JPS62230782A - Imidazoline derivative, production thereof and herbicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula {C is group of formula II-IV [R<2> is H, 1-5C alkyl, alkoxyalkyl, etc.; R<3> is H, 1-4C alkyl, halogen, 1-4C alkoxy, etc.; R<4> is H, di(lower alkyl)imino, (substituted) 1-5C alkyl, etc.], etc.; R<1> is 1-4C alkyl or 3-6C cycloalkyl; R and R<1> may together form a ring of (substituted) 5-6C cycloalkyl} or its optical isomer. EXAMPLE:The compound of formula V. USE:Herbicide. PREPARATION:The objective compound can be produced either by cyclizing the caboxylic acid amide derivative of formula VI in an aqueous solution of an alkali(ne earth) metal hydroxide or cyclizing in an inert solvent in the presence of phosphorus oxychloride, phosphorus pentoxide and hydrogenated alkali(ne earth) metal or cyclizing with a dehydration reagent such as dicyclohexyl carbodiimide.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a novel imidacillin derivative, an optical isomer of the derivative, a method for producing these derivatives, and a novel imidacillin derivative or an optical isomer of the derivative as an active ingredient. This relates to the herbicide contained.

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.

The compound of the present invention has the general formula (■): [In the formula, C is J W represents an oxygen atom or a sulfur atom.

R2 is a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group, a haloalkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a benzyl group, a substituted phenylalkyl group, an acyl group, an alkyl group. May be substituted with a sulfonyl group, an arylsulfonyl group, or 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. Represents a phenyl group or a pyridyl group.

Rff 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, or a lower alkyl group having 1 to 4 carbon atoms. It is a phenyl group optionally substituted with a lower alkoxy group, a halogen atom, a nitro group, a cyan group, or an alkylsulfonyl group of ~4.

R4 is a hydrogen atom, a di-lower alkylimino group, an optionally substituted lower alkyl group having 1 to 5 carbon atoms (such substituents include a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, a hydroxy group, and a lower alkyl group having 1 to 5 carbon atoms) 6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, hensyloxy group, optionally halogen atom, lower alkyl group having 1 to 4 carbon atoms, lower alkyl group having 1 to 4 carbon atoms Indicates a phenyl group that may be substituted with a lower alkoxy group or a nitro group, or a 1-lower alkyl ammonium group), an optionally substituted lower alkenyl group having 2 to 5 carbon atoms (this substituent is
It represents a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, two lower alkoxy groups having 1 to 3 carbon atoms, or a phenyl group. ), a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, a mono-, di- or trihaloalkenyl group having 2 to 5 carbon atoms, a haloalkynyl group having 2 to 5 carbon atoms, a grindyl group, Represents an alkylthioalkyl group, a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms, or 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 3 to 6 carbon atoms which may be substituted with a lower alkyl group having 1 to 3 carbon atoms.

] represents an imidapurine derivative represented by 4, and an optical isomer of the derivative.

[Conventional technology]

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 this.

[Problem that the invention seeks to solve]

As a result of many years of research, the present inventors have discovered that the compounds of the present invention have significantly higher herbicidal effects than conventional herbicides, and that many of the compounds of the present invention are effective against certain types of crops, especially legumes, e.g. The present inventors discovered that the present invention has selectivity for crops such as soybeans and is practically useful, leading to the completion of the present invention. 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 an epoch-making herbicide that can significantly reduce the risk of environmental pollution when applied.

Means for Solving Problem c] The compound of the present invention represented by the general formula (1) is more specifically represented by the following general formulas (Ia) and (Ib).

Displayed as one of (Ic) or (Id).

(In the formula, the numbers W, R, R', R", R3 and R4 have the same meanings as above.) The compound of the present invention represented by the general formula (1) is represented by the following formula (Reaction formula 1). ) The compound of the present invention (
Taking the production of Ia) as an example, it can be more specifically produced easily by (reaction formula 1a).

(Reaction formula 1) (If) (+) (Reaction formula La) (I R2R ↓ R'' (wherein, W, G, R, R', R2, R' and R'' have the same meanings as above). ) That is, a carboxylic acid amide derivative (Ila (R' = old)) is mixed with 1 to 10 equivalents of an alkali metal hydroxide or an alkaline earth metal hydroxide such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, etc. The compound of the present invention (Ia (R' = Na, Mg, etc.)) is obtained by heating to a temperature between room temperature and 100 DEG C. in an aqueous solution having a concentration between % and 50%.

