KR0163591B1 - Uracil derivatives and herbicides containing the same as active ingredient - Google Patents

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Uracil derivatives and herbicides containing the same as active ingredients

The present invention relates to novel uracil derivatives and selective herbicides containing uracil derivatives as active ingredients.

Various herbicides have been manufactured and used in practice to protect important crops such as rice, soybeans, wheat, corn, cotton, sugarcane, etc. from weeds and increase their productivity. Herbicides can be broadly classified into the following three types according to the place of administration: (1) mountain cultivating herbicides, (2) rice herbicides and (3) parenteral herbicides. Herbicides of each class can be subdivided into subgroups, such as soil incorporation type, pre-germination type and post-germination type (leaf surface treatment) type, depending on the method of administration.

With the recent increase in the global population, it is undeniable that the productivity of stock crops has seriously affected the food boundaries of each country, and the productivity improvement of stock crops is now a particularly important issue. Indeed, there is a greater need for people in agriculture to develop effective and economical herbicides to kill weeds or to control the growth of weeds that are harmful to the cultivation of crops.

As such herbicides, it is required to be able to satisfy the following conditions: (1) The herbicidal effect is high even at a small dose. (In particular, from the viewpoint of environmental protection, weeds should be able to kill small amounts of herbicide as much as possible. )

(2) Residual effects are adequate. (Recently, it has been pointed out that the chemicals that maintain their effects for a long time in the soil may cause the next crop to be harmed. It is important to do that.)

(3) Weeds die quickly after administration. (The next crop can be sown and transplanted within a short time after chemical treatment.)

(4) Fewer herbicide treatments (administration). (It is important for farmers to minimize the number of weed-control operations.)

(5) The weeds that are killed or suppressed by one herbicide are widespread. (The administration of one herbicide is preferred to be able to kill or suppress different weeds such as broadleaf weeds, weeds with poapools and perennial weeds. )

(6) There are various methods of administration. (If the method can be administered in various ways such as soil treatment, foliar treatment, etc., the herbicidal effect is enhanced.)

(7) There is no damage to crops. (In farmland where crops and weeds coexist, it is preferable that only weeds are selectively killed by herbicides.)

However, no herbicides can satisfy all of the above conditions.

It is known that some compounds in uracil derivatives have herbicidal activity. For example, the Pesticide Manual, 8th edition, page 89 (The British Crop Protection Council, 1987) describes bromasil as a herbicide with uracil structure.

Also known are the following hetero-ring derivatives which may serve as active ingredients for herbicides:

(1) 3-aryluracil-alkyl, alkenyl and alkynylenol ethers of the following general formula (Japanese Patent Laid-Open No. 63-107967):

이고, R²는 할로겐 또는 시아노이고, R³은 수소 또는 할로겐이며, R⁴는 수소, 플루오르 또는 C_1-4알킬이고, R⁵는 C_1-4알킬 또는 C_1-4할로알킬이며, 또는 R⁴와 R⁵는 함께 트리-또는 테트라-메틸렌일 수 있고, R⁶과 R⁷은 독립적으로 C_1-4알킬이고, m은 1 또는 2이며, X는 O, O-C(O), O-C(O)-O 또는 C(O)-O이다.Wherein R ¹ is C _1-8 alkyl, C _2-6 alkenyl, C _2-6 alkynyl, C _2-8 alkoxyalkyl or

R ² is halogen or cyano, R ³ is hydrogen or halogen, R ⁴ is hydrogen, fluorine or C _1-4 alkyl, R ⁵ is C _1-4 alkyl or C _1-4 haloalkyl, Or R ⁴ and R ⁵ together may be tri- or tetra-methylene, R ⁶ and R ⁷ are independently C _1-4 alkyl, m is 1 or 2, and X is O, OC (O), OC (O) -O or C (O) -O.

(2) The compound of the following general formula and its salt whose R <^1> is hydrogen (Japanese Patent Laid-Open No. 63-41466):

Wherein R ¹ is hydrogen, C _1-4 alkyl, C _1-4 haloalkyl, formyl or C _2-6 alkanonyl, and R ² contains ether or (thio) carbonyloxy or sulfonyloxy And a residue directly bonded to benzene nucleus A via an oxygen atom, R ³ is halogen or cyano, R ⁴ is hydrogen or halogen, R ⁵ is hydrogen, halogen or C _1-4 alkyl, and R ⁶ is C _1-4 alkyl or C _1-4 haloalkyl, or R ⁵ and R ⁶ together may be tri- or tetramethylene.

(3) Benzothiazolone derivatives of the following general formula (Japanese Patent Laid-Open No. 62-155276):

Wherein R is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower haloalkale, lower haloalkynyl, lower alkoxy-lower alkyl, lower alkoxy-lower alkoxy-lower alkyl, cinnamil or Lower cyanoalkyl.

(4) Condensed hetero-ring derivatives of the following general formula (Japanese Patent Laid-Open No. 1-250388):

Wherein X is an oxygen atom or a sulfur atom, and Z is

G is a hydrogen atom or a halogen atom, A is a halogen atom or NO ₂ , E is a hydrogen atom, a halogen atom, C≡N, NO ₂ , NH ₂ , OH, SH, OR ₁ , and R ₁ is C _1-5 alkyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl- (C _1-2 ) alkyl, C _2-4 alkenyl, C _3-4 alkynyl,

CH ₂ C≡N, tetrahydropyranyl, tetrahydrothiopyranyl, CH ₂ COR _{1e '} ,

Or C _1-2 alkoxy- (C _1-2 ) alkyl, SR ₃ , CO ₂ R ₅ , NHR ₆ , or CH = NOR ₇ , Q _a and Q _b are independently an oxygen atom or a sulfur atom, and R _1a is Hydrogen atom or C _1-3 alkyl, R _1b is hydrogen atom, C _1-5 alkyl, C _2-5 alkenyl, C _3-5 alkynyl, C _2-3 haloalkyl, C _1-2 alkoxy- ( C _1-2 ) alkyl, C _3-4 cycloalkyl- (C _1-2 ) alkyl, C _3-6 cycloalkyl, CH ₂ CO _2- (C _1-3 alkyl), or CH (CH ₃ ) -CO _2- (C _1-2 alkyl), or R _1a and R _1b combine to form a 4- to 6-membered ring lactone consisting of a methylene chain, and R _1c and R _1d are independently a hydrogen atom, C _1-5 Alkyl, C _2-5 alkenyl, C _3-5 alkynyl, C _2-5 haloalkyl, C _3-6 cycloalkyl or C _3-6 cycloalkyl- (C _1-2 ) alkyl, or R _1d with R _1c combine to form a 5- to 7-membered ring consisting of a methylene chain, R _1e is C _1-3 alkyl, R _1f is a hydrogen atom, C _1-3 alkyl, CH ₂ CO _2- (C _{1- 3} ) alkyl or COCH ₃ , R ₃ is a phase Has the same meaning as group R ₁ , R ₅ is a hydrogen atom, C _1-5 alkyl, C _3-6 cycloalkyl or C _3-6 cycloalkyl- (C _1-2 ) alkyl, R ₆ is C _{1- 5} alkyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl- (C _1-2 ) alkyl, C _2-4 alkenyl or C _3-4 alkynyl, R ₇ is a hydrogen atom, C _1-5 Alkyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl- (C _1-2 ) alkyl, C _2-4 alkenyl or C _3-4 alkynyl, L is a hydrogen atom or a halogen atom, Y is Oxygen atom or sulfur atom, n is 0 or 1, J is hydrogen atom, halogen atom, C _1-5 alkyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl- (C _1-2 ) alkyl, C _2-4 alkenyl, C _3-4 alkynyl, C _1-5 haloalkyl, C _3-4 haloalkenyl, C _3-4 haloalkynyl, C _1-2 alkoxy- (C _1-2 ) alkyl, CH ₂ C≡N, CH ₂ CO ₂ R ₈ , or CH ₂ CH ₂ CO ₂ R ₉ , R ₈ and R ₉ are hydrogen atoms, C _1-5 alkyl, C _3-6 cycloalkyl or C _3-6 Cycloalkyl- (C _1-2 ) alkyl.

(5) The compound of the following general formula and its salt whose R <^1> and / or R <^2> is hydrogen (Japanese Patent Laid-Open No. 61-221178):

Wherein R ¹ is hydrogen, C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _2-6 alkoxyalkyl, formyl, C _2-6 alkanoyl or C _2-6 alkoxy Carbonyl; R ² is hydrogen, C _1-6 alkyl, C _2-4 alkenyl, C _2-4 alkynyl or C _2-6 alkoxyalkyl; R ³ is halogen or nitro; R ⁴ is hydrogen or halogen; R ⁵ is hydrogen, halogen, C _1-4 alkyl, chloromethyl, bromomethyl, hydroxymethyl, (C _1-5 alkoxy) methyl, (C _1-5 alkylthio) methyl, cyano, nitro or thiooxy Anatomic; R ⁶ is hydrogen, C _1-4 alkyl or C _1-4 fluoroalkyl, or R ⁵ and R ⁶ combined are tri- or tetramethylene, wherein one of the methylene groups may be substituted with oxygen or sulfur Or these groups may be substituted with C _1-3 alkyl; X is oxygen or sulfur, (i) R ⁶ is C _1-4 alkyl or C _1-4 fluoroalkyl when R ₅ is fluorine, and (ii) R ⁶ is hydrogen or C ₁ when R ⁵ is cyano _-4 alkyl and X is oxygen.

