JPH0717641B2 - Imidazoline derivative, its manufacturing method and herbicide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention comprises a novel imidazoline derivative, an optical isomer of the derivative, a method for producing the same, and the derivative or the optical isomer of the derivative as an active ingredient. It concerns herbicides.

The compound of the present invention is a novel compound which has not been described in the literature, and has excellent physiological activity as a herbicide.

The compound of the present invention has the general formula (I): [In the formula, G is 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, a cycloalkyl group having 5 to 6 carbon atoms, a benzyl group, a substituted phenylalkyl group, an acyl group, Alkylsulfonyl group, arylsulfonyl group, or 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 Represents a good phenyl or 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,
It represents an amino group, or a phenyl group optionally substituted with a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, 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 (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, a carbon number 3) To 6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom group, benzyloxy group, optionally halogen atom, lower alkyl group having 1 to 4 carbon atoms, 1 carbon atom To a phenyl group which may be substituted with a lower alkoxy group or a nitro group, or a tri-lower alkylammonium group.), And an optionally substituted lower alkenyl group having 2 to 5 carbon atoms (as the substituent) ,
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 cation 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 to 6 carbon atoms
Represents a cycloalkyl group.

R ¹ and R ² together can 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 imidazoline derivative represented by and an optical isomer of the derivative.

[Conventional technology]

Conventionally, it has been generally pointed out that when using a herbicide, the economic cost of using the herbicide depends on the amount of the active ingredient treated per unit area. The research of the compound showing is has been continued for many years.

[Problems to be solved by the invention]

The present inventors have studied for many years, and as a result, the compounds of the present invention have a significantly higher herbicidal effect than conventional herbicides, and many of the compounds of the present invention are used in certain crops, particularly legumes such as soybeans. The present invention has been completed by discovering that it has selectivity for such crops and is practically useful. That is, the compound of the present invention can significantly reduce the amount of active ingredient dropped per unit area as compared with these conventionally known compounds, its economic effect is extremely large as compared with conventional herbicides, and a large amount of pesticide is required. It can be said that it is an epoch-making herbicide that can significantly reduce the risk of environmental pollution caused by application.

[Means for solving problems]

More specifically, the compound of the present invention represented by the general formula (I) is represented by the following general formula (Ia), (Ib), (Ic) or (I
It is displayed as a type of d).

(In the formula, W, R, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above.) The compound of the present invention represented by the general formula (I) is represented by the following (Reaction formula 1). Easy to manufacture. The compound of the present invention (I
Taking the production of a) as an example, more concretely (reaction formula 1
It can be easily manufactured by a).

(In the formula, W, G, R, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above.) That is, a carboxylic acid amide derivative (II a (R ⁴ = H)]
1 to 10 equivalents of an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or magnesium hydroxide or an alkaline earth metal hydroxide in an aqueous solution at a concentration of 1% to 50% from room temperature to 100. The compound of the present invention (I a (R ⁴ = Na, K, Mg, etc.)) is obtained by heating to a temperature between ° C.

By neutralizing this with a mineral acid such as hydrochloric acid or sulfuric acid, the compound of the present invention (I a (R ⁴ = H)] can be obtained. By treating this with ammonia or an organic amine, the compound of the present invention [I a (R ⁴ = ammonium, organic ammonium cation)] is obtained.

The compound of the present invention [I a (R = H)] is treated with various R ^{4 in} an acid catalyst.
The compound (I a) of the present invention can be obtained by esterification with the alcohol R ⁴ OH corresponding to. Alternatively, by treating the compound of the present invention [I a (R = H)] with diazomethane in an inert solvent, the compound of the present invention [I a (R = C)
H ₃ )] is obtained, and the compound (I a) of the present invention is obtained by subjecting it to transesterification with an alcohol R ⁴ OH corresponding to various R ⁴ .

In addition, a carboxylic acid amide derivative [II a (R ⁴ = CH ₃ )]
If necessary, by using an inert solvent such as benzene, hexane, ether or the like, treatment with phosphorus oxychloride, phosphorus pentachloride, sodium hydride, etc., the compound of the present invention (I a
(R = CH ₃ )] can be obtained.

The starting carboxylic acid amide derivative (II a (R ⁴ = H)] can be synthesized according to the synthesis route of the following [Method A].

