KR950004699B1 - Herbicidal n-substituted phengl-3,4-dimethylmaleimide derivatives and process for preparing the same - Google Patents

Abstract

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Description

Herbicidal N-substituted phenyl-3,4-dimethyl maleimide derivatives and preparation methods thereof

The present invention relates to novel N-substituted phenyl-3,4-dimethyl maleimide derivatives of the following general formula (I), their preparation and the use of these compounds as herbicides or plant growth inhibitors.

[Formula 1]

Wherein R ¹ is C ₁ -C ₆ alkyl, phenyl, a phenyl group substituted with halogen, R ² is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl , C ₃ -C ₇ cycloalkyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkylthioalkyl, benzyl or alkoxycarbonyl alkyl group.

N-substituted phenylmaleimide derivatives with herbicidal action are reported in EP 260228.

[Formula 2]

In the formula (a), R ¹ is hydrogen or fluorine, R ² is halogen, Y is C ₁ -C ₈ alkyl, Z is hydrogen or C ₁ -C ₈ alkyl, and A is H or the following organic substituents.

Wherein ^{R 3, R 4, R 5} , R 6, R 7, R 8 is a normal organic substituent, X is oxygen, sulfur, SO, SO _2, NH, alkyl, etc. The alkenyl Mino Mino or Al.

However, the compounds represented by the general formula (I) according to the present invention are considered to be spatially empty in a state in which the Y and Z portions of the formula (a) are fixed with methyl, R ¹ with fluorine, and R ² with chlorine Losing part A is longer and bigger.

Particularly, European Patent No. 260228, in which the A portion is directly linked with carbon atoms, provides a better efficacy and improved selectivity between weeds and crops by inserting the -O-CH ₂ -group at the A position. have.

Hereinafter, the present invention will be described in detail.

The present invention relates to an N-substituted phenyl-3,4-dimethyl maleimide derivative represented by the general formula (I), wherein in the general formula (I), R ¹ is a phenyl group substituted with methyl, phenyl or chloro , And R ² is hydrogen, C ₁ -C ₃ alkyl, C ₃ -C ₄ alkenyl, C ₃ alkynyl, C ₃ haloalkenyl, C ₃ alkylthioalkyl, or C ₃ cycloalkyl group, Specifically, the case of the compound represented by the following general formula (I-a) or (I-b) is particularly preferable.

[Formula 3]

[Formula 4]

The present invention will be described in detail with reference to the manufacturing method of the general formula (I) as follows.

According to the present invention, by reacting 2,3-dimethyl maleic anhydride represented by the following general formula (II) with 2-fluoro-4-chloro-5-hydroxyaniline represented by the following general formula (III), To prepare a compound of formula (IV) and to react the α-halocarbonyl compound represented by the following general formula (V) to obtain a compound of the following general formula (VI), hydroxylamine hydrochloride is added to distilled water Suspended in a mixed solvent of and a lower alcohol and the base was added to obtain a compound of the following general formula (VII), and then reacted with R ² -X in the presence of a base to prepare a new compound represented by the general formula (I). A].

Scheme 1

In the formulas, R ¹ and R ² are as defined in the general formula (I), respectively, and X is chloro or bromo as leaving group.

To explain in more detail the production method of the present invention, 2,3-dimethyl maleic anhydride of the general formula (II) and 2-fluoro-4-chloro-5-hydroxy aniline of the general formula (III) to glacial acetic acid Dissolve using as a solvent, reflux for 4-5 hours under anhydrous conditions and cool to room temperature.

This reaction solution is poured into cold stirring water to obtain compound (IV). Compound (IV) and α-halocarbonyl compound (V) are refluxed for about 2 to 14 hours using an inorganic base in an organic solvent and separated by a conventional method to obtain compound (VI).

The organic solvent used at this time is acetone, dimethylformamide and the like, and acetone is usually used.

As the base, alkali metals such as sodium and potassium carbonate are mainly used.

The compound (VI) and the hydroxylamine hydrochloride are suspended in a mixed solvent of distilled water and a lower alcohol, and a base is added thereto. The reaction is carried out at room temperature for 2 to 24 hours, and then the solvent is blown about half. The reaction solution is poured into cold water to obtain a solid. This solid is separated by suction filtration and dried to obtain compound (iii). The lower alcohol used here is methyl alcohol or ethyl alcohol, and the base is pyridine or alkali metal carbonate.