(6) Tetrahydrophthalimide derivatives of the following general formula (Japanese Patent Laid-Open No. 61-85385):

또는

이고, R²및 R³은 수소 또는 메틸이다.Wherein R ¹ is C _1-5 alkyl, C _3-5 alkenyl, C _3-5 alkynyl or C _1-3 alkoxymethyl, X is hydrogen, fluorine or chlorine, and A is a nitrogen atom in the benzene ring Combined

or

And R ² and R ³ are hydrogen or methyl.

(7) Tetrahydrophthalimide derivatives of the following general formula (Japanese Patent Laid-Open No. 61-30586):

Wherein R ¹ is alkyl, alkenyl, alkynyl, alkoxyalkyl or alkoxyalkoxyalkyl and R ² is hydrogen or methyl.

(8) Tetrahydrophthalimide derivatives of the following general formula (Japanese Patent Laid-Open No. 61-76486):

Wherein R ¹ is alkyl, alkenyl, alkynyl, alkoxyalkyl or alkoxyalkoxyalkyl and R ² is hydrogen or methyl.

(9) Tetrahydrophthalimide derivatives of the following general formula (Japanese Patent No. 61-43188):

Wherein R is C _1-5 alkyl, C _3-5 alkenyl, C _3-5 alkynyl or C _1-3 alkoxymethyl, and X is hydrogen or fluorine.

(10) herbicidal compounds of the general formula and substituted derivatives thereof (US Pat. No. 3,981,715):

Wherein X is hydrogen or hydroxy, R ¹ is hydrogen or halo, and R ² is alkyl, cycloalkyl, phenyl, alkenyl.

(11) herbicidal compounds of the general formula and substituted derivatives thereof (US Pat. No. 3,869,457):

Wherein X is hydrogen or hydroxy, R ¹ is hydrogen or halo, and R ² is alkyl, cycloalkyl, phenyl, alkenyl.

(12) A compound of formula (I) and an enol ether and salt thereof (WO 88/10254):

이고, 또는 R¹이 할로알킬, 수소, C_1-8알킬, C_2-8알켄일, C_2-8알킨일 또는 C_2-8알콕시알킬인 경우, R³은 할로겐 또는 시아노이며, R⁴는 수소 또는 할로겐이고, R⁵는 수소, 플루오르 또는 C_1-4할로알킬이다.Wherein R ¹ is hydrogen, C _1-4 alkyl, C _3-4 alkenyl, C _3-4 alkynyl or C _1-4 haloalkyl, R ² is

When R ¹ is haloalkyl, hydrogen, C _1-8 alkyl, C _2-8 alkenyl, C _2-8 alkynyl or C _2-8 alkoxyalkyl, R ³ is halogen or cyano, R ⁴ is hydrogen or halogen and R ⁵ is hydrogen, fluorine or C _1-4 haloalkyl.

Herbicides capable of meeting the above conditions (1) to (7), i.e., have no effect on crops (crop damage) and are effectively selective and exhibit excellent herbicidal effects against a wide range of weeds at low doses. There is also a strong demand for the development of herbicides that can achieve the desired effect by both soil treatment and foliar treatment.

As a result of diligent study by the present inventors, the uracil derivatives of the following general formula (I) having a haloalkyl group at the 5-position and a phenyl group at the 2-position have permeability transfer activity and very high herbicidal activity. Compared with herbaceous compounds, the uracil derivatives can be administered by soil treatment or foliar treatment, thus causing rapid and high herbicidal effects at very low dosages for a variety of weeds, including perennial weeds and exhibiting residual effects over an appropriate period of time. It has been found to have properties.

In a first aspect of the invention, uracil derivatives of the general formula (I) are provided:

Wherein R ¹ is hydrogen, C _1-3 alkyl, hydroxymethyl or C _1-3 haloalkyl, R ² is C _1-6 haloalkyl, R ³ is hydrogen, C _1-6 alkyl, C _{1 -6} haloalkyl, hydroxymethyl, halogen or nitro, R ⁴ is hydrogen or halogen, (i) when R ⁵ and R ⁶ are taken separately, R ⁵ is halogen, nitro or cyano, R ⁶ Is -SB ¹ ,

B ¹ is hydrogen, C _1-5 alkyl, C _3-6 cycloalkyl, C _2-4 alkenyl, C _3-4 alkynyl, cyanomethyl, hydroxymethyl, chloromethyl, benzyl,

CH _2- (CH ₂ ) _n -CO ₂ B ²² , CH ₂ -YB ²³ , CH ₂ -Y-CH (B ²¹ ) CO ₂ B ²² , or CH ₂ -Y-CH _2- (CH ₂ ) _n- CO ₂ B ²² , B ²¹ is hydrogen, C _1-3 alkyl, methylthio, phenylthio or methoxymethyl, B ²² is hydrogen, sodium, potassium, ammonium, isopropylammonium, C _1-5 alkyl, C _2-5 alkenyl, C _3-5 alkynyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-2 alkyl, C _2-3 haloalkyl, phenethyl, α-methylbenzyl, 3- Dimethylaminopropyl; Halogen, C _1-4 alkyl, C _1-3 alkoxyl, C _1-2 alkylamino, dimethylamino, C _1-2 alkoxy-carbonyl, C _2-3 acyl, C _1-2 haloalkyl or C _1- Phenyl which may be substituted by one or more substituents selected from ₂ haloalkyloxyl; Halogen, C _1-4 alkyl, C _1-3 alkoxyl, C _1-2 alkylamino, dimethylamino, C _2-3 acyl, trifluoroacetylamino, C _1-2 alkoxy-carbonyl, methylsulfonyl, Benzyl which may be substituted by one or more substituents selected from trifluoromethyl-sulfonyl, C _1-2 haloalkyl or C _1-2 haloalkyloxyl, n is an integer from 1 to 4, B ²³ is hydrogen , C _1-5 alkyl, cyanomethyl, C _2-5 acyl, chloroacetyl or dimethylcarbamoyl, Y is oxygen or sulfur, D ²¹ is hydrogen, C _1-3 alkyl, C _1-3 alkoxyl Or C _1-3 alkoxy-C _1-2 alkyl, D ²² is hydrogen, C _1-4 alkyl, C _3-6 cycloalkyl, C _2-3 haloalkyl, phenyl or benzyl, D ²³ is hydrogen or C _1-3 alkyl, D ²⁴ is hydrogen, C _1-3 alkyl or C _1-3 alkoxy-C _1-2 alkyl, Z is oxygen, sulfur or NH, D ²⁵ is hydrogen, sodium, C _1-4 Alkyl, C _2-5 alkenyl, C _3-5 alkynyl, C _2-5 acyl, C _1-4 alkylsulfonyl or C _1-3 alkoxy-C _1-2 alkyl, D ²⁶ is C _1-4 alkyl or C _1-3 haloalkyl, D ²⁷ is hydrogen, C _1-6 alkyl, C _3-6 cycloalkyl, C _{1- 3} haloalkyl, C _1-4 alkoxyl, C _1-4 alkylthio, C _1-4 alkoxy-carbonyl, mercapto, hydroxyl, C _1-3 alkoxy-C _1-2 alkyl, C _1-4 alkyl Amino, ND ²⁸ (D ²⁹ ), dimethylcarbamoyl, CONHSO ₂ CH ₃ , C _1-4 alkylsulfonyl, or N (D ³⁰ ) SO ₂ D ³¹ , and D ²⁸ and D ²⁹ are independently C _{1- 4} alkyl, D ³⁰ is hydrogen, sodium, C _1-4 alkyl, C _1-4 alkylsulfonyl, C _1-3 alkoxy-C _1-2 alkyl, D ³¹ is C _1-4 alkyl or C _{1- 3} haloalkyl, D ³² is C _1-6 alkyl or C _3-6 cycloalkyl, D ³³ , D ³⁴ and D ³⁵ are independently hydrogen or C _1-6 alkyl, and D ³⁶ and D ³⁷ are independently Hydrogen, C _1-6 alkyl or dimethylamino, D ³⁸ is hydrogen, halogen, mercapto, hydroxyl, C _1-6 alkyl, C _3-6 cycloalkyl, C _1-3 haloalkyl, C _1-4 al Coxyl, C _1-4 Alkyl Tea Oh, C _1-4 alkoxy-carbonyl, dimethylcarbamoyl, C _1-3 alkoxy-C _1-2 alkyl, C _1-4 alkylamino, ND ²⁸ (D ²⁹ ), CONHSO ₂ CH ₃ , C _{1- 4} alkylsulfonyl, phenyl, benzyl or N (D ³⁹ ) SO ₂ D ³¹ , where D ³⁹ is hydrogen, C _1-4 alkyl, sodium, potassium, C _1-4 alkylsulfonyl or C _1-3 alkoxy-C _1-2 alkyl, D ⁴⁰ is hydrogen, C _1-6 alkyl, C _3-6 cycloalkyl, phenyl, benzyl or 2-pyridyl, D ⁴¹ is hydrogen, halogen, mercapto, hydroxyl, amino, C _1-6 alkyl, C _1-4 alkylamino, ND ²⁸ (D ²⁹ ), C _1-4 alkylthio, CO ₂ D ²⁸ , C _1-4 alkylsulfonyl, C _1-4 alkoxyl or N (D ³⁹ ) SO ₂ D ³¹ , D ⁴² is hydrogen, halogen, nitro, amino, cyano, C _1-4 alkylamino, N (D ²⁸ ) D ²⁹ , C _1-4 alkylcarbonyl or C _1-4 alkoxy- Carbonyl, D ⁴³ is hydrogen, hydroxyl, methoxy, amino, benzoyl or C _1-4 alkyl, D ⁴⁴ is hydrogen, cyano, acetyl, C _1-4 alkyl, carboxyl or C _1-4 alkoxy Ka A carbonyl, D ⁴⁵ and D ⁴⁶ are independently hydrogen, phenyl, hydroxyl, methoxy or a C _1-4 alkyl, D ⁴⁷ and D ⁴⁸ are independently hydrogen or C _1-4 alkyl, X is oxygen or sulfur And (ii) when R ⁵ and R ⁶ form a ring, the uracil derivative is of the general formula