The compound of the present invention (I a (R' = H)) can be obtained by neutralizing this with a mineral acid such as hydrochloric acid or sulfuric acid. By treating this with ammonia and an organic amine, the compound of the present invention (1,a (R'=ammonium, cation of organic ammonium)) is obtained.

The compound of the present invention (Ia (R-H)) was synthesized in various acid catalysts (
7) The compound (Ia) of the present invention can be obtained by esterifying alcohol R'OH'q corresponding to R'. Alternatively, the compound of the present invention (Ia(R-tl)) is treated with diazomethane in an inert solvent to obtain the compound of the present invention CI a (R=CR3)), which is further treated with various alcohols R' corresponding to R4. Compound (Ia) of the present invention can be obtained by transesterification with OH.

Also, carboxylic acid amide derivatives (IIa (R' = C
■(:l)] with phosphorus oxychloride, phosphorus pentachloride, sodium hydride, etc., using an inert solvent such as benzene, hexane, ether, etc., if necessary, to produce the compound of the present invention (I a ( R=CH3)) can be obtained.

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

[Method A] (I[[a) (Va) R3 R2R1 (Ila (R4=H)) R31? [■a (R' = H)) (In the formula, W, R, R', R'', R' and R4 represent the same meanings as above, and R5 represents a hydrogen atom or an alkyl group.) 5-Amino The enamine compound (IVa) is obtained by heating pyrazole (I[[a) and acetylene dicarboxylic acid ester in an alcoholic solvent such as methanol or other organic solvent to a temperature between 0 and 80°C.The reaction temperature is It varies greatly depending on the basicity of pyrazole.

Enamine body (IVa) is 5-aminopyrazole (lI [
a) and ogizaloacetate (R'0OCCIl□C0
It can also be synthesized by reaction with COOR'). enamine bodies (,
IVa) and Willsmeier's reagent (N, N-dimethylformamide-phosphorus oxychloride system, or other reagent system (see literature))] in chloroalkanes or chloroalkenes of 1,2-dichloroethane from room temperature to 100% ℃
pyrazolo(3,4-b)pyridine-
A 5,6-dicarboxylic acid diester (Va) is obtained.

References 8dv, Heterocyclic Ch
em, +31+207 (1982).

Adv, Org, Chem, 9.225~3
42 (1976) The corresponding dicarboxylic acid form CVaCR'=H) is obtained by treating the diester form (Va) with a water-alcoholic solution containing 2 equivalents or more of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. ]. This dicarboxylic acid is dissolved in acetic anhydride, trifluoroacetic anhydride, etc. at a temperature between room temperature and reflux temperature, preferably at 60°C.
The corresponding acid anhydride (Vra) is obtained by heating to a temperature between -100<0>C.

Carboxylic acid amide derivatives (I
la (R'=H)) can be obtained. Carboxylic acid amide derivative which is an isomer [■a (R'-H)
) may also be produced as a by-product. On the other hand, a carboxylic acid amide derivative (ff a (R' = CH*)) can be synthesized according to the synthesis route of [Method B] below.

[Method B]

[■a(R'=Cll5) ) +1lJCCWNl!
z-” [IIa(R'=Cl1z):1(B-2)
R (Vla) +1IzNC-CN
'噸R+ (Xa) (W=O) ([1a (R' = CH3)) (W=O) (In the formula, W, R, R', R'', R', R' and R5 are as above. The same meaning is expressed.) The Hafester body [■a (R5-CH:+)) is the corresponding diester body ((V a (R5=C1)
3) Separate water decomposition reaction of ) or acid anhydride (VI a
) can be synthesized by methanol decomposition. Compound (■a (
After converting R' = CH, )) into an acid chloride with thionyl chloride or the like or into an active ester with chloroformate, etc., the compound (Ila (R' = CHx )) is converted by reacting with an α-aminoamide. Obtainable. Alternatively, compound (IX a ) can be obtained by reacting acid anhydride (VTa) 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. is obtained. 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.