(In the formula, W, R, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above, and R ⁵ represents a hydrogen atom or an alkyl group.) 5-aminopyrazole (III a) and acetylenedicarboxylic The enamine form (IV a) is obtained by heating the acid ester in an alcohol solvent such as methanol or other organic solvent to a temperature between 0 to 80 ° C. The reaction temperature greatly varies depending on the basic strength of aminopyrazole. The enamine form (IV a) can also be synthesized by reacting 5-aminopyrazole (III a) with oxaloacetate (R ⁵ OOCCH ₂ COCOOR ⁵ ). The enamine form (IV a) and Vilsmeier reagent [N, N-dimethylformamide-phosphorus oxychloride system, or other reagent system (see literature)] at room temperature in chloroalkanes or chloroalkenes such as 1,2-dichloroethane The reaction at a temperature between 1 and 100 ° C, more generally between 70 and 80 ° C, gives the pyrazolo [3,4-b] pyridine-5,6-dicarboxylic acid diester (V a).

References ADv. Heterocyclic Chem., 31 , 207 (1982). ADv.Org.Chem., 9 , 225-342 (1976). By treating the diester body (V a) with a water-alcohol solution containing 2 equivalents or more of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, the corresponding dicarboxylic acid body [V a (R ⁵ = H )] The corresponding acid anhydride (VI a) can be obtained by heating the dicarboxylic acid with acetic anhydride, trifluoroacetic anhydride or the like to a temperature between room temperature and reflux temperature, preferably 60 to 100 ° C. It is possible to obtain a carboxylic acid amide derivative (II a (R ⁴ = H)] by reacting an acid anhydride (VI a) with an α-aminoamide compound in an inert solvent (eg, acetonitrile, acetone, methylene chloride, etc.). In some cases, a carboxylic acid amide derivative [VII a (R ⁴ = H)] is produced as a by-product, while a carboxylic acid amide derivative [II a (R ⁴
= CH ₃ )] can be synthesized according to the synthesis route of the following [Method B].

(In the formula, W, R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above.) The half ester [VIII a (R ⁵ = CH ₃ )] is a corresponding diester. It can be synthesized by a semi-hydrolysis reaction of [(V a (R ⁵ ═CH ₃ )] or methanol decomposition of the acid anhydride (VI a). The compound (VIII a (R ⁵ ═CH ₃ )) is acidified with thionyl chloride, etc. The compound [IIa (R ⁴ = CH ₃ )] can be obtained by converting the compound into an active ester with a chloride or a so-called chloroformate or the like, and then reacting with an α-aminoamide. The compound (IXa) is obtained by reacting VI a) with α-aminonitrile in an inert solvent, removing the solvent, and heating with an acetic anhydride solvent in the presence of catalytic amounts of sodium acetate and potassium acetate. Then use a strong acid such as sulfuric acid, and if necessary, a halogen such as chloroform, methylene chloride or carbon tetrachloride. Compound (X a) is obtained by treating with emissions of carbon hydrocarbon solvent. Compound by such a X a) compound obtained by the treatment with methanol solvent methoxide anion [II a (R ⁴ = C
H ₃ )] is obtained.

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

From (V b), (V c) and (V d) in the same manner as in [Method A], the corresponding compounds of the present invention (I b), (I c) and (I
d) can be synthesized.

Aminopyrazole (III) as a raw material can be synthesized in the same manner as in the following known documents or by a similar method.

USP 3,414,580.USP 3,686,171.J.Med.Chem., 27 , 1396
(1984) .J. Heterocyclic Chem., 12 , 1303 (1975) .ibi
d., 15 , 1447 (1978) .ibid., 16 , 1141 (1979) .ibid., 21 6
89 (1984) Beil., 25III , 2028-2034 JP-A-52-77086 J. Am. Chem. Soc., 81 , 2456 (1956) Compound of the present invention (I) For example, the compound of the present invention (I a) is as follows. (Reaction formula 2a) can be easily produced.

(In the formula, W, R, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above.) That is, the tetracyclic compound (XI a) is added to an inert aprotic solvent such as tetrahydrofuran, R ⁴ OH corresponding to various R ⁴ such as dioxane is added at a reaction temperature of about 20 to 50 ° C., if necessary, with an inorganic base such as sodium hydride or an organic base such as triethylamine as a catalyst. By reacting, the compound (Ia) of the present invention can be obtained.

The tetracyclic compound (XI a) as a starting material can be synthesized according to the synthetic route of the following [Method C].