, C_3-6시클로알킬,

, C_3-6시클로알킬-C_1-2알킬, C_1-2알콕시-C_1-2알킬; C_1-4알킬, C_1-4알콕시, C_1-4알콕시-카르보닐, C_1-4알콕시-C_1-2알킬 또는 할로겐에 의해 치환될 수 있는 페닐; 또는 C_1-4알킬, C_1-4알콕실, C_1-4알콕시-카르보닐, C_1-4알콕시-C_1-2알킬 또는 할로겐에 의해 치환될 수 있는 벤질이다., A ¹ is hydrogen and C _1-4 alkyl, A ² is hydrogen, C _1-5 alkyl, C _2-5 alkenyl, C _3-5 alkynyl, C _3-6 cycloalkyl-C _1-2 Alkyl, C _1-6 haloalkyl, C _1-6 haloalkenyl, C _1-6 haloalkynyl, cyanomethyl, hydroxymethyl, chloromethyl, C _1-3 alkoxy-C _1-2 alkyl, -CH ₂ C0 ₂ A ²¹ , -CH ₂ CON (A ²² ) A ²³ ; Phenyl which may be substituted by C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy or halogen; Benzyl which may be substituted by C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy, C _1-4 alkoxy-carbonyl, C _1-3 alkoxy-C _1-2 alkyl or halogen; Or —CH ₂ A ²⁴ , A ²¹ is hydrogen, C _1-5 alkyl, sodium, phenyl which may be substituted by halogen, or benzyl which may be substituted by halogen, and A ²² and A ²³ are independently hydrogen Or C _1-3 alkyl, A ²⁴ is 2-pyridyl, which may be substituted by C _1-4 alkyl or halogen; 2-pyridazyl, which may be substituted by C _1-4 alkyl or halogen; 3-isothiazole or 3-isoxazole, J is hydrogen, C _1-4 alkyl, C _2-4 alkenyl, C _3-4 alkynyl, hydroxymethyl, chloromethyl, carbamoylmethyl, cyano Methyl, C _1-4 alkoxy-carbonylmethyl,

, C _3-6 cycloalkyl,

, C _3-6 cycloalkyl-C _1-2 alkyl, C _1-2 alkoxy-C _1-2 alkyl; Phenyl which may be substituted by C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkoxy-carbonyl, C _1-4 alkoxy-C _1-2 alkyl or halogen; Or benzyl which may be substituted by C _1-4 alkyl, C _1-4 alkoxyl, C _1-4 alkoxy-carbonyl, C _1-4 alkoxy-C _1-2 alkyl or halogen.

In a second aspect of the invention there is provided a herbicidal composition comprising an herbicidally effective amount of the uracil derivative defined in the first aspect and an acceptable carrier or diluent.

In a third aspect of the present invention, there is provided a method for killing or inhibiting weed growth, comprising administering an effective amount of the uracil derivative herbicide defined in the first aspect.

According to the invention the uracil derivatives represented by the general formula (I) are novel.

Among the uracil derivatives of general formula (I), the compounds of general formulas (II), (III) and (IV) are preferred for the purposes of the present invention. That is, the uracil derivatives of general formula (II) are as follows:

Wherein R ¹ is hydrogen, C _1-3 alkyl, hydroxymethyl or halomethyl, R ² is C _1-6 haloalkyl, R ³ is hydrogen, C _1-6 alkyl, C _1-6 haloalkyl , Hydroxymethyl, halogen or nitro, R ⁴ is hydrogen or halogen, A ¹ is hydrogen or C _1-4 alkyl, A ² is hydrogen, C _1-5 alkyl, C _2-5 alkenyl, C _{3 -5} alkynyl, C _3-6 cycloalkyl-C _1-2 alkyl, C _1-6 haloalkyl, C _1-6 haloalkenyl, C _1-6 haloalkinyl, cyanomethyl, hydroxymethyl, chloro Methyl, C _1-3 alkoxy-C _1-2 alkyl, —CH ₂ CO ₂ A ²¹ , —CH ₂ CON (A ²² ) A ²³ ; Phenyl which may be substituted by C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxyl or halogen; Benzyl which may be substituted by C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxyl, C _1-4 alkoxy-carbonyl, C _1-3 alkoxy-C _1-2 alkyl or halogen; Or —CH ₂ A ²⁴ , A ²¹ is hydrogen, C _1-5 alkyl, sodium, phenyl which may be substituted by halogen, or benzyl which may be substituted by halogen, and A ²² and A ²³ are independently hydrogen Or C _1-3 alkyl, A ²⁴ is 2-pyridyl, which may be substituted by C _1-4 alkyl or halogen; 2-pyridazyl, which may be substituted by C _1-4 alkyl or halogen; 3-isothiazole or 3-isoxazole and X is oxygen or sulfur.

The uracil derivatives of formula (III) are as follows:

Wherein R ¹ is hydrogen, C _1-3 alkyl, hydroxymethyl or halomethyl, R ² is C _1-6 haloalkyl, R ³ is hydrogen, C _1-6 alkyl, C _1-6 haloalkyl , Hydroxymethyl, halogen or nitro, R ⁴ is hydrogen or halogen, R ⁵ is halogen, nitro or cyano, B ¹ is hydrogen, C _1-5 alkyl, C _3-6 cycloalkyl, C _{2- 4} alkenyl, C _3-4 alkynyl, cyanomethyl, hydroxymethyl, chloromethyl, benzyl,

CH ₂ -YB ²³ , CH ₂ -Y-CH (B ²¹ ) CO ₂ B ²² , or CH ₂ -Y-CH _2- (CH ₂ ) _n -CO ₂ B ²² , B ²¹ is hydrogen, C _{1- 3} alkyl, methylthio, phenylthio or methoxymethyl, B ²² is hydrogen, sodium, potassium, ammonium, isopropylammonium, C _1-5 alkyl, C _2-5 alkenyl, C _3-5 alkynyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-2 alkyl, C _2-3 haloalkyl, phenethyl, α-methylbenzyl, 3-dimethylaminopropyl; Halogen, C _1-4 alkyl, C _1-3 alkoxyl, C _1-2 alkylamino, dimethylamino, C _1-2 alkoxy-carbonyl, C _2-3 acyl, C _1-2 haloalkyl or C _1- Phenyl which may be substituted with one or more substituents selected from ₂ haloalkyloxyl; Or halogen, C _1-4 alkyl, C _1-3 alkoxyl, C _1-2 alkylamino, dimethylamino, C _2-3 acyl, trifluoroacetylamino, C _1-2 alkoxy-carbonyl, methylsulfonyl Benzyl which may be substituted by one or more substituents from trifluoromethyl-sulfonyl, C _1-2 haloalkyl or C _1-2 haloalkyloxyl, n is an integer from 1 to 4, B ²³ is hydrogen , C _1-5 alkyl, cyanomethyl, C _2-5 acyl, chloroacetyl or dimethyl-carbamoyl, and X and Y are oxygen or sulfur.