By treating the compound (Xa) thus obtained with methoxide anion in methanol solvent, the compound [
U a (R' = CHz) ) is obtained.

Pyrazolopyridine dicarboxylic acid ester (V), which is an important intermediate in the present invention, can be synthesized from the corresponding aminopyrazole (II[) through the Vilsmeier reaction in the same manner as [Method A].

([[b) (Vb) (IIlc)
(Vc) (ITId)
(Vd) (Vb), (Vc) and (Vd) to produce the corresponding compound of the present invention ([b) in the same manner as in [Method A].

Nc) and (Id) can be synthesized.

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

USP 3,414,580. tlsP 3,68
6,171゜J, Med, Chem, 27. 1
396 (1984).

J, Heterocyclic Chem, ↓2.
1303 (1975).

1bid,, 15.1447 (197B), 1b
id,, Kawa, 1) 41 (1979), 1bid
, 21.689 (1984) Beil, , 251) [
, 2028-2034J, Am; Chem, So
c,,81. 2456 (1959) Compound of the present invention <1
) For example, the compound (I a) of the present invention can be prepared according to the following (reaction formula 2).
It can be easily manufactured by a).

(Reaction formula 2a) R30 (Xla) (I a) (In the formula, W, R, R', R'', R'' and R4 represent the same meanings as above.) That is, when the tetrafunctional compound (XIa) is in an active aprotic solvent, such as tetrahydrofuran, dioxane, etc.
R'OH corresponding to various R4 at reaction temperature of about 20-50
The compounds of the present invention (
Ia) can be obtained.

The tetrafunctional compound (X I a) as a starting material can be synthesized according to the synthesis route of [Method C] below.

[C method]

R' 0 (Xa) R' 0 (Xla) (XIIa) (In the formula, W, R, R', R2 and R'' have the same meanings as above.) The amide form (Xa) is converted into benzene, toluene, xylene. A tetrafunctional compound (X[a) is synthesized by treatment with an alkali metal hydride such as sodium hydride, an organic base such as DBU, or an organic acid such as p-toluenesulfonic acid in an aromatic hydrocarbon solvent such as can.

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

This will be specifically explained using the following synthesis example.

50 g (0.3 mol) of H3 5-amino-4-ethoxycarbonyl-1-methylpyrazole and 300 ml 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. Redissolve the hydrochloride in water and add powdered hydrogen carbonate l-I
After adjusting the pH of the aqueous solution to 8 by adding Jum, 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, resulting in 5-amino-1
-methylpyrazole (Illa (R2=C1)3,
R3=H)) was obtained. 200 m/m of methanol without purifying the 5-amino compound? While cooling with water solution, acetylenedicarboxylic acid dimethyl ester 29
．． After 4 g (0.21 mol) was added dropwise over 1 hour, methanol was distilled off under reduced pressure. The dark red oil was dissolved in chloroform, washed with water, dried, and distilled off. 48.6 g of the obtained oil was purified by column chromatography to obtain a yellow oil enamine form (IVa (R) =Rs
=CH3゜R3=1)) 27.8 g (0,
12 mol) was obtained.

N,N-dimethylformamide 8.34 g (0,
A mixture of 414 mol) and 200 ml of 1,2-dichloroethane was cooled and 17.5 g of phosphorus oxychloride
) was added dropwise, and the mixture was further stirred at room temperature for 1 hour, and then cooled with an aqueous solution. Next, the enamine body (IVa (R”='
R' = CH3, R' = Ir) 327.3 g (
A solution prepared by dissolving 4 mol of 0,1) in 49 ml of 1,2-dichloroethane was added dropwise over 30 minutes, and the mixture was further heated at reflux temperature for 3 hours. After cooling to room temperature, water was added and stirred, the organic layer was separated, dried, and evaporated under reduced pressure. The obtained crude product was purified by column chromatography to obtain the title dicarboxylic acid ester (Va (R2=R' =CH3,R”
7.5 g (0,030 mol) of white crystals of =H)) were obtained.

(mp 141-143°C; NMR (CDCl i)
:3.95 (s, 31)).

4.04 (s, 31)), 4.18 (s, 3
1), 8.18(s, III), 8.75(s
, l1l);Mass(m/z): 249(M”
, 782), 218(100), 190(70).