The intermediate represented by formula (VII) and R ² X are refluxed for 3 to 18 hours with a base in an organic solvent to obtain a compound represented by formula (I). The organic solvent and base used at this time are as above-mentioned, and R <^{2> is} also as above-mentioned.

The compound represented by the general formula (I) thus prepared has a strong herbicidal action. In addition, there is a wide range of selectivity between crops and weeds, and is particularly useful for weed removal during wheat cultivation in pre-germination and post-germination treatments.

It also shows excellent herbicidal action and selectivity under freshwater conditions. In particular, it has a very good selectivity with the non-piramids, a problem weed during rice cultivation, and is very useful for removing weeds during rice cultivation.

As such, the compound represented by the general formula (I) of the present invention is useful as a herbicide or a plant growth inhibitor. A composition having a herbicidal or plant growth inhibitory effect containing the compound of the present invention can be prepared and used according to a conventional method. have.

Representative compounds of the general formula (I) are specifically illustrated in Table 1 below.

[Formula 5]

TABLE 1

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the Examples.

Example 1

Preparation of N- (2-fluoro-4-chloro-5-hydroxyphenyl) -2,3-dimethyl maleimide (IV).

2,3-dimethyl maleic anhydride (24.0 g, 190 mmol) and 2-fluoro-4-chloro-5-hydroxy aniline (30.0 g, 192 mmol) were dissolved in 120 ml of glacial acetic acid and refluxed in an oil bath for 12 hours. The reaction solution was cooled to room temperature and poured into 1 l of cold water to obtain a light brown solid. The solid was filtered off with suction, washed with distilled water and dried to give 49 g of crude product. This was separated by a column packed with silica gel (developing solvent; dichloromethane) to obtain the desired product as a pale yellow powder, which was recrystallized from 2-propanol to give a very pure acicular white crystal.

Yield: 27.5 g (53.7%)

Melting Point: 167 ~ 168 ℃

¹ H NMR (acetone-d ₆ ): δ 2.03 (s, 6H), 7,02-7.41 (q, 2H), 9.16 (s, 1H).

Mass spectrometry (EIMS, 70 eV) m / z 54 (100), 269 (M ⁺ ).

Example 2

Preparation of Intermediate (VI, R ¹ = CH ₃ )

Compound (IV) (8.09 g, 30 mmol) and chloro acetone (3.2 g, 34.5 mmol) synthesized in Example 1 were dissolved in 100 ml of dried acetone, and then 5.0 g of potassium iodide and potassium carbonate (4.15 g, 30 mmol) were added thereto. Reflux for 18 hours. The solvent was blown off under reduced pressure, and the oil thus obtained was separated by a column packed with silica gel (developing solvent: 300 ml of hexane, then dichloromethane / hexane = 6: 4). The desired portion was collected and the solvent removed to afford the desired compound as a white solid.

Yield: 9.15 g (94%)

Example 3

Preparation of Intermediates (I, R ¹ = CH ₃ , R ² = H)

Compound (IV, R ¹ = CH ₃ , 8.14g, 25mmol) and hydroxylamine hydrochloride (1.8g, 25.8mmol) synthesized in Example 2 were suspended in 300 ml of methyl alcohol and 200 ml of distilled water, followed by DMAP (dimethyl aminopyridine). ) 200 mg and pyridine (2.0 g, 25.3 mmol) were added and stirred at room temperature for 24 hours. The solvent was blown off at about 300 ml under reduced pressure, and the remainder was poured into cold water (600 ml) to obtain a white solid. The solid was separated by suction filtration, and dried to obtain the target product in the form of a white solid.

Yield: 8.40 g (99%)

m.p. : 194-196 ℃

¹ H NMR (dimethylsulfoxide-d ₆ ) δ 1.88 and 1.92 (two s, 3H, CH ₃ ), 2.01 (s, 6H), 4.59 and 4.89 (two s, 2H), 7.25-7.80 (m, 2H), 10.92 and 11.06 (two s, 1H, oxime protons). mixture of syn ⁺ anti

Example 4

Preparation of Compound 2 (I, R ¹ = CH ₃ , R ² = -CH ₂ C≡CH)

Compound 1 (1.02 g, 3.5 mmol) synthesized in Example 3 and propazyl bromide (80% w / w toluene solution, 0.67 g, 4.5 mmol) were dissolved in 50 ml of anhydrous acetone, followed by anhydrous calcium carbonate (0.52 g, 3.7). mmol) was added and refluxed for about 7 hours. The reaction solution was poured into diluted aqueous hydrochloric acid and extracted with ether (2 x 100 ml). The combined organic layers were washed once with cold water, dried over MgSO ₄ and the solvent was blown off under reduced pressure. The oil thus obtained was separated by a column packed with silica gel (developing solvent: hexane / acetone, 1: 9) to obtain a pale yellow solid of the desired product.