The uracil derivatives of general formula (IV) are as follows:

Wherein R ¹ is hydrogen, C _1-3 alkyl or C _1-3 haloalkyl, R ² is C _1-6 haloalkyl, R ³ is hydrogen, C _1-6 alkyl, C _1-6 haloalkyl , Hydroxymethyl, halogen or nitro, R ⁴ is hydrogen or halogen, (i) when R ⁵ and D ¹ are taken separately, R ⁵ is halogen, nitro or cyano, and D ¹ is

or

D ²¹ is hydrogen, C _1-3 alkyl, C _1-3 alkoxyl or C _1-3 alkoxy-C _1-2 alkyl, D ²² is hydrogen, C _1-4 alkyl, C _3-6 cycloalkyl , C _2-3 haloalkyl, phenyl or benzyl, D ²³ is hydrogen or C _1-3 alkyl, D ²⁴ is hydrogen, C _1-3 alkyl or C _1-3 alkoxy-C _1-2 alkyl, Z Is oxygen, sulfur or NH and D ²⁵ is hydrogen, sodium, C _1-4 alkyl, C _2-5 alkenyl, C _3-5 alkynyl, C _2-5 acyl, C _1-4 alkylsulfonyl or C _1-3 alkoxy-C _1-2 alkyl, D ²⁶ is C _1-4 alkyl or C _1-3 haloalkyl, D ²⁷ is hydrogen, C _1-6 alkyl, C _3-6 cycloalkyl, C _{1- 3} haloalkyl, C _1-4 alkoxyl, C _1-4 alkylthio, C _1-4 alkoxy-carbonyl, mercapto, hydroxyl, C _1-3 alkoxy-C _1-2 alkyl, C _1-4 alkyl Amino, ND ²⁸ (D ²⁹ ), dimethylcarbamoyl, CONHSO ₂ CH ₃ , C _1-4 alkylsulfonyl, or N (D ³⁰ ) SO ₂ D ₃₁ , and D ²⁸ and D ²⁹ are independently C _{1- 4} alkyl, D ³⁰ is hydrogen, sodium, C _1-4 alkyl, C _1-4 al Kilssulfonyl or C _1-3 alkoxy-C _1-2 alkyl, D ³¹ is C _1-4 alkyl or C _1-3 haloalkyl, D ³² is C _1-6 alkyl or C _3-6 cycloalkyl, D ³³ , D ³⁴ and D ³⁵ are independently hydrogen or C _1-6 alkyl, D ³⁶ and D ³⁷ are each independently hydrogen, C _1-6 alkyl or dimethylamino, D ³⁸ is hydrogen, halogen, mercapto , Hydroxyl, C _1-6 alkyl, C _3-6 cycloalkyl, C _1-3 haloalkyl, C _1-4 alkoxyl, C _1-4 alkylthio, C _1-4 alkoxy-carbonyl, dimethylcarba Moyl, C _1-3 alkoxy-C _1-2 alkyl, C _1-4 alkylamino, ND ²⁸ (D ²⁹ ), CONHSO ₂ CH ₃ , C _1-4 alkylsulfonyl, phenyl, benzyl or N (D ³⁹ ) SO ₂ D ³¹ , D ³⁹ is hydrogen, C _1-4 alkyl, sodium, potassium, C _1-4 alkylsulfonyl or C _1-3 alkoxy-C _1-2 alkyl, D ⁴⁰ is hydrogen, C _{1- 6} alkyl, C _3-6 cycloalkyl, phenyl, benzyl or 2-pyridyl, D ⁴¹ is hydrogen, halogen, mercapto, hydroxyl, amino, C _1-6 alkyl, C _1-4 al Kylamino, ND ²⁸ (D ²⁹ ), C _1-4 alkylthio, CO ₂ D ²⁸ , C _1-4 alkylsulfonyl, C _1-4 alkoxyl or N (D ³⁹ ) SO ₂ D ³¹ , D ⁴² Is hydrogen, halogen, nitro, amino, cyano, C _1-4 alkylamino, N (D ²⁸ ) D ²⁹ , C _1-4 alkylcarbonyl or C _1-4 alkoxy-carbonyl, D ⁴³ is hydrogen, Hydroxyl, methoxy, amino, benzoyl or C _1-4 alkyl, D ⁴⁴ is hydrogen, cyano, acetyl, C _1-4 alkyl, carboxyl or C _1-4 alkoxy-carbonyl, D ⁴⁵ and D ⁴⁶ are each independently hydrogen, phenyl, hydroxyl, methoxy or C _1-4 alkyl, D ⁴⁷ and D ⁴⁸ are each independently hydrogen or C _1-4 alkyl, X is oxygen or sulfur, (ii) When R ⁵ and D ¹ form a ring, the uracil derivative is a general formula

, C_3-6시클로알킬,

, C_3-6시클로알킬-C_1-2알킬, C_1-2알콕시-C_1-2알킬; C_1-4알킬, C_1-4알콕실, C_1-4알콕시-카르보닐, C_1-4알콕시-C_1-2알킬 또는 할로겐에 의해 치환될 수 있는 페닐; 또는 C_1-4알킬, C_1-4알콕실, C_1-4알콕시-카르보닐, C_1-4알콕시-C_1-2알킬 또는 할로겐에 의해 치환될 수 있는 벤질이다.And J is hydrogen, C _1-4 alkyl, C _2-4 alkenyl, C _3-4 alkynyl, hydroxymethyl, chloromethyl, carbamoylmethyl, cyanomethyl, C _1-4 alkoxy-carbonyl methyl,

, C _3-6 cycloalkyl,

, C _3-6 cycloalkyl-C _1-2 alkyl, C _1-2 alkoxy-C _1-2 alkyl; Phenyl which may be substituted by C _1-4 alkyl, C _1-4 alkoxyl, C _1-4 alkoxy-carbonyl, C _1-4 alkoxy-C _1-2 alkyl or halogen; Or benzyl which may be substituted by C _1-4 alkyl, C _1-4 alkoxyl, C _1-4 alkoxy-carbonyl, C _1-4 alkoxy-C _1-2 alkyl or halogen.

Among the compounds of the formulas (II), (III) and (IV), the following are more preferred.

Uracil derivatives of the general formula (II ′)

Wherein R ¹ is hydrogen or C _1-3 alkyl, R ² is C _1-4 haloalkyl, R ⁴ is hydrogen or halogen, A ² is hydrogen, C _1-5 alkyl, C _2-5 al Kenyl, C _3-5 alkynyl, C _3-6 cycloalkyl-C _1-2 alkyl, cyanomethyl, hydroxymethyl, chloromethyl, C _1-3 alkoxy-C _1-2 alkyl, -CH ₂ CO ₂ A ²¹ , -CH ₂ CON (A ²² ) A ²³ ; Benzyl, which may be substituted by C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy or halogen; Or -CH ₂ A ²⁴ , A ²¹ is hydrogen or C _1-5 alkyl, A ²² and A ²³ are independently hydrogen or C _1-3 alkyl, A ²⁴ is substituted by C _1-4 alkyl or halogen 2-pyridyl which may be used.

Uracil derivatives of the general formula (III ′)

Wherein R ¹ is hydrogen or C _1-3 alkyl, R ² is C _1-4 haloalkyl, R ⁴ is hydrogen or halogen, R ⁵ is chlorine or nitro, B ¹ is hydrogen, C _{1- 5} alkyl, C _3-6 cycloalkyl, C _2-4 alkenyl, C _3-4 alkynyl, cyanomethyl, hydroxymethyl, benzyl,

CH _2- (CH ₂ ) _n -CO ₂ B ²² , CH ₂ -OB ²³ , or CH ₂ -O-CH (B ²¹ ) CO ₂ B ²² , B ²¹ is hydrogen, C _1-3 alkyl or methoxy Methyl, B ²² is hydrogen, C _1-5 alkyl, C _2-5 alkenyl, C _3-5 alkynyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-2 alkyl, C _{2 -3} haloalkyl; Or selected from halogen, C _1-4 alkyl, C _1-3 alkoxyl, dimethylamino, C _2-3 acyl, C _1-2 alkoxy-carbonyl, C _1-2 haloalkyl or C _1-2 haloalkyloxyl Benzyl, which may be substituted by one or more substituents, n is an integer from 1 to 3, and B ²³ is hydrogen, C _1-5 alkyl, cyanomethyl, C _2-5 acyl, chloroacetyl or dimethylcarbamoyl to be.