CH2 dimethyl ester (Va (R”=R3=R’=
Cl-1z ) ) 17.0 g (0,0646
-1 nil), 5.69 g (0,142
-1-/I/), water 30mj! and ethanol 30
The mixture at 0 mA was stirred and heated to reflux (5 hours). The precipitated white crystalline disodium salt (Va (R” = R”
=CHz, R' =Na)) was separated, redissolved in water, and made strongly acidic with concentrated hydrochloric acid to precipitate white crystals. When cut into pieces and dried, 13.0 g of white crystals of the title compound were obtained (
0,0553-r-ru) was obtained.

Cmp 233°C (decomposition); NMR (DMSO-d6
): 2.54 (s, 3H).

4.02 (s, 31)), 8.64 (s, III), 1
). 5-12.5(b, 2H) ) cycarphonic acid form (V
a (R" = CHt, R" = C,, I
Is, R' = Il) ) 12.5 g (
0,0421-El) and 200 ml of acetic anhydride at 90-1
The mixture was heated and stirred at 00°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 10.2
g (0,0366 mol) was obtained.

(mp 278-280℃; NMR (DMSO-d6)
:4.29(s, 31)), 7.5-7.7(m, 3
1)), 8.0-8.2 (m-2H), 9.30 (s,
1) 1)) In the same manner as Synthesis Examples 1 to 3, (Va) and (Vla) shown in Table 1 can be synthesized.

【Regulation】d Eko C1l :l C1l (CHz)
2(II a(R=R''=C)l:++ R'=i
-Pr, R344□lI)) pyrazolo(3,4
-b) Pyridine-5,6-dicarboxylic anhydride (VIa
(R2=CH3,R”=H)) 4.0 g (20 mmol), 2-amino-2,3-dimethylbucunamide 2.56 g (20 mmol) and acetonitrile 10
0mj! The mixture was stirred vigorously at room temperature for 2 days. The precipitated white crystals were separated daily. (5, Og (15 mmol)
, mp 215-218℃ (decomposition)) IIPLC
And from the NMR analysis results, the title 5-carboxylic acid form [■a
(R=R,'=CH,,R'=i-Pr,
R' = R' = H)) as the main product, and is an isomer of 6-carboxylic acid [■a (R=R2=C
It was found that H3, R'=i-Pr, 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 separation.

Chi 1 Tsuji 1 CH30 CHff 0 (IXa(R=R"=R'=Cll3. R'=i-
Pr)) pyrazolo(3,4-b)pyridine-5,6
-Dicarboxylic acid anhydride (■a (R”=R3=CH:
+ )) 9.30 g (43 mmol), 2-amino-2
A mixture of 5.04 g (45 mmol) of , 3-dimethylbutanenitrile and 100 ml of acetonitrile was heated under reflux for 2 hours. After heating, acetonitrile was distilled off and 100m7 of acetic anhydride! Then, 1 g of anhydrous sodium acetate was added and heated at 120-130°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 ml of chloroform. When the chloroform layer was treated with activated carbon and chloroform was distilled off, the title target imide compound (IXa (R=R" = R' = Cl-1,1, R'
12.0 g (39 mmol) of white crystals were obtained.

(mp 248-252°C; NMR (CDCl3)
:1.15(d,61)), 2. IHs.

31)), 2.68 (s, 31)), 3.
00(qq, 1)1) , 4.20(s, 31)
) , 8.48 (s, III))
)) The imide synthesized in Synthesis Example 5 (IXa (R=
R"-R'=CHx, R'=i-Pr))
12.0 g (39 mmol) of the powder was added portionwise to 80 g of ice-cold concentrated sulfuric acid. 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. After separating the days, water and heavy +,! ! After thoroughly washing with T aqueous solution, it was air-dried. 10.0 g (30 mmol) of white crystals were obtained.

(mp 278-281'c; NMR (DMSO-d
6): 0.86 (d, 31)), 1.06 (d,
31)), 1.75(s, 31)), 2.5
7(s, 31)), 2.75(qq, l1l)
.

