WO2010034153A1

WO2010034153A1 - New 2-pyrimidinyloxy (sulfo) benzoxy olefin acid ester compounds and uses thereof

Info

Publication number: WO2010034153A1
Application number: PCT/CN2008/072516
Authority: WO
Inventors: 李斌; 白丽萍; 崔东亮; 冀海英; 张弘; 刘广昕; 于海波
Original assignee: 沈阳化工研究院
Priority date: 2008-09-25
Filing date: 2008-09-25
Publication date: 2010-04-01

Abstract

2-pyrimidinyloxy (sulfo) benzoxy olefin acid ester compounds of general formula (I) or (II) the substituting groups in said general formulas are defined as in the present specification. The present compounds of general formula (I) or (II) are herbicidal active. Comparing with the known compounds of the prior arts, the present compounds can be used for effective controlling of simple/double leaf weeds with much lower dosage in pre-sprouting and/or post-sprouting phase.

Description

2-pyrimidineoxy(thio)benzoyl enoate compound and application thereof

The present invention belongs to the field of herbicides, and specifically relates to 2-pyrimidinyloxy(thio)benzoyl enoate compounds and uses thereof.

Due to the succession and changes of weed populations and the emergence and rapid development of resistance to chemical pesticides, people's awareness of ecological environmental protection has been strengthened, awareness of chemical pesticide pollution, impact of pesticides on non-target organisms, and pesticide ecological environment. The emphasis on the issue of the home is constantly improving. With the gradual reduction of the world's cultivated land area, the growing population and the increasing demand for food, people are forced to rapidly develop agricultural production techniques, improve and improve farming systems, and continuously invent new and improved herbicidal compounds and compositions.

The following 2-pyrimidine oxy(thio)benzoic acid compounds are disclosed in EP0223406 for herbicidal activity:

Wherein R is a hydroxyl group, a lower alkoxy group or -0-(CH ₂ ) nR ³ (wherein R ³ is a lower alkoxycarbonyl group or the like, n is an integer of 1 or 2) and the like.

The following 2-pyrimidine oxy(thio)benzoic acid compounds are disclosed in EP 0 249 708 for herbicidal activity:

Wherein 1 ^ is COOR4 (hydrogen, dC ₆ alkyl group, a benzyl group, alkali metal atom, an alkaline earth metal atom or an organic ammonium) and the like.

The following 2-pyrimidine oxy(thio)benzoic acid compounds are disclosed in EP 0 321 846 for herbicidal activity:

among them,

(Ri is a lower alkyl group, n is an integer of 0-2) and the like.

The following 2-pyrimidine oxy(thio)benzoic acid compounds are disclosed in EP0435170 for herbicidal activity:

Wherein R is an OR ³ group {R ³ is a hydrogen atom, d ₄ alkyl (wherein the alkyl group may be substituted by the following group: R'COO- (R' is a d- ₈ alkyl) or d- ₈ alkoxycarbonyloxy Base, etc.), C ₂ _-8 alkenyl or halogenated C ₂ _-8 alkenyl, etc.

None of the prior art relates to the preparation and use of 2-pyrimidinyloxy(thio)benzoyl enoate compounds as shown in the present invention.

Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel 2-pyrimidinyloxy(thio)benzoyl enoate compound and its use as a herbicide.

The technical solution of the present invention is as follows:

The present invention provides a novel 2-pyrimidinyloxy(thio)benzoyl enoate compound as shown in the general formula (I) or (II):

In the formula:

X is selected from oxygen or sulfur;

Selected from H, halogen, acetyl, 4,6-dimethoxypyrimidine-2-oxy or the following groups:

Wherein, the nitrogen-oxygen bond and the double bond

R _{2 is} selected from CC ₃ alkyl, C ₃ -C ₅ alkenyl or C ₃ -C ₅ alkynyl;

R _{3 is} selected from CC ₃ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl.

