KR100685473B1 - Hydantoin derivatives having herbicidal activity - Google Patents

Abstract

Hydantoin-based derivatives having herbicidal activity are provided to selectively control weeds without harmful effects to useful crops such as corn, and prevent environmental pollution by reducing the use amount of herbicides. The hydantoin-based derivatives having herbicidal activity, represented by the formula(1) are provided, wherein n is an integer from 0 to 3; R1 is hydrogen atom, C1-C6 alkyl group, C1-C6 haloalkyl group, C2-C6 alkoxyalkyl group, C1-C6 hydroxyalkyl group, C2-C6 alkenyl group or C2-C6 alkynyl group; R2 is hydrogen atom, C1-C6 alkyl group, C1-C6 haloalkyl group, C2-C6 alkenyl group or C2-C6 alkynyl group; and X is hydrogen atom, halogen atom, cyano group, hydroxyl group, C1-C4 alkyl group, C1-C4 alkoxy group, C2-C4 alkenyl group, C2-C4 alkynyl group, C2-C4 alkoxyalkyl group or C1-C4 hydroxyalkyl group. The hydantoin-based derivatives having herbicidal activity, represented by the formula(1) are prepared by halogenization of hydantoin carboxylic acid represented by the formula(2) to prepare compounds represented by the formula(4), and reacting the compounds represented by the formula(4) with compounds represented by the formula(3). A herbicidal composition comprises the hydantoin-based derivatives having herbicidal activity, represented by the formula(1).

Description

Hydantoin derivatives having herbicidal activity

The present invention relates to a hydantoin-based compound having herbicidal activity, and more particularly to non-selective herbicides such as orchards, as well as to effectively control flowering plants and broadleaf weeds without harming useful crops such as corn. It relates to a hydantoin-based compound represented by the formula (1) and a herbicide containing the compound as an active ingredient.

[Formula 1]

In Formula 1, n is 0, 1, 2, or 3; R ₁ is a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkoxyalkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ alkene group, or a C ₂ ~C ₆ alkynyl group, and the; R ₂ represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₄ alkenyl group, or a C ₂ -C ₄ alkynyl group; X is an alkynyl group of a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, C ₁ ~C ₄ alkyl group, C ₁ ~C ₄ alkoxy group, C ₂ ~C ₄ alkenyl group, C ₂ ~C ₄ of, C ₂ -C ₄ alkoxyalkyl group or C ₁ -C ₄ hydroxyalkyl group.

Weed control is very important for improving the productivity of agriculture, and various kinds of herbicides have been used. However, there are still many weeds that cause agricultural losses, so the research and development of new herbicides continues. In particular, there is still a need for the development of a highly active drug that can selectively control only the problem weeds without harming the cultivated crops.

In corn cultivation, triazine herbicides such as atrazine, or anilide herbicides such as Alachlor or Metolachlor have been used, but the properties of these agents require high dose treatment. Because of the undesirable environmental problems, the development of new herbicides is urgently required.

Known compounds having a structure similar to that of the hydantoin-based compound represented by Chemical Formula 1, characterized by the present invention, are as follows.

U.S. Patent 4,437,877 discloses a compound represented by the following formula (A).

In formula (A), X is a halogen atom and R is an alkyl group, allyl group, propazyl group and the like.

Japanese Patent Laid-Open No. 60-233075 discloses a compound represented by the following formula (B):

In the above formula (B), X is a halogen atom and R ₁ is a hydrogen atom or an alkyl group, R ₂ , R ₃ are an alkyl group, an alkenyl group, an alkynyl group, an arylalkyl group, or the like.

U.S. Patent 5,221,318 discloses compounds represented by the following formula (C):

In formula (C), X is a hydrogen atom and a halogen atom and R is a substituted alkyl group, alkenyl group, alkynyl group or cycloalkyl group.

However, no document known to date has known the hydantoin-based compound represented by the formula (1) characterized by the present invention, or the herbicidal activity of these compounds has not been tested.

An object of the present invention to provide a hydantoin-based compound represented by the formula (1).

Another object of the present invention is to provide a herbicide in which the hydantoin-based compound represented by Chemical Formula 1 is contained as an active ingredient.

The present invention is characterized by a novel hydantoin-based compound represented by the following formula (1), which is not only a non-selective herbicide such as an orchard, but also safe for corn, and has an effect of selectively controlling broadleaf, flowering and weeds.

[Formula 1]

In Formula 1, n is 0, 1, 2 or 3; R ₁ is a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkoxyalkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ alkenyl group , C _{2 to} C ₆ alkynyl group; R ₂ represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₄ alkenyl group, a C ₂ -C ₄ alkynyl group; X is an alkynyl group of a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, C ₁ ~C ₄ alkyl group, C ₁ ~C ₄ alkoxy group, C ₂ ~C ₄ alkenyl group, C ₂ ~C ₄ of, C ₂ -C ₄ alkoxyalkyl group, C ₁ -C ₄ hydroxyalkyl group.

In the compound represented by Formula 1 according to the present invention, preferably n is 0, 1, or 2; R ₁ is an alkyl group of C ₁ ~C _6; R ₂ is a hydrogen atom, a C ₁ -C ₆ alkyl group, or a C ₂ -C ₆ alkynyl group; X is a compound showing an alkoxyalkyl group, or a hydroxyalkyl group of C ₁ ~C ₄ alkyl group for a hydrogen _{atom, C 1 ~C 4, C 2} ~C 4.