Yield: 1.07 g (81%)

m.p. : 70-72 ℃

Example 5

Preparation of Compound 3 (I, R ¹ = CH ₃ , R ² = -CH ₂ CH≡CH ₂ )

The target product was obtained as a yellow oil by the reaction of allyl bromide and compound 1 using the same method as the method of synthesizing compound 2 in Example 4.

Yield: 0.93 g (70%)

Example 6

Preparation of Compound 4 (I, R ¹ = -C (CH ₃ ), R ² = H)

In the same manner as in Example 2, intermediates (IV, R ¹ = -C (CH ₃ ), 1.03 g, 2.8 mmol) and hydroxyl amine hydrochloride (0.29 g, 4.2) synthesized from compound IV and α-bromo pinacolon mmol) was dissolved in 300 ml of ethyl alcohol, 10 mg of 4-dimethyl amino pyridine was added as a catalyst, pyridine (0.33 g, 4.2 mmol) was added, followed by stirring at room temperature for 2 hours. The reaction solution was poured into cold water to produce a white solid, which was separated by suction filtration, and dried to obtain the target product.

Yield: 0.86 g (80%)

m.p. : 151-153 ℃

¹ H NMR (dimethylsulfoxide d ₆ ) δ 1.26 (s, 9H), 2.06 (s, 6H), 4.89 (s, 2H), 6.94 -7.30 (twod, 2H), 8.70 (brs, 1H).

Mass spectrometry (EIMS, 70 eV) m / z 41 (100), 55 (88), 57 (94), 83 (71), 269 (50), 347 (M ⁺ -Cl, 34).

Example 7

Preparation of Intermediate (VI, R ¹ = -C ₆ H ₅ )

Compound (IV) (8.09 g, 30 mmol) and phenacyl chloride (4.64 g, 30 mmol) synthesized in Example 1 were dissolved in 100 ml of dried acetone, followed by 5.0 g of potassium iodine and anhydrous potassium carbonate (4.15 g, 30 mmol). The mixture was refluxed for about 18 hours. The solvent was blown off under reduced pressure, and the oil thus obtained was separated by a column packed with silica gel to obtain the desired product as a white solid.

Yield: 11.5 g (99%)

¹ H NMR (chloroform-d ₃ ) δ 2.00 (s, 6H), 5.30 (s, 2H), 6.75-8.00 (m, 7H).

Example 8

Preparation of Compound 5 (I, R ¹ = -C ₆ H ₅ , R ² = H)

Compound VI (R ¹ = -C ₆ H ₅ , 9.7 g, 24 mmol) and hydroxylamine hydrochloride (1.80 g, 25.8 mmol) synthesized in Example 7 were suspended in a mixed solvent of 150 ml of ethyl alcohol and 150 ml of distilled water. 200 mg of 4-dimethylaminopyridine and pyridine (2.0 g, 25 mmol) were added as a catalyst and stirred at room temperature for 24 hours. The ethyl alcohol is almost blown off at reduced pressure and poured into 500 ml of cold water to form a white solid. The solid was filtered off with suction and dried to obtain the target product as a white solid.

Yield: 9.50 g (94%)

Example 9

Preparation of Compound 6 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₂ CH≡CH ₂ )

Using the same method as in Example 4, Compound 6 was obtained from Compound 5 and allyl bromide synthesized in Example 8.

Example 10

Preparation of Compound 7 (I, R ¹ = C ₆ H ₅ , R ² = -CH ₂ C≡CH)

Compound 7 was obtained in the same manner as in Example 9.

Yield: 1.14 g (87%)

Example 11

Preparation of Compound 8 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₂ CH ₂ CH ₃ )

Compound 8 was obtained in the same manner as in Example 9.

m.p. : 71-73 ℃

¹ H NMR (chloroform-d ₃ ) δ 0.95 (t, 3H), 1.70 (m, 2H), 2.04 (s, 6H), 4.15 (t, 2H), 5.25 (s, 2H), 6.70-7.80 ( m, 7H).