A more preferred compound of the present invention is in the formula (I) or (Π)

X is selected from oxygen or sulfur;

Wherein, the nitrogen-oxygen bond and the double bond

R _{2 is} selected from dC ₃ alkyl;

R _{3 is} selected from the group consisting of CC ₃ alkyl.

More preferred compounds of the invention are those of formula (I) or (II)

X is selected from oxygen or sulfur; Selected from H, chloro, acetyl, 4,6-dimethoxypyrimidin-2-yl or the following groups:

CH ₃

N _n 0" _R ^K 3

Wherein, the nitrogen bond and the methyl group on the double bond are cis or trans;

R _{2 is} selected from ethyl;

R _{3 is} selected from a methyl group.

The alkyl group represented by the formula (I) or (II) includes a linear or branched alkyl group. The alkenyl group means a group having 1 to 2 carbon-carbon double bonds in a straight-chain or branched form, such as a propenyl group, an allyl group and the like. An alkynyl group means a group having 1 to 2 carbon-carbon triple bonds in a straight or branched form, such as propynyl, propargyl and the like. Halogen includes fluorine, chlorine, bromine, and iodine.

The compound of the formula (I) of the present invention can be produced by a method wherein the X, Ri R ₂ and R ₃ groups are as defined above. method one:

(VI) (I)

Compound (III) (for preparation, see Pestic. Sci. 1996, 47, 115-124) and compound (IV) (for preparation, see J. Org. Chem. 32: 3229 (1967)) are dissolved in an organic solvent, for example Toluene, acetone, hydrazine, hydrazine-dimethylformamide, tetrahydrofuran or dioxane; etc.; adding a base such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Advantageously, the reaction is carried out at a temperature between -10 ° C and the boiling point for 0.5 to 48 hours to prepare the compound (V).

Compound (V) and a suitable base are added to a mixed solvent of a suitable organic solvent and water at a temperature of

The reaction is carried out at -10 ° C to the boiling point for 0.5 to 48 hours, and the reaction solution is acidified with hydrochloric acid or sulfuric acid to obtain an intermediate acid, Compound (VI). The organic solvent is selected from the group consisting of chloroform, dichloromethane, carbon tetrachloride, n-hexane, benzene, toluene, ethyl acetate, methanol, ethanol, tetrahydrofuran or dioxane; the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, and carbonic acid. Sodium or potassium carbonate, etc.

Compound (VI) and compound (VII) (for the preparation of VII, see Synthetic Chemistry, 13(3), 315-316, (2005)) are dissolved in a suitable solvent such as toluene, acetone, hydrazine, hydrazine-dimethyl methacrylate. Amide, tetrahydrofuran or dioxane; etc. The alkali substance, such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc., is favorable for the reaction, and the reaction is carried out at a temperature of -10 ° C to the boiling point for 0.5 to 48 hours to prepare a compound (1). ). In the compound (VII), Y may be chlorine, bromine or iodine.

Method Two:

(I)

The compound (IV-1) and the compound (VII) are dissolved in a suitable solvent such as toluene, acetone, hydrazine, hydrazine-dimethylformamide, tetrahydrofuran or dioxane, etc.; and a base such as triethylamine is added. Pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or the like is advantageous for the reaction, and the reaction is carried out at a temperature of from -10 ° C to the boiling point for 0.5 to 48 hours to obtain a compound (VIII). In the compound (VII), Y may be chlorine, bromine or iodine.

The compound (VIII) and the compound (III) are dissolved in a suitable solvent such as toluene, acetone, hydrazine, hydrazine-dimethylformamide, tetrahydrofuran or dioxane; and a base such as triethylamine is added. Pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like are advantageous for the reaction, and the reaction is carried out at a temperature of from -10 ° C to the boiling point for 0.5 to 48 hours to obtain a compound (1).