In the compound represented by Formula 1 according to the present invention, particularly preferably, n is 1 or 2; R ₁ is an alkyl group of C ₁ ~C _6; R ₂ is a hydrogen atom or a C _{2 to} C ₆ alkynyl group; X is a compound showing an hydroxyalkyl group of C ₁ ~C ₄ alkyl group, an alkoxyalkyl group of C ₂ ~C _4, or C ₁ ~C _4.

In more detail, the compound represented by Formula 1 according to the present invention is shown in Table 1 below.

Compound number n R ₁ R ₂ X ¹ H NMR (CDCl ₃ ) One 0 Me H H 2 0 Me Me H 3 0 Et H H δ1.05 (t, 3H, J = 7.2 Hz), 1.40-1.85 (m, 4H), 1.95-2.35 (m, 4H), 2.85-3.0 (m, 1H), 3.85-4.7 (m, 4H), 6.7 (br s, 1H), 6.93 (d, 1H, J = 5.6 Hz), 7.15-7.35 (m, 5H), 7.43 (d, 1H, J = 8.4 Hz) 4 0 Et Me H δ1.08-1.1 (m, 3H), 1.40-1.85 (m, 4H), 2.0-2.38 (m, 4H), 2.85-3.05 (m, 4H), 3.85-4.05 (m, 1H), 4.15-4.35 (m, 1H), 4.4-4.95 (m, 3H), 6.9-7.45 (m, 7H) 5 One Me H 2-Me δ 1.40-1.85 (m, 4H), 1.64 (d, 3H, J = 6.6 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.25 (s, 3H), 2.82-2.98 (m, 1H), 3.88-4.05 (m, 1H), 4.18-4.28 (m, 1H), 4.38-4.60 (m, 2H), 4.81 (q, 1H, J = 6.6 Hz), 6.80 (br s, 1H), 6.88 (d, 1H, J = 5.6 Hz), 7.11 (s, 4H), 7.37 (d, 1H, J = 8.6 Hz) 6 One Me H 3-Me δ 1.45-1.88 (m, 4H), 1.67 (d, 2H, J = 6.4 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.33 (s, 3H), 2.82- 2.98 (m, 1H), 3.88-4.05 (m, 1H), 4.18-4.28 (m, 1H), 4.38-4.58 (m, 2H), 4.80 (q, 1H, J = 6.4 Hz), 6.80 (br s , 1H), 6.95-7.25 (m, 5H), 7.43 (d, 1H, J = 8.4 Hz) 7 One Me H 4-Me δ 1.42-1.88 (m, 4H), 1.67 (d, 3H, J = 6.4 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.32 (s, 3H), 2.82- 2.98 (m, 1H), 3.98-4.05 (m, 1H), 4.20-4.28 (m, 1H), 4.38-4.58 (m, 2H), 4.80 (q, 1H, J = 6.4 Hz), 6.8 (br s , 1H), 6.96 (d, 1H, J = 5.2 Hz), 7.4 (s, 4H), 7.43 (d, 1H, J = 8.8 Hz) 8 One Me Me 2-Me δ 1.4-1.85 (m, 7H), 2.0-2.15 (m, 1H), 2.2 (s, 3 / 2H), 2.29 (s, 3 / 2H), 2.2-2.4 (m, 1H), 3.9-4.0 (m, 1H), 4.15-4.25 (m, 1H), 4.22-5.2 (m, 3H), 6.55-6.65 (m, 1H), 6.85-7.45 (m, 6H)

Compound number n R ₁ R ₂ X ¹ H NMR (CDCl ₃ ) 9 One Me Me 3-Me δ 1.4-1.85 (m, 7H), 2.0-2.15 (m, 1H), 2.2-2.4 (m, 1H), 2.24 (s, 3 / 2H), 2.28 (s, 3 / 2H), 2.8-3.0 ( m, 1H), 2.93 (s, 3 / 2H), 3.0 (s, 3 / 2H), 3.9-4.0 (m, 1H), 4.15-4.25 (m, 1H), 4.4-5.15 (m, 3H), 6.75-6.8 (m, 1 H), 6.85-7.45 (m, 6 H) 10 One Me Me 4-Me 11 One Me Et 2-Me 12 One Me Et 3-Me 13 One Me Et 4-Me 14 One Me H 2-CH ₂ OH δ 1.42-1.84 (m, 4H), 1.66 (d, 3H, J = 6.8 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.70 (br s, 1H), 2.8 -2.98 (m, 1H), 3.90-4.6 (m, 4H), 4.59 (s, 2H), 4.78 (q, 1H, J = 6.8 Hz), 6.89 (br s, 1H), 6.93 (d, 1H, J = 5.6 Hz), 7.10-7.39 (m, 1H), 7.43 (d, 1H, J = 8.6 Hz) 15 One Me H 3-CH ₂ OMe δ 1.40-1.90 (m, 4H), 1.70 (d, 3H, J = 6.6 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.80-3.05 (m, 1H), 3.38 (s, 3H), 4.0-4.6 (m, 6H), 4.75 (q, 1H, J = 6.6 Hz), 6.85 (br s, 1H), 6.93 (d, 1H, J = 5.8 Hz), 7.2- 7.4 (m, 4H), 7.45 (d, 1H, J = 8.6 Hz) 16 One Me H 4-CH ₂ OMe 17 One Me H 2-Et δ1.21 (t, 3H, J = 7.2 Hz), 1.42-1.84 (m, 7H), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.60 (q, 2H, J = 7.2 Hz), 2.8-2.98 (m, 1H), 3.90-4.0 (m, 1H), 4.1-4.32 (m, 1H), 4.40-4.65 (m, 2H), 4.80-4.95 (m, 1H), 6.70- 6.85 (m, 1H), 6.9-7.1 (m, 1H), 7.20-7.35 (m, 4H), 7.43 (d, 1H, J = 8.6 Hz) 18 One Me H 3-Et δ1.21 (t, 3H, J = 7.4 Hz), 1.45-1.85 (m, 4H), 1.69 (d, 3H, J = 6.4 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.63 (q, 2H, J = 7.4 Hz), 2.80-2.98 (m, 1H), 3.90-4.0 (m, 1H), 4.10-4.35 (m, 1H), 4.40-4.60 (m, 2H) , 4.82 (q, 1H, J = 6.4 Hz), 6.85 (br s, 1H), 6.92 (d, 1H, J = 5.8 Hz), 6.98-7.30 (m, 4H), 7.42 (d, 1H, J = 8.6 Hz)