(In the formula, W, R, R ¹ , R ² and R ³ have the same meanings as described above.) The amide compound (X a) is used in an aromatic hydrocarbon solvent such as benzene, toluene, xylene, sodium hydride and the like. The tetracyclic compound (XIa) can be synthesized by treating with an alkali metal hydride, an organic base such as DBU, or an organic acid such as p-toluenesulfonic acid.

The tetracyclic compound (XIIa), which is an isomer, may be by-produced in a small amount, but can be removed by a separation means such as column chromatography. Alternatively, even when the isomer mixture of (XI a) and (XII a) is used as it is in the next reaction (see reaction formula 2a), the compound (I a) of the present invention can be easily separated and purified from the reaction crude product. .

This will be specifically described by the following synthesis example.

Synthesis example 1 5-Amino-4-ethoxycarbonyl-1-methylpyrazole (50 g, 0.3 mol) and concentrated hydrochloric acid (300 ml) 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 was redissolved in water and powdered sodium hydrogen carbonate was added to adjust the pH of the aqueous solution to 8. Then, the water was completely distilled off under reduced pressure.
The crystalline residue is dissolved in ethanol to separate insoluble inorganic matter, and then ethanol is distilled off to give 5-amino-1.
- methylpyrazole _{^{[III a (R 2 = CH 3}} , R 3 = H) ] was obtained. Methanol 20 without purification of 5-amino compound
29.4 g (0.21 mol) of acetylene carboxylic acid dimethyl ester was added dropwise over 1 hour while dissolving in 0 ml and cooling with ice, and then methanol was distilled off under reduced pressure. The dark red oil was dissolved in chloroform, washed with water, dried and evaporated to obtain 48.6 g of an oil, which was purified by column chromatography to obtain a yellow oil enamine (IV a (R ² = R ² = R ⁵ = CH
₃ , R ³ = H)] 27.8 g (0.12 mol) was obtained.

N, N-dimethylformamide 8.34 g (0.114 mol) and 1,2-
A mixture of 200 ml of dichloroethane was cooled, 17.5 g (0.114 mol) of phosphorus oxychloride was added dropwise, and the mixture was further stirred at room temperature for 1 hour and then cooled with ice. Then the enamine form [IV a (R ² =
_{^{R 5 = CH 3, R 3}} = H) ] 27.8 g (added dropwise at 0.114 mole) 30 minutes a solution of the 1,2-dichloroethane 40ml and heated further at reflux temperature for 3 hours. After cooling to room temperature and adding water and stirring, the organic layer was separated, dried and evaporated under reduced pressure. The obtained crude product was purified by column chromatography to give the title dicarboxylic acid ester [V a (R ² = R ⁵ ＝ CH ₃ , R ³ ＝
H)] was obtained as a white crystal (7.5 g, 0.030 mol).

_{[Mp141-143 ℃; NMR (CDCl 3)} : 3.95 (s, 3H), 4.04 (s, 3
H), 4.18 (s, 3H), 8.18 (s, 1H), 8.75 (s, 1H); Mass (m
/ z): 249 (M ⁺ , 78%), 218 (100), 190 (70), 133 (4
0)] Synthesis Example 2 Dimethyl stellate [V a (R ² = R ³ = R ⁵ = CH ₃ )] 17.0 g
(0.0646 mol), caustic soda 5.69 g (0.142 mol), water 30
A mixture of 300 ml of ethanol and 300 ml of ethanol was heated to reflux with stirring (5 hours). Precipitated white crystalline disodium salt (V a (R
_{^{2 = R 3 = CH 3,}} R 5 = Na) ] was filtered off and redissolved in water and strongly acidic with concentrated hydrochloric acid white crystals were precipitated. After separation by filtration and drying, 13.0 g (0.0553 mol) of white crystals of the title compound were obtained.

[Mp233 ° C. (decomposition); NMR (DMSO-d ₆ ): 2.54 (s, 3H), 4.0
2 (s, 3H), 8.64 (s, 1H), 11.5-12.5 (b, 2H)] Synthesis Example 3 Dicarboxylic acid [V a (R ² = CH ₃ , R ³ = C ₆ H ₅ , R ⁵ = H)] 1
2.5 g (0.0421 mol) and 200 ml of acetic anhydride were heated and stirred at 90-100 ° C for 8 hours. After completion of the heating reaction, the reaction mixture was cooled and the precipitated light green crystals were separated by filtration. Target product 10.2 g (0.0366 mol)
Got

(Mp 278-280 ° C; NMR (DMSO-d ₆ ): 4.29 (s, 3H), 7.5-
7.7 (m, 3H), 8.0-8.2 (m-2H), 9.30 (s, 1H)] Similar to Synthesis Example 1 to Synthesis Example 3, shown in Table 1 (V
a) and (VI a) can be synthesized.