The compound of the formula (II) of the present invention can be produced by a method wherein the X, Ri R ₂ and R ₃ groups are as defined above. method one:

(VI) (II)

Compound (VI) and compound (IX) (for the preparation of IX, see CN1927811) are dissolved in a suitable solvent such as toluene, acetone, hydrazine, hydrazine-dimethylformamide, tetrahydrofuran or dioxane; Such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc., the reaction is favorable, the temperature is between -10 ° C and the boiling point Compound (11) is obtained in an amount of from 0.5 to 48 hours. In compound (IX), Z may be chlorine, bromine or iodine _t method two:

(iv-i) (X)

(Π)

The compound (IV-1) and the compound (IX) are dissolved in a suitable solvent such as toluene, acetone, hydrazine, hydrazine-dimethylformamide, tetrahydrofuran or dioxane; and a base such as triethylamine is added. Pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. have a reaction for the reaction, and the reaction is carried out at a temperature of -10 ° C to the boiling point for 0.5 to 48 hours to obtain a compound (Χ). In the compound (IX), hydrazine may be chlorine, bromine or iodine.

The compound (X) and the compound (III) are dissolved in a suitable solvent such as toluene, acetone, hydrazine, hydrazine-dimethylformamide, tetrahydrofuran or dioxane; and a base such as triethylamine is added. Pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or the like has a reaction for the reaction, and the reaction is carried out at a temperature of -10 ° C to the boiling point for 0.5 to 48 hours to obtain a compound (11).

In the preparation of the compound (I) or (Π) described above, when! ^ When selected from the following groups:

Depending on the starting materials and the reaction conditions, a mixture of a nitrogen-oxygen bond and a double bond may be a J ί or trans compound, or a mixture of cis and trans compounds in different proportions.

The structural and physical properties of some of the compounds of the general formulae (I) and (II) are shown in Tables 1 and 2.

H

Table 1

Compound

X Ri R ₂ substance properties

Object

1 0 H CH ₃ colorless oil

2

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9TSZ.0/800ZN3/X3d £SIW0/0I0Z OAV Proper conductivity plays an important role in the efficacy of the drug. The suitability of bioactive molecular transport properties is unpredictable and requires a large amount of creative labor to be known.

The compound of the formula (I) or (II) of the present invention has unexpectedly high herbicidal activity compared to known alkyl ester compounds, and is effective for use in pre- and post-emergence at lower doses. Control single and double cotyled weeds. Therefore, the technical solution of the present invention includes the use of the compound of the formula (I) or (II) for controlling weeds.

The present invention also encompasses a herbicidal composition having the compound of the formula (I) or (II) as an active ingredient. The herbicidal composition has a concentration of the active ingredient of from 5 to 90% by weight. Also included in the herbicidal composition is an agriculturally acceptable carrier.

The herbicidal compositions of the invention can be administered in a variety of formulations. The compound of the present invention is usually dissolved or dispersed in a carrier to prepare a formulation to be more easily dispersed as a herbicide. For example: These chemicals can be formulated as wettable powders or creams. Therefore, in these compositions, at least one liquid or solid carrier is added, and it is usually necessary to add a suitable surfactant.

A further embodiment of the present invention is a method of controlling weeds which comprises applying a herbicidally effective amount of the herbicidal composition of the present invention to the surface of the weed or the weed growing or the surface of the growth medium thereof. A more suitable effective amount is usually selected from 10 g to 1000 g per hectare, and an effective amount is preferably 20 g to 500 g per hectare. For some applications, one or more additional herbicides may be added to the herbicidal compositions of the present invention, thereby providing additional advantages and benefits.

The compound of the present invention may be used alone or in combination with other known insecticides, fungicides, plant growth regulators or fertilizers.