Compound number n R ₁ R ₂ X ¹ H NMR (CDCl ₃ ) 19 One Me H 4-Et δ1.22 (t, 3H, J = 7.2 Hz), 1.45-1.85 (m, 4H), 1.65 (d, 3H, J = 6.6 Hz), 2.0-2.15 (m, 1H), 2.25-2.40 (m, 1H), 2.64 (q, 2H, J = 7.2 Hz), 2.85-3.0 (m, 1H), 3.85-4.0 (m, 1H), 4.2-4.30 (m, 1H), 4.35-4.60 (m, 2H) , 4.74 (q, 1H, J = 6.6 Hz), 6.80 (br s, 1H), 6.90 (d, 1H, J = 5.8 Hz), 7.25 (s, 4H), 7.42 (d, 1H, J = 8.6 Hz ) 20 One Me Me 2-Et 21 One Me Me 3-Et 22 One Me Me 4-Et 23 One Et H 2-Me 24 One Et H 3-Me δ1.05 (t, 3H, J = 7.2 Hz), 1.40-1.82 (m, 4H), 1.95-2.35 (m, 4H), 2.27 (s, 3H), 2.85-3.0 (m, 1H), 3.85- 4.0 (m, 1H), 4.2-4.3 (m, 1H), 4.3-4.7 (m, 3H), 6.6 (br s, 1H), 6.93 (d, 1H, J = 5.6 Hz), 7.16 (br s, 4H), 7.43 (d, 1H, J = 8.4 Hz) 25 One Et H 4-Me 26 One Et Me 2-Me 27 One Et Me 2-Me 28 One Et Me 3-Me 29 One Et Me 4-Me 30 One Et H 2-CH ₂ OMe

Compound number n R ₁ R ₂ X ¹ H NMR (CDCl ₃ ) 31 One Et H 3-CH ₂ OMe 32 One Et H 4-CH ₂ OMe 33 2 Me H 2,3-diMe δ 1.40-1.85 (m, 1H), 1.67 (d, 1H, J = 6.6 Hz), 2.0-2.35 (m, 2H), 2.18 (s, 3H), 2.28 (s, 3H), 2.80-2.95 ( m, 1H), 3.90-4.0 (m, 1H), 4.2-4.35 (m, 1H), 4.4-4.65 (m, 2H), 4.78 (q, 1H, J = 6.6 Hz), 6.70 (br s, 1H ), 6.94 (d, 1H, J = 5.4 Hz), 7.0-7.18 (m, 3H) 34 2 Me H 3,5-diMe δ 1.40-1.82 (m, 4H), 1.65 (d, 3H, J = 6.6 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.25 (s, 3H), 2.29 ( s, 3H), 2.80-2.95 (m, 1H), 3.85-4.0 (m, 1H), 4.15-4.30 (m, 1H), 4.35-4.60 (m, 2H), 4.74 (q, 1H, J = 6.6 Hz), 6.40 (br s, 1H), 6.85 (s, 1H), 6.92 (d, 1H, J = 5.8 Hz), 7.41 (d, 1H, J = 8.6 Hz) 35 2 Me H 2,5-diMe 36 2 Me H 3,4-diMe δ 1.40-1.85 (m, 1H), 1.67 (d, 3H, J = 6.6 Hz), 2.0-2.35 (m, 2H), 2.23 (s, 6H), 2.80-2.95 (m, 1H), 3.95- 4.1 (m, 1H), 4.2-4.35 (m, 1H), 4.35-4.50 (m, 2H), 4.78 (q, 1H, J = 6.6 Hz), 6.70 (br s, 1H), 6.90-7.15 (m , 4H), 7.42 (d, 1H, J-8.6 Hz) 37 2 Me H 2,6-diMe δ 1.40-1.85 (m, 1H), 1.66 (d, 3H, J = 6.6 Hz), 2.0-2.15 (m, 1H), 2.2-2.35 (m, 1H), 2.34 (s, 6H), 2.80- 2.95 (m, 1H), 3.90-4.0 (m, 1H), 4.2-4.35 (m, 1H), 4.4-4.65 (m, 2H), 4.78 (q, 1H, J = 6.6 Hz), 6.45 (br s , 1H), 6.92 (d, 1H, J = 5.4 Hz), 7.0-7.18 (m, 3H), 7.42 (d, 1H, J = 8.4 Hz) 38 2 Me H 2,4-diMe δ 1.40-1.82 (m, 4H), 1.66 (d, 3H, J = 6.6 Hz), 2.0-2.15 (m, 1H), 2.2-2.35 (m, 1H), 2.27 (s, 3H), 2.29 ( s, 3H), 2.80-2.95 (m, 1H), 3.90-4.0 (m, 1H), 4.2-4.35 (m, 1H), 4.35-4.60 (m, 2H), 4.75 (q, 1H, J = 6.6 Hz), 6.65 (br s, 1H), 6.85-7.15 (m, 4H), 7.42 (d, 1H, J = 8.6 Hz) 39 2 Me H 2-Me, 6-Et 40 2 Me Me 2,3-diMe 41 2 Me Me 2,4-diMe