Synthesis example 4 Pyrazolo [3,4-b] pyridine-5,6-dicarboxylic anhydride _{^{[VI a (R 2 = CH 3}} , R 3 = H) ] 4.0 g (20 mmol), 2
A mixture of 2.56 g (20 mmol) of -amino-2,3-dimethylbutanamide and 100 ml of acetonitrile was vigorously stirred in the greenhouse for 2 days. The precipitated white crystals were separated by filtration. 〔Five.
0 g (15 mmol), mp 215-218 ° C. (decomposition)] HPLC and
From the NMR analysis results, the title 5-carboxylic acid compound [II a (R = R ² C
^{_{H 3, R 1 = i-}} Pr, R 3 = R 4 = H) ] containing as a main product, the isomers of 6-carboxylic acid derivative ^{[VII a (R = R 2 =} C
H _3, it was found to contain ^{R 1 = i-Pr, R} 3 = R 4 = H ] as a by-product. Separation of both isomers was difficult and used for the next reaction without separation.

Synthesis example 5 Pyrazolo [3,4-b] pyridine-5,6-dicarboxylic anhydride ^{[VI a (R 2 = R 3} = CH 3) ] 9.30 g (43 mmol), 2-
A mixture of 5.04 g (45. mmol) of amino-2,3-dimethylbutanenitrile and 100 ml of acetonitrile was heated under reflux for 2 hours. After heating, distill off the acetonitrile, add 100 ml of acetic anhydride and 1 g of anhydrous sodium acetate, and add 120-130.
Heated at ° 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 object imide [IX a (R = R ² = R ³
= CH ₃ , R ¹ = i-Pr)] white crystals 12.0 g (39 mmol)
Got

_{[Mp248-252 ℃; NMR (CDCl 3)} : 1.15 (d, 6H), 2.11 (s, 3
H), 2.68 (s, 3H), 3.00 (qq, 1H), 4.20 (s, 3H), 8.48
(S, 1H)] Synthesis example 6 Synthesized an imide material in Synthesis Example 5 (IX a (R = R 2 = R 3 = CH 3,
R ¹ = i-Pr)] 12.0 g (39 mmol) of powder was added little by little to 80 g of ice-cooled concentrated sulfuric acid. When it became a homogeneous solution, it was left standing overnight at room temperature. When a concentrated sulfuric acid reaction solution was carefully added to ice water, white crystals were formed. After separating the mixture, it was thoroughly washed with water and an aqueous solution of sodium bicarbonate, and then air-dried. White crystal 10.0
g (30 mmol) was obtained.

[Mp278-281 ℃; NMR (DMSO-d 6): 0.86 (d, 3H), 1.06
(D, 3H), 1.75 (s, 3H), 2.57 (s, 3H), 2.75 (qq, 1H),
4.08 (s, 3H), 6.7-7.5 (b, 2H), 8.70 (s, 1H)] Synthesis example 7 Synthesized amide in Synthesis Example 6 ^{[X a (R = R 2 =} R 3 = CH 3, R
¹ = i-Pr)] 10.2 g (31 mmol), 50% sodium hydride 1.93 g (40 mmol), 400 ml of dry toluene were heated at reflux temperature for 42 hours. The reaction solution was hot filtered through a Celite 545 filter, and the filtrate was distilled off under reduced pressure to obtain 5.0 g of a charcoal yellow crystal.

[Mp205 ° C. (decomposition)] The crude product is the title tetracyclic compound as a main product [XI a (R = R ² = R ³ = CH ₃ , R ¹ = i-Pr)]
_{[NMR (DMSO-d 6):} 0.95 (d, 3H), 1.13 (d, 3H), 1.69
(S, 3H), 2.35 (qq, 1H), 2.68 (s, 3H), 4.20 (s, 3H),
8.70 (s, IH)] include isomers tetracyclic compound as a by-product ^{[XII a (R = R 2 =} R 3 = CH 3, R 1 = i-Pr) ] to be included small amounts NMR measurements It turned out from the result. Both isomers were used in the next reaction without separation.