Uracil derivatives of the general formula (IV ′)

Wherein R ¹ is hydrogen or C _1-3 alkyl, R ² is C _1-4 haloalkyl, R ⁴ is hydrogen or halogen, and (i) when R ⁵ and D ¹ are taken separately, R ⁵ Is chlorine or nitro, and D ¹ is

D ²¹ is hydrogen, methyl, methoxy or methoxymethyl, D ²² is hydrogen, C _1-4 alkyl, C _3-6 cycloalkyl or benzyl, D ²³ is hydrogen or methyl, and D ²⁴ is hydrogen , Methyl or methoxymethyl, Z is oxygen, sulfur or NH, D ²⁵ is hydrogen, C _1-4 alkyl, C _2-5 alkenyl, C _3-5 alkynyl, or C _1-4 alkylsulfonyl D ²⁶ is C _1-4 alkyl, D ²⁷ is hydrogen, C _1-6 alkyl, C _1-4 alkoxyl, C _1-4 alkoxy-carbonyl, mercapto, hydroxyl, C _1-3 alkoxy -C _1-2 alkyl, C _1-4 alkylamino, ND ²⁸ (D ²⁹ ), dimethylcarbamoyl, CONHSO ₂ CH ₃ or N (D ³⁰ ) SO ₂ D ³¹ , wherein D ²⁸ and D ²⁹ are each C _1-4 alkyl, D ³⁰ is hydrogen, C _1-4 alkyl or C _1-4 alkylsulfonyl, D ³¹ is C _1-4 alkyl, D ³² is C _1-6 alkyl, D ³⁶ and D ³⁷ is each independently hydrogen or C _1-6 alkyl, D ³⁸ is hydrogen, C _1-6 alkyl, C _1-4 alkoxyl, C _1-4 alkoxy-carbonyl, mercapto, hydroxyl, C _1-3 alkoxy-C _1-2 alkyl, C _1-4 alkylamino, ND ²⁸ (D ²⁹ ), CONHSO ₂ CH ₃ or N (D ³⁹ ) -SO ₂ D ³¹ , D ³⁹ is hydrogen, C _{1- 4} alkyl or C _1-4 alkylsulfonyl, D ⁴⁷ and D ⁴⁸ are each independently hydrogen or C _1-4 alkyl, and (ii) when R ⁵ and D ¹ form a ring, the uracil derivatives are expression

, C_3-6시클로알킬, C_3-6시클로알킬-C_1-2알킬, C_1-2알콕시-C_1-2알킬; 또는 C_1-4알킬, C_1-4알콕실, C_1-4알콕시-카르보닐, 메톡시메틸 또는 할로겐에 의해 치환될 수 있는 벤질이다.And J is hydrogen, C _1-4 alkyl, C _2-4 alkenyl, C _3-4 alkynyl, hydroxymethyl, chloromethyl, carbamoylmethyl, cyanomethyl, C _1-4 alkoxy-carbonyl methyl,

, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-2 alkyl, C _1-2 alkoxy-C _1-2 alkyl; Or benzyl which may be substituted by C _1-4 alkyl, C _1-4 alkoxyl, C _1-4 alkoxy-carbonyl, methoxymethyl or halogen.

Among the compounds of the general formulas (II ′), (III ′) and (IV ′), the following are more preferred.

Uracil derivatives of the general formula (II)

Wherein R ¹ is hydrogen or methyl, R ² is C _1-2 haloalkyl, R ⁴ is hydrogen or fluorine, A ² is hydrogen, C _1-5 alkyl, C _2-5 alkenyl, C _{3 -5} alkynyl, cyanomethyl, methoxymethyl, -CH ₂ CONH ₂ ; Benzyl which may be substituted by C _1-4 alkyl, trifluoromethyl, methoxy or halogen; Or -CH ₂ A ²⁴ , A ²⁴ is 2-pyridyl.

Uracil derivatives of the general formula (III)

이며, B²¹은 수소 또는 메틸이고, B²²은 수소, C_1-5알킬, C_2-5알켄일, C_3-5알킨일, C_3-6시클로알킬 또는 벤질이다.Wherein R ¹ is hydrogen or methyl, R ² is C _1-2 haloalkyl, R ⁴ is hydrogen or fluorine, R ⁵ is chlorine, B ¹ is hydrogen, C _1-5 alkyl, C _{3- 6} cycloalkyl, C _2-4 alkenyl, C _3-4 alkynyl, benzyl, or

And B ²¹ is hydrogen or methyl and B ²² is hydrogen, C _1-5 alkyl, C _2-5 alkenyl, C _3-5 alkynyl, C _3-6 cycloalkyl or benzyl.

Uracil derivatives of the general formula (IV)

Wherein R ¹ is hydrogen or methyl, R ² is C _1-2 haloalkyl, R ⁴ is hydrogen or fluorine, and (i) when R ⁵ and D ¹ are taken separately, R ⁵ is chlorine , D ¹

And D ²⁷ is C _1-6 alkyl and (ii) when R ⁵ and D ¹ form a ring, the uracil derivative is of the general formula

, C_1-2알콕시-C_1-2알킬; 또는 C_1-4알킬, 메톡시 또는 할로겐으로 치환될 수 있는 벤질이다.J is hydrogen, C _1-4 alkyl, C _2-4 alkenyl, C _3-4 alkynyl, cyanomethyl,

, C _1-2 alkoxy-C _1-2 alkyl; Or benzyl, which may be substituted with C _1-4 alkyl, methoxy or halogen.

Among the compounds of the present invention, compound numbers A-1 to A-33, B-1, B-2 and C-1 to C-3 are particularly preferred for use as active ingredients of herbicides.

The uracil derivatives of the present invention can be synthesized according to the following reaction scheme.

(1) In Scheme 1, β-aminoacrylic acid ester (V) and phenyl iso (thio) cyanate (VI) are reacted in the first step to produce uracil derivative (I '), and in the second step, the derivative (I) After isolating ') or without isolation, the 1-position of the uracil ring is alkylated to give the uracil derivative of formula (I).

[Reaction in Step 1]

Phenyl iso (thio) cyanate (VI) is usually used in 0.5 to 1.5 equivalents, preferably 0.9 to 1.1 equivalents, relative to the β-aminoacrylic acid ester (V).

The reaction can proceed without solvent, but usually a solvent is used to promote the reaction. Solvents usable for this purpose in this reaction include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether; Aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; Halogenated hydrocarbons such as chloroform and methylene chloride; Ethers such as diethyl ether, dioxane and tetrahydrofuran; Ketones such as acetone and methyl ethyl ketone; Nitriles such as acetonitrile and isobutyronitrile; Tertiary amines such as pyridine and N, N-diethylaniline; Acid amides such as formamide, N, N-dimethylformamide and N-methylpyrrolidone; Sulfur-containing compounds such as dimethyl sulfoxide and sulfolane; And mixtures thereof. Of these, aliphatic hydrocarbons, acid amides, sulfur-containing compounds and mixtures thereof are preferred.

Although the reaction can be carried out without using a base, in general, 0.5 to 10 equivalents, preferably 1.0 to 2.0 equivalents, are used for the β-aminoacrylic acid ester (V). Bases such as nitrogen-containing organic bases such as pyridine, triethyramine and 1,4-diazabicyclo-2,2,2-octane; Inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; Metal alcoholates such as sodium methoxide, sodium ethoxylate and tert-butoxylate can be used, of which sodium hydride, sodium hydroxide and potassium hydroxide are preferred.

The reaction temperature is usually -40 to 200 ° C, preferably room temperature to reflux temperature of the reaction mixture.

The reaction time is usually 10 minutes to 72 hours, preferably 30 minutes to 24 hours.

After the reaction is completed, the derivative (I ') is isolated by making the reaction product acidic using inorganic acid (e.g. hydrochloric acid) or organic acid (e.g. acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, etc.). can do.

[Reaction in Step 2]

In the second stage of the reaction, the alkylating agent is alkylated using an alkylating agent in an amount of 1.0 to 10 equivalents, preferably 1.0 to 5.0 equivalents, relative to the derivative (I '). Alkylating agents include, for example, alkylsulfuric acids such as dimethylsulfuric acid and diethylsulfuric acid; Alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide and ethyl iodide can be used.

The reaction can proceed without the solvent, but usually a solvent is used to promote the reaction. As a solvent which can be used for this purpose in the said reaction, Aliphatic hydrocarbons, such as hexane, heptane, ligroin, and a petroleum ether; Aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; Halogenated hydrocarbons such as chloroform and methylene chloride; Ethers such as diethyl ether, dioxane and tetrahydrofuran; Ketones such as acetone and methyl ethyl ketone; Nitriles such as acetonitrile and isobutyronitrile; Tertiary amines such as pyridine and N, N-diethylaniline; Acid amides such as formamide, N, N-dimethylformamide and N-methylpyrrolidone; Sulfur-containing compounds such as dimethyl sulfoxide and sulfolane; Water and mixtures thereof are exemplified. Of these, aliphatic hydrocarbons, acid amides, sulfur-containing compounds and mixtures thereof are preferred.

In this reaction, the base is usually used in an amount of 1.0 to 10 equivalents, preferably 1.0 to 2.0 equivalents, relative to derivative (I ′). As the base, nitrogen-containing organic bases such as pyridine, triethylamine and 1,4-diazabicyclo-2,2,2-octane; Inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate can be used. Of these, inorganic bases such as sodium hydride and potassium carbonate are preferred.

The reaction temperature is usually from 0 to 150 캜, preferably from room temperature to the reflux temperature of the reaction mixture.

The reaction time is usually 10 minutes to 96 hours, preferably 30 minutes to 48 hours.