It is to be understood that various changes and modifications may be made within the scope of the appended claims.

detailed description

The following examples and biotest results can be used to further illustrate the invention, but are not meant to limit the invention. Synthesis example

Example 1 : Synthesis of Compound 4

Add 4,6-dimethoxy-2-methanesulfonylpyrimidine 7.00 g (0.036 mol), methyl salicylate 6.00 g (0.047 mol), potassium carbonate 6.00 g (0.043) to a 250 mL one-neck round bottom flask. Mol), hydrazine, hydrazine-dimethylformamide 100 mL. The temperature was 110-130 ° C, and after stirring for 4 hours, it was cooled to room temperature. 200 mL of ethyl acetate and 180 mL of water were added to the reaction solution, and the mixture was extracted, washed with 50 mL of 1% diluted hydrochloric acid, and washed with 50 mL of saturated sodium hydrogen carbonate. The organic phase was washed with 3 X 50 mL of a saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate, and the residue obtained after purification was purified by silica gel column chromatography ( petroleum ether / ethyl acetate = 5 / 1 ) to give 2- , 6-Dimethoxy-2-pyrimidinyloxy)benzoic acid formazan is 8.35 g, yield 80%.

To a 150 mL single-neck round bottom flask, 2.93 g (0.01 mol) of methyl 2-(4,6-dimethoxy-2-pyrimidinyloxy)benzoate, 50 mL of tetrahydrofuran, and 50% aqueous sodium hydroxide solution were added. mL (0.4 g of sodium hydroxide dissolved in 50 mL of water) was stirred at room temperature overnight. After the reaction was completed, tetrahydrofuran was distilled off under reduced pressure. To the residue, 200 mL of ethyl acetate, 2 mL of concentrated hydrochloric acid, 50 mL of water, and 3 X 50 mL of saturated aqueous sodium chloride aqueous solution were washed, dried over anhydrous magnesium sulfate, and then evaporated to give 2- (4, 6- Dimethoxy-2-pyrimidinyloxy)benzoic acid 2.05 g, yield 74%.

To a 100 mL three-neck round bottom flask was added 1.00 g (3.6 mmol) of 2-(4,6-dimethoxy-2-pyrimidinyloxy)benzoic acid, 30 mL of hydrazine, hydrazine-dimethylformamide. Potassium carbonate 0.50 g (3.6 mmol), ethyl 2-bromomethyl acrylate 0.69 g (3.6 mmol). The temperature was 40-6 (rC, after stirring for 8 hours, ethyl acetate 200 mL and water 180 mL were added to the reaction solution, and the organic phase was washed with 180 mL of a saturated aqueous solution of sodium chloride, and then anhydrous magnesium sulfate was used. The residue obtained after drying and purification was purified by silica gel column chromatography ( petroleum ether / ethyl acetate=3/1) to give 2-(ethoxycarbonyl) allyl-2-(4,6-dimethoxy) -2-pyrimidinyloxy) benzoate 1.05 g, yield 75%.

Example 2: Synthesis of Compound 9

0.44 g (1 mmol) of dipyryloxybenzoic acid and 0.16 g (1.1 mmol) of PK ₂ CO ₃ were placed in a 150 mL reactor, 10 mL of N,N-dimethylformamide was added, and the mixture was stirred at room temperature for 10 minutes. A solution of 0.17 g (1 mmol) of 2-bromoethyl methacrylate in hydrazine, hydrazine-dimethylformamide was added dropwise, and the reaction was completed after 2 hours. The residue was dissolved in ethyl acetate (150 mL), washed with EtOAc EtOAc EtOAc EtOAc. The organic layer was dried over anhydrous MgSO.sub.

Example 3: Synthesis of Compound 16

Add 6-chloro-2-(4,6-dimethoxy-2-pyrimidinylthio)benzoic acid 0.32 g (0.9 mmol) to a 100 mL three-neck round bottom flask, hydrazine, hydrazine-dimethyl 10 mL of amide, 0.17 g (1.2 mmol) of potassium carbonate, 0.34 g (1.5 mmol) of ethyl 4-bromobutanoate. After stirring for 4 hours at 80 ° C, ethyl acetate 200 mL was added to the reaction mixture. 180 mL of water, extracting, washing the organic phase with 200 mL of a saturated aqueous solution of sodium chloride, and then drying over anhydrous magnesium sulfate. The residue obtained after desolvation was subjected to silica gel column chromatography ( petroleum ether / ethyl acetate = 3/1) Purification gave 0.28 g of 4-(6-chloro-2-(4,6-dimethoxy-2-pyrimidinyl)benzoic acid) crotonate in a yield of 71%.