The compound of the present invention represented by the general formula (I) can be synthesized by the method of any one of the above (reaction formula 1) or (reaction formula 2). Specific examples are shown in Table 2. However, the compound of the present invention is not limited to these.

The compound No. of the present invention in Table 2 is referred to for the following synthesis examples, formulation examples and test examples.

Next, the compound of the present invention will be described with some specific synthetic examples. However, it is not limited to these.

Synthesis example 8 Synthesized amide in Synthesis Example 4 ^{[II a (R = R 2 =} CH 3, R 1 =
i = Pr, R ³ = R ⁴ = H)] 5.0 g (15 mmol) and sodium hydroxide 2.4 g (6.0 mmol) in an aqueous solution containing 20 ml
And heated at a temperature of 70-80 ° C. for 5.5 hours. After cooling, the insoluble matter was removed, and acetic acid was added to make the solution acidic, whereby crystals were precipitated. The separated crystals were dried to obtain 2.2 g (7 mmol) of white crystals of compound No. 1 of the present invention.

(Mp260-262 ° C (decomposition); Mass (m / z): 315 (M ⁺ , 4%), 2
97 (45), 271 (55), 228 (100); NMR-δ value (DMSO-
d ₆ ), 0.93 (d, 3H), 1.08 (d, 3H), 1.35 (s, 3H), 2.04
(Qq, 1H), 4.18 (s, 3H), 8,28 (s, 1H), 8.86 (s, 1H)] Synthesis example 9 A mixture of the compound of the present invention No. 1, synthesized in Synthesis Example 8, 900 mg ethanol 100 ml and concentrated sulfuric acid 3 ml was heated at reflux temperature for 5 days. After the alcohol was distilled off, water was added and the mixture was extracted with chloroform, the chloroform layer was dried, and then chloroform was distilled off under reduced pressure to obtain a pale yellow oily substance. Separation and purification by column chromatography (distillate: chloroform / methanol 200/10 v / v) gave the compound No. 2 of the present invention.
470 mg of white crystals of [mp215-220 ° C; NMR-δ value (CDC
l ₃ ), 0.95 (d, 3H), 1.12 (d, 3H), 1.38 (t, 3H), 1.42
(S, 3H), 2.11 (qq, 1H), 4.22 (s, 3H), 4.40 (q, 2H),
8.12 (s, 1H), 8.29 (s, 1H), 10.0 (b, 1H)] Synthesis example 10 The tetracyclic compound synthesized in Synthesis Example 7 [XI a (R = R ² = R ³ =
CH ₃ , R ¹ = i-Pr)] 930 mg (3 mmol) was added to a tetrahydrofuran 50 ml solution containing propargyl alcohol 335 mg (6 mmol) and 50% sodium hydride 144 mg (3 mmol), and the mixture was stirred overnight at room temperature. . After acetic acid was added to make the mixture acidic, the solvent and the like were distilled off under reduced pressure, and water was added to the obtained residue to precipitate crystals. After drying the precipitated crystals, the crude product (780 mg) was purified by column chromatography to give 320 mg of white crystals of the present compound No. 5.
(0.87 mmol) was obtained. [Mp 211-213 ° C. (decomposition); NMR
−δ value (CDCl ₃ ), 0.93 (d, 3H), 1.09 (d, 3H), 1.43 (s,
3H), 2.13 (qq, 1H), 2.50 (m, 1H), 2.59 (s, 3H), 4.13
(S, 1H), 4.90 (d, 2H), 8.25 (s, 1H), 9.8 (bs, 1H)] Synthesis Example 11 Amide _{[II a (R = CH 3,} R 1 = i-Pr, R 2 = Et, R 3 = R 4 =
H)] 7.0 g was mixed with 50 ml of an aqueous solution containing 3.2 g (0.08 mol) of sodium hydroxide, and the mixture was heated with stirring at 80 ° C. for 8 hours. After cooling, the insoluble matter was removed, and acetic acid was added to make the solution acidic, whereby crystals were precipitated. The separated crystals are dried to obtain the compound of the present invention.
4.1 g (0.013 mol) of No. 8 crystals was obtained.