4.08 (s, 31)), 6.7-7.5 (b, 2
1)), 8.70 (s, 18)) (X Ia (R=R”
=R"=CH3,R'=i-Pr)) Amide CXa synthesized in Synthesis Example 6 CR=R2=R"=CH3,R
' = i-Pr) ) 10.2 g (31 mmol), 50% sodium hydride 1.93 g (40 mmol), dry toluene 40 Qm7! The mixture was heated at reflux temperature for 42 hours. The reaction solution was heated to Celite 54.
The solution was passed through a 5-filter, and the mouth liquid was distilled off under reduced pressure to obtain 5.0 g of pale yellow crystals.

(n, p, 205°C (decomposition)) The crude product contains the title tetracyclic compound (X ta (R=R2=R
3=CH3, R”=i-Pr) ) (NMR(DM
SO-d6): 0.95 (d.

3H), 1.13 (d, 3H), 1.69
(s, 31)), 2.35 (qq, III)
, 2.68 (s.

31)), 4.20(s, 31)), 8.70(s, 1
)1) ), and the by-product is an isomeric tetracyclic compound (Xlla (R=R2=R3=CH2, R'=i-
It was found from the NMR measurement results that it contained a small amount of Pr)). Both isomers were used in the next reaction without separation.

-FQ The compound of the present invention represented by formula (1) is the above-mentioned (
It can be synthesized by either reaction formula 1) or (reaction formula 2). Specific examples thereof are listed in Table 2.

However, the compounds of the present invention are not limited to these.

The compounds of the present invention in Table 2 refer to the following synthesis examples, formulation examples, and test examples.

Next, the compound of the present invention will be explained by giving some specific synthesis examples. However, it is not limited to these only.

Jin Bojugang (invention compound Yin 1) Amide synthesized in Synthesis Example 4 (Ila (R=R”=
CHz, R'=i=Pr, R"=R'
=H) ) 5.0 g (15 mmol) in 20 mj of an aqueous solution containing 2.4 g (6.0 mmol) of sodium hydroxide! and heated at a temperature of 70-80°C for 5.5 hours.

After cooling, insoluble materials were removed and acetic acid was added to make the mixture acidic, and crystals were precipitated. The crystals separated on a daily basis are dried to form a compound of the present invention.
2.2 g (7 mmol) of white crystals were obtained.

(mp 260-262℃ (decomposition); Mass (m/z
): 315 (M”, 4χ).

297 (45), 271 (55), 228 (100);
NMR-δ value (DMSO-di,).

0.93 (d, 31)), 1.08 (d, 31)
)) , 1.35(s, 31)) , 2.04
(qq.

IH), 4.18(s, 31)), 8.28
(s, Hj) , 8.86(s, III) )(
Compound of the present invention 2) A mixture of the compound of the present invention N[Ll synthesized in Synthesis Example 8, 900 μl, 100 ml of ethanol, and 3 ml of concentrated sulfuric acid was heated at reflux temperature for 5 days. After distilling off the alcohol, water was added and extracted with chloroform, the chloroform layer was dried, and then chloroborm was distilled off under reduced pressure to obtain a pale yellow oil. Separation and purification by column chromatography (distillate: chloroform/methanol 200/10 v/v) yielded 470 mg of white crystals of the present compound Kan 2.
(mp215-220℃, NMI?-δ value (C
D+13), 0.95 (d, 3+1), 1.12 (d,
31)) , 1.38 (t, 31)) , 1
．． 42(s, 31)), 2.1) (qq, I
II).

4.22 (s, 31)), 4.40 (q+ 2
H), 8.12(s, 1)ri, 8.29(s
, l1l).

10.0 (b, il+)) Reiken JLLl (Compound of the present invention 5) The tetragenic compound synthesized in Synthesis Example 7 (Xla (R=R”
=R'=CH,,R' =i-Pr))930N(3
to a 5 Qml solution of tetrahydrofuran containing 335 μm (6 mmol) of propargyl alcohol and 144 μm (3 mmol) of 50% sodium hydride 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. When water was added to the resulting residue, crystals were precipitated. After drying the precipitated crystals, the crude product (780 cm) was purified by column chromatography to give 320 mg (0,
87 mmol) was obtained. (mp 21) -213°C (
decomposition); NMR-δ value (CDC1z), 0.93 (d
, 31)) , 1.09(d, 31)) , 1
．． 43 (s, 31)) 2, 13 (qq, III
), 2.50 (m, III), 2.59 (
s, 31)), 4.13 (s, III).