(2) According to Scheme 2, in the first step, N-phenyl carbamate (VII) is reacted with β-aminoacrylic acid ester (V) to produce uracil derivative (I '), and derivative (I') is isolated. The uracil derivatives of general formula (I) are prepared by alkylating the 1-position of the uracil ring after this or without isolation in a second step.

[Reaction in Step 1]

N-phenyl carbamate (VII) is used in 0.5 to 1.5 equivalents, preferably 0.9 to 1.1 equivalents relative to β-amino acrylic acid ester (V).

In general, the reaction requires a solvent. Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether; Aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; Halogenated hydrocarbons such as chloroform and methylene chloride; Ethers such as diethyl ether, dioxane and tetrahydrofuran; Ketones such as acetone and methyl ethyl ketone; Nitriles such as acetonitrile and isobutyronitrile; Tertiary amines such as pyridine and N, N-diethylaniline; Acid amides such as formamide, N, N-dimethylformamide and N-methylpyrrolidone; Sulfur-containing compounds such as dimethyl sulfoxide and sulfolane; alcohols such as methanol, ethanol, propanol and butanol; water; And mixtures thereof. Of these, aliphatic hydrocarbons, acid amides, sulfur-containing compounds and mixtures thereof are preferred.

In this reaction, the base is usually used in 0.5 to 10 equivalents, preferably 1.0 to 2.0 equivalents, relative to the β-aminoacrylic acid ester (V). Bases that can be used for the reaction include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; Metal alcoholates such as sodium methoxylated, sodium ethoxylated and tert-butoxylated; And metal alkyl mercaptides such as sodium methyl mercaptide and sodium ethyl mercaptide. Among them, inorganic bases such as sodium hydride and metal alcoholates such as sodium methoxide are preferable.

The reaction is usually carried out at 0 to 200 ° C, preferably at room temperature to the reflux temperature of the reaction mixture.

The reaction time is usually 10 minutes to 72 hours, preferably 30 minutes to 12 hours.

After the reaction is complete, the derivative (I ′) can be isolated from the reaction mixture by acidifying with an inorganic acid (eg hydrochloric acid) or an organic acid (eg acetic acid, trifluoroacetic acid and p-toluenesulfonic acid).

[Reaction in Step 2]

The derivative (I ′) is alkylated under the same reaction conditions as in the second step of Scheme 1.

(3) In Scheme 3, phenyl iso (thio) cyanate (VI) is reacted with N-substituted β-aminoacrylic acid ester (VIII) in a single step to prepare uracil derivatives of general formula (I). The same reaction conditions as those used in Scheme 1 can be used.

(4) In Scheme 4, N-phenyl carbamate (VII) is reacted with N-substituted β-aminoacrylic acid ester (VIII) in a single step to prepare uracil derivatives of general formula (I). The reaction can be carried out under the same reaction conditions as those used in Scheme 2.

The uracil derivatives of the present invention can be administered as herbicides for mountainous, paddy, and parentage lands through soil treatment or foliar treatment. They also show high herbicidal activity at low doses, for example against the following weeds: Solanaceae weeds such as Solanum nigrum and Datura nigrum, Abutlon teoplasti Malvaceae weeds, such as Abutilon theophrasti and Seed spinosa, Ipomoea species (eg, Ipomoea purpurea), and calendulas such as Calistegia species Amaranthaceae weeds such as Convolvulaceae weeds, Amaranthus lividus and Amaranthus retroflexus, Xantbium pensylvanicum, Ambrosia Artemisia efolia ( Ambrosia artemisiaefolia, Helianthus annuus, Galinsoga ciliata, Cisium arvense, Senesio vulgaris and Erice Compositeae weeds, such as the Erwinon annus, mustard plants such as Rorippa indica, Sinapis arvensis, and Capsella bursapastris, and polygonum. Polyzonaceae weeds such as Polygonum blume and Polygonum convolvulus, Purslane and Wenopodium album, such as Portulaca oleracea ), Chenopodiaceae weeds, such as Kenopodium ficifolium and Kochias coparia, Caryophyllaceae weeds such as Stellaria media, Veronica persica ) Scrophulariaceae weeds, Commelinaceae weeds such as Commelina commelina communis, Lamium amflexiuale Labiatae weeds such as plexicaule and Lamium purpureum, Euphorbia supina and Euphorbia maculata, Euphorbiaaceae weeds, and Galium spurium ), Rubiaceae weeds, such as Gallium aparine and Rubiaakane, Violaceae weeds such as Viola arvensis, Serbania exaltata and Cassia orb Broad-leaved weeds such as Leguminosae weeds, such as Cassia obtusifolia; Sorgham bicolor, Panicum dichotomiflorum, Sorphum halepense, Echinochloa crus-galli, Digitaria Adsendens Poop grasses and weeds such as Digitaria adscendens, Avena fatua, Eleusine indica, Setaria viridis, and Alopecurus aequalis; Roomworms and weeds such as Cyperus rotundus; And Alismataceae weeds such as Alisma canaliculatum, Sagittaria trifolia and Sagittaria pygmaea, Cyperus difformis. Scrotulans, such as Cyperaceae weeds such as Cyperus serotinus, Scirpus juncoides, and Eleocharis kuroguwai, and Lindemia pyxidaria. Scrothulariaceae weeds, Potenderiaceae weeds like Monochoria vaginalis, Potatogegeton distinctus weeds, Potamogetonaceae weeds, Rotala indica Paddy weeds such as Lythraceae weeds, such as indica, and Gramineae weeds, such as Echinochloa crus-galli. It is also prominent that the uracil derivatives of the present invention do not harm important crops such as wheat, corn, barley, soybean, rice, cotton, sugar cane and salt (sorghum).

The uracil derivatives of the present invention are also useful as defoliants.

When the compounds according to the invention are used as herbicides, they are usually carriers, for example solid carriers such as mud, talc, bentonite, diatomaceous earth and white carbon (fine silica powder), or water, alcohols (isopropanol, butanol, benzyl alcohol, furfuryl Alcohols, etc.), aromatic hydrocarbons (toluene, xylenes, etc.), ethers (anisoles, etc.), ketones (cyclohexanone, isophorone, etc.), esters (butyl acetate, etc.), acid amides (such as N-methylpyrrolidone), and Mixed with a liquid carrier such as halogenated carbon (chlorobenzene, etc.). If necessary, suitable auxiliaries such as surfactants, emulsifiers, dispersants, penetrants, spreaders, thickeners, cryoprotectants, anticoagulants, stabilizers and the like may be added, and liquid preparations, emulsion concentrates, wetting ingredients, anhydrous agents Various formulations can be provided for practical use, such as flow agents, sprays and granules.

If necessary, during preparation or administration of the formulation, the compounds of the present invention may be mixed with other types of herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like.

As a class of herbicides which can be mixed in the use of the compounds according to the invention, mention may be made of the compounds described in, for example, Farm Chemicals Handbook (1989).

The dosage rate of the compound according to the present invention depends on the place of administration, the time of administration, the method of administration, the type of crops to be treated, etc., but the compound of the present invention is usually about 0.0001 to 10 kg / ha, preferably 0.001 to 10 based on the active ingredient It is suitable to administer as much as 5kg / ha.

Compared with conventional herbicides, the compounds of the present invention have a rapid and high herbicidal effect even at very low dose levels and can be administered to a wide range of weeds through soil treatment or foliar treatment.

The present invention is explained in more detail in the following Examples, but the scope of the present invention is not limited to these Examples.

Example A-1

3- (7-fluoro-3-oxo-4-propargyl-2H-1,4-benzooxazin-6-yl) -1-methyl-6-trifluoromethyl-2,4 (1H, Synthesis of 3H) -pyrimidinedione (Compound A-1)

At room temperature, in a solution of dimethylformamide (2 ml) in which 0.02 g of sodium hydride (purity: 55%) was suspended, 3- (7-fluoro-3-oxo-4-propargyl-2H-1,4-benzooxane Photo-8-yl) -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione 0.18 g was added. After standing for 20 minutes, 0.09 g of dimethyl sulfuric acid was further added to the solution and stirred overnight. Dimethylformamide was distilled off and water was added to extract the residue with ethyl acetate. The extract was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off to obtain the crude product. The crude product was purified by preparative thin layer chromatography using hexane / ethyl acetate (3: 1) as developing solvent to afford 0.15 g of the target compound in the form of a colorless viscous oil. It solidified when left as it was.

Example A-2

3- (7-fluoro-3-oxo-4-propargyl-2H-1,4-benzooxazin-6-yl) -6-trifluoromethyl-2,4 (1H, 3H) -pyri Synthesis of Middinedione (Compound A-2)

1.10 g of 3-amino-4,4,4-trifluorocrotonate was added to a mixture of 0.33 g of sodium methoxide and 5 ml of dimethylformamide at room temperature. After standing for 20 minutes, 1.76 g of 6-ethoxycarbonylamino-7-fluoro-3-oxo-4-propargyl-2H-1,4-benzoxazine was added to the mixed solution, and the mixture was stirred at 130 deg. Heated for 4 hours. After the solution was cooled to room temperature, the solution was poured into iced water and the resulting solution was extracted twice with diethyl ether. The aqueous layer was made acidic with dilute hydrochloric acid and extracted three times with ethyl acetate. The ethyl acetate extract was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. After distilling off ethyl acetate, the residue was purified by column chromatography using chloroform as developing solvent to give 0.20 g of the target compound as pale yellow crystalline form.