[Melting point 252-253 ° C .; NMR-δ value (DMSO-d ₆ ), 0.92 (d, 3
H), 1.04 (d, 3H), 1.33 (s, 3H), 1.49 (t, 3H), 2.02 (q
q, 1H), 4.67 (q, 2H), 8.29 (s, 1H), 8.81 (s, 1H), 9.5
−10.5 (d, 2H)] Synthesis Example 12 (12 mol) as an aqueous solution containing 2.0 g of sodium hydroxide 3
It was dissolved in 0 ml and heated with stirring at 80 ° C. for 5 hours. After cooling, the insoluble matter was removed, and the mixture was acidified with acetic acid to precipitate crystals. When the crystals were separated by filtration and dried, 2.0 g of the compound of the present invention No. 14 (5.3
mmol) was obtained.

[Melting point 142-144 ° C .; NMR-δ value (DMSO-d ₆ ), 0.92 (d, 3
H), 1.03 (d, 3H), 1.30 (s, 3H), 2.01 (qq, 1H), 7.36−
7.56 (m, 2H), 7.95-8.25 (m, 1H), 8.45-8.62 (m, 1
H), 8.67 (s, 1H)] 9.50-10.50 (b, 2H)] The present invention shown in Tables 3 to 6 using either reaction of (Reaction Formula 1) or (Reaction Formula 2). Compound (I) can be synthesized.

In applying the compound of the present invention as a herbicide or a plant growth regulator, generally, a suitable carrier, for example, solid carrier such as clay, talc, bentonite, diatomaceous earth or water, alcohols (methanol, ethanol, etc.), aromatic carbonization Hydrogens (benzene, toluene, xylene, etc.),
It can be applied by mixing with a liquid carrier such as chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate etc.), acid amides (dimethylformamide etc.), and if desired, an emulsifier, a dispersant, a suspending agent, etc. Add turbidity agents, penetrants, spreading agents, stabilizers, etc. to prepare liquids, emulsions, wettable powders, powders, granules,
It can be put to practical use in any dosage form such as a flowable agent. The content of the active ingredient compound in these preparations is not particularly limited, but is preferably in the range of 1.0 to 90% by weight. Further, if necessary, various herbicides, various insecticides, plant growth regulators, synergists and the like may be mixed and applied at the time of formulation or spraying. The types of herbicides to be mixed are, for example, Farm Chemicals Handbook, 70th edition (1984).
And the like.

The compound of the present invention can be applied to the control of various weeds in non-agricultural fields such as fields, paddy fields, orchards in fields other than agricultural and horticultural fields such as orchards, and its application dosage is Although there are differences depending on the time of application, method of application, target grass species, cultivated crops, etc., generally an effective amount of about 0.005 to 10 kg per hectare is suitable.

Next, examples of blending a herbicide or a plant growth regulator containing the compound of the present invention as an active ingredient will be shown, but the invention is not limited thereto. In the following formulation examples, "part" means part by weight.

Formulation Example 1 Wettable powder Compound No. 1 of the present invention ...... 50 parts Dexrite PFP (kaolin clay: product name of Sigmalite Co., Ltd.) ...... 43 parts Solpol 5039 ...... 5 parts (nonionic surfactant And anionic surfactant: Toho Chemical Industry Co., Ltd. product name Carplex (anti-caking agent) …… 2 parts (white carbon: Shionogi Pharmaceutical Co., Ltd. product name) And make wettable powder. In use, the wettable powder is diluted 50 to 10,000 times and sprayed so that the amount of the active ingredient is 0.005 kg to 10 kg per hectare.

Formulation Example 2 Wettable powder Compound No. 3 of the present invention ...... 50 parts Diquelite A ...... 46 parts (Kaolin clay: Siglite Industrial Co., Ltd. trade name) Sorpol 5039 ...... 2 parts (Nonionic surfactant And anionic surfactant: Toho Chemical Industry Co., Ltd. product name Carplex (anti-caking agent) …… 2 parts (white carbon: Shionogi Pharmaceutical Co., Ltd. product name) And make wettable powder.

Formulation Example 3 Emulsion Compound No. 2 …… 10 parts Xylene …… 70 parts Dimethylformamide …… 10 parts Sorpol 2680 …… 10 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Kagaku) Kogyo Co., Ltd. product name) The above is uniformly mixed to form an emulsion. At the time of use, the above emulsion is diluted 50 to 1000 times and sprayed so that the amount of active ingredient is 0.005 kg to 10 kg per hectare.