Example 12

Preparation of Compound 9 (I, R ¹ = -C ₆ H ₅ , R ² = -CH (CH ₃ ) ₂ )

Compound 9 was obtained in the same manner as in Example 9.

m.p. : 102-104 ℃

¹ H NMR (chloroform-d ₃ ) δ 1.25 (d, 6H), 2.00 (s, 6H), 4.10-4.50 (m, 1H), 5.20 (s, 2H), 6.80-7.90 (m, 7H) .

Example 13

Preparation of Compound 10 (I, R ¹ = -C ₆ H ₅ , R ² = -CH (CH ₃ ) COOCH ₃ )

Compound 10 was obtained in the same manner as in Example 9.

m.p. : 100-102 ℃

¹ H NMR (chloroform-d ₃ ) δ 1.55 (d, 3H), 2.00 (s, 6H), 3.70 (s, 3H), 5.50-5.00 (q, 1H), 5.30 (s, 2H), 6.90-7.90 (m, 7 H).

Example 14

Preparation of Compound 11 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₃ )

Compound 11 was obtained in the same manner as in Example 9.

m.p. : 77-78 ℃

¹ H NMR (chloroform-d ₃ ) δ 2.00 (s, 6H), 3.95 (s, 3H), 5.20 (s, 2H), 6.75-8.00 (m, 7H).

Example 15

Preparation of Compound 12 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₃ C ₆ H ₅ )

Compound 12 was obtained in the same manner as in Example 9.

m.p. : 80-82 ℃

¹ H NMR (chloroform-d ₃ ) δ 2.00 (s, 6H), 5.20 (s, 4H), 6.75-8.00 (m, 12H).

Example 16

Preparation of Compound 13 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₂ CH ₃ )

Compound 13 was obtained in the same manner as in Example 9.

¹ H NMR (chloroform-d ₃ ) δ 1.30 (t, 3H), 2.00 (s, 6H), 4.10 (q, 2H), 5.20 (s, 2H), 6.65-7.85 (m, 7H).

Example 17

Preparation of Compound 14 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₂ CH = CH-CH ₃ )

Compound 14 was obtained in the same manner as in Example 9.

¹ H NMR (chloroform-d ₃ ) δ 1.60-1.80 (d, 3H), 2.05 (s, 6H), 4.50-4.85 (m, 2H), 5.20 (s, 2H), 5.50-5.80 (m, 2H) , 6.70-7.80 (m, 7 H).

Example 18

Preparation of Compound 15 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₂ -C (CH ₃ ) = CH ₂ )

Compound 15 was obtained in the same manner as in Example 9.

m.p. : 79-80 ℃

¹ H NMR (chloroform-d ₃ ) δ 1.76 (s, 3H), 2.05 (s, 6H), 4.65 (s, 2H), 4.80-5.15 (m, 2H), 5.25 (m, 2H), 6.75-7.80 (m, 7 H).

Example 19

Preparation of Compound 16 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₂ -C (Cl) = CH ₂ )

Compound 16 was obtained in the same manner as in Example 9.

m.p. : 79-81 ℃

¹ H NMR (chloroform-d ₃ ) δ 2.06 (s, 6H), 4.76 (s, 2H), 5.30 (s, 2H), 5.37-5.70 (m, 2H), 6.78-7.72 (m, 7H).

Example 20

Preparation of Compound 17 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₂ OCH ₃ )

Sodium hydride (67.5 mg, 2.8 mmol) was put in a plastic and 10 ml of anhydrous tetrahydrofuran was slowly added dropwise while cooling with an ice bath under nitrogen. Here, the compound 5 (0.63 g, 1.4 mmol) synthesized in Example 8 was dissolved in 5 ml of anhydrous tetrahydrofuran. Thereafter, bromomethyl methyl ether (0.30 g, 2.4 mmol) was dissolved in 5 ml of anhydrous tetrahydroxyfuran and added slowly for about 5 minutes. After the temperature of the reaction solution was raised to room temperature, stirring was continued for 5 hours. The reaction solution was poured into water and extracted with ether. The combined organic layer was dried (MgSO ₄ ) and the solvent was blown off under reduced pressure to give crude product 17 in the form of an oil. This was separated by a column packed with silica gel (electrosol: hexane / ether, 10: 1) to obtain desired compound 17.