Example A-3

3- (7-fluoro-3-oxo-4- (2-pyridylmethyl) -2H-1,4-benzooxazin-6-yl) -1-methyl-6-trifluoromethyl-2, Synthesis of 4 (1H, 3H) -pyrimidinedione (Compound A-3)

At room temperature, 3- (7-fluoro-3-oxo-2H-1,4-benzoxazine- in a N, N-dimethylformamide solution (5 ml) in which 0.05 g of sodium hydride (pure: 55%) was suspended. 0.20 g of 6-yl) -1-methyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione was added. After standing for 20 minutes, 0.09 g of 2-chloromethylpyridine hydrochloride was added to the solution and stirred for 4 hours. N, N-dimethylformamide was distilled off and water was added to extract the residue with ethyl acetate. The extract was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off to obtain the crude product. The product was purified by preparative thin layer chromatography using hexane / ethyl acetate (2: 3) as developing solvent to afford 0.09 g of the target compound as pale yellow crystalline form.

Example A-4

3- (7-fluoro-3-oxo-2H-1,4-benzooxazin-6-yl) -1-methyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione Synthesis of (Compound A-4)

0.85 g of 3- (7-fluoro-3-oxo-2H-1,4-benzooxazin-6-yl) -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione is N It was dissolved in 8.5 ml of N-dimethylformamide. 0.17 g of anhydrous potassium carbonate and 0.15 ml of methyl iodide were added and the mixed solution was stirred for 4 hours. After the reaction was completed, N, N-dimethylformamide was distilled off and water was added to extract the residue with ethyl acetate. The extract was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off to obtain the crude product. The product was purified by column chromatography using chloroform as the developing solvent to give 0.53 g of the target compound in the form of pale yellow crystals.

Example B-1

3- (4-Chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl) -1-methyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione (Compound B- 1) Synthesis

At room temperature, in a suspension of 0.16 g of sodium hydride (purity: 55%) in 5 ml of dimethylformamide, 3- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl) -6 in 10 ml of dimethylformamide A solution of 1.5 g of -trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione was added dropwise. When hydrogen no longer generated, 0.59 g of dimethyl sulfate was added and the resulting solution was stirred at room temperature for 3 hours. The reaction mixture was poured into 300 ml of water and extracted twice with ethyl acetate. The extract was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate and then ethyl acetate was distilled off to give the crude product. The obtained product was purified by preparative thin layer chromatography (developing solvent: CHCl ₃ ) and preparative high performance liquid chromatography (eluent: CHCN / H ₂ O (5: 1)) to obtain 0.1 g of the target compound in the form of a viscous oil. .

Example B-2

Synthesis of 3- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl) -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione (Compound B-2)

To a solution prepared by suspending 1.14 g of sodium hydride (purity: 55%) in 110 ml of dimethylformamide, a solution of 4.75 g of ethyl 3-amino-4,4,4-trifluorocrotonate in 5 ml of anhydrous toluene was added dropwise. It was added dropwise as above with stirring at 0 ° C. over 15 minutes. The resulting mixture was further stirred at 0 ° C. for 15 minutes. The reaction mixture was cooled to −30 ° C. and a solution of 50 ml of anhydrous toluene and 6.9 g of 4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl isocyanate was added dropwise thereto. The resulting reaction mixture was returned to room temperature and stirred for 2 hours. After distilling off the solvent, ethyl acetate was added to the remaining solution, washed twice with a solution of 20 ml of 2N hydrochloric acid and 500 ml of water, washed with a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and the ethyl acetate was distilled off to obtain a crude product. . The crude product was preliminarily purified by silica gel column chromatography using CHCl ₃ as the developing solvent and silica gel column chromatography using ethyl acetate / hexane (3: 1] as the developing solvent to give the desired compound 1.5g. Obtained in oil form.

Example C-1

3- (4-chloro-2-fluoro-5- (5-methyl-1,3,4-oxadiazol-2-yl) phenyl-1-methyl-6-trifluoromethyl-2,4 ( Synthesis of 1H, 3H) -pyrimidinedione (Compound C-1)

At 25 ° C., in a suspension of 0.31 g of sodium hydride (oil, purity: 55%) in 13 ml of dimethylformamide, 20 ml of N, N-dimethylformamide and 3- (4-chloro-2-fluoro-5- (5- A solution consisting of 2.5 g of methyl-1,3,4-oxadiazol-2-yl) phenyl) -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione was added dropwise. 1.02 g of dimethylsulphuric acid was added over 15 minutes when hydrogen no longer occurred. The mixed solution was stirred at room temperature for 2 hours and extracted with ethyl acetate by adding water. The extract was dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was purified by preparative high performance liquid chromatography using acetonitrile / water (5: 1) as eluent to afford 0.78 g of the desired compound.

Example C-2

3- (4-chloro-2-fluoro-5- (5-methyl-1,3,4-oxadiazol-2-yl) phenyl) -6-trifluoromethyl-2,4 (1H, 3H Synthesis of) -pyrimidinedione (Compound C-2)

Over 15 minutes at 0 ° C., in a suspension of 1.04 g of sodium hydride (oil, purity: 55%) in 75 ml of dimethylformamide, 58 ml of toluene and 4.3 g of ethyl 3-amino-4,4,4-trifluorocrotonate Solution was added dropwise. The solution was then stirred at 0 ° C. for 15 minutes, then cooled to −30 ° C. and 60 ml of toluene and 4-chloro-2-fluoro-5- (5-methyl-1,3,4-oxadiazole-2- A solution of 5.7 g of 1) phenyl isocyanate was added dropwise. The resulting mixed solution was stirred at room temperature for 3 hours.

The solvent was distilled off under reduced pressure, and 300 ml of water and 13.3 ml of 2N hydrochloric acid were added to the resulting oily substance, followed by extraction twice with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The solvent was distilled off and the resulting crude product was purified by preparative high performance liquid chromatography using acetonitrile / water (5: 1) as eluent to afford 1.78 g of the desired compound.

The uracil derivatives of the present invention synthesized according to the above examples and according to processes similar to the above examples or schemes are described in Tables 1a, 1b and 1c, and the physical properties of these compounds are described in Tables 2a, 2b and 2c. It is. However, the uracil derivatives obtainable by the present invention are not limited to those listed in the table below.

According to the above examples, the uracil derivatives of the present invention synthesized according to the above examples or schemes are described in Tables 3aa to 3cj. However, the compounds obtainable according to the invention are not limited to those shown in the table below.

Shown below are examples of formulations using the compounds of the invention. However, formulations belonging to the gist of the present invention are not limited to the following. In the description of the formulation examples below, all parts are by weight unless otherwise indicated.

Formulation Example 1

Wettable powder

The ingredients are uniformly mixed and ground to formulate wettable powders.

Formulation Example 2

Emulsion concentrate

The components are uniformly mixed to prepare an emulsion concentrate.

Formulation Example 3

Fluid

The ingredients are uniformly mixed to formulate a flow agent.

Formulation Example 4

Granular Wetting Powder (Anhydrous Fluid)

The components are uniformly mixed and powdered to produce anhydrous fluidizing agents.

Formulation Example 5

Wettable powder

The ingredients are uniformly mixed and ground to produce a wettable powder.

Formulation Example 6

Emulsion concentrate

The components are uniformly mixed to prepare an emulsion concentrate.

Formulation Example 7

Fluid

The components are mixed uniformly to prepare a flow agent.

Formulation Example 8

Granules

The ingredients are uniformly mixed and pulverized, then a small amount of water is added to knead with stirring, granulated with an extruder granulator and dried to prepare a granule.

[Formulation Example 9]

Granular Wetting Powder (Anhydrous Fluid)

The components are uniformly mixed and powdered to obtain anhydrous flow agent.

Formulation Example 10

Wettable powder

The ingredients are uniformly mixed and ground to produce a wettable powder.

Formulation Example 11

Emulsion concentrate

The components are uniformly mixed to prepare an emulsion concentrate.

Formulation Example 12

Fluid

The components are mixed uniformly to prepare a flow agent.

Formulation Example 13

Granules

The ingredients are uniformly mixed and pulverized, kneaded with the addition of a small amount of water and stirred, followed by granulation with an extruder granulator and drying to prepare a granule.

Formulation Example 14

Granular Wetting Powder (Anhydrous Fluid)

The components are uniformly mixed and powdered to produce anhydrous fluidizing agents.

In practical use of the formulations, for wettable powders, emulsion concentrates, flow agents and granular wettable powders, they are diluted 50 to 1,000 times with water and administered so that the active ingredient is supplied at a rate of 0.0001 to 10 kg per hectare.