Formulation Example 4 Granules Compound of the present invention No.1 …… 5 parts Bentonite …… 54 parts Talc …… 40 parts Calcium lignin sulfonate …… 1 part The above are uniformly mixed and pulverized, and a small amount of water is added and mixed with stirring. Granulate with an extraction-type granulator and dry to obtain granules. When using, the amount of active ingredient in the above granules is 0 per hectare.
Sprinkle so that it is 005kg-10kg.

Formulation Example 5 Flowable agent Compound of the present invention No.1 …… 25 parts Solpol 3353 …… 10 parts (Nonionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Lunox 1000C …… 0.5 parts (Anionic surfactant : Toho Chemical Industry Co., Ltd. 1% Zansan gum aqueous solution …… 20 parts (natural polymer) Water …… 44.5 parts Solpol 3353, Lunox 1000C and 1% Zansan gum aqueous solution are uniformly dissolved in water, and then the invention compound No. .1
After adding well and stirring well, wet milling is carried out with a sand mill to obtain a flowable agent. When using the above flowable agent
Dilute 50-1000 times and the amount of active ingredient is 0 per hectare.
Sprinkle so that it is 005kg-10kg.

Next, the effectiveness of the compound of the present invention as a herbicide will be specifically described in the following test examples.

Test Example-1 Herbicidal Effect Test by Soil Treatment 30 cm in height, 22 cm in width, and 6 cm in depth put sterilized diluvial soil in a plastic box, and then rice, novier, green croaker, Johnsongrass, cyperaceae, dogwood, dogtail, spruce, velvetleaf. , Swordfish, corn, wheat, soybean, cotton, barleygrass and Malaga morning glory were sown, covered with soil for about 1.5 cm, and then uniformly sprayed on the soil surface so that the amount of the active ingredient became a predetermined ratio.

The chemical liquid for spraying was prepared by diluting the wettable powder, emulsion or flowable agent of the above formulation example with water and spraying it over the entire surface with a small spray.

The herbicidal effect against various weeds was investigated 3 weeks after spraying the chemical solution according to the following criteria.

Criteria 5 …… Weeding rate 90% or more (almost complete death) 4 …… Weeding rate 70 to 90% 3 …… Weeding rate 40 to 70% 2 …… Weeding rate 20 to 40% 1 …… Weeding rate 5 to 20 % 0 ...... Hericidal rate 5% or less (almost no effect) However, the above-mentioned herbicidal rate is calculated by the following formula by measuring the above-ground weed weight of the chemical treatment area and the above-ground weed weight of the untreated area. It is a thing.

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

Criteria 5: Almost complete death of crops 4 ... Significant damage to crops 3 ... Significant damage to crops 2 ... Significant damage to crops 1 ... Almost no damage to crops 0 ... … No crop damage to crops is shown in Table 7.

Test Example 2 Herbicidal effect test by foliar treatment 30 cm in length, 22 cm in width, 6 cm in depth and put in a sterilized diluvial soil in a plastic box, rice, novier, green croaker, Johnsongrass, cyperaceae, dogpea, dog pepper, lobster, velvetleaf , Sword deer, bark-snapper, malva morning glory, corn, wheat, soybean, cotton,
Seed beet seeds in spots, about 1.5 cm
Covered with soil. When various plants reached the 2-3 leaf stage, the active ingredients were sprayed evenly on the foliage so that the amount of the active ingredient became a predetermined ratio.

The chemical solution for spraying was prepared by diluting the wettable powder, emulsion or flowable agent of the above formulation example with water and spraying it over the entire surface of the foliage of various crops and weeds with a small spray. Four weeks after spraying the chemical solution, the herbicidal effect on various weeds and the chemical damage on various crops were investigated according to the criteria of Test Example-1.

The results are shown in Table 8.

Front page continuation (72) Inventor Tsutomu Namaki 1470 Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Prefecture Masato Ikeda Examiner, Biochemical Research Institute, Nissan Chemical Industries, Ltd.