Yield: 0.20 g (30%)

m.p. : 101-103 ℃

¹ H NMR (chloroform-d ₃ ) δ 2.00 (s, 6H), 3.25-3.50 (s, 3H), 5.00-5.30 (m, 4H), 6.70-7.80 (m, 7H).

Example 21

Preparation of Compound 18 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₂ -CH ₂ SCH ₃ )

Compound 18 was obtained in the same manner as in Example 9.

m.p. : 105-106 ℃

Example 22

Preparation of Compound 19 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₂ (CH ₂ ) ₄ CH ₃ )

Compound 19 was obtained in the same manner as in Example 9.

m.p. : 83-85 ℃

¹ H NMR (chloroform-d ₃ ) δ 0.85-2.15 (m, 7H), 2.00 (s, 6H), 4.10 (m, 2H), 5.20 (s, 2H), 6.75-7.95 (m, 7H).

Example 23

Preparation of Compound 20 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₂ (CH ₂ ) ₄ CH ₃ )

Compound 20 was obtained in the same manner as in Example 9.

¹ H NMR (chloroform-d ₃ ) δ 0.85-2.00 (m, 11H), 2.05 (s, 6H), 3.80-4.50 (m, 2H), 5.25 (d, 2H), 6.85-7.90 (m, 7H) .

Example 24

Preparation of Compound 21 (I, R ¹ = -C ₆ H ₅ , R ² = -CH ₂ )

Compound 21 was obtained in the same manner as in Example 9.

¹ H NMR (Chloroform-d ₃ ) δ 0.30-1.30 (m, 5H), 2.03 (m, 6H), 3.45-4.10 (m, 2H), 5.20 (s, 2H), 6.75-8.00 (m, 7H) .

Example 25

Preparation of Intermediate (VI, R ¹ = -4-ClC ₆ H _4- )

Compound IV (0.27 g, 1 mmol) and 1- (4-chlorophenyl) -2-chloroethanol (0.19 g, 1 mmol) synthesized in Example 1 were dissolved in 20 ml of dried acetone, followed by 0.1 g of potassium iodide and potassium carbonate. (0.14 g, 1 mmol) was added and refluxed for 5 hours. The solvent was blown off under reduced pressure, and the obtained crude product was separated by a column packed with silica gel to obtain the desired purpose as a white solid.

Yield: 0.35 g (83%)

m.p. : 150-152 ℃

¹ H NMR (chloroform-d ₃ ) δ 2.00 (s, 6H), 5.18 (s, 2H), 6.80-7.85 (m, 6H).

Example 26

Preparation of Compound 22 (VI, R ¹ = -4-ClC ₆ H _4- , R ² = H)

Compound 22 was obtained in the same manner as in Example 3 using Intermediate VI (R ¹ = -4-ClC ₆ H _4- ) and hydroxyamine hydrochloride synthesized in Example 25.

Yield: 0.44 g (66%)

m.p. : 141-143 ℃

Example 27

Preparation of Compound 23 (I, R ¹ = -4-ClC ₆ H _4- , R ² = -CH ₂ C≡CH)

Compound 23 was obtained from the compound 22 synthesized in Example 26 using the same method as in Example 9.

¹ H NMR (chloroform-d ₃ ) δ 2.00 (s, 6H), 2.33-2.73 (m, 1H), 4.53-4.87 (m, 2H), 5.30 (s, 2H), 6.80-7.85 (m, 6H) .

Example 28

Preparation of Compound 24 (I, R ¹ = -4-ClC ₆ H _4- , R ² = -CH ₂ CH≡CH)

Compound 24 was obtained in the same manner as in Example 9.

m.p. : 102-105 ℃

¹ H NMR (chloroform-d ₃ ) δ 2.00 (s, 6H), 4.50-4.75 (m, 2H), 5.00-5.50 (m, 2H), 5.25 (s, 2H), 5.90-6.10 (m, 1H) , 6.60-7.30 (m, 6 H).

Mass spectrometry (EIMS, 70 eV) m / z 41 (96), 137 (100), 441 (35), 477 (M ⁺ +1, 1).

Example 29

Preparation of Compound 25 (I, R ¹ = -4-ClC ₆ H _4- , R ² = -CH ₂ C (Cl) ≡CH ₂ )

Compound 25 was obtained in the same manner as in Example 9.