4.90 (d, 21)), 8.25 (s, 1) 1), 9
．． 8 (bs, l1l)) (compound of the present invention 8) Amide form (Ila (R=CH,, R' = i-P
r.

R2 = E t, R' = R' = H)) 7.0 g,
The mixture was mixed with 50 ml of an aqueous solution containing 3.2 g (0.08 mol) of sodium hydroxide, and the mixture was heated and stirred at 80 ml for 8 hours. After cooling, insoluble materials were removed and acetic acid was added to make the mixture acidic, and crystals were precipitated. The separated crystals were dried to obtain 4.1 g of crystals of the present compound N [L8 (0, OL 3 mo
! ) was obtained.

[Melting point 252-253℃, NMrl-δ value (DMSO
-d6), 0.92(d.

31)), 1.04 (d, 31)), 1.
33 (s, 31)), 1.49 (t, 31)
), 2.02 (qq.

l1)), 4.67(q, 21)), 8.29(s, 1
ll), 8.81(s, III), 9.5-10.
5(d,21)) ) amide body (If a (R=M e + R'
=i-P r + R'' (12 mmo+) was dissolved in 30 ml of an aqueous solution containing 260 g of sodium hydroxide, and heated and stirred at 8° 0°C for 5 hours. After cooling, insoluble matter was removed, and the solution was acidified with acetic acid. Then, crystals precipitated. When the crystals were separated and dried, 2.0 g (5
, 3 mmol) was obtained.

[Melting point 142-144℃, NMR-δ value (DMSO-
di), 0.92 (d.

3H), 1.03(d, 31)), 1.30
(s, 31)) , 2.01 (qq, 1ll)
, 7.36-7.56 (m, 21)) , 7
．． 95-8.25 (m, Iff), 8.45-
8.62 (m, LH).

8.67 (s, 1) 1), 8.89 (s, IIIL
9.5040.50(b,21)) )(Reaction formula 1)
Or, using either reaction of (reaction formula 2), the third
From the table, the compounds (I) of the present invention shown in Table 6 can be synthesized.

When applying the compound of the present invention as a herbicide or plant growth regulator, it is generally necessary to use a suitable carrier, such as a solid carrier such as clay, talc, bentonite, or diatom, or water, alcohols (methanol, ethanol, etc.), Aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (
It can be applied by mixing with liquid carriers such as ethyl acetate, etc.), acid amides (dimethylformamide, etc.), and emulsifiers, dispersants, suspending agents, penetrating agents, spreading agents, stabilizers, etc. can be added if desired. However, it can be put to practical use in any form such as a liquid, emulsion, wettable powder, powder, granule, or flowable preparation. The content of active ingredient compounds in these preparations is
Although not particularly limited, a range of 1.0 to 90% by weight is generally desirable. Further, if necessary, various herbicides, various insecticides, fungicides, plant growth regulators, synergists, etc. may be mixed and applied at the time of formulation or spraying. As for the type of herbicide to be mixed, for example, Farm Chemicals Handbook (Farm Chemicals Handbook)
ndbook) 70th edition (1984).

The compound of the present invention can be applied to control various weeds in agricultural and horticultural areas such as fields, paddy fields, and orchards, as well as in non-agricultural areas such as playgrounds, vacant lots, and railway edges, and the amount of the applied drug depends on the application situation. Although there are differences depending on the application period, application method, target grass species, cultivated crops, etc., the appropriate amount of active ingredient is generally about 0.005 to 10 kg per hectare.

Next, examples of formulations of herbicides or plant growth regulators containing the compound of the present invention as an active ingredient will be shown, but the invention is not limited thereto. In addition, in the following formulation examples, "parts" mean parts by weight.

On the drinking plate Wettable powder Compound of the present invention Patient 1 ・−・−・−・−・−・・−・・
-50 copies Sieglite PFP-・-・・−・−・−・−
...--43 parts (Kaolin clay: Sieglite Kogyo A1 trade name) Tsurupol 5039 ...--
−・−・・・ 5 parts ・(Mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industry ■Product name) Carflux (anti-caking agent)・−2 parts (White carbon: Shiono Gisei Seiyaku <40 product name) and above are mixed and pulverized uniformly to make a wettable powder. When used, the above-mentioned hydrating agent is diluted 50 to 100 times and sprayed so that the amount of the active ingredient (2) is 0.005 kg to 10 kg per hectare.

