with a lower alkoxy group having 5 to 5 carbon atoms, or a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, or an oxacycloalkyl group having 2 to 5 carbon atoms. mono-, di- or trihaloalkenyl group, haloalkynyl group having 2 to 5 carbon atoms, glycidyl group,
It represents an alkylthioalkyl group or a cationic group selected from alkali metal atoms, alkaline earth metal atoms, ammonium or organic ammonium. R represents a lower alkyl group having 1 to 4 carbon atoms. R^1 is a lower alkyl group having 1 to 4 carbon atoms or 5 carbon atoms
~6 cycloalkyl group. Furthermore, R^1 and R^2 can be taken together to form a ring, and represent a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with a lower alkyl group having 1 to 5 carbon atoms. . A herbicide comprising an imidazoline compound represented by the following formula and one or more optical isomers of the compound as active ingredients.