¹ H NMR (chloroform-d ₃ ) δ 2.00 (s, 6H), 4.48-4.73 (m, 2H), 5.0-5.60 (m, 2H), 5.20 (s, 2H), 7.00-7.60 (m, 6H) .

Example 30

Preparation of Intermediate (VI, R ¹ = 2,4-Cl ₂ C ₆ H _3- )

Compound IV (0.40 g, 1.5 mmol) and 1- (2,4-dichlorophenyl) -2-bromoethanone (0.40 g, 1.5 mmol) synthesized in Example 1 were used in the same manner as in Example 25. An intermediate (VI, R ¹ = 2,4-Cl ₂ C ₆ H _3- ) was obtained.

Yield: 0.58 g (85%)

Example 31

Preparation of Compound 26 (I, R ¹ = 2,4-Cl ₂ C ₆ H _3- , R ² = H)

Compound 26 was obtained in the same manner as in Example 3 using intermediate VI (R ¹ = 2,4-Cl ₂ C ₆ H _3- ) and hydroxylamine hydrochloride synthesized in Example 30.

Yield: 0.57 g (75%)

m.p. : 159-161 ℃

¹ H NMR (dimethylsulfoxide-d ₆ ) δ 1.99 (s, 6H), 5.26 (s, 2H), 7.27-7.72 (m, 5H), 12.08 (s, 1H).

Example 32

Preparation of Compound 27 (I, R ¹ = 2,4-Cl ₂ C ₆ H _3- , R ² = -CH ₂ C≡CH)

Compound 27 was obtained in the same manner as in Example 9.

¹ H NMR (Chloroform-d ₃ ) δ 2.07 (s, 6H), 2.49 (t, J = 2.4 Hz, 1H), 4.81 (d, J = 2.4 Hz, 2H), 5.23 (s, 2H), 6.75 -7.46 (m, 5 H).

Example 33

Preparation of Compound 28 (I, R ¹ = 2,4-Cl ₂ C ₆ H _3- , R ² = -CH ₂ CH = CH ₂ )

Compound 28 was obtained in the same manner as in Example 9.

¹ H NMR (chloroform-d ₃ ) δ 2.05 (s, 6H), 4.55-4.72 (m, 2H), 5.04-5.48 (m, 2H), 5.23 (s, 2H), 5.93-6.05 (m, 1H) , 6.74-7.41 (m, 5H).

In using the present invention represented by the general formula (I), it can be used as it is or in the form of a preparation such as a hydrating agent, an emulsion, a granule, a liquid or a powder.

Solid carriers or liquid carriers can be used to make such preparations. Solid carriers include inorganic powder (kaolin, bentonite, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite, synthetic silicon hydroxide), plant powder (soybean flour, flour, sawdust, tobacco powder) , Starch powder, crystalline cellulose), polymer materials (petroleum resin, vinyl chloride resin, ketone resin), alumina, wheat tower, and the like can be used. Liquid carriers include alcohols (methanol, ethanol, ethylene glycol, benzyl alcohol), aromatic hydrocarbons (toluene, benzene, xylene, methyl naphthalene), halogenated hydrocarbons (chloroform, carbon tetrachloride, chlorobenzene), ethers (dioxane, tetrahydrofuran ), Ketones (acetone, methyl ethyl ketone, cyclonucleic acid temperature), esters (ethyl acetate, butyl acetate, ethylene glycol acetate), amides (dimethylformamide), nitriles (acetonitrile), ether alcohols (ethylene glycol ethyl Ether) and water.

Nonionic, anionic, cationic or amphoteric materials may be used as the surfactant used for emulsification or dispersion. Examples of the surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene fatty acid esters, oxyethylene oxypropylene resins, polyoxyethylene alkyl phosphates, fatty acid salts, alkyl sulfates, alkylsulfonates, alkylarylsulfonates , Alkyl phosphates, polyoxyethylene alkyl sulfates, quaternary ammonium salts and the like.

However, the surfactants that can be used are not limited to these. If necessary, glue, casein, starch, agar, polyvinyl alcohol or lignin sulfonic acid may be used as a supplement.

When preparing as a herbicide, the content of the substance represented by the general formula (I) can be used in a weight ratio of about 1 to 95%, preferably 3 to 80% by weight.

The compound (I) may be used together with other kinds of herbicides to improve the herbicidal effect, and in some cases, synergism may be expected.

Moreover, compound (I) can be used together as an insecticide, nematicide, fungicide, plant growth regulator, fertilizer, etc. as needed.