Compound number n R ₁ R ₂ X ¹ H NMR (CDCl ₃ ) 42 2 Me Me 2,5-diMe 43 2 Me Me 2,6-diMe 44 2 Et H 2,3-diMe 45 2 Et H 3,4-diMe 46 2 Et H 2,4-diMe 47 2 Et H 2,5-diMe 48 2 Et H 2,6-diMe 49 2 Me

3,5-diMe δ 1.40-1.80 (m, 7H), 2.0-2.40 (m, 3H), 2.18 (s, 3H), 2.24 (s, 3H), 2.8-3.0 (m, 1H), 3.90-4.30 (m, 4H ), 4.45-4.95 (m, 2H), 5.0-5.20 (m, 1H), 6.58 (s, 1H), 6.70-7.05 (m, 3H), 7.21-7.45 (m, 1H) 50 3 Me H 2,4,6 -triMe 51 One Et H 4-Et δ 1.04 (t, 3H, J = 7 Hz), 1.21 (t, 3H, J = 7.6 Hz), 1.40-1.85 (m, 4H), 2.0-2.15 (m, 3H), 2.20-2.35 (m, 1H) , 2.6 (q, 2H, J = 7 Hz), 2.90-3.0 (m, 1H), 3.90-4.05 (m, 1H), 4.15-4.65 (m, 4H), 6.70 (br s, 1H), 6.92 (d , 1H, J = 5.2 Hz), 7.05-7.20 (m, 4H), 7.42 (d, 1H, J = 8.4 Hz)

On the other hand, the present invention includes a method for producing a compound represented by the formula (1). In the preparation method according to the present invention, as shown in the following Scheme 1 by halogenating the hydantoin carboxylic acid represented by the following formula (2) to synthesize a compound represented by the following formula (4), and the compound represented by the following formula (3) Compounds represented by the following formula (1) may be prepared by combining and reacting.

In Scheme 1, n, R ₁ , R ₂ and X are as defined above, respectively.

In the preparation method according to Scheme 1, the hydantoin carboxylic acid represented by Chemical Formula 2 is subjected to halogenation using a suitable halogenation reagent, and concentrated under reduced pressure to remove excess volatile halogenation reagent. When the amine compound and the tertiary base represented are added and stirred for 1 hour to 10 hours at a temperature of 0 to 30 ° C. under a suitable solvent, the compound represented by Chemical Formula 1 can be obtained. As the halogenation reagent, thionyl chloride, oxalyl chloride, phosphorus oxychloride and phosgene may be used. As the base, tertiary amines such as triethyl amine, dimethyl aniline and pyridine may be used. Dichloromethane, dichloroethane, ethyl acetate, acetonitrile, toluene, diethyl ether, dimethyl formamide, and the like may be used as the solvent used in the halogenation reaction and the reaction with the amine compounds. After the reaction is completed, the reaction mixture may be diluted with a general separation process, for example, diluted with an organic solvent, washed with water, and then the organic layer may be concentrated under reduced pressure or purified by chromatography if necessary. In the preparation method according to Scheme 1, the compound represented by Formula 4 synthesized as an intermediate may be used in a coupling reaction with the following amine compounds after separation and purification, if necessary.

In addition, the compound represented by Formula 2 used as a starting material in the preparation method according to Scheme 1 is prepared by reacting hydantoin benzyl ester represented by the following Formula 5 with hydrogen under a catalyst, as shown in the following Scheme 2 can do.

In Scheme 2, R ₁ is as defined above.

In the preparation method according to Scheme 2, the compound represented by Chemical Formula 2 may be obtained by dissolving the hydantoin benzyl ester represented by Chemical Formula 5 in a suitable solvent and reacting with hydrogen under a palladium catalyst. The reaction is stirred under excess hydrogen, 10- 40 It progresses over 10 to 20 hours at the temperature of ° C. In this case, methanol, ethanol, dichloroethane, dichloromethane, acetonitrile, ethyl acetate, diethyl ether, dioxane, tetrahydrofuran and the like may be used as the solvent. As a catalyst, palladium may be used in an amount of 0.001 to 0.01 equivalent, and palladium may be used as a reagent adsorbed to carbon at 5 to 10%. Upon completion of the reaction, the reaction solution is filtered through celite, washed with a solvent and the filtrate is concentrated to give the desired product.

In addition, the hydantoin benzyl ester represented by the formula (5) used as a starting material in the preparation method according to Scheme 2, after the phosgenation reaction of the compound represented by the following formula (6), as shown in Scheme 3, To the isocyanate compound represented by the following formula (7) can be prepared by combining the compound represented by the following formula (8) and cyclization reaction.

In Scheme 3, R ₁ is as defined above.