Example 4: Synthesis of Compound 21

0.44 g ( ₁ mmol) of dipyryloxybenzoic acid and 0.16 g (ll mmol) of PK ₂ C0 ₃ (ll mmol) were placed in a 150 mL reactor, 10 mL of N,N-dimethylformamide was added, and the mixture was stirred at room temperature for 10 minutes. A solution of 0.17 g (1 mol) of ethyl 4-bromobutenoate in hydrazine, hydrazine-dimethylformamide, and the reaction was completed after 2 hours. The residue was dissolved in ethyl acetate (150 mL), washed with water (100 mL), EtOAc (150 mL) The organic layer was dried over MgSO4q.

Example 5: Synthesis of Compounds 22 and 23

(x-i)

To a 50 mL reaction flask was added 0.70 g (3 mmol) of 2-hydroxy-6-(l-(methoxyindole)ethyl)benzoic acid. For the preparation method, see Pestic. Sci. 1997, 49, 76-84. The methyl configuration on the nitrogen-oxygen bond and the double bond was not determined. Acetone 5 mL was added dropwise 1 mL of a sodium hydroxide solution (containing 0.13 g of sodium hydroxide), and the mixture was stirred at room temperature for 1 hour. The solvent was removed under reduced pressure, and 5 mL of N,N-dimethylformamide was added to the residue, and a solution of ethyl 4-bromobutenoate (0.51 g, 3 mmol) in 2 mL of N, N-dimethylformamide was added dropwise. The reaction was carried out for 2 hours at room temperature. Ethyl acetate and water were added to the reaction solution. 50 mL, and extracted with 50 mL of ethyl acetate. The organic phase was washed with water, sodium bicarbonate solution and brine (100 mL). The residue was purified by column chromatography (ethyl acetate: petroleum ether = 1 : 6)

Compound 22 compound 23

Add intermediate (X-1) 0.70 g (0.75 mmol), 4,6-dimethoxy-2-methanesulfonylpyrimidine 0.18 g (0.75 mmol) K ₂ C0 ₃ 0.12 g to a 50 mL reaction flask. (0.75 mmol) 10 mL of hydrazine, hydrazine-dimethylformamide, and the mixture was heated to about 50 ° C for 3 hours while stirring. After the reaction was completed, 50 mL of ethyl acetate and water were added to the reaction solution, and the mixture was extracted with 50 mL of ethyl acetate. The mixture was washed with water, sodium bicarbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. , a yellow oily liquid is obtained. The residue was purified by column chromatography (ethyl acetate: petroleum ether = 1 : 4) to give two products: compound 22 as a lesser compound and 0.06 g as a yellow oil, which is a Z-type configuration, ie, a nitrogen-oxygen bond and a double The methyl group on the bond is trans; the more polar one is compound 23, and the yellow oil is 0.13 g, which is in the E-type configuration, that is, the nitrogen-oxygen bond and the methyl group on the double bond are cis. The total yield was 55%.

The other compounds in Tables 1 and 2 can be obtained by a similar method as above.

Biometric example

Depending on the solubility of the test compound, the original pharmaceutically acceptable acetone or dimethyl sulfoxide is dissolved, and then 1% is used. The Tween 80 solution is formulated into a desired concentration of 50 mL of the test solution, and the content of acetone or dimethyl sulfoxide in the total solution is not more than 10%.

Spray treatment was carried out using a crawler crop sprayer (designed and manufactured by Engineering Research Ltd., UK) (spray pressure 1.95 kg/cm ² , spray volume 50 ml/m ² , crawler speed 30 cm/s, nozzle nozzle fan).

Pre-emergence test: The seeds of quantitative weeds (ramie, valerian, and crabgrass) were separately planted in culture rafts with a cross-sectional area of 100 cm ² , and the soil was covered with soil for 1 cm after sowing. The test compound was sprayed on the soil surface and placed after treatment. The greenhouse is then watered to 1%. Tween 80 was placed in tap water treatment as a control.