Hydrating agent Compound of the present invention 3.
-50 parts Sieglite A ・・・・・・・・・−・−
・・〜・−46 parts (Kaolin clay: Zikrite Kogyo 01 product name) Tsurupol 5039 ・・〜・−・・
−・・−・・・・・ 2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industry ■Product name)
Carplex (anti-caking agent) - 2 parts (white carbon: Shionogi & Co., Ltd. (1 part trade name) or more are uniformly mixed and pulverized to make a wettable powder.

Sara Libunyu Emulsion Compound of the present invention 2 -------------10
Part number −−−−・・・−1−−
−−−・・・・−・−・70 parts Dimethylformamide ・・・−・−・−・10 parts Tsurupol 2680
10 parts or more (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industry ■ trade name) are uniformly mixed to form an emulsion. When used, the above emulsion is diluted 50 to 1000 times and sprayed at an amount of active ingredient of 0.005 kg to 10 kg per hectare.

■Katsuko Granules Compound of the present invention 1 ----------------・-・・-
・ 5 parts bentonite −・・−・−・−・−・
Part 54 talc −・・−・−・・・−・
-・-40 parts calcium ligninsulfonate---
One or more parts are uniformly mixed and pulverized, a small amount of water is added, the mixture is stirred, the mixture is granulated using an extrusion type granulator, and the mixture is dried to form granules. When used, the above-mentioned granules are dispersed so that the amount of active ingredient is 5 kg of O, OO per hectare = 10 kg.

Flowable agent Compound of the present invention 1) hl ・・・・・・−・−・−・−
--1-・25 parts Tsurupol 3353-----
-・・------・10 parts (nonionic surfactant:
Toho Chemical Industry ■Product name) Lunosox 100OC--------0.5 parts (anionic surfactant: Toho Chemical Industry ■Product name) 1% xanthan gum aqueous solution---- −20 parts (natural polymer) Water −1−−−−−−−−・−・−・−−−−
......--1...--44.5 parts Turpol 3353, Lunosox toooc and 1% xanthan gum aqueous solution are uniformly dissolved in water, and then the compound of the present invention NIIL is added (stir After that, it is wet-pulverized in a sand mill to obtain a flowable agent.

When using, the above flowable agent is diluted 50 to 1000 times and the amount of active ingredient is 0.005 k per hectare.
Spray it so that it weighs between 10g and 10kg.

Next, the usefulness of the compounds of the present invention as herbicides will be specifically explained in the following test examples.

Goji Seiwa Soil treatment herbicidal effect test box 30LJ,
Sterilized diluvial soil was placed in a plastic box with a width of 22cm+++ and a depth of 6cm, and rice, wild grass, foxtail grass, johnson grass, cyperus grass, cyperus japonica, dogfish, Japanese fir tree, Japanese staghorn grass, corn, corn, etc.
Wheat, soybean, cotton, leafminer soybean, and morning glory were sown and covered with soil to a depth of about 1.5 cm, and then the active ingredients were 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 Criteria 5--Weed killing rate 90% or more (almost complete death) 4-
Weed killing rate 70-90% 3--Weed killing rate 40-70% 2--Weed killing rate 20-40% 1--Weed killing rate 5-20% 〇 -Weed killing rate 5% or less (hardly effective) ) However, the above-mentioned weed killing rate was determined by measuring the weight of above-ground plants in the chemically treated area and the weight of above-ground plants in the non-treated area using the following formula.

In addition, phytotoxicity to various crops was investigated according to the following criteria.

Judgment Criteria 5 - Crops are almost completely dead 4 --- Significant phytotoxicity to crops 3 --- Phytotoxicity to crops is observed 2 --- Slight phytotoxicity to crops is observed 1 ---
- Almost no chemical damage to crops was observed. - No chemical damage to crops was observed. The results are shown in Table 7.