In the preparation method according to Scheme 3, a compound represented by Chemical Formula 6 is phosgenated in a suitable solvent to prepare an isocyanate compound represented by Chemical Formula 7. In this case, phosgene, diphosgene, triphosgene, and the like may be used as the phosgenation reagent, and the amount thereof is used in an amount of 1.5 to 5 equivalents, preferably 2 to 3 equivalents. As a solvent, aromatic hydrocarbons such as toluene, xylene, chlorobenzene, dichlorobenzene, etc. may be used, and the reaction temperature is 100 to 130. It is C and reaction time progresses over 1 to 10 hours. The isocyanate compound represented by the formula (7) produced as a result of the phosgenation reaction is not isolated and purified immediately, only the volatile compound is removed, and then the compound represented by the formula (8) is added thereto, and a suitable base and 1,8-diazabicyclo [5, 4,0] Unde-7-sen by heating under reflux to obtain the compound represented by compound 5. Examples of the base used herein include tertiary amines such as triethyl amine, trimethyl amine and pyridine, and the amount of 1,8-diazabicyclo [5,4,0] unde-7-cene catalyst is 0.01 to 0.1 equivalents. Use At this time, the coupling reaction time is 1 hour to 10 hours.

On the other hand, US Patent No. 5,221,318 as a conventional manufacturing method similar to the reaction scheme 3 is shown in the following scheme 4.

In addition, the compound represented by the formula (6) used as a starting material in the preparation method according to Scheme 3 is a known compound and the following formula shown in US Patent No. 5,221,318 represented by the following formula (9) as shown in Scheme 5 The compound represented by 10 can be synthesized by binding reaction.

In the preparation method according to Scheme 5, for example, carbonates such as calcium carbonate and sodium carbonate or triethyl amine, pyridine, N, N- dimethyl aniline, 1,8-diazabicyclo [5,4,0] ] Organic bases such as undec-7-cene can be used. At this time, as a solvent, ketones such as acetone, aromatic hydrocarbons such as toluene and xylene, ethers such as tetrahydrofuran and dioxane, nitriles of acetonitrile and propionitrile, or N, N- dimethyl formamide Amides such as N, N- dimethyl acetamide and N- methyl pyrrolidone can be used. Reaction temperature is 0 Any temperature range from ℃ to the reflux temperature at which the reaction proceeds, preferably from 30 to 90 When the reaction time is in the range of 5 to 24 hours, the desired product can be obtained with good yield.

   After the reaction is completed, the reaction mixture may be diluted with a general purification process, for example, diluted with an organic solvent, washed with water, and then the organic layer may be concentrated under reduced pressure or purified by chromatography if necessary.

The present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example 1: Synthesis of 2- (5-amino-2-cyano-4-fluorophenoxy) propionic acid benzyl ester

5 g of 5-amino-2-cyano-4-fluorophenol was dissolved in 100 mL of acetonitrile, and 12.1 g of 2- (p-toluenesulfonyloxy) propionic acid benzyl ester and 5.5 g of K ₂ CO ₃ were heated to reflux. . After 10 hours, the reaction mixture was cooled, diluted with 200 mL of ethyl acetate, washed with 150 mL of water, and the organic layer was dried over MgSO ₄ and concentrated. The concentrate was separated and purified by silica gel column chromatography to obtain 8.8 g of the target compound.

¹ H NMR (CDCl ₃ ) δ 1.64 (d, 3H, J = 6.6 Hz), 4.0 (br s, 2H), 4.62 (q, 1H, J = 6.6 Hz), 5.15 (s, 2H), 5.93 ( d, 1H, J = 7.2 Hz, 7.06 (d, 1H, J = 10.2 Hz), 7.20-7.38 (m, 5H)

Example 2: of 2- [2-cyano-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4-fluorophenoxy] propionic acid benzyl ester synthesis

5.5 g of 2- (5-amino-2-cyano-4-fluorophenoxy) propionic acid benzyl ester was dissolved in 100 mL of anhydrous toluene, and 35 mL of a 23% phosgene solution dissolved in toluene was added and heated to reflux for 1 hour. The volatile compound was concentrated under reduced pressure, 50 mL of toluene was added to the reaction solution, 4.1 g of ethyl pipecolinate hydrochloride, 1.7 mL of triethylamine, and 0.1 mL of 1,8-diazabicyclo [5,4,0] ound-7 -Sene (DBU) was added and heated to reflux for 1 hour. After cooling the reaction solution, 100 mL of ethyl acetate was added to dilute the reaction solution, washed with 100 mL of 5% hydrochloric acid solution, and the organic layer was dried over MgSO ₄ and concentrated. The concentrate was separated and purified by silica gel column chromatography to obtain 6.1 g of the target compound.

¹ H NMR (CDCl ₃ ) δ 1.40-1.85 (m, 4H), 1.64 (d, 3H, J = 6.6 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.82- 2.98 (m, 1H), 3.88-3.98 (m, 1H), 4.18-4.28 (m, 1H), 4.82 (q, 1H, J = 6.6 Hz), 5.18 (s, 2H), 6.80-6.86 (m, 1H), 7.23-7.40 (m, 6H)

Example 3: Synthesis of 2- [2-cyano-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4-fluorophenoxy] propionic acid

3 g of 2- [2-cyano-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4-fluorophenoxy] propionic acid benzyl ester ethyl acetate It was dissolved in 30 mL, and 150 mg of 10% Pd / C was added, followed by hydrogenation by hanging a hydrogen balloon. Upon completion of the reaction, the reaction solution was filtered through celite and washed with ethyl acetate. The filtrate was concentrated to give 2.3 g of the target substance.