In the post-emergence test, the seeds of the quantitative weeds (ramie, foxtail, and crabgrass) were separately planted in a culture raft having a cross-sectional area of 100 cm ² , and the soil was covered with lcm after sowing, and cultured in a greenhouse according to a conventional method. When the weeds grow to 1.5 leaf stage, the test materials are selected to be sprayed after the seedlings are sprayed to 1%. Tween 80 was placed in tap water treatment as a control. After the test materials are treated, they are placed in a dry and ventilated place. After the liquid is naturally dried, it is placed in a greenhouse and managed according to conventional methods. 48 hours after treatment. The method of watering from the bottom is adopted to prevent the liquid from being washed away.

Visual inspection was conducted 4 weeks after the treatment, and the inhibition rate was various degrees of damage compared with the control, including killing of dead spots, distortion, deformity, growth inhibition, or leaf burning. Some test results are shown in Table 3 - Table 8.

Table 3 Herbicidal activity of some compounds of general formula (I) or (II) (pre-emergence / post-emergence, % inhibition)

Table 4 Herbicidal activity of some compounds of formula (I) or (II) (post-emergence, % inhibition)

20 20 40 0

160 98 100 60

80 95 98 55

26

40 70 100 55

20 75 100 60

Compound 12 was selected in parallel with the known compound Kd (Compound 17 in EP0223406) for herbicidal activity. The results are shown in Table 5.

Table 5 Parallel comparison of compound 12 with herbicidal activity of known compounds (post-emergence, % inhibition)

Compound 6 was selected to be parallel to the herbicidal activity of the known compound KC ₂ (compound 54 in EP 0249708). The results are shown in Table 6.

Table 6 Parallel comparison of the herbicidal activity of Compound 6 with the known compound KC ₂ (post-emergence, % inhibition)

Compound 9 was selected to be parallel to the known compound KC ₃ (Compound 1 in EP0321846), and the results are shown in Table 7.

Table 7 Parallel comparison of the herbicidal activity of Compound 9 with the known compound KC ₃ (post-emergence, % inhibition)

40 100

20 98

160 100

80 98

KC ₃

40 95

20 85

Compound 10 was selected to be parallel to the known compound KC ₄ (compound 9 in EP0435170), and the results are shown in Table 8.

Table 8 Parallel comparison of the herbicidal activity of Compound 10 with the known compound KC ₄ (post-emergence, % inhibition)

The structural formulas of the known compounds Kd, KC ₂ , KC ₃ and KC ₄ are as follows:

Claims

Request

A 2-pyrimidinyloxy(thio)benzoyl enoate compound, as shown by the formula (I) or (II):

In the formula:

X is selected from oxygen or sulfur;

Selected from H, halogen, acetyl, 4,6-dimethoxypyrimidin-2-oxy or the following groups:

2. A compound according to claim 1 wherein: in formula (I) or (II)

X is selected from oxygen or sulfur;

R _{2 is} selected from dC ₃ alkyl;

R _{3 is} selected from the group consisting of CC ₃ alkyl.

3. A compound according to claim 2, characterized in that: in the formula (I) or (II)

X is selected from oxygen or sulfur;

Selected from H, chloro, acetyl, 4,6-dimethoxypyrimidin-2-yl or the following groups:

Wherein, the nitrogen-oxygen bond and the double bond

R _{2 is} selected from ethyl;

R _{3 is} selected from a methyl group.

4. Use of a compound of the formula (I) or (II) according to claim 1 for controlling weeds.

A herbicidal composition comprising the compound of the formula (I) (II) as an active ingredient according to Claim 1 and an agriculturally acceptable carrier, the weight of the active ingredient in the composition The percentage is 5-90%.

A method for controlling weeds, characterized by: applying a herbicidally effective amount of the herbicidal composition according to claim 5 to a table where weeds or weeds grow or a form thereof.