Claims (3)

[Claims] 1. General formula (I): [In the formula, G is 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, a cycloalkyl group having 5 to 6 carbon atoms, a benzyl group, a substituted phenylalkyl group, an acyl group, Alkylsulfonyl group, arylsulfonyl group, or 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 Represents a good phenyl or 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,
It represents an amino group, or a phenyl group optionally substituted with a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, 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 (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, a carbon number 3) ~ 6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group,
Optionally a halogen atom, a lower alkyl group having 1 to 4 carbon atoms,
A phenyl group which may be substituted with a lower alkoxy group having 1 to 4 carbon atoms or a nitro group, or a tri-lower alkylammonium group is shown. ), An optionally substituted lower alkenyl group having 2 to 5 carbon atoms (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, two lower alkoxy groups having 1 to 3 carbon atoms) Group, or a phenyl group), a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, and 2 carbon atoms.
To mono-, di- or trihaloalkenyl group having 5 to 5 carbon atoms, haloalkynyl group having 2 to 5 carbon atoms, glycidyl group, alkylthioalkyl group, cycloalkyl having 3 to 6 carbon atoms which may be substituted with alkyl group having 1 to 3 carbon atoms Represents a group or a cation group selected from an alkali metal atom, an alkaline earth metal atom, ammonium and 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 to 6 carbon atoms
Represents a cycloalkyl group. Further, R and R ¹ represent a cycloalkyl group having 5 to 6 carbon atoms which may form a ring together and may be substituted by a lower alkyl group having 1 to 3 carbon atoms. ]
An imidazoline derivative represented by or an optical isomer of the derivative. 2. A general formula: [In the formula, G is 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, a cycloalkyl group having 5 to 6 carbon atoms, a benzyl group, a substituted phenylalkyl group, an acyl group, Alkylsulfonyl group, arylsulfonyl group, or 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 Represents a good phenyl or 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,
It represents an amino 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 group, 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 (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, a carbon number 3) ~ 6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group,
Optionally a halogen atom, a lower alkyl group having 1 to 4 carbon atoms,
A phenyl group which may be substituted with a lower alkoxy group having 1 to 4 carbon atoms or a nitro group, or a tri-lower alkylammonium group is shown. ), An optionally substituted lower alkenyl group having 2 to 5 carbon atoms (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, two lower alkoxy groups having 1 to 3 carbon atoms) Group, or a phenyl group), a lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, and 2 carbon atoms.
To mono-, di- or trihaloalkenyl group having 5 to 5 carbon atoms, haloalkynyl group having 2 to 5 carbon atoms, glycidyl group, alkylthioalkyl group, cycloalkyl having 3 to 6 carbon atoms which may be substituted with alkyl group having 1 to 3 carbon atoms Represents a group or a cation group selected from an alkali metal atom, an alkaline earth metal atom, ammonium and 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 to 6 carbon atoms
Represents a cycloalkyl group. R ¹ and R ² together form a ring. And a cycloalkyl group having 5 to 6 carbon atoms which may be substituted with a lower alkyl group having 1 to 3 carbon atoms. ]
Cyclization of the carboxylic acid amide derivative represented by with an aqueous solution of an alkali metal hydroxide or an alkaline earth metal hydroxide, phosphorus oxychloride, phosphorus pentoxide, an alkali metal hydride or hydrogenation with an inert solvent. Cyclizing in the presence of an alkaline earth metal, or cyclizing using a dehydrating reagent such as dicyclohexylcarbodiimide, or optionally esterifying the cyclized product with diazomethane, or formula, characterized in that the alcohol R ⁴ OH by esterification or transesterification corresponding to R ⁴ (I): (In the formula, W, G, R, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above.) A method for producing an imidazoline derivative or an optical isomer of the derivative. 3. General formula (I): [In the formula, G is 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, a cycloalkyl group having 5 to 6 carbon atoms, a benzyl group, a substituted phenylalkyl group, an acyl group, Alkylsulfonyl group, arylsulfonyl group, or 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 Represents a good phenyl or 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,
It represents an amino group, or a phenyl group optionally substituted with a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, 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 (as the substituent, a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, a carbon number 3) To 6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom group, benzyloxy group, optionally halogen atom, lower alkyl group having 1 to 4 carbon atoms, 1 carbon atom To a phenyl group which may be substituted with a lower alkoxy group or a nitro group, or a tri-lower alkylammonium group.), And an optionally substituted lower alkenyl group having 2 to 5 carbon atoms (as the substituent) ,
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 cation 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 to 6 carbon atoms
Represents a cycloalkyl group. R ¹ and R ² together can 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 containing the imidazoline derivative represented by or one or more of the derivatives as an active ingredient.