Weeding effect test using stem and leaf treatment, height 30cm,
Sterilized Hongcheong soil was placed in a plastic box measuring 22 cm wide and 6 C1 deep, and rice, wild grass, foxtail grass, Johnson grass, cyperus grass, Japanese dogbuck, Japanese dogwood, Japanese fir tree, Japanese velvet, golden deer, leafminer, Japanese morning glory, corn, wheat, etc. Sow soybean, cotton, and beetroot seeds in spots, with approximately 1.5
cm was covered with soil. When each plant reached the 2-3 leaf stage, the active ingredient was uniformly sprayed onto the stems and leaves so that the amount of the active ingredient was 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 of the foliage of various crops and weeds using a small sprayer.

Four weeks after spraying the chemical solution, the herbicidal effect on various weeds and the chemical damage to various crops were investigated according to the criteria of Test Example-1.

The results are shown in Table 8.

Shark compound B in Table 8 in the margin below [-Ship name Acifluorophene (
The structural formula of llcifluorfen-Sodium) is shown below.

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.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formula , chemical formulas, tables, etc. ▼ or ▲ mathematical formulas, chemical formulas, tables, etc. ▼ represent. W represents an oxygen atom or a sulfur atom. R^2 is a hydrogen atom, a lower alkyl group having 1 to 5 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, an optionally substituted lower alkyl group having 1 to 5 carbon atoms (such as a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, or a lower alkyl group having 1 to 3 carbon atoms) 3 to 6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group, optionally halogen atom, lower alkyl group having 1 to 4 carbon atoms, 1 carbon number - 4 phenyl group which may be substituted with a lower alkoxy group or nitro group, or tri-lower alkylammonium group), an optionally substituted lower alkenyl group having 2 to 5 carbon atoms (this substituent is ,
It represents a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, two lower alkoxy groups having 1 to 3 carbon atoms, or a phenyl group. ), a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, a mono-, di- or trihaloalkenyl group having 2 to 5 carbon atoms, a haloalkynyl group having 2 to 5 carbon atoms, a glycidyl group, Represents an alkylthioalkyl group, a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms, or 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. R^1 is a lower alkyl group having 1 to 4 carbon atoms or 3 carbon atoms
~6 cycloalkyl group. Moreover, R and R^1 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. ] or an optical isomer of the derivative. (2) General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [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. ▼ Represent. W represents an oxygen atom or a sulfur atom. R^2 is a hydrogen atom, a lower alkyl group having 1 to 5 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, an optionally substituted lower alkyl group having 1 to 5 carbon atoms (such as a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, or a lower alkyl group having 1 to 3 carbon atoms) 3 to 6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group, optionally halogen atom, lower alkyl group having 1 to 4 carbon atoms, 1 carbon number - 4 phenyl group which may be substituted with a lower alkoxy group or nitro group, or tri-lower alkylammonium group), an optionally substituted lower alkenyl group having 2 to 5 carbon atoms (this substituent is ,
It represents a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, two lower alkoxy groups having 1 to 3 carbon atoms, or a phenyl group. ), a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, a mono-, di- or trihaloalkenyl group having 2 to 5 carbon atoms, a haloalkynyl group having 2 to 5 carbon atoms, a glycidyl group, Represents an alkylthioalkyl group, a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms, or 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. 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 5 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 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, W, G, R, R ^1, R^2, R^3 and R
^4 represents the same meaning as above. ) or an optical isomer of the derivative. (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. ▼ Represents. W represents an oxygen atom or a sulfur atom. R^2 is a hydrogen atom, a lower alkyl group having 1 to 5 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, an optionally substituted lower alkyl group having 1 to 5 carbon atoms (such as a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, or a lower alkyl group having 1 to 3 carbon atoms) 3 to 6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group, optionally halogen atom, lower alkyl group having 1 to 4 carbon atoms, 1 carbon number - 4 phenyl group which may be substituted with a lower alkoxy group or nitro group, or tri-lower alkylammonium group), an optionally substituted lower alkenyl group having 2 to 5 carbon atoms (this substituent is ,
It represents a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, two lower alkoxy groups having 1 to 3 carbon atoms, or a phenyl group. ), a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, a mono-, di- or trihaloalkenyl group having 2 to 5 carbon atoms, a haloalkynyl group having 2 to 5 carbon atoms, a glycidyl group, Represents an alkylthioalkyl group, a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms, or 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. 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. . A herbicide characterized by containing an imidazoline derivative represented by the following formula or one or more of these derivatives as an active ingredient.