The utility of the compounds according to the invention as herbicidal active ingredients is clearly assessed from the results of the following test examples.

[Test Example 1]

Test of herbicidal effect by soil treatment

The sterilized redness soil was placed in a 15 cm x 22 cm x 6 cm plastic container. Followed by barnyardgrass (Echinochloa crus-galli), crabgrass (Digitaria adscendens), annual herb (syperus microiria), black nightshade (Solanum nigrum), hairy Hairly galinsoga (Galinsoga ciliate), fieldcress (Rorippa indica), rice (Oryza sativa), corn (Zea mays), alf (Triticum aestivum), soy (Glycine max) and cotton (Cossipium) herbaceu

m) seeds were mixed and seeded in a container, covered about 1 cm with soil, and then evenly sprayed with a liquid test herbicide on the soil surface using a small atomizer so that the active ingredient was supplied at a predetermined rate. Each liquid test herbicide was prepared by diluting the formulation prepared according to the appropriate formulation example above with water. Three weeks after the administration (spray) of the liquid test herbicide, the herbicidal effects on each species of the weeds and crops were examined and evaluated according to the following standard grades. The results are shown in Tables 4-A-1, 4-A-2, 4-B, 4-C-1 and 4-C-2.

[Standard grade]

5: Growth rate is over 90% (plant is almost completely withered)

4: growth control rate is 70-90%.

3: The growth control rate is 40 to 70%.

2: growth control rate is 20 to 40%.

1: Growth control rate is less than 5% (almost no effect)

Growth control rates were determined from the following equations after weighing the ground areas of the plants in the treated and untreated areas:

[Test Example 2]

Herbicide effect test by foliar treatment

Barnyardgrass (Echinochloa crus-galli), crabgrass (Digitaria adscendens), annual soybean weed (Cyperus microiria), in a plastic container filled with sterile redness soil. Black nightshade (Solanum nigrum), hairy galinsoga (Galinsoga ciliate), fieldcress (Rorippa indica), rice (Oryza sativa), corn (Zea mays), wheat ( Seeds of Triticum aestivum, Glycine max, Cotton (Cossipium herbaceum) and Sugarcane (Beta vulgaris) were sown and covered with soil about 1 cm in length. Liquid test herbicides were evenly sprayed on the leaves of the plants to be fed at a predetermined rate.

Each liquid test herbicide was prepared by diluting the formulation prepared according to the appropriate formulation example above and sprayed over the leaves of the weeds with a small atomizer. Four weeks after spraying the liquid test herbicide, the herbicidal effects on the species of weeds and useful plants were examined and evaluated according to the same standard grade as used in Test Example 1. The results are described in Tables 5aa, 5ab, 5b, 5ca and 5cb.

[Test Example 3]

Herbicide test in watered paddy fields

After alluvial soil was placed in a 1/5000 Wagner pot, water was poured to knead the soil and a small model of rice paddy filled with water up to 2 cm above the soil. The pot was then mixed with seeds from barnyardgrass (Echinochloa crus-galli), duck salad (ducksalad (Monochoria vaginalis)), toothcup (Rotala indica) and Boulrush (Bullrush (Scirpus juncoides)). In addition, stems of perennial weeds (Syperus serotinus) and arrowhead (arrowhead (Sagittaria pygmaea)] were planted in the soil layer and seeded with 2.5 leaves. Pots were transplanted in a greenhouse at 25 to 30 ° C. On the second day after planting, the scale herbicide was used to drop the diluted test herbicide solution on the water surface of each pot to provide the desired amount of compound. Three weeks later, herbicidal effects on rice and the weed species were examined and evaluated according to the same standard grade as used in Test Example 1. The results are shown in Table 6.

The underlined symbols in the table have the following meanings:

N: Barnyardgrass [barnyardgrass (Echinochloa crus-galli)]

M: Crabgrass (Digitaria adscendens)

K: 1 year old Weed (Cyperus microiria)

H: Solanum nigrum

D: Hairy galinsoga (Galinsoga ciliate)

I: Field Cress (Rorippa indica)

R: Rice (Oryza sativa)

T: Zea mays

W: alf (Triticum aestivum)

S: Glycine max

C: cotton (Cossipium herbaceum)

B: sugar cane (Beta vulgaris)

Bromacil having the following structure was used as a control compound:

Claims (3)

Uracil derivatives represented by the following general formula (IV):

Wherein R ¹ is hydrogen or C _1-3 alkyl, R ² is C _1-6 haloalkyl, R ³ is hydrogen, R ⁴ is hydrogen or halogen, R ⁵ is halogen, nitro or cyano , D ¹

D ²¹ is hydrogen, C _1-3 alkyl, C _1-3 alkoxyl or C _1-3 alkoxy-C _1-2 alkyl, D ²² is hydrogen, C _1-4 alkyl, C _3-6 cycloalkyl, C _2-3 haloalkyl, phenyl or benzyl, D ²³ is hydrogen or C _1-3 alkyl, D ²⁴ is hydrogen, C _1-3 alkyl or C _1-3 alkoxy-C _1-2 alkyl, Z is oxygen , Sulfur or NH, D ²⁵ is hydrogen, sodium, C _1-4 alkyl, C _2-5 alkenyl, C _3-5 alkynyl, C _2-5 acyl, C _1-4 alkylsulfonyl or C _{1- 3} alkoxy-C _1-2 alkyl, D ²⁶ is C _1-4 alkyl or C _1-3 haloalkyl, D ²⁷ is hydrogen, C _1-6 alkyl, C _3-6 cycloalkyl, C _1-3 halo Alkyl, C _1-4 alkoxyl, C _1-4 alkylthio, C _1-4 alkoxy-carbonyl, mercapto, hydroxyl, C _1-3 alkoxy-C _1-2 alkyl, C _1-4 alkylamino, ND ²⁸ (D ²⁹ ), dimethylcarbamoyl, CONHSO ₂ CH ₃ , C _1-4 alkylsulfonyl, or N (D ³⁰ ) SO ₂ D ³¹ , and D ²⁸ and D ²⁹ are independently C _1-4 alkyl and, D ³⁰ is hydrogen, sodium, C _1-4 alkyl, C _1-4 alkylsulfonyl And one or a C _1-3 alkoxy -C _1-2 alkyl, D ³¹ is a C _1-4 alkyl or C _1-3 haloalkyl, D ³² is a C _1-6 alkyl or C _3-6 cycloalkyl, D ³³ , D ³⁴ and D ³⁵ are independently hydrogen or C _1-6 alkyl, D ³⁶ and D ³⁷ are independently hydrogen, C _1-6 alkyl or dimethylamino, D ³⁸ is hydrogen, halogen, mercapto, hydroxide Hydroxyl, C _1-6 alkyl, C _3-6 cycloalkyl, C _1-3 haloalkyl, C _1-4 alkoxyl, C _1-4 alkylthio, C _1-4 alkoxy-carbonyl, dimethylcarbamoyl, C _1-3 alkoxy-C _1-2 alkyl, C _1-4 alkylamino, ND ²⁸ (D ²⁹ ), CONHSO ₂ CH ₃ , C _1-4 alkylsulfonyl, phenyl, benzyl or N (D ³⁹ ) SO ₂ D ³¹ , D ³⁹ is hydrogen, C _1-4 alkyl, sodium, potassium, C _1-4 alkylsulfonyl or C _1-3 alkoxy-C _1-2 alkyl, D ⁴⁰ is hydrogen, C _1-6 alkyl , C _3-6 cycloalkyl, phenyl, benzyl or 2-pyridyl, D ⁴¹ is hydrogen, halogen, mercapto, hydroxyl, amino, C _1-6 alkyl, C _1-4 alkylamino, N D ²⁸ (D ²⁹ ), C _1-4 alkylthio, CO ₂ D ²⁸ , C _1-4 alkylsulfonyl, C _1-4 alkoxyl or N (D ³⁹ ) SO ₂ D ³¹ , D ⁴² is hydrogen, Halogen, nitro, amino, cyano, C _1-4 alkylamino, N (D ²⁸ ) D ²⁹ , C _1-4 alkylcarbonyl or C _1-4 alkoxy-carbonyl, D ⁴³ is hydrogen, hydroxyl, Methoxy, amino, benzoyl or C _1-4 alkyl, D ⁴⁴ is hydrogen, cyano, acetyl, C _1-4 alkyl, carboxyl or C _1-4 alkoxy-carbonyl, D ⁴⁵ and D ⁴⁶ are each Independently hydrogen, phenyl, hydroxyl, methoxy or C _1-4 alkyl, D ⁴⁷ and D ⁴⁸ are each independently hydrogen or C _1-4 alkyl, and X is oxygen or sulfur. A herbicidal composition comprising the herbicidal effective amount of the uracil derivative of claim 1 and an acceptable sieve or diluent. A method of killing or inhibiting weed growth, comprising administering an effective amount of the uracil derivative herbicide of claim 2.