¹ H NMR (CDCl ₃ ) δ 1.40-1.85 (m, 4H0, 1.70 (d, 3H, J = 6.8 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.82-2.98 (m, 1H), 3.88-4.05 (m, 1H), 4.18-4.28 (m, 1H), 4.82 (q, 1H, 6.8 Hz), 6.82-6.88 (m, 1H), 7.44 (d, 1H, J = 8.4 Hz)

Example 4: N- (2-methyl) benzyl-2- [2-cyano-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4- Synthesis of Fluorophenoxy] propionamide (Compound No. 5)

Thionyl chloride 2 in 300 mg of 2- [2-cyano-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4-fluorophenoxy] propionic acid 2 After adding the mL and refluxed for 5 hours, cooled and concentrated under reduced pressure. 5 mL of dichloromethane was added to the residue, and the reaction solution was cooled to 0 ° C., and 120 mg of 2-methyl benzylamine and 0.14 mL of triethyl amine were added thereto. The reaction temperature was raised to room temperature and stirred for 3 hours. The reaction solution was diluted with 50 mL of dichloromethane and washed with 20 mL of 5% hydrochloric acid solution. The separated organic layer was dried over MgSO ₄ and concentrated. The concentrate was separated and purified by silica gel column chromatography to obtain 200 mg of the target substance.

¹ H NMR (CDCl ₃ ) δ 1.40-1.85 (m, 4H), 1.64 (d, 3H, J = 6.6 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.25 ( s, 3H), 2.82-2.98 (m, 1H), 3.88-4.05 (m, 1H), 4.18-4.28 (m, 1H), 4.38-4.60 (m, 2H), 4.81 (q, 1H, J = 6.6 Hz), 6.80 (br s, 1H), 6.88 (d, 1H, 5.6 Hz), 7.11 (s, 4H), 7.37 (d, 1H, J = 8.6 Hz)

Example 5: N- (3-methyl) benzyl-2- [2-cyano-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4- Synthesis of Fluorophenoxy] propionamide (Compound No. 6)

Using 300 mg of 2- [2-cyano-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4-fluorophenoxy] propionic acid as starting material The reaction in Example 4 was carried out with 120 mg of 3-methyl benzylamine to obtain 220 mg of the target substance.

¹ H NMR (CDCl ₃ ) δ 1.45-1.88 (m, 4H), 1.67 (d, 2H, J = 6.4 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.33 ( s, 3H), 2.82-2.98 (m, 1H), 3.88-4.05 (m, 1H), 4.18-4.28 (m, 1H), 4.38-4.58 (m, 2H), 4.80 (q, 1H, J = 6.4 Hz), 6.80 (br s, 1H), 6.95-7.25 (m, 5H), 7.43 (d, 1H, J = 8.4 Hz)

Example 6: N- (4-methyl) benzyl-2- [2-cyano-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4- Synthesis of Fluorophenoxy] propionamide (Compound No. 7)

Using 300 mg of 2- [2-cyano-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4-fluorophenoxy] propionic acid as starting material The reaction in Example 4 was carried out with 120 mg of 4-methyl benzylamine to obtain 235 mg of the target substance.

¹ H NMR (CDCl ₃ ) δ1.42-1.88 (m, 4H), 1.67 (d, 3H, J = 6.4 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.32 ( s, 3H), 2.82-2.98 (m, 1H), 3.98-4.05 (m, 1H), 4.20-4.28 (m, 1H), 4.38-4.58 (m, 2H), 4.80 (q, 1H, J = 6.4 Hz), 6.8 (br s, 1H), 6.96 (d, 1H, J = 5.2 Hz), 7.4 (s, 4H), 7.43 (d, 1H, J = 8.8 Hz)

Example 7: N- benzyl-2- [2-chloro-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4-fluorophenoxy] propion Synthesis of Amide (Control Compound 1)

 Using 300 mg of 2- [2-chloro-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4-fluorophenoxy] propionic acid as a starting material, Reaction with 110 mg of benzylamine was carried out by the method in Example 4 to obtain 210 mg of the target substance.

¹ H NMR (CDCl ₃ ) δ 1.42-1.88 (m, 4H), 1.64 (d, 3H, J = 6.6 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.82- 2.98 (m, 1H), 3.89-4.05 (m, 1H), 4.20-4.28 (m, 1H), 4.35-4.65 (m, 3H), 6.86 (d, 1H, J = 6.2 Hz), 6.90 (br s , 1H), 7.20-7.38 (m, 6H)

Example 8: N- (4-methyl) benzyl-2- [2-cyano-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4- Synthesis of Fluorophenoxy] propionamide (Control 2)

Using 300 mg of 2- [2-chloro-5- (1,3-dioxohexahydroimidazo [1,5-a] pyridin-2-yl) -4-fluorophenoxy] propionic acid as a starting material, The reaction in Example 4 was carried out with 120 mg of 4-methyl benzylamine to give 215 mg of the target substance.

¹ H NMR (CDCl ₃ ) δ 1.42-1.88 (m, 4H), 1.64 (d, 3H, J = 6.6 Hz), 2.0-2.15 (m, 1H), 2.20-2.35 (m, 1H), 2.34 ( s, 3H), 2.82-2.98 (m, 1H), 3.89-4.05 (m, 1H), 4.20-4.28 (m, 1H), 4.28-4.58 (m, 2H), 4.80 (q, 1H, J = 6.6 Hz), 6.88 (d, 1H, J = 6.6 Hz), 6.90 (br s, 1H), 7.14-7.32 (m, 3H)

Those skilled in the art can easily synthesize the compounds illustrated in Table 1 by using or applying the synthesis methods exemplified in the above examples.