The dosage of the compound (I) depends on the kind of the compound, the kind of the crop, the treatment method and the like. Generally, the dosage is about 60 g to 1 kg per 3000 pyeong, preferably 120 g to 500 g.

Examples of use as actual herbicides according to the invention are illustrated in the following test examples.

Test Example

Biological assessment

Sand loam mixed with an appropriate amount of fertilizer was sterilized and placed in a test pot (foot condition: 348 cm ² , paddy condition: 115 cm ² ). At this time, the number of pots used was 2 pots for development condition and 1 pot for non-conditioning per compound. Thereafter, as seizure and weeds, tomatoes (L. esculentum), wheat (T. aestiuum), soybean (G. max), corn (z. Mays), orchard grass (D. glomerata), sesame (A. uridis) Seeds, or underground, such as D. sanguinalis, R. japonicus, P.hydropi per, A. indica, C. japonica, etc. Seeds of rice crops (O. sativa), E. oryzieola, C. difforis and A. keisak as paddy crops and weeds were sown in fine pots After the clay was buried, it was placed in a greenhouse. 4 ml / ha of test compound (field condition: 14 mg / pot, paddy condition: 4 mg / pot) was mixed with the same amount using acetone as a solvent, and in the field condition, 14 ml of the pot was sprayed. The amount of 4 kg / ha or less was diluted and sprayed in an appropriate amount according to the ratio.

Soil treatment before germination was treated with the preparation prepared on day 1 after sowing, and foliage treatment after germination 9-14 days after sowing. After treatment, they were grown in a greenhouse for 2 to 3 weeks, and their herbicidal effects were examined by morphology and physiological basis. That is, 0% means no herbicidal effect, 10-30% slightly herbicidal effect, 40-60% moderate effect, 70-90% severe effect, and 100% means full herbicidal effect.

The herbicidal effect before germination and the herbicidal effect after germination of the representative compounds of the general formula (I) of the present invention are as shown in Tables II and III.

TABLE 2

TABLE 3

Test Example

Herbicidal effect in freshwater conditions

Rice herbicide screening in fresh water was tested using rice (O. sativa), E. oryzieola, tadpole rings (s. Juncoides) and M. vaginalis. As in the case of dry herbicide search, the herbicide effect was searched 2 days after treatment with the drug, and the results are summarized in Table IV.

TABLE 4

Claims (12)

N-substituted phenyl-3,4-dimethyl maleimide derivative represented by the following general formula (I). Wherein R ¹ is C ₁ -C ₆ alkyl, phenyl or halogen substituted phenyl group, R ² is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl , C ₂ -C ₆ alkynyl, C ₂ -C ₇ cycloalkyl, C ₂ -C ₅ alkoxy alkyl, C ₂ -C ₆ alkylthioalkyl, benzene or alkoxycarbonyl alkyl group. The compound of claim 1, wherein R ¹ is a phenyl group substituted with methyl, phenyl or chloro. A compound according to claim 1, wherein R ² is hydrogen, C ₁ -C ₃ alkyl, C ₃ -C ₄ alkenyl, C ₃ alkynyl, C ₃ halo alkenyl, C ₃ alkylthioalkyl or C ₃ cycloalkyl group . The compound according to claim 1, wherein the general formula (I) is represented by the following general formula (I-a). The compound according to claim 1, wherein the general formula (I) is represented by the following general formula (I-b). To the compound represented by the following formula (IV), hydroxylamine hydrochloride was suspended in a mixed solvent of distilled water and a lower alcohol, and a base was added to obtain a compound of the following formula (VII), and then reacted with R ² -X in the presence of a base. A method for producing an N-substituted phenyl-3,4-dimethyl maleimide derivative represented by the following general formula (I). In the formulas, R ¹ and R ² are as defined in general formula (I) of claim 1, respectively. A herbicide containing N-substituted phenyl-3,4-dimethyl maleimide derivative represented by the following general formula (I) as an active ingredient. 8. The herbicide according to claim 7, which is used in the cultivation of tomatoes, wheat, soybeans, or corn in pre-germination or post-germination treatment. The herbicide of Claim 8 used in wheat cultivation in the pre-germination process. The herbicide of Claim 8 used in wheat cultivation in a post-germination process. 8. The herbicide of Claim 7, which is used in freshwater conditions. The herbicide according to claim 11, which is used for selective control of blood when growing rice under fresh water condition.