[Suggestions]

When the compound of the present invention is used as a herbicide, a carrier, a surfactant, a dispersant, an adjuvant, and the like, which are commonly used in formulating the compound of the present invention and pesticides, may be mixed and formulated into various forms such as a hydrating agent, an emulsion, a powder suspension and a liquid. do. These formulations can be used directly and can be processed by dilution in appropriate media. The spray volume can be used from several hundred liters to several thousand liters per hectare.

The formulations may contain up to about 0.1% to 99% by weight of the active ingredient, which may contain from about 0.1% to 20% of the surfactant or from 0% to 99.9% of a solid or liquid diluent. It may be. A summary of this is shown in Table 2 below.

The proportion of the active ingredient can be adjusted according to the use, and it is sometimes necessary to use a higher proportion of the surfactant than the active ingredient, and may be added in the preparation or used in tank mixing.

When using a solid diluent, a high absorbent diluent is good for making a hydrate. The liquid diluent and the solvent are preferably stable without phase separation even at 0 ° C. All formulations are added with small amounts of additives to prevent foaming, cakes, corrosion and microbial growth.

The method of making the composition is a conventional method, and the liquid preparation only needs to mix the components, and the fine solid composition may be mixed and ground in a hammer or a flow mill. Suspensions are compounded in a wet mill and granules are made by spraying an active substance onto the granular carrier.

Representative examples of preparation using the compounds according to the invention are as follows.

Formulation 1: Hydration

The following components were thoroughly mixed and the liquid surfactant was mixed while spraying onto the solid components. Grinding in a hammer mill brought the particle size to 100 μm or less.

Compound (Compound No. 5) 20 wt%

2% by weight of decylphenol polyethylene glycol ether

Sodium Lignin Sulfonate 4 wt%

Sodium silicon aluminate 6% by weight

Montmorillonite 68% by weight

Formulation 2: Hydration

The following ingredients were mixed and ground in a hammer mill until the particle size was 25 μm or less and packaged.

Compound (Compound No. 5) 80 wt%

Sodium Alkyl Naphthalene Sulfonate 2 wt%

Sodium Lignin Sulfonate 2 wt%

3% by weight of synthetic amorphous silica

13% by weight kaolinite

Formulation 3: Emulsion

The following components were mixed and uniformly dissolved to give an emulsion.

Compound (Compound No. 5) 30 wt%

20% by weight of cyclohesanone

11% by weight of polyoxyethylene alkylaryl ether

Alkylbenzenesulfonate calcium 4% by weight

Methylnaphthalene 35 wt%

Formulation 4: granulation

The following components were mixed and ground uniformly, 20 parts by weight of water was added to 100 parts by weight of the mixture, mixed and processed into granules of 14 to 32 mesh using an extruder, followed by drying to prepare granules.

Compound (Compound No. 5) 5 wt%

Sodium lauryl alcohol sulfate ester salt 2% by weight

Sodium Lignin Sulfonate 5 wt%

2% by weight of carboxymethyl cellulose

Potassium Sulfate 16% by weight

70% by weight of the gypsum preparations are diluted and sprayed to a suitable concentration for practical use.

[Usage]

The compound of the present invention is particularly useful for corn farming because it exhibits high selectivity for corn during foliage treatment, and at the same time shows excellent control of not only grasses but also broadleaf weeds. In addition, since it exhibits a wide range of herbicidal effects at low concentrations, it is very useful as a non-selective herbicide such as an orchard.

The herbicide of the present invention can be used up to 10 g to 1 kg per hectare (ha) as an active ingredient, preferably 10 g to 400 g. The choice of dosage is determined by factors such as weed generation, growth level, and preparation.

In addition, the herbicide of the present invention can be used alone or in combination with other herbicides, insecticides or fungicides. Especially bentazone, quinclolac, furofanyl, cetmethrin, 2,4-D, phenoxapuroethyl, linyuron, MCPA, azaphenidine, carfentrazone, molinate, thiobencarb, pendimethalin, Bensulfuronmethyl, pyrazosulfuronethyl, metsulfuronmethyl, thifensulfuronmethyl, tribenuronmethyl, trifluurine, amidosulfuron, brooxynyl, butaclo, mecofurop, metreuxin, biphenox, ben One or more selected from purazate, isopururoron, thihalopopbutyl, mefenacet, pentrazamide, pyriminobac methyl, bispyribac sodium, azimsulfuron, cyclosulfamuron, and peanker It is also useful to use in combination with a medicament.

As the weeds of the present invention, weeds represented by varieties, weeds, node grasses, etc. represented by varieties, weeds, beetles, etc. Branches represented by weeds, buckwheats, etc. represented by weeds and buckwheat represented by cruciferous weeds and silkworms represented by amaranth, weeds and waxes Hyunsam, weeds, weeds, and plantains, represented by weeds, prickly grass, and the like.

The following is an example of testing the weed control effect exhibited by the compounds of the present invention.

Test Example 1: Foliar Treatment Test

After the sterilization of the sandy loam mixed with an appropriate amount of fertilizer, the seeds of each plant such as corn, American open field, barley, crow, purple grass, buckwheat, mother's nest, and lizard were planted in 600 cm 2 test pots and covered with 0.1-1 cm. . Post-germination treatment was treated with the prepared drug 8 to 12 days after sowing. The test agent was dissolved in a mixture of 1 part by weight of the test agent, 5 parts by weight of acetone, and 1 part by weight of an emulsifier, and diluted with water, and a water-soluble agent prepared by spraying at a rate of 2000 L per hectare (ha). The amount of active compound was chosen to be the specific amount desired.

On the 14th day after the drug treatment, the drug efficacy test evaluated the damage of the plant by visual comparison with the control group without treatment with the drug.

The evaluation values are shown as follows.

0% invalid (equivalent to no medication)

20% slight effect

70% herbicidal effect

100% annihilation (complete test)

As a result of the experiment, the compound represented by the formula (1) according to the present invention showed high selectivity in corn and particularly showed strong herbicidal effect on broadleaf weeds.

Comparison of foliage treatment herbicidal activity with control drug (60 g a.i./ha) Test substance weed  wire grass United States Under the hood Fidget Silkworm Compound number 5 100 100 100 100 100 Compound number 7 100 100 100 100 100 Compound number 33 100 100 100 100 100 Compound number 34 100 100 100 100 100 Compound number 36 100 100 100 100 100 Compound number 37 100 100 100 100 100 Control Compound 1  40 40 100 100 100 Control Compound 2 50 30 100 100 100

대조화합물 2 :

Control Compound 1:

Control Compound 2:

Foliage Treatment Weakness and Drug Test (16g a.i./ha) Test substance crops weed corn  Under the hood Silkworm Fidget Macaw convolvulus Compound number 5 0  100 100 100 80 100 Compound number 6 0 100 100 100 100 100 Compound number 7 0 100 100 100 100 100 Compound number 36 10 100 100 100 100 100 Compound number 37 10  100 70 100 100 100 Compound number 38 10  100 95 100 100 100

As described above, the novel compounds according to the present invention showed excellent selectivity and herbicidal activity as a result of greenhouse experiments. In addition, the novel compounds according to the invention increase the efficiency, particularly as non-selective herbicides such as orchards and corn farming.

Claims (19)

Hydantoin-based compound, characterized in that represented by the following formula (1): [Formula 1]

In Formula 1, n is 0, 1, 2 or 3; R ₁ is a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkoxyalkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ alkenyl group , C _{2 to} C ₆ alkynyl group; R ₂ represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₄ alkenyl group, a C ₂ -C ₄ alkynyl group; X is an alkynyl group of a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, C ₁ ~C ₄ alkyl group, C ₁ ~C ₄ alkoxy group, C ₂ ~C ₄ alkenyl group, C ₂ ~C ₄ of, C ₂ -C ₄ alkoxyalkyl group, C ₁ -C ₄ hydroxyalkyl group. The compound of claim 1, wherein n is 0, 1, or 2; R ₁ is an alkyl group of C ₁ ~C _6; R ₂ is a hydrogen atom, a C ₁ -C ₆ alkyl group, or a C ₂ -C ₆ alkynyl group; X represents a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₂ -C ₄ alkoxyalkyl group, or a C ₁ -C ₄ hydroxyalkyl group. The compound of claim 1, wherein n is 1 or 2; R ₁ is an alkyl group of C ₁ ~C _6; R ₂ is a hydrogen atom or a C _{2 to} C ₆ alkynyl group; X is a compound wherein represents a hydroxyalkyl group of C ₁ ~C ₄ alkyl group, an alkoxyalkyl group of C ₂ ~C _4, or C ₁ ~C _4. The compound of claim 1, wherein n is 1, R ₁ is a methyl group, R ₂ is a hydrogen atom, and X is a 2-methyl group. The compound of claim 1, wherein n is 1, R ₁ is a methyl group, R ₂ is a hydrogen atom, and X is a 3-methyl group. The compound of claim 1, wherein n is 1, R ₁ is a methyl group, R ₂ is a hydrogen atom, and X is a 4-methyl group. The compound of claim 1, wherein n is 2, R ₁ is a methyl group, R ₂ is a hydrogen atom, and X is a 2,3-dimethyl group. The compound of claim 1, wherein n is 2, R ₁ is a methyl group, R ₂ is a hydrogen atom, and X is a 2,4-dimethyl group. The compound of claim 1, wherein n is 2, R ₁ is a methyl group, R ₂ is a hydrogen atom, and X is a 2,6-dimethyl group. The compound of claim 1, wherein n is 2, R ₁ is a methyl group, R ₂ is a hydrogen atom, and X is a 3,4-dimethyl group. The compound of claim 1, wherein n is 2, R ₁ is a methyl group, R ₂ is ethynyl, and X is a 3,5-dimethyl group. Herbicide composition, characterized in that any one of the hydantoin-based compound selected from claims 1 to 11. After a halogenation reaction of the hydantoin carboxylic acid represented by the following formula (2), and then reacting with the compound represented by the following formula (3) to produce a hydantoin-based compound represented by the following formula (1):

[Formula 1]

In Chemical Formulas 1, 2, or 3, n, R ₁ , R ₂ , and X are as defined in Claim 1, respectively. The method of claim 13, wherein the intermediate compound produced by the halogenation reaction is a compound represented by the following formula (4):

In Formula 4, R ₁ is as defined in claim 1 above. 15. The method according to claim 13 or 14, wherein the intermediate compound represented by the formula (4) is added to the reaction solution, and the compound represented by the formula (3) is added to the reaction solution to perform the coupling reaction. The method of claim 13, wherein the halogenation reaction is performed using a halogenation reagent selected from thionyl chloride, oxarylyl chloride, phosphorusoxychloride, and phosgene. The method of claim 13, wherein the coupling reaction is carried out at a temperature of 0 to 30 ℃ in the presence of an amine base. Hydantoin carboxylic acid represented by the following formula (2): [Formula 2]

In Formula 2, R ₁ is as defined in claim 1 above. Hydantoin benzyl ester represented by the following formula (5):

In Formula 5, R ₁ is as defined in claim 1 above.